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Nanocoatings Nanosystems Nanotechnologies 1st Edition
Alexander Pogrebnjak Digital Instant Download
Author(s): Alexander Pogrebnjak; Vyacheslav Beresnev
ISBN(s): 9781608054169, 1608054160
Edition: 1
File Details: PDF, 14.79 MB
Year: 2012
Language: english
Nanocoatings Nanosystems Nanotechnologies

AUTHORED BY

Alexander D. Pogrebnjak
Sumy State University
Sumy Institute for Surface Modification, R.-Korsakov Str.
2, 40007 Sumy
Ukraine

&

Vyacheslav M. Beresnev
Kharkov National University V.M. Karazina, sq. Svobody
4, 61022 Kharkov
Ukraine
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 CONTENTS

Introduction i

About the Authors ii

Foreword iii

Preface iv

CHAPTERS

1. Structural Features of Nanocrystalline Materials 3

Alexander D. Pogrebnjak and Vyacheslav M. Beresnev

2. Nanoporous Materials 15
Alexander D. Pogrebnjak and Vyacheslav M. Beresnev

3. Amorphous Materials 21
Alexander D. Pogrebnjak and Vyacheslav M. Beresnev

4. Fulerene, Fulerite and Nanotubes 31

Alexander D. Pogrebnjak and Vyacheslav M. Beresnev

5. Nanocomposite Material 39
Alexander D. Pogrebnjak and Vyacheslav M. Beresnev

6. Methods Employed for Nanomaterial Fabrication 47

Alexander D. Pogrebnjak and Vyacheslav M. Beresnev

7. Methods of Nanomaterials Investigation 84

Alexander D. Pogrebnjak and Vyacheslav M. Beresnev

8. Structure and Properties of Nanostructured Films and Coatings 95

Alexander D. Pogrebnjak and Vyacheslav M. Beresnev

9. Application of Nanomaterials in Engineering 122

Alexander D. Pogrebnjak and Vyacheslav M. Beresnev

Terms 143

Index 145
 i

INTRODUCTION

NANOCOATINGS, NANOSYSTEMS, NANOTECHNOLOGIES

This Reference eBook deals with an existing classification of a nanosized structure and an
analysis of its properties. It summarizes an information about how a grain size affects physical,
mechanical, thermal, and other properties of a nanostructured material. A basic method, which is
employed for a fabrication of an isolated nanoparticle, an ultradisperse powder, a compact
nanocystalline, nanoporous, and amorphous material, a fullerene, a nanotube, and a
nanostuctured coating, is considered. Investigation methods, which are applied to study the
nanostructured material, are briefly described. A modern understanding of a formation of the
nanostructured and nanocomposite coating, which are fabricated using a ion-plasma deposition
method, is reposted. A potential application of the nanostructured material and coating in a field
of engineering is demonstrated.

Readership: Graduate, Postgraduate, Ph.D. Students, Researchers and Industry

Professionals.

The eBook contains 9 Chapters, 87 Figures, 14 Tables, 411 References-totally, 155 Pages. It
was approved by two Scientific Boards from National Kharkov University and Sumy State
University.

A main content of this eBook is a basis for lectures presented for students at Sumy State
University (the Physical-Technical Faculty), Kharkov National University (the Physical Faculty),
Omsk State University (the Physical Faculty, the Department of Material Science), East-
Kazakhstan State Technical University (Ust-Kamenogorsk, Kazakhstan), and Moscow State
University (the Physical Faculty, Moscow, Russia).

A source of this eBook is original papers of leading world-known scientists, who ware involved
in a field of new nano composite material fabrication, nanotechnologies, and researches. This
version had not been published elsewhere. It is interesting for a wide circle of specialists,
Masters, aspirants, scientific researchers, and a technical staff of Higher Education System,
Research Institutes and Laboratories. It covers recent data since 2008 to 2010 year.
ii

About the Authors

Pogrebnjak Alexander Dmitrievich-Director Sumy Institute for

Surface Modification, Sumy State University. Professor, Dr. Sc.
227 referred papers, 52 Author Certificates, 15 patent, 14 review
papers, 7 Books. Member of JEC/PISE since 2006. Regular
Member of Organizing Committee of 7 International Conferences:
AEPSE, PSE, ION, NEET, etc. Member of Scientific Board for
Ph.D and Dr.Sc. Sc since 1993.

Field of interests: material modification using ion, electron, and

plasma beams, ion implantation, deposition of protective and
nanocomposite coatings, electrolyte-plasma treatment of steels,
micro-arc oxidation and combined coatings, duplex methods of
treatment.

Beresnev Vyacheslav Mikhailovich-Professor, Dr. Sc., Professor

of Kharkov National University of Ministry of Science and
Education. 59 referred papers, 25 patents and Author Certificates,
3 Books.

Field of interests: nanocomposite and nanocrystalline films and

coatings, ion implantation, and combined technologies.
 iii

FOREWORD

This manual is as a course of lectures for students of physical, technical, and engineering faculties, whose
future field of interest is Fabrication of Nanomaterials, Nanosystems, and Nanocomposites as well as
Studies of Their Properties”. The Manual also deals with relating Methods of Analysis, which are employed
for Researches of above mentioned materials, as well as considers Original Works of Leading Specialists
Working in the Field of Nanomaterials”.

The manual is composed of 9 Chapters. The 1st Chapter reports a general information about nanosized
structures, describes mechanical, thermodynamic, electrical, and magnetic properties, and presents the
structure classification. The 2nd Chapter is devoted to nanoporous materials, and presents their modern
classification. The 3rd Chapter briefly describes fundamentals of amorphous material fabrication and their
properties with the purpose of their comparison with nanostructured materials. The 4th Chapter considers
fullerenes, fullerites, and nanotubes, as well as briefly describes their definitions and properties. The 5th
Chapter briefly describes nanocomposite materials, methods of their fabrication, and properties. The 6th
Chapter describes methods of nanomaterial fabrication and their classification as well as methods of
nanomaterial and amorphous material fabrication, which are employed in powder metallurgy. Methods of
an intensive plastic deformation, which are currently employed for a material fabrication, as well as CVD
and PVD methods, which are employed for thin film fabrication, are considered. In addition, the Chapter
deals with methods employed for fullerene and nanotube fabrication. It describes a particle micro-and
nanoprobe applied for an analysis of the nanosized material. The Chapter 7 presents methods applied for
nanomaterial researches, such as structure and chemical analysis, a mechanical testing of solids, for
example, measurements of nanohardness, an elastic modulus, etc. Chapter 8 considers structure and
properties of a nanostructured film and coating. This Chapter is the biggest one in its volume. It considers
many problems, such as role of energy in a coating formation, effect of an ion bombardment on the
formation of the nanocrystalline coating. It presents information about a mixing process, the formation of a
multi-layered coating, fabrication of super-hard coatings, thermal stability, and oxidation resistance of a
solid coating, as well as describes their mechanical properties. The Chapter reports why temperature and
potential applied to a substrate play a crucial role in the formation of the nanocrystalline coating.

The manual is written by specialists involved for many years in researches of a material modification by
particle beam and plasma, problem of new nanostructured material and combined coating fabrication, as
well as all aspects of an ion implantation. The content of this eBook is well written and expressed in a
compact and intelligible form. This manual is interesting not only for senior students, PhD students, but
also for researchers, physicists, and chemists, whose field of interest is material science and solid, as well as
for various Institutions such as Universities, Institutes, and Enterprises.

Prof. F. F. Komarov
Corresponding Member of the National Academy of Sciences of Belarus
UK
iv

PREFACE

Alexander D. Pogrebnjak1 and Vyacheslav M. Beresnev2

1
Sumy State University, Sumy Institute for Surface Modification, R.-Korsakov Str., 2, 40007 Sumy, Ukraine;
E-mail: [email protected] and 2Kharkov National University V.M. Karazina, sq. Svobody, 4, 61022 Kharkov,
Ukraine; E-mail:[email protected]

In Recent years, a research of materials, which are composed of submicron nanosized grains and clusters,
are swiftly developing due to already existing and/or potential applications in many technological fields
such as electronics, catalysis, magnetic data storage, structure components, etc.

Metallic and ceramic materials with a submicron and nanocrystalline grain structure are now widely used as
construction elements and functional layers in a modern microelectronics, as sites of devices in aviation and
space engineering, and as hard wear resistant coatings in industry. To satisfy the technological requirements
of these industrial fields, the size of structure elements is to be decreased to a submicron and a nanometer
range. However, when a size of structure element decreases to a nanometer range, a material starts to
demonstrate radically new physical and mechanical properties in comparison with a bulky base. Researches
of these nanosized structures (nanostructures) rank among nanotechnological directions. Development and
researches of nanostructured materials (further referred to as nanomaterials) and nanostructure properties
obtained under various conditions are very important components of these scientific-technological
directions. A material, a structure of which is composed of grains of about 0.3 to 0.04 µm size, is
considered as a submicrocrystalline [1-3]. A material of smaller grain size is considered as a nanomaterial.

A nanomaterial (a nanocrystal, a nanocomposite, a material with a nanophase structure, etc.) is to be

understood as a material, in which structure elements (a grain, a crystallite, a fiber, a layer, a pore) do not
exceed a limit of 100 nm (1 nm = 10-9 m), at least, along one crystallographic direction. According to size
of a structural unit, the nanomaterial is conventionally subdivided into a nanocluster and nanocrystalline
material. A nanocluster material is subdivided into small (3 to 12 number of atoms, 100% of surface atoms,
without an inside layer), big (13 to 150 number of atoms, 92 to 63% of surface atoms, including 1 to 3 inner
layers), and giant nanocluster material (151 to 22000 number of atoms, 63 to 15% of surface atoms,
including 4 to 18 inside layers). Conventionally, a cluster top boundary corresponds to such amount of
atoms that an addition of one more atom already cannot change physical-chemical properties of this cluster.
Theoretical calculations, which were confirmed by experimental researches for a cluster containing not less
than 300 atoms, demonstrated that an icosahedrons structure is the most stable one. When an amount of
cluster atoms increased, an elastic deformation energy quickly rouse in a proportion to their volume, and
consequently, this icosahedrons structure is destabilized forming a face-centered cubic lattice [4].
A structure unit with a higher amount of atoms and 3 to 40 nm grain size ranks among a nanocrystal. This
nanocrystalline material has various forms and demonstrates unique chemical, physical, and mechanical
properties. A grain size is limited by the maximum size of the nanostructure elements and depends on some
critical parameters (a size effect): a free range length of carriers participating in an energy transfer, a size of a
domain/a domain wall, a diameter of a Frank-Reed loop, a de Broglie wave length, etc. This size effect sharply
changes quality and properties of the nanostructured system and indicates a special condensed material state,
which exists only in the nanostructured material. Today, the nanostructured material can be formed on the basis
of various metals and alloys, and with the help of specially developed technological methods.
In recent years, a definite progress had been achieved in physical researches and technologies of the
nanostructured material fabrication. In particular, an important stage of these researches is a systematic
study of microprocesses occurring in a phase interface in the course of nanostructured system formation.
This systematic study stimulated an appearance of calculation methods, which are employed to predict
optimal technological parameters and promising ways of the nanostructured material formation.
A whole number of publications, monographs, and papers [5-11] report about technologies, structures,
properties, and applications of the nanomaterial and the nanostructure.
 v

Here, we present only a description of individual representatives and classes and do not reflect, to a full
extent, features of this modern direction. Why is there this modern interest in a nanotechnology, in general,
and in a nanostructure study, in particular?

On one hand, nanotechnologies allow formation of a principally new material, which can find its application in
future, since it is compact and functionable. It plays an important role in the formation of principally new
elements for future nanodevices, which are dependent on physical principles employed for their functioning.

On the other hand, the nanotechnology is an extremely wide interdisciplinary direction, uniting specialists
working in a field of physics, chemistry, materials science, biology, technology, directions of
intellectual/self-organized systems, high-technological computer engineering, etc. Finally, solving
problems arising in the field of nanotechnologies, and, first of all, in the process of researches, scientists
find many gaps existing both in fundamental and technological knowledge. All above mentioned excites a
concentrated interest of a scientific and engineering society to this direction [12-21].

In many technologically advanced countries such as USA, United Kingdom, Japan, China, Russia, national
programs, which are specified at an intensive development of various directions of the nanotechnology and
formation of new nanostructures, are accepted and have started to be actively introduced into a practice.

Now, several basic types of the nanomaterials are known [1, 4].

VARIETY OF NANOMATERIALS

A nanomaterial has a number of structure characteristic features, which are the parameters relating to a
structure as a whole and those identifying its individual elements. In their turn, the structure characteristic
features of the nanomaterials are reflected in an unusual display of their properties. Since the nanomaterial
is a basic unit of a nanosystem, properties of the nanosystem to a considerable degree depend on the
nanomaterial properties.

Variety of nanomaterials is immense and every type is characterized by a specific structure and, as a
consequence, specific properties. The characteristic features of the nanomaterial and the system formed on
its basis, first of all are manifested in a size effect, among which a quantum effect takes a special place.

According to degree of their structure complexity, the variety of nanomaterials is subdivided into materials
composed of individual nanoparticles and those composed of nanostructures (Fig. 1).

A nanoparticle is a nanosized complex of atoms and molecules, which are interrelated in a definite way.

Photon cyrstal

Figure 1: A classification of nanomaterials according to their structure characteristic features.

vi

The following types of the nanoparticles are identified:

– Nanocluster, which is sorted as an ordered cluster characterized by a definite order in an

arrangement of atoms and molecules and a strong chemical bond and a non-ordered
nanocluster characterized by a disordered arrangement of atoms and molecules and a weak
chemical bond;

– Nanocrystal (a crystalline nanoparticle), characterized by the ordered arrangement of atoms

and molecules and the strong chemical bond like a bulky crystal (a macrocrystal);

– Fullerene, which is composed of carbon atoms (or atoms of another element) forming a
structure looking like a spherical carcass;

– Nanotube, which is composed of carbon atoms (or atoms of another element) forming a
structure looking like a cylindrical carcass closed at its both ends;

– Supermolecule, which is composed of “a host molecule” with a three-dimensional structure,

in a cavity of which a “guest molecule” is arranged;

– Biomolecule, which is a complicated molecule of biological origin characterized by a

polymer structure(DNA, a protein);

– Micelle, which is composed of molecules of a surface-active matter forming a sphere-like

structure;

– Liposome, which are composed of molecules of a special organic compound like a

phospholipid forming a spherical structure;

A nanostructured material is an ensemble of nanoparticles. Nanoparticles play a role of a structure element

in such material. A type of the nanostructured material depends on a character of interrelation existing
between nanoparticles: a consolidated material and a nanodispersed one.

The consolidated material is a compact solid-phase material, which is composed of nanoparticles with a
fixed spatial position in the material volume and rigidly-directly bound to another one.

The consolidated material is:

– Nanocrystalline material, which is composed of nanocrystals usually called a nanograin or a

nanocrystallite;

– Fullerite, which is composed of fullerenes;

– Photon crystal, which is composed of ordered-in-space elements, a size of which is

comparable with a half-length of a photon wave in one, two or three directions;

– Layered composite material (with a superlattice), which is composed of various material

layers of a nanosize thickness;

– Matrix component, which is composed of a solid base (a matrix), in the volume of which
nanoparticles (nanowires) are distributed;

– Nanoporous material, which is characterized by the presence of nanopores;

– Nanoaerogel, which is composed of an interlayer of a nanosize thickness separating pores.

 vii

A nanodispersed material is a dispersed system with a nanosized dispersion phase.

In addition to the above mentioned matrix nanocomposite materials and nanoporous materials, the
nanodispersed materials cover:

- Nanopowder, which is composed of contacting other nanoparticles;

- Nanosuspension, which is composed of nanoparticles free-distributed in the liquid volume;

- Nanoemulsion, which is composed of nanodrops of a liquid free-distributed in a volume of

another liquid;

- Nanoaerosol, which is composed of nanoparticles and nanodrops free-distributed in a volume

of a gaseous medium.

Specimens of various nanostructured materials are often bulky, i.e. are characterized by a micro-and macro-
size, whereas their structure elements are nanosized.

Effects, which are related to the small size of composing structures, may manifest themselves in a different
way in various nanomaterials.

For example, a specific surface of the nanocrystalline and nanoporous material is crucially larger, i.e. a
fraction of atoms arranged in a thin (about 1nm) near-surface layer radically arises. This increases the
reaction ability of the nanocrystal, since atoms, which are arranged in the surface, have unsaturated bonds
in contrast to atoms, which are arranged in the material bulk, since they are bound with surrounding atoms.
A change in atomic ratio between the surface and the bulk atoms may result in atomic reconstruction, in
particular, in a change of an atomic arrangement order, an interatomic distance, and a crystalline lattice
period. The size dependence of a nanocrystalline surface energy predetermines a corresponding dependence
of a melting temperature, which is lower for the nanocrystal than for the macrocrystal. As a whole, heat
properties of the nanocrystal are crucially different, which is related to a character of atomic heat
oscillations.

When the size of ferromagnetic particle decreases to a certain critical value, the domain separation becomes
energetically disadvantageous. As a result, polidomain nanoparticles become single domain and acquire
special magnetic properties, which are manifested in supermagnetism.

The fullerene and the nanotube are characterized by very unusual properties due to their specific structure.
This is true also for the molecular and biomolecular complex functioning according to laws of molecular
chemistry and biology.

Peculiarities of a structure and properties of an individual nanoparticle affect in a definite way a structure
and properties of the consolidated materials and the nanodispersion, which are formed on their basis.

A typical example is a nanocrystalline material, which is characterized by a decreased grain fraction, and,
respectively, an increased fraction of interfaces occurring in the material volume. Simultaneously, a change
of structure characteristics of both grains and interfaces takes place. As a result, mechanical properties of
the nanocrystalline material significantly change. The material demonstrates a superhardness of a
superplasticity under definite conditions.

Electron properties of the nanostructure, which are conditioned by quantum effects, are of a special interest
for practical applications.
viii

Figure 2: A classification of types of nanosystem-based devices according to their functional purposes.

The nanomaterial serves as a basis for the development of nanosystems with various functional purposes,
which in their turn are subdivided into an electron, an optical, and a mechanical nanosystem, according to
the principle of functioning, Fig. 2. An action of the electron nanosystem is based on transformation of an
electrical signal, that of the optical one-on transformation of an optical signal (light) into the electrical one
and vice versa, and the mechanical nanosystem transforms a mechanical motion.

Sets of definite characteristics of nanosystems are employed in definite fields of engineering such as
nanoelectronics, nanooptics, and nanomechanics. Development of various types of nanosystems is closely
interconnected and results in fabrication of more constructively complicated and integrated nanosystems,
such as nanooptical-electron, nanoelectrical-mechanical, nano optical-mechanical, and nano optical-electro-
mechanical systems.

The development of nanosystems is undoubtedly a new step, which will enable a future progress of
microsystems. In practice, nanosystems are built-in various Microsystems forming in this way a promising
direction of a modern system units (devices) such as a micronanosystem equipment.

A consolidated material-is a compact, a film, or a coating formed from a metal, an alloy, or a compound using a
powder technology, an intensive plastic deformation, a controlled crystallization from an amorphous state, and
various other techniques, which are currently applied for deposition of a film and a coating.

A nanosemiconductor, a nanopolymere, and a nanobiomaterial may exist in an isolated or a partially mixed

(consolidated) state.

Fullerene and nanotube became an object of researches since the moment, when Sir Harold (Harry) Walter
Kroto (1985) found a new carbon allotrope form-a cluster C60 and C70, which was called fullerene. This
new carbon form attracted much more attention, when the carbon nanotube was revealed in a graphite
product after an electrical-arc evaporation (Sumio Iijima, 1991).

Nanoparticles and nanopowder represent a quasizero grain size structure having various compositions and
a size of which usually does not exceed a nanotechnological limit. A difference is that the nanoparticle is
isolated, while the nanopowder is an aggregate. In a similar way, the nanoporous material is characterized
by a pore size, which, as a rule, is not less than 100 nm.

A supermolecular structure is a structure, which is formed as a result of so-called non-covalent synthesis

accompanied by formation of weak bonds (a Van der Waals, a hydrogen type, etc.) between molecules and
their ensembles.

The nanomaterial is not a “universal” material; it is a vast class of many various materials joining different
families. In addition, there exists a delusion that the nanomaterial is a material composed of very small
 ix

“nano”-particles. In reality, many nanomaterials are not composed of individual particles; they are
complicated micro objects nanostructured either in a surface or in a volume. Such nanomaterials are
considered as a special state of matter, since properties of these materials, which are composed of
nanostructured and nanosized elements, are not identical to properties of a volume material.

So, the nanomaterial is characterized by several basic features, which position it beyond any competition in
comparison with other matters.

First, the nanomaterial is composed of very small objects, which cannot be seen with a naked eye. It
represents a “super miniaturization”, which leads to a possibility that more and more quantity of functional
nanodevices can be placed at an area unit. This is vitally important, say, for nanoelectronics or very dense
magnetic information recording, which can reach 10 Tirrabit per a square centimeter.

Second, the nanomaterial has a large surface area, which promotes a hastened interaction inside and within
a medium, to which it is placed in. For example, a catalytically active material can hasten a chemical and
biochemical reaction by a factor of ten, thousand, and even a million [22-30].

Decomposition of water into hydrogen and oxygen for needs of a hydrogen power engineering, which is
realized in the presence of titanium dioxide nanoparticles (everyone knows it as a component of titanium white
paint), seems to be very interesting. A nanofilter can screen bacteria or efficiently absorb impurities and toxins.

Third, the nanomaterial has unique physical and mechanical properties, and this means that such a matter is
in a specific “nanosized” state. Changes found in the nanomaterial fundamental characteristics are
conditioned not only by a small grain size, but also by a quantum-mechanical effect, in which an interface
plays a dominating role. The effect arises when the grain size is so “critical” that is commensurable to a so-
called correlation radius or other physical parameters (for example, a free electron and a phonon range, a
coherence length in superconductors, a magnetic domain or a nucleon size of solid phase, etc.). This makes,
in particular, a semiconducting material to be an ideal element for a perfect energy-consuming laser and
light emission. Hardness of an individual carbon nanotube exceeds that of the best steel by a factor of ten.
At the same time, it has many-fold advantage in a specific mass. All above-mentioned characteristics fully
explain the fact that even a gram of the nanomaterial may be much more efficient than a ton of an ordinary
matter, and that its industrial production is not a problem of quantity, ton, and kilometer, but that of a
human thought quality, i.e. “know-how”.

Nanotechnology is an extremely complicated, professional, interdisciplinary field, which needs joined

efforts of chemists, physicists, specialists in material science, mathematicians, medics, specialists in
calculation methods, etc. Deep scientific fundamentals are admirably interwoven in a field of nanomaterials
with aspects of a human knowledge and practical applications.

In this eBook, we report fundamental data concerning structure, properties, and application of the modern
nanomaterials. In the First Chapter, we present general information about nanomaterials, their structure
features, size effect on structure formation and on physical-mechanical properties.

In Chapters 2 and 3, we present information about structure and properties of a nanoporous and an
amorphous material.

In Chapter 4, we consider certain properties of fullerene and nanotube. Chapter 5 deals with a
nanocomposite based on a polymer. Chapter 6 is devoted to methods, which are currently employed for the
nanomaterial fabrication, since these new methods really gave rise to a violent development of this field.

Physical research methods, namely, novel methods employed for surface studies are presented in Chapter 7.

In Chapter 8, we consider mechanical and thermal properties of a nanocrystalline film and a nanocomposite
coating, which are fabricated using physical deposition methods.
x

Chapter 9 is devoted to an application of the nanocrystalline material, which is employed in an engineering

society.

REFERENCES

[1] Morokhov ID, Trusov LI, Chizhij SP. Unltradipersion Metallic Media. M Atomizdat 1977.
[2] Gleiter H. Nanostructured Materials. Basic Concepts and Microstructure. Acta Materialia 2000; 48: 1-29.
[3] Seigel RW. Nanostructured Materials-Mind over Matter nanostruct. Mater 1993; 3: 1-18.
[4] Larikov LN. Nanocrystalline Compounds of Metals Metallo-Fizika I Noveishie Tekhnologii 1995; 17: 56-68.
[5] Andrievskii RA, Ragulia AV. Nanostructured Materials. Moscow: Academia 2005.
[6] Roko MK, Wiliyams PS, Alivisatos P. Nanotechnologies in the Next Ten years. Prediction of Researching
Directions; Translation. Ed. Andrievskii RA. Moscow: Mir 2002.
[7] Liakishev NP, Alymov MI. Nanomaterials for Structural Materials. Nanotechnologies in Russia 2006; 1: 71-81.
[8] Gusev AI. Nanomaterials, Nanostructures, Nanotechnologies. Moscow: Fizmatlit 2005.
[9] Gusev AI, Rempel AA. Nanocrystalline materials. Moscow: Fizmatlit 2000.
[10] Pozdniakov VA. Physical Material Science for Nanostructured Materials. Moscow: MGIU 2007.
[11] Ragulia AV, Skorokhod VV. Consolidated Nanostructured Materials. Kiev: Naukova Dumka 2007.
[12] Sergeev TB. Nanochemistry Moscow: MGU 2003.
[13] Andrievskii RA, Glezer AM. Size Effects in Nanocrystalline materials. I. Features of Structure. Thermal-Dynamics.
Phase Equilibrium. Kinetic Phenomena. The Physics of Metals and Metallography 1999; 88: 50-73.
[14] Andrievskii RA, Glezer AM. Size Effects in Nanocrystalline Materials. II. Mechanical and Physical Properties. The
Physics of Metals and Metallography 2000; 89: 91-112.
[15] Pogrebnjak AD, Shpak AP, Azarenkov NA, Beresnev VM. Structure and Properties of Hard and Superhard
Nanocomposite Coatings. Physics Uspekhi. 2009; 52(1): 29-54.
[16] Noskova NI, Muliulukova RR. Submicrocrystalline and Nanocrystalline Metals and Alloys. Ekaterinburg: Ural’skoe
Otdelenie RAN 2003.
[17] Suzdalev IP. Nanotechnology: Physical Chemistry of Nanoclusters, Nanostructures, and Nanomaterials. Moscow:
KomKniga 2006.
[18] Valiev RZ, Aleksandrov IV. Nanostructured Materials, Fabricated by Intensive Plastic Deformation. Moscow: Logos
2000.
[19] Andrievskii RA. Nanomaterials: Concepts and Modern Problems. Rus Chem J 2002; XLVI: 50-56.
[20] Glezer AM. Amorphous and Nanocrystalline Structures: Similiarities, Difference, Mutual Transitions. Rus Chem J
2002; XLVI: 57-63.
[21] Andrievskii RA. Thermal Stability of Nanomaterials. Russ Chem Rev 2002; 71: 967-981.
[22] Demikhovskii VJ, Vugalter GA. Physics of Quantum Small Grain Size Structures. Moscow: Logos 2000.
[23] Harris P. Carbon Nanotubes and Related Structures. New Materials of XXI Century. Translated by
L.A.Chenazatonskii. Moscow: Tekhnosfera 2003.
[24] Pomogailo AD, Pozenberg AS, Ufliand IE. Nanoparticles of Metals in Polymers. Moscow: Khimiia 2000.
[25] Shevchenko SV, Stetsenko NN. Nanostructured States in Metals, Alloys, and Intermetalloid Compounds: Methods of
Fabrication, Structure, Properties.Progress in Physics of Metals 2004; 5: 219-255.
[26] Shik AJ, Bakuleva LG, Musikhin SR, Rozhkov SA. Physics of Small Grain Size Systems St.-Peterburg: Nauka 2001.
[27] White Book on Nanotechnologies: Researches in the Field of Nanoparticles, nanostructures, and Nanocomposites in
Russian Federation (Materials of the First All-Russia Meeting of Scientists, Engineers, andfabricationrs in the Field
of Nanotechnologies) Moscow: LKI 2008.
[28] Pul Ch, Ouens F. Nanotechnologies. Translation by Moscow: Tekhnosfera 2004.
[29] Golovin YuI. Introduction in nanotechnology Moscow: Mashinostroenie 2003.
[30] Shorshorov MKh. Ultradispersion Structure State of metallic Alloys. Moscow: Nauka 2001.
 Nanocoatings Nanosystems Nanotechnologies, 2012, 3-14 3

CHAPTER 1
Structural Features of Nanocrystalline Materials
Abstract: In this Chapter, general information about a nanosized structure is presented, as well as terms and
definitions are introduced. Effect of the nanostructure on mechanical, thermo-dynamical, electrical, and
magnetic properties of materials is described. Questions for self-control are presented at the end of this
Chapter.

Keywords: Classification, properties, nanostructured materials, interface.

1.1. GENERAL INFORMATION ABOUT NANOSIZED STRUCTURE

Recently, an interest to researches of materials with a nanocrystalline structure grew higher, since it was
found that a decrease of a crystallite size (or any other structure element) below some threshold value
resulted in a radical change of material physical properties. On one hand, a tendency to a further
miniaturization of devices, which are employed in microelectronics, is a beginning of a new spire in
researches. On the other hand, this spire is stimulated by works, which appear in the middle of 80’S, and
present a classification of such materials [1-8]. A great contribution of Prof. Gleiter, who is the author of
these works, is not only an assumption that a big class of different materials (such as an ultradispersed, a
composite, a granulated material, powder, etc.) is the same class of nanostructured materials, united by one
common property-a size of their structure elements. Prof. Gleiter also reveals that they own some
characteristic special properties [9]. Both these features and the nanocrystallite size are a reason of their
different physical properties. According to a chemical composition and phase distribution, four structure
types are distinguished (Table 1): a single-phase structure, a static many-phase structure with identical and
non-identical interface surface, and a matrix multi-phase structure.

Table 1: A classification of a consolidated nanomaterial.

According to a form, three structure types are distinguished : a plated, a columnar, and a form containing equal-
axes inclusions. Here, a possible segregation at a crystalline interface is also taken into account. A single-and
multi-phase matrix, a static object, a columnar, and a multi-layered structure (a film) are most popular.

Here, a possible segregation at a crystalline interface is taken into account.

Alexander D. Pogrebnjak and Vyacheslav M. Beresnev
All rights reserved-© 2012 Bentham Science Publishers
4 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

In general, an abundance of interface surfaces (a grain interface and a triple-junction, which are a junction
of three grains) characterizes the nanomaterial structure. Schematically, this triple-junction looks like a
tetrahedral dodecahedral structure (Fig. 1a).

Figure 1: A scheme of a triple-junction (a) and a grain size effect (b) on a total interface fraction (1),a grain interface
(2), and a triple-junction (3) when s = 1 nm.

According to Fig. 2a, a total fraction of interfaces is

Vn.p. = 1-[(L-s)/L]3 ~ 3s/L (1)

A fraction of grain interfaces per se is

Vm.r. = [3s(L-s)2]/L3, (2)

And, correspondingly, a fraction of triple-junctions

Vt.c. = Vn.p.-Vm.r., (3)

where: L is a grain size, s is an interface width (a zone near the interface).

Fig. 1b presents how a total fraction of interface surfaces, grain interfaces, and triple-junctions depend on a
grain size. It is seen, that an essential fraction of interface surfaces (several per cent) corresponds to a grain
size L < 100 nm. Thus, even when L < 10 nm, the fraction Vn.p. is about several tens of percent. Within
this interval of L values, the fraction of triple-junctions quickly increases. The fraction of interfaces (Vn.p.)
over the whole material volume is approximately equal to 3s/L. So, for example, for s = 1nm and L ≈ 6 nm,
the fraction Vn.p. already amounts 50% [9-18].

Relaxation processes, which are inevitable under thermal action and in a power field, should affect
physical-chemical, physical-mechanical, and other properties and influence also servicing resources of the
nanomaterial. Therefore, studies of their stability are very important.

Fig 2. presents an effect of the grain structure state (the size effect) on nanomaterial properties.

Figure 2: An effect of a grain structure state on nanomaterial physical-mechanical properties.

Structural Features of Nanocrystalline Materials Nanocoatings Nanosystems Nanotechnologies 5

The nanostructure features the following properties:

- When an element size decreases, a role of the interface surface increases (a fraction of near
surface atoms increases from one percent to several scores of percent);

- Properties of a material with the interface surface ranging within a nanometer interval may
differ essentially from a big-sized crystal (an edge effect);

- Size of the nanostructure element is commensurable with a range of a certain physical

phenomenon (for example, with a free pass length of carriers under transfer);

- Thermodynamically “profitable” self-organization and a self-construction, which decrease a

redundant free energy of a system;

- An effect of the nanostructure size may have a quantum character (when a localization area
of free carriers becomes commensurable with L, a de Broglie wave length λB (Fig. 3) is

2 h
B  (4)
2mE

where m is an efficient electron mass; E is a carrier energy; ħ is Plank constant.

A square-law dependence of an electron state density N(E) on an energy is characteristic for a microscopic
structure. A decrease of the carrier localization areas up to λB in one, two, or three directions, as it follows
from a solution of a Schrődinger equation under corresponding boundary conditions, is accompanied by a
change of N(E ) dependence character.

Figure 3: A charge carrier state density N(E) for structures of various grain sizes.

A free motion of charge carriers in two-and one-dimensional structures is two-and one-dimensional,

respectively. An electron energy spectrum at quantum points is quantized in three dimensions and
represents a set of discrete levels, which are separated by zones of a forbidden state [19-28].

Additionally, when the size of the nanostructure element decreased:

- Width of the forbidden zone increased;

- An absorption band shifted towards high energies, according to theoretical calculations E ~

1/R;
6 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

- “Blue” shifting took place (i.e. a shift of a luminescence spectrum towards a short-wave
band);

- Dependence of electrical properties on the size became non-monotonous inducing a

modification of nanostructure electron properties.

Carbon tubes are different in their forms, electron structures, and properties. An important characteristic of
the nanotube structure is a chirality, which is a mutual orientation of hexagonal graphite net with respect to
the nanotube longitudinal axis. A conductivity type of a single-layered nanotube depends on the chirality:
for example, a zigzag tube has a metallic-type conductivity and a chirality tube has a semiconductor one.
The forbidden zone width correlates to a tube radius (for a p-type semiconductor ΔEg ~ R-2, for an n-type
semiconductor ΔEg ~ R-1).

Fig. 4 shows the nanocomposite material consisted of unlikely-charged crystallites: a) a p-crystallite (the p-
type semiconductor) and an n-crystallite (the n-type semiconductor); b) phases of a different Fermi energy;
c) a metal and a semiconductor. An application of an external electromagnetic field changes a charge of the
interface surface.

Figure 4: A nanocomposite structure containing phases of different charges [15].

1.2. MECHANICAL PROPERTIES

Properties of the nanocrystalline structure differ from bulky analogs. In particular, an extraordinary
hardness seems to be the first among mechanical characteritics. Since hardness characterizes a material
resistance to plastic deformation under diamond indentation, it is natural to assume a proportional relation
of hardness to a material fluidity limit (σy).

Historically, namely, the material fluidity limit is the first parameter, which is subjected to a detailed
analysis for its size dependence. As a result, a relation, which is called a Hall-Petch law, is derived:

 y   0  k y D n , (5)

where: σ0 is an internal voltage preventing a dislocation motion, ky is a coefficient relating to a grain

interface penetrability for dislocation motion. A value of n changes from ½ (a classic Hall-Petch law) to
values within ¼ …… 1 interval. It is accepted that every n-value corresponds to a certain mechanism
characterizing a dislocation interaction with the grain interface. When the grain size exceeds 10-6m, this
classic law is successfully fulfilled: this index is n = ½ for a metal and an alloy.

Fig. 5 shows how hardness and a fluidity limit change in the case when the grain size decreases to a critical
value of about 10 nm. High-resolution electron microscopy data confirm that this value is critical for a
formation of dislocations.

Dislocations are absent in crystallites of d < 10 nm, and a phase structure of the grain interfaces is close
amorphous.
Structural Features of Nanocrystalline Materials Nanocoatings Nanosystems Nanotechnologies 7

When the grain size decreases to 7nm and smaller, an inverse Hall-Petch effect is observed instead of the increased
hardness, which seems to be a result of the decreasing grain size, i.e. a material looses its strength.

Figure 5: A change of hardness and a fluidity limit with a decreasing grain size.

To explain this anomalous behavior of the nanocrystalline material, the grain size of which is smaller than
the critical value, several mechanisms are offered. A sliding along the grain interface (which is sometimes
called as a rotation strength loss), a triple junction effect, a presence of nanopores and inclusions, etc. are
among them.

A change of metal mechanical properties depending on the grain size is presented in Tables 2 and 3 [9-31].

Tension strength of the nanocrystalline material is 1.5 to 2 times higher than that of big-grained analogs.
When the grain size decreases below some critical value, hardness decreases due to an increasing amount of
triple junctions at the grain interface, which prevents the dislocation motion. The strength increases further
with the grain size since a density of already existing dislocations decreases and new ones fail to be formed.

Table 2: Mechanical properties of an ordinary nanocrystalline nickel.

Properties Microcrystalline Size,10 mkm Nano-Ni

100 nm 10 nm
Strength (hardness), MPa (25 оС) 103 690 >900
о
Limiting tensile strength, MPa (25 С) 403 1100 >2000
Hardness by Vickers(250C) 140 300 650

Table 3: A change of mechanical properties depending on a grain size.

Мaterial Grain Size, μm Т, °С Strength Limit, MPа Relative Elongation Till Destruction, %
Titanium alloy 50 20 380 29
ВТ1-00
0,1 730 18
(Ti99%, Fe,Si,O)
10 20 1050 9
Titanium Alloy 0,4 1300 7
Ti-6Al-4V 10 600 585 46
0,4 200 200
5 20 1050 45
Titanium Alloy ВТ8 (Al6%, Mo3,5%, Si0.4%,Ti)
0,06 1400 53
100 20 375 30
Alloy of Ni RSR Rene 80
0,2 850 33
8 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

10 20 450 5
Alloy Al-Mg-LiSc-Zr
0,2 600 6
50 20 485 26
Steel Fe-25%Cr-0,2%Ti0,12C
0,2 730 17

Fig. 6 presents a strength-to-ductility ratio for a steel.

Figure 6: An alternation of mechanical properties for different materials.

A nanocrystalline steel 12X18H10T has a good strength-to-ductility ratio. In some cases, a low ductility of
the nanocrystalline material is probably induced by a complexity in a formation of dislocations, in a
multiplication, and in a motion, as well as by a porosity, by a presence of microcracks, and inclusions. A
wear resistance of aluminum alloy with the nanocrystalline structure is essentially higher that that of big-
grained one (Fig. 7) [ 29-31].

Figure 7: A wear resistance of an aluminum alloy.

Such brittle material as an intermetalloid gained a plasticity when its grain size decreases to some critical
value, which is explained by a specific mechanism of multiplication and propagation of microcracks [15-
17]. Thus, the nanosize material structure opens a unique chance to reach a new level of properties: high
strength, hardness, and wear resistance together with essentially high plasticity.
Structural Features of Nanocrystalline Materials Nanocoatings Nanosystems Nanotechnologies 9

Knowledge of size regularities open a possibility to realize transition to a new generation of materials,
which properties are controlled by a size and a form of their structure elements. These peculiarities may be
employed also in units and sites of devices.

1.3. THERMODYNAMICAL PROPERTIES

Speaking about peculiarities of thermal-dynamical properties and phase equilibrium states, we cannot find
any unambiguous interpretation. There is an opinion [16] that traditional concepts about surface energy can
be more readily applied to particles, a size of which exceeds 10 nm. When the size varies from 1 to 10 nm,
properties need some individual specification, and when it is lower than 1nm, a particle gains properties of
a whole surface layer and needs a special approach. For the first approximation, these considerations are
applicable for a consolidated material thermodynamics [17-19, 27-31].

The following thermodynamical features characterize the nanostructure:

- Certain thermodynamical regularities are not fulfilled since an additional degree of freedom
arises due to appearance of identical and independent small-size particles (systems);

- A fluctuation of thermodynamical variables becomes commensurable to an average value of

properties themselves;

- A considerable heat effect starts to manifest itself ΔH;

- A phase transformation temperature changes;

- Certain thermodynamical properties (for example, a free Gibbs energy, G) may loose a
monotonous character.

As it follows from general considerations, a great number of near surface atoms seems have a significant
effect on a background spectrum and related to it thermal properties (a heat capacity, a thermal expansion, a
melting temperature, lattice components of a heat conductivity, etc.). Additional low-and high-frequency
mode is found in nanostructure background spectra. Practically in all cases, the heat capacity increases
(under T < 1K) in a non-monotonous way, the characteristic temperature decreases, a factor reflecting an
atomic shift (Debye-Waller factor) increases, and the melting temperature decreases.

1.4. ELECTRIC PROPERTIES

It is known, that an electrical resistance of a metallic solid is determined mainly by an electron scattering at
phonons, structure defects, and impurities. It is noted that a specific electrical resistance ρ increases in
many metal-like nanomaterials (Cu, Pd, Fe, Ni, Ni-P, Fe-Cu-Si-B, NiAl, nitrides, borides of transition
metals, etc.) when the size of structure element decreases. It is due to an increased role of defects and
peculiarities of a phonon spectrum. At T ≈ 1 to 10 K, practically all metal-like nanomaterials demonstrate a
high residual electric resistance and a low value of electric resistance temperature coefficient (ERTC). A
significant change of the electric resistance appeares, when L ≤ 100 nm. Evaluations demonstrate that the
specific electric resistance at the grain interface is ρib ~ 3 x 10-12 Ohm cm and is practically the same for
materials with the nano-and the big-size crystallite [1]. In such a way, the nanomaterial electric resistance
may be calculated according to the formula:

  0  ib ( S / V ) , (6)

where: ρ0 is an electric resistance of a single-crystalline material with a given content of impurities and
defects; S is an area of the grain interface; V is a volume.
10 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

In addition, a porosity, an impurity content, and other factors should be taken into account in a
determination of the electric resistance.

The electric resistance of a thin film depends on an electron scattering at an external surface, a topography,
and structure features. An important role is played by the film thickness and the structure element size
normalized to a free-range length.

Studies of a nanomaterial superconductivity, for example, of a refractory compound NbN, VN, TiN, NbCN,
demonstrates a significant effect of the particle size on a critical magnetic field [17], and a decrease of
temperature found in the course of transition to a super conductivity.

As it was noted above, a decrease of the grain size of the semiconductor resulted in an increase of the
forbidden zone width to a level of a dielectric material (for example GaAs). Many other factors (like an
origin, an increased number of segregations at the interface surface, a change in stoichiometry deviations, a
perfect grain interface, etc.) also affect semiconductor properties. Therefore, a dependence of the electric
resistance and the dielectric penetrability on the structure element size seems to be ambiguous.

Properties of a hybrid material, which is based on the nanocomposite, also attract interest. For example, a
conductivity of a non-conducting matrix with metallic nanoparticles sharply increases when a certain
percentage of conducting components is reached. It seems to be either due to barrier transition or to
dominating tunneling (jump transition). A thermoelectric nanomaterial is characterized by an increased
quality-factor (Q-factor). For such devices as a nanodiode, a nanotransistor, a nanoswitcher, etc., an
account of an increasing effect of the quantum factor (an oscillation, etc.) on a nanostructure conductivity is
specially important.

1.5. MAGNETIC PROPERTIES

An actively studied magnetic characteristics are also sensitive to the structure element critical size. A keen
interest is paid to magnetic properties of a small particle of the well known ferromagnetic material: an iron,
a nickel, and a cobalt. A question arises: whether such properties as a coercitive field Hc, a magnetic
anisotropy K, an initial magnetic permeability µ, a Curie temperature Tc, and others stay unchangeable, if a
volume of the ferromagnetic material decreases to a negligibly low value of 103 to 104 atoms. What is a
minimum amount of ferromagnetic atoms (for example, of the iron or cobalt), which should be picked-up
together, in order that a particle would acquire ferromagnetic properties?

Before starting to discuss ferromagnetic properties of the small particle, let us consider a physical sense of
applied terms-the Curie temperature and the magnetic anisotropy. A physical sense of the coercitive field
Hc and magnetic permeability µ is reported in [18].

As it is known, a ferromagnetic state arises in a metal and an alloy due to an action of an electrostatic force,
which orders a magnetic momentum of atoms. A domain, which is a region with a parallel magnetic atomic
moment, is formed. When a ferromagnetic material is heated, thermal atomic motion gradually initiats its
influence on the ordered arrangement of atomic magnetic moments, and fully destroys this arrangement at a
certain temperature. A temperature, at which the oriented ordering of magnetic moments inside the domain
is fully destroyed, is called the Curie temperature in an honor of an outstanding French physicist Pierre
Curie. Above Tc, the ordered arrangement of magnetic moments is absent, and the ferromagnetic state is
changed for the paramagnetic one.

Let us consider a concept of a magnetic anisotropy. Let us imagine such singlecrystal of the ferromagnetic
material as an iron. Magnetic properties of this single crystal are strongly dependent on a direction of an
applied external magnetic field due to the ordered atomic arrangement. Experiments demonstrate that two
directions (in relation to magnetic properties) for the iron single crystal can be distinguished: when the
crystal is easily magnetized along one direction (an axis of easy magnetization) and hardly magnetized
along another (an axis of hard magnetization). This phenomenon is called a magnetic anisotropy. An
Structural Features of Nanocrystalline Materials Nanocoatings Nanosystems Nanotechnologies 11

anisotropy constant K is a difference in energies, which are spent to magnetize a unit of a ferromagnetic
volume along axes of the easy and the hard magnetization. This K value for an iron is 4.2 x 104 J/m3 at room
temperature.

When a volume of a magnetic material decreases, the magnetic order undergoes a significant change.
Conceptually, this may be understood as an increasing indeterminacy of mechanical moment ρ and electron
energy occurring at a certain volume region d. Let us remember, that an electron is a carrier of a spin and
orbital magnetic moment. A region of existing ferromagnetic state decreases according to a Heisenberg's
relation Δρ = h/d, where h is a Plank constant. When d is low, the energy is undetermined and, as a result, a
long-range magnetic order is smoothed. The magnetic order of the iron is destroyed when d = 1 nm.

Experimental studies of ferromagnetic properties of a small iron, nickel, and cobalt particle demonstrate
that its transition to a paramagnetic state dependes on a its size and temperature. The ferromagnetism
disappeares when the iron or nickel particle size is about 6 to 7 nm. When the particle size is below these
values, the material becomes paramagnetic. The iron particle of 6nm transferres to the ferromagnetic state
only at Tc = 170 K. For a comparison, the Curie temperature of a bulky iron sample is Tc = 1090 K.

In such a way, experimental data demonstrate that the particle diameter “destroying” the long-range
magnetic order essentially exceeds evaluations derived in the Heisenberg's relation (d = 1 nm for the iron).
It is worth noting, however, that the above evaluations come closer to each other, if to take into account that
an essential quantity of atoms occurs in a surface when the particle size decreases. Therefore, when the
particle diameter is 2.5 nm, the quantity of atoms lieing in the surface exceeds 50% (it is assumed that the
surface is covered by two layers of atoms). The nanoparticle coercitive field Hc also depends on the size.
Fig. 8 [8] shows that 4nm crystallite has almost zero Hc value.

The low value of the coercitive field, which is conditioned by a heat effect, transforms the magnetic order
into paramagnetic. A maximum Hc value of the nanocrystalline ferromagnetic material is observed when a
particle is single-domain. Experimental data and theoretical evaluations almost coincide and demonstrate
that Hc value for the iron with 20 to 25 nm crystallite size is maximal at room temperature.

Figure 8: A change of a coercitive field vs. a particle diameter.

It follows from here, that the nanocrystalline ferromagnetic material is promising for a memory device of a high
information density. For the first time in 1988, it was demonstrated that an iron-silicon alloy with the nanometer
grain size and a random mutual orientation had a zero magnetic anisotropy. As it is known, that an absence of
an anisotropy results in an essential growth of an initial magnetic penetrability both of a low and a high
frequency. A little later (in 1991), Fe73.5Si13.5B9Nb3Cu1 alloy with 10 to 20 nm grain size was fabricated [3]
(figures indicate an atomic percentage of every element in this alloy). The alloy has also a low coercitive field
(Hc = 0.58 SA/m), a high initial penetrability (µ = 105), and a saturation induction Bs = 1.25 T.

A model presented in [10] explains a low magnetic anisotropy of a nanocrystalline alloy. According to this
model, a macroscopic region of L area are formed in the ferromagnetic material. Magnetization inside these
12 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

regions is such as if it follows a local magnetic anisotropy characterizing every crystallite of d-size. Taking
into account a randomly directed magnetic anisotropy of every grain (a microscopic L size essentially
exceeds d), an effect of the local anisotropy can be averaged, i.e. ‹K›→ 0. When L << d, the resulting
averaged anisotropy effect for an ensemble of randomly oriented and ferromagnetically interacting regions
with d-size grains is ‹K› ~ d 6. As it follows from this expression, this averaging could hardly allow a total
elimination of the local anisotropy effect, but averaging at low d value essentially reduces its action. In this
case, a role of this characteristic value (d) is very high, since d is introduced in this expression for the sixth
order mean anisotropy. Experiments show that 10 to 20 nm size efficiently averages out the magnetic
anisotropy effect. A decrease of the ferromagnetic anisotropy is accompanied by an increase of its magnetic
penetrability and a decrease of its coercitive field. Regularities of a change of an electromagnetic
susceptibility occurring in a diamagnetic and paramagnetic material depending on the crystallite size are
now not yet clear. However, a material having a high concentration of deformation defects demonstrates the
increased magnetic susceptibility.

Magnetic properties essentially depend on an interatomic distance, therefore, it is natural to assume that a
saturation magnetization Is, a Curie temperature Tc, and other parameters characterizing the nanomaterial
ferromagnetic and a big-sized crystalline object are be different. So, Is value for the nanocrystalline Fe (L =
6 nm) is lower by 40%. A superparamagnetism of nanoparticles (nanocrystallites) of a ferromagnetical, a
ferrimagnetical, and an antiferromagnetical material becomes evident when an energy of heat fluctuations
becomes comparable to a turn energy of a particle magnetic momentum. Table 4 schematically shows
characteristics of various ferromagnetic materials, which are changed by an action of a corresponding field
taking into account a dispersion.

The coercitive force Hc for various soft magnetic materials depends non-monotonously on the crystallite
size. It increases and has a flat maximum up to 40 to 70nm. Then, it decreases together with the crystallite
size. In general, optimal characteristics (a min Hc, a max magnetic penetrability µ = B/H, and a saturation
inductivity Bs) of a soft magnetic material are realized when the crystallite size is less than 20 nm.

Table 4: An effect of a size factor on characteristics of a ferromagnetic, a ferroelectric, and a ferroelastic material.
Structural Features of Nanocrystalline Materials Nanocoatings Nanosystems Nanotechnologies 13

A multi-layered film (a superlattice), which is composed of alternating nanolayers of the ferromagnetic and
non-magnetic material (Fe/Cr, Co/Cu, Ni/Ag, etc.) and a powder of the nanocomposite material with the
same composition, feature a giant magnetic resistance. When the magnetic field is applied, the electric
resistance of these structures significantly decreases in comparison with a similar uniform material. A
magnetic superlattice and a hard-magnetic material demonstrate transition to a superparamagnetic state
when a film thickness and a crystallite size decrease. This transition is accompanied by a destruction of the
magnetic order (a decrease of the magnetic characteristics).

A dependence of the magnetization on an applied magnetic field for the antiferromagnetic nanomaterial
CuO and NiO has a typical form demonstrating hysteretic properties.

In addition, the magnetic material features a magnetocaloric effect i.e. an ordered magnetic spin of doped
magnetic particles, which are introduced into a non-magnetic structure or a weak magnetic matrix along a
direction of an applied magnetic field.

An increase of hardness and strength, a change of plasticity, elastic characteristics, stability, catalysis, and
diffusion properties of the nanomaterial are now intensively studied. These properties may also be employed for
a development of new elements of devices and open a possibility of transition to a new generation of materials,
which properties can be radically changed by the grain size and the form of their structure elements.

QUESTIONS FOR CONTROL

1. What are nanotechnologies?

2. What is a place of nanoworld objects in a classification of general size scale?

3. What space sizes have nanoobjects?

4. What is a nanoconsolidated material?

5. To what an enhanced strength of the nanocrystalline material is related?

6. Describe a specific structure of a grain interface of a nanocrystalline material.

7. What is a fraction of nanocrystalline matter at a grain interface?

8. Cite the formulae describing a dependence of summary fraction of an interface surface, a

grain interface, and a triple junction on a crystal size.

9. What are thermodynamic features of a nanostructure?

10. How is a nanomaterial electric resistance calculated?

11. What are features of a nanoferromagnetic material?

12. How does a ferromagnetism change under transition to a nanometer range?

13. What is a superparamagnetism?

14. What is a dependence of a coercitive force of a nanoferromagnetic material on a particle size?

REFERENCES

[1] Gleiter H. Nanostructured Materials: Basic Concepts and microstructure Acta Materialia 2002; 48: 1-29.
[2] Golovin YuI. Introduction in nanotechnology. Moscow: Mashinostroenie 2003.
14 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

[3] Andrievskii RA, Glezer AM. Grain Size effects in Nanocrystalline Materials. 1. Features of Structure. Thermal
Dynamics. Phase Equilibrium. Kinetic Phenomena. The Physics of Metals and Metallography 1999; 88: 50-73.
[4] Andrievskii RA, Ragulia AV. Nanostructured Materials. Text Book. Moscow: Academiia 2005.
[5] Palumbo G, Erb U, Aust K. Triple Line Disclination Effect on the Mechanical Behavior of Materials Scripta
Metallurgica et Materialia 1990; 24: 1347-1350.
[6] Gleiter H. Nanostructured materials: State of the Art and Perspectives. Zeitschrift fur Metallkunde 1995; 86: 78-83.
[7] Valiev RZ, Aleksandrov IV. Nanostructured Materials Fabricated by Intensive Plastic Deformation. Moscow: Logos
2000.
[8] Zhou Y, Erb U, Aust KT, Palumbo G. The Effects of Triple Junctions and Grain Boundaries on Hardness and
Youngs Modulus in Nanostructured Ti-P Scripta Mater 2003; 48: 825-838.
[9] Gleiter H, Weissmuller J, Wollersheim O, et al. Nanocrystalline Materials: A Way to Solids with Tunable Electronic
Structure and Properties. Acta Materialia 2001; 48: 737-745.
[10] Zhang S, Sun D, Fu Y, Du H. Recent Advances of Superhard Nanocomposite Coatings: A Review. Surf Coat
Technol 2003; 167: 113-119.
[11] Liakishev NP, Alymov MI. Nanomaterials for Structured Materials. Nanotechnologies in Russia 2006; 1: 71-81.
[12] Ragulia AV, Skorohkod VV. Consolidated Nanostructured Materials. Kiev: Naukova Dumka 2007.
[13] Andrievskii RA. Nanomaterials: A Concept and Modern Problems. Rus Chem Jour 2002; 46: 50-56.
[14] Andrievskii RA, Glezer AM. Grain Size Effects in Nanocrystalline Materials. II. Mechanical and Physical Properties.
The Physics of Metals and Metallography 1999; 88: 50-73.
[15] McGrea JI, Aust KT, Palumbo G, et al. Electrical Resistivity as Characterization Tool for Nanocrystalline Metal In:
Kommarneni EdsS, Parker JC, Hahn H. Nanophase and Nanocomposite Materials III. Warrendale Materials research
Society 2000; 461-466.
[16] Troitskii VN, Domashnev IA, Kurkin EN, et al. Plasmo-Chemical Synthesis and Properties of Ultradispersion NbN.
High Energy Chemistry1994; 28: 275-279.
[17] Zolotukhin IV, Kalinin YuV, Sognii OV. New Directions of Physical Material Science. Voronezh: VGU 2000.
[18] Newnham R. Size effect and NonLinear Phenomenon in Ferroic Ceramics. Third Euro-Ceramics eds P.Duran, J.
Fernandes Faenza Editrice Iberica 1993; 2: 1-9.
[19] Kolobov YuR, Valiev RZ, et al. Diffusion at Grain Interfaces and Properties of Nanostructured Materials.
Novosibirsk: Nauka 2001.
[20] Nalwa HS. Nanostructured Materials and Nanotechnology St.-Peterburg: Nauka 2001.
[21] Reithmaier JP, Kulisch W, Petkov P. Nanostructured Materials for Advanced Technological Applications.
Netherlands: Springer 2000.
[22] Knauth Ph, Schoonman J. Nanostructured materials. Selected Synthesis Methods, Properties and Applications New
York: Kluwer Academic Publishers 2004.
[23] Peidong Y. Chemistry of Nanostructured Materials. World Scientific Publishing Company 2004
[24] Advani GS. Processing and properties of nanocomposites. World Scientific Publishing 2007
[25] Aliofkhazraei M. Nanocoatings: Size Effect in Nanostructured Films. Springer 2011
[26] Bhushan B. Handbook of Nanotechnology. Springer 2010.
[27] Rodriguez JA, Fernandez-Garcia M. Synthesis, Properties and Applications of Oxide Nanomaterials. Wiley 2007.
[28] Kanellopoulos N. Nanoporous Materials: Advanced Techniques for Characterization, Modeling, and Processing CRC
2011.
[29] Books New Nanotechnologies/edit. A. Malik and R.J. Rawat. A.D.Pogrebnjak, A.P.Shpak, V.M.Beresnev. Chapter 2
(p. 25-114). Structure and Properties of Protective Composite Coatings and Modified Surface Prior and After Plasma
High Energy Jets, Nova Science Publisher. 2009; 687.
[30] Pogrebnjak AD, Lozovan AA, Kirik GV, et al. Structure and Properties of nanocomposite, hybrid and polymers
coatings,Publ. House URSS, Moscow, 2011, 344.
[31] Azarenkov NA, Beresnev VM, Pogrebnjak AD, et al. Fundamentals of Fabricated Nanostructured Coatings,
Nanomaterials and Their Properties, Publ. House URSS, Moscow 2012; 352.
 Nanocoatings Nanosystems Nanotechnologies, 2012, 15-20 15

CHAPTER 2
Nanoporous Materials
Abstract: This Chapter describes a whole complex of nanoporous materials. A classification of porous
material (an inside pore, an opened pore, a perforating pore, an opened-line-end pore) is considered.
Three different ways of interaction of the nanoporous material with a surrounding medium are
demonstrated: a-adsorption; b-filtration, c-catalysis using: 1) small molecule and 2) big molecule. The
problem of how to control size, form of pores, and uniformity of their distribution is considered.

Keywords: Types of nanoporous materials, applications.

2.1. INTRODUCTION

Formally, a nanoporous material may be considered as a nanocomposite, in which a pore plays a role of a
second phase, which is randomly or regularly distributed in a matrix (Fig. 1). However, there are several
physical reasons to single out the nanoporous material as an individual class of materials.

Figure 1: Main types of a nanoporous material.

A detailed consideration of genesis, behavior, and influence of pores on solid properties seems to be more
reasonable to start from determination of free volume and porosity concepts, since every of these two
concepts is not always unambiguous [1-15] if to take into account multiple variations of existing
nanoporous systems, when a universal criterium of their description is absent.

A free volume. Let us define a free volume Vf in a solid as a space, which is not filled with atoms, and an
electron density of which is close to zero. A distribution character of the free volume is conditioned by a
degree of atomic packing uniformity over this volume and may be set in the course of analysis of an
electron density distribution function. A concretization of the free volume concept, taking into account a
way of its determination, is important. Therefore, a geometrically free volume Vr is

Vr = V Σω, (1)

where Σω is a summary specific atomic value, which characterizes a solid volume, which was occupied by
a “void” phase. In this case, a pore may be considered as a local free volume unit of a definite form,
location, sizes of which essentially exceed interatomic distances of a material matrix. Then, a relation of
solid summary volume V-Vk, which was occupied by the “void” phase, to a full volume characterizes a
volume fraction (a percent volume concentration) of pores, or a solid porosity, C. A value, which is
opposite to the porosity, is called a degree of occupation (population) density. A volume of compact solid
of chemically identical composition, a mass of which is equal to a porous solid, is designated as Vk.

If Σω/V is an atomic packing coefficient, then a relative geometrical free volume represents a value 1-Kpack.
Alexander D. Pogrebnjak and Vyacheslav M. Beresnev
All rights reserved-© 2012 Bentham Science Publishers
16 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

Also, various types of interstitial voids, which, however, according to selected criteria, cannot be
considered as pores, are integral components of the free crystalline volume.

To identify a porosity term, two approaches are applied. One of them is based on an idea that pores are
characteristic and integral components of structure and define an origin, properties, and purposes of
material. This approach is usual for objects containing essential number of voids (soils, foam materials,
fabrics, activated coals, gels, zeolites, porous ceramics, certain kinds of fine-fibred structures, porous
sintered composition materials). In this case, they speak about a porous state of material, since an
individually considered pore cannot be clearly defined with respect to some of the above mentioned
systems. Therefore, a statistical geometry, a stereology, methods of statistical and stochastic physics,
methods of molecular analogy, as well as empirical methods with a theory of random functions, etc. are
applied to describe them. To facilitate studies of morphological characteristics, which specify a course of
various processes in a porous medium, real porous systems are classified according to a formation
mechanism (growing systems or substance porous systems, addition(composition) systems, as well as
combined systems) and a structure character (systems with an ordered and non-ordered arrangement of
structure elements).

A growing system is formed when a macroscopically continuous medium is dispersed in the course of
sublimation, condensation, and solidification and/or biological processes. Solidified foams, sponges, cokes,
activated coals, pumices, zeolites, fine condensed layers of thermally stable materials, which were
deposited to chemically neutral substrates under a significant overcooling and an absence of chemical
adsorption, fibers of cellulose, skeletons of certain plants and organisms are among them.

An addition system is formed when a reasonable number of elements, a specific porosity of which may be
neglected (for example, a colloid system (a gel in a dry state), a granular material, a filter fiber, a yarn, a
paper, etc.) are added occasionally and randomly. A combined (or complicated) system is a combination of
growing and addition system, in particular, a product of pressing and sintering applied in a powder
metallurgy, a ceramics, a fabric, a building material, a porous glass, and others, in which a formation of
pores formation is preceded by a random or regular addition (an elimination) of individual elements of the
given system. Various condensates, which are deposited under conditions of overcooling, can also be
attributed to such systems, if they are unfairly frozen and there is a possibility of structure transformations
during a post-condensation period.

A consideration of pores as three-dimensional imperfections (defects) of solid structure together with zero-,
one-, and two-dimensional defects is one more approach, which is applied for a determination of porosity.
Such presentation of pores works for materials, which origin and purposes are not directly related to pores
as characteristic structure “components”. Cast metals and alloys of low porosity, rolled stock materials, the
majority of minerals and glasses, etc. can be attributed to such materials.

However, one should bear in mind that terms “a low porosity” and “a high porosity” are conventional, and
their correctness is evident only in the case of statistic methods taking into account a dispersion ability, a
form, an orientation, and a dimensional distribution of pores. Analyzing an effect of pores on material
properties, one does not need this conventional division, because a sensitivity of properties to pores, their
number, a dispersion, a form, and a volume distribution character is different. Both above-mentioned
approaches may be changed for a single one when pores are considered as foreign phase inclusions or
phase-structure non-uniformities in solids. This is convenient for a thermodynamic description of porous
systems and their diagram presentation. This approach allows an evaluation of lability of any system and
determination of optimum thermodynamic parameters for states, when a given system is truly considered as
a conventionally “solidified” one.

Morphological Characteristics of Pores. Morphological features of pores as volume non-uniformities are

determined by their construction (Fig. 2).
Nanoporous Materials Nanocoatings Nanosystems Nanotechnologies 17

Figure 2: Types of pores in solids: a-an inside (closed) pore; b-an opened throughout pore; c-an opened dead end pore.

An isolated body closed in a volume, a solitary non-continuity, and a “sealed” pore ensemble, which may have
a mutual communication, refer to an inside pore. A surface of an inside pore is not taken into account in
calculations of overall body surface. An open pore is a throughout (b) and a dead-end (c) pore representing
capillaries of arbitrary forms closed from one side. In such a way, a body overall porosity C is a sum:

C = Cin + Cop = Cin + Cth + Cd, (2)

where Cin and Cop is an inside and an open porosity; Cth and Cd is a volume fraction of throughout and dead-
end pores. Pores, which in a general case have arbitrary forms and dimensions, may be localized both
inside solid structure elements (for example, inside crystallites, fragments, blocks, cells, or granules) and
along their boundaries, depending on a matter prehistory, an energy balance, and a structure. A chaotic and
an ordered arrangement of pores is distinguished by an analogy with a modulated structure, which is related
to a formation of pore superlattices (simple and complicated) or subsystems with periodically changing
hollow cells of various ordering degree. In many materials (for example, anisotropic deposited films,
composites, and other materials, which were subjected to an oriented action) a pronounced dominating
orientation of pore arrangement can be observed.

A great number of small pores and channels (their transverse sizes may vary from 0.3-0.4nm to a
micrometer range) imparts a number of special physical properties to nanoporous materials. Methodically,
according to a classification of International Chemical Union, porous materials are divided into three
classes: microporous (with a characteristic pore size R < 2 nm), mezzoporous (2 < R << 50 nm), and
macroporous (R > 50 nm) materials. This differs, a little, from a classification adopted for nanostructural
materials in a material science, because a difference between these mentioned groups is shifted towards
lower R. However, the division itself, its principles, and consequences remain the same. A free surface
accessible for an interaction with gases and liquids exceeds a surface of continuous solid by orders of
magnitude reaching 1000m2/g. This leads to an enhancement of conditions for a heterophase chemical and
catalytic reaction, amends a sorption capacity, etc. However, a simple increase of specific surface is not the
only reason of increased activity characterizing nanoporous materials.

A relatively high amount of atoms arranged in a surface itself and high curvature near-surface layers may
drastically change properties of material itself, properties of molecules and atoms, which were adsorbed
from a surrounding medium by its pores.

An important characteristic of porous bodies is also their penetrability for gases and liquids. In the case of a
nanorange transversal pore size, it may vary adapting itself to molecules of different forms and sizes, i.e. a
18 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

nanoporous material may be used as a selective molecular sieve and filter (K is a catalyst particle; A and B
are initial reagents; A + B is a synthesized product) (Fig. 3).

Figure 3: Three main types of interaction of nanoporous materials with a surrounding medium: a-an adsorption; b-a
filtration, a separation of mixtures; c-a catalysis; 1-small molecules; 2-big molecules.

Porous penetrable materials are widely employed as filters for a mechanical purification, a drying, a heating
of liquids and gases, a selected filtration, a separation, and an enrichment of gases, an aeration of liquids
and powder materials, reactions in a boiling layer, a dosing and a uniform distribution of liquids or gases,
an evaporization cooling of constructions working under high-temperatures, mixture regenerators, dust
collectors, humidifiers, desalters, nuclear membrane filters, etc.

A character and a kinetics of these processes for gases and liquids flowing through a porous media are
determined mainly by a size ratio of pores and fluid molecules, an action of adsorption and electrostatic
forces, a concentration, a form, and an orientation of pores, their dimension distribution over material, as
well as an interphase tension at a nanopore output.

A rate, with which a liquid is sucked into the nanopore of R radius, can be approximately evaluated from
the following expression:

lliq/τ = R2ρliq/8ηliq {(2αcosθ/Rρliq R)-gsinβedg}, (3)

where lliq-is a length of liquid column in the nanopore, which was absorbed for τ time, ηliq and ρliq-are a
viscosity coefficient and a specific weight of absorbed liquid; α and θ-are a liquid surface tension and an
edge angle of wetting; βedg-is a slope of nanopore axis to a horizon; g-is a gravitation acceleration.
However, according to the formula (3), the calculation of sucking-in rate for a complicated system of
branching nanopore is only a reference point.

Main qualities of filtering porous materials are their permeability, a degree of fine cleaning, a retaining ability,
and a mechanical strength, a chemical and a thermal resistance for filtration of aggressive fluids and an
operation under enhanced temperatures, as well as their chemical and thermal resistance. The degree of material
permeability is determined by a fluid velocity flowing through a unit of area and a unit of material thickness
under a given pressure. Three types of fluid transportation through a porous medium are distinguished. A
diffusion is induced by an action of concentration and temperature gradients under a constant pressure. An
effusion is a free-molecular flow (Knudsen Flow), when an impact frequency of fluid molecules is negligible, in
comparison to an impact frequency to the nanopore surface. A viscous laminar flow or a transpiration follows a
convection mechanism, when a fluid is flowing like a continuous medium under an action of pressure gradient
and intermolecular impacts dominate over impacts of free surface molecules.

From the point of view of a basic material or a technology of nanoporous materialfabrication, they may be
divided into a ceramics, a semiconductor, a polymer, and a biological material. They are applied for gas
masks, autonomous life support systems of submarines and habitable space ships, fine cleaning filters for
Nanoporous Materials Nanocoatings Nanosystems Nanotechnologies 19

an air and water (including a filtration of chemical and bacteriological toxic agents). For their efficient
action, it is important to overcome a percolation limit, out of which pores and channels having no earlier
communications begin to form through-passes for a fluid medium. Materials having through-passing
channels of regular geometrical forms and similar sizes have a especial value for these applications, since
the lower is their difference, the better are filter properties.

In a chemical, metallurgical, and biotechnological industry, one of the most popular types of nanoporous
materials is a ceolite-an alumosilicate, which is fabricated from a special clay. Pores of about 0.1 to 10 nm
size, with a three-dimension structure and through-passing channels are formed after a special thermal
treatment. A pore size depends on a number of oxygen atoms in a cyclic structure, which form the ceolite
allowing an easy absorption of definite molecules or a separation of their blends in a membrane filter.

Last century, at the beginning of 90th, Mobile Oil OH firm reported about a finished development of a new
class of alumocilicates (CMC-41, etc.) containing ordered cylindrical pores of 2 to 10 nm diameter with a
low size difference and a high separation ability.

A key problem in a fabrication of porous nanomaterials is a control of pore size, its form, and spatial
distribution uniformity. The Institute for Material Science of NAN of Ukraine offered a simple method for
a fabrication of porous materials with a pronounced submicron microstructure. The method is based on a
self-construction of nucleus-shell structures using a heterophase coagulation. A monodispersion submicron
polymer sphere was applied as a nucleus template, and a nanosized ceramic particle-as material model. A
heterocoagulation made possible a nanoparticle surface modification and a polymer mixing. A nucleus-
shell structure started its self-construction under an action of Coulomb forces. Packing laminated particles
formed a closely packed structure under a vacuum filtration,. Then the polymer was disposed in the process
of calcinations, as a result of which they formed a desired porous structure. The pore size may be controlled
by changing a size and a form of polymer nucleus. A porosity can be easily specified by a volume ratio of
polymer/ceramics particles. This process allows a formation of various porous structures.

An application of porous materials is highly important for a transformation of exhaust gases, a purification
(a refinement) of liquids, a catalytic reforming employed in a chemical industry, etc. Properties of porous
materials properties can be optimized by a control of pore structure. So, for example, micropores should
have an equal size when a porous aluminum oxide Al2O3 is used as a carrier of silver catalyst (which is used
in an ethylene fabrication). A microfiltration on ceramic membranes is a promising application of
nanoporous aluminum oxide. However, a typical ceramic membrane-fabricated by a sintering of
nanodispersion aluminum oxide powder demonstrates a relatively low permeability due to a relatively low
porosity. To fabricate the membrane filters of high permeability, we needs some alternative method, which
is a sol-gel condensation or a deposition from chemical vapors. The deposition of ultradispersion powder to
a porous substrate also is an alternative for the membrane filter.

A great interest was attracted by a discovery of the 90th-a luminescence of porous silicon in a visible light. It
was absent in an ordinary silicon singlecrystal, which, as it was known, detected only a weak fluorescence of
1.0 to 1.2 eV quantum energies in an infrared spectrum with about a forbidden zone width. In addition to the
photoluminescence, the porous silicon demonstrated also an electroluminescence, a cathode luminescence (i.e.
a visible light emission induced by an applied voltage and by electrons falling to its surface).

Porous materials attract a great interest, since they open a possibility to combine nanoparticles, which are
arranged in mezzopores.

QUESTIONS FOR CONTROL

1. What are the types of nanoporous materials?

2. What characterizes a porosity?
3. What is a key problem now in a fabricationof nanoporous materials?
20 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

4. What types of interaction exist between nanoporous materials and a surrounding medium?

5. What is a ceolite and where is it applied?

REFERENCES

[1] Cheremskoi PG, Slezov VV, Betekhin VI. Pores in Solids. Moscow: Energoatomizdat 1990.
[2] Shpak AP, Cheremskoi PG, Kunitskii YuA, Sobol OV. Cluster and Nanostructured Materials. Kiev: VD
Akademperiodika 2005; 3: 516.
[3] Denisova NE, Shorin VA, Gontar IN, et al. Tribological Material Science and Tribology. Penza: PGU 2006.
[4] Ragulia AV, Skorokhod VV. Consolidated Nanostructured Materials. Kiev: Naukova Dumka 2007.
[5] Sokolov S, Bell D, Stein A. Preparation and Characterization of Macroporous Alpha-Aluminum. J Amer Ceram Soc
2003; 86: 1481-1486.
[6] Kanellopoulos N. Nanoporous Materials: Advanced Techniques for Characterization, Modeling, and Processing CRC
2011.
[7] Roque-Malherbe Rolando MA. Adsorption and diffusion in nanoporous materials. CRC Press Taylor & Francis
Group 2007.
[8] Sattler KD. Handbook of Nanophysics: Nanoelectronics and Nanophotonics. CRC Press 2010.
[9] Shenderova OA, Gruen DM. Ultrananocrystalline Diamond: Synthesis, Properties, and Applications. NY: William
Andrew Publishing 2006.
[10] Steiner T. Semiconductor Nanostructures for Optoelectronic Applications. Artech House Inc. 2004.
[11] Yangyang S. Study on the nanocomposite underfill for flip-chip application. Biochemistry Georgia Institute of
Technology 2006.
[12] Sung J, Lin J. Diamond Nanotechnology. Syntheses and Applications. Pan Stanford Publishing Pte. Ltd. 2010.
[13] Vo-Dinh T. Nanotechnology in Biology and Medicine. Methods, Devices, and Applications. CRC Press, Taylor &
Francis Group 2007.
[14] Pogrebnjak AD., Uglov VV, Il'yashenko MV, et al. Nano-Microcomposite and Combined Coatings on Ti-Si-N/WC-
Co-Cr/Steel and Ti-Si-N/(Cr3C2)75-(NiCr)25 Base: Their Structure and Properties Nanostructured Materials and
Nanotechnology IV: Ceramic Engineering and Science Proceedings 2011; 31(7):115-126.
[15] Pogrebnjak AD, Sobol OV, Beresnev VM, et al. Phase Composition, Thermal Stability, Physical and Mechanical
Properties of Superhard On Base Zr-Ti-Si-N Nanocomposite Coatings Nanostructured Materials and Nanotechnology
IV: Ceramic Engineering and Science Proceedings 2010; 31(7): 127-138.
 Nanocoatings Nanosystems Nanotechnologies, 2012, 21-30 21

CHAPTER 3
Amorphous Materials
Abstract: A definition of amorphous material is presented. It is considered as a transition from an
amorphous to a nanocrystalline state. An atomic structure of amorphous body is considered.
Mechanisms and classes of amorphous bodies, which are genetically bound with crystals or liquids, are
briefly described. Methods employed for an investigation of the amorphous structure are described. A
atomic structure of glasses is considered from the point of view of radial distribution functions (RDF).
A model of atomic structure free volume for the amorphous materials is presented. Properties of
amorphous materials are briefly described.

Keywords: Polycluster, models properties of amorphous metallic.

3.1. INTRODUCTION

Recently, an amorphous solid attracted a great interest of scientists working in the field of fundamental and
applied physics. An absence of long-range order in a mutual atomic arrangement is a determinant point of
amorphous body. Such system is characterized, on one hand, by the absence of long-range order, i.e. a strict
periodicity of atomic arrangement in a microvolume, on the other hand, by a presence of short-range order,
i.e. an ordered distribution of coordinates of nearest neighbors for any atom. The absence of long-range
translation order often leads to an alternation of properties, which are difficult or impossible to reach in a
solid with a crystalline structure. Some of these properties turned out to be very important both for practical
applications and for a scientific understanding of atomic disorder.

An application of amorphous solid attracts a great interest since it is a material with preliminarily “given”
properties. First, an optical glass started to draw a great interest for fiber-optical communication systems. Then,
an amorphous metallic alloy (a metallic glass) found its application as a magnetic cap core, a magneto-
mechanical pickup, a regulated delay line, etc. An amorphous semiconductor is a photodetector, a relatively
cheap solar battery, a sensitive layer for a xerography. The practical interest dictates a necessity to fabricate a
new non-crystalline material. The following relation is necessary in order to reach desired macroproperties: a
composition-fabrication conditions-a structure-properties. Today, scientists, who are working in the field of
solid state physics and physical-chemical material science, are involved in this problem.

An amorphous state-is one of the existing forms of solids. The amorphous solid is a thermodynamically
nonequilibrium or a metastable system tending to gain a crystalline structure and to go to a stable state.
Regions with a definite atomic order (nucleuses) may arise in the metastable state due to fluctuations.

On one hand, if nucleus size exceeds certain critical value (critical radius), free system energy gets lower
with growing nucleus. On the other hand, if nucleus size is lower than this critical value, free system
formation and its growth need higher free energy in comparison with initial equilibrium state.

A time of metastable state ordering depends on a nucleation rate-a formation frequency of nucleuses
exceeding a critical size, which is normalized to a volume unit and on a growth rate of supercritical
nucleuses. An ordering time of non-equilibrium amorphous body depends on a local reconstruction
frequency of atomic configurations resulting to the ordering.

An atomic structure of amorphous body depends not only on a character of interatomic forces, but also on
the formation conditions. There are two classes of amorphous bodies, one of which is genetically related to
crystals, another one-to liquids. If a crystal contains random dislocation nets or if it is a polycrystal
composed of randomly oriented crystallites, then pair correlation radii of their lattice sites are comparable
to an average distance between dislocations and crystallite sizes. Extended defects-dislocations and grain
interfaces-play a dual role: first, they introduce a topological disorder destroying correlations in atomic

Alexander D. Pogrebnjak and Vyacheslav M. Beresnev

All rights reserved-© 2012 Bentham Science Publishers
22 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

arrangements at distances, which are comparable to average distances between defects, and, second, they
destroy a local order of dislocation nuclei and boundary layers. In addition, dislocations are surrounded by
fields of elastic deformations slowly decreasing with distances (like L/r, where r is a distance to a
dislocation). A Bloch theorem is not applicable and electron wave functions (this is valid also for other
quasiparticles) cannot be described by Bloch functions for a topologically disordered crystal. A good
accuracy description of disordered crystal electron properties can be obtained if a topological disorder is
neglected, the Bloch functions are taken as initial wave electron functions in a zero approximation, and a
scattering at defects is taken into account. In such a way, a satisfactory description of considered
amorphous bodies can be obtained if the topological disorder generated by extended defects is ignored and
a resulting local disorder within the framework of perturbation theory is taken into account.

When a temperature exceeds a crystal melting point Tm, a liquid is a thermodynamically equilibrium
condensed body. It may transfer to a metastable state if a temperature abruptly falls below Tm. First, the
crystallization rate of overcooled liquid increases with a degree of overcooling (ΔT = Tm-T) and, then,
quickly decreases. So, a deep liquid overcooling transforms a liquid into an amorphous solid having an
enormous crystallization time. Atomic configurations of this overcooled liquid are reconstructed both due
to atomic diffusion displacements and changes of atomic interactions. Since atoms have no time for a
serious reconstruction by a diffusion mechanism in the course of fast cooling, and average interatomic
distances (which have a little difference both for a liquid and for a crystal) and atomic interactions do not
essentially change, local topological changes of atomic configurations will not be great, and a structure of
resulting solid and initial liquid will be similar. Many overcooled liquids have a characteristic temperature-
a so-called glass-transition temperature Tg, when a viscosity is sharply increased, a specific heat capacity
and a density decreased. Fig. 1 shows schematically a behavior of specific heat capacity and body viscosity
for various aggregate states. The overcooled liquid when T < Tg is called a glass, where Tg is considered as
a temperature, at which the overcooled liquid is transformed into the amorphous solid. Fig. 1 shows a
temperature dependence of specific heat capacity. Within (Tg, Tm) temperature interval the liquid is
overcooled. Arrows indicate directions of temperature changes.

Figure 1: A dependence of specific heat capacity on a temperature: 1-for a liquid and a glass; 2-for a crystal.

However, as a rule, the glass-transition temperature depends on a cooling or heating rate, and, in most
cases, changes at about Tg are not abrupt and are partly irreversible. A jump of Cp indicates that when T ≈
Tg, the solid inside freedom degrees abruptly change. The irreversibility of these changes indicates a
structure non-equilibrium state. Many glasses, first of all, metallic glasses (amorphous metals and alloys
obtained by a fast quenching from a melt) are crystallized at Tc temperature, which a little exceeds Tg. In
some cases, crystallization prevents the glass-to-liquid transition, because this transition temperature
interval is smoothed or Tg coincides with a crystallization temperature.

In spite of an indefinite and a conventional character of a glass-transition temperature and a glass-to-liquid

transition, this narrow temperature interval, which is characterized by essential changes of
thermodynamical values and mechanical properties, allows an identification of matter state (liquid or solid).

Consequently, a cooling liquid has to reach such temperature level, at which a kinetic factor decreasing a
formation rate of crystallization centers with a temperature will dominate. In a literature, terms “an
Amorphous Materials Nanocoatings Nanosystems Nanotechnologies 23

amorphous state” and “a glass-like state” are often mentioned and understood as synonyms. Indeed, these
terms are very close but “the amorphous state” is common. One can say that any glass-like state is
amorphous, but not any amorphous state is a glass [1-4].

A main peculiarity of glass-like state, which differs it from other amorphous states, is that a glass can have
a reversible transition from the glass-like state to a melt and from the melt to the glass-like state. This
property is characteristic only for the glass. In the course of heating, other types of amorphous states, first,
start a transition to a crystalline state and only when the temperature increases to a melting one, they start a
transition to a liquid state. A gradually increasing viscosity of glass-forming melt prevents the
crystallization, i.e. the transition to a more stable thermodynamic state with a lower free energy. Glasses are
characterized by a number of physical properties. Practically, all glasses have a weak luminescence. Local
mechanical stresses and structure non-uniformity yield a double refraction. As a rule, glass-like matters
feature diamagnetic properties, and a doping of rare-earth metal oxides makes them paramagnetic materials.
In contrast to a glass-like state, a metallic amorphous matter does not feature the reversible transition to the
amorphous state (a melt). When the matter is heated, first, it transits to a crystalline state, and subsequently-
to a liquid one. When it is cooled, in order to reach a crystalline state, the matter needs strictly definite
conditions. The amorphous metallic state of matter does not demonstrate luminescent features. The
majority of such matters is either a ferromagnetic or an antiferromagnetic material.

A structure of amorphous metallic system (AMS). The amorphous solid state is one of the most poorly
studied fields of a modern structure material science. The main difficulty is a way employed to a
description of amorphous state structure, since an absence of translation symmetry elements and concepts
of elementary cells deprive a researcher of terms and concepts accepted in a crystallographic science, as
well as powerful instruments for a structure analysis. The amorphous solid structure is similar to a liquid
one, therefore, density fluctuations, local surroundings, and a chemical composition should be taken into
account. This introduces a probabilistic and statistical character into the structure description.

An amorphous solid structure is studied using an X-ray, electron and neutron diffraction, and an EXAFS
method (Extended X-Ray Absorption Fine Structure). Also, important methods are an electron microscopy,
a small-angular scattering of neutrons, an X-ray analysis, measurements of Mossbauer effects, and a
nuclear-magnetic resonance. The structure state and changes are reflected in magnetic, elastic, non-elastic,
electrical, and other properties, which are studied using an AMS method [5-9, 17-23].

So for example, a structure of disordered system in a thermodynamic equilibrium state (a gas, a liquid) may
be described with the help of distribution functions in a one-, two-or many-particle approximation. As for a
theoretical description of non-equilibrium system structure, any reliable systematic approach is still
unavailable. The AMS helps to determine a spatial atomic arrangement by an X-ray (or neutron) scattering
intensity using an integral Fourier transformation. An information about the spatial atomic arrangement in a
solid is taken from a structural model. Today, a direct observation of glass atomic structure is impossible.
Indirectly, it can be determined using statistical characteristics such as a radial distribution function (RDF)
and others. Experimental observations indicate a notable RDF similarity of a liquid and a glass, which
confirm their structure similarity.

Thus for example, the radial distribution function (RDF) for a system composed of one sort of atoms is
determined by the expression:

W(r) = 4πr2 ρ(r), (1)

where r is a distance from a picked-up atom; ρ(r) is an atomic distribution function or a twin atomic
distribution function.

This function has the following physical sense. If a coordinate system is aligned with a center of one
particle, a product ρ(r)dV is an average number of particles displaced in a volume unit dV with a
24 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

characteristic radius-vector r. A function W(r) is a weight number of atoms in a spherical cell of an r-radius
and a layer thickness of unity.

When the r value is lower than the atomic sphere diameter, this function is equal to zero. And when the r
distance increases, a correlation between particles is gradually dying and tends to an average value ρ0 =
N/V when r → ∞ρ(r). Here, N is the number of particles in a volume V, The RDF is characterized by a first
high peak corresponding to nearest neighbors, which, in their turn, correspond to the second, third, etc.
neighboring particles around the picked-up atom. Most often, instead of W(r) function, the above
mentioned radial distribution function G(r) = 4πt {ρ(r)-ρ0} is used, which is a twin function of radial
distribution g (r) = ρ(r)/ρ0 and an interference function J(k)~ JnF2, where f is an atomic factor and Jn is a
scattering intensity.

In a description of amorphous solid containing atoms of different elements (n), the RDF is expressed as:

W(r) = 4πr2 Σ Σ ωij ρij (r). (2)

The expression includes a partial function of atomic distribution ρij (r) with a definite weight multiplier ωij.
The partial function of atomic distribution ρij(r)(i, j = 1, 2, ….n) represents an average particle density of
the ith sort in a volume unit dV of an r coordinate, if a particle of the ith sort occurs at a point of an r = 0
coordinate.

An area under the first RDF peak allows a determination of the average coordination number, i.e. the
number of nearest neighbors in a single-component amorphous system:

Z    ( r )4 2 r  d  (3)
0

An average interatomic distance for the given structure can be derived from the first maximum position.
Here, rmin is the first RDF minimum.

For a multi-component system, a calculation of short-range order parameter is complicated, since one needs
a sum of atomic distribution partial functions with their weight multipliers, which indicate a relative
contribution of individual components to a total interference function or the total RDF. A comparison of
experimentally measured RDF for a liquid and an amorphous metal shows a satisfactory similarity.

Models for an amorphous solid. Today, there is a number of models describing a structural state of
amorphous solid. Among them, a Bernal model (a free space model (FSM)) is mostly developed and widely
employed to explain the amorphous solid properties. Every atom occupies a void among its nearest
neighbors. If this void vh exceeds a certain value vc, which is approximately equal to a space of one atom in
a closely-packed structure, then

Vr = vh-vc (4)

This model was initially derived to explain a diffusion in a liquid. Later, it was developed and applied to
describe diffusion properties and a plastic current of amorphous solid [9-16].

In the process of further development, the FSM was used for a description of plastic deformation and a
solid state-liquid transition in an amorphous solid, as well as an explanation of tunneling state origin and a
structure change kinetic occurring in the process of annealing.

Assumptions about cells containing a free space and premises about a density and a distribution of these
cells under various conditions, as well as types of the relating structure reconstructions are significant
elements of FSM. Here, details concerning configurations of “normal” cells and regions containing an
excessive space are insignificant. This allows a formulation of free space model based on a representation
Amorphous Materials Nanocoatings Nanosystems Nanotechnologies 25

that cells containing the free space play a crucial role in a plastic deformation, a diffusion, and a structure
relaxation of glasses. This model has been developed in details and is now widely applied in a physics of
amorphous solids. The free space model is based on the following assumptions:

- A free space may be redistributed between cells and this distribution occurs without a change
of summary free space and a solid free energy;

- An atomic transfer by a diffusion is possible when a neighboring free space exceeds a certain
critical value g* comparable to vc and this space was formed by a fluctuation-induced
redistribution;

- An amount of free space may change when a temperature changes near Tg and as a result of
stress action inducing a plastic deformation (Tg is a glass-transition temperature, at which a
viscosity sharply increases but a specific heat capacity and a density decrease).

There are two interpretations of RDF. The first one comes to a consideration that an amorphous solid is
considered as a system of close-packed stochastic spheres with an excessive (in comparison with a
crystalline solid) specific space per every atom. This excessive atomic space or interatomic voids, may be
randomly redistributed between atoms without a change of summary excessive space. A distribution

P (vf) = {γ/ v f } exp (-vf/vf) (5)

seems to be the most probable.

Here, P is a distribution function; γ is a geometrical factor of unity order; vf is a free space per one atom, and

vf = α (T-T0), (6)

where α is a heat expansion coefficient and T0 is a phenomenological parameter.

Taking into account that an atom may be displaced to a void, a volume of which exceeds v*, a diffusion
coefficient can be calculated using (5) and (6):

D = α · u exp (-v*/vf), (7)

where α is an interatomic distance; u is a thermal atomic rate.

From here, an expression for a viscosity coefficient for a uniform liquid and glass flow can be derived:

η = AkBT/aD, (8)

where A is a constant of unity order; kB is a Boltzmann constant.

The distribution (5) is valid, in one hand, if a local reconstruction of cells occurs so often that gives rise to a
metastable equilibrium, on the other hand, a structural reconstruction leading to a crystallization is
depressed. Both these conditions, a realization of which could be controlled within a macroscopic
description of structure reconstruction theory, may happen to be mutually exclusive. Relations (5) and (6)
loose their validity when a temperature is lower than glass-transition one. However, the diffusion and
viscosity stay still dependent on a density of free space cells, which are able for a reconstruction under an
action of heat fluctuations and stresses.

A thermodynamic approach for a description of amorphous solid containing an excessive free space is one
more interpretation of FSM. It is assumed that a solid has cells with and without the free space: a liquid-like
26 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

and solid-like cell. A state and a concentration of liquid cell is described by a Gibbs distribution, a free
atomic energy depending only on vf. A transition of amorphous solid to a liquid state in this approach, is
related to a formation of infinite (leaking through) liquid-like cluster, which appears when a concentration
of liquid-like cells reaches a certain critical value (0.15… 0.3).

A polycluster model. A polycluster model, which was introduced and investigated by Prof. Bakai A.S., has
no disadvantages of the above considered models. It involves a construction-based determination of
topologically disordered structure. A polycluster has a more perfect local order in the most volume fraction
in comparison with a system of balls with a stochastic close-packing. At the same time, its topological
disorder is stronger in comparison with paracrystals. The fairly perfect local order of polyclusters may go
together with a strong topological disorder and with a broken mutual atomic arrangement at finite distances.
It is more important that a region with local disorder is only two-dimensional. This is a source of
characteristic kinetic and fluctuation properties of polyclusters. Structure defects and a number of
polycluster properties have been already described: a mechanism of atomic transfer, mechanical states in a
field of external forces and structure fluctuations. And, in spite of the fact that now a polycluster character
of real amorphous body structure is not clear, a comparison of theoretical results with experimental data
does not indicate serious disadvantages of this model.

An analysis of literature data allows the following conclusions:

- There is no a universal model with an adequate description of structure and properties of

amorphous metallic alloy;

- An absence of translation symmetry in an atomic arrangement causes great difficulties in a

model construction. A concept of elementary cell can hardly be applicable to an amorphous
system. In addition, methods based on a solid interaction with an electromagnetic emission
(radiation) have a low efficiency for an amorphous material.

- Offered models can only give only a good description of definite properties but fail to give a
full description of amorphous material properties.

A computer modeling plays an important role in a research of amorphous solids. A potential of computer
modeling is limited and restrained within a structure containing several thousands of atoms, a simplified
description of their interactions for a short time period. However, the computer modeling can be
successfully employed for studies of microscopic processes taking place in a volume, which is essentially
smaller than a model one, and a relation of these processes to solid macroscopic properties due to a
comprehensively full diagnostics. At present, several algorisms for a structure modeling of balls with a
random close-packing had been developed. In spite of their difference, they all lead to a formation of solid
with similar structure properties. A numerical model is employed for an identification of various structure
elements and a statistical description, studies of mechanical properties and a dynamics of amorphous solid.
The results of computer modeling are widely applied for an interpretation of various experimental data and
yield an information about properties of an amorphous solid.

3.2. PROPERTIES OF AMORPHOUS METALLIC SYSTEM

Recent decades, a solid state physics goes through a vigorous development of direction relating to
fabrication and application of an amorphous metallic system (AMS). An amorphous metallic material
features so amazing physical and technical properties that their wide application in an engineering can
undoubtedly lead to an essentially increased quality and reliability of tools and an essential economy in
energy and material resources. An amorphous metallic material can be divided into four main groups:

1. A “transition metal (Fe, Ni, Co)-a metalloid (B, Si, P, C)”. Today these materials are most
important from a practical viewpoint;
Amorphous Materials Nanocoatings Nanosystems Nanotechnologies 27

2. A “transition metal (Fe, Ni, Co)-a rare earth metal (Dy, Nd, Gd)”;

3. A “transition metal-metal-lanthanide (Sm, Cu, Ho)”;

4. A binary and multicomponent material, which is composed of an alkaline-earth and another

metal.

At the beginning of 60th, a first amorphous material was obtained using a quenching from a melt. We
should underline that this method was employed to fabrication an amorphous alloy in a form of strip or
wire, which were separated from a crystalline substrate. A spectrum of their compositions, physical, and
technical properties was very wide. Since that time, a quantity off fabricated metallic systems in the
amorphous state was constantly increasing.

However, a fast melt quenching and a fabrication of disordered crystal do not exhaust all possibilities of
amorphous solid fabrication. An amorphous structure takes part in all possible processes involved in a
formation of nonequilibrium structures. A deposition of atomic, ion and plasma flows on substrates, a surface
treatment by a glow discharge, a laser, or an electron beam, an irradiation by a neutron or ion flow of high
energy under special conditions result in a formation of amorphous structure and are widely used for
technological purposed. In most cases, the above methods (this does not concern materials fabricated by a
neutron emission) are used to fabricate a relatively thin film. A kinetics of structure formation by the above
methods essentially differs from a fast melt quenching, but, probably, there exists a great similarity in a
structure and properties of amorphous solids of the same composition, which are obtained by different methods.
Unfortunately, today this problem is so poorly understood, that we can hardly present some full comparison.

Mechanical properties. Both for an amorphous metallic alloy (AMA) and for a crystalline solid under low
deformation, a Hooke's law is valid. An elastic modulus of amorphous alloy is lower than that of a
crystalline metal employed as a basis for the alloy. This is related to an excessive free space and reflects a
lower average force of interatomic interaction of amorphous states in comparison with crystals. A structure
relaxation resulting in a decrease of free space increases an elastic modulus of non-magnetostrictive
amorphous alloy by several percent.

In addition to the excessive free space, an essential effect on a value of elastic modules is played by a value
and a character of chemical bond, which depends on an alloy composition. An increased amount of
metalloid atoms results in a growth of Young modulus from 158 to 187 GPa in Fe-Si-B alloys, from 140 to
152 GPa in Fe-p-C, and from 173 to 175 GPa in Co-Si-B. This indicates an identity in a mechanical
behavior of amorphous and crystalline metallic alloy. Like a crystalline metal, AMA demonstrates
deviations from an elastic behavior in a region of elastic deformation, where the Hooke’s law works. Non-
elastic phenomena observed under low stresses are the main cause of an internal friction characterizing an
irreversible energy loss inside a solid under mechanical oscillations [12-15].

Experimental data on the internal friction for many AMAs demonstrated an attenuation maximum, which
was present in a temperature dependence at T = 200 to 400K. A height of this maximum depended on an
alloy composition and a material structure state. The existence of internal friction peak for many AMAs is a
proof of atomic configurations with a short-range order characterizing defects of an amorphous structure,
which response for an action of external mechanical stress by a local atomic reconstruction. An elementary
act of such reconstruction is an atomic jump. A thermal annealing decreases a height of internal friction
peak, which seems to be related to a structure relaxation and a decreased defect concentration

Electrical properties of an amorphous metal have two peculiar features: an electric resistance of amorphous
metallic alloy at a room temperature is 2 to 4 times higher than that of a corresponding crystalline alloy; a
temperature dependence of the amorphous metal, irrespective of its composition, demonstrates a minimum,
as a rule, at temperatures below the room one. A higher resistance of amorphous metallic alloy, in
comparison to a crystalline one, may be explained as a result of strong action of chemical and configuration
disorder on an electron free range. A disorder of atomic arrangement results in that the conductivity
28 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

electrons of amorphous alloy are scattered more often than it was in their crystalline analogs. The value of
electric resistance for the majority of amorphous metals is close to that of liquid of the same composition.
In the case of amorphous ferromagnetic materials, a magnetic ordering strongly affects electric properties.
A minimum observed at a dependence of resistance on a temperature, may be explained due to a structural
disorder and the strong scattering of conductivity electrons, which always exist in an amorphous alloy.

Magnetic properties of an amorphous metal. It was found that an isotropic amorphous structure permits
only four types of magnetic ordering: an ordered ferromagnetic; a non-ordered ferromagnetic; a non-
ordered antiferromagnetic, and a spin glass. Fig. 2 demonstrates an isotropic amorphous structure of a
magnetic material.

Figure 2: Types of magnetic ordering in an amorphous structure: a-for an ordered ferromagnetic; b-for a non-ordered
ferromagnetic, c-for a spin glass.

An existence of the amorphous ferromagnetic material was theoretically confirmed, however, such type of
magnetic ordering was not found experimentally in amorphous samples.

Recent decades, a ferromagnetic amorphous alloy (a metallic glass) based on an iron doped with Nb, Cu,
Si, B, on Co, and Fe doped with Si and B attracted a special interest. As a result of crystallization, such
amorphous alloy transforms into a nanocrystalline material with a grain size 8 to 25 nm and with unique
magnetic properties. In a literature, a nanocrystalline alloy Fe-Cu-Nb-Si-B is called a “finemet”. It is a
magnetic material with a very low coercitive force, which is comparable to Hc of an amorphous alloy based
on cobalt. It also owns a high magnetic saturation, which is close to that of the iron-based amorphous alloy.
The crystallization of amorphous alloys results not only in the formation of magnetically soft, but also a
magnetically hard nanocrystalline material with the high coercitive force. For example, a fast crystallization
during 10 seconds at 750oC in an amorphous soft magnetic alloy Fe5Co70Si15B10 with Hc = 1 Am-1
transforms into a nanocrystalline alloy with 15 to 50 nm average grain size with Hc = 8800 Am-1, and an
enhanced residual magnetization. At the same time, a slowly crystallizing of an alloy with the same
composition has Hc = 3300 Am-1 [13-15].

An amorphous semiconducting material is a solid system with a dominating covalent chemical bond, which
is characterized by a short-range order (a coordinated arrangement of nearest neighbors) and an absence of
long-range order, i.e. a translation symmetry at a macro level. A forbidden zone (0.01 to 3.5 eV) is typically
present in both an amorphous and a crystalline semiconductor. The forbidden zone is a region of electron
energy spectrum, in which a density of states becomes zero (with the exception of a localized state). Active
researches of the amorphous semiconducting material started after the Second World War. A first system,
which attracted a significant interest of researchers and practical scientists was an amorphous selenium,
which took a dominating position as a material applied for fabrication of photosensors, and later-for a
xerography. Recently, fundamental and practical researches are directed to an amorphous silicon, which
found its application in fabrication of elements for solar batteries, because its cost was essentially lower
than that of a single-crystalline silicon (though the latter had a higher efficiency coefficient). An amorphous
metallic-silicide resistive alloy also found its practical application.

A non-ordered material (a glass, an amorphous solid, a melt, a polymer, a biological medium, etc.)
represents an important class of objects. In spite of that chaos, with which usually a structure of glass and
Amorphous Materials Nanocoatings Nanosystems Nanotechnologies 29

amorphous solid (a semiconductor, a dielectric and a metallic material) is associated, there is one universal
spatial scale (~ 1nm), which is a parameter playing so important role for a theory like an elementary cell for
a crystal. A disorder of non-ordered solids is not absolute. A periodicity of atomic arrangements, which is
common for all crystals, remains within the limits of several coordination spheres and is broken in some
way in a periphery. The character of broken order differs a glass from an amorphous solid by a form of
their structure correlation function. The non-uniformities, which we report about, are not an exotic,
individual formation, or an analog of a crystal defect. They are a fragment, which forms the amorphous
solid and glass as a whole. A spatial non-uniformity of non-ordered solid with a characteristic ~ 1nm scale
gives rise to peculiar features of oscillation properties, a change of electron excitation relaxation
mechanism, and determines a specific character of charge transfer.

From the point of view of a fundamental science, a structure of amorphous solid and glass is one of the
basic problems for a solid state physics. How this world is organized under conditions of disorder, with
which these matters are usually associated? To answer this question is not easier than to answer many
fundamental questions of astrophysics and a physics of elementary particle.

Only a crystalline state, which is characterized by a geometric order of atomic arrangement at far distances,
stands apart from all matter states. As a result, a great progress was reached in an apprehension of
crystalline state by experimental methods and satisfactory theoretical models were derived. However, a
non-crystalline material (a great number of amorphous solids finds an application in practice like a glass
and a liquid) does not own this order, if they are considered using a “crystallization” criterion. They do not
demonstrate a universality of compositions, and every matter has to be studied individually, to construct a
model of its structure, and to find some individual signs for a control of its properties. This does not look
productive, but is widely spread [12-16, 24-26].

Physical properties and a geometry of amorphous material are closely related. A disorder of amorphous
solid has a topological character, and topological defects can hardly be liquidated by low atomic
displacements-it needs a global reconstruction of whole structure.

QUESTIONS FOR CONTROL

1. Give a definition of solid amorphous state.

2. What are a short-and a long-range order in a solid?

3. What is a basic difference between the terms of an amorphous and a glass-like state?

4. What is characterized by a radial distribution function?

5. What are the main ways applied to fabrication of an amorphous alloy.

6. What is the main difference between a zone structure of amorphous semiconductor and its
crystalline analog?

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 Nanocoatings Nanosystems Nanotechnologies, 2012, 31-38 31

CHAPTER 4
Fulerene, Fulerite and Nanotubes
Abstract: A definition of fullerene, fullerite, and nanotube is presented. Various models, forms, and a
geometry of nanotubes (a one-dimension and a three dimension image) are considered. A definition of
nanotube chirality and polygonization is presented.

Keywords: Fulerens, fulerites, nanotubes, CNT.

4.1. INTRODUCTION

A carbon is a widely abundant element. In nature, its solid state is met in a form of graphite and diamond.
Such artificial modifications of carbon like a carbyne and a lonsdaleite were fabricated. The lonsdaleite was
revealed as a meteorite component. In 1985, a group of researchers-Kroto H. W., Heath J. R., O’Brien S.
C., Richard Smalley, Robert F. Curl Jr. studied a mass-spectrum of graphite vapor formed by a laser
ablation and found a peak of maximum amplitude corresponding to a cluster, which contained 60 to 70
carbon atoms (Fig. 1) [1-3, 24-31].

A subsequent study of these formations demonstrated that among all known compounds, the most stable
one is a molecule with an even number of atoms, first of all, containing 60 to 70 atoms of C60 and C70. The
compound C60 has a spherical form looking like a football, and C70 resembles a melon (Fig. 2).

Figure 1: A mass-spectrum of carbon cluster, which was formed in a graphite by a laser ablation [1].

Figure 2: A fullerene molecule: a-a C60 molecule; b-a C70 molecule, c-a predicted fullerene molecule containing more
than 100 carbon atoms [3].
Alexander D. Pogrebnjak and Vyacheslav M. Beresnev
All rights reserved-© 2012 Bentham Science Publishers
32 Nanocoatings Nanosystems Nanotechnologies Pogrebnjak and Beresnev

Carbon atoms are arranged in a sphere surface at a vertex of pentagons and hexagons. The molecule looks
like a football with 12 black pentagons and 20 white hexagons. The C60 molecule is able to crystallize
forming a cubic lattice. A polyhedral carbon cluster was named a fullerene, and the most widely abundant
molecule C60 was named as a Buchminster fullerene after an architect Buckminster Fuller, who constructed
a dome for an USA pavilion for the Montreal exhibition 1967 looking like junctions of pentagons and
hexagons. As an architect, Mr. Fuller proposed a construction looking like a polyhedron spheroid, which
could serve as a ceiling covering a big area, and as a mathematician, Mr. Fuller applied a systematic
approach for an analysis of structures with different origins and demonstrated that a structure is a self-
stabilizing system. However, to tell the truth, this form already existed among the semi-regular forms of
Archimedes. In addition, a figure of wooden model of such form, which was fabricated by Leonardo da
Vinci, was saved, and Leonhard Euler derived a formula, which allowed a calculation of polygon number
for various surfaces.

A fullerene is the fourth allotropic form of carbon (the former three are a diamond, a graphite, and a
carbide). Further, for a good accuracy, we shall call the solid phase C60 like a fullerene, and an individual
molecule C60 like a fullerene molecule. The molecule C60 contains fragments with a five-fold symmetry
(pentagons), which are forbidden for a non-organic molecule in nature. In this connection, we have to agree
that the fullerene molecule is an organic matter, and the fullerene itself represents a molecular crystal
serving as a joining element between an organic and a non-organic matter.

One should note that a discovery of fullerene has its own history: an assumption that the high-symmetry carbon
molecule resembling a football existed, for the first time, was predicted by Japanese scientists E. Osawa and Z.
Yoshida in 1970. Later, Russian scientists D.A.Bochvar and E.G.Galperin performed a first theoretical
quantum-chemical calculation for this molecule and proved its stability. In 1985, English scientists Walter
Kroto with colleagues [4] synthesized the C60 molecule. For this purpose, a solid graphite target was subjected
to a powerful laser radiation. As a result, a chaotic plasma of 5000 to 10 000oC temperature was formed. In this
plasma, the molecule C60 was synthesized and identified using a mass-spectrometry device, which allowed
atoms and molecules to be sorted according to their mass. The formation of fullerene molecule from the plasma
represents an excellent example of how to organize a structure ordering from a chaos, that now, it is one of the
most interesting and thrilling fields in a modern science! As we have already mentioned, the molecules C60 are
ordered in a space under definite conditions and arrange inside a narrow crystal lattice, or, as they say, the
fullerene forms a crystal. In order that the C60 molecules were regularly arranged in the space, they must be
bound to each other like a molecule atom. Binds between the fullerene molecules are weak. They are called
Van der Waals’ binds in an honor of Holland scientist.

The fullerene is known by an unusual crystallographic symmetry and unique properties [5]. All its covalent
bonds are saturated, therefore, an individual molecule can interact with another one only due to a weak Van
der Waals force. These bonds arise because a negative electron charge and a positive nucleus charge of
electrically neutral molecule are spatially separated. As a result, the molecules polarize each other, i.e. shift
a center of positive and negative charge in a space and induce their interaction. This interaction is sufficient
to form a crystalline structure of spherical molecules. Such material is called a fullerite. A stable molecule
is characterized by a chain configuration, which is formed by a five-and six-member ring.

In most cases, their carbon atom has three spatial bonds (similar to a diamond lattice). A length and an
angle of these bonds are also similar to the diamond structure.

Later, it was revealed that a natural fullerene also exists. In 1992, the fullerene was found in a natural carbon
mineral schungite (the mineral was named after a small village Schunga in Karelia Region, Russia). To tell the
truth, an amount of fullerene content in the schungite is low, it does not exceed 10 to 3 %. In 1993, another
multi-atomic molecule and a carbon microparticle C70 (a nanotube, a nest-doll, a bulb) were found in
schungites.

A classic way to fabricate a fullerene is an vaporization of carbon in a vacuum resulting in an overheating

of carbon vapor to 104 K [6]. This overheated vapor is intensively cooled in a jet of inert gas (for example, a
Fulerene, Fulerite and Nanotubes Nanocoatings Nanosystems Nanotechnologies 33

helium). As a result, a powder with a significant amount of two groups of clusters (molecules) (of a small
size with an odd number of carbon atoms (to C25) and of a big size with an even number of carbon atoms
(C60 and C70)) is deposited. They can be separated using methods applied in a powder metallurgy.
Moreover, clusters referring to the first group are unstable. A formation of molecules with a high amount of
atoms (C100 and more) is also possible by a selection of process parameters. There is a number of other
methods of fullerene fabrication [7, 32-34].

Today, people are able to fabricate a doped fullerene by doping different atoms and molecules to their
molecules including an introduction of doping element atoms into an inside molecule volume. Two
fullerene molecules can be joined into a dimer or an initial monomer structure can be subjected to a
polymerization due to an action of high pressure or laser irradiation. A method of vacuum thermal
deposition of a blend of desired composition to a substrate, for example GaAs (Fig. 3), is employed to
fabricate a thin composite film of 200 to 600 nm thickness based on a fullerene matrix [8, 24-27, 35]. A
blend of C60 powder of 99.98 % purity and CdTe was prepared by their simultaneous comminuting to 1µm
size and sintering at 300oC temperature.

Figure 3: A surface of “fullerene C60 40%CdTe” film [8].

The deposition was performed in a vacuum of 10-6 Torr pressure and at about 160 oC substrate temperature.
A resulting film did not have a notable spatial non-uniformity of chemical composition.

A very high fullerene hardness successfully employed for a fabrication of fullerite micro-and nanotools,
which are applied for a treatment and a testing of superhard materials including a diamond. For example, a
fullerite pyramid made of C60 can be applied in an atomic force microscope for diamond and diamond film
hardness measurements. The fullerene is a promising material for an electronics and an optics [9]. The
fullerene and the compound based on it have also a high potential for a nanostructure formation. A
fullerene film may be applied tofabrication a two-dimension photon crystal. Optical properties of fullerene
films may be changed by a semiconductor material doping, for example, CdSe and CdTe [8].

In 1991, a report of scientists from the Bell Laboratory (USA) attracted a great interest. They reported that
a potassium-doped fullerene was a superconductor and a temperature of its transition to about to a
superconducting state was 18K [3]. Later, it was found that a fullerite, which was formed on the base of
other alkaline (excluding a sodium) and alkaline-earth metal, was also a superconductor. A maximum
transition temperature turned to be 42K, i.e. a certain fraction of metallic fullerenes turned out to be a high-
temperature semiconductor. In 1994, the authors of works dealing with an identification of superconducting
carbon-containing phase, which was found in a schungite, discovered a metallic fullerene CunC60. Its
transition temperature was higher than that of a liquid nitrogen.

Another interesting property of the doped fullerene is a ferromagnetism discovered in 1991 [10]. That time,
a soft organic ferromagnetic material C60-TDAE was fabricated (TDAE was a tetradimethylaminoethylene
with a Courier point TC = 16 K). In 1992, a ferromagnetic with TC = 30 K based on a fullerene doped by an
iodine and a bromine was formed [10-14].
Exploring the Variety of Random
Documents with Different Content
not want to be ordered about by kana ipu o Laamaomao a lawe
anyone. In this departure of pu ae la i kana hoe, o
Pakaa he took with him the Lapakahoe. Ua kapa ia kana
kapas, malos and all the hoe i kona kaikaina ia
personal effects of Lapakahoe.
Keawenuiaumi and placed them
within his calabash,
Laamaomao. He [74]also took
with him his paddle, called
Lapakahoe, so named in honor
of his younger brother,
Lapakahoe.

When Pakaa was about to leave, Olelo aku o Pakaa i kona

he said to his younger brother, kaikaina ia Lapakahoe: “E noho
who was a chief in possession alii ana no kekahi mau aina o
over certain lands in the district Hilo, ua hoowahawaha ka haku
of Hilo: “Our master somehow is o kaua ia’u, ua lawe aku i na
displeased with me and has pono a pau loa, a koe no he mau
taken back everything I once aina, mahope paha pau loa,
owned, leaving me only a few nolaila, a i pau kou noho aina
pieces of land, which I suppose ana, noho a kanaka aku no
he will take away by and by. malalo o ka haku o kaua.
Since I am going away I want Nolaila, ke hele nei au, aole i
you to live on your lands; but be akaka ko’u wahi e noho ai.”
faithful to our master. I am going
away now, but am not certain
where I shall locate.”

With these words, he boarded Kau aku la o Pakaa ma ka waa a

his canoe and set out, going by holo mai la, a hala o Maui a me
way of Lele, Maui; then on until Lele, a hiki i Molokai, ma ka huli
he came to Molokai; on the Kona ma Kona, e nana ala ia Lanai,
side of that island, overlooking noho iho la o Pakaa ilaila, a moe
Lanai, where Pakaa made his i ke ’lii wahine o ia aina, a hapai
home, and took unto himself a ke keiki, a hanau, kapa iho la o
wife, a chiefess, belonging to the Pakaa i ka inoa, o Kuapakaa.
land. In time his wife bore him a Eia ke ano o ia inoa, o ke
boy and he gave the child the akaakaa mahuna, o ka ili o
name of Kuapakaa. 4 The Keawenuiaumi i ka awa, a waiho
meaning of the name is this: “the wale mai ka io me he pakaa la.
cracked skin,” given because the
skin of Keawenuiaumi was
cracked by the constant use of
the awa, so much so that the
flesh was exposed in places.

After Kuapakaa had grown up to A loaa ia Kuapakaa ka olelo,

the age when he could talk and olelo aku o Pakaa: “E ao kaua ia
think, Pakaa said to him: “I want oe i ke mele o ko haku, a me na
to teach you the meles relating mea a pau loa, malama o noho a
to your master and also the aloha imi mai, e noho aku ana
general knowledge of all things; oe me ka makaukau.” Aole i loihi
for it is possible that in time he na la o laua i ao ai, ua pau loa i
will miss me and will come to ka loaa ia Kuapakaa, a ua lilo ia i
make a search; if he does I want mea wale waha ia ia i na la a
you to be in a position of pau loa.
readiness to meet him.” The
course of instruction did not take
many days, for Kuapakaa was a
bright boy and everything was
mastered in a way that gave him
a thorough knowledge of the
different subjects.

A short time after this a canoe Mahope o laila, pae mai la

came in from Hilo and word was kekahi waa mai Hilo mai, a olelo
brought that Keawenuiaumi was mai la i ke aloha o
beginning to feel keenly the loss Keawenuiaumi ia Pakaa, aole
of Pakaa. Pakaa during the nae ia i olelo i kona inoa i ua
recital of this piece of news did waa ala.
not tell the Hilo man that he was
Pakaa himself.

After the information had been A mahope o keia lohe ana, moe
imparted to Pakaa he dreamed a iho la o Pakaa i ka moe uhane, a
dream in which his spirit met the ma ka uhane, ua loaa ko
spirit of Keawenuiaumi. In this Keawenuiaumi uhane ia Pakaa. I
meeting the spirit of mai la o Keawenuiaumi: “Eia au
Keawenuiaumi said to his spirit: a huli aku ia oe.” I aku o Pakaa:
“I am coming in search of you.” “Aia au i Kaula kahi i noho ai.”
The spirit of Pakaa answered: “I Hikilele o Keawenuiaumi, a olelo
am living on Kaula.” 5 i na ’lii eono o Hawaii, e
Keawenuiaumi also dreamed the makaukau na waa a me na
same dream and on receiving kanaka, alaila, imi ia Pakaa, no
the reply from Pakaa, jumped ka hemahema o Hookeleihilo ma
out of his bed and immediately na hana a pau loa.
requested of the six district
chiefs of Hawaii to get their
canoes ready and to summon
their attendants; for he wished
them to accompany him in his
search for Pakaa, for he had at
last realized the utter lack of
knowledge, in most cases of
Hookeleihilo and Hookeleipuna, 6
the men that took the place of
Pakaa.
Pakaa awoke from his sleep and Ala ae la no hoi o Pakaa, a olelo
said to his son: “Let us go to the i ke keiki, e pii e mahiai; ae mai
uplands and do our farm work.” la ke keiki. Ma keia pii ana a
The boy consented and the two laua, eono mala, he uwala ka ai,
started up. Their fields were six ua hoohalike ia me na moku
in number and the food planted eono o Hawaii. [77]
was sweet potatoes. Each field
was shaped after each of the six
districts of Hawaii. [76]

When the preparations were A makaukau o Keawenuiaumi e

finally completed and holo mai, loaa hou ia Pakaa ma
Keawenuiaumi was ready to ka moeuhane ko Keawenuiaumi
make the start, Pakaa again uhane, I mai o Keawenuiaumi:
dreamed a dream wherein his “Aia a na la o Ku, holo aku au e
spirit again met the spirit of imi ia oe.” Hikilele ae la o Pakaa,
Keawenuiaumi, which said to a olelo aku la i ke keiki: “E pii
him: “In the days of Ku, 7 I will set kaua i uka i lau hawane” (oia ka
out on my search for you.” loulu). Ua nui loa ko laua amo
Pakaa awoke with a start and ana i ka lau hawane, i mea
said to his son: “Let us go to the malumalu ua, ke hiki i na ku, ua
uplands for palm leaves.” With piha kekahi hale o laua.
this the two proceeded to the
uplands and cut down a large
number of palm leaves and
much time was spent by them in
bringing the leaves to the beach
and a whole house was filled
with them. The leaves were to be
used in the rainy days of Ku.

In the Ku days, Pakaa and his A hiki i na ku, holo aku la laua i
son boarded their canoe and set ka moana e kali ai i na waa o
out to sea to await the coming of Keawenuiaumi. Mamua o Pakaa
Keawenuiaumi. Pakaa sat in the o ko laua waa, mahope ke keiki,
front seat of their canoe, while he lawaia uhu ka Pakaa lawaia,
the boy took the hind seat. The manao ia, o kona wahi ia e nalo
two took up uhu 8 fishing as the ai, no ka mea, he lawaia kulou i
kind to be engaged in, Pakaa lalo ka uhu. A ua lawe pu no hoi
thinking this the best kind of laua ia Laamaomao i kai, ma
fishing in order to prevent him keia holo ana, a hiki laua, puka
from being discovered, for one ana na waa. [78]
has to keep on looking down
when fishing for uhu. On this trip
they took the wind calabash,
Laamaomao. As soon as they
arrived out at sea the canoes in
the advance of the expedition
were seen to be approaching.
[73]

1 Keawenuiaumi, one of the sons of

King Umi, by Kapukini, his wife. ↑
2 Kanoa was the name of the bowl or
receptacle for the preparation of awa
at the chewing and straining process,
ready for distribution by the cups. ↑
3 Laamaomao, the Hawaiian Æolus,
or god of the winds. ↑
4 Ku-a-Pakaa, Ku the son of Pakaa
becomes the leading character in
the story and life of his father, as in the
case of Aiai-a-Kuula, and other
Hawaiian stories. ↑
5 Kaula is the small islet to the
southwest of Kauai, the most distant
of the group proper. ↑
6 The names of these successors to
Pakaa may be significant of their
scheming characters, Hookele meaning
a steerer; a director of a vessel’s
course; one, Hookeleihilo being toward
Hilo and the other Hookeleipuna being
toward Puna, as if, possibly, to wean
the king from his natural leanings
toward Kona, his birthplace, as it was
that of Pakaa also. ↑
7 The Ku days of the month were from
the third to the sixth day, inclusive, of
the moon, though the days in which the
Ku kapu prevailed were the first three
of the moon. ↑
8 Uhu, parrot-fish (Calotomus
sandwichensis). ↑

[Contents]

Legend of Kuapakaa. He Kaao no Kuapakaa.

CHAPTER I. MOKUNA I.
 Kuapakaa Prepares to Meet Hoomakaukau o Kuapakaa e Hui
Keawenuiaumi in Search of me Keawenuiaumi.—Na Auwaa o
Pakaa.—Canoe Fleet of Six na Alii Aimoku Eono, Ike ia e
District Chiefs, Recognized by Pakaa a Leoleowa ia e Kuapakaa
Pakaa, Are Taunted by Kuapakaa i ko Lakou Kaalo ana ae.—Lohe
as They Pass.—Keawenuiaumi o Keawenuiaumi i ke Mele o ke
Greeted with a Chant and Ola, Kono ia Oia e Pae.—No ka
Warned of Coming Storm Is Olelo a’o a na Hookele, Holo
Invited to Land.—On Advice of loa Ke ’lii.
the Sailing Masters the King
Sails on.

Kuapakaa was the own son of Oia no ka Pakaa keiki ponoi, i

Pakaa, born to him while living in loaa ia ia ma ka noho ana i
Molokai, of his wife, a high Molokai, me kana wahine alii, a
chiefess. The name of Kuapakaa ua hoopili ia no hoi kona inoa me
was given to the boy after the ko ka makuakane, a ua ao aku
father. As the boy grew up the no hoi kona makuakane iaia ma
father educated him in all the ke ano o na mea o ke ’lii, a me
things pertaining to the office of na mea e pili ana ia ia. A
an immediate servant under the makaukau o Kuapakaa i keia
king; and also in the different mau mea, holo laua i kai e kali i
branches of learning of those ka holo mai o Keawenuiaumi e
days until his education was imi ia Pakaa. Ma keia holo ana,
complete. After Kuapakaa had o ka hoe a Pakaa o Lapakahoe,
been educated in these things, ia Kuapakaa ia mahope o ko
they went to the shore to await laua waa, mamua o Pakaa, e
the coming of Keawenuiaumi in lawaia kaka-uhu ana, me ke kuu
his search of Pakaa. o ka lauoho i lalo e loloa ai. A
lana mua laua i kai, mahope hiki
In the trip out [to meet na waa, ka waa elua kanaka, ka
Keawenuiaumi], Pakaa’s paddle, waa ekolu kanaka, a pela aku,
Lapakahoe, 1 was taken by na waa aipuupuu, na waa pu
Kuapakaa, who took the
important seat, the one in the kaua, na waa o ka wahine, na
stern, while Pakaa took the front waa o na koa.
seat. When they saw the canoes
coming, Pakaa kept his eyes
down, making believe that he
was looking for uhu, 2 with his
long hair let down over his eyes.
They were in this position when
the canoes came along; some
with two men, some with three
men and so on; some bearing
the food and stewards, some the
commanding officers, some the
women and some the warriors.

When the canoes were Ninau aku o Kuapakaa i ka

approaching them, Kuapakaa makuakane ia Pakaa: “Auhea ka
asked of his father, Pakaa: waa o kuu haku?” I mai o Pakaa:
“Where is the canoe containing “Aia a o ke kukuna o ka la, holo
my master?” Pakaa replied: mai ka waa o ko haku. Eia ke
“When the rays of the sun make ano o kona waa. Ua aki ia ka
their appearance, then the canoe pea ma waena, i mea e
bearing your master will come. maopopo ai kona akua, ke ku
The signs by which you will know mai, o Kaili ka inoa, a he lumi
his canoe are these: The sail is kiekie mamua, a mawaena,
doubled down, so that his god malaila ko haku, a mahope na
could be seen, Kaili 3 by name, hookele.”
standing at its place. You will
also see a high compartment in
front in the middle of the raised
platform; there your master sits;
the sailing masters are directly
behind him.”
While the two were conversing, Ia laua e kamailio ana, holo mai
the canoe of Keawenuiaumi was ana ka waa o Keawenuiaumi,
seen approaching with its sides hinuhinu ana na aoao o ka waa i
glittering, being struck by the ka loaa i ke kukuna o ka la, a
sun’s rays while the paddles of lilelile ana ka hoe a na hoewaa i
the rowers were bathed in light. ka la. I aku la ia i kona
When Kuapakaa saw the signs makuakane: “Eia kuu haku.” “Aia
as described by his father, he mahea?” “Aia ma waho o kaua.”
said: “Here comes my master.” I aku o Pakaa: “Oku ia ko hoe i
“Whereabouts?” “On the outside luna.” Ia oku ana o ka hoe, ike
of us.” Pakaa said, “Hold up your mai la o Lapakahoe, e ku ana i
paddle.” 4 When this was done, luna o na waa o ke ’lii, hai ae la
Lapakahoe who was standing up ia i ke ’lii: “E! He wahi waa uuku
in the king’s canoe saw it and so hoi keia e lana mai nei maloko o
reported to the king, saying: kakou, eia la ke oku mai nei i ka
“Say, there is a small canoe hoe.” Olelo aku la o
floating there inside of us; some Keawenuiaumi i na hookele:
one is holding up a paddle.” “Kau pono ae olua i ka ihu o na
Keawenuiaumi then said to the waa i kela wahi waa, malama he
sailing masters: “Point the bow olelo [81]kana.” O ke kumu o ke
of the canoe for the small canoe; ’lii i olelo ai pela, no ka maa ia
possibly it has [80]a word for us.” Pakaa, ia Pakaa e noho ana me
The reason why the king said ke ’lii, aole e haalele ka waa o ke
this was because while Pakaa ’lii i ka waa e oku mai ana i ka
had command of his canoe, it hoe, nolaila, ua maa ke ’lii. A
was his custom to make a call on kokoke loa ka waa o ke ’lii ia
any canoe that made signals of laua, ninau aku o Pakaa i ke
this kind; hence the king being keiki: “Auhea ka waa o ko
accustomed with this, ordered haku?” I mai ke keiki: “Eia la ua
that the canoe be directed for the kokoke.” “Kahea ia ka hana o ko
small one. When the king’s haku,” pela mai o Pakaa. Alaila,
canoe drew near, Pakaa asked kahea o Kuapakaa:
of his son: “Where is the canoe
of your master?” The boy
replied: “It is here near us.”
“Then question your master as to
his reason of being here,” said
Pakaa. Kuapakaa then called
out:

Hold back there! Hold back! Kipu la, kipu!

Be still there! Be still! Hoolai la, hoolai!
Be calm there! Be calm! Hoopohu la, hoopohu!
Gently there! Gently! Hoomalino la, hoomalino!
The query, the question, whose Ouiu, o ninau, nowai he waa?
the canoe?

“To Keawenuiaumi belongs the “No Keawenuiaumi he waa.”

canoe.” The boy again asked: “A Ninau aku ke keiki: “He waa e
canoe and where is it going to?” holo ana i hea?” “He waa e holo
“It is a canoe going in search of ana e imi ia Pakaa.” “Imi ia
Pakaa.” “Search for Pakaa, what Pakaa, heaha o Pakaa?” “He
is Pakaa?” “A servant.” At this kauwa.” I aku o Kuapakaa i kona
Kuapakaa turned and said to his makuakane, ia Pakaa: “Ka i no
father: “I thought you were a he ’lii oe, he kauwa ka oe.
chief. I see that you are a Heaha la, he kauwa no oe, a he
servant. Well, what of that any ’lii no wau ma ka aoao o ko’u
way? Supposing you are a makuahine, nolaila, alii no ko’u
servant. I am a chief on my noho ana ia Molokai nei.” I aku o
mother’s side and shall continue Pakaa i ke keiki, ninau ia aku:
to be so as long as I live in “He kauwa io?” Nolaila, ninau o
Molokai.” Pakaa said to the boy: Kuapakaa: “He kauwa io.” “Aole
“Ask them again if he is a real he kauwa io; he iwi kuamoo, he
servant.” Kuapakaa therefore paa kahili, he lawe ipu kakele.”
asked: “Is he a real servant?” Maopopo ma keia olelo, he
“No, he is not a real servant, but kaukau alii kona makuakane o
a backbone, 5 a holder of the Pakaa, i aku ia ia Pakaa: “O kou
kahili and bearer of the king’s wahi alii auanei, o ko kuu
calabash of ointment.” 6 By this makuahine, alii no ko’u noho ana
answer the boy was satisfied ia Molokai nei.”
that his father was, after all, of
chiefly grade; so he said to his
father: “Your rank as a chief and
my mother’s position as a
chiefess, make me a chief of
some importance and I shall live
as such, here in Molokai.”

The chiefs under Keawenuiaumi, No na ’lii malalo o

they being the six district chiefs, Keawenuiaumi, oia na ’lii aimoku
were the first to come by. Before o Hawaii, eono moku, eono alii.
Kuapakaa spoke to the canoe of Mamua ae o ke kamailio ana o
Keawenuiaumi, he first called Kuapakaa me ka waa o
each of the six chiefs by name, Keawenuiaumi, oia ka wa i hea
in their order, for Pakaa had pakahi ia ai na inoa o na ’lii, e
already instructed his son in like me ko lakou noho ana, a ua
everything pertaining to them. ao no hoi o Pakaa ia mea i kana
keiki. I ka wa i hiki mai ai ka mua
Wahilani’s was the first canoe, it o na waa, hoomaka ia e ninau i
being a beautifully made double kona makuakane. O Wahilani ka
one; Kuapakaa asked his father waa mua. Hiki ana he kaulua
as to its owner. The father maikai, ninau aku o Kuapakaa:
answered: “That is the canoe of “No wai keia waa?” “No
Wahilani, the district chief of Wahilani, oia ke ’lii o Kohala.” Ia
Kohala.” Kuapakaa then manawa, oli aku la o Kuapakaa:
chanted: 7

He is our chief of Kohala, O ua alii o makou o Kohala, o

Wahilani. Wahilani.
He is not a chief by birth, he is a Aole no hoi he ’lii, he kaukau alii
petty chief, no,
One who played hide and seek He peepee puko no Kohala,
in the sugar cane hills of Kohala. Ka ia o ia aina, he unihi,
The fish of that land are the I ka lau o ke ko, i ka pua o ka
grasshoppers, mauu.
On the leaf of the sugar cane, on He aina ia ole,
the grass blade. O ka uala ka ai,
It is a land without fish, O ke kee ia o ia aina,
And the food is the sweet potato, Aole no hoi o Wahilani he ’lii;
That is the fault found against O ka ai ana ia Kohala,
the land. Olelo ia he ’lii.
Wahilani is not a chief; [83]
Being a ruler of Kohala,
He has been called a chief.
[82]

By these words of the boy, Ma keia olelo a ke keiki, huhu o

Wahilani was made very angry Wahilani, a olelo aku la: “I nahea
and so he made reply: “When kou ike ana, e na keiki
did you ever know that, you hoopunipuni?” Nolaila holo o
deceitful boy?” With this Wahilani Wahilani.
set off.

The second canoe was Ehu’s. O Ehu ka waa alua. Hoea hou
Another beautiful double canoe he waa kaulua maikai, o Ehu ia,
came along, the one belonging o ke ’lii o Kona. Ninau aku o
to Ehu, the chief of Kona. On the Kuapakaa i ka makuakane: “No
approach of this canoe, wai keia waa?” “No Ehu ke ’lii o
Kuapakaa asked of his father: Kona.” Ia manawa, oli aku la no
“Whose canoe is that?” “It is the o Kuapakaa:
canoe of Ehu, the chief of Kona.”
Kuapakaa then chanted out:

Our chief of Kona, Ehu, is not a O ua ’lii o makou o Kona, o Ehu,

chief by birth; aohe alii;
But as Keawenuiaumi went and O ka hele ana aku o
lived in Kiholo, Keawenuiaumi a noho i Kiholo,
Ehu came down from the Iho mai o Ehu me na kiki uala,
uplands with bundles of A haawi i ke ’lii.
potatoes, Lilo o Ehu i keiki hookama,
And gave them to the king. Haawi o Keawenuiaumi ia Kona
Ehu then became an adopted nona,
son, Nolaila, alii o Ehu.
And Keawenuiaumi gave him
Kona,
Therefore Ehu became a chief.

Because of this chant of Ma keia olelo a Kuapakaa huhu

Kuapakaa, Ehu became angry loa o Ehu, a olelo aku la: “He oi
and said: “You are the most oe o ke keiki hoopunipuni; i hea
conceited boy I know of. Where kou ike ana i ko makou ano?”
did you ever know of me?” With Holo aku ia me ka huhu.
this he sailed off in a rage.

The third canoe was Huaa’s. As O Huaa ka waa akolu. Hoea hou
this canoe approached mai la he waa. Ninau o
Kuapakaa asked of his father: Kuapakaa i ka makuakane:
“Whose canoe is this?” “It is the “Owai keia waa?” “O Huaa, o ke
canoe of Huaa, the chief of Kau.” ’lii o Kau.” Oli mai la o
Kuapakaa then chanted as Kuapakaa:
follows:

Our chief of Kau, Huaa, O ua ’lii o makou o Kau, o Huaa,

He is not a chief [by birth], but a Aohe alii, he kaukau alii no.
petty chief. He kaka lau ilima no Kamaoa,
He is a beater of the ilima of Ka wai auau no ia o ia aina,
Kamaoa; A o ko laila kee no ia,
By this way the people of that Ua noho au i laila a ike.
land get water to wash in,
And it is the main fault of that
land
For I have lived there and know.

This angered Huaa and he too Huhu o Huaa a holo aku la.
sailed off.

The fourth was the canoe of O Hikinaakala ka waa aha. Hoea

Hikinaakala. Another canoe hou mai la he waa hou, ninau no
approached, and the boy asked keia ia Pakaa, hai mai la no, o
of Pakaa, and was told that it ke ’lii o Puna, o Hikinaakala. Oli
was the chief of Puna, mai la o Kuapakaa:
Hikinaakala. 8 Kuapakaa then
chanted:

Our chief of Puna, Hikinaakala, O ua ’lii o makou o Puna, o

is not a chief [by birth]; Hikinaakala, aohe alii,
He is like the prickly edges of the He makakokala, lauhahala ooi;
hala leaf; O ka ai ana ia Puna,
But since he became possessed Olelo ia ai he alii,
of Puna, Aohe alii.
He is said to be a chief.
He is not a chief.

This angered Hikinaakala and he Huhu o Hikinaakala a holo aku

sailed away. la.

The fifth canoe was that of O Kulukulua ka waa alima. Hoea

Kulukulua. As it approached hou mai la he waa, ninau no o
Kuapakaa again inquired of his Kuapakaa i ka makuakane:
father: “Whose canoe is this?” “Owai keia waa?” “O Kulukulua,
“That is the canoe of Kulukulua, 9 ke ’lii o Hilo.” Oli mai la o
the chief of Hilo.” Kuapakaa then Kuapakaa: [85]
chanted as follows: [84]

Our chief of Hilo, Kulukulua, is O ua ’lii o makou o Hilo, o

not a chief [by birth]; Kulukulua, aohe alii;
He is a snarer of the shrimps of He pahelehele opae no
Waiakea; Waiakea;
After the snaring, A pau ke pahelehele ana,
He places the outside covering Kau ae la i ka pulu niu i ka
of the coconut on his ears. pepeiao.
This is the fault of the land; O ke kee no hoi ia o ia aina,
But since he became possessed O ka ai ana ia Hilo,
of Hilo, Olelo ia ai he ’lii.
He is called a chief.

This angered Kulukulua and he Huhu o Kulukulua a holo aku la.

sailed off.

The sixth was the canoe of O Wanua ka waa aono. Hoea

Wanua. Upon its approach the hou he waa, ninau no ia Pakaa,
boy asked of Pakaa as to its hai mai la no o Pakaa: “O
owner, and Pakaa replied: “It is Wanua, o ke ’lii o Hamakua.”
Wanua, the chief of Hamakua.”

Our chief of Hamakua, Wanua. O ua ’lii o makou o Hamakua, o

He is not a chief by birth; Wanua,
He is a snarer of the eels of Aole alii maoli;
Hamakua. He pahelehele puhi no
Hamakua,
The fingers with the bait are Waiho aku na manamana lima i
placed on the rocks, ka paala me ka maunu,
The small eels would then crawl Pii mai la ka puhi a komo i na
between the fingers manamana
And the eels placed in the Hoolei iho la i ka ipu.
calabash. O ka ai ana ia Hamakua,
But since he became possessed Olelo ia ai he ’lii; aohe alii.
of Hamakua
He is called a chief.
He is not a chief.

This chief also became angry Huhu ia alii a holo aku la.
and sailed off.

These chiefs all went on, and all Pau na ’lii i ka holo i mua, me ko
angry with the boy, because he lakou inaina i ke keiki, i ka hoole
had told them that they were not ia lakou aohe alii, a i ka hai i ke
chiefs by birth, and also for kee o ka aina.
telling the faults relating to their
respective districts.

(We will now take up the facts (Maanei e hoomaka ai ka olelo

relating to the canoe of no ka waa o Keawenuiaumi i
Keawenuiaumi, aforementioned, olelo mua ia ae nei: aka, no ka
which the narrator said should olelo mua ana mai o ka mea
be inserted later, and was malama kaao mahope o keia;
therefore out of place; care, nolaila, ua kau e ia na olelo no
however, should be taken in its Keawenuiaumi a me kona waa
perusal by which it may be mamua, aka, he pono no e
plainly seen that the six canoes noonoo i ka heluhelu ana, a
bearing the district chiefs were malaila e maopopo ai, he mua
the first to meet the canoe of na waa o na ’lii eono o Hawaii.)
Kuapakaa.)
It was Lapakahoe, 10 the younger O Lapakahoe ka mea nana i
brother of Pakaa, that replied to olelo mai no Keawenuiaumi ka
the question, that it was the waa; nolaila, paha aku ai o
canoe of Keawenuiaumi. At this Kuapakaa, penei:
reply Kuapakaa chanted as
follows: 11

When the canoe is pushed A nou ka waa,

ahead, Ua hiki ke kumu ino,
The cause of the storm is come. Ke kakai kepa, ua lauli elehiwa
Like a slanting cliff, dark and Ke poo o ka mauna o Aluli i ka
black ino,
Is the top of the Aluli mountain, Me he aahu eleele la i lohia
because of the storm, Ke aloalo pali o Kawaikapu,
Like black raiment that is worn I holoa e ka holopoopoo,
Is the face of the cliffs of Moku kihe o ka wai.
Kawaikapu. Pihapiha na mauna ke ike aku,
Running as though seeking Lele koha i ka lani,
every crevice Ka leo o ke kuaiwa lea,
Is the water that comes. Ka leo o ke kai uwe, [87]
The mountains appear to be E hoeu aku ana i ke kai awe,
filled, Ua like me ke ao i Kikiopua,
The sound is heard in the Ke ama lele aukai o Malelewaa.
heaven, Hoolewa ka ukana i ke kua,
The voice is echoed back, Pii Kua o Kaula mahope.
The voice of the weeping sea, Pali kui pali hono Wailau ma,
[86] Kui aku, hono aku ka pali,
Urging onward the rising sea. I luna o Pueohulunui,
Like the clouds at Kikiopua I ka pali pueo e lele la.
Is the flying and swimming
outrigger of Malelewaa.
The burden is swung to the
back,
Kaula looks as though climbing
from behind.
The cliffs of Wailau are joined
and plated one on top of another,
They are joined and plated,
On the top of Pueohulunui,
The cliffs where the owls fly.

Kuapakaa then chanted of the Alaila, paha hou o Kuapakaa no

storm: ka ino:

Gently! Gently! Gently! Kiauau! Kiauau! Kiauau!

Comes the rain, the wind, the Hiki ka ua, ka ino, ka makani,
storm, No Puulenalena, no Hilo,
From Puulenalena, from Hilo, No Hokukano, no Waiolomea,
From Hokukano, from No ka ina a ka hoe i ka eke,
Waiolomea, A ka noonoo, ka iliili,
From the raising of the paddle A kua iako i Kainaliu,
from under the buttock, A ka iako i ka hope,
At the thought, at the pebbles, A ka poho i na hookele.
At the cutting down of the iako, Eu mai ka lemu,
at Kainaliu, E pana na hoe,
The iako at the rear, Huki ka lana,
At the opening between the two Nana ia ka ale
sailing masters. O ka wili, o ke pani,
Get up from your seats, O ke kaa mai na o ka ale
Take out your paddles, Hue ma waho o ka waa;
Pull up the weight, Ke hoolulu la i ka ihu o ka waa
Watch for the waves la,
As they twist and rise, Hookaa ia ka waa ku maloko,
As the waves twist and beat O ka wai mawaho a hui me ka
On the outside of the canoe; puka,
Punahele kaele i ka olulo.
The wave is become quiet at the Eia hoi au, e ka make!
bow, A make oe i ka ale iki,
Swing the canoe around and let A make oe i ka ale nui,
the wave pass between, A make oe i ka ale loa,
The water on the outside meet at A make oe i ka ale poko,
the opening, O ka ukali o Kuloko,
The wave is a welcome thing to O ka hakui o ka nei,
a castaway. O ka opuu o ka lau loa,
But here I am, O death! O ka ale hue,
Death to you is the small wave, E hue mai auanei ka ale i ou
Death to you is the large wave, waa.
Death to you is the long wave, Make! no ka waa iki ka make,
Death to you is the short wave, Make ka waa nui.
The follower of Kuloku, Pua mai o na hoe,
The roaring, the trembling, O ka ukana ia a ka waa make;
The oopu, 12 the lauloa, 13 O ka hoe iki, o ka hoe nui,
The waves that open up, O ka hoe loa, o ka hoe poko; [89]
The waves that will perchance O ke ka iki, o ke ka nui,
open up my canoe. O ke ka loa, o ke ka poko,
It will swamp. Because of the O ke ka peekue, o ke ka lahilahi.
swamping of the small canoe, Pau ka hemahema o ka waa
The large canoe will also make,
swamp. Manao hoolana ka waa.
Bind the paddles together, O kela lona o keia lona,
For they will be the only burden Ume kela kaula ume keia kaula;
of a swamped canoe; Holo kela kini holo keia kini,
The small paddle, the large Ku ka nalu nui,
paddle, Popoi ka nalu iki,
The long paddle, the short Lele na laau ihu,
paddle; [88] Lele na laau hope.
The small bailing cup, the large Kai ka pili a ke kahuna,
bailing cup, Ke paa kuleana ole o ka la
make,
The long bailing cup, the short Wehe ke kai anu ka lia,
bailing cup, Pulu ka uku, kela mea i koki.
The coarse bailing cup, the thin Alina oukou e na hookele,
bailing cup. A me ke kilo, ke kahuna,
After rescuing the several things E ike ai e na hookele i ka hoku
from the swamped canoe, la,
Comes the thought to refloat the I na la ua pae i uka.
canoe.
That block of wood, this block of
wood [the waves],
That rope is drawn, this rope is
drawn;
Some will rush there, some will
rush here,
The large wave will rise,
The small wave will break,
The sticks at the bow will fly off,
The sticks at the stern will fly off.
The priest is at last separated
[from the king],
The connection is become of no
value, on a day of peril,
The sea separates them, the
cold is intense,
The uku is softened, that snub-
nosed thing,
Your reputation, ye sailing
masters,
Ye prophet and priest, is injured.
Had the sailing masters seen the
star
You would have reached land.