High-Pressure Shock Compression of

Condensed Matter

Editors-in-Chief
Lee Davison
Yasuyuki Horie

Founding Editor
Robert A. Graham

Advisory Board
Roger Cheret, France
Vladimir E. Fortov, Russia
Jing Fuqian, China
Yogendra M. Gupta, USA
James N. Johnson, USA
Akira B. Sawaoka, Japan

Springer Science+Business Media, LLC

High-Pressure Shock Compression of Condensed Matter

L.L. Altgilbers, MDJ Brown, I. Grishnaev, B.M Novac, I.R. Smith, I. Tkach, and
Y Tkach: Magnetocumulative Generators
T Antoun, L. Seaman, D.R. Curran, G.l. Kanel, S V Razorenov, and A. V Utkin:
Spall Fracture
J Asay and M Shahinpoor (Eds.): High-Pressure Shock Compression
of Solids
SS Batsanov: Effects of Explosion on Materials: Modification and
Synthesis Under High-Pressure Shock Compression
R. Cherh: Detonation of Condensed Explosives
L. Davison, D. Grady, and M Shahinpoor (Eds.): High-Pressure Shock
Compression of Solids II
L. Davison, Y Horie, and T Sekine (Eds.): High-Pressure Shock
Compression of Solids V
L. Davison, Y Horie, and M Shahinpoor (Eds.): High-Pressure Shock
Compression of Solids IV
L. Davison and M Shahinpoor (Eds.): High-Pressure Shock
Compression of Solids III
A.N. Dremin: Toward Detonation Theory
VE. Fortov, L. V AI'tshuler, R.F. Trunin, and A.l. Funtikov (Eds.): High-Pressure
Shock Compression of Solids VII
R. Graham: Solids Under High-Pressure Shock Compression
Y Horie, L. Davison, and NN Thadhani (Eds.): High-Pressure Shock
Compression of Solids VI
IN. Johnson and R. Cheret (Eds.): Classic Papers in Shock
Compression Science
G.l. Kanel, S V Razorenov, and VE. Fortov: Shock-Wave Phenomena and the
Properties of Condensed Matter
VF. Nesterenko: Dynamics of Heterogeneous Materials
M Suceska: Test Methods for Explosives
JA. Zukas and WP. Walters (Eds.): Explosive Effects and Applications
V.E. Fortov L. V. AI' tshuler
R.F. Trunin A.I. Funtikov
Editors

High-Pressure Shock
Compression of Solids VII
Shock Waves and Extreme States
of Matter

With 223 Illustrations

i Springer
V.E. Fortov L.V. Al'tshuler (deceased)
Russian Academy of Sciences
32a Leninsky Prosp.
Moscow 117993
Russia
[email protected]

R.F. Trunin A.I. Funtikov

Russian Federal Nuclear Center Institute for High Energy Densities
All-Russian Research Institute Russian Academy of Sciences
of Experimental Physics Izhorskaya 13/19
607190 Sarov Moscow 127412
Nizhnii Novgorod Region Russia
Russia [email protected]
[email protected]

Editors-in-Chiej:
Lee Davison Yasuyuki Horie
39 Caiioncito Vista Road MS F699
Tijeras, NM 87059 Los Alamos National Laboratory
USA Los Alamos, NM 87545
[email protected] USA
[email protected]

Library of Congress CataIoging-in-Publication Data

High-pressure shock compression of solids VII : shock waves and extreme states of matler
/ V.E. Fortov ... [et aI.], editors.
p. cm. - (High pressure shock compression of condensed matter)
Includes bibliographicaI references and index.
ISBN 978-1-4419-1919-9 ISBN 978-1-4757-4048-6 (eBook)
DOI 10.1007/978-1-4757-4048-6
1. Materials-Compression testing. 2. MateriaIs at high pressures. 3. Shock (Mechanics)
1. Fortov, V.E. II. Series.
TA417.7.C65H4552003
620.1'1242--dc22 2003066024

ISBN 978-1-4419-1919-9 Printed on acid-free paper.

© 2004 Springer Seience+Business Media New York

Originally published by Springer-Verlag New York, Iue. in 2004
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 Lev Vladimirovich AI'tshuler
November 9,1913-December 23,2003

Professor Lev Al'tshuler was a renowned scientist and one of the founders of the
study of condensed matter under the extremely high pressures and temperatures
achieved with shock compression. Al'tshuler was a pioneer of the Soviet Atomic
Bomb Project, a laureate of three State Prizes of the Soviet Union (1946, 1949,
1953), winner of the Lenin Prize in 1962, and the Prize of the Government of
Russia in 1999. He attended several AIR.APT conferences in the 1970s and
1980s. In 1991 Al'tshuler received the Shock Compression Science Award of
the American Physical Society "in recognition of seminal and major contribu-
tions in the development of the field of shock wave compression of condensed
matter."
vi Dedication

Al'tshuler believed strongly that new technology for national defense should
be finnly based on scientific research. As he himself put it in his recent mem-
oirs, "At Arzamas-16, science not only served defense, but defense seIVed sci-
ence as well." As demonstration of this point, he is an author of over 60
publications in the scientific literature. ill the 1950s he began publishing papers
on equations of state at pressures up to 1 TPa (10 Mbar) obtained with impactor
velocities up to 15 km/s, twice the velocity obtained with two-stage guns and
three times the velocity obtained with plane-wave explosive systems of the type
used in the United States. Al'tshuler's data has achieved a standard of excel-
lence that still prevails 50 years after the experiments were performed.
For almost half a centwy American researchers were not sure how such a
high impact velocity was achieved. Finally in 1996 the experimental design was
declassified and published. High impact velocities were generated by conver-
gence in hemispherical systems driven by high explosives. This method was
used to generate unique equation-of-state data for a wide variety of materials
and formed the basis of a new scientific discipline called the physics of high
energy density.
- Apart from providing equation-of state data for many chemical elements and
compounds over a very wide range of pressure and temperature, the shock wave
also seIVed as a tool for physical research. By this means, Al'tshuler and his
colleagues were able to obtain high temperature boiling point CU1Ves, to produce
strongly nonideal plasmas, to discover previously unknown electronic recon-
struction in metals, to investigate shock-induced phase transformations, and to
study numerous other phenomena that occur at extremely high pressures.
Al'tshuler was born in Moscow in 1913. He began his career in 1932 when
he joined the X-ray Laboratory of the Machine Building illstitute in Moscow.
While working in this Laboratory, Al'tshuler met his life-long friends Veniamin
Tsukerman and Vitalyi Ginzburg, who won the Nobel Prize in Physics in 2003.
Al'tshuler entered Moscow State University in 1934 and graduated in 1936. ill
1940 he entered the Soviet Army as a aviation mechanic. He seIVed on the
German war front until 1942 when he was returned to the Academy of Sciences
where, together Tsukerman, he began to develop pulsed x-radiography to diag-
nose the effects of shaped-charge jets striking tank armor. For this work
Al'tshuler was awarded his first State Prize in 1946. That same year Yulii
Khariton, Scientific Director of Arzamas-16, invited Al'tshuler and Tsukerman
to join the Soviet Atomic Project and asked them to develop pulsed x-radiogra-
phy to diagnose what happens to a metal sphere placed inside an explosive sys-
tem.
During the years 1946-1969 Altshuler worked in the Russian Nuclear
Center Arzamas-16 located in the city of Sarov. Today this Institute is called the
All-Russia Research illstitute of Experimental Physics (VNlIEF). Experimental
work at VNIlEF was carried out in close. cooperation with Va. B. Zel' dovich,
 Dedication vii

A. D. Sakharov, and other prominent scientists. In collaboration with

Zel'dovich, Al'tshuler devised a method of determining the equation of state of
fissionable materials-the method of nonexplosive chain reactions (hydraulic
nuclear processes). In ~e 1960s Al'tshuler proved that it was possible to use
underground nuclear explosions for measuring the compressibility of materials
in the range of extremely high pressures and temperatures.
In recent years Al'tshuler wrote about the history of the Soviet Atomic
Project, including articles entitled The Lost World of Khariton and Next to
Sakharov. Al'tshuler always held independent positions on questions in political
and public life and he was not bashful about expressing them. In 1951, during
Stalin's regime, he told an important government commission that he disagreed
with the Communist Party's political position on biology. Al'tshuler expressed
his disagreement with the official Communist position regarding events in
Hungary in 1956, the Arab-Israeli war in 1967, and so forth. In 1969 the
resentment of the Communist Party resulted in their refusal to continue
supporting his work. Al'tshuler then left Arzamas-16 for Moscow and never
returned.
In 1969 he became head of a laboratory in the Institute of Optical-Physical
Measurements in Moscow and in 1989 he became a Chief Scientific Researcher
in the Institute for High Energy Densities of the Russian Academy of Sciences.
He was responsible for the development of shock compression research, contrib-
uted much to the education of students, and was always ready and willing to
help his successors.
Preface

In the mid 1950s, experimental studies of condensed matter at extremely high

pressures (i.e., high energy densities) began to appear in the scientific literature.
These studies were made possible by the use of strong shock waves to alter the
state of the substance being studied. The analysis of thennomechanical proc-
esses accompanying shock-wave compression of condensed matter is insepara-
ble from examination of the fundamental physical and chemical properties of the
materials themselves.
Apart from providing equation-of-state data for many chemical elements and
compounds over a very wide range of thermOdynamic states, shock-wave ex-
periments served as a tool for physical research that allows scientists to obtain
high-pressure melting curves, to produce strongly non-ideal plasmas, to discover
previously unknown electronic transformations accompanying fast, intense
deformations, and to study many other phenomena that occur at extremely high
values of physical parameters that are unattainable by other methods. The data
obtained have both fundamental scientific and practical value. The knowledge of
shock-wave properties of various materials and their equations of state over a
wide range of the thermodynamic variables is necessary for the solution of many
scientific and technical problems including those involving high-speed impact
and civil and military nuclear engineering projects.
The chapters of this book present a detailed account of the development of
Russian technology for conducting dynamic experiments to study material prop-
erties and behavior and some of the basic results so far obtained. The book,
enveloping a wide circle of problems, consists of surveys prepared by the lead-
ing scientists in the field. On many of the problems discussed, experimental and
theoretical results of the authors are presented and a generalization and sys-
tematization of the extensive material on the physics of shock waves and high-
pressure phenomena is provided.
The first chapter, written by L.V. Al'tshuler, one of the founders of this field
of investigation, reflects Russian development of dynamic research techniques
for studying high pressure and anticipates the material enunciated in more detail
in subsequent chapters. (Professor Al'tshuler passed away on 23 December, 2003
just as this book was going to press.)
In the second chapter, some problems of detonation of condensed explosives
used for excitation of shock waves and creation of high-velocity-impact devices
for producing high pressures are discussed. It contains a review of the experi-
x Preface

mental methods used and an analysis of the results obtained. The actual modes
of detonation of both single- and multi-component explosives are emphasized
The following chapters are devoted to experimental investigations that have
quantified effects of shock compression of metals at high- and hyper-pressures.
In the third chapter, some results of examinations of shock compression of met-
als are analyzed. Hugoniot curves are classified by the form of the relation
between wave and particle velocities. The observed data, which have been
obtained by the most reliable absolute methods of measuring shock-wave pa-
rameters in the laboratory and in the vicinity of underground nuclear explosions,
reach maximum pressures of 2.5 TPa in first case and 10 TPa in second. Meas-
urements of relative compressibility, which have been carried out in under-
ground explosions, extend to even higher pressures. The observed data are
compared to dependencies calculated using various theoretical models.
In the following chapter, computational models of shock compression of
condensed matter are considered further, and the results of approximation of
experimental data on shock compressibility in the form of wide-range Hugoniots
are given. Reference data for 80 substances are also given, and six metals are
recommended as shock-wave standards because they have been identified as
having the most precise Hugoniot curves available.
In the fifth chapter, the results of measuring the shock compressibility of po-
rous of iron, copper, nickel, and tungsten are given. These results were obtained
in the laboratory and under the conditions provided by underground nuclear
explosions.
Chapters 6-10 are devoted to problems of the structure of shock waves in
solids. The results of experimental examination of shock-induced phase changes
in solids are given in Chapter 6. Data from static and dynamic experiments at
multi-megabar pressures and an analysis of the phase diagram of iron are pre-
sented. In the following chapter, some qualitative regularities of thermodynam-
ics and kinetics of shock-induced phase changes and problems of stability of
shock waves in substances with phase changes are considered. The behavior of
quartz subjected to shock-wave compression is examined in more detail.
In Chapter 10, computational models of the structure of shock waves in sol-
ids and the main effects, stress relief, and the changing yield strength of metals,
exhibited in shock and rarefaction waves are considered. This allows description
of shock-wave deformation of metals as a nonequilibrium process of develop-
ment of elastic-plastic flow behind a shock front
The next chapters are devoted to problems of description of compressed and
plasma states.
In Chapter 11, the results of optical studies of shock-compressed dielectrics
are analyzed for application to measurement of equations of state. Temperature
 Preface xi

measurements on ionic crystals and liquid argon and xenon considerably im-
proved the EOS of these materials and extended the melting curves of ionic
crystals. It was found that the Mie-Griineisen equation. combined with a Debye
heat capacity function. yielded accurate values of the Hugoniot temperature up
to melting curve for solids. A number of nonequilibium processes of optical
radiation and absorption have been observed.
In Chapter 12, quasi-isentropic compression data for molecular hydrogen
and deuterium are presented. The parameters of the EOS of the solid and liquid
phases are found
An alternative approach to construction of an EOS for the liquid phase is a
generalized van der Waals model using the elastic compression isotherm as a
covolume for material compressibility. At high temperatures, the thermal ioni-
zation of atoms is included and a Saha-type equation is employed for describing
ionization equilibrium.
In Chapter 14, an EOS is given covering the wide pressure-temperature
range that can be accessed by shock compression and isentropic decompression
of highly porous metals. This EOS is based on a model of a highly nonideal
plasma. At the heart of this quasi-chemical approach is a calculation of the equi-
librium ionization composition. which is based on minimization of the free en-
ergy corrected for the interparticle interaction of electrons and ions. The validity
of the chemical model is, to a large extent, related to such additional features as
the proper volumes of atoms and ions of various degrees of ionization. interpar-
tic1e attraction, etc.
In Chapter 15, the concept of fracture of materials is discussed, in particular,
as it applies to large structures subjected to the action of intensive inertial reac-
tion forces. Criteria involving the stored elastic strain energy and a simplified
phenomenological model allow description of dynamic fractures and estimation
of the load resulting in fracture of the structure.
The book contains an extensive bibliography on the majority of problems
discussed. For convenience, the relevant entries are placed at the end of each
chapter.
Moscow, Russia V.E. Fortov
Moscow, Russia L. V. Al'tshuler
Sarov, Russia R. F. Trunin
Moscow, Russia A. I. Funtikov
Contents

Dedication ....................................................................................................... v
Preface ........................................................................................................... ix
Contributors ................................................................................................. xix
CHAPTER 1
Development of Dynamical Methods ofInvestigation of
High Pressures in Russia ........................................................................... 1
L. V. AI'tshuler
1.1. Introduction .................................................................................... 1
1.2. Detonation of Condensed High Explosives ...................................... 2
1.3. Hugoniots of Metals: Techniques and Results.................................. 7
1.4. The Hundred-MegabarPressure Range ......................................... 14
1.5. Isentropic Compressibility and Polymorphic Transformation
in Shock Waves ............................................................................ 18
1.6. Wide-Range Phase Diagram of Shock Compression
of Metals ...................................................................................... 20
1.7. Description of Extreme States ....................................................... 25
1.8. Optical Measurements of Shock-Compressed Dielectrics ............... 28
1.9. Conclusion ................................................................................... 30
References .............................................................................................. 31
CHAPTER 2
Detonation of Condensed Explosives ............................................................. 39
L. V. AI'tshuler, V. S. Zhuchenko, and A. D. Levin
2.1. Introduction .................................................................................. 39
2.2. Experimental Techniques .............................................................. 39
2.3. Detonation Pressure ...................................................................... 49
2.4. Modes of Detonation .................................................................... 54
2.5. Conclusions .................................................................................. 69
References .............................................................................................. 71
CHAPTER 3
Hugoniot Curves of Metals ............................................................................ 77
R F. Trunin
3.1. Introduction .................................................................................. 77
3.2. Measurement Techniques .............................................................. 79
3.3. Laboratory Measuring Devices ...................................................... 80
xiv Contents

3.4. Design of Polygon Measurement Configurations Used

at Underground Test Sites ............................................................. 83
3.5. Compressibility Data Obtained from
Laboratory Measurements ............................................................. 86
3.6. Compressibility Measurements in Underground
Nuclear Explosions ....................................................................... 91
3.7. Comparison of Experimental Data and
Computational-Model Representations ........................................ 103
References ............................................................................................ 107
CHAPTER 4
Wide-Range Characteristic Thermodynamic Curves .................................... 109
N. N. Kalitkin and L. V. Kuzmina
4.1. Quantum-Statistical Hugoniots of Porous Substances .................. 109
4.2. Wide-Range Principal Hugoniots ................................................ 123
4.3. Copper Standard Global Isotherm ............................................... 142
4.4. Plasma Microfields and the Thermal Properties of Materials ........ 151
References ............................................................................................ 173
CHAPTERS
Shock-Wave Compression of Porous Metals ................................................ 177
R. F. Trunin, K. K. Krupnikov, G. V. Simakov, and A. I. Funtikov
5.1. Introduction ................................................................................ 177
5.2. Design of Experiments ................................................................ 180
5.3. Experimental Data ...................................................................... 182
5.4. Thermodynamic Parameter Evaluation-Equation of State
with Variable Specific Heat ........................................................ 185
References ............................................................................................ 193
CHAPTER 6
Shock Waves and Polymorphic Phase Transformations in Solids .................. 197
A. I. Funtikov and M. N. Pavlovsky
6.1, Introduction ................................................................................ 197
6.2. Sound Speeds and the Strength of Shocked Metals ...................... 199
6.3. Phase Transformation in Shock Waves ........................................ 201
6.4. Mechanism of Polymorphism of Group IVElements ................... 206
6.5. Experimental Data for Quartz and Other Minerals ....................... 212
References ............................................................................................ 217
CHAPTER 7
Phase Diagram of Iron ................................................................................. 225
A. I. Funtikov
7.1. Introduction ................................................................................ 225
7.2. Phase Diagram of Iron From Static and
Shock-Wave Measurements ........................................................ 227
 Contents xv

7.3. Melting During Isentropic Expansion of

Shock-Compressed Iron .............................................................. 231
7.4. Calculations of Melting Isentropes and the Melting Curve
Within the Range of the e Phase .................................................. 233
7.5 Conclusion ................................................................................. 242
References ............................................................................................ 243
CHAPTER 8
Some Questions of Phase Transition in Shock Waves ................................... 247
N. M. Kuznetsov
8.1. Introduction ................................................................................ 247
8.2. Kinetics and Mechanisms of Phase Transition in
Shock Waves .............................................................................. 247
8.3. Hysteresis ................................................................................... 252
8.4. The Possibility of Realizing Diffusive and Martensitic
Transformation Mechanisms ....................................................... 253
8.5. Kinks of the Hugoniot.. ............................................................... 258
8.6. Hugoniots of Two-Phase Liquid-Vapor Systems ....................... 262
8.7. Hydrodynamic Stability of Shock Waves.
Rarefaction Shock Waves ........................................................... 264
8.8. On the Possibility of Shock-Wave Superheating of Solids............ 267
References ............................................................................................ 270
CHAPTER 9
Kinetics of Shock-Induced Phase Transition of Quartz ................................. 275
N. M. Kuznetsov
9.1. Introduction ................................................................................ 275
9.2. Amorphization of Quartz ............................................................ 278
9.3. On the Nature of the High-Pressure Phase ................................... 282
9.4. Calculation of the Hugoniot in the Two-Phase Range .................. 284
9.5. The Mechanism of High-Pressure Phase Formation ..................... 286
9.6. Activation Model of Shock Compression
and Unloading of Quartz ............................................................. 287
9.7. Conclusion ................................................................................. 291
References ............................................................................................ 292
CHAPTER 10
Shear Strength and Viscosity of Metals in Shock Waves ............................... 297
P. V. Makarov
10.1. Introduction ................................................................................ 297
10.2. Strong and Weak Shock Waves ................................................... 298
10.3. One-Dimensional Model of Elastic-Plastic Flow
in a Plane Shock Wave................................................................ 303
10.4. Attenuation of Elastic Precursors and Structure
of Shock Waves .......................................................................... 309
xvi Contents

10.5. The Shear Strength of Metals in Shock Waves ............................. 310

10.6. Simulation of the Structure of Strong Shock Waves ..................... 318
10.7. Viscosity of Metals in Shock Waves ............................................ 321
References ............................................................................................ 331
CHAPTER 11
Temperature Measurement and Equation of State of Condensed Matter ........ 337
V. D. Urlin
11.1. Introduction ................................................................................ 337
11.2. Investigation of the Reflective Power ofa Shock Front... ............. 339
11.3. Measurement of the Refractive Index of
Shock Compressed Ionic Crystals ............................................... 340
11.4. Measurement of the Optical Absorption Factor and
Mechanism of Light Absorption and Conductivity....................... 343
U.5. Temperature Measuring Technique for Shock.Compressed
Condensed Materials .................................................................. 345
11.6. Equation of State for Solid and Liquid Phases ............................. 348
11.7. Temperature Measurement of Shock-Compressed Ionic Crystals
and Experimental Melting Curves ............................................... 356
U.8. Polymorphic Transitions in Ionic Crystals ................................... 363
11.9. Nonequilibrium Radiation at Low Temperatures of
Shock Compression .................................................................... 369
U.I0. Electron Screening of Radiation at High Temperatures ................ 370
11.11. Measurement of Brightness Temperatures in
Shock-Compressed Liquid Argon and Xenon .............................. 375
U.12. Hugoniots of Highly-Rarefied Condensed Substances.................. 375
11.13. Conclusion ................................................................................. 377
References ............................................................................................ 379
CHAPTER 12
Isentropic Compressibility and Equation of State of Hydrogen up to 1 TPa ... 383
V. P. Kopyshev and V. D. Urlin
12.1. Introduction ................................................................................ 383
12.2. Experimental Determination of the Density of
Isentropica1ly-Compressed Hydrogen .......................................... 384
12.3. Equation of State of Solid and Liquid Molecular Hydrogen ......... 385
12.4. Equation of State of Molecular and Atomic Hydrogen in
Covolume Form .......................................................................... 388
12.5. Zero-Temperature Isotherm of Atomic Hydrogen ........................ 393
12.6. Comparison of Calculated Thermodynamic Values
with Experiment ......................................................................... 396
References ............................................................................................ 400
 Contents xvii

CHAPTERl3
Modification of the van der Waals Model for Dense States of Matter............ 403
A. B. Medvedev
13.1. Introduction ................................................................................ 403
l3 .2. Model of a Simple Liquid ........................................................... 404
l3 .3. Model of Liquid Mixtures ........................................................... 411
13.4. Consideration of Melting ............................................................ 420
References ............................................................................................ 431
CHAP1ERI4
Thennodynamic Properties of Shock-Compressed Plasmas Based
on a Chemical Picture ........................................................................... 437
V. K. Gryaznov, I. L. Iosilevskiy, and V. E. Fortov
14.1. Introduction ................................................................................ 437
14.2. Chemical Model. Low Densities ................................................. 441
14.3. The Problems of Extrapolating the Chemical Model to
lligh Compressions ..................................................................... 445
14.4. Effective Charge Interaction: Modified
Pseudopotential Approach .......................................................... 448
14.5. Thennodynamics of Shock Compressed Xenon and
Cesium Within the Pseudopotential Model .................................. 452
14.6. Thennodynamics of Shock-Compressed Argon and
Cesium in Terms of the Confined-Atom Model ........................... 457
14.7. Extrapolation of the Chemical Model to the Region of
lligh Densities: Hugoniots of Porous Metals ............................... 464
14.8. Ultrahigh Heating and Compression: Hugoniots of
Solid Aluminum, Iron, and NickeL ............................................ 475
14.9. Chemical Model: A Wide-Range Equation of State (WEOS) ...... 480
14.10. Conclusion ................................................................................. 482
References ................................................. '" ........................................ 483
CHAP1ER 15
Fracture of Structures Caused by Explosive Loading: Scale Effects .............. 491
A. G. Ivanov
15.1. Introduction ................................................................................ 491
15.2. Integral Approach to the Fracture Problem .................................. 494
15.3. Design Methods for Decreasing the Risk of Failure ..................... 503
15.4. Explosive Fracture of Vessels ..................................................... 507
15.5. Other Examples of Using the Integral Approach .......................... 513
15.6 Conclusion ................................................................................. 523
References ............................................................................................ 525
Index ........................................................................................................... 529
Contributors

L.v. Al'tshuler (deceased)

V.E. Fortov
Russian Academy of Sciences
32a Leninsky Prosp.
Moscow 117993
Russia
[email protected]
A.I. Funtikov
Institute for High Energy Densities
Russian Academy of Sciences
Izhorskaya 13/19
Moscow 127412
Russia
e-mail: [email protected]
V.K. Gryaznov
Institute of Problem of Chemical Physics
Russian Academy of Sciences
Chemogolovka
Russia
I.L. Iosilevskiy
Moscow Institute of Physics and Technology (State University),
Dolgoprudny
Moscow Region 141700
Russia
A.G. Ivanov
Russian Federal Nuclear Center,
All-Russian Research Institute of Experimental Physics
Sarov 607190
Nizhnii Novgorod Region
Russia
N.N. Kalitkin
Institute for Mathematical Modeling
Russian Academy of Sciences
Moscow
Russia
xx Contributors

V.P. Kopyshev
Russian Federal Nuclear Center,
All-Russian Research Institute of Experimental Physics
Sarov 607190
Nizhnii Novgorod Region
Russia
K.K. Krupnikov
All-Russian Research Institute of Technical Physics
Snezynsk:
Chelyabinsk Region
Russia
L. V. Kuzmina
Institute for Mathematical Modeling
Russian Academy of Sciences
Moscow
Russia
N.M. Kuznetsov
Institute of Chemical Physics
Russian Academy of Sciences
Moscow, Russia
A.D. Levin
All-Russian Scientific Reaserch Institute for Optical and Physical
Measurements;
Moscow, 119361, Russia
P.V. Makarov
Institute of Physics of Strength and Science of Materials
Siberian Section, Russian Academy of Sciences
Tomsk, Russia
A.B. Medvedev
Russian Federal Nuclear Center,
All-Russian Research Institute of Experimental Physics
607190 Sarov,
Nizhnii Novgorod Region
Russia
M.N. Pavlovsky
Russian Federal Nuclear Center,
All-Russian Research Institute of Experimental Physics
607190 Sarov,
Nizhnii Novgorod Region
Russia
 Contributors xxi

G.V. Simakov
Russian Federal Nuclear Center,
All-Russian Research Institute of Experimental Physics
607190 Sarov,
Nizhnii Novgorod Region
Russia
RF. Trunin
Russian Federal Nuclear Center
All-Russian Research Institute of Experimental Physics
607190 Sarov
Nizhnii Novgorod Region
Russia
e-mail: [email protected]
V.D. Urlin
Russian Federal Nuclear Center
All-Russian Research Institute of Experimental Physics
607190 Sarov,
Nizhnii Novgorod Region
Russia
V.S. Zuchenko
Mechanical Engineering Research Institute
Moscow, 125212, Russia
 CHAPTER 1

Development of Dynamical Methods of

Investigation of High Pressures in Russia

L.V. AI'tshuler

1.1. Introduction
The progress of natural sciences today is characterized by dramatic advances in
our understanding of the extreme states of matter. This is due in large part to the
development of dynamic methods [1,2] which involve the generation and meas-
urement of very short-lived, high-density, and high-temperature states of matter
occurring at megabar pressures behind strong shock waves. Information about
shock-wave compression helps interpretation of static experiments as well.
Today, it is mainly dynamic measurements that provide reference data for the
static megabarpressure range [3,4].
Use of the shock wave as a tool for physical research helped scientists to
construct equations of state for many substances over a very wide range of pres-
sure and temperature, to obtain melting curves for transparent dielectrics, to
produce strongly non-ideal plasmas, to find numerous electronic reconstructions
in metals, and to study shock-induced phase transitions. The data obtained
proved to be useful for geophysics and essential for nuclear energy.
The development of dynamic methods is inseparable from the history of
atomic weapons. Military-oriented shock-wave research was initiated in the
United States within the framework of the Manhattan project in 1945 [5]. In the
Soviet Union this program was launched independently in 1947 [6].
It is sometimes argued that Soviet scientists and design engineers should not
have participated in the nuclear weapons project and that, given the totalitarian
regime then in power, there is even something immoral in that they did. To say
this, however, is to forget that the early postwar years was a time when all the
devastating power of the nuclear bomb was a monopoly of the United States.
For those recognizing the advent and harsh reality of the atomic era, it was im-
portant to redress the world balance as soon as possible. Physics also gained
from that. As Academician GoI'danskii has recently put it, "The explosion of the
Atomic Bomb saved Soviet physics" from the sad fate that genetics, cybernetics,
and other sciences met in the grim years of the "cosmopolite campaign" [7].
V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII
© Springer Science+Business Media New York 2004
2 L. V. Al'tshuler

As a result of this special attention on the part of the Government, the

Russian Nuclear Center Arzamas-16 and the All-Union Research Institute of
Experimental Physics, or VNIIEF, under YuB. Khariton, were set up in 1946 in
total isolation from the outside world This was in a sense a "hidden Khariton' s
world" where a multidisciplinary team of physicists, mathematicians, designers,
and experimentalists was given most favorable working conditions and where
fundamental science and defense mutually benefited each other.
Experimental work at VNIIEF was carried out in close cooperation with
Ya.B. Zel'dovich, AD. Sakharov, D.A Frank-Kamenetski, and E.!. Zababakhin,
all prominent Soviet scientists and trailblazers. In fact, an entirely new scientific
discipline of the physics of high energy densities was created. The author of the
present work had the good fortune to experience the inimitable creative atmos-
phere of the unique scientific school promoted by these scientists.
The most important contribution into this field of science was made by
Zel'dovich. His scientific life was devoted to more and more powerful explo-
sions: detonation and chemical explosions, chain reactions and nuclear explo-
sions, and finally the Big Bang from which the Universe emerged 15 billion
years ago. Combustion and detonation were Zel'dovich's first and lifelong love,
a passion to which he remained faithful until his last day.
Zel'dovich's school for the study of the extreme states of substances was
recognized internationally. When speaking at the 1969 International School of
Physics of High Energy Density, E. Teller along with Los Alamos physicists,
also distinguished Zel'dovich and Al'tshuler who, in his words, "seem to have
contributed most in the discovery of this new research area" [8]. Al'tshuler re-
ceived the American Physical Society Compression Science Award in 1991 "In
recognition of seminal and major contributions in the development of the field
of shock wave compression of condensed matter" [9].
V.A. Tsukerman, the founder of the method of pulse radiography, played a
key role in the experimental research in the Soviet atomic project [10].
The Russian Federal Nuclear Center in Snezhinsk and the Academy of
Sciences counterparts in Moscow, Chemogolovka, and Novosibirsk were in-
strumental in developing dynamic measurement techniques and undertaking
investigation of extreme states of matter, based on application of shock waves in
high-pressure physics.

1.2. Detonation of Condensed High Explosives

The role of the products of detonation of condensed explosives in atomic
weapon prototypes is one of a ''working fluid," the same role that water vapor
plays in a steam engine. It so happened that the problem Zel'dovich and VNIIEF
group heads Tsukerman, Zavoiskii, and Al'tshuler had to face in 1947 was to
determine the detonation pressure of condensed explosives. The reason was that,
 1. Dynamical Methods of Investigation of High Pressures 3

whereas the power of the atomic devices then under development was dependent
on the pressure of the detonation products in convergent detonation waves, the
theoretical pressure values predicted by different models differed by a factor
exceeding 1.5. In the shortest time, reliable experimental data were collected,
and these data enabled the results of the first Soviet atomic test of 1949 to be
predicted
The works which form milestones in the theory of detonation processes are
those of Michelson [11], Chapman [12], Jouguet [13], and Zel'dovich [14]. The
main difference between the shock wave and the self-sustained detonation wave
is that the latter propagates at constant velocity. The first analysis of this effect
was produced by Professor Michelson at the Moscow Agricultural Institute. In a
pUblication of 1893 [11] he wrote: "As regards detonation, here we encounter an
extraordinarily interesting case in which, owing to the specific chemical and
thermal processes involved, the conditions for constant velocity propagation are
indeed satisfied." In the pressure-volume diagram of Fig. 1.1, the steady propa-
gation velocity corresponds to a straight line which Zel'dovich [15] quite justi-
fiably dubbed the Michelson line. According to Chapman (1899), the velocity of
a detonation wave is the smallest possible, and states behind the detonation front
are remarkable in that, due to the condition Jouguet established in 1904, the
sound speed in the detonation products is exactly equal to the velocity of steady
detonation relative to those products.
Zel'dovich [14], von Neumann [16], and DOring [17] independently carried
out analyses of, and provided justification for, Jouguet's state selection mecha-
nism in 1940, 1942, and 1943, respectively. According to their collective ZND
concept, the key structural elements of the detonation transformation are the
shock compression front in the original explosive, the steady-flow region of
chemical decomposition, and a region containing self-similarly expanding deto-

Figure 1.1. A P- V diagram for a steady detonation. The state changes along the line
from state 1 to state 2 as the reaction zone passes a material point State 2 is called the
Chapman-J ouguet point
4 L. V. AI'tshuler

nation products adjacent to the chemical reaction zone. The calculated detona-
tion wave amplitudes at the boundaries of the reaction zone (i.e., the predicted
detonation pressures) depend on the assumed fonn of the equation of state
(BOS) for the compressed and heated detonation products.
In the van der Waals covolume EOSs most commonly used in the mid-
1940s, the "occupied volume" of the detonation products played the role of the
covolume (generally a function of pressure). According to another concept
(1945) of Landau and Stanyukovich [18], rather than using a gas EOS, a more
valid approach is to compare the decomposition products with a liquid that ex-
pands adiabatically from the Chapman-Jouguet state and in which the pressure,
P, and the volume, V, are related by an expression of the type pv n = const.
According to the covolume approach of Gennan authors [19], the detonation
pressure of TNT (trinitrotoluene) was estimated to be 12 GPa as compared with
19 GPa given by Landau and Stanyukovich. Zel'dovich and Kompaneets, who
basically followed the approach of [18], wrote, in 1955, "The results obtained
with the Landau-Stanyukovich equations of state appear as predictions yet to be
verified" [20].
In the United States, experimental work on this subject was initiated in 1945,
although it was only in the mid 1950s that results were published [21,22]. As
mentioned earlier, in 1948 VNIIEF experimenters independently developed a
~umber oftechniques for measuring detonation pressures. Those included [2]:

• Pulsed x-ray photography of x-ray-opaque markers behind the detonation

wave front (Tsukerman).
• The spall technique, which measures the initial velocities of plates of
various thicknesses attached to the charge (Al'tshuler, Krupnikov).
• The magnetoelectric measurement of the velocity of detonation products
behind the detonation wave front based on the velocity with which a
conductor inserted into the charge moves in a unifonn magnetic field
(Zavoiskii).
All three methods went through many ups and downs in their early develop-
ment [23] but showed the Landau-Stanyukovich approach to be correct. Exten-
sive efforts at improving, developing, and extending these techniques have
subsequently been made at VNIIEF and Russia's other research centers. For
example, Zubarev's pulsed x-ray technique for measuring the velocity of deto-
nation products [24] enabled the asymptotic detonation parameters of heteroge-
neous explosives to be estimated. Special mention should be made of the
Institute of Chemical Physics of the Russian Academy of Science (Russian ab-
breviation: IKhF), where Nobel laureate Academician N.N. Semenov, friend and
colleague of Academician Yu.B. Khariton, initiated the study of combustion and
detonation processes and where YaB. Zel'dovich began his illustrious career.
 1. Dynamical Methods of Investigation of High Pressures 5

As a natural extension of the spall method, a variety of techniques for the

precision measurement of shock-wave attenuation in barriers adjacent to the
explosive were developed. Of these, the most sensitive technique is that due to
Voskoboinikov and his colleagues at IKhF [25), in which the brightness of ra-
diation from the shock front is measured in a liquid window material adjacent to
the charge and previously calibrated for shock compression. Liquid window
materials have been used in studying a number of explosives [26,27), and
through their use, data on the detonation temperature of condensed explosives
have been collected [28).
A very effective time-tested technique for studying the detonation regimes of
condensed explosives is that of A. Levin, which involves the laser measurement
of wave velocities (the "LMWV method") in layered transparent barriers adja-
cent to the charge [29,30). In Fig. 1.2a, results on detonation wave profiles in
TNT are represented by curves for wave velocity attenuation in plexiglas barri-
ers for various charge lengths. Consistent with the classical ZND theory, ex-
periments indicated a steady zone of explosive chemical decomposition
followed by a self-similar rarefaction wave. For desensitized explosives [31], the
existence of detonation wave profiles was first demonstrated in the steady weak-

D,kms- I
6.5

6.0

5.5

6.0

6.5

o 2 4 6 8 I,mm

Figure 1.2. Variation of the shock wave velocity in plexiglas with the distance from the
(a) 'INT, (b) desensitized PErn, and (c) agatized RDX charge. Numbers alongside the
curves show the charge length in mm. Reprinted with permission from V.K. Ashaev, G.S.
Doronin, and AD. Levin, About structure ofdetonation front in condensed explosives, in
Fiz. Gor. Vzr. 24(1), pp. 95-99 (1988).
6 L. V. AI'tshuler

detonation regime predicted by Zel'dovich [32]. Measurements on a desensi-

tized PETN (Fig. 1.2b) show a steady zone of successive decomposition of an
explosive and a desensitizer followed by a self-similarly extending plateau. An
LMWV study also revealed an unusual detonation regime in high-density (so-
called agatized) RDX and HMX charges [33] (Fig.1.2b). In this regime, the
explosive decomposes completely or partially in the shock front with no pres-
sure increase occurring in the chemical reaction zone.
A magnetoelectric method capable of directly measuring the velocities and
pressures of explosion products was used by Zubarev in the mid 1950s [34] and
re-introduced at IKhF in the mid 1960s [35-37]. Although inferior to LMWV in
terms of resolving power, the method permitted an extended measurement time
and made it possible to extrapolate data to effective pressure values. The tech-
nique was widely used to determine the parameters of many explosives and
explosive mixtures with desensitizing and inert additives. Since 1970, the tech-
nique has also been used by American workers [38].
The use of manganin sensors offers yet another possibility for measuring
pressure profiles in detonation products. Kanel [39,40], the first to apply the
technique to detonation studies in the USSR, investigated, in particular, shock-
wave propagation and detonation wave formation in TNT and other explosives.
These results, combined with laser interferometry data on the detonation reac-
tion zone [42], provided insight into the kinetics of energy release in shock and
detonation waves [41,42].
Analysis of extensive work performed in this country and the United States
shows that detonation parameters are now known to within 2-3% [31].
Table 1.1 swnmarizes the initial densities, Po, detonation velocities, D, experi-
mental pressures, P [31], and temperatures, T [29], for steady detonation of the
most widely used explosives. For most high-energy explosives, the isentropic
exponent, n, accounting for the thermodynamics of the detonation products in
the Landau-Stanyukovich equation is 3, to a good accuracy.
In the early 1960s, on Zel'dovich's initiative, experimental work was
launched at VNIIEF to elucidate the nature of the high pressure observed in
detonation products: To what extent is it determined by the thermal motion of

Table 1.1. Explosive parameters.

Explosive Po, g/cm3 D, mls P, GPa T, K n

lNT (Trinitrotoluene) 1.6 6895 18.4 3140 3.12

RDX (Hexogen) 1.71 8400 30.9 3740 2.9
PErn 1.66 7950 27.0 2.9
HMX (Octogen) 1.80 8735 36.1 3700 3.1
lNT-RDX 50/50 alloy 1.67 7650 25.0 3460 3.0
 1. Dynamical Methods of Investigation of High Pressures 7

molecules and to what extent by their response to cold (OK) compression. For
this, additive EOSs of explosion products were constructed from EOSs of the
basic decomposition components of explosives [43,44]. Specifically, the
Hugoniot curves of carbonic acid and nitrogen were measured and used together
with already known Hugoniots for water and graphite. The result was that 30-
55 % of the pressure is of a thennal nature. It was a real revelation for theoretical
physicists when Brish, Tarasov, and Tsukerman [45] observed the large electri-
cal conductivity of detonation products in the layer adjacent to the detonation
wavefront.

1.3. Hugoniots of Metals: Techniques and Results

In 1947, VNIlEF experimenters were confronted with the massive challenge of
investigating the EOSs of fissionable materials and determining their shock
compressibility at megabar pressures. At that time, uncertainties in EOSs of
fissionable materials, as in detonation pressure values, prevented estimation of
the energy yield of the first nuclear weapon test scheduled for 1949. These un-
certainties also prevented gauging the effectiveness of other atomic projects. In
the shortest possible time, methods for determining the shock-wave characteris-
tics of compressed materials and the necessmy facilities involving the use of
explosive power were developed.
The first to develop dynamic methods for studying compressibility were the
Los Alamos researchers Goranson et al. [5] and Walsh and Christian [46] in the
USA and independently VNIIEF researchers in the USSR [47,48]. All of the
American and some of the early Soviet studies employed spall techniques (see
[47]), which measure the velocity, W.p. of the specimen free surface (a broken
off layer) after it reflects the shock wave. This free-surface velocity is the sum
of the particle velocity behind the shock front, U, and the additional velocity
imparted by the decompression wave. For shock waves of relatively low ampli-
tude, the former is, to a good approximation, U - W. p /2. In the megabar pressure
range the spall method is invalid
Instead, in 1948, Al'tshuler proposed the "arrest method", later to be de-
scribed in [47], in which the measured parameters are the shock velocity in the
specimen, D, and the velocity, W, of the shock-producing ilnpactor. In contrast
to the approximate spall technique, Al'tshuler's method has no pressure restric-
tions. For a specimen and an impactor made of the same material, U= W/2. For
dissimilar materials, this relation does not hold. To overcome this, an impactor
of a reference material with a known Hugoniot is used. Iron and aluminum gen-
erally fulfilled the role of a reference material at VNIIEF. Knowledge of the
Hugoniot curves of reference materials made it possible to determine the dy-
namic compressibility by means of the reflection method developed by the
authors of [48] in cooperation with G.M. Gandel'man.
8 L .V. AI'tshuler

The spall technique was used in Russia only for pressures of up to 50 GPa.
Experimental data were obtained by using tailor-made explosive charges which
had a planar detonation front. The specimens were arranged on a plate placed in
contact with the charge. To extend the shock pressure range to 200 GPa for
medium-atomic-number metals, and to perform arrest measurements, the so-
called "flat speed-up impact systems," which use detonation products to propel a
plate impactor, were employed [49,50).
In Russia, laboratory pressures of up to 1 TPa-much higher than in the
United States-were achieved for many metals in the early history of the work
but, until recently, no information has been available on the specific shock-wave
generators used. As recently as 1988, Livermore researchers wrote [51]: "The
absolute Cu and Pb data near 1 TPa of Altshuler, Bakanova, and Trunin [52] and
Kormer et al. [53] were obtained by an un-described shock generation system
and until now never reproduced."
The history of creation and design of explosive laboratory devices for dy-
namic compressibility measurements are described in a 1996 publication [54].
Since its introduction in 1948 by Al'tshuler, Zababakhin, Zel'dovich, and
Krupnikov [55], a hemispherical charge initiated simultaneously over its outer
surface (Fig. 1.3) has been an ideal tool for shock compressibility work at
VNIIEF. In this scheme, a thin-walled metallic shell inserted into the explosive
charge is propelled to the center of the charge by the products of a convergent
detonation wave, thus making the shell strike the hemispherical specimen.
In terapascal studies at VNIIEF, so-called cascade measuring systems have
become widely used. In 1948, Academician Zababakhin [54] advanced a scheme
of plane cascade plate acceleration, in which a plate driven to a high velocity by

! Z J 5
Figure 1.3. Schematic of a hemispherical explosion measuring device. 1: explosive
charge, 2: shell, 3:screen, 4: samples, and 5: electrocontact sensors for measuring shock
wave velocities
 1. Dynamical Methods offuvestigation of High Pressures 9

the detonation products of the first charge impacts the second charge creating a
strong detonation wave in the latter which, in tum, drives another, thinner plate.
Pressures close to 1 TPa were reached using the hemispherical two-stage
scheme of AI'tshuIer, Kormer, Krupnikov, and Ledenev {54]. The hemispherical
single-stage charge described above was used as the first stage. Within this, a
second stage (Fig. 1.4), a hemispherical explosive layer with a 2-mm-thick steel
shell adjacent to its inner side, was mounted. With this measuring device pres-
sures of up to 1.3 TPa in Fe {56,57] and 1.8 TPa in U {58] were obtained in the
late 1950s (Fig. 1.5). This corresponds to an Fe-shell impactor velocity of
15.5 km/s.
The earliest results, on Fe and eight other metals, were published in 1958
and covered pressures up to 500 GPa {47,48], which is an order of magnitude
higher than that reached in American work at the time {5,46]. In the United
States, the 200 GPa level was reached in 1960 {50], and a pressure of 430 GPa,
in the early 1980s, when two-stage light-gas guns were introduced {59].
Apart from Fe, Hugoniots for Ni, Cu, Zn, Cd, Sn, and Pb were measured for
pressures of up to 900 GPa [52]. The Hugoniots of Au and W are shown in Fig.
1.6 and the Hugoniots of AI and Cu shown in Fig. 1.7 compare Russian and
American data obtained with explosive measuring devices and two-stage light-
gas guns [48,49,59,60-63]. The close similarity of the results is indicative of the

Figure 1.4. Schematic of a two-stage hemispherical explosion device. 1-5: see Fig. 1.3,
6: explosive charge of the second stage, 7: shells of the second stage.
10 L.V. Al'tshuler

P,TPa
Z

01
,.2
oJ

Figure 1.S. Hugoniots for (a) Fe and (b, 0"+0.5) U. 1: data obtained by a plane cascade
device, 2: data obtained by a hemispherical cascade device, 3: data of [59].

P,GPa P,GPa

600 a 600 b

.f00 SOU

40tJ 400

JOo JOO

ZOO 100 AI
02
100 100
01

0
I.Z II, IJ 16 cr I II l~ 16 1I cr

Figure 1.6. Hugoniots for (a) Au and (b) W. 1: data obtained by an explosion measuring
device [48],2: [49,50]; 3: data obtained by using a light-gas gun [63].

high precision of the dynamic methods involving pneumatic and explosive

measuring devices. In the work abroad, the application of the hemispherical
measuring devices is mainly limited to compressibility studies ofU and Fe [59].
Originally intended for the study of nuclear explosive materials, shock-wave
methods have been widely used in investigating a large number of elements,
 1. Dynamical Methods of Investigation of High Pressures 11

P,GPA P,GPA
ZOO
If
1,00
!5O

\
0

Joo A,
'20 01
b. oJ

~
ZOO
10

100
4IJ

0 0
0..1 D.i 0.7 0.1 D.1Yfl; U.s D.6 0.7 8.1 0.1 ~

Figure 1.7. Hugoniots of (a) Cu and (b) AI. 1: data obtained by an explosive measuring
device [49],2: [46,50],3: data obtained by using a light-gas gun [63).

chemical compounds, and minerals. Shock compressibility values have now

been obtained in various pressure ranges for more than 60, i.e. the majority of,
naturally occurring metals. Particular attention has been given to refinement of
the Hugoniots of AI and Fe, the reference metals.
Russian and foreign dynamic data on metals up to 1977 are surveyed in [57].
The results are classified according to the form of the D(U) dependencies,
which involve five types of Hugoniots. The first three are smooth linear and
parabolic Hugoniots. The fourth and fifth types will be discussed below.
In the 1960s, the properties ofrare-earth and alkaline-earth metals came un-
der the scrutiny of the shock-wave community. When in a normal state, a rare-
earth metal has a close-packed crystal structure and is trivalent owing to its
4fA5d16s2 electron configuration with fully (in La) or partially filled f-shells
containing a different number of f-electrons. A common belief was that megabar
pressure would force s-electrons into the unfilled f-shell, giving rise to a super-
high-density metal as a result of a structural transformation. These, however,
were overly naive expectations, as even early studies [64J showed. The P-cr
data in Fig. 1.8a [65J indicate kinks occurring in the Hugoniot at certain criti-
cal compression parameters, implying that the compressibility of metals de-
creases discontinuously and corresponds to second-order phase transitions
involving the reconstruction of electronic spectra. The pioneering data of [64-
66] were corrected and revised in the works of foreign researchers [67,68] in
1973-1975. The D- U diagram in Fig. 1.9 compares data for Nd and Dy.
12 L. V. AI'tshuler

P,GPa

300

200

100

o ~~~--~~~~----------~----~
200 ,-----------------y------------,.----T""'1

P,GPa

100

2 3

Figure 1.S. Hugoniots for (a) rare-earth metals, La, Er (0'+0.3), Nd (0'+0.6), Dy
(0' + 0.9), and (b) alkaline-earth metals, Mg, Ca, Sr (0'+ 0.5).

Analogous processes give rise to kinks in the Hugoniot of alkaline-earth

metals, first observed by Bakanova and Dudoladov [65] in 1967 (see Fig. 1.8b).
Figure 1.10 illustrates the change in atomic volume as dynamic pressure lev-
els become progressively higher. As pressure increases, it is seen that periodic
volume changes decrease in amplitude, and at 1 TPa the periodicity reflecting
the atomic shell structure is only weakly seen. The slopes of the Hugoniot
curves D(U) show a similar smoothing behavior.
 1. Dynamical Methods of Investigation of High Pressures 13

D,km/s

U, km/s

Figure 1.9. D-U dependencies forNd and Dy (U+2 km/s). Data are from 1: [64],2:
[67], and 3: [68].

V, \03 run 3
\0 Fe Cu Mo Cd P=3TPa Pb
AI
0
10 Na AI K Ti FcCu Mo Cd p= 1 TPa
Ta Pb
0

10
0
Cs p= 100GPa
20

20

60

40

20

0
20 40 60 80 Z
Figure 1.10. Atomic volume curves V(Z) at nOTIlla! conditions (P =0) and various shock
pressure levels.
14 L.V. Al'tshuler

1.4. The Hundred-Megabar Pressure Range

P.W. Bridgman, the classic experimental physicist. wrote in his last review arti-
cle: "The very highest press1U'es will doubtless continue to be reached by some
sort of shock-wave technique. Perhaps some fortunate experimenters may ulti-
mately be able to command the use of nuclear explosives in studying this :tield"
[69]. It so happened that researchers at VNIIEF were that fortunate late in the
1960s. By working in the near vicinity of an underground nuclear explosion, it
proved possible to dramatically increase the amplitude of shock waves and to
resolve a number of fundamental problems in dynamic high-presS1U'e physics.
The significance of the results so achieved can hardly be exaggerated. In the
very :tirst experiments, the relative compressibility of Fe, Pb, Cn. Cd [70-72],
and U [58] were determined in the presS1U'e range 4-5 TPa In the mid 1970s,
Trunin and coworkers performed absolute measW"ements of the kinematic pa-
rameters of shock waves in Fe using the arrest method in the vicinity of an un-
derground explosion [73,74]. The experimental scheme chosen and optimized
by the researchers satisfied the impactor acceleration requirements of the
method. The absolute compressibility of iron was measured at 4.1,5.5, and 10.5
TPa. The results of these measW"ements, published in 1992-1993 [73,74], were
analyzed together with the laboratory data and actually granted Fe the status of a
reference metal [54]. A comparison of underground explosion data with the
predictions of the quantum-statistical TFPK model (Russian abbreviation for the
Thomas-Fermi model corrected for quantum and exchange effects by Kalitkin
[75] and for inter-nuclear intemction by Kopyshev [76]) yielded the low-pres-
S1U'e applicability limit of this quasi-classical model.
Knowing the Hugoniot of Fe up to 10 TPa allowed, with necessary recalcu-
lations, to consider as absolute meas1U'ements made for other metals when Fe
was used as the shield The main results of shock compressibility meaS1U'ements
in underground explosions are reviewed in [77]. Figures 1.11 and 1.12 present
the Hugoniots of Mo, Fe, Pb, U, Cn. and Cd after all necessary processing is
done; the arrows mark the results for Fe (after [70)) obtained using the Pb
Hugoniot as the standard.
In 1986, Avrorin et al. [78] used Fe as a standard in comparative measure-
ments on Pb and AI. For Pb, a presS1U'e rnnge from 8 TPa to the record value of
50 TPa was examined. Trunin et al. [79] carried out comparative measurements
for Pb and Cu at 20 TPa, and for Ti at 14 TPa. The results obtained were used to
calculate shock compression parameters for these metals and to compare the
experimental data with calculated TFPK Hugoniots in the presS1U'e rnnge near 20
TPa. Once more, a comparison of theoretical predictions with experimental data
was made. Using the Fe standard made it possible, with the aid of loading de-
vices already available [80,81], to extend the laboratory presS1U'e rnnge to 2.4
TPa in Mo and Ta, and to 1 TPa in AI and Ti.
 1. Dynamical Methods of Investigation of High Pressures 15

P,GPa
105r----------------.~-----,

;;
Mo 'I 7
10 4

; /1
• I
10 3 . " Z

/I
" 1
o f
o J
+ f
I )( 7

r
--I
-·-1

10 2
1 3 4 5 cr
Figure 1.11. Laboratory and undergrOlmd shock compressibility data on Mo (0"-0.6),
Fe, and Pb. 1: [57], and 2: [51]: data of laboratory experiments, 3-7: data from under-
ground measurements, 3: [73,74], and 4: [82], absolute measurements, 5-7: data from
relative measurements (5: [71,72,79],6: [83,84], and 7: [78]), 8, and 9, calculations based
on models (8: TFPK model [75,76], and 9: SCF model [120]).

P,GPa
10 5

2 3 4 5
0"

Figure 1.12. Laboratory and underground shock compressibility data on U (0" - 0.5), Co,
and Cd. For notation, see Fig. 1.11.
16 L.V. AI'tshuler

The underground explosion experiments conducted by Ragan and his col-

leagues at Los Alamos [82-84] measured terapascal states in many elements
and in some chemical compounds by using Mo as a standard. These data gener-
ally show a fairly satisfactory US-Russia agreement (see Fig. 1.11).
There is a significant scatter in the shock compression data for Al above 200
GPa, partly obtained by Skidmore and Morris [59] and partly obtained using
laboratory loading devices in Russia (where they were published after 1960
[53,57,85,86]). Data obtained in the vicinity of underground explosions and with
greater shock-propagation distances are more trustworthy. Examples of such
work are measurements by the reflection technique [77] and, most important, by
the y-benchmark method developed by Simonenko and others at VNII1F in
Snezhinsk [87].
Throughout the pressure range studied, the laboratory and testing ground re-
sults on six metals are amenable to a description by D- U relations with pa-
rameters whose values are listed in Table 1.2. The lowest-pressure portions of
the curves represent the laboratory work, the upper, the asymptotic quantum-
statistical results from the TFPK model [75,76]. At the matching points, equat-
ing the functions and their derivatives up to the second order produces
monotonicity of the curves. The monotone behavior of the Hugoniots is ex-
plained by band broadening due to the shock-induced overlap of the atomic
wave functions. Of the elements listed in the table, each can serve equally well
as a standard for dynamic measurements.

Table 1.2. Hugoniot parameters of metals for D =ao + a1 U + a2 U2 .

Range of
Metal ao, kmls a1 a2, sIkm applicability
Fe 3.664 1.79 -0.0342 1.4<U<8
5.869 1.239 0.00017 8< U<22
6.982 1.190 0.00011 U>22
Cu 3.899 1.534 -0.0129 U< 12.5
5.905 1.212 3.76 xlO-s U> 12.5
Cd 2.456 1.734 -0.0424 U<6.5
4.251 1.182 7 xlO-s U>6.5
Mo 5.08 1.294 -0.00288 U<22.5
6.711 1.149 34.1 xlO-s U>22.5
Pb 1.972 1.571 -0.0335 U<6
3.18 1.169 5.52 xlO-s U>6
AI 5.331 1.417 -0.015 U<8.2
6.371 1.164 1.0 xlO-s U>8.2
 1. Dynamical Methods of Investigation of High Pressures 17

P,GPa

Be AL FI.' Cu MIl Cd W Pb U

10i

1O"
I... .: •
•
•
t •
.. I ..
1
• •
• • +
10J X

10
o 100
-z~

.1 .2 xJ I~ +5 .6
Figure 1.13. Ranges of absolute and relative measurements achieved in laboratory and
underground experiments. The shaded region designates the range of absolute laboratory
measurements. The symbols 1 and 2 designate absolute and relative measurements, re-
spectively, made at VNIIEF. The symbols 3 and 4 designate the same types of measure-
ments made at VNllTF. The symbols 5 and 6 designate the same types of measurements
from American work.

In Fig. 1.13, the dynamic compressibility ranges achieved in laboratory and

underground work at VNIIEF, VNIITF, and in the United States are presented
on a logarithmic scale for the elements studied.
In 1957, Al'tshuler, Zel'dovich, and Styazhkin at VNIIEF proposed a fun-
damentally innovative and particularly sensitive method for evaluating the isen-
tropic compressibility and EOS of the fissionable materials U and Pu [89]. The
method was put into practice in the late 1950s and came to be known as the
nonexplosive-chain-reaction method. Simultaneously, the same method was
developed in the United States, where it was called the method of "hydro-
dynamic nuclear processes" [6,90].
The idea of the method was to experiment with spherical explosive charges
containing insufficient fissionable material to cause a macroscopic energy re-
18 L.V. Al'tshuler

lease. The maximum allowable energy release was taken to be that equivalent to
1 kg of TNT, implying a huge (_1017) number of fission events and the corre-
sponding number of neutrons escaping the sample. The samples to which this
method is applied are sufficiently massive that the nuclear energy released has
virtually no effect on the compression and divergence of the hydrodynamic
process.
The rate of neutron multiplication, and hence the total number of fission
events in an explosion experiment, depends to a great extent on the maximum
pressure achieved in the sample. The quantitative relation between the number
of fission neutrons detected and the densities achieved is obtained from hydro-
dynamic and neutronic calculations. A 1% variation in compressibility changes
the neutron flux by two orders of magnitude. Work along these lines has pro-
vided very accurate data not only on the isentropic compressibility and EOS of
fissionable materials at pressures of 10-15 TPa, but also on the physical proc-
esses taking place.

1.5. Isentropic Compressibility and Polymorphic

Transformation in Shock Waves
In solids, the velocity of shock waves of amplitude up to the Hugoniot elastic
limit (HEL) is close to the initial longitudinal elastic sound speed. A shock wave
of amplitude slightly greater than the elastic limit separates into a shock of am-
plitude equal to the Hugoniot elastic limit and another shock that propagates
much more slowly and compresses the material to the full shock amplitude.
Information on isentropic compressibility of shock-compressed matter is neces-
sary for constructing real equations of state.
In the megabar range, the isentropic sound speeds in shock-compressed
matter can be determined by the method of "overtaking unloading" (91). The
method consists in recording the attenuation of the shock wave in the target after
the impact of a thin plate. In the 1950s, experimenters at VNIIEF studied AI, Fe,
Cu, and Pb by this method [92J. In 1971, this work was extended to include Fe
and Cu [93J. Typical particle velocity attenuation curves for copper, corre-
sponding to the expansion from the Hugoniot state and from the solid state to the
pressure of shock melting, are shown in Fig 1.14. In the latter case (expansion
from a solid state on the Hugoniot curve), attenuation is accompanied by a
leading elastic unloading wave, characterizing elasticity and dynamic yield
strength.
Shock compression of solids causes numerous phase transitions. Shock-
induced polymorphic transitions of many substances, including metals, semi-
conductors, ionic compounds, oxides, and practically all minerals and rocks,
have been measured. Original works are reviewed by Duvall and Graham [93J
and by AI'tshuler [94J.
 1. Dynamical Methods offuvestigation of High Pressures 19

U.kmls U.kmls
2.0 a b
3
1.8
2
1.6
1
4 5 6 7 x,rom 2 5 8 11 14 x,rom

Figure 1.14. Attenuation of a shock wave (particle velocity) for Cu measured by the
method of "overtaking unloading". a: data obtained at 120 GPa [92], b: data obtained at
200 GPa [91).

Shock-induced phase transitions must be martensitic (based on shear defor-

mation of the lattice) because they are very fast. Before formation of the high-
pressure phase, the motion of an elastic precursor is observed. During the phase
transition, many defects are created at the wave front, becoming centers of
crystallization under supercritical conditions. In the words of Alder [95], "the
shock front could be likened to a mill, which atomizes the low-density material
ahead of it and deposits the atoms at the high-density side in whatever state is
stable under these conditions."
For the first time (in the 1940s) shock-induced structural martensitic trans-
formations were observed in experiments conducted in the x-my labomtory of
the Institute of Machine Science under the leadership of Tsukerman (the creator
of flash mdiogmphy) [96]. Interesting pictures of intemction of colliding shock
waves in iron were obtained in strong samples subjected to the explosive action
of several charges. The pressure field produced by the intemction of six shock
waves is shown on Fig. 1.15. The results were explained correctly [2] only after
discovery of the (x.-s phase tmnsition in iron (Bancroft, Peterson and Minshall
[97]): The dark zone corresponds to the phase transition and the zone boundary
corresponds to the 13 GPa transition pressure. The centml spot results from the
superposition of six waves.
At VNIIEF, shock-induced phase transitions, as well as their special features
and mechanisms, were intensively studied by Pavlovsky and his collaborators.
Mainly, the group IV elements (C, Si, Ge, Ti, Zr, and Sn) and alkali metal hal-
ides were tested [98-102].
An investigation of the phase transition in iron led Ivanov, Novikov, and
Tamsov [103,104] to the experimental discovery ofmrefaction shock waves that
occur when the metal is re-tmnsformed as it is decompressed to the initial phase.
In these experiments, the collision of expansion shocks has led to unique phe-
nomena involving smooth spall of iron.
20 L.V. Al'tshuler

Figure 1.15. Macrostructure of the metal in a cross section of an iron cylinder when six
charges are detonated simultaneously [96].

1.6. Wide-Range Phase Diagram of Shock Compression

of Metals
Dynamic high-pressure studies of the compressibility of metals [1,2J provide
information about energy, pressure, and density on an Hugoniot curve.
Zel'dovich, in his seminal 1957 paper [105J, proposed two methods capable of
extending the range of the phase diagram. One involved the Hugoniots of porous
materials (i.e., of those with a reduced initial density) and the other involved
measuring expansion isentropes of the shocked material. The former idea was
implemented in the early stages of dynamic work, in 1949, when the Hugoniots
of both solid and porous Fe and U were measured. Results on shocked Fe were
presented in the first Soviet publication on the high-pressure shock compressi-
bility of solids [51). Although the 20% initial porosity of the material did not
allow the range of investigation of the state to be extended very much, the re-
sults thus obtained yielded the Griineisen coefficients and made it possible to
refine the EOSs of these metals over comparatively narrow ranges of the phase
diagram.
The first comprehensive shock compressibility study for different initial po-
rosities (up to m = 4, m, being the ratio of the normal density to the initial den-
sity) was made on W by Krupnikov et al. [61). Experimental results (Fig. 1.16)
confirmed the paradoxical theoretical prediction that states of lower-than-normal
density were produced in shock-compressed porous materials under high-pres-
sure conditions.
 1. Dynamical Methods of Investigation of High Pressures 21

.1
02

o~------~--~----~--~---
8.1 1 1.Z I;
Figure 1.16. Hugoniots for porous tungsten of various initial densities [61). Nwnbers
designate the porosity, m. 1: experimental data, 2: intetpolation of experimental data
using relations for one-device data. Reprinted with permission from K.K. Krupnikov,
M.I. Brazhnik, and V. P. Krupnikova, Shock compression a/tungsten, in Zh. Eksp. Tear.
Fiz. 42(3), pp. 675-685 (1962).

Konner, Funtikov, Sinitsyn, and coworkers provided further insight into the
problem by working at pressures of up to 800 GPa in AI, Cll, Ni, and Pb [53]
and in four ionic crystals [106]. Similar to the results presented in [61],
Hugoniots of other porous metals were found to have portions with positive and
negative slopes owing to the thermal excitation of the lattice and the electrons
[53].
The next step in extending the range of achievable states was taken by
Trunin and colleagues [107-109] who studied the shock compression of Cll,
Mo, Til. and Ni specimens having about twice the porosity studied previously.
Underground explosion technology made it feasible to study porous materi-
als at much higher pressures. Terapascal data were obtained for porous Cll, W,
and Fe [77]. Laboratory results for porous Cu and Ni are plotted as P-cr dia-
grams in Figs. 1.17 and 1.18.
According to Zel'dovich [105], the region of accessible P- V space can also
be extended by using the release isentropes that fonn unloading paths from
shocked states of solid or porous specimens. In this context, experiments with
rarefaction waves involving nearly critical states are especially noteworthy. Ex-
22 L.v. Al'tshuler

P,GPa
~~.~~~--r-----~----~

111 7.%
,
I
I
I
I
100 I
I

,,
I
I

,
100
I
I
I •
I
IOU I _I
I --2
----I

Figure 1.17. Hugoniots for porous copper of various initial densities. Numbers denote
porosity, m. 1: calculations from [53], 2: [122],3: melting boundaries after [118).

P,GPa
I
I
I
I
10 ~ U
I
JOQ I
I

,,
I
I
21J(J
I
I
I
100 l

Figure 1.18. Hugoniots for porous nickel of various initial densities. The numbers de-
note porosity, m. 1: calculations from [53], 2: [122], and 3: melting boundaries after [118).
 1. Dynamical Methods offuvestigation of High Pressures 23

tensive expansion isentrope measurements using the so-called "soft barrier"

scheme were made at the Institute of Chemical Physics in Chemogolovka
(IKhFCh) and at VNIIEF [110-113]. As barriers, materials with known
Hugoniots, such as AI, Mg, polymers, Ar, Xe, and air at various pressures, were
used.
Results on release isentropes for shocked solid and porous specimens of Cu
and Pb unloaded to near-criticality were published by AI'tshuler [110] and
Bakanova et al. [112]. In a survey paper, Glushak et al. [113] presented new data
on AI and Bi and also additional Cu data for an initial shock pressure of 1.4 TPa
achieved with laboratory explosive devices [114]. The P-U diagram of Cu is
shown in Fig. 1.19 .
Expansion isentropes link the isentropic states of degenerate superbigh-den-
sity plasmas to near-critical states of weakly ionized vapor. On entering the two-
phase liquid-vapor region, the values of the energy and volume on the
isentropes are consistent with equilibrium-curve parameters and, as shown in
[105], the temperatures and entropies known for the low-pressure, low-density
region on the lower sections of an isentrope allow one to calculate these pa-
rameters all along the isentrope, thus yielding the complete P-V- T diagram for

P,GPa
m·r---------------------~~~~,

IJ /8 10 U,krnls

Figure 1.19. Hugoniots and expansion isentropes of copper [113]. Points represent
experimental data. Curves marked by the corresponding initial porosity, m, are calculated
Hugoniots. The falling curves are expansion isentropes of shock-compressed samples
obtained from an equation of state [111].
24 L. V. Al'tshuler

the substance. Detennination of the temperature from shock experiments and by

measuring adiabatically unloaded final states was first realized by Fortov et al.
[115,116] who obtained BOS data for Cs and Cu.
Figure l.20 shows the phase diagram of Cu obtained using the Bushman
equation of state [Ill] based on the shock-wave data, incorporating the melting
region and the equilibrium liquid-vapor curve, as well as isotherms in the 10-
500 kK temperature range.
The peculiar generalizing phase diagram (Fig. l.21), taken from [117]
and supplemented by the data of [109], characterizes the range of extreme
states of matter for several elements. Here, the density is plotted along the
abscissa (mole/liter), and the specific energy is plotted along the ordinate
(kJ/g). Regions 1-3 are determined for shock-compressed porous tungsten,
copper, and nickel. Region 4 is determined from shock tube experiments
with xenon. The large region of strongly nonideal dense plasma contains
scarcely any experimental data except for the data on isentropic expansion
of copper and lead [111] and of porous nickel [109].

P,GPa

IO~

o J 16 1.1 p, glcm3

Figure 1.20. P-p phase diagram of copper [111]. M: melting, R: curve of liquid-vapor
equilibrium, T: isotherms, m: Hugoniots of porous samples; experiment [107,108].
 1. Dynamical Methods of Investigation of High Pressures 25

E,kJ/g
!O~r------------------------------------,
.-...-.-._-----
T= 100 eV

10 eV
.-.-.-.-.-.-.~.~.-.
o
o o
10

,
4'~----------~------------~----------~
, m m1 C, molell

Figure 1.21. Total C-E phase diagram of several elements. Shock-compressed porous
metal ranges are: 1 for tungsten [61],2 and 3 for nickel and copper [107,108], 4 for xe-
non plasma studied by dynamical methods [115], 5 from expansion isentropes of copper
[113], and 7 and 8 are Hugoniots oflead and copper.

1.7. Description of Extreme States

At present, the highly developed methods of quantum mechanics and statisti-
cal physics provide an adequate picture of a substance at either high or low
densities, when interparticle interactions are described by the classical
(Debye-Hiickel) or the quasi-classical (Thomas-Fermi) approximation,
respectively. In the intermediate highly nonideal region, theoretical analysis
faces a strong-interaction disorder situation which prevents applying pertur-
bation theory to a quantum mechanical many-body system. The conventional
approach is therefore to employ simplified physical models using functional
relations having forms dictated by theory and coefficients determined by
experiment [118].
For a material initially of normal density, a theoretical picture of shock com-
pressibility at superhigh pressures is obtained by invoking the solid-state con-
cept of the Wigner-Seitz cell, on which a number of boundary conditions are
imposed. For the purpose of comparison with experiment, the statistical
Thomas-Fermi model was initially adopted [72] for electrons and a perfect
monatomic gas of nuclei, which was later improved by introducing quantum and
26 L.V. Al'tshuler

exchange corrections [75) and interactions between nuclei as, for example, in
[76] (the TFPK model). This model is statistical and, although it predicts that the
thermodynamic characteristics depend monotonically on the atomic number of
the element, it fails to account for the shell structure of atomic electrons. To
remedy this at high pressures, high temperatures, and successive shell ioniza-
tion, the Hartree-Fock model [119] with Slater's exchange interaction or the
pseudo-band self-consistent field (SCF) model [120] can be employed. The shell
models differ considerably from one another and typically yield thermodynamic
parameters that vary in a highly non-monotonic manner-in some cases unre-
alistically so-in the range of high compressions. In this range one therefore
prefers quantum statistical models, which agree better with experimental data on
shock-compressed metals. The lower limit of applicability of TFPK Hugoniots
lies in the 15-20 TPa range [72]. Figures 1.11 and 1.12 illustrate the applicabil-
ity of TFPK results by P-cr diagrams for metal Hugoniots in the hundred-
megabar range.
A theoretical picture of states in a wide pressure-temperature range corre-
sponding to the shock compression of highly porous metals and to expansion
isentropes has been developed by Gryaznov, Iosilevskii, and Fortov [121,122]
based on a highly non-ideal plasma model. At the heart of this "quasi-chemical"
approach is a calculation of the equilibrium ionization composition, which is
performed by minimizing the free energy corrected for the interparticle interac-
tion of atoms and ions. Notice that the megabar-pressure normal-density region
corresponds to states of a highly nonideal, partly degenerate plasma with an
ionization degree of up to 4-5. Apart from the introduction of partially degener-
ate free electrons, Coulomb nonideality, and multiple ionization, the success in
describing shock compression data on highly porous metals [107 -109] depends
crucially on adding a strong short-range repulsion between ions due to their own
volume ("Iimited-atomic-volume model") [121]. As discussed in [121], the
validity of the chemical model in the range of states of interest is to a large ex-
tent related to such additional features as the proper volumes of atoms and ions
of various degrees of ionization, interparticle attraction, and the correction of
these parameters based on the characteristics of the material under normal con-
ditions (density, energy, sublimation). The calculated Hugoniots of Cu and Ni
are shown in Figs. 1.17 and 1.18.
An alternative approach to the construction of an EOS of the liquid phase
[123] is a generalized van der Waals model using the cold compression isotherm
as a covolume for material compressibility. At high temperatures, the thermal
ionization of atoms is included and Saba-type equations are employed for de-
scribing ionization equilibrium. This EOS also adequately describes the existing
data on porous and highly-porous metals and on expansion isentropes.
One of the major high-pressure research directions is the compressibility
of materials at zero and normal temperatures. In [124], cold-compression
 1. Dynamical Methods ofhtvestigation of High Pressures 27

isotherms for the EOS of ionic crystals are represented by the Born-Meyer
potential, an approach that was first applied to metals in [52] and was further
developed in [125]. As discussed in [126], the parameters of the Born-Meyer
potential can be directly determined from the D- U Hugoniot relations in
terms of the initial bulk modulus and its pressure derivative. In the same
paper, potential parameters obtained in this way are given for 25 metals.
Compared to the American reference isotherms [51], the normal-temperature
isotherms calculated for pressures up to 400 GPa are essentially the same for
Cu, agree fairly well for Pb, and agree not SO well for AI. Good agreement is
also observed for Au, which has been suggested as a standard material in the
metrology of static measurements [4] (Fig. 1.22).
In [127,128] the elastic compression curve in the EOS of a condensed
material was represented as an expansion in powers of the cube root of the
density. The interpolation coefficients were obtained from the static bulk
compressibility curve at low pressures and by matching this curve to the
TFPK behavior at high pressures [75,76]. The correction of the interpolated
dependence of elastic compression using a single datum point on an
Hugoniot in the megabar range [128] enabled Hugoniots and isotherms to be
described satisfactorily over a wide pressure range for a whole series of met-
als.
The principle underlying the semi-empirical EOS of [53], namely, the repre-
sentation of the thermodynamic potential as a sum of lattice and electronic con-
tributions, was later developed for, and used in, the so-called multi-parametric
wide-range EOSs [111,118]. Using the resulting EOS models, thermodynamic

D~--~------~------~------~
0.6

Figure 1.22. Calculated isothenns at T =300 K of AI (1), Cu (2), Pb (3, VN0 + 0.25)
[51], and Au (4, VNo+0.15) [4], and calculated points [126].
28 L.V. Al'tshuler

characteristics of metals, including liquid-vapor phase boundaries and melting

behavior, can be described over a wide pressure-temperature range from normal
to extremely high values. Importantly, a correct description of theoretical
asymptotic behavior is secured. Reference [Ill] presents EOSs for Cu and Pb,
and Ref. [118] for 25 more metals.

1.S. Optical Measurements of Shock-Compressed Dielectrics

A strong shock wave heats the compressed material to several tens of thousands
of Kelvin and, if the material is transparent, radiation can pass through the un-
compressed layer thus providing information about the state of the material
behind the shock. The first measurement of brightness temperature in the front
of a strong shock wave in a gas was performed by Model' [129]. In the mid
1950s, the optical properties of transparent, shocked, condensed materials were
most comprehensively studied by Kormer and his colleagues, Sinitsyn, Kirillov,
Urlin. Yushko, and others. Much of their success was due to Zel'dovich's direct
participation in the analysis of the results. These studies, in turn, triggered the
research work of Kormer et al. [130], which appears unique in many respects
even today. Temperature measurements on transparent, shock-compressed ionic
crystals and dielectrics [131] considerably improved the EOS data for this class
of materials and extended their melting curves previously limited to the range of
only few GPa to as high as 50-250 GPa. For high pressures, a latent heat of
melting that increases almost linearly with temperature and a significantly re-
duced volume jump were observed. It was shown for the first time that, when
shock-compressed to one-half their normal volume, the crystals of LiF, NaCI,
KCl, and CsBr remain solid up to -4000 K [131]. Also, assuming a Debye heat
capacity function, it was found that the Mie-Grilneisen EOS for the solid phase
of these crystals quite satisfactorily describes not only the pressure-density
relation along a Hugoniot but also the temperature of the shocked solid body up
to the melting curve. This implies that anharmonicity of lattice thermal vibra-
tions has little effect on the heat capacity of the solid phase of these crystals.
Reference [106] summarizes the equations of state and melting curves obtained
for the materials studied. A comparison of computed curves with experiment is
presented in Fig. 1.23 for the KCI phase diagram.
The optical properties of the shock-wave front in a transparent dielectric also
depend on the reflecting power and transparency of the material behind the
shock, the reflecting power depending, in particular, on the smoothness and
thickness of the front. A technique for measuring the reflecting power of trans-
parent, shock-compressed, condensed materials was developed by Kormer,
Yushko, and Krishkevich [132]. It was found that the density jump in a shock in
condensed materials occurs in a layer less than 10-6 cm thick and takes less
thanl0- 12 s to form. The shock front is to a large extent smooth, its roughness
being less than 10-6 em. Wave front roughness an order of magnitude higher was
 1. Dynamical Methods of Investigation of High Pressures 29

T,kK

Figure 1.23. Phase diagram and melting curve of KCI obtained from data giving the
temperature of shock-compressed material [130,131]. 1 and 2: temperature values at
A= 0.478 and 0.625 J.IlIl, respectively.

observed in a detonating liquid explosive [133]. The same study also showed
that the refractive index of both liquid and solid materials increases linearly over
a wide range of compressions and can reach twice its original value. Up to
pressures of the order of 100 GPa, it was found that, for most materials, the
reflecting power of the shock front is 20/0. Owing to the high sensitivity of the
method to changes in the density gradient, it proved possible to see shock front
structure in materials undergoing polymorphic transformations [134]. The reader
is referred to [131] for a survey of optical shock wave investigations of
dielectrics in the 1960s.
Brightness temperature measurements of shocked ionic crystals at low pres-
sures of a few GPa showed the detected light fluxes to be well in excess of what
might be expected from the calculated temperatures [135]. For NaCl, these
measurements correspond to pressure points at 27 and 40 GPa (See Chapter 11
for further details.). This nonequilibrium glow is found to be of a luminescent
nature. As the shock pressure increases, the brightness of luminescence fades to
a subthermallevel thus ceasing to affect the temperature values measured.
Another kind of nonequilibrium emission was observed in shock-wave ex-
periments on five ionic crystals in the pressure range 200-500 GPa [136]. In
these crystals, a brightness of radiation far below the equilibrium-temperature
value was found, an effect that Zel'dovich, Konner, and Urlin [137] explained
by invoking the kinetics of thennodynamic equilibration between the electrons
and the lattice in the shock-wave front.
Optical shock-wave studies were also carried out for liquid Ar [138] and liq-
uid Xe [139] (see Fig. 1.24). In these works yet another class of materials lends
support to the ideas involved in the construction of the multiphase BOS and in
the theory of heating kinetics of shock front electrons [137].
30 L.V. Al'tshuler

T,kK

II lD GO P,GPa

Figure 1.24. Dependence of shock front brightness tempemture for presSlU'e in liquid Ar
[138]. Reprinted with permission from F.V. Grigoriev, et aI., Shock compression and the
radiance temperature of a shock wave front in argon~ Electron screening of radiation. in
Zh. Eksp. Teor Fiz. 88(4), pp. 1271-1279 (1985).

1.9. Conclusion
The total amount of data collected in Russia on all the subjects discussed above
is too large to cover in a single chapter, even a review. Some comprehensive
studies on shock strength and the deformation of metals and on shock compres-
sion of quartz, rocks, and dense plasma were only briefly mentioned. Because of
the lack of space, neither the methods used nor the results obtained were dis-
cussed. The list of omissions includes shock compression of metallic alloys,
hydrides, carbides, and nitrides of metals, of fusible metals initially in the liquid
state, double-compression data, pulsed x-ray diffraction analysis in shock waves
(including shock polymorphism), pulsed x-ray compressibility studies, a huge
amount of work on organic materials (both liquid and solid), chemical reactions
in shock waves, and many other aspects of the field. These aspects include the
generation of powerful shock waves using high-intensity beams (lasers, soft x-
rays, relativistic electrons, and light or heavy ions), and the electro-explosion of
metals, having their origins in the dynamic high-pressure techniques that have
been discussed. All these topics deserve special discussion and have been ad-
dressed in detail in a number of monographs and review papers in recent years.
The comprehensive dynamic shock wave data presented in this survey re-
sulted from the pioneering efforts of Russian researchers and are of fundamental
importance for an understanding of the physics of extreme states of matter.
 1. Dynamical Methods of Investigation of High Pressures 31

References
[1] Ya.B. ZeI'dovich and YuP. Raizer, Physics o/Shock Waves and High-
Temperature Hydrodynamic Phenomena, Vol. I (1966) and Vol. IT (1967),
Academic Press. New York. Reprinted in a single volume by Dover Publications,
Mineola. New York: (2002).
[2] L.V. Al'tshuler, Sov. Phys.-Usp. 8, pp. 52-91, (1965). [trans. from Usp. Fiz.
Nauk85(2), pp. 197-258 (1965).]
[3] H.K. Mao andP.M. Bell,J. Appl. Phys. 49(6), pp. 3776-3283 (1978).
[4] D.L. Heinz andR Jeanolz,J. Appl. Phys. 55(4), pp. 885-893 (1984).
[5] RW. Goranson, D. Bancroft, B.L. Bmton, T. Blechar, E.E. Houston,
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 1. Dynamical Methods of Investigation of High Pressures 35

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36 L.V. Al'tshuler

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p. 689 (1965). [trans. from Zh. Eksp. Teor. Fiz. 48(4), pp. 1033-1049 (1965).]
[131] S.B. Kormer, Sov. Phys.-Usp. 11(4) pp. 229-254 (1968). [trans. from Usp. Fiz.
Nauk 94(4), pp. 641-687 (1968).]
[132] S.B. Kormer, KB. Yushko, and G.V. Krishkevich,JETP Lett. 3(2), pp. 39-42
(1966). [trans. from: Pis'ma Zh. Eksp. Teor. Fiz. 3(2), pp; 64-69 (1966).]
[133] Ya.B. Zel'dovich, S.B. Kormer, KB. Yushko, and G.V. Krishkevich, Dolel. Akad.
NaukSSSR 158p.l057(1964).
[134] KB. Yushko, G. V. Krishkevich, and S.B. Kormer, Sov. Phys. -JETP Lett. 7(1),
pp. 7-10 (1968). [trans. fromPis'ma Zh. Eksp. Teor. Fiz. 7(1), pp. 12-16
(1968).]
[135] G.A. Kirillov, S.B. Kormer, and M. V. Sinitsyn, Sov. Phys. -JETP Lett. 7(10),
pp. 290-291 (1968). [trans. fromPis'ma Zh. Eksp. Teor. Fiz. 7(10), p. 368
(1968).]
[136] S.B. Kormer, M. V. Sinitsyn, and AI. Kwyapin, Sov Phys.-JETP 28(5), pp. 852-
854 (1968). [trans. from Zh. Eksp. Teor. Fiz. 55(5), pp. 1626-1630 (1968).]
[137] Ya.B. Zel'dovich, S.B. Kormer, and V.D. Udin, Sov Phys. -JETP 28(5), pp.
855-859 (1968). [trans. from Zh. Eksp. Teor. Fiz. 55(5), pp. 1631-1639 (1968).]
[138] F. V. Grigoriev, S.B. Kormer, O.L. Michailova, MA. Mochalov, and V.D. Urlin,
Sov Phys.-JETP 61(4), p. 751 (1985). [trans. from Zh. Eksp. Teor. Fiz. 88(4),
pp. 1271-1279 (1985).]
[139] V.D. Urlin, M.A. Mochalov, and O.L. Mikhailova, High Pressure Res. 8, p. 595
(1992).
 CHAPTER 2

Detonation of Condensed Explosives

L.V. AI'tshuler, V.S. Zhuchenko, and A.D. Levin

2.1.. Introduction
This chapter presents a basic description of the modes and parameters of deto-
nation of condensed explosives. It contains a review of experimental techniques,
analysis of experimental data on detonation pressure, and discussion of detona-
tion modes of single-constituent and mixed explosives. A number of fundamen-
tal problems of initiation and development of detonation, temperature of
detonation products, etc., that were considered in a recently published mono-
graph [1], are not discussed here.

2.2. Experimental Techniques

As a rule, the same experimental methods are used for research on detonation
waves in condensed explosives as on shock waves in inert materials. Most of
these methods are described in available reviews and monographs. (See, for
example, [1-4] and the references cited in Chapter 1.) Nevertheless, the authors
have found it useful to consider methodological questions to permit critical
comparison of results obtained by different techniques so that the subsequent
sections can be focused specifically on detonation research.
The experimental methods used can be divided into two groups-internal
and external measurements. Internal methods permit measurement of the pa-
rameters of a detonation wave within an explosive charge; they include pulsed
x-ray techniques, magneto-electrical measurement of particle velocities, and
measurements of pressure using manganin gauges. In the group of external
methods, shock-wave parameters are measured in an inert layer (called a barrier)
placed on the downstream face of the charge. The velocity of the free surface of
the barrier (spall method), parameters of the shock wave within the barrier
(brightness indicator method, laser measurement of wave velocities, and the
electrocontact method), or the velocity of the interface between the explosive
and the barrier (laser interferometry) can be measured. The detonation parame-
ters are determined by calculation of their values in the charge from the values
V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII
© Springer Science+Business Media New York 2004
40 L. V. Al'tshuler, V.S. Zuchenko, and A.D. Levin

measured in the barrier. It is necessary to know the dynamic compressibility of

the barrier material to make this calculation.

2.2.1. The Spall Method

Following a suggestion of Goranson, stated in a 1945 Los Alamos laboratory
report and in [5,8], the Chapman-Jouguet pressure of detonation in condensed
explosives and the structure of their reaction zones can be investigated by meas-
uring the initial velocity of the free surface of barrier plates as a function of their
thickness. In Russia the spall method, based on the same idea, was independ-
ently advanced in 1947-1948 by Al'tshuler and Krupoikov [6]. Measurement of
the velocity, W, of the free surface of the plate establishes the particle velocities
U = W /2 at different distances from the downstream face of the charge. The
shock pressure, P( U), is then determined using the known Hugoniot of the plate
material. The shape of the attenuation curve thus determined reflects the con-
secutive influences of the zone of reaction and the Taylor rarefaction wave on
the barrier. If one assumes that the Landau-Stanukovich equation of state with
the adiabatic parameter n adequately represents the products of detonation, the
Chapman-Jouguet parameters, UC1 , and PC1 , and the parameters Ub , and P b of
the shock wave at the explosive-barrier interface are related by the equation [7]

(2.1)

From the known initial charge density, Po, and the detonation velocity D, Eq. 2.1
together with expressions P C1 = poIY/(n+l), and Uc1 =D/(n + 1) determine the
adiabatic parameter n and the detonation parameters Ucr , and PC1•
The velocity of the free surface of the plate is measured with electrocontact
gauges [6,8] or with the help of a streak camera [9-10]. These gauges are placed
on the free surface of the plate and at precise measuring-base distances from it
The moments at which short circuits develop between the gauges and the plate
are recorded by a high-speed oscilloscope. To preclude formation of a short
circuit by an air shock, the gauges in [6] were protected by special thin caps. In
[8] the measuring gap was filled with a non-conducting gas (for example, meth-
ane). In experiments employing optical recording, a stepped block of transparent
material (for example, PMMA) is placed on the plate. Brief flashes of light are
produced, then the shock closes argon-filled gaps between the plate and the
transparent block. The time of each flash is recorded with a high-speed streak
camera.
The traditional spall method always results in an underestimate of the deto-
nation pressure. This systematic error is connected with the decrease of velocity
of the free surface of the plate as it moves. This decrease occurs because of the
decreasing pressure at the interface of the plate and the detonation products. The
 2. Detonation of Condensed Explosives 41

differences of the measured average velocity from its initial value are minimal at
small measuring-base distances and long charge lengths [11]. The limiting de-
crease of the velocity of the free surface is determined by the spall strength of
the material of the barrier [12]. In an advanced variant of the method [6], correct
values of the initial velocity can be measured using a laminated barrier consist-
ing of the basic barrier followed by a second plate of the same material (an arti-
fidal spall layer) a few tenths of a millimeter thick. This second plate separates
freely from the basic barrier at the maximum particle velocity at the front of the
shock wave at the moment of its approach to the free surface. For the measure-
ments of particle velocity profiles in TNT and TH 50/50 reported in [13], artifi-
cial spall layers of aluminum having a thickness of 0.05 rom or polyethylene
having a thickness of 0.1 rom were used. A further reduction of the thickness of
the indicator is inexpedient because of breakdown by an air shock wave.
A necessary requirement for using the spall method is making the correct
choice of the measuring-base distance. The one-piece plate should pass the de-
tector before a second shock wave arrives at the free siUface. For the laminated
plate, the choice of measuring-base distance should preclude overtake of the
artificial spall layer by the basic plate as it is accelerated by the detonation prod-
ucts.
Using a vel)' thin barrier (a foil of thickness about 0.1 rom) and a small
measuring-base distance allows the spall method to achieve high temporal reso-
lution (10-20 ns) [8,13].
Since 1947, the spall method has become one of the basic techniques used by
both Russian and foreign researchers for studying detonation. Besides measure-
ments of detonation pressure, the reaction zones in TH 37/63* [8], TNT of sev-
eral densities [14], and TH 50/50 [13J have been detennined.

2.2.2. The Electromagnetic Method

The electromagnetic technique for measuring the particle velocity of detonation
products was offered by Zavoiskii and, together with the x-ray method and the
spall method, has been applied to experimental determination of detonation
pressure at VNIIEF since 1948. The circuit for implementing the method is
given in [2]. At the beginning of the 196Os, the method was adopted at the In-
stitute of Chemical Physics [15 -17], and then at other Russian institutes.
In the U.S., the first communications reporting use of electromagnetic
gauges appeared in 1970 [18,19]. The technique was actively developed at the
Los Alamos and Livermore laboratories and is now widely used for measure-
ment of shock- and detonation-wave parameters [4].

* TIl 37/63 is an alloy of 37% 1NT and 63% RDX (by weight). Analogous notation is
used for mixtures of these explosives in other proportions.
42 L. V. AI'tshuler, V.S. Zuchenko, and A.D. Levin

The electromagnetic gauge takes the form of a IT-shaped strip cut from a
thin, conducting foil. The experimental assembly is placed in an homogeneous
magnetic field created by a stationary electromagnet or an expendable solenoid.
The gauge is placed so that its cross-piece, being the sensitive element, is
aligned perpendicularly to the lines of force of the field and parallel to the deto-
nation front. Upon passage of a detonation wave through a charge, the gauge
moves with the detonation products. The EMF arising in the gauge as a result of
crossing the magnetic lines of force is recorded by an oscilloscope. The magni-
tude of the induced EMF is related to the velocity of the conductor, U, its length,
L, and the magnetic field induction, B, by the equation E(t) = B L U(t) .
When an electromagnetic gauge is placed inside an explosive charge, it gen-
erates a profile of the particle velocity history as a running detonation wave
passes by. In [16], a method is described for measuring the returning rarefaction
wave with the help of an electromagnetic gauge. A block of paraffin having a
smaller dynamic impedance than the detonation products was placed on the
downstream face of a charge. The rarefaction wave arising as a result of reflec-
tion of the detonation front from the paraffin propagates toward the flow of
detonation products. The arrival of this wave increases the velocity of the gauge,
producing a characteristic rise of the waveform U(t). The time of arrival of the
return wave, as measured in experiments, allows calculation of the sound ve-
locities in the rarefaction wave and, using the Landau-Stanukovich equation of
state, of determining the distributions of density and pressure behind the detona-
tionfront.
In the first experiments, which were carried out by zavoiskii, the electro-
magnetic gauges were produced from copper foil having a thickness of 0.3 mm.
Because of the large inertia of these gauges, the front of the oscillograms was
obscured and the particle velocities were understated. Experimental checks
[20,21] have shown that aluminum gauges having a thickness of about ~0.1 mm
are optimal. A further reduction of thickness is inexpedient, as the gauges are
frequently tom by the detonation products and their own conductivity becomes
comparable to that of the detonation products themselves [22].
During development of the electromagnetic method, experimental checks of
gauges of different forms-IT-shaped gauges, step gauges allowing simultane-
ous registration of wave and particle speed, and stapes-shaped gauges in the
form of a disk of thin foil to which wire terminals are connected. At the
Livermore laboratory, multi-channel measuring systems have been used in
which flat electromagnetic gauges were placed between the layers of a charge
made of several disks of the explosive under investigation [4]. In another variant
of this method, a set of flat gauges is united in a uniform package placed in a
charge that has been split at an angle to the detonation product flow. The ele-
ments of the package are located at various depths in the flow, and this depth
can easily be adjusted by changing the distance between elements and the angle
 2. Detonation of Condensed Explosives 43

at which the package is placed. Multi-channel systems are mther informative,

however their application is not always expedient The gauges placed in these
charges are covered with an insulating film that causes undesimble perturbation
of the flow. In an unsteady flow, for example that occurring during evolution of
an initiating shock wave, these perturbations can appreciably alter the process
and even prevent initiation of the chemical reaction. The association of gauges
in a uniform package allows avoidance of these difficulties, however inclined
placement of gauges, as shown by direct experiments [23], alters the one-dimen-
sional chamcter of the flow and leads to under-valuation of the actual velocities
by as much as 10%.
In [24], axisymmetric magnetic gauges are used for measurement of particle
velocities. A measuring device consisting of a permanent magnet, an axial coil,
and a Teflon screen was placed at the downstream face of a charge under inves-
tigation. A 75-J.l.m-thick aluminum foil was placed between the screen and the
explosive. Movement of the foil in the field of the permanent magnet induces
voltage in the measuring coil and this voltage is measured with an oscilloscope.
The time resolution of this electromagnetic method depends on a number of
factors: the material of the gauge, its thickness, the distance between its termi-
nals, the curvature of the detonation front, and the speed of the recording
equipment. In precision experiments [25] using gauges of 25-l!m thickness and
with extremely careful assembly of devices it was possible to achieve a time
resolution of approximately 10 ns.
The electromagnetic technique is widely used for study of detonation of
condensed explosives. The greatest contribution here was made in the early
work of Dremin and Shvedov, geneI3lized in the monograph [20], and their
numerous subsequent researches.

2.2.3. The Manganin Gauge Method

For direct measurement of detonation pressure, piezoresistive manganin gauges
capable of covering the wide range of pressures from 0.1 to 100 GPa are used.
The first measurements of detonation pressures were made with manganin
gauges in 1976-1978 [26,27].
The principle of the manganin gauge is based on the high sensitivity of the
specific electrical resistivity of manganin to pressure and its low sensitivity to
tempemture changes. The gauge takes the form of a piece of manganin foil or
flattened wire connected to an electrical current contact terminal. The thickness
of the gauge is 25 -50 J.I.ffi. Both high-resistance (resistance from 5 to 50 Ohm),
and low-resistance (resistances of tenths to hundredths of an Ohm) gauges are
used in experiments. The gauge is located between layers of the explosive being
investigated and is separated from the detonation products by insulating films
because these products have significant electrical conductivity [22]. Teflon,
44 L.V. Al'tshuler, V.S. Zuchenko, and A.D. Levin

epoxy resin, mica, and lavsan are used as insulating materials. Because of the
presence of the insulating films, manganin gauges exhibit slower temporal re-
sponse than electromagnetic gauges.
In the Livermore laboratory several variants of the gauge are used, including
multi-element gauges placed on an inclined surface within a sample [4]. The
elements are located at fixed distances from each other in a protective dielectric
covering. The assembled "sandwich" is placed in an evacuated chamber, heated
to the melting point ofthe insulating material, and pressed to form the assembly.
Manganin gauges have found wide application in research on initiation and
development of detonation. The pressure profiles measured in experiments have
given direct information on the development of pressure transients and were
used for validation and improvement of numerical models.
The manganin gauge method has been used to measure detonation pressures
in 1NT [27], baratol, and TH 40/60 [26], in desensitized explosives made from
RDX and PETN [28], and in mixtures ofHMX and TATB with plasticizer [29].
During the measurement, the gauges are protected from each layer of the charge
by insulating films that are 0.20-0.25-mm thick. The temporal response of such
gauges is too slow (~0.1 J.1S) to register narrow reaction zones in high density
charges, so determination of detonation pressures required extrapolation of pres-
sure profiles to the initial moment of time.

2.2.4. The Pulsed X-Ray Imaging Method

The x-ray method of measuring the motion of detonation products was devel-
oped at the end of the 1940s in VNIlEF by Tsukerman and Sofina [2]. The ex-
periments were carried out on so-called zebra charges consisting of several disks
of explosive separated by thin lead foils. The detonation parameters were deter-
mined by measuring the relative displacement of foils at different distances from
the detonation front at a specific moment in time. In [30,31] the zebra-charge
method was used in investigations of detonation of mixtures of TNT with RDX.
In a variant of the method [32], a single foil was placed at an angle to the run-
ning front of the detonation wave. The advantage of this method is that it allows
continuous measurement of the foil displacement as it moves with the detona-
tion products. This reveals the structure of the flow in the vicinity of the detona-
tionfront.
In [33], detonation product measurements were made without use of metal
foils. A PMMA barrier was placed at the end of a TH 40/60 charge. The position
of the rarefaction wave produced by reflection of the detonation wave from the
barrier was determined by x-ray snapshots as it propagated through the detona-
tion products. The velocity of the return wave is equal to the difference between
the local velocity of sound, C, in the detonation products and their particle ve-
locity, U. Behind the detonation front, C and U decrease. However, their differ-
 2. Detonation of Condensed Explosives 45

ence remains constant in a returning rarefaction wave in a polytropic gas with

n = 3. Therefore, the experimentally detennined values of C - U and D, together
with the condition D = U + C at the detonation front, allows determination of
the velocity of the detonation products in the Chapman-Jouguet plane:
UCJ =+[D-(C-U)].
For TIl 40/60 the particle velocity UCI measured in this way and, accord-
ingly, the detonation pressure, PCJ, coincide with values found in experiments
with zebra charges to within 3 %.

2.2.5. The Brightness-Indicator Method

The brightness-indicator method was developed by Voskoboinikov in 1974 [34],
was advanced in subsequent works, and is used fruitfully in researches by
Gogulia and associates at the Institute of Chemical Physics [35 - 38].
The method is based on measurement of the luminescence of the shock front
in an indicator medium placed contiguous to a charge. The measurements are
made using the relationship between dynamic pressure and brightness. Materials
maintaining transparency under the influence of a shock wave in the interval of
pressure under investigation, such as lithium fluoride, glass K8, bromoform,
carbon tetrachloride, chloroform, glycerin, and water, are used as indicator me-
dia Preference is given to liquids over solids, because of the absence of elasto-
plastic deformation and the better contact with the explosive sample under
investigation that is provided. The luminescent signal is measured with a pho-
tomultiplier tube and recorded using a high-speed oscilloscope. The end of the
charge contacting the indicator is covered by a thin layer of black varnish to
obscure parasitic radiation from the detonation products.
The brightness-indicator method has the advantages of high time resolution,
continuity of measurement, and high sensitivity caused by the strong depend-
ence of radiation brightness on shock-wave amplitude. In experiments [35], the
time resolution of the shock-wave front in the indicator is - 30 ns. At the inter-
face of the charge with the indicator the corresponding time is 'tp -10 ns. In [35]
it is emphasized that the time resolution of the method can be improved by using
faster recording equipment
The detonation pressure of a number of individual and mixed explosives has
been detennined using the brightness-indicator method: TNT [34,35,37], RDX
[34,37], PETN [34], HMX [37], TIl 50/50 [35,37], mixtures ofRDX and HMX
with a desensitizer [37], and mixtures of HMX with aluminum in amounts
varying from 3 to 40% [38]. In TNT and TIl 50/50, reaction zones with in-
creased pressure were observed [35]. According to results presented in [35], the
chemical reaction peak in RDX is either absent or its duration does not exceed
10 ns.
46 L. V. Al'tshuler, V.S. Zuchenko, and A.D. Levin

2.2.6. Laser Measurement of Wave Velocities (LIVS)

The idea for laser measurement of wave velocities was offered by Levin [39] in
1979 and developed together with Doronin and Ashaev [40-42], at the Institute
of Mechanical Engineering (Dzerjinsk). A schematic drawing of the configura-
tion of an LIVS experiment is represented in Fig. 2.1. A barrier made from
several thin, transparent, flat plates with precisely mated surfaces is placed on
the end of the sample of explosive under investigation. With careful machining
of the plates, but without taking special measures to establish optical contact
between adjacent plates, there is a gap of ~ 1 ~ between them. The thickness
of the plates is measured to within 1 ~. The probing laser beam is directed
perpendicularly to the face of the sample. The face of each plate forms an inter-
face between the transparent material and air. The probing laser beam is par-
tially reflected from each interface. All reflected beams are directed onto a
photomultiplier tube by a system of mirrors and lenses and its signal recorded
with a high-speed oscilloscope. As the shock wave passes through the stack of
plates, it consistently closes the gaps between them, establishing optical contact.
Thus, the total intensity of the reflected light beam decreases by jumps as the
reflection disappears from each successive interface. The time of passage of the
shock wave through the plate is thus precisely measured, and the shock-wave
velocity is determined using the known thickness of each plate.
The LIVS method measures local values of velocity of the front of the shock
wave in a barrier (the cross-sectional area of the laser beam is ~0.03 mm2). The
evolution of the shock wave in the barrier is determined from the motion of the

C=:l
7
1 v 8

fI'
4 5
6 I
I
Figure 2.1. Configuration of an experiment conducted using the LIVS method. 1:
explosive charge, 2: barrier plates adjacent to the material under investigation, 3: lens, 4
and 7: mirrors, 5: beam splitter plate, 6: laser, and 8: photomultiplier tube.
 2. Detonation of Condensed Explosives 47

contact interface of the explosive with the barrier. If the dynamic compressibil-
ity of the barrier is known, the parameters of the shock-wave pulse from the
shock front to the interface separating the explosive from the barrier can be
calculated.
The high time resolution of this method is achieved by using thin plates
having only micron gaps between them, high-resolution recording devices, and a
gas-dynamic measuring concept (events occurring at the interface on a time
scale of 0.1 IlS influence a -2-mm-thick layer at the shock front). The shock
wave in the barrier represents the structure of the reaction zone in only a thin
layer near the interface with the explosive. Therefore, the opportunity to meas-
ure the velocity of the shock wave in thin plates (thickness about 0.1 mm) di-
rectly in contact with the explosive makes this method especially attractive.
In precision measurements made by the LIVS method, PMMA plates of
-0.1 mm thickness were used [42]. High-speed photomultiplier tubes and os-
cilloscopes allowing measurement of time intervals with an accuracy 0.1 ns
were used for recording the signals. The resolution achieved in measurements at
the interface of the charge with the barrier was 2 ns. For processing the results of
the experiments, the Hugoniot of PMMA given in [40] was used. Statistical
processing of the most reliable data gave D =2.580 + 1.525 U, for 0.5 < U <
2.63 kmls and D =3.156 + 1.305 U for U > 2.63 kmls.
The laser measuring device has shown itself to be an effective tool in ex-
periments with explosives. With the help ofLIVS, the classical Zel'dovich-von
Neumann-Doring (ZND) wave structure with a steady reaction zone of 70 ns
duration followed by a self-similar rarefaction wave was observed in pressed
TNT of density 1.58 glcm3• A Chapman-Jouguet pressure of 18.6 GPa was also
measured [41,42]. Steady weak detonation with its characteristic attributes-
lowered pressure and a self-similarly-extending plateau-was recorded for two
desensitized explosives, PETN and RDX [41]. In a high-density mixture of
RDX and HMX unusual detonation profiles, with pressure increasing at the front
of the wave, were recorded [42]. Some results of measurement of profiles of
wave velocities in barriers for various modes of detonation are given in Fig. 1.2.
Discrete measurements of wave velocities in layered barriers can be made
without a laser. In [43] two methods were used to measure the detonation pres-
sure of PETN. In experiments with charges of density po> 0.5 glcm 3 , signals
produced when the front of the shock wave caused a short circuit to fonn in
electrocontact gauges in a PMMA barrier were recorded with an oscilloscope. In
[44], a similar technique was used to study the modes of a detonation in water-
filled RDX. Records with an accuracy of a few ns fixed the time of arrival of the
shock wave for each interface in a stack of PMMA plates in contact with the
charge. The traditional method of slreak-camera recording of flashes of air in
gaps between layers of a barrier was used for measuring the detonation pressure
in low-density charges of PETN (po < 0.5 glcm3 ). In an advanced variant of the
48 L.V. Al'tshuler, V.S. Zuchenko, and AD. Levin

method that was more sensitive and employed sensors located near the axis of a
charge [41], nanosecond flashes occurring in micron gaps were recorded using a
photomultiplier tube and an oscilloscope. In [45], the light signals arising in the
gaps were transferred to a photomultiplier tube using an optical fiber attached to
the external surface of the barrier. All the techniques listed are inferior to the
LIVS method from the standpoints of sensitivity and accuracy, but they do not
require use of a laser.

2.2.7. Laser Interferometry

Laser interferometers provide the method of highest time resolution for meas-
uring the structure of detonation waves. With this method, the velocity of a thin
metal foil or film on the interface between a charge and a transparent window is
measured. The interferometer records the shift of frequency of the laser emission
reflected from the moving surface of a charge under investigation and analysis
of this Doppler effect yields the surface velocity. The frequency shift is meas-
ured using either the change of intensity of target radiation (VISAR interfer-
ometer [46]), the displacement of interference bands (ORVIS interferometer
[47]), or interference rings (Fabry-Perot interferometer [48]), depending on the
optical configuration of the interferometer. High-speed photomultipliers with
time resolution of 1-5 ns are used in VISAR interferometers, and electron-
optical chambers with time resolution about 0.3 ns are used in ORVIS interfer-
ometers. The time resolution of the Fabry-Perot interferometer is limited to a
few nanoseconds because of multibeam interference.
As with the LIVS method, laser interferometry provides high spatial resolu-
tion because the probing laser radiation is focused on a spot of small diameter
(~0.1 mm) on the surface of the sample.

In [47], a number of explosives, including TNT, were investigated using an

ORVIS interferometer. At extremely high subnanosecond resolution, the time of
observation in the majority of experiments did not exceed 100 ns. Interfero-
grams demonstrate dying reverberation and monotonic decrease of velocity
outside of the reaction zone. Experiments were conducted on a series ofTATB-
based compositions using a Fabry-Perot interferometer with significantly
poorer time resolution (6 ns) [48]. Results of measurements on charges oflength
13,25, and 50 mm had a common a feature for all compositions: an increase of
the velocity of the reaction zone boundary with increasing charge length that is
characteristic of an unsteady detonation.
Interferometric methods allow measurement of fast decomposition reactions.
In [49], the reaction zone in charges of desensitized RDX was measured to have
a duration of 25 ± 5 ns. A variant of these experiments was reported in [50].
Initiation was produced by impact of a Mylar foil and monocrystals of lithium
fluoride were used as the window material because their impedance is close to
 2. Detonation of Condensed Explosives 49

that of the explosive under investigation (LX~14). The thickness of the reflecting
aluminum layer did not exceed 0.2 lUll. The basic result of interferometric
measurements consists in determination of the maximum pressure in the reaction
zone and reliable estimation of the rate of decomposition of the explosive.

2.2.8. High-Time-Resolution Spectroscopy

In contrast to the methods considered above for measuring detonation wave
parameters, spectroscopic methods allow direct study of the kinetics of chemical
decomposition of detonating explosives. These methods have undergone devel-
opment by Gupta and his associates, who investigated the intensity of spectral
lines of Raman scattering [51,52] and absorption of optical emission [53] in
unreacted explosives and the products of their decomposition. This was done
with nanosecond time resolution. Each of the spectral lines is characteristic of
certain chemical bonds or functional groups, and their intensity is proportional
to the concentration of the appropriate substances. As the lines of Raman scat-
tering have weak intensity, this method is most suitable for study of the initial
stages of decomposition of the explosive when the self-luminescence of the
decomposition products is not intense. Sufficiently powerful pulsed sources of
probing visible and near UV radiation can be used to measure absorption in the
presence of intense background radiation from detonation products. The spectro-
scopic methods are subject to the essential restriction that the substance under
investigation must be transparent to the probing radiation. Therefore, the first
experiments were carried out on nitro methane, a liquid explosive. The existence
of a delay of some nanoseconds between arrival of the shock-wave front and the
first evidence of chemical decomposition of nitromethane and also formation of
many intermediate reaction products during decomposition of the explosive was
found using Raman and absorption spectroscopy. The authors of [51] assume
that spectral methods can also be used for study of detonation processes in solid
explosives.

2.3. Detonation Pressure

The experimental measurements of the detonation pressure of brisant explosives
are characterized by an extraordinarily large inconsistency. This circumstance
has been discussed repeatedly in the literature [2,33,54-56]. For the most thor-
oughly investigated explosive, TNT at a charge density of 1.63-1.64 g/cm3,
detonation pressures from 17.7 to 21.3 GPa have been reported.
The steady detonation parameters now being reported have become quanti-
tatively definite and highly reliable, as shown by the analysis carried out below
for several of the most common explosives. This result is achieved because of
increased accuracy of measurements, development of new techniques, and use
of new models of detonation processes for interpretation of the experiments.
50 L.v. AI'tshuler, V.S. Zuchenko, and AD. Levin

To compare experimental data it is necessary to take into account the de-

pendence of the detonation pressure, P CJ, on the initial density, Po, of the explo-
sive. For this purpose it is possible to use the equation
poD2
PCJ=-- (2.2)
n+l
that follows from the Landau-Stanukovich equation of state for the detonation
products. Detonation pressures measured for different values of Po, are consid-
ered to be coordinated among themselves if they can be obtained from Eq. 2.2
for a single value of n. Experimental data for some explosives, and lines
bounding the uncertainty of the value of n, are given in PCJ-Po coordinates on
the diagrams of Figs. 2.2-2.4. For calculation of n using Eq. 2.2, the empirical
dependencies of detonation velocity D on initial density, Po, were used.
For TNT, the experimental data are given on Fig. 2.2. The detonation veloc-
ity was calculated from the equation (D in kmls and po in glcm3)
D = 1.873 + 3.187po - 25. 102 (po -1.534)2 + 115.056(po -1.534)3

developed in [57] using careful measurements and describing the numerous data
of other authors in the best way. The diagram reflects the experimental informa-
tion found by the spall method using a continuous [12] and a layered [6] barrier
by measurement of wave velocities in the barrier using a streak camera [5] and
with the help ofLIVS [1,2], electromagnetic [4,8-11], and manganin [3,7] gauges.

P,GPa
2'~·----------------~

Figure 2.2. P-po diagram for lNT. Data are from the following references. 1, 2:
[41,42],3: [102],4: [103], 5: [66]; 6: [13]: 7: [27], 8: [104], 9, 11: [20], 10: [18], and 12:
[9].
 2. Detonation of Condensed Explosives 51

P,GPa
J5

JO

LIS 110 17S Po. g/cm3

Figure 2.3. P-Po diagram for RDX. Data are from the following references. 1-3: [34],
4: [42]. 5: [41].6: [28],7: [102],8: [20]. 9: [9], and 10: [37].

P.GPa

I I I

tii l70 llf Po. yjcm3

Figure 2.4. P-Po diagram for PElli. Data are from the following references. 1-3: [34].
4 and 5: [65],6 and 9: [41],7: [28],8: [20].
52 L.V. Al'tshuler, V.S. Zuchenko, and AD. Levin

The obviously erroneous data (for example 17.7 GPa [58] and 21.3 GPa [59] at
Po= 1.63-1.64 glcm3) were not used. The dashed line designates the
overestimated results of early spall measurements [60,61], recognized later in
[17,62] as erroneous. The data on the diagram form a band of uncertainty of
width -1 GPa. The dark points designate results of two internal methods-
electromagnetic and manganin gauges. The light points represent results of all
variants of the barrier method. No systematic distinction among results obtained
by these techniques was observed. In the set of measurements made inside the
charge and in a barrier the value of n determined for TNT was 3.125 ± 0.125.
The experimental data for RDX are presented in the diagram in Fig. 2.3,
where a 1.5-GPa wide band of uncertainty is shown. In calculating the borders
of this band, the dependence D = 5.71 + 3.79 (po-I) given in [63] was used. The
band includes points obtained by the spall [9], LIVS [4], electromagnetic gauge
[8], and manganin gauge [7] methods. Less reliable results [1-3] obtained by
the brightness indicator method [34], fall beyond the limits of the band and do
not agree among themselves. In general, the strip of uncertainty determines the
value n = 2.88 ± 0.08 for RDX. The lowered pressures in desensitized RDX,
characteristic of the weak detonation mode, were measured by the manganin
gauge [6], LIVS [5], and brightness indicator [10] methods.
The results for pure PETN are shown in Fig. 2.4. The strip includes meas-
urements by the brightness indicator method of [1-3], by recording shock elec-
trical effects in a layered PMMA barrier [4,5], and by the LIVS method [6]. For
constructing the band, the equations
D=4.78+3.70(Po-0.8) for Po<1.65 glcm3
D=7.92+3.05(Po-1.65) for po>1.65g1cm3
were used [64].
The reliability and accuracy of the data on dynamic characteristics of pure
PETN increased significantly after revision in [65] offormer measurements [64]
in a layered barrier as specified on the diagram by a dashed line. The designated
strip corresponds to n = 2.9 ± 0.1. Data for desensitized PETN, obtained using
electromagnetic [8] and manganin ]7] gauges and the LIVS method [9] fall
within the band.
The data on detonation pressures of composition PBX-9404 (Po = 1.84
glcm3 ) have a wide range of scatter, -3 GPa. The largest value P cr = 37.4 GPa,
given in [65] was measured by recording shock electrical effects in a layered
PMMA barrier. The value Pcr =36±0.6 GPa was obtained by more rigorous
processing of the primary experimental information given in [65] (using Eq. 2.1
instead of the equation obtained using the acoustical approach) and taking into
account the statistical weight of separate measurements. The value P cr = 34.5
GPa, found in [66] by optical measurement of wave speeds in a PMMA barrier
 2. Detonation of Condensed Explosives 53

with the use of the Hugoniot D =2.695 + l.538 U requires revision. Processing
of results given in [66] using the equation D=3.156+1.305U [40] gives
P Cl = 35.7 GPa. The pressure 35.6 GPa was given in [24] on the basis of meas-
urements of the speed of the detonation products at the interface with a Teflon
screen with the help of a magnetic gauge. In view of the adjustment mentioned
for composition PBX-9404, it is necessary to accept the value PCl = 36 ± 0.5 GPa
that corresponds to n = 2.95 ± 0.05. This value is in agreement with experimental
data of Los Alamos laboratory (PCl = 36.5 GPa at Po= 1.844 glcm3) given in
[67].
The analysis of numerous researches executed in Russia and the United
States has shown that the detonation pressure of many explosives is determined
with an error not exceeding 0.5 GPa, and the parameters of the detonation-prod-
uct Hugoniots are determined to within a possible deviation /),.n - 0.1 . For a
group of the most common single-component and mixed explosives, the detona-
tion parameters are given in Table 1.1 of Chapter l. On generalizing Fig. 2.5,
the experimental detonation pressures of several explosives are given at their
maximal density. The numbers on the figure are the average values of the adia-
batic parameters. It is obvious that both single-component and mixed explosives
are described by the adiabatic parameter n = 3, consistent with an early hypothe-
sis of Landau and Stanukovich.

HMX
P,GPa
PB~ n
RDX~\E
PE~ \Yl
Ji

JD
TH40~60'~
::-\. \1.1
TH5~ ~

10
UZ

Figure 2.5. Detonation pressures for very dense explosives. The numbers are the isen-
tropic indices of the detonation-product Hugoniots.
54 L.V. Al'tshuler. V.S. Zuchenko, and A.D. Levin

The parameters of strong detonation of the hemispherical devices described

in Chapter 1 and intended for production of high and ultrahigh pressures are of
special interest. The estimated characteristics of the converging detonation were
given for the first time in 1959 by Zel'dovich [68]. For explosive measuring
systems, they were found by calculations based on Chapman-Jouguet parame-
ters and the Landau-Stanukovich equation of state. Later, in [69], the parame-
ters of a strong detonation for a TH 50/50 alloy explosive were determined
experimentally over a wide range of pressure up to 300 GPa The experiments
were carried out on laboratory measuring devices and in the zone near an under-
ground nuclear explosion. The experiments have confinned the legitimacy of the
description of strong detonations with the Landau-Stanukovich equation with
the same adiabatic parameter, n, as for nonnal detonation, i.e., close to 3. As
shown in [70], the same correspondence occurs for TNT, TH 50/50, composition
B, PBX-9404, and baratol.

2.4. Modes of Detonation

The classical theory of detonation [71-73] is based on the premise of instanta-
neous chemical reaction in the explosive transition: The front of the detonation
wave is considered to form a surface of discontinuity separating the unreacted
explosive from the detonation products. According to the Chapman-Jouguet
hypothesis, the nonnal steady detonation advances with minimal velocity deter-
mined by the condition of contact of the Michelson-Rayleigh line with the
detonation-product Hugoniot. At the point of contact, the velocity of the detona-
tion products is equal to the velocity of sound: C =D - U . The strong detona-
tion corresponding to a point on the upper branch of the Hugoniot (C > D - U )
is unsteady because the detonation products move away from the shock front
with subsonic velocity so a refraction wave catches up to the detonation front.
Detonations corresponding to points on the lower branch of the Hugoniot
( C > D - U ) are excluded on the basis of the Chapman-Jouguet hypothesis.
Further development of the classical theory was carried out by Zel' dovich
[74] (later, similar results were obtained independently by von Neumann [75]
and DOring [76]). In this new theory, designated by the abbreviation ZND, a
physical model of the detonation wave structure was included. It was suggested
that no reaction occurred in the shock wave itself, but a reaction proceeding at a
finite rate begins immediately after passage of the shock. On the P- V diagram
of Fig. 1.1, point 1 designates the state of the explosive at the shock front and
point 2 designates the :final equilibrium state of the detonation products in the
Chapman-Jouguet plane. All intennediate states comprise a mixture of unre-
acted explosive and detonation products and lie on the wave line 1-2 (subse-
quently named the Michelson-Rayleigh line) and move with the same velocity
as the detonation front. The detonation complex includes a shock jump, a steady
zone of reaction (the chemical peak or reaction zone) and a following self-simi-
 2. Detonation of Condensed Explosives 55

lar expansion wave. This wavefonn is illustrated, in particular, by experimental

data given in Fig. 1.2 for TNT.
In the ZND theory, the Chapman-Jouguet selection rule received strict sub-
stantiation for the first time. It was shown that the lower branch of the detona-
tion-product Hugoniot (weak detonation), as opposed to the upper branch, is
quite compatible with boundary conditions imposed on solutions of the equa-
tions of gas dynamics for the steady detonation. The states on the lower branch
of a detonation-product Hugoniot are excluded in the rigorous theory based on
the assumption that, after compression of the unreacted explosive, the shock-
wave transition to condition 2 occurs. This is followed by an exothennic de-
composition reaction of the explosive, producing the final products. This state
can be realized if, in the reacting system, there are two independent chemical
reactions with the endothermic reaction proceeding at the lower rate [77]. In this
case (Fig. 2.6) the detonation velocity is determined by the slope of the
Michelson-Rayleigh line 0-2 to the Hugoniot I of intermediate composition,
and the pressure of detonation (point 3) at which the Michelson-Rayleigh line
intersects the Hugoniot II of the final composition. A typical feature of the weak
mode is increased detonation velocity compared with the normal mode, for
which the Michelson-Rayleigh line is tangent to the final detonation-product
Hugoniot (in Fig. 2.6 these lines are shown dashed). At point 3, the flow is su-
personic (C + U < D ), the rarefaction wave lags behind the reaction zone, and a

,
p.---~------------------~

J
o
o y
Figure 2.6. P- V diagram. The curve 0-1 is the Hugoniot of the unreacted explosive, the
line 0-2-1 is the Michelson-Rayleigh line, I is the Hugoniot of the partially-reacted
explosive, and II is the Hugoniot of the fmal detonation products.
56 L.V. AI'tshuler, V.S. Zuchenko, and AD. Levin

self-similar, lengthening horizontal plateau forms on the detonation profile. One

of the important consequences of the ZND theory is the dependence of the mode
of a detonation on the course of reaction in the detonation wave.
The ZND theory was developed for detonation in gaseous systems; in par-
ticular, weak detonation was considered for a mixture of chlorine and hydrogen,
for which the reaction combining these gases was exothermic, and dissociation
of HCI molecules was endothermic. The theory becomes appreciably more
complicated when extended to condensed explosives. This is because both shock
compression and chemical decomposition processes are more complicated in
condensed explosives than in gases. This is especially true of solid explosives,
which are almost always somewhat heterogeneous. As early as the 1970s, dis-
cussions begin regarding hot spots in which the decomposition of the explosive
occurred (Dremin and co-workers [78]), and also regarding partial or complete
decomposition of an explosive at the shock-wave front (Chen and Kennedy [79],
Klimenko and Dremin [80,81]). Now, rather complete consideration of the suc-
cession of processes occurring in condensed explosives has given rise to a mul-
tiprocess model of detonation, the latest version of which is stated in [81]. This
model is based on the concurrent action of two physical processes-
homogeneous and heterogeneous decomposition of the explosive. The hetero-
geneous decomposition proceeds by means of a mechanism involving centers of
decomposition, whereas the mechanism of homogeneous decomposition is
associated with the shock-wave front. The front mechanism has two stages, an
intra-front stage and a post-front stage. The intra-front stage proceeds in the
shock front and the controlling process is overheating of translational degrees of
freedom and excitation of molecules. This results in breakup of the molecule
with formation of primary radicals. The duration of this stage is 0.1-1 ns.
During the post-front stages the radicals formed earlier activate a whole set of
consecutive and concurrent reactions forming intermediate products. The post-
front stage proceeds to complete decomposition of the explosive and has a
duration of 10-8 _10-7 s.
The possibility of direct excitation of molecules of a solid explosive by a
shock wave can also be seen from results of molecular-dynamic modeling of a
detonation. For example, Trevino et al. [82] consider a model of a diatomic
molecular monocrystal. The kinetic energy of a shock wave produces nonequi-
librium, nonthermal excitation of molecules and breaking of chemical bonds on
a time scale of about 10-13 s. The authors of [82] call this decomposition "by
almost instant reaction." Similar results were also obtained from molecular-
dynamic analyses by Woker [83].
The influence of chemical reactions on the mode of a detonation that is im-
plicit in the ZND theory is naturally most pronounced for condensed explosives.
Even for a single-component condensed explosive, many intermediate products
are formed during reaction. Even more complicated processes can proceed in
 2. Detonation of Condensed Explosives 57

mixed explosives and explosives with inert additives. Therefore, in condensed

explosives, and most prominently in solid explosives, it is possible (probable)
that detonation occurs in non-ideal modes.
Several important questions connected with the detonation modes of con-
densed explosives are considered in the following sections. The greatest atten-
tion is given to self-sustaining, weak detonations observed in mixed
compositions including widely used desensitized explosives. Observed modes
were analyzed on the basis of equilibration processes occurring in detonating
media. The features of detonation of mixtures of TNT with RDX that have been
the subject of much debate are discussed. Experiments are considered in which
an individual agate explosive yielded an unusual detonation profile exhibiting
increasing pressure in the reaction zone.

2.4.1. Desensitized Explosives

Experimental investigations of detonation of the condensed explosives PETN
and RDX containing 5-6% paraffin [28,41], have shown the particle-velocity
waveform to be that peculiar to the self-sustaining weak mode. Pressure wave-
forms measured by manganin gauges and the LIVS technique exhibited a nar-
row steady zone of increased pressure (the chemical peak or reaction zone) of
50 ns duration followed by a horizontal plateau that stretches as the detonation
wave propagates through the charge. Typical results obtained using the LIVS
method in charges from desensitized PETN of different lengths, are shown in
Fig. 1.2b. It turned out that the addition of a small amount of paraffin desensi-
tizer resulted in an explosive exhibiting only an insignificant increase of detona-
tion velocity (on the order of 10-200 mls) but an appreciable reduction of
detonation pressure (on the order of 1.5-2 GPa).
Experimental results [28,41] have served to stimulate theoretical investiga-
tions directed toward determining the detonation mechanism in desensitized
explosives. According to the initial assumptions [28,41], the weak mode sug-
gested by the theory and caused by non-monotonic generation of heat in chemi-
cal reactions [77] is realized in the mixture investigated. The reason for the non-
monotonicity is the slow endothermic decomposition of the desensitizer.
According to the treatment in [84], the model problem of propagation of a shock
wave in a reacting medium with a two-step sequence of reactions is considered:
An exothermic reaction occurs instantly in the plane of the detonation front and
an endothermic reaction proceeds slowly according to an exponential evolution-
ary law. The analyses have revealed typical evolution of flow with yield of the
endothermic zone in the steady mode and subsequent formation of a stretched
plateau. The increase of energy absorbed during the endothermic stage produces
a reduction of pressure and an increase in the duration of the plateau.
In [85], an analysis of the detonation features of PETN and RDX containing
various quantities of paraffin additive (5-25%) has been carried out. These
58 L.V. Al'tshuler, V.S. Zuchenko, and A.D. Levin

calculations employed a technique based on minimization of Gibbs' free energy

of the mixture of the gaseous and condensed components of the detonation
products in conditions of complete thermodynamic equilibrium or a fixed partial
perturbation of the thermal and chemical equilibrium of the separate phases [86].
In Table 2.1, the calculated values of detonation velocity, D, particle velocity, U,
pressure, P, adiabatic parameter, n, and specific heat of detonation, Q, of the
mixture compositions ofRDX and PETN are given for two limiting cases of the
condition of the paraffin additive.

Table 2.1. Detonation parameters of desensitized explosives.

Composition Calculation
and density 1 2 Experiment
(Po, g1cm3) Parameters a b [70]

RDX-paraffm D, kmls 8.357 8.437 8.223 8.33

94/6 U, kmls 2.083 2.074 2.048 1.94 (1.71)
(1.66) P, GPa 28.89 29.01 27.96 27.0 (23.6)
n 3.013 3.069 3.014
Qp.T MJ/kg 5.811 5.896

PElli -paraffm D, kmls 8.076 8.136 7.981 8.12

95/5 P, GPa 27.33 27.43 26.66 25.0 (22.0)
(1.65) n 2.938 2.982 2.942
Qp,T MJ/kg 5.978 6.049

For explanation of the results of this analysis, let us use the P-V diagram of
Fig. 2.6. Version 1 (point 2) corresponds to the Chapman-Jouguet condition on
the intermediate Hugoniot I, describing additive compression of the detonation
products and the paraffin. In this model it is also assumed that the additive is not
in thermal and chemical equilibrium with the detonation products and its com-
pressibility is calculated using the Hugoniot of the initial (continuous) sub-
stance. Sub-versions a and b correspond to different Hugoniots for paraffin:
D=3.32+1.24U [87] and D=3.12+1.47U [88]. In version 2 (point 4) the
Michelson - Rayleigh line is tangent to the Hugoniot II of the :final completely
equilibrated composition. In this model it is also assumed that the paraffin de-
composes simultaneously with decomposition of the explosive in the reaction
zone, producing a :final mixture in complete chemical, thermal, and phase equi-
librium. In the last column of Table 2.1, measured detonation parameters taken
from [70] are presented. The values of U and P at the point of intersection of the
measured Michelson-Rayleigh line with the calculated Hugoniot II are speci-
fied in parentheses. In Table 2.2, for the same variants, the calculated detonation
velocities of mixtures PETN containing different amounts of paraffin additive
are given.
 2. Detonation of Condensed Explosives 59

Table 2.2. Detonation velocities of desensitized PErn containing

various amounts ofparaffm additive.
Composition Calculation Experiment
and density 2
(Po, glcm3) a b
95/5 (1.650) 8.076 8.136 7.981 8.12 [41]
90110 (1.575) 7.893 7.999 7.692 7.90 [41]
80/20 (1.440) 7.536 7.700 7.090 7.60 [70]
75/25 (1.265) 6.911 7.037 6.373 7.23 [70]

The analyses have shown that the difference between the thermal effect, Q,
for the intennediate and final mixtures is small. The downward displacement of
the final Hugoniot is caused not by heat loss, as was supposed in [28,41], but by
a change of chemical composition and thennodynamic properties of the final
detonation products because of the decomposition of the paraffin. The detona-
tion velocities calculated using the additive approach correspond well with the
experimental results. The calculated values of pressure given in Table 2.1 in
brackets are significantly (on the order of3-3.5 GPa) below the actual values.
The discrepancy between the calculated and measured pressures suggests
that the hypothesis of simultaneous and complete decomposition of paraffin in
the narrow relaxation zone that is incorporated in the model [85] is idealized and
too restrictive. In real charges, the desensitizer is distributed nonunifonnIy, as
rather large inclusions and micron-thick films covering the surface of the explo-
sive granules. This initial structure of the charge results in a two-stage relaxation
process. During the first stage, the detennining role is played by the thin film of
paraffin surrounding the explosive granules. The rapid completion of reaction
during this stage results in local balances. The second, longer-duration, stage
proceeds with participation of the remaining large inclusions of paraffin and is
completed in the unloading wave. Based on these premises, the authors of [89]
have carried out gas-dynamic analyses for desensitized PETN of density 1.56
glcm3. For these analyses, calculated data were used for chemical composition
and equations of state for two limiting cases [85]: (1) A non-equilibrium state of
the detonation products and shock-compressed undecomposed paraffin, and (2)
final equilibrium of the mixture of detonation products and the products of com-
plete decomposition of the paraffin. The kinetics of decomposition of paraffin
behind the detonation front were represented by an exponential law. The equili-
bration time was taken to be 50 ns, according to experiment [41], and the initial
and final proportions of undecomposed paraffin in the equilibration zone were
varied parametrically.
In Fig. 2.7, calculated diagrams of detonation velocity and pressure at the
plateau, depending on the parameter Ie, are shown. The points specify experi-
60 L.V. Al'tshuler, V.S. Zuchenko, andA.D. Levin

mental values D = 8.12 km/s and P = 25 GPa. The diagram shows that, to
achieve the observed value of D, 20% of the paraffin must decompose in the
reaction zone of the explosive. The condition arising at the end of this zone
determines an intermediate Chapman-Jouguet plane and, hence, the detonation
velocity. In the subsequent reaction zone, 80% of the paraffin decomposes in a
self-similarly-extending plateau.
The model developed in [89] is not considered complete. In particular, issues
remain open about the kinetics of decomposition of the desensitizer, the degree
of mixing of the diverse components behind the detonation front, and the choice
of appropriate equations of state for description of the mixture. Nevertheless, the
model can be considered as the next step in revealing the real mechanism of
detonation of desensitized explosives.

D,km/s P,GPa

6.1

o az ~4 aN 0.6 LOA

Figure 2.7. Dependence of detonation speed (D) and plateau pressure (P) on the reacted
fraction of the large paraffm inclusions.

2.4.2. Mixture of an Explosive with Tungsten

The additive principle [90,91] is used for calculation of detonation parameters
for explosives containing inert impurities. According to this principle, the deto-
nation-product Hugoniot of the mixture is calculated by addition of specific
volumes of the detonation products and the shock-compressed impurities under
the assumption that they are at the same pressure. The detonation parameters are
determined from the tangency of the Michelson-Rayleigh line to the additive
Hugoniot. If the impurity particles are of a relatively incompressible metal, the
additive calculation predicts a curious result: the addition of an inert substance
to an explosive, naturally, will reduce the detonation velocity. However, the
detonation pressure remains the same as for the pure explosive, irrespective of
the amount of the impurity.
 2. Detonation of Condensed Explosives 61

Experimental results [92] obtained for mixed charges containing tungsten

powder as an impurity do not agree with the calculation. These experiments
were conducted on high-density charges made by mixing a powerful explosive
(D = 8.9 km/s) with 5-1O-J.lIO-diameter tungsten particles. The detonation ve-
locity, measured with electrocontact gauges and a streak camera, is slightly
above the value for the pure explosive, and the pressure found by the spall
method using aluminum plates is much lower than the calculated value. The
P-V diagram of Fig. 2.8, taken from [92], shows calculated additive Hugoniots
of mixtures with different mass concentrations of the tungsten additive: a = 20,
40, and 60%. The dashed Michelson-Rayleigh lines correspond to calculated
detonation velocities and the open points, at which they intersect the detonation-
product Hugoniots, determine the Chapman-Jouguet pressure. The continuous
Michelson-Rayleigh lines correspond to the experimental detonation velocities,
and the solid points on these lines specify the pressure measured in experiments.
With a = 60%, the measured detonation pressure is only one-half of the calcu-
lated value.
In discussing these unexpected experimental results, the authors of [92] be-
lieved that, in the mixtures investigated, the modes of forced detonation pre-
dicted by Zel'dovich [93] prevailed. Their velocities exceeded those satisfying
the Chapman-Jouguet condition. These high nonhydrodynamic wave velocities
are explained in [92] by forward expansion of the detonation through the gran-
ules of explosive in the material between the metal particles. Because of the
large slope of the detonation-product Hugoniots, even the insignificant increase
of detonation velocity resulted in a sharp reduction of pressure.
The paradoxical results of [92] are not exceptional. In researches conducted
at the Los Alamos laboratory at the end of the 1960s, the same tendency was

P, GPa , - - - - - - - - - - - - ,
JO

+0
JO

10

10

Figure 2.S. P- V diagram for mixtures of an explosive with tungsten.

62 L.V. Al'tshuler, V.S. Zuchenko, and A.D. Levin

observed: The addition of lead or tungsten powder to explosive materials based

on RDX and HMX resulted in reduction of the detonation pressure (in compari-
son with the normal value) of approximately 10 GPa The analysis of the ex-
perimental observations [67] showed nonideal behavior of explosives with
additives of heavy metals, including those noted in the "impressive researches"
reported in [92].
An attempt was made in [94] to explain experimental results [92] from the
standpoint of a weak detonation caused by relatively slow thermal equilibration
of the metal particles. It was shown that the small nonmonotonicity of heat gen-
eration connected with heating of the impurity particles leads to a large decrease
of pressure of the detonation wave, but the result does not agree with experi-
mental data [92] on the detonation velocity. The author of [94] believes that the
determining part is played by another process, that of rapid velocity equilibra-
tion of the heavy metal particles. The authors of [95] came to the same conclu-
sion independently, based on results of analyses that were carried out in the
context of a model with thermal equilibration, and also results of experiments
with manganin gauges which have measured abnormal pressure waveforms in
charges from a mixture ofRDX with tungsten [95].
A generalized model, allowing quantitative description of the influence of
temperature and velocity nonequilibrium on detonation parameters of explosives
containing an inert impurity, was suggested in [96]. In this model the reaction
zone of the detonation wave is regarded as a thin portion of the front of the
shock wave where the processes of chemical decomposition and rapid equilibra-
tion proceed together, resulting in equalization of velocities and temperatures of
the detonation products and the impurity particles. It is supposed that equilibra-
tion of specified parameters cannot occur within the typical time of complete
decomposition of the explosive. This means that the detonation products and the
impurity particles can have different values of temperature and velocity on exit
from the reaction zone. In this case, the equilibration process is completed in the
flow behind the wave front.
For estimating the influence of equilibration processes on the detonation
wave parameters. calculations of the parameters were carried out for mixtures of
RDX with particles of tungsten for different limiting modes of detonation and
different values of the mass concentration of tungsten. The calculations have
shown that velocity equilibration is the dominant effect. Taking account of the
particle acceleration leads to a strong change in the basic detonation parameters
with increasing impurity concentration.
The results of calculations for the mixtures used in experiments reported in
[92] are shown in Fig. 2.9. These diagrams describe the dependencies of veloc-
ity and detonation pressure on the velocity of the tungsten particles in the wave
for different impurity concentrations, without taking temperature equilibration
into account The dependencies proceed from a common point corresponding to
 2. Detonation of Condensed Explosives 63

a frozen initial state (the particles of tungsten are motionless) to complete

equalization of particle and detonation product velocities. Markers specify the
experimental values of D and P given in [92]. As evident from Fig. 2.9, values
measured in the detonation velocity experiments correspond to incomplete ve-
locity equilibration of the tungsten particles in the reaction zone, and indicate
that the disequilibrium decreases with increase of mass concentration of parti-
cles. The pressures at the end of the reaction zone (specified by arrows on Fig.
2.9) are above the experimental values, with the maximum difference being
observed at small concentrations (a = 20 %). These differences decrease with
increasing concentration and, for a = 60%, when complete velocity equilibration
is achieved in the reaction zone, the experiment and analysis are in agreement.
Under conditions of incomplete equilibration, the flow of the mixture exiting
the reaction zone is characterized by large velocity differences. An intensive
relaxation process producing a condition velocity equilibrium should begin just
behind the front of the wave. This process, obviously, must be accompanied by
energy transfer from the detonation products as the impurity particles are accel-
erated. This, in turn, leads to a decrease of pressure in the detonation products

D,km/s

i~
I J
-I

I
I
o D.J I.Z 1.6 Uw , km/s
P,GPa

I
JO

20

IJ.~ 0.1 I.Z 1.1 Uw , km/s

Figure 2.9. Parameters at the detonation front depending on the speed of the tungsten
particles. The mass concentration of tungsten is 20 % for curve I, 40 % for curve 2 and
60% for curve 3.
64 L.V. Al'tshuIer, V.S. Zuchenko, and AD. Levin

in a narrow region behind the reaction zone. For quantitative estimation, a

numerical solution of the time-dependent problem of propagation of detonation
in a relaxing heterogeneous fluid was carried out in the context of a two-velocity
model developed in [97]. Heating of particles of the additive was not considered
because this effect is small.
The important resuIts are shown in the Fig. 2.10, where the spatial distribu-
tion of velocities of explosion products and particles (a) and also pressures be-
hind the front of the detonation wave (b) at distances of 20, 40, 60, and 80 mm
from the plane at which the impurity concentration was a = 20%, are presented.
According to the analysis, the flow of the detonation products and impurities
behind the wave front is typically separated into three zones. The first zone,
directly adjacent to the front of the wave, is a narrow zone at the end of the
relaxation process where rapid equilibration of velocities takes place (Fig. 2.10a)
and the pressure falls sharply to a certain equilibrium value (Fig. 2.10b). This is
followed by a plateau of increasing thickness in which the flow parameters are
constant Behind the plateau there is a trailing rarefaction wave. The waveform
conforms to the classical self-sustaining weak detonation mode.
CalcuIations made using the model suggested in [96], as opposed to the ac-
cepted additive approach, agree well with experimental data on both velocity
and detonation pressure. For mixtures with different concentrations of the tung
sten impurity (a = 20, 40, and 60%), the maximum difference between the cal-
cuIated values and the experimental data does not exceed 5 %.
The features of detonation of mixtures of water-filled RDX with tungsten
were investigated in [44]. The explosive on which the mixture was based was
powder-like crystals of RDX mixed with 3 % of an aqueous solution of car-
bomethylcelluIose in the ratio 35/25 by weight The added tungsten powder was
a mixture of3-5 Jlm and 30-50 JlID particles. The mass fraction of tungsten in
the mixtures was 20 and 40% and the density of the water-filled RDX in the
mixed charges was held constant at 1.45 g/cm3• The structure of the gas-dy-
namic flows was investigated by electromagnetic gauges and by the barrier
method. The measurements showed a rather weak reduction of pressure on the
order of 10-20%. The analyses have shown that weak detonations are caused
by insufficiently rapid entrainment of met8l particles in the flow of detonation
products and not by slow thermal equilibration. The "effective" (average) value
of viscosity of dense, high-temperature fluid detonation products of water-filled
RDX is found from comparison of experimental and calcuIated detonation ve-
locities.

2.4.3. Mixture of TNT with RDX

Numerous investigations of the detonation of mixtures of TNT with RDX exe-
cuted with different methods, leads to obviously discordant resuIts. It turned out
 2. Detonation of Condensed Explosives 65

U,km/s a

1.0

/.0

15 .to x, mm
P,GPa b

JO

20

0
Ii J'D x,mm

Figure 2.10. Distribution of gas-dynamic parameters behind the front of a detonation

wave. a) Speed of the detonation products (1) and tungsten (2); b) pressure of the detona-
tion products.

that detonation pressures found by external methods regularly exceed values

obtained using direct measurements inside the charge. In Table 2.3, the experi-
mental data are assembled for cast and extruded charges of different initial den-
sities and with different weight ratios of TNT to RDX. The last two columns of
the table in which the pressure and adiabatic parameters corrected to an initial
charge density of 1.73 g/cm3 and the identical ratio b = 40/60 are given to allow
comparison of the results. The calculation was made using adjustment formulas
given in [9J. The average value of detonation pressure obtained from measure-
ments in a barrier is 29.2 ± 0.4 GPa, and from measurements inside the charge
one obtains 27.0 GPa. The duration of the chemical reaction zone in mixtures of
TNT with RDX, based on data by different authors, vary by more than an order
of magnitude: from 0.025 [8,l3J to 0.67 J,LS [17]. This discrepancy became the
subject of discussions and special investigations (see, for example, [33J).
66 1. V. Al'tshuler, V.S. Zuchenk:o, and A.D. Levin

Table 2.3. Experimental data on detonation parameters of mixtures of TNT

withRDX.
Methods PO'3
g/cm
b, P, P, 'if
% GPa GPa
External 1.715 35/65 29.2 [58] 29.0 2.72
1.670 37/63 27.2 [9] 29.0 2.74
1.713 36/64 29.2 [8] 29.2 2.72
1.730 40/60 29.2 [30] 29.2 2.72
1.692 40/60 28.1 [66] 29.6 2.67
Average 29.2 2.72
Internal 1.71 36/64 26.6 [20] 26.5 3.09
1.73 40/60 26.8 [30] 26.8 3.05
1.73 40/60 27.5 [30] 27.5 2.95
1.73 40/60 27.4 [24] 27.4 3.02
1.73 40/60 26.4 [98] 26.4 3.11
1.67 40/60 27.5 [26] 27.5 2.95
Average 27.0 3.02

The first measurement of the chemical reaction zone peak in a condensed

explosive was made in 1955 by Duff and Houston [8], investigating detonation
of the mixture TH 37/63. In experiments, the free-surface velocity of aluminum
plates of different thicknesses, I, placed on the downstream face of the charge
were measured The experimental dependence W(/) had a shmp break at / = 0.13
mm, a dimension appropriate to a chemical reaction zone peak of 't = 0.025 IJ-S
duration
The authors of [17,20] came to other conclusions by studying detonation of
explosives with the help of electromagnetic gauges. For mixtures TH 36/64 and
TH 50/50, wider reaction zones (from 0.26 IJ-S) are observed. The long duration
of chemical decomposition of mixtures is explained in [17] as follows: First, the
separate components (RDX and TNT) react, and then these reaction products
mix and further reaction occurs, which requires additional time. A break in the
function W(/) at 1 = 1 mm determined in [8], is caused by spall in the plate, in
the opinion of the authors of [17].
This last conclusion appears erroneous. In [13], experiments were carried out
with charges from alloy TH 50/50 that had lengths varying over the wide range
from 10 to 440 mm. The artificial spall method was applied to exact measure-
ment of W using a plate with a thin (0.05-0.I-mm thick) artificial spall disk
placed on the downstream face of the charge. The results of experiments shown
in Fig. 2.11 clearly reveal a narrow, steady reaction peak of duration 't = 0.025
IJ-S, the same as was reported in [8].
 2. Detonation of Condensed Explosives 67

Z.1 a U,kmIs b
2.•

•o
l7 ..:

lf~
D 10 IJ I, mm 0 0.1 t, J.ls

Figure 2.11. (a) Attenuation of particle speeds in an aluminum barrier loaded with
1H 50/50 charges of different lengths; (b) particle velocity wavefonns in 1H 40/60. The
solid lines are magnetic gauge measurements and the broken lines are from calculations.
The charges were of length 203.2 mm for curve 1, 101.6 mm for curve 2, 50.8 mm for
curve 3, and 25.4 mm for curve 4.

Measurement and analysis of particle velocity profiles in the mixture

TH 50/50 [21] have shown that the condition of the detonation products is de-
scribed by a variable adiabatic parameter increasing :(rom n = 2.7 at the front to
n = 3.0 at positions removed from the front. The instability of self-similar flow
was also observed in a study [98] of the mixture TH 40/60. In Fig. 2.11 the con-
tinuous lines show profiles of particle velocities measured by magnetic gauges
and the dashed lines were obtained from analyses of self-similar waves with the
best estimate of the reaction zone thickness removed from the flow. The in-
creased velocity and pressure at the head of the wave are caused, according to
[98], by incompleteness of the chemical transformation of the explosive. In
[24,98], two-phase kinetics of decomposition were observed in mixtures of TNT
with RDX. The majority, more than 90%, of the energy of explosive transfor-
mation is released in the fast first stage; the subsequent after-burning stage is
strongly delayed. The flow during the second stage is unsteady, approximating
the self-similar mode.
The structure of detonation waves in mixtures of TNT with RDX matches
the mode of weak detonation with a brief, 0.025-J.lS-duration stationary chemical
reaction zone peak and a subsequent delayed reaction zone, asymptotically
passing into a self-similar rarefaction wave. The untraditional structure of the
detonation wave is the cause of the disagrement between measurements of pres-
sure by external and internal methods. The measurements in barriers determined
the transient (relaxation) region of increased pressure contiguous to the station-
ary chemical reaction zone peak ("sole" of the chemical reaction zone peak), and
68 L.V. Al'tshuler, V.S. Zuchenko, and A.D. Levin

the direct measurement inside the charge determined the state :further removed
from the front The extrapolation of this measurement to the initial moment of
time resulted in the lowered pressure. Let us note that the mechanism of equili-
bration in mixtures of TNT with RDX remains obscure.

2.4.4. Mixture of Explosives with Silicon

Typical features of a weak detonation have been observed in investigations of
mixtures of TH 25175 with 25% silicon [99,100]. A group of experiments was
conducted in which the density of the charges was varied from 1.1 to 1.8 '{/cm3
and the size of the silicon particles was varied from 1 to 500 j.llll. The particle
velocity profiles were measured with electromagnetic gauges. For low density
charges, the velocity profiles had the usual form with a smooth transition of the
reaction zone into the rarefaction wave. For the densities po = 1.55 and 1.64
'{/cm3, the particle velocity at the front was reduced and there was a region be-
hind the front of the wave in which the particle velocity was constant.
These experimental data are explained in [100] as follows: For low initial
charge densities, the explosive decomposes much more slowly than for high-
density charges. In the low-density case, the silicon additive is heated almost
completely in the reaction zone, and the mixture detonates in the normal regime.
With increase of density, the duration of the explosive decomposition process
decreases. Above a certain density, the time required to heat the additive be-
comes more than the time required for decomposition of explosive, and an en-
dothermic final stage, leading to occurrence of the weak mode, appears. With
further increase of density the degree of heating of the additive in the reaction
zone decreases, so the quantity of heat absorbed during the endothermic of stage
increases.

2.4.5. RDX and HMX of High Density

In [42] an unique regime of detonation of high density, so-called "agate,"
charges from RDX and HMX was detected. Specimens were produced by a
process of pressing with solvent with subsequent evaporation that produced a
homogeneous glassy charge of density close to that of a monocrystal. Shock-
wave velocities were measured by the LNS method in a layered bar of PMMA
adjoining the charge. Use of very thin (-0.1 mm) PMMA films separated by
small (-2 J,lm) gaps allowed achievement of the extremely high time resolution,
' t - 2 ns.

The results of experiments presented on Figs. 1.3 and 2.12 show unusual
detonation wave structures. During the initial stage, the detonation profiles have
a normal form with typical recession in the rarefaction wave. Subsequently, the
detonation wave passes through a stage of super-compression, and a narrow
(duration 10-20 ns) stable zone with increasing pressure arises in the estab-
lished mode instead of a conventional reaction zone peak.
 2. Detonation of Condensed Explosives 69

D, km/s

8.0

lJ

7.0

I z J .f I,mm

Figure 2.12. Speeds of shock wave in PMMA barrier loaded by charges from agate
HMX of different lengths.: Curve 1: 50 mm, curve 2: 20 mm, curve 3: 10 mm, and curve
4:5mm.

The authors of [42] believe that, in the homogeneous high-density charges

investigated, chemical transition takes place in the front of the shock wave. The
chemical reaction is thus a relaxation process that produces a steeply sloping
shock front. The results presented in [42] require an experimental check, first of
all a demonstration that a stationary state is established. These experiments
present an opportunity to compare the measured rates of decomposition of the
explosive at the shock wave front to some theoretical models of detonation in
the condensed explosives considered at the beginning of the section.

2.5. Conclusions
The experimental and theoretical work yielded information about modes of
detonation of condensed explosives. The new results are of basic importance for
understanding self-sustaining modes of weak detonation in solid multi-compo-
nent explosives. The reasons for the occurrence of the weak mode can include
various relaxation effects accompanying chemical decomposition of explosives:
endothermic decomposition of impurities, secondary reactions resulting in a
change of chemical composition and thermodynamic properties of explosion
products, heating and melting of impurities, and delayed acceleration of solid
particles. A necessary condition for propagation of a detonation in the weak
70 L.V. Al'tshuler, V.S. Zuchenko, andA.D. Levin

mode is nonmonotonic change of the position of the partial-reaction Hugoniots

in the pressure-specific-volume plane. The top Hugoniot describes the mixture
present at the moment the chemical transformation of the explosive ends. The
slope of the Michelson-Rayleigh line tangent to this Hugoniot determines the
detonation velocity with the point of contact defining the state of the material in
the intermediate Chapman-Jouguet plane. The bottom Hugoniot describes the
final condition of the detonation products present after the end of all equilibra-
tion processes. The transition from the top to the bottom Hugoniot can occur
along the Michelson-Rayleigh line or in the rarefaction wave penetrating into
the relaxation zone. In the first case, all intermediate states propagate with the
detonation velocity, the relaxation zone is steady, and a self-similarly extending
plateau is formed behind the relaxation zone. In the second case in which the
rarefaction adjoins the intermediate Chapman-Jouguet plane, the plateau is
absent and the wave structure is qualitatively the same as a normal detonation
wave.
Generally, any delayed relaxation process displacing the detonation-product
Hugoniot downward should lead to detonation in the weak mode. The character
of the flow in relaxing media depends on the kinetics of the relaxation process
and the intensity of unloading determined by the longitudinal and transverse
dimensions of the detonating charge. The structure of weak detonation waves
arising as a result of non-monotonic generation of heat behind the wave front,
taking into account the influence of lateral unloading waves, was considered in
[101]. It was shown that, for a long-duration endothermic stage, a "classical"
attribute of weak detonation, the plateau behind the relaxation zone is absent.
In this chapter some modifications of weak modes of detonation caused by
different relaxation effects, such as decomposition of desensitizing impurities,
heat transfer to an additive, and gradual acceleration of heavy metal particles,
are analyzed. It is possible that the basic condition for existence of a weak deto-
nation, downward displacement of Hugoniots of the final detonation products,
occurs in some other cases. For example, when there is a secondary exothermic
reaction in intermediate detonation products. It is known that approximately one
third of the pressure in the detonation products is of thermal origin and two
thirds is determined by their cold compression behavior (see Chapter 1). As a
result of the exothermic reaction occurring, the thermal component of pressure,
naturally, should increase. It is possible, however, that the total pressure can
decrease and the Hugoniot be lowered by reduction of the cold compression
component. This could happen, for example, because of a difference of the
electronic structure of the products of exothermic reaction and that of the initial
components.
Note, that the self-sustaining weak mode of detonation is, apparently, typical
of many multi-component explosives, in particular, for conventional explosive
compositions containing various impurities.
 2. Detonation of Condensed Explosives 71

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 2. Detonation of Condensed Explosives 75

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 CHAPTER 3

Hugoniot Curves of Metals

R.F. Trunin

3.1. Introduction
Scientific investigation of shock parameters of metals, and primarily of their
shock compressibility, was initially related to the problem of designing nuclear
weapons. In the United States, experiments of that kind were started in 1945,
and two years later the compressibility of uranium at pressures up to 50 GPa was
first measured in Russia. For a long time thereafter work was done to refine the
measured position of shock-compression curves (Hugoniots) for materials which
had already been studied and to extend the range of pressure investigated. This
is because a great many scientific and technical problems are currently solved on
the basis of knowledge of shock properties of various materials. These include
problems of high-velocity impacts, in particular of spacecraft and meteorite
protection, the inner composition of the Earth and of other planets, verification
of theoretical models of material behavior under extreme loading conditions,
synthesis of novel materials, high pressure chemistry, etc. In 1995, as a result of
work done to increase the range of pressure open to investigation, laboratory
shock generators driven by high explosives were built and used in Russia to
generate pressures higher than 2.5 TPa in heavy metals. Those pressures were
approximately two-fold higher than those produced earlier in our country and
five-fold higher (for the same materials) than pressures produced in research
centers of other countries. Even higher pressures, up to 10 TPa. were generated
in underground nuclear tests. Both these values were measured by the so-called
absolute investigation technique. When this technique is used, the accuracy with
which kinematic and thermodynamic parameters of material compression are
determined depends only on the accuracy of the experiment itself and not on the
validity of additional assumptions.
In underground experiments when relative measurements of material com-
pressibility were performed and the equation of state of one of the materials had
been determined by either a theoretical model or a selected interpolation curve
correlating calculated and experimental data, even higher pressures of 20 TPa
were measured at VNIIEF (Sarov) and enormous pressures of 700 TPa were
produced at VNIITF (Snejhinsk). In our opinion, the latter metal compressibility
measurements were not quite accurate, but the results obtained proved that

V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII

© Springer Science+Business Media New York 2004
78 R.F. Trunin

shock waves generated by nuclear explosions could be used to perform com-

pression measurements.
In addition to the use of high explosives and nuclear explosions as energy
sources for generating strong shock waves, so-called light-gas guns employing
compressed and heated light gases (hydrogen, helium) as a source of initial
energy have been widely used, especially in foreign countries. The highest dy-
namic parameters were produced by two-stage guns in which the working gas in
the main barrel (the second stage) was compressed and heated by the piston-
impactor of the first stage. The advantage of gas guns is better guidance of the
accelerating flat impactor relative to the surface of the stationary target. When
the impactor hits the target, a highly symmetric shock wave is generated and
accurate measurements of material shock compression can be made in individual
experiments. Of course, one more advantage of gas guns is that they are station-
ary reusable facilities. Their actual design, however, restricts them to perform-
ance of compression measurements at considerably lower pressures than those
generated by laboratory facilities driven by explosives (the record pressure for
measurements made using a light-gas gun is 700 GPa for heavy metals). In this
chapter, measurements made at the relatively low pressures generated by light-
gas guns will be compared with results obtained using devices driven by high
explosives.
The research at VNIIEF has followed two paths of investigation: the labora-
tory path, for which the shock waves are generated by devices employing
chemical explosives, and the test-site path, for which strong shock waves are
generated by underground nuclear explosions.
The first path has been especially highly developed. The great number of di-
verse measuring devices available allows very rapid measurement of the com-
pressibility of materials under investigation. The opportunity to perform as
many experiments as are needed at assigned initial parameters is a distinctive
feature of laboratory measurements. This is one of the advantages of laboratory
experiments over test-site experiments, for which it is actually impossible to
repeat measurements at initially selected conditions. This means that one has to
accept the results of a single experiment Nevertheless, the conditions of this
experiment are unique in tenns of making available a wide range of pressure
from units up to tens, hundreds, and thousands of GPa in one and the same ex-
periment Fortunately, the conditions of nuclear explosions make it possible to
perform these measurements in samples having basic dimensions that are ten-
fold larger than those of laboratory samples. This is why the accuracy of test-site
measurements of shock wave velocities is often comparable to the accuracy
achieved in laboratories.
A huge amount of experimental data on the shock compressibility of various
materials, and of metals in particular, has been accumulated. The information on
metals comprises data on investigation of
 3. Hugoniot Curves of Metals 79

• a majority of metallic elements of the Periodic Table at initial densities

equal to those of the crystalline state;
• a great number of porous metal elements at initial densities that have been
deliberately lowered;
• low-melting elements that have been preheated (to the melting point of
400-500°C) or precooled (T= -180°C).
We will discuss the results of investigations of solid metallic elements. Ele-
ments for which the compressibility has been studied under both laboratory and
test-site conditions will be considered in the most detail. These are iron, alumi-
num, copper, lead, cadmium, molybdenum, tungsten and titanium. Hugoniot
curves for other metals will be given on the basis of laboratory measurements.

3.2. Measurement Techniques

Two experimental methods are widely used to make dynamic measurements.
The methods are based on recording kinematic parameters of shock waves in
tested samples. In the first method, the so-called deceleration technique [1], an
impactor and a target are made of the same material. The impactor velocity and
the shock front velocity in the target., D, are measured. Because of the symmetry
of the experiment., the particle velocity, U, produced in the target is exactly one-
half of the impactor velocity. By the laws of conservation of momentum, mass,
and energy, the pressure,
P=poDU, (3.1)

the mass density,

D
p=po I)-U' (3.2)

and the internal energy density,

E-Eo = P (_1
_!)=!U2, (3.3)
2 Po P 2

of the shock-compressed material can be expressed in terms of these parameters.

This technique is rather labor-intensive and is used, on the whole, to deter-
mine Hugoniots of so-called reference materials. Hugoniots of the two main
reference metals, iron and aluminum, have been obtained by means of this tech-
nique. The range of pressures studied in these metals was up to 1.8 TPa for Fe
and 1 TPa for AI in laboratory conditions and up to 10 TPa and 1.7 TPa, respec-
tively, at test sites.
The second method is the impedance-matching technique [2]. Unlike [1], the
impactor and the target used are made of different materials. The equation of
state, or at least the Hugoniot, of the shield material must be known. In this
80 R.F. Trunin

setup, the parameters of the shock wave propagating in the shield are established
by measuring its velocity. The shock velocity in the samples tested is also meas-
ured directly in the experiment. As in [1], the technique is based on considera-
tion of the change in amplitude of the shock discontinuity that occurs at the
interface between the shield and the sample being tested. The P - U diagram is
considered, where the state behind the shock wave propagating through the
reference material of the shield is determined by the intersection of the straight
line defined by the equation Pe = pOe De U with its known Hugoniot curve. The
parameters of the shock in the sample are determined by the intersection of the
expansion isentrope (or the double-compression Hugoniot curve) of the shield
with the straight line defined by the equation Pi = POi Di U , related to the sample
material being tested. The compressibility of most materials was measured by
this technique.
In the impedance-matching technique, the expansion isentrope (or the dou-
ble-compression Hugoniot) is often approximated by the mirror reflection of the
Hugoniot curve. It has been shown in [3] that this substitution is permissible to
an accuracy of 1% of U (this is the accuracy of experimental particle velocity
measurement) over a wide range of shock-wave parameters. For example, when
iron is used as a standard, the region of one-percent deviation of the reflected
Hugoniot from the expansion isentrope includes all the states between the iron
and aluminum Hugoniots in the P- U coordinate plane. We have reasons to
suppose that one can arrive at a similar conclusion when comparing double-
compression Hugoniots with mirror reflections of standard Hugoniots. We
should note that, for the experimental setup itself, the shield material selected is
one having an Hugoniot lying sufficiently close to that of the sample material (in
the P-U coordinate plane) to permit correct application of the reflection ap-
proximation.
In practically all of the measurements-in both the laboratory and at the test
site-the electrocontact technique based on closing a gap between two current-
carrying electrodes by the propagating compression wave was used. The signals
from the electrodes were recorded by high-speed oscilloscopes having a time
resolution of ± 5 x 10-9 S •
It is natural to consider all the measurements performed under laboratory
conditions to be absolute. As to the test-site measurements, those in which the
states studied are located between the expansion isentrope of iron (up to 10 TPa)
and that of aluminum should also be considered absolute.

3.3. Laboratory Measuring Devices

Laboratory measuring devices use high explosives to provide the energy that
generates shock pressures from units to 2500 GPa in tested samples.
 3. Hugoniot Curves of Metals 81

Actually, there are three types of laboratory devices. In the first of them (Fig.
3.1) the high explosive (HE) charge contains an explosive lens that transforms a
divergent detonation wave into a plane wave [4]. After this wave has reached the
end of the charge, the expansion of the detonation products and their decelera-
tion against the shield generates a steady wave in it. The amplitude of this wave
is constant and its duration is sufficient to preserve the desired states during the
period of recording. As a rule, the air gap between the charge face and the metal
shield providing this stability is about 5 mm. By varying the mass of the charge,
its composition, and the shield material, these contact charges allow production
of pressures from 8 to 26 GPa in materials having densities close to that of iron
and up to 36 GPa in materials having densities close to that of aluminum.
The second type of device is a plane plate-accelerating system [5]. Its opera-
tion is based on using explosion products to accelerate a thin-plate impactor to
velocities (in full-scale systems) of ~6 krn/s. The two types of these systems,
called "guns," are shown in Fig. 3.2. In the first of them the 2-6-mm thick (the
thickness is different in different devices) aluminum impactor is pressed into a
steel disk of equal thickness. The detonation wave arriving at the metal surface
generates a superhigh pressure in the steel disk, which provides an additional
thrust acting on the outer area of the aluminum impactor and prevents it from
lagging. In the available designs, the plane aluminum impactors reached veloci-
ties ranging from 2 to 6.5 krn/s (the pressure in aluminum was from 45 GPa to
120 GPa).

Figure 3.1. The contact measuring device. 1: lens-shaped HE charge, 2: plane-wave

lens, 3: main HE charge, 4: simultaneous-impact layer, 5: reference-metal shield, 6:
tested sample, 7: shorting-pin detectors, and 8: air gap.
82 R.F. Tnmin

(a) (b)
Figure 3.2. (a) Measuring device with an accelerated aluminwn impactor. 1-7: the same
as in Fig. 3.1, 8: peripheral iron ring. (b) Measuring device with an accelerated steel
impactor. 1-7: the same as in Fig. 3.1, and 8: plexiglas spacer.

The steel impactors are disks of diameter 60-70 mm and thickness of 1.1-
2.2 mm, with a gradual transition to a 5-mm-thick peripheral area. The function
of the latter is to flatten the flying impactor plate. The velocity of steel plates is
from 4.9 to 6.1 km/s in the inertial region of acceleration. The impact of the
plate, accelerated to such velocities, produces pressures from 60 to 210 GPa in a
steel target and from 37 to 130 GPa in an aluminum target
The highest pressures, ranging up to 2.5 TPa, are produced by generators of
spherical geometry [6] (Fig. 3.3). The detonation of the HE charge is triggered
simultaneously over the entire outer surface. The explosion products of the
spherically convergent detonation wave, expanding across the small air gap,
accelerate the steel hemispherical impactor (shell) to a velocity that increases
continuously as it converges toward the center of the device. In the available
devices, the shell velocity varies from 6.2 to 22.7 km/s, corresponding to pres-
sures in iron from 270 GPa to 1.8 TPa.
The general requirements placed on the devices considered are:
• good symmetry of the flying impactor, i.e., upon its arrival at the target
the spread of the impact time of its different parts must be within
5 x 10-8 s;
• the impactor temperature must not be higher than that of samples at the
moment the plane detonation wave arrives at their surface;
 3. Hugoniot Curves of Metals 83

5 J 1 I

Figure 3.3. Measuring device with a spherically accelerated impactor shell. I: HE

charge, initiated simultaneously over its entire exterior surface, 2: impactor-shell (Fe),
3: shield (Fe), 4: tested samples, 5: shorting-pin detectors, and 6: air gap.

• the impactor must not disintegrate during its flight;

• the device operation must be steady in terms of reproducibility of results.
The last requirement necessitates precise accomplishment of the technologi-
cal procedures for preparation and execution of the experiment Technical re-
quirements regarding composition and density variations of HE parts, access to
the measuring devices, etc., must be specified and strictly executed. About fifty
available measuring devices meet these requirements. The mean-square error of
measuring shock-wave kinematic parameters by means of these systems is ap-
proximately 1-1.5%. This value is obtained by averaging the required number
of separate time recordings taken from 4-10 experiments carried out by a se-
lected measuring device.

3.4. Design of Polygon Measurement Configurations Used at

Underground Test Sites
We will consider the setup used for measuring the parameters of shock waves
produced by a relatively high yield nuclear device (its energy release is more
than 100 kilotons) placed in a special chamber excavated in a rock [7].
The explosion energy propagates as radiation energy and the kinetic energy
of the evaporated nuclear device (the temperature of the explosion is 10 6 -10 8
K). This energy evaporates the rock of the chamber walls. The expanding rock
vapor and the radiant energy deposited in the rock are promptly converted into
the shock. In the rock close to the chamber walls, the shock waves generate
pressures from units up to tens of TPa, depending on the explosion energy.
Equal or even higher pressures are produced in metallic samples affected by
these shock waves.
84 R.F. Trunin

As the wave propagates through the rock mass, its amplitude decreases due
to the divergence. At a distance of several tens of meters (let us remind our-
selves that a high-yield explosion is being considered) from the explosion center
the pressure in the rock has decreased to a few GPa.
This means that the compressibility of the samples can be measured over a
range of pressures from those typical for laboratory experiments up to pressures
higher by factors of tens and hundreds, and can do this using a single explosion.
The setup for making compressibility measurements under test-site conditions is
shown in Figs. 3.4-3.6.
Figure 3.4 shows two setups for making absolute compressibility measure-
ments for iron in the terapascal pressure range by the impedance-matching tech-
nique. The experimental assembly is comprised of an attenuating low-density
foam spacer (Po::::: 0.03 glcm\ a steel (St-3) impactor, and a steel target There is
an air gap between the rock and experimental assembly.
The requirements that must be met by accelerating systems driven by an un-
derground nuclear explosion are:
• The impactor velocity at the moment when it hits the target must be as
close as possible to the velocity of the shock wave in the target, i.e.,
W=2U.
• The impactor velocity must be constant when it approaches the target.
• The impactor preshock heating due to the waves generated in it and the
radiation from the nuclear explosion must be as low as possible.
• The flying impactor plate must not disintegrate in flight and must remain
flat to a good accuracy.
As calculations performed and experiments conducted show, the systems de-
veloped met these requirements. This allowed carrying out three effective ex
periments in which the compressibility of iron was measured at pressures higher
than those produced in laboratories.

<:XXX:
"j}ciofOllll Rock
J ~
Pt~ic: rouo;'
s.rikcr(F~)
Rock ~ ju'ker(F.) Shidcl (F.)
hMid (F t) K>
~:

§., g..
".
- ~F' IF.)
- t--=- .It......
~:
r=
- ~: --:- I-
IOU""
-.
'
~:
:~:
:~,

~ :» 'h. To",", I Fe)

Figure 3.4. Variants of the experimental setup used for measuring parameters of shock
waves driven by an underground nuclear explosion. The velocity of the impactor flight
and that of the shock in the target are measured.
 3. Hugoniot Curves of Metals 85

Figure 3.5 shows the scheme of wave velocity measurements in a setup

comprised of three samples of various materials placed one behind the other.
The first sample is a standard for which the equation of state is known. The
samples being tested are placed behind it. The velocities of shock waves are
measured as they propagate through the samples. When experimental data are
interpreted, the wave attenuation and divergence peculiar to shock waves in-
duced by underground explosions are taken into account. The wave velocities at
the sample-shield interface are compared. The transition from average to in-
stantaneous D values is based on numerical simulation.
Figure 3.6 explains how aluminum compressibility measurements are made
using the so-called y-reference technique [8,9]. According to this method,
y-active pellets embedded into the aluminum sample being tested are activated
by n-y flow from the nuclear explosion. The radiation from the pellets passes
through collimating slits as the pellets pass by due to the action of the propagat-
ing shock wave. The counters placed behind the collimating slits convert y-
radiation into electrical signals which are recorded by oscilloscopes. The
configuration is such that both shock and particle velocity can be measured.
The maximum parameter values of the aluminum compressibility obtained
by this technique are approximately two-fold higher than those achieved in the
laboratory.

26 26.18

25

23

22

Electric-contacl sensors

Figure 3.5. Scheme and results of wave-velocity measurement in one of the experi-
ments. The symbol 0 designates experimental data related to the point midway through
the thickness of the sample and the broken line - - - - designates calculated values.
86 R.F. Trunin

1
5

Shock-wave front

Figure 3.6. Configuration for measurements by the 'Y-reference technique. 1: aluminum

block, 2: reference pellets, 3: collimator, 4: collimator slits, 5: photo-detectors. Reprinted
with permission from L.P. Volkov, et aI., Shock compression of aluminum at pressure
10 Mbar, inPis'ma Zh. Eksp. Fiz. 31(11), pp. 623-627 (1980).

If the Hugoniot (the equation of state) of the reference material used as the
shield has been determined experimentally, the measurements are absolute.
Otherwise, the experiment yields the compressibility of the sample relative to
the equation of state accepted as a description of the shield material.

3.5. Compressibility Data Obtained from Laboratory

Measurements
Shock compressibility in various pressure ranges has been determined for sixty
metallic elements of the Periodic Table, i.e., for the majority of metals.
Under laboratory conditions, the maximum pressure values were 1.8 TPa for
iron, 2.5 TPa for tantalum, 1.3 TPa for titanium, and 2.1 TPa for molybdenum.
More than 11 metals were studied at pressures up to 1 TPa and those remaining,
depending on the initial density, were studied in the pressure range from 60 GPa
(Li) to 500 GPa (W).
As the values measured directly in experiments are the kinematic parameters
D and U, these variables will be used, on the whole, for experimental data
analysis. First of all, let us point out a remarkable feature of Hugoniots, i.e.,
experimental data taken over a very wide range of the kinematic parameters are
approximated by linear or nearly-linear relations. This rule of the linearity of the
D(U) relation for the Hugoniots (in certain ranges of D and U) was experimen-
tally proved for hundreds of cases studied with various materials from gases to
solids. Of course, this representation is a fairly rough approximation to the real-
ity and, to a certain extent, depends on the accuracy of shock parameter meas-
urements and on the density of experimental points on the plots. In reality,
existing perturbations of linear D( U) curves are related to such physical proc-
esses as melting, the response of electron orbits to the compression, etc. These
deviations from linearity are, however, not so great to cause one to disregard the
general tendency toward quasi-linearity ofHugoniots onD(U) diagrams.
 3. Hugoniot Curves of Metals 87

A very detailed analysis of the D( U) relations for metals was given in [10]. It
has undergone only minor modification since its publication. Therefore, making
some corrections, we will stick to the classification of Hugoniots given there.
According to this classification, the Hugoniots of all the metals can be distrib-
uted among five groups.
The first group (Fig. 3.7) includes metals having D( U) relations that are lin-
ear over the entire range of wave velocities studied:
D=co+aU, (3.4)

where Co is the so-called sound velocity, i.e., the extrapolated value of D(U), at
U = O. In many cases Co is close to the bulk sound velocity and the constant coef-
ficient, a, is the slope of the Hugoniot Within a permissible error, the
Hugoniots of the eleven metals, Li, K, Be, Mg, Mo, W, Jr, Au, Ba, Ga, and Re,
are linear in the range of wave velocities studied. For four of them (K., Mg, W,
and Mo) the Hugoniot slope is in the range a =1.2-1.25. For Li and Be a =1.1
and, for the rest of the metals of this group, a > 1.35 .

D, kmls
14r----------------------m

11

'0

.,
o[

o 5 U, kmls for Mo
o 2 :I U,kmls

Figure 3.7. The D- U diagram for metals of the fIrst group in the Periodic Table. I: Mo,
2: Jr (D+ 1),3: Au (D+ 1),4: W, and 5: Re (D-2). The symbol. indicates data by
foreign authors and the symbol 0 designates data by Russian researchers.
88 R.F. Trunin

It is known that. in the range of superhigh pressures when the value of the
compression is close to its limit ( cr =p I po > 4 ), evaluation of Hugoniot slopes
D'(U) =dDI dU with up-to-date theoretical models yields D'(U) =l.2-l.3.
These values agree with the Hugoniot slopes of K, Mg, W, and Mo studied in
the experiments. This allows us to suppose that, for these metals, the D( U) rela-
tions are linear in the range up to states that can be described by theoretical
models valid in a superhigh pressure range. As to the rest of the metals of this
group, the difference between the experimentally measured and the calculated
slopes of Hugoniots shows that, for D and U parameters higher that those cur-
rently measured, the existing slopes of the D( U) curves will be replaced with the
limiting value 1.25. These transitions have been studied in the other metals dis-
cussed below.
The second group (Fig. 3.8a) includes 13 metals having parabolic Hugoniots:
(3.5)

These metals are AI, Cr, Ni, Cd, Zn, Ag, Cu, Pd, Pt, Lu, Pb, Cs, Te. The initial
slopes of their Hugoniots are considerably different from the limiting values.
The minimum slope of 1.55 is that of Cr and Pt, the maximum slope of l.9 is
measured for Ceo For many metals of this group the change in the Hugoniot slope

D,kmIs
14
D,~s

12 12

10 10

8 8

6 6

4 4

2 2

0 0
0 2 4 6 U,kmIs 0 2 4 U,kmIs

Figure 3.8. (a) TheD-U diagram for metals of the second group. 1: Ni (D+ 1),2: Cu,
3: Zn, 4: Cd, 5: Pb, and 6: Ce (D-l ). (b) TheD-U diagram of metals of the third group:
1: Co (D+ 1), 2: V, 3: Nb, and 4: Ta. The symbols are the same as those in Fig. 3.7.
 3. Hugoniot Curves of Metals 89

D'(U) takes place in the pressure range studied experimentally. For example,
AI, Cu, Cd, Pb and some other metals fall in this class.
The third group (Fig. 3.8b) incorporates the metals having parabolic
Hugoniots but with positive coefficients Co, 01 and 02. Metals such as Na, V, Nb,
Ta, Co, Rh are included into this group. The initial slopes of their Hugoniots are
1.1-1.3, so one should not expect a large change of slope in the range of higher
shock-wave parameters.
Many of the Hugoniots of the second and third groups (AI, Ta, Zn, V, Cd,
Ag, Cr, Cll, Ni, et al.) can be approximated by straight lines over some ranges of
kinematic parameters D and U, starting from D = Co . Copper, aluminum, and
nickel have the widest linear ranges of D: from Co to 11, 12, and 11 km/s, re-
spectively. For the other elements, this range is rather narrow and for some of
them the Hugoniots are linear only in the range Co < D < Dlirn, where Dlirn is
some limiting value of the shock velocity.
The fourth group (Fig. 3.9a) incorporates 17 elements having Hugoniots that
can be approximated by two intersecting straight lines with different slopes.
These are rare-earth elements of the sixth period of the Periodic Table (Y, S~,
La, Pr, Nd, Sm, Gd, Tb, Dy, He, Er, Tu, Yb, Lu) and also Rb, Sr, Ca. The slopes
of the first section of all the Hugoniots, except for that of Ca, are less than 1,
those of the second section range from 1.0 (Y, Sm, Dy, Ho, Tu) to 1.7-1.8 (La,
Pr). The distinctive feature of Ca is the "inverse curvature" of its D- U curve,
i.e., the slope of the first section is greater than that of th~ second one. In the
pressure range studied, the slopes of the second sections are constant. A slope
change should take place at higher values of the shock parameters. The small
slopes of the first sections of the Hugoniots correspond to high-compressibility
states. Beyond the cusps, the Hugoniots switch to high slopes corresponding to
lower compressibility (high D'(U) values). These Hugoniot shapes derive from
the electronic structure of these metals in which the internal d shells are not
filled and the external s electrons can be transferred, due to compression, to
internal d shells. This results in a high compressibility of the outer s shells [10].
These transitions of electrons to d shells result in the formation of closed inter-
nal shell configurations that have considerably lower compressibility. The
switch-over from the flatter Hugoniot section to the steeper one corresponds to
the completion of the electronic transitions. We should note that the presentation
of experimental data in the form of two intersecting straight lines is only an
approximation to the real state of things. Such electronic transitions should,
probably, result in smooth curves between the two linear portions of the
Hugoniots.
The fifth, and last, group includes those elements that undergo first-order
phase transitions when compressed so that the initially loose structures become
denser. The well-known and most extensively studied transition of this kind is
the a ~ g transition in iron. The following elements are also incorporated into
90 R.F. Trunin

D,kmls
D, kmls
10
12
4

10 8

8 5
6

6
4
4

2
2

o o
U, kmls 5 U,kmls

Figure 3.9. (a) The D-U diagram for metals of the fow1:h group. I: Pr (D+2),
2: La (D+ I), 3: Nd, 4: Gd (D-I), and 5:Y (D-3). (b) The D-U diagram for metals of
the fifth group. I: Fe, 2: Zr, 3: lIf, 4: En, and 5: Ti (D - 5). The symbols are the same as
those in Fig. 3.7.

this group: Bi, Ti, Sn, Zr, Hf, Eu and Pu. The Hugoniots of these metals (Fig.
3.9b) are represented in three sections. The first one corresponds to the compres-
sion of the initial phase, the second, horizontal section, describes the phase tran-
sition, i.e., the range in which the initial and the denser phase coexist. The third
section corresponds to the Hugoniot of the denser metal phase.
This is a possible classification of Hugoniots of metals. It is arbitrary to a
certain extent, because experimental data are sometimes insufficient for the
correct classification of the Hugoniots under consideration.
Let us note one feature, common for all the Hugoniots of metals that have
been considered: Their D( U) relations at U = 0 correspond satisfactorily to the
values of sound velocities derived from the values of the isentropic bulk
modulus. Kso = Pc6 Without carrying out a statistical analysis of uncertainties of
measurements of Kso, and extrapolated values of D'(U) lu=o = Co in the equation
D = Co + a) U + a2U1. , we should note that, upon the whole, the values are within
the limits of possible errors for Kso. This indicates that, under conditions of
shock compression, even in the range of comparatively low pressures, the states
realized are close to those of uniform bulk compression.
The a) constant can be expressed in terms of the derivative of bulk modulus
at P=O: a) =[(dKs/dP)so+l]/4. The a2 constant can be represented by a
slightly more complicated relationship.
 3. Hugoniot Curves ofMeta1s 91

In practice, however, when it is necessary to describe an experiment over a

wide range of parameter variations, the constants Co, al and a2 are usually se-
lected to provide the best description of experimental data (including, of course,
the bulk modulus).

3.6. Compressibility Measurements in Underground

Nuclear Explosions
Iron. Let us come back to the discussion of the set-up and results of measure-
ments performed during underground explosions. First of all, let us dwell upon
measurements of iron compressibility by the deceleration technique. Layouts of
two versions of the experimental arrangement are shown in Fig. 3.4.
A polished base plate with a diameter of about one meter oriented perpen-
dicular to the line to the explosion center was embedded in the rock mass on the
path of the propagating shock wave. A 250-mm-thick light Styrofoam spacer
with a diameter of one meter was placed parallel with the base plate at some
distance from it. Its function was to moderate the intensity of the first shock
waves in the impactor and to generate a thrust (a small additional pressure acting
on the rear face of the impactor) as the evaporated foam expands. The flight of
the impactor was recorded with electrical shorting-pin detectors. Their design
ensured that they would respond only to the impact of the flying plate. They
were not sensitive to the relatively strong shock generated in the air ahead of the
flying impactor.
The experimental setup with which the kinematic parameters were recorded
was optimized using multiple calculations by Podurets. These calculations took
into account all the processes (starting from the nuclear explosion) including
generation of the shock in the rock. its propagation through the rock, scattering
of rock fragments and their impingement on the Styrofoam, propagation of the
shock through the Styrofoam, the impactor flight (the character of the accelera-
tion due to the additional thrust because of the spacer evaporation), its impact
against the target, and propagation of the shock wave in the target The gas-
dynamic stage of the shock propagation was calculated using the simplest Mie-
Griineisen equations of state. Polystyrene was described by the equation of state
for an ideal gas with a polytropic exponent 'Y =5/3 and Poo =0.03 glcm3 •
It is practically impossible to build an ordinary system for which the equa-
tion W= 2U is exactly fulfilled under intense shock wave conditions. It is im-
possible because the impactor is preheated by the shock wave and its initial
density is changed. For example, in the system shown in Fig. 3.4, the calculated
parameters were as follows: the amplitude of the first shock wave in the impac-
tor was P < 0.5 TPa, the temperature was T < 2 x 104K, and the average density
P = 1.05 Po was due to the additional thrust generated by the expanding evapo-
rated polystyrene. Nothing can be done to change this situation because a thrust
92 R.F. Tnmin

of this or that origin and intensity is present in all cases. Its variations, for exam-
ple due to a change in the polystyrene spacer position or its removal, led to
variations in pressure in the impactor but seldom brought about the desired con-
ditions of plate acceleration. Therefore, the optimal configuration had to be
selected. The system was optimized by fitting W = 2 U(D), where D was the
average shock velocity in the target. The velocities D and W were measured in
the experiment and the function U(D) was derived from the equation of state
used for iron. The calculations showed that the impactor velocity became almost
uniform in the final phase of its flight. This fact was proved by direct measure-
ments of W,
The optimality of the selected system can be described with the coefficient
a= U(D)/w' When Wis exactly equal to 2U, a=0.5 and U(D) = W12. Under
real conditions, our system was considered optimal when the deviation of a
from 0.5 was within 0.5-1%. In that case, the experimental uncertainty in
measurement of kinematic parameters was surely larger and there was no need
to introduce calculated corrections.
In the case under consideration, a = 0.498, i.e., the system was optimized.
The correction due to W *- 2U on the shock front was small and could be ig-
nored according to our criteria for system optimization. Similar a values were
obtained in the two other experiments (a = 0.497 and 0.503). In the latter case
the experiment was performed using a considerably more energetic nuclear
explosive for which, at the same acceleration path length, the pressure in the
iron target was 10 TPa, i.e. two-fold higher than in the two previous experi-
ments. These are some calculated parameters for this system: the pressure in the
rock, before the shock wave as launched into the air, was 2.5 TPa. The pressure
generated by the first shock in the impactor was 0.4 TPa, even lower than in the
previous cases. The impactor velocity becomes nearly constant before it collides
with the target.
The x-t diagram of the impactor flight and shock wave propagation through
the target, as recorded by shorting-pin detectors, is given in Fig. 3.10. The iron
data obtained in underground nuclear experiments are given in Table 3.1, and all
the collected results are given in Figs. 3.11 and 3.12 in D-U and P-(J coordi-
nates. There is a good agreement among all the results. This is related to the
agreement among laboratory results that have been obtained with fundamentally
different devices producing steady plane and convergent spherical waves as well
as to the agreement between the laboratory and test site results.
Table 3.1. Data for iron obtained from absolute measurements.
WI, W2, Way, D, U, P, p, 0"
krn/s krn/s krn/s krn/s krn/s TPa g/em3
36.5 36.5 36.5 ± 1.0 28.85±0.7 18.25 4.13 21.34 2.72
42.7 42.7 42.7± 1.2 32.4±0.8 21.35 5.42 22.99 2.93
48.6 58.8 60.8±2.5 43.5 ± 1.0 30.60 10.50 26.50 3.37
 3. Hugoniot Cmves of Metals 93

t, J.1S
W= 28.85 ± 0.7
12 W= 36.5 ± 1.0
~
7IJ r:tl
iI
-:• t!J
IS/I 1/1/1 .flI /I .YO x, mm
Fe -

Shiel.

~~
Electric-contact sensors

Figure 3.10. The diagram of the distance vs. the time of flight of the plate and that of the
shock in the target I: experimental points, and 2: plate velocity on the target surface.

The Hugoniot of iron is approximated [6] by the expressions:

DI = 3.664 + 1.79U -0.034U2 for 1.4 <U <8km1s

D2=5.869+1.2394U-0.000174U2 for 8<U<22km1s (3.6)
D3=6.982+1.19U-0.000llU2 for U>22km1s.

At the points where they meet, these relations not only have equal wave ve-
locities but also equal derivatives. At U=22 kmls (P= 5.7 TPa) the experimen-
tal Hugoniot joins smoothly with the calculated Hugoniot obtained using
Kalitkin's version of the quantwn-statistical model [12] taking into account the
interaction of nuclei by Kopyshev [13] (the TFQC model).
Aluminum. Up to pressures of -0.5 TPa, the Hugoniot of aluminum has been
studied under laboratory conditions. It is classified as an Hugoniot of the second
group corresponding to a parabolic D( U) curve.
In the relatively high pressure range (P> 0.5 TPa) the test-site data obtained
by two methods prevail. Those are, first of all, measurements performed by the
impedance-matching technique, in which the aluminum samples are placed
behind steel shield plates. The majority of these measurements were performed
by VNIITF researchers. Measurements of the second type were made using the
y-reference method mentioned above (Fig. 3.6). Let us consider this method in
more detail. A pellet of europium dioxide, the nuclei of which have a neutron
capture cross-section approximately a thousand-fold larger than that of alumi-
num nuclei, was compressed to a density equal to that of aluminum under stan-
dard conditions and was used as a gamma-active reference material.
94 R.F. Trunin

D,kmls
1,$

J5

-!
25 ---1

.....-
.-.- J
~

15 • .f
0 6'
• 7

'0 10 20 JO U,kmls

Figure 3.11. Hugoruot plot tor !fon m lJ- U coordmates. 1: expenment, 2: SCF,
3: MHFS, 4: TFQC, 5: laboratory measurements, 6: absolute measurements, and
7: relative measurements.

P,GPa

10J

.
10 1

I
! 1 J 4 5 (1

Figure 3.12. mterpolation Hugoniot plot for iron. The symbols are the same as those in
Fig. 3.11.
 3. Hugoniot Curves of Metals 95

In the initial condition, all y references are outside the field of vision of the
phototubes. When a shock wave propagates in the sample, the y references are
displaced and appear in the visual field of the collimators of the phototubes that
measure the y-photon flux emitted by the references. The corresponding optical
signals are converted into electrical signals that are recorded by oscilloscopes.
When the initial location of the reference materials is known, the shock-wave
velocity is determined on the basis of the time measurement The particle veloc-
ity is determined on the basis of the transit time of one of the references, moving
with the particle velocity of aluminum (that has been assumed) past the two
collimators. The thermodynamic parameters are calculated as usual using the
conservation laws.
Using this technique, two experimental points corresponding to similar pres-
sures of about I TPa (VNIITF) and one point corresponding to a pressure of 1.7
TPa (VNllEF) were determined. Those pressures are significantly higher than
available laboratory results.
The main uncertainty regarding the y-reference technique was the absence of
a reliable proof that the velocity of an embedded pellet was equal to the particle
velocity of the surrounding aluminum. The extent to which that assumption was
correct was not known. That problem had not been resolved for a long time,
through judging by the relative positions of the experimental points on the
Hugoniot curve of aluminum, there was a coincidence. However, the problem
was completely resolved only in 1995 when direct measurements of the shock
compression of aluminum were made under laboratory conditions using a spe-
cial spherical system operating under intense conditions (the measurements were
performed at shorter distances, i.e., closer to the center of the system) [14], in
which aluminum was shock-compressed to a pressure of 1 TPa equal to values
measured at VNll1F in underground nuclear tests. The kinematic parameters of
the motion happened to be very close as well. Those agreements confirmed the
correctness of measurements by the y-reference method. 1bat, in the long run,
completely confirmed the location of the aluminum Hugoniot in the terapascal
pressure range.
The data on aluminum obtained in underground nuclear tests and from labo-
ratory experiments in the terapascal pressure range are given in Table 3.2. The
measurement results are shown in Figs. 3.13 and 3.14. Though the experimental
data spread for aluminum is a little more than that for the other metals (espe-
cially in the range 11 < D < 17 kmls where abnormal behavior of aluminum had
been supposed to occur [11,IS]), the aggregate results testify to the conventional
shape of the Hugoniot curve classified by us as a parabolic Hugoniot curve of
the second type. Its analytical expression is:
D=S.331+1.417U-O.OlSU2 for U<8.2km1s
(3.7)
D =6.371+1.164U -O.OOOOIU2 for U>8.2km1s.
96 R.F. Trunin

Limiting the interval of wave velocity changes to 11 <D < 80 km/s, the alwni-
num Hugoniot can be plotted in D( U) coordinates as the straight line:
D =5.90+1.19U. (3.8)

Table 3.2. Data for alwninum obtained from absolute measurements.

Experiment D, U, P,
Number kmls kmls TPa cr Ref.
1 24.2::1:0.7 15.l::I: 0.4 0.99::1:0.03 2.65 ::1:0.1 [9]
2 23.4::1:0.6 14.5::1: 0.3 0.93::1:0.02 2.63::1:0.7 [9]
3 40.0::1:5.0 30.0::1:2.0 3.20::1:0.5 3.90::1: 1.2 [9]
4 30.5::1:0.7 21.0::1:0.6 1.73 ::1:0.07 3.21 ::1:0.2 [20]

D/km 5- 1

0-1 X-7
'-2 --8 .~
60 *-36-9
0---4 a -10 ./
V-5'-JJ
50 ''---is +-12

40

30

20

10

30 40 SO U/km .-1

Figure 3.13. Hugoniot plot of alwninum. 1-6: labomtory measurements, 7-10: absolute
method data in underground tests, II and 12: relative measurements. The ellipses are the
possible variants of data processing from [21], the chain curve is the result of interpola-
tion data [28], and the dash line gives the result of a calculation made using the TFQC
model.

Copper, Lead, Cadmium, and Molybdenum. Calculation of the iron

Hugoniot (the shield used in implementing the impedance-matching technique)
by absolute methods allowed determination of the compression parameters of
copper, lead, cadmium, and molybdenum, for which the relations among their
wave velocities, and between each of them and that of iron, had been determined
earlier. These data are given in Table 3.3 and compared with those obtained in
 3. Hugoniot Curves of Metals 97

P,GPa

Figure 3.14. Interpolation Hugoniots. 1: Mo, 2: AI, and 3: Cd. The symbols are the same
as those in Fig. 3.11.

laboratories and parameters measured by foreign researchers in underground

tests (Fig. 3.15). One can see a quite satisfactory agreement between the labo-
ratory and the test-site measurements for all of the metals. In the range of high
shock parameters for lead and cadmium there is a good agreement between the
data obtained in Russia and those obtained in the United States. For molybde-
num and copper, some results obtained by American authors differ from the
averaged D(U) relation and exceed the permissible experimental errors. First of
all we consider molybdenum, for which the experimental points from [16,17]
are on the both sides of the averaged Hugoniot curve. One of the reasons for this
difference in data is a poor experimental setup. In [17] aluminum is used as a
shield. The aluminum Hugoniot curve is separated from that of molybdenum (in
p- U coordinates) by an amount that, most probably, exceeds the range of appli-
cation of the reflection approximation for the Hugoniot. Let us note that, in this
case, the position of the double-compression Hugoniot curve depends on the
equation of state used. It is not clear to what extent it is correct to use the equa-
tion of state from [17] to calculate the double-compression Hugoniots needed to
determine particle velocities on P- U diagrams. Similar questions arise when
98 R.F. Trunin

you consider the data for copper presented by the same authors. In this case, the
deviation from the copper Hugoniot curve has the same character and sign as in
the case of molybdenum. As for the data on molybdenum taken from [16], the
author himself assumed the considerable error of - 5 % in determination of U.

Table 3.3. Data for Cll, Cd, Pb, and Mo obtained from relative measurements.
Initial state Compression parameters
of shield for materials investigated
D-Ucurve Initial
Exp. of standard D, U, density D, U, P, P, er
No. D,km/s km/s km/s Po, g/cm3 km/s km/s TPa g/cm3

I Fe 25.70 15.91 Pb: 11.34 20.72 15.02 3.529 41.22 3.635

6 Al + 1.213U

2 Fe 31.90 21.01 Pb: 11.34 26.12 19.76 5.853 46.57 4.107

6041 + 1.213U

3 Pb 14.65 9.815 Cu: 8.93 17.82 9.96 1.585 20.25 2.267

3.19+ 1.167U

4 Pb 22.17 16.26 Cu: 8.93 26.18 16.67 3.897 24.58 2.753

3.19+ 1.167U

5 Cu 17047 9.725 Cd: 8.64 16.08 10.14 10410 23040 2.707

5.137+ 1.268U

6 Cu 25.30 15.90 Cd: 8.64 23.88 16041 3.386 27.62 3.197

5.137+ 1.268U

7 Fe· 17.25 9.20 Mo: 10.07 16.10 8.58 1.391 22.06 2.138
5.68+ 1.257U

* The D- U relationship D = 5.68 + 1.257 U for experiment 7 is valid in the range 13 < D < 25 kmls.

This data disagreement required experimental verification of the molybde-

num Hugoniot position in the section of maximum differences, corresponding to
pressures higher than 1.5 TPa.
The first attempt at such verification was made in one of the underground
nuclear experiments in 1981 [18]. The experimental setup excluded uncertainties
related to the use of aluminum: A molybdenum sample was placed behind a
steel shield. A particular feature of this experiment was good symmetry of the
shock wave (the difference in time of the shock arrival at the shield was not
worse than 5 x 10-8 s). Unambiguous results were obtained, but they did not
give an exhaustive answer to the question because the measured pressures (1.3
TPa) happened to be lower than had been expected and correspondingly lower
than those measured in molybdenum in [16]. Unfortunately, it became impossi-
ble to repeat these measurements because of the underground nuclear test ban.
 3. Hugoniot Curves of Metals 99

D, km/s
40

Jo
7

20

10

o /0 14 10 21, JO "0 U, km/s

Figure 3.1S. Hugoniots of metals. 1: W (D+ 10),2: Fe, 3: Pb, 4: Cu (U+ 10),5: Mo
(U+ 14),6: AI (U+20), 7: Cd (U+24). 1: laboratory measurements, 2: relative meas-
urements, 3: absolute-method data.

Laboratory devices designed later allowed this problem to be solved [6,14].

In particular, by means of a hemispherical system used to measure the com-
pressibility of aluminum at terapascal pressures. Data on molybdenum com-
pressibility at pressures of 2 TPa were obtained, i.e., data which agreed with
those obtained in [16]. However, the other parameters, such as D and U, the
mass density, and the energy density, happened to be different so the new point
on the Hugoniot curve of molybdenum did not coincide with that from [16] but
did correspond to the linear D(U) relation obtained in [10] at lower pressures
(Fig. 3.14).
This, together with the data on aluminum compressibility given above, was
the first case when a laboratory experiment performed at terapascal pressures
was used to verify the results of test-site measurements.
Hugoniot curves of all the metals (with the exception of Mo) given in Fig.
3.15 are rather flattened parabolic curves (their slopes, dDldU, decrease as the
velocities increase) which, in the section corresponding to high kinematic pa-
rameters, become almost the same and equal to dDldU ~ 1.25. For Mo these
slopes are approximately constant over the entire range of pressures investigated
and, apparently, will not change significantly at even higher compression.
What does this behavior of the D- U relations mean? When shock waves
pass through the metals tested, various physical processes, such as lattice com-
pression accompanied by thermal excitation of nuclei and electrons, melting,
100 R.F. Tnmin

electronic transitions, etc., take place. These processes also influence the posi-
tions of Hugoniots in D- U coordinates. At lower pressures, where the elastic
component of pressure prevails, the slopes of Hugoniot curves are considerable.
The dD/dU slopes decrease as the pressure and thermal excitation of the atoms
increases. The stage of material melting corresponds to complicated changes in
which the slope of the D- U Hugoniot curve changes three times over a com-
paratively short !ill interval. The slope corresponding to the solid state changes
to that peculiar to the solid-liquid state and then to the slope corresponding to
the liquid phase. For some metals from [19], for example, tin, for which more
complete measurements have been made, the slope change corresponding to
melting is quite obvious. At even higher pressures ionization of atoms and exci-
tation and collectivization of electrons takes place. The completion of these
processes means that some smoothed metallic state is established in which indi-
vidual features of crystals do not manifest themselves. This smoothing, resulting
in the loss of individual features of the elements, apparently comes to an end
(depending on the specific metal from the Periodic Table) at pressures of 1-2
TPa. After that, their D- U curves are characterized by almost constant slopes.
This can be illustrated by Fig. 1.12 that shows the change of atomic volumes of
elements for several shock-compression pressures. Under standard conditions
(P = 0) there is a pronounced periodic dependence of element atomic volumes
on the atomic number, Z, that corresponds to the consecutive filling of atomic
energy levels with electrons. Loose structures of alkaline and alkaline-earth
elements are characterized by loosely bonded electrons of s levels and depicted
by the higher section of the diagram corresponding to the maximum atomic
volumes. Densely packed structures, with a great number of electrons filling d
levels, correspond to the minimum atomic volumes and are peculiar to transition
metals.
As pressures increase, atomic volumes of elements become more nearly
equal. In this case, the maximum volume change takes place in elements with
loose structures. At pressures of 300 GPa the V(Z) periodicity is not obvious and
for P> 1 TPa it practically disappears, i.e., the elements lose their individual
features.
The average experimental slope of Hugoniots of the metals studied using
underground explosions is dD/dU::d.25±0.04 (from 1.15 to 1.35). It corre-
sponds approximately to the values of the Hugoniot slope calculated taking
nuclear interaction into account [13] by the modified Thomas-Fermi model [12]
(the TFQC model) at pressures of more than units and tens of TPa when this
model is assumed to be valid. Fig. 3.16 shows data on metal compressibility
obtained by the absolute technique in underground nuclear tests. Lead is the
most compressible material in the group of heavy metals. Cadmium, molybde-
num, copper, and iron come after it.
 3. Hugoniot Curves ofMclals 101

P,GPa
1O.51Pa
600

400

200

15 25

Figure 3.16. Relative compressibility studied using underground explosions. 1: labora-

tory measurements and 2: underground measurements.

Relative Compressibility of Metals. In this section we discuss measurements

of shock-wave parnmeters in iron, copper, lead, and titanium at pressures of 15-
20 TPa. The experimental setup [20] is shown in Fig. 3.17. An almost-steady
quasi-plane wave was generated in a measuring device located close to a nuclear
explosive. The alignment of the plane of the measuring device with respect to
the center of the energy release provided the symmetry of wave. The total di-
ameter of the device where the shock wave was produced was 1000 mm. Cylin-
drical samples with a diameter of 250 mm and thickness of 70 mm were placed
on a common steel shield. The time needed for the shock wave to propagate
through the samples was measured by a technique based on detecting the light
emitted by the shock front at the moment of its arrival at the surfaces of the
samples.
The detecting channels were evacuated to prevent early air luminescence
caused by the 'Y-radiation from the nuclear explosion. The inner surface of each
pipe was polished to minimize light losses. Shielding was used to maintain reli-
able operation of detectors that would be affected by the 'Y-photon flux. The
symmetry (difference in time) of arrival of the shock front at the shield was
quite satisfactory (!It = 4 x 10- 8 s) but the errors of velocity measurements were
1.5 % for Fe and Cll, 3 % for Pb, and 4 % for Ti. The processing and analysis of
the oscillograms resulted in the following data on shock-wave velocities
DFe =57.4 ± 0.9, DPb =48.8 ± 1.5, Deu =55.9 ± 0.8, and DTi =62.3 ± 2.5 (in
kmls).
It is clear that the shock velocities were quite reasonable with respect to the
velocity of the standard iron shield. Indeed, the initial experimental data on the
relationship between the wave velocities in the shield and those in the materials
tested, as plotted on Fig. 3.18, are almost linear and indicate that the laboratory
102 R.F. Trunin

*---
F.nergy
source

Figure 3.17. Experiment layout for measurements of the relative compressibility of Fe,
Cu, Pb, and Ti at pressures of 15-20 TPa.

III •I
01
+J
50

o~--~------~------------~
10 lO 50 D, kmls

Figure 3.18 Comparative compressibility curves. DFc-D dependencies. 1: Fe-Pb,

2: Fe-Cu, and 3: Fe-Ti. The plotted symbols signify 1: laboratory measurements,
2: absolute measurements, and 3: relative measurements.

and test-site measurements are in agreement nus figure also gives data on the
relative measurements performed in [21] in the Fe-Pb system under record
super-high pressures at test sites. The agreement between our results and those
 3. Hugoniot Cwves of Metals 103

from [21J is evident The DFe(DpJ relationship starting from DFe =15 km/s up
to the maximum parameter values studied is almost linear.

3.7. Comparison of Experimental Data and Computational-

Model Representations
There remains the problem of choosing the theoretical model that best fits the
experimental data. Researchers have been trying to solve this problem since the
first experiments performed at high (> 100 GPa) pressures. The problem arose,
in particular, because, for many years, measurements performed at tempascal
pressures had been relative to the choice of the Hugoniot of the standard metal
used. The first interpolated relations were presented in the late 1960s and early
1970s in [22,23J in which the Hugoniots were calculated by the only well-
known and widely used model at that time, the Thomas-Fermi model. Later,
this model was improved by taking into account quantum and exchange correc-
tions (the TFQ model) [12J. Non-ideal properties of nuclei were also taken into
account [13J. One could hope that the combination of these two models (the
TFQC model) would lead to better agreement between calculated and experi-
mental data in the mnge of high pressures, but the real state of things and the
values of those pressures were not clear. It was only known that, as a rule, there
was a difference between the calculated and experimental Hugoniots in the pres-
sure mnge of labomtory experiments (P< 1-2 TPa). It was also generally ac-
cepted that the statistical models corresponded to a regular asymptote at limiting
values, cr ~ 4.5-5.5, of shock-wave compression.
We should also note that the TFQC model ignores the shell structure of at-
oms. The Hugoniots calculated using it correspond to smooth monotonic curves
without any deviations indicative of abrupt changes in electronic states. If we
take into account an electronic structure consisting of atomic shells that are
consecutively ionized, it should result in oscillations of Hugoniots against the
background of the "mean" monotonic curves. Such results are derived from
calculations performed using the Hartree-Fock quantum-mechanical model,
taking into account the exchange intemction in the Slater approximation (XFS),
the modified Hartree-Fock-Slater model (MHFS) [24J, the self-consistent field
model (SCF) [25J, and some others. Calculation of thermodynamic functions in
the mnge of high tempemtures and densities using these models is mther cum-
bersome and labor intensive, so only Hugoniots of the metals used as standards,
aluminum, iron, and lead, have been calculated.
It would not be correct to think that the development of all three models has
been completed. The progress of their development is known. For example, for
the quantum-statistical model this progress lies in the tmnsition from the TF to
the TFQ and then to the TFQC model. It is possible that a more accumte ac-
counting of electronic and ionic components will bring about further change in
the quantitative relationships of parameters on Hugoniots calculated using this
104 RF. Trunin

model. The quantum-mechanical models have also developed: both the positions
of Hugoniots and the characteristics of their oscillations have changed. In this
context special attention is paid to agreement with experimental measurements
as a criterion for chosing the most adequate theoretical model.
The results of compressibility measurements performed by absolute methods
in Fe, AI, Cu, Pb, Cd, Mo, and Ti at terapascal pressures in laboratories and
underground nuclear tests allows a direct comparison of the calculated and
measured Hugoniots of those metals. Figure 3.11 gives the comparison between
the models and the experimental data for Fe. It shows the comparison of ex-
perimental data with Hugoniots obtained using the three models, MHFS, SCF,
and TFQC. One can see that, starting from D = 20 km/s, calculated curves differ
very little from the experimental curves, being practically within their error
limits. However, preference should be given to the TFQC model because the
Hugoniot curve calculated using it actually coincides completely with the ex-
perimental Hugoniot. A similar conclusion can be made from a comparison of
the curves calculated using the TFQC model and the experimental curves for the
other metals, as shown in pressure-density coordinates on Figs. 3.14 and 3.19.

P,GPa

Figure 3.19. Interpolation Hugoniots. 1: Cu, 2: Cd and 3: Ti. Symbols are the same as in
Fig. 3.14.
 3. Hugoniot Curves of Metals 105

In Fig. 3.12, comparison of the experimental Hugoniot curve of iron with

curves calculated using the three models shows that preference should be given
to the TFQC model. The Hugoniot curve plotted on the basis of this model coin-
cides almost completely with the experimental curve for P> 4.0 TPa. The curve
calculated by MHFS is considerably displaced to the right and that calculated by
SCF is to the left of the experimental curve but quite close to it, especially at a
pressure of 10 TPa. The positions of Hugoniots and their interpolation and that
of curves calculated by TFQC for molybdenum and cadmium are shown clearly
in Fig. 3.14.
There is no such clarity for aluminum. Experimental data from [9] formally
agree with those calculated by SCF, but not by TFQC (MHFS is close to
TFQC). This conclusion would be correct if it were not for the considerable
errors of these experiments. These errors are related to the fact that there were
some uncertainties in addition to the shock velocity measuring errors which, in
this case, exceeded those usually allowable, i.e. 1-2 %. First of all, all possible
deviations of expansion isentropes from mirror Hugoniots (on P-U diagrams)
should be referred to these Hugoniots. Actually, the position of expansion isen-
tropes in this pressure range allows correction for deviations from the reflection
approximation not only of different values, but also of different sign, depending
upon the equation of state used for iron. Thus, when the equation of state from
[27] is used, these deviations are negative values ranging from 0.3 to 0.7 km/s. If
this correction is taken into account, the experimental points are displaced to the
left by an amount which is marked with arrows in Fig. 3.14. In this case there is
a satisfactory agreement between the experiment and calculations made using
the TFQC model. Interpolation Hugoniots for copper, lead, and titanium (Fig.
3.19) are, upon the whole, in good agreement with those calculated using the
TFQCmodel.
On the basis of this assessment, we conclude that the TFQC model provides
the best fit to the experimental data. To verify the adequacy of the model at even
higher pressures we must rely on a relative comparison because we cannot carry
out a direct, "absolute," comparison. In this case only the adequacy of one se-
lected theoretical model has been verified. The method of comparison is as fol-
lows: shock velocities of several materials are measured in a single experiment.
One of the materials is considered to be standard (it is used as a shield placed
upstream of the sample). Samples of the shield material and the other materials
to be tested are placed on the shield. The Hugoniots of all of these materials are
calculated using the selected model. The particle velocity and pressure, i.e., the
initial parameters required to analyze the change of amplitude of the discontinu-
ity when the shock encounters the shield-sample interface, are determined using
the calculated Hugoniot for the shield material and the experimental value of the
wave velocity, De, in the shield. Then, using this technique, the wave velocities
De are determined on the calculated Hugoniots of the other materials tested and
are compared with the experimental wave velocities. If the difference between
106 R.F. Trunin

the calculated value and the experimental value, Dm, does not exceed the ex-
perimental errors, the model under consideration is thought to fit the experiment
adequately. The minimal number of materials compared is two: a standard
(shield) and a tested material. When these two materials are compared at the
same assigned shock wave parameters, an accidental (although most unlikely)
agreement of the parameters compared is possible. To exclude this, it is advis-
able to compare the data obtained at different pressures and in several materials.
If the calculated and experimental velocities coincide in this case, one can state
that the verified model fits the experiment adequately and can be recommended
for calculations of the other thermodynamic parameters.
It is not necessary to perform a number of relative measurements at different
pressures. As a rule, the selection of such pairs in underground tests is similar to
that in laboratories and the De{Dm> relation is close to linear over the entire
diagram. This relation makes it possible to compare the parameters calculated
using some chosen model with the experimental parameters of the shock wave at
any values of the kinematic parameters. This approach was applied for the first
time for the Pb-Fe pair in [21] and the Al-Si~ pair in [26]. It is desirable that
the materials from the chosen pairs should be optimally dynamically rigid with
regard to each other, i.e., their Hugoniots in P- U coordinates in a first approxi-
mation should be separated (in terms of the compared parameters) by the mag-
nitude of the half initial pressure in the shield when the reflection approximation
can be used. In [20], the adequacy of the TFQC computational model was veri-
fied in this manner for Fe, Pb, Co, and Ti. In that case (Fig. 3.17) the shock
velocities were measured in tested metal samples that were placed behind a
common steel shield. The experimental results were given above. According to
the foregoing scheme, and on the basis of the Hugoniot calculated using the
TFQC model, the wave velocity D = 57.4 kmls will correspond to U= 42.3 kmls,
and P= 19.06 TPa. By analyzing the change in amplitude of discontinuity we
will get the corresponding shock velocities in the other metals calculated using
the TFQC model: DPb =49.59 kmls, Deu =55.80 kmls, and DTi =62.81 kmls .
For calculating these velocities, we used the mirror approximation, i.e., the
transition from initial states to those at the interface of the two metals was de-
termined using the Hugoniot. As is evident from the comparison, the calculated
and experimental data are vety similar. This means that the TFQC model fits the
experiment adequately. Taking into account that the velocities obtained using
the model agree (within the experimental error) with those measured in the ex-
periment, even at lower pressures, one arrives at the general conclusion that the
model fits the experiment adequately, at least in the range of pressures
5 <P < 20 TPa. To answer the question about the applicability of this model at
even higher pressures let us take the data from [21], where the measurements of
shock velocities in the iron {shield)-lead pair at pressures of up to 70 TPa are
considered. The approach is similar to that in the case discussed above. The
results are given in Table 3.4. One can see that the difference between the
 3. Hugoniot Curves of Metals 107

calculated and experimental shock velocities in lead is within 1-2 %. With the
aggregate errors taken into account, the agreement of the results is quite
satisfactory. Therefore the Hugoniots calculated by the TFQC model for this
pair of metals can be considered coincident with those obtained in the
experiments throughout all the range of comparison starting from P = 3 TPa. It
was shown above that there is the same coincidence (up to P = 20 TPa) for
copper, molybdenum, titanium, aluminum, and cadmium.
Table 3.4. Measurements of shock velocities in the iron (shield)-lead pair and
values calculated on the basis of the TFQC model (D, kmls).
Experiment Calculation
Shield Sample Sample
89.6 78.4 77.71
62.6 53.4 54.20
42.6 35.4 35.89
36.8 30.4 30.66

The Hugoniots of all the metals considered in this chapter are shown in Figs.
3.14 and 3.19. These are smooth monotone curves through all the investigated
range of measured parameters. They indicate that there are no existing experi-
mental errors. The comparison of the compressibility results obtained at high
pressures with those calculated by various theoretical models shows that the
TFQC quantum-statistical model fits the experiment most adequately. Its ade-
quacy was substantiated in the pressure range from units up to hundreds of TPa.

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[1] L.V. Al'tshuler, KK Krupnikov, B.N. Ledenev, V.I. Zhuchikhin, and
M.I. Brazhnik, Sov. Phys.-JETP 34 pp. 6O~14 (1958). [trans. from Zh. Eksp.
Teor. Fiz. 34(4), pp. 874-885 (1958).]
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[7] RF. Trunin, Usp. Fiz. Nauk 164(11), pp. 1215-1237 (1994).
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[9] V.A. Sirnonenko, N.P. Voloshin, AS. Vladirnirov, AP. Nagibin, V.N. Nogin,
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(1985). [trans. from Zh. Eksp. Teor. Fiz. 88(4), pp. 1452-1465 (1985).]
108 RF. Trunin

[10] L. V. Al'tshuler, AA Bakanova, I.P. Dudoladov, EA D}1lin, RF. Trunin, and

B.S. Chekin,J. Appl. Mech. Tech. Phys. 22(2), pp. 145-169 (1981). [trans. from
Prikl. Mekh. Tekh. Fiz. 2, pp. 3-34 (1981).]
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[trans. from Usp. Fiz. Nauk 96(2), pp. 193-215 (1968).]
[12] N.N. KalitkinandL.V. Kuz'mina,Ins. ofAppl.Math. Akad. NaukSSSR 35,1975,
73 p. Preprint.
[13] V.P. Kopishev, Chisl. Met. Mekh. Sploshn. Sredi. 8(6), pp. 54-67 (1977).
[14] RF. Trunin, N.V. Panov, and AB. Medvedev, Sov. Phys..,JETP Letters 62(7),
pp. 591-594 (1995). [trans. fromPis'ma Zh. Eksp. Teor. Fiz. 62(7), p. 572-575
(1995). ]
[15] RF. Trunin, Izvestia Russian Academy ofSciences Physics ofthe Earth 22(2),
pp. 22-28 (1986). [trans. from: Izv. Akad. Nauk SSSR, Ser. Fiz. Zemli. 2, p. 26.]
[16] C.E. Ragan, M.G. Silbert, and B.C. Diven,J. Appl. Phys. 48(7) pp. 2860-2870
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High Temperature 32(5), pp. 736-737 (1994). [trans. from Teplojiz. Vys. Temp.
32(5), pp. 786-788 (1994).]
[19] S.P. Marsh (ed.), LASL Shock Hugoniot Data, University of California Press,
Berkeley, (1980).
[20] RF. Trunin, LA ll'kaeva, MA Podurets, L.V Popov, B.Y. Pechenkin,
L.V Prokhorov, AG. Sevast'yanov, and VY. Khrustalev High Temperature 32(5),
pp. 647-649 (1994). [trans. from TeploflZ. Vys. Temp. 32(5), pp. 692-695 (1994).]
[21] Ye.N. Avrorin, B.K. Vogolaga, N.P. Voloshin, G.y' Kovalenko,
V.F. Kuropatenko, VA Simonenko, and B.T. Chernovolyuk:, Sov. Phys.-JETP
93(2), pp. 347-354 (1987). [trans. from Zh. Eksp. Teor. Fiz. 93(2), p. 613-626
(1987).]
[22] L.V. Al'tshuler, B.N. Moiseev, L.V Popov, G.V. Simakov, and RF. Trunin, Sov.
Phys-JETP 27 pp. 420-422 (1968). [trans. from Zh. Eksp. Teor. Fiz. 54(3), p. 785-
789 (1968).]
[23] RF.Trunin, MA Podurets, G.V. Simakov ,L.Y. Popov, and B.N. Moiseev, Sov.
Phys..,JETP 35, pp. 550-552 (1972). [trans. from: Zh. Eksp. Teor. Fiz. 62(3),
pp. 1043-1048 (1972).]
[24] AF. Nikiforov, V.G. Novikov, and V.B. Uvarov, Mathematical Modeling.
Physical and Chemical Substance Properties, Nauka, Moscow, 1989. 162 p.
[25] G.V. Sin'ko, High Temperature 21(6), pp. 783-793 (1983). [trans. from Teplojiz.
Vys. Temp. 2(6), pp. 1041-1052 (1983).]
[26] RF. Trunin, G.V Simakov, MA Podurets, B.N. Moiseyev, andL.V. Popov, Izv.
Adad. Sci. USSR, Phys. Solid Earth (1), pp. 8-12 (1971). [trans. from Izv. Akad.
NaukSSSRFiz. Zemli (1), pp. 13-20 (1971).]
[27] AB. Medvedev, VoprosyAt. Nauki Tekh. Ser. Teor. Prikl. Fiz. 1, pp. 12-19 (1992).
[28] I.Sh. Model', AT. Narozhnyi, AI. Kharchenko, SA Kholin, and VV. Khrustalev,
Sov. Phys.-JETP Letters 41(6), pp. 332-334 (1985). [trans. from: Pis'ma Zh. Eksp.
Teor. Fiz. 41, pp. 270-272 (1985).].
 CHAPTER 4

Wide-Range Characteristic
Thermodynamic Curves

N.N. Kalitkin and L.V. Kuzmina

4.1. Quantum-Statistical Hugoniots of Porous Substances

4.1.1. The Problem

The thermodynamic properties of materials are investigated at megabar pres-
sures with experimental and theoretical methods. At pressures of 0-1 Mbar
(sometimes up to 3 Mbar) there are numerous experiments on static compressi-
bility. In the range 0.2-20 Mbar there are also numerous shock-wave compres-
sion experiments done using explosive devices and light-gas guns. Some shock-
compression experiments have been performed near underground nuclear
explosions at pressures of 20-500 Mbar. No experiments have been conducted
at higher pressures and none can be conducted in the near future.
There are, however, a few competing theoretical models that are claimed to
be valid at pressures above 100 Mbar and on up to infinity. Choosing the most
accepted model, and joining theoretical calculations at superhigh pressures to
experiments at modest pressures, one can construct good semi-empirical equa-
tions of state or characteristic thermodynamic curves. Many of the appropriate
experiments and models are described in detail in other chapters of this book,
reviews [1-5], and compendia [6-8].
Modem models are rather complicated and usually cannot be described by
simple explicit equations. They demand huge numerical calculations, resulting
in large tables of thermodynamic functions. These tables are stored on comput-
ers but are seldom published because of their volume. Moreover, they are awk-
ward for comparison to experimental data. The best solution of this problem is
to approximate the tables with simple equations of good precision. Since the
thermodynamic functions exhibit rather complicated behavior, it is difficult to
construct such equations in a purely mathematical way. One must choose them
from the physical point of view.
V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII
© Springer Science+Business Media New York 2004
110 N.N. Kalitkin and L. V. Kuzmina

We chose the quantum-statistical (QS) model of the atom, and calculated ta-
bles ofHugoniot curves for 83 elements and some chemical compounds at poro-
sities from m =I (solid substances) to m =10. The region of validity was
established for these curves. The appropriate parts of Hugoniots were approxi-
mated with simple equations of accuracy about 0.05 % for shock wave velocity
and 0.3 % for density.
These approximations are recommended as standards in the pressure range
from 10-30 Mbar up to 10-30 Ghar. The equations are useful for interpolating
between experimental Hugoniots of porous substances and for constructing
wide-range equations of state.

4.1.2. Quantum-Statistical Model

The Thomas-Fermi statistical model (IF) provides the Simplest description of
the behavior of hot, compressed atoms [9,10]. It may be interpreted as a special
quasi-classical approximation to the Hartree-Fock model, not accounting for
the shell structure of atomic electrons. Nevertheless, the IF model is successful
for describing the qualitative behavior of matter under extreme conditions.
Better accuracy is provided by the quantum-statistical model (QS), which in-
cludes first order quantum and exchange corrections to the IF model. There are
two variants of the QS model. One of them is almost as simple as the IF model,
and all expressions are self-similar with respect to the atomic number Z [11-13].
This is especially convenient, because only one table of each thermodynamic
function is needed to describe an arbitrary substance (this variant is also denoted
as lFC). The other variant is not self-similar, but has some theoretical advan-
tages [14,15]. The quantitative difference between these variants is significant
only for P< 10 Mbar, where neither is valid. For this reason, only the first vari-
ant is used in our subsequent work.
The QS model describes electronic components of all state variables. The
nuclear input to thermodynamics at extreme conditions is properly described by
the nuclear oscillation model [16,17]. It is based on the idea of ionic cores os-
cillating near equilibrium positions within a background of free electrons. This
model explains qualitatively the transition of condensed matter to hot dense
plasma, although it can't properly describe melting or vapori7Jltion at low pres-
sures.
The QS model does not account for the shell structure of atomic electrons
and represents a real atomic cell as a sphere of the same volume (the so called
Wigner- Seitz cell). Because the shell structure is neglected, this model com-
pletely smoothes the oscillations of the thermodynamic functions. This leads to
low accuracy of the model at gas densities and at ultrahigh temperatures (above
I keY), where shell effects are essential.
 4. Wide-Range Characteristic Thennodynamic Curves III

Nevertheless, there is an important region in which the QS model has good

accuracy. This is the region in which matter exists as superdense strongly cou-
pled plasma with nonideality parameter r= z /(RT)>> 1, where z is an effective
ionization rate, R is the radius of the Wigner- Seitz cell, and T is a temperature
(all values are measured in atomic units). Such plasma exists at, and above, the
densities of condensed substances and at temperatures providing at least one-
fold ionization, but insufficient for ionization of inner shells.
The physical reason that the QS model is valid in this region is that the
strong microfield present in superdense plasma turns atomic levels into very
wide quasi-bands. This smooths shell oscillations of thermodynamic curves
almost completely, and the QS model prevails over all other models in accuracy,
including those as sophisticated as the density-functional method [18,19], the
self-consistent field model [3], and the modified Hartree-Fock-Slater model
[2].
The superdense plasma region is important because Hugoniots of condensed
substances and substances of modest porosity (m < 10) pass through it Figure
4.1 shows schematically a principal Hugoniot in pep} form. It is seen that a true
Hugoniot contains shell oscillations, and the QS model leads to a non-oscillating
curve with only one turning point (the circle). Nevertheless, large parts of these
two curves coincide both below and above the turning point.
The QS codes calculate detailed tables of thermodynamic functions and
some other quantities as functions of T and p for substances of arbitrary compo-
sition. If one knows the initial condition of the substance (density Po and energy
Eo), he can calculate a table of all thermophysical variables as functions of T for
the appropriate Hugoniot.

P• '..
\ \', ....

..........
... ...
' .... '-,

o ~
Figure 4.1. Hugoniot curves. The true curve is designated by a solid line, the QS model
by a dotted line, the linear DCu} approximation by long dashes, the quadratic approxima-
tion by short dashes, and the cold compression curve by a chain of dots and dashes. The
circle is the fIrst turning point
112 N.N. KaIitkin and L. V. Kuzmina

4.1.3. Velocity Variables

To work with tables is rather tiresome. It is better to find simple approximations
for the most important thermodynamic curves and functions. Physicists usually
prefer the P(p) form for Hugoniots, but the curves in Fig. 4.1 are difficult to
approximate. The problem is significantly simplified when the shock-wave
velocity, D, and mass velocity, u, are chosen as variables.
Figure 4.2 shows schematically the D(u) dependence. The initial part of the
true curve (where the QS model is invalid) may have a complicated structure
connected with phase transitions, but the part where the QS model is nearly
coincident with the true curve is almost linear (its boundaries are marked with
two cross bars in Fig. 4.2). The accuracy of approximation may be significantly
improved by adding a small positive quadratic term:
D(u)~C+Bu+Au2, C,B,A >0, A «l. (4.1)

The least square error of the measured shock velocity, D, for most of elements
lies in the range 0.02-0.1 %; it is not as accurate as the QS model. Maximal
compression on QS Hugoniots does not exceed 5-6 fold, and the equation
p=PoDI(D-u) shows that the density error will not be greater than 0.1-0.5%.
When a substance has zero initial pressure and mass velocity, the laws of
momentum and mass conservation on the Hugoniot curve have the form
P = PoDu, cr == pI Po =D I(D -u). (4.2)
For the quadratic D(u) apprOximation (4.1), these equations may be expressed in
the P(cr) form

P(cr) = 4po C 2 cr(cr-l) (4.3)

~
[cr- B(cr-l) ± [cr- B(cr-l)]2 -4AC(cr _1)2 y
D

o~ ________ ~u~
u.
______~

Figure 4.2. Hugoniot curves in velocity variables (notations of Fig. 4.1). Cross bars are
limits of the validity of the QS model.
 4. Wide-Range Characteristic Thennodynamic Curves 113

In this equation the plus sign corresponds to the lower part of the curve, and the
minus sign corresponds to the upper part. Equation (4.3) describes a first turning
point (maximal compression on a Hugoniot curve). Pmameters of this point
depend on the coefficients ofEq. (4.1):

B+2.JAC
0.= u.=.JCIA, P.=P ou;(B+2.JAC). (4.4)
B-I+2.JAC'
The linear approximation of the function D(u) follows from Eq. (4.1) with
A =0. It gives the P(o) curve

P(o) = poC2 0 (o-l) (4.5)

[o-B(o-I)]2
instead ofEq. (4.3). This curve is denoted with long dashes in Figs. 4.1 and 4.2.
The compression, 0, depends monotonically on P and its limit is
0 00 ;: o(P = 00) = BI(B -I). This curve can't describe a turning point as given by
Eqs. (4.4), so its deviation from the true curve (solid line) becomes significant
even for velocities u~0.5u •. Therefore, the limits of applicability of a linear
D(u) approximation are narrow, and the parabolic approximation ofEq. (4.1) is
much better.
Earlier, we fitted parabolic approximations (4.1) for the principal Hugoniots
of 52 substances [20], but their error reached 0.05-0.1% in velocity, which
corresponds to 3-5% in density. This accuracy doesn't meet modem require-
ments. Now we have improved the accuracy more than 10 fold, included poros-
ity of the initial state, and performed calculations for 83 substances.

4.1.4. Algorithm
The initial numerical data are values of thermodynamic functions obtained using
the QS model, for instance P(T, p) or E(T, p) in the tables. The physical accu-
racy of the QS model in the region of interest is about 0.5% for the function
p(T, P) and 0.1% for the functionD(u). The mathematical accuracy of all initial
data is better than 0.01% for most entries, although the error sometimes rises to
O.I%. (These calculations were performed in 1975 when the capabilities of
Russian computers were modest.) Calculations of P(p) and D(u) tables for
Hugoniot curves were performed with the same mathematical accuracy. In all
cases the mathematical error of all data was less than the physical error.
We now consider a preliminary treatment of tabulated D(u) dependencies
with the least square method. The linear approximation in the region
0.1 Sulu. SO.6 or the parabolic approximation (4.1) in the region 0.1 S ulu. s2
provided an accuracy of about 0.1% for each porosity m. This corresponds to the
physical accuracy of the QS model. However, the dependence of these approxi-
mations upon m proved insufficiently smooth.
114 N.N. Kalitkin and L. V. Kuzmina

It is more convenient to use a region 0.125~ulu.~1.6 for fitting coeffi-

cients ofEq. (4.1). The error decreased to 0.03-0.05%, and the dependence on
m became smoother and more suitable for analysis. This region was used in final
calculations (although its results were of good accuracy even in the initial region
0.I~ulu.~2).

One essential improvement was introduced into the algorithm. At first the
parameters U. and cr. of the turning point were calculated by especially accurate
interpolation of Hugoniot tables with the help of the equation dcrldP = O. Then it
follows from Eqs. (4.1), (4.2), and (4.4) that, for arbitrary u,
C== [D -ucr.. I(cr .. -1»)/(l-u I U.. )2. (4.6)

Let us propose that all tabulated values Dj == D(uj) have the same relative accu-
racy. Then the least square approximation for C according Eq. (4.5) is

(4.7)

where both sums are calculated with Uj from the region mentioned above. Put-
ting the value of C from Eq. (4.7) into Eq. (4.4) gives
C cr.. C
A ==2' B==---2-. (4.8)
u.. cr .. -1 u..

Calculations with Eqs. (4.7) and (4.8) lead to smoother dependence of the coef-
ficients on porosity.

4.1.5. Porosity
The variable m is the ratio of the normal density of the substance to its actual
initial density. In 1986 we found that the coefficients C and B for porous sub-
stances had approximately a power-law dependence on m, and calculated these
dependencies for AI and Fe. However, their accuracy was insufficient to satisfy
modem requirements.
Now we have revised those results. For each substance, a set of Hugoniot
curves was calculated for porosities from m== 1 to m== 10 (values of logm == 0.0,
0.2, 0.4, 0.6, 0.8, and 1.0). The dependence of the coefficients on m was ap-
proximated with specific equations that described the turning point especially
carefully:
10gC(m) == c+ylogm

10gA(m) == a +alogm (4.9)

log~(m) -1 + 2~A(m)B(m) ]== b + ~logm.

 4. Wide-Range Characteristic Thennodynamic Curves 115

From this, it follows that

logu.(m) = O.5[c - a + (y -a)logm].

The coefficients a, b, c, a, 13, and y were calculated from previously prepared

tables of the fimctionsA(m), B(m), and C(m) by the usual least square method. It
was proposed that all coefficientsA(m), etc., had the same relative error, i.e., the
same absolute error for 10gA(m), etc. Then, the final approximation D(u, m) was
compared with all initial tabulated values Dj(uj) for all six porosities, and its
error was calculated in the chosen region of velocities.

4.1.6. The Results

The results of the calculations described are presented in the Table 4.1 for more
than 80 substances. The columnar entries are as follows:
• Z is the atomic number of the element or the mean atomic number for a
chemical compound. The atomic weight isn't given; it corresponds to the
usual isotopic composition.
• Name is the name of the element or compound (H2, D2, N2, and CO are in-
cluded).
• The symbol Po is the normal density in glcm3; it is taken from [21] and partly
from other reference books. Its value may explain the phase of the substance
in the case of polymorphism. Substances mruked with asterisks are liquids
(liquified gases are at their boiling temperature).
• The symbol Eo is the bond energy at nonnal conditions in kJ/g; it is taken
from [21] for elements. Its choice for the four chemical compounds is dis-
cussed below.
• The quantities a, b, c, a, 13, and y are coefficients inEq. (4.9). The first three
of them correspond to velocities D and u measured in km/s; the proper unit
of pressure is GPa.
• 8 % is the mean error of the approximations of Eqs. (4.1) and (4.8) in percent
for all six porosities (1 ~m~ 10). The region of velocities 0.125 ~u/u.~ 1.6
used corresponded to the correct value of u.(m) for each porosity.

Light Elements. Shell effects are significant for light elements with Z< 10,
especially at low densities (large porosities). Therefore, the QS model accuracy
is less for these elements. This is why the treatment described gave large errors,
up to 1.5 %, for almost all light elements except He.
Nevertheless, the principal Hugoniots (m = 1) are satisfactorily approximated
even for light elements. This means that the coefficients a, 13, and y are not de-
termined, but a, b, and c are given in Table 4.1 for 6 elements with accuracy 8
for the principal Hugoniot curve.
 .-
Table 4.1 0\

Z Name Po -Eo c b a y J3 a 8%
~
1 H2 0.076 2.117 0.50512 -0.51598 -3.68813 -0.11702 -0.05804 0.38143 0.547 ~
1 D2 0.203 1.477 0.39102 -0.51008 -3.55655 -0.14778 -0.05559 0.34391 0.562 ~
I»
2 *He 0.118 0.021 0.43066 -0.56475 -3.35508 -0.33734 -0.07776 0.10651 0.544 ~

3 Li 0.534 23.040 0.47689 -0.55091 -3.55027 -1.11807 -0.08556 -0.52538 1.431

3 Li 0.534 23.040 0.41741 -0.55255 -3.61168 1.160
~
§
4 Be 1.850 35.730 0.84832 -0.53073 -3.52926 -1.27952 -0.08028 -0.64233 1.831 p..
4 Be 1.850 35.730 0.73146 -0.53302 -3.64450 0.496 t-'
5 B 2.340 50.660 1.08534 -0.53554 -3.38550 -2.16564 -0.08458 -1.50547 3.422 :<
5 B 2.340 50.660 0.76839 -0.53770 -3.69767 0.505
6 C 2.280 59.120 0.92654 -0.54476 -3.59331 -1.54272 -0.08937 -0.87538 1.831
6 C 2.280 59.120 0.76951 -0.54694 -3.74225 0.563
I»
7 *N2 0.804
0.804
33.811
33.811
0.73505 -0.59303 -3.52012 -1.60995 -0.10080
0.53023 -0.59398 -3.71199
-0.91559 1.544
0.654
r
7 *N2
7 *CO 0.790 38.420 0.70550 -0.59384 -3.54785 -1.56609 -0.10184 -0.83527 1.397
7 *CO 0.790 38.420 0.50921 -0.59488 -3.72499 0.675
10 *Ne 1.203 0.087 0.69107 -0.60496 -3.67860 -0.55085 -0.10053 0.03763 0.103
11 Na 0.970 4.740 0.60297 -0.62413 -3.67710 -0.62487 -0.10256 -0.02059 0.106
12 Mg 1.740 6.080 0.72141 -0.60496 -3.74090 -0.58879 -0.10258 0.02847 0.133
13 AI 2.710 11.930 0.78191 -0.59416 -3.78374 -0.60139 -0.10222 0.02818 0.181
14 Si 2.330 16.010 0.74724 -0.60518 -3.80290 -0.65555 -0.10440 -0.01294 0.208
15 P 2.340 10.140 0.72629 -0.61206 -3.79944 -0.62754 -0.10532 0.01423 0.167
16 S 2.070 8.600 0.69767 -0.62175 -3.82059 -0.63369 -0.10589 0.01405 0.140
18 *Ar 1.412 0.163 0.54099 -0.65462 -3.80288 -0.61059 -0.10561 0.01427 0.073
19 K 0.860 2.323 0.43448 -0.67969 -3.82062 -0.66679 -0.10449 -0.03576 0.063
20 Ca 1.545 4.400 0.57799 -0.65594 -3.85226 -0.66200 -0.10646 -0.02362 0.082
21 Sc 3.140 7.456 0.69617 -0.63049 -3.88441 -0.63053 -0.10755 0.01958 0.086
22 Ti 4.530 9.811 0.75986 -0.61874 -3.91141 -0.62194 -0.10759 0.03179 0.097
23 V 6.100 10.027 0.80979 -0.61019 -3.92918 -0.60618 -0.10707 0.04597 0.075
24 Cr 7.l90 7.610 0.85203 -0.60556 -3.94772 -0.59385 -0.10694 0.05533 0.073
 Table 4.1 (Continued).
Z Name Po -Eo c b a y ~ a. 1>%
25 Mn 7.470 5.098 0.84587 -0.60799 -3.95262 -0.58730 -0.10739 0.06057 0.068
26 Fe 7.870 7.452 0.85932 -0.60823 -3.96616 -0.59594 -0.10782 0.06335 0.064
27 Co 8.820 7.225 0.86827 -0.60717 -3.97909 -0.59472 -0.10765 0.06287 0.052
28 Ni 8.890 7.297 0.88009 -0.60820 -3.99560 -0.59578 -0.10792 0.05832 0.048
29 Cu 8.930 5.324 0.85263 -0.61305 -3.99487 -0.59502 -0.10847 0.06208 0.042
30 Zn 7.140 1.985 0.79445 -0.62602 -3.99400 -0.59400 -0.10928 0.06283 0.037
31 Ga 5.905 3.885 0.72164 -0.63943 -3.99104 -0.61142 -0.10981 0.05690 0.044
32 Ge 5.325 5.120 0.68195 -0.64778 -3.99158 -0.62743 -0.11008 0.04668 0.048 ~
33 As 5.780 1.604 0.69795 -0.64695 -3.98987 -0.60756 -0.10986 0.05082 0.039
34 Se 4.800 2.609 0.63044 -0.65982 -3.98994 -0.62239 -0.10994 0.05054 0.043 ~
36 *Kr 2.270 0.108 0.42471 -0.70219 -3.97716 -0.63568 -0.10689 0.04343 0.032 0-
t"O
37 Rb 1.530 0.990 0.31536 -0.72388 -3.97189 -0.66916 -0.10424 0.01323 0.038 ~
38 Sr 2.600 1.878 0.44678 -0.70051 -3.99631 -0.66431 -0.10763 0.02500 0.047 §
(JQ
39 Y 4.475 4.596 0.57746 -0.67576 -4.03193 -0.65479 -0.11038 0.04238 0.054 t"O
40 Zr 6.508 6.687 0.66746 -0.65988 -4.04966 -0.65474 -0.11145 0.04274 0.047 Q
41 Nb 8.582 7.855 0.73454 -0.64861 -4.06860 -0.64604 -0.11172 0.04980 0.030
42 Mo 10.210 6.856 0.77091 -0.64293 -4.07529 -0.64000 -0.11176 0.05343 0.028 ~
43 Tc 11.460 6.500 0.79670 -0.63941 -4.08564 -0.63906 -0.11192 0.05683 0.031 ~r
{II
44 Ru 12.390 6.379 0.80844 -0.63838 -4.08282 -0.64027 -0.11198 0.05150 0.035 r:t.
(")
45 Rh 12.420 5.411 0.80489 -0.64018 -4.09230 -0.63649 -0.11209 0.05791 0.027
46 Pd 12.010 3.537 0.78367 -0.64441 -4.09371 -0.63077 -0.11225 0.06543 0.024
;l
47 Ag 10.494 2.651 0.74471 -0.65262 -4.09858 -0.62751 -0.11221 0.07057 0.021 ~
48 Cd 8.643 0.998 0.67680 -0.66529 -4.09512 -0.62170 -0.11191 0.08167 0.020
49 In 7.300 2.093 0.62317 -0.67562 -4.09697 -0.63134 -0.11178 0.07823 0.Q25
50 Sn 7.284 2.539 0.60896 -0.67838 -4.09968 -0.63592 -0.11176 0.07965 0.026
t§.
(")
51 Sb 6.690 2.142 0.57787 -0.68485 -4.10089 -0.63703 -0.11145 0.08253 0.026
(')
52 Te 6.240 1.529 0.54105 -0.69166 -4.09309 -0.63652 -0.11104 0.08333 0.025
54 *Xe 3.520 0.096 0.38200 -0.72366 -4.07830 -0.63577 -0.10757 0.08463 0.028
{II
55 Cs 1.870 0.606 0.20794 -0.75653 -4.05393 -0.66296 -0.10242 0.05403 0.032
~
56 Ba 3.700 1.305 0.37859 -0.72536 -4.08628 -0.65870 -0.10772 0.07491 0.030 .....
57 La 6.180 3.071 0.51190 -0.70118 -4.11589 -0.66055 -0.11076 0.07475 0.029 .....
-.J
 ....
....
Table 4.1 (Concluded). 00
Z Name Po -Eo c b a '1 p a B%
58 Ce 6.770 2.925 0.53473 -0.69796 -4.12624 -0.65526 -0.11118 0.08044 0.029
59 Pr 6.775 2.549 0.53612 -0.69919 -4.12755 -0.65301 -0.11103 0.07750 0.026 ~
60 Nd 7.005 2.203 0.53767 -0.69951 -4.13404 -0.65074 -0.11109 0.08750 0.020 ~
61 Pm 7.132 1.849 0.54263 -0.69963 -4.14209 -0.64685 -0.11121 0.09204 0.020 ~
62 Sm 7.538 1.398 0.54247 -0.69951 -4.14385 -0.64347 -0.11129 0.09773 0.021 ~
63 Eu 5.260 1.182 0.44061 -0.71893 -4.13386 -0.64792 -0.10931 0.09549 0.027
64 Gd 7.910 2.202 0.53903 -0.70097 -4.14955 -0.65391 -0.11139 0.09245 0.021 8-t-'
65 Tb 8.260 2.368 0.54821 -0.70010 -4.15535 -0.65538 -0.11159 0.09153 0.022
66 Dy 8.550 1.724 0.54907 -0.70022 -4.15848 -0.64945 -0.11166 0.09665 0.023 :<
67 Ho 8.800 1.790 0.55219 -0.70030 -4.16285 -0.65108 -0.11169 0.09406 0.024
68 Er 9.056 1.770 0.55519 -0.70029 -4.16967 -0.64997 -0.1l182 0.10091 0.025
69 Tm 9.325 1.445 0.56088 -0.70002 -4.17525 -0.64775 -0.1l197 0.10144 0.025
II>
70 Yb 6.968 0.975 0.47017 -0.71673 -4.16684 -0.64554 -0.1l049 0.1l600 0.023
r.
71 Lu 9.845 2.364 0.56329 -0.70046 -4.18296 -0.65780 -0.1l232 0.09913 0.026
72 Hf 13.260 3.413 0.64065 -0.68710 -4.19384 -0.66351 -0.11354 0.09353 0.022
73 Ta 16.700 4.320 0.70692 -0.67688 -4.19999 -0.67587 -0.1l404 0.07830 0.023
74 W 19.350 4.548 0.74428 -0.67091 -4.20652 -0.67676 -0.11443 0.07651 0.024
75 Re 21.020 4.187 0.76588 -0.66819 -4.20453 -0.67755 -0.11442 0.06842 0.027
76 Os 22.530 4.120 0.77673 -0.66639 -4.21247 -0.67705 -0.1l461 0.07458 0.028
77 Ir 22.500 3.461 0.77372 -0.66761 -4.21625 -0.67477 -0.11462 0.07847 0.026
78 Pt 21.450 2.893 0.75477 -0.67134 -4.21880 -0.67245 -0.11459 0.08417 0.025
79 Au 19.300 1.862 0.72185 -0.67774 -4.22013 -0.66745 -0.1l437 0.09136 0.026
80 *Hg 13.550 0.322 0.60930 -0.69732 -4.21437 -0.64942 -0.11308 0.11840 0.032
81 Tl 11.860 0.889 0.56358 -0.70574 -4.21259 -0.65268 -0.11251 0.12252 0.032
82 Ph 11.342 0.950 0.54596 -0.70931 -4.21402 -0.65400 -0.11228 0.12473 0.032
83 Bi 9.810 1.002 0.50091 -0.71777 -4.21375 -0.65392 -0.11139 0.12920 0.035
88 Ra 5.000 0.778 0.27798 -0.75881 -4.18062 -0.65367 -0.10621 0.12853 0.034
90 Th 11.690 2.467 0.51295 -0.71823 -4.23175 -0.67486 -0.11227 0.12277 0.026
91 Pa 15.400 2.392 0.59948 -0.70452 -4.24578 -0.67891 -0.11336 0.10812 0.027
 4. Wide-Range Characteristic Thennodynamic Curves 119

Dissociation. Four of the substances investigated, H2, D2, N2 , and CO, have
stable molecules. The last two are interesting because their mean atomic number
and weight are equal, and densities, boiling tempemtures, and energies of liquid
phases are almost the same. The main difference lies in their dissociation ener-
gies; the influence of this factor on Hugoniot curves was investigated in Ameri-
can experiments.
Tempemture rises along a Hugoniot curve, and molecules begin to dissoci-
ate. However, the QS model doesn't account for this and is applicable only after
full dissociation of the molecules. This is why the dissociation energy was in-
cluded in Eo along with the heat of vaporization for N2 and CO.
Another situation arises for H2 and D2. For these substances, and for He, the
values of Po are very small and the pressures at the turning points are P.-I0
Mbar instead of Gbar. The QS model is unreliable at such pressures and, moreo-
ver, Z is also small for these substances. If dissociation energy is included in Eo,
then the turning point of the P(p) curve is barely perceptible and the parabolic
approximation for D(u) is inaccumte. This is why only the heats of melting and
vaporization were included in Eo for H2 and ~, and molecules were considered
as non-dissociating (monatomic He does not present this difficulty).

4.1. 7. Discussion
Table 4.1 shows that the mean error, 8, is about 0.1 % for elements in the mid-
mnge of atomic number (10 s: Z s: 25) and decreases to 0.03% for heavy ele-
ments (Z> 25). A mathematical error of this magnitude doesn't exceed the
physical error of the QS model. This permits use of the approximation of Eq.
(4.9) for 74 substances in the region of velocities (0.125 S:u/u. s: 1.6) and poro-
sities (1 S:m s: 10) described.
The mathematical accumcy is worse for light elements with Z<10, but the
QS model is also unreliable for them. Nevertheless, 8~0.5% was reached for
3 porous and 6 solid (m = 1) substances. This is a satisfactory result.
The dependence of coefficients of the approximation on Z is interesting. It is
shown for c, b, a in Fig. 4.3. One sees that it has a non-smooth character con-
nected with the shell structure of the outer electrons. Sharp peaks of the curves
correspond to alkali metals (for c and b these peaks are minimums and for a they
are maximums). The main input in these peaks is made by normal density de-
pendence on Z; the behavior of the bond energy has a smaller influence. Let as
describe some details.
The coefficient C (m = 1) =10 C corresponds to the normal sound velocity in
the QS model. It changes about 5 fold (from 1.6 km/s to 8 km/s), and its change
from one Mendeleev period to another is less than from alkali metals to heavy
metals within one period. The dependence C(m)-m"Y on m and Z is rather weak
120 N.N. Kalitkin and L. V. Kuzmina

-0.56
c
0.8 b
-0.60

-0.64
0.6

-0.68
0.4
-0.72

Z. Z
0.2 -0.76
0 20 40 60 80 100 0 20 40 60 80 100

-3.6 a

-3.8

-4.0

-4.2

Z
-4.4
0 20 40 60 80 100

Figure 4.3. Dependence of the coefficients of the approximation on Eq. (4.9) on Z.

because y~O.64±O.04. Nevertheless, it is a great mistake to use y=const. be-

cause the accuracy of the approximation (4.9) will worsen significantly.
The coefficient B(m= 1) lies within the narrow limits 1.15-1.19. It differs
strongly from experimental values at nonnal densities (they are usually -1.5).
Therefore, the low-velocity part of the true D(u) curve must differ significantly
from that predicted by the QS model.

4.1.8. Experimental Proof

Pressures that can be produced by explosives or light-gas guns are insufficient to
test the validity of the QS model. However, shock compressions produced by
underground nuclear explosions are much greater and may be compared with the
results of theoretical calculations presented in Table 4.1. The most advanced
experiments of this kind were performed in Russia, and a good review of their
data is given in [22]. Let us compare data in Table 4.1 and [22] and analyze the
reliability of the experimental data.
 4. Wide-Range Characteristic Thennodynamic Curves 121

Table 4.2 contains 20 experimental points for 6 metals. Seven points for AI
and Fe are marked with asterisks that designate absolute measurements, i.e., not
only were shock wave velocities, D, directly measured, but also mass velocities
u (this was done using the y-reference method for AI and the impact method for
Fe). Table 4.2 gives experimental errors for D and u, with the summary error for
D being shown in parentheses. This error was calculated by transfonning the
error in u into an equivalent increase of the error in D. The separate column 8.
gives summary errors of D in percent; they are rather large.
The last two columns of Table 4.2 show theoretical values DQs according
Eqs. (4.1) and (4.9) with coefficients from Table 4.1, and their deviations, A,
from the experimental data. These deviations are a few times less than the ex-
perimental error and their absolute values are small, about -0.5% (except one
point for AI, for which the experimental error is huge). This is excellent agree-
ment.
The other experimental measurements are relative and were made by the im-
pedance-match method. A shock wave is passed through two materials: a stan-
dard material and the material investigated. The only measurement was of the
value of D in each material. The equation of state of the standard material was
considered to be known from experiments previously performed. Equations
describing a shock wave passing through, or reflecting from, the contact bound-
ary permit calculation of the values of u in the substance investigated. This is
why one must add the uncertainty of the equation of state of the standard to the
experimental error; this makes these results significantly less reliable than the
absolute measurements.
These relative measurements include the pairs of metals: Fe ... Mo, Fe ... Pb,
Pb ... Cu, and Cu ... Cd. The reliability of the corresponding experimental data
from Table 4.2 is worse for Mo and Pb than for Fe, worse for eu than for Pb,
and worse for Cd than for Cu. It is difficult to give a quantitative estimate of the
decrease of accuracy in this set
It can be seen, from Table 4.2, that agreement of the QS model with relative
experiments is excellent for Fe and Mo (one point for each element) and good
for Ph. It is worse for Cu and Cd, but the most probable explanation is that the
treatment of the experiments for these metals is unreliable; the QS model seems
more reliable than these experiments.
Table 4.2 also shows that all QS Hugoniots coincide with experiments at
significantly lower pressures than cautious theoretical estimates indicate. The
estimate of the lower boundary for heavy and middle elements was
u~0.125u.~30 km/s, but one sees good agreement with experiments at one-
half of that velocity, u ~ 15 km/s. This corresponds to P ~ 9 Mbar for AI and ~30
Mbar for Fe and heavier elements. The QS model is currently the only one
among a priori theoretical models that provides this agreement without fitting
122 N.N. Kalitkin and L. V. Kuzmina

parameters, although the QS equations were written in 1957-1960 and haven't

been improved since, and the initial tables of the thennodynamic functions were
calculated in 1974.

Table 4.2. Comparison of the QS model with experiments.

r::JP U, experiment QSmodel
Element m Mbar kmls Dkmls ~e% DQs(u) ~%

AI 1* 9 14.5 ±0.3 23.4±O.6 (0.70) 3.0 23.363 -0.2

1* 10 15.1 ±0.4 24.2±O.7 (0.85) 3.5 24.081 -0.5
1* 17 21.0±0.6 30.5±O.7 (1.00) 3.3 30.516 0.1
1* 32 30.0±2.0 40.0±5.0 (5.54) 14 41.945 4.9
Fe 1* 41 18.25 ±0.5 28.85±O.7 (0.92) 3.2 28.997 0.5
1* 54 21.35 ±0.6 32.4±O.8 (1.07) 3.3 32.701 0.9
1* 105 30.60 ± 1.25 43.5±1.0 (1.80) 4.1 43.765 0.6
1 190 42.3 57.4±O.9 >2 57.787 0.7
Mo 1 14 8.58 16.10 ? 16.057 -0.3
Pb 1 35 15.02 20.72 ? 21.042 1.6
58 19.76 26.12 ? 26.533 1.6
217 39.3 48.8±1.5 >3 49.433 1.3
Cu 16 9.96 17.82 ? 18.985 6.5
39 16.67 26.18 ? 26.989 3.1
204 40.8 55.9±O.8 ? 55.845 -0.1
4 14 21.35 28.71 ? 28.205 -1.8
4 16 22.76 31.10 ? 29.865 -4.0
4 21 26.22 36.00 ? 33.941 -5.7
Cd 14 10.14 16.08 ? 16.695 3.8
34 16.41 23.88 ? 24.088 0.9
• The asterisks designate absolute measurements.

4.1.9. Conclusions
Simple, explicit equations have been constructed for Hugoniot curves of 83
porous condensed substances. They are applicable at porosities 1 ~ m ~ 10 and
velocities 15 km/s ~ u ~ 2u.1:::1 500 km/s, as proven by experiments. Their error
D(u) is about 0.5% at low velocities and decreases rapidly to 0.02-0.1% at
higher velocities. Absolute measurements of shock compression in underground
nuclear explosions [22] have real errors of velocities -0.5%; they are signifi-
cantly better than one usually thinks. However, the accuracy of relative (imped-
ance-match) measurements is often worse than one would like.
 4. Wide-Range Characteristic Tbennodynamic Curves 123

4.2. Wide-Range Principal Hugoniots

4.2.1. Shell Effects on Hugoniots

Electron shells of middle and heavy elements may be divided in the imagination
into external, intennediate, and internal shells. This proves useful for qualitative
explanation of the thennodynamic properties of materials and the behavior of
their Hugoniots.
An external electron shell is responsible for the normal density, the com-
pressibility, polymorphic phase. transitions, and other properties of materials at
modest temperatures and pressures. These properties may differ significantly for
neighboring elements. Theoretical methods have achieved significant success in
this field [18,19]: The so called density functional method (OF) describes cl)'s-
tals rather well using Hartree-Fock-Slater equations (HFS) with Bloch-band
boundaty conditions. It has made calculation of satisfactOl)' cold compression
curves possible for many substances. But, the OF method has two restrictions.
First, the Bloch conditions are invalid at tempemtures above the melting point
and adequate conditions are still unknown. Second, good agreement of the OF
method with experiments is achieved only by fitting some minor pammeters of
the method; it is not pure theol)'.
When pressure increases along a Hugoniot curve, a condensed substance
melts and then turns into a superdense plasma The latter material can't be de-
scribed by traditional nonideal plasma models. Many attempts have been made
to describe this region with a modified HFS model (MHFS), where thermally
exited electron shells are considered in quasi-classical (WKB) approximation.
Two variants of the MHFS model are the most advanced: one with Bloch-band
boundary conditions [2] and the other with pseudo-band boundaty conditions
[3]. These latter conditions significantly simplify numerical calculations. Both
variants use a Wigner-Seitz spherical atomic cell instead of a true cell. The
second variant lies nearer to the experimental data, but neither of them is suffi-
ciently accumte. A possible reason for this may be inadequacy of the boundaty
conditions (see below).
The QS model [11-15] is in better agreement with experiments at pressures
of 30 to 500Mbar (this is the highest pressure reached in accumte measurements
[22]). At first this seems stmnge, because the QS model is significantly simpler
than the MHFS models: All electron shells in it are changed to a quasi-classical
electron gas. This was later explained using a quasi-band (QB) model [1,5] (see
the detailed discussion below).
Atoms of solid substances lie at specific sites of a Cl)'stal lattice. So called
close order of atoms exists in liquids, but long-range order is absent. In gases, no
order of atomic position exists. Atomic cells may be formally introduced, but
their mdii fluctuate because of thermal motion of the atoms. Therefore, energies
124 N.N. Kalitkin and L. V. Kuzmina

of each electron level fluctuate, and a multitude of electron levels with the same
quantum numbers in different atoms have an energy distribution. A level trans-
forms into a stripe reminiscent of a band in crystal (a so called quasi-band).
Numerical calculations show that: i) the width of a quasi-band is practically
independent of its quantum numbers, although there is strong variation :from one
band to another (inner bands are narrow and outer bands are wide) and, ii) quasi-
bands are much wider than completely-filled and partly-filled bands in a crystal
at the same density.
The quasi-band width in superdense plasma is so large that it exceeds differ-
ences of electron ionization potentials not only within one electron shell but also
between neighboring shells. This leads to significant widening of all electron
shells, and neighboring shells (except the innermost shells) form a continuous
spectrum of electrons, appearing as a classical electron gas. This effect becomes
significant when the temperature and density are high enough. Estimates show
that this occurs at -30 Mbar along principal Hugoniots. This is the lower limit of
applicability of the QS model on Hugoniots.
At superhigh pressures on Hugoniots, temperature increases enormously, so
inner electron shells (quasi-bands) become exited. For example, at p~ 30 Gbar
the internal energy is E~ 50-200MJ/g and T~ 1-2keV. Distances between
inner shells are large, exceeding the width of quasi-bands. The QS model be-
comes inapplicable, and one may expect shell oscillations on Hugoniots (see
Figs. 4.1 and 4.2). However, radiation begins to influence the thermodynamics
and masks shell effects at such temperatures.
That is why shell effects are barely perceptible on principal Hugoniots of
heavy elements. They are distinct only for light elements where one outer shell
and one inner shell are present but middle shells are absent
For porous substances all densities are less, quasi-bands are narrower, and
shell effects increase. For condensed substances with porosities m:S; 10 this is no
longer significant For gases, where thermodynamics may be excellently de-
scribed with the Ionization Chemical Equilibrium (ICE) model, shell effects on
Hugoniots and isotherms are large [23].
Let us note that some corrections accounting for charged particle interactions
in plasma permit application of the ICE model to dense gases. However, the
well-known Debye correction is almost inapplicable. The Debye-Hiickellarge
canonical ensemble model [24] and the generalized Larkin model [25] gave
significantly better results. The best description of experimental data was
achieved using the Micro-Field-Nonidea1ity (MFN) model [26,27]. Its limit of
applicability lies near the QS model region, and a gap between them may be
satisfactorily filled with special interpolations [5] based on the QB model. These
questions will be discussed below in detail.
 4. Wide-Range Characteristic Thennodynamic Curves 125

4.2.2. Wide-Range Hugoniots

We have shown that the QS model gives good accuracy for Hugoniots of con-
densed substances at mass velocities in the range 15 kmls ~ u ~ 500 kmls. These
Hugoniot curves can be described by the simple explicit equations (4.1)-(4.5)
and (4.9), with coefficients from Table 4.l. Note that, although the quadratic
term in Eq. (4.1) is very small, it is extremely important because a turning point
of a Hugoniot cannot be described by a linear approximation of the function
D(u). Therefore, one should take C with an adequate number of significant dig-
its.
The upper boundary of applicability exceeds all practical needs. The ques-
tion is: How might one describe Hugoniots in the region 0 ~ u ~ 15 kmls
(0 ~ P ~ 30 Mbar)? These parts of the curves are affected by the outer electron
shell, so the QS model is invalid. More sophisticated models, constructed strictly
from first principles, also fail in this region. They achieve a proper description
of experiments only by fitting some model parameters; but this is some kind of
interpolation.
We should not be ashamed of interpolation, and may use the following
method. Suppose that there are no phase transitions of any kind so the D(u)
curve contains no breaks in the function itself or in its first derivative. In this
case the initial part of a Hugoniot curve may be approximated with a specific
equation that includes a few adjustable parameters. A form of approximation
should be chosen so as to join smoothly with the QS approximation ofEq. (4.1).
Its parameters should be selected to provide a satisfactory description of ex-
perimental data.
The simple behavior of the true D(u) dependence for many substances leads
us to expect good results.

4.2.3. Experimental Data Estimation

Low-Pressure Data. The majority of shock wave experiments have been per-
formed using explosive devices with plane or hemispherical geometry at pres-
sures P ~ 5 Mbar (there are also light-gas gun measurements in this region, but
we used them only for Fe). A few experiments with explosives have been made
atPI'l:I 10 Mbar and recently up to 25 Mbar. Most of these publications and some
of the reports have been collected in compendia [6-8].
Not all of these papers contain estimates of errors in the measurements of the
velocities D and u. Ifan estimate is given, it is usually -1%, which translates to
- 2 % for the D(u) dependence. One may gain an impression of the random com-
ponent of error from the deviation of points from a mean D(u) curve in each
publication; it is often - 2 % in accordance with the previous estimate. The dif-
126 N.N. Kalitkin and 1. V. Kuzmina

ference between mean curves of different laboratories is usually less than 1 %

and indicates the magnitude of systematic errors.
Some points were measured by the impact method, which invokes no model
assumptions, and hence produces absolute measurements. They are the most
reliable. Many points were measured at low velocities by the free-surface veloc-
ity method. These points are a little less reliable because the analysis contains a
small model correction in calculation of the mass velocity, u, from the measured
free-surface velocity. Most measurements have been made by the impedance-
match method, which requires use of properties of standard substances. These
are relative measurements, and are the least reliable.
There are also static compression measurements by Bridgman and others
with piston devices for P ~ 0.1 Mbar, and on diamond anvil cells at P ~ 1 Mbar
and sometimes more. These experiments measure the isothermal compression
curve P(p) but not the Hugoniot curve. However, at such low pressures, these
curves lie close enough together that their difference is negligible for condensed
materials (except the lightest ones such as alkali metals and condensed gases).
This permits a special treatment of these data in which they are transformed to
fictitious velocities [1]:

D=~P. a , u=~P .a-I, a =..£..., (4.10)

Po a-I Po a Po

corresponding D(u) curves are easily compared with shock-wave data. However,
different Bridgman publications for the same substances often diverge signifi-
cantly and contain neither estimates of errors nor discussions of divergences.
Measurements in diamond anvil cells are very careful but have one unreliable
aspect, the use of a ruby pressure gauge. This gauge is calibrated with shock
compression data. This last difficulty will be discussed below.
Shock-wave measurements have been made for a few substances using un-
derground nuclear explosions. Record pressures of 20-550 Mbar were achieved
in these experiments [22]. They include some points with absolute measure-
ments and estimated errors of velocities of -1%, but most of the measurements
are relative (and are significantly less reliable at such pressures).

Analysis of Errors of Low-Pressure Data. Measurements recorded in refer-

ences [6-8,22] and elsewhere have now been made for more than 500 con-
densed substances including almost all elements. There are usually 30-50 points
for each substance, and up to 500 points for a few substances. Experiments for
the same substance have often been made at different laboratories or in different
years, and with different devices. When using these data, one needs reliable
expert estimates of the accuracy of each point. Let us discuss this problem.
 4. Wide-Range Characteristic Thennodynamic Curves 127

It is well known that, for condensed substances without phase transitions, the
D(u) dependence is almost linear,
D(u)~co+bou, (4.11)
at low pressures, P:S; 5 Mbar. Usually each laboratory treated a series of its
measurements with least square method for fitting the approximation of
Eq. (4.11), and found coefficients Co, and bo with their statistical errors. How-
ever, coefficients reported by different laboratories diverged significantly,
sometimes by much more than their reported errors. One can see that from the
data of [6,7].
A much more reliable procedure is to collect measurements of different years
and laboratories for a certain substance and treat them together by the least
square method, using the reported errors of separate points [28-30]. We im-
proved this procedure in the following way.
At first we treated all data given with their reported errors in [28-30].
Where errors were not indicated, we supposed them to be -1%. When the coef-
ficients Co and bo were found, we calculated deviations of each exPerimental
point from the corresponding line (4.11). Then we separated all points of one
laboratory or one series of experiments and calculated their mean deviation from
the line (4.11). This may be considered to be the systematic error of this labora-
tory. The scatter of all points of the laboratory around the mean deviation of this
laboratory is their random error.
Then we discarded data from laboratories with large systematic errors, and,
for the other laboratories, we discarded points with large random errors. Quali-
tative criteria defining "large" depend on the number of laboratories and of
points according the usual rules of statistics.
After that we attributed the error calculated above to each laboratory and
point, and we repeated the whole procedure. If new errors differed only slightly
from previous values, we stopped the calculations; if error changes were signifi-
cant, we continued this procedure.
Here is one example of this analysis. Figure 4.4 shows the most accurate
measurements for Fe made using light-gas guns (three series of experiments).
They have a very small scattering of points, a rather wide range of velocities and
excellent coincidence with the mean line. Such data are included and even used
for especially careful checking. On the contrary, Fig. 4.5 shows data of one
Swedish laboratory (see [6], p.130). They have a huge scatter and a small range
of velocities. These data were excluded from the final analysis.
This approach gives us more than archives of experimental data as in [6,7]. It
gives a data base with consistent error estimates. These estimates are even better
than expert estimates because they are objective. We constructed such data bases
for 10 metals: AI, Ti, Fe, Ni, Cll, Mo, Cd, Ta, Pb, and U.
128 N.N. Kalitkin and L. V. Kuzmina

,.
6.5
0- u km/s '

6.0 Fa

5.5

,
5.0

4.5 -f.L........- r - - r -........- r - - r -........- - ,

2 3 4 5
Fe, IIl1ht lias lIun

Figure 4.4. The solid line is a mean approximation line for Fe; marks are results of
specific experiments conducted using light-gas guns.

D-U km/s

U km/s
4 r-~~~,--r--r-r-r........- ,
o 1 2 3 4 5

Figure 4.5. The solid line is a mean approximation for eu and the dots are experiments
from [6], p.130.

Analysis of Higher-Pressure Data. The method just described is suitable for

experiments at low pressures when D(u) is practically linear. For dense metals
this is the region P:5:5Mbar. When the pressure exceeds this limit, the D(u)
dependence begins to deviate from a stIaight line. This is typical for data ob-
tained using powerful hemispherical explosive devices and underground nuclear
explosions. For AI this limit is less than 1 Mbar, as will be shown below. Pres-
sures in this range arise even in traditional plane devices. It is important to note
that this method can't be applied to phase transitions, i.e., where breaks occur in
the D(u) curve.
 4. Wide-Range Characteristic Thermodynamic Curves 129

For each low pressure phase the D(u) dependence is linear, so the method
described can be applied to each phase separately. But, for the high pressure
phase, D(u) is CUIVilinear and one essential alteration was made. Another for-
mula was constructed instead of Eq. (4.11), and the least square method was
used for it. Now we consider this question in detail.

4.2.4. A High Pressure Phase

The approximation for the experimental D(u) curve for the high-pressure phase
must be joined smoothly with that obtained using the QS model, Eq. (4.1), at a
mass velocity near u = 15 kmls (for heavy elements). The process will be suc-
cessful only when the form of the approximate equation for D(u) is adequate.
At first we approximated the experimental part of D(u) with a quadratic
function [31,32]. It had three parameters and joined the QS curve (4.1) at an
undetermined point Uo so that the total D(u) function and its first derivative were
continuous. In applying this method, we imposed two conditions for adjusting
two parameters to join the two curves smoothly. The other two parameters were
determined by the least square method. This gave a good accuracy of !5:0.3 % for
both low and high pressures, but errors increased to 0.5-1.0% at intermediate
pressures.
We later improved these results and constructed the single equation
C -co bo-B
D(u) ~DQs(u)- 2 2 where J.1=-- (4.12)
l+J.1u+J.1 u C -co

for principal Hugoniots over the entire range of velocities. Here DQs(u) corre-
sponds to Eqs. (4.1) and (4.9) with coefficients from Table 4.1 at m= 1. The
coefficients Co and bo are determined by the least square method for optimal
description of all experiments.
Equation (4.12) has three advantages. First, it joins the QS curve (4.1) so
smoothly that all derivatives are continuous. Second, it takes the form
(4.13)

at small velocities. It is practically linear, i.e., of the form ofEq. (4.11) because
A « 1, and this permits description of experiments at low pressures. Finally,
although there are only two adjustable parameters, the method produces results
of excellent accuracy.
The low-pressure part of Eq. (4.13) is almost linear for J.1u!5:0.3. Then the
curve (4.12) bends and approaches the QS curve (4.1). Errors of the approxima-
tion (4.12) are small on the linear part of the true curve (as is easily seen from
comparison with experiments) and also on the QS part (according theoretical
arguments). Note that each of these parts is practically linear. The accuracy of
130 N.N. Kalitkin and L. V. Kuzmina

the intermediate curved part can be established for those few substances (AI, Fe,
Co, Mo, Cd, and Pb), for which experiments have been performed in this region.
Especially many experiments of satisfactory accuracy exist for Fe and Cu. We
shall see further that they convincingly confirm the approximation (4.12).

Polymorphism. When a substance has many different crystalline phases, the

approximation (4.12) describes only the high-pressure phase or, more correctly,
the high-pressure crystalline and liquid phases, because melting at a shock wave
usually changes the Hugoniot curve only slightly. For lower-pressure crystalline
phases one must use a linear approximation (4.11), :titting the coefficients Co and
bo separately for each phase.
It is known that a two-wave structure may exist if the shock pressure slightly
exceeds phase transition pressure. In this case, pin detectors measure only the
velocity of the :first shock wave, which has amplitude corresponding to the point
of phase transition and not depending on the pressure of the second (main)
shock wave. This part should be described with the approximation
D(u) ~ Co = const. When the shock pressure increases so that the second wave
overtakes the:first wave, one should use the linear approximation ofEq. (4.11).
Finally, there is a phenomenon in which the :tilling order of electron shells
changes with increasing pressure [33]. This does not change the crystal lattice of
solid substances, and may occur in the liquid phase. In the 1960s the question of
whether it leads to a true phase transition of any kind or only to bends on
Hugoniots, isotherms, and another thermodynamic curves, was discussed. Ex-
periments [6-8) show that Hugoniots of some lanthanides at pressures
O.I-IMbar have a sharp change of slope, though for other lanthanides this
change is distinct but smooth. This was investigated in detail in [34]. Metals
such as Ti, V, and Ta are even more interesting: They undergo a similar change
when the shock compressed material melts at megabar pressures. At this time,
neither theory nor experiment can indicate whether one should expect a sharp or
a smooth transition.

4.2.5. Calculations
The approximation (4.12) depends linearly on the coefficient Co and nonlinearly
on J.1 or boo This permits construction of an effective special algorithm imple-
menting the least square method for finding these coefficients: The squares-of-
errors sum was minimized with respect to Co by traditional transformation to a
linear equation, and on J.I. by the golden cross method. This algorithm provides
robust convergence when all experimental points belong to one (high-pressure)
phase. The algorithm fails only if one uses points belonging to different phases,
but such calculations are senseless.
 4. Wide-Range Characteristic Thermodynamic Curves 131

Numerical calculations were perfonned for 10 metals: AI, Ti, Fe, Ni, Co,
Mo, Cd, Ta, Pb, and U. Three metals (Ti, Fe, and Ta) have phase transitions,
even two transitions for Ti. We treated a total of 2153 experimental points; all
points were estimated, and 1907 of them were approved and included in the final
analysis. The results of these calculations are shown in Table 4.3.
This table contains coefficients C, B, andA for the QS limit, Eq. (4.1), of the
high-pressure phase and coefficients Co, and bo and their statistical errors corre-
sponding to probability 68% for the other phases. We recall that one must use
the approximation (4.12) for the high-pressure phase and (4.11) for all other
phases.
There are some additional columns in the lower section of the table. Values u
and P are the boundaries of mass velocity and pressure regions in which the
proper approximation with these coefficients is applicable and BDa is the error
estimate for this approximation. Two values, N, give number of "good" and
"bad" experimental points, 8De is the mean error of the good points for the D(u)
dependence, and Pe is the maximum experimental pressure. The values Ul and
PI. show the upper limit of the initial part of the curve (4.12), which is linear
within an accwacy 5%. This means that one can use the linear fonn (4.11) with
slightly changed coefficients, and it will deviate from the accurate curve by
about ±2 % (this deviation is hardly seen against a background of the usual
scattering of experimental points, and may be found only by our methods of data
analysis). Finally, Ua and Pa show the lower bound for which the approximation
(4.12) differs by 1% from the QS line (4.1). This difference is also less than the
experimental error.
Comment. The coefficients Co and bo are usually shown with their statistical
errors in publications. One usually checks whether coefficients of different pub-
lications coincide within the reported errors. However, these comparisons are
unreliable for two reasons. First, coefficients Co and bo in each publication are
calculated from the same set of measurements, so Co and b o are strongly corre-
lated. We calculated their pair correlation coefficient and found it to be up to
0.9, but this circumstance is never taken into account, or even noticed. Second,
when calculating statistical errors one usually assumes implicitly that the chosen
D(u) dependence is exact; but it is really only an approximate form, and chang-
ing it leads to changed results.

4.2.6. Discussion
The results were analyzed on graphs drawn in the non-traditional variables D-u
versus u. These variables make even small deviations or errors distinct Consider
several different metals.
Copper. This metal has a dense-packed crystal lattice. Polymorphism is absent,
jumps of volume and compressibility at the melting point on the Hugoniot are
132 N.N. Kalitkin and L. V. Kuzmina

Table 4.3. Principal Hugoniot approximations.

Element Po C B A X 104 Co
Z g/cm3 km/s s/km km/s bo 'OD.%
Cu,29 8.93 7.0924 1.19013 0.999 3.923±O.002 1.511±O.003 0.16

Fe, 26 7.87 7.2220 1.18959 1.099 3.671±O.013 1.753±O.007 0.14

4.629±O 1.241 0.1

AI, 13 2.71 5.7889 1.19380 1.568 5.236±O.009 1.470±O.014 0.13

U,92 18.93 0.26

Ph, 82 11.342 3.5521 1.16591 0.622 1.976±O.006 1.567±O.008 0.45

MO,42 10.21 5.8666 1.18323 0.834 5. 127±O.008 1.243±O.006 0.25

Cd, 48 8.643 4.7370 1.17731 0.799 2.325±O.006 1.835±O.010 0.29

Ni,28 8.89 7.5431 1.19155 0.983 4.251±O.033 1.696±O.026 0.66

Ta, 73 16.70 5.1035 1.17459 0.634 2.920±O.116 1.467±O.049 0.66

3.445±O.010 1.204±O.008 0.29

Ti,22 4.53 5.5987 1.18836 1.202 1.938 1.516 1.41

4.796±O.025 1.090±O.011 0.34
4.876 0.973 0.49

Element u P N p. Ut Pi u. p.
Z km/s Mbar ~ood/bad 'OD.% Mbar kmls Mbar kmls Mbar
Cu,29 0-533 0-32000 227-75 1.05 204 4.8 4.7 23 73

Fe, 26 0.8-513 0.310-26000 250-10 1.12 467 2.5 1.6 18 41

0-0.333 0-0.132 8-0 0.06 0.132 0.33 0.13

AI, 13 0-384 0-5100r 608-31 1.60 246 1.0 0.2 3.4 0.9

U,92 0.2-562 0.150-72300 306-38 1.95 67 2.0 2.1 12 42

Ph, 82 0.16-478 0.040-31200 140-48 1.45 540 1.7 0.9 10 18
MO,42 0-530 0-35000 83-5 1.07 66 13 27 14 31
Cd, 48 0.6-487 0.2-25100 48-13 0.96 34 1.4 0.6 11 17

Ni,28 0.1-554 0.040-34400 90-3 2.92 9.7 2.7 2.1 18 46

Ta, 73 2.2-567 2.2-65600 10-0 0.89 25 3.7 5.2 17 72
0.4-2.2 0.3-2.2 38-3 0.87 2.2 2.2 2.2
Ti,22 8.2-432 5.1-10600 3-0 1.12 137 28 48
0.78-8.2 0.2-5.1 53-0 1.14 5.1 8.2 5.1
0-0.78 0-0.2 6-0 0.60 0.2 0.8 0.2
 4. Wide-Range Characteristic Thermodynamic Curves 133

small and seen only in especially precise experiments. Pure copper is very
ductile. That is why its shock-wave measurements are in excellent agreement
with Bridgman's static compression data for both the sound velocity, Co, and its
derivative, bo (this is a rare case). Note that this comparison employs the special
treatment ofEq. (4.10).
For copper there are very many experimental shock-wave measurements at
modest pressures. Russian and American data are in a good agreement, and
scatter of the points isn't large (Fig. 4.6). French and especially Swedish data
are insufficiently accmate (Fig. 4.5 and crosses in Fig. 4.6), and were discarded
after the first stage of data analysis.
At pressures p~ 10 Mbar there are only a few reliable experimental points
(Fig. 4.7). However, they uniformly cover the entire intermediate rnnge between
the initial straight part and the QS line, and confirm the good accuracy of ap-
proximation (4.12). Figure 4.7 also shows two joined parabolas, i.e., a spline
approximation [31,32] that can be seen to be significantly worse: It has a sys-
tematic deviation -1.4% from experimental points in the intermediate rnnge,
and its maximal difference from the smooth approximation (4.12) is slightly in
excess of 2 %.
All this provides a very small statistical error of approximation (4.12) for
copper; it is 0.1 % in the pressure rnnges 0-5Mbar and 50 Mbar-70 Gbar, and is
no worse than 0.2% at intermediate pressures (value BDa = 0.16% in Table 4.3 is
the mean estimate). This accmacy is unique; it makes pure copper the best stan-
dard metal for shock-wave measurements by the impedance-match method in
any region of pressures beginning from tens kilobars to gigabars.

0- u km/s
•
Cu

&

4 u kmls
o 2

Figure 4.6. The lower-pressure part of the Cu Hugoniot. The dots designate good explo-
sive experiments, crosses designate bad experiments, the thick line is the approximation
(4.12), and the dashed line is the linear relation (4.11).
134 N.N. Kalitkin and L. V. Kuzmina

This accumcy may seem exaggerated, because the mean point scattering is
1.05% for all good points of the compendia. But this isn't so. There are N= 225
good points, and we approximated them with 2 fitting parameters. This permits
the scatter to increase by N I12 times (if the approximation formula is adequate, of
course) and confirms our estimate.
Note that brass in American experiments and Fe in Russian experiments
were chosen as standards. The copper standard proposed here has significantly
better accuracy and a much wider range of applicability. It would be very inter-
esting to revise old experiments (where copper was one of two contacting met-
als) with this new standard. Probably it will improve their interpretation.
It is also interesting that copper has a long initial straight part of the D(u)
curve. This is why the values Co and bo given in different publications [6-8,
28-32] coincide satisfactorily.
Finally, we mention the circles in Fig. 4.7. They designate English meas-
urements made at pressures of 10-20 Mbar using a powerful laser and the best
modem diagnostics [35]. They lie around our approximation and have no visible
systematic error, but their scatter is -10 times more than for traditional explo-
sively-driven systems (and -50 times worse than for the best measurements on
light gas guns). Detailed analysis shows that the accuracy of measurement of
laser target thickness is quite sufficient, but errors of time measurement are too
large to permit obtaining useful results (we predicted this in the 1970s, when
many investigators enthused concerning laser driven shock waves). Perhaps
laser-driven shock-wave experiments have no chance of producing useful data in
the immediate future.

o 10 20 30 40

Figure 4.7. The Cu Hugoniot for high pressures. The dots designate good explosive
experiments, the crosses designate bad experiments. the circles designate laser experi-
ments. the thick line is the approximation (4.12), thin solid lines represent results ob-
tained using the QS model and spline [32], and the dashed line is the straight Hugoniot
(4.11).
 4. Wide-Range Characteristic Thermodynamic Curves 135

Iron. This metal has several phases, but only one polymorphic transition on the
main Hugoniot at P = 132 kbars is easily seen. This transition occurs when the
body centered cubic lattice transfonns to an hexagonal lattice (melting is only
slightly perceptible). The Hugoniot of the first phase is almost coincident with
the cold compression curve, and shock wave measurements by Bancroft et. al.
(they are included in [6,7]) are in excellent agreement with static measurements
by Bridgman for both Co and bo; these values are shown in Table 4.3.
A slightly stronger shock wave splits into two waves: The fIrSt wave corre-
sponds to the phase transition point and the second wave propagates at a lower
velocity and compresses the high-pressure phase to its final density. When
P ~ 0.3 Mbar the second wave overtakes the :first, forming a single shock dis-
continuity. An elastic predecessor propagating with the longitudinal sound ve-
locity Cl =5.934±0.016km1s is easily seen in Fe. Pin contacts respond to it
instead of the shock wave at the very low pressures, P = 6-15 kbar.
This is why the approximation (4.12) can be used for Fe only for
P~0.3Mbar. The compendia [6-8] contain 250 good experimental points at
modest pressures and in the intermediate region Some Russian measurements
among them were made by the impact method, so they are absolute and espe-
cially reliable. Therefore, the approximation (4.12) for Fe has excellent accu-
mcy, 0.1-0.2%, and is as precise and reliable as for Cu. These data are shown
in Fig. 4.8. One may also see that Eq. (4.12) is certainly better than a spline
approximation [32]. In the intermediate region the spline deviates systematically
by 1-2 % from experiments.
An additional proof of the reported accumcy gives an assessment of the er-
rors of different labomtories. Figme 4.4 shows 22 precise measurements made
using light-gas guns at P= 1-4Mbar, Their scatter is 0.3%, and systematic
deviation from the approximation is only 0.02 %, i.e., the agreement is excellent.
This permits recommending the Hugoniot (4.12) for Fe as the second shock-
wave standard in the mnge 0.3 Mbar:S: P:s: 26 Gbar. This is a revision of the old
Russian standard, so it would be very desirable to revise all data analysis of old
measurements that employed this standard. The new Fe standard has the same
accumcy as the Cu standard, and has only two small defects. First, it is invalid
for P < 0.3 Mbar and, second, its initial straight part covers a significantly nar-
rower mnge than for copper, so values of bo and Co vary more strongly among
the different labomtories and forms of approximation.
Aluminum. Data analysis proved very difficult for this metal. There were espe-
cially many measurements, more than 600 points, covering a huge mnge up to
superhigh pressures without interruption However, the accumcy was low, the
data having a mean scatter of 1.6%. Russian measurements were made with
almost pure aluminum, but most American experiments used AI alloys contain-
ing 3 -4 % (by weight) of Cu and other elements.
136 N.N. Kalitkin and L. V. Kuzmina

20 O-U km/s
.
+

Fe
15

10

U km/s
0
0 20 40 60

Figure 4.8. The Fe Hugoniot. The dots designate good experiments, the crosses desig-
nate bad experiments, the thick line is the approximation (4.12), the thin solid lines repre-
sent the QS model and the spline [32], and the dashed line is the linear approximation
(4.11).

At :first it seemed that properties of different shock loaded alloys differed

significantly. Separate data analysis of each alloy gave different values of bo
from 1.36 to 1.69 and, with small statistical errors, even values of Co differed
significantly. For pure aluminum, the value of Co coincided with all Bridgman
static compression data. and bo was close to the value given in one Bridgman
publication. Differences from other publications [6-8,28-30] were significant
(although these publications didn't agree among themselves). A more detailed
analysis showed another reason for this discrepancy.
The approximation (4.12) for AI tends to the QS line vel)' rapidly, and the
two are vel)' close together even at P -1 Mbar. The high-pressure limit of its
initial straight part doesn't exceed P~0.2Mbar. Nevertheless, nobody noticed
this because of large experimental errors, and all data analyses for points up to
P~2Mbar were made with the linear approximation (4.11). This data analysis
could not give correct results. Therefore, all analyses previously performed for
AI are unreliable for P>0.2Mbar. This circumstance is vel)' unpleasant, be-
cause old AI Hugoniots were used for many years as shock-wave standards in
both the United States and Russia (though Vodolaga noticed in 1985 that data
analysis of experiments conducted using old Fe and AI standards gave easily
seen distinctions).
A similar situation arises for the prediction [33] of a peculiarity of the AI
Hugoniot at pIPo ~ 2 because of details of the way in which inner electron shells
are filled. This compression corresponds to P ~ 5 Mbar and u ~ 10 km/s, at which
point the D(u) curve practically coincides with the QS line and is almost
 4. Wide-Range Characteristic Thermodynamic Curves 137

straight Experiments that seemed to confinn the reported peculiarity were rather
inaccurate, so the issue was obscured.
Joint treatment of all experimental data for pure aluminwn and alloys was
performed. The results obtained are shown in Fig. 4.9. One sees a huge scatter-
ing of experimental points at both low and high pressures, including the location
of the predicted peculiarity. The nwnber of points is large enough that the accu-
racy of the approximation (4.12) can be estimated to be 0.1-0.2%. This permits
its recommendation as the new shock-wave standard for experiments with light
substances (although it seems less reliable than the Cu and Fe standards). In this
case one should use pure AI (admixtures less 1% by weight) rather than hard
alloys. Then the approximation (4.12) will be applicable even for very weak
shock waves.

Uranium. This metal is reminiscent of AI. There are also many measurements
up to the very high pressure P'i'l:l67 Mbar [36]. The mean scatter of the points is
large, - 2 %. Russian experiments used natural uranium, but most American
publications dealt with weapon-grade U23S, as far as one can infer from the re-
ported normal density. There are many measurements for alloys, but we didn't
use them even when admixtures were small. Here the range of the initial linear
part of the D(u) curve is rather small: P~ 2Mbar. The trend toward the QS line
is neither fast nor slow. Two high-pressure experimental points [36] correspond
to sufficiently high pressures that they lie almost on the QS line (Fig. 4.10).
Equation (4.12) yields a satisfactory approximation for the Hugoniot of U.
The nwnber of points is so large that, in spite of their significant scatter, the
final accuracy can be estimated to be 0.2-0.3%. This permits use of the U
Hugoniot (4.12) as a shock-wave standard for especially dense substances. Its
accuracy is slightly worse than that of the Cll, Fe, and AI standards.

8 D • u km/s +
+
+

•
7

+
+

o 4 8 12
Figure 4.9. The AI Hugoniot. Notation as given for Figs. 4.6 and 4.7.
138 N.N. Kalitkin and 1. V. Kuzmina

u km/s
o 4 8 12 16

Figure 4.10. The U Hugoniot. Notation is as for Figs. 4.6 and 4.7.

Shock-wave data begin at P = 25 kbars, and they are in a good agreement

with approximation (4.12) even at this low pressure. However, Bridgman's
static measurements made in different years for pressures up 10, 40, and
100 kbars don't agree among themselves or with shock-wave data This may be
caused by polymorphism at pressures of tens of kilobars, which is difficult to
detect in both dynamic and static experiments. Nevertheless, it would be reason-
able to use the uranium standard for P > 150 kbar.
Lead. This metal exhibits two polymorphic transitions for P < 40 kbar, so it is
difficult to describe static and dynamic compression data in a consistent manner.
Lead melts in a shock wave of amplitude in the range 100-300kbar, but this
does not significantly affect the Hugoniot. Therefore, approximation (4.12) is
applicable in the range P ~ 40 kbars.
Experimental points for Pb are well distributed over all interesting pressure
ranges, including the record P -500 Mbar. The number of points is large, but
fewer than for Fe or Cu, and their scatter is larger. Therefore, the accuracy of
approximation (4.12) is significantly worse and may be estimated as 0.4-0.5%.
At superhigh pressures in the range 300-500Mbar the difference between ex-
periments and the approximation is 1-2%, but this means nothing because ex-
periments were made by the impedance-match method using old standards, and
are therefore unreliable.
The new Pb Hugoniot is significantly better than the old one, but is less ac-
curate than the new U, or especially Fe and Cll, standards. Therefore Pb cannot
be recommended as a standard for dense substances. Note also, that the range of
the initial straight part of the Hugoniot curve is small (P < 1 Mbar), so one
should pay no attention to differences of the values of Co and b o obtained by
different authors (moreover they are not large).
 4. Wide-Range Characteristic Thennodynamic Curves 139

Molybdenum. This metal has been investigated experimentally at the modest

=
pressures P < S Mbar. Its static and dynamic values of Co at P 0 agree well, and
the scatter of experimental points is small. The approximation (4.12) is applica-
ble from very low pressures and the accuracy of the initial part is estimated to be
0.2-0.3%. It is difficult to estimate accuracy for P> 5Mbar, because the inter-
val from this boundary to the QS line is very large and no experiments exist
there. All this makes Mo a good standard for investigation of materials of mod-
erate and high densities, but only for P ~ S Mbar. Note also, that the initial
stmight part of (4.12) for Mo is extremely long.
Cadmium. This metal has been investigated experimentally for pressures
P < 4 Mbar, but there are also 3 points at high pressures. The dynamic and static
measurements made for Cd differ significantly at small compressions. The num-
ber of experimental points is not large, but their scatter is small so the reliable
part of approximation (4.12) occupies the range 0.2~P~4 Mbar with estimated
accuracy of =0.3 %.
Nevertheless, the approximation (4.12) tends to the QS line quickly, so the
accuracy in the intennediate pressure range may be -0.4 %. This makes Cd a
good standard at modest pressures.
Nickel. This metal has been investigated for pressures P < S Mbar, but there are
few experimental points and they have a large scatter. Bridgman's statistical
data obtained in different years are contradictory; their Co value varies from
4.2 to 4.7 km/s (dynamic experiments give about 4.2 km/s), but the b o value is
meaningless. With these data, the estimated accuracy of approximation (4.12) is
0.7% from 40 kbar to S Mbar. The accuracy above S Mbar is difficult to esti-
mate, though it is probably only a little worse.
This accuracy is insufficient for acceptance of Ni as a standard, but it is sig-
nificantly better than previous approximations. In [6-8,28-30] there are quite a
few reported values of Co and bo calculated with linear approximations for the
range P ~ 4.S Mbar or the parabolic approximation for P ~ 10 Mbar. Both meth-
ods are unsatisfactory and the results are unreliable because the true initial range
is very small: P < 2 Mbar.
Tantalum. A graph of experimental measurements for Ta in (D-u) versus u
variables exhibits a discontinuity of slope at u - 2 km/s, P - 2 Mbar (Fig. 4.11).
The change of slope is significantly greater than for the usual polymorphic tran-
sitions, and these transitions lie mostly below 0.1 Mbar and some of them at
0.1-0.S Mbar. Therefore only a change in the filling of electron shells can ex-
plain this discontinuity. This effect was investigated in [33] for some other met-
als, but not for Ta.
The approximation (4.12) can be used only above a discontinuity; below it
one must use the linear equation (4.11). In the case of the Ta data, the significant
scatter of the experimental points precludes finding the location of the disconti-
140 N.N. KalitkinandL.V. Kuzmina

TFP •

o 2 4 6 8 10

Figure 4.11. The Ta Hugoniot. The notation is as on Figs. 4.6 and 4.7. The electronic
phase transition occurs at the point at which the two lines cross.

nuity by examination of the graph, so we used the method that brought success
in [34]: We varied the location of the discontinuity in our calculations as an
additional parameter of least square method. Therefore, we fitted 5 parameters,
including two above and two below the discontinuity. The final parameters of
each approximation are shown in Table 4.3, and the parameters of the transition
point are
u=2.l6km1s, D=6.04km1s, P=2.l8Mbar, and p/po=1.559. (4.14)

The resulting broken line is shown in Fig. 4.11.

Previously, no one noticed the electronic transition in this metal. Only our
sensitive method permitted finding it with assurance and calculating its parame-
ters. Our Ta Hugoniot has a good accuracy, RjO.3 % for the lower-pressure part,
where more than 20 measurements were made. Even for the higher-pressure part
the accuracy is sufficient, -0.7%.
What is the type of this transition? If it is a first-order phase transition, then
density must increase discontinuously and two shock waves will exist simulta-
neously above the transition point (as for Fe), with the velocity of the first shock
being independent of the pressure of the main (second) shock wave. In that case,
the graph of Fig. 4.11 must contain a part for which D = const. when D-u is a
decreasing function of u. However, Fig. 4.11 shows that the curve of D-u ver-
sus u increases monotonically and continuously but has a discontinuity of slope.
This behavior certainly corresponds to a second-order phase transition.
In the 1960s investigators discussed the question of whether electronic tran-
sitions were true phase transitions or smooth but strongly curved graphs. Judg-
ing by Fig. 4.11 in case of Ta, it is a sharp change of slope and most probably a
 4. Wide-Range Characteristic Thennodynamic Curves 141

true phase transition (though low accuracy of the experimental data doesn't
pennit guaranteeing this conclusion). Perhaps experiments on light-gas gun may
finally answer the question because of their high accuracy.
Note also that, for the lower-pressure phase, the dynamic curve doesn't coin-
cide with the static curve as P~O. Therefore, one should use the linear ap-
proximation (4.11) only for P~0.25 Mbar.
Titanium. This metal behaves like Ta, but is more complicated. A polymorphic
transition at P ~ 0.2 Mbar has been discovered experimentally. A slightly
smoothed electronic transition was predicted [33] on the cold compression curve
at P~ 2.8Mbar with a density change p ~ 7.9-11.7 glcm3, but experimentalists
have not seen it on Hugoniots.
We surely saw both transitions on the Ti Hugoniot with our method. The ex-
perimental accuracy for Ti is good (~1.1%), parts of first and second phases
contain a sufficient number of experimental points, and dynamic and static ex-
periments for the first phase are in good agreement. Therefore, the coefficients
for these two phases shown in Table 4.3 are reliable. However, the part of the
Hugoniot on which the material is in the third phase contains only 3 experimen-
tal points, so the estimate of its coefficients and the phase transition point is
rough.
The final results follow. Taking Co and bo for the first phase from Bridgman's
static data, we find the parameters of the polymorphic transition point:
u = 0.778km1s, D = 5.644km1s, P = 200kbar, p = 5.254 glcm3 . (4.15)

The density given corresponds to the first phase at the transition point. The value
of D practically coincides with the velocity D = 5.633 ± 0.097 kmls of the first
shock wave in the two-wave structure, measured in experiments in the range
0.4 ~ u ~ 0.8 km/s. This seems strange because the two-wave structure must
appear at u values above, but not below, the transition point; perhaps this can be
explained by a significant error of the static value of bo (co is reliable).
Experimental points are rare in the vicinity of the second transition, but we
are definitely assured that there is no part of the Hugoniot with D = const. (D-u
decreasing). Therefore, it is a second-order phase transition (that may be
smoothed) and not one offirst order. Its approximate parameters are:
u=8.17km1s, D=13.70km/s, P=5.07Mbar, p=I1.21g1cm3 . (4.16)

The fact of this electronic transition and the value of p surely confirm the pre-
diction [33] and illustrate the possibilities of our method of data analysis.

4.2.7. Conclusion
Wide-range principal Hugoniots for 10 metals are constructed in the form of
simple, explicit D(u) equations. Their accuracy is 3 -10 times better than for any
142 N.N. KaIitkinandL.V. Kuzmina

previous publication. They are applicable throughout the huge pressure range
from tens (or hundreds) kbar up to tens of Ghar.
Record precision of 0.1-0.2 % was achieved for Cll, Fe, and Al, which
makes these materials unique shock-wave standards. Using these new standards
for another analysis of existing experimental data may significantly improve
accuracy and eliminate some discrepancies apparent when the data were ana-
lyzed using old standards.
Electronic transitions were found on Ti and Ta Hugoniots at P - 2-5 Mbar
(they are induced by changing of the order of filling of electron shells). They
were predicted for Ti and sought in vain for more than 30 years. Only this
method has pennitted their discovery in the experimental data. This indicates its
sensitivity.

4.3. Copper Standard Global Isotherm

4.3.1. Global Zero Isotherms
The important problem is to construct wide-range equations of state. The essen-
tial part of this problem is to find global zero isotherms, i.e., cold static com-
pression curves P(p), applicable and precise at pressures 0 :s; P < 00. Geophysical
and planetary models, processes of shockless compression of thermonuclear
targets, etc., are very sensitive to them Low-pressure parts of these curves are
usually found from static and shock compression experiments, and high-pressure
parts of the curves are calculated from theories. However, there is a very wide
gap between the ranges that can be studied by each of these methods. It is com-
monly filled with approximations based on certain model arguments.
Some realistic global approximations were constructed in Russian publica-
tions fu 1960s-1990s (we know of no analogous publications abroad, though
such approximations surely were constructed, judging by the SESAME library
of material properties prepared at Los Alamos). We compared these publications
and found that their P(p) curves differed by as much a 25 %, and none of them
had a serious basis. Therefore, the problem of construction of precise global
curves is still open.
Here we propose a method for constructing global P(p) zero isotherms for
materials without phase transitions. Copper is chosen as an example. Its crystal
fcc (face centered cubic) lattice is dense packed, so no phase transitions occur
due to static compression. Pure copper is plastic, and this provides isotropy of
static compressions and their good agreement with dynamic compressions.
Though copper melts when subjected to strong shock compression, this phase
transition affects the Hugoniot only slightly. The number of experimental meas-
urements for copper is very large, and their accuracy is better than for other
substances. Therefore, copper is the most suitable material for use as a standard.
 4. Wide-Range Characteristic Thennodynamic Curves 143

Here we constructed a precise room-temperature cooper isothenn (it is more

convenient for applications than a zero-temperature isotherm). Its errors don't
exceed 0.2-0.3% at compressions 0"=p/Po<2.4 or 0">60, and not more than
1-2% at intermediate compressions. This is 7-10 times better than any curve
previously constructed. This isotherm is recommended as the standard for analy-
sis of experimental data on relative compressibility with other substances.
Pressure for static compression in diamond anvil cells is measured by the
ruby gauge. We found its systematic deviation from our Cu standard to be about
1-2% at pressures O:s; P ~ 1 Mbar; this testifies to the gauge calibration error.
We proposed a new gauge calibration that decreases the pressure measurement
error to 0.2-0.3%, i.e., improves experimental accuracy 5-7 fold.

4.3.2. Theoretical Data

Hypercompressed matter with 0" = p/Po ~ 106 behaves as a homogeneous electron
gas (HEG), and its pressure is
p ~ 1003.60(pZ I A)5/3 . (4.17)

In this equationA is the atomic weight of the element (the mean atomic weight
for compositions). Pressure, density, velocity, and light wave length here are
measured in
[P]-GPa, [p]-glcm3 , [u]-km/s, [A]-nm. (4.18)

Equation (4.17) is valid up to the compressions at which the atom begins to

transform into the neutron state.
When compressions decrease, the accuracy of Eq. (4.17) becomes insuffi-
cient so, for O"~ 104, one should use the 1F model [9,10,37]. At lower densities,
0" ~ 60, the QS model [11-15] must be used. These models are constructed from
the first principles only, but they account for neither the atomic shell structure
nor the solid-state band structure. Therefore, the lower boundaries of their appli-
cability lie far from normal (room) conditions.
At hypercompressions both models have REG (4.17) as the asymptotics.
Their thermodynamic functions expand in power series of the variable p-I13, and
some of the lowest order coefficients are known. However these series converge
rapidly only when 0" ~ 10 4, so they are almost useless.
The 1F model is the quasi-classical (WKB) approximation to the
Hartree-Fock model, and the QS model accounts for the first quantum and
exchange corrections; the last ones are the first even term of the series expansion
on iliV powers, the second term being omitted. Therefore, the relative error of
the TF model may be estimated as its ratio to the QS model:
144 N.N. Kalitkin and L. V. Kuzmina

£(p)=I- PQs(p) . (4.19)

PTF(p)

The value £2(p) may be a reasonable estimate of the relative error of the QS
model. The lower boundaries of applicability for these models, shown above,
correspond to £ R:I 0.01 for the 1Fmodel and £2=0.01 (£= 0.1) for the QS model.
Let us recall that there are complicated FD, HFS, MHFS, and other quantum
mechanical· models that might be expected to provide a better description of
compressibility. However, pure first-principle models gave no better agreement
with experiments than the QS model. Models with adjustable parameters were
more accurate, but the fact of fitting them to experimental data reduces them to a
certain kind of complicated interpolation so the simple interpolation, described
below, is no less meaningful.

4.3.3. Dynamic Data

These data and their analysis in D(u) variables were described above in detail.
Equation (4.13) for Co with coefficients from Table 4.3 gives the principal
Hugoniot, PH(p), with high precision [38]. At low pressures this approximation
tends to the classical form (4.11):
D R:I Co +bou, Co =3.923 ±0.OO2 km/s, bo =1.511±0.003. (4.20)

For P~ 1-2 Mbar the accuracy of Eq. (4.20) may be estimated to be 0.10-
0.15%.
The principal Hugoniot CUlVe begins at the normal (room) state of the sub-
stance: P(Po) = 0 and To R:l20 -26°C. The normal density of Cu varied in experi-
ments [6-8] from 8.90 to 8.93, but its influence on the coefficients (4.20) is
very small. So, henceforth, we choose the crystallographic measurements for the
normal density of Cu:
po =8.934 g/cm3 • (4.21)

Variations of room temperature don't influence these figures. The coefficients

(4.20) are responsible for the initial slope and CUlVature of the Hugoniot CUlVe:

(dPH/dp)o=c~, (d2pH/dp2)O=(4bo-2)c~/po. (4.22)

Pure copper is plastic, and its shear strength is small. It behaves almost as a
liquid, so its normal isentrope has an initial slope and CUlVature practically coin-
ciding with Hugoniot values (4.22). But, at high pressures, this isentrope has
nothing in common with the Hugoniot CUlVe and almost coincides with the
room-temperature isotherm. This is because the normal entropy is small and
both CUlVes tend to the zero isotherm. Therefore, Eq. (4.17) will be its asymp-
tote.
 4. Wide-Range Characteristic Thermodynamic Curves 145

Note that one must use initial values of Eqs. (4.20)-(4.22) for construction
of the normal isotherm, but not as the complete information about the principal
Hugoniot: The difference between these curves increases rapidly as a function of
compression (1 % at cr ~ l.09 and 10% at cr ~ l.37 for copper).

4.3.4. Approximation
The idea to use a power series expansion in terms of the variable p- l13 for ap-
proximation was proposed by Kormer in 1960. The most successful was the cold
compression curve approximation by the sum [30,39,40]

(4.23)

the other form [41] gave worse results. The coefficient ~5 in [39,40] was taken
from the asymptote (4.17), but did not satisfy it in [30] (it was bad). Additional
requirements were also imposed: fIrst, to satisfy the normal density condition
P(po) = 0 and, second, to describe other reliable theoretical and experimental
data as well as possible. Different authors formulated the second requirement in
a different ways, and their resulting curves differed radically.
Moreover, the coefficients ~n alternate in sign so one must write them with
many signifIcant fIgures. One can eliminate this defect and simultaneously ful-
fIll the normal density condition by transforming (4.23) to the form

(4.24)

the connection of coefficients bn and ~n is evident. One may extend Eq. (4.24)
by summing to arbitrary N. In this case the coefficients may also be chosen so
that this equation has the asymptote (4.17). The coefficient b n needs fewer fIg-
ures than ~n. The sensitivity of cold compression curves to the second type of
requirement does not decrease.
Table 4.4 contains coefficients bn for copper corresponding to the approxi-
mations of [39,30,40]. It is seen that coefficients of different publications differ
enormously. This is connected with the sensitivity of the coefficients to addi-
tional constraints, and is evidence of certain difficulty.

Table 4.4. Coefficients bn for Cu approximation (4.24).

reference bl b2 b3 b4 bs
[39] 10.726 37.l19 45.232 142.786 34.095
[30] 10.967 32.967 23.241 351.199 -194.775
[40] 1l.855 -20.771 558.967 -91l.557 645.150
this chapter 10.727 32.887 53.763 81.101 93.011
146 N.N. Kalitkin andL.V. Kuzmina

Another approximation proved the most successful although it had fewer co-
efficients than Eq. (4.24):
3
P(p) ~ p5/3(I-x)exp[y(x)), y(x) = ~>n(l-x)n. (4.25)
11=0

This equation is not equivalent to Eq. (4.24), but describes the normal density
correctly. For proper description of the REG asymptotics (4.17), one must take

(4.26)

Let us also demand that the equation reproduce the initial slope and curvature of
the cold compression curve corresponding to Eqs. (4.22). This requires that

(4.27)

The fourth condition is the least square deviation of the approximation (4.25)
from the QS model, with account being taken of the estimated error of the
model, S2(p). This requirement can be expressed in the form

J[1-
1
o
PQS(p)]2 s-4(p)dx= min,
P(p)
(4.28)

where P(p) is the approximation (4.25).

Two coefficients for copper that follow from Eqs. (4.20), (4.21) and (4.27)
are
ao = 2.3724, a1 = 3.0660. (4.29)

The last two coefficients, a2 and a3, may be found by numerical solution of the
system of two equations, (4.26) and (4.28). Equation (4.28) is nonlinear, but this
problem transforms to minimizing a function of one variable and is easy to solve
by the golden cross method. The numerical results are shown in Table 4.5 and
Fig. 4.12. This room-temperature copper isotherm is recommended as the stan-
dard
Figure 4.12 also contains curves for the TF model, the QS model, and the
principal Hugoniot. It is seen that the standard (4.25) lies very close to the QS
model for 0~x~0.25 (i.e. cr~60), when S2~0.01. Therefore, our global ap-
proximation (4.25) is confirmed convincingly by the theory in this region. When
x increases, the accuracy of the QS model worsens quickly, and the global ap-
proximation deviates from it
 4. Wide-Range Characteristic Thennodynamic Curves 147

5.5

5.0

4.5-
:::::..................
,.,........
........
Y ............
4.0 -
................ ,
3.5
• \
"

3.0
"
.
"
~~.".
2.5

0.0 0.2 0.4 0.6 0.8 1.0

x
Figure 4.12. The room-tempemture isothenn of Cu in special variables. The solid line
designates the standard (4.25), the dashes designate the QS model, the dots designate the
TF model, and dashes and dots designate the principal Hugoniot.

Table 4.5. Coefficients an for Cu approximation (4.25).

reference ao al a2 a3 x interval

this standard 2.3724 3.0660 0.8355 -0.6700 0.00-1.00

[42] 2.3727 2.9822 0 0 0.99-1.00
[43] 2.3621 2.7450 4.2183 0 0.90-0.99
[44] 2.2284 4.8669 -4.8025 0 0.84-1.00
[29] 2.3309 3.2243 0.8013 0 0.81-1.00
[45] 2.3628 3.4842 0 0 0.76-0.90

4.3.5. Static Compression

Only the very beginning of a Hugoniot curve coincides with an isentrope and,
for decreasing x, a Hugoniot deviates quickly upward from the isentrope (it is
noticeable even at x = 0.97). For this reason, static compression experiments are
needed to provide a better foundation for the standard approximation in a large
regionx~ 1.

Bridgman's measurements for Cu made using a piston device [42] are very
accurate and agree well with the Hugoniot standard described above, but they
cover only a tiny region P~30 kbar (0.99~x~I). Diamond anvil cells [43]
cover a rather wide region P~ 1 Mbar (0.9 ~x~ 1). Densities measured in these
cells by the crystallographic method have the high accuracy, 0.15%. However,
148 N.N. Kalitkin and L. V. Kuzmina

pressures were detennined by ruby gauges calibrated from shock-wave experi-

ments with old reference metals. Their accuracy is insufficient for our purpose,
so these data need special consideration.
There are also isothenns [29,44,45] constructed from shock-wave experi-
ments by special treatment with a model that accounts for the heat tenns in
equations of state. For this reason, they are less reliable. However, they cover a
significantly wider region P ~ 4 Mbar (0. 75 ~ x ~ 1). These data may be counted
as semi-experimental.
Experimental and semiexperimental data [29,42-45] were approximated
with Eq. (4.25) by the least square method. The requirement that they describe
the HEG asymptotics, Eqs. (4.17) or (4.26) was not imposed. Corresponding
coefficients a" are presented in Table 4.5, and the relevant curves are shown in
Fig. 4.13 along with the standard isothenn and standard Hugoniot. The differ-
ence Ay = 0.01 corresponds to a pressure deviation of 1 %. The standard
Hugoniot has high accuracy, 1'110.1% as x--+ 1, and all isotherms must be tangent
to this Hugoniot at the point x= 1. Experimental isothenns (except Bridgman's)
deviate from the standard Hugoniot by about 1-4 % for x I'll 1, and these devia-
tions measure their accuracy (the large deviation of the curve [44] is connected
with inadequate calculation of the normal density and should not be minded).
Deviations of the experimental isothenns from the standard isothenn don't
increase when x decreases from 1 to 0.75. On the contrary they often decrease,
so we may say that the static compression data confirm the global Cu isothenn
in the region 0.75 ~x ~ 1.0 (1 ~ cr ~ 2.4).

3.0

2.5

0.8 0.9

Figure 4.13. The initial part of the room-temperatw"e isotherm of Cu. The bold line
represents the proposed standard, thin lines represent experiments (figures near curves
show references), and the dash and dot line represents the standard Hugoniot.
 4. Wide-Range Characteristic Thennodynamic Curves 149

4.3.6. Discussion
The proposed standard is excellently confinned by theory in the range
0s;xS;0.25 and by experiments in the range 0.75S;xS;1. In the range
0.25 <x < 0.75 no theory is sufficiently precise or reliable, and static experi-
ments are impossible, so there are no data to check our approximation (4.25) in
this range. But, this range is not large in comparison with known regions, and
the low-compression part of the global approximation in variables y(x) is practi-
cally linear and "looks" to its high-compression part, which is also linear. One
may expect that this global approximation will be close to a straight line, and
our interpolation will be reliable.
An additional check was to construct a global approximation in the less suc-
cessful fonn (4.24), for which the curve differs significantly from a straight line.
Here the coefficients b n were also chosen from the requirements that it describe
the REG asymptote (4.17), tangency (4.22), and the least square approximation
for the QS model (4.28). Note that these coefficients are more sensitive to algo-
rithm details than the coefficients an. The calculated values bn are shown in
Table 4.4.
Figure 4.14 shows the deviation of all pressure curves (in percent) from our
standard global approximation (4.25). It can be seen that the deviation of our
control approximation (4.24) doesn't exceed 0.7% in the most unfavorable
range of x and tends quickly to zero near the boundaries. We may surely esti-
mate errors of the standard as 0.2-0.3% for OS;xS;0.25 or 0.75s;xS;1 (i.e.,
er ~ 60 or er S; 2.4), and up to 1- 2 % at intennediate compressions.

Ii%
25

20

15

10

-5

-10+----',.----,..-~-.-~-_._-~__,r__~---'-...,
X
0.0 0.2 0.4 0.6 0.8 1.0

Figure 4.14. Deviations from the standard Cu global isothenn. The bold straight line
corresponds to 8 =0 (the standard), thin solid lines represent previous global approxi-
mations of different authors, dashes represent static or related experiments, and the dash
and dot line is the standard Hugoniot. Figures near curves are numbers of the references
and 0 is our control approximation (4.24).
150 N.N. KalitkinandL.V. Kuzmina

Let US consider some known approximations shown in Fig. 4.14. This is in-
teresting because nobody has compared them and their large difference, easily
seen in Fig. 4.14, was unexpected.
One of the oldest publications [41] used a small number of experimental
points and an inadequate form of the approximation. First, two pieces were
joined at Xliii 0.8, as one may see from the discontinuity of the curve (though
formally it is smooth, it has large curvature at this spot). Second, the upper piece
does not satisfy the HEG asymptotics (4.17). Third, the curve converges too
quickly to the QS curve in both value and slope at (J l1li10-15. At such compres-
sions the QS curve itself has errors of -10 % and leads to large errors up to 20 %.
The approximation [40] has an even larger error, up to 260/0, though it used
an adequate form (4.23) and almost satisfied the HEG asymptotics (4.17). The
main reason for its failure is the requirement that it coincide with the QS curve
at (J l1li 8, which is too early. The other reason is inappropriate use of experimen-
tal data: The curve [40] in Fig. 4.14 crosses experimental curves instead of
blending smoothly into them. The strange values of coefficients bit [40] in Table
4.4 also indicate that this approximation is unsuccessful.
The approximation [30] has smaller errors, up to 150/0, though it doesn't ap-
proach the asymptote (4.17). The better results are explained by more accurate
fitting to experiments for x -+ 1, and also by a less precise approach to the QS
model. Nevertheless, errors are still significant
The approximation [39] has significantly better accuracy, S8%, although it
matches the experiments somewhat less closely than the curve [30]. The main
advantage of [39] is more careful fitting to the QS curve on the basis of the
criterion (4.28). The exact agreement of the asymptote with Eq. (4.17) also im-
proves the result. The defect of this approximation is that it requires the next
theoretical term of the expansion in powers of p -113 •
We see that the new global standard isotherm has at least 7-10 times better
accuracy than the best curves previously proposed. This is a new level of accu-
mcy. Moreover, the special variables y and x, and the form (4.25) have special
interest as the basis for the prospective method of constructing cold compression
curves of high precision for substances that don't undergo pressure induced
phase transitions.

4.3.7. The Ruby Gauge

Figure 4.14 shows that experiments conducted using diamond anvil cells [43]
deviate from our standard isotherm, and therefore the standard Hugoniot, up to
2% in pressure even at (J-+1. The standard Hugoniot accumcy is l1li0.1% in this
region, so this deviation must be induced by experimental errors in [43]. Let us
analyze possible reasons.
 4. Wide-Range Characteristic Thennodynamic Curves 151

Compressions in [43) are determined by x-ray measurements of crystallat-

tice parameters with a scatter of 0.15 %; evidently this is a real estimate of their
accuracy. However, pressures are measured using shifts of the ruby fluorescence
line (Ao = 693 nm) according to one of the two equations

AJ.~36.4P-3.SP' or P.3.808[(I+~~)' -1].

where A. is in nm and P is in Mbar. These equations coincide within 0.2 % at
pressures 0 ~ P ~ 0.8 Mbar. They were constructed by fitting to about 60 shock-
wave experiments with some metals (Ag, Cll, Mo, Pd) for which the experi-
mental pressures were determined by the usual dynamic compression techniques
with an accuracy of 1-2% and significant scatter. This calibration of the ruby
gauge pressure may have insufficient accuracy and lead to discrepancy.
At pressures P ~ 1 Mbar our standard Cu isotherm has accuracy better than
0.2 %. So it is natural to choose it instead of shock-wave experiments for ruby
gauge calibration. We fitted the function P(flA.), which combines our standard
curve and the [43) curve, with accuracy 0.1%:

flA.
P=2.784M ( 1 + -
)114 ,for50kbar~P~IMbar, (4.30)
73.8
where P is in GPa.
The calibration equation (4.30) decreases the pressure errors of the ruby
gauge to 0.2 - 0.3 %. This means that the accuracy of the diamond anvil cell
method can be improved 5 -7 times.
It would be very interesting and important to undertake a new analysis of all
previous experiments with the new calibration, Eq. (4.30), of the ruby gauge.

4.4. Plasma Microfields and the Thermal Properties

of Materials

4.4.1. Introduction
Equations of state have always been important in physics and technology. Wide-
range equations of state are usually constructed by joining different models at
the boundaries of their ranges of applicability [46-48). There are several meth-
ods for constructing such equations of state. The model of ionic-chemical equi-
librium (ICE) is used in all of them for the gas-plasma area.
The gas-plasma mixture becomes non-ideal at high densities, and therefore
the ICE model should take particle interactions into account. Usually this is
152 N.N. Kalitkin and 1. V. Kuzmina

provided by a model correction for non-ideality. Many such corrections have

been proposed [49-52]. Debye-type models or those for a one-component
plasma are the best known. However, none of these has been justified either
strictly theoretically or experimentally.
Over the last 20 years, the spectrum of experiments that have been carried
out directly indicates that microfields are the main factor determining particle
interactions in a plasma. The microfield interaction model gives the correct
number of spectrum lines, whereas the other models do not. However, no ther-
modynamic functions have been constructed on the basis of these representa-
tions.
Therefore, we propose an ICE model that can be used to calculate an equa-
tion of state. It is based on the notion of the microfield non-ideality (MFN) of
the plasma. We decided to develop a wide-range model of the microfield (be-
cause the existing models are either restricted in application, or require awkward
calculations). A comparison between calculations using the MFN method and
the best known nonideality models has shown that the MFN method is the best.
However, even this model becomes less accurate at liquid densities, and the
quantum-statistical model of the atom becomes applicable [1]. We show, using
the quasi-band model [5], how the ICE model transforms into the quantum sta-
tistical model, and we construct a wide-range equation of state that is more accu-
rate in the supercritical domain than all previously known equations of state.
The atomic system of units is used throughout this section.

4.4.2. Microfields and the Decrease in Ionization Potential

Microfield Models. The problem of how to calculate the microfield arose ini-
tially when computing the spectrum coefficient of absorption and the shapes of
the spectrum lines in a plasma. However, recent theoretical and experimental
studies show that fluctuating electric microfields significantly affect both the
optical and the thermodynamic properties of matter.
In the method described below, the distribution function of the ionic compo-
nent of the plasma microfield has to be recalculated repeatedly for a very wide
range of densities and temperatures (we assume that the rapidly changing elec-
tron fields do not substantially decrease the ionization potentials). Therefore, a
wide-range model of the ionic microfield is necessary, and it should not require
awkward calculations.
Let us consider the existing models. At first., the distribution function p (E)
of the microfield, i.e., the probability that a microfield of intensity E arises
spontaneously at the point where a neutral atom or ion is located, was found by
Holtsmark [53] for an ideal plasma. Various approximations were proposed for
 4. Wide-Range Characteristic Thennodynamic Curves 153

P (E) in strongly coupled plasma. but most of them are of no interest because of
their restricted applications.
Simulations of p (E) by the Monte-Carlo (MC) method are considered to be
the most accurate. This method can be applied to a plasma that is arbitrarily non-
ideal, and it simulates the distribution function well at the limit of an ideal
plasma (Holtsmark approximation) and for a dense superheated fluid (the model
of simple harmonic oscillators [54]). This method can even be used in calculat-
ing the crystallization of plasma fluids at very large densities. Electrons can also
be taken into account by the MC method [55] but: i) This multiples the calcula-
tion time by 100-1000 and, ii) A model for the pseudo-potential of the elec-
tron-ion interaction has to be specified and this decreases the reliability of
results and, iii) It is not clear how to accurately take into account the effect of
the rapidly changing field of the electrons on the decrease in the ionization po-
tential.
Golosnoy [56] considered the influence of electrons on the distribution func-
tion of the ion microfield. Three wide-spread models were compared: i) elec-
trons form a uniform neutralizing background (the one-component plasma,
OCP), ii) the ion component of the microfield, ICM, which is calculated in a
real electron-ion plasma and, iii) the low-frequency component of the micro-
field, LFCM, is taken into account (the quasi-steady state part of the electron
microfield given by a model that is added to the ion field).
For a nonideal plasma, it has been shown that the distribution functions of
the microfield as calculated by these models differ by a large factor (Fig. 4.15).
However, the distribution of microfield can be obtained quite accurately in these
three cases using the same mathematical apparatus, namely the approximation of
non-interacting quasi-particles (the models differ only in the approximations of
the effective interaction potentials and the effective fields of the ions in the
plasma). This approximation was first applied with the OCP [57], and then
adapted to the LFCM [58]. Calculations [58,59] showed that this approximation
yields a fairly accurate description of the test MC calculations corresponding to
the OCP and LFCM models. Only the ICM model remains untested. Let us
show how to use the approximation of noninteracting quasi-particles for the
ICMmodel.
Model of Polarization Cbarge for ICM. Consider a plasma at a temperature
T. It consists of i type of atoms and their ions baving various levels of ionization
(the maximum degree of ionization is Zi) and it also contains electrons. The
relative concentrations of the ions is Xik (k is the ion charge), and that of the
electrons is Xe. We search for the probability density p(E) that an instantaneous
ion microfield with intensity E arises at a point where a particle with a charge ko
is located. For p(E) the integral representation [54] is
154 N.N. Kalitkin and L. V. Kuzmina

,'
,, ,
1.2 " \---~
\
\
~o.a : \",~"v""ocp

kpO.4 ' ,,
,,,
", l' ..

,
l
0.0 0.5 1.0 l.5 h\
o.o.j.J'~+----+--':".........-+-~j::;:+~;::::;:~
U 3.5 4.0

Figure 4.15. The distribution function peE) of the microfield in a hydrogen plasma
(k l = 1 , Xl = 1) with r = 1.28 determined by various models. The charge of the test particle
is k o= 1. The model names label the curves.

2E
p(E)=- foo
sin(fE)Q(f)fdf, (4.31)
1t 0

where

Q( £) = (exp (ilE) ) (4.32)

and 1 is the vector of the microfield. The intensity vector of the microfield,
which is not averaged over the directions, is

E=L krjk
3 '
j,k r jk

and rjk are the points at which the surrounding charges are located. The angle
brackets in Eq. (4.32) denote the statistical average.
We introduce the common concentration of particles with a given charge:
Xk = LjXjk. The average radius of an atomic cell, R, and the average electron sepa-
ration, Re , are obtained from the relations (41t/3) R 3 = V and (41t 13)Ri Xe =V ,
respectively (V is the volume of one heavy particle, and X. = Lkkxk is the relative
concentration of electrons). We measure the microfield in the units of
Eo =11 m n
and r = 1/(R. is taken as the plasma parameter.
In the model of noninteracting quasi-particles, which was initially proposed
for the OCP [57], the function Q(f) is approximated by

InQ(f) =- ~
~k
{Xk 41tne
Xe
fOO r2gok(r) E!(r)
0 Ek(r)
[1- Sin[f;k(r)]]}dr, (4.33)
fEk(r)
 4. Wide-Range Characteristic Thermodynamic Curves 155

where gOk(r) is the pairwise distribution function of the test particle and an ion
with a charge k, Ek(r) is the field produced by the ion of type k on the test parti-
cle, E; (r) is the effective field of an ion of type k in the plasma, and ne is the
absolute concentration of the electrons in the plasma.
In the OCP and ICM models we have Ek(r) = klt.z, and in the LFCM model
we have Ek(r)=k[(1 +der)/"zJexp(-der), where de=(3r)II2/Re [58]. The effec-
tive field E;(r) is chosen so that the function p(E) calculated by Eqs.
(4.31)-(4.33) satisfies the rule of second momentum,

(EE)reaJ = f
0'" E2 p(E)dE . (4.34)

However, the form of Ek(r) remains arbitrary. The exponential approximation,

E k*()
r = k(l+akr)
2 exp (-ak r ) , (4.35)
r

happens to be appropriate for the LFCM and OCP models [58,59J. In this case,
Eq. (4.34) splits into k independent equations, one for each of the ak.
In a real plasma the nonuniform distribution of the ions around the test parti-
cle means that the test charge is not completely screened, and complete screen-
ing can only be obtained when considering two subsystems, namely the electron
and the ion systems. Therefore, for the ICM, we approximate Ek(r) [56J by:

Ek(r) = ~ [A +B(l+Pk r) exp (-Pk r)], B=l-A

(4.36)

If the electron gas is far from degenerate, then for r ~ 1 we can put

A ~ - 1- , where k. =
ks+l
(I k
Xkk2)112
- -
Xe

For Eq. (4.36) the rule of second momentum stated in Eq. (4.34) takes the
form

(4.37)
= ~
.LJ k
3xk k 2 f
0
00 gOkY) [A+B(l+Pk r) exp (-Pk r)]dr,
r

where
156 N.N. Kalitkin and 1. V. Kuzmina

J~I) = J 00

o
gOk;r) dr,
r
J
J~~ = 0;2 hkP(q)dq,
J~3)(q) = J O;Ok(r) j!(qr) dr, J)4)(q) = Jo;op(r)jl(qr)dr

and h(x)=(sinx-xcosx)/~ is a first-order Bessel spherical harmonic,

hkp(r) = gkp(r) -1, and hkp(q) is the Fourier image of the function hkp(r). Here
and subsequently, we measure r in units of Re and q in units of Rei. When
obtaining Eq. (4.37), we assumed that the triple distribution function
g~ii,(rk>rp) is the product of the pairwise distribution functions, namely,

g~ii,(rk>rp) = gOk(rk)gok(rp)g pk(1 rk -rp I).

This is justified when the plasma is not very strongly nonidea1 (r s: 10).
Equation (4.37) holds if all the Pk satisfy the following equations for all k:

2~2 L p {xp p J q2f,kp(q)I~3)(q)I)4)(q) ~q

0
00
[ }
(4.38)

Given the composition, temperature, and density of the material, Eq. (4.38)
gives k nonlinear equations for the /3 k, and these can easily be solved by
Newton's method. Note that all the integrals converge in Eq. (4.38) for any ko,
including ko = O. This means that we do not have to consider the case ko = 0
separately, as was the case for the OCP model [60].
Following [56], we use the acronym PCM (polarized charge model) for the
proposed model, viz., Eqs. (4.31), (4.33), (4.36), and (4.38).
The PCM is not convenient for applied problems since the existing methods
for calculating the gkp(r) are rather tedious. Therefore, we construct some simple
approximations for calculating the ICM in the next section.
Approximation. In this section we shall assume that the electron component of
the plasma is partially degenerate. Consequently, another parameter should be
introduced to describe the state of plasma, namely the degree of electron degen-
eration e =TITF, where TF =(3.,rn e)213/2 is the Fenni temperature for electrons.
For a weakly non-ideal plasma we can use the Debye approximation, which
takes into account that electrons are partially degenerate [50]. This case has been
considered by Golosnoy [56]. The Debye approximation yields good results for
k; r s: 1 but the accuracy of this approximation falls at large nonidealities.
 4. Wide-Range Characteristic Thennodynamic Curves 157

In this chapter we use exponential approximations for gOk(r) and EZ(r) , in

which the screening parameter for large nonidealities is determined by the aver-
age interparticle distance, and not by Debye's theory. We approximate the pair-
wise distribution function and effective fields of ions in the plasma by the
expressions
gOk(r) = exp[ -kko rexp(-~r)lr], Ek(r) = k[A + B(1 + ~r)exp(-~r)]lr

A=~~/~2, B=I-A=~;/~2, ~2=~~+J31

(~eRet2 =_1_[1+0.8138- 312 +(2/3)1168-112)211 + 25 (4.39)

3r 81

In what follows we shall use the abbreviation APCM to refer to the ap-
proximation inEq. (4.39).
Results. We used the PCM and APCM approximations to calculate the distri-
bution of the microfield in the ICM approximation for a one-charge plasma at
various non-ideality parameters r. The calculations were carried out for
e = 25 »1. In the PCM the pairwise distribution functions gpk(r) were deter-
mined by the method of the hypemetted-chain equation [61], with the pseudo-
potentials of the pairwise particle interactions approximated by the simple
expression
1
upk(t) ~-k pRe [1-exp(~r)]
r

where ",<+)(r) is the wave function of the charged particle after scattering in a
Coulomb field. Quantum physics [62] requires that

I'¥C+)(0)1 2 = 27tIApk I ,Apk =-kpreI/2(3/2)2137t-1I6.

11-exp(-27tApk)I
We compared our calculations with calculations using the MC method [55]
and the mean force field (MFF) approximation [63]. At small non-idealities
(r = 0.28) all four methods give close results (Fig. 4.16). When the non-ideality
is higher (r = 1.28), the MFF method gives a poorer description of the test MC
calculations for ko =0 than the PCM or APCM methods (Fig. 4.17). Note that for
r ~ 1 the APCM method is as accurate as the PCM method, but is much simpler.
When r.=2.2 (Fig. 4.18), the PCM model describes the test MC calculations
better than the other models for both charged ko = 1 and neutral ko = 0 test parti-
158 N.N. Kalitkin and L.V. Kuzmina

0.4

f:t>
0.2

Figure 4.16. The distribution functionp(E) of the ion component of the microfield in a
classical hydrogen plasma. The charge of the test particle is ko=O. The microfield is
measured in units of Eo. The non-ideality parameter is r = 0.28. The calculations by
PCM, APCM and MC methods are close and shown by a single continuous line. The
dashed curve is the MFF -approximation.

des. It is doubtful whether the MFF method can be applied for re = 2.2 and
ko = 0 because the effective field EZ (r) becomes negative in the model for some
value of r. The APCM approximation is also not too accurate and yields an error
of 30% for some values of E. However, this accuracy suffices when calculating
the decrease in the ionization potential in the microfields.
Note that if the degenerate electron component (9« 1) is an ideal gas
(ECooIITF ~ ree« 1, where ECooI is the energy of Coulomb interactions between
particles), then the OCP approximation can be applied to the plasma. For 9 « 1
and r e 9 « 1 we obtain p= Pi, A = 0, and B = 1 from Eq. (4.3 9). Calculations of
the microfield distribution function by the APCM method with these
parametersdo not significantly differ from the MC calculations in the OCP
approximation (the latter were taken from [59]). Thus, the APCM method also
yields good results when the plasma electrons are strongly degenerate.

0."
f
~
0.2

2 3 .
Figure 4.17. The notation is similar to that in Fig.4.16, ko = 0 and r = 1.28.
 4. Wide-Range Characteristic Thennodynamic Curves 159

r
0.'
(-> (b)

kp O.

0.4

Figure 4.18. The notation is similar to that in FigA.16, r = 2.2. The continuous curve is
the MC method, long-dashed curve is the MFF approximation, the short-dashed curve is
the PCM, and the dot-dashed curve is the APCM. The charge on the test particle is /co=O
in FigA.18(a), and ko= 1 in FigA.I8(b).

Decrease in the Ionization Potential. The intraplasma field leads to a decrease

in the ionization potential. For a long time it was assumed that this phenomenon
could be described by the Debye screening of charges. The classical variant of
the Debye-Hiickel model (OHM) for k-th ionization, i.e., for the ionization of
(k-l )-multiple ion, gives the following decrease [64]:

CPk =k- ro= ( TV/41C ~ x"k 2 )In , (4.40)

rn L.Jk=I.e

where 1'n is the Debye radius, and we sum over ions and electrons (k., = -1).
Later plasma models, such as the OCP model [65], or the Debye-Hiickel model
in the large canonical ensemble (LDH) [24], give more complex expressions,
but reduce to Eq. (4.40) in the limit of a weakly nonideal plasma.
These models all use averaged fields. However, over the last 20 years ex-
periments have shown that fluctuating microfields and not the averaged fields
are dominant [66], at least in dense hot plasmas. The phenomenon is described
in [66-69]. An instantaneous microfield ofintensity E leads to a decrease in the
ionization potential of an ion with a charge k -1, and this decrease is equal to the
depth of the saddle point of the potential U(r) = (kJr) + Er (Fig. 4.19), viz.,

(4.41)

If the fluctuations in the microfield are taken into account, the decrease in the
ionization potential CPA: of the plasma is a random variable with a density [67]

(4.42)

where the dimensionless potential and its characteristic unit are

160 N.N. Kalitkin and L. V. Kuzmina

U(r)

Figure 4.19. An atom (ion) in the external unifonn field The figure shows a cut along
the field direction. Bold lines are non-excited levels and thin lines are excited levels.

~ =CPk I CPo, and CPo =-2(kEo)112 ,

respectively. The particular distribution law,/@, the characteristic value, CPo, of
the shift, and the mean decrease in the ionization potential,

ACPk =
cpo
fCXl~/(~)d~,
0
(4.43)

depend on the charge k-l of the ionized ion and the plasma's state (composi-
tion, temperature, and density). It is clear that Eqs. (4.31)-(4.33) can be used to
calculate cP (~) and Acp k.
The decrement defined by Eqs. (4.41) and (4.43) differs qualitatively from
the Oebye change. This may lead to an important result. Ions with various ioni-
zations can be contained in the plasma simultaneously. The potentials Ik of suc-
cessive ionizations for each element increase with increasing k, so it is more
difficult to ionize ions with larger multiplicities. Since the Oebye decrement
defined in Eq. (4.40) increases rapidly as a function of k, it may happen that
1,.+ CPk decreases when k is increased within one shell, i.e., ions with larger mul-
tiplicities can be ionized more easily. This effect has been observed in numerical
calculations of thermal ionization based on the OHM model. This is purely an
artifact of the model and is not reasonable from the physical point of view.
However, the decrement in Eqs. (4.41) and (4.43) is proportional to kll2, and
not to k, i.e., it increases more slowly. Therefore it is less probable that Ik + cP k
decreases as k rises and the phenomenon may not exist at all (we have not ob-
served it in the numerical calculations). Hence the model of thermal ionization
that follows from the microfield assumptions is physically more realistic.
 4. Wide-Range Chamcteristic Thermodynamic Curves 161

At large densities the particles of matter are packed closely, and the fluctu-
ating microfields are not large. In this case, overlapping between electron orbits
of nearest neighbors has the greatest influence on the level population, and not
the microfields. This results in a merging of the levels into a continuous spec-
trum (ionization by compression). This case is considered below.
When deriving an equation of state, we use a mean decrease in the
ionization potential (4.43) in a microfield (see Section 4.4.3). It can be seen
from Eqs. (4.41)-(4.43) that this value depends on the distribution function of
the microfield, and consequently on the microfield model (viz., OCP, ICM or
LFCM) chosen for the calculations. Test calculations show that the microfield
decrease in ionization potentials for various microfield models differs by no
more than 20% (see Table 4.6), which is close to the physical accuracy of the
models themselves. Hence the simplest and most convenient approximation
can be chosen to calculate the equation of state. The OCP approximation has
been studied most in theory. It is the most suitable for constructing a wide-
range model of the microfield. Therefore we restrict ourselves to a
consideration of electrons as a uniform neutralizing background.

Table 4.6. Average decrease in the ionization potential L\CPA/CPO for various ions in a
one-charge plasma according to various microfield models.
Ion He+ He+ Ne+9 Ar+ 17
Model r 0.01 0.05 0.1 0.2 0.3 0.6 0.13
OCP 1.525 1.500 1.469 1.413 1.366 1.259 1.462 1.276 1.167
LFCM 1.499 1.475 1.444 1.386 1.335 1.219 1.408 1.219 1.099
ICM 1.536 1.520 1.503 1.471 1.443 1.374 1.491 1.373 1.286

Wide-Range Model of the Microfield (MAPEX). The most accurate method

for calculating p(E) in the OCP approximation is the APEX technique [59]. It
involves a complicated model and the authors themselves do not clearly describe
the physical principles on which the model is based. However, it takes into ac-
count interactions between surrounding ions and the test ion and, less accurately,
accounts for their interactions with each other. Multiple correlations are taken
into account to some extent. The results from the APEX method are practically
the same as those from the MC method. Our APCM approximation for the OCP
case is practically as accurate as the APEX, but requires significantly less cal-
culation. However the APCM method is rather cumbersome; this is not conven-
ient ifp (E) must be computed several times in calculating some properties of the
medium.
We propose a simple approximation (MAPEX) for p(E), and it can be ap-
plied to a multicomponent plasma with any degree of non-ideality. It differs
from the test MC calculations by no more than the error of the APEX method.
This approximation is consistent with the Hoitsmark model and that of harmonic
162 N.N. Kalitkin and L. V. Kuzmina

oscillators in the limit cases of ideal plasma and strongly compressed overheated
liquid, respectively. Besides, the MAPEX approximation requires one-thousand-
fold less calculation time than APEX.
We approximate Q(£) by the following equation (MAPEX):

Q(l) = exp(Lkxk Wk(l»). (4.44)

where Wk(l) depends on the composition and temperature of the plasma (more
precisely, on the parameters E j =IIR2 and rj=l/(RT», on the charge ko of the test
particle, and on the charge k of the type of ion considered:

Wk(l) = l...(k lEj )3/2

C;k

c;k=.!..a(klEi)II2+~k(1.2+0.8
2
~~/2 2)
(1+~k )

(4.45)
2(3ri Xe) 1/2 ks arctan [ 2 .112
41 8]
112
(3rj ) Xe ks
a=------------~~~----~
0.64r;k; Xe
71:+ 2
1+2.5r;~ Xc

~k =r;kko(klEi)-1/2

The microfield distribution functions calculated by the MAPEX and MC

methods for the OCP approximations for various nonideality parameters r; and
plasma compositions are compared in Figs. 4.20 and 4.21. It can be seen that the
MAPEX has an excellent accuracy.

4.4.3. Microfield Model of Nonideality

Statistical Sums. A system of interacting particles can be completely described
by specifying its thermodynamic potential. If T and the mean atomic volume, V,
are chosen as independent variables, the free energy F is such a potential. In the
ICE model, this is equal to the sum of the free energies of the electrons, all the
possible ions and atoms, and the term describing particle interactions (the non-
ideality correction), i.e.,
z/
F=Fe+ LL(x k1';k)+AF.
j

j /c=o
The free energy of electrons with the degeneration taken into account is cited in
[1]. The free energy of atoms and ions is of the classical form
 4. Wide-Range Characteristic Thennodynamic Curves 163

0.8

0.4

o.o.Jl4~......--.--:'~~~;:::::::::::=;:;:;;;;;;=;;::;;;;;;:;",!
o 2 3 4
EIE,
Figure 4.20. The distribution function p(E) of the microfield in a one-charge plasma
(kl =l, XI = 1) in the OCP approximation (the numbers near curves correspond to r i ). The
microfield is measured in units of E i . The continuous line is MAPEX, dashed lines are
the MC calculations corresponding to the OCP approximation.

~.2:+-~--+-~ __+-__--~~~--__~--~-+--P-~--~-+

{•
r.r-
0.8

0.4

o.o.JL.....-+-....-+---+-.......:;::::;:::::~;::;;=:;::::F=;:::4
0.0 0.' 1.0 1" 2.0 2.' 3.0 3.5 EIE 4.0
I

Figure 4.21. The distribution functionp(E) of the microfield in the OCP approximation
for a two-component plasma with r j = 1, kl = 1, XI =0.97, k2=3, and x2=0.03. Ions with
ko= 3 and ko= 1 were chosen as test objects (the numbers labeling the curves correspond
to the ko). The continuous curve is MAPEX, and the dashed line corresponds to the MC
calculation.

where Sik is the energy of the main ion state calculated from the main state of a
neutral atom, M; is the mass of the ion, and Gik is its statistical sum:
164 N.N. Kalitkin andL.V. Kuzmina

(4.46)

Sjk and gjk are the energy and statistical weights, respectively, of the j-th excited
level. However, an isolated atom (ion) has an infinite number of levels whose
energies are less than its ionization potential. Therefore the sum in Eq. (4.46)
diverges. To avoid this, a model form factor, OOjk, is introduced to account for the
particle interactions and decreases the realization probability for each excited
state, i.e.,

(4.47)

Generally speaking, the form factor is a function of T and V and the set of con-
centrations {Xik, xe }.
Thus, in order to determine the free energy, F, completely, we not only have
to construct a model correction AF({Xik, xe }, T, V) for nonideality, but also
indicate how the statistical sums should be truncated.
Sevast'yanenko [66] and Koval'skaya and Sevast'yanenko [70] were the
first to attempt to take into account the influence of the microfield on composi-
tion, and on the thermodynamic and optical properties. Although they calculated
the population of the energy levels according to the simplest field concepts, they
did not take into account the particle interactions. In [68,69] the authors obtained
the form factor, 00, as a function of the distribution of the microfield. This form
factor is currently the only one correctly describing the newest experimental
data. Therefore, it is worthwhile to construct a completely consistent ICE model
in the plasma based on microfields. It is logical to choose the decrease of ioni-
zation potentials caused by the particle interactions as the initial physical princi-
ple.
Interactions in the Plasma. For an ion with a charge k-1, the microfield leads
to an average shift in the ionization potential (4.43) which, for convenience, is
approximated to within 10% by the simple expression [71]
2(k Xe I R2)1/2
ACPk == (4.48)
[0.027(xe Ikh)4 +0.27(x~ k.,2k1 kvr; +0.17(xek r;)2 ]1/8

where
213
kh == ( Lk xkk 3/2 ) .

At large densities the microfields result in a quasi-band electron spectrum

and soften the shell effects [5]. This also holds at low temperatures, where the
quasi-bands become bands. However, as the temperature is decreased the
 4. Wide-Range Characteristic Thermodynamic Curves 165

MAPEX approximation reduces asymptotically to the model of harmonic oscil-

lators, in which the potential shifts Arp tend to zero. This is a contradiction of the
previous assertion.
The point is that the concentration, Xo, of neutral particles is significant at
low temperatures and large densities. Their influence was taken into account in
the following way. The geometrical form factor, 0), which determines the popu-
lation of energy levels in dense-packed atoms and ions, was calculated quite
accurately [68]. Given certain assumptions, it can be written as

8= 321t .
81

Using the apparatus proposed in [72], we can obtain the corresponding shift in
the potential, i.e.,
(4.49)

The geometrical truncation ofEq. (4.49) provides reasonable ionization by com-

pression for dense gases, although it naturally cannot accurately describe the
band structure in a cold crystal.
Model of Nonideality. We have chosen two models that determine the shifts in
the ionization potentials in the plasma, namely the microfieId model with shift
Arpa and the geometrical model with shift Arpb. Since the microfield shift is due
only to the influence of the charged particles, and the geometrical shift is due
only to neutral particles, we can see that these two factors are independent. We
can obtain a relation
Arpa Arpb
Arp = Arpa + Arpb - -'----'-- (4.50)
Arpa +Arpb
for the complete shift. Given the shifts, and using the method from [72], we can
calculate the correction to the free energy of the system, i.e.,

(4.51)

Here Aql;-( X, Xk-), ... , XI) is the shift in the ionization potential for the (j - 1) - st
ion in a system of particles consisting of all ions with multiplicity less or equal
tok.
The expression for the form factor corresponding to the potential decrease

I
given by Eq. (4.50) is

ro(,) = l-exp[-Ir(l +l~~.(l. -')1"

166 N.N. Kalitkinand L.V. Kuzmina

where the free pammeter n ~ 2 defines the "rigidity" of a fonn factor step, and r
is Euler's gamma-function.
The asymptote of Eq. (4.51) for small non-idealities is of interest In this
case the MAPEX model reduces to the Holtsmark model [53] for an ideal gas,
and Eq. (4.51) can be integrated analytically, i.e.,
llF--kNR. (4.52)

This is a cell-type asymptote. Recall that for Debye-type models, namely the
DHM, OCP, and LDH models, this asymptote has the fonn
(4.53)

and rD differs from R by an order of magnitude. This results in a serious draw-

back in the equations of state calculated by Debye models. We shall discuss this
later and the drawbacks of Debye models are discussed in more detail in [73].

4.4.4. Comparison of Nonideality Models

Spectmm Data. The validity of the model corrections for non-ideality cannot
be proved theoretically. Although some qualitative ideas (the uniqueness of
solution to the ICE equations, the absence of plasma phase transitions, the
monotonicity of the isochores of electron concentIation and energy, etc.), indi-
cate the reliability of a model [52], its accuracy should be assessed by compar-
ing the theoretical and experimental data. Experiments on shock compression
[74-76] are commonly used for such comparisons because of the high densities
and significant nonidealities of the plasma in such experiments. However,
Kalitkin [5] points out that the results of these experiments can involve rather
large systematic errors.
The validity of fonn-factor models for statistical summation were checked in
[68] by comparing the calculated populations of ion energy levels with the ex-
perimental data on the spectra of nonideal plasmas. But each fonn factor is con-
sistent with its own correction for nonideality. Thus, we can check the accuracy
of thennodynamic models of nonideality by spectral data.
Gavrilov and his staff (State Optical Institute) investigated the radiation
spectrum of a dense hydrogen plasma at T= 20000K. Under these conditions
the hydrogen is completely dissociated and partially ionized. At N. = 2 X 1018 the
first three lines of the Balmer series are visible, but not the fourth line. At
N. = 4 X 1018 the y line disappears, and the others are weaker and wider. Only the
a. line remains at N. = 8 X 1018 • Recall that the transition from the (n + 2)-nd level
to the second level corresponds to the n-th line of the Balmer series. Therefore,
the fifth, fourth., and third lower levels, respectively, are substantially occupied
at the electron densities mentioned.
 4. Wide-Range Characteristic Thermodynamic Curves 167

A high-density laser plasma was studied by Hooper et aI. [77]. In the most
interesting experiment the plasma achieved a temperature of T= 1100 eV, with a
density p = 0.50 g/cm3, and a composition (as a percentage of atoms present):
H - 27.3, C - 13.6, 0 - 27.3, AI- 13.6, Si - 13.6, Ar - 4.6.
Under these conditions, AI and Si have a small number of hydrogen-like ions,
and Ar has a small number of hydrogen- and helium-like ions. The lines of these
ions were observed against the background of a continuous spectrum in the
range 2-4keVat a resolution of about leV.
Let us consider which popular models of nonideality and form factors corre-
spond to these data. The numbers of lines observed according to the different
models are given in Table 4.7. The models are located in the table according to
their deviation from the experiment on one or another side. An asterisk is placed
on the right-hand side of a number if the lines are much more intense in theory
than experimentally and on the left-hand side for much less intensity.

Table 4.7. Numbers of spectrum lines.

Series Balmer Lyman
Ion It Al+ 12 Ar+17
NH+=N. Laser plasma
Model Conditions 2xlO+l8 4xlO+18 8xl0+ 18 T=l100 eV, p=O.5 g/cm3
cutting by T 0 0 0 0 0
Larkin method *1 *. *. *1 *.
experinent 3 2 1 2 3
MFNmodel
OHM
3
4*
2
3* 2* • 2
3*
3
4*
OCPmodel 5 4 3 4 5
tum point 6-7 5-6 4-5 5 6
LDH 10* 9* 8* 10* 11*

Temperature cutting means that no line should arise in the spectra of these
experiments; this method clearly contradicts the experiment.
According to the well-known Larkin form-factor model [78] only one line
should be observed under these conditions. Hence this model is also inconsistent
with the experiment.
Truncation by the Oebye radius, as in the OHM model, yields 1 or 2 more
lines than are observed. Besides, when the density increases, the population of
calculated levels does not change until it disappears abruptly, whereas the actual
populations were observed to decrease smoothly. Therefore, this model does not
describe the experiment.
Truncation by the turn point predicts a substantial population for a large
number of levels. This results in 3 or 4 fairly intense lines. which is more than
are observed. Thus, the form-factor model is inconsistent with the experiment
168 N.N. Kalitkinand L.V. Kuzmina

There are even more occupied levels for the LOH model. This clearly illus-
trates that the model underestimates the interaction contribution in an ionized
chemical equilibrium.
The OCP model is intermediate between the OHM and truncating by the tum
point In each case two more visible lines are predicted than are observed.
Only the MFN model-the microfield model of non-ideality-and the asso-
ciated form factor describes this experiment, correctly predicting the number of
observed lines.
Note that the models are ordered by the laser plasma experiment in the same
way as they are for the hydrogen discharge experiment, although the tempera-
tures and densities differ by three orders of magnitude in these examples.
Equations of State. An important criterion for verifying any non-ideality
model is the resultant equation of state. If the equation of state has a qualitative
behavior that is physically improper, the model is invalid.
The most popular models, namely the OCP and LOR, and MFN models,
were chosen for a comparative analysis of their equations of state. The OHM has
too many real disadvantages (multiple solutions to the ionization chemical equi-
librium equations, even for small nonidealities, plasma condensation, etc., see
[52] for more detail), and is practically unused by most scientific groups. There-
fore we do not consider it.
The PLASMA-5 [79] software was used to calculate the equation of state.
This allows a calculation of the composition and thermodynamic functions of
complicated nonideal gas-plasma mixtures. Aluminum was chosen as a test
material (three shells allow one to accurately trace the softening of shell effects
at high densities). The equations of state were constructed as tables in T and p
variables on a double logarithmic grid in the ranges log T eV = -0.6 to 3.0 and
log p g/cm3 = -5.0 to 2.0. This covers the whole range of states of a gas-plasma
mixture, involving ideal and strongly nonidea1 states, weakly ionized and com-
pletely ionized states, rarefied states and practically liquid densities.
Various models of statistical summation were taken into account (including
those that agreed with the non-ideality model). The way the statistical summa-
tions were taken into account did not qualitatively change the form of the equa-
tion of state and they were only seen in moderate quantitative differences.
However, bad form-factor models make the result worse. For example, truncat-
ing by temperature results in an increase in shell effects at large densities. The
calculations which agreed with the statistical summations were used for accurate
comparisons between non-ideality models.
The isolines of the energetic non-ideality parameter, i.e., y = -EpotlEkin are
shown in Fig. 4.22 for various models, including the MFN model.
 4. Wide-Range Chamcteristic Thennodynamic Curves 169

3~--------~----~,--,~--~--~
>.

18 19 20 21 loiN

Figure 4.22. !solines of the non-ideality parameter y for AI. The continuous lines corre-
spond to the MFN model. the long-dashed lines correspond to the OCP model, and the
dashed lines correspond to the LDH model; the numbers near curves are the values of y.

The LDH model clearly underestimates the non-ideality at large densities.

Besides, in this model y is pmctica1ly independent of the density at low tem-
peratures and falls abruptly as tempemture decreases. This is reasonable for a
mrefied plasma; at low T there are few charged particles and the intemction
contributes little energy. However, when the density increases, ionization by
compression begins, the inter-particle distances become much smaller, and
charge intemctions have to increase. Hence the LDH does not behave physi-
cally.
In contmst, the OCP model overstimates the contribution of nonidea1ity. At
some densities, y is 2 or more, which results in a negative pressure, i.e., a plasma
phase tmnsition, and this was not verified experimentally. (This tmnsition is
predicted by the model at low temperatures for a concentmtion of heavy parti-
cles of N ~ 4 x 10 21 cm3, with y changing abruptly from 0 to 2.)
The MFN model describes the change of the non-ideality parameter reasona-
bly. The maximum value is y ~ 1.6, which does not lead to negative pressures,
but implies a quite strong nonideality.
Isotherms of electron concentmtion, Xe , are shown in Fig. 4.23 for the OCP,
LDH, and MFN models. A phase tmnsition can be clearly seen for the OCP
model, which manifests itself in an abrupt ionization by compression (at low
temperatures) at p ~ 0.01 glcm3 (this is not a very compressed material). The
model results in a negative pressure and energy. Beginning with the same den-
sity, we have an area with 8P18T<0 and 8EI8T<0, which contmdicts common
sense.
170 N.N. Kalitkin and L. V. Kuzmina

-
".----
/'

0.' ____ --=:

- ...........
......

-6

II 19 21

Figure 4.23. Isothenns of the degree of ionization for AI. The continuous lines are the
MFN model, the long-dashed lines are the OCP model, and the dashed lines are the LDH
model; the numbers near curves are the values of T (eV).

In contrast, the isothenns of the LDH model do not describe ionization by

compression and, in general, differ slightly from the calculations by the ideal gas
model.
The MFN model is intennediate between the LOH and OCP models. It leads
to smooth ionization by compression, which is the case at large densities, and
this process is not like a phase transition.

4.4.5. Quasi-Bands and Equations of State

Quasi-Band Spectra. Consider the reasons for the restriction on the application
of the ionization and chemical equilibrium model with microfield non-ideality.
In the model itself the decrease in the ionization potential is a number. In fact,
any atom or ion is located in its own microfield at each moment of time; A<p ik is
therefore a number, and atomic levels remain discrete and are shifted by A<p ik.
But different atoms exist in different microfields, and therefore each electron
level becomes a quasi-band for all the same atoms or ions. The density of states
in the quasi-band corresponds to the distribution ofEqs. (4.41) and (4.42).
This resembles the band in a cold crystal (Fig. 4.24). However, significant
differences exist, namely: i) a band has sharply defined boundaries, whereas the
"tail" of the quasi -band is not bounded, ii) deep bands are very narrow due to the
very large under-threshold exponent, whereas all the quasi-bands are narrow,
and, iii) quasi-bands are much wider than even the upper bands at the same
density of the material (especially for the plasma of multicharged ions).
 4. Wide-Range Characteristic Thermodynamic Curves 171

1
2

II

Figure 4.24. Electron spectra: 1 denotes the level, 2 denotes the band and 3 denotes the
quasi-band.

An ion (atom) has a system of levels, which thicken near the ionization
boundary. Quasi-bands for various densities of substances are shown qualita-
tively in Fig. 4.25. At small densities the quasi-bands for each level are narrow
and sharply separated from each other; therefore, the ionization chemical equi-
librium model can be well applied. At moderate densities the outer close quasi-
bands begin to merge, which weakens the shell effects and decreases the
accuracy of the ICE model. At large densities, all the quasi-bands (excluding the
deepest ones) merge in one continuous spectrum; therefore, the model of an
ionization and chemical equilibrium is not applicable, but the quantum-statistical
model can be applied [1,5]. This consideration shows that the shell effects de-
crease, and the ionization equation of state transforms into the quantum statisti-
cal equation as the density increases. Note that, if we decrease the temperature at
a fixed (large) density, then the quasi-bands are narrower due to the decrease in
the ion multiplicity. Quasi-bands transform to bands at the crystallization tem-
perature. But in compressed solids the outer bands are essentially wider, and the
QSM still holds.
Equation of State. A wide-range equation of state can be constructed from
only three strands (see Fig. 4.26). These are the ionization and chemical equilib-
rium (ICE) model in the gas-plasma domain, the quantum-statistical model
(QS) for very compressed matter, and the quasi-band model (QB) between these
states. However, this equation of state is not global; it does not describe the
liquid-vapor mixture, nor the beginning of cold compression or melting of a
solid.
However, the equation is much simpler in its domain of applicability than
other similar equations of state. The SESAME library [46-48J, for example,
uses seven different models to describe the same range (Fig. 4.26). Besides, the
application boundaries of some models, for example, the Thomas-Fermi model,
are unjustified, as cap. be seen from the discussion above.
172 N.N. Kalitldn and 1. V. Kuzmina

(1)

(2)

•
(3)

(4)

o
Figure 4.25. Quasi-bands at various matter densities. (1) corresponds to zero density; (2)
corresponds to a small density; (3) corresponds to a modemte density; and (4) corre-
sponds to a high density. The total curve is shown by the dashed line.

3
:::
~
.r c
1
d
r-
I
I

,
I 3
I
I
----04I
b
I
0

/I

-3 -2 -1 2 Io,p

Figure 4.26. Wide-range equation of state for AI. The continuous lines show the
boundaries of models: 1) corresponds to the ICE model. 2) corresponds to the quasi-band
model, and 3) corresponds to the quantum statistical model. The dashed lines show the
boundaries of the models in the SESAME library: a) corresponds to the model of soft
spheres; b) corresponds to the Saba model; c) corresponds to the ACTEX model; d)
corresponds to the Thomas-Fermi model; e) corresponds to the semi-empirical model of
Griineisen; f) corresponds to the pseudo-potential model of liquid metals, and g) is the
region in which interpolation is needed.
 4. Wide-Range Characteristic Thermodynamic Cwves 173

The equation of state given here is also the most accurate. This was verified
by experiments in underground explosions [80], where the shock compressibility
of AI, Fe and Ph were measured at pressures 100-500Mbar. For AI the mean-
square deviation of the density calculated from our equation of state from the
experimental density was 2.4 0/0, whereas the same parameter calculated using
SESAME was 4.1 %.

References
[1] N.N. Kalitkin, in: Mathematical Modeling: Physical and Chemical Properties 0/
Substances, Moscow, Nauka, (1989), pp. 114-161.
[2] AF. Nikiforov, V.G. Novikov, and V.B. Uvarov, in: Mathematical Modeling:
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 CHAPTER 5

Shock-Wave Compression of Porous

Metals

R. F. Trunin, K. K. Krupnikov, G. v. Simakov, and

A. I. Funtikov

5.1. Introduction
Zel'dovich was the first to note the importance of investigating shock
compressibility of materials with decreased initial density [1]. It is known that
data on shock compressibility of dense matter, i.e., matter initially at its normal
crystalline density, can be used for construction of semi-empirical equations of
state. These data can be used to determine thermodynamic properties in the
region of the pressure-density plane between the Hugoniot and the cold
compression curve (the isotherm corresponding to the temperature T= 0 K).
However, it is also of interest to study states for which the temperature at a
given pressure significantly exceeds (by an order of magnitude more) the
temperature of states on the Hugoniot of the crystalline-density material (called
the "dense Hugoniot"). In the following, we present results of investigations of
shock compressibility of porous samples of iron, copper, nickel, and tungsten
carried out in VNITEF under laboratory conditions and under the conditions
provided by underground nuclear explosions. The data obtained yield
thermodynamic parameters of condensed matter corresponding to the most
extreme states attainable using existing experimental techniques.
The proposal of Zel' dovich led to the study of states of high pressure and
temperature using data on compressibility of porous materials (i.e., materials
that have artificially decreased initial density). The decrease of density is
achieved, as a rule, by pressing weighed batches of a fmely-dispersed powder of
the material under investigation into measured forms. The average density of the
porous sample is Poo = palm, where m is the degree of porosity, and Po is the
crystalline density of the material. Variation of m allows investigation of shock
compression of the material over a wide range of values of initial density-from
densities close to the initial crystalline density, m ~ 1, to densities Poo ~ Po120.
Shock Hugoniots corresponding to these initial states occupy a wide region
situated to the left of the dense Hugoniot in the P-p plane. This occurs because
the density of shock compressed porous matter at a given pressure is less than
V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII
© Springer Science+Business Media New York 2004
178 R.F. Tnmin, KK Krupnikov, G.V .Simakov, andA.I. Funtikov

that of the crystalline-density matter at the same pressure. As porosity is

increased, this effect increases, i.e., the larger the value of m, the lower the
density of the material when shock-compressed to a given pressure. The
explanation of this fact is connected with the thermal processes that occur during
compression of the material.
Let us consider the qualitative plot in Fig. 5.1 in which the effect of shock
compression of dense and porous materials is illustrated in P-V coordinates
(V= IIp is the specific volume). At a given PH, the thermal energy, Eili, of
conipression of the porous material, as given by
(5.1)

significantly exceeds the thermal energy· of compression of dense matter, as

given by
(5.2)

On Fig. 5.1, the curve labeled Pc represents the pressure of isothermal cold
compression, i.e., compression at T= 0 K. The figure also shows why shock
compression of porous matter heats it to a temperature exceeding the
temperature achieved when the dense matter is shock compressed to the same
pressure. This excess heating is inversely related to the porosity, m: The greater

V
Figure 5.1. P- V diagram of compression of dense porous matter.
 5. Shock-Wave Compression of Porous Metals 179

the porosity, i.e. the greater Voo becomes, the more the temperature is increased
at a given pressure. It is natural that the thermal pressure, PIh , that results from
compression of porous matter also exceeds the thermal pressure on the dense
Hugoniot. Increasing the thermal pressure hinders the compression of matter,
i.e., the greater the porosity, the lower the density achieved by shock
compression.
The first Hugoniot of porous iron was published in 1958 [2]. The magnitude
of the porosity, m = 1.2, was not sufficient to produce significant expansion of
states under investigation. The big step in this direction was made in
publications of 1962 on shock compression of porous tungsten [3] and four other
metals AI, Cu, Pb, Ni [4]. Hugoniots of different forms were obtained for
several values m ~ 4, and filled the space of the P-p diagrams from the shock
Hugoniot of the dense metal to Hugoniots for which the function P(p) was
almost vertical for densities of shock compression p ~ Po. Analysis of the data
obtained provided quantitative information about the magnitude of the
Gtiineisen coefficient (including its electronic analog) and allowed obtaining a
new type of interpolation equation of state [4] in which, for the first time,
transitions from solid to fluid and gaseous states occurred.
Samples to be investigated were produced by cold pressing the finely
dispersed metals obtained by sifting common industrial powders through
measured sieves to produce the necessary and possible porosities. By employing
this technology it is quite possible to obtain samples of porosity m = 4, the so-
called poured porosity, for which the measured volume of the mold in which the
sample is formed is filled with a weighed amount of powder with essentially no
additional pressing.
The next step of increasing porosity yielded results [5] giving data on
compression of copper, molybdenum, and tantalum for different values of
porosity up to m ~ 8. Obtaining such porosity became possible due to transition
to a new technology based on dehydrogenation of hydrides of the corresponding
metals. Even greater porosities, reaching the present record value m = 20, were
obtained by cold pressing special ultra-disperse powders of metals containing
grains as small as 10-20 nm. The :first measurements of compressibility of Ni
samples of these high porosities were published in 1993 [6]. Data on shock
compression of super-porous AI, Cu, Fe, and Ta have also been obtained.
The next significant step in investigation of compressibility of porous metals
in these works was the extension of measurements to pressures both
significantly less [5,6] and significantly more [7,8] than were studied in [3,4]. In
the last case, terapascal pressures were obtained and measurements of
compression of porous copper (m =3 and 4), tungsten (m =4), iron (m =3), and
uranium (m = 3) were made under proving ground conditions for canying out
underground nuclear explosions.
180 R.F. Trunin, KK Krupnikov, G.V .Simakov, and A.I. Funtikov

AIl investigations, both at the proving ground and in the laboratory, used the
electrocontact technique for measuring wave velocities. At pressures less than
5-6 GPa in samples, piezoceramic gauges were usually used to provide time
markers because they are more sensitive than the usual electrocontact gauges.
For a number of the metals investigated, systematic tests were carried out to
clarify the possible influence of several experimental parameters on shock-wave
measurements. In some tests [4,6] the sizes of individual particles of the
powders, the humidity of the samples, and the sample thickness were varied.
The effect of air, which filled pores between individual particles of the powder,
was under control. These systematic measurements were carried out mainly at
pressures ~ 5 GPa. Factors considered separately in the tests included variation
of the size of the particles from I to -100 ~m. variation of the humidity from
the natural value to nearly zero, and 2-3 fold variation of the thickness of the
samples. In [8], results of two tests of porous copper at pressures within the
laboratory range were presented. In these tests, the thickness of the samples was
about 80 mm, i.e., they exceeded the standard thickness of 3-6 mm by more
than an order of magnitude. Experiments with vacuum treatment of samples
were carried out on copper of poured density with air pressure in the samples
being only a few mm of mercUty column.
These methodical measurements showed that the factors mentioned
produced no detectable influence on the velocity of shock waves. These
measurements justified declaring that the shock-wave procedures used for these
experiments produced states of compression of the porous samples that were
close to equilibrium. This fact justified use of a standard construction of the
experiments and significantly simplified interpretation of the experimental data.

5.2. Design of Experiments

Of all of the porous metals that have been investigated to the present time, AI,
Mg, Mo, Fe, en. Cr, Til, Ni, Pb, Re, V, Ti. W, U, Pu, and Zn, we shall consider
only those studied most thoroughly in both the laboratory and at the proving
ground. We include copper, iron, tungsten, molybdenum, and nickel in this
group. The porous samples to be used in laboratory experiments were prepared
in the same configuration as samples for our investigations of dense materials.
We used the standard explosive loading devices developed for shock
compression of dense metals: generators of plane shock waves [9], "guns"
(accelerators of metal plates by gaseous detonation products) [10,11], and
generators of spherically converging shock waves [12].
As a rule, samples took the form of cylindrical tablets made from powder
pressed to the required density, Poo, in metal rings. It was found difficult to press
powders to a specific density in the large volume of the experimental ampoules
because it was necessaty to use special powerful pressing equipment. Besides
 5. Shock-Wave Compression of Porous Metals 181

this, we were confronted by the additional problem of decreasing density

through the thickness of the sample. We took the simplest decision for
underground experiments: rings filled with powder of its poured density. It
turned out that Hugoniots for poured-density powders were nearly vertical
functions P ~ Po in the P-p plane.
In all cases, the reflection method [13J was used to carry out investigations
of compressibility.
Let us consider in more detail the construction of tests to be conducted under
proving ground conditions. Figure 5.2 shows the test configuration. Aluminum
was used as a screen in most proving ground tests because it had been studied in
detail to a pressure of ~2 TPa [14J and its P- U Hugoniot falls close to the
Hugoniots of the porous metals under investigation. The dimensions of the test
configuration were as follows: The aluminum screen through which the shock
wave was transmitted to samples under investigation was ~ 100-mm thick and
the samples were ~250-mm thick. The diameter of the screen was 500 mm and
the diameter of the samples was 250 mm. Minor attenuation of the shock wave
took place in the course of its passage through rock and the samples under
investigation. The magnitude of the attenuation was taken into account in
calculations and, as a rule, did not exceed 1 % of the measured velocities in the
screens and samples.
Velocities were measured using the electrocontact method in the same way
as under laboratory conditions. We installed 4-6 separately standing gauges at
the rock-screen, screen-sample, and sample-air interfaces. Arrival of the
shock wave at any of the interfaces was accompanied by electrical closure of the
air gap between the gauge electrodes, which was recorded on high-speed oscillo-

Screen

Rock JOOC>OC>I

Sample

Figure 5.2. Scheme of measurements of compression at underground implosions. The

standard metals, AI or Fe, were used as screens.
182 RF. Trunin, K.K. Krupnikov, G.V .Simakov, and AI. Funtikov

scopes or digital counters. The accuracy of the measurement was 5 ns. As a

rule, the simultaneity of emergence of the shock-wave on planes monitored by
electrocontact gauges was not worse than llt5.10-7 s. Appropriate corrections
were introduced if non-simultaneity of the shock-wave arrival exceeded this
amount.
The shock parameters were inferred from the interaction at the screen-
sample interface. To determine particle velocities and pressures of porous metals
by the reflection method, we used the so-called mirror reflection of the Hugoniot
of the screen material because the mirror reflection rule is valid [15] at the
pressure decreases that actually occur between the Hugoniots of the screen and
the porous metals under investigation.

5.3. Experimental Data

We begin by presenting experimental data (e.g. for Ni) in coordinates D(m), as
shown in Fig. 5.3, where every curve gives the wave velocity as a function of
the porosity for each given loading device, i.e., for a given amplitude of the
shock wave in the screen. These are so-called "lines of one charge" (after
terminology from [3]), which allow calculation of the position of the Hugoniot
for every value of m after the experimental data have been obtained. Similar
lines can also be constructed for the other metals considered in this work; Ni is
only a typical example.

9r-------------------------------~

D, kms- i

5 10 15 20 25 m

Figure 5.3. The functionD(m) for nickel.

 5. Shock-Wave Compression of Porous Metals 183

A general feature of the functions under consideration is the fundamental

change of slope, D;"', that occurs along a line of one charge. For small m, the
derivative dD/dm is negative as a rule, i.e., the wave velocities decrease as m is
increased. In the range 3 > m > 2, D'm Rj 0 and, at much larger values of m, the
derivative remains close to zero (Co, Mo) or becomes positive. The gradient of
the initial fall of D(m) at small porosity depends upon the amplitude of the
wave: The larger the amplitude, the lower the gradient of the fall of the wave
velocity. For some wave parameters D(m) can become constant (D'm = 0) and,
at much larger amplitudes, the gradient becomes positive, D'm > 0 . The reason
for this is not clear.
Let us consider plots of the portion of the Hugoniots for wave velocities
D < 10 km/s (Figs. 5.4 and 5.5). These plots show that shock Hugoniots of
porous metals form a fan of lines issuing from a neighborhood of a single point
but having quite different slopes Db. For all metals under investigation, this
single point or a small interval, ADo, close to it corresponds approximately to a
single initial value, Do ~ 0.1 km/s. Most probably this is a consequence of some
single, general physical characteristic. One may suppose that it corresponds to
the sound velocity in air, decreased by entrainment of particles of metal in the
air within the samples. This mechanism must certainly lead to different values of
Do as a function of porosity, i.e., as a function of the air volume within the
sample that is filled with particles of metal. However, the experimental accuracy
of the low-pressure portion of the Hugoniots does not allow clarification of this
issue. Nevertheless, this explanation seems to be logical for large m. However,
at small porosity, when the initial density of samples differs from the crystalline
density by only 10-20% (as occurs, e.g., for the Ni Hugoniot with m = 1.1), this
explanation is hardly believable. It is possible that the initial point represents
some intervalllDo and Do has a different value for every porous Hugoniot.
Somehow or other, but for every metal that we consider here, there is a large
discrepancy (some km/s) between the extrapolated value of D at u=o for the
dense Hugoniot, as a rule close to bulk sound velocity, and appropriate values of
Do for Hugoniots of the porous metal.
Hugoniots with small m have the most importance on plots for D < 10 km/s.
Their slope significantly exceeds the slope of the dense Hugoniot. In the D- U
plane, these Hugoniots quickly approach the' dense Hugoniot, after which their
slope decreases to conform to the slope of the dense Hugoniot. As m is
increased, the initial slope, Db, of the Hugoniots decreases and at m = 3-4 it
becomes equal to the slope of the dense Hugoniot. At much larger porosity, the
slope continues to decrease and for m > 10 (for Fe, Co, Ni) it approaches 1. The
Hugoniots come close to the line D = U bisecting the D- U plane. They cannot
cross this line (the shock wave is stable only for D> U) so, starting with some
value of Dcr , and Ucr, the Hugoniots of very porous materials must increase their
slope (see Figs. 5.4 and 5.5).
184 R.F. Trunin, KK Krupnikov, G. V .Simakov, and A.I. Funtikov

D,kmls

I 1 .J G U,kmls

Figure 5.4. Shock Hugoniots for Ni for several values of porosity. Hugoniots labeled I-
n are for m =1, 1.1, 1.41, 1.72, 2.0, 2.3, 2.7, 4.55, 5.58, 7.21, 10, 15, and 20,
respectively. All data shown are from laboratory measurements.

As kinematic parameters increase, the slopes of some Hugoniots approach

equality and they become a beam of approximately parallel straight lines of
similar slope. For copper (Fig. 5.5), this takes place in the range of laboratory
measurements.
Let us observe the way in which the slopes Db of the Hugoniots change at
wave velocities exceeding the range of laboratory measurements. Figure 5.6
shows results of appropriate tests. We note here that there is a difference in
kinematic parameters of proving ground experimental points of porous
Hugoniots from those reported in the first publications [7,8,14]. This change
arises from correction for changes in the measuring-base distances of the
electrocontact gauges because of the effect of a diverging wave from a nuclear
explosion propagating through flat samples.
It can be seen from Fig. 5.6 that an insignificant change of the slope of the
Hugoniots of these metals takes place starting with D ~ 16 km/s for copper,
D ~ 12 km/s for iron, and D > 7 km/s for tungsten. In this case, the slopes of both
porous and dense Hugoniots of the same metal even out in the first approach.
They become approximately equal to 1.2-1.3 and are in reasonable agreement
 5. Shock-Wave Compression of Porous Metals 185

D,kmIs

1 I I U,kmIs

Figure 5.5. Shock Hugoniots for copper for several values of porosity. Hugoniots 1-8
are for: m = 1, 1.41,2.0,3.0,4.0,5.45,7.2, and 10, respectively. Data from measurements
at underground nuclear explosions are shown by the large symbols + and O.

with the slope of Hugoniots obtained from theoretical models [16,17]. These
slopes can be considered to be the same, certainly within experimental error.
Unfortunately, errors in these measurements exceed the normal 1.5% for
laboratory measurements, being approximately 3 % of D for the two worst cases.
Error bars for wave velocities are shown on Fig. 5.6. Despite these rather large
errors, the general picture of the position of the shock Hugoniots is very
definitely clarified.

5.4. Thermodynamic Parameter Evaluation-

Equation of State with Variable Specific Heat
Now let us consider the experimental results in the thermodynamic variables
pressure and density. Data are given on Figs. 5.7 and 5.8. Hugoniots of the
porous metals under investigation fill the major part of the P - P diagram over
the range of compression cr = piPo ~ 0.3 - 3. In this case, the Hugoniot for every
initial density Poo on its low-pressure plot (P < 10 GPa) takes the form of a
gently sloping branch on which the density of the shock-compressed samples
approaches the crystalline density of the given metal at modest pressures. This is
the so-called "packing pressure," the pressure at which the difference between p
and po is minimized for the porous Hugoniot under consideration. The slope
(dPldp)H of the low-pressure plots of the Hugoniot is positive.
186 RF. Tnmin, K.K. Krupnikov, G.V .Simakov, andA.I. Funtikov

JJ
D,kmls

JO

IfI IJ 10 u,kmls

Figure 5.6. Shock Hugoruots of porous ITOn, copper, and tungsten. Hugoniots 1-4 are
for Cu withm= 1,3,4, and 10, respectively. Data obtained at underground explosions are
shown as 0 I:l. Hugoniots 5, 6, 7, and 9 are for Fe with m = 1, 3.26, 20, and 3.50,
respectively. Underground explosion data are designated in the same way as for copper.
Hugoniot 8 is for W with m = 3.1. - - - experimental description, --------- - TFPC
calculation.

At higher pressure, the Hugoniots have significantly larger and different

slopes (steep branches). In this case, for the small porosity m < l.8, (dPldp)H> 0
in the whole region under investigation. In some interval of m, the Hugoniots
correspond to approximately vertical functions with (dPldp)Hf'ljOO. In the region
of high porosity, m > 5, the derivative (dPldp)H changes sign, i.e., its value
changes from negative magnitudes for pressures moderately above the packing
pressure (decrease of density and increase of pressure takes place on this plot of
Hugoniots) to positive at high pressures.
As shown in [4], the reversal in the sign of (dPldp)H is explained by the fact
that, at small pressures and temperatures, the character of function PH(p) is
governed by the behavior of the lattice, whereas at high pressures it depends on
the behavior of the electrons. In other words, the sign of (dPldp)H is determined
by the relationship of the compression m cr to the GrOneisen coefficient for the
lattice, y, and that for the electrons, Yo. In the region cr> I, the derivative
(dPldp)H> 0 whereas, in the region cr< I, (dPldp)H changes sign. The GrOneisen
coefficient y.<PH/pEH= 2/(mcr-I). When the situation reverses, y. > PH/pEH.
The density limit (dPldp)H=OO is reached when Yo=2/(mcr-I).
 5. Shock-Wave Compression of Porous Metals 187

p,GPa

JlD

260

1~0

200

!60

128

80

40

0 2 6 10 11 p, glcm3

Figure 5.7. The P - p diagram for Ni. The numbers 1-12 designate porous Hugoniots for
m = 1, 1.41, 1.72, 2.0, 2.3, 2.7, 4.55, 5.58, 7.2, 10, 15, and 20, respectively, --------- -
computed isotherms [19] corresponding to the temperatures shown on the curves.

P,GPa

JOO
---/
I
I
IfI!

lDO

T!lJ

11/
!tJO

II!

o
Figure 5.8. P-p diagram for Cu. Shock Hugoniots 1-10 correspond to m = 1, 1.41,2.0,
2,5,3.0,3.5,4.0,5.45, 7.2, and 10, respectively. Isotherms are as indicated as on Fig. 5.7.
188 R.F. TI1ll1in. KK Krupnikov, G.V .Simakov, andA.I. Funtikov

Let US see how the total Grtineisen coefficient y=V(8PI8E)v changes along
Hugoniots in the region of high porosity. Data for Ni are given in Fig. 5.9. It
shows that the functions y(p) are quite complicated. However, their general
feature is similar asymptotic values of y in the low-density region for all four
functions presented on figure (this region corresponds to high pressures for the
Hugoniots under consideration). The asymptotic value is approximately y ~ 0.65.
The improbably large values of y in the region of relatively moderate pressures,
i.e. close to the packing pressure, can be explained by the high sensitivity of the
derivative (8PI8E)v to variations of the Hugoniot parameters. Actually, small
changes of Hugoniot parameters (for porosity m = 10, Aco = ±O.3 km/s and
D~ = ±0.05) significantly change the Grtineisen parameter as shown by the
dashed curves on either side of this function.
Estimating the mean Grtineisen coefficient using the equation
y= V(APlAE)v, where AP and AE are the differences of pressure and energy on
two porous Hugoniots at a measured value of V, provides a value for this
coefficient approximately equal to 0.5. However, it is necessary to note that the
character and position of porous Hugoniots (especially for large m) in the P- V
plane is such that it is possible to compare the pressures on two Hugoniots, at
the same volume V, in only a very narrow interval AV (see Figs. 5.7 and 5.8).
This makes it practically impossible to obtain reliable estimates of y in any wide
interval of changes of shock-wave parameters.
An approach that does not have this disadvantage employs the coefficient
'T1(P) = P(AVI AE)p [19]. The advantage of'T1(P) comes immediately from its
determination: It can be found from comparison of porous Hugoniots at
P = const., providing the opportunity evaluate the function for many values of P.
The connection between y and 'T1 is given by the equation
'T1(P) = Py(p)/[pC 2 -Py(p»), (5.3)
where C is the sound velocity. It can be seen from this relation that 'T1 ~ P as

r
2.f

z.o 0'
o Z
.. J
/.5 .~

/.8

o.s
z.o 2.5 .1.0 J.S 4.0 $.0

Figure 5.9. Computed values ofy(p) for Hugoniots corresponding to several values of
porosity for Ni. 1: m = 7.21,2: m = 10,3: m =15, 4: m =20.
 5. Shock-Wave Compression of Porous Metals 189

P ~ 0, which is why T\(P) passes through the origin in the P-T\ plane (Fig.
5.10). This figure shows T\(P) for Ni. Despite the rather large discrepancies of
single points (the function for m = 1.41 differs most significantly from the other
functions), the values of T\(P) obtained from the experimental data are well
represented by a single function. A similar presentation can be made for other
metals.
Using the simplest equation of state with T\(P) = P(8V/8E)p in [7,18] we
formally succeeded in satisfactorily describing the states of shock compression
on various Hugoniots for which the the thermal characteristics differ by orders
of magnitude. However, it is necessary to note that the given equation leads to
rather overstated values of the initial Griineisen coefficient and does not exhibit
correct asymptotic behavior at the transition to an ideal gas. In other words, use
of this equation of state is restricted to states of high pressure and density.
Isotherms are given on Figs. 5.7 and 5.8 corresponding to various tempera-
tures obtained using the equation of state from [19]. These temperatures agree
with the Hugoniot temperatures at points of intersection of the isotherms and the
Hugoniots. For copper, the maximum temperature obtained in a laboratory ex-
periment is ~ 7 x 10 4 degrees and occurs at P ~ 80 GPa on the Hugoniot of cop-
per with m = 10. The same temperature is realized on the dense Hugoniot at
pressure of ~ 1.2 TPa. For nickel at a pressure 50 GPa, the temperature on the
Hugoniot with m = 20 is about 80000 K. The maximum temperature achieved is
T ~ 3.5 x 10 5 degrees and occurs at P ~ 2 TPa on the Hugoniot of copper of
porosity m = 4.
There is no doubt at all that the majority of Hugoniots of highly porous
materials correspond to states of compressed and heated gas with actively
interacting metal ions. It should be accepted that the values of the specific heat

(J
0,5
• * x
, •
~
.+.o
0,4
+
", * x (J
• •
•
-t6 (I

0,:1
•
(I
•
+
•
0,1
•
0,1

o 20 +0 60 60 100 110 ,1,0 P,GPa

Figure 5.10. Function Tj(p) for nickel. Various symbols correspond to the values of Tj,
calculated based on the experimental points for Hugoniots of porous nickeL
190 R.F. Trunin, KK Krupnikov, G.V .Simakov, and AI. Funtikov

P(,GPa

600

608

1,00

1fK1

!.z 1.6 z:o

Figure 5.11. Cold compression isotherms from the following references. 1: [24],2: [19],
3: [25],4: [22], 5: [23], and 6: [4].

and the GIiineisen coefficient for such hot gases are close to their limiting values
3rJU2 and 2/3, respectively. Equations of state take into account changes of the
thermal characteristics of matter that occur as a result of compression. The first
equation in which these changes were taken into account was the equation of
state of metals from [4]. The basis and choice of this equation was immediately
connected with the analysis of experimental data on compression of porous
metals. It was the first to show the necessity of determining the change with
temperature of thermal capacity and GIiineisen coefficient. In [4] a precise
algorithm for determining the specific heat and GIiineisen functions was also
suggested. The equation of state is taken in the form
P=Pc+Pt+Pe, E =Ec +Et +Ee. (5.4)

In this case, the first terms, Pc and Ec , describe elastic interaction of atoms at the
temperature T = 0 K and the second and third terms describe effects of thermal
excitation of ions and electrons, respectively. The equation of state addresses
transitions of the thermal capacity of the lattice, Cv , from the value 3<1{
describing the solid at temperatures of the order of the Debye temperature, e, to
the value 3rJU2 for temperatures T» e corresponding to a highly heated gas,
and the analog GIiineisen coefficient, A, from its value 'Yo at normal conditions to
2/3 as T ~OO. The two limiting values are connected through the coefficient
Z=IC}{T/Cc2 (5.5)
 5. Shock-Wave Compression of Porous Metals 191

where I is a free parameter, Cc = V(-dPcldV)lf2 is the cold sound velocity (the

value on the T= OK isothenn), and '.1{ is a constant The transition equations for
the lattice are

Cv =%<1{ [1+ (1 +IZ )2 J. (5.6)

A, _ Pt _ 2 (3y+Z)
(5.7)
p - VEt - 3 (2 + Z) ,

R _ '.1{T (3y+Z)
(5.8)
I-V l+Z '
and
3 2+Z
Et =-'.1{T--. (5.9)
2 l+Z
In this case the Grtineisen coefficient, y, is expressed through Cc by the equation
1 dlnCc
y=-+--. (5.10)
3 dlnp

It can be seen from this relationship that, in limit situations, Pt and E t transition
into the Mie-Grtineisen equation for a solid with Cv =3'.1{ and A, =y as Z ~ 0
and into the gas equation PV='.1{T, Cv =3rJU2 and A,=2/3 as Z~oo. At
intennediate values of Z, the influence of temperature, T, and density, p, through
Cc on Pt and through Cv and A, on E t lies in Z itself.
Tenns corresponding to the elastic interaction of atoms are taken in the form
[20]
Vc )1+<i/3)
Pc = ~ a( j - (5.11)
£..Ji V '

where Vc is the volume of the material at T=OK and P=O. The first three
coefficients of this series can be found from handbook data giving initial
density, Grtineisen coefficients, and compressibility. The next two coefficients
are determined from parameters of the Hugoniot of the condensed material, and
two more coefficients are found from values of the function Pc and its derivative
P; calculated from the Thomas-Fermi (TF) model [16].
An approximation of Latter's data [21] is incorporated into the equation of
state in the form of the electronic tenns

(5.12)
192 R.F. Trunin, K.K. Krupnikov, G.V .Simakov, and AI. Funtikov

where b is an adjustable parameter, P is the coefficient of electronic specific

heat, and
dlnp
Ye=---. (5.13)
dlnp

Taken together, the foregoing relationships define an equation of state. In

this equation the limit transitions from solid states to liquid states take place
through variation of the parameter Z. An algorithm for calculating the melting
curve is given in [22], where it is assumed that the parameters of the equation of
state of a liquid differ from those of the solid by the addition of empirical
functions of density and temperature. Constants of the additional summand can
be found from a description of the experimental melting line and the melting
line itself can be found by minimizing the Gibbs potential.
This equation of state contains about ten free parameters that can be varied to
obtain the best description of dynamic experimental data. As a rule, agreement
of calculation with experiment is achieved within measurement errors. At the
time of this work (1962), the advantage of the equation under discussion
compared to others was absolute. This is why the majority of equations
suggested later incorporated some preconditions based on it in one way or
another. Thus, in [23], where the description of thermophysical features was
extended to cover the expansion of initially compressed matter into the low-
density region, forms of lattice and electronic terms differing from those in [4]
were used. However, they provide, as in [4], thermal terms that capture the
transformation of condensed matter into a gas in the limits p ~ 0 and T ~ 00.
The equation in [24] is a combination of those in [4] and [22]. The first two
terms (cold and lattice thermal) are taken in form used in [4] and the electronic
terms are taken in form used in [23].
In [25] as in [4], the cold pressure for cr> 1 is given by arithmetic series in cr;
at cr < 1 in the region of densities less than the crystal density it is given by a
polynomial. A smooth transition from one branch to the other is obtained. In the
lattice thermal part of the potential, the transition from the solid to the liquid
state is captured and the thermal capacity changes from 3 <1\. to 3 cJij2 at the
transition to gaseous states, in which case Y~ 2/3. The electronic part of the
potential is represented by a quadratic function of temperature in the condensed
phase and by a linear function at high temperatures. The value of the electronic
Griineisen coefficient changes from its initial value at zero temperature to 2/3 as
T ~ 00 when cr = 0 and cr = 00.
Basic approaches from [4,22,24] are summarized in an equation of state in
[25]. The form of this equation is traditional: a cold compression function, a
lattice-thermal function, and an electronic function. The functions given for the
thermal capacity of the lattice and the Griineisen coefficient provide correct
 5. Shock-Wave Compression of Porous Metals 193

asymptotic values for Cvand 'Y, i.e., from a solid at low temperatures to a gas at
high temperatures. Electronic terms are taken in a form similar to that in [22].
Despite the use of different approaches to the description of shock-wave data,
cold compression isotherms obtained from the different equations turn out to be
close to each other. This is shown in Fig. 5.11, which is a plot of cold
compression curves for copper obtained from equations of state given in [4,23-
26]. At a pressure of 800 GPa, the range of compression on the various
isentropes falls within t.cr = ±O. 03 5 of the mean cmve, Pc. Similar agreement is
observed for other metals.
Calculations based on the Thomas-Fermi model with quantum and
exchange corrections [16] and nuclear interactions [17] (the 1FQC model)
showed better agreement with experimental data than other existing models for
shock compression of dense metals at pressures P>3-5 TPa [12,14]. It was
important to see how well experimental data and results of Thomas-Fermi
calculations agree for Hugoniots of porous metals. Unfortunately, the range of
experimentally investigated pressures for these Hugoniots is not large and, as
already noted, a number of experimental points are characterized by a larger
than usual measurement error. But, because there are no other experimental data·
at the present time, we must be satisfied with what we have.
Comparison of results for copper, iron and tungsten is given on Fig. 5.6. The
error bars shown for experimental points were obtained based on study of the
gauges used to register the passage of the wave through the porous sample under
investigation. It can be seen from comparison of data on iron, that both
experimental points are situated a little higher than the calculated values. The
excess is -3% for the point with porosity m = 3.27 and -2% for the point with
porosity m = 3.45. Calculated Hugoniots are within experimental errors; they
have approximately the same slope dD/dU ~ 1.2 as Hugoniots of iron samples of
normal density. Somewhat better agreement of calculation and experiment was
obtained for copper. Similar results were obtained for porous tungsten.
We come to the conclusion that the position of Hugoniots calculated using
the Thomas-Fermi model does not contradict experimental data in the region of
terapascal pressures. On this basis, our conclusion, in agreement with previous
findings, is that predictions of the Thomas-Fermi model agree with experimen-
tal Hugoniots.

References
[1] Ya.B. Zel'dovich, Sov. Phys.-JETP 5(6), pp. 1287-1288 (1957). [trans. from
Zh. Eksp. Teor. Fiz. 32(2), pp. 1577-1578 (1957).]
[2] L.V. Al'tshuler, KK Krupnikov, B.N. Ledenev, V.I. Zhuchikhin, and
M.I. Brazhnik, Sov. Phys. -JETP 34, pp. 606-614 (1958). [trans. from Zh. Eksp.
Teor. Fiz. 34(4), pp. 874-885 (1958).]
194 RF. Trunin, KK Krupnikov, G.V .Simakov, and AI. Funtikov

[3] KK Krupnikov, MI. Brazhnik, and VP. Krupnikova, Soy. Phys.-JETP 15(3),
pp. 470-476 (1962). [trans. from Zh. Eksp. Teor. Fiz. 42(3), pp. 675-685,
(1962).]
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15(3), pp. 477-488 (1962). [trans. from Zh. Eksp. Teor. Fiz. 42(3), pp. 686-702
(1962).]
[5] RF. Trunin, G.V. Simakov, Yu.N. Sutulov, A.B. Medvedev, B.D. Rogozkin, and
Yu. E. Federov, Sov. Phys.-JETP 69(3), pp. 580-592 (1989). [trans. from Zh.
Eksp. Teor. Fiz. 96(3), pp. 1024-1038 (1989).]
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Pressures, VNlIFTRl, (1974), Vol. 1, pp. 61-64.
[8] RF. Trunin, AB. Medvedev, AI. Funtikov, MA Podurets, G.V Somakov, and
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Solid State. 5(1), pp. 203-211 (1963). [trans. from Fiz. Tverd. Tela 5(1), pp. 279-
290 (1963).]
[10] L.V Al'tshuler, S.B. Kormer, AA Bakanova, and RF. Trunin, Sov. Phys.-JETP
11(3), pp. 573-579,(1960). [trans from Zh. Eksp. Teor. Fiz. 38(3), pp. 790-798
(1960).]
[11] Al'tshuler, L.V, Soy. Phys-Usp. 8(1), pp. 52-91, (1965). [trans. from Usp. Fiz.
Nauk 85(2), pp. 197-258 (1965).]
[12] Al'tshuler, L.V., Trunin, RF., KK Krupnikov, and N. V. Panov, Phys-Usp. 39(5),
pp. 539-544 (1996). [trans. from Usp. Fiz. Nauk 166(5), pp. 575-581 (1996).]
[13] L.V. Al'tshuler, KK. Krupnikov, and MI. Brazhnik, Sov. Phys. -JETP 34(7),
pp. 614-619 (1958). [trans. from Zh. Eksp. Teor. Fiz. 34(4), pp. 886-893 (1958).]
[14] RF.Trunin,Phys.-Usp. 37(1), pp. 1123-1145 (1994) [trans. from Usp. Fiz. Nauk
164(11), pp. 1215-1237 (1994).
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684-690 (1996).
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1977.
[17] V.P. Kopyshev, Numerical Methods of Continuum Mechanics 8(6), pp. 54-67
(1977).
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41(3), pp. 544-548 (1976). [trans. from Zh. Eksp. Teor. Fiz. 68(3), pp. 1099-1107
(1975).]
[19] AB. Medvedev, Problems ofAtomic Science and Technology. Theor. and Appl.
PhYSics 1, pp. 12-19, (1992).
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(1960). [Trans. from Dokl. Akad. NaukSSSR 131(3), pp. 542-545 (1960).]
[21] R Latter,Phys. Rev. 99(6), p. 1854 (1966).
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Teor. Fiz. 49(8), pp. 485-492 (1965).]
 5. Shock-Wave Compression of Porous Metals 195

[23] AT. Sapozhnikov and A.Y. Pershina, Vapr. At. Nauki Tekh. Ser. Tear. Prikl. Fiz.
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Tear. Prikl. Fiz. (2), pp. 57-62 (1991).
 CHAPTER 6

Shock Waves and Polymorphic Phase

Transformations in Solids

A. I. Funtikov and M. N. Pavlovsky

6.1. Introduction
Propagation of shock waves in solids is profoundly affected by elastic-plastic
properties and first-order phase transitions [1]. The Hugoniot curves of a solid
that do, and do not, undergo a pressure induced phase transition are shown
schematically in Fig. 6.1.
Flows encountered in plane shock-wave experiments involve one-dimen-
sional (uniaxial) motion. The front of a relatively weak shock disturbance has a
two-wave configuration consisting of an elastic precursor propagating with the
longitudinal sound velocity, CL , followed by a plastic wave for which the veloc-
ity, D, depends on the applied pressure. The precursor amplitude, PI, is determin-

p a p

,,
\ ,,
,
\
,
\

or 6 0 Y

Figure 6.1. P- V diagrams for shock compression of solids. H is the Hugoniot adiabat, P
is the three-dimensional (bulk) compression curve, point 1, at the pressure PI, is the
Hugoniot elastic limit, and the curve 1-2 is the Hugoniot of the fIrst phase. (a) Elastic-
plastic solid without a phase transition. (b) Elastic-plastic solid that can undergo a phase
transition at the point 2, where the pressure is P2. The curve 4-3-6 is a decompression
adiabat from the high-pressure phase, and the curve 2-4 falls in a region in which two-
wave confIgurations exist.
V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII
© Springer Science+Business Media New York 2004
198 A. I. Funtikov and M. N. Pavlovsky

ed by the dynamic yield point in shock compression (often called the Hugoniot
elastic limit). Measured values of the dynamic yield point are known very
accurately for many materials [2].
In the pressure range from PI to P2 , shock disturbances have a two-wave
structure. Following the elastic precursor traveling at the speed CL , the second
wave producing further compression propagates at a lower velocity, D 12 • Small
volume perturbations propagate at the bulk sound speed, CB . At pressures near
PI the difference between CL and CB is very great, being, in particular, for steel
CL = 5.9 km/s, and CB = 4.6 km/s. At P2 the relation UI + DI2 = CL is valid and a
single front is restored.
The profile of two-wave structures in iron and copper were recorded by
Ivanov, Novikov, and Divnov using a capacitive transducer [3,4]. Data illus-
trating the structure of shock waves in iron are shown in Fig. 6.2 [4].
When P>PI , shock compression is accompanied by three-dimensional de-
formation of volume elements. This is accompanied by transformation of cubic
volumes into smaller cubic volumes determined by the macroscopic compres-
sion parameters. Such a transformation has the features of a first-order phase
transition: The number of atomic cells in a layer of material occupying a given
volume of space increases but the total number of such layers in the material
body decreases. The transformation mechanism was discussed in more detail in
[6].
According to the concept presented in [5], the initial formation of a shock-
wave front in a linear atomic chain involves nonequilibrium oscillations of the
crystal lattice points and, as a consequence, violation of the Rankine-Hugoniot
equation. However, later analysis by Dynin [7] has indicated the estimates ob-
tained earlier to be significantly overrated and the Hugoniot conditions to hold
strictly for experimental measurements of macroscopic scale.

V,kmIs
1.5

1.0

0.5

0.0 """"---.......-~-.......- .......

0.5 1.0 1.5 t, J1S

Figure 6.2. Free surrace VelOCIty prome measurea m )fon wnen 1t is shock compressed
to the pressure P = 36 GPa [4]. Reprinted with permission from SA Novikov, I.I.
Divnov, and A. G. Ivanov, Investigation offailure of steel, aluminum and copper under
explosive loading, inFiz. Met Metall. 21(4), pp. 607-615 (1966).
 6. Shock Waves and Polymorphic Phase Transfonnations in Solids 199

Compression of a substance by a strong shock wave produces melting that

causes the Hugoniot of the solid to join smoothly to that of the liquid phase. For
shock waves that are strong, but much below the strength required to produce
melting, the Hugoniot of the solid phase can also be close to the hydrostatic
curve. This is connected with processes of relaxation of shear stresses at the
shock-wave front as was first shown by Dremin and Kanel [8] who studied cop-
per and aluminum at pressures of 35 and 18 GPa, respectively. This relaxation
of the shear stress behind the shock-wave front causes the stress behind the
discontinuity to be close to isotropic [9]. Nevertheless, some shear strength
remains and, in all ranges of shock compression of solids, the initial portion of
rarefaction waves from the Hugoniot state includes a region of uniaxial
deformation that is followed by further isentropic volume expansion.

6.2. Sound Speeds and the Strength of Shocked Metals

The speed of sound behind a shock in the megabar pressure range was first
measured in [10]. In this work, two techniques were developed in which the
propagation of sound perturbations was examined by detecting the arrival of
sound at the shock front. In one technique, known as the lateral surface unload-
ing method, sound speed measurement involved shock-wave propagation along
a cylindrical specimen with a step-wise lateral surface profile. Expansion waves
starting from the origin on the ledge overtake the front. causing a pressure drop
in the peripheral zone. The velocity of the leading rarefaction wave is deter-
mined from the difference in shock wave arrival times at the specimen end sur-
face.
The second approach, the so-called overtaking unloading technique proposed
by the authors of [10] together with Academician E.!. Zababakhin, is to measure
shock-wave attenuation in a target that had been impacted by a thin plate. The
sound speed was calculated from the shock pressure change along the unloading
portion of the wave path. This method provided bulk sound speeds in shocked
AI, Fe, Cll, and Pb in the pressure range 40-350 GPa.
Using the lateral surface unloading method, two sound wave propagation
velocities, CB and CL , were discovered for the first time [10]. The lower veloc-
ity, CB , was that of the "plastic" wave characterizing the bulk compressibility
and the higher velocity, CL , was the velocity of the elastic longitudinal wave of
uniaxial compression. Measurements were made at -40 GPa for Cu and Fe.
Further studies of the propagation of elastic and plastic rarefaction waves relied
on the more informative overtaking unloading method [11,12] and provided
more details on the flow behind the shock during the incipient interaction of the
wave under study with the overtaking elastic rarefaction waves in the 30-80
GPa [11] and 110-180 GPa [12] pressure ranges.
In the 19805, Brown, McQueen, Shaner, and other American researchers
[13-18] made a significant contribution to the method of overtaking unloading
by using optical attenuation detection techniques in their shock-wave studies
200 A. I. FlUltikOV and M. N. Pavlovsky

using transparent liquid indicators. The variation of the elastic sound speed CL
with the shock pressure was examined for AI, Fe, Ta, and Mo. Using calculated
CB(P) dependences consistent with the AI and Fe data [10,12], the melting point
of a shocked material was estimated from a decrease in the CL - CB difference
(the decrease reflects the variation of Poisson's ratio and its approach to the
liquid-state value ofO.5).
The amplitude of the elastic rarefaction wave, like that of the elastic precur-
sor, determines the value of the dynamic strength under shock compression. By
estimating this amplitude from the particle velocity of the shock wave along its
trajectory, it proved possible to evaluate metal properties such as the bulk
modulus, the coefficient of elasticity, the shear modulus, the dynamic strength,
and Poisson's ratio, for the material behind the shock [11,12].
Referring to Fig. 6.3, the CL(P) and CB(P) dependencies for AI [10,13,17]
and Cu [10,12,18,l9] demonstrate the foregoing methods to be fully consistent.
The decrease in the CL - CB difference for Cu agrees well with the theoretical
estimate for the melting point of the shocked material [20].
Data on deformation of material behind a shock wave were obtained by
Kanel from pressure profile measurements made using the manganin gauge
technique [2]. In Ref. [8], measurements on rarefaction and reshock waves were
made for AI and Cu at 18 and 25 GPa, respectively. It was shown that the re-
laxation of shock-front shear stresses, which causes the stress field in the mate-
rial behind the shock to become isotropic, occurs at pressures far below the shock

o
12
Jltt "
0/
10
rI~
I
I
I
I 7 III
11.1
D Z
6 I" 01
¢ ~
(a), AI (b),Cu
i~--~----~--~----~
o50 100 150 P, GPa 100 100 JOO P,GPa

Figure 6.3. (a) Pressure dependence of the longitudinal (dashed line) and bulk (solid
line) velocities in AI. The data are from I: [10), 2: [13], and 3, [17]. (b) Pressure depend-
ence of the longitudinal (dashed line) and bulk (solid line) velocities in Cu. The data are
from 1: [10],2: [12], 3: [18], and 4: [19].
 6. Shock Waves and Polymorphic Phase Transfonnations in Solids 201

melting point. Taking into account the stress relaxation, the shear strength, Y,
determined by the overtaking unloading method is 5.4 GPa for Fe at
P = 185 GPa and 3.2 GPa for Cu at P= 122 GPa-values several times the
initial shear strength in both cases [12].
An alternative technique for determining shear stresses in a shocked material
involves making a manganin gauge measurement of the principal stresses on
two mutually perpendicular planes [8,21-25]. This, however, is hardly a practi-
cal method to implement because perturbations advancing in the longitudinal
slots containing the lateral-stress gauges complicate the measurement of lateral
stresses in high-density materials like Cu or Pb [8,24]. The method under dis-
cussion fails to relate the measured shear stresses to their critical values [25].
Critical shear stresses (and their separation into instantaneous and equilibrium
components behind the shock) are determined by the Asay-Lipkin "self-con-
sistent" method [26]. Shear strengths have been obtained for AI, Be, and other
metals [27,28]. In Ref. [24], a dynamic strength comparison of self-consistent
and principal stress measurements is made for the case of AI. There is evidence
[8,24,27] to confirm the occurrence of shear stress relaxation in the pressure
range above 10 GPa.
Shear strength evaluation is currently one of the most controversial problems
in the calculation and theoretical analysis of elastoplastic deformation in shock
waves [29].

6.3. Phase Transformation in Shock Waves

A solid may undergo a variety of shock-induced phase transitions. This phe-
nomenon is called shock polymorphism. Shock-induced polymorphic transitions
have been found in many metals, semiconductors, ionic compounds, and in virtu-
ally all known minerals and rocks. A characteristic feature of polymorphic transitions
is that they usually occur at the same pressure under both static and dynamic
conditions. This is true of Fe, KCl, S~ Ge, and some other substances. One excep-
tion is quartz, for which the shock transition pressure corresponds to the elastic limit
of shock compression and exceeds the static value. The reader is referred to review
papers [1,30,31] for a discussion of original work.
The high rate at which phase transitions occur in shock waves is indicative
of their martensitic nature due to the shear strain of the material. The formation
of a high-pressure phase is preceded by the passage of an elastic precursor and,
at the front of the wave that corresponds to a phase transformation, defects are
produced which become nuclei for re-crystallization under supercritical conditions.
The features of flows with phase transitions become apparent during both
compression and the following decompression. These peculiarities are con-
nected with the existence of a convex portion passing through the cusp point P2
on compression curves in the P-V diagram (Fig. 6.1b). Two-wave configura-
tions with an elastic precursor arise at pressures P<P2 and P>P4 and corre-
202 A. I. Flllltikov and M N. Pavlovsky

spond to the states below and above Michelson-Rayleigh line 1-2-4. Within
the regionP2 <P<P4 , "splitting" of the shock wave into two waves related to
the plastic states of the initial phase of the material and of its high-pressure
phase were observed. The shock splitting is caused by instability of compressive
shocks when their amplitude exceeds the critical pressure at which the low-pres-
sure phase ceases to exist. A two-phase mixture is present in the region 2-3.
Phase changes in shock waves have received considerable attention at
VNIIEF. The list of methods employed in experimental investigations spans the
available shock compression techniques, including electromagnetic- and manganin-
gauge methods for measuring bebind-the-shock parameters, determination of opti-
cal and electrical parameters, pulsed x-ray structuml analysis, and the study of
structuml changes in specimens recovered after shock compression. The materials
covered, apart from a large number of elements, also include the alkali halides, car-
bides and nitrides, oxides, rocks, and organic substmces. In the late 1960s nu-
merous and previously unknown shock-induced transitions were identified for
alkali-earth and rare-earth elements in pioneering investigations by AI'tshuler,
Bakanova, and Dudoladov [32]. These investigations were summarized in [68].
AI'tshuler and Pavlovsky have studied the peculiarities and mechanism of
polymorphic transformations in the group N elements [34], boron nitride [35],
and alkali halides [36].
Ivanov, Novikov, and colleagues [3,4,37], in their study of phase transfonna-
tions in Fe, measured shock-wave profiles and found the phase tIansition front
width to be 2 x 10-7 s. For the first time, "smooth" spalls formed by colliding
rarefaction shock waves were observed. An analysis of the experimental data
obtained in Refs. [3,4] was given by Zel'dovich [33]. A rarefaction shock wave
was measured directly using a manganin pressure gauges [38].
The specific character of shock-induced polymorphic transitions in solids is
connected with the peculiar properties of shock discontinuities [39]. The influ-
ence of temperature on shock compression is reasonably small. Formation of the
high-pressure phase takes place during propagation of the shock wave following
the elastic precursor. Its front is a surface on which point, linear, and planar
defects arise. These defects become re-crystallization centers at supercritical
pressures.
Phase transformations in shock waves generally follow the pattern seen in
martensitic transformations. Martensitic nondiffusional rearrangements make
ultrahigh speed transformations from one crystallographic lattice to another
possible on the basis of co-operative displacement of many atoms over small
distances. Such athermal transformations do not require an activation energy,
and proceed at sonic velocities in material at very high temperatures. This per-
mits the growth of single grains in a time of -10 -8 s.
 6. Shock Waves and Polymorphic Phase Transfonnations in Solids 203

The martensitic character of transformations in shock waves was established

from data on ctystal orientation in recovered iron samples that underwent 0.-6
and o.-y transitions [40,41], in titanium samples that underwent the o.-co transi-
tion [42], and in samples of many other substances considered below. Asymme-
tty of transformation under compression with impulsive loading relates to a
monotonic decrease in pressure in the isentropic rarefaction wave.
Direct information on the martensitic character of transformations was ob-
tained in [43], where the use of pulsed x-ray diffraction analysis permitted re-
cording of transformations at the shock-wave front from monoctystalline boron
nitride to monoctystalline borazon with a cubic zinc blende structure.
Shock-induced polymorphic transformation in solids was first discovered
from a cusp on the Hugoniot of iron at the pressure P3 = 13 GPa [44]. This phase
transition, initially assumed to lead to the y phase, was later found under static
conditions as evidenced by a jump of conductivity [45]. Studies of the macro-
structure of the samples after shock compression [40] have elucidated a region
of a new phase on the phase diagram. X-ray diffraction analysis under static
pressure [46] has shown that the new high pressure 6 phase corresponds to a
close hexagonal packing.
In [44], the profile of a two-wave configuration was established by recording
the velocity of the free surface of the compressed sample with a great many
electrocontact pins positioned along the path of motion of the free surface. Us-
ing a more elaborate procedure permitting continuous recording of the velocity
of a free surface, and the profile of the shock wave in iron was determined in [4]
(see Fig. 6.2).
The appearance of methods for continuous recording of wave profiles at in-
terior planes of the sample with manganin gauges has enabled Anan'in, Dremin,
and Kanel to determine stresses behind the first plastic compression wave and

P,GPa

20

10

o 2 3 t, J.I.S

Figure 6.4. Stress profiles in iron produced by an impacting plate having a velocity of
2 kmls [47].
204 A. I. Fl.Ultikov and M N. Pavlovsky

before the front of the rarefaction shock wave. These positions correspond to the
beginning of direct and reverse (X.-S transitions, which occur at 12.6-14 and
12.3 GPa, respectively [38]. In the case of a shock wave of sufficiently large
amplitude, the recorded profile corresponds to a three-shock configuration and
to an isentropic decompression wave followed by a rarefaction shock wave
connected with the reverse phase transition [47] (Fig. 6.4).
According to measurements of mass-velocity profiles in shock waves [48]
the steepness of the phase-transformation wave increases with an increase of the
shock-wave pressure. Data [44,48] on the change of the state of iron during
shock compression and decompression are shown on the P- VI Vo diagram (Fig.
6.5). Alternative lines of phase equilibration are indicated on the same diagram
[49,50].
The critical pressures of the (X.-S transformation [38,48] are in close agree-
ment, whereas data from [48] on the reverse (X.-S transition are given in [38] and
characterized by hysteresis. The value P= 9.8 GPa [40] accords well with the
results of static measurements [51,52], which are also considered in the context
of a martensitic transition in iron corresponding to an equilibrium pressure of
10.7 GPa of reverse transition
The interesting kinetic peculiarities of phase transformations from an initial
structure of the NaCI type into the more closely packed CsCllattice were dis-
covered in studying shock compression of potassium chloride and other halides,
which was a subject of numerous and detailed investigations in 1963-1967 [36,

P,GPa
~O~----------------~

A ,
JO o
__ 3
Z
_.- ~

8,85

Figure 6.S. TheP-V diagram ofphasetransfonnations in iron. 1: data of [44], 2: data of

[38], 3: calculation from [49], 4: calculation from [50).
 6. Shock Waves and PolymolJlhic Phase Transfonnations in Solids 205

54,55], as well as in more recent works [56-59]. Shock compression of

potassium chloride in the region of comparatively low pressures of phase trans-
formations, -2 GPa, involves negligible heating. Thus, the Hugoniot closely
approximates the static compression curve obtained by Bridgman [60]. By re-
cording mass-velocity profiles in dynamic compression and decompression [53],
as well as the shock impulse [59], the authors have observed splitting of shock
waves at pressures above that of the phase transformation. The data of [53] have
revealed dependence of transformation time on the magnitude of the applied
load. The strong hysteresis of reverse re-crystallization and formation of a rare-
faction shock was established for the decompression wave. After averaging all
data with the exception of dropping out the result of [58], the pressures of direct
and reverse transformation are equal in accordance with [59]; P2 = 1.97 GPa
(Fig. 6.6). The proximity of the value of P2 to the equilibrium value obtained
from static tests [60] is evidence of the martensitic character of transformations
at shock discontinuities. This is related to the formation of active re-crystalliza-
tion centers due to the action of shear stresses. In the isentropic rarefaction
wave, the conditions for formation of active nucleation centers are degraded and
the hysteresis of reverse transformation arises. The strong hysteresis of reverse
recrystallation and formation of a rarefaction shock was established for the de-
compression wave at the pressure P3 = 1.15 GPa [59].
At high pressures, when the two-wave profile fails to arise, the transforma-
tion times in KCl were estimated by Kormer [61] from optical reflectance of the
shock-wave front. At such pressures the formation of the compacted phase oc-
curs across the thickness of a single compression shock wave in a time less than
10-12 s.

P,GPa
,
J

2 0'Z
6

, D J
--'-

DAI V,cm3/g

Figure 6.6. HugoniotforKCl. The data are from I: [53],2: [56], 3: [59], and 4: [54].
206 A. I. Funtikov and M N. Pavlovsky

6.4. Mechanism of Polymorphism of Group IV Elements

High-pressure phases of the three transition metals of group IV, titanium, zirco-
nium, and hafnium, were studied in the pressure range up to one megabar in
static [62,63] and dynamic experiments [32,64-68], as well as by examining
samples recovered after shock compression [69,70]. Under normal conditions,
the three metals crystallize in the hexagonal close packing of the a. phase. High
pressures initiate a transition to the more dense packing of the hexagonal co
phase, which was :first discovered in titanium and zirconium by Bridgman [60].
The equilibrium pressures of the a.-co transformation of titanium and zirconium
were refined in [62] in which static compression was produced under conditions
of supplementary shear deformation. These measurements indicated that equilib-
rium transition pressures at room temperature fell close together and amounted
to -2 GPa The a.-co transition itself has, however, a marked hysteresis, which
allows identifying its isothermal martensitic character. The rate of this transfor-
mation proved to be strongly dependent on the purity of the material and the
loading conditions. This appears to explain existing scatter in data at the begin-
ning of the a.-co transformation in these metals [62,63], corresponding to the
pressures from 3 to 9 GPa
Refinement of the data on the beginning of the a.-co transformation of tita-
nium and zirconium and prediction of similar data for hafnium was carried out
by Kutsar [70] on the basis of similarity of their physicochemical properties and
curves of phase equilibrium on the T-P diagrams. Realistic phase diagrams of
titanium and zirconium were obtained in [42,69] by analyzing the formation of
the co phase in samples SUbjected to short duration (-5 x 10-6 s) shock loading.
The data obtained reflect a difference in martensitic transformations under static
[62] and shock loading [42,69] (Figs. 6.7 and 6.8). An analysis of the kinetics of
isothermal transformation under static conditions and that of athermal marten-
sitic transformation under dynamic conditions using these data have been made
by Vohra [71). He determined the pressures, 5.8, 6.8, and 23.6 GPa, respec-
tively, at the beginning of athermal martensitic transformation for the three
metals discussed above. These values are somewhat higher than the threshold of
isothermal static martensitic transformations at ambient temperatures and again,
as in static deformation, are characterized by a considerable hysteresis.
Direct measurements of shock-wave profiles in titanium and zirconium (us-
ing the manganin-gauge technique) were carried out by Pavlovsky et al. [72,73].
Later, Morris [74] made shock-wave measurements in titanium using the
VISAR technique and Kanel et al. [75] used the ORVIS technique and loading
with a pulsed ion beam in the nanosecond time range. The phase transformation
pressures in titanium, obtained with explosive loading, were 11.9 GPa [72] and
10.4 GPa [74]. The corresponding value for zirconium was 6.5 GPa [73]. The
results of [75] show that the phase transition pressure in titanium depends on the
loading pressure and falls within the range 2.2-4.3 GPa. The reason for these
differences between the data from [72,74] and [75] remains unknown.
 6. Shock Waves and Polymorphic Phase Transfonnations in Solids 207

T,K
jJ

fOOO

5UU

20QL---------~~--------~----------~
o 10 20 P,GPa

Figure 6.7 The T-P phase diagrams for titanium. 1: a region of a.-m transfonnation at
static pressures [62]; 2, 3: Hugoniot and boundary of phase transfonnation [42,69], 4: a
region ofHugoniot bend [67], and 5: phase boundaries [70].

T,K

z~L---------L---------~--------~--~
o fO 20 JD P, GPa

Figure 6.8 The T-P phase diagram for zirconium. 1: a region of a.-m transfonnation at
static pressures [62], 2, 3: Hugoniot and phase boundary [42,69],4: a region of Hugoniot
bend [67], 5: data on m-13 transfonnation [76). Phase boundaries, 6: [70], and 7: [78].
208 A. I. Funtikov and M. N. Pavlovsky

In measurements of shock-wave profiles in titanium and zirconium [72,73]

elastic precursors of amplitude 1.5 and 1.4 GPa, respectively, were recorded.
Independent information on phase transformations, obtained with common
methods, lies in the shape of the Hugoniot, which is, particularly, represented by
a non-monotonic relationship between shock-wave velocity and mass velocity.
Hugoniots of titanium, zirconium, and hafnium were obtained in [32,64-67].
These data are presented in Fig. 6.9 after systematization and statistical analysis
of the experimental results in [67]. The D- U relations for these metals consist
of three portions: an initial portion of the Hugoniot, a horizontal plateau where
conventional measurement technique records a constant velocity of the advanc-
ing shock wave corresponding to the beginning of transformation, and the
Hugoniot of the second phase after the two-wave profile collapses to a single
discontinuity surface. The smooth Hugoniot for titanium was discussed in [66].
A small discontinuity in the data of [64] relates to a change of 0.65-0.88 kmls
in mass velocity. There is close agreement between the measurements for zirco-
nium and hafnium. Hugoniot pressures at the points of inflection are equal to
16.7, 26.5, and 44.5 GPa, and appreciably exceed the pressures of the a.-co
transition, as established in the works cited above. That these Hugoniot features
remained unnoticed might well be attributed to the small density change at the
a.-co transformation.
Special investigations of static compression together with heating in the
tempemture range 290-450 K have been carried out in [76] to analyze the pos
sibility that a break would be present in the Hugoniot of zirconium. X-my dif-

D,kmIs
~----------------~~
1
o

Figure 6.9. Shock-wave velocity versus mass velocity for titaniwn, zirconiwn, and
hafuiwn [67]. 1: Ti, 2: Zr(D+2), 3: Hf(D+ 1).
 6. Shock Waves and Polymorphic Phase Transformations in Solids 209

fraction analysis of the compressed metal showed that. at pressures near 35 GPa.
a transformation proceeds from the 0) phase to the body-centred lattice of the j3
phase. An equilibriwn boundary of the 0) - j3 transition in this domain of the
phase diagram relates to the negative slope of the curve equal to 39 KlGPa [76].
This phase interface describes the phase transformation under shock compres-
sion established from a break of the D- U relation (Fig. 6.9) at P = 26.5 GPa and
a calculated temperature of 540 K. It seems probable that a similar phenomenon
occurs for titaniwn and bafniwn.
Further examination of the behavior of zirconiwn under shock compression
has been carried out in VNllTF by Kozlov et al. [77]. The structuml changes
were studied in a spherical sample subjected to loading by a quasi-spherical
shock wave. The previously published experimental data [60,62,69,70,76) were
analyzed in [78), where it formed the basis for complete equations of state of the
phases of zirconiwn. The Hugoniot, decompression isentropes, and the phase
boundaries shown in Fig 6.8 are calculated from this equation of state.
Determinations of shock compression [67] and measurements of pressure
pulse profiles with manganin gauges [72,73) afford complete information on a
sequence of phase transitions under shock loading in titanium, zirconiwn, haf-
niwn.
Silicon and Germanium. Under normal conditions, silicon and germaniwn are
semiconductors and have the structure of a diamond. As shown in investigations
carried out under static compression [79] at pressures of 14-15 and 12 GPa.
respectively, they undergo phase transformation. In silicon the transition is
stimulated by shear deformation and results in the appearance of metallic con-
duction X-ray analysis [80] indicated re-crystallization into a tetragonal struc-
ture of the white tin type. The Hugoniots of silicon and germanium were
determined in [81-85]. Pavlovsky [83] has studied shock compression of these
elements in the pressure range up to 250 GPa. Propagation of elastic precursors
of the high amplitudes 4.0 and 4.2 GPa and formation of three-wave structures
over a wide range of shock pressures was recorded for silicon and germaniwn
with electromagnetic gauges [83]. Shock-wave profiles at pressures -20 GPa are
shown in Fig. 6.10. Values of the Hugoniot elastic limits and phase transforma-
tion pressures of 11 and 14 GPa [83] are in good agreement with dynamic data
by Graham et al. [82] as well as with earlier results for silicon and germaniwn
[81].
The results of the determination of static and dynamic compressibility of
silicon and germaniwn are shown on the P-V diagram (Fig. 6.10). For germa-
nium, the phase transformation under shock compression occurs at a hydrody-
namic pressure of 12 GPa, in agreement with the static data [79,80). Similar
agreement is observed for the change in specific volwne at the transition to the
high-pressure phase.
210 A. I. Funtikov and M. N. Pavlovsky

P,GPa
P Sl

Figure 6.10. Hugoniots for Ge and Si [83). Inset: shock wave profilep(t) in Si.

A different, and somewhat ambiguous, situation arises for silicon. The

Hugoniot of its dense phase is displaced leftwards from the isotherm obtained
under static conditions [80]. The static phase transition pressure at a low level of
shear stress was 20 GPa [79], but decreased to 14-15 GPa when substantial
shear stress was present [79]. The most recent data establish the change in vol-
ume at the phase transition to be 9.2%. Reduction of the mean hydrostatic pres-
sure of the silicon phase transformation under shock compression to 9-10 GPa
[82,83] could be accounted for by a significant increase of the shear stress at the
front of the plastic phase transformation shock wave. Gust and Royce [84,85]
have observed the effect of crystal orientation on the silicon phase transition
under shock compression. In this case an additional phase transition at a pres-
sure of 14 GPa was recorded for the [Ill] orientation.
Carbon. Shock-induced phase transition in carbon has been an object of many
investigations. Interest in this phenomenon is associated with the study of car-
bon polymorphic transformation characteristics and the problem of production
of artificial diamonds. Carbon is a group IV element, as are silicon and germa-
nium. Its initial state often takes the form of graphite of various types (pyroli-
thic, natural, pressed).
The first direct evidence of the existence of a phase transformation in graph-
ite under shock compression was obtained in 1961 by DeCarli and Jamieson
[86] and by Alder and Christian [87]. In this last work, the authors determined
dynamic compressibility up to a pressure of 90 GPa and found a double bend of
the Hugoniot related, in their opinion, to the formation of a compact metallic
phase of carbon along with a tetrahedral diamond phase.
 6. Shock Waves and Polymorphic Phase Transformations in Solids 211

In VNIIEF Pavlovsky and Drakin, in 1966 [88], and Trunin et al., in 1969
[89], carried out detailed investigations of shock compression of graphite where,
particularly, the problem of existence of a metallic phase was discussed. Data
[86-89] agree well up to the 40 GPa pressure of transition to the diamond phase
and on up to the 55 GPa limiting pressure for the existence of a mixed phase.
Above this pressure a smooth Hugoniot is reported in [88,89], roughly relating
to the Hugoniot of diamond obtained by Pavlovsky with natural monocrystals in
the pressure range from 50 to 580 GPa [88,90] (Fig. 6.11).
The lack of any metallic phase in graphite and diamond according to [88-
90], as well as dependence of the position of experimental points from [87,88]
on the thickness of the samples permitted the authors to point to the inaccuracy
in data of [87] in the pressure range above 55 GPa. This inaccuracy is probably
related to the effect of decompression waves on the shock-wave propagation in
the samples under investigation. The foregoing is substantiated by the measure-
ments of [89], carried out with large propagation distances at a pressure of 62
GPa produced by an underground nuclear explosion [89], as well as by a study
of the effect of propagation distance [88].
McQueen and Marsh [91] and Dremin and Pershin [92] have further refined
the data on shock compression of various modifications of graphite, indicating
that the pressure of phase transition from graphite into diamond depends on the
initial density and temperature (after cooling) of the sample.
Certain disagreement in pressures between the results of measurements of
shock wave and free surface velocity related to kinetics of the phase transforma-
tion have been recognized from investigations carried out by Kanel et al. using

P,GPa

IDO
I
80

5/J
I
I
I
... z
I
I
I... .....
1,0

10

0
o,z o,J

Figure 6.11. TheP- V diagram of carbon shock compression. Experimental data 1: [90],
2:[88],3: approximation of the data from [89], and 4: the Hugoniot for diamond [87].
212 A. I. Funtikov and M. N. Pavlovsky

manganin gauges [93,94]. Similar results were obtained by the indicator-liquid

method, where recording the pressures involved measurement of the brightness
of the shock front in an indicator liquid adjacent to the sample [95]. The effect
of the shock-wave velocity relaxation, which is characteristic of the region of
shock-wave splitting in graphite, results in incorrect determination of the critical
pressures of phase transformation from the nonmonotonic form of the Hugoniots
[95]. Various measurements of the relation between the sound velocity behind
shock front and the pressure, including those made using the overtaking decom-
pression wave method [96,97], have shown that the phase transformation from
graphite to diamond begins at pressures of 24-35 GPa and is completed at 29-
40 GPa, depending on the type of graphite under investigation.

6.5. Experimental Data for Quartz and Other Minerals

The first papers that considered shock compression of quartz appeared in 1962
independently by Wackerle and by Dremin and coworkers [98,99]. An interest-
ing effect was discovered in these first papers. At a pressure of 10 GPa, a den-
sity jump was detected in the compression curve of quartz, which was explained
in [99] as a phase transition from a-quartz (Po = 2.65 glcm3 ) to coesite (Po = 2.98
glcm\ However, this interpretation proved to be wrong. Wackerle [98J, who
studied a-Si~ in the same pressure range, also detected a phase transition, but,
based on a more careful experiment, another explanation of its nature was sug-
gested, namely, as a transition from a-Si~ to stishovite (Po = 4.28 glcm3 ). Later
on, this interpretation of the data became generally accepted.
The megabar limit of compression studies for quartz was overcome in 1965
[100]. In 1971, the pressure threshold was raised to 350 GPa for laboratory con-
ditions and to 550 GPa (quartzite) for underground nuclear explosions [101].
The relative compressibility of the AI-Si02 system was measured up to 2 TPa
[101]. Later on, this pressure was raised to ~13 TPa [102J, the record value for
measurements of the relative compression of quartz.
Figure 6.12a shows the joint results of compression measurements of quartz
single-crystal samples, Po = 2.65 g/cm3, quartzite (polycrystalline samples)
Po=2.65 g/cm3, coesite, Po=2.92 g/cm3 , amorphous quartz, Po=2.2 glcm3 , and
cristobalite, Po=2.13 g/cm3, as well as the results for quartzite obtained in un-
derground nuclear explosions. The main difference of the latter from the labo-
ratory measurements is the use of significantly thicker samples (by two orders
of magnitude). The thickness of laboratory samples was several millimeters,
whereas it reached 1 m in underground explosions. Therefore, the coincidence
of both results indicates that the shock-wave front plays a special role in the
phase-transition kinetics: Formation of the new phase takes place mainly at the
shock front and does not depend on the scale of the experiment
After the a-quartz-to-stishovite phase transition, the experimental Hugoniot
for quartz (quartzite) up to a pressure of 13 TPa shows a smooth, monotonic
 6. Shock Waves and Polymorphic Phase Transfonnations in Solids 213

D, a D,
kms- I kms- I

15 35

13
30

11
25

20
7

15
5

3 10
2 4 6 8 10 U, km 5- 1

P,GPa b 4
5
60
6
.,,
7
v

40

20

2 3 4 p,gcm- J

Figure 6.12. (a) The D-U diagram for silica ffi: a-quartz; 0: quartzite; .: quartzite
(measurements in underground nuclear explosions); 1: coesite, 2-4: quartz-quartzite
(scales for dependence 4 are on the right and on the top), 3: amorphous quartz (+) and
cristobalite (6). (b) P - p diagram for silica: 1: the shock adiabats for coesite (m = 1.0);
2: a-quartz (quartzite); 3: cristobalite (m= 1.22); 4-13: porous a-quartz with initial
densities 1.75, 1.55, 1.35, 1.15,0.8,0.65,0.55,0.40,0.20, and 0.13 g cm-3, respectively.
214 A. I. FlUltikov andM N. Pavlovsky

behavior without additional jumps of mass velocity, i.e., without density jumps.
The reason for lack of a denser-than-stishovite silica modification could be the
strong shock heating of silica.
The conclusion that the phase transition in silica is indeed from a.-Si02 to
stishovite is based in [98] on the agreement between the value of density ob-
tained from the extrapolation to P = 0 of the steep branch of the quartz Hugoniot
and the stishovite density. The correctness of this conclusion could be verified
by studying shock compression of quartz with various initial densities (porous
quartz). If the quartz-to-stishovite transition really takes place, then the
Hugoniots of the porous samples will form a fan of ascending superdense
branches centered on the initial density of stishovite. The results of studies of
porous samples [103-107] are plotted in Fig. 6.12b. It is seen that data for silica
can be, somewhat arbitrarily, classified into three groups. The first group con-
sists of Hugoniots with the initial density Poo> 1.55. Extrapolation of the steep
parts (dense phase) of the Hugoniots to P = 0 (bearing in mind the differences in
the shock compression temperature) yields a density in good agreement with the
initial density of stishovite (108].
The compression curves for initial densities in the range 0.06 < Poo < 0.8
g/cm3 may be associated with coesite Hugoniots. The extrapolation of their
high-density parts to zero pressure does not contradict the initial density of coe-
site (Po =2.98 yJcm3). Finally, there are three Hugoniots (Poo = 1.15, 1.35, and
1.55 g/cm3) between the Hugoniots we associate with coesite and stishovite.
The goal of two-step compression studies of silica is to try to investigate the
phase transitions on the stishovite Hugoniots for less (in comparison with a
single compression) heating of the samples. The setting of experiments is essen-
tially similar to the reflection method [109]. The difference being that here the
material to be studied (quartz or quartzite) is used as the screen. Samples of the
standard metals are installed behind the screen. In this case, the sample being
studied is compressed in two steps: the first compression step is due to passage
of the direct shock wave. The second step occurs when this shock is reflected
from the standard metal. The final results are illustrated in Fig. 6.13. Obviously,
the two-step compression Hugoniots have bends that can be interpreted as an
indication of a transition of the stishovite to a new superdense phase. Therefore,
two-step quartz-compression experiments point to the possible existence of a
denser-than-stishovite phase of Si02•
Rocks. An extensive body of information on shock compression of minerals
and rocks has been obtained in the works of Russian and American scientists.
The first investigations were undertaken by Hughes and McQueen [110] who
determined Hugoniots of gabbro and dunite up to 70 GPa. One dunite point at a
shock compression pressure of 230 GPa was obtained by Bakanova [111]. Sys-
tematic investigations of rocks and minerals, along with quartz, up to pressures
of 100-300 GPa were carried out by Al'tshuler and Trunin and their co-workers
 6. Shock Waves and Polymorphic Phase Transformations in Solids 215

GPa

200 ...

100 ...

OL---------~----------~------~
o 5 6 p,glcm3

Figure 6.13. Two-step shock compression Hugoniots for silica.

[101,113]. There are now data on shock compression for both abyssal and super-
ficial magmatic rocks and minerals and the pressure range has been increased to
100-400 GPa [112-117].
The shock-wave experiments demonstrated that almost all minerals and
rocks undergo phase transformation at critical pressures from 10 to 50 GPa
resulting in formation of dense modifications of relatively low compressibility.
Below these pressures the shock-compression curves are characterized by a
great variety of shape, but above the phase transition the curves appear similar.
The most complete work devoted to surface rock compression [112] generalizes
the results of studies of more than 100 individual rocks of magmatic and sedi-
mentary types. Their average values are shown in Fig. 6.14.
Qualitatively, the majority of Hugoniots for magmatic rocks represent simi-
lar dependences with nearly equal parameters, namely, a flat initial part (treated
as a phase transition in rocks) and a steep second part (compression of dense
phases) with a slope varying (atD= 11-12 km/s). Note that, in the dense-phase
region, the slopes of Hugoniots of magmatic-type rocks are similar to each other
and to the slopes of Hugoniots of quartz and silica-type rocks. The first flat part
of the Hugoniots of the magmatic rocks having a complex mineral composition
and structure possibly reflects "average" (under the effect of pressure) properties
of separate minerals.
No such a similarity is observed for Hugoniots of sedimentary rocks. The
compression curves for clay and calcite rocks are characterized by qualitatively
different D( U) dependencies, except for shale and sandstone, for which the
Hugoniots are similar to those of magmatic rocks.
Paper [113] summarized the results of studies of deep-seated rocks, mostly
of olivine and enstatite types, and reported the compression of a great number of
216 A. I. Funtikov and M N. Pavlovsky

D, km/s D,km/s
J

14
14

12
12

10
10

o 2 4 U, km/s 4 8 U, kmls

Figure 6.14. (a) A D-U diagram for magmatic rocks. 1: gabbro (D+2), 2: sienits
(D + 2), 3: tuffs, 4: granites, 5: porphyries (D + 1), 6: average adiabat for magmatic rocks
(D + 3). (b) A D-U diagram for sedimentary rocks. 1: magnesite, 2: dolomites, 3: lime
stone, 4: aleurolites, 5: clays, 6: shale (D + 3), 7: sandstone CD - 4).

ultrabasic and basic rocks up to a maximum pressure of 200 GPa (in some cases
up to 500 GPa). This pressure range exceeds the pressures reached by foreign
scientists by more than an order of magnitude. The Hugoniots that have been
obtained represent lines with similar slopes in D- U coordinates and are charac-
terized by breaks in D( U) dependencies related to phase transformations.
As mentioned above, phase transitions occurring at certain pressures from
the initial states to denser and strongly compressed phases are a common prop-
erty of rocks and minerals. According to data of [118,119], phase transitions in
these systems result in the formation of an isochemical mixture of close-packed
oxides of metals and silicon. This fact was used in [120] to reproduce from ox-
ide compositions the additive equations of state for minerals and rocks and to
obtain Hugoniots of the corresponding compounds. The experimental results and
 6. Shock Waves and Polymorphic Phase Transfonnations in Solids 217

calculations (Fig. 6.15) were compared in [120] and the agreement was found to
be very good. However, in some cases, the slopes of the calculated additive
Hugoniots are greater than the slopes of experimental Hugoniots.
In [121] the problem of correlation of the oxide composition with Hugoniots
was considered. For all rocks, minerals, and rock-forming oxides, a method of
correlation-regression analysis of experimental data-was applied to obtain
the simplest analytic dependencies which were chosen in the form of multi-
regression equations. These dependencies can be used to calculate Hugoniots of
rocks and minerals. Figure 6.15 shows a satisfactory agreement between calcu-
lations and experimental results for certain mineral Hugoniots.

P,GPa

100

50

O'--_ _ _.L.-_ _ _-'--_ _ _...L-_ _ _- - ' - - '

4.0 4.5 5.0 5.5 p, g/cm3

Figure 6.15. Calculated Hugoniots for minerals and rocks. 1: MgO, 2: Si02, 3: enstatite
rock (p + 2), 4: calcite (p + 1), 5: granite (p + 2), 6: albitite (p + 1.3). The dashed line
represents calculations in [120] and the solid line represents calculations in [121].

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222 A I. Ftmtikov and M N. Pavlovsky

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 6. Shock Waves and Polymorphic Phase Transfonnations in Solids 223

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31 (1980).
 CHAPTER 7

Phase Diagram of Iron

A. I. Funtikov

7.1. Introduction
In experiments with strong shock waves, iron is used as a standard to detennine
the dynamic compressibility of other materials [1]. Thus, when the reflection
method is used, the parameters of a material under investigation are defined
through the use of a double-compression Hugoniot or a decompression isentrope
of iron. Particular difficulties arise when these processes lead to states in the
field of phase changes of iron. Hugoniot data for iron are also of great interest
for problems of impact and shock-wave loading of targets.
The phase diagram of iron at pressures of a few megabars and at tempera-
tures of up to a few thousand degrees is of vital importance for geophysics.
Experimental geophysics has provided a great deal of data supporting a model in
which the Earth has an iron core. The basic information was obtained by inter-
pretation of seismic data. It was determined that, down to a depth of 2900 km,
the spherical shell consists of solid sedimentaIy and magmatic rocks. Below
this, to a depth of 5120 kIn, the material of the Earth is known to be fluid be-
cause seismic shear waves do not pass through this layer. The interior core,
lying below this fluid layer, is solid. The presence of a fluid skin on the interior
core is key for an explanation of the magnetic field of the Earth.
From geochemical data, it is known that approximately 90 % of the core of
the Earth consists of iron, and the interior core is almost pure iron. Therefore,
knowledge of the melting curve of iron is particularly important for under-
standing the temperature distribution in the Earth's interior. A reliable estimate
of the melting temperature of iron at the pressure of about 330 GPa at the inner-
outer core boundary would place a much-needed constraint on core tempera-
tures. Because the melting temperature of iron cannot be measured at this pres-
sure, it is important to obtain data over a large pressure range. A simplified
temperature distribution in the Earth's core, and the melting curve correspond-
ing to these fields, is shown in Fig. 7.1.
The most important experimental evidence has been obtained from shock-
wave data. During the early stages of these studies the shock compressibility of
iron was studied by Al'tshuler et al. at pressures up to 500 GPa [2]. This
pressure range included the states of iron at the pressure prevailing at the bottom
V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII
© Springer Science+Business Media New York 2004
226 A. I. Funtikov

T~
i'" I
I I
1 II 2 II 3
I I
I I
I I

,
Depth,km I ,

tJI JII.1II
Pressure, GPa
Figure 7.1. Schematic temperature profile in the Earth. The solid curve is the geothenn
and the dotted line is the melting curve. 1: solid mantle, 2: molten outer core (composed
mostly of iron), 3: solid iron inner core.

of the Earth's solid mantle, 130 GPa, and the pressure at the core center, 360
GPa, and made it possible to test various hypotheses concerning the composition
of the Earth's core. As early as the mid 1960s, comparison of the pressure de-
pendence of density on Hugoniots of iron and its compounds, nickel, and other
substances, with geophysical data in terms of the Bullen and Birch models [3,4],
was performed in VNIlEF by Al'tshuler, Funtikov, Kormer, Trunin, et al. [5-7].
This work showed that the outer core, besides iron as the main constituent,
should contain lighter elements. Hugoniots of iron [2] and an alloy of iron with
silicon, FeO.81 Sio.\9 (ferrosilicon) [6] in comparison with calculated dependencies
for the Bullard model [8] and for the more modem preliminary reference Earth
model (PREM) [9] are shown in Fig. 7.2.
Further investigations in this field were conducted with the use of both dy-
namic and static methods. Compressibility data for iron were produced by
Al'tshuler et aI. [10] and Mao et al. [11]. At this time, the static and shock-wave
constraints on melting curves and phase transitions at high pressures obtained by
various methods [12-15] were inconsistent due to the technical difficulties of
such measurements [16].
Related uncertainties are also present in the semiempirical equations of state
developed from these data and used for the thermodynamic description of the
Hugoniot [17-20] and for the construction of the phase diagram of iron with a
partial [21-24] and a more detailed localization of the phase boundaries [25-
28].
In most of this computational work, a particular group of experimental data
was preferred. Therefore, the inconsistencies mentioned above have not been
removed. This resulted in differing estimates of such geophysical reference
values as the temperature at the 330 GPa boundary between the inner solid and
outer liquid core. These estimates range from 4000 to 9000 K.
 7. Phase Diagram of Iron 227

p, g/cm3

11

11

/I

100 100 JOO

P.GPa
Figure 7.2. Experimentalresults: 1: Hugoniot of iron [2], 2: Hugoniot offerrosilicon [6],
Calculated curves: 3: density dependency for the Bullard model [8], and 4: the prelimi-
nary reference Earth model (PREM) [9).

7.2. Phase Diagram of Iron From Static and

Shock-Wave Measurements
The phase diagram of iron is complicated by the presence of the a and 8 phases
with a body-centered cubic lattice (bcc) structure, the y phase having a face-
centered cubic (fcc) lattice structure, and the s phase, which has a hexagonal
close packed lattice structure (hcp). Shock-wave experiments provided impor-
tant high-pressure constraints on this diagram. The a ~ s transition was first
discovered from data on shock compression of iron [29], and was afterward
confirmed by static measurements [30].
Important results were obtained from measuring the longitudinal elastic (Cd
and bulk plastic (CB ) velocities of sound behind a shock-wave front. These
measurements were made for the first time by Al'tshuler et al. [31,33], who re-
corded unloading waves traveling behind the shock front and arising as a result
of reflection of the shock wave from the free surface of an impacting projectile.
Later, these waves were studied in more detail by Brown and McQueen [20,32].
The resulting sound velocities are shown in Fig. 7.3 as functions of pressure
behind the shock wave. Data introduced on Fig. 7.3 correspond to the conver-
sion of the data of [20] carried out in [34].
A decrease in the difference between CL and CB observed at 243 GPa was
consistent with melting and corresponded to a value of Poisson's ratio close to
0.5. The nonmonotonic behavior of CL(P) was interpreted in [20] as an s ~ y
transition at 200 GPa. These results have been used for a long time for compari-
son with other data on the phase diagram of iron in this range.
228 A. I. Funtikov

11

10

It. -1
8
. ' -2
<> -3

7 -

o 100 300 400

P.GPa
Figure 7.3. The elastic (CL) and bulk (CD) sound velocities in iron versus the shock
pressure_ 1: [17],2: [20],3: [35].

In 1999 Nguyen and Holmes reported new data on the longitudinal elastic
sound velocity measured at pressures from 190 to 320 GPa [35). Their data, in
contrast to results of Brown and McQueen, disproved the non-monotonicity of
the pressure dependence reported in [20) as the s ~ y phase transition on the
Hugoniot at the pressure 200 GPa. Apparently, melting occurred at 220 GPa on
the Hugoniot
Data validation of shock melting was obtained in [36) with the help of addi-
tional definition of shock compression of iron in the range of pressures 160-440
GPa. Statistical data analysis [36) together with the data obtained earlier [37),
carried out separately for ranges of the Hugoniot corresponding to the solid and
liquid states reported in [20), has shown nonmonotonicity of the Hugoniot and
some difference between it and the average dependence assumed in [10,37).
The results of optical measurements of temperature from the brightness of
radiation from the shock compressed iron were also complicated and ambiguous
[13-15). Such measurements in metals, unlike previous experiments with shock
compression of transparent dielectrics executed by Kormer [38), are difficult
due to the small thickness of the radiation absorbing layer. The accuracy of
temperature measurements in shock compressed iron, which partially expands
into the window material placed behind the sample, is largely determined by the
 7. Phase Diagram ofJron 229

introduction of calculated corrections that account for the variation in the state at
the contact boundary between the iron and the window material and for the
optical (emissive and absorptive) characteristics of both materials [39). As in
[38), the melting curve was determined in these experiments from non-mono-
tonic features of the pressure as a function of the measured temperature on the
Hugoniot. The optical method of measuring shock temperatures has previously
been applied to iron by Ahrens and coworkers [13,14), however, the measured
shock temperatures have considerable scatter. Apparently, the optical measure-
ments ofYoo et al. [15) are more accurate. According to these data in the pres-
sure range 150-340 GPa, the Hugoniot is consistent with melting in the 235-
300 GPa range, which roughly agrees with the pressure data from sound velocity
measurements [20). Direct temperature measurements are subject to large un-
certainties due to the small time scale and the unknown thermal and optical
properties of the window material (single-crystal sapphire or lithium fluoride)
through which the iron surface is observed [40).
Before the mid 1990s there were two types of static measurements of the
melting curve which were based on either laser heating of a foil sample com-
pressed in a diamond anvil cell or the electrical heating of a wire sample. How-
ever, the results based on application of both methods [12,13) showed a
considerable discrepancy, reaching 1500 K at a pressure of 120 GPa. Later,
preference was given to the laser-heating data of Boehler who extended the
pressure range to 200 GPa [41]. These data were revised by Saxena et al. in
[42,43) at pressures to 150 GPa. The resulting data have a scatter in temperature
within -100 K and demonstrate a comparatively small increase in the melting
temperature in this range. However, the static melting temperatures differ con-
siderably from shock-wave data. The phase diagram of iron, constructed from
the experimental data presented above, is shown in Fig. 7.4.
The positions of the triple points (a, y, E) and (8, y, I), p= 11 GPa,
T= 750 K and P= 5.2 GPa, T= 1990 K, respectively, were rather reliably de-
termined from static data (see in particular [28). The parameters of the third
triple point (y, E, I), corresponding to the intersection of the y-E phase boundary
and melting curve, differ considerably among the estimates given by the above
authors. Thus, according to [12,21,25), this point corresponds to a pressure of
about 70-100 GPa and temperatures from 2800 to 3200-3800 K. On the other
hand, the phase diagram in [13,16,27,28) reconciled static and shock-wave data
by locating this triple point at 200-330 GPa and 5300-7500 K. The results of
measuring the melting curve and the y-E phase boundary [41-43) showed that
the triple point can be at a pressure of about 100 GPa. The triple point in Fig. 7.4
corresponds to the measurements of [41).
The position of the Hugoniot on the diagram, as well as the position of the
E ~ Y phaseline and the melting point, were defined using the accepted equation
of state in [20). The possible error in position of these points was estimated in
230 A. 1. Ftmtikov

Il1O /00 JIJI1 P, GPa

Figure 7.4. Phase diagram of iron. Dotted lines designate the melting curves 1: [13], 2:
[15],3: [41], and the phase botmdaries [41]. Solid lines are the Hugoniots 4: [15], 5: [20].

this work as the inaccuracy of the temperature values. Based on this, it was
supposed in [12,22] that the phase transition revealed from shock-wave data was
a transformation from the y phase to a hypothetical new phase. This phase,
called the 13 phase, was discovered at a pressure over 50 GPa, to all appearances
independently, by Boehler [41] and Saxena et al. [42], although disagreements
about the stability region still exist. In this case, the E ~ Ptransformation occurs
at a lower shock pressure and suggests the existence of one more triple point at
the intersection with the melting curve or the boundary separating the y and E
phases. The existence of the p phase was still under discussion.
The updated phase diagram of iron to the mid 1990s (see Fig. 7.4) still ex-
hibits inconsistency of the static and dynamic melting curve data. Thus, the
melting curve [50] and Hugoniot [20] intersect at pressure 160 GPa and tem-
perature 3500 K.
The discovery of the hypothetical new phase of iron stimulated numerous
detailed studies of its structure under static conditions. These investigations have
been carried out since the mid-1990s by six key groups of researchers in the US
Geophysical Laboratory, Livermore, Uppsala, Mainz, Tokyo, and Paris [44-50].
Much progress has been made in conducting such experiments with laser-
heated samples compressed in diamond anvil cells and in the in situ examination
of the structural parameters in a compressed sample with the help of diffraction
of synchrotron x-radiation. These measurements, which varied in experimental
 7. Phase Diagram ofJron 231

details and covered various regions of the iron phase diagram in the pressure
range up to no GPa and at temperatures from 1400 to 3500 K, gave somewhat
divergent results. In the first series of measurements and some others, the struc-
ture of the new phase was identified by Saxena et al. as a two-layer hexagonal
close packing (dhcp) [44-47]. Other investigations carried out by Andrault et al.
[48] showed transformation from the I> phase to an orthorombic structure [48].
The origin of this difference is unclear, but could be due in part to the smallness
of differences between these structures.
Using more uniform heating of a sample by laser radiation, the region of the
new phase was examined by Funamori et al. [49] and Shen et al. [50], who
found only y- and I>-phase iron within this pressure and temperature range. They
did not find other phases. Results presented in [50] appear more reliable in the
range of the y phase. In this work, the y-I> phase boundary and parameters of the
(y, 1>, /) triple point were defined: P = 60 ± 5 GPa and T= 2800 ± 200 K. In [50]
individual measurements of the melting temperature at pressures to about 70
GPa were performed and a new melting curve was obtained at pressures to 100
GPa. This curve lies on the phase diagram at a somewhat higher temperature (by
up to 300 K) than indicated by previous measurements [41,43].
Boehler, in [51], interpreted all static data available on the melting curve at
pressures to 200 GPa, taking the dependence within the range of the I> phase in
the form of a band accounting for a scatter of ± 150-200 K. He excluded from
his analysis the aforementioned data of [50], because they are 100-200 K away
from this temperature interval. The data from [13] were also rejected because of
their inaccuracy. In the opinion of Boehler [50] the existence of the high-pres-
sure p phase remained a subject for discussion and the location of the (y, 1>, /)
triple point and the y-I> phase boundary were also somewhat uncertain in the
pressure range from 50 to 100 GPa.

7.3. Melting During Isentropic Expansion of

Shock-Compressed Iron
Resolving the inconsistency between the static and dynamic data on the melting
curves of iron requires additional experimental constraints. For this purpose,
Chen and Ahrens [52] measured the sound velocity behind the shock front in
preheated samples of iron. They measured the initial release-wave velocity,
which is equal to the longitudinal sound velocity in solids and the bulk sound
velocity in liquids. Results were obtained up to 74 GPa for preheated samples
with an initial temperature of 1570 K. The point at a pressure of 74 GPa agrees
with the bulk sound velocity CB(P) of [20,31] and with the static melting curve
of [51] so the iron can be considered to be molten at this pressure. This result is
close to that measured in [41-43].
232 A. I. Funtikov

New experimental results for checkout of the adequacy and consistency of

data can be obtained. These results, in particular, represent measurement of the
shock pressure giving rise to melting during subsequent isentropic unloading to
normal pressure. During a sequence of processes at increasing pressure, one first
encounters melting during isentropic expansion of the material behind the shock.
Upon further increase of the shock pressure, melting occurs in the compressed
material before expansion begins. Since some increase of entropy occurs with
increasing pressure on the melting curve [53], this curve on the phase diagram
lies above the isentrope passing through the melting point at standard atmos-
pheric pressure.
Experiments to ascertain indications of melting in samples in which the pres-
sure was maintained after shock compression were carried out under the super-
vision of Litvinov in VNIlTF [54] and Osipov et al. in VNIIEF [55]. In [54]
structural changes were studied in spherical samples recovered after loading by
a convergent spherical shock wave that increases in amplitude as it approaches
the center of the sphere. After reflection of the shock wave from the center, a
cavity forms in the sample. The local pressure of the shock wave propagating in
the sample before formation of the cavity was calculated for various distances
from the center. This pressure produced different local structural changes in the
material after loading and unloading. The y phase formed in the sample at pres-
sures in the range from 140 GPa to the onset of melting at 200 GPa according to
estimates [54] of the amplitude of the shock wave.
In [55], the onset of melting was investigated in samples recovered after
compression by shock waves of various amplitudes. The sample was subjected
to the action of a plane wave produced by a specially designed device in which a
cylindrical sample was loaded by an explosive charge surrounding its lateral
surface. When the charge is detonated, the initial conical shock wave propagates
along the cylindrical surface of the sample. When this wave reflects from the
sample axis, it is transformed into a three-wave Mach configuration propagating
along the axial zone and consisting of incident, reflected conical, and reflected
central plane shock waves. The plane wave produces transient compression of
the material followed by decompression due to the arrival of lateral rarefaction
waves.
Steady-state propagation of such a system of shock waves produces single
compression of the sample material over a fairly extended region in the vicinity
of the axis. The sample being investigated was located in this region of steady
flow. The pressure in the shock wave was determined from the results of gas-
dynamic calculations [55]. These results of divergence of the oblique conical
shock wave for the loading device employed in the investigations also con-
firmed the fact of formation of the steady triple-shock configuration of the shock
waves and enabled one to select the location of the sample to be investigated.
 7. Phase Diagram of Iron 233

The melting of the sample is identified in [56] by the appearance of the axial
cavity that forms in the sample after loading. The shock-wave amplitude was
varied by changing the composition and density of the explosive charge and by
proper selection of spacers between the explosive and the sample. The value of
the shock compression pressure leading to melting of the sample was deter-
mined by interpolating the data of measurements to zero thickness of the chan-
nel. The threshold shock pressure for melting on the isentrope of iron was
estimated at 140 GPa [55].
Disagreement of data from [54] and [55] is probably attributable to an inex-
act account of heating in the wave reflected from center in [54] and errors of the
equation of state used in the calculation. Therefore, preference is given to the
more reliable results obtained in [55].

7.4. Calculations of Melting Isentropes and the Melting Curve

Within the Range of the 8 Phase
The melting curve and the isentrope through the initial melting point at normal
pressure bound a local region of the phase diagram in which it is possible to
compare the thermodynamic parameters, P, p, and T. The local region of these
curves obviously lies above the ~-s phase boundaty. In a single-phase region,
in particular, as a first approximation for the y phase of iron, it simplifies calcu-
lations. Parameters of the isentrope were estimated from the equation of state of
the y phase. This allows determination of the point at which the isentrope inter-
sects the boundary with the s phase. Another approach was applied to the s
phase. Parameters of the equation of state within the region of the s phase were
determined from the available experimental data on the compressibility and the
shock pressure at points on the isentrope that passes through the melting point at
P = o. Then the melting curve of the s phase, which has as its initial point the
(y, s, /) triple point, was estimated
The release isentrope changes its slope when crossing phase boundaries be-
cause the Gibbs free energy has the same value for each of the phases. The re-
lated changes, AS and AV, result in variation of the temperature and pressure
along the phase boundaty. The temperature difference between the states on the
isentropes continued without regard to the phase transition process and upon its
completion is determined from the relation
CvAT=TAS-PAV, (7.1)

where the AS and AV values are connected with the slope of phase boundaty
according to the Clausius-Clapeyron equation
dT AV
(7.2)
dP = AS·
234 A. I. FWltikOV

The thennal effect is small at the y-S phase boundary due to the high value
dT/dP= 65 KlGPa and the related value AS= 0.02 kJ/(kgK) [27]. The tempera-
ture decrease is only 50 K. Owing to the small extent of the S phase range, this
correction shifts the expansion isentrope through the melting point at atmos-
pheric pressure toward the initial point with Tmo= 1860K instead of the initial
melting point of the S phase at TlimO = 1810 K. The position of this point, which
is accepted as the initial point for calculating the isentrope in the range of the y
phase, is a little bit lower than the point obtained by interpolating the melting
curve in the interval between the triple points (S, y, /) and (y, &, /) to zero pres-
sure.
The main temperature decrease occurs at the intersection of the isentrope and
the y-& boundary. Calculations of isentropes and melting curves were per-
fonned using a semi-empirical equation of state of the y and &phases of iron in
the Mie-Griineisen fonn with separate cold (elastic) and thermal components of
pressure and energy:

P=Pc+Pt
(7.3)
E=Ec+Et,
where it is convenient to represent the cold components as
SII-l
Pc=poq--, (7.4)
n

Ec = CJ
n(n-l)
nS n] .
[SII-1 + -1 _ (7.5)

In these equations, S = p/po is the relative density, po and Co are the density and
bulk sound velocity under normal conditions, and n is a parameter.
The cold components of the equation of state of the &-phase were determined
from measurements of the isothermal compressibility at normal temperature,
which were successively improved starting from the data of Takahashi and
Bassett [30]. At present, the curve of static isothermal compressibility has been
measured by Mao et al. [11] up to pressures of 304 GPa. These data, when repre-
sented by an equation of the fonn (7.4), give Po = 8.26 glcm3, Co = 4.37 km/s,
andn=4.81.
The compression isothenn of the y phase at T= 300 K was determined by
Besson and Nicol [57] using experimental data on high-temperature compres-
sion isothenns obtained by Boehler et al. [58] at static pressures of up to 40 GPa
and temperatures ranging from 1200 to 2300 K. The values Po = 7.98 glcm3 ,
Co = 4.57 km/s, and n = 4 are consistent with the results of [57].
 7. Phase Diagram of Iron 235

The thennal components of the equation of state are

Pt=ypEt
(7.6)
Et =Cv(T-To),
where y(p) is the Griineisen parameter, C v is the heat capacity, and To= 300 K
In calculations above the Debye temperature, en, and in the range from near the
melting curve up to crossing the Hugoniot, the heat capacity is taken equal to the
Dulong-Petit value, C v = 3R, and the contribution due to thennal excitation of
electrons may be neglected.
We used the approximation yp = const. for the Grfineisen parameter in local
y and s phase areas adjacent to the melting curve.
The density dependence of the temperature, Ts , on an isentrope is described
by a functional dependence similar to that of the Griineisen parameter y,
dInTs
dlnp =y, (7.7)

and the temperature along the isentrope is given by the equation

Ts=TieXP[YP(:i -~)], (7.8)

where 1j and Pi are parameters of the initial point of the isentrope and p is
evaluated on the isentrope.
Since the portions of isentropes and appropriate the portions of the melting
curve account for comparatively narrow density and temperature ranges of the Y
and I> phases, the Lindemann relation

dlnTm =2(Y-'!) (7.9)

dlnp 3

was used for the local interpolation of the melting curve. The melting curve
consistent with Eq. (7.9) for Griineisen's parameter yp = const. can be repre-
sented by the equation

Tm =Tmo (ppmo)213 exp [2yp (1 -P1)] .

PmO (7.10)

Equation (7.10) describes Tm (p) along the solid phases. The complete Pm (Tm> is
obtained when the pressure is determined from equations (7.3)-(7.6).
If the isentrope and the melting curve have a common point with the pa-
rameters Pi and 1j, the relation
236 A. I. Funtikov

2/3
Tm _ ( Pi ) Ts
- - - - (7.11)
Ts P Ti

is valid for each value of density and proves convenient for calculations.
The melting curve in the y-phase region is bounded by the two triple points
(8, y, /) and (y, e, I). The location of the melting curve as given by Eq. (7.10)
corresponds to the value yp = 9.5 glcm3 . Within this range, the densities vary
from 7.9 to 9.6 glcm3 and, accordingly, the Grtineisen parameter varies from 1.2
to 1. These parameters of the equation of state of the y phase agree with the
high-temperature compressibility data in [58]. Several expressions for the
Grtineisen parameter as a function of density are plotted in Fig. 7.5.
The isentrope in this region was found from Eq. (7.8) with due regard for the
discontinuity of slope of the isentrope at the 8-y phase boundary as was shown
above (see Fig. 7.6).
In the e-phase region, the value of parameter yp was determined by the posi-
tion of the isentrope in this region. The first point is located on the the y-e phase
boundary. The discontinuity of the isentrope was determined by the slope of the
boundary and the change of the specific volume, AV, of the y and e phases. The
average slope of the y-e boundary is dTldP=41.8K1GPa [57] and AV=2.5
cm -3/kg [27]. The difference of the specific volume is not large and does not
change along the boundary [48]. These data correspond to a discontinuity of the
isentrope by the amount AT= 170 K. The initial point parameters are P = 53
GPa and T= 2520 K.

2.2
Y
2.0

1.8

1.6

1.4

1.2

1.0
8 10 12 p, g/cm3

Figure 7.5. Dependence of the Groneisen parameter on density. 1: [20],2: [24], 3: [34],
4: [27], 5: [62], 6: [73], 7: [69], 8: [71],9: [62], 10, 11: present data.
 7. Phase Diagram of Iron 237

4 liquid

ai
o l
o 50 100 150 200
P,GPa

Figure 7.6. Phase diagram of iron. Hugoniotsplotted are 1: [20] and 2: [67]. Melting
curves plotted are 3: [51],4: [50] (dotted line), and 6: present data. Curve 5 is a decom-
pression isentrope. The solid phase boundaries (thin dotted lines) are from [50]. The point
corresponds to shock melting of preheated iron [52).

Saxena and Dubrovinsky [59] and Andrault et al. [60] have continued to in-
vestigate the existence of the ~ phase using in situ x-ray diffraction measure-
ments of samples compressed in a diamond-anvil cell and heated by a laser. In
[59] the structure was considered to be dhcp but the structure was interpreted to
be an orthorombic (Pbcm) lattice in [60]. The &-~ boundary was determined in
[59,60] and has a nearly horizontal slope. In [59] dTldP was rather less than
zero, but in [60] it was somewhat greater than zero. The difference of slopes was
explained on the basis that the ~ phase was in a metastable state near the &-~
boundary [61]. In view of some divergence of the data [59-61], the &-~ phase
boundary is not shown on Fig. 7.6.
The new triple point (y, &, ~) was revisited [59-61] and determined in [59]
to be at the point P = 37 GPa and T= 1550 K. Therefore, the initial slope of the
y-& phase boundary exceeds its average slope and above the triple point is less
than this average value. The triple point at which the y-~ phase boundary inter-
sects the melting curve, (y, ~, I), corresponds to the point previously designated
238 A. I. Funtikov

(y, s, I). The parameters of the triple point (a., y, s) were defined more exactly in
[61]:P=8 GPa; T=680K.
The difference of densities of the s and ~ phases is small [60]. Therefore, the
Hugoniot l1I(V) is not significantly reftacted where it crosses the s- ~ phase
boundary [62]. The densities of the s and ~ phases coincide at the triple point
(y, s, ~) and may be very close in the investigated range of the ~ phase up to 300
GPa [63].
In order to find the location of the release isentrope in the range of the s
phase one must calculate the temperature at the initial point on the Hugoniot at
the pressure P = 140 GPa
Shock compression of iron from the initial state of density Po = 7.85 r/cm3 is
treated as though the iron were porous with the effective porosity m = PeO/Po
with respect to the density of the s phase in the metastable region at normal
conditions. This results in somewhat higher heating under shock compression
than if the iron were not assumed to be porous. The thermal effect is also insig-
nificant at the intersection on the a.-s curve and the Hugoniot (dT/dP = -270
KlGPa).
The thermodynamic representation of the Hugoniot of iron corresponding to
the results of gas-dynamic measurements [10,64,65] is based mainly on the
generalized Mie-GrOneisen equation with separation of the thermal and cold
(elastic) components of pressure and energy as in Eq. (7.3). In a number of
studies [18,54,66,67], the state on the Hugoniot is treated as corresponding to
the generalized solid and liquid s phase, whereas in [34] it is treated as corre-
sponding only to the liquid s phase. The Hugoniot, including the a. ~ & phase
transition, was calculated in [19] and, accounting for the y, s and liquid phases,
in [26,27]. Kopyshev and Medvedev [24] obtained the Hugoniot with identifica-
tion of melting of the s phase using the compressed covolume thermodynamic
model (a generalized van der Waals model).
In spite of some differences in the choice of the form of representation of the
elastic and thermal components of the equation of state for iron in
[20,23,26,28,54], the differences in the position of Hugoniots on the phase dia-
gram at pressures below 200 GPa are not very great [56]. The greatest deviations
are observed for the Hugoniot obtained in [15], where the equation of state was
oriented to overestimated data on the melting curve [13], as well as for the
Hugoniot adopted in [54]. In [18], the understated position of the Hugoniot is
due to overestimation of the contribution of electronic components to the equa-
tion of state.
The uncertainty of the Hugoniot temperature is attributed to uncertainties of
the GrOneisen parameter and the heat capacity.
 7. Phase Diagram of Iron 239

The calculated estimate of temperature in [20] was obtained using the equa-
tion

po)"Ye
(p (7.12)
Cv =D(T)+~o T,

for the heat capacity, where D(l) is the Debye function (D(T) = 3R for T >9D),
and ~o is the coefficient of electronic heat capacity. As in [23,66], the value
~o = 0.091 J/(kg K2) and the Griineisen parameter for electrons, 'Y. = 1.34, were
assumed for the s phase. The inclusion of electronic components in the equation
of state leads, in fact. to a correction AT= 120 K in temperature for the pressure
P= 140 GPa on the Hugoniot. For lower pressures, this correction is even
smaller, and the thermal components may be given by the Mie-Griineisen
equation with the effective values of the Griineisen parameter without identify-
ing the electronic part as was done in [64].
In [20], under the assumption that 'YP is constant. this value was calculated
from shock-wave data of bulk sound velocity for the liquid phase above 240
GPa. It was determined that 'YP= 19.6 glcm3• This value exceeds results pro-
vided from porous-iron data [64] and was not in agreement with the intersection
with the melting curve obtained using the Lindemann calculation with the
Hugoniot at this pressure. To match the experimentally determined melting
pressure [20], the value of'Y must be decreased so that 'Yp-13 glcm3 •
The pressures and temperatures on the Hugoniot of the close-packed phase
of iron were calculated by Wasserman, Stixrude, and Cohen using a tight-bind-
ing total-energy method and a cell model of the vibrational partition function
[67,68]. The calculated dependencies P(V) are in good agreement with data of
the T= 300 K static isotherm [11] and the experimental Hugoniot [20). At the
pressure PH = 140 GPa the contribution of the thermal excitation of phonons (the
vibrational contribution) to the pressure amounts to 30%, and the contribution
due to excitation of the electrons is -3 %. The thermodynamic description
[67,68] involves the volume and temperature dependencies of the heat capacity
and the total Griineisen parameter. The temperature dependence of the lattice
Griineisen parameter was relatively weak. The location of the Hugoniots is
shown in Fig. 7.6.
For calculating the isentrope corresponding to the melting upon expansion,
the value of temperature on the Hugoniot [67] was taken to be T= 3100 K. We
assumed for the s phase range the validity of'YP= const. and Eq. (7.8) to derive
for the expansion isentrope 'YP = 14.3 glcm3 corresponding to variation of the
Griineisen parameter from 1.47 to 1.26. Accordingly, the density varied from 9.7
to 11.3 glcm3 within this range. The experimental and calculated dependencies of
the Griineisen parameter for iron obtained from the density are shown in Fig. 7.S.
240 A. I. Funtikov

Another approach to construction of the equation of state of y iron was

adopted by Anderson [27], who used the melting curve obtained in [13]. In this
case, it was accepted that the triple point (y, s, /) exists at P = 280 GPa and
T= 5750 K and that the slope of the y-s boundary decreases from 25 to 16.5
KlGPa. Using the Lindemann relation (7.9) and the density dependence of the
Griineisen parameter

:0 =(p;y, (7.13)

where q is parameter, the melting curve is found to be given by

Anderson [27] used the initial-point parameters PmO = 5.2 GPa, Tmo = 1990
K, and Proo =7.54 y/cm3 for the melting curve and found Ymo=2.09 and q=1.7.
The "cold" part of the pressure [27] in the form (7.4) was taken from the iso-
therm To = 1990 K (characterized by Po=7.313 y/cm3 , Co =4.68 km/s, and
n = 4), which was measured by Jeanloz [69]. The result from [27] is shown in
Fig. 7.5 as curve 4. The initial range of the density variation on the melting
curve (up to 100 GPa) in [27] is nearly the same: from 7.5 to 10 glcm3 • In order
to fit experimental data, the Griineisen parameter varied from 2.09 to 1.3 within
this density range.
A similar variation in the Griineisen parameter (from 2.1 to l.7) was ob-
tained by Kopyshev and Medvedev [24] for the equation of state extended to the
y and s phases and also based on overestimated experimental data [14] (curve 2).
The value ofy of [20] is also overstated (curve 1).
The calculation of the melting curve of the y phase in the range up 100 GPa
and the Griineisen parameter dependence were obtained by Anderson and Isaak
[62]. The method combined an analysis of the melting data with the Lindemann
law and the Debye model of the equation of state in the Vinet form [70]. The
experimental melting curve [50] with the initial point Tmo = 1810 K was used.
The initial value of the Griineisen parameter was calculated by means of the
equation derived by Stacey [71]: Yo = 1.55 at initial density PmO = 7.34 glcm3 .
The variation of y with density along the melting curve (curve 9) corresponded
to the value y = 0.95 at P = 9.6 glcm3• The value of density depends on pressure
and increases as the temperature is decreased. This dependence at T = 300 K lies
a little bit above the curve 9. Thus, at P = 0, T= 300 K, Yo = l.55 corresponds, as
in [27], to Po = 8.00 y/cm3. With increasing pressure, the distinction in curves
y(p) corresponding to different temperatures decreases so, at T= 300 K and
p= 9.6 glcm3, y= 1.4.
 7. Phase Diagram of Iron 241

The dependence y(p) for the & phase was obtained by the analogous method
in [62]. The analysis used data on the static compression of iron [11] and the
calculated point of Hugoniot melting at P= 240 GPa and Tm = 5010K. These
parameters were at the lower bound of the range recommended by Brown and
McQueen [20] for melting on the Hugoniot The initial point of the melting
curve was taken to be Tmo= 1810 K. This was adjusted to represent the melting
curve over a vety wide temperature range. The dependence y(p) for the & phase
is shown in Fig. 7.5, curve 5.
Stacey [71] found theoretically the GIiineisen parameter for the range 11-13
g/cm3 assuming it as independent of temperature in Eq. (7.13) and interpolated
to the initial value Yo = 1.7 at P =O. The similar dependence y (p) was obtained
by Anderson in [72].
The calculated GIiineisen parameter by Jeanloz [69] (curve 7) was based on
analysis of Hugoniot data for initially porous and nonporous samples of iron
[20,64] and was fit to Eq. (7.13) with Yo =2.2, and q = 1.62.
A method based on combination of the thermal equation of state and the
measured mean-square atomic displacement from in situ high pressure and tem-
perature x-ray investigations of the & phase was used to determine the GIiineisen
parameter by Dubrovinsky et al. [73]. When these data were fit by Eq. (7.13),
the parameters yo= 1.78, q= 0.69, and Po= 8.3 glcm3 were obtained (curve 6).
Anderson and Ahrens have used a wide range of experimental data to obtain
the equation of state for liquid iron [34]. Its parameters, centered at the normal
melting point and isotherm T= 1811 K, were determined for the GIiineisen pa-
rameter as a function of density and specific internal energy. The predicted
Hugoniot temperature agreed with the experimental data of [15]. The initial
value of the Gliineisen parameter was Yo= 1.735. Other values of y were ob-
tained from experimental data of Hixson et al. [74] for pulse Joule-heated iron
wire and the bulk sound velocity in shocked iron of Brown and McQueen [20].
The function y(p) obtained is shown as curve 3 in Fig. 7.5.
A thermodynamic GIiineisen parameter depends explicitly on both density
and temperature. However, in a restricted range of temperature the main de-
pendence is y(p). We have chosen a common functional form, y- p-I, for ob-
taining this dependence from the release isentrope. Then, the melting curve for
the & phase of iron was obtained by using the Lindemann relation (7.10). Its
initial point was taken at the intersection of the y-& phase boundaty [50] with
the melting curve of the y phase [41] at P = 57 GPa and T= 2700 K. These pa-
rameters are a little bit below the values obtained in [50] and agree well with the
estimate [60]. The melting curve thus obtained is shown on Fig. 7.6.
242 A. I. FWltikov

7.5 Conclusion
The field of the y phase on the phase diagram of iron is now well enough ex-
plored in static conditions of compression and heating of a sample. Up to pres-
sure -80 GPa the observed melting data of different authors are in good
agreement with each other. There are different estimates of parameters of the
equation of state in this range. The Hugoniot of iron centered on the state with
normal initial density does not enter this range.
The discrepancy of observed data of the melting curve by static and dynamic
methods is present for the e or ~ phase. The static measurements are carried out
in the range of pressures up to 200 GPa, and the results of shock-wave meas-
urements of the sound velocity behind the front of the shock wave and tem-
perature measurements at the shock-wave front are obtained at pressures above
200 GPa.
The measurements of the sound velocity [20,35] are carried out on enough
major measurement bases and correspond to equilibrium states of compression
behind the shock-wave front. The results of definition of melting by comparison
of data for longitudinal and bulk sound velocities for aluminum have shown the
applicability of this method. In [75] the agreement of static and dynamic results,
and also theoretical calculations was obtained. It is possible that. for iron, the
discrepancy of data is attributable to the inexactness of the calculated tempera-
ture dependence of the Hugoniot Except for the uncertain definition of parame-
ters of the thermal component of the equation of state of the e or ~ phases, the
location of the Hugoniot on the P- T diagram is determined by taking account of
its discontinuity at the a,-e and e-~ phase boundaries.
The inaccuracy of the data obtained from optical measurements, apparently,
is defined by introduction of the calculated correction. Besides, as noted in [76],
shock compression of the very thin samples used for these measurements occurs
in uniaxial deformation behind the shock-wave front and the value of the uniax-
ial stress should exceed the pressure of shock volume compression.
One of the reasons for the discrepancy of data is probably related to over-
heating of the material at the shock front. as was apparent in some optical meas-
urements [77].
The parameters determined for the e phase of iron with the help of shock
compression pressure corresponded to melting during isentropic expansion in
[78,79], based on the establishment of the location of the isentrope on the field
of the e or ~ phases. The estimates of the melting curve obtained are conserva-
tive enough. as they were extended from the initial point on the y-e phase
boundary. The data obtained do not contradict those from the static measure-
ments in this range, although they correspond to an upper bound of these data
[51]. These data are also consistent with the same regular trends of the melting
curves of transition metals determined in [SO].
 7. Phase Diagram of Iron 243

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244 A 1 Funtikov

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246 A I. FWltikOV

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 CHAPTER 8

Some Questions of Phase Transition in

Shock Waves

N. M. Kuznetsov

8.1. Introduction
The thermodynamic and the kinetic chamcteristics of phase transitions of solids,
liquids, and dense gases cannot be, as a rule, predicted theoretically on the basis
of first principles. Calculations of phase diagrams are additionally hindered by
the fact that their most important characteristics, such as transition heat, the
difference of phase densities, etc., are small differences of large quantities that
cannot be computed accurately enough. Shock-induced polymo:rphic transitions
are not, as a rule, in thermodynamic equilibrium, and the well-known thermody-
namic relations for phase transitions (coincidence of chemical potentials in the
two-phase region and the Clapeyron-Clausius equation) are useful only as
approximations.
A general quantitative theory of phase transitions has not yet been con-
structed, but there are many semi-empirical approaches to both some special
problems of the theory and to investigation of phase transitions of specific mate-
rials.
This chapter deals with some qualitative regularities of the thermodynamics
and kinetics of phase transitions and with the stability of shock waves in materi-
als that may undergo phase transitions. Some quantitative results on the thermo-
dynamics of two-phase systems and on their shock compressibility are also
presented.

8.2. Kinetics and Mechanisms of Phase Transition in

Shock Waves
According to the thermodynamic inequalities, transition from an initial phase
(that is thermodynamically stable at P = 0 and T= 0) to a high pressure or a high
temperature phase results in an increase of density or entropy, respectively [1].
Both compression and heating of the material take place in a shock wave. In
comparatively weak shock waves in cold materials, the relative pressure in-
V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII
© Springer Science+Business Media New York 2004
248 N.M. Kuznetsov

creases mainly because of compression, and it increases much more than the
relative tempemture. In this case, the energy of cold compression is considerably
more than the thermal energy. With increasing shock-wave amplitude, thermal
components of pressure and energy also increase and become dominant in very
strong shock waves producing compressions exceeding 1.7 (compression = p/Po).
Most observed polymorphic tmnsitions are associated, in this sense, with com-
pamtively weak shock waves where conditions, or in the general case essential
grounds, are created for thermodynamic stability of the high-pressure phase.
Among well-known classifications of polymorphic transitions are those
based on different properties of the process: thermodynamic, crystallogmphic
(symmetry ofBmvais lattices), the number of the coordination sphere (where the
number of lattice points changes), by preservation or change of the type of
bonding between atoms, etc. [2,3J. A kinetic classification of tmnsitions ac-
cording to the mte at which they proceed is also available.
Two basic kinetically-different mechanisms of phase transition are known: a
diffusive mechanism based on activation of individual atoms or molecules and a
martensitic mechanism based on cooperative, coherent rearmngement of the
crystal lattice. Either of these mechanisms can be fast and slow depending on the
tempemture and applied stress. Martensitic transitions can proceed slowly only
within a very narrow stress range. Outside this range it is either fast or pmcti-
cally does not proceed at all. The wide range of pressures over which the transi-
tion proceeds from its beginning to its end points to a complex mechanism. The
martensitic reconstruction is, possibly, only one of several stages of the whole
process as is the case, for example, for the graphite-to-diamond transition and
the transition from the graphite-like modification of boron nitride to the dia-
mond-like sphalerite modification [4].
Note that the necessity of overcoming activation barriers is determined by
the difference between the initial and final phases and not by the specific kinetic
mechanism. The martensitic tmnsition occurs after some of the energy barriers
have been diminished by deformations of the crystal lattice that are homogene-
ous on scales larger than the molecular scale. IT a diffusive transition takes
place, atoms are overcoming the barriers at the expense of their kinetic energy.
Their motion is chaotic under conditions of thermal equilibrium or partial equi-
librium of different subsystems (translational, rotational, vibmtional, and other
degrees of freedom) of the phase space. The probability of synchronization of
their motion and sufficient concentmtion of the kinetic energy to permit over-
coming of activation barriers by many particles (macroscopic scale) at the same
time is infinitesimally small. This is why each atomic particle, or several neigh-
boring particles, overcome energy barriers individually in the case of a diffusive
transition. Such a tmnsition is called "diffusive" quite arbitrarily since atomic
particles move over distances not exceeding the lattice period, and the macro-
scopic diffusion equation is not applicable to this case.
 8. Some Questions of Phase Transition in Shock Waves 249

The rate at which processes of crystal lattice rearrangement occurring in na-

ture and under laboratory conditions proceed can vary considerably (they can be
very slow and very fast). In contrast to crystallization of a gas or liquid, where a
thermodynamically stable phase grows at a measurable finite rate after the nu-
cleation of crystals, nucleation in a solid is not sufficient for the subsequent
growth of a new thermodynamically stable phase. In most cases, natural fonna-
tion of equilibrium crystal structures proceeds so slowly that the structure of
crystalline substances, with rare exceptions, is not quite in equilibrium. Some
memory of the conditions of their formation is retained. For example, according
to thermodynamic criteria, large monocrystallites of the material should grow at
the expense of adjacent., smaller monocrystallites in a polycrystal. This would
eventually result in the formation of a single large monocrystal. However, even
a geological time scale is insufficient for such recrystallization. This is why
natural solids are polycrystalline or amorphous. Large natural monocrystals are
very unusual and were formed, probably, not by recrystallization but, under
special favorable conditions, from melt.
When a solid is compressed, intermolecular repulsion becomes stronger.
Correspondingly, the compressibility decreases and activation barriers for dis-
placement and rotation of molecules over large distances and angles increase.
Therefore, diffusive rearrangement of a crystal lattice in homogeneously com-
pressed matter (out of "hot zones," see below) remains kinetically forbidden in
weak shock waves [5-9].
Microscopic defects of the lattice that are always present in material in its
initial state, and that also form during shock compression, may cause the alle-
viation of activation barriers for the molecules next to them. But, due to the low
relative concentration of such molecules, this effect is far from sufficient to
accelerate a rearrangement of the whole crystal lattice at low temperatures. Dif-
fusion coefficients tend to decrease with increasing pressure without any change
of defectiveness of the crystal. The diffusion rate can increase with pressure as
observed in a number of systems, but only due to an increase in the number of
microscopic defects (vacancies, dislocations) [8] concentrated in comparatively
small zones of plastic shear and other inhomogeneities.
Those minerals that are metastable in nature do not undergo phase transfor-
mations in sufficiently weak shock waves. Similarly, thermodynamic equilib-
rium is not achieved in two-phase liquid-vapor systems subjected to shock-
wave compression under laboratory conditions. This is why the velocities of
sound and shock waves observed in such systems at low relative concentrations
of vapor are well above the equilibrium velocities and correspond more closely
to those for "frozen" phase composition [10,11]. The list of systems for which
phase equilibrium cannot be achieved in shock waves could be considerably
expanded. Nevertheless, the duration of shock-wave compression appears to be
sufficient for realization of a great many phase transitions [9,12 -14].
250 N.M Kumetsov

Diffusive transitions proceed mpidly at high temperatures and martensitic

transformations (if appropriate for the required lattice rearrangement) proceed
mpidly at sufficiently large stresses and strains. Certainly, high tempemture in
the former case and large stresses in the latter case should not contradict ther-
modynamic conditions for the existence of a new stable or metastable phase.
Therefore, the appropriate kinetic conditions for shock-induced diffusive poly-
morphic tmnsformations are present mainly in "hot zones" such as plastic shear
bands, zones of brittle fracture, and near compamtively large defects such as
cmcks, pores, gmin boundaries, etc., that are initially present in the material
[9,15]. The remaining volume of a compamtively cold material that has been
subjected to shock compression tmnsforms to a new crystalline modification
according to a martensitic mechanism if it does so at all.
Sometimes diffusive tmnsition, in contmst to martensitic transition, is called
normal, although this term does not seem to be appropriate for description of
both shock- and quasi-static pressure-induced formation of a high-pressure
phase. Martensitic tmnsformation, if it is possible in principle, occurs in shock
waves propagating in cold material at the same or approximately the same pres-
sures as under low-tempemture quasistatic compression (Fe [12,13], Bi [16], Si,
Ge [17], KCI and KBr [18,19], and others). Let us stress that this points to the
similarity of pressure hysteresis only, and not to the equilibrium chamcter of the
transition.
Sufficiently large external stresses or thermoelastic forces arising under cer-
tain conditions upon heat treatment of metals and alloys [20,21] cause extensive
defonnation of a solid with subsequent loss of mechanical stability. As a conse-
quence of this process, plastic flow, brittle fracture, martensitic polymorphic
tmnsformations [20-27], or amorphization [28,29], proceed.
All these processes proceed very mpidly even if the applied stresses only
slightly exceed the local stability threshold, which depends on the local distribu-
tion of crystal lattice defects. In particular, the mte of motion of the phase
boundary in small segments of the initial matrix in the case of martensitic tran-
sition is about one tenth of the sound speed [26]. For crystallites having a linear
dimension of about 10-4 -10-3 cm, this corresponds to times of 10-8 _10- 7 -So In
this case the relative stability (metastability) of the new phase is sufficient for its
formation. The new phase may not even be absolutely thermodynamically stable
[30]. Examples of such phases are lonsdaleite (hexagonal diamond) [31,32], the
crystalline modification of carbon obtained as an intermediate state of the
gmphite-to-diamond tmnsformation, and wurtzite [4], one of the diamond-like
modifications of boron nitride.
Martensitic tmnsition cbamcterized by coopemtive displacement of the lat-
tice atoms was discovered as a specific phenomenon in metallurgy well before
any shock-wave experiments were conducted. It was observed first for the y ~ <X
phase tmnsition in iron and steels (the reversible transition from a face-centered-
 8. Some Questions of Phase Transition in Shock Waves 251

cubic to a body-centered-cubic or to a centered hexagonal lattice) during rapid

cooling of the y phase, and appeared to be rather common [25,26]*. Especially,
it concerns shock waves, where only very fast processes can proceed to comple-
tion.
The history of development of kinetic representations of polymorphic trans-
fonnations is rather interesting: During the 1950s and 1960s, when mechanisms
of extremely fast phase transitions and other physicochemical processes ob-
served in shock waves were being sought [9,13], martensitic transitions were
well-known experimentally in many alloys and were extensively studied theo-
retically. The direct application of the martensitic mechanism to the explanation
of fast polymorphic transitions of comparatively cold shock-compressed matter
was hindered by the fact that it was observed in heated but not compressed ma-
terials where thennoelastic stresses played the dominant role [20].
Polymorphic transitions observed during heat treatment of metals and alloys
without application of external pressure are characterized by a very small
change of volume. For instance, when heated Co is cooled to a temperature
below 420°C the face-centered-cubic crystal lattice present at high temperature
changes to a hexagonal-close-packed lattice with the relatively small decrease of
relative volume of3.6 x 10-3 [33]. This is why the homogeneous defonnation of
a material undergoing such a transfonnation is often described as shear [25,26].
In this case, the maximal bulk defonnation, e.g., expansion (dilatation) in com-
bination with fonnation of microscopic lattice defects, is concentrated in a nar-
row transition layer having a thickness of the order of the translational lattice
period. This layer provides structural and mechanical Conjugation of the original
and the newly forming lattices (see Fig. 8.1).

Figure 8.1. Schematic picture of conjugation of an original lattice with a martensitic

plate [33).

*Being extraordinarily important for industry, martensitic transitions have been studied
under continuous cooling as far back as at the end of the 19 111 and the beginning of the
20 111 century (for a brief history of the problem and bibliography, see [15]) and under
isothermal conditions from 1929-1930 (Kurdjumov and others [20]).
252 N.M. Kuznetsov

When a high pressure phase is fonned as the result of a pressure-induced

phase transition, the volume changes much more than for a martensitic trans-
formation and any relationship can hold between relative amplitudes of the shear
and compression.
Martensitic transitions (nucleation, orientation and sizes of martensite plates,
stresses at which the transition starts, etc.) have been intensively studied theo-
retically [20-27,34].

8.3. Hysteresis
The most important manifestation and reliable signature of the non-equilibrium
position of a phase boundary and of the non-equilibrium state of a two-phase
system is hysteresis [35,36] observed in both diffusive and martensitic phase
transitions. The magnitude of the hysteresis decreases with increasing tempera-
ture for transitions of both types [36]. However, the magnitude of the hysteresis,
its dependence on the time the system spent in the nonequilibrium state, and the
degree of asymmetry in the direction of the phase transition are determined by
the type of-the transition.
The intensity of the stress or pressure hysteresis, defined as the magnitude of
the difference of stresses measured at the starting point of nonequilibrium tran-
sition and at the intersection of the isothenn with the phase equilibrium line, can
be estimated for a low-temperature martensitic transition if hysteresis is identi-
fied with a limit of plasticity of the initial phase, provided the new phase is
fonned mainly by homogeneous shear, i.e., without a large change of density.
For transitions with a large density change, usually followed by variation of the
first coordination number, or for isomorphic transitions, the intensity of hystere-
sis can be estimated using variation of pressure of elastic compression of the
initial phase on the isothenn while the density changes from PI up to P2, where
PI and P2 are the densities of the initial and final phases at the point P=Po
where the isothenn intersects the phase equilibrium line. Both the limit value of
the plastic shear stress and the bulk modulus of the phases are different There-
fore, the intensity of hysteresis depends on which of the two phases is the one
initially present. However, in most cases, the values of these mechanical char-
acteristics of the phases are rather close and, therefore, the asymmetry of hys-
teresis is not very large. Let us note in this connection that the conclusion that
the hysteresis asymmetry associated with shock compression and unloading of
KCI [19] is large was made on the assumption that the decompression shock
wave arises at the same time as the phase transition. However, this assumption is
not always justified since, if the pressure dependence of the concentration of
phases is rather weak during unloading, the phase transition starts earlier, i.e., at
a higher pressure than that at which the decompression shock wave fonns.
 8. Some Questions of Phase Transition in Shock Waves 253

Let us define AP+ as the intensity of the pressure hysteresis in the case of
fonnation of a high-pressure phase and p. as the pressure at the intersection
point of the isothenn and the phase equilibriwn line. Then, the inequality
AP+ > P e is a criterion for the relative stability of the high-pressure phase fonned
following complete unloading [24].
The hysteresis for a diffusive transition at low temperature under static con-
ditions [36], or fonned out of "hot" plastic shear bands during compression by
weak shock waves, is practically infinite. Inside these bands the hysteresis is
temperature dependent and strongly asymmetric: Its intensity may be much
lower for unloading since, in most cases, the heated material in shear bands
remains hot enough for fast reverse phase transition to occur just after intersect-
ing the phase equilibriwn line, e.g., unloading of shock-compressed quartz. This
is properly not an asymmetry of hysteresis, but an asymmetry of thermal re-
gimes of loading and unloading. The heating is rapid at shock compression and
the cooling is slow compared with the rate of unloading.
The intensity of hysteresis in the case of a diffusive transition is a conven-
tional characteristic that depends on the time the initial phase spent in the region
of its thennodynamic instability. At the martensitic transition associated with
mechanical instability of the lattice, the initial phase is not thermally activated in
the limit T -+ 0, and the intensity of hysteresis does not depend on the time (ex-
cluding times which are small compared with the characteristic time of marten-
sitic transition), but depends, of course, on the concentration and distribution of
microscopic defects.

8.4. The Possibility of Realizing Diffusive and

Martensitic Transformation Mechanisms
Not taking into account the duration of a phase transition, we can say that tran-
sition into any thennodynamically equilibriwn phase can occur by the diffusive
mechanism. However, a diffusive transition out of local high-temperature inho-
mogeneities within a comparatively cold body usually takes a very long time.
This means that fonnation of a new thennodynamically stable or metastable
phase by shock compression can, as a practical possibility, occur only by means
of a martensitic transition.
It is a necessary, but not always sufficient, condition for the transition be-
tween two phases to be martensitic that the new crystal lattice can be fonned
from the old one by macroscopically homogeneous compression and shear. Such
deformations cause relative displacement of atomic layers of the crystal in di-
rections perpendicular and parallel to the layers, and all equivalent lattice points
of an atomic layer move together and in the same manner. It can be shown from
a formal, purely geometric point of view without taking into account interaction
of atoms and stability of the lattice during the deformation, that all crystallat-
254 N.M Kumetsov

tices from triclinic to hexagonal and cubic (including those that are close-
packed) tbat are formed by one population of equivalent lattice points (atoms)
can be mutually transformed by such a method. For simple lattices that are not
close-packed this is lather obvious. For instance, a simple cubic lattice can be
transformed into a tettagonallattice by uniaxial compression along the direction
of one of its sides and into a rhombic lattice by compression along the direction
of two sides. The ways in which a simple cubic lattice can be converted into a
close-packed lattice-bee or bet and fcc-or in which a close-packed lattice
can be converted into another such lattice are less evident Figure 8.2 shows an
example of the formation of a bet lattice from a simple cubic lattice by the shear
of each atomic layer parallel to one of cube faces in the direction of the diagonal
of this face by one-half of the diagonal with respect to the neighboring plane. If
all displacements are measured from a layer numbered 1, then all odd layers will
go over into themselves and each lattice point of the even layers will occupy the
position in the center of the appropriate rectangular parallelepiped with a square
base and an altitude equal to twice the length of the side of the initial cubic unit
cell. The lattice obtained by this means can be transformed to a bee lattice by
being compressed perpendicularly to the displacement of the planes or by
sttaining in two other mutually perpendicular directions.
Figure 8.3 shows an fcc lattice with a body-centered-tetragonal (bet) cell
[33,37) outlined in it The bet lattice and the original fcc lattice being com-
pressed as ../2 is transformed into the bee lattice. The direction, the value, and
the succession of homogeneous deformations of compression, elongation, and
shear, with the help of which it is possible, formally, on the basis of only con-
ceptual, purely geometrical grounds to convert an original lattice into a final
one, are not unique. The mechanism of martensitic bee-fcc ttansition in steel
was stated by Kurdjumov and Sachs [38].

Figure 8.2. Formation of bet lattice from a simple cubic lattice by a uniform shear. The
direction and value of the shear relative to the bottom face of the cube are labeled with
arrows.
 8. Some Questions of Phase Transition in Shock Waves 255

I I
I 0 I 0
o I 01 •
1 • 1 I· I
f--i--- +---;t--
----- """"-

Figure 8.3. An fcc lattice with an outlined body-centered-tetragonal (bet) cell [37].

Except for phase transitions with a change of symmetry of the Bravais lat-
tice, compression of a crystal at arbitrarily low temperature may, surely, also
cause an isomorphic transition into a lattice of the same symmetry, but with
other parameters, e.g., with smaller diameter of "spheres" of the same close-
packed structure, if this new lattice is thermodynamically possible. One example
of such a transition is the first-order electronic phase transition that occurs in
cerium with preservation offcc symmetry [1,39].
Both of the "elements" of rearrangement of a crystal lattice described
above-dilatation and the relative sliding of crystal planes-are the micro-
scopic manifestation of macroscopic deformation of the crystal under external
stress, both static and dynamic. The ratio of amplitudes of the dilatation and
shear deformations depends on both the degree of anisotropy of the applied
loading and on the crystal orientation. But, to some or another extent, both kinds
of deformation are always present, especially in polycrystalline substances, for
which a wide distribution of amplitudes of dilatation and shear is observed at
any orientation of the external load due to the random orientation of the crystal-
lites.
Real macroscopic deformations do not coincide exactly with any conceptual
schemes of continuous, macroscopic, spatially uniform conversion of an initial
crystal lattice into a fmal thermodynamically stable lattice. Therefore, even if all
types of cooperative displacements of atomic layers in crystallites are present, a
low temperature martensitic phase transition would be impossible without some
additional degrees of freedom in the form of free parameters that help the de-
formation of the lattice and its transition into the new eqUilibrium state conform
to the applied external stresses. Among these free parameters are the following:
1. Orientation of the newly forming lattice with respect to the initial lattice
and the related orientation of a martensitic plate. The orientation realized
is that at which the initial and forming lattices are coherent to an accu-
racy of low relative concentration of microscopic defects. Almost all
256 N.M Kuznetsov

neighboring lattice points of the original lattice remain neighbors not

only in the fonningphase, but also at the phase boundaIy [25,30].
2. Size of martensite plates.
3. Amount and spatial distribution of microscopic defects.
4. Plastic shears in the initial and fonning phases.
5. Corrugation or other inhomogeneous deformation of the initial phase in
the region of contact with the side surface of the plate [4,25,30].
6. Residual elastic stresses in each phase.
7. Finite size of the grain and possible output of the plate on its boundaIy.
With an increase of temperature, the difference between martensitic and dif-
fusive transitions becomes more conditional. At finite temperatures the thermal
vibrations of atoms and the microscopic defects caused by heating change (usu-
ally reduce) the thresholds of lattice stability with respect to dilatation and shear.
A temperature increase causes an increase in the number of thermal defects and
acceleration of relaxation processes, including diffusive processes. Thermal
relaxation processes also occur during the final stage of martensitic transition,
even if the original lattice was absolutely cold because the loss of mechanical
stability leads to energy dissipation and heat release. The more the potential
energy of the deformed original lattice at the point of stability loss differs from
that of the fonning lattice, the more dissipative is the transition. The potential
energy converts both directly into heat and into the energy of fonnation of mi-
croscopic defects, which is also partly converted into heat Therefore, at this
stage of phase transition, the thermally activated "shuffling" of atoms inside the
lattice cell is possible, depending weakly on what happens at greater distances
[25]. Nevertheless, this, the final, stage can formally resemble a cooperative
transformation because it starts at almost the same state of equivalent lattice
points at the same time under the same initial conditions for their further motion.
These and other factors ensure a high probability of realization of martensitic
polymorphic transition in the cases for which the fonning lattice can be repre-
sented as a superposition of homogeneous deformations of the original lattice.
If there are several types of equivalent points in a crystal lattice, i.e., if the
lattice is formed from several Bravais lattices inserted into each other, then,
under the microscopic homogeneous deformations mentioned above, the number
of lattices is conserved and all of them are transformed identically. However,
due to both the physical difference of Bravais lattices and the difference of
power constants determining the interaction of non-equivalent lattice points with
surrounding atoms, these lattices are displaced relative to each other [25]. This
displacement, however, does not make a new phase, because the structure of a
new stable or metastable phase is detennined only by the thermodynamic re-
quirement that the thermodynamic potential take its minimum value and can
 8. Some Questions of Phase Transition in Shock Waves 257

have essentially different relative displacements of Bravais lattices. For exam-

ple, in the initial phase the neighboring lattice points of two Bravais lattices can
be maximally separated, but in the forming thermodynamically stable phase they
can be maximally close in pairs and their position does not necessarily corre-
spond to the relative displacement of two lattices at homogeneous deformations
of an initial crystal. Such microscopically inhomogeneous displacement of lat-
tice points is possible only during a diffusive phase transition. Othenvise it
needs, in general, so microscopically inhomogeneous a stress field that it is not
feasible in either static or shock wave experiments. Diffusive rearrangement of
the crystal lattice takes place, e.g., if the phase transition is accompanied by
chemical reaction with breakage of some and formation of other chemical bonds
or precipitation of some component of an alloy.
Shock induced polymorphic transformations without any preheating of a
sample of the metals Fe [12-14], Bi [16], Ge [17], as well as of other elements
and potassium and sodium halide compounds [18,19], if they take place out of
hot zones, are, as a rule, martensitic.
The first stage of the two-stage transformation of carbon or boron nitride
(BN), is martensitic (see [4,30,32,40]):
graphite ~ lonsdaleite ~ diamond
BNG~BNw~BNs,

where the subscripts G, W and S stand for graphite-like, wurtzite, and sphalerite
modifications of boron nitride.
Since the atomic layers in a monocrystal are displaced in definite directions
at a martensitic transition, the values of pressure at which the transition begins
and ends depend on the orientation of the crystal with respect to the direction of
the shock compression [32,41,42].
Nonmartensitic kinetics of a shock-induced transition are observed at shock
compression of crystalline and amorphous silica, where the high-pressure phase
is formed in hot zones, possibly well before the establishment of a local equilib-
rium distribution of energy of vibrational and other degrees of freedom accord-
ing to the diffusive mechanism.
Substances formed by strongly nonspherical rigid radicals composed of sev-
eral atoms combined together by an atom with low co-ordination frequently
equal to two, e.g., oxygen atoms, under normal conditions, form lace structures
having a relatively low density. When subjected to cold compression, such
structures either undergo martensitic transition to a new phase by means of a
gradual change and then, at the first-order phase transition, the sudden change of
angles between bonds that is required for the new phase direction (a so-called
distortion transition, common for systems, forming glasses [2]). Alternatively,
258 N.M. Kuznetsov

the structure becomes become amorphous in the case of a loss of mechanical

stability [28,29].
Loss of mechanical stability of the crystal lattice, resulting from large de-
formations and accumulation of structural defects, was obselVed when mono-
crystalline graphite was statically compressed to 23 GPa [43]. According to
Aksenkov et al. [44], graphite that has been shock compressed to 20 GPa is
~70% amorphous.

In amorphous matter, martensitic transitions can't occur because atoms can't

move coherently to the lattice points. Generally speaking, an A-phase to
B-phase transition can be martensitic only if these phases are crystalline and
neither amorphous nor liquid. Let us note in this connection, that diamond forms
in a mixture of 90% copper and 10% polycrystalline graphite, by volume [44],
when it is shock compressed to 60-70 GPa. This transition is not martensitic,
but occurs by amorphization of the graphite followed by crystallization in plastic
zones in which the conditions are created for diffusive nucleation and fast
growth of diamond grains in a manner similar to the growth of monocrystals in a
liquid.
The dynamics of collective interactions of atoms of a polycrystal, being ex-
traordinarily diverse and complex, cannot be described quantitatively by any
available general analytic theory. Also, the capabilities of theoretical prediction
of mechanisms of polymorphic transformation are mther limited. Model repre-
sentations of various aspects of martensitic kinetics are developing both on mac-
roscopic and microscopic levels of description. Undoubtedly, the latter is the
more interesting and, thanks to computer simulations, the most feasible. But, on
the way to its realization, there are many obstacles, the principal one of which is
the necessity of dealing with a very large number of particles, and, respectively,
with limited options of even very perfect computer engineering. This obstacle is
fundamental if martensitic transitions and plastic flow or brittle fracture are
modeled by molecular dynamics simulation. It is impossible to avoid dealing
with the large number of particles by using periodic boundary conditions, as is
done, e.g., in calculation of thermodynamic functions. The real progress of the
theory in the nearest future can be achieved, evidently, by joint application of
macroscopic and microscopic approaches with mutual refinement of the models
used.

8.5. Kinks of the Hugoniot

First order polymorphic transformations, as first order phase tmnsitions in gen-
eral, are chamcterized by very unusual thermodynamic properties (discontinuous
thermodynamic functions at the phase boundary, infinite heat capacity, Cp , of
the two-phase mixture, etc.) Such properties give rise to kinks on Hugoniots at
the boundary of the two phase region [45-47].
 8. Some Questions of Phase Transition in Shock Waves 259

As is shown in [46], the direction (sign) of a kink on the Hugoniot entering

the two-phase mixture (comprising phases I and IT) from phase I in the direction
of increasing stress is defined by the sign of the product

(S.l)

where Q is the phase transition heat, dT/dP is the derivative of temperature with
respect to pressure on the phase equilibrium line, and (oT/oP)s.l is the isen-
tropic derivative of temperature with respect to pressure for phase I. All the
values are taken at the point where the Hugoniot enters the two-phase region.
Conventionally, Q> 0 if the transition from phase I to phase IT is accompanied
by heat absorption. The character of kink depending on the sign of Aio is shown
on Fig S.4.
At the point where the Hugoniot crosses from the two-phase region into the
single-phase region (into phase IT or back into phase I) the sign of the kink is
defined by the product

Aout EQ[(OT) _dT], (S.2)

fJP S.i dP

where all values are taken at the point where Hugoniot leaves the two-phase
region. the label i designates the phase the Hugoniot is entering (i = I or 11).
Equation (S.l) can be used to detennine the sign of the kink on the Hugoniot
only if the Hugoniot of phase I intersects the boundaIy of phase equilibrium.
Such intersection, however, is possible only if the restriction

Q[(OT)
fJP
_dT]>o
dP
H.I
(8.3)

-1
_._-_.- 2
Ai. >0

o~----------------------~
V
Figure 8.4. Direction of the Hugoniot kink depending on the sign of Ain• The line 1
designates the state of the substance before the shock wave and the line 2 is the boundary
between the original phase and the two-phase mixture.
260 N.M Kuznetsov

on Q and dT/dP is satisfied. where (aT/ap)H.I is taken along the Hugoniot of

phase 1.

Q < 0, °
The inequality (8.3) imposes additional restrictions on the sign of the kink: If
Ain can only be positive, but if Q> (e.g., at melting) both signs of Ain
are possible. However, in the latter case the possibility that Ain is positive is
restricted by the fairly strong condition,

(:)H.I> a; >(:)8.1' (8.4)

that must be satisfied by dT/dP at the intersection point.

Because of Eq. (8.4) it is rather unlikely that Ain < 0, at least for relatively
weak shock waves, and this case is called, by convention, an "anomalous kink"
of the Hugoniot. Notice also, that it follows from Eq. (8.4) that Ain can't be
negative for weak (nearly isentropic) shock waves, which is in full agreement
with the well-known inequality Ccr) > Co, where C", and Co are the nonequilib-
rium (high-frequency) and the equilibrium values of the speed of sound [48].
The qualitative pattern of the kink on the Hugoniot, the only one possible if
Q is negative (e.g., at the input of the Hugoniot from the vapor phase into the

°
liquid-vapor two-phase mixture) and the most likely if Q is positive e.g., at
melting, corresponds to the case Ain> on Fig. 8.4.
At the critical point, the phase transition heat equals zero and, in accordance
with Eqs. (8.1) and (8.2), the Hugoniot does not exhibit any kinks. Furthermore,
in the vicinity of the critical point the kink size is next to the leading order as
compared with Q because dT/dP = (aT/ap)s at the critical point. This follows
from the Clapeyron-Clausius equation, dT/dP= (av/aS)p, written for differen-
tials of entropy and phase volume, and from the thermodynamic relation
(aV/8S)p= (aT/8P)s.
Each direction (sign) of the kink on the Hugoniot is accompanied by special
structural features of the shock wave caused by phase transition or plasticity
[49]. In the case of positive Ain leading to the formation of a two-wave configu-
ration, a second shock wave is always structurally weak according to the
Zel'dovich classification [50,51] and is characterized by a diffuse front and
smooth increase of pressure [49], as shown in Fig. 8.5. AI; the amplitude of the
second wave increases, it should become stronger with a sharp leading front and
further smooth increase of pressure in the relaxation zone caused by relatively
slow phase transition but, before then, the second wave becomes strong and the
two-wave configuration coalesces into a single shock wave [49].
For Ain < 0, the pressure and density in the relaxation zone of the shock wave
decrease as the phase composition approaches thermodynamic equilibrium, i.e.,
in this case the structure of the shock wave is the same as that of a detonation
 8. Some Questions of Phase Transition in Shock Waves 261

wave, the heat release zone of which is characterized by a so called chemical

peak as shown in Fig. 8.6.
A two-wave configuration is usually fonned at a phase transition or onset of
plasticity. At the point of its disappearance, i.e., at the shock pressure at which
the two waves merge into one shock wave, point 3 on Fig. 8.7, the Hugoniot of
the second wave intersects the Hugoniot drawn from the initial state (PI, VI) for
the first wave. Below point 3, shock compressibility P(V) is defined by the
Hugoniot of the second wave and above this pressure it is defmed by the
Hugoniot of the first wave. Therefore, the P(V) curve has a kink at point 3
[13,52]. The sign of this kink is defmed by the sign of (8PtaT)v on the
Hugoniot of the second wave at the point where the two-wave configuration
appeared (point 2 on Fig. 8.7) [52]. If the two-wave configuration is fonned at
the phase transition, then the Hugoniot of the second wave at point 2 is in the
two-phase region and therefore (8PtaT)v= dPldT. The signs of the kinks de-
pend on the sign of (8PtaT)v as shown on Fig. 8.7. The dotted line denotes the
continuation of the Hugoniot of the second shock wave.
In conclusion, it may be said that the thennodynamic criteria given above for
the sign of the kink on the shock Hugoniot have been obtained for equilibrium
phase transitions. Therefore they can be applied directly only to phase transi-
tions with a negligibly small hysteresis, e.g., melting and evaporation, and as
approximate reference points for other phase transitions with a large hysteresis.

p l - - - - -__

Figure 8.S. Two-wave configuration in the case of a smooth increase of pressure in the
second wave.

Pl-------

Figure 8.6. Shock wave structure for Ain < o.

262 N.M Kuznetsov

oL-------------------~
V
Figure 8.7. Signs ofkinks of the shock compression curve P(V} depending on the sign
of (dP/dT}v. Point 3 is the point at which the two-wave configuration disappears. The
dotted line shows a smooth continuation of the second-shock Hugoniot. Kinks a and b
correspond to positive and negative values of (dP/dT}v at point 2, respectively.

8.6. Hugoniots of Two-Phase Liquid-Vapor Systems

To solve problems of hydrodynamics of two-phase liquid-vapor systems it is
necessary to know the equation of state of these systems. An analytical form of
the equation of state is the most convenient However, experimental values of
thermodynamic functions of liquid and vapor on the saturation line, under which
the equation of state can be constructed, are, as a rule, tabulated. Moreover, for
many systems the data are available only for a very limited number of points on
the saturation line.
It has been possible to overcome these shortages by constructing the unique
analytical equation of state of the two-phase liquid-vapor system for a wide
class of substances [53]. It expresses internal energy of the system in terms of
pressure and volume (as well as of temperature and volume) and contains pa-
rameters determined by only two points on the saturation line. Moreover, the
analytical two-parameter dependence of temperature on pressure on the satura-
tion line is found. The equation of state is represented as
E=fi(P}+ j2(P)V (8.5)

with

j2(P) =ElI -EI ,

VII -JIi
where E and Vare the specific energy and volume of the two-phase system, and
E 1, En, JIi, and Vn are the specific energies and volumes of liquid (I) and vapor
(IT) on the saturation line at the same pressure at which E is calculated. The
termjj (P) is approximated in the parametric form
 8. Some Questions of Phase Transition in Shock Waves 263

fi{P(T)}=A+BT (8.6)

with the temperature as a parameter. The coefficients A and B are determined by

two arbitrarily selected points PI and P 2 on the phase equilibrium line P(T). It is
supposed that the specific energy and volume of each phase, as well as the tem-
perature, are known at these points (PI is usually selected to be 1 kglcm2). The
factor h (P) is approximated as

f2(P) =a PI ( P)718 ' (8.7)

where a is the value ofh (P) at P = Pl.

The error of the approximations of Eqs. (8.6) and (8.7) for a wide class of
substances (water, C{}z, CO, alkanes, freons, and others) is, on average, a few
tenths of a percent (maximally about 1%) and maximally in the vicinity of the
melting or critical point up to 4%, sometimes up to 6-10%, respectively
[53,54]. The physical meaning and the reason of approximation (8.7) and of the
exponent 7/8 in it is discussed in [53].
From the second identity (8.5) and the Clapeyron-Clausius equation, it fol-
lows that

!2(P)=T dP -Po (8.8)

dT
Substitution of Eqs. (8.6) and (8.7) into Eq. (8.8) and integration results in the
equation

T= a(a+z)8 where z== (:J/8 (8.9)

for the phase equilibrium curve.

When parameters a and a are calculated using two widely separated points
on the phase equilibrium line, the error in T determined by Eq. (8.9) is, as a rule,
about 0.01-0.1 % relative to the corresponding value given in the reference book
[55]. For some substances the error increases up to 1-2% in the vicinity of the
critical point.
For example, for water we have a=12.5085, a=3.3564 x lO-7 K, P 1 =1
kglcm2, and the error in T calculated using Eq. (8.9) does not exceed 0.08% in
the ranges of pressure from 0.6 kg/cm2 up to the critical pressure [54].
An equation of state such as Eq. (8.5) gives the analytic expression of the
Hugoniot curve V(P)H of the two-phase mixture explicitly resolved with respect
to V. In particular, for the water-vapor system [56],
264 N.M Kuznetsov

V(P) = 341.27(~O.24S _p O.24S) +0.03997 (P+PI) Jil +Jil ~7/8 (S.10)

H p7/8 +0.03997(P+PI) ,

where the initial (PI, VI) and:final (P, V) points of the Hugoniot are in the two-
phase region. Specific volume and pressure in Eq. (S.10) are expressed in cm3/g
and kglcm2, respectively.
The Hugoniot, Eq. (S.10), as well as those of other two-phase liquid-vapor
systems [57] usually have a vel)' specific form (Fig. S.S). However, under real
conditions the state of thermodynamic equilibrium behind the shock wave can
hardly be achieved in such systems due to both slow heat and mass exchange
between phases [10,11] and rising of vapor bubbles in the gravitational field.

8.7. Hydrodynamic Stability of Shock Waves. Rarefaction

Shock Waves
Hugoniots satisfying known criteria for hydrodynamic instability of waves [5S-
61], though not contradicting thermodynamic inequalities, appear to be, never-
theless, so "anomalous" thermodynamically that until now no substances have
been found for which equations of a stable single-phase state (without plastic
flow) would result in such Hugoniots.
However, the Hugoniots crossing phase equilibrium boundaries are unique
from this point of view. It is precisely in the case offirst order phase transitions
that Hugoniots of actual (not hypothetical) substances meet one of the criteria,

J 2 (8V) <-1 (S.l1)

8P H '

of hydrodynamic instability of shock waves. In this inequality, J is the flow

density of the substance through the shock wave and (8V18P)H is the derivative
of specific volume V with respect to pressure P taken along the Hugoniot. This
criterion is satisfied for Hugoniots with kinks or smooth bends (Fig. S.9) caused
by phase transition (POlymorphic transformations, melting) or initiation of plas-
tic flow.
When the inequality (S.I1) is valid, the Mach number, M, behind the shock
front is more than unity, i.e., one of the fundamental "one-dimensional" condi-
tions of shock wave stability appears to be violated [4S,62,63].
The inequality (S.I1) is also a criterion for corrugation instability of shock
waves [5S-60]. Corrugation instability in the case that (S.I1) is satisfied can be
explained rather easily [62] on the basis ofthe fact that on the segment S-, S+
of the Hugoniot (see Fig. S.9) a decrease of the velocity of the shock wave cor-
responds to an increase of the pressure. In the case of the kink shown in Fig. S.7,
 8. Some Questions of Phase Transition in Shock Waves 265

log P

1.5

1.0

2
0.5 Jt-.......:--__

0.0 L-_--"-~=::r..----L-~.,p...~~~~---l~Io.__---l
0.0 0.5 1.0 1.5 2.0 2.5 3.0 log V

Figure 8.8. Hugoniots of an equilibrimn water-vapor two-phase mixture. The initial

pressure is 1 atm. and the initial volmnes VI (cm3/g) are 1: 100,2: 134.6; 3: 200, 4: 211.4,
5: 300,6: 500, and 7: 1038.7. D is the two-phase boundary. To the left of the line S the
conditions for resonant reflection of sound are fulfilled for these Hugoniots.

0'------------..-
v
Figure 8.9. Kinked or smooth (dotted line) Hugoniot at the Point S- . The point S+ is
the point where the line drawn from the initial state I contacts the Hugoniot.

rarefaction shock waves are also possible. The existence of rarefaction shock
waves has been associated earlier with the violation of positivity of the second
isentropic derivative of specific volume V with respect to pressure P :

(88p2V)
2

S
>0. (8.12)
266 N.M Kuznetsov

The entropy increases in a compression shock wave (and would decrease in a

rarefaction shock wave), if the inequality (8.12) holds everywhere on the
Hugoniot.
Otherwise, within some pressure range depending on the position of the ini-
tial point on the Hugoniot and on the position and size of the region where the
inequality (8.12) is violated, rarefaction shock waves (Zel'dovich [50)) become
possible. Inequality (8.12) is violated vel)' seldom and only within a restricted
region of thermodynamic parameters. In particular, this takes place in gases with
a large intrnmolecular specific heat near the line of equilibrium with the liquid
phase and not far from the critical point [50]. Rarefaction shock waves predicted
theoretically for this case were later obtained experimentally [64].
The derivative (fPV/OP2)S does not exist at the kink point but, as far as the
sign and the value of the entropy change in the shock wave are concerned, the
above kink is equivalent to a smooth bend of the Hugoniot leading to violation
of inequality (8.12) within some vicinity of the kink point. Kinks on Hugoniots
are encountered more frequently than situations where inequality (8.12) is vio-
lated.
Interestingly, the feasibility of generating rarefaction shock waves in materi-
als having Hugoniots that exhibit kinks remained unnoticed for a long time,
although substances and states for which the derivative (02V/Op2)swas negative
were searched to obtain rarefaction shock waves. It is now clear that systems
whose Hugoniots exhibit kinks are undoubtedly of major interest, both for the
number of possible cases where rarefaction shock waves can be generated and
for the practical importance of experimental results. This was realized after
experiments performed by Bancroft with co-workers [12] showed that, for Fe,
shock compression followed by plastic flow and phase transition led to forma-
tion of two or three shock waves instead of one. After compression, rarefaction
shock waves are generated under certain conditions in the course of expansion
[65]. For the first time rarefaction shock waves were obtained experimentally in
Fe by Ivanov and Novikov [66].
Another sufficient criterion of hydrodynamic instability of a shock wave is
expressed by the inequality
L>I+2M, (8.13)
where M is Mach number behind the shock wave.
Not so many systems are known for which Hugoniots have segments with
positive derivative of specific volume with respect to pressure and a positive
value of the parameter L. Among them are dissociating and ionizing gases (e.g.,
air [67]), solids with large initial porosity, and a two-phase liquid-vapor sys-
tems [56,57] (see Fig. 8.7). At thermodynamic equilibrium in the two-phase
region, vel)' large positive values of the parameter L can be achieved (so far
 8. Some Questions of Phase Transition in Shock Waves 267

only computationally, because practical achievement of thermodynamic equilib-

rium upon shock compression of such two-phase systems is a problem (see
below». However, in all known cases, the value of this parameter appears to be
too small for the criterion (8.13) to be fulfilled. Even the weaker criterion L > 1
for instability of a shock wave interacting with a piston is not satisfied [68-70].
In the theory of shock-wave stability, the values of L in the range
Lo <L<l+2M (8.14)

are also rather important. In this expression

1-8M2-M2
Lo == 1+8M2 _M2

and 8 = Ii) /V2 is the compression ratio of the material at the shock wave.
When the parameter L is in the range (8.14), resonant reflection of sound by
the shock wave takes place: Every value of the parameter L from the range
(8.14) corresponds to a definite angle of incidence of a sound wave on the sur-
face of the shock wave such that resonant reflection takes place. Nonlinear
analysis showed that shock waves under conditions (8.14) are stable with re-
spect to thermodynamic fluctuations [71,72]. Shock wave stability under condi-
tions (8.14) was discussed in detail in the reviews [62,63].
Phase transitions (thermodynamic properties of two-phase mixtures) are also
unique in respect of conditions (8.14). Thus, for a variety of thermodynamic
properties of substances considered so far, it is only for two-phase systems that
values of the parameter L satisfying inequalities (8.14) are known. Such values
of L can be obtained in some region of states of equilibrium two-phase liquid-
vapor systems (copper [73], water [74]). Generality of thermodynamic proper-
ties of two-phase liquid-vapor systems (see [57,75]) allows us to suggest that
the interval (8.14) exists also on Hugoniots of other two-phase systems, e.g.,
freons. However, in all such systems, resonant reflection and other peculiarities
of interaction of a shock wave with small perturbations coming at an angle that
is close to the resonant angle are rather difficult to observe due to the rising of
vapor bubbles and the large relaxation time of heat and mass exchange.

8.8. On the Possibility of Shock-Wave Superheating of Solids

From the viewpoint of both thermodynamic theory of phase equilibrium and
nucleation theory (which takes into account surface tension and surface energy
of small particles of a new phase) superheating of solids is undoubtedly possi-
ble. This possibility was indicated, e.g., by Bridgman in his review of high pres-
sure phenomena [1], in which he warned of errors while interpreting shock-wave
measurements. However, it is known that, in contrast to supercooled liquid
268 N.M Kuznetsov

which can be obtained mther easily by a very slow cooling without abrupt me-
chanical impacts ("shakes"), superheated solid is very difficult to obtain. The
principal problems are associated with the following:
1. A solid body melts when its surface contacts a hotter environment. How-
ever, the thermodynamic equilibrium tempemture, Tms , of melting of the
first one or two monolayers at the surface of the body is lower than the
melting temperature, Tm , inside the solid due to the smaller binding en-
ergy at the surface particles. Moreover, the surface usually has a lot of
microscopic inhomogeneities of different nature that can serve as nuclei
of a new liquid phase. That's why the surface layer becomes molten
when the body is slowly heated to the tempemture Tms' Subsequent heat-
ing of the sample by heat flow through the surface causes the liquid-
solid boundary to move deeper inside the body. Deeper layers heated to
the tempemture Tm are already in contact with the macroscopic surface of
the liquid phase and, therefore, melting occurs without any significant
superheating.
2. Surface melting will not affect superheating* if the body is heated
throughout its volume and sufficiently fast as compared with the charac-
teristic time 't - L2/'X of the crystallite cooling (L is the crystallite linear
size and 'X is the thermal diffusivity coefficient.) The heating time has to
be smaller than 't in order that the heat being deposited into the body
would not have time to escape to the surface and to the melting boundary
moving away from the surface. Otherwise the tempemture of the whole
crystallite will be close to the melting tempemture, and the heat will be
spent not on superheating but only on melting as the phase boundary
moves deeper into the crystallite.
Heat can be deposited throughout the volume of a metal body by transmis-
sion of electric current through the sample (see, e.g., [83] and references given
there). However, shock-wave compression is a universal technique for fast
heating that can be applied to all materials. The most intensive heating as com-
pared with the heating of the whole solid in the shock wave takes place in "hot
zones" such as in plastic shear bands [9,15). The large quantity of microscopic
defects formed during plastic shear evidently eliminates the possibility of sig-
nificant superheating within the shear bands. In the following, we shall deal with

* It is supposed that temperature is restricted to the solid lability limit (beyond which it
becomes absolutely unstable). It is known that melted metals can be supercooled by about
O.2Tm [76]. Because of the approximate symmetry of supercooling and superheating,
under conditions when the surface does not affect the process, superheatings of the same
order can be expected. Thermodynamic properties of superheated solids and the lability
boundary have been theoretically investigated in [77-82]. According to calculations [82]
(lattice dynamic numerical simulation), temperature on the lability boundary of rare gas
solids exceeds Tm by 1.2-1.4 times.
 8. Some Questions of Phase Transition in Shock Waves 269

superheating and melting of shock-compressed matter outside of plastic shear

bands.
The kinetics of shock-wave melting of polycrystals have been investigated in
[84]. Melting of a monocrystal in a shock-compressed polycrystalline solid has
been considered. The amplitude of the shock wave was such that the tempera-
ture, T, inside the monocrystal before melting was higher than Tm. The mecha-
nism of the process was considered to be as described above (melting not
limited by the nucleation time occurs on the surface owing to heat transfer from
the bulk medium). The melting time, 'tm , determining the width of the shock
front is given by

-R2 [1 CpAT]
- - - +'to, for (8.15)
'tm ~ { 3X q
CpAT
'to, for 1---<0, (8.16)
q

where q is the specific heat of melting, R = Ll2 is the effective radius of the
crystallite, 'to = (3-10)RIC. is the time required for the melting front to pass
from the surface of the monocrystal to its center under the condition that super-
heating is sufficient for melting of the whole monocrystal, and C. is the shear
wave speed [84]. In this case, the inequality (8.16) should be valid, which means
that each portion of the shock-compressed material can melt without any extra
input of heat
The thermal conductivity coefficient, X, of different substances varies from
1 cm2/sec for copper to values of the order of 2-2.5 times smaller (fused silica,
wood) [85]. If R - 10 -3 cm, then the lifetime of superheating of the crystal up to
values CpAT of the order of ql10 derived from Eq. (8.15) is about 1-100 J.lS,
which is easily obtainable in shock-wave experiments. However, the crystallites
can fracture in strong shock waves. As this takes place, the melting time and the
degree of superheating decrease, and the dependence of the shock-wave struc-
ture on superheating becomes experimentally unresolvable against a background
of other relaxation processes .
From the foregoing discussion it follows that considerable solid superheating
in a shock wave is possible only if rather severe restrictions, which are mutua1ly
exclusive in many cases, are fulfilled. So, for melting (and, respectively, for
superheating) a strong shock wave is usually needed (with pressures from tens to
hundreds of GPa). But in the front of such waves crystallites are being frag-
mented and saturated by defects which prevents superheating. This obstacle can
be eliminated, or essentially reduced, if the initial substance (monocrystalline or
rather large-grained) is preliminarily heated to a temperature, close to Tm. Then
melting can be observed in relatively weak waves which do not destroy the
initial structure of the material. Experimental study of superheating of solids
270 N.M Kuznetsov

under these conditions would be rather interesting for kinetic theory of phase
transitions in a condensed material.

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 8. Some Questions of Phase Transition in Shock Waves 273

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 CHAPTER 9

Kinetics of Shock-Induced Phase

Transition of Quartz

N. M. Kuznetsov

9.1. Introduction
The behavior of statically and dynamically loaded and then unloaded quartz is
associated with a broad spectrum of complicated physical phenomena-change
of strength, amorphization, non-equilibrimn phase states, phase transitions, etc.
For this reason, quartz is a rather popular material for experimental study of
pressure-induced processes. As to the nmnber of scientific publications devoted
to high pressure states of matter, only carbon (probably because of the problem
of making diamond), and iron can be compared with quartz. This chapter re-
views some experimental data on shock compressibility of quartz as well as the
analysis of these data [1-61].
The experimentally observed Hugoniot of quartz in the pressure range
10 GPa <P<40 GPa (9.1)
differs significantly from Hugoniots of single-phase systems in that the increase
of pressure during compression is much weaker in the former case than the latter
[9,10] (see Fig. 9.1). This form of the Hugoniot and the closeness of the density
in the vicinity of the upper limit of the flat segment of the Hugoniot to the den-
sity of a well-known crystalline high-pressure phase, stishovite [8], suggests
some relationship of the observed form of the Hugoniot with polymorphism of
quartz. However, the observation cannot to be explained solely by the coexis-
tence of low pressure and high pressure phases in thermodynamic equilibrimn in
the shock compressed material. The segment of the equilibrimn Hugoniot in the
quartz-stishovite mixed-phase region would lie in a narrow range of pres-
sures PI < P < PI + 8P, with 8P« PI where, by various estimates, PI = 6-9 GPa
(see [23,26] and the references in [9]).
There are various qualitative representations of the structure and mechanism
of formation of the shock-induced high-pressure phase (HPP) of quartz. Unfor-
tunately, most suggestions can't be verified experimentally because the HPP
structure usually disappears during unloading.
V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII
© Springer Science+Business Media New York 2004
276 N. M. Kuznetsov

P,GPa
.1fJ

10

20

TO

o
o.ZO 0.10

Figure 9.1. Averaged experimental Hugoniot of a quartz.

As a whole, there is no unanimity among scientists on the answers to the

following questions:
1. Is the HPP stishovite or dense amorphous silica with the same co-ordina-
tion number for silicon, 6, as stishovite?
2. What is the mechanism of shock-induced HPP formation? Is it formed
directly from crystalline quartz or through an amorphous low density
"phase" with the same co-ordination number, 4, as common quartz glass?
3. What is the history of the glass observed after unloading of shock-com-
pressed crystalline quartz? Has it been formed from stishovite by amor-
phization of compressed quartz or from melt?
4. Is the formation of the HPP diffusive, caused by activation and move-
ment of individual molecules, or martensitic, caused by coherent rear-
rangement of the crystalline lattice as a whole?
5. Is the HPP formed by continuous compression, or by a sudden change of
volume and co-ordination number as in a first order phase transition?
All the data available on special features of shock-compressed quartz of
various initial densities, on unloading adiabats, on low-temperature quasi-static
compression, and on the rheological properties of quartz melt, make it possible
to reduce considerably the indeterminacy of answers to the questions listed
above and to select, in particular, the most credible conclusions on the nature of
the HPP and on the kinetic mechanism of the pressure-induced quartz --+ HPP
transition.
 9. Kinetics of Shock-Induced Phase Transition of Quartz 277

The following experimentally detennined qualitative features of the behavior

of dynamically and statically loaded quartz of various initial densities, as well as
the peculiarities of silicon dioxide phase transition kinetics, are of principal
importance when answering the foregoing questions:
1. The Hugoniots of crystalline and fused silica are characterized by an
extended segment (9.1) in which the volume dependence of pressure is
comparatively weak [9].
2. The Hugoniots of crystalline and fused silica intersect (actually, they
have two points of intersection) [9,22,40,46,52].
3. The Hugoniot and the curve of subsequent adiabatic unloading from
pressures exceeding 20 GPa form a large hysteresis loop in the P-V
(pressure-volume) plane [27,45,56].
4. The density at the upper boundary of the flat segment of the Hugoniot is
close to the density of stishovite [8-10].
5. Quartz becomes amorphous as a result of low-temperature (300 K) static
compression. Amorphization starts at about 25 GPa and is completed at
about 30 GPa [49,50].
6. Some amorphous silica is observed in compressed and subsequently
unloaded crystalline quartz samples. Its relative concentration increases
from 0 to 1 when the shock-wave pressure increases from 15 to 30 GPa
[36,57].
7. The structure of amorphous silica, observed spectroscopically in shock-
compressed and then unloaded samples, differs from the "liquid-like"
structure of fused silica. Spectroscopic data indicate an extremely fine-
grained structure of randomly misoriented quartz crystallites of diame-
ters less than 10 om [36].
8. Analysis of recovered quartz samples testifies to the spatial inhomoge-
neity of shock-induced deformations and associated localization of ob-
served structural transformations [43,57].
9. Almost all amorphous silica observed in crystalline quartz after shock
compression (at least for pressures less than 45 GPa) is due to solid-
phase processes. The quantity of quartz formed from melt is small
[43,57].
10. Quartz melt is characterized by extraordinarily large viscosity [7].
11. As a whole, silicon dioxide is characterized by slow polymorphic trans-
formations [4-6,12,16].
12. Stishovite, as a long-range ordered crystalline phase, is observed in only
trace amounts in quartz that has been shock compressed without pre-
heating [5,43].
278 N. M. Kumetsov

13. In crystalline quartz, the plastic wave propagating behind its elastic pre-
cursor does not separate into two waves (a two-wave configuration does
not form) either in the whole pressure range (9.1) or at least for pres-
sures up to 23 GPa There is some experimental evidence for the possi-
ble existence of a two-wave configuration at pressures in the range 23-
35 GPa [47,60,61].

9.2. Amorphization of Quartz

Static amorphization of quartz at room temperature was observed [49,50] at
sufficiently high "over-compressions." Crystalline quartz, which is too friable to
withstand the shear stress usually associated with static compression experi-
ments, becomes amorphous without passing through an equilibrium crystalline
modification. A similar breakdown of a crystalline lattice was observed earlier
when ice was compressed statically [62]. Static amorphization of quartz starts at
about 25 GPa and is completed at about 30 GPa. It can proceed, certainly, at any
low temperature. Quartz transforms from a metastable state into an absolutely
unstable state [5,31]. This process does not require overcoming any energy bar-
riers and, correspondingly, any thermal activation. Therefore, we can expect that
it proceeds very rapidly at every point (to an accuracy of weak activated after-
effects) for about the period of molecular vibrations, 1O-14 _10-13 S. The move-
ment of the transformation boundary from sites where, due to local
inhomogeneities, the lattice is the least resistant to transformation in some small
crystalline areas, proceeds at a velocity comparable to that of sound. It is also
natural to suppose that, at any finite temperature, amorphization will start at
somewhat lower pressure than Pit due to additional thermal activation, and pro-
ceed more slowly for higher values of Pat - P. The pressure also determines the
average extent of translational and rotational disordering of molecules after the
loss of mechanical stability of the crystal lattice. Both for this reason and since
the local loss of stability starts at different pressures due to microinhomogenei-
ties such as lattice defects, dispersion of grains, and their relative orientation,
quartz becomes completely amorphous in some finite pressure range AP rather
than at a definite pressure. As stated above, AP = 5 GPa in static experiments.
Quartz, undoubtedly, has to become amorphous under dynamic loading as
well as static loading if, of course, there is insufficient time for it to pass into a
modification in thermodynamic equilibrium, and if the pressure at which the
initial crystal lattice becomes absolutely unstable is close to Pat in the bulk of the
sample and is lower than Pit in places at which the temperature is elevated, e.g.,
in shear bands or on grain boundaries. It can be expected, therefore, that shock-
induced amorphization of quartz starts and stops at pressures somewhat lower
than in statics, i.e., somewhat lower than 25 GPa and 30 GPa, respectively. Ac-
cording to [36], quartz transforms completely into an amorphous state when
shock compressed to about 30 GPa. Approximately the same pressure range for
 9. Kinetics of Shock-Induced Phase Transition of Quartz 279

shock-induced amorphization was obtained in [57]. According to spectroscopic

research [36], the structure of this amorphous solid-state glass differs signifi-
cantly from the fused silica structure that is characterized by only short-range
translational order of Si 0 4 tetrahedrons. This state is supposed to be formed by
randomly misoriented, extremely small quartz crystallites of diameter less than
10 nm. The density of this state is slightly greater than the density offused silica
(2.25 glcm3 compared with 2.20 glcm3 ).
The pressure range mentioned above (-5 GPa) within which quartz becomes
amorphous is only a small part of the pressure range (9.1), over which shock
compressibility is abnormally high as compared to single-phase systems. Simi-
larly, the density of statically amorpbized quartz is considerably lower than the
HPP (stishovite) density at the same pressures in the shock wave [50]. There-
fore, the properties of the Hugoniot in the range (9.1) can probably not be ex-
plained solely by amorphization.
When studying quasi-static compression of brittle materials, we can't elimi-
nate dynamic effects related to the formation and fast uncontrollable movement
of cracks. The energy of elastic deformation that is released in this case can
produce local heating the material that is sufficient for amorphization at a lower
pressure than the pressure at the beginning of bulk amorphization. More accu-
rate analysis [51] as compared with [50] revealed that traces of the amorphous
phase had already formed at a pressure of 12.5 GPa. However, for P < 25 GPa
under quasi-static conditions, the concentration of the amorphous phase is well
below the HPP concentration in shock waves at the same pressure.
Qualitatively, the shape of the Hugoniot of quartz can be explained if we
suppose that fused quartz is continuously densified up to the HPP density
[48,50] or to some lower [52] density. The idea of continuous compression of
amorphous silica was used by Wackerle [9] while he was interpreting his own
fundamental experimental results on shock compression of crystalline and fused
silica. However, he did not rule out the possibility of other mechanisms. Never-
theless, when the new high-density crystalline modification of quartz, stishovite
[8], was obtained under static conditions, the mechanism including phase transi-
tion to stishovite became absolutely preferred (see the note added in proof in
[9]).
The concept of continuous compression of amorphous quartz to the HPP
and, in particular, an attempt [48,53] at qualitative explanation of the form of the
Hugoniot in the range (9.1) by gradual change of angles between O-Si-O
bonds is not convincing. Strong compression of the material (crystal, liquid, or
amorphous) always causes changes in molecular bonds-lengths, angles, or
both. Details of this process in specific materials are, certainly, of special inter-
est. But the potential energy of such molecular deformations and the related
"cold" component of pressure usually depends far more strongly on the com-
pression rate over a wide pressure range (excluding the vicinity of the boundary
280 N. M. Kuznetsov

of absolute instability of the crystal lattice) than on the Hugoniot of quartz in the
range (9.1).
In their model of continuous transition of compressed amorphous silica to
the HPP, Stolper and Ahrens [48] supposed that densificatiori takes place not
only by uniform mechanical deformation of the amorphous microstructure, i.e.,
by deformation and rotation of molecular fragments under the action of pressure
alone (displacive compression), but also by the breaking of chemical bonds that
requires overcoming activation barriers and is accompanied by diffusion. IIi the
author's opinion, the hysteresis effects can be explained by this means. The first
of the mechanisms mentioned, the reversible, continuous, pressure-induced
variation of the amorphous structure, is considered to be determining. IIi par-
ticular, in accordance with [48], the HPP forms gradually without any disconti-
nuity of density due to such a process.
But, in our opinion, all available experimental data show that this is not so. It
is just the activation mechanism, involving slight thermal or local disequilibrium
(as examined in Section 9.6), that determines the kinetics of transformation of
shock-compressed quartz and, consequently, the form of the Hugoniot. The
concept of continuous compression of amorphous quartz is also inconsistent
with the quantitative evaluation given below, which is based on data regarding
the intersection of the Hugoniots of crystalline and fused quartz.
If one accepts the concept of continuous compression of amorphous quartz
from the low-density phase to the HPP, it is very difficult to explain why the
Hugoniot of fused quartz is lower in some pressure range than that for ex. quartz
[52,63] (see Fig. 9.2). Let us consider, for example, the upper intersection of
Hugoniots at a pressure just over 30 GPa. At this point quartz is amorphous on
each of the Hugoniots being considered. If we suppose that there is no HPP
impurity there, then both Hugoniots are characterized by the same equation of
state. At this point, the average specific volume is the same on each of the
Hugoniots, but the average specific energy is significantly different. The differ-
ence of the energies (AE) on the Hugoniots of fused and crystalline quartz at the
point of their intersection at pressure P is expressed by the relationship

AE=tP(VI g -VIc)+El g +Elc , (9.2)

where VIs> E ig and VIc> E lc are the initial specific volume and energy of fused
and crystalline quartz, respectively. Substitution of Vi g = 112.2 cm3/g,
Vic= 112.65 cm3/g [64], P=33 GPa, and E lg -Elc =O.13 kJ/g [65] gives
AE= 1.41 kJ/g. IIi uniform fused quartz this energy difference on an isochore
would correspond to the difference between the thennal components of pressure,
APr=ypAE, (9.3)
where y is the GIiineisen ratio and p is the density of fused silica. Using y for the
fused quartz in its initial state (y =Yo =0.84 [53]) and supposing that y = const.
 9. Kinetics of Shock-illduced Phase Transition of Quartz 281

or yp= const., we obtain APT =4.3 GPaor 2.6 GPa, respectively, from Eq. (9.3).
Therefore, if the material behind the shock wave is uniform, the Hugoniot of
fused quartz in the P-V plane in the vicinity of the isochore under consideration
has to be placed at 3-4 GPa above the Hugoniot of crystalline quartz. However,
the experimental Hugoniots intersect on this isochore. Moreover, at 25-30 GPa,
the Hugoniot of fused quartz is located lower than that of crystalline quartz by
approximately 2-2.5 JGPa (see Fig. 9.2). This rather large discrepancy of the
observed course of Hugoniots as compared with what it would be expected for a
uniform state of shock-compressed fused quartz for both Hugoniots and, all the
more, if such uniformity takes place only after compression of fused quartz and,
in the case of compression of a, quartz, the HPP being formed, can't be ex-
plained by different equations of state of quartz on the two Hugoniots. A differ-
ence does exist due to averaging of the equation of state over thermal
inhomogeneities of the material compressed from different initial states, but it is
rather small.
It is much better to suppose that the observed Hugoniot corresponds to a
mixture of crystalline and amorphous quartz with an essentially more dense HPP
phase formed not by continuous compression of amorphous silica, but spas-
modically by a first order phase transition: If this is so, the observed arrange-
ment of Hugoniots of crystalline and fused silica can be easily explained on the
basis of an activated kinetic mechanism of phase transition: at the same pres-
sure, the HPP concentration is higher in fused quartz.
Assuming that the Hugoniot of quartz initially in the a, phase is that of a
mixture of two phases, a, quartz and the HPP, and that the HPP is stishovite,·

P,GPa
i8

50

40

.10

18

III

II

Figure 9.2. Averaged experimental Hugoniots. 1: a, quartz, 2: fused quartz.

• ill fact, only on the assumption that the HPP has the same equation of state as stishovite
has been used.
282 N. M. Kuznetsov

and using the Hugoniot data. Swegle [56] has calculated the HPP concentrations
over the entire range of shock-wave amplitudes. In accordance with his
calculations [56], the observed extraordinarily high shock compressibility of
quarlz at pressures over 10-15 GPa is determined by early formation of the
HPP. That is, the shock-induced transition to the HPP starts at considerably
lower pressure than the pressure of the beginning of static amorphization (25
GPa, [50)) at T= 300 K and is completed at a much higher pressure (45 GPa)
than the pressure, 30 GPa, of complete amorphization. At 30 GPa the HPP con-
centration in a shock wave is about 50% [56].
The foregoing facts and considerations are an important argument in favor of
the following: The amorphous phase, which can be formed out of local regions
of heterogeneous heating during shock compression as in the static case, is not
the HPP and has the low coordination number for silica, Z = 4. Final resolution
of this problem could be obtained by measuring the P(V) dependence for static
compression of <X. quarlz in the 25-30 GPa pressure range, i.e., the range where
quarlz is becoming amorphous. This dependence differs so significantly, both
qualitatively and quantitatively, for the cases of formation of glasses of high
Z =6 or low Z =4 density that its interpretation would be quite unique. At pres-
ent, experimental points on the P(V) curve are available only at lower pressures
[1,50].

9.3. On the Nature of the High-Pressure Phase

Unfortunately, the physical state of quartz that has been shock-compressed to
pressures exceeding 45 GPa, i.e., over the flat zone of the Hugoniot, is not re-
tained after unloading. That's why the most important experimental information
about the HPP is that its density is close to the density of stishovite and that
there is a very large hysteresis loop characterizing the difference between the
Hugoniot and the unloading adiabat in the P-V plane. The shape of the unload-
ing adiabat resembles an isochore more closely than the Hugoniot, which corre-
sponds to extraordinarily large compressibility. These two facts suggest that, at
high pressures, shock-compressed silicon dioxide exists in a HPP, being either
stishovite in which, as in every crystalline phase, there is a long-range order of
atomic arrangement, or its amorphous analogue, not quite ordered, which is
characterized by a stishovite-like equation of state and the same (six-fold) co-
ordination of silicon. All researchers, Wackerle [9], McQueen et al. [11], and
DeCarli and Milton [12], agree that the choice lies between these two alterna-
tives. However, which of the alternatives, stisbovite or the amorphous phase, is
correct is not yet conclusively resolved. Nevertheless, there are some rather
weighty arguments in favor of the amorphous phase. The only argument in favor
of stishovite is the fact that it does exist at normal pressure as a metastable
phase, but its amorphous analogue, apparently, does not [12]. This proves noth-
 9. Kinetics of Shock-Jnduced Phase Transition of Quartz 283

ing in the present case. Arguments in favor of the amorphous phase are given
below.
All experimental data on crystallographic modifications of quartz produced
by shock and static compression of quartz having different values of porosity, on
unloading adiabats, and on rheological properties of quartz melt, allow one to
form the following conclusions (if not unambiguous, then the most reliable)
about both the HPP obtained by shock compression of quartz and some kinetic
factors of its formation.
l. The conjecture that the high-pressure phase produced by shock compres-
sion is stishovite (in the form of crystallites large enough that the surface
energy is much smaller than the energy stored within the volume of the
crystallite), i.e., that the amorphous state has time to crystallize during a
shock-wave experiment., is scarcely consistent with data demonstrating
anomalously slow crystallization of quartz even from melt [7] and with
the slow polymorphic transformations characteristic of all silicates
[4,6,12,16,31,36].
2. If we assume that stishovite, as a long-range-ordered phase, has a chance
to form in a shock wave, we should also expect that it remains suffi-
ciently hot during unloading that it can easily recrystallize into quartz.
However, this contradicts data on the phase composition of samples re-
covered after unloading from the pressure range within which a large part
of the quartz is transformed to the HPP. The concentration of amorphous
silica in recovered samples increases with pressure in the shock wave
[36,57]. Therefore, the obseIVed extended range of large shock com-
pressibility is most likely determined by the formation of a non-equilib-
rium, amorphous, high-pressure phase with stishovite-like short-range
order of the atomic arrangement (six-fold coordination of silicon
[9,11,12,36]). It is also probable that., as for the amorphous structure of
compressed quartz mentioned above [36], the structure of the HPP is
formed with randomly misoriented, extremely small, crystallites of
stishovite (less than 10 nm in diameter). This fine-grain structure can be
regarded as extremely defective stishovite. Such small crystallites have
more than 10% of all lattice sites in two monolayers near the surface of
the crystallite. The thermodynamics of both the formation of the fme-
grain structure from other phases and the reverse transitions preserves the
main features of thermodynamics of phase transitions, inherent to macro-
scopically homogenous systems, but is characterized by some displace-
ment and degradation of boundaries of phase equilibrium and
metastability. Let us agree call this phase "stishovite glass," similarly to
quartz glass.
284 N. M. Kuznetsov

3. Taking into account rheological properties of quartz glass, its huge vis-
cosity [7,16] and the kinetic features mentioned above (slow polymor-
phic transformations of silicates), we can suppose that stishovite glass is
very viscous on the molecular level so that translational and rotational
motion of molecules is strongly hindered and its crystallization (growth
of crystallites and establishment of long-range order) in the region of
thennodynamic stability of stishovite is kinetically prohibited. Upon un-
loading, after reverse transition of stishovite glass into quartz glass, the
formation of crystalline quartz is also kinetically forbidden owing to the
large viscosity of quartz glass.

9.4. Calculation of the Hugoniot in the Two-Phase Range

Hugoniots can be calculated in the region of variable nonequilibrium phase
composition if, in addition to equations of state of both phases, the kinetic equa-
tion of phase transition is specified. However, our knowledge of the kinetic
mechanism of the process is still insufficient for calculating the temperature-
and pressure-dependent rate constants of the phase transitions of silica. There-
fore, kinetically, the Hugoniot has not yet been calculated.
Podurets and Trunin [46] attempted to explain the experimental fact that, in
the P-V plane, the Hugoniot of quartz in the two-phase mixture almost coincides
with the Rayleigh line. Their analysis was based on a special mechanism re-
stricting the maximum concentration of the HPP by some condition preventing
the formation of a two-wave configuration. According to [46], when two succes-
sive shock waves pass through the material, the kinetic conditions for HPP
(stishovite) formation (presumably, tensogenic [39], i.e., requiring shear stress)
are satisfied only for the first wave. Therefore, at any shock-wave amplitude, the
amount of the HPP fonned is such that, if it were more, the shock wave would
split into two parts. The shock structure was calculated on the basis of this
model [39]. According to the result of the calculations, the maximum concen-
tration, X, of the HPP is limited: X <Xmax. But the following things remain un-
certain:
a. the mechanism that prevents X from increasing to the value Xmax , and
b. the slope of the Rayleigh line and, correspondingly, the shock-wave ve-
locity, which is, according to experimental data, smaller than that of an
elastic precursor [9].
Another attempt to provide a qualitative explanation of the quartz -+ HPP
phase transition mechanism was undertaken by Tan and Ahrens [53]. According
to [53], the quartz -+ stishovite phase transition is triggered by transition of
quartz into the amorphous or, probably, into the liquid state due to heating in
shear bands or as a result of intersection of the Hugoniot with the metastable
 9. Kinetics of Shock-Induced Phase Transition of Quartz 285

melting curve in the P-T plane. This curve is the continuation of the melting
curve of coesite from the coesite-stishovite-liquid triple point into the region
of thennodynamic equilibrium of stishovite. Equations for the Hugoniot written
with consideration for the quartz ..... stishovite transition as well as the results of
calculations are given in [53]. However, they are principally erroneous. It can be
shown that the system of equations in [53] is not complete. The number of inde-
pendent equations is less than the number of unknown variables, and no equa-
tions are written to describe, kinetically or thennodynamically, the dependence
of the phase concentration on the shock-wave amplitude.
The inverse problem of calculation of the concentration of stishovite from
both the data on equations of state of the phases and the Hugoniot, PH(V),
measured experimentally was solved by Swegle [56] (see also [58]). The ex-
perimental results were analyzed in [56] in a way that it gives us grounds to
consider the computed phase concentrations on both the Hugoniot and the un-
loading adiabats as approximate experimental data.
Phase concentrations, and then the Hugoniot of the two-phase mixture, can
be determined if the composition of recovered samples is known. An amorphous
diaplectic glass phase observed in quartz samples recovered after shock com-
pression was shown, with various degrees of certainty, to be genetically related
to the HPP [9,11,12,19,36]. This doesn't mean that all or nearly all amorphous
silica observed after unloading of (X. quartz shock-compressed to any pressure in
the range (9.1) results from reverse transition from the HPP. But it is natural to
suggest that for P<25 GPa, i.e., unless shock-induced amorphization has be-
come a parallel process not necessarily leading to HPP formation, all quartz
glass observed after unloading of shock-compressed aystalline quartz is the
product of reverse transition from the HPP [44]. The Hugoniot was calculated
by Zhugin [59] who used this approach and data giving the concentration of the
amorphous phase in recovered samples. The results obtained are consistent with
the experimental Hugoniot, confirming the validity of the suggestion mentioned
above on the nature of the amorphous phase. However, the calculations in [59]
were not restricted to P < 25 GPa, but were also performed for P> 25 GPa
where the initial suggestion was not valid because, at such shock-wave pres-
sures, quartz amorphization proceeds in addition to HPP formation, and the
concentration of amorphous silica in the recovered samples is, therefore, higher
than the HPP concentration in the shock wave. This fact was not taken into ac-
count in calculations and led to underestimating the derivative (-dPldV)H along
the Hugoniot for P> 23 - 25 GPa. As already mentioned, amorphization in the
shock wave probably starts at a somewhat lower pressure than in static compres-
sion, i.e. lower than 25 GPa The calculated segment of the Hugoniot at pres-
sures from 23 to 35 GPa is located below the Rayleigh line in the P-V plane,
passing through the 23 GPa point This form of the Hugoniot in the range 23 - 35
GPa leads to a two-wave configuration. In [59], this result is regarded as proof
of the existence of a two-wave configuration. But, in the case of the underesti-
286 N. M. Kumetsov

mated derivative (-dP/dV)H, no conclusion can be made on the existence of this

configuration, based only on the shape ofHugoniot. Experimental data and other
arguments in favor of the two-wave configuration are presented below.

9.5. The Mechanism of High-Pressure Phase Formation

Assuming that the HPP is formed not by the process of continuous densification
as upon compression of liquid, but as a result of a first order phase transition, we
should determine the kinetic mechanism that best corresponds to the available
experimental data. One possibility is that activation barrierS are overcome at the
expense of kinetic energy concentrated on the required degrees of freedom when
the material is in thennal equilibrium or over all modes of motion of atoms and
molecules or before establishment of a Boltzmann distribution of energy in the
shock wave. The other possibility is that the transition takes place by macro-
scopically homogeneous compression and shear deformations and, specifically,
for martensitic transition, whether the initial and the new phase are coherently
joined by definite relative orientation of martensite plates. For a truly amorphous
phase, for example fused silica, martensitic transitions are not possible. But, in
systems formed from crystallites, even as small as those observed in quartz
amorphized in a shock wave [36] and in the HPP, coherence conditions for the
transition may be approximately fulfilled. Therefore the martensitic mechanism
can't be eliminated beforehand. Experimental data supporting the activated
transition and against the martensitic transition are presented below.
1. The pressure hysteresis is comparatively small, AP = 4-5 GPa, for the
beginning of the shock-induced phase transition [36,56] and enormous,
I1P = 30 GPa, for the end of the transition [9,56].
2. The pressure hysteresis is comparatively small for the reverse transition
into the low density phase, i.e., the HPP ~ amorphous quartz transition
during the final stage of unloading in the vicinity of the quartz-HPP
(stishovite) stability boundary [27,45J. Such features of hysteresis are not
typical for martensitic transitions [66-68]. In particular, differences of
transition and phase-equilibrium pressures, measured at the same tem-
perature, are comparable in magnitude for forward and reverse marten-
sitic transitions.
3. There is a clearly defined qualitative distinction between static and dy-
namic compression (low-temperature static compression does not result
in HPP formation [50)). The static compression isotherm lies above the
Hugoniot on the P-V plane in the pressure range where the Hugoniot cor-
responds to the two-phase mixture. However, the conditions for realiza-
tion of the martensitic transition mechanism and the results of its action
are approximately the same for static and dynamic loading. If the kinetics
were martensitic and the degree of conversion was determined mainly by
 9. Kinetics of Shock-fuduced Phase Transition of Quartz 287

pressure, then the difference between the Hugoniot and the static com-
pression isotherm would be comparatively small. Under those conditions,
the Hugoniot is usually (when (dPldT)v> 0) located above the static
compression isotherm in the P-V plane.
4. In the two-phase region, Hugoniots of low density quartz (fused quartz,
porous quartz) are located below the Hugoniots of the more dense ex.
quartz on the P-V plane [9,22,40,46,52]. This indicates more favorable
conditions for formation of the HPP from fused quartz because the ther-
mal energy is greater. This is typical for activated transitions. The rate of
activated phase transition is strongly (exponentially) dependent on tem-
perature and, in the non-equilibrium case, until the energy distribution
among the molecular degrees of freedom is equilibrated, on the specific
internal energy stored in the degrees of freedom responsible for the phase
transition. Therefore, an activated phase transition produced by shock
waves of low amplitude as compared with the amplitude required for
melting of all of the material, proceeds almost exclusively in places
where the specific energy and the temperature increases most, i.e., in
plastic shear bands, on initial inhomogeneities (grain boundaries, pores),
etc. [28,30,37,69-71].
5. Hugoniots for quartz of various initial densities, crystalline, fused, or
very porous, are qualitatively similar [9,22,52]. They do not show any
change from a martensitic to an activated of kinetic mechanism when the
initial density is decreased. That is, the kinetic mechanism is qualitatively
the same in all instances and is not martensitic because the initial phase
should be crystalline for its realization.
6. Data on unloading adiabats in the two-phase region, along with the facts
cited above, are especially indicative of the mechanism of formation of
the HPP and, correspondingly, of the reverse transition. Therefore, we
will consider them in greater detail below.

9.6. Activation Model of Shock Compression and

Unloading of Quartz
In contrast to the Hugoniot, unloading adiabats are characterized by very strong
density dependence of pressure (Fig. 9.3) and the whole process of dynamic
compression followed by unloading is of an explicitly expressed hysteretic na-
ture. The sharp decrease of the density dependence of pressure observed at 8 -10
GPa along unloading adiabats for which the initial pressure is less than 50 GPa
is evidence that a phase transition occurs [27,45].
The analysis of experimental data performed by Swegle [56] makes it possi-
ble to separate contributions to the unloading curve into a part due to the com-
288 N. M. Kuznetsov

P,GPa
m~~---------------------------,

,
\
10
, \
\
,
20 \
\2 , \ Z
\
,.....
--
'\
10 \ ...
o
o.zo 0.25 o.JII

Figure 9.3. lllustration of hysteresis. 1: Hugoniot of a. quartz, 2: measured release adia-

bats [44].

pressibility of the phases for fixed phase concentration and to the change of
concentration, and to establish that the phase composition remains unchanged
("quenched") during unloading down to 8-10 GPa
Experimental data on the unloading adiabat can't be explained on the basis
of a smooth variation of coordination number with pressure as suggested in
[48,50,52]. Due to the comparatively low pressure of the phase transition, mani-
fest as a sharp decrease of the dependence of pressure on density and almost
total absence of shear stress during unloading, this reverse transition from the
HPP is difficult explain even by a tensogenic mechanism similar to that offered
in [39,46] for the transition from quartz to the HPP. However, the observed
regularities of unloading find a natural explanation on the basis of an activation
mechanism. Indeed, when samples are unloaded in the region of thermodynamic
stability of the HPP this phase is retained, but quartz remaining after compres-
sion doesn't transform to the HPP since the mechanism of heterogeneous heat-
ing due to plastic flow or brittle comminution of quartz is "turned of!" during
unloading. The HPP expands very little during unloading due to its high com-
pression modulus and, correspondingly, cools very little during unloading, re-
maining sufficiently hot for the fast thermally activated transition into
amorphous quartz (diaplectic glass) without any significant pressure hysteresis,
according to experimental data at the transition pressure [27,45]. Due to the very
large viscosity, crystallization of quartz is kinetically forbidden in this case as is
 9. Kinetics of Shock-Induced Phase Transition of Quartz 289

stishovite fonnation during compression. To a much greater extent, this kinetic

prohibition relates to that part of the quartz that has become amorphous upon
compression without heterogeneous heating, it being out of the "hot bands."
Note, that transition of stishovite glass into amorphous quartz during un-
loading to a sufficiently low pressure would take place, apparently, even at low
temperature. Stishovite glass consisting, presumably, of extremely fine-grained
«10 om) stishovite crystallites, has a narrower range of absolute thermody-
namic stability and metastability than stishovite consisting of much larger crys-
tallites. It is likely that, being unloaded, it is absolutely unstable at any
temperature, including low temperatures. The suggestion about the absolute
instability of unloaded amorphous silica with six-fold coordination of silicon
and about its transition into the amorphous phase with the four-fold coordination
of silicon was stated by De Carli and Milton [12].
On the basis of the qualitative description of the high-pressure phase men-
tioned above and of the activated nonmartensitic mechanism of its formation
proposed in [72], an activated model of the shock induced transition of crystal-
line or fused quartz to the HPP is presented below.
It is supposed that the shock-induced transition occurs only when the thermal
energy of the quartz, ET, attains a rather high value, ETo. It is not necessary that
local thermodynamic equilibrium prevail. Therefore, Ero is not a function of
temperature, and is defined as the difference of the total internal energy and its
elastic part. In the model, ETo is a parameter determined by only one experi-
mental point on a Hugoniot. Kinetic conditions under which the shock induced
HPP formation occurs are realized, apparently, well before local thermodynamic
equilibrium of all vibrational degrees of freedom has been established. This is
indicated by the comparatively low value of ETo = 1.75 kJ/g, which would corre-
spond to T - 1500 K in a state of local thermodynamic equilibrium. At this tem-
perature the relaxation times of rotation of the SiCh and Si04 molecular
fragments through large angles are longer than the time of shock compression.
It's supposed that the "heating" up to ETo occurs first in narrow shear bands that
arise due to instability of plastic flow. Once the phase transition has started in
these bands, local viscoplastic flow of quartz due to the volume decrease that
occurs upon formation of the HPP (the volume decreases by about 30% at the
quartz -+ stishovite transition) plays a decisive role in heating of new quartz
layers and, hence, in further progress of the transition.
Plastic flow in inhomogeneities works as a buffer for homogeneous parts of
the compressed substance, making the process almost adiabatic. In calculations
of Hugoniots of homogeneous crystalline or amorphous quartz, the volume
dependence of pressure was supposed to be adiabatic and was identified with the
isentrope through the initial state of the quartz. The approximation that the proc-
ess is isentropic is not of principal importance for the problem.
290 N.M Kuznetsov

The proposed phenomenological kinetic approach, based on the activation

model, makes it possible to describe qualitatively and quantitatively (approxi-
mately) Hugoniots of quartz of various initial densities in the mixed two-phase
and the HPP regions. Results of the calculations of Hugoniots are shown on
Figs. 9.4 and 9.5.
The calculated Hugoniot of quartz is not kinked in the two-phase region, as
is necessary for formation of the two-wave configuration. But, in the calcula-
tions, the change of compressibility due to amorphization of a quartz was not
taken into account. At the pressures at which quartz is becoming amorphous, its
density is well below the HPP density. That's why amorphization of quartz
induced by high pressure is not followed by as great a change of volume as
occurs upon pressure-induced formation of the HPP. Nevertheless, amorphiza-
tion, as a contributor to the volume decrease, is favorable for establishment of
the two-wave configuration. This contribution begins to take effect at a some-
what lower pressure compared with statics, i.e., 25 GPa. Its contribution may
suffice to split the shock wave into two waves, in accordance with the interme-
diate wave process observed by Zhugin and Krupnikov [47,61].

so
4Q
--1
~ 30 ------ 2
o
~20

10

o
0.20 0.24 0.28 0.32 0.36
V,em 3 lg

Figure 9.4. Averaged experimental (1) and calculated (2) Hugoniots of a quartz.

60

50
--1
.
!S
40

30
------ 2
..·......·3

~20

10

0
I
0.20 0.25 0.30 0.3S 0.40 O.4S
V. cm3 1g
Figure 9.5. Hugoniot of fused quartz. 1: averaged experimental data, 2: calculation
without REL, 3: calculation with REL.
 9. Kinetics of Shock-Induced Phase Transition of Quartz 291

9.7. Conclusion
Relying on the experimental data on crystallographic modifications of quartz
that were reviewed above, on shock and static compression of quartz having
different values of porosity, on unloading adiabats, on rheological properties of
quartz melt, and on the analysis of these data, we can most often chose among
mutually exclusive alternatives to make the most reliable, if not unambiguous,
conclusions on the high pressure phase of quartz and on the kinetics of its for-
mation.
The observed extended range of large shock compressibility of quartz is
mainly due to formation of a non-equilibrium, amorphous high-pressure
phase-"stishovite glass," which has a stishovite-like short-range order of
atomic arrangement.
It is also probable that the structure considered is formed with randomly
misoriented, extremely small crystallites of stishovite of diameter less than
10 nm similar to the amorphous structure of compressed quartz [36]. This fine-
grain structure can be regarded as extremely defective stishovite. In the 23 to
25-30 GPa pressure range, in parallel with formation of this phase, there also
occurs shock-induced amorphization of quartz with retention of both the atomic
arrangement and the four-fold coordination of silicon. Experimental data show
that the forward and reverse quartz-HPP phase transition is not martensitic, but
activated.
At low amplitude shock waves compared with the high amplitude shock
waves capable of melting the whole substance, the HPP is formed from both
crystalline and amorphous quartz by a first order phase transition with a sharp
change of density in places where the shock compression energy dissipates
most: in plastic shear bands and at inhomogenieties initially present in the mate-
rial (pores, grain boundaries, etc.). For the phase transition to proceed further,
local plastic flow of quartz due to the sharp volume decrease that occurs when
HPP is formed is rather important.
By analogy with rheological properties of quartz glass, we may suppose that
stishovite glass is very viscous on the molecular level so that translational and
rotational motion of molecules is strongly hindered and crystallization in the
region of thermodynamic stability of stishovite is prohibited. After reverse tran-
sition of stishovite glass into quartz glass upon unloading, formation of crystal-
line ex quartz is also kinetically forbidden due to the large viscosity of quartz
glass.
A phenomenological kinetic approach has been proposed on the basis of the
activation model. This makes it possible to describe qualitatively and quantita-
tively (approximately) the Hugoniots of quartz of various initial densities in the
mixed two-phase quartz and HPP region. The model uses one "energetic" pa-
292 N. M. Kuznetsov

rameter, the heat energy of quartz sufficient for fonnation of the HPP during the
period of shock compression. This parameter can be determined using only one
experimental point on the Hugoniot. The value of this parameter is not very
high, pointing to a non-equilibrium transition that occurs well before the equilib-
rium distribution of energy on various vibrational degrees of freedom can have
been established.
To check and refine all of the above concepts, it might be well to carry out
further experiments with statically and dynamically loaded quartz. Among these
are:
• measurement of the density of fused quartz during static compression
up to about 40 GPa;
• experimental analysis of materials formed by shock compression and
subsequent unloading of very porous quartz.

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 CHAPTER 10

Shear Strength and Viscosity of Metals

in Shock Waves

P. V. Makarov

10.1. Introduction
Elastoplastic deformation phenomena observed when metals are subjected to
shock-wave loading have been investigated theoretically and experimentally for
over:fifty years and remain topical today for the following reasons. First, shock-
wave experimental techniques give unique information about fundamental
physical mechanisms of high-rate plastic deformation because the shock-wave
amplitudes are precisely controlled, leading to control of the plastic strain, parti-
cle velocity, total and plastic strain rates, etc. Second, relaxation processes are
most conspicuous in shock waves because the deformation rate is close to the
rate at which the stress relaxes. This allows one to study the stress relaxation
history resulting from both the development of strain through the wave front and
the evolution of the material defect structure and its self-organization during the
shock-wave loading. Finally, solutions are in demand for many applied prob-
lems including armor ballistics, explosive welding, and containment of explo-
sive events.
Extensive experimental data on material parameters and microstructural
evolution under shock-wave loading are available at the present time. Overviews
of the problems have been presented by Al'tshuler [1-3], Meyers [4],
Mogilevskii [5], Kanel et al. [6,7], Sobolenko [8], Aklunadeev [9], and Stepanov
[10,11]. These results were used to validate the mathematical model and the
choice of its parameters presented in this chapter.
To analyze shock-wave phenomena, numerical simulations of plane wave
experiments are widely performed using independent data for material micro-
structure under shock-wave loading. Since highly accurate Hugoniots have been
obtained for many materials, the calculated and experimental shock-wave pro-
files can be shown to agree providing the model is adequate and the numerical
technique applied is rather exact. That is, macroscopic parameters such as the
particle velocities, velocities of elastic and shock wave fronts, strain rates, wave
amplitudes, etc. are obtained with reasonable accuracy. In fact, forging agree-
V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII
© Springer Science+Business Media New York 2004
298 P. V. Makarov

ment between measurements and calculated results is a technique for determin-

ing parameters that cannot be measured directly. It is apparent that an adequate
physical model would describe not only a specific peculiarity (for example,
decay of an elastic precursor) but also all of the main phenomena related to the
formation and evolution of shock waves.

10.2. Strong and Weak Shock Waves

One-dimensional flow is found in the shock-wave front produced in a plane
wave experiment Figure 10.1 shows the elastic Hugoniot, (lIe, (representing the
instantaneous response of the material to shock compression) and the Hugoniot,
crlh (representing the equilibrium response). Material response curves and com-
pression waveforms for weak shock waves are illustrated in Figs. 10.la and
10.lb, respectively. Let us consider the elastoplastic flow occurring in weak
shock waves. The total strain, el , is purely elastic in the elastic precursor front,
i.e., el = ef (and e~ = e~ = ei = ej = 0) . Plastic shear occurs in the shock front
propagating in the wake of the elastic precursor. However, the total deformation
is ei,3 = 0 = et3 + e~,3 so e~,3 = - e~,3' Thus, the concept of an elastic Hugoniot
is meaningful only for the elastic precursor. States of the material behind the
precursor lie in the interval from the initial state on the elastic Hugoniot, (lIe,
produced at the instant of collision (see Fig. 10.la: point N on the elastic
Hugoniot) to the Hugoniot steady state (see Fig. 10.la: point E). All the inter-
mediate states are in the spatial-temporal area where stress relaxation takes
place in the elastic precursor.

2~------------~-----------'--~N~-----------------'

\
15T----------,~_r~L-------~
\
\ _ _--...M

5+---~~L---~------------~

E
10 eT1 , % 20 x
(a) (b)
Flgure 10.1. (a) elastic and equilibrium Hugoniots (TIe and (Tlh. respectively. (b) Dia-
gram of weak shock-wave formation.
 10. Shear Strength and Viscosity of Metals in Shock Waves 299

Stress levels exceeding the theoretical shear strength of the material can be
reached immediately upon formation of the elastic precursor. For example, for
aluminum at ale II:! 10 GPa, the shear stress is "t II:! J.1ej II:! 2 GPa This value is
close to the theoretical shear strength, "tT ("tT II:! 2.5-2.7 GPa [12,13) for alumi-
num). The stresses develop near the impact surface and result in rapid nucleation
of dislocations [4,14-16). This causes the fast decay of the elastic precursor that
takes place over distances up to several millimeters [17-20).
The weak shock front is formed immediately behind the elastic precursor. In
this shock front, plastic shear occurs and the crystal lattice is rearranged as one-
dimensional elastic compression changes to triaxial compression on the
Hugoniot. It has been experimentally established that an area exists where the
shock-wave front is unsteady [21-23). That this should occur is clear from
general considerations. The steady front results from competition between two
factors. On the one hand, a decrease in the material compressibility with in-
creasing compression gives rise to an increase of the wave propagation velocity.
As a result, the shock-wave front becomes steeper. On the other hand, energy
dissipation and viscous effects give rise to dispersion of the shock-wave front.
Thus, the shape of the shock-wave front and its evolution are determined by
microstructural processes, i.e., by development of plastic shear and energy dissi-
pation related to the plastic flow. A large body of data on the material micro-
structure [4,5,8,9,14,15,24-30) shows that the physical mechanisms of plastic
deformation occurring in weak shock waves are similar to those associated with
quasistatic loading. However, there are differences between the formation of
plastic shear in shock waves and in quasistatic tests. The most important of them
are the following:
1. The dislocation density in the wake of the elastic precursor often exceeds
its initial value by 2-3 orders of magnitude [5,25-30).
2. The crystal lattice in the elastic precursor is in the unstable state of one-
dimensional compression and already experiences appreciable plastic
shear.
3. The deformation in the shock wave occurs in conditions of triaxial com-
pression at higher levels of shear stress than are present in quasistatic de-
formations.
The shear stress can be written in the form
(10.1)

where tV is the nonequilibrium (viscous) relaxation component of the total shear

stress and "t'o is the elastic component of the shear stress. The latter corresponds
to the material shear strength under shock-wave loading and depends strongly
on the shock-wave loading conditions.
300 P. V. Makarov

As shown in Fig. 10.1, the viscous stresses reach 1 GPa in the center of a
shock-wave front having an amplitude of about 10 GPa This value significantly
exceeds the quasi-static shear strength, 'to, of aluminum alloys (for 6061-T6
aluminum, 'to =0.1 GPa).
The magnitude of the shear strength under shock-wave compression is of
particular importance for developing an adequate model of material response.
The shear strength of aluminum under rapid quasi-isentropic compression can be
one order of magnitude greater than 'to [31-34] whereas, in a shock wave, the
material can also lose strength for a time. Then 't'o may be equal or close to zero
[7,10,35-37]. However, the shear strength can recover before arrival of release
or reshock waves [3,35,38,39]. This results in the occurrence of an elastic pre-
cursor in reshock waves [7,35,39]. Due to the high density and wide variety of
defects generated by the shock wave, the unloading wave exhibits viscoelastic
behavior [7,35,38-40]. The release wave velocity varies smoothly from its
elastic value, C1, at the beginning of elastic unloading to its bulk wave velocity,
.J
Co = (k I p), when plastic shear has developed. Thus, inelastic behavior is
superimposed on the elastic unloading. The most mobile defects begin moving
during the early stages of elastic unloading and, as a result, the release wave
velocity decreases.
A fundamentally different physical situation arises during deformation of a
material by a strong shock wave. In this case, D > cl- (Cl- is the elastic wave
velocity that corresponds to the Hugoniot point (see point E on Fig. 1O.2a), and
the Hugoniot point ceases to playa role in the analysis. An initial state related to
the instant of collision corresponds to the point A on the elastic Hugoniot. The
states in the elastic front lie along the line OA. The shear stresses in a strong
shock wave are extremely large and comparable to the theoretical strength for
the majority of metals. This results in rapid nucleation of defects and formation
of a shock-wave front (Fig. 10.2b) with C e =D .
Thus, the states in the strong shock wave lie along the line OCB. The loading
is purely elastic up to the point C and corresponds to the elastic adiabat, O'le.
The dissipation of energy is due to heat conduction [41,42] (see the crosshatched
region between OB and O'le). Beyond the point C, plastic shear is underway and
the dissipation of energy rises sharply due to viscoplastic mechanisms (see the
crosshatched region between CB and O'lb on Fig. 10.2a). However, the normal
stress remains continuous since, at point C,

where O're and O'rb are stresses at the point C on the elastic Hugoniot and at the
strain ei on the equilibrium Hugoniot, respectively.
According to Eq. 10.1 and Fig. 10.2a, for states beyond point C, the excess
of the stress on the Rayleigh line CB over that at the same strain on the equilib-
 10. Shear Strength and Viscosity of Metals in Shock Waves 30 I

cr, GPa
~~~----------.---------~~~====~-----------------,

~~------------~----~~---r~
B

Ce>D
C.=D

10
x
(a) (b)
Figure 10.2. (a) Elastic and equilibrium Hugoniots (Jle and (JIb, respectively. (b) A
diagram of strong shock-wave fonnation.

rium Hugoniot crIb is the value of the viscous stress [41,43]. The relaxing non-
equilibrium component of the shear stress is reduced to zero at point B where
relaxation processes are complete and the maximum amplitude of the shock
front is reached.
We now state the main requirements to be satisfied by an adequate model (a
theory of plasticity) capable of describing elastoplastic deformation under
shock-wave loading.
The proposed model is based on the following notions of the microscopic
plastic strain history and the regularities of microstructure formation.
1. An assumption of a uniform distribution of deformation defects (and
consequently, of uniform deformation over the volume of the medium) is
correct during the initial stages of plastic deformation not exceeding a
few percent.
2. Plastic strain localization occurs as plastic deformation develops. This
appreciably influences the metal shear strength under shock-wave load-
ing.
3. Spatial redistribution of the dislocations and strain localization results in
the development of a fragmented structure including cells, blocks, and
shear bands.
4. Further deformation results in the rotation of structure fragments relative
to each other, formation of disoriented cell structures, etc. These proc-
302 P. V. Makarov

esses contribute to both the macroscopic plastic strain rate, yP, and the
material yield stress (i.e., the shear strength).
5. Dissipative structures (for example, cell structures) are formed as plastic
deformation develops. It is possible to consider this process as an exam-
ple of self-organization under high-rate plastic deformation
6. Under plastic deformation, the material may become plastically aniso-
tropic due to distinctions between the microstructure and the work hard-
ening on different directions. This is caused by differences in the amount
of plastic deformation in these directions.
7. Due to the wide variety of dislocations generated by a shock wave, it is
necessary to take into consideration a distribution of properties of ele-
mentary carriers of plastic deformation (structural defects).
8. It is necessary to take into account the effect of a non-equilibrium com-
ponent of stress (i.e., viscous stress) on the plastic strain history through
the shock-wave front
9. It is necessary to take into account the influence of defect nucleation on
microstructural heterogeneities formed under high stress gradients.
10. The front of the strong shock wave should be described to take into ac-
count the uniaxial elastic compression in the range of elastic loading and
the transition to triaxial compression beyond the intersection point of the
Michelson-Rayleigh line and the elastic shock adiabat, with homogene-
ous nucleation of defects being possible.
By and large, the model should reflect the following peculiarities of shock-
wave loading that have emerged from experiments:
• elastic precursor decay,
• the shape of the shock wave front behind the elastic precursor and the rise
time of the normal stress, crt. up to its maximum value,
• the evolution of unsteady shock-wave fronts,
• the shape of the unloading wave in the elastic and inelastic ranges, with
consideration given to dissipative processes and the Bauschinger effect,
• the shape of a reloading wave with a reloading elastic precursor (when it
occurs),
• evolution of the shear strength with regard to temporaty loss of the shear
strength in the shock-wave front and its recovery prior to arrival of un-
loading or reloading waves,
• the shape of a strong shock wave with an elastic range of uniaxial load-
ing,
 10. Shear Strength and Viscosity of Metals in Shock Waves 303

• the processes of going from the strong to the weak shock-wave range
during attenuation of the shock-wave amplitude due to overtaking release
waves.
A joint description of the interrelated processes is necessary to make the
model suitable for analysis of high-rate elastoplastic deformation of metals and
solving applied problems.

10.3. One-Dimensional Model of Elastic-Plastic Flow

in a Plane Shock Wave
To numerically simulate the response of a material to loading by a plane shock
wave. we write a set of equations of conservation laws for a macrovolume in the
Lagrangian variables [44.45].
In one dimension. UI * 0 and U2 = U3 = 0, where Uj is the projection of the
particle velocity vector u on the Xi axis. The principal strain components are
el *0 and eI =ej =0.
We suppose that the total strain rate, ef. is the sum of an elastic component:,
e; . and a plastic component, er:
(10.3)

Since there is no transverse motion, eI = ej = 0 and, due to the symmetry.

ei =e; and e~ =ef. With the postulate of plastic incompressibility,
ef + e~ + ef =ef + 2 e~ =0, we have
(10.4)

where e is called the volumetric strain.

The plastic shear mte, yP , and the shear stress, 't, are given by the equations
yP =t(ef -en =-tef
(10.5)
't=t(0"1-0"2).
For the total stress we have the expressions
0"1 =-P+SI
0"2 =- P + S2 =0"3 =- P + S3 (10.6)

where s is the stress deviator tensor,

304 P. V. Makarov

The continuum-mechanical equations descri6ing plane-wave propagation in

a medium include the equation of motion
au\ 00\
P at = ax ' (10.7)

the continuity equation (law of conservation of mass)

av au\ h
- = - were -=e\
au\ ·T
(10.8)
at ax' ax '
and the law of conservation of energy (in this case in the form of balance)

(10.9)
where E is the internal energy density and V= Pol P is the specific volume ratio.
This system of equations is closed by inclusion of a constitutive equation
determining the relationship between the stress and strain tensors. According to
Eq.10.6,
OJ =-p(p,E)+Sj, for ;=1,2,3. (10.10)
For shock waves of low amplitude (o~ 10 GPa), the barotropic equation
p = p(p) is used to describe the pressure. It is often expressed in the form
p=AS+BS2+CS3 , (10.11)
where S =(p/po)-l. Values of the coefficients A, B and C are given in [46,47]
for a number of materials.
The foregoing equations are augmented by the relaxation-type constitutive
equation

(10.12)

for the shear stress. Equation 10.12 implies that the shear stress increases in
response to an increment in total deformation, and relaxation is due to accumu-
lation of plastic strain. For an adequate description of the plastic flow in a shock
wave, it is necessary to determine and describe the physical mechanisms of
stress relaxation Two main mechanisms of stress relaxation can be identified.
These are the dislocation mechanisms and the supercritical shear. The latter
occurs when the material is subjected to a shear stress approximating f.11 n
(n = 15-30) that corresponds to the theoretical shear strength of crystalline ma-
terial. The same mechanisms operate in strong shock waves, where the shear
stress reaches the theoretical strength.
The system of Eqs. 10.7-10.11 and the relaxation constitutive equation
10.12 can be solved numerically, providing that an equation for the plastic shear
rate, yP, is provided (for instance, using dislocation dynamics).
 10. Shear Strength and Viscosity of Metals in Shock Waves 305

We shall identify the plastic strain rate with a flow of like defects described
by the Orowan law [12]. This concept is expressed by Gilman [48] in the fonn
of the equation
yP =gbNfv. (10.13)

Since motion of defects occurs primarily in the planes of maximum shear

stress [12,49], the orientation factor Ig I in Eq. 10.13 is equal to 0.5. To defme
the dislocation density, N, the fraction of these dislocations that is mobile, f
(where N m= Nf, with Nm being the number of mobile dislocations), and the aver-
age velocity of their collaborative motion, v, semiempirical expressions [48-52]
reflecting the most general tendencies of dislocation behavior are used. Kelly
and Gillis [49] have obtained expressions for N in the fonn

A yP ) ,
N=N * +(No-N* )exp ( -Iglb (10.14)

where the parameter N* can be interpreted as a limiting dislocation density

under loading. The analogous expression,

(10.15)

is written for the fraction of the dislocations that is mobile.

Because direct measurement of defect velocities (for instance, by means of
the etch-pit technique) is possible only under stresses comparable to the static
yield stress and at moderate defect densities, the problem of detennination of an
adequate expression for dislocation velocities remains open to discussion
[5,14,15,24,25,51-56]. Computational experience shows that there are good
reasons to use the expression

(10.16)

where to is the average Peierls-Nabarro stress [52]. This equation determines

the value to which the stresses relax following quasi static loading.
Work hardening is taken into account as a decrease in the fraction of the de-
fects that are mobile as the remote back stress, tbs, increases [53]. The remote
back stress impedes defect motion and results in hardening. The effective stress,
tef, as well as the elastic component of the shear stress, to, are given by the
equations
'tef = 't -'tbs
(10.17)
'to = 'to + 'tbs .
306 P.V. Makarov

The remote back stress is given by the conventional equation

"tbs =a.l!b./N (10.18)

from the physics of plasticity.
Since the increment of plastic shear is dictated by dislocation flow due to the
effective stress, 'tef, the sign of the plastic shear rate, yP, is detennined by the
sign of 'tef:
yP =Ig IbNfv("tef) sign("tef). (10.19)

This addition to the kinetic equations of Kelly and Gillis allows one to
achieve a good agreement with experiments involving uniaxial loading of rods
and to take into account work hardening at different constant deformation rates,
e"{ =const. [53].
A description of unloading requires correct consideration of the non-ideal
Bauschinger effect and contributions of relaxation processes attributed to ine-
lastic behavior of the material during unloading.
During reverse deformation, when e"{ changes sign, the quantity yP appear-
ing in Eq. 10.14 begins to decrease. This leads to non-physical effects on the
stress-strain curve. Really, the plastic strain is irreversible and the strain his-
toI)', yP, is replaced in Eq. 10.14 by the accumulated plastic strain, Yk' where

y~ = I:lyP1df .
The more correct description of dislocation pile-up leads to a more accurate
value of 'tbs .
Thus, consideration of the complex histoI)' of loading allows one to take into
account the ideal Bauschinger effect due to the introduction of Yk and a more
correct description of 'tbs .
To take the nonideal Bauschinger effect into account, it is necessary to de-
scribe the difference between resistance to dislocation motion during direct and
reverse loading. It has been assumed [49] that reversible plastic strain Yk de-
scribing dislocation pinning during reverse loading is introduced in equation
10.15 for the fraction of mobile defects,/, so that Yk = Yk during reverse load-
ing.
This modification allows description of the non-ideal Bauschinger effect, but
results in an abrupt transition from elastic unloading to plastic flow and a too-
high rate of stress relaxation when the deformation changes sign. This does not
correspond to experimental data. The effect is attributed to the fact that the ex-
pression Yb- =Yk assumes pinning of all the dislocations. Really, this is not the
 10. Shear Strength and Viscosity of Metals in Shock Waves 307

case. If the equation Yb- = y~ [1- (N / N·) J is adopted at the change of sign of
'tef, the calculations correctly describe the non-ideal Bauschinger effect. This
corresponds to pinning of only a part of the dislocations, with the capability of
allowing dislocation pinning to decrease as the dislocation density increases.
In addition, the model allows the stress at which motion of dislocations is in-
duced to differ for different dislocation groups. The total plastic deformation
during each loading time step is the sum of the contributions from every dislo-
cation fraction:

yP = I i gbN;fvi

and (10.20)

Ni=NPi('t), with Pi('t)=f1:1 _1_.exp[_('tci-~0)2]dtc.

"/-I 8.,fi; 28

The i-th dislocation group moves at the velocity Vi providing that l't 1> 'tci and
Vi = 0 when l't 1S; 'tci, where 'tci is the stress required to induce dislocation
motion (the start stress). This approach allows one to take into consideration the
inelastic processes occurring in the elastic precursor, the viscoelastoplastic be-
havior during unloading, and the rate sensitivity of the material.
The mesolevel contribution is taken into consideration through the probabil-
ity Pi that meso-substructures will form at a given level of deformation. Ac-
cording to Eq. 10.20, the probability of formation of cellular mesostructures is
given by the normal distribution law. Disintegration of the structure implies that
the probability of its existence changes from its current value to zero and the
formation of a new mesostructure means that there is approximately a unit prob-
ability of its existence. This process is synergetic and is presented in terms of
dissipative structure formation under loading. Then the elastic component of
shear stress, 'to, must be replaced by a new value

'to ='tc +a~b..JN +P'R(Ci,YP, ... )

where (10.21)
p; =f yP _1_. exp [ (YP_yi)2]dyp.
0.05 cr.,fi; cr 2

To define the functions F i , it is necessary to determine, by theoretical or ex-

perimental means, conditions for the formation and disintegration of the
mesostructure. In accordance with experimental data [53J, the expression for F
was given as
308 P. V. Makarov

where yf is the value of the-plastic defonnation at which the cellular structure

begins to form.
The fonnation of localized shear bands is simulated in a like manner. Ap-
propriate functions are introduced to account for the contribution of shear bands
to hardening.
At rather high pressures, p is given by an equation of state of the type
p = p (p, E), or p = p(p, T). The most frequently used equation,
0(a1 +a21 0 I) +E[ho +O(hI + i>2 0) +E(co +Ci 0)]
p=~--~~~~--~~--~--~--~
Epo -<po (10.22)
was developed at the Los Alamos National Laboratory by Osborn [57]. It ap-
proximates Hugoniot curves and unloading isentropes with a high degree of
accuracy.
Because the elastic moduli change with compression, it is necessary to con-
sider their dependence on pressure and temperature so, for the shear modulus,
we have 1.1. = I.I.(P, T). The dependence of the bulk modulus is already taken into
account in the expression for p(p, E) because the stress tensor is expressed as a
sum of spherical and deviatoric components by Eq. 10.10. The effect of com-
pression on the shear modulus, 1.1., remains to be taken into account. The depend-
encies have been studied experimentally for a wide range of materials [55,58-
61].
According to [58], we can express the function 1.1. = I.I.(P, T) in the form

1.1.=1.1.0 [1 +01.1.Op-1.1.011
--+
113
P 01.1. (T -TO)]
aT 1.1.0 '
(10.23)

where 11 = Vo / v =p / pO and 1.1.0 is the shear modulus at the temperature

To ~300K.

The system of equations including Eqs. 10.7-10.9, the relaxation constitu-

tive equation 10.12, appropriate kinetic equations for plastic shear rates, and
initial and boundary conditions, has been solved numerically using an explicit
second order differential scheme of approximation [45,62,63].
It is fundamentally important that artificial viscosity is not used to smear the
shock-wave front. Only in this case can an actual shock waveform be repro-
duced with some tens of spatial intervals. There is a physical dissipative mecha-
nism in the model. The width and shape of the wave front is attributed to the
plastic shear rates. That is, due to the explicit consideration of the relaxation
mechanism, the actual wave fronts can be reproduced. The nonequilibrium (vis-
cous) stress is explicitly calculated as the difference between the actual shear
stress, 't, (that acts at the instant) and the instantaneous shear strength 't~ given
byEq.l0.1.
 10. Shear Strength and Viscosity of Metals in Shock Waves 309

10.4. Attenuation of Elastic Precursors and

Structure of Shock Waves
Shock waves are produced for experimental investigation by impacting a plate
of the material to be studied by a projectile plate moving at high velocity. Since
the stress level after the collision is extremely high, plastic shear will develop
even in the elastic precursor. This causes stress relaxation and the elastic precur-
sor decays to an equilibrium amplitude customarily called the Hugoniot elastic
limit, crlE.
Estimates show that the critical shear stress for nucleation of defects near
crystal heterogeneities is well below the theoretical shear strength and also be-
low the level of stress at which homogeneous nucleation of defects is possible
[4,5].
A simple linear equation for defect density that agrees well with experiments
is

(10.24)

As an example, the elastic precursor decay calculated for steel by means of a

dislocation model that includes this heterogeneous nucleation mechanism is com-
pared with the experiments [18,22,64] in Fig. 10.3. The shape of the weak
shock-wave front is controlled by the two mechanisms of multiplication and
heterogeneous nucleation of defects.

2.0

\
\ r.---- ·
1.5

oj

fs 1.0
u
6' ··
0.5

0.0
o 20 40 60
x,mm
Figure 10.3. Amplitude of elastic precursor decay for low-carbon steel. Experimental
data from [64].
310 P. V. Makarov

In Fig. 10.4, calculated shock-wave fronts in Al6061-T6 are compared with

experimental data [22]. The model accurately describes the shape of the shock-
wave front and its evolution to the steady state. The calculations show that
shock-wave fronts propagating in iron and steels are essentially unsteady for
shock amplitudes of several GPa (see Fig. 10.5).
The experiments [38,40] were simulated numerically. Figures 10.6 and 10.7
show the complete loading-unloading profile calculated for iron and Al6061-
T6. It follows from the experimental data that the material response to the un-
loading is not purely elastic. According to the elastoplastic model, the shock-
wave front in the interval AB of Fig. 10.7 should propagate at the elastic wave
velocity. However, for aluminum [38], the shock wave velocity changes con-
tinuously from the elastic velocity Ct == 0.636 cmIj.lS to the bulk velocity
Co == 0.532cm1J.Ls.

10.5. The Shear Strength of Metals in Shock Waves

The evaluation and modeling of material shear strength is one of the most acute
and most discussed problems of shock-wave physics [1,3,31,57,65,67-81]. In
earlier calculations, the yield strength used for analyzing plastic flow in the
shock wave was frequently taken to be that at the Hugoniot elastic limit As
evidenced by the foregoing results, this is absolutely wrong because the micro-
structure responsible for material resistance to the shear in the shock-wave front
behind the elastic precursor undergoes radical reorganization; the defect densi-
ties are frequently close to the maximum, N~ 101l_1012cm-2. In the 1970s an
idea was put forward that the shock-compressed state can be close to hydro-
static, i.e., the shear strength of the material, 16, in the wave front is approxi-

"1' rom 1119 CJI' GPa "t, GPa

0.15 r ' - - - - r - - - , . - - - - , r----.----.-----,.-----.0.3

0.10 f - - - - + - - - - / t - - - - - i 1.6 +'~-_+_l'--I-_+.f_-+-+_--~ 0.2

.
-., - - ..
, :~'
~
j
:""-.
I ' •

/ '1I
,
,! : . :
0.8
,~
r' I,,'
0.05 f - - - - + - . , ; L - - - + - - - - - i 0.1
I

0.00 '-:------:--'::---:-'-:-----=-' 0.0 -f-T,..m"TT'1....+rTTTT't"\-mmt-rrl'TTil-+nrT'nr'r-rrl 0.0

0.0 0.2 0.4 0.6 0 2 4 8
t, ~ x, rom
(a) (b)
Figure 10.4. (a) Experimental (points) [22] and calculated (solid line) loading wave
profiles of amplitude 2.1 GPa in AI6061-T6. (b) Calculated wave proflles for a plane
shock wave of amplitude 2.1 GPa propagating in AI 6061-T6.
 10. Shear Strength and Viscosity of Metals in Shock Waves 311

UI,GPa
0.20

,p.=-

11 .1
0.15 2

/,
I

I II
0.10

0.05
r
I
I
~
0.00
1.0 1.5 2.0 2.5 3.0 t, J.I.S
Figure 10.5. Experimental (solid lines) [7] and calculated (dotted lines) shock-wave
profiles in low-carbon steel. The thickness of the bamer in which the wave profile was
measured was: (l)Hb=6.35 mm, and (2)Hb = 12.7 mm.

UI,mm/J.1.S

0.32 i----+-.------'---t------l

0.24 1---+-tAr--:=:1'\--_+_-___j

0.16 i-----'~t_____jH.t--_+_-___j

0.08 i-----+,I--___j----''rl-_+_-___j

0.00 L---L-'--_---'_ _--L-_---'

0.8 1.2 1.6 2.0 t, ~s

Figure 10.6. Calculated (solid line) and experimental [40] (dotted line) profiles in iron.
The profile was measured at the contact surface between a barrier (Hb = 6.3 mm) and a
sapphire window. The velocity of the 1.185-mm thick sapphire impactor was
Vo = 0.4825 mmlJ.1.S, producing a stress at impact of 0') <>; 9 GPa.

mately zero. However, some experiments [1,3,4,70-72,81], yielded estimates of

'to that were far in excess of the yield strength under quasistatic loading. This
increase of 'towas attributed to high strain rates. It is pertinent to note here that
direct shear strength measurements are possible at considerably lower strain
rates (up to el 1'::110" S-I) than those that occur under shock loading. For this
pmpose use was made of pendulum (el max 1'::1300 S-I) and flywheel type
stretching machines (el max 1'::110" S-I) [82]. Figure 10.8 shows the dependence of
yield strength on loading rate for mild steel [83].
312 P.v. Makarov

u,m/s
160 r - ' - - - - , - - - - , - - - - , - - - - ,
A

120 i---t-IF---j-+--+----t

40 1'----If-7-+--+---+-\,----+

0.4 0.8 1.2

tlh,jJ.s/cm
Figure 10.7. Calculated loading and unloading wave profiles in aluminwn:
- - - - elastic-viscoplastic model with dislocation kinetics of plastic shear and
- - - - - - ideal elastoplastic model, '0 = 0.12 GPa.

400
293K

300 I,v
~ 200
~
bOO

o10'"4

Figure 10.S. Lower yield point vs. both temperature and deformation mte for mild steel
[83].

The area of high strain rate, area IV in which el > 104 S-I , is virtually unin-
vestigated experimentally [83]. The estimates reported in [84] for AI 6061-T6
and Be in this range of stress rates are presented on Fig. 10.9. Thus, in area IV,
the rate of stress increase decreases appreciably with increasing strain rate.
A method for determining the shear strength in a plane shock wave by ex-
trapolating the experimental curve to a general isochore is presented in
Fig.l0.lO.
 10. Shear Strength and Viscosity of Metals in Shock Waves 313

t,GPa t,GPa 0.8

0.28

0.24 f---+---+----+----t-----:7'1""----i 0.6

0.20 f---+---+----+--F--.,L...j--+----i 0.4

0.16 f---+---+---+-+---t--+----i 0.2

eI,s-1
Figure 10.9. Dependence of shear strength on strain rateto(ep). (a) Alwninum 6061-
T6, and (b) beryllium [84]. Reprinted with pennission from v.P. Glazurin and T.M.
Platova, Viscous properties a/metals under impact loading, in The Engineering-Physics
Collection, Tomsk: Izdat Tomsk Univ. (1987), pp. 101-109.

B'
--f------------·------------
4 tete -to) A'
"3;e .!~~t----------­
T-----~------------- ---
4
"3 tc
pOrn

o
Figure 10.10. Schematic for determination of to and to by extrapolating the measured
stress in reshock and release waves to a general isochore (the line B' C' ).

In the tests of Al'tshuler et al. [85] (point A on the Hugoniot OEA and point
C on the unloading line ADC), the total magnitude of OOsd = to + te is defined
by the method of overtaking unloading, where the amplitude of the elastic un-
loading is measured. For Fe, OOsd "'" 2.7 ±O.7 GPa at 001"'" 185 GPa and
OOsd =l.l±O.4 GPa at 001 "",110 GPa; for Cu OOsd "",1.6±0.4GPa GPa at
001 "'" 122 GPa.
314 P. V. Makarov

In such tests, the estimate for crsd can have a maximum error of 100% be-
cause only the sum 'to + 'to is measured. Indeed, if the material maintains its
strength and the points A and B on the diagram coincide, then 'to = 'tc, and
magnitude cr.d = 2't is measured. If the material has completely lost its shear
strength, then 'to == 0 (the points A and D on the diagram coincide). In this case
the magnitude of 'to, i.e., only one-half shear strength in comparison with the
case of 'to = 'to, is measured.
This temporary loss of material shear strength was attributed to local adia-
batic heating of shear bands [35-37,53,69] and the recovery of shear strength
after the shock front has passed was attributed to cooling of the shear bands.
Therefore, if there was sufficient time for the shear strength to have recovered,
there is an elastic precursor upon reloading in a reshock wave with an amplitude
determined by 'tc -'to (Fig. 10.10). The method offered by Asay and
Chhabildas [35] is based on measurement of 'tc + 'to in the release wave and of
'to -'to from the elastic precursor amplitude in the reshock wave. Their meas-
urements are shown in Fig. 10.11 (for alloy AI 6061-T6). Similar measurements
(but not as complete as for aluminum) were carried out for alloy Be S-200
[21,39,86].
Another method is based on the direct measurement of the principal stresses
cr x and cry in two mutually perpendicular directions by the manganin gauge
method, cr.d = 'to + 'to = crx-cry [3,7,66,70-72]. Measurements for aluminum alloy
ADI [3] carried out by Pavlovski using these two methods are presented in
Fig. 10.11 in comparison with other data [7,35,71].
Calculations are carried out to simulate equilibration to the steady stress in a
plane shock wave as it passes through a horizontal slot containing a gauge. Cal-
culated times to reach the steady stress for clearance widths smaller 0.3 mm
does not exceed 0.4 J.ls. Hence, in the tests presented, crx is reliably recorded
before arrival of overtaking or lateral unloading waves.
Two-dimensional simulations were conducted to study shock-wave propa-
gation for an experimental arrangement with slots containing gauges that lie in
the plane of the shock and in a plane perpendicular to the plane of the shock [3].
These calculations revealed that flow is always observed in a slot oriented par-
allel to the direction of the shock-wave propagation (Fig. 10.12). This results in
appreciable decrease in the cry stress component This effect of cumulative flow
is most pronounced for high~ensity materials (Cll, Pb), which are many times
more dense than the spacers in the slot This is capable of causing marked de-
formation of the measured waveform, even if the pressure gauges remain intact.
Measurements of shear strength of AD 1 aluminum performed by two differ-
ent methods (the method of measurement of two principal stresses and the "self-
consistent" method) [2,3,7] give similar magnitudes, falling within the limits of
measurement errors.
 10. Shear Strength and Viscosity of Metals in Shock Waves 315

2.0 ,..----,--- , - ---,---..,----,----,

&!1.5 !-"-..---t--f---t- - - + -- + - -- - i - - - I
~ 2'e

0.0 '---_-L-----''---J'--_-L---=:....:..:J_ _ ....I...._--l

o 10 20 30

Figure 10.11. Solid lines represent the calculations presented in this chapter. The symbol
! represents 2't c , the symbol :! represents 2'to, and the symbol §: represents data
from [35). The method of measurement of two principal stress components, cr x and cry
is given in [1,2), The symbol x represents the measurement of 'to and 'te by a "self-
matching" method of reducing to a general isochore [3]. The line designated Y g repre-
sents data from [71). The symbol !l represents data from [7).

j Shock
wave

Figure 10.12. Calculated progress of flow in a slot. The deformation of part of the
computational grid in the vicinity of a joint of vertical and horizontal slots is shown at
four moments in time.

The measured [3] shear strength, 'te , at reshock and unloading agrees well
with data of Asay and Chhabildas [35] not only qualitatively, but also quantita-
tively.
Magnitudes, 'to, measured by the manganin gauge method [3] reflect the
material condition in the first wave front We remark that, for ADI aluminum,
316 p.v. Makarov

the measured values seem to be independent of the stress amplitude [3]. For
stresses smaller than 10 GPa, the difference in magnitude of 'to and 'tc does not
exceed the experimental error. For amplitudes higher than 10 GPa, this differ-
ence appears to be considerable (Fig. 10.11).
As such measurements performed by various researchers were carried out for
different aluminum alloys, quantitative agreement is not to be expected. It is
possible to speak only about qualitative similarity or difference. In this sense, for
all aluminum alloys presented and for stresses higher 10 GPa, the magnitudes 'tc
and 'to differ appreciably. It is possible also to assume that the distinction in
structures of alloys affects the weakening (Le., 'to) to a greater extent.
There are measurements of the principal stress cry, although a strong caution-
ary note is appropriate, especially for materials having an acoustic impedance
that greatly exceeds the impedance of the material in the vertical clearance, flow
in the shock-wave propagation direction occurs during the measurement. This
phenomenon results in underestimated stress magnitudes cry, especially, if the
clearance is large, and, as the consequence, results in a strong overestimation of
the shear strength. This is apt to affect the data presented in [71].
To our mind, a temporary loss of material shear strength is common, since
local development of plastic shears is an essential feature of plastic deformation
of metals. At later stages, the plastic deformation always proceeds in local areas.·
The degree of localization and the sizes of local areas depend on the micro-
structure, impurities, etc., and on the loading conditions. The essence of this
phenomenon consists of instability of plastic deformation that is observed, for
instance, if the deformation proceeds in nearly adiabatic conditions. Localization
of deformation in shear bands is a self-accelerating thermoplastic process re-
sulting in an increase of deformation in the shear areas where it first began. This
point of view means that plastic deformation always develops as an essentially
local process. The spatial extent of these local areas is extremely small and,
consequently, the rate at which they cool is very high. Competitive processes of
overheating of small areas resulting from localization of deformation, on the one
hand, and from their cooling, on the other hand, should result in characteristic
sizes of localization areas for given loading conditions and material.
In conditions close to adiabatic, this balance can be disturbed and the process
will have the characteristics of an avalanche. In this case, the rate of heat pro-
duction resulting from plastic deformation will exceed the rate of cooling. At the
macro level these processes manifest themselves as a significant decrease of
yield strength because of overheating of local slip areas. This is the well-known
adiabatic shear phenomenon [29,37,87-91].
If many local subareas form at the same time in some area of a material, as is
observed at high degrees of deformation, for example, during high-energy-rate
forming or upon shock loading, the cooling of overheated planes will be compli-
 10. Shear Strength and Viscosity of Metals in Shock Waves 317

cated by the increase of the average background temperature in this area. Ava-
lanche increase of plastic deformation will occur as the yield strength decreases
significantly, i.e., an adiabatic shear band will fonn. As differentiated from slip
planes, adiabatic shear bands are macroscopic patterns.
The microstructure of shock loaded specimens was studied in the experi-
ments reported in [36,37]. If 0'\ = 8 GPa (e\ ~ 108 S-1 and dislocation density
N> 1010 cm-2 ), then the thickness of the slip bands is 0.2-0.3 I!m and the
distance between bands is 1 1J.ffi. Simple estimates following from the solution of
the thermal conductivity equation show the time of cooling of the band (band
thickness is Ah ~ 0.2 -0.3 1J.ffi) is less than 10-7 s even for temperatures close to
the melting point This time falls in the interval At= 10-8_10-7 s for different
temperatures. It gives estimates of the rate of shear strength recovery VB ~ 0.2 - 2
GPallJ.S [53].
In calculations, the temporary loss of shear strength and the subsequent shear
strength recovery were simulated for the most thoroughly investigated materials,
i.e., for alloys Al6061-T6 and Be-S200.
Two rates are considered: the rate of loss of shear strength, Vn , and rate of
shear strength recovery, VB. Thus, the total weakening through each computa-
tional step n will be calculated as follows

(10.25)

Weakening because of heating of slip bands is supposed to be a function of

the work of plastic deformation. This question is considered in greater detail in
[53].
For Al6061-T6, VB falls within the limits of 0.05-2.0 GPallJ.S for intensity
of loading 0'1 = 1-40 GPa.
Notice that, in this range of stresses, the adiabatic compression heating of the
entire macro-particle volumeis not large [36,37] and does not exceed several
tens of degrees for aluminum [37].
The real shear strength ofa material under shock loading ('to on Fig. 10.11)
may be written as

(10.26)

where 'tcT is the yield point ofundefonned material ('tcT ='to on Fig. 10.11 for
0'\ ~ 0). The second tenn accounts for the micro-level contribution to the yield
strength and the third tenn represents the contribution from the meso level (in
this case, because of self-organization of the defect structure to a cell structure),
P is the probability of existence of cell structure, F is a function of plastic de-
formation, Eq. 10.21 [53], and the last term, A'tp, accounts for effects of both
318 P. V. Makarov

temporary loss of shear strength and shear strength recovery after the shock
front has passed. Thus, in the shock front, 'to coincides with 'to (Fig. 10.11)
and 'to reaches 'tc after shear strength recovery.
It is worth noting that the shock-wave structure already contains information
about shear strength. As mentioned above [92,93J, it may fit the calculated
shock front to the experiment for a stress of several GPa if it is granted that the
material in the shock front is weakening. This predictive capability of the model
is possible only for those stress amplitudes (al I':j 2-5 GPa) where the total error
of calculations is less than the weakening effect.
Reshock precursor calculations in comparison with the experiment [35J for
A16061-T6 are shown in Fig. 10.13. The model satisfactorily accounts for both
reloading and unloading in the material for waves of different amplitudes.

10.6. Simulation of the Structure of Strong Shock Waves

After the shock wave has been initiated (Fig. 10.2a) and the equilibrium shock
front configuration has been established, states in a strong shock wave lie on the
line OCB. Up to point C, loading corresponds to the elastic Hugoniot. Hence,
one-dimensional plane elastic compression occurs at the shock front in this
stress range.
If shear stresses were completely elastic up to the point C, the stress differ-
ence between points C and D (corresponding to the stress difference between the
curves alh and ale at same deformation el) results from nonequilibrium or
viscous effects

(10.27)

- ,
IJr=: 1
1.6
Ii
1.2
:- ~
~
EI 0.8
...: 2
~

;i

0.4

0.0
1.6 1.8 2.0 2.2 2.4
t, JIll

Figure 10.13. Calculated reloading and unloading waveforms for Al606I-T6 (shown as
dotted lines). 1: reloading, 2: unloading, the solid line represents experimental results
[35], al = 14.8 GPa (1) and al = 14.2 GPa (2).
 10. Shear Strength and Viscosity of Metals in Shock Waves 319

Here sb is the stress deviator at point C corresponding to the state on the equi-
librium Hugoniot.
To our mind it is necessary to separate the area of plastic shears into two
sub-areas: (a), an area of rapid relaxation in which the lattice undergoing recon-
struction and relaxation of shear stress is proceeding, and (b), an area of slow
relaxation and evolution of a non-equilibrium defect structure.
The area (a) is recorded in experiments. In fact, this is the area in which the
stress increases to approximately its maximum value. The thickness of this part
of the shock wave is Il. == tp D, where tp is the time required for the stress to
reach its maximum value. This time is estimated to be tp ~ 10-10 _10- 8 s for
various wave amplitudes [22,34,94-96]. Then Il. ~ 5 x (10-5-10-3 ) em. For alloy
Al6061-T6 [94] at O"le ~ 41 GPa, the time measured is tp ~3xI0-9 s. The
shock front velocity for this amplitude is close to 0.8 cmlJ.IS, so
Il. == 2.4 x 10-3 em.
Due attention should be given to the area (b), since the defect structure im-
mediately behind the shock front is in an essentially nonequilibrium state. In
[97], a material subjected to shock pulses of identical amplitude is studied. The
pulse duration was varied in the range t < I JlS. Mechanical chamcteristics of the
material proved to be different
Immediately upon completion of the elastic lOading, dislocations are nucle-
ated under shear stresses of high intensity. This results in three-dimensional
compression. This process occurs continuously as the shock wave. propagates
into the material. Atomic planes rearrange themselves, but normal defect densi-
ties should provide the needed plastic deformation (e~.3 + ei.3 = 0 and
el = ef + ef) at each point of the front, in accordance with the total deforma-
tion achieved in the front. This point of view is close to Meyers's idea offorma-
tion of consecutive dislocation walls [4].
Figure 10.14a shows a calculation of strong shock-wave-front formation in
accordance with Fig. 10.2a, and Fig. 10.14b shows the calculation of strong
shock-wave propagation at a later stage. The values of 'to and 'tc used were in
conformity with the data of [35].
These calculations require construction of the elastic adiabat, O"le, as differ-
entiated from the conventional strong shock-wave Hugoniot.
To settle this question, the third-order moduli were included in the calcula-
tion so that
(10.28)

where J.L = 27.6 GPa, A. = 54.4 GPa, l; = -140 GPa, ~ = 282 GPa for Al606I-T6
[47,98], and the equation O"ly = -p +S]y, where p is a pressure on the equilib-
rium Hugoniot, S] y =(4/3)J.Le( , and e( =ef, where e( =ef on the elastic
Hugoniot.
320 P. V. Makarov

60
b a
--- -- -- -----
----t.fi -f-J,\ ----, --.
--- ----
----,
---l\ I~
-[\
40 \
C
- - -- -
-- 1---
-- - --- C
20

1 2 3 4 S 6 7

o I III III II II 1I1II1 IIII I1II I ill I I I I 1·1

0.00 0.02 0.04 0.06 0.08
X,DIm
(a)

t-oyJl.S t=O.24Jl.S t-0.36 Jl.S

'\ [~ ~
40 8

D
C ~
6
"-
'-
---- --- - -C -
4
.-
Cy=D
~

IS
10 2
~

o ~ ---J o
o 0.1 0.2 0.3 0.4
X;cm
(b)

Figure 10.14. (a) Evolution of strong shock-wave front in Al6061-T6 during the initial
unsteady stage. Structures 1-7 for different times are shown: 0.0017, 0.0031, 0.0045,
0.0059, 0.0073, 0.0087, and 0.0101 ~, respectively, (b) propagation of a strong steady
shock-wave front. The line C separates ID elastic defonnation from triaxial compression
with plastic shear in the wave front

Thus, if the Hugoniot is known and corrections to the shear modulus for
pressure and temperature according to Eq. (10.23) are taken into account, the
elastic shock adiabat can be constructed. It can be seen from Fig. 10.15, where
the elastic shock adiabats calculated by two methods are shown for alloy
AI 6061-T6, that data correlate well.
 10. Shear Strength and Viscosity of Metals in Shock Waves 321

40

30 +---~----~--~~--~--~

~w+---~----~~--~---+----4
6'
10+---~-7~7F----~--_+--__4

10 20

Figure 10.15. Elastic (ale, aie) and equilibrium (alh ) Hugoniots of alloy AI 606l.
The curve ale is calculated in terms of influence of pressure and temperature on the
modulus G, and aie is calculated using terms including the third-order modulus.

10.7. Viscosity of Metals in Shock Waves

Barker, in his earlier experiments [22], recorded the fonn of plane wave fronts at
the free surface of a shock-compressed sample of alloy AI 6061-T6 using a laser
interferometer. After that, it has been possible to estimate viscous characteristics
of materials under shock waves with a high degree of accuracy. There have been
many works in which shock profiles were recorded by various methods and the
strain rates were measured, or at least the rise time of the wave was determined
[2,7,10,11,22,31,32,39,40,94,95,99-102]. A shortcoming of these data is that
they are insufficiently complete and systematic to permit study of materials over
a wide range of applied stress. The exception is tests for alloy AI 6061-T6,
which has been investigated rather completely. Many tests have also been car-
ried out for alloy Be S-200.
Since it is the practice to characterize dissipative properties of materials un-
der shock wave loading by a viscosity coefficient, some remarks need to be
made concerning this characteristic.
Godunov [103] showed that, for isotropic media, where stresses of internal
friction determining viscous dissipation are functions of strain rate only, i.e.,
a i} = Jij{e) , and are determined by a tensor function flV of the tensor argument
e, the appropriate dependence must take the fonn

where the coefficients 00, OJ, and 02 are functions of the invariants JI , J2, and J3
of the strain-rate tensor and can also depend on both the density, p, and tem-
perature, T, of the material:
Oi=Oi(P,T,JI,J2,J3), i=0,1,2.
322 P. V. Makarov

When this approach is employed, the dependence of viscous stresses on de-

formation is neglected. A more general view of the allowable dependencies that
takes deformations into account requires studying tensor functions of two tensor
e
arguments and e P •
It is apparent that this approach is labor-intensive and it has shown little
promise from the viewpoint of derivation of reasonably simple models that ade-
quately describe elastic-plastic deformation in shock waves. The foregoing
discussion makes it obvious that the model in which viscous (nonequilibrium)
stresses for solids are presented by analogy to the model of a viscous liquid,
(10.29)

is severely limited. However, the simplicity and the opportunity to estimate the
coefficient Tt from experimental data have led to widespread use of this simple
equation.
It is apparent that the experimentally estimated viscous coefficients in this
interpretation are instantaneous characteristics that account for dissipative prop-
erties of media under specific conditions and at a specific time in the evolution
of plastic deformation. The function for the viscous coefficient Tt or an equiva-
lent expression for the relaxation time, tp , will depend on both loading condi-
tions and the amount of deformation, as do the microstructural parameters.
We shall now present the relaxation constitutive equation 10.12 in terms of
the relaxation time

. _ (·T P)=f.L (.T

't-f.L e1 - 2·Y e 't-'t
1 ---
o) =f.L (.T
e1 -'t-'to
- -) • (10.30)
Tt f.Ltp

In this equation Tt = f.Ltp, where tp is the relaxation time, to

is the shear
strength of the material, and the difference 't - 'to is to be interpreted as a vis-
cous or nonequilibrium shear stress.
Thus, to estimate the viscous coefficient experimentally, it is necessary to
e
know a minimum of two values: the strain rate, 1T , and the magnitude of the
nonequilibrium stress, tV.
As differentiated from Tt in the model represented by Eq. 10.29, the funda-
mental concept having an obvious physical interpretation is the concept of the
viscous stress 'tv ='t - 'to, where 'tv =(3/4) a V is the nonequilibrium part of the
stress. For the case of shock loading, tV can be determined in first approxima-
tion as the difference between the value on the Michelson-Rayleigh line AB
and that on the Hugoniot C (Fig. 10.16) [104].
The viscous stress (for steady waves of low amplitude) can be expressed in
the form
(10.31)
 10. Shear Strength and Viscosity of Metals in Shock Waves 323

jL----+-
"tV ="tfuax
t=O

(a) (b)
Figure 10.16. Schematic defIning the viscous stresses in plane shock-wave experiments.

with a good degree of accuracy [69J. In this equation, Ul and U2 are values of
the particle velocity at points A and B on the Hugoniot (Fig. 10.16).
Equation 10.31 is derived on the basis of assumptions that
1. The linear relationship between the particle velocity, U, and the velocity
of the shock front, D, is satisfied: D = a + bu .
2. The change in sound velocity with increasing compression is not taken
into account
At the midpoint of the wave profile, where't = 'tmax, -t =0, and 2yP =el ,
(10.32)

Thus,11 or tp can be derived from Eq. 10.32 using a measured value of the strain
rate, el. However, it should be remembered that the viscosity coefficient is
merely a coefficient of proportionality in the expression el = 2yP = 'tV 111 and
accounts for a real situation at only a specific stage of loading. That is why the
estimates derived by different authors are markedly different [10,11,13,69,
96,105,106J. Estimates of 11 as a function of the shock amplitude are shown on
Figs. 10.17 and 10.18 for the most thoroughly studied materials, AI 6061-T6,
Be S-200, U, and Fe. As can be seen from Figs. 10.17 and 10.18, a region of
abnormal behavior is observed for almost all materials. This region has not been
discussed in the literature. It was possible to identify this abnormal behavior
only by combining data of different authors and estimating the experimental
errors.
In aluminum and its alloys there is a transition from weak shock waves to
strong shock waves at the stress ale;: 13-17 GPa In this case, mechanisms of
plastic deformation also change. For strong shock waves, the homogeneous nuc-
leation of defects becomes an essential that requires a high level of shear stress.
324 P. V. Makarov

1000

~
'"
(a) if. 100
.~ ~
' '
s:-
rJ'..'
~Q

10
0 20 40 CJI,GPa

[]

'" 100
0 ....
(b) ~. "
s:- '"

0
8
10
o 10
._. 30 CJI,GPa
20

"1 1000
(c) ~
s:- "- ,..
""'" "
-
D1:; 'bc:o
-
0
100 I I
o 10 CJI,GPa

Figure 10.17. Viscous coefficients vs. shock amplitude for (a) AI 6061-T6. 6 is the

~: [22, 107],0: [107, 108],0: [107], *:

range of transition from weak: to strong shock waves. Experimental data from papers:
[94],0: [57], (the size of these mark-
ers corresponds to the maximum possible error.) (b) Be 8-200. Experimental data from
papers: 0: [21,39,86, 107], 0:
[21,39,86]. (c) Uranium. Experimental data from
papers: ~: [107,108],0: [109], 0 : [107].

In iron and steels the (X, ~ & phase transition is observed at a stress
<Jl e== 13 GPa. This leads to an appreciable change of volume and to decompo-
sition of a shock into a two-wave configuration for shock waves of amplitude up
 10. Shear Strength and Viscosity of Metals in Shock Waves 325

to O"le == 24 GPa. Above this amplitude the second shock wave merges with the
first wave. It is possible that the change of mechanisms of deformation attrib-
uted to lattice rearrangement results in nonmonotonic behavior of the viscosity
coefficient.
Since the unsteady relaxation part of the shear stress, 'tV , is free from arbi-
trariness of model representations and completely determines the shape of wave
fronts, mechanisms of energy dissipation at the macrolevel should be attributed
to 'tV alone. The nonequilibrium stress, 'tv, can always be calculated as the
difference between the current value of 't and the instantaneous shear strength,
't~ ,at each point of the wave profile. In Fig. 10.19, values of viscous stress for
steady shock-wave fronts calculated for the midpoint, C, of the front, i.e., for
'tV = 'tfuax, are shown as a function of the shock-wave amplitude, O"le.

The section MN for iron accounts for the two-wave structure that includes a
second plastic wave caused by the phase transition. Above the point N a single
shock wave is again observed.
Calculations of wave-front evolution show that wave fronts in AI 6061-T6
are unsteady for amplitudes 0"1 :s; 4 GPa. Calculations of wave-front evolution
in AI 6061-T6 are presented on Fig. 10.20 and values of 'tfuax derived from
Eq. 10.32 are shown. On steady-state sections, the numerical calculation agrees
well with the analytical estimate provided by Eq. 10.32.
Over the unsteady regime, nonequiIibrium stresses may far exceed (by more
than in two times, as shown on Fig. 10.20) the value derived from the assump-

1000 , , 1000
¢: :
. '" ..
J.. ,

Ll. f"\
,.
I~""
rIl
PI J (:1 IDI
~
181 0 00 -() ~J*
I=" 100 I=" 100

,.
I..JV 1 ,

10 I
Ii
I I I 10 I
I I
I I I I I I

o 25 (1"GPa o 25
(a) (b)

*:
transformation. Experimental data from papers: (a)
[40], ~: [108], [110].
*:
Figure 10.lS. Viscous coefficients vs. amplitude for Armco iron. 8 is the region of phase
[2],6.: [12],0: [11). (b) *:
326 P. V. Makarov

4~----r-----r-----r-~~

3~----+-----+---~+-r-+-1

.
f5 2 f------+------f---7£...-,.?-,Hf---1
,,"...

o__ ~~~~~~ ____ ~~~

o 10 20

Figure 10.19. Nonequilibrum components of shear stress, tV, vs. amplitude, CYI, for:
A: alloy Al606l-T6, B: uranium, and C: Armco iron.

2.4 1.12 8 0.4

tl t2
-..::., t3 t4 t l t 2 t3 t4 efl
2.0 -\ I~ ~ 0.10
\ efl 6
V-' 0.3
1.6 0.08
P! "- I'--- P! P! P!
C!:1 1.2
"--...,
...."
0.06 C!:1
. C!:14 0.2 C!:1
"
I I ( " b
l-
b I
I 0.04
~
~

0.8 f "tV

In !" J 1\ / ~
2
0.4

I ~ /\. I" /
,, , \~,/ ".0: 0.02

0.00
234 S
x,mm x,mm
(a) (b)
Figure 10.20. Calculations of wave front evolution. The lines - - designate viscous
stress obtained from calculations for 1U1steady fronts and the lines - - - - designate the
viscous stress estimated assuming that the front is in a steady state. (a) Results for
Al6061-T6 loaded to CYI=2.1GPa. The times indicated are tl=10-7 S and
t4 = 7 X 10-7 S • (b) Results for low-carbon steel loaded to efl = 8.0 GPa . The times indi-
cated are tl =10-7 s and t3 = 3 X 10-7 S •

tion that the wave front is steady, Calculated results for mild steel loaded to
(jl == 8 GPa are presented on Fig. 1O.20b. A peculiarity of iron and its alloys is
that wave fronts are highly unsteady.
To solve applied problems of high-speed impact it is tempting to use simple
forms of the relaxation equation such as that ofEq. 10.30, which is the general-
ized equation of Maxwell media, and for which the functional form of the vis-
cosity coefficient, 11, (relaxation time) is to be defined.
 10. Shear Strength and Viscosity of Metals in Shock Waves 327

Dependencies for Tl were approximated as Tl =Tl(cru, yP) , where cru is the

second invariant of stress tensor which. for a plane wave, is given by cr u =2't .
As we can see from Fig. 1O.21a, dependencies for the viscosity coefficient
(alloy Al1100) form a family of similar curves for different values of total
plastic deformation ei = (4/3)yP . The curves move far apart at the bottom of a
shock wave in the neighborhood of point A on Fig. 10.16 and are practically
merged for large deformations.
Figure 1O.21b shows the calculated dependencies of the viscosity coefficient
in the time-dependent shock-wave front. The shock amplitude is crle == I GPa.
Data are presented for different times as the shock wave propagates into this
material. These curves account for changing viscosity caused by evolution of the
time-dependent shock front.
The curves crossing lines 01 equal deformation reach their minimum value in
middle of the front (at point C, where the shear stress is a maximum), as the
stress crl increases in the shock front from point A at the bottom of the front.
Then the curves increase rapidly as the stress approaches the maximum ampli-
tude at point B, where yP and 'tv == 0 . The viscosity increases as the maximum
shear stress relaxes in the middle of the front. This is seen because of displace-
ment of point C (Fig. 1O.21b) upwards. The following approximate functional
forms of the viscosity coefficient Tl have been derived for alloys Al 1100, Be S-
200, and Al6061-T6:

~ ~----~------~----~
B A
10 !\.,
301-++-~~~----~------4
8
il ,\\.,

~ ., \ 1\ \
\\ '.
~201--~-+~~--~~------4 ~ 6

-
b" 1,\
'I" '.

x
8x \
I=' 1='4 \ \ \
,,",'\
101----~~~~---b~--__4

2
~l\ \
"-
>c
, \2 \, )

~ . 3 ~ 4",
- ~/--
O'---------L..----__-'-____-----I o
6 8 10 12 6 10 14 18 22 26

(a) (b)
Figure 10.21. Viscosity coefficient vs. stress in the shock-wave front for AI 1100 alloy.
(a) for different values of total plastic defonnation in %: I: 0.6::1: 0.2, 2: 0.2, 3: 0.06,
4: 0.03, 5: 0.01 . (b) for unsteady fronts at different times: I: 0.3 J.lS, 2: 0.1 J.lS, 3: 0.03 J.lS,
4: 0.02 J.lS, 5: 0.01 J.lS.
328 P.V. Makarov

( P)
11 O"u,e1 ={ exp (0.103 0.00751 967)} 105
o"u -0.047 + \e P \ +0.0025' x
P
a·s
(10.33)

11 ={0.15·exp[2000(0.6-O"u)]+0.013 }x105 Pa·s (10.34)

11 ={ exp ( 0.352 + . 0.01751 II)} x 105 P a·s. (10.35)

o"u - 0.24 \e P \ + 0.005

In these equations, 0" u is in units of GPa and plastic defonnation is in percent.

The calculated wave profile for Al1100 is presented on Fig. 10.22 in com-
parison with experiment [52]. The relaxation constitutive equation 10.30 is used
taking into account the dependence for Eq. 10.35. On Fig. 10.23 calculations of
the time-dependent wave front in Be 8-200 are presented in comparison with
experiments [21,39,86].
Application of simple elastic-plastic models does not allow one to describe
the behavior of polymethylmethacrylate, an organic glass (PMMA), under de-
fonnation in a shock wave since viscoplastic effects are essential here. The vis-
cosity coefficient was selected to fit the calculated wave profile to the
experiments [111,112] (Figs. 10.24 and 10.25).
Using the coefficient 11 determined by the trial-and-error method,
11 = {0.01exp[1500(0.22-O"u)]+0.01}x 105 Pa·s,

the experiments [111,112] were simulated. The experiments differ in the stress
amplitude at the shock front (Fig. 10.25). Calculations of shock-wave propaga-
tion in PMMA are also interesting because of the low sound velocity,
C1 == 0.26-0.27 cm/I-ls. Therefore, elastic precursors are not observed in acrylic

c -
'\
-...:0.
120
f

80
B I
I

40

\
o
0.8
iA 1.6 24
t, jl'I
Figure 10.22. The calculated wave profile for AlllOO alloy. The line - designates the
experimental wavefonn [52] and the line - - - designates the calculated wave profile.
 10. Shear Strength and Viscosity of Metals in Shock Waves 329

plastic. A strong shock wave of characteristic shape propagates in acrylic plas-

tic, even at small amplitudes of shock loading.
Since the main physical mechanisms resulting in plastic shear in shock
waves are those responsible for deformation under more usual conditions, the
relaxation constitutive equation derived from simulation of quasistatic experi-
ments forms the basis for description of the plastic flow. Viscous nonequilib-
rium stresses increased appreciably in importance as the shock amplitude
increases. Therefore, changing of defect structures and physical mechanisms of
deformation in shock waves proceeds faster than under quasi static loading. This
circumstance, and also the high strain rates, make it necessary to change the kine-

150 f----+--~~_'_j

100 f----+--+--+--_'_j

0.2 0.4 0.6

t,~

Figure 10.23. Calculations of wave fronts of different amplitudes (1: 2.12 GPa, 2: 1.12
GPa, 3: 0.62 GPa) for Be S-200 in comparison with experiment (points) [21,39,86). The
thickness of the sample was 0.617 cm.

1\
I I
eJqleriment 2106 R

'"h
1.5 0.1

~ ~
"~ 1.0
ef. \
0.0
"..
tl-

0.5
r;- -p ~ \--
-0.1
I

0.0
2 4 6
" 8
-0.2

t,~

Figure 10.24. Computer simulation of strong shock wave propagation in PMMA. lJl
designates the normal stress, p designates the pressure, and Sl designates the stress
deviator. The line - - - - is the calculated result and - - - is the experimental result
[112).
330 P. V. Makarov

experiment
318 calculation

,
300 ~ l
~

200 L
2106 ~ \

~
316
I"
100

~\
314

313

o
2 4 6 8
t, !IS
Figure 10.25. Computer simulation of experiments [112] of shock wave loading in
PMMA by waves of different amplitudes.

matic equations. Heterogeneous nucleation of defects, even in front of the elastic

precursor, has been taken into account. This allows one to achieve agreement of
the macro- and micro-parameters with the experiments. Both the mechanisms of
heterogeneous and homogeneous (for strong shock waves) nucleation of defects
should be taken into account, as must the multiplication of defects.
The model presented allows one to simulate the shape of both release and re-
shock waves. This requires consideration of relaxation processes because of
evolution of the defect structure in strong and weak shock waves. The model for
response to strong shock waves describes the one-dimensional elastic loading
that is appropriate to the state on the elastic Hugoniot. When the stress in the
wave exceeds this level, there is a lattice reconstruction, plastic shears are accu-
mulating, and there is a transition to triaxial compression on the Hugoniot. The
leading mechanism for plastic shear to proceed in strong shock waves is the
process of homogeneous nucleation of defects. The model was derived to de-
scribe the temporary loss of shear strength. This model is based on the idea of
local heating of microscopic areas of plastic shear. Cooling of these areas results
in shear strength recovery after the shock front has passed.
Since the magnitude of the plastic shear stress can far exceed the shear
strength under quasistatic loading. the nonequilibrium relaxation part of the total
stress (the viscous stress, "tV) is shown to playa main role when plastic shear is
underway in the shock front. These nonequilibrium stresses are especially high
for time-dependent waves and for unsteady parts of the wave evolution process
before the front reaches its steady-state shape.
 10. Shear Strength and Viscosity ofMeta1s in Shock Waves 331

References
[1] L.v. Al'tshuler,Sov. Phys.-Usp. 8(1), pp. 52-91, (1965). [trans. from Usp. Fiz.
Nauk 85(2), pp. 197-258 (1965).]
[2] L.V. Al'tshuler, D.M Tarasov, MP. Speranskaya, 13(5), p. 95 (1962). [trans.
from Fiz. Met. Metall. 13(5), p. 738 (1962).]
[3] L. V.Al'tshuler, MN. Pavlovsky, V. V. Komissarov, and p.v. Makarov, Comb.
Expl. Shock Waves 35(1), pp. 92-96 (1999). [trans. fromFiz. Gor. Vzr. 35(1),
pp. 102-107 (1999).]
[4] M.A. Meyers and L.E. Murr, in: Shock Waves and High-Strain-Rate Phenomena
in Metals (eds. MA. Meyers and L.E. Murr) Plenum Press, New York, (1981),
pp. 121-151.
[5] M.A. Mogilevskii, Mechanisms ofStrain at Fracture by Shock Waves, Dep. No.
2830-80, VINITI, (1980).
[6] G.I.Kanel, S.V. Razorenov, and V.E. Fortov, Sov. Phys-Dokl.(physics) 29(3), pp.
241-242 (1984). [trans. from Dokl. Akad. Nauk SSSR, Ser. tekhn. 275, pp. 369-
372. (1984).]
[7] G.I. Kanel, and V.E. Fortov, Uspekhi mechanics 10(3), pp. 3-81 (1987).
[8] T.M Sobolenko (ed.), High-Speed Impact: Hardening ofMetals and Alloys by
Shock Waves, Sib. otd. AN SSSR Novosibirsk: NIl hydrodynamics, (1985).
[9] N.Kh. Akhmadeev, Dynamic Fracture ofSolid Bodies in Stress Waves, Ufa: Izdat
BFAN SSSR, (1988).
[10] G.v. Stepanov, Behaviour ofStructural Materials in Elastoplastic Relief Waves,
Naykova Dymka, Kiev, (1978).
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 CHAPTER 11

Temperature Measurement and Equation

of State of Condensed Matter

v. D. Urlin

11.1. Introduction
A dynamic method for creation and measurement of high pressures that has been
developed in Russia and in the U.S. during the past 50 years allows study of
condensed material properties over a wide range of densities and temperatures
that cannot be reached by any other method [1-3]. A strong shock wave, having
a velocity exceeding 10 km/s, heats the compressed substance up to several tens
of thousands of degrees. If the substance is transparent in its initial state, e.g., an
ionic crystal or noble gas, then measurement of the radiation passing from the
shock-heated material through its uncompressed layer makes it possible to ob-
tain unique information about its properties at the high pressure. Fundamental
studies of the role of radiation in strong shock waves in gases were made by
Zel'dovich and Raizer [1]. Model' made the first measurements of the bright-
ness temperature of a shock front in a gas [4]. Those pioneering studies showed
the phenomenon of a sharp decrease of the brightness temperature from the
shock front to the material behind the front. A large body of experimental data
on the radiating properties of shock waves in dense gases is presented in [5]. At
VNIIEF, Kormer was the absolute leader in experimental study of optical prop-
erties of shock compressed, transparent, condensed substances. He and
Zel'dovich gathered around themselves a team of young enthusiasts who started
investigations in the 1960s and 1970s [6]. This work is still unique.
The study of shock compression of transparent condensed materials is espe-
cially interesting in terms of physical processes. The special point of interest is
the kinetics of processes that occur at the shock-wave front. A significant part of
the kinetic energy imparted to the substance by shock compression is irreversi-
bly converted into heat within several tens of inter-atomic distances behind the
front. The pressure, density, and temperature are several times greater than their
initial values. A shock wave in a crystal also generates defects during the accu-
mulation of large plastic deformation at the front. All of these processes deter-
mine the thermal, optical, and electrical properties of the compressed material.
V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII
© Springer Science+Business Media New York 2004
338 V.D. Urlin

Optical methods using a light beam as a tool of investigation enable meas-

urement of the change of state in layers with a thickness of about 1% of the
wavelength of the light. This resolution cannot be achieved by other methods
used to study fast processes. The specific features of this method made it possi-
ble to determine experimentally [6-8] that a strong shock in a condensed sub-
stance occupies a layer less than 10 nm thick and the maximum compression is
reached within the time 1: I'll 10-12 s. The shock front in a solid turned out to be
very smooth. The investigations of reflection and refraction of light incident on
a shock-compressed substance shows [6-8] that the refractive index in both
liquid and solid materials increases linearly with the density over a wide range
of compression up to cr = p/po 1'112, where Po is the normal density of the mate-
rial. The strong response of the method to the density gradient enabled determi-
nation of the shock front structure in materials undergoing polymorphic
transformation [8].
Measurement of shock front brightness in ionic crystals made possible the
first determination of the temperature and optical absorption coefficient of a
compressed condensed substance at high temperatures [9,10]. The absorption
coefficient obtained exceeds the values in normal conditions by a factor of -100.
Temperature measurements permitted determination of melting curves for a
number of ionic crystals up to record pressures of 50-250 GPa [9]. Only the
position of the initial portion of the curve up to 2-4 GPa was previously known.
The materials remained solid up to TRl4000K when compressed by a factor of
1.7. The role of anharmonic thermal oscillations of the lattice of an ionic crystal
was determined and it was shown [9] that their effect on its thermal conductivity
was small.
When ionic crystals were compressed to a pressure of several tens of GPa,
nonequilibrium radiation significantly more intense than the thermal radiation
appeared [6]. Another type of non-equilibrium radiation from shock-compressed
ionic crystals was measured for pressures from 200 to 500 GPa [11]. In these
conditions the brightness of the radiation appeared to be less than that corre-
sponding to the equilibrium temperature. This phenomenon can be explained by
the screening of equilibrium radiation from the bulk of the shock-compressed
material by layers immediately behind the shock front in which the electron
temperature had not yet reached the equilibrium value [12].
The study of optical properties of transparent condensed materials under
shock compression still continues successfully at VNIIEF. Special attention was
paid to the study of liquid noble gases having a symmetrical electron structure of
the atoms and the most close-packed crystal lattice [13,14]. The ideas of both a
multiphase equation of state [15] and a theory of the kinetics of electron heating
[12], which define the electronic structure of the shock front, were confirmed
when this work was extended to ionic crystals.
 11. Temperature Measurement and Equation of State of Condensed Matter 339

11.2. Investigation of the Reflective Power of a Shock Front

It is important to know the reflective power of a shock front to detennine the
light emitting capability of shock heated materials. This is necessary if tem-
perature measurements based on radiation are to be made. Optical properties, in
particular the reflective power of the shock front, are related to its smoothness
and thickness. The method used to investigate the reflective power of shock-
compressed transparent condensed materials was developed by Kormer together
with Yushko, Sinitsyn, and Krishkevich [6-8]. Zel'dovich greatly advanced the
success of these studies.
In this method, the light reflected from a shock front is measured as the
shock wave propagates into a layer ofuncompressed transparent material. Using
the equations of geometrical optics, it is possible to detennine the refractive
index of the compressed material by measuring the motion of a beam of light in
a specific experimental configuration. Since the shock-front thickness is very
small compared to the thickness of the compressed material, it does not affect
this method of measuring the refractive index. The experimental configuration
presented in Fig. 11.1 allows determination of the reflection factor by compari-
son of the intensity of a single light beam reflected from both a shock front and
an interface having a known reflective power [6]. The resolution of the method
in the conditions of an explosive experiment, when the sample under investiga-
tion is located from 10-15 m from a recording facility, is ~ 10-3 • The error of a
single measurement of the reflection factor is Mf I Rf ~ 5-10% .
As a result of viscosity and heat conductivity, a shock wave in any material
has a certain thickness. For example, the thickness of the front in liquids at a
shock amplitude of several MPa is -1 ~ [16]. It is also known that the front
thickness decreases with an increase of wave amplitude [1]. Estimates showed
that, at a transition layer of thickness L, incident light of wavelength A. is re-
flected in accordance with the Fresnel formula at LIA. ~ 10-2 so that, if A. = 500
nm, then L ~ 5 nm. On the other hand, for L ~ A.121t ~ 50 nm, almost no light will
be reflected from the optical interface. This indicates that the front thickness is
-10 nm, a result that is unobtainable using other methods.
Increasing the brightness of the external light source, especially through use
of a laser, makes it possible to turn to spectral studies of the change of the re-
fractive index dispersion due to compression of the material, and to detennine
the edge of the absorption band. These measurements can provide information
on changes of the electronic structure of condensed dielectrics and on their tran-
sition into a metallic state. Application of the light reflection method in the con-
ditions when a powerful shock wave is created by impact of a plate accelerated
in a hydrogen or helium gun rather than by an explosive is promising. The abil-
ity to locate the recording equipment close to a test object, combined with the
ability to increase the brightness of the extemallight source, leads to a signifi-
cant increase in the accuracy and resolution of the method.
340 V.D. Urlin

I ~ 6 (a) IT ,
~

IF DI 0 LIl
(b) (c)
Figure 11.1. (a and b) The configuration of an experiment for measuring the refractive
index of a shock-compressed material and the reflectivity of the shock front. (c) A streak
photograph obtained during the experiment. n and IV are light beams reflected from the
fixed interfaces B-C and A-B. ill and V are light beams reflected from the shock front
and the moving bOlmdary A-B. 1: the material under study, 2 and 3: the high explosive
charge, 4: an explosive light source, 5: prism, and 6: streak camera.

11.3. Measurement of the Refractive Index of Shock

Compressed Ionic Crystals
Optical properties of shock-compressed alkali halides were measured using the
methods discussed above [8]. The results for single crystals of LiF, NaCI, and
CsBr, which are not subject to polymorphic transitions within the pressure range
investigated, are given in Fig. 11.2. The reflecting power of a shock front was
measured experimentally for NaCI, CsBr, KCl, and KBr, for pressures below
that at which they lose their transparency. The values of the refractive indices
were determined on the basis of the assumed validity of the Fresnel equations.
For LiF, which was sufficiently transparent up to -70 GPa, the refractive index
values in compressed states are determined directly by a geometrical method
based on a ray diagram. The data on the refractive index as a function of crystal
compression are presented in [9,17,18]. Figure 11.2 shows clearly that the de-
pendence of the refractive index on density can be written in the form
dn
n(cr) = no+-(cr-l), (11.1)
dcr
with dn/dcr = const. for each crystal.
 11. Temperature Measurement and Equation of State of Condensed Matter 341

In contrast to liquids, it turned out that dn/dcr < (no -1) for all crystalline
solids. The same difference was found earlier [19,20] based on the results of
investigations of photoelastic properties of ionic crystals (see Table 11.1). Direct
measurements of the refractive index of NaCI, KEr, and LiF at static pressures
up to 0.1 GPa [21] showed good agreement between measurements for two
crystals. It is proven in [22] that the refractive index of LiF increases linearly
with pressure in the range up to 0.7 GPa. The value, dn/dcr = 0.13 from [22], is
close to the results from investigations of photoelastic properties and to the
results obtained under shock compression in [8] (see Table 11.1).
The experiments reported in [8] to study n(cr) for shock compressed ionic
crystals also cover the density range in which the crystals transform to the liquid
state. * The measurements showed that, when crystals melt in a compressed state,
both the refractive index and its derivative increase sharply. Fusion of CsBr
results in an increase of the refractive index from 2.05 to ~2.45 (Fig. 11.2).
Experimental points measured for the liquid phase of shock compressed
CsBr, KCI, and KEr are described by Eq. ILl, the same as for the solid phase,
but with the slope higher by a factor of 1.5-1.7 (Table ILl).
Results from investigations of the reflective power of a shock front in KCI
and KEr are rather interesting [8]. The results for KEr are given in Fig. 11.3,
where it is seen that, for cr= 1.7-1.9, the experimental points are described by
Eq. 11.1 with the value dn/dcr taken from the works studying photoelastic prop-
erties. This is the same as for other crystals. A significant difference in this de-
pendence is found for KEr at cr = 1.54 and for KCI at cr = 1.52. Here the
reflection factor appeared to be a factor of 2-3 less than the value expected. In
[8], this difference was associated with the fact that polymorphic transition of
KCI and KEr into the CsCI structure (phase II) requires a time 't > 10-12 s for

1.0

"'"
0
l:!
I 0.5 / a
l:! /1
/
/
/
/
0.0 I I

0.0 0.5 1.0

cr-I
Figure 11.2. Dependence of the refractive index of ionic crystals on the compression,
cr =p/po. 1: CsBr(~), 2: NaCI (0),3: LiF (0), a and b: CsBr and NaCI melting zones.

* Melting under shock compression will be considered below.

342 V.D. Urlin

P < 15 GPa. In this case the incident light is reflected from a layer of material at
the shock front that is in a metastable state (point 1 in Fig. 11.4) corresponding
to the Hugoniot of phase I. Since the latter is steeper than the Hugoniot of phase
n, the smaller density jump at the shock front results in a smaller refractive
index. Non-equilibrium states of phase I in KCl and KBr, determined in [8], are
presented in Fig. 11.4 (points A). The same picture shows nonequilibrium
Hugoniots calculated using the equation of state for phase I of these crystals.
When the pressure in a shock wave increases, the temperature also increases.
This causes the re1axation time to decrease and the phase transition to occur in a
layer of thickness «A/2n. In this case, the refractive index fits the total jump of
the volume behind the shock front (point 2, Fig. 11.4), as can be observed (Fig.
11.3). Consequently, for shock compression to a pressure P= 20-21 GPa,
polymorphic transition ofKCl and KBr occurs during the time "t < 2 X 10-12 S.

Table 11.1. Refractive properties of crystalline and molten alkali halides.

Crystal LiF KCI NaCI KBr CsBr
no 1.392 1.490 1.544 1.559 1.698
Compression 1.30-1.48 1.68 1.45-1.68 1.70 1.63
Solid dn [8] 0.1 0.25 0.24 0.35 0.48
phase dcr
( tin ) [19,20] 0.1 0.23 0.24 0.35 0.48
dcr a"'l
Compression 1.83-1.98 1.88 1.8-2.07
Liquid
phase tin [8] 0.35 0.53 0.9
dcr

20

n
I.B

1.6

1.0 1.S 20
p/Po

Figure 11.3. Dependence of the refractive index ofKBr on the compression, p/Po. The
symbol 0 designates the experimental result [8], a: point corresponding to the metastable
state on the shock front. The cross-hatched region is the melting zone under shock com-
pression.
 11. Temperature Measurement and Equation of State of Condensed Matter 343

P,GPa

0.2 0.3 0.4 O.S

V, cm 3 /g
Figure 11.4. Equilibrium (-) and nonequilibrium (_._) shock adiabats ofKCI and KBr.
0: experimentally measured states on the nonequilibrium and equilibrium Hugoniots [8],
1 (1') and 2 (2') states respectively on the nonequilibrium and equilibrium Hugoniots.

11.4. Measurement of the Optical Absorption Factor and

Mechanism of Light Absorption and Conductivity
In nonnal conditions, single crystals of alkali halides transmit light in a wide
wavelength range from 0.2-0.3 to 60-130 J.lffi. The visible light absorption
factor in these conditions is ex. R:I 5 x 10 - 2 em-I if they do not have specially
introduced impurities. It has been observed that shock compression significantly
decreases the transparency of ionic crystals [9,10]. The characteristic feature of
these results is an increase of radiation brightness as a shock wave propagates
through a sample up to a point where it becomes stable starting with some thick-
ness. Having determined in experiments the dependence of the brightness of
thennal luminescence on time, and knowing the wave speed and the material
density behind the front, it is possible to calculate the absorption factor of the
compressed material. These results are shown in Fig. 11.5. The values of ab-
sorption factors, measured at wavelengths of 625 and 478 nm, appeared to be
very close and are higher by a factor of30-100 than the values at T = 300K. It is
evident how strongly the absorption factor depends on temperature.
Absorption in condensed materials takes place both as a result of excitation
of optical oscillations of the crystal lattice (infrared absorption) and also as a
result of electronic excitation. In nonnal conditions the infrared absorption band
lies within a range of wavelengths greater than 10 J.lffi (for NaCI the dispersion
frequency is given by hv =0.02 eV and for CsBr hv = 0.0095 eV). Keeping in
mind the weak dependence of the absorption factor on the wavelength and the
strong dependence on temperature, it seems clear that light absorption in shock-
compressed ionic crystals results from interband electronic transitions. Based on
344 v.n Urlin
5
NaCl
4 0
0
3 -1
0
~ III ~
co2 -2 co

~
.9 .9
0 -3

0 -4

-1 -5
1 2 3 4 S 6 7 8
10lT (kK)
Figure 11.5. Temperature dependence of the electrical conductivity L (Ohm-Icm- I) and
the absorption coefficient a (em-I) ofNaCl. 0 and 0: experiment, L from [25] and a
from [12], - - : calculated from [12].

these ideas, it would be natural to interpret electrical conductivity measured in

shock-compressed dielectrics [23 - 25] as an electronic effect caused by the same
carriers. Having two independently measured values (an absorption factor a. and
conductivity 1:), and considering that the same carriers determine both of these
parameters, it is possible to find the mobility, jl, and the electron concentration
in the conduction band, N •. In the context of classical theory, the absorption
factor is related to the concentration of free carriers, the frequency, v, of the
incident light, and a damping parameter, q (the frequency of collision between
electrons and lattice ions) as:
L =ejlNe
2Ne e2 q
a= (11.2)
em v 2 _q2
e
q=--.
21tmjl

In these equations e is the velocity of light and m is the effective electron mass.
Figure 11.6 presents values of the free-electron mobility in shock com-
pressed NaCI given in [10] based on measured values of conductivity [25] and
an absorption factor [10] (Fig. 11.5) using Eqs. 11.2. These values, allowing for
the temperature dependence of ).I., agree well with the data of other authors
[26,27).
In ionic crystals, the dominant factor is electron scattering by optical oscilla-
tions of the lattice. According to Ziman [28),
0.27h2
jl=--== (11.3)
Com~mkT
 11. Temperature Measurement and Equation of State of Condensed Matter 345

for this case. In this equation Co = (1/800) - (1/eo), and 800 and eo are high fre-
quency and static dielectric penneabilities, respectively. The function Il(T)
according to [10] agrees well with the experimental points in Fig. 11.6 at
Co = 0.2. The good agreement of the electron mobility values with data of other
authors and with the calculation according to Eq. 11.3, favors the. mechanism
proposed to explain the phenomenon [6,10]. The electron concentration in the
conduction band at T=3400K and 0'= l.7 is N o = 10 18 cm- 3, and the damping
parameter is q ::1$1014 S-I.
To explain the values of electron concentration in [6,10] it was assumed that
donor levels, which in NaCI stay below the bottom of the conduction band by
W= 2.4 eV, are the source of the free electrons. This value was obtained from
the dependence ~(lIT) in Fig. 11.5. The necessary donor concentration based
on the equation

N ="Nd W)
r.:r(27r.mkT)o.75 exp ( - - -
h2 2kT
is Nd ::1$1.6 x lO19 cm- 3 at T=3400 K and 0'= l.7 (N::I$1018 cm- 3, W=2.4 eV).
This exceeds the concentration of defects that is characteristic of ionic CI)'stals
in normal conditions by a factor of about lOS.
Thus, a shock wave is a strong generator of defects, with electrons localized
on the defects. Thermal excitation of these electrons results in their appearance
in the conduction band.

NaCI

:i
2

O~---r---.----.---~----~
o 2 3 4 5
T,kK
Figure 11.6. Temperature dependence of free carrier mobility for NaCl. Experiment: a
[49,50], • [12], -'., calculated from [12], a: melting zone.

11.5. Temperature Measuring Technique for Shock

Compressed Condensed Materials
In measurements of the temperature of shock-compressed air and noble gases,
perfonned by Model' [4,29] and by Roth [30], high explosives were used to
346 V.D. Urlin

create powerful shock waves. Since explosive experiments are very complicated
and time consuming, the study of thermodynamic properties is limited, as a rule,
to measurement of kinematic parameters of shock waves-the shock velocity,
D, and the particle velocity, U. The pressure, P, density, p, and internal energy
density, E, are found by substituting D and U into equations expressing the laws
of conservation of mass, momentum, and energy. The temperature, T, one of the
main thermodynamic parameters characterizing the state of the material, is de-
termined by calculation. Direct temperature measurement makes it possible to
check and obtain a better understanding of the equation of state and properties of
a condensed material at high pressures. We shall consider some principal issues
of these measurements.
Optical methods based on the dependence of radiation from a material on its
temperature appear to be the most reasonable for measurements since a material
is in a shock compressed state for a very short time, and the temperatures are
very high (from about one thousand to tens of thousands of degrees). Transpar-
ent dielectrics are of interest because radiation from the compressed material can
pass through the material not yet compressed by the shock wave and on to in-
strumentation with which it can be measured. Material radiation, if it is thermal
radiation and is in equilibrium with the material, characterizes its temperature.
When a crystal is compressed by a shock wave, the mechanical energy is first
imparted to the lattice and then to the electrons. It is the temperature of the elec-
trons that is of interest to us since this determines the radiation Thermodynamic
equilibrium is established by interaction between phonons and electrons and
between phonons and phonons. The time for phonon-phonon equilibration is
equal to the ratio of the phonon mean free path, ~l run, to the sound velocity, ~4
km/s, i.e., 10-13 _10-12 s. The time of electron-phonon interaction is from 10- 14
to 10- 13 s. Keeping in mind that, during each interaction, an electron gains the
energy hv, where v is the lattice vibration frequency, equilibrium between the
electrons and the lattice is established at T ~ 1 eV in a time of 10 -12 - 10 -11 s. It
is necessary to allow for the additional time required for thermal electron exci-
tation into the conduction band. If this process is taken into account, then the
equilibrium temperature between electrons and a lattice is established within
10- 10 _10- 9 s after passage of the density jump, i.e., in a layer _10- 4 em thick.
This layer will not screen the equilibrium radiation from the compressed mate-
rial if its absorption factor is cx.< 10 3 em-I. In this case, shock-front radiation is
in equilibrium and can be used for temperature measurement. Estimates show
that radiation losses at T:S: 4 eVare not more than 0.1 % and may be neglected.
We shall consider one more aspect of this issue. It was determined theoreti-
cally and experimentally that, when strong shock waves luminesce in gases, the
brightness temperature at the front is significantly lower than the value expected
from calculations [1]. This happens because, at T> 1 eV, the gas ahead of the
front that is heated by the radiation flow becomes opaque and screens the hotter
 11. Temperature Measurement and Equation of State of Condensed Matter 347

shock front. Simple estimation shows that this phenomenon does not play any
significant role in shock compressed condensed materials.
Measurement of the shock-front temperature in optically transparent materi-
als is based on comparison of the radiation intensity from the shock front with
the intensity of radiation from an absolutely black body. If a body is not com-
pletely black, then the temperature thus inferred does not agree with the true
temperature. The fundamentals of modem pyrometry of true temperatures in
radiating materials in a condensed phase are presented in [31]. When measuring
high material temperatures with a continuous radiation spectrum, the brightness
method is the most reasonable of the various available optical methods. It is
based on the Planck and Kirchhoff laws. According to these laws the true mate-
rial temperature, T, is deduced from the equations

exp( -C2 ) -1
AT =&O(A, T) a (A, T) , (11.4)
C2 )
exp( - - 1 &(A, T)
ATo

a (A, T) = & (A, T) 1- 't - Rf . (11.5)

&O(A, T)

In Eqs. 11.4 and 11.5, C2 = 1.438 cm K is a radiation constant, A is a wave-

length, &0 is the spectrum brightness of a reference source with temperature To,
and & (A, T) and &0 (A, T) are the spectrum brightnesses of the body under inves-
tigation and a black body, respectively. The spectrum blackness, a(A, 1), may
differ from unity as a result of both the material transparency, 't, behind the
shock front and the reflective power, Rf, of the front. As experience has shown,
condensed materials become opaque in much thinner layers than do shock com-
pressed gases [6]. This makes it possible to either neglect transparency starting
with some thickness of the compressed material or allow for a necessary error,
which does not exceed 10% of the measured temperature. Up to pressures of
-100 GPa, the reflective power of a shock front appears to be small enough
(Rf S:2%) that it may be neglected when determining the temperature [6].
When measuring temperatures of shock-compressed materials, optical phenom-
ena last Il:j 1 1lS, which requires application of equipment that is highly sensitive
and responds rapidly. Thus, the measurements are performed by photographic
[4,9,32] or photoelectric [9,10,30] techniques.
In certain conditions of an explosive experiment, the photoelectric technique
allows measurement of temperatures above Tmin Il:j 1200 K and can accommodate
light flows about a factor of 105 less than can be recorded with photographic
techniques (Tmin Il:j 4500 K), if the spectrum range is narrowed by a factor of 3-
5. If a photomultiplier is placed close to the sample, then the lower limit of the
temperature may be significantly decreased. The advantage of the photoelectric
348 V.D. UrIin

technique is in simplicity of the data analysis. However, the photorecording

technique allows spatial resolution of the brightness emitted from the surface.
The temporal resolution for both techniques can be 50 -100 ns.
Use of glass (.:1 A. ~ 50 nm) and interference filter (.:1 A. ~ 10 nm) light filters
allows isolation of narrow spectral ranges in various parts of the entire spectrum.
A pulsed xenon lamp of Icr-K type can be used as a reference light source for a
visible part of the spectrum [9,33]. The lamp is calibmted using a filament lamp
of SI-16 type and the same measuring equipment. The most reasonable way to
analyze the data is to use a technique of actinium flows [34). The details of the
experimental arrangement and the equipment features are given in [4,9,10).

11.6. Equation of State for Solid and Liquid Phases

It is impossible to describe the properties of a material over a wide range of its
thermodynamic parameters without knowing its equation of state (EOS). When
analyzing tests to measure the tempemture and optical properties of a substance,
the EOS must be used in a form that allows description of the phase diagmm of
various structural modifications for each crystal as well as the melting curve and
liquid phase. LiP and CsBr occupy the last places in the row of alkali halides.
The first has the maximum heat conductivity and the maximum width of the
energy gap between the filled band and the conduction band. The second has the
minimum values of these pammeters. NaCI, KCI, and KBr occupy the interme-
diate positions. A study of these five compounds gives a clear enough idea of
the equation of state for ionic crystals.
The solid state EOS was proposed by Mie, GrOneisen, and Debye, and its
form has not changed as a result of subsequent research. The free energy of a
crystalline solid substance has the form
Fr =Ex (V)+1.l25Re+RT[3In(l-e- 9IT ) -D(e/T)], (11.6)

where T and V are the tempemture and the volume, R is the gas constant, e(V) is
the Debye tempemture, and

is the Debye function.

The Debye function is deduced in the context of the harmonic theory of lat-
tice oscillations in which the terms higher than the second order are neglected in
the decomposition of the potential energy in terms of displacement, which is
necessary to transfer to the system of independent linear oscillators. However,
the role of anharmonic phenomena may be described in this decomposition if we
formally assume the frequencies to be dependent on the density. Equation 11.6
 11. Temperature Measurement and Equation of State of Condensed Matter 349

has been derived in this approximation, which is called quasi-hannonic. The

first two tenns in Eq. 1l.6 represent the internal energy of the body at absolute
zero temperature. The last tenn describes the contribution of the thennal oscilla-
tions of the crystal lattice to the free energy. Having defined the pressure, P, and
the internal energy, E, by the standard thennodynamic fonnulae, we get

P =Px +3Ryp[0.375E>+T D(E>/T)]

E = Ex + 3R[0.375E> + T D(E>/T)] ,

where Px = -dEx / dV, y = -d In E> / d In V, P = 1IV is the density, and the

subscript x designates cold (0 K) compression. The following equations appear
to be the most justified:

Ex = ao +-
3
Pk
I4 aj .3
--,-(8//
j=1 I
-1) (11.7)

(11.8)

where Ci = dPx / dp and 8 = p / Pk .

The four coefficients aj in these equations are empirical parameters. Three of
them are determined from the density of the solid phase at room temperature, the
melting temperature at zero pressure, and the binding energy. The value of the
fourth coefficient is determined from the conditions describing one experimental
point on the isothenn. The coefficient E>e is the experimental Debye tempera-
ture.
The foregoing equation for y (p) is a qualitatively correct reflection of the
physical nature of this parameter and quantitatively describes the experimental
values of y at p - Po. It is also a convenient interpolation fonnula in a majority
of practically interesting cases. Zubarev and Vashenko [35] demonstrated that,
for an isotropic Debye solid,

1 dlnCx 4-5fl
y=-+--- . (11.9)
3 dlnp [3{l-fl2)(1-2fl)][dfl/dlnp]

On the other hand, it is evident that

dln(Ci - 21; Px)

1 1 3p
y="3+ 2 dlnp , (11.10)

i.e., if the function fl(P) is defined by the equation

350 v.n Urlin

(1- ~)(1 + ~)(1- 2~)-3 = const.(l-~Px),

3pCx

the Eqs. 11.9 and 11.10 are identical.

Pastine [36] repeated the conclusion of the work [35] for an isotropic solid
body and made the following extension ofEq. 11.9 to single-atom cubic crystals
with central interaction forces. For the latter he obtained y(p) in the fonn

y="3+
1 dlnCx 1 d
dlnp +6dlnpln
{1-~[ ~
1+~ 1+~ -
2
3pCi Px
]2} . (11.11)

Again it is possible to reduce Eq. 11.11 to Eq. 11.10 when ~(p) satisfies the
equation

(1- 3pCi
2n 3 1-~ ( ~
Px ) =const'l+~ 1+~ - 3pCi Px
2 )2 (11.12)

The dependence of Poisson's ratio on density, ~(p), calculated by Kopyshev

[37], turned out to be a monotonically increasing function from ~ l:= 0.27 at small
densities up to ~ ~ 0.5 as p ~ 00. Hence, some restrictions on the value of ~, a
quantity appearing in Eq. 11.10, can be obtained. It is evident that ~ > 0 for
d"udp > 0 [35]. The same result holds for Eq. 11.12. This means that, in an iso-
tropic or cubic body, y(p) is approximated best by Eq. 11.10 with ~ = 1 or ~ = 2.
In case of more complicated crystal structures the issue of validity of this or that
equation remains open. Following are the calculations in which we take ~ = 1
for ionic crystals. For metals Eq. 11.10 is used, where ~ is an empirical pa-
rameter.

11.6.1. The Equation of State of a Liquid Phase

The study of the equation of state of a liquid phase is a challenge because ther-
mal motion of the atoms makes it impossible to create a model that is as illus-
trative as the models for crystals or ideal gases. Presently there are two main
directions in the approach to detennination of the equation of a liquid. The first
approach is associated with a concept of liquid as a distorted crystal in which the
long-range order is lost. Ya.I. Frenkel played a great role in detennination and
development of that concept of a liquid in the region from the melting curve up
to the critical point [38]. The second direction in building the equation of state
for a liquid is based on study of the particle group molecular distribution mo-
lecular functions or so called correlation functions. This direction began to de-
velop in works by J. Kirkwood, N.N. Bogolubov, M. Born, and X Green [39].
This work has a strong theoretical basis. It does not need any hypotheses on the
 11. Temperature Measurement and Equation of State of Condensed Matter 351

liquid structure, because the structure arises from the correlation functions.
However, there are presently some serious mathematical difficulties on the way
to development of this theory. Thus, its quantitative successes are not yet great.
It is a challenge to use the foregoing equations of state for quantitative cal-
culation of the Hugoniot in the region of a liquid phase. More convenient here is
an analytical equation of state having a form based on physical considerations
and incorporating numerical parameters chosen to provide the best description
of the experimental data. The form of the equation of state of the liquid phase
and the method for determination of its parameters were proposed by the author
in [15]. The equation of state of the liquid phase in a region near the melting
curve is close to the equation of state of the crystalline solid. Thus, we express
the free energy of a liquid in the form
FL =Ex (V) +3RTln(E>/T)-3RTlna(p, T). (11.13)

The function a(p, T) must satisfy two limiting conditions:

1. FL transforms smoothly into the free energy of an ideal gas at high tem-
peratures, and
2. The given values of entropy AS = SL - Ss and the specific volume
AV = VL - Vs at the melting point must follow from the equation of state
for the function a(p, T) chosen.
To satisfy these conditions we assume the function a(p, T) has the form

a=(I+ztO.SeXP[b(cr)- /(cr)~ J. (11.14)

where z = lRT /[C,r -(2~Px /3p»). l =const., and To is the melting tempera-
ture at P= O. The limiting conditions do not restrict the functions/(cr) and b(cr).
For convenience of calculations, assume that they are of the form

/(cr) = £!.(cr r -I) +C2 ([I + C3( cr -I)]exp [C3(cr -I)] -1}+C4
r
b(cr) = bo +b)cr b1 ,
where cr = p/Po, Po is the density of the liquid phase at To, and c) through Cs and
bo through b2 are empirical constants. The numerical values of these constants
are determined from the values of the thermodynamic parameters on the melting
curves at the normal pressure and at one or two points at a high pressure. The
values b) and b2 determine the pressure dependence of the melting heat along the
melting curve. For all alkali halide crystals investigated, the value b2 appeared to
be negative. Note that the function/(cr) in Eq. 11.14 effectively accounts for the
appearance of holes in the liquid phase structure and the following change of the
elastic interaction energy of the atom.
352 V.D. Urlin

11.6.2. The Electronic Component in the Equation of State

for Dielectrics
When the tempemtme of a material is higher than 1 eV it is necessary to take the
contribution of the electronic component of the free energy into account. For
dielectrics this component takes the form

4kT r:::-:-(21tm*kT) exp ( - -W)

Fe =---",npnn - (11.15)
p h2 2kT '
where m* is the geometric mean of the effective electron and hole mass, np and
nn are orbital degenemcy in zones, W= WoLn <Pm/p), m*=mocr2l3-G, Pm is the
density when the gap closes, and G is an empirical constant determined to pro-
vide the best description of the Hugoniot in the region of high tempemtures.
Table 11.2 presents recently revised numerical values of the parameters for
the equation of state of five alkali halide salts for which temperatmes were
measured under shock compression.

11.6.3. Liquid Structure

There is an agreed-upon issue regarding the existence of structme in a liquid
phase. From the modem standpoint, a gas in any state of nonzero density has
some structure. Since the region of the phase diagram occupied by the gaseous
phase does not bound that occupied by the liquid for pressures above the critical
point, there must be a continuous transition from gaseous to liquid ordering [40].
A great number of works on liquid structure research have been devoted either
directly to experimental diffraction studies, which are successful in studies of
solid structmes, or indirectly, i.e., to the building of liquid structme models and
subsequent investigation of the thermodynamic consequences resulting from
these models. Up to now the theory of the liquid structme has been developed in
three directions:
1. Genemlization of a dense gas theory. This is based on study of a mutual
potential intemction of two, three, four, or more, atoms in the liquid.
2. Considemtion of a liquid as a non-ideal solid body. This approach as-
signs too high a degree of ordering to the liquid, and thus fails to yield a
good understanding of entropy and properties associated with entropy.
3. An approach associated with the name of Eyring is a compromise be-
tween the first two. It interprets a liquid as a mass of submicroscopic
crystals that are ordered internally but are disordered in various ways
relative to their neighbors.
In an approach in which a number of distribution functions are used to
describe the positions of atom groups in a liquid, the liquid structure results from
 Table 11.2. EOS parameters of ionic crystals.

LiF I LiF II NaCII NaClII KCII KClII KBrI KBrII CsBr

Pk g/cm3 2.761 3.1 2.241 2.359 2.061 2.387 2.848 3.264 4.616 ;-

~ 1 1 1 1 1 ~
77.00
.g
ee Ks/km 116.06 101.48 83.29 75.01 75.33 71.69 76.05 71.50
110 JIg 0 3165 576.77 117.77 0 71.50 0
0
al GPa -57.0 -29.2 -3.85 -0.45 -0.12 -0.04 -0.45 -0.20 -13.89
i
~
I»
a2 GPa 144.8 14.0 -9.98 -37.24 -12.82 -5.65 -10.13 -4.33 83.06
~
a3 GPa -355.4 -266.1 -53.92 -8.96 -38.09 -73.61 -30.18 -60.12 -179.55
a4 GPa 267.6 281.3 67.75 46.65 51.03 79.3 40.76 64.65 110.38
Tm(P=O) K 1121 4040 1073 2418.8 1045 1327.2 1007 1283.1 910
-8-~
t!i
pliquid g/cm3 1.80 4.0767 1.555 2.4927 1.525 1.8252 2.125 2.5455 3.13 ..c
Pliquid GPa 0.0001 125.98 0.0001 14.057 0.0001 1.9125 0.0001 1.7020 0.0001 ~.
§l
f, 18 18 16 30 12 12 16 16 18 0
......
c:n
bo 0.9703 1.1288 0.97 0.9881 0.8933 0.9474 1.0129 0.9491 1.1005 fl
0
bl 0 -0.35 0 0 0 -0.2 0 -0.12 -0.25 0
......
b2 -3.0 -3.0 -3.0 -2.0 n
0

CI 1.755 2.1167 1.7369 1.3486 1.417 2.6616 1.4184 2.4517 2.2857

8.
0
::s
C2 0.1098 0.0 0.0955 0.3 41.51 0.45 0.1596 0.3 0.0 8-
C3 3 4 4 0.25 4 4 4 s::
C4 0.0616 0.5843 0.2068 0.5550 0.2712 0.1611 0.3779 0.2399 0.0615 ...W
r 0.738 w
0 0 0 0 0 0 0 0 Vl
w
354 Y.D. Urlin

the theory itself. Bernal [41] proposed and developed a geometrical view of the
liquid structure. He interprets a liquid as a homogeneous, coherent, but irregular,
particle cluster that is free of crystalline regions and holes that are large enough
to locate other particles at low temperatures. The general problem of all theo-
retical approaches is the difficulty of obtaining mathematical solutions. As a
result, application of the various models usually involves adoption of simplify-
ing assumptions.
The issue of the structure of a liquid is associated with the issue of the ther-
mal motion of its particles. According to the views introduced into physics by
Frenkel [38], the thermal motion of atoms of a liquid in states far from the criti-
cal point is irregular oscillations at an average frequency, Uto, close to the fre-
quencies of atomic oscillations in a crystal. The center of oscillation is defined
by the field of adjacent particles and shifts with the motion of these adjacent
particles. The time 't ('t »'to) is the time required for the oscillation center to
shift by an amount corresponding to the inter-atomic distance. That is the time
of a "settled life" of a particle in a temporary position of equilibrium. In the case
of liquids of low viscosity, 't _10-11 s. This time increases with increasing vis-
cosity and becomes as great as hours and days with glasses. For processes with a
characteristic time t«'to, the liquid will be absolutely disordered. However, a
quasi-structure will be observed in small volumes for t in the range 'to «t« 'to
Finally, for t» 't, the quasi-structure again appears to be lost and only short
range order remains. With an increase of temperature or volume, 't may ap-
proach 'to. Liquid equilibrium properties will be determined by the characteristic
time for a process of interest. For example, the liquid structure significant for
shock waves must exist for a time t - 10- _10- 6 s.
The experimental data on structural analysis of liquid metals [40] show that
their atom packing is associated with their packing in a solid state, with the
character of this association depending on the type of the metal. The coordina-
tion number of metals after melting either increases or does not change. Metals
that have dense packing in a solid phase (coordination number 12) have about
11 atoms in the first coordination sphere after melting.
The structures of melted alkali halide crystals have been studied reasonably
well [42,43]. Experimental data, taken from [42J, are presented in Table 11.3.
The interesting point here is the fact that the inter-ion distance in a liquid is less
than in a crystal at room temperature. Also, each ion in a liquid has fewer near-
est neighbors. This confirms the fact that structural voids exist in a liquid phase.
Thus, It is easy to assume that there are "holes" behind the voids in the structure,
as in the crystalline solid phase.
Cesium salts are noteworthy. Close to the melting point in a solid phase,
CsCI has a coordination number 6; for CsBr and CsI the number is 8. In a liquid
phase these compounds have a similar average number of nearest neighbors,
about 4.5. Thus, one may assume that Cs halides have a similar liquid structure.
 11. Temperature Measurement and Equation of State of Condensed Matter 355

Table 11.3. Structural features of melted alkali halide crystals.

Crystal Cathode-anode ion interval Average number of
10- 8 cm nearest neighbors in
the liquid
for crystals at for crystals at the for liquid at the
298K melting point melting point
LiF 2.01 2.10 2.0 3.7
LiCI 2.57 2.66 2.47-2.55 3.5-4.1
LiBr 2.75 2.85 2.68 5.2
LiI 3.00 3.12 2.85 5.6
NaF 2.31 2.4 2.3 4.1
NaCI 2.81 2.95 2.88 4.7
NaI 3.23 3.35 3.15 4.0
KF 2.66 2.8 2.65 4.9
KCI 3.14 3.28 3.1-3.2 3.7-5.8
CsCI 3.57 3.53 3.5-4.6
CsBr 3.71 3.55 4.6-4.7
CsI 3.95 3.85 4.5

If we compare the value of the relative volume jump at melting, AVIVr, we'll see
that both CsF and CsCI have AVIVr= 14% and 10%, respectively. For CsBr and
CsI the jump is 26% and 28%, respectively. This is also evidence that the as-
sumption of structural similarity is correct. However, nothing can be said about
the nature of the virtual structures with the coordination number 6 or 8 since the
proximity of the coordination number in a liquid to this number in a crystal
cannot answer the question about the lattice on which basis the given short-
range order appeared. On the other hand, Furukawa [43] presents some indirect
arguments in favor of a lattice of the NaCI type with the coordination number 6
for all liquid alkali halide salts.
Thus, it seems probable that, in a liquid phase (but close to the melting
curve), the coordination of cells remains the same as it is in the solid state; only
the number of holes increases. Moreover, crystals with large anisotropy melt
into a liquid that has a more symmetrical virtual structure, similar to a cubic or
hexagonal close packed crystal structure. The issue considered in this paragraph
is not related to the issue of equation of state of a liquid phase, but it becomes
very acute when explaining anomalies in shock compression of alkali halide
salts.
356 V.D. Urlin

11.7. Temperature Measurement of Shock-Compressed Ionic

Crystals and Experimental Melting Curves
Measurement of the temperature of alkali halides under the shock compression
is very convenient because of the optical isotropy and transparency of their
monocrystals over the entire visible spectrum. The dynamic compressibility of
this type of ionic crystal has been studied in detail in [9,17,18,25,44].
A theoretical analysis of how fusion affects the shape Of the Hugoniot
showed that it does not greatly affect either the kinematic parameters of a shock
wave or the shape of the Hugoniot in P-V coordinates [15,45].* This explains
why melting of condensed materials was not taken into account when dynamic
methods were used to investigate their equation of state. However, measurement
of the temperature a shock-compressed material is a very sensitive way to de-
termine its melting curve since the energy consumption for fusion results in a
sharp discontinuity of the Hugoniot in the T-P plane. This picture is typical of
all first-order phase transitions that are completed at the shock front and have a
large entropy jump. This is because the pressure can only increase along the
Hugoniot but states on Hugoniots passing through a two-phase region must lie
on the phase equilibrium curve in the T-P plane.
Experimental values of temperature as a function of pressure in a shock
wave for NaCI, KCl, KBr, LiF and CsBr [6,9,11] and their Hugoniots in the P-p
plane are given in Figs. 11.7-11.16. The differences between the temperatures,
measured in blue (A. = 478 nm) and red (A. = 625 nm) regions of the spectrum
apparently characterize the accuracy of the measurements. The general view of
the Hugoniot in T-P coordinates is characteristic of all the crystals studied: first
the temperature increases with an increase of the wave amplitude, then it re-
mains almost constant followed by the further increase with increasing pressure.
The temperature "step" in the experimental dependence T(P) was identified in
[9] with the fusion of ionic crystals.
We shall stop at conclusions that can be made from analyses of data from
temperature measurements. The crystals studied demonstrated that the
Griineisen equation of state, Eq. 11.6, with the Oebye function for heat conduc-
tivity that arises in the quasi-harmonic approximation, satisfactorily describes
not only the connection between the pressure and density along the Hugoniot,
but also the temperature of a shock compressed solid body up to the melting

* However, for a number of materials, it is possible (though approximately) to detennine

melting based on a measured discontinuity of the shock wave velocity dependence, D(U)
[IS]. For example, these materials can be simple metals or, among those considered in
this chapter, there can be KCI and KBr. However, it is practically impossible to
detennine the melting point for NaCI based on the function D(U). Van Thiel and Alder
[46] detennined the point of transition of liquid argon into a two-phase region based on a
discontinuity ofD(U).
 11. Temperature Measurement and Equation of State of Condensed Matter 357

curve. This proves that the effect of thermal ionic oscillation anhannonicity on
the heat capacity of a solid phase of these materials is small (flCvlCv S;; 10%).
Comparison of the state parameters reached behind a shock wave shows
(Table 11.4) that the various ionic crystals transform into a liquid state at sig-
nificantly different pressures, but at a similar value of compression (cr ~ 1.7 -1. 8)
and temperature. The temperature at which melting occurs on the Hugoniot
exceeds the melting temperature at atmospheric pressure by a factor of 4-5.
When ionic crystals are compressed by a factor of 1.7, they remain in a solid
state up to a temperature of ~4000K, which is above the melting temperature for
the most refractory metals.

Table 11.4. Melting curve parameters.

LiF NaCl KCl KBr CsBr
Parameter values atP =0
Tp=o K Il21 1073 1045 1007 910
Po g/cm3 2.65 2.165 1.99 2.75 4.45
(!!sIR)p=o 3.7 3.5 3.0 3.8 3.1
(,WI V)p= 0 0.29 0.24 0.17 0.16 0.27
(dTldP)p=o KlGPa 106 240 240 245 450
Parameter values at the melting point on the Hugoniot
T K 6500 3600 4000 4000 4700
P GPa 240 55 42 34 44
P g/cm3 5.08 3.68 3.54 4.87 7.57
!!SIR 2.1 2.8 1.9 2.5 1.65
,WIV 0.049 0.027 0.027 0.036 0.011
dTldP KlGPa 14 18 36 41 20

The experimental data allowed the parameters of a liquid-phase equation of

state and a melting curve to be determined. The computed results given in Figs.
11.7-11.16 describe the phase diagrams of the crystals studied reasonably well.
It follows from these calculations that the entropy jump changes relatively little
along the crystal melting curves. This means that the heat of fusion increases
approximately proportionally to the melting temperature, i.e., by about a factor
of three. When the compression, cr, is ~ 1.8, the heat of fusion is about 20-30%
of the total increase of the internal energy under shock compression and 50 % of
the heat energy delivered to the material. On the contrary, the volume jump
decreases significantly at melting. If flVIV. ~ 20-25% at atmospheric pressure,
then it is only 1-3% when melting is caused by shock compression. Thus, a
number of properties of liquids, at least at the melting temperature, must differ
less from those of a solid in the conditions of high compression than at atmos-
pheric pressure. The parameter values defining the melting curves for both
phases ofKCI and LiF are given in Tables 1l.5 and 1l.6.
358 V.D. Urlin

8~----------------------------------~

NaCl .0- 0

liquid

O+-~~=r~+-~__s~o~li=d~II~~__- r__~~
o 20 40 60 80 100
P,GPa

Figure 11.7. NaCI phase diagram.•,0 experimental temperatures measured at A. =0.478

J.IlIl and A. = 0.625 J.IlIl. Solid curves: calculated Hugoniot and melting curve for phase I.
Dashed line: Hugoniot for the "superheated" solid phase. Dotted line: Hugoniot and
melting curve for phase ll.

400 NaCl . .:

1
300

.'
.'
...•.'
200
.~ ... ,

.. ....
'

100 .... .'

o~~~~~~~~~~~~~~
1.0 1.5 2.0 2.5 3.0
p/Po

Figure 11.8. Hugoniots for NaCI of different porosities. 1-4: m =1,2: m =1.51,
3: m = 1.76,4: m =2.19, dashed line: m =1 Hugoniot for phasell, dotted lines: bounda-
ries of melting curve.
 11. Temperature Measurement and Equation of State of Condensed Matter 359

o 10 20 30 40 50 60
P, GPa

Figure 11.9. KCl phase diagram. the symbols. and 0 designate experimental tempera-
tures measured at ),,=0.478 J.IIIl and )..=0.625 J.IIIl. Solid curves represent the calculated
Hugoniot and the melting curve for phase II. The dotted line represents the nonequilib-
rium Hugoniot and melting curve for phase I.

400

KCI
300

~ 200
, ,,
,
0

Q.,ft o ' ,
o P::'//S
o "
0",'",
a::-"
.. ",:... '
;;:::::/

0
1.0 1.5 2.0 2.5 3.0
p/Po

Figure 11.10. Hugoniots for KCl for different porosities. 1: m = 1, 2: m = 1.41,

3: m = 1.8,4: m = 2.51. The dashed lines (5) designate boundaries of the melting curve.
360 VD. Urlin

6
G
KEr
5

~ 3
~"

O~~~~--~--.---~~--~--.---~~
o 10 20 30 40 50
P, GPa

Figure 11.11. KEr phase diagram. Symbols are the same as in Fig. 11.7 .

•
400 KBr

300

~ 200
•
~"
•
100
•
•
0
.,. ......
1.0 1.5 2.0 2.5 3.0
p/Po

Figure 11.12. Hugoniots for KEr (m = 1). The dotted lines designate boundaries of the
melting curve.
 11. Temperature Measurement and Equation of State of Condensed Matter 361

15

~ 10
e-.."

100 200 300 400 500

P, GPa

Figure 11.13. LiF phase diagram and Hugoniots for different porosities. 1-5: m = 1,
2: m = 1.55, 3: m = 2.88, 4: m = 3, 5: m = 4.68. Symbols are the same as in Fig. 11.7.
Solid lines: melting curve and phase boundaries. Hugoniot m = 1: variants of calculated
brightness temperature.

500

LiP
400

300
~
Co:)
Q","
200
,,
,,
100 ,,
,,
, -
"
,,-,,' 6
,,' "

0
0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
p/Po
Figure 11.14. Hugoniots for LiF. 1-5: the same porosities as in Fig. 11.13. Dashed line
(6): P x; dotted lines (7): boundaries of melting.
362 YD. Urlin

500 CsBr

400

~ 300
~.

200

100

0
1.0 1.5 2.0 2.5 3.0
pl po

Figure 11.15. Hugoniots for CsBr for different porosities. 1-3: m = 1, 2: m = 1.51,
3: m = 2.2. The dashed lines (4) designate boundaries of the melting curve.

10~---r~"",---'------~--------'

0.40 0.45 0.50 0.55

V, cm'!g
Figure 11.16. Rarefaction isentropes and Hugoniot curves for KCI for the same porosi-
ties for curves 1-4 as in Fig. 11.10. Solid lines 1-4: equilibrium Hugoniots for phases I
and II. Dotted lines 1-4: nonequilibrium equilibrium Hugoniot for phase I. Dotted line:
boundaries of melting curve for nonequilibrium phase II. Dashed line: boundaries of
melting curve for equilibrium phase II. Chain lines: release isentropes.
 11. Temperature Measurement and Equation of State of Condensed Matter 363

11.8. Polymorphic Transitions in Ionic Crystals

Alkali halide crystals that have a structure with 6 nearest neighbors at nonna!
conditions (NaCI, KCI, KBr, LiF) but transform. to a CsCI structure with 8 near-
est neighbors when compressed. Bridgman [47] first observed a phase transition
from one crystal structure to another during isothermal compression of a halide.
Much work to study these transitions using x-ray structural analysis has been
done by Drickamer [48,49] and Bassett [50]. A large volume change AVIV ~ 10-
14 % and little positive or negative heat of a phase transition are characteristic of
polymorphic transitions of alkali halide salts.
Phase transitions in KCI and KBr were studied in dynamic measurements by
Al'tshuler [17]. LiF and NaI were studied in the same work up to the pressure
p= 100 GPa. As for NaCI, no anomalies associated with the phase transition
have been observed. In [18] Hugoniots of NaCI, LiF, KCl, CsBr and KBr were
studied up to 500 GPa. These same works provided data on shock compressibil-
ity of porous crystals of the first four of these compounds. An anomaly of the
Hugoniot of LiF of normal density has been discovered at a pressure of about
140 GPa This showed the possibility of a polymorphic transition into a CsCI
structure. Additional considerations involving the entire set of experimental
facts known for LiF are given below to demonstrate the validity of this conjec-
ture. An interesting phenomenon, a "frozen" phase transition in liquid NaCI, was
illustrated in [18]. This transition manifests itself on the Hugoniots of both solid
and porous substances.

11.8.1. Description of Phase Transitions and Hugoniots

in a Solid Phase
The equation of state for solid ionic crystals and methods for determining their
parameters are described above. Phase equilibrium curves were calculated on
the basis of equations of state that were determined They are almost straight
lines. Their agreement with the experimental curves (Fig. 11. 7) is not surprising,
as the latter were considered when the equation of state of the second phase was
determined.
Isotherms for T= 293K were calculated. Their agreement with the experi-
mental curves obtained in [47] for KBr and CsBr, in [49] for LiF and NaCI, and
for KCI in [48], is reasonably good. In KCI and KBr crystals the region of co-
existence of two phases for polymorphic transition has practically zero extent
along the pressure axis, which results in a two-wave configuration when a mate
rial with little porosity is subjected to shock compression. In the T-P plane a
phase transition of this kind results in a discontinuity of the Hugoniot. The
Hugoniot of the second phase has higher temperatures than the superheated first
phase. This is associated with the fact that the second phase must be heated to a
364 v.D. Urlin

Table 11.5. Melting eurve parameters ofKel.

T p Psolid Pliquid !!.S12R tlVIV Z
K GPa g/em3 g/em3 %
1045 0 1.793 1.528 1.945 17.3 0.435
1200 0.9 1.870 1.696 1.694 10.3 0.354
1327 1.9 1.960 1.825 1.610 7.4 0.317
1327 1.9 2.246 1.825 1.604 23.1 0.336
1500 2.6 2.273 1.978 1.401 14.9 0.290
1700 3.7 2.325 2.097 1.296 10.9 0.275
2000 6.0 2.440 2.265 1.243 7.7 0.260
2500 ll.5 2.702 2.556 1.276 5.7 0.237
3000 19.4 2.999 2.856 1.337 5.0 0.218
3500 29.4 3.304 3.160 1.387 4.6 0.202
4000 42.0 3.615 3.472 1.424 4.1 0.l89
4500 57.4 3.937 3.796 1.453 3.7 0.176

Table 11.6. Melting eurve parameters ofLiF.

T P Psolid Pliquid !!.S12R tlVIV Z
K GPa g/cm 3 g/em3 %
1121 0 2.330 1.800 1.860 29.5 0.934
1320 2.0 2.356 1.951 1.520 20.7 0.782
1600 5.5 2.420 2.123 1.239 14.0 0.698
2000 12.0 2.569 2.359 1.052 8.9 0.624
2500 24.5 2.845 2.688 1.008 5.9 0.541
3400 68.2 3.557 3.431 1.120 3.7 0.406
4040 126.0 4.194 4.077 1.216 2.9 0.335
4040 126.0 4.397 4.077 0.801 7.9 0.353
4500 140.5 4.488 4.198 0.820 6.9 0.370
5000 159.2 4.610 4.344 0.858 6.1 0.383
6000 209.5 4.932 4.690 0.977 5.2 0.392
7000 280.6 5.350 5.112 1.123 4.7 0.385
8000 376.7 5.845 5.603 1.270 4.3 0.369

higher temperature to compensate for the pressure decrease on the elastic com-
pression curve. The figures show rather satisfactory description of the experi-
mental data on shock compression of the crystals.
The method of describing phase transitions appeared to be more effective
when applied to the crystal LiF. In [18], two experimental points that were ob-
tained on the Hugoniot offully dense LiF in the pressure region from 140 to 160
 11. Temperature Measurement and Equation of State of Condensed Matter 365

GPa were located abnonnally relative to the other experimental data. When
describing the experiment in [18] this anomaly was neglected. However, more
experimental data that were obtained to determine the equation of state resulted
in a new calculated Hugoniot having a good agreement with the experimental
Hugoniot up to P - 100 GPa. The validity of this equation of state is also con-
firmed by comparison with the isotherm [49] that formed the basis for more
firmly establishing the elastic interaction curve. Comparison of the calculated
and experimental curves also argues for a polymorphic transition at P - 140
GPa. The melting curve calculated using the equation of state based on experi-
mental Hugoniots of LiP lies in the region of much lower temperatures than
those determined experimentally by shock compression of the material to states
in the fusion region (Fig. l1.l3). The published experimental data determine the
possible region of the phase transition to be 100-140 GPa. M.V. Sinitsin meas-
ured one more experimental point on the Hugoniot at P = l30 GPa, which is still
in the low-pressure phase (Fig. 11.14). This result required adjustment of the
estimate of the transition pressure.
In [50], the empirical linear dependence of the change in entropy with
changing volume at the phase transition in alkali chlorides (KCI, RbCI, CsCI)
was derived and validated. It takes the form
AS (kcal-I mol-I K) =20(AV lVo) =2.25, (1l.16)

where Vo is the crystal volume at the normal conditions. This dependence also
corresponds to the experimental data for KBr.
When describing experimental data for LiP it was assumed that the structural
transition in the crystal takes place at P= 135.8 GPa with a volume decrease
AVIV1 =-48%. The entropy change at the given transition based on Eq. 11.16 is
equal to AS= 0.27 Jig. The result of the description of the complete data pack-
age on shock compression is presented in Figs. 11.13 and 11.14. It is clear from
the graphs that the agreement between the calculation and the experiment is
reasonably good. This is a convincing argument in favor of the accepted inter-
pretation of the experimental data.
Satisfactory description of the polymorphic transitions in ionic crystals once
again confirms applicability of the given form of the equation of state for the
solid up to the melting curve.

11.8.2. Polymorphic Transition in NaCI and Hypothesis of

Different Structures in a Liquid
American experiments [50] performed in static conditions using x-ray structural
analysis showed that the transition of NaCI into the CsCI structure takes place at
P=30±IGPa and T=300K with the volume jump AVIV! =-5.8±0.3%. For this
366 V.D. Urlin

transition we have AS= 0.11 JIg and dPldT= 26.4 MPaK-l according to Eq.
11.16. These values were taken into consideration when determining the
parameters of the NaCI II equation of state.
Static measurements show that the polymorphic transition in solid NaCI is
very slow. Thus, it can not manifest itself under shock compression where the
characteristic time is 10-7_10- 6 s. Therefore, the experiment measures
Hugoniots and temperatures of the :first phase. Interesting data were published
by Alder [51] on the shock compressibility of NaCl. He found that a shock-in-
duced phase transition takes place in NaCI starting a P - 30 GPa. The transition
goes faster if the shock wave propagates along the (111) crystallographic axis.
These tests were repeated by Al'tshuler and Pavlovskii [2], whose results con-
firmed only the presence of the initial stages of a transition process, and did not
result in quantitative agreement with Alder's data. The crystallographic orienta-
tion had the opposite effect to that reported in [51]: The phase transition goes
faster when the shock propagates in the (001) direction. It is evident from Fig.
11.8 that, apparently, the phase transition reported in [51] did not have time
enough to proceed to completion and the measurements gave an intermediate
Hugoniot. This assumption is supported by the data in [2].
Many efforts to study the shock compressibility NaCI of different porosities
at pressures up to 400 GPa were presented in [18]. This work disclosed anoma-
lies on the Hugoniots of solid and porous samples at P ~ 150 and 70-80 GPa,
respectively. Measurement of the NaCI melting curve [9] showed that the anom-
aly appears in the liquid phase region so it cannot be directly associated with a
polymorphic transition. In [18] a structural transition from a lattice of the NaCI
type to a lattice of the CsCI type in the liquid had been suggested as an explana-
tion for the anomaly. Here the hypothesis is being developed and there is an
attempt to coordinate the major part of the data available.
We proceed from the assumption that, at temperatures close to the melting
point, the liquid has the same cell arrangement (part of which is occupied by
ions) as in the solid state. In other words, NaCI I melts into a liquid having a
structure with coordination number 6. NaCI II melts into a liquid having a
structure based on the coordination number 8. The real number of closest neigh-
bors in the liquid will always be less than in the associated solid At the point
common to all three phases, liquid NaCI I and liquid NaCI n have the same
values of volume and entropy, but their equations of state are different The
first-order phase transition in a solid state will be continued by a second-order
phase transition in a liquid As a result of the slow polymorphic transition, the
Hugoniots and the first phase temperatures are measured in the experiment.
When the proper temperature is reached, NaCI I will melt and the Hugoniot will
be that of liquid NaCl1. As a result of the same mechanism, the NaCI n liquid
phase does not have time enough to form in the conditions of a shock compres-
sion experiment up to pressures of -150 GPa, even though it would be in ther-
 11. Temperature Measurement and Equation of State of Condensed Matter 367

modynamic equilibrium starting from P - 80 GPa (Fig. 11.7). All of the EOS
parameters for solid and liquid NaCI I and NaCI II are presented in Table 11.2.
The computed results are shown in Figs. 11.7 and 11.8 by the solid curves for
NaCI I and the dotted line for NaCI ll. It is evident from Fig. 11.8 that all the
low pressure experimental points, including the Hugoniot with m = 1.76 ob-
tained by Pavlovskii in [2], are quite reasonably described by the NaCI I equa-
tion of state.
Temperature measurements behind the shock front in the range P> 150 GPa,
where the NaCI II Hugoniot [43] occurs, do not provide any additional informa-
tion on a phase transition, since the difference between Hugoniots in liquid
NaCI I and NaCI II is not large. The hypothesis regarding the existence of two
different liquid phase structures is accepted for description of abnormal NaCI
behavior and is confirmed by experimental data for other ionic aystals. When
finding the equations of state for liquid KCI and KBr, it is accepted that the first
and second solid phases of these crystals melt into liquid phases of the corre-
sponding structure. Only by using this approach is it possible to describe all
experimental data, including data on the melting curves, reasonably well. In [9]
the equation of state for liquid KCI was accepted to be the same in the whole
range of liquid phase existence, and the pressure and temperature on the
Hugoniot, including the melting curve at high pressure, were described satis-
factorily. However, the calculated melting curve ofKCI for P < 1.9 GPa did not
agree with the experimental curve determined by static measurements [52,53].
Interesting results, which are in a good agreement with the hypothesis on
various liquid structures, were obtained in [54]. These investigators measured
states on Hugoniots of porous KCI and their experimental data appeared to be on
the Hugoniots calculated using the equation of state ofliquid KCI I (Fig. 11.10).
This equation of state was derived based on the equation for the solid phase
KCI I. The curve for the elastic interaction for the latter material was found
based on the experimental portions of Bridgman's isotherm and the P = 0 isobar.
The melting curve calculated as an interface is in good agreement with the ex-
perimental melting curve [52]. The validity of a given equation of state for solid
KCI I is confirmed by practical agreement between the calculated non-equilib-
rium portion of the Hugoniot and the experiment from [8]. It is clear from Fig.
11.4, where nonequilibrium Hugoniots for KCI and KBr I are shown by a dotted
line. The solid lines denote Hugoniots of KCI and KBr II and the first-phase
Hugoniots for pressures below the pressure of polymorphic transition.
The results from [54] show that the equilibrium liquid phase, KCI n, does
not have time to form in a shock wave. In the solid phase the experimental data
from [54] lie between the calculated Hugoniots ofKCI I and KCI ll. In [54] an
interesting phenomenon was noticed: When the material porosity is increased,
the fraction of the second phase behind the shock front decreases even though
the temperature at a given pressure increases with an increase of the porosity.
368 V.D. Urlin

This phenomenon points to the fact that phase transition in a shock wave has a
rather specific mechanism. Thus, the experimental data on NaCI and KCI shock
compressibility provides a strong proof for the hypothesis about structural tran-
sitions in a liquid phase.

11.8.3. Rarefaction Shock Waves

Phase transitions, in particular polymorphic transitions, are associated with one
more interesting phenomenon: rarefaction shock waves. They were predicted
theoretically by Drummond [57], and were discovered experimentally by
Ivanov, Novikov, and Tarasov [58,59J and by Erkman [60J in iron in the pres-
sure range P - 13 GPa. Rarefaction shock waves are described in greater detail
in [1).
A rarefaction shock wave may form in a medium for which (fy2P/oV 2 )s < O.
This situation often appears at phase transitions. Theoretically, it is possible at
any first-order phase transition since the slope of the isentrope is always less in
the area of coexistence than outside it [15,45]. Practically, this wave is easy to
observe for polymorphic transitions characterized by a large volume jump and
low transition heat. Laws of conservation of mass, energy, and momentum are
similar for shock waves of both compression and rarefaction. The condition of
shock wave stability also remains valid. A rarefaction wave is stable if its veloc-
ity is supersonic relative to the initial state and subsonic relative to the final
state. The shock wave begins at the interface between a two-phase region and
zero amplitude and develops up to the amplitude determined by the stability
condition. If the phase interface is not in the region of stability, then a shock
wave is preceded by a usual release wave. The same situation prevails behind
the shock wave.
For illustration we will consider a rarefaction shock wave induced by a
polymorphic transition in KCI. This wave was found experimentally in [54J.
Figure 11.16 shows Hugoniots KCI with m= 1 and m= 1.41, calculated using
equations of state for KCI I and KCI II. Circles and squares show the experi-
mental points from [17,54J. The points with squares are significantly to the right
of the calculated adiabat with m = 1. 41. This is associated with the kinetics of
the phase transition in a shock wave. Figure 11.16 shows by a double dotted line
two isentropes coming out from Hugoniots at P = 6.5 GPa. Isentropes for KCI n
continue into the region of metastable states at P < 1.9 GPa. In addition, the plot
shows an equilibrium portion of an isentrope coming out of the Hugoniot with
m = 1, at P < 1.9 GPa in the region of existence of KCII. It is evident from the
graph that polymorphic transition at release from a pressure lower than P < 1.9
GPa results in the appearance of a rarefaction shock wave that releases the pres-
sure to P = O. The solid circles show experimental pressure values on each side
of the rarefaction shock wave, which were determined in [54]. The locations of
 11. Temperature Measurement and Equation of State of Condensed Matter 369

experimental points is evidence of the slow process of recrystalization in a re-

lease wave, which was mentioned in [54]. Consequently, after the release to
P = 0, KCI remains partially in a solid phase. The final points are located at a
smaller volume than predicted by the calculation.

11.9. Nonequilibrium Radiation at Low Temperatures of

Shock Compression
When measuring the brightness temperature of shock-compressed ionic crystals
[6], it has been found that, at relatively low pressures, the measured light flows
significantly exceed the flows predicted by calculations based on the tempera-
ture equation of state. This effect emerged for LiF, NaCl, and CsBr in the pres-
sure range where the crystals are still in the solid phase behind the shock front.
Calculated and experimental temperature values are compared in Table 11.7.
Table 11. 7. Equilibrium and experimental brightness temperatures of shock
compressed ionic crystals.
Crystal P, GPa T, K T, K
calculation Experiment
1..=478 nm 1..=625 nm
LiF 34 550 2080 2020
64 lIOO 2750 2600
77.5 1420 3430 3370
104 2150 3980 3920
NaCI 27 1250 2440 2270
40 2120 2700 2450
CsBr 20.5 1750 2850 2650
25.5 2300 3170 3000

The greatest difference occurs for LiF. The density of light intensity within
the spectral range A')... = 10 nm at the pressure 34 GPa is equal to 7.7 mW/cm2
and is higher than the calculated value by a factor exceeding 1000, which is far
beyond the experimental error. The measured radiation cannot be of thermal
origin. The total increase of the internal energy for LiF that has been shock
compressed to a pressure of 34 GPa is 1.5 kJ/g. Almost half of it (about 0.65
kJ/g) goes to overcome the elastic repulsive force. The temperature T= 2080K
cannot correspond to thermal radiation because heating the LiF to this tempera-
ture would require almost 5 times as much thermal energy as could be delivered
to it by the shock. Thus, it is evident that, in the pressure range in Table 11. 7, the
luminescence of LiF, NaCI, and CsBr has a nonequilibrium character. The fact
that shock compression of ionic crystals and other dielectrics generates high
intensity fields is confirmed by work in which it was observed that an electric
current appeared that does not have a source of emf [61-65]. But, according to
370 V.D. UrIin

[6J, donor levels with localized electrons appear at a shock wave front in a di-
electric as a result of plastic defonnation. The combination of the electrical field
(-105 V/cm) and the donor levels as the electron sources is enough to inject
charge carriers into the conduction band and accelerate them to a significant
energy. The electrons have a higher temperature than the lattice. The lumines-
cence is of Planck character, as is demonstrated by the brightness temperature
within the 400-625 nm wavelength range.
Studies performed by Ahrens [66-68J confirmed the luminescent effect in
shock compressed ionic crystals. When the shock-wave amplitude increases, the
luminescent brightness becomes less than the thermal brightness and does not
have any further impact on the measured temperatures.

11.10. Electron Screening of Radiation at High Temperatures

At megabar pressure amplitude in a shock wave the temperature of compressed
alkali halides reaches values between 1 and 5 eV. At these temperatures the
contribution of electrons, exited from the valence band to the conduction band,
becomes significant for the equation of state. Especially, this refers to CsBr with
its small energy gap (~6 eV). The wave-front brightness temperature measured
by Kormer, Sinitsin and Kuryapin [I1J showed some interesting results. In
NaCl, KCI, and KEr (Figs. 11.18 and 11.19) the brightness temperature ap-
peared to saturate at a level of ~2 eV. The brightness temperature measured in
CsBr at P =500 GPa appeared to be about 0.5 eV, whereas the calculated value
of the equilibrium temperature was about 6 eV (Fig. 11.20). There is also a
difference, though not significant. between the measured temperature and the
calculated equilibrium temperature in LiF at P = 500 GPa. All of these crystals
are characteristic of practical agreement between the measured and equilibrium
temperatures up to T~0.6 eV. The calculations [12,18] showed that the results
cannot be explained by a contribution of thermal excitation of electrons to the
heat capacity. Direct measurement of the shock-front reflection factor, R r,
showed that the difference between the two temperature values does not result
from high reflective ability of the compressed material. Thus, in CsBr at P = 500
GPa the necessary value is R r ~ 99 %, whereas the measured value is R r ~ 7 %. A
similar contradiction was also found for other crystals.
The effect was explained by Zel' dovich, who paid attention to the necessity
of taking into consideration the process of thermodynamic equilibration between
the electrons and the lattice behind the shock front. The quantitative theory of
that phenomenon was evaluated by Zel'dovich, Kormer, and Urlin in [12]. The
sense of the theory is the following. When the shock wave propagates through
the material, the energy delivered to it goes to both overcoming the elastic inter-
action forces and heating the lattice. The time for relaxation of phonon - phonon
interaction is 10-13 _10-12 s. During this time the equilibrium according to pho-
non temperature, Ta , is reached at a thickness of about 10 nm. When electrons
 11 . Temperature Measurement and Equation of State of Condensed Matter 371

collide with phonons they take and give the energy in small amounts. An elec-
tron, which stored enough energy due to electron-phonon interaction, causes
transfer of another electron into the conduction band and formation of a "hole"
in the valence band. This process, shock ionization, results in an increase of the
free-electron concentration. The observed temperature corresponds to the optical
thickness

L =LXa.dx.
If L = 1 is reached in the zone where electron heating is occurring, then it is the
temperature of these electrons that will be measured. This is a lower value than
the final equilibrium temperature.

1.5
(a)
j
,j
co ;
~ 1.0 ----------.-------------
h

0.5

II III

0.0 r:...--,r-M"TTnT--,.-.-~,...,__.-.-..,....,..~.,___~~

0.001 0.01 0.1 1.0 X,I»"

o ................... --.................... .. :.. ..

~.=~-

(b)
-2

~ - 4
I
~
2' - 6
-8 III
II

- I 0 ~..-.,-...-.-T.....--..,-..,.-,-;.".,.n--.-...".......----,."T'T,...
0.001 0.Ql 0.1 1.0 x,)lm

Figure 11,17, Qualitative picture of the time-dependent distribution of the free electron
temperature (a) and the free electron concentration (b) behind the shock front.
372 V.n. Urlin

25

20

~ 15
e-.,"

10

0
0 100 200 300 400
P, GPa

Figure 11.18. Pressure dependence of the shock front brightness temperature in NaCl. •
and 0 represent experimental values at A. = 0.478 j.Ill1 and A. = 0.625 j.Ill1, repectively. The
solid curves are calculated brightness temperatures: 1: A. = 0.625 j.Ill1, 2: A. = 0.478 j.Ill1,
3: A. = 0.32 j.Ill1, 4: equilibriwn temperature.

~~-------------------,----------~

2S

20

10

100 200 300

P,GPa
Figure 11.19. Pressure dependence of the shock-front brightness temperature in KCl.
Symbols are the same as in Fig. 11.18. Pressure dependence of the shock-front brightness
temperature in KCl. Symbols are the same as in Fig. 11.18. (The symbol 0 represents
experimental values at A. = 0.625 j.Ill1.)
 11. Temperature Measurement and Equation of State of Condensed Matter 373

During the first stage, when their concentration is small, the electrons are
heated very quickly due to the energy from the lattice (Fig. 11.17). During the
second stage, the temperature of the electrons does not increase since the total
energy goes to increasing their concentration as a result of ionization. When the
electron concentration increases to the extent that their recombination with holes
(2e - + e + = e-) plays a role comparable with the ionization, stage III will begin.
During this stage the rate of electron concentration growth decreases because a
part of the energy goes to increase their temperature. As a result, electrons come
into thermodynamic equilibrium with the lattice. During the third stage the most
interesting is the point when the electron concentration is such that the optical
thickness is reached in a layer that is thinner than the layer in which the equilib-
rium between the electrons and the lattice is reached. In this case the light beam
measured in the experiment was radiated by this layer in which the temperature
had not yet reached its equilibrium. This resulted in a lag between the measured
and real temperatures. This is the qualitative picture of this phenomenon.
The system of equations qualitatively describing the kinetics of electron
heating has the form

20

15
~
E--,"

10

•
5
o

100 200 300 400 500

P,GPa
Figure 11.20. Pressure dependence of the shock front brightness temperature in CsBr.
Symbols are the same as in Fig. 11.18.
374 V.D. Urlin

d~N ~+'ex+ :r)-(~Jl

No =6xl021~npnn (::ys (11.17)

dT
-=a(T )dlnN
a -T)- -+T - - .
(W
dt 3k dT

In these equations T and N are the tempernture and electron concentration,

Ta is the tempernture of the lattice, a =ao T -1.S is a parameter characterizing the
energy exchange between the electrons and the lattice, and b = bo T -2.5 is the
parameter characterizing shock ionization of electrons from the valence band
The third equation is the equation of state with different electron and lattice
temperntures. •
The results of calculations for CsBr compressed by a shock wave of ampli-
tude 500 GPa showed that, up to the time t - 4 ns, the free electron concentIation
reaches N= 10 20 cm-3 • Further rnpid growth of N results in the fact that the
absorption coefficient (X. increases and only a thin layer dropped behind the
leading front interface by ~4 ns appears to be rndiating. The luminescence of
deeper layers in which the electron temperature reaches its equilibrium rather
quickly (M~ 1 ns), is screened by the layers ahead of it where T < Ta . The ef-
fective temperature is about a factor of 5 less than the lattice temperature. In
NaCl, effective temperatures are somewhat higher than in CsBr as a result of a
larger energy gap. For LiF, in both the experiment and the calculation, the lag
between the effective and equilibrium temperntures is the least even at P ~ 500
GPa. This results from a wider energy gap and a relatively small value of Ta .
Both these circumstances result in a lower concentIation of free electrons and,
consequently, less screening.
The mechanism of this phenomenon allows better understanding of why the
reflective power of a shock front is small despite the high electron concentIa-
tion, which reaches values of about 1022 cm-3, comparable with the concentIa-
tion of free electrons in metals. Even in CsBr, where N is the largest, the free
electron concentIation increases from N ~ 1018 cm-3 when it does not affect the
reflection factor up to N ~ 10 22 cm-3 for the time 1.4 ns or in a layer of thickness
A ~ 14 J.Ull, whereas to reflect the incident light it is necessary that this thickness
be small, A«0.5 J.Ull. In other cases, the electron density grndient is even less,
so that even the light reflection method, sensitive to density grndients, does not
allow experimental determination of the increase of free electron concentIation
at the shock front.

• Here the system is more accurate compared to [12]. The qualitative picture of the
phenomenon has not changed.
 11. Temperature Measurement and Equation of State of Condensed Matter 375

11.11. Measurement of Brightness Temperatures in

Shock-Compressed Liquid Argon and Xenon
Study of the thennodynamic and optical properties of shock-compressed inert
gases is interesting because they are transparent in their initial state, their crystal
structure has the closest packing, and filled electron shells have high symmetry.
Thus, these materials are very convenient for theoretical description of their
properties aiming for subsequent comparison of the theoretical predictions with
the experimental observations.
The first data on measurement of brightness temperatures of the shock front
in liquid Ar up to pressures of 20 GPa were achieved in [69]. At VNIIEF, the
range of investigation was enlarged to 70 GPa in Ar [13] and 90 GPa in Xe [14].
American scientists in one of their works [70] measured the brightness tem-
perature of shocked compressed Xe in UV part of the spectrum, which allowed
observation of radiation from deeper layers of the compressed material and,
consequently, a temperature closer to equilibrium. The results are shown in Figs.
11.21 and 11.22. It is interesting that in these materials, as in ionic crystals,
starting from T ~ 1 eV the brightness temperature is less than the thennodynamic
equilibrium temperature calculated using the equation of state. This behavior
was explained in [13,14] using the kinetic theory of electron heating, which is
more highly developed for ionic crystals and is described by Eqs. U.l7. The
latter says that the theory is more generally valid since it describes properties of
another class of condensed materials.

11.12. Hugoniots of Highly-Rarefied Condensed Substances

Compression of a finely divided powder of a solid substance by a strong shock
wave enables study of the thennodynamic properties of the condensed substance
at high pressures and temperatures for lower densities than nonnal. Results were
obtained on shock compression of porous copper and nickel with minimum
initial density corresponding to a porosity m -10 and 20. The experimentally
explored field involves shock-wave velocities in Ni up to values -15 km/s, and
in Cu up to -56 km/s. All of the experimental data on these metals shows that
the equation of state in the fonn of Eq. 11.13 features physical discontinuity of
the behavior of this class of substances at high pressures.
The good agreement between measured and calculated Hugoniots for solids
of various porosities and liquids near the melting curve is shown in [15]. The
calculated estimates presented here are carried out with values of the parameters
of equations of state obtained in [15]. At densities p < 5.4 g1cm3 for Ni and
p < 3.4 g1cm3 for Cu, the parameters of the elastic interaction curve are those for
which the denominator of the function z in Eq. 11.14 becomes small. Therefore,
for smaller densities, the thermal contribution of atoms had the features associ
ated with the van der Waals gas law. However it is necessary to rema.rk that, in
376 V.D. Urlin

25

Ar 2
20

15
~
..:.=
e-.,"
10

5 g&

0
0 10 20 30 40 50 60 70
P,GPa
Figure 11.21. Pressure dependence of the shock front brightness temperature in Ar.
Experiment at A. = 0.67 JllD: ~ is from [13], 0 is from [69], and the vertical lines denote
the measurement error. 1: calculated brightness temperature with electron excitation
kinetics taken into account, 2: calculated equilibrium temperature.

o 20 40 60 80
P,GPa
Figure 11.22. Pressure dependence of the shock front brightness temperature in Xe.
Experiment: 0: at 1.=0.67 JllD [14], ~: at 1.=0.32 JllD [70]. 1: Calculated brightness
temperature at A. = 0.67 JllD [14]; 2: Calculated brightness temperature at A. = 0.32 JllD
[14],3: Calculated equilibrium temperature.
 11. Temperature Measurement and Equation of State of Condensed Matter 377

the high temperature range for Hugoniots, these features of an equation of state
have no key value. For very high speed shock waves, D> 10 km/s, the com-
pressed substance is heated to temperatures >4 eV. In these conditions ioniza-
tion begins despite the high density. In carrying out calculations, the ionization
equilibrium is defined using the Saba equations, in which the numerical values
of ionization potentials are taken equal to those of the free atoms.
Calculated Hugoniots of Cu and Ni of several porosities are shown in D- U
coordinates in Fig. 11.23. Results of experiments are given in [71-75].
The analysis shows that the calculated Hugoniots of porous metals are de-
termined, in many respects, by the electronic component in their equation of
state. The contribution to an equation of state from thermal excitation of elec-
trons in the conduction band of a metal is represented by the interpolation equa-
tion offered by the author in [71]:

Fel =-1.5RT'I1 Jo
x
lncosh(~)~, with
T
X=~el--.
1. 5R 'I1

In this equation ~el is the coefficient of electronic heat capacity, defined at low
temperatures, and '11 is the number of electrons per atom in the conduction band.
For highly porous Cu and Ni in the range of shock wave velocities from 3 to
14 km/s, the form of the Hugoniot is fundamentally dependent on the value of
the so-called electronic Gliineisen coefficient, gel = -din ~etl dIn p, or the relation
p.tI(pEel). The form of the function g.l(p) assumed for satisfactory representa-
tion of experimental Hugoniots of porous Cu and Ni was approximated by the
equations g.1 = 1.1 5- 0.5 for Cu and gel = 1.65-0.7 for Ni in the range of relative
densities close to, and exceeding, 5 = 1. From Fig. 11.23, the coincidence of the
calculated results with those from experiments can be seen to be quite satisfac-
tory. The particular discrepancy can be related to inexact description of the
electronic component in the equation of state and to some experimental error.
For example, in the range of densities significantly smaller than normal, the
metal can become a dielectric having a forbidden band because of reorganiza-
tion of electronic levels.
Let us also remark that, within the framework of the equation of state dis-
cussed, the Hugoniot of nonporous copper up to the high pressures produced by
underground nuclear explosions. P = 20 TPa, is rather well represented [75].

11.13. Conclusion
It turns out that the technique developed to study optical radiation from shock
compressed dielectrics provides experimentalists with the possibility to study
thermodynamic and optical material properties at high pressures and tempera-
tures. Because only in this way is it possible to subject a condensed material to
extreme conditions, even though for only a very short time. Only by using this
378 V.n. Urlin

15
a Copper

0
0 2 4 6 8 10
U,km Is

16

b. Nickel
12

~
e
~
8
c::i

0
0 2 4 6 8 10
U,km/s

Figure 11.ll. Experimental and calculated D-U diagrams for Cu (a) and Ni (b) for
different porosity. (a) 1-6: m = 1, 1.4,2,3,4, and 10. (b) 1-7: m = 1, 1.4, 1.72,2.7,4.56,
10, and 20.

technique is it possible to obtain data on the kinetics of the processes occurring

at the shock front during the times from 10-11 to 10-6 s. The examples of these
processes are the foregoing data on polymorphic transitions, fusion, excitation of
thermal electrons, and thermodynamic equilibration between the electrons and
the lattice phonons. The temperature measurement results made it possible to
specify the form and parameters of the equation of state of a material in a solid
or liquid phase.
However, it should be noted that the results not only answered a number of
questions, but also put forward many new questions which can be resolved only
 1 i. Temperature Measurement and Equation of State of Condensed Matter 379

through conduct of complex experiments under the conditions of dynamic load-

ing. It would be vel)' interesting to perform electric and magnetic measurements
(e.g., Hall effect) at the same time and under the same conditions as optical
measurements are made. Many new data could be obtained from the study of
reflection of laser radiation of various wavelengths from the shock front

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[47] P.w. Bridgman,Phys. Rev. 57, p. 237 (1940), andProc. Amer. Acad. Arts Sci. 78,
p. 1 (1945).
[48] E. Perez-Albuerne and H Drickamer, J. Chern. Phys. 43(4), p. 1381 (1965).
[49] M. Pagannone, and H Drickamer, J. Chem. Phys. 43, p. 2266 (1965).
[50] W.A. Bassett, T. Takahashi, H. Mao, and J.S. Weaver, J. Appl. Phys. 39(1),
pp. 319-325 (1968).
[51] B. Alder, in: Solids Under Pressure (eds. W. Paul and D.M. Warshauer) McGraw-
Hill, New York, (1963), p. 385.
[52] S. Clark,J. Chern. Phys. 31, p. 1526 (1959).
[53] C.w. Pistorius, J. Phys. Chern. Solids. 26, p. 1543 (1965).
[54] L.V. Al'tshuler,M.N. Pavlovsky, and G.V. Simakov Sov. Phys.--JETP 25(2),
pp. 260-265 (1967). [trans. from Zh. Eksp. Teor. Fiz. 52(2), pp. 40~08 (1967).]
[55] L. V. Al'tshuler and M.N. Pavlovsky, J. Appl. Mech Tech. Phys. 12(2), pp. 268-272
(1971). [trans. fromPrikl. Mekh. Tekh. Fiz. 12(2), pp. 110-114 (1971).]
[56] L. V. Al'tshuler, M.N. Pavlovsky, and V. V. Komissarov, J. Exp. Theo. Phys. 79(4),
616-621 (1994). [trans. from Zh. Eksp. Teor. Fiz. 106(10), pp. 1136-1145 (1994).]
[57] W. Drummond, J. Appl. Phys. 28, p. 998 (1957).
[58] AG. Ivanov and S.A. Novikov, Zh. Eksp. Teor. Fiz. 40(6), pp. 1880-1882 (1961).
[59] AG. Ivanov, S.A. Novikov, and Yu.A. Tarasov, Sav. Phys.-Solid State 4(1),
pp. 177-185 (1962). [trans. fromFiz. Tverd. Tela 4(1), pp. 249-260 (1962).]
[60] J.o. Erkman,J. Appl. Phys. 32, p. 939 (1961).
[61] P. Harris,J. Appl. Phys. 36, p. 739 (1965).
[62] R. Linde, W. Mum. andD. Doran,J. Appl. Phys. 37, p. 2527 (1966).
[63] T. Ahrens, J. Appl. Phys. 37, p. 2532 (1966).
[64] AG. Ivanov, B.N. Mineev, E.Z. Novitskii, V.A. Yanov, and I.G. Bezruk:ov, JETP
Lett. 2(8), pp223-224 (1965). [trans. from Pis 'ma Zh. Eksp. Teor. Fiz. 2, p. 353
(1965).]
[65] V.N. Mineev, Yu. N. tunyaev, AG. Ivanov, E.Z. Novitskii, and Yu V. Lisitsyn,
Sov. Phys.-JETP 26(4), pp. 728-731 (1968). [trans. from Zh. Eksp. Teor. Fiz.
53(4), p. 1242 (1967).]
[66] T. Ahrens, G. Lyzenga, and AC. Mitchell, in: High Pressure Research in
Geophysics 12 (ed. S. Akimoto), Manghnani Center for Academic Publication,
Japan, (1982), p. 579.
[67] K. Kondo and T. Ahrens, in: Physics and Chemistry o/Minerals 9, (1983), p. 173
[68] D. Schmitt, B. Svendsen, and T. Ahrens, in: Shock Waves in Condensed Matter
(ed. Y.M. Gupta), Plenum Press, New York, (1986), p. 286.
[69] 1M. Voskoboinikov, M.F. Gogulya, and Yu.A. Dolgoborodov, Sav Phys.-Dokl.
24(5), pp. 375-376 (1979). [trans. from Dokl. Akad. Nauk SSSR 246, pp. 579-582
(1979).]
[70] H.B. Radousky and M. Ross, Phys. Lett. A 129, p. 43 (1988).
382 V.D. Urlin

[71] S.B. Konner, AI. FWltikOV, YD. Urlin. and AN. Kolesnikova, Sov. Phys.-JETP
15(3), pp. 477-488 (1962). [trans. from Zh. Eksp. Teor. Fiz. 42(3), pp. 686-702
(1962).]
[72] RF. TfWlin. G.Y Simakov, YuN. Sutulov, AB. Medvedev, B. D. Rogozkin, and
Yu.E. Federov, Sov. Phys.-JETP 69(3), pp. 580-588 (1989). [trans. from Zh. Eksp.
Teor. Fiz. 96(3), pp. 1024-1038 (1989).]
[73] RF. TfWlin and G.V. Simakov, J. Exp. Theo. Phys. 76(6), pp. 1090-1094 (1993).
[trans. from Zh. Eksp. Teor. Fiz. 103(6), pp. 2180-2188 (1993).]
[74] RF. TfWlin. AB. Medvedev, AI. FWltikov, M.A. Podurets, G.Y. Simakov, and
AG. Sevastyanov, Sov. Phys.-JETP 68(2), pp. 356-361 (1989). [trans. from Zh.
Eksp. Teor. Fiz. 95(2), pp. 631-641 (1989).]
[75] RF. TfWlin. Phys.-Usp. 37(11), pp. 1123-1145 (1994). [trans. from Usp. Akad.
Nauk 166(11), pp. 1215-1237 (1994).]
 CHAPTER 12

Isentropic Compressibility and Equation

of State of Hydrogen up to 1 TPa
v. P. Kopysbev and V. D. Urlin

12.1. Introduction
Interest directed towards the equation of state of hydrogen and its isotopes
comes from the fact that it is the main constituent of stars and some large plan-
ets. It is also the simplest element in nature and this makes it the preferred ele-
ment in calculations of properties from first principles. Besides, at high densities
hydrogen is predicted to undergo transitions from the dielectric to the metallic
state and possibly to the superconducting state. Knowledge of the hydrogen
equation of state (EOS) is also important in solution of the problem of thermo-
nuclear reaction ignition. In the last 25 years great advances have been made in
the technology for obtaining high pressures in diamond anvil cells. In these
devices, hydrogen has been compressed to a density of p ~ 1 g/cm3 under iso-
thermal conditions.
At VNIIEF as far back as 1957 a group of investigators headed by Kormer
started to work on the development of methods for isentropic compression of
matter under dynamic conditions. The main content of this work is as follows
[1]. In the experiment, a steel shell with gaseous hydrogen in its internal cavity
is accelerated toward the center by a spherical or cylindrical explosive charge.
The trajectory of the shell up to the moment of stopping and subsequent onset of
its backward motion was fixed by a powerful gammagraphic facility with a
small exposure time, which was developed by Pavlovsky with coworkers [2].
Pressure was determined from a gas-dynamic calculation using the EOS of the
construction materials and various versions of the hydrogen EOS. Calculations
show that, after passage of the first relatively weak shock wave, further com-
pression of the hydrogen is practically isentropic. The measured results on hy-
drogen compressibility performed by using these methods were published in the
1970s. The maximum value of the density of compressed hydrogen achieved
was -2 g/cm3 at 1 TPa and this achievement remains unique up to the present
time. Moreover, precision calculations and analysis of experimental results have
shown the existence of an anomaly in the isentrope at p ~ 1-1.1 g/cm3 • This
V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII
© Springer Science+Business Media New York 2004
384 v.P. Kopyshev and V.D. Urlin

anomaly is identified with the transition of molecular hydrogen to the atomic

phase [1,3,4].
Investigations of isentropic compression of matter conducted using these
methods have continued to the present time. In particular, a series of special
cryogenic devices has been developed to allow study of the compressibility of
liquid inert gases: argon up to p::::J 10 g/cm3 [5,6] and xenon up to p::::J20 g/cm3
[7,8]. These investigations have also been performed with the objective of veri-
fying the proposed methods by conducting experiments on another class of ma-
terials.
The problem of calculating the hydrogen equation of state in its exact for-
mulation has not been solved up to the present moment Therefore, one is forced
to use physical models or formal interpolations. Below, we give two such semi-
empirical models and show how various experimental data are described within
their framework.

12.2. Experimental Determination of the Density of

Isentropically-Compressed Hydrogen
To perform compression experiments on hydrogen, a special device was devel-
oped by Grigoriev et al. [1]. The basic part of this device was a sufficiently
strong steel shell intended for hydrogen pressures above 160 MPa. The inner
surface of the shell was covered with a special coating to prevent diffusion of
the hydrogen into the iron. Its outer surface was in contact with the shell of an
RDX-based high explosive. The outer radius of the entire assembly was 108 mm
and the radius of the inner cavity containing the hydrogen varied from 51 to 66
mm. After initiating the explosive on the outer surface of the device, a shock
wave passed through the shell and, upon reaching the shell-gas boundary, it
continued its way into the hydrogen in the form of a relatively weak shock
wave. The main hydrogen compression occurred during the subsequent rather
slow convergence of the shell towards the center. This process was named
quasi-isentropic compression of matter. The compressibility of the hydrogen
was determined over a sufficiently wide density range by varying the charge
parameters and the initial gas pressure.
A total of seven series of experiments has been conducted. Using the gase-
ous hydrogen equation of state of Michels et al. [9], the initial density Po can be
determined from the measured pressure, Po, and temperature, To. The mass of
the hydrogen can then be calculated from the inner dimension of the cavity.
Finally, the average density of the hydrogen at its maximum compression is
calculated from the measured shell radius at the moment it stops. The starting
and calculated data are given in Table 12.l.
 12. Isentropic Compressibility and Equation of State of Hydrogen 385

Table 12.1. Quasi-isentropic compression of hydrogen.

Stating parameters of Hydrogen Parameters at the moment of
at To= 323K maximum compression
Po,MPa Po, glcm3 SIR Rmin,mm P, glcm3 P,GPa T,K
75 0.0390 9.4 29.0-30.4 0.42-0.48 38 1800
60 0.0635 8.6 22.8-23.6 0.64-0.70 llO 1000
100 0.0470 9.l 19.1-20.3 0.90-1.06 320 2800
75 0.0390 9.4 17.0-18.0 1.04-1.26 340 3300
50 0.0292 9.8 14.5-15.5 1.26-1.54 490 3700
25 0.0164 10.5 1l.2-12.0 1.54-1.90 870 5200
15 0.0104 11.0 9.1-1O.l 1.70-2.30 l300 7000

12.3. Equation of State of Solid and Liquid

Molecular Hydrogen
This section describes the equation of state in its classic form, which has been
proven to be provide a good description of ionic crystals, metals, and inert gases
in solid and liquid phases. The free energy of a crystalline solid can be written as

Fsolid = Ex(p)+1.l25REHRT[31n(l-e- 8IT )-D(E>/T)]+Ji;.ot +Fvib +Fe,

(12.1)
where T and p are the temperature and density, R is the gas constant, E>(p) is the
Debye temperature, and

3
D(x)=- - IX
x 3 dx
-
x 3
o eX -l
is the Debye function.
The first term in Eq. 12.1 expresses the intermolecular potential in the crys-
tal, the second and third terms describe zero-point and thermal oscillations of the
crystal, the next two terms describe rotation and vibration of atoms in a mole-
cule, and the last term represents the electronic contribution to the free energy.
For practical purposes, the following dependencies turned out to be the most
validated:
3
Ex=ao+-
Pk
I4 1
-:-ai«(,)iI3-1)
i=l I
(12.2)

(12.3)

where Px = p 2 dEx / dp, C~ = dPx / dp, and (') = p/pk.

386 V.P. Kopyshev and yn. Uriin

In these equations the four coefficients 0i are empirical parameters. Three of

them are determined from knowledge of the density of the solid phase at zero
temperature, the melting temperature at atmospheric pressure, and the value of
the binding energy. The fourth of these coefficients is determined from knowl-
edge of one experimental point on the isothenn. The value of eo is determined
from the experimental value of the Debye temperature. For hydrogen and deute-
rium the values n = 2 and n = l.5, respectively, have been taken.
The form of the equation of state of the liquid phase and the method for de-
termining its parameters were developed in [10]. Their use was successfully
demonstrated by the example of ionic crystals and metals in other chapters of
this book. The equation of state of the liquid phase near the melting curve is
quite close to the equation of state of the crystalline phase. The free energy of
the liquid can be written in the form
Fliquid = Fsolid - 3R T In a(p, T) . (12.4)

The function a(p, T) satisfies the two limiting conditions:

1. progressively transforms to the free energy of an ideal gas at high
Fiiquid
temperatures; and
2. The jumps of the entropy 6S=Sliquid-Ssolid and the specific volume
6V= Viiquir Vso1id at the melting point at atmospheric pressure agree with
the preset values. To satisfy these conditions, the function a(p, T) is
taken in the form

a=(l+Z)-05 exP[b(cr,'t)- f(cr)~ J. (12.5)

where z = £zRT /(C~ -2nPx /3p), £z is a constant, and To is the melt-

ing temperature at P = o.
These limiting conditions do not impose constraints on the functions f( cr) and
b(cr,'t). For definiteness and convenience of calculations they are taken in the
form

where cr = p/po, Po is the liquid-phase density at To, 't = T/To, and Co through C4
and b o through b3 are empirical constants. For the liquid atomic phase,
cr =p / Ptr, "t =T / Ttr, where Ptr and Ttr are the parameters at the triple point
where the pressure isPtr .The numerical values of these constants are determined
from the values of thermodynamic parameters on the melting curve at normal
pressure and.at one or two points at a high pressure. The values of b), b 2 , and b 3
 12. Isentropic Compressibility and Equation of State of Hydrogen 387

detennine the pressure dependence of the melting heat along the melting curve.
For hydrogen, values of hI and h3 were found from the condition of description
of the liquid hydrogen heat capacity value at the melting point at atmospheric
pressure. It turned out to be possible to set h2 = O. It is also to be noted that the
function!(cr) in Eq. 12.4 effectively takes into account the appearance of holes
in the liquid phase structure and the change in the energy of elastic interaction of
atoms that is connected with it.
Molecules of hydrogen isotopes have a value of the rotational quantum that
is noticeably higher than the normal melting temperature: 8 roto = 87.6K for H2
and 8 ooto = 43.8K for D2 [ll]. Therefore, in describing the melting curve this
component should be taken into account in the equation of state. In the concrete
calculations of this work it takes the form

Frot =-RTln(l+ I:l(4i+1)Xi(2i+1)),

where X =exp(-28oot IT) and 800t =8 roto (p/pk)G r

The value of the vibrational quantum in the hydrogen molecule is apprecia-
bly higher than that of the rotational quantum. The vibrational component is
defined as
Fvib = RTln[l-exp(-evib IT)],

where evib = (p/pk)G • . For H2 we have evibo=6331K and for D2 we have

evibo = 4483K [ll].
One should take the electronic contribution to the free energy into account at
temperatures above leV in condensed hydrogen. For dielectrics, this component
is of the form

4kT r.::-:::-(21tm*kT)J.5
Fe =---Vnpnn 2
W)
exp ( - - - , (12.6)
P h 2kT

in accord with the band theory (see, e.g., [12]). In this equation m* is the geo-
metric average of effective masses of an electron and a hole, np and nn are the
orbital degeneracies in bands, W = Wo In(Pm I p), m* = mo 8 213 - G., Pm is the
density at which the band gap is closing, and Ge is an empirical constant that is
evaluated to establish the best description of the Hugoniot in the region of high
temperatures. At present, the choice of the value Pm remains a problem. The
value of Wo is determined by the value of W at normal density. In the calcula-
tions of the present work we take Pm = l.538 g/cm3 for H2 and Pm = 3.16 g/cm3
for D 2, and, for both isotopes, we take Wo = 5.2 eVand Go = l.
At high temperatures one should also take into account dissociation of mole-
cules located at the nodes of the crystal lattice of molecular hydrogen to atoms.
The molecular dissociation energy is 4.48 eV.
388 V.P. Kopyshev and VD. Urlin

The difference between experimental thennodynamic values for hydrogen

and deuterium is small, and this difference becomes smaller with increased
pressure. Nevertheless, this difference exists at low pressure. Therefore, pa-
rameters of the solid and liquid deuterium equation of state have been found that
give a more exact description of its thermodynamic properties. The numerical
values of the equation of state parameters for two isotopes of hydrogen, H and
D, are given in Table 12.2.

12.4. Equation of State of Molecular and Atomic Hydrogen

in Covolume Form
References [9,13-15] report experimental data on the equation of state for the
liquid phase of hydrogen in the range of temperatures from 100 to 430K and
pressures up to 2 GPa. In [16] a rather simple fonn of the EOS is given con
taining only one undefined function Vc of one argument, the pressure P. It turned

Table 12.2. EOS parameters of hydrogen and deuterium.

Molecular phase Atomic phase
H2 D2 Hatom Datom
Pk, glcm3 0.1167 0.2536 Ao kJ/g 1298 649
n 2 l.5 Al kJ/g 1486.5 743.25
EJo,Ks/km 68.12 87.66 A2 kJ/g -2535 -1267.5
ao, kJ/g 0 0 A3 kJ/g -40 -20
a}, GPa -0.915 -0.359 A4 kJ/g -90.8 -45.4
a2,GPa 7.746 3.894 As kJ/g -20.2 -10.1
a3, GPa -16.158 -9.355 A6 kJ/g -10.9 -5.45
a4,GPa 11.312 5.7 BI kJ/g 49.2 24.6
as,GPa -l.715 0 B2 kJ/g -50.8 -25.4
To,K 14 18.6 B3 kJ/g -16.9 -8.45
PL, glcm3 0.0773 0.1731 B4 kJ/g 37 17.25
P, GPa 0.0001 0.0001 TIr K 2984 4576
Rz 3 6 PIr glcm3 0.96045 1.79301
bo 0.5032 0.6331 PIr GPa 302.1 3086
bl 0.1 0.1 Rz 528.9 159.6
b3 -2.0 -2.0 blr 0.4776 0.5794
CI -69.9 -17.2 bal 0.5 0.63
C2 51.7 6.3 ba3 -2 -2
C3 -16.7 -3.7 Cal -0.23 -11.01
C4 5 5 Co2 1.93 7.47
Co 0.4793 0.5336 Cao 0.8518 1.0442
 12. Isentropic Compressibility and Equation of State of Hydrogen 389

out that all the experimental data mentioned above can be described with rather
high accuracy by an EOS of this form if the function Vc(P) is properly chosen.
In this EOS the pressure, P, and temperature, T, are independent variables and
the specific volume, V(T, P), is a dependent variable.
References [9,13] give experimental points. In [14] the direct experimental
data for V(T, P) are not given, but they are approximated by an equation con-
taining 9 constants. According to [14], this equation is applied in the range of
temperatures from 75 to 410K and pressures from 0.2 to 2 GPa The melting
curve passes within this T-P rectangle. This formula can be applied only in the
liquid phase region. The error resulting from use of the function V(T, P) is esti-
mated to be 0.4%. The data of [9,13,14] agree well with each other. The inter-
polation formula for V(T, P) from [14] describes the experimental data of all
three works with an error not exceeding 0.4%. However, this equation cannot be
extrapolated to small pressures because V at P = 0 tends to infinity as liP.
Moreover, the greatest error in the description of data from [9] is observed in
just this region of small P. Therefore, it is desirable to find another interpolation
for V(T, P) that is devoid of these drawbacks.
Consider the equation for V(T, P) arising from the "compressed covolume
model". This model was first formulated in [16] in 1971 before the experimental
data of [13,14] were available. It was further developed in [17,18]. The starting
point of this model is the van der Waals equation of state, in which the term
taking into account intermolecular attraction is omitted:

P(V,T)=~. (12.7)
V-Vc
In this equation R is the universal gas constant and Vc is a constant called the
covolume. For independent variables T and P, Eq. 12.7 can be rewritten in the
form
RT
V(T,P)=Vc +-. (12.8)
P
Reference [16] gives arguments for this generalization: If there is no attraction
between molecules, then Vc should be considered as a function of one (and only
one) argument, P. The model generalizing Eq. 12.8 is
RT
V(T,P)=Vc(P)+-, (12.9)
P
and is called the "model of compressed covolume" (MCC).
On the basis of the experimental data in the region of P from 0.1 to 0.3 GPa
the covolume can be written as
Vc(P) =A+BP, (12.10)
with the constants A = 16.69426 cm3/mole andB=-O.6038631 cm3/(mole kbar).
390 V.P. Kopyshev and V.D. Urlin

In the region of pressures P<O.1 GPa, the second tenn in Eq. 12.9 is much
larger than the :first one so even a sizeable error in Vc has no strong effect on the
value V(T, p). The maximum error of Vc is 0.140/0. This is better than for the
extmpolated equation of state from [14], where the maximum error reaches
+0.4%. The error in the experimental description of P from 0.1 to .0.3 GPa does
not exceed 0.002%.
Thus, there has been found a new fonn of the equation of state in the pres-
sure range up to 0.3 GPa, which is simpler than that from [14] (two fitting con-
stants A and B instead of nine in [14]) and gives a better description of the
experimental data for low pressures (0-0.1 GPa) and makes possible extrapola-
tiontoP=O.
Naturally, the experimental data for pressures from 0.3 to 2 GPa should be
processed in the same manner. We will assume that the experimental data in this
region are exactly described by the fonnula for V(T, p) from [14]. We will de-
termine the covolume from the isothenn at T= To = 273 K:
RTo
Vc(P) =V(To,P)-p' (12.11)

The error in the description of the EOS from [14] using the covolume EOS is
0.005%, which is much less than the given experimental error (0.4%). Equation
12.11 is reduced to
(12.12)

where x = p- J/3 •
In Eq. 12.12, the coefficients a, b, and c are 36.25736, -23.01750, and
2.426636, respectively; P is in kbar and V is in cm3/mole. Equation 12.12 gradu-
ally goes to Eq. 12.10 at P=0.3 GPa Thus, there are only 3 constants in the
description of the experiment by Eq. 12.12 instead of 9 constants in the equation
from [14].
In generalizing the thermal EOS, we will write the Gibbs thennodynamic
potential, G, as
G(T, P) =Gc(P) + RTln(P I Po) - T Fo(T) , (12.13)

J:
where

Gc(P) = Vc(P)dP.

In this equation Vc is the covolume and Po is a constant equal to 1 atm (l.01325

bar). Note that at T = const and P --+ 0 the state of the material should be that of
an ideal gas. At very small values of P the :first tenn on the right-hand side of
Eq. 12.13 is small, and the second and the third terms correspond to the Gibbs
 12. Isentropic Compressibility and Equation of State of Hydrogen 391

potential for an ideal gas. In this case the function Fo(T) is called the Gibbs
reduced energy. It is tabulated in handbooks on thermodynamic properties of
individual materials. Thus, the Gibbs potential has been completely determined.
Any thermodynamic value can be derived from it
A characteristic feature of the MCC represented by Eq. 12.13 is that the iso-
baric thermal capacity, Cp = T(8S/8T)p, depends only on temperature, and this
dependence is the same as that for an ideal gas. In the range of temperatures
considered, rotations of molecules are nearly completely excited and, in con-
trast, vibrations of atoms in them are nearly completely "frozen" so Cp is nearly
equal to the constant 3.5R.
In thermodynamics there exists the identity

Cp(T,P)=Cp(T,Po)-T i (82V)
p

Po
-2
8T p
dP.

In [14] it is assumed thatPo= 0.2 GPa. In MCC the second derivative of V with
respect to temperature is equal to zero so Cp is independent of the pressure. No
experimental data on Cp are available in the pressure range mentioned. Refer-
ence [14] also gives measurements of the sound speed, U, which is connected
with Cpo Now let us consider the data obtained in this work. In thermodynamics
there is an identity

v_
U
M[ (8V)
8P
T(8V) 2]
Cp 8T p ,
T
(12.14)

where U is the sound speed andM= 2.016 is the hydrogen molecular mass. The
value of u is not very sensitive to Cp variations because the second term in
brackets in Eq. 12.14 is small if compared to the first one. In [14] V and U are
measured simultaneously, but their experimental values are not presented. In this
work it is stated that values of u calculated using Eq. 12.14, where Cp at P = Po
has been found by a method that is discussed, coincide with the experimental
values within the limits of their accuracy. To be more exact, 9 constants of the
V(T, P) function were selected by the method of least squares from the condi-
tion of optimal description of all experimental data for both Vand u. In the fol-
lowing discussion, these values of u are called experimental (from 0.2 to 2 GPa
and from 100 to 300K).
Now let us see how the MCC describes the experimental data for u. The
sound speed u will be also calculated using Eq. 12.14, but with values of the
thermal capacity, Cp , that depend only on T. Above, we have assumed
Cp = 3.5R. Deviation of the experimental sound speed from the value calculated
using the MCC with this value of thermal capacity is within the range -1 to
+0.5 %. Thus, the model of compressed covolume gives a good description of
the experimental data on the sound speed.
392 v.P. Kopyshev and V.D. Urlin

Above, only the liquid phase of hydrogen was considered. We limit our-
selves to an approximation in which the liquid and solid phases do not differ.
Then the covolume at T= 0 is taken to be the zero isothenn Vx(P). We will
denote the inverse function by Px(V), which is usually called the "cold pres-
sure". The experimental isothenn of solid hydrogen at T= 4.2K differs from the
covolume given by Eq. 12.12 by only a few percent.
Note that, on the basis of optimal description of experiments on isentropic
compression of hydrogen up to hundreds of GPa, the equation
Px(p) = 289 p3 , (12.15)

has been offered in [17) for the "cold pressure" of the molecular phase. In this
equation P is given in GPa and density is in glcm3• After the above refinement
of the covolume for P < 2 GPa we consider that Eq. 12.15 can be applied only
for P > 40 GPa. In the interval from 2 to 40 GPa a third-order polynomial is used
for the function Vc(P). The four coefficients in this equation are detennined
from the condition of smooth joining with the functions for P < 2 GPa and
P> 40 GPa. The accepted dependence of Vc on 10gP is given in Fig. 12.1 (upper
curve).
The authors of [17,18) give the physics underlying the foregoing general
features and offer far-reaching generalizations assuming additivity of the co-
volume. In particular, the Gibbs potential for a mixture of hydrogen molecules
and atoms takes the fonn
G(P, T, a) =Gc (P,a) + Gid (P, T, a),

200

150

(3 100
0.... 4

50

G+-~~~~~~--'-~~--~~~--~~~
0.1 0.2 0.3 0.4 . 0.5 0.6 0.7 0.8
p, glcm3

Figure 12.1. Hydrogen compressibility at pressures up to 200 GPa. 1: 300 K isotherm, 2:

dashed lines represent boundaries of the melting curve. The isentropes are 3: SIR = 8.5
and 4: SIR = 10.8. 5: Hugoniot, • and *: points of experimental isentrope.
 12. Isentropic Compressibility and Equation of State of Hydrogen 393

where ex. is the preset concentration of atoms (changes from 0 to 1), Gid is the
Gibbs potential of an ideal gas mixture of molecules and atoms, and Gc is the
integral of the sum of covolumes of molecules and atoms. The equilibrium con-
centration is found from the condition that the Gibbs potential be a minimum,
which leads to the equation

_1 = 1+4cr(T)(TI)4oS ~exp[Ga(P)-Gm(P)],
ex. 2 T PI RT

where cr (T) is the vibrational statistical sum of the molecule, Gm (P) and Ga (P)
are covolume components of the thermodynamic potential for molecules and
atoms, TI = 120.7 K, and PI = 0.842 GPa.
Thus, presetting of covolumes of molecules and atoms completely deter-
mines the equation of state of their mixture.

12.5. Zero-Temperature Isotherm of Atomic Hydrogen

The atomic hydrogen equations of state in their classic form for the solid and
liquid phases are analogous to Eqs. 12.1 and 12.4 but without vibrational and
rotational components. At high temperatures one should take into account the
thermal contribution of electrons as in metals. However, in the region of rela-
tively low temperatures, which is of interest to us, the main contribution is made
by elastic interaction of atoms.
It is evident that atomic hydrogen surely exists in the condensed state at
pressures above 200 GPa. In this region of pressures experimental data are prac-
tically absent and numerous calculational and theoretical data differ noticeably
from each other. First of all, we will make the simplest estimates of the curve of
elastic interaction or the zero isotherm. Theoretical asymptotics at high densities
are obtained assuming that the electrons are uniformly distributed in space (in
further considerations this assumption is retained):
A B
Ex(r) =---+1.1645, (12.16)
r2 r
where Ex is the internal energy in Rydberg/atom and r is the radius of the
Wigner-Seitz cell in atomic units. The first term in Eq. 12.16 is the kinetic
energy of degenerate electrons, and A = 2.210. The second term includes the
contribution of the energy of exchange interaction of electrons (Bex = 0.916) and
the Madelung electrostatic energy (Be. ~ 1.8) depending weakly on the type of
cubic lattice. The value of the latter contribution can be obtained as follows. We
will assume that hydrogen consists of independent spherical cells with a uni-
formly distributed negative charge (background) and a proton in the center.
Then the electrostatic energy of the cell exactly equals (Bep + Bee)/r, where
Bep = 3 is the contribution of the interaction of the proton with the background,
394 v.P. Kopyshev and V.D. UrIin

and Boa = -1.2 is the contribution of interaction of the background with itself so
that Be. = Bep + Bee = 1.8, and, in Eq. 12.16, B = 2.716. Finally, in Eq. 12.16, the
constant 1.1645 (the sum of the ionization potential of an atom and half the
dissociation energy of a molecule) is introduced for matching with the onset of
the energy of the molecular phase.
Note that, in [19], one-electron Bloch wave functions were modulated by the
periodic function that is the sum of real exponents. The exponential index was
found by the method of variations. After complex calculations, the result at
Mbar pressures was practically the same as the asymptotic result given by
Eq. 12.16. The same is true of the more complex calculations in [20]. In [19] the
following drawback of this approach is noted: "The obtained formulas in the
case V ~ 00 , at first glance, go into the energy of isolated atom. In reality, the
energy tends to a higher limit. The cause of this is that such calculation does not
take into account correlation of positions of electrons, thus leading to the possi-
bility of interaction of two electrons within one atom even if atoms are infmitely
far from each other. As a result, there appears additional positive energy. The
fact that the minimum of the obtained curve is above the ionization potential can
also be related to this circumstance."
We will make an attempt to correct the foregoing drawback. We will try to
assess the zero isotherm from the point of view of small densities. We assume
that each electron is strongly bound to its nucleus and atoms are spherically
symmetric. Then, in each atom, the electron interacts only with its proton. Again
we arrive at an equation of the form ofEq. 12.20, but now B =Bep = 3. For ease
of calculation we assume B = 2.JA = 2.973 and now E = -1 at P = 0, and the
virial theorem is exactly fulfilled: 3PV = 2(A/r) + [-2 (.JA)/r] . Finally, we
take
A .JA
Ex(r)=--2-+1.1645. (12.17)
r2 r

The covolume of the atomic phase according to Eq. 12.17 is shown in Fig. 12.2
(lower curve). Calculations of hydrogen isentropic compression with this zero
isotherm for the atomic phase (and according to Eq. 12.15 for the molecular
phase) agree with the experimental results.
A meticulous and more complicated calculational-theoretical investigation
of the properties of atomic hydrogen has been performed by Kagan with co-
workers [20]. Here we give equations for the dependence of the energy of elastic
interaction of atoms and the energy of zero-point oscillations on the density with
parameters calculated in [20]:
Ex(p) =Ao+AIX2 +A2X+A3X- 1+A4X-2 +(A5 +A6x-I)lnp, (12.18)

(12.19)
 12. Isentropic Compressibility and Equation ofSta1e of Hydrogen 395

where x 3 = p (glcm1 and Ezp is the zero point oscillation energy. Numerical
values of the parameters A and B are given in Table 12.2. The values of these
parameters in units per mole are taken to be equal for hydrogen isotopes. The ab-
solute value of the parameter As has been increased twofold if compared to the
value calculated in [20].
The approximation of the density dependence of the energy of elastic inter-
action of atoms taken by the American investigators in [21] is as follows.
Ex(P) =Ex(P) =Ao+AlX2 +A2X+A3X-1+A4X-2 + [As/(A6+X-1)]. (12.20)

Numerical values of parameters Al and A2 in Eqs. 12.18 and 12.20 coincide.

Values of the elastic pressure corresponding to Eqs 12.18 and 12.20 are also
practically coincident.
It is interesting to note that when we insert E,.(p) from Eq. 12.18 into
Eq. 12.3, one can see that it coincides with the dependence E>(p) in Eq. 12.19
with a 5 % accuracy if we take n = 1.2.

1200

1000

~ 800
~
~ 600

400

200

0.5 1.0 1.5 2.0

p,g/cm 3

Figure 12.2. Hydrogen compressibility at pressures up to 1000 GPa. 1: Px of the atomic

phase, 2: OK isothenn of the molecular phase, 3: OK isothenn of the atomic phase, 4:
isentrope of the molecular phase,S: isentrope of the atomic phase, .: experimental points
of isentrope, 0: experimental points of 0 K isothenn.
396 V.P. Kopyshev and Vn. Urlin

12.6. Comparison of Calculated Thermodynamic Values

with Experiment
In Figs. 12.1, 12.2, and 12.3 a comparison with the experimental data is given
for hydrogen and in Figs. 12.4 and 12.5 for deuterium. Figure 12.1 gives the
calculated isotherm, Hugoniot, and melting curve for hydrogen calculated with
the use of the solid- and liquid-phase equations of state, Eqs. 12.1 and 12.4.
Experimental data of [22-25] are also shown on this figure, which shows that
the calculated isotherm gives a quite satisfactory description of the experiment
up to a density of 0.8 g/cm3.
A quite satisfactory agreement with the experiment has been also obtained
for other thermodynamic quantities such as the isobar at P = 0 and the speed of
sound calculated using the solid phase EOS. This coincidence is not a result of
using additional parameters in the EOS and confirms that its form has been
chosen correctly.
In the liquid phase EOS, the constant" z in Eq. 12.5 was selected by taking
into account the position of the Hugoniot and the experimental value of the
sound speed in liquid hydrogen at its freezing point at P = O. The melting curve
as a thermodynamic boundary between the liquid and solid is determined by the
form and values of parameters of the function f( cr) and, to a certain degree, of the
function b(cr, B) in Eq. 12.5. Therefore, their proper selection giving description
of the slope and curvature of the experimental melting curve permits obtaining a

12"r---------------------------~~__.

10

200 400 600 800 1000 1200

P,GPa
Figure 12.3. Phase diagram of molecular and atomic hydrogen. Isentropes: 1:
SIR = 10.8,2: SIR = 10.2, 3: SIR = 9.6, 4: SIR = 9.2, 5: SIR = 8.9. 6: Hugoniot. Solid lines
designate the melting curves of molecular and atomic hydrogen and the boundary of the
calculated phase transition of molecular to atomic phase.
 12. Isentropic Compressibility and Equation of State of Hydrogen 397

,
t
17
S I
r· · ~' · -;~

p, glem 3

Figure 12.4. Deuterium compressibility. 1: liquid deuterium Hugoniot, 2: double-com-

pression Hugoniot, 3: computed 300K isotherm, 4: molecular deuterium melting curve,
5: atomic deuterium melting curve.

7
6
4
5
~ 4
f..,,"

2
5

100 200 300 400 500 600

P,GPa

Figure. 12.5. Molecular and atomic deuterium phase diagram. 1: liquid deuterium
Hugoniot, 2: second shock Hugoniot, 3: molecular deuterium melting curve, 4: atomic
deuterium melting curve, and 5: the calculated phase transition of molecular to atomic
deuterium. a, b, and c are experimental temperatures of shocked deuterium.
398 V.P. Kopyshev and V.D. Urlin

rather accurate liquid-phase EOS near the melting curve. It is to be noted that
the values of the parameters can be varied only within a very limited range.
During writing of [3,4J the experimental melting curve was known up to
P = 1 GPa. That is why its eXtrapolation to pressures of -300 GPa using the
liquid phase EOS given in these works is not reasonable: It has a very large
curvature. Presently, the melting curve of hydrogen and deuterium has been
measured up to P= 9 GPa [26J. With the new experimental data taken into ac-
count, the liquid phase EOS parameters of hydrogen have been determined
anew. Their values are listed in Table 12.2. Table 12.3 gives the calculated
thermodynamic parameters of hydrogen along the melting curve. The hydrogen
phase diagram calculated using the new solid and liquid phase EOSs is given in
Fig. 12.3.
Figures 12.1 and 12.3 give the hydrogen Hugoniot centered on the state at
the normal boiling point. The experimental data obtained by American investi-

Table 12.l. Melting-curve parameters of molecular and atomic hydrogen.

T, P, Psolid, Pliquid, MIR L\VIV. z
K GPa g/cm1 g/cm1 %
14 0.0001 0.0868 0.0773 1.147 12.33 0.145
20 0.026 0.0941 0.0855 1.299 10.06 0.118
50 0.241 0.1215 0.1125 1.428 7.97 0.108
100 0.816 0.1546 0.1451 1.417 6.49 0.109
150 1.63 0.1823 0.1725 1.402 5.68 0.110
200 2.66 0.2073 0.1971 1.386 5.17 0.110
300 5.38 0.2533 0.2423 1.360 4.53 0.110
400 8.94 0.2956 0.2839 1.344 4.13 0.110
500 13.31 0.3356 0.3231 1.334 3.87 0.110
700 24.45 0.4108 0.3%8 1.322 3.53 0.109
1000 46.9 0.5156 0.4993 1.311 3.25 0.109
1500 98.3 0.6755 0.6556 1.298 3.02 0.110
2000 166.0 0.8239 0.8004 1.288 2.93 0.112
2500 247.6 0.9628 0.9358 1.279 2.88 0.114
2913 321.0 1.0673 1.0373 1.269 2.88 0.119
3200 323 1.1646 1.0312 0.189 12.9 0.129
3700 335 1.1628 1.0334 0.445 12.5 0.149
4000 347 1.1678 1.0404 0.547 12.3 0.160
5000 402 1.2057 1.0833 0.736 11.3 0.189
6000 475 1.2648 1.1454 0.813 10.4 0.212
8000 667 1.4192 1.3014 0.857 9.1 0.242
10000 917 1.6033 1.4831 0.856 7.4 0.274
12000 1226 1.8069 1.6818 0.844 6.7 0.288
 12. Isentropic Compressibility and Equation of State of Hydrogen 399

gators [21,27,28] are also given. Coincidence of the calculated pressure and
density of shock-compressed hydrogen with the experiment was expected be-
cause these data were taken into account when selecting the EOS pamme-
tersGv =0.2 and Gr =0.2. Good coincidence of the calculated and experimental
temperature of shock-compressed hydrogen is an independent confinnation of
the correct choice of the EOS.
Figures 12.1 and 12.2 give density and pressure corresponding to the hydro-
gen state at the moment the shell compressing the gas stops. The calculated
isentropes are also given on these figures. The position of the three experimental
points in the region of pressures of 300-400 GPa is of essential importance. The
lower point at a density of ~ 1 g/cm3 is well described by the accepted EOS. The
other two points are abruptly displaced towards higher densities. Such anoma-
lous behavior can be explained (if you are sure of the correctness of the experi-
ment) only by a phase transition with a large density jump. Calculations show
that this transition cannot be freezing of molecular hydrogen under isentropic
compression because the density jump during this process is very small (see
Table 12.3). Therefore, it is identified in [1,3,4] with the transition of molecular
hydrogen to the atomic phase.
From analysis of the phase diagram in Fig. 12.3 it follows that the melting
temperature of molecular hydrogen at P = 300 GPa should not be below 2700K
if the third experimental point is considered to refer to the molecular phase. But
the fourth point lies in the region where the molecular and atomic phases co-
exist. Therefore, it is reasonable to suppose that the triple point is in the region
ofP> 300 GPaandT>3000K.
The equilibrium curve between the molecular and atomic phase at low tem-
peratures is defined principally by the EOS of the solid atomic phase. Descrip-
tion of the experimental value of pressure at the triple point required selection of
the value of coefficient Ao in Eq. 12.18. The zero-point energy or the value of
the Debye temperature have a great influence on the position and type of the
equilibrium curve below the triple point.
The computational-theoretical analysis of hydrogen properties has shown
that the forms of the equation of state of the material in the solid and liquid state
and the methods for detennining its parameters that have been developed to
describe the properties of metals and ionic crystals and illustrated in other chap-
ters of this book can be applied for molecular crystals as well. This indicates that
such an equation of state reflects the fundamental nature of a solid and liquid
material in a sufficiently wide range of density and temperature variation The
physically substantiated equation of state permitted analyzing the available ex-
perimental data more exactly to find possible anomalies.
400 V.P. Kopyshev and V.D. Urlin

References
[1] F. V. Grigoriev, S.B. Konner, O.L. Mikhailova, AP Tolochko, and V.D. Urlin,
JETP Lett. 16(5), pp. 201-204 (1972). [trans. fromPis'ma Zh. Eksp. Teor. Fiz.
16(5), pp. 286-290 (1972).]
[2] AI. Pavlovsky, G.D. Kuleshov, G.v. Sklizkov, Yu.A. Zysin, and AI. Gerasimov,
Sov. Phys.-Dokl. (Physics) 10(1), pp. 30-32 (1965). [trans. from Dokl. Akad. Nauk
SSSR 160(1), pp. 68-71 (1965).]
[3] F.V. Grigoriev, S.B. Konner, O.L. Mikhailova, AP. Tolochko, and V.D. Urlin,
Sov. Phys.-JETP 42(2), pp. 378-381 (1976). [trans. from Zh. Eksp. Teor. Fiz.
69(8), pp. 743-749 (1975).]
[4] F.V. Grigoriev, S.B. Konner, 0.1. Mikhailova, AP. Tolochko, and V.D. Urlin,
Sov. Phys.-JETP 48(5), pp. 847-852 (1978). [trans. from Zh. Eksp. Teor. Fiz.
75(11), pp. 1683-1693 (1978).]
[5] I.A Adamskaya, F. V. Grigoriev, O.L. Mikhailova, M.A. Mochalov, AI. Sokolova,
and V.D. Urlin, Sov. Phys.-JETP 66(2), pp. 366-368 (1987). [trans. from Zh. Eksp.
Teor. Fiz. 93(8), pp. 647-651 (1987).]
[6] V.D. Urlin, MA MochaIov, O.L. Mikhailova, J. Exp. Theo. Phys. 84(6),
pp. 1145-1148 (1997). [trans. from Zh. Eksp. Teor. Fiz. 111(6), pp. 2099-2105,
(1997).]
[7] V.D. Urlin, MA MochaIov, and O.L. Mikhailova, High Pressure Research 8,
pp. 595-605, (1992).
[8] V.D. Urlin, MA MochaIov, and O.L. Mikhailova, Zh. Eksp. Teor. Fiz. 38(1),
(2000).
[9] A Michels, W. DeGraaff, T. Wassenaar, et aI.,Physica 25(1), pp. 25-42 (1959).
[10] V.D. Urlin, Sov. Phys-JETP 22(2), pp. 341-346 (1966). [trans. from Zh. Eksp.
Teor. Fiz. 49(2), pp. 485-493 (1965).]
[11 ] V.P. Glushko (ed.), Thermodynamic Properties ofIndividual Substances;Nauka,
Moscow, (1978-1982).
[12] AI. Ansel'm, Introduction to Semiconductor Theory, FizMatGiz, Mosccow (1962).
[13] D.S. Tziklis, V. Ya Maslennikova, et aI., Dokl.-Phys. Chern. Section 220(6), p. 189
(1975). [trans. from Dokl. Akad. NaukSSSR220(6), pp. 1384-1386 (1975).]
[14] R. Mills, D. Liebenberg, J. Bronson, and L. Schmidt, J. Chern. Phys. 66(7),
pp. 3076-3084 (1977).
[15] D. Liebenberg, R. Mills, and J. Bronson, Phys. Rev. B 18(8), pp. 4526-4532
(1978).
[16] v.P. Kopyshev, J. Appl. Mech Tech. Phys. 12(1), pp. 103-107 (1971). [trans. from
Zh. Prikl. Mekh. Tekh. Fiz. 12(1), pp. 119-122 (1971).]
[17] v.P. Kopyshev and V. V. KhrustaIev, Zh. Prikl. Mekh. Tekh. Fiz. 1, pp. 122-128
(1971).
[18] V.P.Kopyshev and AB. Medvedev, Sov. Tech. Rev. B. Therm. Phys. 5, pp. 37-93
(1993).
[19] AA Abrikosov,Astronomical J. 31(2), pp. 112-123 (1954).
[20] Yu.M Kagan, V. V. Pushkarev and A Kholas, Sov. Phys.-JETP 46(3), pp. 511-
522 (1977). [trans. from Zh. Eksp. Teor. Fiz. 73(3), pp. 967-987 (1977).]
 12. Isentropic Compressibility and Equation of State of Hydrogen 401

[21] N.C. Holmes, M. Ross and W. Nellis,Phys. Rev. B 52, p. 15835 (1995).
[22] M.S. Anderson and C.A. Swenson,Phys. Rev. B 10(12), pp. 5184-5191 (1974).
[23] H. Shimizu, E. Brody, H. Mao, and P. Bell,Phys. Rev. Lett. 47(2), pp. 128-131
(1981 ).
[24] H. Mao and R. Hemley, Rev. Mod. Phys. 66(2), pp. 671-692 (1994).
[25] P. Loubeyre, R. LeToullec et aI., Lett. Nature 383, pp. 702-704 (1996).
[26] V. Diatschenko, C. Chu, D. Liebenberg, et aI., Phys. Rev. B 32(1), pp. 381-389
(1985).
[27] M. van Thiel, M. Ross, B. Hord, et aI., Phys. Rev. Lett. 31(16), pp. 979-982
(1973).
[28] W.J. Nellis, A. Mitchell, M. van Thiel, et aI., J. Chern. Phys. 79(3), pp. 1480-1486
(1983).
 CHAPTER 13

Modification of the van der Waals Model

for Dense States of Matter

A. B. Medvedev

13.1. Introduction
Modeling the behavior of matter under various influences requires a knowledge
of the equation of state. Equations of state are often required to cover a wide
range, including solid, liquid, gas, and plasma states. If the material is chemi-
cally complicated, it is necessary to take possible chemical reactions into ac-
count. The problem of calculation of an equation of state from basic principles
has not yet been solved by modem methods. This causes practical use of various
semi-empirical models having free parameters that are chosen based on the
description of experimental and theoretical data. Forms of model equations are
rather varied [1]. The models have different kinds of complication, different
numbers of free parameters, and describe a variety of states. Desirable properties
of models are a wide range of applicability, simplicity, and the capability to
describe limiting situations of high pressure and temperature where theoretical
techniques of calculation are suitable. It is rather difficult to reach such a com-
promise, which is why models often have either local validity, agreeing with
experimental data within only narrow ranges of states, or are complicated and
have a large number of free parameters whose selection is often difficult because
of lack of the information needed to carry it out.
A simple and wide-range model of the equation state of a fluid which is a
modification of the van der Waals model is considered in the present work. The
modification extends the applicability of the van der Waals model to the region
of high densities. This model is formulated for simple liquids in Section 13.2.
Generalization of the model to cover mixtures is considered in Section 13.3. In
Section 13.4, a method of constructing an equation of state that takes melting of
a simple material into account is presented. The modification the van der Waals
model for description of liquids and the Mie-Griineisen model for description
of solids are used in this approach. The melting curve is calculated using an
analog of the Lindemann criterion. The adequacy of the model is demonstrated
by examples of good agreement with various experiments for different sub-
stances subjected to high pressures and temperatures.
V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII
© Springer Science+Business Media New York 2004
404 AB. Medvedev

13.2. Model of a Simple Liquid

The van der Waals model is one of the simplest models of liquids. The thermal
equation of state, defining the connection between pressure, P, temperature, T,
and volume, V, takes the form

(13.1)

where NO is the number of particles in the volume V, k is Boltzmann's constant,

a is the attraction constant, and Vc is the covolume, which is the volume of the
particles when they are brought close to each other. The second term in Eq. 13.1,
patt , reflects the presence of attractive forces between particles, which are con-
sidered in the mean-field approximation (elongating and weak). The first com-
ponent in Eq. 13.1 is the kinetic pressure, prep , which is caused by collisions of
the moving particles. The latter is modeled by analyzing the motion of material
points in a free volume, V - Vc. Because of the finite size of the particles, as
reflected by the covolume, a collision pulse is transmitted over a longer distance
than in an ideal gas; therefore prep in Eq. 13.1 is greater than NO kT IV . The
van der Waals model describes evaporation of a liquid: At a given value of T,
the equation of state transforms to that of an ideal gas as V ~ 00. A serious dis-
advantage of the van der Waals equation arises from the fact that, since
Vc = const. , it is inaccurate at high densities and pressures, particularly those
arising due to shock compression.
A method of correcting for this disadvantage was suggested in [2] for the
case when the attraction term in Eq. 13.1 can be neglected (or can be supposed
to be constant). The covolume is supposed to be dependent on pressure so that
Vc =Vc(P) . The validity of this assumption is confirmed by experiments con-
ducted on various materials. This model [2] expands applicability ofEq. 13.1 to
the range of high compressions but, in view of the fact that consideration of
attraction is simplified, it lacks the capability to describe evaporation.
The model of [3,4] is a further development of that discussed in [2]. Equa-
tion 13.1 can be rewritten in the form
p = prep + pall (V) , (13.2)
where
prep = N°kT (13.3)
V-Vc
and pall (V) can be a more general function than that in Eq. 13.1, but must still
satisfy the condition pall (V) ~ 0 as V ~ 00 . In the mean-field approximation,
attraction has no effect on the kinetic characteristics of particles, i.e., they move
freely between collisions. The pressure prep results from these motions and
collisions. During collisions, particles are affected by the pressure prep , which
 l3. Modification of the van cler Waals Model for Dense States of Matter 405

causes their size to decrease due to the compression. That is why it is supposed
that Vc = Vc(prep) . After that the thennal equation of state, defined by Eqs. 13.2
and 13.3, is written in terms of the variables T and prep in the form
p = prep + patt (V) (13.4)

NOkT
V =Vc(prep)+--. (13.5)
prep
The empirical functions patt (V) and Vc (prep) are supposed to be given. The
covolume is assumed to be a decreasing function of the kinetic pressure. The
function prep varies over the range from 0 to +00, with Vc ~ 0 as prep ~ 00.
The equation of state undergoes a transition to that of an ideal gas,
p = N°kT IV , at high temperatures. This can be observed if we fix prep in Eqs.
13.4 and 13.5 and approach the limit T ~ 00 (with account for limiting behavior
of patt (V) as V ~ 00: P = prep ).
In some cases, instead of the function Vc(prep) , it is convenient to use the
inverse form, prep (Vc). Variables of the model in this case are T and Vc and
Eqs. 13.4 and 13.5 are rewritten inform
p=prep+patt(V) (13.6)

v=v, + NOkT (13.7)

c prep(Vc)

From Eq. 13.7, it follows that V =Vc at T = 0 and Eq. 13.6 becomes the equa-
tion for pressure on the cold compression curve, Px:
Px (V) = prep (V) + patt (V) . (13.8)
When a realistic choice of prep andpatt is made, Eq. 13.8 reflects characteristic
features of compression of liquids. The functions patt and Px ~ 0 as V ~ 00
and, accordingly, prep ~ 0 in this limit. The function prep (V) will be supposed
to be a more rapidly decreasing function than Ipatt (V) I in Eq. 13.8. The reverse
situation is supposed to prevail during compression.
The internal energy function, E, that asymptotically approaches that of an
ideal gas as V ~ 00 (with T = const.) is obtained by integration of the thermody-
namic identity

( aE) =T(ap) _P. (13.9)

av T aT v
The solution for the thennal equation of state corresponding to Eqs. 13.4 and
13.5 takes the form

E=Erep(prep)+Eatt(V)-NOkT(I+ dlnT;~:;(T)r). (13.10)

406 A.B. Medvedev

where

(13.11)

J:
and

E att (V) =- p att (V)dV . (13.12)

In this equation r =k5/2(m/21t1i2)312, Ii is Planck's constant, m is the mass of

the particle, and cr(T) is the internal statistical sum of the particle, which is
defined by its rotational and vibrational characteristics and by its electronic
excitation.
After transforming to Eqs. 13.6 and 13.7, Erep takes the fonn

Erep (prep) = Erep (Vc) = - J v.:

co prep (Vc) dVe . (13.13)

The expression for the entropy, S, that is asymptotic to that for an ideal gas, as
was the case for the energy, is obtained from the equation dE = TdS - PdV and
has the fonn:

(13.14)

The equation
F = Erep (prep) + Eatt (V) - k NO TIn( eT ;;:;T) r) ,
5
(13.15)

for the free energy, F = E - TS, is obtained using Eqs. 13.10 and 13.14. In the
latter equation e = 2.718... is the base of the natural logarithms.
When Vc = const., the model described transfonns to the van der Waals
model and also accounts for the phenomenon of evaporation of a liquid. In the
case patt =0 this model transfonns to the model of [2], taking into account the
compressibility.
In a number of cases, the covolume and attraction functions can be expected
to depend on temperature. This is possible, for example, in the case when the
internal characteristics of particles change rather significantly as a result of
thermal excitation of internal degrees of freedom. For this case the model takes
thefonn

F =Erep (prep T) + Eatt (V T) _ kNoTln eT 512cr(T) r (13.16)

" prep'
where
 13. Modification of the van der Waals Model for Dense States of Matter 407

v = v.e (prep , T) + NOkT

prep' (13.17)

Erep =-JPnp prep(Ov,,(prep,T») dPrep, (13.18)

° oprep T

and
Eatt =-J: Patt(V,T)rdV. (13.19)

The integrals inEqs. 13.18 and 13.19 are taken at T=const. The equation
P = prep + p att (V, T) (13 .20)
for P = -(oF IOV)T is obtained from Eqs. 13.16-13.19, and represents a gen-
eralization of Eq. 13.2. The entropy, S = -(oF I OT)v , and energy, E = F + TS,
functions can be found using Eqs. 13.16-13.17.
Besides covolume and attraction, the internal properties of particles, as rep-
resented by the function o(T) , are needed to carry out calculations using the
model described. For a very large number of substances there are tabular data
and fitted equations giving Gibbs' potential, (1)0 (T), in the standard ideal gas
state (P=Po=l atm=l.01325 x lO- 4 GPa) and the energy HO in the cold
(T = OK) state. The function

Jlid(T) = -k Tln( T5/2;~T) r) (13.21)

is connected with these quantities by the equation

Na Jlid = HO - T (1)0 (T), (13.22)
where Na is Avogadro's number (HO and (l>°(T) are mole characteristics).
The model described was used for the construction of equations of state of
various substances, particularly, of the major constituents of detonation products
of CHNO explosives (explosives formed from carbon, hydrogen, nitrogen, and
oxygen). These detonation product constituents include hydrogen, H2, nitrogen,
N2, oxygen, 02, water, H20, carbon monoxide, CO, carbon dioxide, C02,
methane, CH4, ammonia, NH3, formic acid, CH202, etc. To represent the
covolume and attraction functions, the following technique was used. The tem-
perature function, Vc , in Eq. 13.17, was not taken into account. In the range of
expansion (V00 1Ve <1, where V00 is the volume of the liquid at T = 0, and
P = 0) and moderate degrees of compression (V00 IVe > 1 ) the simple function

(13.23)
408 A.B. Medvedev

was used to represent the covolume. In this equation, A and ~ are positive con-
stants. This equation has the limit Vc ~ 00 as prep ~ o. It would be more cor-
rect to use an equation providing the fmal value of the covolume, but Eq. 13.23
is acceptable to pressures of prep - I atm = 1.01325 x 10- 4 GPa. At this pressure
Vc = (2 -4) Voo in the gas region (where P ~ prep) with the parameters used
there for different substances, i.e., the effective model volume of a gas particle is
2-4 times that of a liquid particle for pressures near one atmosphere.
At high degrees of compression the inverse function to Eq. 13 .23,

prep =Aexp[a(Vo~:Vc)J. (13.24)

does not provide realistic behavior of the cold-compression curve of Eq. 13.8.
For this reason, the relation
B D
Vc =
(prep)C
+--::-
(prep)F'
(13.25)

where B, C, D, and F are constants, was used instead of Eq. 13.23 at higher
degrees of compression. (From the materials mentioned above, Eq. 13.25 was
used for H2. For the rest of the materials Eq. 13.23 was used in the range of
pressures P :s: 50 GPa.) Three of these constants were chosen to effect a smooth
connection (including the second derivative) to Eqs. 13.25 and 13.23, and the
fourth constant was adjustable. Equations 13.23 and 13.25 allow analytic
evaluation of the integral ofEq. 13.18.

r
The empirical function

patt(V,T) = -A (V;o Z(T) (13.26)

was used to represent patt, whereA and Voo are parameters inEq. 13.23, n = 2,
Z(T) = 'I1exp(-xT)+1 , (13.27)
'11+1
and '11 and X ( X > 0) are constants.
The function <I>°(T) in Eq. 13.22 was taken in analytical form from [5]. The
choice of the constants Voo, A,~, F, '11, and X was made by fitting the model to
experimental data including the temperature dependence of density and sound
velocity at P = 1 atm and the isothermal, isentropic, and Hugoniot compression
curves.
Let's consider some comparisons of calculations with experiment. Hugoniots
of initially liquid Hz, Oz, CO z, and CHzO z , and solid CO 2 are shown in Figs.
13.1 and 13.2 inP-p coordinates (p = IIV is the density). The T= 300K com-
pression isotherm of liquid Hz is also shown in Fig. 13.1. Almost the same de-
 13. Modification of the van der Waals Model for Dense States of Matter 409

scription of shock-wave data in the range P:S; 50 GPa is given for all the fore-
going condensed materials with the exception of CO (for which an experiment
from [13] is well described for P=20-50 GPa). Experimental and calculated
isotherms for H2 in the range of lower densities and also liquid-vapor equilib-
rium curves (the model curve is defined on the basis of the rule of Maxwell's
squares) are shown in Fig. 13.3. Experiments of the same kind for the other
materials mentioned are described in approximately the same way, with the ex-
exception of the range of states in immediate contact with the liquid-vapor
equilibrium curve for the polar molecules H20 and NH3 . Isotherms of H2 at
higher pressures than those of Fig. 13.3 are given in Fig. 13.4. Experimental and
calculated dependence of sound velocity on pressure along isotherms of liquid
H2 are shown in Fig. 13.5.

P, GPa r - - - - - - - - - - . . . ,
II

P,GPa 60

+
I

10
i
50

i
~
i 40 /
j J.'
l'-i
f
30
5 ; • 1
f l
r/
20
• 2
i .. 3
.I 10 / I"

)J
~

o o .!'----'----'---~
0.1 0.2 p,g/cm 3 1 2 3 p,g/cm 3

(a) (b)

Figure 13.1. (a) Pressure of liquid hydrogen as a function of density on the Hugoniot
and the T = 300 K isotherm. Curves 1 and 2 represent the computed Hugoniot and iso-
therm, the plotted points define the experimental Hugoniot [6], and the curve 3 is the
isotherm [7]. (b) Calculated Hugoniots of liquid oxygen (1) and formic acid (2). Experi-
mental data are represented by the points 1: [8],2: [9], 3: [10].
410 AB. Medvedev

60'

40

~ p-0.5
Q,,"

20

o 1
- 2

0
1 2 3 p,glcm 3

Figure 13.2. Graphs similar to those of Fig. 13.1b, but for initially solid (1) and liquid
(2) carbon dioxide. Experiment, 1: [11],2: [12].

P,MPa
10 1

10-f......_...1.._ _ _......._ _ _~_ _ _........,

10-1 p, glcm 3

Figure 13.3. Calculated isotherms and liquid-vapor phase equilibrium curves for hy-
drogen. Experiment: 1: [14]; 2: [12].
 13. Modification of the van der Waals Model for Dense States of Matter 411

SO

40

0:1 30
~
Q..."
20

10

0
2 4

Figure 13.4. Graphs similar to those of Fig. 13.3 in the region of high pressures. Experi-
ment: [15].

C, kmls C,kmls
2.a

1.0

~~~ __~~~~~~__~~~~2
o 20 40 1000 3000 5000 P, MPa
Figure 13.5. SOWld velocity as a function of pressure on isothenns for hydrogen. Ex-
periment, 1: [151,2: [71, calculation, 3.

13.3. Model of Liquid Mixtures

The possibility of generalizing models defined for simple liquids to the case of
mixtures is significant, and both the van der Waals model and the model from
[2J allow this. Generalization of this kind is also possible for the model repre-
sented by Eqs. l3 .16 -l3 .19. The model expression for the free energy function,
F, of the mixture is presented in the parametric form
412 AB. Medvedev

F = pep (prep ,T, NS) + £ott (V, T, NS)

(13.28)

where
v =v.c (prep " T NS)+ NkT
prep , (13.29)

Erep =-JPrep prep(8Vc(prep,T, NS») dPrep (13.30)

o 8prep T,NS '

and

£ott =-J: patt(V,T,NS)r,NS dV. (13.31)

In Eq. 13.28 the subscript i designates the various types of particles considered
(atoms, molecules, ions, electrons), N j is the number of particles of the type i in
the volume V, N = LjNj is the total number of particles (here and in Eq. 13.28
the sum is carried out over all particles present in the mixture). The quantity NS
is the sum total of all values N j determining the composition of mixture. The
quantities aCT) and r are as in Eq. 13.16. In the general case, the covolume and
the attraction are assumed to depend on NS. The integrals of Eqs. 13.30 and
13.31 are taken at T= const. and NS= const. Functions expressing the depend-
ence of the covolume and the attractive term on their variables are supposed to
be given.
The expression
p = prep +patt(V, T,NS) (13.32)

for P = - (8F / 8V)T,NS generalizing Eqs. 13.2 and 13.20 is obtained from Eqs.
13.28-13.31. Expressions for the entropy, S = -(8F / 8T)v,Ns, the internal en-
ergy, E = F + TS, and the chemical potential, J.l j = (8F / 8Nj )1 v, T,j#j, of any
particle j (where the notation of this last equation means that the derivative is
taken at all N j = const. with the exception ofj = i) are obtained from Eq. 13.32.
The resulting expressions are

(13.33)
 13. Modification of the van der Waals Model for Dense States of Matter 413

E = Erep + Eatt - fprop (aVe)

o aT Prop,NS
dprep +

(13.34)
+TfV(apatt) -NkT+kTL Ni d[lnT5/2cri(T)nJ
00 aT V,NS i dinT

j.l.j = qJj(prep, T, NS)-~j (V, T, NS)

N prep. (13.35)
-kTln-+kTln-+j.l.1(T)
Nj Po

.-f
qJJ- prop ( -
o
aVe
-)
aNj P'''',T,j"1'i
d'P rep (13.36)

~j= fv (apatt)
00
--
aNj V,T,j"1'i
dV (13.37)

(13.38)

and Po = 1 atm. The simplest variables of the mixture model are prep, T, and Ni .
If they are given, V is found from Eq. 13.29, and then the other thermodynamic
functions follow.
In the state of thermodynamic equilibrium the numbers of particles Ni are
not independent and are detennined by two other variables of the equation of
state. General conditions for equilibrium values Ni, which can be obtained from
the condition that F be a minimum, are

L rVnr j.l.r = L mVnm j.l.m , (13.39)

where n designates the reaction (dissociation, ionization, etc.), r designates the

initial reaction products, m designates the final reaction products, and the quan-
tities Vij are the stoichiometric coefficients. Substitution of Eqs. 13.35-13.38
onto Eq. 13.39 leads to the following system of equations for the concentrations
nr =NrIN and nm =NmIN:

(13.40)
414 AB. Medvedev

where
A<Pn = Lr
Vnr <pr - Lm
Vnm <pm (13.41)

(13.42)
r m

Aid_~ id ~ id
L\lln - L..J V nr Ilr - L..J Vnm Ilm • (13.43)
r m

The system of equations 13.40 is rather difficult to solve because the right-hand
members are functions of V and NS (through A<pn from Eq. 13.41 and A~n
from Eq. 13.42). Its simplification is possible if some assumptions concerning
covolume and attraction of the mixture are made. They will be considered fur-
therbelow.
If we suppose that the mixture covolume Vc is obtained by adding the co-
volume components Vci (calculated for one particle) we have

Vc (prep, T, NS) = L i NiVci (prep, T) . (13.44)

Then <p j , as given by Eq. 13.36, is equal to

(13.45)

i.e. they, and therefore A<pn obtained from Eq. 13.41, do not depend on the
composition of the mixture. The assumption of additivity of covolumes is rather
widely used in construction of equations of state of mixtures based on van der
Waals' model (and it is confirmed by agreement with experiment) and the
model allowing for covolume compression [2,16].
Construction of the attraction term for the mixture is made on the basis of a
method which is used rather often in the van der Waals mixture models [17],

(13.46)

where the quantity amix determined using the characteristics of attraction of the i
component, ai, (referred to one particle) is presented as

(13.47)

In its turn

(13.48)
 13. Modification of the van der Waals Model for Dense States of Matter 415

where nip is the number of "simple" particles from which particles of the mix-
ture can be formed (e.g. H20 = 2 H + 0). The characteristics a p, ai, and amix
can be functions of temperature. Substitution of Eqs. 13.46-13.48 into Eq.
13.37, leads to the equation

L1~n = 2~ L p ra; [L r Vnrnrp - L m Vnm nmpJ (13.49)

for L1~n, as given by Eq. 13.42. The requirement for mass and charge conserva-
tion in reactions implies that the expressions in the brackets vanish, leading to
the result that
(13.50)

Substitution of Eq. 13.48 into Eq. 13.47 and use of the fact that
LiN;nip = const.p (the condition of conservation of total mass of the mixture and
its electro-neutrality) leads to the situation when amix does not depend on the
detailed composition of the mixture, but only on its initial composition. If the
initial compound is fixed, amix = amix (T) .
In developing the equation of state of metals in [4], with ionization taken

r,
into account, it was assumed that the attractive term could be taken in the form

patt = -A(V; (13.51)

where A, n (;t: 2; >1), and Voo( -Li Ni, where i designates the ions) are constant
parameters. In this case L1~n = 0 as well.
Taking into account Eqs. 13.45 and 13.50, the system of equations 13.40 is
written in the form

Using the equations of material balance, electro-neutrality, and Li ni = 1, Eq.

13.52 allows calculation of the composition of the mixture at given values of
prep and T. With this, the thermodynamic functions are determined by the tech-
nique described above. Equations 13.52 are similar to the system of equilibrium
equations for mixtures of ideal gases and evolve to this form in the limit V --+ 00
(T= const.). Accordingly, the mixture model undergoes a transition into the
equation for a mixture of ideal gases.
Equation 13.52 is much simpler than Eq. 13.40 and can be further simplified
ifwe suppose that Vci is the sum of the covolumes of "simple" particles:
416 A.B. Medvedev

Vci = L p nipvcp(Prep, T), (13.53)

where nip is the same as in Eq. 13.48. Substitution ofEq. 13.53 into Eq. 13.45,
and substitution of this result into Eq. 13.41, taking into account that

as in the case ofEq. 13.49, gives

A<pn =0. (13.54)

Substitution of Eq. 13.53 into Eq. 13.44 leads to independence of the total co-
volume of the mixture on its detailed composition, as was previously observed
for attraction, so that Vc =Vc (prep, T) .
In the case that only ionized matter initially consisting of neutral atoms is
present in the system, Eqs. 13.52 can be written in a form similar to that of the
Saba equations,

(13.55)

provided that Eqs. 13.53 are satisfied. In these equations i designates the ion of
the corresponding number, e designates electrons, cr7(T) is the internal statisti-
cal sum of the ion with consideration of energy relative to the main level, and Ii
is the ionization potential.
If T, V ~ ex:> then prep ~ P and Eqs. 13.55 transform to Saba equations. If
Eq. 13.53 is supposed not to be satisfied, an additional factor exp(A<pnlkT)
comes from Eq. 13.52 into Eq. 13.55, where A<Pn is the shift of the ionization
potential.
The model described, with accepted simplifications, was used for construc-
tion of the equation of state of a number of mixtures, particularly detonation
products of condensed CHNO explosives. The substances forming the detona-
tion product mixture were those for which equations of state were constructed in
Section 13.2, along with solid carbon, C. The equation of state of this latter
material was constructed using a simplified form, similar to the form of Section
13 .2, directed at description of shock wave and thermophysical characteristics of
diamond. Covolumes Vci given by Eq. 13.44 and ....:d given by Eq. 13.38 were
taken to be the same as in Section 13.2. Attraction of the detonation product
mixture was constructed on the basis of Eqs. 13.46-13.48 using the following
technique. The principal components of the detonation products of CHNO ex-
plosives are usually taken to be N 2, H20, CO, and C02. Using the attraction
term, p att , given by Eqs. 13.26 and 13.27, the quantities ai (i= N2, H20, CO,
and C02) were calculated in Eqs. 13.47 and 13.48. Then the quantities ap
 13. Modification of the van der Waals Model for Dense States of Matter 417

(where p = N, H, C, and 0) were detennined from Eq. 13.48. After obtaining

a p , all other aj (i = H2, NH3, CH4, etc.) were calculated for the components
of the detonation product using Eq. 13.48. Using this mixture model, Eqs. 13.28
and 13.29 transform exactly into the equations of state of N2, H20, CO, and
CO2 of Section 13.2, provided that the mixture contains only one of these four
compounds. Because of over-determination of attraction and some difference of
the latter from the function patt of Section 13.2, the analogous exact transfor-
mation is not realized for the other components. This disadvantage is not signifi-
cant because it influences only the description of states under conditions which
are not characteristic for detonation processes.
Using the equation of state constructed in this way for the detonation prod-
ucts, some detonation characteristics of explosives of different power, HMX,
RDX, PETN, TNT, TATB, nitroglycerin, octol, Compo B, cyclotol, PBX-9404
(the small amounts of chlorine and phosphorous contained in this explosive
were not taken into account), and some others were calculated. Table 13.1
shows experimental [18] and calculated detonation velocities, Dexp and D, re-
spectively, the pressure, Pcr, and temperature, Tcr, at the Chapman-Jouguet
(CJ) point. This state is defined from the condition that it lie on the detonation
product Hugoniot, which can be found using the equation
E = EH + t P(VH - V) , (13.56)

where EH,andVH , the initial energy and volume of the explosive ahead of the
wave front, and the condition
D=C+U, (13.57)
where

Table 13.1. Parameters of explosives at the CJ point.

Explosive Dexp D Pcr Tcr
km/s km/s GPa K
HMX. 9.10 9.09 44.0 3140
RDX 8.75 8.76 36.7 3400
PEIN 8.30 8.44 29.5 4280
}NT 6.95 7.43 25.2 2260
TATB 7.85 8.33 37.9 1960
Nitroglycerin 7.58 7.57 20.4 4740
Nitromethane 6.29 6.09 10.7 3530
Tetranitromethane 6.36 6.59 14.5 2580
Octol 8.48 8.48 35.8 2920
CompB 8.03 8.06 30.9 2950
Cyclotol 8.25 8.27 32.4 3100
PBX-9404 8.80 8.86 39.6 3180
418 A.B. Medvedev

is the velocity of sound (equilibrium), and U is the particle velocity. In these

calculations, the equations P =DU IVH, and V IVH = (D-U)/ D are also used.
The values of EH andVH for condensed explosives were taken from [18]. One
can see, from Table 13.1, that calculated and experimental detonation velocities
are in good agreement for the explosives under considemtion, with the exception
of TNT and TATB. The latter differ from the others in that a large amount of
carbon is calculated to exist at the CJ point. A possible reason for the
discrepancies is the major simplification of the equation of state used here for
theC.
Release isentropes from the CJ state were also calculated. They were com-
pared with isentropes calculated using the JWL equation of state. This latter
equation leads to the relation
Ps =Aexp(-RI V IVH) + Bexp(-R2 V IVH) +C (V IVH)-OO (13.58)

between the pressure, Ps, and the volume, V, where A,RI,B,R2, C, andro are
constants and VH is the initial volume of the explosive. Some of the parameters
are chosen based on description of experimental chamcteristics at the CJ point
and those remaining are chosen based on description of experiments on expan-
sion of cylindrical tubes filled with detonating explosive. Several different val-
ues of the constants have been published [19-21]. The working ability of an
explosive under adiabatic processes (shock compression and the following isen-
tropic release) can be cbamcterized by the work

W(V) = f
VCJ
v Ps(V)dV -tPCJ(VH -VeJ) (13.59)

done during the expansion of the detonation product to the volume V. The
maximum possible work done under unlimited expansion of the detonation
products W is sometimes called the heat of detonation, Q. Figure 13.6 shows the
value of B=(W - WJWL) / QJWL as a function of the degree of expansion, V IVH .
In this expression, W is the work calculated using the model under considem-
tion, and WJWL,andQJWL are calculated using the JWL equation of state [19-
21] for the degree of expansion of the detonation products of composition B.
Similar agreement (I B 1< 5%) with data [19,20,21] for PBX-9404, RDX, and
nitromethane is also obtained. For HMX and PETN, 1B 1< 5 % compared to the
JWL isentrope calculated using the data from [20,21], but more for the JWL
isentrope calculated using the data from [19].
The equation of state of hydrogen was constructed with dissociation and
ionization taken into account using the mixture model. A mixture of five com-
ponents, H2, H~, H, H+, and e was considered. Description of experimental
data at relatively low tempemtures and pressures is the same as in Section 13.2.
At high pressures and tempemtures, when the influence of attmction is not sig-
nificant, the model considered transforms into the generalized compressed co-
 13. Modification of the van der Waals Model for Dense states of Matter 419

0.1

0.0 /' \1

-0.1

o 2

Figure 13.6. The deviation. 8, from isentropic expansion of the detonation product of
composition B as functions of V /VH. 1: [19],2: [20],3: [21].

volume model [2] for mixtures. Using this model, a wide-range equation of state
of hydrogen was constructed in [16]. When the temperature functions ofintemal
characteristic terms and the covolume functions under high pressures in the
model considered are chosen to be close to those used in [16], the results of
model calculations of equation of state are close to results in [16].
The mixture model was also used for construction of equations of state for
various liquid metals, in particular for Cs. [22]. The assumptions of Eqs. 13.51
and 13.53 were used. Covolume and attraction were supposed to be independent
of temperature. Under expansion and small compression, the function Vc(prep)
was taken in the form 13.23 (equivalently, prep(V) can be obtained from Eq.
13.24). Under increased compression a representation anologous to that of Eq.
13.24,

(13.60)

was applied instead of Eq. 13.23. In this equationAk and bk are constant pa-
rameters that are chosen to fit experimental results on shock compressibility at
high pressures. Statistical sums were restricted to the lowest-order term. Appli-
cation of this approach for Cs was revealed in [23,24] in comparison to experi-
mental data in the range of significant ionization with calculations on the model
of ideal plasma.
Parameters of the equation for Cs are given in [22]. Figure 13.7 shows de-
scription of data on isothermal and shock compression of Cs. Figure 13.8 shows
experimental and calculated isotherms and isentropes that are situated relatively
close to the liquid-vapor phase equilibrium curve. Data on isothermal and isen-
tropic compression are accurately described except in the immediate neighbor-
hood of the critical point. Thermodynamic characteristics of Cs vapor were
investigated over a wide range of supercritical states, including the range of
420 AB. Medvedev

significant thennal ionization, in experiments on shock compression. Particu-

larly, these experiments reveal the behavior of the compressibility factor PVIRT
(R is the gas constant). ill Fig. 13.9 calculation of the latter is compared with
experiment on the T= 5000, 7000, and 10000K isotherms. The region of higher-
energy states (compared to [23]) was investigated in experiments on isobaric
electro-explosion of wires [24]. Figure 13.10 demonstrates comparison of model
calculations with these data, showing the enthalpy, H = E + Pv, as a function of
the variable PVon experimentally investigated isobars for P = 12.5, 25, and 50
MPa. Values of the degree of ionization, a.e = Ne I NO, and temperature, T, are
shown at some points on the calculated P = 25 MPa isobar.
P,GPa
40

30'

20 .1
.2
10'

1.0

0.5

0.0'
5.0 6.0
p,g/cm 3
Figure 13.7. Calculated T=493K isothenn (1) and Hugoniot (2) centered on the initial
density l.826 glcm3 for cesium. Experiment, 1: [25],2: [9].

13.4. Consideration of Melting

A relatively simple technique for constructing a wide-range equation of state of
simple materials with evaporation of liquids, thennal ionization, and melting is
described in this section. ill order to describe the liquid phase, the model is used
in the form of Section 13.2 or, under high temperatures when significant ioniza-
tion is observed, in the form of Section 13.3 (with the same assumptions con-
cerning covolume and attraction that is higher for Cs). IT the functions
Vc (prep) and patt (V) are given, the model relations for liquid (i) allow deter-
mination of the functions Vt(Prep, T), Pt (prep , T), Fl(Prep, T), Sl(Prep, T) ,
etc. Possible structural transformations in the solid state are not considered. The
Mie-Grtineisen model is used to describe the solid phase:
 13. Modification of the van der Waals Model for Dense States of Matter 421

8 II 8 • & 1 -6
Do.&2 -·--7
.4
.3
• 5
--8

8
10-2 10° p, glcm 3

Figure 13.8. Isotherms, isentropes, and liquid-vapor equilibrium curves for Cs. Iso-
thermal compression experiment, 1: [26], 2: [27). Isentropic compression experiment
[28],3: initial state P=4.25 atm., T= 1290K., 4: P=6 atm., T= 1266K. Experimental
liquid-vapour equilibrium curve [26], 5: critical point; the numbers 1-8 correspond to
the temperature values 1900-1200K Calculation, 6: isotherms (temperature values are
shown are on isotherms), 7: isentropes from initial states [28], 8: Liquid-vapor equilib-
riumcurve.
PVIRT

1.5

1.0 --+H1l1l1l'ttt1ll1lrtttllll~~~_

10-1 10 1 P, MPa
Figure 13.9. Compressibility parameter on isotherms T= 5000, 7000 and 10000K.
Stroked strip shows experimental errors [23].
422 A.B. Medvedev
H,kJ/g
25

20 lie -1.38

1.25
15 29800

1.09
10 27000
0.98
23200
0.90
17600

9900
OM-~--~----~----~--~--~
5 PV, GPa.cm3/g

Figure 13.10. Enthalpy of cesium on isobars for P= 12.5, 25 and 50 MPa. The shaded
strip shows the experimental error [24]. Degrees of ionization and temperatures are
shown on theP = 25 MPa isobar.

F(V, T) =Ex (V) +3N° kTln edi) (13.61)

P(V, T) =Px(V) + y(V) 3No k T IV (13.62)

Px(V)= dEx(V) (13.63)

dV
dlned(V)
y(V) = (13.64)
dlnV

S(V,T)=-3N Ok(ln edi) -1). (13.65)

where ed is the effective oscillatory temperature, y is the GIiineisen coefficient,

and Ex and Px are the cold (T= OK) energy and pressure. The function
ed(V) , and therefore y(V), is supposed to be known from some suggestions.
The conditions
Ps =pt=pm (13.66)

Ts =Tt=Tm (13.67)
 13. Modification of the van der Waals Model for Dense states of Matter 423

(13.68)

dT m Vf-Vsm
--=-=--- (13.69)
dpm Sr -Sf?
where the subscript s designates the solid state are fulfilled under melting (des-
ignated by the superscript m). Double indices mean that the value refers to either
the liquid or the solid phase on the melting curve. The analog of the Lindemann
equation is used as the melting criterion Matter is assumed to exist in the liquid
phase when the portion of the free volume within which the particles can move
is equal to or greater than a small fixed magnitude, i.e., it is postulated that the
volume Vf on the melting curve obeys the condition
v.m -Vc(prep)
-!~'----=-.:.-....:.. = f3 = const. (13.70)
Vc(prep)

Using Eq. 13.70 and the equation of state for the liquid, values Vf, Tl = Tm,
PI. = pm, Sr , and Ff, and dT m I d pm can be calculated on the melting curve
as functions of prep. The temperature function Sf? in Eq. 13.65 can also be
determined. With this, the Clapeyron-Clausius equation 13.69 can be written in
the form

dT m (prep) _ Vf(prep)-Vsm
(13.71)
dP m - Sr(prep)-Sf?(Prep, Vsm) ,

and the function Vsm(prep) can be found from Eqs. 13.61 and 13.68. The
GIiineisen coefficient, y (V) , is assumed to be a known function The pressure
Px (Vsm ) can be obtained by evaluating Eq. 13.62 on the melting curve
(pm =Px +y(Vsm)3NO kTm IVsm ) and Ex (Vsm )can be found fromEq. 13.6l.
As a result of the automatic satisfacti.on of the equilibrium conditions 13.66-
13.69, the equation of state of the solid phase, 13.61-13.65, is defined. Simi-
larly, the full multiphase equation of state is also defined. The attraction of the
liquid, patt, is used in the form ofEq. 13.51, which does not take the tempera-
ture dependence into account Equation 13.23 was used for the covolume in the
region of expansion and small compression. The equation

Sd =soexp[Yo(l- ~)] (13.72)

was used to determine Sd (V) under moderate compression. In this equation

So =const., Vo = 11 po, and yo are the experimental values of volume (po is the
density) and the GIiineisen coefficient of solid matter at normal conditions. It
should be noted that Eqs. 13.72 and 13.64 give y as the linear function
424 AB. Medvedev

v (13.73)
'1='10-
Vo
of V that is often used in constructing models in the Mie-Griineisen form. The
parameters Voo , A, a, n, ~, and 80 are chosen based on data about the com-
pressibility of solid matter under normal conditions, the binding energy, the
tempemture, and the melting energy at atmospheric pressure. Expressions of the
type 13.60 instead of the representation prep(Vc) in the form ofEq. 13.24 were
applied under higher degrees of compression. Coefficients were chosen from
conditions of smooth (including the second derivative) connection of Eqs. 13.24
and 13.60 and description of the experimental Hugoniot for initially solid mate-
rial at high pressures. The correct behavior of the cold compression curve was
also provided (P =bV-5/3 , where b is the theoretical coefficient for the gener-
ated electron gas in the limit of high compression).
Experimental data and theoretical models give evidence that the entropy
jump during melting, ASm = Sf - Sf! , is almost constant (- NO k ) at high pres-
sures. The extrapolation given by Eq. 13.72 in the region of high compression
leads to a violation of this rule. Because of this, a method of finding Px and Ex
of the solid state that differs from the one described above was used in this re-
gion. The entropy jump is given by the function

Asm(Vc) =0.8+ ~3 Sr(~)r, (13.74)

NO k L.Jr=l Voo

where Sr =const. Taking Eq. l3.74 from Eq. l3.69 (13 was already found in Eq.
13.70 as well other parameters and functions of fluid) v.m is defined as before.
Then, using Sf and Eq. 13.74, one obtains Sf, after which 8d can be obtained
from Eq. 13.65, and '1 from Eq. 13.64. After this, the cold curve of the solid
phase is found in a similar way to the procedure described above. The coeffi-
cients Sr in Eq. 13.74 are found from conditions of smooth connection of the
entropy jump on the lower, Eq. 13.72, and upper parts of the melting curve. The
connection ofEq. 13.74 with Eq. 13.72 is produced under the same degrees of
compression as Eq. 13.60 with Eq. 13.24.
The functions prep (or, equivalently, Vc ) and T are always variables in sin-
gle-phase regions in complete equations of state. If it turns out that T < Tm ,
calculations are carried out based on Eqs. 13.60-13.65. In the contrary case it is
done based on model relationships for the liquid. The equation of state is con-
structed using the standard additive technique in two-phase regions.
The model was used for a large number of metals, AI, Fe, Ni, Cll, Mo, Ta,
W, Pb [4,29-31], Zn [32], etc., and values of the model parameters are given in
[29,30]. As for Cs, only the main states of the ions were taken into account and
the ionization potentials, Ii , were assumed constant
 13. Modification of the van der Waals Model for Dense States of Matter 425

Figure 13.11 shows Hugoniots of some initially-solid metals in the region of

moderate and high pressures in coordinates of shock velocity, D, and particle
velocity, U. The beginning and end of melting due to shock-wave compression
are shown by strokes in Fig. 13.lla. Calculated values of pressure, temperature,
and density at the point at which melting begins are given in Table 13 .2.
Experimental measurements of pressures at the onset of melting are available
for some metals (GPa), AI: 125 [54], Fe: 243 [55], Mo: 390 [56], Ta: 290 [57],
and Pb: <54 [58]. Calculated values are generally in good agreement with these
measurements.
Figure 13.12 shows, in P - (p / po) coordinates, experimental data on shock
compression of solid AI, functions calculated using the TFPK model [62,63],
and the function considered here, which takes into account all ionization. Figure
13.13 gives experimental and calculated T= 300K isotherms of solid metals (for
D,kmls

D,kro/s
11"

40
8
.. 1
• 2 30
6 •... 43

5 a 5
20 I-
• 6
4 • 7
o 8

3 • 9 10

o 1 2 3 4 5 6 U, kmls 0'----1.... ....,~k-ml-:-'s

0---2'-0-U
(a) (b)
Figure 13.11. (a) Hugoniots of solid AI, Cll, Ta, and Pb in the region of moderate pres-
sures. Experimental data, I: [33],2: [34],3: [35],4: [36],5: [37],6: [38], 7: [9], 8: [39],
9: [40]. (b) Hugoniots of solid AI, Fe and Cu under high pressures. Experimental data, 1:
[41],2: [42], 3: [43],4: [44], 5: [45],6: [46], 7: [47],8: [48], 9: [49], 10: [50], 11: [51],
12: [52], 13: [53], 14: [38], 15: [33].
426 A.B. Medvedev

Table 13.2. Melting parameters of metals.

Metal P,GPa T,K p, g/cm3
AI 120 4700 4.36
Fe 249 7900 12.34
Ni 362 10100 14.38
Cu 260 7700 14.11
Mo 403 13550 16.53
Ta 320 13750 27.64
W 496 17600 31.91
Pb 39 2250 15.88

logP, [P], TPa

.,
3

•
• \ , \
2
I
l
/.

1 /
/
...
/.

v 1
• 7
0
y
y 3
2 * 8
• 9
• 4
• 10
• 5 --11
e 6

2 3 4 (J

Figure 13.12. Hugoniot of solid AI. Experimental data, I: [51],2: [49],3: [50],4: [48],
5: [47],6: [44],7: [45],8: [60], 9: [59], 10: [61]; 11: TFPK calculation.

Fe here and subsequently on Fig. 13.14, po =7.85g1cm3 ). Figure 13.14 com-

pares calculated and experimental sound velocities behind the wave front. Drops
of the calculated functions correspond to mixed solid and liquid phases. Figure
13 .15 shows release isentropes of shock compressed solid copper in P- U coor-
dinates (U is the particle velocity defined in calculations using the Riemann
relation). The first isentrope lies entirely in the solid phase. The second isentrope
 13. Modification of the van der Waals Model for Dense States of Matter 427

originates in the solid phase and then, at low pressures, enters the mixed-phase
region. Finally, solid, mixed-phase, and liquid states occur on the third isen-
trope. Figures. 13.16 and 13.17 show Hugoniots of porous samples of AI, Ni,
and Pb (the porosity is defined by relation m = po I poo , where poo is the initial
density of the material). A similar description of experimental data is valid for
other metals. Figure 13.18 shows experimental and calculated sound velocities
of liquid Ta and Pb as functions of density in the region of decreased densities.
Results of especially detailed experiments on isentropic release of previously
shock compressed solid and porous Cu, Mo, and Pb are shown on Figs. 13.19
and 13.20. Changes of calculated functions are caused by vaporization.
More detailed comparison with experiment, calculated curves of melting, pa-
rameters of critical points. etc., are given in [4,29-32].
The model considered in this section for construction of equations of state
usually requires a relatively small amount of experimental information, i.e. data
of shock compressibility of solid samples, thermophysical characteristics at
atmospheric pressure, and ionization parameters. Nevertheless, the model is in
good agreement with experimental data without any special adjustment and can
be used with good accuracy to estimate the equation of state of poorly investi-
gated materials at high pressures and temperatures.

P,GPa.-------------------~
300

200'

100

..
+ 1
2
----3
1.2 1.6 1.8 0
I I I
0.8 1.0 1.2 1.4 1.6 ope

Figure 13.13. Isotherms T= 300 K Fe, ell, Mo and Ta. Experimental data: 1: [64], 2:
[65], 3: [66] (analysis).
428 A.B. Medvedev

C, kmls
AI (C+l)
.1
02
11 63
04
.5
_6
9
Cu (C -1)

3","--~-'----_.&..._--J
1.0 1.5 2.0 (J

Figure 13.14. Calculated sound velocity in shock compressed solid AI, Fe, Cu, Mo and
Pb. Experimental data, 1: [40],2: [67], 3: [54],4: [55],5: [56],6: [58].

P,GPa

200

100

OL---~-~--~~~
o .2 4 6 U,kmfs
Figure 13.15. Release isentropes of Cu from states on the principal Hugoniot. Experi-
ment: [68].
 13. Modification of the van der Waals Model for Dense States of MaUer 429

P,GPa
200r----------------------,

100'

G _ 1
-2
o •• 3
--4
oL-~~~~ __ ~ ____ ~

0.0 1.0 1.2 1.4

Figure 13.16. Calculated Hugoniots of porous AI (the numbers on the curves designate
the porosity). Experimental data are 1, 2: [51] (analyzed similarly to [69]), 3: [70], 4:
solid-liquid phase boundary.

P,GPa P.GPa
800

600
600
• 3.0

400
400

200
.1
-2
·3
0 0
0.5 1.0 1.5 cr 1.0 1.5 2.0 cr
(a) (b)
Figure 13.17. (a) Similar to Fig. 13.16 forNi. Experimental data, 1: m = 1.4, 2: m = 1.75,
3: m = 3 [51], the rest: [69]. (b) Similar to Fig. 13.16 for Pb. Experimental data from [69].
430 AB. Medvedev

C, kmls

ITa(.
3

o L.-_ _--'-_ _ _-J

5 10 15
p,g/cm3

Figure 13.18. Sound velocity in liquid

mental data from 1: [71],2: [72].
Ta and Pb in the region of low densities. Experi-

logP, [Pl, GPa

2
0\ 2
I

-1

o 5 10 15 20 U,km/s

Figure 13.19. Release isentropes of porous and solid Cu. Experimental data: 1: [73]; 2:
[74).
 13. Modification of the van der Waals Model for Dense States of Matter 431

Jog P, [P], GPa

P,GPa:
2 : }1
100
• : :}2
/ 1 ~.

•
,!
U)
0

l'
-1 •

0.1 -2 •

0
0 2 4 6 U,km/s 0 ·5 10 U,km/s
(a) (b)
Figure 13.20. (a) Release isentropes of porous Mo (m=2.3). Experiment: [31).
(b) Release isentropes of porous and solid Pb. Experimental data: 1: [73], 2: [75).

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(1986). [trans. from: Pis'ma Zh. Eksp. Teor. Fiz. 43(5), pp. 241-244 (1986).]
[60] I.Sh. Model', AT. Narozhny, AI. Kharchenko, S.A. Kholin, and V.V. Khrustalev,
JETP Letters 41(6), pp. 332-334 (1985). [trans. from Pis 'ma Zh. Eksp. Teor. Fiz.
41(6), pp. 270-272 (1985).
[61] AS. Vladimorov, N.P. Voloshin, V.N. Nogin, V.A. Nogin, AV. Petrovtsev, and
V.A. Simonenko, JETP Letters 39(2), pp. 82-85 (1984). [trans. from Pis 'ma Zh.
Eksp. Teor. Fiz. 39(2), pp. 69-72 (1984).]
[62] N.N. Kalitkin, Sov. Phys.-JETP 11(5), pp. 1106-1110 (1960) [trans. from Zh.
Eksp. Teor. Fiz. 38(5) pp., 1534-1540 (1960).
[63] V.P. Kopyshev, in: NumericalMethods ofContinuous Media Mechanics 8(6),
(1977),pp. 54-67. (in Russian)
[64] H.K. Mao, P.M Bell, J.W. Shaner, and D.l Steinberg,J. Appl. Phys. 49(6)
pp. 3276-3283 (1978).
[65] J. Wu, H.K. Mao, and P.M Bell, High Temp.-High Press. 16, pp. 495-499 (1984).
[66] H.K. Mao, Y. Wu, L.C. Chen, et al. in: High Pressure Science and Technology.
(ed. W.B. Holzapfel andP.G. Johansen) Gordon and Breach, New York (1989),
pp.773-775.
[67] L.V. Al'tshuler, MI. Brazhnik, and G.S. Telegin, J. Appl. Mech Tech. Phys. 12
pp. 921-926 (1971). [trans. fromPrikl.Mekh. Tekh. Fiz. 6, pp. 159-166 (1971).]
[68] M. V. Zhernokletov, V.N. Zubarev, and Yu.N. Sutulov, Appl. Mech. Tech. Phys.
25(1), pp. 107-110 (1984). [trans. fromPrikl. Mekh. Tekh. Fiz. 25(1), pp. 119-123
(1984).]
[69] RF. Trunin, G.V. Simakov, YU.N. Sutulov, AB. Medvedev, B.D. Rogozkir, and
YU.E. Fedorov, Sov. Phys.-JETP 69(3), pp 580-588 (1989). [trans. from: Zh. Eksp.
Teor. Fiz. 96(3), pp. 1024-1038 (1989).]
[70] M. van Thiel (ed.), Compendium o/Shock WaveData, Lawrence Livermore
National Laboratory report UCRL-50108, Vol. 1, Livermore, CA, (1977).
[71] RS. Hixon, M.A. Winkler, and lW. Shaner,High Temp.-HighPress. 18, pp. 635-
638 (1986).
 13. Modification of the van der Waals Model for Dense states of Matter 435

[72] R.S. Hixon, M.A. Winkler, and J.W. Shaner,Physica 139/140, pp. 893-896
(1986).
[73] L.V. Al'tshuler, AV. Bushman. M V. Zhernokletov, V.N. Zubarev, AA Leont'ev,
and V.E. Fortov Soy. Phys.-JETP 51(2), pp. 373-383 (1980). [1rans. from Zh.
Eksp. Teor. Fiz. 78(2), p. 741-760, (1980).]
[74] P. De Beaumont and J. Leygonie, in: Proc. Fifth Symp. (International) on
Detonation, Report ACR-I84, Office of Naval Research, Arlington, VA, (1970)
pp.430-439.
[75] L.V. Al'tshuler, AA Bakanova, AV. Bushman et al., Soy. Phys.-JETP 46(5),
pp. 980-983 (1986). [1rans. from: Zh. Eksp. Teor. Fjz. 73(11), pp. 1866-1872
(1977).]
 CHAPTER 14

Thermodynamic Properties of Shock-

Compressed Plasmas Based on a
Chemical Picture

v. K. Gryaznov, I. L. Iosilevskiy, and V. E. Fortov

14.1. Introduction
Calculation of an equation of state and thennodynamic functions is the starting
point for a whole set of calculations of thennophysical properties of a substance
under strong shock compression and heating [1-6]. Thermodynamic calculation
is also an inherent part of hydrodynamic simulation of shock compression. The
feature of this interrelation is that the thermodynamic data employed as input
infonnation for a very wide and important class of hydrodynamic flows such as
adiabatic flows (irreversible shock compression, reversible isentropic compres-
sion and expansion, throttling, etc.) are limited in principle by the use of a re-
duced caloric equation of state that is incomplete from the thennodynamic point
of view. This equation of state is an expression for the internal energy (or en-
thalpy) as a function, U (P, V), of the conjugate thermodynamic variables, pres-
sure and specific volume.
This incompleteness involves, in principle, the possible existence of different
thermodynamic systems described by the same reduced caloric equation of state.
This insensitivity of gas-dynamics to thermodynamics results, in tum, in incom-
pleteness of experimental information obtained in classical dynamic experiments
(involving the fonn of Hugoniots and release isentropes in the P - V plane, com-
pression isentropes in adiabatic tubes, enthalpy as a function of density in ex-
periments on isobaric explosion of electrical conductors, etc.). Nevertheless,
emphasis is constantly placed on the role of temperature as a parameter directly
defining (along with density and pressure) physical processes occurring in the
system when constructing and interpreting theoretical models. As a result of this
disparity, difficulties associated with the direct experimental verification of
theoretical predictions arise, and sometimes it is impossible in principle to a
select the best fitting theoretical model using experimental data of the type con-
sidered above.

V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII

© Springer Science+Business Media New York 2004
438 V.K. Gryaznov, I.L. Iosilevskiy, and V.E. Fortov

In the theoretical description of the thermodynamics of a shock-compressed

substance (first of all the disordered states-gas, liquid, and plasma) the tradi-
tional semi-empirical approach which was developed fruitfully for a long time
by S. Kormer, V. Urlin, and V. Kopyshev should be noted (see Chapters 11, 12,
and 13 of this book and [1-6]).
As far as the microscopic description is concerned, the main defining factor
is a duality of coexistent methods of description, which are commonly called
"physical" and "chemical" models of the substance (physical and chemical
pictures) [7-9]. The strict physical model is based on a description of the sub-
stance as a collection of nuclei and electrons with pure Coulomb inter-particle
interaction. All free and bound states of the particle groups actually existing in
the system can be described, basically, in a uniform and conforming manner as
diverse manifestations and consequences of nonideality, that is the result of the
interaction (simple in structure) of the same elementary particles-,-electrons and
nuclei. With this approach, almost all problems of thermodynamic description of
a substance seem to be transformed into a branch of nonideal plasma physics.
The strictness and structural simplicity of the physical model results, however,
in a complicated way of actual realization of the theoretical approach. A suffi-
ciently comprehensive presentation of current theory can be found, for example,
in the proceedings of regular conferences on nonideal plasma physics [10 -l2].
The real possibilities of the present theory in the framework of the physical
model are limited in practice to the first terms of the perturbation theory [13-
16]. Noticeable progress was achieved in recent years in the description of
equilibrium quantum many-particle systems using direct numerical simulation
[17] or density functional theory [18,19]. The possibility of obtaining a thermo-
dynamic description based on a physical model of shock-compressed sub-
stances, besides hydrogen and possibly helium, presently seems a distant
prospect.
Most practical thermodynamic calculations for real substances are performed
within the framework of the chemical model. This model employs, as conven-
tional elementary constituents, numerous kinds of composite particles, that have
internal structure and internal degrees of freedom. They range from atoms,
molecules, and atomic and molecular ions, up to clusters and macromolecules.
The loss of rigor in the chemical model is the price paid for maximum proximity
of the system as a whole and a zeroth-order approximation of the model, for
example the ideal gas (with variable composition relative to the complexes
mentioned above), to a given restricted situation, whatever it may be-cold
(relatively) molecular gas or low-density partially ionized plasma. The results
discussed below are associated just with such an approach.
According to the present theoretical concepts and numerous approximate
calculations made within the framework of the chemical model, the very general
structure of common thermodynamic relationships for any substance at tem-
 14. Thennodynamic Properties of Shock-Compressed Plasmas 439

peratures below the binding energy of the atom (T ~ Z713 Ry) can be character-
ized as follows [20]. The entire phase diagram of the substance in the density-
temperature plane can be conventionally divided into three regions:
1. Two asymptotic limits of the ideal-gas model: first. a region of very
low densities, p ~ 0, in which the substance forms a classical nuclear
and electron ideal gas and, second, a region of very high densities,
p ~ 00, also ideal, but a degenerate and homogeneous gas of the same
nuclei and electrons.
2. Located between these limiting cases is an intermediate region that can
be called a "nonideality valley" [9].
The foregoing term may be illustrated [21-23], for both thermal and caloric
equations of state, when the behavior of corresponding thermodynamic proper-
ties on isotherms are represented as those depending on density of dimensionless
complexes selected in specific manner: a thermal equation of state, in form of
the generalized compressibility factor Z
P
Z:: .deal ' (14.1)
pI (nnucl,nelect,T)

and a caloric equation of state in the form of the nontranslational part of the
internal energy divided by an energy value characteristic of plasma,
Uidea! = (3/2)PV,

(14.2)

In the limit p ~ 0, the dimensionless ratio 14.1 is transformed into the well-
known dimensionless ratio Z:: PVIRT. In the limit p ~ 00 the denominator in Eq.
14.1 corresponds to the pressure of an ideal system of degenerate nuclei and
electrons. In both of the limits, Eq. 14.1 tends to unity and Eq. 14.2 tends to
zero. Furthermore, for electro-neutral systems with Coulomb interaction, the
inequalities
Z~1 and GsO
are valid for any values of the parameters.
Figure 14.1 shows the degree of ionization, C1.::NeINnuc!' obtained from a
calculation for a nickel plasma. The calculated value of the total internal energy
U, similar to that of Eq. 14.2 for the same nickel plasma, is shown in Fig. 14.2
[24]. The boundaries of Coulomb nonideality and degeneracy of electrons are
plotted in both figures. At very low temperatures (below the evaporation heat)
the structure of the phase diagram for the variables Z and G of Eqs. 14.1 and
14.2, similar in a qualitative sense to Figs. 14.1 and 14.2, is considerably com-
plicated due to features associated with the behavior of the condensed substance.
440 V-K Gryaznov, I.L. Iosilevskiy, and V.E. Fortov

o~~~--==~~~~~~
10.2

Figure 14.1. Behavior of the degree of ionization of compressed nickel plasma [24]. The
calculated degree of ionization on isotherms (solid lines) and experimental data [5,122]
on Hugoniots(points) for solid and porous nickel samples are presented. The dotted and
dashed lines shown correspond to constant values of the Coulomb nonideality parameter
(ro=[41t(e2/kBT)31:"n"z~]112=1) and the free electron degeneracy parameter
(n.M =1), respectively.

10'
OIl
;::,
~

104 T=1O*lo3

Figure. 14.2. Density-energy diagram for nickel plasma [24]. Calculated isotherms and
experimental points are presented for shock-compressed solid and porous samples [5,
122]. Lines corresponding to constant parameters of Coulomb nonidea1ity (ro= 1) and
free electron degeneracy in plasma ( n. M =1 ) are shown.
 14. Thennodynamic Properties of Shock-Compressed Plasmas 441

The vast gas and plasma nonideality valley region shown in the figures, is
split into two distinct parts, those of high and low densities, which can be called
using figurative tenns of [9] as the "gaseous and condensed slopes" of the
nonideality valley. A transition region is located between them. This region is
characterized by both minimal values of the ratios Z and G, and by maximal
violation of the "weak nonideality" condition, which is the smallness of the
mean interaction energy of particles contained in the chemical model compared
with their mean kinetic energy. The depth and location of minima of the thermal
and caloric dimensionless ratios ofEqs. 14.1 and 14.2 on isothenns can be con-
ventionally considered as a focus of maximum uncertainty of thennodynamic
properties of the heated substance. The regions of the phase diagram adjoining
these minima from the sides of low and high densities correspond to traditional
spheres of applicability of the two main approaches that have been carried out to
date and which are the actual basis of the majority of calculations of thennody-
namic properties of plasmas fonned when matter is subjected to high-energy
impact. From the side of low densities this is the so-called chemical model of
plasma (see below) and from the side of high densities, the cell model of con-
densed matter [20].

14.2. Chemical Model. Low Densities

The chemical model is based on representation of the system free energy,
F({Ni},v, T)= F;~ +AF'int({Ni },V,T)

(14.3)

as a sum of a zero approximation tenn, F;~, corresponding to an ideal-gas mix-

ture with varying composition of a wide spectrum of simple and complex parti-
cles (electrons and ions, atoms, molecules, etc.) and of additional tenns
describing the interactions among these particles. In this equation N j is the num-
ber of particles of type i, V is a volume, T is the temperature, kB is Boltzmann's
constant, Ai is the thermal de Broglie wavelength, and Qj is the partition func-
tion for a particle of type j. In the general case, complex particles have internal
degrees of freedom corresponding to excited states in thennodynamic equilib-
rium with the system as a whole, i.e., with its translational degrees offreedom.
The traditional scope of application of the chemical model is partially ion-
ized plasma oflow (gaseous) density. In this case the following assumptions and
restrictions are believed to hold:

• The contribution of all the effects of interparticle interaction of the free

particles to the equation of state or to the total thennodynamic func-
442 V.K. Gryaznov, I.L. Iosilevskiy, and V.E. Fortov

tions is small compared with the ideal-gas terms in both Eq. 14.3 for
the free energy and in expressions for the caloric, P({N;}, V, T), and
thermal, U({N;}, V, T), equations of state, and for the chemical poten-
tials of the particles, !J.;({N;}, V, T), obtained by differentiation of Eq.
14.3:

P({Ni }, V, T)= _{8F({Ni},v, T)} , (14.4)

8V {Nt},T

U({Ni}, V, T)= F({Ni}, V, T)- T{8F({~~ V, T)} , (14.5)

{Nt}, V

({ N} V T)={8F({Ni},V,T)} (14.6)
!J. '" 8N. .
J {Nt,j;ti},v,T

• Distortions in energy and statistical weights of internal excited states of

complex particles (ions, atoms, molecules, etc.) under the effect of sur-
rounding particles are insignificant and can be neglected.
• Uncertainty, peculiar in principle to the chemical model, concerning a
restriction of the number of excited states taken into account in calcu-
lation of the partition function Qi(T) exists in fact, but does not really
affect the equation of state and total thermodynamic functions. The
question as to whether these factors exert an influence on optical and
transport properties is considered to be beyond the problem of the
equation of state of matter.
The most important consequences of the foregoing assumptions are:
• The equations of state (thermal and caloric) and equations for chemical
potentials corresponding to a classical ideal-gas mixture of the particles
with possible small nonideality corrections modified to account for
electron degeneracy are used.
• Spectral and thermochemical characteristics (measured in experiments
or calculated) corresponding to bound states of isolated particles (at-
oms, ions, molecules, etc.) are employed.
Boundaries of applicability of the chemical model are characterized in the
following Sections.

14.2.1. Nonideality Related to Different Interactions of

Free Particles
1. Nonideality related to Coulomb interaction (charge-charge interaction)
is characterized by the dimensionless parameter
 14. Thennodynamic Properties of Shock-Compressed Plasmas 443

2. Non-ideality related to polarization or charge-dipole interaction (inter-

action of electrons and ions with neutral atoms, molecules, etc.) [4,27]
is characterized by the dimensionless parameter
21t<le 2 n. 1
'Yai = «
r.
where a. and n. are the polarizability and the concentration of neutral
particles (atoms), and r. is the cut-off mdius of polarization interaction,
that is, a value close in "size" to that of the neutral particles (atoms).
3. The van der Waals short range attraction between the particles must
satisfy the condition
kBT» min Cl>ii(r),
where Cl>ii(r) is the effective inter-particle short-range attraction poten-
tial. As an efficient indicator of the smallness of this interaction be-
tween neutral particles it is commonly assumed [4] that one should
consider the smallness of the critical temperature of the corresponding
gas-liquid transition in comparison with the temperature of the plasma:
kBT» kBTe - min t1>ii (r).
4. Short range particle repulsion of neutral atoms must be small. An ef-
fective measure of the smallness of this interaction is the smallness of
the "self size" of the particle compared with the mean distance between
particles:

5. As an indicator of this smallness, the ratio of plasma density, P, to the

density at the critical point of the gas-liquid transition, Pc, is often
used. For the majority of substances, the latter constitutes a small but
comparable part of the density in the nonna! state, Po, which charac-
terizes the "self size" of the particles of the material [4]:
P«Pe<PO.
6. For a nondegenerate electron gas we have
ne M «1.

14.2.2. The Effects of Quantum Statistics: Free-Electron

Degeneracy
The chemical model of plasma is widely used to calculate thermodynamic prop-
erties of "gaseous plasma" [1,8,9,25,26] and, in particular, the parameters of
444 V.K. Gryaznov, I.L. Iosilevskiy, and Y.E. Fortov

shock-wave compression in this region. This application of the chemical model

is exemplified by calculation of argon and xenon Hugoniots in [28].
The structure of the system of equations used to calculate the chemical and
ionization equilibrium composition and thermodynamic functions of weakly
nonideal "gaseous" plasma is now standard and has been described repeatedly in
the literature (see for example [1,8,9]). The solution of the corresponding
system of equations is unique [29]. The main feature of the calculated thermo-
dynamic relationships is their smooth and almost monotonic behavior every-
where in the ideal-gas region of the phase diagram (conventionally called the
"gas slope of the nonideality valley"). Against this background of generally-
smooth behavior, nonmonotonicities accompanied by spikes or oscillations of
thermodynamic derivatives can be discovered. From the viewpoint of the equa-
tion of state, these nonmonotonicities are clearly demonstrated and interpreted
[30,31] for specially selected dimensionless thermodynamic parameters. In the
case of the thermal equation of state it is convenient, for this purpose, to use a
compressibility factor (Z = P VIR T) and, with the caloric equation of state, a
nontranslational part of the internal energy U - (3/2)PV, related to any energy
value characteristic of plasma, for example, to the ionization potential Ii. In
these variables the entire area of gaseous plasma is distinctly separated into
sections of quasi-ideal behavior,
PVIRT=const., and (U-3/2PV)/NI=const., (14.7)
and transition regions. From the point of view of plasma processes, these regions
of nonmonotonicity join the parts of phase diagram corresponding to so called
ionization "bands" (ill) [8,21,30]. The presence of such ionization bands leads
to qualitatively approximate quasi -stepped structures for both Eqs. 14.7.
The following are characteristic of ionization bands in the gaseous region:
• Diffuse ionization-band boundaries.
• The proximity of ills corresponding to electron ionization of the same
electron shell and more distinct separation of ills for different shells.
On this basis, the nonmonotonicities discussed are often called shell
oscillations.
• Progressively distinct stratification (separation) of ills as they advance
into the region of low densities and, in contrast, their overlap as they
approach the high-density area.
• Primary sensitivity of thermodynamic quantities inside an ill to varia-
tion of temperature, which is expressed as a clear manifestation of os-
cillations when isochores, isobars, and (to a decreasing degree)
isentropes intersect an ill and smoother behavior when an isotherm in-
tersects a band.
 14. Thermodynamic Properties of Shock-Compressed Plasmas 445

The situation, schematically described above (for more details see [8]), is
typical for classical ideal rarefied plasma. Density rise results in diffusion of IB
boundaries even for an ideal-gas scheme. This process is affected, in addition,
by various nonideality mechanisms resulting, as a rule, in further diffusion of IB
boundaries [8]. As a zeroth-order approximation for describing partially ionized
weakly nonideal gas plasma, wide application is found, for example, of the
approximation of a classical ideal mixture with arbitrary chemical reactions that
is allowed to be multi-ionized and have restricted intra-atomic and intra-ionic
partition functions at binding energies of the order of kBT. The calculation also
takes into account corrections for Coulomb nonideality in the so-called Debye
approximation in the Grand Canonical Ensemble [32], modified for the case of
multiple ionization [8,28,33], as well as corrections for electron degeneracy in
the related ideal gas term of the free energy given by Eq. 14.3. The advantage of
using such an approximation is the absence, in principle, of the possible loss of
thermodynamic stability, which is characteristic of any approximation expressed
compactly as a single formula in variables of the Grand Canonical Ensemble
[8,33]. This is also the reason for uniqueness of the solution for the equilibrium
composition at arbitrary values of thermodynamic parameters and ionization
multiplicity [27].
As a peculiar reflection of the presence in the gaseous region of the
"stepped" structure discussed, it is possible to consider the question of the very
existence and dimensions of such oscillations in the area of extremely high
compressions. The problem is actively discussed in literature and a search for
such oscillations is one of the objects of intensive experimental efforts. The
question of the existence of shell oscillations in the region of compressed matter
remains open (for more detail see Chapter 1 as well the Chapters 3, 4, and 13).

14.3. The Problems of Extrapolating the Chemical Model to

High Compressions
The sources of difficulties arising in extrapolation of theoretical models to the
nonideal plasma area can be conditionally separated into three parts:
1. The consequences of the long-range character of the Coulomb poten-
tial.
2. Quantum effects involving diffraction and quantum statistics of elec-
trons (degeneracy).
3. The presence of strong attraction at small distances between charges of
opposite sign.
446 V.K. Gryaznov, 1.1. Iosilevskiy, and V.E. Fortov

The features of the most interesting cases of real strongly nonideal plasma are
that the three difficulties listed above interfere with the use of theoretical meth-
ods developed for description of them individually.
The special role played by the third of the three items noted above is that it
compels us to pass from a strictly physical description of the plasma character-
ized by a collection of electrons and nuclei to the seemingly more simple and
intuitively clear concepts of the chemical model when the temperatures do not
exceed those required for complete ionization of atoms (to form nuclei).
The problems related to extrapolation of the chemical model to the high den-
sity region may be separated, conditionally, into two parts:
1. The problems of nonideality itself, i.e., calculations of inter-particle
interaction effects based on known (given) interaction potentials.
2. The problems associated with peculiarities of the process of strict theo-
retical transition from the explicit representation of the physical model
to an "efficient" representation of the chemical model.
The problems lie with the necessity to renorrnalize the initial pure Coulomb
interaction between electrons and nuclei to pass to a set of effective interaction
potentials between newly introduced particles. This is necessary, first of all, for
avoiding the so called "double count" when the same portions of phase space of
the initial electrons and the system of nuclei can be repeatedly taken into ac-
count with various combinations of the same particles first as free particles and
later as bound particles [7,8,21].
The main feature of such a renorrnalization in the chemical model is that the
result is not uniquely defined and depends on the specific manner of definition
of the new types of complex particles, i.e., on the selection of conditions for
separating states called free from those called bound. Due to the conditionality
of this separation in the case of strongly nonideal plasma, works dealing with
this problem usually invoke a principle of plasma description (rule) which might
be now considered to be common [7,8,34-36]. According to this principle the
approximation describing plasma should be so constructed that all of the ther-
modynamic variables are independent of the arbitrariness cited above that is
associated with separating the states. In so doing, the selection of the actual
separation method can even be taken beyond the limits of thermodynamics itself
and subordinated to requirements following from one or another peculiarity of
the approximate apparatus employed in calculation of transport properties of
plasma. In particular, it can be different depending on the destination of the
calculated equilibrium composition either for calculation of optical properties or
for determination of transport properties, etc.
One of the immediate consequences of the noted conditionality associated
with division into free and bound states and transition to effective interaction
 14. Thennod}11amic Properties of Shock-Compressed Plasmas 447

both outside and inside of newly introduced complex particles (atoms, mole-
cules, ions, etc.) is supplementary dependence of the partition functions,
Qi(T, s({nj}, T», and the entire ideal gas term of the free energy,
F;d(T, V, {N;J), as well on the thermodynamic parameters by means of a variable
"cut off boundary" s(n, T). This results directly in the appearance of additional
"indirect" corrections to all thermodynamic quantities involving the derivatives
aQI(s({nj},T»/Os. These corrections,

AP ' " nj OlnQj alns (14.8)

L.iNikBT = £..J j -;; alns 81nV'

AU ' " nj alnQj alns hAl (14.9)

L.iNikBT = £..J j -;; alns aln~' were l-' == kBT '

and
All/ ' " n j alnQj alns (14.10)
L.iNikBT = £..J j -;; alns Olnn/ n,

differ fundamentally from the common Coulomb corrections obtained by differ-

entiating the nonideal part of the free energy, AF'CouJ(T, V, {Aj}), and, in the
great majority of cases, are ignored in practical calculations. Comparative analy-
sis of the above effects carried out in [33] for a number of widely used methods
of limiting the atomic partition functions shows that they are specific to a given
substance and depend on the structure of the complex particles. As a whole,
these effects reveal themselves in the region of high pressures of the order of
several GPa, where the ionization approaches the high-temperature area. This is
just the situation realized in compression of matter with strong shock waves. For
example, for Ar and Xe at P-3 x 10 4 bar and T-3 x 10 4 K, the derivatives
8lnQJ8lns involved in Eqs. 14.8-14.10 and taken at the cut off depth kBT are
equal to -0.25. When this restriction method is used, this value is a dimension-
less correction to the internal energy given by Eq. 14.9, whereas the corrections
to Eqs. 14.8 and 14.10 are equal to zero. For hydrogen, the same sum with the
same parameters is equal to -0.1. For alkali metals, particularly for Cs, the cor-
rections of Eqs. 14.8-14.10 are appreciable even at P-1O bar and T-7000K
and are comparable in value in this region with the common Coulomb correc-
tions. It is of great significance that, in employing the restriction of excited
states depending on density, which is inherent to the dense plasma produced by
strong shock-wave compression of condensed matter, the uncommon corrections
discussed appear in general in the expression ofEq. 14.10 for the chemical po-
tential of all particle species. This results in the shift of ionization and chemical
equilibrium affecting mostly the total thermodynamic effect of the mechanism
considered. The analysis [33] indicated that the main qualitative result from
including the corrections ofEqs. 14.8-14.10 is the following:
448 V.K. Gryaznov, I.L. Iosilevskiy, and YE. Fortov

• It is equivalent to additive repulsion.

• It appears simultaneously with intersection of the nonideality boundary

rD~1.

• It is comparable in magnitude with the usual Coulomb corrections.

The neglect of the corrections ofEqs 14.8-14.10 leads to inconsistency ofther-
modynamic values. The inconsistency does not arise when the excited states
boundary and the equilibrium composition are found from the condition of
minimum of free energy. For the existence of such a minimum the boundary
E(n, T) must determine simultaneously the depth of the effective pseudopoten-
tial associated with interaction of free charges and this relationship should be
involved in explicit form in the term AFCouJ describing Coulomb nonideality in
the free energy F.
It should be emphasized that this internal consistency is usually implied as a
correctness criterion inherent to separation of free and bound states in the
chemical model. It is also necessary for the above-mentioned independence of
total thermodynamic quantities from the conditions of such a division in the
region of strongly nonideal plasma In the case of practical calculations, espe-
cially for preliminary estimates, wide (and appropriate) use is made of simpli-
fied restrictions of partition functions at some level independent of the
thermodynamic parameters, for example at the ground states of the atoms, ions,
etc. The restriction of excited states of partition functions by a quantity depend-
ing only on the temperature is also widely applied. The same is true, for exam-
ple, of the widely used so called convergent Planck-Larkin form of the partition
function [37-40] (see also discussion in [7] and [40]). As a whole, the problem
is far from being settled for the strongly compressed plasma produced by strong
shock compression as discussed here.

14.4. Effective Charge Interaction: Modified Pseudopotential

Approach
Extrapolation of the chemical model into a region of strongly nonideal plasma
requires avoiding a double count which can be done, in principle, by introducing
parts of the phase space that are inaccessible to new types of particles [41].
An alternative way consists in one of the two formally correct variants of
action: either division of s-particle Slater sum [42-44,36], or division and corre-
sponding over-determination of the terms obtained by expanding the plasma
thermodynamic potential in the degrees of freedom [45,46]. This approach is
possible (see the discussion in paragraph 1.4 [8]), but is associated with great
formal difficulties. As a result, in the great majority of cases, this solution of the
problem is attempted by introducing a set of effective pair pseudopotentials,
 14. Thennodynamic Properties of Shock-Compressed Plasmas 449

both "external," operating between free particles and "internal," used in calcula-
tion of bound states of (composite) particles. In doing so any limitations (exclu-
sions) on coordinates and momenta of both free and bound particles are
removed.
It should be emphasized that formally correct transition from the physical
model to the chemical model by introducing pseudopotentials results in the
pseudopotentials that, in the general case,

• depend on thermodynamic parameters by means of a variable "cut off

boundary" s(n, T); this results directly in the appearance of additional
"indirect" corrections to all thermodynamic quantities involving the de-
rivatives 8Qi(s({nj}, T)/&,

• are not binary-additive pseudopotentials,

• are not central pseudopotentials, and

• depend on momenta.

In real calculations the problem is always approximated by use of central and

binary-additive pseudopotentials such as those depending on coordinates and,
possibly, thermodynamic parameters (as a rule only on the temperature) [7,9,34,
36,47]. The main qualitative feature of the effective pseudopotentials in the
chemical model, which takes explicitly into account a selection of bound states,
is that they involve an additive effective repulsion compared with an initial
Coulomb potential. The dimensions and intensity of the repulsion are essentially
dependent on the selection of the boundary separating free and bound states and
the specific separation method. A canonical example of such a renormalization
for short-range classical attraction and pair approximation is the work by T. Hill
[48].
The pseudopotential model for the plasma involving a concept of the pseu-
dopotential close to that of [48] was proposed in [42-44] and a series of studies
[36,49] in which the pseudopotential was calculated using hydrogen-like atomic
wave functions. Pseudopotentials of complicated form [49] were then replaced
by a simplified pseudopotential of zeroth-order approximation with a fixed ratio
between the potential depth and the temperature [36]. An important, in principle,
consequence of such a selection was conservation of the relationship between
corrections to pressure and internal energy for free charges, I!J. U = 3 VflP, that is
inherent to classical Coulomb systems.
A variant of the pseudopotential model that is different from [36,49] was
proposed in [21,35] for classical nondegenerate partially ionized plasma. The
basic principles of the model are the following.
450 V.K Gryaznov, IL. Iosilevskiy, and VE. Fortov

• The depth of the electron-ion pseudopotential, <Pie, is correlated with

the location of the adopted aroitraIy boundary, E, separating the free
and bound states:

m~ ( r ) _- -Zie
'VIe
2
- - (1 -e -rler)
r
(14.11)

where cr == cr(n, 1).

• Simultaneously, the same value, E, is the upper boundary of bound

states taken into account in calculating the partition function for atom
and ion. Selection of the meaning and magnitude of the value E (n, T) is
not restricted by the usual separation on relative energy of bound pairs
and may be arbitraIy and correspond, particularly, to a coordinate-wise
principle of the separation, etc.

• The Coulomb form was reserved for ion-ion and electron-electron

pseudopotentials:

m~.( r) -
'VI)
_ ZjZ je 2
--
r

• Once the pseudopotential of inter-particle interaction has been selected,

further approximations necessary to calculate the corrections for
nonideality are considered in terms of the pair correlation function. In
doing so the approach of [8,21,22,27,33,50] was developed and
checked with the Coulomb models characterized by preservation of the
functional dependence ofEq. 14.12 for pair correlation functions

Fab(r) = I±A e- pr -e qr 1± 'Po e-vr sinh(ror) (14.12)

r ror
corresponding to the limit of the weak nonidea1ity [51].

• At the same time, the parameters of this dependence are selected from
general conditions, independent of the smallness of the interaction
(nonideality). Some of these relationships are dominant; those are the
so-called local electro-neutrality rules 14.13 and 14.14-the rules of
zero and second moments of Stillinger and Lowett [52], as well the
thermodynamically correlated interrelation between the electron-ion
correlation amplitude ("screening cloud") and the depth of the corre-
sponding pseudopotential <P •ei (r = 0) of Eq. 14.1 0:
 14. Thennodynamic Properties of Shock-Compressed Plasmas 451

f
n [F+(r)-F-(r)]dr = 1, (14.13)

f
n [F+(r) -F-(r){;~ )dr = 3, (14.14)

- '1'0 == -lnF+ ~ ~[«I>~ (0) - Aile - All;) . (14.15)

• In calculating the effects of nonideality in corrections to the thermo-

dynamic quantities, a shift in the mean kinetic energy of free charges,
AUkin , arising from the virial theorem, is explicitly included through
Eq.14.18:

AUpot =-vnf «I>coul(r){F+(r)-F-(r)}dr, (14.16)

f
AU = -Vn {«I>:i (r)F+ (r) -«I>!e(r)F-(r)}dr (14.17)

V AP = t(2 AU - AU pot} = t(2 AUkin + AU pot), (14.18)

Alli =Aile ~(Ni +NctIAU, (14.19)

where Upot is the potential energy of interaction and Ili and Ile are the chemical
potentials of the free charges. In this case Eq. 14.17 is exact when the pseudo-
potential does not depend on the thermodynamic parameters, and Eq. 14.18 is a
corollary of the virial theorem [53].
A widely used relationship between corrections to the pressure and the inter-
nal energy of free charges, AU = 3 V AP, being valid within the region of weak
nonideality, is no longer valid in the region of appreciable nonideality (rD-1).
This results, in the first place, from explicit consideration of quantum effects
affecting the contribution of the free and bound states and, secondly, is a conse-
quence of the specific method of deducing the chemical model, which expresses
itself in appearance of limitation from below on the momenta at small electron-
ion distances [54,55].
In a qualitative sense, the foregoing effect leads to additive electron-ion re-
pulsion compared with standard Coulomb approximations, where the dimen-
sionless Coulomb corrections depend only on nonideality parameters [55].
The resulting variant of the pseudopotential model [21,35] leads to an ap-
proximation which, in the limit r D -+ 0 (n -+ 0 and T = const.), coincides with
that of Debye and, with increasing density, differs from it by smaller values of
appropriate corrections that are able to eventually change sign and become posi-
tive at (JIm ~ 1* (Fig. 14.3). A plot of the dimensionless configurational energy

• This is the resuh of the adopted division of the particle species when a free electron, near a free
ion, cannot by definition have smaU momentum [41].
452 V.K. Gryaznov, 1L. Iosilevskiy, and YE. Fortov

for the so-called zeroth-order approximation pseudopotential from [36], which is

somewhat different from the pseudopotential ofEq. 14.11, is shown there. One
can see from Fig. 14.3a,b that, for equivalent pseudopotentials, the results
obtained on the basis of the simple relationships 14.6-14.19 given above are in
satisfactory agreement with that of direct numerical simulation using the Monte
Carlo method [36]. This can be considered as confirmation of the conclusion in
[8,33,50] that the general relations 14.12-14.14 are the key conditions for
successful construction of a satisfactory description of strongly nonideal
Coulomb system thermodynamics.

-1

.... .
~

-2
,-,.'
2 "
'I' . /

-5

-6
5/'
0.0 0.5

Figure 14.3a. Effective electron-ion pseudopotential, cD;i(r) (divided by kBT) [35].

Curve 2 is the simplified (zeroth-order) electron-ion pseudopotential of Nonnan et al.
[36] (l3cD;i(0)=-3), curve 3 is the equivalent pseudopotential cDci(r) of the present
model in the fonn ofEq. 14.11 [35] (l3cDci(O) = -6), curve 5 is the electron-ion pseudo-
potential of hydrogen plasma (Nonnan et al. [49]) at T = 103 K, and curve 6 is the
Coulomb potential.

14.5. Thermodynamics of Shock Compressed Xenon and

Cesium Within the Pseudopotential Model
Among the earliest experiments on generation of nonideal plasma in the range of
gaseous densities seems to be the dynamic compression of argon and cesium
using explosive generators, compression of cesium plasma in a preheated shock
tube [58,59], and experiments with electrically exploded wires [60]. Character-
istics of the plasma produced in these experiments are given below.
 14. Thermodynamic Properties of Shock-Compressed Plasmas 453

..
,,
2

/
," PIPo = 1
0.0 k-------,-r----'I,-----,-----j

3
-0.5

-1.0 -

om 0.1 0.5 1.0

y3 =(pe2)3n

Figure 14.3b. Dimensionless configuration energy tl.UINckT of the free charge subsys-
tem given by Eq. 14.17. Curve 1 is the Debye approximation (Debye-Huckellimiting
law - DHLL), curve 2 is the configuration energy of Norman et al. calculated via Monte
Carlo simulation for the simplified (zeroth-order) electron-ion pseudopotential with
jj<Pci(U) = -3 [36] (curve 2 of Fig. 14.3a); curve 3 is the present approximation (line-
arized version, Eqs. 14.11-14.19) for the equivalent pseudopotential IP;i (r) (Eq. 14.11)
with PIPci (0) =-7 , and curve 4 is the nonlinear approximation [21,50] for the equivalent
pseudopotential IP;i (r) with P<ll ci (0) = -6 .

The range of the specific volumes, ~100-3000 cm3/mo1, corresponds to

dense gaseous plasma, p« Po, nrc3 :s: 1, and the "gaseous" parameter
p/Pc~0.01-0.5 for Ar, ~0.05-l.0 for Xe, and~0.0015-0.1 for Cs.

• Pressurerange~0.01-5MPa

• Internal energy of ~ 1000 kJ/mol.

• Temperature range (estimated) is 15-25 xl0 3 K for Ar, 20-50 x10 3 K
forXe, and3-20xl0 3 KforCs.
• Plasma is nondegenerate, i.e., neA/ :S: l.
• Plasma is moderately nonideal, i.e., r D:S: l.
• Estimated ionization is single- or weakly double-order, i.e.,
Ne/(Ne+ M) ~ 0.1-l.2.
It is known that the shock-wave experiment gives information on the caloric
equation of state U(P, V). The ratio (U-3I2PV)/NI is observed experimen-
tally, and it is the nearest quantity to the degree of ionization. It coincides
454 V.K. Gtyaznov. IL. Iosilevskiy. and V.E. Fortov

closely to the mean excitation energy with the degree of ionization in the weakly
nonideal gas plasma [8,35]. The above values agree with such estimates [57].
Experimenters estimate the accuracy of their measurements for Ar and Xe to be
aV-(7-20)% and aH-(3-5)%. The estimates of the accuracy ofa measure-
ment in cesium plasma performed in a preheated shock tube are greater in value
than those given above, especially for the latter series of measurements [59]:
aV-±(4-6)%; and aH -±(2-5)%.
It should be noted that the accuracy and scatter of the experimental data for
Ar and Xe [56,61] are such that their analysis permits no more than determina-
tion of the character and scale of the general deviation as a whole, outlining the
global trend, without the possibility of exact selection from the variety of theo-
retical models proposed in the literature for description of partially ionized,
weakly and moderately nonideal, nondegenerate plasma
In spite of the limited accuracy of the experimental data on the equation of
state of moderately nonideal gas plasma obtained in the dynamic experiments
[56-61], a comparative analysis of these results as well the results ofmultivari-
ant calculations, made using the approximate models [8,21,35,57,59], permits
finding a general trend-the existence of disregarded additional mechanisms of
the effective repulsion compared, for example, with calculation employed as a
zeroth-order or reference approximation (see Fig. 14.2), and involving the
Planck -Larkin atomic statistical sum and essentially all proposed forms of
Coulomb corrections for nonideality in terms of single-parameter functions of
the nonideality parameter r D [21,23].
The inclusion of repulsion in the approximation of the second (and third)
virial coefficients using reference data of [62,63] corresponding, in the physical
sense, to the case of moderately high temperature kT«Ir, i.e., for atoms in the
ground state, fails to explain all the experimental data for Ar and Xe [8,57].
In the case of partially ionized xenon plasma, calculations were carried out
[57] using the above variant of the pseudopotential model [35]. The boundary
between free and bound states of atoms and ions, as well the corresponding
restriction of the atomic statistical sum, have been selected in these calculations
at binding energy depth -kBT, which practically coincides with the known and
often recommended procedure for calculating the statistical sum with the
Brillouin-Planck-Larkin formula [7]. The comparison showed (Fig. 14.4) that
the proposed variant of the pseudopotential model [35] makes it possible to
describe qualitatively and, with the accuracy and scatter of experimental data
being taken into account, quantitatively, the parameters of the measured
Hugoniot curves for xenon. The shift of the Hugoniots obtained with the model
of [35] is, in this case, associated directly with the presence of an explicit (posi-
tive) correction to the mean kinetic energy of free charges, which is equivalent
to the effect of additive repulsion when compared with the majority of ordinary
approximations.
 14. Thennodynamic Properties of Shock-Compressed Plasmas 455
P,kbar

O,QI L-.J~.L...L.u..L._---'-_'---'--'-"""""'L..L.C""""";~_'--'

1 10 Y, cm3/g

Figure 14.4L The phase diagram of xenon [57]. The boundaries of two-phase region
and the critical point, C, are marked. Open circles and triangles designate the experimen-
tal data from [57] and [56] after the real gas EOS corrections [63] for the uncompressed
xenon into which the shock is propagating. Dotted lines designate low temperature
isothenns in the one- and two-phase regions from the handbook [63]. The dash-dot line is
the critical isochore (V = Vc), the broad gray lines are the boundaries of single ionization,
I, [XXe+ = XXe, where (XXe" NXe lNtota1)] and double ionization, II, (XXe++ = XXe+).

An analogous result has been obtained in comparative calculations, based on

the models in [21,35], of the parameters of the shock-compressed cesium plasma
[58,59]. The experiments [58,59] pennitted achievement of a higher accuracy
and coverage of a wider range of pressures and specific volumes and, what is
more important, of the values of the nonideality parnmeter, r D (due to the ex-
tremely low cesium ionization potential). A further distinctive feature of the
experiments in [58,59] and a related series of computational and theoretical
works [58,64] is likely one of the :first realizations of the well-known idea of
Ya.B. Zel'dovich [65] on determination of the temperature from the results of
the shock-wave experiments [23]. However, the accuracy of the temperature
inferred in this way and the specific effect of mutual compensation of various
sources of uncertainty in the model equation of state for Cs in an appointed
range of parameters resulted in compatibility of finally recalculated experimen-
tal results on the basis of the thermal P(V, T) equation of state for Cs with prac-
tically all theoretical approximations proposed later for describing these
experimental data.
However, the direct results of experiments [58,59] for determining the ca-
loric equation of state H(P, V) proved to be such that, on the contrary, the re-
sults of most of the preliminary calculations being compared with the equation
456 V.K Gtyaznov, 1.1. Iosilevskiy, and V.E. Fortov

P,kbar
I
I. ! I
60
i'
!
I

,;
0 I ,
4 40
I
J .,
0 a b c
I :
j : 40 \
o 0 I
I
I
'
0 I
i
:0
!
\
2 20 i d 0
c \\ .! \
! :
\ ,.
\ ~ 20 ,:
\

!o \! :'

\ ~
\> - 10 r- \ : 0 - \ 0

~.
0,8 8 ~,I
\\
I, '\\
0,6 6
\\
I'
10 r- \\ -
I \~~ I
8 I \~\
10 20 30 234 0,5 1,0 1,5 2,0
V, cm3Jg

Figure 14.4h. Comparison of experimental Hugoniots and the results of model calcula-
tions for xenon [57]. Solid lines designate the case in which interaction between charged
particles is taken into account in the modified "ring" (Debye) approximation in the Grand
Canonical Ensemble [28,32], the dash-dot lines designate the case including additional
atom-atom interaction in the second virial coefficient approximation [53], and the dotted
line represents a calculation based on the modified pseudopotential model [35] with
lower free- free interaction (pseudopotential depth) and upper bound (intra-atomic) states
chosen to be equal to -kBT. The pressure of the materiaI ahead of the shock is: a) Po = 1
bar; b)Po= 10 bar; andc)Po=20 bar.

of state for Cs [64] fell systematically beyond the experimental corridor around
the smoothed experimental data for H(P, V). A preliminary conclusion from
[58,59] lies in the fact that, for the greater part of the range of temperature and
pressure in the experiments, a satisfactory description of the experimental data
could be achieved only by completely neglecting all of the traditional forms of
Coulomb corrections for nonideality (taken as one-parameter functions of r D),
as well as any variant (from those verified in [64]) of atomic statistical swn
calculations, with exception of the simplest one, considering only the atomic
ground state. Such a relation between the theory and experiment has led some
specialists [66] to a conclusion on the uncertainty of the experimental results of
[58,59] owing to systematic error.
The use of the pseudopotential model from [35] permits describing the main
qualitative effect of the experiments [58,59] in the region of appreciable ioniza-
tion-shift of the caloric equation of state in the direction corresponding to the
presence of additional effective repulsion. This result proved, however, to be
attainable only in the region of marked cesium ionization. The reason is that the
main attention in the variant of pseudopotential model [35] was paid to charged
 14. Thennodynamic Properties of Shock-Compressed Plasmas 457

particles, and the atomic contribution was taken into account in the ideal-gas
approximation so the above mentioned effect of the foregoing chemical
model-the presence of effectively inaccessible mutual coordinates and mo-
menta for all "free" particles, involving atoms, was taken into consideration only
in describing the contribution of free charges. Below, an approximation is de-
scribed in which an effect of additive repulsion of neutral particles (atoms),
ignored in [35], was put forward. This resulted in an additive effect resembling
that in [35], but this time mainly in the region of small degrees of ionization
(Figs. 14.5a and 14.5b).

2.5 [0=0.6 a=0.9

~"=,~.. ,
..

2.0
~
~
~~ 1.5
0...
,......,
--......,
N
M

I
1.0
--1
::::> ...... 2
0.5 --- 3
...... 4

0.0
0 20 40 60 80 100

P, bar

Figure 14.5a. The caloric equation of state of cesium plasma for the isochore V =200
cm 3/g. The shaded band (±5%) corresponds to the smoothed experimental curve
H(P, V) [59). Values of the nonideality parameter, ro, and degree if ionization are
marked. Curve I represents the Debye approximation in the Grand Canonical Ensemble
[32], curve 2 represents the pseudopotential model [35] with the electron-ion pseudo-
potential depth and the intra-atomic states boundary chosen to be equal to -kBT, curve 3
represents the confmed atom approximation [8,9,57], and curve 4 represents the com-
bined approximations including the pseudopotential model [35] for description of the
charge-charge interaction and the confmed atom model [57] for the atom-atom and
charge-atom interactions.

14.6. Thermodynamics of Shock-Compressed Argon and

Cesium in Terms of the Confined-Atom Model
The simplest estimate of the contribution of short-range repulsion may be made
[48,67,68] in the framework of the second virial coefficient approximation,
computed for the Lennard-Jones potential [53]. It is significant that the proper-
458 V.K. Gryaznov, I.L. Iosilevskiy, and YE. Fortov

2.5

2.0
bO
~
;::..A 1.5
~
,-..

--
N
c.-.
'-'
I
1.0
-.-.-. 1
~ --- A 2
0.5 -3
4
0.0
0 5 10 15 20
P, bar

Figure 14.5b. The caloric equation of state of cesium plasma for the isochore V = 1000
cm 3/g. Notations are the same as in Fig. 14.5a.

ties of this potential are constructed on the basis of experimental data obtained at
moderate temperatures when the great majority of the atoms are in ground
states. The comparison of results of these estimates with the experimental shock
adiabats for Xe and Ar presented in Figs. 14.4 and 14.6 indicates that agreement
is markedly improved, although a systematic difference remains at high com-
pressions, demonstrating the presence of additive repulsion in the system.
Indeed, under the high temperatures and pressures characteristic of the ex-
periments, a great majority of the atoms and ions are in excited states for which
the short-range repulsion parameters exceed those for atoms in the ground state.
This suggests that, under experimental conditions [56-59,61J, the surroundings
will enforce deformation of the bound states and distortion of their contribution
to the thermodynamic functions of compressed plasma.
Description of the above effect requires the use of a quantum-theoretical
model that takes account of the influence of the surroundings on the bound
states of atoms and ions in dense plasma. Calculations for hydrogen in the
framework of the simplest model [69,70J have shown that the effect of defor-
mation of the discrete spectrum appears at densities approaching the critical
point (p~Pcr). Hartree-Fock calculations have been carried out in [57,71J to
determine the influence of compression on the energy spectrum and wave func-
tions of multi-electron atoms and ions. A phenomenological model was consid-
ered in which the effect of surroundings on intra-atomic and intra-ionic electrons
was approximated through the use of the effective potential
 14. Thermodynamic Properties of Shock-Compressed Plasmas 459

-Ze 2 /r, r<rc

<l>(r) ={ (14.20)
00, r ~ rc .

The eigenfunctions and excitation energies of atoms and ions for the potential of
Eq. 14.20 are computed with the Hartree-Fock method. It is known that the
atomic wave function in this approximation is constructed as a linear combina-
tion of determinants composed from the single-electron wave functions

'¥n/ms(r, e, cp) = /nl(r) Y,m(e, cp)x(s) .

r
The coefficients of this combination are defined from the condition that the
complete wave function be an eigenfunction for operators of the total orbital and
spin momentum of the system. The use of the quantum mechanical variational
principle results in the system of equations [72]

d2 /(/+1)]
[ -2 +2Vnl(r)--2-- Snl /nI(r)
dr r
(14.21)

J
= :On/(r,r')/nI(r')dr' + L
n'~n
SnI,n'l/n'l (r),

where V",(r) is the self-consistent potential acting on electrons. No additional

simplifications were adopted in calculating the nonlocal exchange integral in the
right part of Eq. 14.21. Nondiagonal factors Sn/,n7 and eigenvalues SnIr were
found from the conditions
/nI(O) =0, (14.22)

J:in,(r)/n',(r)dr = 8"", . (14.23)

The second boundary condition from Eq. 14.22 corresponds to the potential
14.20.
Solutions ofEqs. 14.21-14.23 [71,73] for various values of rc determine the
dependence on this parameter of the partition functions Q;(T, r c ), employed in
the chemical model in calculating the composition and thermodynamic func-
tions. At given Vand T the equilibrium value of rc is determined from the mini-
mized free energy condition

(OF)
orc v T
=0
'
(14.24)

where
460 V.K. Gryaznov, I.L. Iosilevskiy, and VE. Fortov

4-3y
f(y) = y (1- y)2 (14.26)

y = 47tna3 rt na Va,

and
Mi.s _ f'( )-2 2-y
na kB T - Y Y - Y (1- y)3
(14.27)
l\llhs = f( ) + f'( ) = 3y2 - 9y+S .
kB T Y Y Y Y (1- y)3

The free energy is dependent on rc flrst through the partition functions of atoms
and ions Qj(T, rc), and second, through a correction &i'hs describing approxi-
mately the effective short-range repulsion of bound complexes in the hard
sphere approximation [74].
In contrast with conventional cell models of compressed substances [20,75-
SO], this approximation is constructed on the basis of a quasi-chemical approach
involving explicit consideration of translational degrees of freedom of all parti-
cle species. We emphasize that, in this model, all electrons are separated into
two types and located both inside and outside the cells. The volume occupied by
the atomic and ionic cell, Vc = 47tr/ /3, is only a part of the mean volume corre-
sponding to one nucleus.
In calculating the partition function in [SI], a particle is associated with the
entire volume corresponding to this particle, whereas in calculating the hard-
sphere repulsion in Mi'hs using Eq. 14.25, an appreciably smaller volume begin-
ning with that the ground state is markedly shifted. It was established in [S2]
that selection of the cell radius rc such that the flrst maximum of the radial dis-
tribution function of the hard sphere system is coincident with that measured
experimentally at the melting point density results in very close values of the
corresponding packing parameter for a number of metals:

y(Tmelt ) ==
47tn melt rt = na Vmelt ~ 0.45 . (14.26a)
3
 14. Thermodynamic Properties of Shock-Compressed Plasmas 461

The variational procedure employed in [57] is more consistent from the

thennodynamic point of view. Complemented by the standard method of calcu-
lating thennodynamic equilibrium [28], it was employed in [57] in order to
calculate argon Hugoniots. A comparison of these results with experimental data
is presented in Fig. 14.6. It shows that the Hugoniot shift obtained reflects cor-
rectly, as a whole, the tendency emerging in the experiments with Ar and Xe,
but somewhat overestimates the real value of the effect observed in [57], espe-
cially for densities close to those of critical point. This is likely associated with
the fact that the hard sphere repulsion accepted in the above model overesti-
mates the actual repulsion between atoms at short distances, and the model of
"soft" spheres is more accurate for quantitative description [83,84].
The self-consistent variational procedure for Ar was not fully realized in
[57]. This work involved only the atomic part of the complete dependence of
free energy on the boundary radius, Ye , separating free and bound states on the
basis of a coordinate criterion. Due to this fact, the resulting effect manifested
itself first at low degrees of ionization. In tum, the main effect of the pseudo-
potential model in [35] was taken into consideration, in contrast, only for free

P, kbar

00
10

Figure 14.6a. The phase diagram of argon [57). The boundaries of the two-phase region
and the critical point CP are marked. Open circles and triangles designate the
experimental data from [57] and [56] after the real gas EOS corrections [63] for the
uncompressed argon into which the shock is propagating. Dotted lines designate low
temperature isotherms and the T= 290 K isotherm in the one- and two-phase regions
from the handbook [63). The dash-dot line is the critical isochore (V = Vc) and the broad
gray line, I, is the single-ionization boundary (!GAr+ = !GAr, !GAr = NArINU:J,aJ).
462 V.K Gtyaznov, I.L. Iosilevskiy, and V.E. Fortov

P, kbar
2 ,......."....,......r-r-.-r-r-, ,
7 •~
;.
6 ""
a b
5 ib 20
\1
4
0,8
3
0,6 10

2 8
0,4
6

4
20 30 40 3 4 5 6 7 8 9
3
V, cm /g

Figure 14.6b. Comparison of the experimental Hugoniots and the results of model cal-
culations of argon [57]. Solid lines represent the case in which the interaction between
charged particles is taken into account in the modified Debye ("ring") approximation in
the Grand Canonical Ensemble [28,32], the dash-dot line represents the additional atom-
atom interaction in the second virial coefficient approximation [53], and the dotted line
represents a calculation based on the confmed atom model [8,9,57]. The pressure before
shock compression is: a) Po =1 atm., b) Po =5 atm. and c) Po =20 atm.

charges. The calculation combining both of the above approaches has been car-
ried out in the case of the caloric equation of state for cesium in the parameter
range covered in the experiments with a heated shock tube [58,59]. The result
obtained is shown in Figs. 14.5a and 14.5b).
The agreement between computed and experimental data for the caloric
equation of state for cesium points to the importance of an effect specific to the
chemical model that was considered in both approaches-the explicit restriction
of phase volume assigned by definition for realization of bound states of com-
plex particles.
At the same time, it should be noted that the hard wall approximation ("nut-
shell" boundary condition 14.22 modeling, in the potential of Eq. 14.20, the
effect of dense plasma surroundings on the bound states) on the one hand, Eq.
14.26, and mutual impenetrability described by the Carnahan-Starling correc-
tion of free complexes on the other, are too rough and qualitative. As a result,
the total effective repulsion in the model proved to be overstated This fact
manifests itself in the thermal equation of state both for Ar and Cs, where the
 14. Thennodynamic Properties of Shock-Compressed Plasmas 463

use of the confined atom model results in overstated pressures when the model
is extrapolated to high densities. Thus, a partial description of temperature
measurements in argon [8,56,61] is possible (Fig. 14.7). However, the results of
temperature measurements cannot be completely reproduced in such a manner.
Therefore, further efforts are necessary to improve the confined atom model in
order to develop more realistic models of effective intra- and extra-atomic po-
tentials in the chemical model.
It should be noted that results of direct measurement of the equation of state
for argon presented in Fig. 14.7 [56,61] were not of very high accuracy, so the
main substantial conclusion from these experiments lies first of all in fixing the
general qualitative trend-a noticeable influence of additive repulsion mecha-
nisms not included in the majority of models used in applied calculations. The

2,0

1,9 1--1 -1 /
o -2 i
/
1,8 ---3 /
/ 1/
-------- - 4
-.-.-._-.-. - 5
1,7 !
!

1,6 !
/ /
/
i

!:2 1,5
:>
~
! /

1,4 , T=20000K
.,........., .....

1,3

1,2
T= 16000K ____
--.--.~

1,1

o
1,0
0,1 1,0 10
P, khar

Figure 14.7. The thennal equation of state of argon plasma within the parameter range:
P = 0.1 -20 kbar and T = 5000 - 23000 K [8]. Curve 1 represents the experimental data of
[56,61], points 2 represent a calculation of the specific volume V(Pexp. T""I') for each
experimental point using a charge-charge interaction within the modified Debye ap-
proximation in the Grand Canonical Ensemble [28,32]. Curves 3, 4, and 5 are calculated
isothenns for T= 16000 K and 20000 K. The approximations used are, 3: calculations
based on a modified pseudopotential model [35] (pseudopotential depth and boundary of
intra-atomic states are chosen to be equal to -kBT), 4: approximation 2 with additional
inclusion of the second and third argon virial coefficients [53], and 5: calculation based
on the confmed atom model [8,9,57].
464 V.K. Gryaznov, I.L. Iosilevskiy, and V.E. Fortov

same conclusion follows independently from an analysis of the results of meas-

urement of the caloric equation of state of argon carried out in the same experi-
ments [56,61] in parallel with measurement of the thermal equation of state. The
results of comparison of the complex of theoretical and experimental data ob-
tained in [56,61] are presented in Fig. 14.8, where a general gap of the experi-
mental data relative to calculations is distinctly demonstrated. Such a gap may
be reproduced in the coordinates used as an effect of the absence of a contribu-
tion of excited states and conventional attractive Coulomb corrections [8,21].

14.7. Extrapolation of the Chemical Model to the Region of

High Densities: Hugoniots of Porous Metals
The complete variational procedure described above, considering explicitly a
peculiarity of the chemical model of matter when applied to a region of high

30 ~~~~-.~--.-.-~~~--~.-~~-.~

I?:{j~

i--------4 - 1 T=20000 ~/
t:. - 2
[] - 3
~
I
II
20
o - 4
(j~ ~ II
--------. - 5

10

o ~~~~~~~~~-L~~_ _~~~~~~

o 2 4 6 8
PV,kJ/g

Figure 14.8. The caloric equation of state of argon plasma [8]. Curve I represents the
experimental data from [56,61]. Points 2, 3, and 4 represent calculations of specific
volume V(Pexpo Hexp) for each experimental point in the following approximations: points
2: modified pseudopotential model [35] (the pseudopotential depth and the boundary of
intra-atomic states are chosen to be equal to -kB1), points 3: calculation with the use of
the modified Debye approximation in the Grand Canonical Ensemble [28,32] for charge-
charge interaction, points 4: the confmed atom model [8,9,57], and curve 5: calculated
isotherm for T = 20000 K according to the modified pseudopotential model [35].
 14. Thennodynamic Properties of Shock-Compressed Plasmas 465

densities-a restriction of the phase volume assigned by definition to achieve

bound states of composite particles-is rather complicated and bulky in its
formal aspects. To perform a preliminary test for the possibilities of extrapola-
tion of the chemical model to the region of high and ultrahigh densities it was
found appropriate to employ a simplified version that qualitatively reflects the
main features of the complete variational procedure for realization of the con-
fined atom model. Such an approach [24,85-88] was used in investigating the
physically important temperature and pressure range corresponding to densities
intermediate between the cases of rarefied gaseous plasma on the one hand and
normal or even compressed states on the other. According to the figurative terms
employed in [9], this region corresponds to the assumed position of the so called
nonideality valley and can be achieved in experiments on shock compression of
porous samples of condensed matter (see Figs. 14.1, 14.2, and Chapter 5). The
following constituents of a complete thermodynamic approximation were used
in the simplified version of the model under consideration.
The free energy of a quasi-neutral mixture of electrons, ions, and atoms may
be written as the sum of ideal gas components and a term relating to inter-parti-
cle interaction:

(14.28)

The atoms and ions were supposed to conform to Boltzmann statistics, and their
contribution is of the standard form

(14.29)

where the Qj are the partition functions of atoms and ions.

Electron Degeneracy. Electrons were regarded as a partially degenerate ideal

Ferroigas:

ug = 3 peo = h/z (Ile /kBT)

(14.31)
Ne kB T 2 ne kB T h/z(lle/kBT)

Here the electron density, n., and the chemical potential, Ile, are related by the
equations
466 V.K. Gtyaznov, I.L. Iosilevsldy, and V.E. Fortov

~ 27C1/2IJ/2(~)
neA =

f
kBT
(14.32)
It(x) = ytdy .
l+exp(y-x)

It is of great importance to consider the effects of electron degeneracy in this

region of the phase diagram since the degeneration parameter, ne M, may be as
much as a few units.

Coulomb Interaction. Coulomb interaction was taken into account in the

framework of the Debye approximation for the thermodynamic potential n in
the Grand Canonical Ensemble [28,32]:

n _ F-LoNjJ.1j
J P
--=
VkBT VkBT kBT
(14.33)

where the Coulomb nonideality parameter rh is defined by the equation

_ (e2)2 ( e2 )3 ~ Za (14.34)
r6= rnkBT =41t kBT ~a.l+tz.Hh'
with rD being a screening parameter. We notice that rh differs from the ordi-
nary Debye nonideality parameter ro :[41t(e2/kBT)3La.naZ&]-1/2. The ap-
proximation of Eqs. 14.33 and 14.34 is equivalent to the classical Debye-
r
Huckel approximation in the limit D ~ 0, but is thennodynamically stable
[21] for any values of plasma compression (the matrix II OJ.1i IOni" is positive
definite).

Bound States were limited by the ground state, with unperturbed energy values
of isolated atoms being involved. Their effective shift (as a whole) under the
effect of dense plasma surroundings emerges as an interparticle interaction.
Broadening due to the action of strong plasma microfields was not taken into
account.

Short-Range Atom-Atom and Ion-Ion Repulsion was taken into account.

Because of the high density, the effect of overlapping atomic and ionic electron
shells results in appearance of repulsion between heavy particles at short dis-
tances, which was described in the framework of the hard sphere mixture ap-
proximation (Mansoory fonnula) [89,90]
 14. Thennodynamic Properties of Shock-Compressed Plasmas 467

~
AFHS
k =/HS (V ) =X V 2 +3Y-+(X
V -1)ln(l-v) , (14.35)
int BT (I-v) I-v

4n
v=-nr 3
3

(14.36)
Y =r2 rl V)-I
- Ljnir/
rk =--
Lin;

where, for k = 1, 2, 3. The appropriate contributions to pressure, energy, and

chemical potential of the system are

Mils a/HS (v)

=----:-:-.:...........=....::....:...--.:......:...
Lin;kB T Ov

AUHS =0 (14.37)

Allj = /HS(V)+ ~ nj a/HS(v) .

kBT L...J j Oni
Additional Short-Range Attraction. Calculations based on approximations
14.28-14.37 indicate quite acceptable agreement with experimental Hugoniots
for metals at high shock wave velocities. Allowance for the short range repul-
sion is of great importance and appreciably improves the agreement. However,
no set of radii rj which could describe the experimental data in terms of above
approximation exists in a limited area of the phase diagram. This is associated
with the fact that the relationships 14.28-14.37 do not involve a mechanism
taking into consideration the binding energy related to the condensed state of the
substance. This effect was allowed for by including an additional attraction in
the form

AF=AU=-A( L Ni)I+Il V - 1l

AP= 8 (AUN) (14.38)

AIl=-A{1+8)V-Il( LNir '

where A and 8 are constants.

468 V.K. Gryaznov, IL. Iosilevskiy, and Y.E. Fortov

The summation in Eq. 14.38 is carried out either over atoms or over all at-
oms and ions.
The shock-compression parameters for porous samples of a number of met-
als were calculated using a simplified variant of the theoretical model described
above. The metals most favored for application of the chemical model were
expected to be those for which samples of maximum porosity were subjected to
shock compression to produce compressed samples of minimum density. Thus,
particular attention has been given to the experiments with nickel and copper
plasma [5]. Calculations were also carried out to determine the shock compres-
sion parameters of porous lead [5].
For practical realization of calculations using the above model, it was neces-
sary to solve the problem of selecting values of "intrinsic volumes"- the sizes
of all particles, primarily atoms (molecules) and ions of different multiplicities,
which must be employed in the simplified version of the model replacing the
complete variational procedure. Two approaches have found application in the
calculations of [24,87,88]. The first employed the calculated results from [85],
where ground state energies of copper ions Cu+2 - Cu+7 under confined cell con-
ditions were found by the Hartree-Fock method. The calculations have indi-
cated that the energy for every multiplicity, computed for the potential of Eq.
14.20 (an ion in the "shell"), begins to increase sharply with compression start-
ing from some threshold distance, which is different, generally speaking, for
ions of differing multiplicity. As this takes place, the value of the "intrinsic size"
defined in such a manner decreases monotonically with increasing ion multi-
plicity so a ratio of corresponding sizes remains approximately constant:
(14.39)
Extrapolation of Eq. 14.39 to the atom and first copper ion allows associating
the radii of all ions with a single reference dimension equal to the atomic radius.
The selection of this basic value is of much importance and determines the re-
sults of all subsequent thermodynamic calculations (see [85,91 D. With these
circumstances in mind, the selection of the reference dimension in [87] was
carried out using a semi-phenomenological approach [82]. In line with these
assumptions, the best value from the viewpoint of reproducing experimentally
measured structural factors of liquid metals at the melting point proved to be the
dimension providing a value of the so called packing parameter, the dimension-
less density of the hard sphere system employed to describe short-range repul-
sion, that was approximately equal for all metals:
(14.40)
This condition was used to determine the metal atomic radii, rc , from values of
their known normal density. The radius values of Table 14.1 were obtained for
Cu, Ni, AI, Pb, and Fe.
 14. Thennod}1lamic Properties of Shock-Compressed Plasmas 469

Table 14.1. Adopted values of atomic radii.

Metal Cu Ni AI Pb Fe
rc (atom) 2.00 2.00 2.27 2.80 2.05

The calculated parameters of the Hugoniot for porous copper are given in
Fig. 14.9.
Along with the procedure described above for selecting intrinsic sizes of
heavy particles, it seems to be useful to verify the possibilities of a considerably
simpler (and suitable from a practical point of view) approximation using easily
available information for individual substances that is already involved in cal-
culations using the chemical model-a set of ionization potentials for atoms and
ions. To be more precise, determination of the ratio of intrinsic sizes of atoms

P,GPa

4 6 8 10 6 8 10 6 8 10 6 8 10 8 10 12
p,g/cm3

Figure 14.9. Hugoniots of porous copper, a: m = 3, b: m = 4, c: m = 5.5, d: m = 7.2, and

e: m = 10 (m == Po/Poo is the initial porosity of the Cu samples). For the curves, we have 1:
a calculation based on the model ofEqs. 14.28-14.42, where the summing in Eq. 14.38
extends over the atoms, 2: experimental data [92], 3: experimental data [93], 4 in b:
experimental data [94], and curves 4 in a and 5 in b: calculation based on the model of
Eqs. 14.26-14.36 with the changed atomic and ionic radii r c(atom)=2.0 a.u. and
rc(Cu+ 1-CU+3)= 1.75 a.u.
470 V.K. Gryaznov, I.L. Iosilevskiy, and V.E. Fortov

and ions is carried out using the ratio of the sizes of so called "classically acces-
sible regions" [95,96], corresponding to the simple relationship
(14.41)
The value of the reference "atomic" radius was found as before from a relation
following from the Ashcroft-Leckner rule, Eq. 14.40 [82].
Compared with the previous procedure, the set of radii defined in this way
constitutes, as a rule, a monotonically decreasing sequence having, however,
marked oscillations. They reflect, to some extent, the individual shell structure
of every element For Ni, Cu, Pb, and AI, this approach gives the sequence of
mdii (in au.) presented in Table 14.2.

Table 14.2. Radius values (in au.) adopted for Cu, Ni, AI, Pb, and Fe atoms and ions.
z(i) 3
0 1 2 4 5 6 7 8 9 10 11 12
Cu 2.00 1.700 1.55 1.40 1.25 1.10 0.95 0.8 - - - - -
Ni 2.00 1.684 1.27 1.10 1.00 0.84 0.80 - - - - - -
Pb 2.80 2.800 1.96 1.96 1.75 1.60 - - - - - - -
AI 2.27 1.45 1.25 1.10 1.00 0.92 0.84 0.78 0.71 0.61 0.5 0.2 0.1
Fe 2.05 2.00 1.58 1.18 1.075 0.90 0.904 - - - - - -

The simplified initial procedure described above for determining the mtios of
ionic and atomic radii, Eqs. 14.39-14.41, [10,88,124] was afterward improved
significantly. The Hartree-Fock calculations of electronic structure of atoms as
well as a number of ions have been provided [127,128] as input for determina-
tion of the mtios of the radii. Within this approach, average mdii of all necessary
atoms and ions were calculated for each electronic shell of the atoms and ions
with the use of occupation numbers, qrrl, and mdial wave functionsf",(r):

{r}= ~ foo rqn'f~(r)dr. (14.42)

L.Jn1 0

The mtios of atomic and ionic radii which were obtained with the use of Eq.
14.42 have been used as input pammeters in the thermodynamic model repre-
sented by Eqs. 14.28-14.38.
The results of Hugoniot pammeter calculations for highly-porous Cu, Ni, Fe,
and AI with the use of the "intrinsic sizes" given above are presented in Figs.
14.9-14.12.
The sensitivity of the final Hugoniot to the influence of different constituents
of the accepted variant of nonideality effects theoretical description is illus-
tmted, for example, by the Hugoniot of nickel with porosity m = 10 as shown in
Fig. 14.13.
 14. Thennodynamic Properties of Shock-Compressed Plasmas 471

P,
e d c b a

-1 -1 -1 -1
o 2 o 2 o 2 o 2
• 4 • 4

10 1

246 8 468 468 6 8 10 6 8 10

p, g/cm3

Figure 14.10. Hugoniots of highly porous nickel (m» 1) [24] (a) m=S.4S; (b) m=7,2;
(c) m = 10; (d) m = IS; (e) m =20 (m == Po/Poo is the initial porosity of the Ni samples) For
the numbers of items on the charts, we have 1: calculation based on Eqs. 14.28-14.42,
swruning over atoms in Eq. 14.38, 2: the main part of the experimental data [92,122],
3(a): experimental data for m = S.62 [92,122], 4(d,e): the last two experimental points for
m = IS and m = 20 (124).

The comparison shows, first, two important facts.

1. The key consideration in achieving even rough agreement of calcula-
tions with experimental data in the region of high pressures is an allow-
ance for strong short-range repulsion of atoms at small distances. When
the latter is disregarded, the chemical model markedly overstates the
density values in shock compression.
2. In the absence of the term of Eq. 14.38 describing the mechanism of
metal binding energy, the chemical model under consideration does not
involve a region of reduced pressures on the Hugoniot for whatever
atom and ion radii were selected. Because of the semi-phenomenologi-
cal character of the correction terms 14.38, the variant of the chemical
model presented for this region of reduced pressures is an extrapolation
type of equation of state.
As a whole, comparison of calculated and experimental data for nickel and cop-
per indicates that, with this extremely simplified approximation the chemical
model, it is possible to describe satisfactorily the experimental results on shock
472 V.K. Gryaznov, IL. Iosilevskiy, and Y.E. Fortov

100
m =20 m=10
(--' Po

~
\9. 8-- 3

10

··0 '"

··0····,..,
".
"

2 4 6 8
p, g/cm'

Figure 14.11. Hugoniots of highly porous iron (m =5, 10, and 20) (m;: Po/Poo is the
initial porosity of the samples) [123). Points 1 represent experimental data [124], curve 2
represents results of calculations in the zeroth-order approximation of the chemical ap-
proach of Eqs, 14.28-14.42, and curve 3 represents calculations results with Coulomb
corrections within the modified pseudopotential model ofEqs, 14,11-14.19 [123).

102
--1

13'"
p.;
l:;.
o
3
4
l:;.
o
3
4

10 1
'--
,',
\,.)

0
10°
1 2 3 2 3 4 5 2 3 4 5 6 3
p, g/cm

Figure 14.12. Hugoniots of porous aluminum. (a) m = 2, (b) m = 3, and (c) m = 8

(m == Po/Poo is the initial porosity of the AI samples). Curves 1 represent calculations
based on the model of Eqs. 14.28-14.42, where the sums in Eq. 14.38 run over atoms.
Points 2 represent experimental data from [129], points 3 represent experimental data
from [130], and points 4 represent experimental data from [94).
 14. Thermodynamic Properties of Shock-Compressed Plasmas 473

7 P, bar Po
10
;
i
\ 0
I
~ 2
\\ .......... 3
:',
,\\ ---- 4

\~\ ~.~.~~ ~
\ . \:~,," _._._. 7

'. . .'::2?:~

2 4 6 8 10
3
p,g/cm

Figure 14.13. Nickel Hugoniot for m == Po/Poo =10 [24]. Comparison of results calcula-
tion using various different theoretical approximations. Points 1 represent experimental
data [92,122]. Curve 2 represents the ideal plasma approximation (ground states only for
atomic partition function), curve 3 represents the same calculation as 2 with additional
Coulomb corrections from Eqs. 14.33-14.34, curve 4 is the same as 3, but with Planck-
Larkin partition functions for atoms and ions, curves 5, 6, and 7 are the same as 4 but
with addition of short-range repulsion corrections in the hard-sphere mixture approxima-
tion of Eqs. 14.35-14.37, curve 8 is the same as curves 5-7 but with addition of short-
range attraction corrections from Eqs. 14.28-14.41 with 0 = 1 (only atom-atom
attraction), and curve 9 is the same as curve 8 but with increased (+20%) mdii of atoms
and ions.

compression of samples of sufficiently high porosity. Moreover, as it was previ-

ously, the possibility of extrapolating the chemical model at a given pressure
decreases progressively with advance into an area of Hugoniots corresponding
to lower porosities and higher densities.
Confirmation of this is the fact that, among the results cited (Fig. 14.10), two
experimental points corresponding to maximal pressures at m = 15 and m =20,
were published [124] after the theoretical Hugoniots were calculated. Good
agreement of new experimental data with results of calculations accomplished
earlier additionally manifests the correctness of the basic background of the
474 V.K. Gtyaznov, I.L. Iosilevskiy, and V.E. Fortov

procedure for generalization of the chemical model for extending its extrapola-
tion properties. It should be emphasized that additional experimental data under
discussion correspond to both maximal (for nickel samples of given porosity)
pressures and, in accordance of with present calculation, maximal temperatures
and the degree of ionization of nickel plasma achieved experimentally. This is
illustrated in Table 14.3 where, together with experimental data, a set of calcu-
lated thermodynamic values is presented corresponding to the region of the
nickel phase diagram explored experimentally.

Table 14.3. Comparison of experimentally measured [124] and theoretically calculated

[123] thermodynamic parameters of nickel plasma after shock compression of extra-high
porosity nickel samples (m == Po/poo = 15-20).*
Ni (Poo = 0.592 glcc, m = 15)
D. km/s U. km/s p. kbar p, g/cc H. kJ/g T,K ro I1eA./
Experiment 11.5 9.36 637 3.18 56.65
[124]
Theory 11.5 9.33 637 3.08 56.97 53300 7.1 1.49
Eqs. Xe X. X+ X+2 X+3 a,km/s Gr S,J/gK
14.11-14.19 0.583 0.094 0.064 0.254 0.003 6.32 0.58 3.922

Ni (Poo = 0.444 glee, m = 20)

D. km/s U. km/s p. kbar p, glcc H. kJ/g T,K ro I1eA./
Experiment 11.9 9.74 516 2.42 61.6
[124]
Theory 11.9 9.76 516 2.48 61.3 54000 6.4 1.24
Eqs. Xc X. X+ X+2 X+3 a,km/s Gr S,J/gK
14.11-14.19 0.596 0.076 0.061 0.263 0.003 6.23 0.52 4.075
* Notation: D and U are the shock and mass velocities, P, p, H, S are the pressure, density, enthalpy,
and entropy of shock-compressed nickel, a is the sound speed, Xl is the equilibrium plasma ionization
composition, rD"'e 2lk B Trois theDebye nonideality parameter, l.2",h 2/21tm.kB Tis the thermal
de Brogle length, and Gr '" [p(oHloP)p - 1]"1 is the thermodynamic Gtilneisen paranteter.

The comparison of experimental and calculated data permits drawing the

conclusion that the chemical model of matter discussed is sufficiently adaptable
and has quite suitable extrapolation properties for describing the parameters of
shock compression throughout a wide range of variables. In addition to tradi-
tional fields of application of the chemical model-an area of sufficiently rare-
fied "gas" plasma-it also includes the area covered in dynamic experiments
conducted to study porous metals. It should be noted that, as follows from de-
tailed comparison of calculated and experimental data, it is very important to
include the effect of short-range repulsion between heavy particles in the chemi-
cal model of plasma The essential role of this effect, described in the hard
 14. Thermod)1lamic Properties of Shock-Compressed Plasmas 475

sphere approximation, was pointed out in [85]. Later, a similar statement con-
cerning the use of the hard sphere approximation in calculating the nuclear con-
tribution to the common cell model of shock-compressed matter was advanced
in [97]. Again, it was fruitful the use the hard sphere approximation in extrapo-
lating the chemical model in order to describe dense strongly nonideal plasma
conventional for astrophysical application of dense hydrogen-helium plasma
[90]. We must also emphasize that, as stated earlier, a satisfactory description of
the caloric equation of state does not ensure an adequate description of the ther-
mal equation of state or the reproduction of structural properties of matter in-
cluding, first of all, its equilibrium composition.

14.8. Ultrahigh Heating and Compression: Hugoniots of

Solid Aluminum, Iron, and Nickel
As mentioned above, the conditions in which the modified version of the chemi-
cal model discussed here is applied are more favorable the smaller is the density
of the matter at a given temperature (pressure). There is, however, another limit,
in which this modification of the chemical model yields satisfactory results. This
is the region of states corresponding to conditions of extremely strong shock
compression, i.e., the region of Ultrahigh temperature. These conditions were
obtained in experiments [98] with super-intensive shock waves. They provided
uniquely high pressures, 400 TPa, temperatures, (1-7) x 106 K, and internal
energy densities, 5 xl03 -6 x 104 kJ/g, in aluminum shock compressed to 4-5
times the normal crystalline density. Due to the extremely high temperatures
prevailing under these experimental conditions [98] the matter is expected to be
in a multiply ionized state. The main mechanisms of inter-particle interaction in
this state are the Coulomb interaction and short range repulsion of the ions at
small distances [85], against a background of a relatively small contribution of
electron degeneracy (ne M -1 ).
The work in [85] employed an average radius r e , independent of the values
of temperature, density, and ionization multiplicity. In describing the behavior
of matter over a wide range of temperatures and pressures (1-400 TPa), it is
necessary to take into account the relationship between the ion radius and the
plasma parameters. Such a relationship is associated with successive ionization
of atomic electron shells with increasing temperature, increased ion multiplicity,
and a decrease in the intrinsic size of heavy particles.
In order to estimate the correlation between the radii of the ions of various
multiplicities, calculations were carried out to determine the electronic structure
of all ground states and several states of low excitation for the atom and the ions
AI I-AI XIII by the Hartree-Fock method [9,99]. Calculation of the Hugoniot
for strongly compressed copper [85] has shown that best description is achieved
with radii somewhat less than that at which the corresponding atomic structure is
476 V. K Gryaznov, I. 1. Iosilevskii, and V. E. Fortov

undergoing ionization by compression. The ionic radii, indicated in Table 14.4

(in atomic units), were used in describing shock compressed aluminum plasma.
The dependence of Yc on ionization multiplicity determines the particular form
of configurational part of the Mansoory chemical potential 14.37 associated with
a shift in the direction of larger ionization compared with [85], where
Yc(i) = y c = const. was assumed.

Table 14.4. Adopted radii of effective short-range repulsion for aluminwn atom and ions
[99].
Z o + 1 + 2 + 3 + 4 + 5 + 6 + 7 + 8 + 9 + 10 + 11 + 12
(i)
Yc ,a.u. 2.27 1.45 1.25 1.10 1.00 0.92 0.84 0.78 0.71 0.61 0.50 0.20 0.10

An analysis and comparison of the influence of various values of rc(j) (with

yc(i) = Yc = const.) and other plasma effects on the fonn of computed Hugoniots
indicate [91] that, as under the conditions of [85], in the case of aluminum
plasma of ultrahigh parameters, the contribution of short-range repulsion is the
most essential. Variations of yc(i) within the limits of 10-20% exert the primary
influence on the fonn of the Hugoniot [91], whereas the effects associated with
excitation and degeneracy of electrons introduce an appreciably smaller contri-
bution into the total thennodynamic quantities. The value of plasma nonideality,
r D == 1, pennitted use of the Debye approximation in the Grand Canonical
Ensemble used to describe the Coulomb effects.
Fig. 14.14 presents a comparison of experimental data [98,100-104] and
calculations [76,77,79,105] with calculations based on the model proposed here,
taking into account interaction of charged particles, electron degeneracy effects,
electron excitation, and short-range ion repulsion.
It should be noted that consideration of short-range ion repulsion based on
the hard-sphere model of Eqs. 14.26-14.27 also permitted appreciable im-
provement in the description of Hugoniots for aluminum, even in the framework
of a modified Hartree-Fock-Slater model [106]. Therefore, it may be suggested
that, in the region of ultrahigh plasma pressures and temperatures discussed, the
method used for description of electrons in atomic cells proved to be of compa-
rable, or even less, importance in a thennodynamic sense than inclusion of ion
repulsion at short distances.
Extrapolation of the chemical model to the range of extrahigh pressures and
temperatures has also been attempted for iron plasma [123]. In this case, the
modified version of the pseudopotential model described in Section 14.3, gener-
alized for multistage ionization, was developed. In view of the high values of
density reached under super-strong shock compression of iron, the approxima-
tion of Coulomb interaction described above was combined with restriction of
the partition function bound states of multiply-charged ions to the average dis-
 14. Thermodynamic Properties of Shock-Compressed Plasmas 477

P,GPa
10'r-~~~~-T~~~~~~~~~

D 1
+ 2
•0 3
4
<> S
t::. 6
10' ._-----_. 7 ""
-_. 8 }
- 9
--p'p
10
--11

104

2 3 5

Figure 14.14. The principal Hugoniot of aluminwn (m = 1.0). Points 1-6 represent
experimental data from the following sources: I: [102], 2: [103], 3: [104], 4: [98], 5:
[101], and 6: [100]. Curves 7-11 represent results of calculations made using the follow-
ing models: 7: INFERNO [lOS], 8: MHFS [77], 9: TFC [76], 10: SCA [79], and II:
present calculations based on the chemical model approach ofEqs. 14.28-14.38 (see the
text).

tance between heavy particles (Wigner-Seitz radius). Results of the calculation

are presented in Figs. 14.15(a) and 14.15(b) in comparison with experimental
data.
The comparison demonstrates more than satisfactory agreement with ex-
perimental data of various authors. It should be stressed that the states of the
shock-compressed iron plasma described correspond (in terms of the chemical
model) to the plasma states ranging from those that are strongly coupled to those
that are weakly coupled and have varying degrees of ioni:mtion, electron degen-
eracy, and noticeable temperature variation. This is illustrated in Table 14.5,
where the sequence of thermodynamic parameters mentioned, calculated via the
modified pseudopotential model [35], are presented.
Satisfactory description of Hugoniots for solid metals using the chemical
model may be obtained outside the region of extremely strong heating and com-
pression, as in the case of aluminum. Calculations carried out for the Hugoniot
478 v,K. Gryaznov, I.L. Iosilevskiy, and V.E. Fortov

of solid nickel under the same assumptions were also used in description of its
highly porous Hugoniots (Section 14.7) and have shown a satisfactory
agreement [24] with the results of numerous measurements. In arriving at this
conclusion it is necessary to take into account that the calculations under
consideration were carried out without adjusting the radii (Section. 14.7) of the
nickel atom and ions. The results of calculations are presented in Fig. 14.16.

Table 14.5. Thermodynamic parameters of highly shock-compressed iron plasma

(Po = 7.88 glcm3; m = 1), calculated via the modified pseudopotential model from [123].·
P, GPa T. 103K B,kJ/g S, J/gK a, km/s a;: n.IC'Ln/) ro n;J.../
103 37 89.2 2.480 13.1 1.7 48 21
3x103 109 258 3.687 17.4 2.8 11 6.9
104 350 828 4.887 28 4.3 3.0 2.3
5x10 4 1440 4028 7.311 55.8 6.7 0.6 0.5
• Notation: P = pressure, T = temperature, H = specific enthalpy, S = entropy, a = sound speed,
IX =total ionization degree, r D == e2/kB Tro = Debye nonideality parameter, 'J.... == (h 2/21tm.k B T)11l =
thermal de Broglie length.

90

80

70

60

j 50

0' 40

30 EXPERIMENTAL DATA
() - AHshuler at al. (1977)
20
'" - Trunin at aI. (1993)
- . - - Trunin et aI. (1994)
o - Avrorin et al. (1986)

20 30 40 50 60 70
U,km/s

Figure 14.15a. Principal Hugoniot of iron (m = 1) in the D-U plane (D and U are the
shock and mass velocity, respectively, and the figure is from [123]). The solid line was
obtained from the pseudopotential model [35] of Eqs. 14.11-14.19 modified for multi-
stage ionization and electron degeneracy effects in plasma EOS (restriction of bound
states in partition functions of atoms and ions by average distance between heavy parti-
cles).
 14. Thermodynamic Properties of Shock-Compressed Plasmas 479

3
10 20 30 p, g/crn

Figure 14.1Sb. Principal Hugoniot of iron (m = 1) in the pressure-density plane (figure

from [123]). The points represent experimental data of Al'tshuler et al. [125], Trunin et
al. [126], and Avrorin et al. [100], the solid line is the same as in Fig. 14.14a, and the
arrow designates results for iron at normal density.

P,bar

Figure 14.16. Wide-range properties of the modified chemical model. Hugoniots of

solid and porous nickel (figure from [24,124]). Notation: m == Po/Poo is the initial porosity
of the nickel samples, the arrow designates the normal density of nickel, the points repre-
sent the experimental data [92,107-109,122], and the solid line represents the calcula-
tions based on Eqs. 14.28-14.41. (code SAHA-IV).
480 Y.K. Gryaznov, I.L. Iosilevskiy, and v.E. Fortov

14.9. Chemical Model: A Wide-Range Equation

of State (WEOS)
One of the main problems of nonideal plasma theory and, in a wider sense, of
the equation of state for substances in extreme conditions, is a correlation be-
tween rigorous description ensured by a physical model (considering the sub-
stance as a strongly interacting collection of nuclei and electrons) and the
simpler and intuitively clearer chemical model (using the notions of effectively
bound particles of variable composition). Notice that most of the detailed cell
approximations generally employed to describe extreme states of matter (see the
reviews [20,110,111] and [76-78,80,112-114, etc.]) are not rigorous physical
models, despite the fact that they are based solely on explicit consideration of
nuclei and electrons. The above approach is, essentially, a description of a single
average atomic cell, the results of calculation for which are then supplemented
more or less arbitrarily with contributions from the degrees of freedom of the
nuclei in any of the autonomous approximations, whether it be the ideal gas
approximation [76], hard sphere approximation [97], or an approximation based
on results for the one-component plasma model [115]. In spite of the attractive-
ness and practical advantages of such an approach, it does not include from the
very beginning the most important element-the self-consistent "reverse" influ-
ence of inter-nuclear correlation on the equilibrium electron distribution inside
the cell [30,116]. This provides the main channel of influence of inter-nuclear
corrections on the total thennodynamic functions of a system. This fact is well
known in the plasma chemical model [8], where the main nonideality effect in
total thermodynamic functions, especially in the caloric equation of state, is
associated not with the direct effect of incorporating corresponding corrections
into the equation of state, but with an indirect one arising through shift of ioni-
zation (and chemical) equilibrium attributable to nonideality.
Being rigorous, the physical model does not involve any empirical individual
infonnation on the substance other than its nuclear charge, Z. The chemical
model, in contrast, makes extensive use of empirical infonnation in the fonn of
ionization potentials, heats of chemical reaction, and the spectrum of isolated
excited states of composite particles, atoms, ions, molecules, etc. This is suffi-
cient for description of rarefied "gaseous" states of the substance. A following
step in extrapolating the chemical model to more dense states using the approach
described in Section 14.8 consists, in addition to a number of applied empirical
properties of the substance, in the quantities of normal density and binding en-
ergy of the condensed substance. The logical continuation of the process will be
further extension of the range of empirical characteristics of the condensed state
of the substance that are taken into account, including differential characteristics
such as the Griineisen coefficient, compressibility, and heat capacity. Finally,
the process would be concluded by attribution to the theoretical quantities of
average atom, ion, and molecular volumes, the properties of free parameters
 14. Thermodynamic Properties of Shock-Compressed Plasmas 481

selected by imposing the requirement that they best describe such fundamental
characteristics of the condensed state as the "cold cwve" (T= 0 isotherm) or the
Hugoniot of the solid substance. It is of fundamental importance in this context
that the ionic radii decrease monotonically with an increase of their ionization
multiplicity, as discussed in Section 14.7. Together with the hard sphere model
employed, such a correlation between the radii qualitatively changes the form of
the cold curve and the Hugoniot of the substance since, in contrast to the com-
mon single-component van der Waals equation of state, this makes an "arbi-
trary" degree of compression of the substance possible. This, in combination
with the possibility of multiple ionization included in the calculation, results in
appearance in the theory of one of the most important mechanisms-so-called
pressure ionization. In the work cited above [85] the radius values for higher
copper ions Cu+2 -CU+7 were assumed for simplicity to be equal, which led to
sufficiently close agreement, with allowance for the precision of the experiments
[93], with unique experimental data [93] obtained under conditions of under-
ground nuclear tests in which ultrahigh pressures 010-20 Mbar) were achieved
in samples with porosity m = 3 and 4. According to the calculations discussed,
based on chemical model, the compressed states have temperatures of - (2-
3) x 103 K and ionization multiplicity Ne/(M + No) s: 5. Taking into consideration
a wider range of temperatures and pressures, it is now an easy matter to establish
that the mere change of radii of copper atoms and ions (without changing the
form of other corrections for nonideality), makes it possible to satisfactorily
describe the parameters of experimentally measured Hugoniots [93] with m = 3
and 4. This can be achieved for the combination of radii (a.u.): rc (Cu) = 2.0 and
rc(Cu+l-Cu+3 )= l.75 (see Fig. 14.9). Clearly, this coincidence fails to explain
this combination of dimensions from a physical point of view. Moreover, the use
of radii in a similar way as free parameters permits achieving good agreement
with experimental data of [93] but, at the same time, makes the description of
other experimental data worse [92]. We emphasize that no combination of radii
in the framework of the model under consideration permits simultaneous
description of experimental data from [93] and [92].
The point at issue on optimal combinations of radii associated with the use
of improved forms of corrections for nonideality in the model described above is
not settled at present. The same is true of additional experiments required in
order to carry out the selection of the best approximations amongst those proved
to be equivalent in describing experimental data on the caloric equation of state
(Hugoniots and expansion isentropes). Recall once again that such a parallel
coexistence is possible due to incompleteness in principle of the reduced caloric
equation of state, U(P, V). The foregoing selection is all the more appropriate,
because the use of the plasma chemical model as a component of a single inter-
polated equation of state is now a sufficiently assimilated approach [117,118].
The work of [117] has put forward so called "quasi-zone interpolation" between
the chemical model developed for rarefied weakly nonideal plasma and the
482 V.K. Gryaznov, I.L. Iosilevskiy, and V.E. Fortov

quantum statistical model [76] destined for use under conditions of extreme
compression of the substance. Interpolation in [117] is not a simple mixing of
the two reference models, but based on physically plausible concepts of the
gradual broadening the discrete lines into quasi-zones with increasing compres-
sion of the plasma. The AC1EX model [118] is also interpolational and associ-
ated with a modified chemical model [U9]. Detailed comparison of
interpolational equations of state, gradually distinguished into independent
groups, as well as conventional wide-range, semi-empirical equations of state
(see [3]), has yet to be carried out and is undoubtedly of great interest.
We note, in conclusion, that the transformation discussed here of the chemi-
cal model into a wide-range equation of state brings it closer to the actual result
of counter-evolution of a wide range equation of state [120,121] that is primarily
semi-empirical in concept. This model develops the idea by Kopyshev of an
effective intrinsic volume depending on pressure ("covolume") [120], and was
supplemented by calculation of thermal ionization according to Saba [121]. One
would assume that this development will have as a natural result the modifica-
tion of the equation of state in [121] to take into account Coulomb corrections
and, possibly, variable behavior of ion statistical sums depending on pressure
(density). Once again, notice that the experimental data at hand on shock com-
pression of the substances under consideration are needed in addition to infor-
mation on the temperatures and pressures in the states achieved in shock
experiments. This is necessary in order to perform selection amongst numerous
theoretical approaches employed in describing thermodynamic properties of
dense plasma produced by strong shock waves [3].

14.10. Conclusion
The chemical plasma model is one of the two fundamental concepts based on
microscopic representation and employed conventionally (exclusive of semi-
phenomenological equations of state) for the purpose of theoretical description
of thermodynamic properties of shock-compressed plasma. (Chemical model of
rarefied plasma <=> cell model of condensed matter.)
The main tendency during recent decades is a peculiar mutual permeation-
the counter-extrapolation of each approach to the boundary parameter area,
which is the most complicated for theoretical description, as well the construc-
tion of a sort of "interpolational bridge" accompanied by gradual imparting to
the chemical model of the characteristic features of so called wide-range equa-
tions of state-the object considered up to the present time as a collection of
numerous semi-empirical equations of state.
Comparison of experimental and calculated (within the framework of the
chemical model) data on the parameters of shock-compressed substances per-
mits drawing the conclusion that the main qualitative result of shock-wave ex-
 14. Thennodynamic Properties of Shock-Compressed Plasmas 483

periments, as a whole, in the region of expanded substances, "gaseous" plasma

and "porous" Hugoniots, consists in the existence of effects not involved in
conventional variants of the chemical model which are equivalent in tenos of the
caloric equation of state to additional mechanisms of effective inter-particle
repulsion.
Strong short-range repulsion between atoms and ions at small distances is
the main effect to be included in the plasma chemical model to significantly
improve its extrapolation properties into the region of dense and extremely
dense plasma encountered in shock-wave experiments.
The important property of the modified chemical model is the existence in
the model of a complete and thenoodynamically self-consistent description.
beyond that of the caloric description, a thennal (entropy) equation of state, and
infonnation on the most general characteristics of the structural state. To con-
firm the validity of the elements of the model description it is necessary to per-
form additional experimental measurements outside the traditional framework of
recording only the kinematic characteristics of shock compression and isentropic
release.

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 CHAPTER 15

Fracture of Structures Caused by

Explosive Loading: Scale Effects

A. G. Ivanov

15.1. Introduction
The large number of existing materials and materials under development, and
the variety of conditions under which they are applied, has resulted in many
fracture concepts, semi-empirical theories offracture, and fracture criteria. Each
of these is reasonable for the range of parameters over which it has been investi-
gated experimentally. These individual theories, in conjunction with previous
experience in calculating the strength of structures have, for some time, proven
satisfactory. However, problems have arisen because of further progress of tech-
nology in the field of unique large-sized structures intended for use under con-
ditions of intense dynamic loads. The problem is exacerbated, in some cases, by
the impossibility of performing full-scale tests to determine the actual strength
reserve (safety factor) of a particular structure. Examples of unpredicted failure
of some structures designed according to existing strength norms highlight the
problem. Solution of these problems requires not only development of new
fracture criteria, but also search for a uniform, physically justified, approach to
the problem as a whole without taking into account minor details of the fracture
phenomenon. As the basis of such an approach, the following fundamental
achievement of the linear fracture mechanics (LFM) can be used: Fracture is a
result of work done on the structure. The work required to cause a fracture is
provided by the elastic energy (EE) of deformation stored in the structure. Rec-
ognition of this fact, based on Griffith's idea regarding the condition for transi-
tion of a crack to an unstable state [1), has resulted in critical revision of fracture
criteria and development of new methods for strength testing. Traditional meas-
ures of strength, namely the yield strength, O'y, critical values of stress, 0' u (the
beginning of the neck formation), strain, &u, or combinations of these quanti-
ties, appear to be insufficient. The role of characteristics of a material, such as
the temporary resistance, O'u, was limited by the narrow objective of compari-
son of materials in standard tests. The theoretical strength, from the point of
view of energy criteria, appears to be 2-4 orders of magnitude less (!) than the
strength of real materials (2). Introduction of new failure criteria, including the

V. E. Fortov et al. (eds.), High-Pressure Shock Compression of Solids VII

© Springer Science+Business Media New York 2004
492 AG. Ivanov

specific failure work (2y, G Ic ) per unit of fracture surface area formed com-
bined, as a rule, in the criterion E G 1c - K1c, where E is Young's modulus and
K Ie is the critical value of the stress intensity factor, was required.
The introduction of new fracture criteria has required development of meth-
ods for their determination. The traditional criteria of material resistance can
easily be determined when a stress-strain curve is measured, since the criteria
correspond to some special points on this cmve (Fig. 15.1). For plastic materi-
als, the criterion corresponds to the point au on line 1 and, for brittle materials,
it is the point a r on line 2. Line 3 is an approximation of line 1 that is accepted in
this work, and line 4 is the same as line 3, but for a higher strain rate. To obtain
values of 2 y, G1c or K Ic , K c , etc. in LFM, it is usually necessary to carry out a
series of tests with special samples that are geometrically similar (GS) but of
different sizes. Since the same work can be performed during the action of
forces of different magnitudes, let us assume that fracture can be caused by
application of any macroscopic stress, not limited from below. This assumption
does not seem too strong. Actually, even samples of plastic metals, which frac-
ture at stresses far beyond their yield strength in laboratory tests may, in other
conditions, behave as brittle materials, failing at stresses much less than ay.
When brittle materials such as glass are considered, the dispersion of ar may be
as large as 3 orders of magnitude [3]. This assumption also proves to be true in
LFM where, with other factors remaining constant, ar is function of the defect
size. This assumption allows avoiding consideration of such traditional values of
stress such as a y and au, as well as the threshold stress, a", and critical stress,
a er , as criteria when determining the physical laws governing the process of
fracture of real materials. Until now, the latter have been widely used in empiri-
cal and semi-empirical fracture criteria, including some improved variants of
LFM.
The successes of LFM and its improved variants are well known. Their
shortcomings and difficulties, faced when using research results for specific
practical structures, are also known. This is proved by periodically occurring
catastrophic fracture of large-sized structures designed in accordance with ex-
isting norms for strength. If, in the past, such failures were explained as errors of
the designers, quality of materials used, etc., after LFM and its improved vari-
ants came into use, the ideology of reliability itself has changed. It is assumed
that: "... The strength of a structure is always an undetermined quantity since,
first, the exact location of all defects is not known beforehand and, second, if
this location were known beforehand, it would be impossible to solve the corre-
sponding mathematical task due to its complexity ... " [3]. It is assumed that the
life of a structure is the life of its defects. After a crack achieves its critical size,
its growth can be uncontrollable. In this case, the structure is doomed to fail.
The situation becomes more complicated due to the fact that critical sizes of
cracks decrease when one uses materials with higher strength (higher values of
ay). The situation is similar to sitting on a powder keg. It requires constant use
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 493

Figure 15.1. Typical diagram of stress-strain diagram of (1) plastic and (2) brittle
materials. Cfr is the stress of brittle material fracture, and Cfu is the temporary resistance
(the beginning of the neck formation) of plastic materials. Line 3 approximates the
stress-strain curve as a bilinear function. Cfo is the elastic limit (the yield strength). Line
4 is the same as line 3, but for a higher strain rate.

of a highly-reliable system for identifying defects, and it is scarcely allowable

for crucial designs, or it requires seeking other solutions.
The difficulties encountered in using LFM increase sharply when describing
fracture due to high-intensity dynamic loads because, in this case, it is difficult
to monitor the growth and development of structural defects. In some cases, for
example, during entry of an asteroid into the Earth's atmosphere, such monitor-
ing is simply impossible. The possibility of understanding brittle fracture from
the point of view of LFM results in the questions: Is there an opportunity to
avoid unforeseen brittle fracture? Under what conditions can one take advantage
of this opportunity? Is it realistic to take advantage of this opportunity? There is
one more reason, which is not limited to application of LFM and its improved
variants to the problem of brittle fracture. This follows from the fact that fracture
is considered to be a localized process occurring near defects in the material.
These circumstances provide motivation for seeking other approaches to solu-
tion of the fracture problem which differ from the local considerations assumed
in LFM and its improved variants. Just as knowledge of the laws of growth of an
individual tree does not yet guarantee understanding of processes controlling the
evolution of a forest, limiting consideration to the local approach of LFM or its
improved variants may obscure the physical laws governing failure of a struc-
ture as a whole or of its load-bearing part.
In this work, devoted to solving some problems of fracture mechanics (FM),
the greatest attention is paid to the necessary condition for fracture to occur-
494 A.G. Ivanov

the availability of an adequate deformation EE reserve in a structure or its

characteristic part. A sufficient condition for fracture is the presence of a suffi-
ciently large crack or other structmal defect. This is called the integrated
approach (lA). It is impossible to exclude the possibility that its use can decrease
the accuracy of the final results. However, its use is a smaller loss than employ-
ing an incorrect description of physical processes that occur during failure. The
last result, in a number of cases, is a consequence of use of fracture criteria
based on the strength of materials.

15.2. Integral Approach to the Fracture Problem

In LFM and its improved variants it is tacitly assumed that the structure under
consideration always has a sufficient EE reserve for extension of the main
crack,! since always
Icr<L, (15.1)

where lor is the critical size of the crack and L is the characteristic size of the
structure considered. In a general integrated form, this condition can be written

J ~J
v qdV /"dS, (15.2)

where q is the specific elastic energy of the structure, V is its volume, A. is the
specific work done during:fracture of the structure (analogous to 2y, and Gte in
LFM), and S is the area of the ftacture surface. 2
It is obvious that to preclude the possibility of brittle ftacture which, as a
rule, proceeds in the elastic range of material deformation, i.e., in the range in
which structures are normally used, it is necessary to require that the inequality
15.1 be violated. This requirement is equivalent to the inequality 15.2 being
violated, or that the inequality

J sJ
v qdV /"dS (15.3)

be satisfied. Is fulfillment of this requirement realistic? Formally, yes. Lightly

loaded objects and small structures satisfy this requirement and do not experi-

! In the elastic range of defonnation where structures are nonnally used, fracture is
accomplished within a small interval of time comparable to the vibrational period.
Therefore, change of the EE reserve can be neglected in comparison with the work of
external forces.
2 In the inequality 15.2 it is possible to neglect the contribution of inertial forces to the
work of fracture. The correctness of this approximation follows from investigations of
fracture caused by static loads [4] and fracture caused by high-intensity impulsive loads
[5,6].
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 495

ence brittle fracture. They fracture only at stresses beyond the material yield
strength in range of plastic deformation. Analysis of the possibilities of satisfy-
ing this inequality was considered in [7] using the elementaIy example of ten-
sion of a cube having the edge length L of a material subjected to opposing
forces aL2 applied over two opposite faces. The material deformation law was
assumed, without loss of generality, to be bilinear, i.e.,

E&, for a ~ ao
a- { (15.4)
ao+K(&-&o), for a>ao,

where K and ao are the strain hardening modulus and the limit of elasticity of the
material, respectively. Certainly, the value of ao for real materials depends on
both the rate of stra.in. &, and on the material temperature, T, which can change
because of plastic flow. However, these effects, with not too large a change of
scale, and also considering fracture in the elastic range or at the beginning of the
elastoplastic range, are insignificant and can be taken into account as correc-
tions.
We invoke some additional assumptions. We shall consider the material
cube to be non-porous and unchanging (for example, free from phase transfor-
mations) and the size of the grain structure of the material to be much less than
L. Dispersion of the strength properties is absent. Failure of the cube (fracture,
crack propagation) is possible at any low stress if the BE reserve is sufficient.
The value of A in the elastic range, a ~ ao, shall be considered to be constant. It
coincides with the value 2 y in FM for crack propagation in the stable regime,
except for cases specifically noted.
For the material cube under consideration, the ratio of the EE (a2L312E) and
the fracture work (AL2) is
a2L
A=-. (15.5)
2AE
According to the inequalities 15.2 and 15.3 for the cube, a necessary condition
for fracture is A ~ 1, and a necessary condition for the material to remain intact
isA < 1. On the N-L plane, where N= 2AE/a2, rays from the origin (Fig. 15.2),
correspond to states with a constant value of A. In the range A < 1 (NOB) they
correspond to states with an equal strength reserve and, for A > 1 (BOL) they
correspond to states with an identical degree of risk of possible fracture. The
value a =ao corresponds to the line N =No which, together with the ray A = 1,
divides the plane into four characteristic areas. On the line A = 1, the point L =Lo
corresponds to the value N = No. This is the minimum value of L at which brittle
fracture of the cube is possible in the elastic range of deformation. This is the
brittleness threshold of the material:
Lo = 2AE / aJ . (15.6)
496 AG. Ivanov

t bs
t
t
® t
I
I
I
I
o Lo Ll Li L2 L

Figure 15.2. Possible scheme for construction ofa uniform theory of fracture.

Accordingly, the point of transition of the material into the brittle state, with
increasing size of the object but other things remaining the same, is a physical
property. The value Lo depends, besides A. and E, on the temperature, T, and the
loading rate, cr, or strain rate, &, through 0'0. It depends also on the state of
stress. It is possible to become convinced of this by considering the effect of
changing tension to compression. Assuming that brittle fracture takes place
under compression of the cube after the strain Eo= crolE is reached in the direc-
tion perpendicular to the compression axis, we obtain (Locompression)/(LOtension)=v-2,
where v is Poisson's ratio.
Typical values of L o, calculated for some materials at T= 300K, are given in
Table 15.1, from which we see that the interval over which Lo changes for real
materials is not less than 8 orders of magnitude. Therefore the location of the
line No on the figure (unlike the line OB) is specific to a given material.
Now let us turn to characterization of Areas 1-4 on the N-L diagram.
Area 1. A < 1 and O'!5: 0' o. The condition 15.3 that the cube remain intact is
satisfied. All states in the area are safe for the loaded cube. But, with other con-
ditions being equal, new states appear on rays of lower strength reserve as L is
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 497

Table IS. 1. Physical and mechanical characteristics of some structural materials.

Characteristic Copper Stainless steel Steel St3 Steel40Cr Organic Glass
12Cr18NilOTi (hardened) glass
E, GPa 130 200 200 200 3.6 95
2
A., MJ/m 0.03 0.47 0.1 0.13 0.012 9.2XlO-5
cry, MPa 30.6 350 250 986 120 >3.8xlO+3
Lo, m 8.33 1.53 0.64 0.053 0.006 <1.2xlO-6

increased (transition from state ao to state al) or cr is increased (transition from

a o to aJ. The possible values of L are limited by the line OB, and L = Lo for
cr = cro. The value of Lo decreases after changing the material for another mate-
rial with higher strength, or after a change of the loading conditions (T, &), that
results in an increase of cro at constant A. and E. In particular, for impulsive
loads, when a viscous component of cr appears, cubes of liquid can be found in
Area 1, even though cro = 0 for a liquid under static conditions.
For this area the most essential processes, changing values of A., cro, or E of
the material, are slow processes of structural defect accumulation-aging.
When this occurs, the state of the cube can move into another area.
Area 2. A ~ 1 and cr S; cr o. (The aggregate of states of elastic deformation and
brittle fracture). In this area the necessary condition for fracture is satisfied. The
smaller the slope of the rayon which the point representing the state of the cube
is located, the more the EE reserve exceeds the fracture work, the smaller is the
extent of the material damage necessary for satisfaction of the sufficiency con-
dition, and the more rapidly will the fracture process proceed. However, if the
condition of sufficiency is not fulfilled (there is no critical Griffith crack, struc-
tural defect, abnormal area of overstress, etc.), fracture will not occur. There-
fore, the cube can be considered to be serviceable when subjected to states in
Area 2 or its parts adjacent to the OB line if diagnosis of defects is at rather high
level while the cube is in service, and if fracture does not result in catastrophic
consequences.
Fracture of two cubes of different sizes LI and ~ in the states of Area 2 can
involve strong scale effects (SE). So, if the states are placed on the Bi ray corre-
sponding to states of similar risk (points bl and ~), evaluation of Eq. 15.5 for
different values, LI and~, of L results in the relation:

~= fk. (15.7)
cr2 VI:;
Thus, if the sufficiency condition is fulfilled, the fracture of cubes of differ-
ent sizes will occur at different values of the stress, cr. It is also evident that
cubes of the same size, but having different defects, will fracture at different
498 AG. Ivanov

values of stress, corresponding to rays representing different degrees of risk

(points b2, b 3, and b4). This is dispersion of brittle strength, which, in spite of
expectations, cannot be described by the statistical theory of strength [3]. If the
states LI and L2 can be described by points on different rays, the SE can either
increase (points b l and b 4), or decrease (points b l and b3) in comparison with
that predicted by Eq. 15.7. We shall note that, if the cube is made of traditional
plastic material (the plasticity is determined using the existing standard meth-
ods), but its state lies in Area 2, it is impossible to exclude the possibility of its
experiencing brittle fracture. If other conditions remain unchanged, the prob-
ability of such an event will increase with increasing L.
Area 3. A:<! 1 and cr >cro. Here, as in Area 2, the necessary condition for frac-
ture is satisfied. The fracture is preceded by plastic deformation, which results in
the following peculiarities:
1. Values of lv, E, and v, varying little in Areas 1 and 2, become functions
of E and time, t, in Area 3 in accordance with the growth of structural de-
fects in the material. Description of fracture of the cube will be much
more complicated and will require kn~wledge of these functions.
2. As E increases, the internal friction of the material grows sharply, EE
transfer becomes difficult, and regions near the fracture zone, from which
EE can be removed, decrease in size. Therefore, if the SE and dispersion
of brittle strength are yet possible in the vicinity of cr-cro, these effects
should disappear as the stress increases beyond cro, at least for static
loading. Accumulation of macroscopic defects before fracture occurs
should become increasingly localized and their number and variety
should increase.
3. For relatively small values of E, the character of the damage will be
maintained as a tensile fracture of the material. However, with an in-
crease of E one should expect transition to shear fracture on select planes
that have been weakened by localization of defects. Despite the increased
fracture surface area due to shear of the cube, this fracture process will
probably be energetically favored.
4. With large values of E, especially due to dynamic loading, the energy
fraction spent directly for fracture (_IvL 2 ) is negligibly small in compari-
son with the plastic dissipation and kinetic energy.
Area 4. A < 1 and cr> cr o. For points of this area, as in Area 1, the condition
that the cube remain intact is fulfilled. But, unlike Area 1, the material is ex-
posed to irreversible deformations that, in some cases, can prevent its serving its
intended structural function and, as shown above, complicate the description of
the fracture process. States in this area of can be characterized by processes of
formation and growth structural defects of the material, i.e., aging processes and
so-called distributed fracture within the volume of the material, as was the case
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 499

for Area 3 at high values of e, but without coalescence of these zones to fonn a
fracture surface.
In what measure are the considerations based on a hypothetical cr-e behav-
ior corresponding to Eq. 15.4 and an elementary object such as a cube applicable
for real cr-e behavior of materials and more complex objects with less trivial
states of stress? Where is the place for existing fracture criteria (concepts, theo-
ries) in the N-L scheme?
The transition to the diagrams of real materials, besides some possible com-
plication of calculations, is not fully reflected on the L-N diagram. Transition to
real objects is more complicated. As we did for the example of cubes of various
sizes, L, we will assume that objects of all shapes change their size in a geomet-
rically similar way and the stressed state is the same after changing L (except, of
course, the derivatives of cr and e with respect to the coordinates and time 3).
Thus, considerations on the N-L plane will be limited to equally loaded GS
objects. Narrowing the circle of possible objects by their GS representatives
does not actuaIly interfere with the opportunity to consider any object. It can
always be compared with its GS models. This formal restriction allows signifi-
cant simplification of the search for physical laws of the fracture process.
Let us take any values that are characteristic of the given object as L and cr.
For example, for a spherical vessel it is possible to accept its radius, R, as L, and
the maximum value of the stress for the chosen R as cr. Considering the compli-
cated state of stress, the quantity cr can be assigned the value of the effective
stress, i.e., the detenninative strength. The admitted arbitrariness in detennina-
tion of L and the corresponding value of cr will be compensated by introduction
of a coefficient C instead of 2 in Eq. 15.5. The coefficient A, as before, is the
ratio of the BE reserve to the fracture work. It is obvious that, for each type of
OS object considered, loaded in the specified way, the location of the NOi lines,
analogous to No, and LOi , analogous to Lo, will also be specific to the object.
What else can be added to the characteristics of Areas 1-4 of the diagram on
Fig. 15.2 during transition to elementary GS objects, and where can one use the
most commonly employed criteria of strength? It is obvious that all crucial
structures (or their load-bearing units), the fracture of which can cause cata-
strophic consequences, should comply with states of Area 1 under both normal
conditions of long-term operation, and also cases of emergency and under ex-
treme loads. Since lightly-loaded objects correspond to Area 1, decrease of their
specific material consumption, weight, and increase of acceptable loading, can
sometimes be achieved by complete or partial use of oriented composites and
laminated materials, as will be shown below. They are completely or partially

3 a
Differences in the behavior of materials due to discrepancy of values of and s is
insignificant for GS objects and can be taken into account. For example, a ten-fold
change of s changes the value of the value of CIy for steel by 5 % or less.
500 A.G. Ivanov

free from SEs of an energetic nature (henceforth designated SEEN). Where it is

possible, the same effect can be partially achieved by replacing one object with
large number of GS objects with smaller values of L.
In this area it is allowable to use criteria of strength that are traditional for
the course of strength of materials and are based on certain values of cr, E, and
a 2/2E. The values a =cry and E =ay/E can be used for these quantities, and
strength reselVes can be detennined in relation to them. Actual values of
strength reselVes, as mentioned earlier, depend on the location of points deter-
mining states of GS objects. Traditional values, for example ar, can be signifi-
cantly different for states located on a ray of equal strength reserve (points al
and a2). So, an object from state al can fracture in a brittle way at a < ao, and
from state a2 can fracture only in the stress range of plastic flow, a>cro. Greater
differences in strength reselVe will be obselVed for objects having different sizes
but loaded to the same stress (points ao and al).
Let us turn to Area 2 of the N-L diagram. Production and use of traditional
high-strength materials (materials with a high value of cry) for the purpose of
reducing the weight of structures on the one hand and developing larger objects
on the other hand, causes Area 2 of the diagram to become more important for
engineering and, for just this reason, the problem of brittle fracture has appeared
central in recent decades and has resulted in rapid development of FM. Since the
necessary condition for fracture is satisfied in Area 2, special attention should be
paid to diagnostics of defects with the purpose of preventing fulfillment of the
sufficiency condition Otherwise, the object transforms into the equilibrium
state-fracture. For understanding the extent of possible risk, information on
the value of the coefficient A for the object considered is important. The rate at
which the object is loaded has a strong influence on states in this area. There-
fore, experiments on high-rate impulsive fracture of vessels and material spalla-
tion provide a basis for thinking that, for rather intensive loading, the fulfillment
of the necessary condition of fracture, as a rule, also results in satisfaction of the
sufficiency condition [2,8]. The truth of this statement follows from simultaneity
of the fracture beginning along chosen lines and planes [9,10]. In complete con-
formity with the previous discussion, strong SEs are possible in Area 2 during
fracture and manifestation of dispersion of the value of brittle strength. For
states with large excess of EE (A» I) fracture proceeds explosively with for-
mation of many fragments [11]. These conditions are energetically favorable for
realization of processes of fracture and comminution. With the help of analysis
of the Area 2 states, the greatest successes ofFM are achieved.
After replacing the cube with other GS objects, all of the previous discussion
of Area 3 of the N-L diagram remains completely unchanged. As in Area 2,
strong SEs are displayed during small plastic strains (0.5-1.0%) in Area 3. This
was obselVed during standard static tests [2,12]. Besides manifestation of strong
SEs, other effects, stated below, were also obselVed during dynamic fracture of
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 501

elliptic high-pressure boilers of different thicknesses made from steel 22K at

strains up to 1%[13].
Growth of dissipative losses with increase of the extent of plastic deforma-
tion complicates wave processes and sharply restricts the size of the portion of
the material from which EE can be removed to cause a fracture. These sizes
cease to depend on the characteristic size of the object, and SEs of an energetic
nature disappear. This really proves to be true in standard static tests for fracture
by tension of different-scale samples of "plastic" materials. The more careful
fracture research on samples from steel 12Cr18NilOTi has shown, however, the
existence of a weak SEs (-5 % change of cr at LJIL2 = 6) having, probably, a
metallurgical explanation. Transition to high rate dynamic effects significantly
complicates the processes proceeding, leads to an increase of EE due increase of
cry, and simultaneously imposes temporary restrictions on the process of EE
removal and completion of fracture. The analysis of these phenomena will be
given in Section 15.3.
Addressing existing theories of strength, it should be concluded that FM and
its improved variants [14] are being used successfully at moderate values of Ii in
the elastoplastic area of deformation. In the area of large plastic strain under
static loads, in creep processes, etc., the traditional theories of strength, based
on use of critical values of Ii and cr or combinations of these variables, are used.
It is much more difficult to apply FM to description of fracture of objects at
high rates of strain under conditions of intensive loading when the object is
doomed to fail and it seems to be impossible to identify a place of known weak-
ness. Such objects can include shells or rings loaded from within by suddenly
applied explosive pressure.
In recent decades, criteria based on Taylor's approach changed the tradi-
tional fracture criteria involving critical values of E and cr. According to the
latter, fracture of an internally pressurized shell occurs instantaneously when the
circumferential stress becomes tensile throughout the thickness of the shell.
According to this, two GS shells, loaded in the same way (in view of the small
correction for the difference in s), should be destroyed at Ii = const., independ-
ently of Ro, and pulse-accelerated expanding rings should be destroyed instanta-
neously at the conclusion of the accelerating pulse. The experimental data are in
sharp contradiction with this prediction. It is also impossible to explain the na-
ture of the dynamic peak of plasticity with the use of Taylor's approach (see
Section 15.5, problem 3).
For objects more complex than a cube, Area 4 of the N-L diagram can be
described by the theories of damage accumulation within the material volume.
These theories include those of the type of the kinetic concept of strength (KCS)
[15] and, to a lesser extent, its analogue
s't = const. , (15.8)
502 A.G. Ivanov

where 't is the longevity, i.e., the length of time that the material remains intact
when subjected to the strain rate E.
Equation 15.8 does not always appear to be accurate. Evolving spatially dis-
tributed damage (fracture within the volume of the material) does not invalidate
of the necessary condition, Eq. 15.3, for occurrence of fracture. The process of
coalescence of the distributed fractures into a global crack can be considered as
the consequence of gradual creeping of the N-L state over into Area 3 (points b 6
and b7) of the point (point a 4 of Area 4 or even point a 3 of Area 1) describing the
initial state of the object in accordance with accumulation of structural defects.
The semiempirical approach to study of the growth kinetics of material de-
fectiveness up to achievement of a critical state at which a transition to a fracture
occurs is close in essence to KCS. This approach, suggested by Shockey et al.
[16], along with KCS have become widely used for the description of spall
fracture in recent years. Different authors have different opinions as to the criti-
cal value of defectiveness. Considering this approach more broadly, it should be
noted that the extent of defectiveness can be used as the fracture criterion only in
a narrow interval of change of the initial conditions, since the same material can
be destroyed in both the Area 2 (point b 4), i.e. for cr« cry, and in the Area 3
(point b6) for cr » cry.
The IA scheme suggested above for the fracture problem, based on satisfac-
tion of only the necessary condition for the occurrence of fracture, leads to some
essential conclusions. We will consider three of them.
1. When considering GS objects, there are the areas of states (Areas 1 and 4
on Fig. 15.2), where, contrary to LFM and its improved variants, fracture
is excluded. At first sight, this conclusion seems to be insignificant, since
it concerns only small or lightly-loaded objects. However, it will be
shown below that at least one class of composite materials exists which
can be fractured without manifestation of SEEN, and which allows pro-
duction of structures operating in Area 1.
2. Such properties of the material as brittleness or plasticity, when other
conditions are equal, can be determined by the characteristic size of the
tested material samples and, in particular, by value of the ratio LILo.
3. SEEN should be displayed during fracture of GS objects in Area 2, and
partially in Area 3 (Fig. 15.2). We will explain this conclusion in detail.
Can LFM and its improved variants predict the manifestation of SEEN? In
an explicit form-no. Moreover, as a rule, the nature of scale effects is consid-
ered to be statistical. What is the actual situation? In [17], for an extended plate
of width L with a central cut of length 2/, it is found that the value of Kc is

Kc = cr ~ L tan (nil L) . (15.9)

 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 503

Following LFM and assuming that the length of the cut is a small value, in-
dependent of L, we will obtain the equation

Kc =a~7t/[1+t(7t//L)2 + ...]. (15.10)

by expanding the radicand in Eq. 15.9 in a series.

From this we see that the influence of L is expressed by a 2nd-order correc-
tion in the small parameter II L. The same result also follows when considering
other kinds of cracks (cuts), (See the equations from Sections 25, 26, and 28 of
[3]). Certainly, imposing the additional restriction ilL = const. within the LFM
framework transforms Eq. 15.9 to Eq. 15.7, i.e., to SEEN, but simultaneously it
reduces general statistical consideration of the issue to an individual event with
small probability. On the other hand, this restriction transforms a defect into a
specific peculiarity inherent in the object, and the consideration itself into the
IA.
One more example results in SEEN when using the r -integral in nonlinear
fracture mechanics. In [18] the condition required to ensure that pipelines re-
main intact was obtained. Analysis of this condition has shown that the solution
results in SEEN when insignificant terms are ignored. This solution,

[
E')." ]112 (15.11)
as < 7tR(l-v 2 ) ,

where as is the circumferential stress component, follows easily from the IA, as
shown in [4]. The individual examples considered above, which result in SEEN,
give the basis for hope that condition 15.7 will be inherent in all solutions of
similar problems ofLFM or its later variants.
Thus, the scale effect, which was first discovered experimentally by
G. Galilei during an investigation of fracture of geometrically similar galleys,
was identified by him as an unchangeable property of matter [19] that is given
precise physical substantiation as a manifestation of SEEN by using the ener-
getic fracture criterion.
In the sections below, when describing dynamic fracture of GS objects
(spherical shells and pipes, high-pressure boilers, samples of material undergo-
ing spallation, and disintegration of cumulative jets), and when searching for
ways to avoid SEEN, we will constantly turn to the N-L scheme on Fig. 15.2
and to its interpretation.

15.3. Design Methods for Decreasing the Risk of Failure

The consideration of the N-L diagram shows the paradoxical nature of the
situation. Let us limit ourselves for practice sake to Areas 1 and 2, in which
504 A.G. Ivanov

cr~crY' Area 1, where fracture is forbidden, does not actually appear suitable for
practical structures because of the small values of cr or L defining this region.
Area 2 does not exclude the possibility of fracture and is fraught with possible
dispalys of SEEN. The risk of fracture grows with increased values of A. But, it
is in this very area that the operation of the structures around us takes place.
Increase of the characteristic sizes of structures and the requirements of their
cr
operation (an increase of up to the transition to shock loads and a decrease of
the operating temperature) sharply increases the probability of brittle fracture.
Therefore, despite rapid progress of PM, this problem is not completely solved.
This is demonstrated, for example, by many kilometers of catastrophic fracture
of large pipelines and other structures. In modem PM, the solution of this prob-
lem is sought in development of more perfect diagnostics of defects, methods to
confine them and to stop crack growth, and a search for materials "without de-
fects". The last direction results in production of objects with a high reserve of
EE (A» 1). Fracture of such objects proceeds especially rapidly [11].
The process of designing new objects often proceeds by the method of trial
and error. Therefore, some means for decreasing the risk of fracture have been
found empirically. Let us confirm their correctness from the IA position.
Let us return again to Area 1 of the N-L diagram. We will consider the
problem of tension of an extended rod with a round cross section subjected to a
force F. It is obvious that the cross-sectional area, S, of such a rod should satisfy
the condition
(IS.12)
On the other hand, to exclude the possibility of brittle fracture, the necessary
condition IS.3 that the rod remain intact should be satisfied. Or, what is the
same, the diameter of the rod (0) should not exceed its value at the threshold of
brittleness, 0 0 , The value of 0 0 can be determined from balance of intervals of
time for passage of a crack with velocity vc and removal of EE from its vicinity
with the sound velocity, C, in the rod material.
From Eq. IS.3 we will obtain

(IS. 13)

for the rod.

cr
Evidently, we have 20 0 = const. for C, E, vC ' and A. = const. Assuming that
vc is equal to one half of the shear wave velocity, we fmd that

0 0 =A.E ~ (IS.14)
2crJV~'
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 505

Similarly, the brittleness threshold, ho, for a one-dimensionally extended thin

strip with thickness h can be found to be

ho= 'J..E _1_p+V .

20"~I-v2 2
(IS. IS)

For v = 0.2S, 0 0 and ho coincide with an accuracy of 3%, and the extent of the
area in which the fracture energy is removed exceeds 0 0 and ho by 6.3 times.
The condition that the rod remain intact in the elastic range of strain is

82 1t0
~_ _o
2
or 82 ~ 1t ('J..E)2
-2 (IS.16)
4 8(l+v) 0"0

To satisfy Eqs. IS.12 and IS.16, it is necessary that 8 2 ~ 8\. It is obvious that use
of strong new materials for decreasing the weight of the rod is possible only for
small values of 8 due to the strong dependence of 82 on 0"0' To ensure that
8 2 < 8\ for an arbitrarily given value F it is necessary to use several parallel rods
(wires). But this is a rope! This method of resisting brittle fracture was, in par-
ticular, used for strengthening gun barrels by winding several layers of strong
wire around the breech [20).
In the multirod example considered, the restriction was imposed only on the
section of the rods constituting the assembly. Any number of them could be
used, depending on given load, F. This conclusion is of fundamental impor-
tance. It opens a way to designing of some types of objects, of any size, which
are free of SEEN, or, more correctly, designs of any size from load-bearing
elements having the constant characteristic size, 0. On the N-L diagram (Fig.
15.2), GS structures of different sizes correspond to L = const and are in its
Area l.
One design approach to resolving the problem of reduction of weight of the
whole structure can easily be solved. This solution lies in use of light brittle
materials, for example, glass. Having a density one-third that of steel, a fiber of
homogeneous glass of the VM-I type with 0 = 10 micrometers fractures at
O"f= 4.2 GPa, a value in the elastic range and allowing elastic strain up to
sf~4.8%. (For information: hardened Steel 30CrMnSiAl is characterized by
values O"y ~ 0.8 GPa and O"u ~ 1.2 GPa). A composite material, in which the load-
bearing element is an array of oriented glass fibers and the binding material is
epoxy resin, is widely used in engineering.
The first experimental research on dynamic (explosive) fracture of GS cylin-
drical shells, wound with glass cloth in an epoxy binder and filled with water,
revealed a remarkable property inherent in oriented composites, namely, the
absence of SEEN [21,22]. This permitted the investigations to proceed in Area 1
of the N -L diagram.
506 AG. Ivanov

It is necessary to note one important requirement which should be satisfied

for oriented composite materials: Acoustic interaction between load-bearing
elements should be minimized. Ropes and glass-reinforced epoxy satisfy this
requirement. In the first case the surface of interaction between elements is close
to zero, in the second case the wave impedances of glass and epoxy resin differ
by a factor of 7. This requirement is less effectively carried out when multilayer
shells or rolled pipes are considered. Such designs are more resistant to brittle
fracture than designs from homogeneous material. For this reason, lengths of
rolled pipe (laminated pipe made by rolling a metal sheet into a multilayered
cylinder) are used in gas pipelines to stop rapidly growing cracks. Their im-
proved crack resistance is also manifest in conditions of intense dynamic load-
ing [23]. Nevertheless, the direct research with GS objects made from layered
materials and subjected to static and dynamic loads showed existence of SEEN,
though it is much weaker than is expected for designs from homogeneous mate-
rial. A fourfold increase in the size of a homogeneous steel pipe reduces Er by
2-2.5 times [24]. Increasing the size of a rolled pipe by 10 times (correspond-
ingly, the number of layers is 10 times greater) reduces Er by only l.3 times
[25]. The reason for the existence of SE, though it is weakened, consists, proba-
bly, in the existence of an acoustic connection between the layers.
We should notice that if, during a GS change of the scale of rolled pipe or a
multi-layer shell, we leave the number of layers constant and correspondingly
change their thickness proportionally to the scale change, SEEN should manifest
itself in full measure. For objects operated in Area 2, a decrease of the probabil-
ity of fracture can be achieved by replacement of a large structure with a group
GS small structures [26]. We will illustrate this using pressure vessels as an
example. Let us replace a prototype spherical vessel with m small geometrically
similar vessels. In this case, at the same expense of material and total useful
volume, the value of C5r, according to Eq. 15.7, will be increased m 116 times (so,
for m = 10 3, C5r will increase by a factor of 3). However, this solution is hardly
acceptable in practice because it is associated with a significant increase of ex-
pense for assembly and operation of the vessels.
The problem can be solved more easily if the prototype pressure vessel has a
cylindrical form. The circumferential stress in such a vessel with radius R and
height H is twice as great as the axial stress, independently of the ratio HlR.
Therefore, it is possible to maintain H constant during a replacement of the
prototype with m small vessels from the same material and having the same
relative wall thickness. At the same expense of material and general useful vol-
ume of vessels the value C5r increases by the factor m1l4, and the gross volume
will be increased by only 10% with dense packing of the vessels. For example,
at m = 200 the value C5r will increase by a factor of 4.
Thus, the replacement of a cylindrical pressure vessel with a package of ves-
sels (pipes), with other things being equal, significantly increases the load-bear-
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 507

ing ability and reliability of the structure. Identity of the components of such a
vessel allows placing them in an arrangement that is optimum for operation, and
to experimentally determine their actual strength reserve. Vessels of this type are
ecologically sound, since independent fracture of one of them allows discon-
necting it from the main assembly. Finally, an assembly of small vessels allevi-
ates problems of transporting a single large vessel from the manufacturer to the
consumer.

15.4. Explosive Fracture of Vessels

It is possible to understand some peculiarities of fracture, including brittle frac-
ture, by investigating GS objects. Pulsed loading of GS objects with simultane-
ous fulfillment of the requirement for similarity of loading can be done rather
successfully by detonation of high explosive (HE) charges. For GS vessels
subjected to central or axisymmetric loading, the calculation of the effect of the
HE explosion can be perfonned in the approximation of a short shock. In this
case the values of stresses and strains in the elastic range of deformation at the
same moments of time will be proportional to the value of ~, the ratio of the HE
charge weight to the weight of a structure or some part of it. Therefore, the value
~ can be considered as an analogue of the pressure. In some cases, dynamic
loading allows convenient consideration of the physical laws resulting in frac-
ture.
The response of a shell to internal explosive loading was investigated in sev-
eral works [27,28]. In the last of these, the velocity history of the surface was
recorded using the capacitor-gauge method [29,30]. Besides radial vibrations of
the shell, the method also allows studying the influence of auxiliary structural
elements on these vibrations. The most interesting were the records of small
vibrations, namely, reverberation of shock waves in the shell walls [28]. The
previous load history significantly influences the attenuation of these vibrations.
Let us consider fracture of thick-walled vessels. Historically, justification of
the explosive strength of a large-size vessel began with the testing of a small
model made of Steel 25. The fonn and design of the prototype vessel is depicted
in Fig. 15.3 [8,31]. It was found in the experiments that brittle fracture of the
model (R = 15 cm) occurs in the interval 5.3 x 10-3 < ~ < 7 x 10-3. Fracture of the
prototype vessel (R = 75 cm) also had a brittle character, but at a much smaller
value, ~ = 10 -3. To exclude the influence of some difference of the model mate-
rial from the prototype material (Steel 22K), GS vessels 115 and 1/15 of the size
of the prototype were manufactured from fragments of the prototype vessel.
Both the models and the prototype were subjected to heat treatment for removal
of residual stresses. Values of the mechanical characteristics of Steel 22K, de-
termined from material samples, were O'u = 0.5-0.52 GPa and 0'0.2 = 0.28 GPa.
508 A.G. Ivanov

Figure 15.3. lllustration of the experimental setup for explosive loading of the prototype
vessel and its GS models. [8,31).

Values of I; producmg fracture, based on results of the experiments with GS

vessels, were the following:
1. R=7S cm, 7 X 10-4 <I; < 1.0 x 10-3, s= 0.042%
2. R= IS cm, S.3 x 1O-3 <1;<7 X 1O-3, s=0.3%
3. R=S cm, 1.4 x 10-2 < I; < 1.6 x 10-2, s = 1.47%
From this we see that reduction of R by the factor IS resulted in an increase
by a factor of IS-17 of the relative weight of the charge required to fracture the
vessel. We should notice that the condition I; = const. (with no account being
taken of the 0"02 (8) dependence) corresponds to the identity of stressed states
for different values of R. The maximwn difference of 8 did not exceed 200
when fracture occurred for the vessels under study. This change can cause an
increase of 8 by no more than 20% and cannot explain the IS-17-fold increase
of 1;.
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 509

The amount by which the fracture stress decreases because of the increased
dwation of the load application with the increased value of R, in accordance
with the kinetic concept of fracture, also appears to be negligibly small. The
vessels tested were loaded to the point of fracture by successively increasing the
weight of the charge that was detonated. Therefore, it is impossible to exclude
the possibility of accumulation of irreversible changes in the material of the
vessels. However, the fact that the largest vessel, in which the smallest number
of charges was detonated before fracture, was destroyed at a smaller value of ~
than the other vessels indicates that the SE is stronger when fracture is produced
by a single detonation. Satisfactory description of the experiments appears to be
possible when SEEN is considered. In this case, using the bilinear law of defor-
mation, Eq. 15.4, according to Eq. 10 [31], the R(E) dependence can be ex-
pressed in the form

(
R =Ro l-K+;;-
KE)-2 , (15.17)

for the elastoplastic range. In this equation R is the radius of the vessel fractured
at the yield strength (at E = Eo) and K = KlE. This describes the experiment quite
satisfactorily. For E < Eo and K = 1, Eq. 15.17 will be changed to

R=Ro -; (EO)2 =Ro (0'~0)2 . (15.18)

In the example considered, with the SEEN described by Eq. 15.17 during
fracture of similarly loaded GS objects, the resistance to brittle fracture of a
prototype can be predicted by considering the results of experiments with re-
duced-scale models [32].
The opportunity for manifestation of SEEN for structures subjected to inten-
sive pulse loading was also investigated in [13,33]. A water-filled high-pressure
boiler (HPB) made with different thicknesses of Steel 22K was used as the ob-
ject under study. The HPB design, an illustration of the experimental set-up, and
photographs of fractured vessels are presented in Fig. 15.4. As in the previous
research, several 1I10-scale GS models were produced from fragments of the
HPB prototype. Then they were subjected to the same heat treatment as the
prototype. For analysis of the stress-strain state of the HPB, two-dimensional
calculations in Lagrange coordinates were carried out. First, the problem of the
motion of the detonation products (DP) and the water was solved. The calcu-
lated pressure history at points along the HPB generatrix was used as initial data
for calculation of its dynamic deformation. Results of the calculation quite satis-
factorily described the experiment. At ~ = 0.74 X 10-2 plastic strain, including
local strain, is absent throughout the volume. Of course this would also be true
for the smaller explosive charge, ~ = 0.56 x 10-2 , when the prototype experi-
enced brittle fracture into 5 fragments of approximately equal size without any
510 A.G. Ivanov

trace of plastic deformation. The fracture had a catastrophic character with rapid
crack growth at a velocity of 600-1800 mls from the HPB throat. Analysis of
the fractures showed that no defects were initially present in zones of nucleation
and growth of the cracks. The estimate shows that fracture into 2, rather than 5,
fragments could take place with a much smaller HE charge (~~ 0.36 x 10-2 ) .
Fracture of the model occurred at ~ = 2.91 x 10-2, a value 5-8 times greater than
for the prototype. The cracks had a local character without complete separation
of the HPB model into parts, even for an obviously large HE charge
(~= 4.45 x 10-2 ). The cracks nucleated in the thinnest equatorial area
Research showed that, for a vessel of given radius, it is impossible before-
hand to answer several questions. What is its load-bearing ability? Where is its
weak place? What is the character of the fracture that occurs (brittle, cata-
strophic or viscous, slowly)? When R is reduced to 1110 of its original value
(from R = 1 m to 0.1 m) the relative charge weight,~, increased -5-8 times, the
location of the "weakest" place changed (instead of the crack starting at the edge
of the throat, the point of crack initiation changed to the thinnest equatorial area
of the vessel wall), and the character of the fracture changed from brittle to
viscous. The value of cr r increased by a factor of 3 (from 0.18 GPa to 0.54 GPa),
and the value of &r increased by a factor of 5.6 (from 0.11 % to 0.62 %). Strong
manifestation of SE was also observed during explosively-induced fracture of

Figure 15.4. Dlustration of the high pressure boiler and photos of the fractured prototype
and its GS model. (8) the prototype R = 1 m and (b) the model R = 0.1 m [13,33].
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 511

other GS objects. Strong scale effects, complicated by factors of a metallurgical

nature, were obselVed during explosive fracture of GS cylindrical shells from
titanium alloy (PT-3V) [34). Shells filled with air and with water at normal
atmospheric pressure, and loaded by spherical charges placed at their center,
were investigated. The shell prototype had radius R = 1 In, a wall thickness of 50
mm, and a length of 4R. The model sizes were 1110 of the prototype sizes. The
inteIVal of change of the relative thickness of the shells was 5-14%. Results of
the experimental research allowed formulation of semi-empirical equations
describing the dependence on parameters of the shells and HE charges of the
maximum displacement and velocity of the shell wall motion.
Figures 15.5 and 15.6 present results of experiments comparing the load-
bearing ability of GS shells from Steel 22K (circles) and from glass-reinforced
plastic (squares) subjected to explosive loading by charges placed at their center.
Figure 15.5 presents data on vessels filled with air at normal atmospheric
pressure and Fig 15.6 presents data for vessels filled with water. The solid points
correspond to fracture and the open points correspond to absence of fracture.
Fracture at ~ = const. indicates that SEEN is absent These data unambiguously
testify on the main role of SEEN during brittle fracture of metal shells in com-
parison with SE attributable to other causes, for example those of a statistical
nature.

15
~~
•
~
-#
10 ':-..~

-
'"0I
X
».1'
~"

5
""
," "
" • • - fractured
~"
o []-intact
0
0 0.5 1.0
RminlR

Figure 15.5. Dependence of the load-bearing ability of GS steel and glass-reinforced

plastic shells on the scale (the relative radius) for internal explosive loading. the symbols
o and • are data for shells made of Steel 22K and the symbols 0 and ., are data for
glass-reinforced plastic shells. The shells are fllied with air [62].
512 A.G. Ivanov

00
5

.o 2 -4

-
I

3
x
ll.1'

2
• • - fractured
00 -intact

o ~---------------,----------------.---
o 0.5 1.0

RminlR

Figure 15.6. The same, but for shells fllled with water [62).

Figure 15.7. Fracture of a cylindrical shell in the elastic range of defonnation due to
excitation of bending vibrations. The arrows point to the meridional areas of fracture [9).
Reprinted with pennission from A.G. Fedorenko, et al., Pecularities of dynamic defor-
mation and destruction of cylindrical fiber-glass shells at internal pulse loading, in
Mech. Compo Mat. (1), pp. 90-94 (1983).
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 513

Sf ••

-0.4

-0.2
•
/ • •
0.0 - f - - - - - - , - - - - . . . . - - - - - - - r - - - - -__
2 3 4 5 loge

Figure 15.8. Dependence of the limiting strain on the strain rate [45].

15.5. Other Examples of Using the Integral Approach

It is known that modem fracture mechanics (FM) encounters great difficulties
when calculating strength and estimating reliability of designs under develop-
ment. In some cases its use requires knowledge of details and peculiarities of
crack nucleation, growth, and transition to the unstable state. Usually such in-
formation is absent. However, it is possible to specify some applied problems
for which use of IA allows these difficulties to be overcome. We will consider
some of them. When fracture is fraught with catastrophic consequences for the
life of people and the ecology of the Earth, it is of primary importance that it be
prevented.
Fracture mechanics provides no criterion protecting against brittle fracture of
a structure but, in some cases, a criterion can be obtained from IA and used
successfully. As another example of the use of lA, we will consider cases of
dynamic fracture of elementary objects when diagnosis of structural defects is
complicated or impossible. In these cases some authors suggest use of traditional
criteria of strength of materials. It is obvious that, in this case, some peculiarities
of fracture such as SEEN will not be taken into account. Moreover, as will be
shown below, information on physical processes that occur during fracture can
appear incorrect not only quantitatively, but also qualitatively. Let us proceed to
consideration of particular problems.
Problem 1. In the practice of operation of large pipelines there are many known
cases of their experiencing multi-kilometer fractures by a crack growing with a
velocity of hundreds meters per second [18]. We have remarked on this problem
briefly in earlier sections. Now let us consider it in greater detail. According to
514 A.G. Ivanov

lA, to exclude such fractures, we will require that the necessary condition for
fracture, Eq. 15.2, be violated. We will consider a segment of the pipeline
length. Let us assume the ratio of the thickness of the wall, h, to the pipeline
radius, R, to be small. This condition allows neglect of the change of stress
through the thickness of the pipe, and q can be calculated using only the circum-
ferential stress, 0'6). The latter is related to the pressure in the pipe by the equa-
tion 0'6) = pRlh, and we have

(15.19)

where v is Poisson's ratio and E is Young's modulus of the pipe material. The
condition 15.3 that the pipe remain intact, with account being taken of
Eq. 15.19, will be expressed by Eq. 15.11 or

(15.20)

We note that, for the first time, the consideration of pipeline stability against
brittle fracture was performed in [35] and, using r-integrals in a more complete
analysis taking account of temperature and inertial forces, in [18]. Analysis of
this solution [4] showed that the role of these forces is negligibly small in com-
parison with manifestation of SEEN. In [36], fractures of pipelines associated
with nucleation and growth of a single crack are considered. The scale of possi-
ble fractures, including those due to hydro-impact, is estimated with the help of
lA.
Problem 2. We will try to find conditions in which thin-walled cylindrical and
spherical vessels remain intact when subjected to static and explosive loading
[37]. Let us limit ourselves to consideration of vessels that are not complicated
by auxiliary structural elements such as a throat or stiffening ribs. Let us assume
the arrangement of explosive charges used to load the vessel to be axisymmetric
or centrosymmetric. It is obvious that, with the assumptions taken, the solution
for the statically loaded long cylindrical vessel coincides with the condition
15.20 found for the pipeline.
After performing similar calculations for the spherical vessel, taking into ac-
count the equality of meridional and circumferential stress, and writing down the
expression for q,

(15.21)

we obtain
 15. Fmcture of Structures Caused by Explosive Loading: Scale Effects 515

EGlc ]112
0"< [ , (15.22)
2R(I-v)
or
2h [ EGlc ]1/2 (15.23)
P<R 2R(1-v)

Restriction of fracture to the elastic range of defonnation detennines the

value of Ro below which brittle fracture is impossible for the given material.
Replacing O"a and 0" for O"al in the inequalities 15.11 and 15.23, and changing
the sign of inequality for the sign of equality, we find Ro for the cylindrical and
spherical vessels to be

(15.24)

and
(15.25)

respectively.
Let us proceed to consideration of dynamically loaded vessels. We will as-
sume the "short shock" to be a satisfactory the approximation during explosion
of HE charge. In this approximation, the response of the vessel can be divided
into three stages.
During the first stage, the explosion products accelerate the walls of the ves-
sel to a radial velocity Vo during a time 't equal to several reverberations of the
shock wave in the wall ('t« T, where T is the period of the vessel vibration
itself). Let us consider the further quasi-static pressure on walls of the tbin-
walled vessel to be insignificant and its effect negligible. This approximation is
reasonable when the quantity of HE is SInall. It easily allows finding functional
dependencies, and any discrepancy of the short impact approximation can be
corrected exverimentalIy.
During the second stage of the motion, the kinetic energy imparted to the
vessel causes it to vibrate radially. During tension (when fracture without satis-
faction of condition 15.3 is possible) the maximum value of q is already reached
by the end of the first quarter of the period of vibration, T , and then in each
subsequent period.
During the third stage of motion bending modes of vibration are excited after
a time depending on the extent of imperfection of the real shell [38]. The value
of q in the aggregation of these modes can exceed its maximum value during
mdial vibrations by several times. As one can observe in the experiment with
516 AG. Ivanov

thin cylindrical shells loaded by a pulse, fracture occurs due the bending modes
of vibration. At hlR = 5 %, the shell is simultaneously fractured along 12 axial
cracks located in regular intervals on a circle. This corresponds to excitation of
the sixth vibrational mode (Fig. 15.7).
Why does fracture of thin-walled vessels occur not at the second stage dur-
ing radial vibrations, when less EE is required for fracture, but at the third stage
during excitation of the bending modes, when BE consumption for fracture
increases because it proceeds in several planes in this case? During the second
stage the time of existence of tension of with sufficient magnitude is 0.2-0.3 T,
and transfer of EE to the area of the crack requires a time of 0.5 -1. 0 T (T is the
period of axisymmetric vibrations of the pipe or vessel).
More favorable conditions for fracture are realized at the third stage during
excitation of the bending waves. In this case fracture proceeds independently at
n locations around the vessel circumference where these waves combine to pro-
duce maximum tension, so the time required to transfer the EE to the crack de-
creases by the factor lin, and the time for which the EE of tension exists
doubles, since the period of vibration of the bending waves 4 is about 2T. As
was mentioned above, the EE concentration in aggregations of bending vibra-
tions can exceed the similar characteristic in the case of radial vibrations by
several times. The last circumstance is also rather important for nucleation and
growth of a fracture.
It follows from the above that, for dynamic effects, the calculation of S
should be performed taking into account the number of the most significant
modes of vibration.
So, the n-th mode occurs in an extended cylindrical vessel or pipe [9]
n 2 (n 2 -1)2 h 2
1 (15.26)
3(n 2 +1)[R+(hI2)F

with 2n locations at which the tension is maximized and, hence, 2n cracks.

Therefore
S=2nhL. (15.27)
For a thin spherical vessel
1/2
n=2.12 (Rlh) -0.5. (15.28)
Approximating the form of possible fragments that can be produced by fracture
of the spherical vessel to form circular disks with radius r, we determine r from
the condition of equality of the area of the vessel to the total area of the disks:

4 The bending mode with frequency equal or close to one-half of the frequency of
axisymmetric vibmtions has the strongest excitation [38].
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 517

2 2 -112
47tR =2n7tr; r=2R(2n) (15.29)
1/2
s= 27tRh(2n) . (15.30)
Taking into account Eq. 15.27, Eq. 15.11 for the cylinder can be written as

2nEGrc ]1/2
[ (15.31)
ere < 7tR(I-v 2 ) ,

where n is specified by Eq. 15.26.

In a similar manner, using Eq. 15.22 for the spherical vessel, we find that

(2n)112 EGrc]1/2
ere < [ (15.32)
2R(I-v) ,

where n is specified by Eq. 15.28.

From inequalities 15.31 and 15.32, we also determine Ro for cylindrical and
spherical vessels, respectively:

Ro = 2nEGrc (15.33)
2 7t (1- v 2 )
er 0.2 ,

(2n)1/2 EGrc
Ro= 2 • (15.34)
2erO.2 (I-v)

In Eqs. 15.33 and 15.34 in comparison with Eqs. 15.24 and 15.25 not only
the coefficients 2n and (2ni /2 appear, but value of eroz can also change signifi-
cantly due to the high-velocity loading.
Let us find the relation between the velocity of material expansion, vo, and
the parameters of HE charges in the case of instant explosion of the extended
charge in the evacuated cylindrical and spherical vessels. According to [39],
when the EP expand into the vacuum they are characterized by the integral pulse

8
l=-mD (15.35)
27 '
where m is the HE weight per unit of the cylindrical charge length or the weight
of the spherical charge and D is the detonation velocity.
During derivation of Eq. 15.35, for simplicity of calculations but without
significant loss of accuracy, the index of the EP isentrope is taken to be 3. As-
suming that the pulse is doubled during reflection of the EP from the vessel
wall, we obtain:
518 AG. Ivanov

16
lrefl =-mD. (15.36)
27
Designating weight of a unit length of the cylindrical vessel (Pipe) or weight
of the sphericai vessel by M, we obtain the following:

Mv~ I~fl
--=- (15.37)
2 2M
or, with account ofEq. 15.35,

16
Vo =-~D
27~ , (15.38)

where
~=mIM. (15.39)
When considering only the elastic range of defonnation it is easy to find the
relation between Vo and cr.
During the second stage, all of the kinetic energy initially imparted to the
vessel walls is transformed to elastic energy before the moment of time T14, so
we obtain
l.pv
2 0 =q ,
2 (15.40)

where q is specified by Eq. 15.19 or Eq. 15.21.

Equations 15.38 and 15.40 allow us to proceed easily from values cre and cr
to ~ in the inequalities 15.31 and 15.32.
The condition that the extended thin-walled cylindrical vessel or pipe remain
intact during the HE charge explosion is
112
~<~ [ 2nGlc ] (15.41)
16D npR

and, for the spherical vessel,

< ~[(2n)1I2 Glc ]1/2

(15.42)
~ 16D pR

Inequalities 15.41 and 15.42 are analogs of inequalities 15.11 and 15.22. As
expected, the use of condition 15.3 resulted in formulation of Eqs. 15.11, 15.22,
15.41, and 15.42, where the values of cra, cr, and ~ depend on the vessel size as
R- 1/2 .
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 519

Also prominent is the fact that solutions of these equations do not contain the
shell material thickness in an explicit fonn, though it is accepted in FM that this
size is of crucial importance in selection of the material. The reason is that, in
the problems mentioned above, there was no consideration of the kinetics of
transition to brittle fracture, and its possibility was assumed a priori,5 as exis-
tence of the self-sufficient stationary regime of fracture in conditions of plane
strain under all-round tension [40,41].
Problem 3. We will describe fracture of thin shells in the plastic range of de-
formation. Let us try to understand the nature the of the dynamic peak of plas-
ticity. In books on the strength of materials it is assumed that, with an increase
of the true strain rate 6 (e =v / R), the value of the plastic strain required for
fracture of the material, Er, also increases. However, in [42] the reverse depend-
ence was measured for soft steel for e> 104 s-1 • A similar tendency was also
mentioned in [43]. In [44] a similar anomaly of the function Ec(e) was meas-
ured for stainless steel, annealed Steel 40, and annealed aluminum alloy D-16.
Explanation of the physical nature of this phenomenon and the mathematical
description of it were given from the IA position [45] (Fig. 15.8). A radially
expanding and fragmenting thin ring was considered It was assumed that, at
t = 0, fracture starts in some section, and the unloading waves run from this
section to both sides with velocity C. At t = t*, when the amount of stored EE
removed from the areas covered by unloading is sufficient for fracture of the
ring material, the fracture will be completed. Assuming the ring material to be
incompressible (v = 0.5) and its expanding velocity, Yo, to be constant, the basic
equation ofIA gives

2RC rR!LdR = 1 . (15.43)

A.VO JRo R
Considering the material as viscous-plastic with the yield strength 0"0,
which depends on e,
and with a constant value of the dynamic viscosity, TJ, we
obtain

0" =0"0 +TJe. =0"0 +TJVo- (15.44)

R
and

(15.45)

5 This assumption accounts for the fact that the transition to a steadily propagating crack
should not always proceed according to the given procedure and testing regime for the
material samples. Some factors can be identified (defects of structure, local impact, and
thermal loads, etc.) which significantly accelerate this transition.
6 The true (logarithmic) strain is equalJn( I + &), where &is strain.
520 AG. Ivanov

Equation 15.43 will be changed for the following after integration:

tv 2e2 sr(sf +2) +e(2VSf -a) +In(1+sr) = 0, (15.46)

where v =11/ao and a = 4EAJ(3Ca~). The maximum value ofs£ is reached at

emax =1I[v+(a/8)]. For s£«l, emax ~l/v in this case ao ~11emax and, ac-
cording to (15.44), a ~ 2ao.

From the physical standpoint, the existence of a maximum of s£( e) is clear,

if one takes into account that, at small e, e
ao» 11 accordiIig to Eq. 15.44 and
the value of a does not actually depend on e. Thus, under other similar condi-
tions the plastic strain s£ will be less at smaller e, i.e., the function Sf( e) will
e e
be increasing. In the other case, when > emax , ao« 11 and elastic energy
given by Eq. 15.46 increases rapidly as e increases. That is why the fracture
criterion will be satisfied at smaller Sf, i.e., the function s£( e) will be decreas-
ing.
The experimental data, used in [45], were well described by Eq. 15.46 for
~ = 0.85 X 10-4 s and a = 1.67 x 10-4 s. The experimental data with soft annealed
steel (MV-143) presented in [46] are described by Eq. 15.46 with ~= 0.95 x 10-5
s and a = 2.25 x 10-5 s. Values for description of plastic fracture of cylinders
made from uranium with 1.5% (by we~t) of molybdenum, obtained in [47],
are ~ = 1.667 x 10-5 s and a = 6.667 x 10- s.
Derivation of the formula for destruction of the spherical layer in the plastic
range of deformation, made with the same assumptions as in [45], is obtained in
[47]. It is

tv 2 e2 [1-(1 +Sf )3] + e[a - VSr(Sf + 2)] -Sf = 0, (15.47)

wherev=11/aoand a = E')./(CcrJ).
In [48] the following step performed in description of fracture of metals in
the range of large plastic strains. The equation of state of the material with strain
hardening was used, and when searching for the differential equation the peculi-
arity of motion of the extending shell (the ring) was more completely taken into
account. It is noted that disintegration of a jet from a continuous material, which
has the velocity gradient (one more example of material fragmentation in large-
strain plasticity), can also be described by this differential equation.
A few words about the SEEN manifestation during fracture of GS cylindrical
shells at e< 10 4 S-I. Section 2 specified difficulties of the description of this
phenomenon during plastic strain (Area 3, Fig. 15.2). It is known from strength
of materials that soft steels (Lo> 10-100 cm) SEEN do not actually display it at
quasi-static strain. However, with transition to explosive loading (e - 102 -
10- 4 S-I) it appears to be rather significant. So, with 4 times increase of initial
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 521

radius of GS thin-walled pipe, the strain required to fracture the pipe decreases
2-2.5 times [24]. A similar phenomenon is also observed during explosive
radial compression ofGS pipes [49,50].
Problem 4. When describing the fragmentation of space bodies (SB) entering
planetary atmospheres, traditional criteria of strength of materials are used in the
collection of works known to the author. Obviously, nostalgia for these criteria
is not the reason for their application to solution of this problem, but rather the
impossibility of using FM. There is not enough information on the presence of
defects in SBs and there is no opportunity in this field to carry out diagnostics of
defects. It is assumed in these works that as soon as the aerodynamic resistance
of the planetary atmosphere causes the tensile or shear stress in the SB material
to reach a critical value, it fractures in approximately the time required for an
elastic wave to pass through the SB. In different works this process is described
as the stage of "splitting", "dispersal" [51], "loss of binding" [52], "complete
destruction" [53], or "disintegration" [54]. The further description of the process
of SB energy transfer to a shock wave and heat will be determined by the typical
size of the fragments. There is no such information in the literature. Use of lA,
with possible small loss of accuracy, allows a physically correct description of
the essence of the phenomenon as a whole, as shown in [55]. Low temperature
(100 K), large sizes (~100 and more meters), and rather high rates of loading
(e _10-1 S-1 and more) when a SB enters the planetary atmosphere, allow con-
sidering fracture of the SB to be brittle. Therefore, it should be accompanied by
SEEN manifestation. When describing this phenomenon it was assumed that, as
a rule, real brittle bodies fracture into two approximately equal parts during
quasi-static loading processes. Therefore, the basic equation of lA and the esti-
mated value of q, approximately equal to

(15.48)

give the criterion

3K~
P2 vo~--
4
(15.49)
Do
for the first stage of fracture of a SB in the form of a sphere with diameter Do
[56,57].
Suppose the fragments formed to be spheres from homogeneous material
with the diameter D\ = 2-1/3 Do. As the aerodynamic resistance increases, Eq.
15.49 will again appear satisfactory after changing Do for D\. This process of
fragmentation will continue up to termination of the increase of aerodynamic
resistance. Calculations performed using the proposed scheme and the recur-
rence formulas found showed, in [55,56], that:
522 A.G. Ivanov

l. The process of SB fragmentation has a multi-stage character.

2. Loading of fragments between stages is essentially quasi-static. This al-
lows to us consider the process of fonnation of each fragment independ-
ently of its neighbors.
3. After completion of the fragmentation process, the deceleration of the
fragment swarm reaches a maximum.
Fragmentation under the action of tidal forces has never been observed,
whereas precisely the action of aerodynamic forces can account for the origin of
tektites and a number of other celestial phenomena involved in the interaction of
SB with planetary atmospheres. In particular, the multi-step fragmentation of the
Sikhote-Alin meteorite calculated in [58] and confinned by results of morpho-
logical studies of fragments [59]. The newest approach forms the aerodynamic
model of fragmentation.
The interaction of a small celestial body passing through the atmosphere of a
planet was considered in [60,61]. It was shown that the fragmentation is a multi-
step process with steps separated in space and time. The model was illustrated
using the example of interaction of Comet Shoemaker-Levy 9 with Jupiter's
atmosphere.
Problem 5. As shown in Section 15.3, use of oriented fiberous composites
loaded along the direction of the fibers allows achieving both of the following
objectives.
l. To escape SEEN when designing large, highly-stressed structures, i.e., to
work in Area I of the N-L plane shown in Fig. 15.2.
2. To use light materials with a high value of cry, which are traditionally
considered to be brittle. Woven or wound glass fibers in an epoxy matrix
were the most fully investigated of these materials.
Investigations of these problems are reviewed in [62,63]. The use of glass-
reinforced plastic as the material of a load-bearing shell allowed manufacture of
highly reliable, transportable explosive chambers that withstand detonation of up
to 200 kg of TNT.
Investigations of spherical chambers revealed one more remarkable property.
It is known that the strain to fracture of spherical steel chambers is 4-5 times
less than for their cylindrical analogs. This effect is caused by transition from
uniaxial to biaxial strain Fracture of glass fibers reinforcing spherical fiberglass
chambers occurs at the same strain as for the cylindrical chambers. This prop-
erty of fibrous cotnposites allows manufacture of spherical explosion-proof
chambers (containers), that are about 1110 the weight of chambers made from
traditional materials such as steel. A spherical container from glass-reinforced
plastic with a weight of 1 t and a diameter of 1 m will withstand an accidental
 15. Fractme of Structures Caused by Explosive Loading: Scale Effects 523

explosion of a nuclear charge (-20 kg of TNT). Development of such containers

will solve the problem of improving the degree of safety with which nuclear
weapons can be transported and stored in time ofpeace [64-66].

15.6 Conclusion
Examples presented of the use of IA when fracture should be precluded (Prob-
lems 1, 2, and 5), as well as the cases of at least the qualitative description of the
fracture process without loss of its basic physical regularities (Problems 3 and
4), show its usefulness for FM.
A few words about the place of IA in FM. According to Eq. 15.5, the quan-
tity A is the ratio of the EE reserve to the work that must be done to break a
cube: A > 1 in Area 2 (Fig. 15.2). Brittle fracture is possible. At er =ero, Eq. 15.5
can be written as L= LoA. Therefore, an initial crack of Area Lo2 is enough for
brittle fracture of a cube with the edge length L placed in tension by the force
eroL2. But, in IA the value Lo is the minimum value of the characteristic size of
the object for which brittle fracture is still possible at er = ero. For some materials
this value is not small at all. for example, La is measured in decimeters for uni-
axial tension of the cube from copper, stainless steel (12Cr 18Ni lOTi), or soft
steel at T~ 300 K [8].7 So, brittle fracture is impossible in Area 1 of the N-L
diagram (see Fig. 15.2) from the position of linear FM because the size of the
critical crack exceeds that of the object itself. In the other limiting case, A » 1,
that is characteristic for materials that are brittle in the usual conditions, the state
of the object is one presenting a high risk of fracture. The value of A can be
reduced by a sharp decrease of L. In this case it is possible to use a high value of
ero for brittle materials, as was shown with the example of glass-reinforced plas-
tics.
It was noted above that G,c and 21 are analogs in FM and in IA' The values
of G,c and 21 are determined by experiments with growth of a single crack, and
A, as a rule, is determined by the method of high-rate fracture-spallation. In
the latter case the fracture is initiated and proceeds concurrently at many nu-
cleation sites. In this case A depends on the length (or duration of action) of the
tensile pulse. If we assume that this dependence for GS experimental devices
takes the form i.. - L K [66], the value of K is a characteristic of the material. It is
determined by GS experiments to determine the minimum velocity that results
in spallation in the target 8 when plates collide.

7 Such value of Lo allows understanding why the Melbourne bridge fracture started at a
crack length of -3 m [67].
8 Another possible way to determine i.. of spallation is to impact plates at a velocity that
obviously results in spallation. The value, cr, of spallation is determined by recording the
free surface velocity the target In. this case cr of spallation will depend, besides L, on the
chosen loading pressure [66].
524 A.G. Ivanov

The similar dependence on L should also exist for G'e or 2y. But, as shown in
the last footnote, it is negligibly small. This circumstance leads us to conclude
that in IA it is reasonable to use G'e instead of A when fracture occurs through
the main crack.
Taking into account the previous discussion, let us compare the equations for
the brittleness threshold in lA, Eq. 15.6, and the size of the Irwin plastic zone,
I GleE
ry=--- (15.50)
21t (15

inFM [67].
The expression of the brittleness threshold as a function of the size of the
Irwin zone follows from Eqs. 15.6 and 15.50: Lo = 41try. Thus, at (1=(10, brittle
fracture is possible only for a cube of edge length Lo ~ 41try, and it is impossi-
ble when Lo < 41try.
In investigations cited above, an attempt is made to describe experimental
results of dynamic fracture of GS objects from the IA. In some cases it had the
character of an estimate. To clarify the essence of the processes, simplifying
assumptions were used. They concern the equations chosen to describe the mate-
rial deformation, consideration of the simplest cases of the stress-strain state of
GS objects, and the assumption that the physical properties for the material of
GS objects are independent of their size, including such of its characteristics as
(10 and A (Le., absence of factors of a metallurgical nature and the weak influ-
ence of f: 9).
Let us summarize some results in the problem of description of dynamic
fracture.
1. A possible scheme is proposed for formulation of a uniform theory of
fracture. Areas of states are specified in which fracture, including brittle
fracture, is impossible.
2. The determining role of SEEN is shown during dynamic fracture of GS
objects. Neglect of SEEN when designing and manufacturing load-bear-
ing units of large size causes overestimation of the strength reserve. This
can be one of the main reasons for unforeseen brittle fracture of such ob-
jects.

9 In steels, when & changes by a factor of 10, the value of ao changes by no more than
2-3%. If we do not consider spall fracture, a weak: dependence of G'e (the analog of A.)
on & is also observed. According to [3], 5 orders increase of & causes a 1.5-2.0-fold
increase of K'e When K,cC&) is a linear function, G'e will increase by 0.03-0.04% when
& increses by an order of magnitude.
 15. Fracture of Structures Caused by Explosive Loading: Scale Effects 525

3. Some ways to avoid SEEN when designing objects from traditional ma-
terials are considered. The cycle of investigations concerning dynamic
fracture of shells from glass-reinforced plastic revealed and theoretically
justified the remarkable property of this material: insensitivity to SEEN
when loaded by tension along the direction of the fibers.
4. Peculiarities of fracture of metal shells loaded statically in the elastic
range of deformation and dynamically in the range of large plastic de-
formation are investigated. In the latter case we managed to understand
the physical nature and to describe mathematically the dynamic peak of
plasticity of materials having a viscous component of strength, and also
significantly progress in revealing the mechanism of fracture of compact
objects and shells.
5. Use ofIA for pipe transport allows developing the concept of operational
reliability, taking into account dynamic loads and properties of the mate-
rial. and also to estimate scales of fracture consequences at extreme ab-
normal loads.
6. Use ofIA during description of a small space body entering the planetary
atmosphere showed that its fragmentation proceeds stage by stage in the
quasi-static regime. After achievement of the maximum value of aerody-
namic pressure, the process of stage-by-stage fragmentation changes to
rapid deceleration of the fragments by transfer of their energy to an air
shockwave.

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Index

compressibility Landau-Stanukovich .............. 4,6,53

isentropic ....................... 17,18,20,383 liquid mixtures ............................. 411
isothermal... ............. 147,189,234,393 liquid phase .................... 350,386,404
shock .......................... 11,13,20,86,91 nonideal plasma .................... 151,168
conservation laws quantum statistical (QS) .............. 110
shock waves ................................... 79 SCF ..................................... 15,26,103
smooth waves ............................... 304 specific heat... ....................... 185,192
TFPK ............................. 14, 15,26,426
detonation ............................................ 2 TFQC ........................................... I03
Chapman-Jouguet (Cl) theory ...... .54 Thomas-Fermi (TF) ............ 14,25,110
decomposition mechanisms .. 55,57,59 van der Walls ....................... 4,26,403
explosives elastic-plastic materials .... 197,297,301
containing inert particles ........ 60,68 Bauschinger effect ....................... 306
desensitized ................................. 57 constitutive equations ........... 304,321
high density (agate) ..................... 68 dislocation dynamics ................... 305
mixtures of explosives ................. 64 dynamic shear strength ........ 198,200,
Landau-Stanukovich EOS ...... .4,6,53 297,300,310,313,316
modes of detonation ....................... 54 elastic modulus ..................... 304,308
parameters ........ 6,49,53,58,59,66,417 microstructural processes ..... 299,317
rarefaction wave ............................... 5 strain rate effects ................... 305,312
reaction zone ................................. 5,6 strain state (3D) .................... 298,303
wave structures ....................... 5,66,68 stress relaxation .............. 199,297,322
ZND theory ................................. 3,54 stress state (3D) .............. 201,298,303
dielectrics ................................... 28,337 stress-strain diagram ............ 298,313
viscosity .......................... 297,321,324
equation of state (EOS) ...... 25,109,185, elastic-plastic waves
337,348,385,438 elastic precursor waves ... 197,298,309
chemical model ................ 26,438,480 unloading waves ................... 199,312
cold compression curve .. 145,191,393 waveform structure .. 198,298,310,318
comparison of measurements with electrical conductivity ..................... 344
theory ....................................... .396
Debye-Hiickel ............................... 25 fracture of structures ....................... 491
electron shell effects .............. 110,123 design methods ............................ 503
electronic component 27,110,192,352 explosive fracture of vessels ........ 507
Gruneisen coefficient .... 186,188,192, integral approach ......................... 494
236,349 linear fracture mechanics ............. 491
Hartree-Fock-Slater ............ 103,123
ionization ..................................... .440 Hugoniot curve (also see individual
ionization chemical materials) ......... 7,14,77,86,96,101,
equilibrium model (ICE) ........... 124 109,112,114,123,131,208,284,298,
comparison of models ............... 166 464,475
plasma micro field effects .......... 151 classification by shape .............. 11,87
530 Index

comparison of measurement with calcium (Ca) ............................... 12

theory .......................... 103,120,396 carbon (C) ................................. 210
effect of electronic cerium (Ce) ................................. 88
reconstruction ......................... ll,89 cesium (Cs) ................. .420,452,457
effect of phase transformation ..... 208, cobalt (Co) .................................. 88
258,284 copper (Cu) ........ 11 ,15,16,22,23,24,
electron-shell effects .................... 123 25,27,88,96,99,101,104,122,128,
liquid-vapor system .................... 262 131,142,185,186,187,200
porous materials ...................... 20,109 deuterium (D) .................... 383,388
rarefied condensed matter ............ 375 dysprosium (Dy) ......................... 12
erbium(Er) ................................. 12
instrumentation (see also measurement europium (Eu) ............................ 90
methods) gadolinium (Gd) ......................... 90
electrocontact gauges ........ .40,80, 181 germanium ................................ 209
y-reference gauge ........................... 85 gold (Au) .......................... 10,27,87
laser velocimeter ........................... .48 hafnium (Hi) ........................ 90,208
liquid brightness indicator ................ 5 hydrogen (H) ............... 383,388,409
magnetoelectric particle velocity iridium (lr) .................................. 87
gauge .................................... .4,6,41 iron (Fe) ...... 10,15,16,90,91,99,101,
manganan pressure gauge .... 6,43,201, 122,128,135,186,204,225,228,
314 230,325,425,428,430
ruby gauge .................................... 150 lanthanum (La) ...................... 12,90
transverse stress gauge ................. 201 lead (Pb) ....... 15,16,25,27,88,96,99,
x-radiography ............................. .4,44 101,122,138,425,428,430
isentrope (compression) ................ 17,18 magnesium (Mg) ........................ 12
molybdenum (Mo) ....... 15,16,87,96,
isentrope (decompression) .... 20,23,231,
99,101,122,139,427,430
428,430
neodymium (Nd) ................... 12,90
isotherm ...................... 142,189,427,440 nickel (Ni) .......... 22,25,88,139,182,
184,187,188,189,428,440,472,
light emission .................................... 29 475
liquid structure .......................... 352,365 niobium(Nb) .............................. 88
oxygen ...................................... 409
materials data praseodymium (Pr) ..................... 90
compounds (inert) ........................ 115 rhenium (Re) .............................. 87
AI 20 3 ........................................ 150 silicon ....................................... 209
CH 20 2 ······································.409 strontium (Sr) ............................. 12
CO2···········································.410 tantalum (Ta) .......... 88,139,425,430
H20 ........................................... 265 titanium (Ti) ... 90,104,139,141,206,
halides .................... 29,205,340,353 208
rocks and minerals .................... 213 tungsten (W) ..... 10,21,25,87,99,186
Si0 2 (quartz) ...................... 212,275 uranium ........................... 10,15,137
dielectrics ................................ 28,337 vanadium (V) ............................. 88
elements ....................................... 115 xenon (Xe) ........................... 25,452
aluminum (AI) ........ 11,16,27,93,99, yttrium (Y) ................................. 90
101,122,135,200,425,428,472, zinc (Zn) ..................................... 88
475, zirconium (Zr) ............... 90,206,208
argon (Ar) ............................. 30,457
cadmium (Cd) ........ 15,16,88,96,99, explosives ........................................ .
101,104,122,139 PETN ............................. .5,51,58,59
 Index 531

RDX .................................... 5,51,58 Rayleigh line .................................. 3,54

RDX/HMX .................................. 68 refractive index ........................ 338,340
TNT .......................................... 5,50
TNT/RDX ................................... 64
shock wave
metal alloys
generators
Al 1100 ..................................... 327
laser .......................................... 134
AI6061-T6 ......................... 310,324
nuclear explosion ......... 14,21,83,91,
Be S200 .............................. 313,328
181
PMMA ......................................... 328
plane explosive system ............ 8,81
porous materials ........ 20,115,177,464
plate impactor. ......................... 8,81
spherical implosion system ...... 8,82
nuclear weapons ............................. 1,77
two-stage gun .................. 9,127,339
electron screening of radiation ..... 370
optical properties ............................... 28 light absorption ............................ 343
light reflection ............................. 339
phase transformations ........ 197,201,247 light radiation ....................... 337,341
amorphization of quartz ................ 278 measurement methods (see also,
effect on Hugoniot... 208,237,258,284 instrumentation) ........................... 1
melting ..... 199,227,231,233,240,356, brightness pressure indicator ... 5,45
398,420 brightness temperature ...... 337,345
phase diagram .... 24,207,225,227,237, y-reference ............................. 85,93
358,396,410 impedance matching ................... 79
polymorphic transitions ....... 18,20,89, laser measurement of wave
201,197,225,247,275,342,363 velocity ............................. 5,46
carbon ........................................ 210 optical. ........................................ 28
effect on shock structure ... 197,201, plate impact ............................. 7,79
260 spall technique (free surface
electronic reconstruction ....... 11,89, velocity) ......................... 4,7,40
139 spectroscopy ............................... 49
hysteresis ............................ 204,252 stress state (3D) ........................ 314
iron ..................................... 225 ,23 7 x-ray diffraction ........................ 203
mechanism ..... 19,201,206,248,253, x-ray imaging ............................. 44
286 non-equilibrium radiation ............ 369
quartz ................................. 212,275 stability ........................................ 264
rarefaction shock .... 19,204,264,368 temperature ........................... 356,375
rocks and minerals ............. 213,275 thickness ...................................... 339
superheating of solids ................ 267
transformation time/rate ..... 205,248 sound velocity ............... 18, 199,428,430
porous materials ........... 20,114,177,428
spall........................................... 19,202
rarefaction shock .......... 19,204,264,368