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 Guarrotxena
Research Methodology in Physics and Chemistry of Surfaces and Interfaces

Guarrotxena
This book covers a selection of recent research studies and new developments in the physics and chemistry
of surfaces and interfaces. It brings together research contributions from eminent experts in the field from
Research Methodology in
Physics and Chemistry
both academic and industry, providing the latest developments in advanced materials chemical domains.

The book:

Physics and Chemistry of Surfaces and Interfaces

• features classical topics that are conventionally considered as part of physical chemistry
• covers the physical chemistry principles from a modern point of view

of Surfaces and Interfaces

• focuses on topics with more advanced methods

Physics and Chemistry of Surfaces and Interfaces

• emphasizes precise mathematical development and actual experimental details

ABOUT THE EDITOR

Nekane Guarrotxena, PhD, is Head of the Division in the Institute of Polymer Science and Technology in

Research Methodology in
Madrid, Spanish National Research Council, Spain. She is a well-known scientist in the field of organic
chemistry, chemistry and physics of polymers, and composites and nanocomposites. She has published 10
books and volumes and about 500 original papers and reviews. She was the Vice-Director of the Institute
of Polymer Sciences and Technology from 2001-2005. From 2008-2011, she was a visiting professor in the

esearch Methodology in
Department of Chemistry, Biochemistry and Materials at the University of California, Santa Barbara, and
the Center for Chemistry at the Space-Time Limit (CaSTL) at the University of California, Irvine. She is an
editorial board member of the Polymer Research Journal and ISRN Journal. Her research interests focus on
the synthesis and assembly of hybrid nanomaterials, nanoplasmonics, and their uses in nanobiotechnology
applications, such as bioimaging, drug delivery, therapy, and biosensing. Editor
Reviewers and Advisory Board Members:
A. Pourhashemi, PhD, A. K. Haghi , PhD, and Gennady E. Zaikov, DSc
Nekane Guarrotxena, PhD

ISBN: 978-1-77188-011-4
90000

www.appleacademicpress.com 9 781771 880114

RESEARCH METHODOLOGY IN
PHYSICS AND CHEMISTRY OF
SURFACES AND INTERFACES
This page intentionally left blank
RESEARCH METHODOLOGY IN
PHYSICS AND CHEMISTRY OF
SURFACES AND INTERFACES

Edited by
Nekane Guarrotxena, PhD

A. Pourhashemi, PhD, Gennady E. Zaikov, DSc,

and A. K. Haghi, PhD
Reviewers and Advisory Board Members

Apple Academic Press

TORONTO NEW JERSEY
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ABOUT THE EDITOR

Nekane Guarrotxena, PhD

Nekane Guarrotxena, PhD, is Head of the Division in the Institute of Poly-
mer Science and Technology in Madrid, Spanish National Research Council,
Spain. She is a well-known scientist in the field of organic chemistry, chem-
istry and physics of polymers, and composites and nanocomposites. She has
published 10 books and volumes and about 500 original papers and reviews.
She was the Vice-Director of the Institute of Polymer Sciences and Technol-
ogy from 2001 through 2005. From 2008 through 2011, she was a visiting
professor in the Department of Chemistry, Biochemistry and Materials at the
University of California, Santa Barbara, and the Center for Chemistry at the
Space-Time Limit (CaSTL) at the University of California, Irvine. She is an
editorial board member of the Polymer Research Journal and ISRN journals.
Her research interests focus on the synthesis and assembly of hybrid nano-
materials, nanoplasmonics, and their uses in nanobiotechnology applications,
such as bioimaging, drug delivery, therapy, and biosensing.
This page intentionally left blank
REVIEWERS AND ADVISORY BOARD
MEMBERS

A. Pourhashemi, PhD
Dr. Ali Pourhashemi is Professor of chemical and biochemical engineering
at Christian Brothers University in Memphis, Tennessee. He was formerly
an Associate Professor and Department Chair there and also taught at How-
ard University in Washington, DC. He is a member of several professional
organizations on the international editorial review board of the International
Journal of Chemoinformatics and Chemical Engineering, and has published
many articles and presented at many professional conferences.

Gennady E. Zaikov, DSc

Gennady E. Zaikov, DSc, is Head of the Polymer Division at the N. M. Eman-
uel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow,
Russia, and Professor at Moscow State Academy of Fine Chemical Technol-
ogy, Russia, as well as Professor at Kazan National Research Technologi-
cal University, Kazan, Russia. He is also a prolific author, researcher, and
lecturer. He has received several awards for his work, including the Russian
Federation Scholarship for Outstanding Scientists. He has been a member of
many professional organizations and on the editorial boards of many interna-
tional science journals.

A. K. Haghi, PhD
A. K. Haghi, PhD, holds a BSc in urban and environmental engineering from
University of North Carolina (USA); a MSc in mechanical engineering from
North Carolina A&T State University (USA); an DEA in applied mechan-
ics, acoustics and materials from Université de Technologie de Compiègne
(France); and a PhD in engineering sciences from Université de Franche-
Comté (France). He is the author and editor of 65 books and 1000 published
papers in various journals and conference proceedings. Dr. Haghi has re-
ceived several grants, consulted for a number of major corporations, and is
a frequent speaker to national and international audiences. Since 1983, he
viii Reviewers and Advisory Board Members

served as a professor at several universities. He is currently Editor-in-Chief

of the International Journal of Chemoinformatics and Chemical Engineering
and Polymers Research Journal and on the editorial boards of many interna-
tional journals. He is a member of the Canadian Research and Development
Center of Sciences and Cultures (CRDCSC), Montreal, Quebec, Canada.
CONTENTS

List of Contributors............................................................................... xi
List of Abbreviations ...........................................................................xiii
List of Symbols...................................................................................... xv
Preface................................................................................................ xvii
1. Highly Filled Composite Materials with Regulated Physical and
Mechanical Properties Based on Synthetic Polymers and Organic
and Inorganic Fillers................................................................................... 1
O. A. Legonkova, A. A. Popov, A. A. Bokarev, and S. G. Karpova

2. Prediction of Photoelectrochemical Properties of Selected Molecules

by their Structure....................................................................................... 11
V. A. Ilatovsky, G. V. Sinko, G. A. Ptitsyn, and G. G. Komissarov

3. Poly(Ethylene-co-Vinyl Acetate) Composites in Nanoscale: Research

Methodology and Developments............................................................... 39
Dhorali Gnanasekaran1, Pedro H. Massinga Jr, and Walter W. Focke

4. Pore Structure of Poly(2-Hydroxyethyl Methacrylate) Scaffolds......... 79

D. Horák and H. Hlídková

5. Progress on Application of Fire-Retardant Coatings Based on

Perchlorovinyl Resin................................................................................ 101
G. E. Zaikov

6. The Dependencies of Dissociation Energy of Binary Molecules and

Formation Enthalpies of Single-Atom Gases on Initial
Spatial-Energy Characteristics of Free Atoms...................................... 113
G. А. Коrablev, N. G. Korableva, and G. Е. Zaikov

7. Nanohydrodynamics and Liquid–Solid Interfaces:

A Comprehensive Review........................................................................ 135
A. K. Haghi, A. Pourhashemi, and G. E. Zaikov

8. Correlation Between the Conductive Properties of Poly(Methyl

Methacrylate) and Its Microstructure................................................... 239
Nekane Guarrotxena and Miguel Mudarra
x Contents

9. Development of Electrohydrodynamics and Thermo-Electro-Hydro

Dynamics Principles for Electrospun Fiber Reinforced Through
in situ Nano-Interface Formation........................................................... 259
A. K. Haghi and A. Pourhashemi

10. Liquid Jet–Air Interface in Electrospinning Processes........................ 271

A. K. Haghi and A. Pourhashemi

Index ..................................................................................................283
LIST OF CONTRIBUTORS

A. A. Bokarev
Moscow State University of Applied Biotechnology, Moscow, Russia

W. W. Focke
Institute of Applied Materials, Department of Chemical Engineering, University of Pretoria, Pretoria
0002, South Africa
Tel: (+27) 12 420 3728, Fax: (+27) 12 420 2516

D. Gnanasekaran
Institute of Applied Materials, Department of Chemical Engineering, University of Pretoria, Pretoria
0002, South Africa
Tel: (+27) 12 420 3728, Fax: (+27) 12 420 2516

N. Guarrotxena
Instituto de Ciencia y Tecnología de Polímeros (ICTP) , Consejo Superior de Investigaciones Cientí-
ficas (CSIC) , Juan de la Cierva 3, 28006 Madrid, Spain
E-mail: [email protected]

A. K. Haghi
University of Guilan, Rasht, Iran

H. Hlídková
Institute of Macromolecular Chemistry Academy of Sciences of the Czech Republic, v.v.i.
Heyrovský Sq. 2, 162 06 Prague 6, Czech Republic

D. Horák
Institute of Macromolecular Chemistry Academy of Sciences of the Czech Republic, v.v.i.
Heyrovský Sq. 2, 162 06 Prague 6, Czech Republic
E-mail address: [email protected]

V. A. Ilatovsky
N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 Kosygin Street, Mos-
cow 119991, Russia

S. G. Karpova
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia

G. G. Komissarov
N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 Kosygin Street, Mos-
cow 119991, Russia
E-mail: [email protected]; [email protected]

G. А. Коrablev
Izhevsk State Agricultural Academy, Russia, Izhevsk 426000
Е-mail: [email protected]

N. G. Korableva
Izhevsk State Agricultural Academy, Russia, Izhevsk 426000
Е-mail: [email protected]
xii List of Contributors

O. A. Legonkova
Moscow State University of Applied Biotechnology, Moscow, Russia
E-mail: [email protected]

P. H. Massinga Jr
Universidade Eduardo Mondlane, Faculdade de Ciências, Campus Universitário Principal, Av. Julius
Nyerere, P.O. Box 257, Maputo, Moçambique
M. Mudarra
Dept. Física i Enginyeria Nuclear. ETSEIAT, Universitat Politècnica de Catalunya,Colom, 11 Terrassa
08222, Barcelona, Spain

A. A. Popov
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia

A. Pourhashemi
Department of Chemical and Biochemical Engineering, Christian Brothers University, Memphis, Ten-
nessee, USA

G. A. Ptitsyn
N.N. Semenov Institute of Chemical Physics,Russian Academy of Sciences, 4 Kosygin Street, Mos-
cow 119991, Russia

G. V. Sinko
N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 Kosygin Street, Mos-
cow 119991, Russia

G. E. Zaikov
Institute of Biochemical Physics N. M. Emanuel, Russian Academy Sciences, 4 Kosygina Street, Rus-
sia, Moscow 119991
E-mail: [email protected]
LIST OF ABBREVIATIONS

1DNSMs one-dimensional nanostructures

2DNSMs 2-D nanostructures
CXR cyclohexane regain
DSC differential scanning calorimeter
EHD electrohydrodynamic
EPR electron paramagnetic resonance
eV electron volts
EVA (ethylene-co-vinyl acetate
FNI Mozambican Research Foundation
HOMO highest occupied state
HRR heat release rate
HVSEM high-vacuum SEM
IRDP Institutional Research Development Programme
LDHs layered double hydroxides
LUMO lowest free state
LVSEM low-vacuum scanning electron microscopy
MFI melt flow index
NRF National Research Foundation
NSMs nanostructured material
Pcs phthalocyanines
PMMA poly(methyl methacrylate)
POSS polyhedral oligomericsilsesquioxane
SEC size exclusion chromatography
TEG thermal expanded graphite
TEM transmission electron microscopy
THF tetrahydrofuran
THR total heat release
TPCs tetrapyrrole compounds
TPP tetraphenylporphyrin
VA vinyl acetate
WL weight loss
XRD X-ray diffraction analysis
This page intentionally left blank
LIST OF SYMBOLS

h Planck constant
Iph photocurrent (μA)
W absorbed light power (W)
λ wavelength (m)
c speed of light (m/s)
ϑ total concentration of adsorbed molecules
W activation energy of the transition to the charged form
Ea distance from the surface acceptor level to the Ev
Fs distance from the Fermi level at the surface to Ev
Ev ceiling of the valence band
ww weight of hydrated sample
wd weight of dry sample
p porosity of the hydrogels
W bond energy of electrons
Ei ionization energy of an atom
Wi bond energy of an electron
ni number of elements of the given orbital
ri orbital radius of iorbital
Z* and n* effective charge of a nucleus and effective main quantum number
Р0 spatial-energy parameter
РE value of effective Р-parameter
РС parameter of a complex structure
N1and N2 number of homogeneous atoms
N bond order
К maxing or hybridization coefficient
D0 dissociation energy of a molecule
КE equilibrium constants of chemical reaction
Т thermodynamic temperature of the process
DΦ T change in the reaction of considered reduced thermodynamic
*

potential
R universal gas constant
∆НG0 formation enthalpy of gaseous substance
xvi List of Symbols

∆Н0SD formation enthalpy of solid in nonstandard state

∆НS sublimation enthalpy
R radius
n main quantum number
r dimensional characteristic of atom structure
N0 number of particles in the sphere volume of the radius R
σ0 DC conductivity
A temperature-dependent parameter
n fractional exponent
t* relaxation time
Tg glass transition temperature
εε0 ratio of the dielectric permeability
ρe local free charge density
E electric field strength
P polarization
Q dipole charge
d orientation
δ two-dimensional vector
σ the surface charge density; the stress on the element
R1 and R2 principal radii of curvature
a surface tension coefficient
a average radius of aan segment of the jet between two beads
h distance
ε strain of the element
µ viscosity of the material
PREFACE

The aim of this book is to provide both a rigorous view and a more practical,
understandable view of the interfaces of physics and chemistry in micro and
nanoscale materials. This book intends to satisfy readers who have both direct
and lateral interest in the discipline.
This volume is structured into different parts devoted to micro and nano-
structured systems and their applications. Every section of the book has been
expanded where relevant to take account of significant new discoveries and
realizations of the importance of key concepts. Further, emphases are placed
on the underlying fundamentals and on acquisition of a broad and comprehen-
sive grasp of the field as a whole.
This book brings together research contributions from eminent experts
on subjects that have gained prominence in material and chemical engineer-
ing and science. The uniqueness of the topics presented in the book can be
gauged from their fundamental and practical importance, particularly the lat-
est developments in advanced materials chemical domains. With contribu-
tions from experts from both industry and academia, this book presents the
latest developments in the identified areas. This book incorporates appropriate
case studies, explanatory notes, and schematics for more clarity and better
understanding.
This book will be useful for chemists, chemical engineers, technologists,
and students interested in this research and its applications.
This new book
• features classical topics that are conventionally considered as part of physi-
cal chemistry.
• covers the physical chemistry principles from a modern viewpoint.
• focuses on topics with more advanced methods.
• emphasizes on precise mathematical development and actual experimental
details.

— Nekane Guarrotxena, PhD

This page intentionally left blank
CHAPTER 1

HIGHLY FILLED COMPOSITE

MATERIALS WITH REGULATED
PHYSICAL AND MECHANICAL
PROPERTIES BASED ON SYNTHETIC
POLYMERS AND ORGANIC AND
INORGANIC FILLERS
O. A. LEGONKOVA, A. A. POPOV, A. A. BOKAREV,
and S. G. KARPOVA

CONTENTS

1.1 Aims and Backgrounds........................................................................... 2

1.2 Introduction............................................................................................. 2
1.3 Experimental........................................................................................... 2
1.4 Results and discussions........................................................................... 3
1.5 Conclusions............................................................................................. 9
Keywords....................................................................................................... 10
References...................................................................................................... 10
2 Research Methodology in Physics and Chemistry of Surfaces and Interfaces

1.1 AIMS AND BACKGROUNDS

The aim of this study was to upgrade the highly filled composite materials
with regulated physicomechanical properties based on synthetic polymers and
organic and inorganic fillers that can be used in the creation of environment-
friendly biodegradable products for different purposes. Features that are es-
sential for technology, such as physical, chemical, structural, and rheological
properties, were investigated. Electron paramagnetic probe and IR-spectrom-
etry methods were used to prove that inorganic filler plays the role of plas-
ticizer in the creation of hybrid composites. Microbiological aspects will be
discussed in another article.

1.2 INTRODUCTION

One of the promising trends from the viewpoint of ecology is the development
of biodegradable polymer composites. These materials, along with the poly-
mer base more resistant to biodegradation, comprise fillers that are not only
accessible for microbial degraders but are also agroindustrial wastes to be
utilized. [1] Search for cheap fillers and development of polymer composites
makes it possible not only to reduce the cost of product, but it is also a solution
to ecological problems.

1.3 EXPERIMENTAL

Third-grade threshed grain wastes (size of particles, 63–240 µm; bulk density,
350 kg/m3; and humidity, 4%) were used as organic filler. As inorganic filler,
a Rastvorin-A water-soluble mineral fertilizer (OST 10-193-96, produced by
the Buysk Mineral Fertilizer Plant) was taken in the following composition
(in %): (NH4)2SO4, 35; NH4H2PO4, 6; KNO3, 32; and MgSO4·7H2O, 27.
The physicomechanical properties of specimens within a broad range of
ingredient ratios were determined according to GOST 14236-82; the rheo-
logical characteristics of filled compositions were determined by the capillary
viscosimetry method.
In this study, electron paramagnetic probe method was used, which was a
stable nitroxyl radical 2,2,6,6-tetramethylpiperidine-1-oxyl. The radical was
introduced into films from vapors at T = 25°C up to a concentration of 10–3
Highly Filled Composite Materials with Regulated Physical 3

mol/L. A reference solution of the radical in ССl4 with a known number of

spins was used for determining the concentration of radicals in films. The
number of spins in a specimen was determined by comparing the areas under
the absorption curves of the specimen studied and the reference. The rota-
tional mobility of the probe was characterized by the correlation time τ. The
values of τ were assessed from the electron paramagnetic resonance (EPR)
spectra by the method outlined by Antsyferova et al. [2]

1.4 RESULTS AND DISCUSSIONS

While introducing fillers into SEVA irrespective of its grade, it was found
that the strength and relative elongation decreased with an increase in filler
content in both organic and inorganic fillers in two-component polymer–filler
systems (see Figures 1 and 2). Introduction of organic filler made the speci-
mens more rigid; with the introduction of inorganic filler even at a high con-
centration (60 wt %), specimens preserve a high plasticity (the breaking strain
is 400%).

FIGURE 1 Change of the physicomechanical properties of a two-component system

(SEVA/inorganic filler, wt %): 1, 100/0; 2, 80/20; 3, 60/40; 4, 50/50; and 5, 40/60.
4 Research Methodology in Physics and Chemistry of Surfaces and Interfaces

In the case of three-component systems too (SEVA/inorganic filler/organic

filler, Figure 3), an increase in the content of inorganic filler leads to more
plastic specimens.

FIGURE 2 Change of the physicomechanical properties of a two-component system

(SEVA/organic filler, wt %): 1, 100/0; 2, 80/20; 3, 60/40; 4, 50/50; and 5, 40/60.
Highly Filled Composite Materials with Regulated Physical 5

FIGURE 3 The physicomechanical properties of a three-component system based on

SEVA-113, wt %: 1, SEVA/organic filler, 50/50; 2, SEVA/inorganic filler, 50/50; 3, SEVA/
inorganic filler/organic filler, 50/37/13; 4, SEVA/inorganic filler/organic filler, 50/25/25;
and 5, SEVA/inorganic filler/organic filler, 50/13/37.

Figure 4 presents electron micrographs of the fracture faces of composites.

The systems are considered to be heterogeneous. The systems with inorganic
filler include both crystallites of filler salts and their more complex forma-
tions. Defects in the system are “pressed into” the homogeneous structure of
the composite. For this reason, a decrease of strength of polymer–composite
material occurs, owing to a decrease of the content of polymer in the composi-
tion.
The EPR method supports the data obtained (Table 1): the higher the con-
centration of organic wastes in a hybrid composite, the greater the correlation
time, that is, the more rigid the system is, the smaller the deformability of the
system. At the same time, the higher the concentration of inorganic filler, the
more plastic the systems are.
Noteworthy is the behavior of two ternary systems: 50 percent sevilene
at 25/25 of organic and inorganic filler and 15 percent sevilene at 50/35 of
organic and inorganic filler, for which the correlation time of all ternary sys-
tems studied is minimal. Both the systems are plastic and capable of being
processed by commercial equipment into particular articles.
6 Research Methodology in Physics and Chemistry of Surfaces and Interfaces

1. 4.

FIGURE 4 Electron micrographs of the fracture faces of two-component systems of

polymer–composite material based on sevilene and inorganic filler (1, 2, 3); sevilene and
organic filler (5, 6); three-component PCM (4): 15 percent sevilene, 50 percent organic
filler, 35 percent inorganic filler (magnification ×200 µm).
Highly Filled Composite Materials with Regulated Physical 7

TABLE 1 Correlation time of the paramagnetic probe in PCM specimens depending on

the extent of filling with various fillers
Extent of τ Extent of filling τ Extent of filling τ
filling with with inorganic with organic/inor-
organic filler filler ganic filler
(%) (%) (%)

10 6.1∙10–10 20 7.7∙10−10 18.75/18.75 6.1∙10–10

15 6.8∙10–10 40 7.4∙10−10 25/25 5.1∙10–10

20 7.1∙10–10 50 7.1∙10−10 50/25 6.2∙10–10

35 6.3∙10–10 60 6.8∙10−10 60/25 6.5∙10–10

40 7.0∙10–10 80 6.4∙10−10 30/35 6.0∙10–10

50 7.1∙10−10 – – 50/35 6.2∙10–10

60 8.0∙10−10 – – 50/35 5.7∙10–10

As inorganic filler is a mixture of salts (potassium, and magnesium chlo-

rides; magnesium sulfates; and potassium and ammonium nitrates), the ni-
trogen-containing salts led to a significant increase of the melt flow index in
sevilene-based PCMs (Table 2).

TABLE 2 Effect of the composition and concentration of inorganic salts on the melt flow
index (g/10 min) of sevilene-based composites
Content Unfilled speci- MgCl2 KCl MgSO4 KNO3 NH4NO3
men
(wt %)

1 7.8 7.5 6.7 8.1 2.9 4.3

2 7.5 7.1 6.3 7.1 Too high flow rate

made its measure-
ment impossible

To assess the possibility of chemical interaction of fillers with polymers,

we used the method of IR spectroscopy. The following IR bands were found
to be characteristic of SEVA: 1740 cm–1 (vibrations of the aldehyde group),
1380 cm–1 (vibrations of the vinyl acetate group), 1240 cm–1, 1050 cm–1, 797
cm–1, and 607 cm–1 [3].
8 Research Methodology in Physics and Chemistry of Surfaces and Interfaces

According to Nakanishi [3], vibrations in the region of 1440 cm–1 can be

assigned to

−C −
|
OCOCH 3

The methylene groups –СН2– in SEVA have characteristic valent vibra-

tions at 2850 cm–1. The NH4+ group has the absorption band in the region
of 3,300–3,030 cm–1; the group Р–О–Сalkyl, 1,180–1,150 cm–1; the groups
SO42−, 1,130–1,080 cm–1; S–CH2, 2,700–2,630 cm–1; the groups PO43, HPO42−,
H2PО4−, in the region of 1,100–1,000 cm–1; and NO3−, 1,380 cm–1.
Ratios of the optical densities of the bands 1,440 cm–1 and 1,380 cm–1 to
the optical density of the band 2,850 cm–1 taken as the internal standard of the
specimens of mixtures of SEVA with the salts KNO3, NH4NO3, and K2HPO4
shown in Table 3.
The table shows that while heating the salts KNO3, NH4NO3, and K2HPO4,
there is an insignificant splitting-off of the vinyl acetate group from the main
chain. Heating of polymer with K2HPO4 produces a band responsible for the
interaction of Р–О–Сalkyl (D1180 = 0.62).
In the case of the other salts (KH2PO4, (NH4)2HPO4, (NH4)2SO4, MgSO4),
such an effect could not be identified due to the coincidence of the spectra of
the characteristic absorption bands.

TABLE 3 Ratios of the optical densities of the bands 1,440 cm–1 and 1,380 cm–1 to the
optical density of the band 2,850 cm–1 taken as the internal standard of the specimens of
mixtures of SEVA with the salts KNO3, NH4NO3, and K2HPO4
Sevilene Sevilene Sevilene Sevilene + Sevilene
+ + K2HPO4 + inorganic filler
KNO3 NH4NO3

D1440/D2850 0.66 0.47 0.46 0.42 0.41

D1380/D2850 0.59 0.42 0.43 0.31 0.36

Table 4 presents the melting heats of polymers and polymer–composite

materials at temperatures of solid-phase transitions of nitric salts, coinciding
with sevilene fluidity temperature of 80°C. According to Chemist’s Reference
Book, Moscow [4], ammonium nitrates have solid-phase transitions at
Highly Filled Composite Materials with Regulated Physical 9

temperatures of 80°C and 130°C with ∆Нm equal to 0.32 ccal/mol and 1.01
ccal/mol, respectively; the salt KNO3 has the solid-phase transition at 130°C
with ∆Нm equal to 1.3 ccal/mol.

TABLE 4 Melting heats of polymers and their composites at temperatures of solid-phase

transitions of nitric salts (J/g)
Material 80°C 130°C

Sevilene unfilled (Тt = 80°C) 49.9 –

KNO3 – 54.2

NH4NO3 10.1 53.9

Sevilene filled with 20% NH4NO3 49.9 9.8

Sevilene filled with 20% KNO3 44.9 7.6

Sevilene filled with 2% KNO3 65.1 1.1

Sevilene filled with 40% inorganic filler 50.4 –

Sevilene/organic filler/inorganic filler (15:50:35) – 94.9

At 80°C, for polymer–composite material based on sevilene an increase

of melting heat at the introduction of 2 percent KNO3 is due to the fact that
densely packed structures are formed in polymer’s liquid phase at a small
content of solid filler at the interface with solid particles of filler KNO3. [5] At
an increase of the content of salt up to 20 percent, the decrease of the melting
heat is due to a decrease of the content of polymer per 1 g of specimen studied.
At the introduction of NH4NO3 into this system, there is no change of
melting enthalpy compared with pure polymer. At 130°C, when the tempera-
ture of the solid-phase transition of the salts is higher than the melting tem-
perature of sevilene, the enthalpy of the composite decreases, which is due to
a decrease of the content of salt per 1 g of specimen studied.

1.5 CONCLUSIONS

Thus, the thermal effect of two-component hybrid systems formed from the
melt is minimal when Тm (Тt) of the polymer is equal to or lower than the
solid-phase transition temperature of the salts. By the extent of a decrease of
enthalpy of the measured component, an indirect judgment can be made on
10 Research Methodology in Physics and Chemistry of Surfaces and Interfaces

the looseness of the filled system when compared with the individual compo-
nents of the composite.
The process properties of hybrid composites are related not only to the
decrease of the concentration of the matrix in the bulk of the composite but
also to the plasticizing action of inorganic filler.

KEYWORDS

•• Correlation time
•• Hybrid composites
•• Hybrid composites
•• Industrial wastes
•• Inorganic fillers
•• Melt Flow index
•• Organic fillers
•• Physical and chemical properties
•• Polymers
•• Structure

REFERENCES

1. Legonkova, O. A.; Biodeterioration of polymer-based composite materials in the envi-

ronment. Mater. Sci. 2008, 2, 50–55.
2. Antsyferova, L. I.; Wasserman, A. M.; Ivanova, A. I.; Lifshits, V. A.; and Nazemets, N.
S.; Atlas of the Spectra, Moscow: Nauka Publishers; 2012, 160 (in Russian).
3. Nakanishi, K.; Infrared Spectra and Structure of Organic Compounds. Moscow: Mir
Publishers; 2012, 200 p.
4. Chemistry Handbook, Moscow–Leningrad: Khimiya Publishers; 2011, 1, 1070 p. (in
Russian).
5. Bryk, M. T.; Utilization of Filled Polymers, Moscow: Khimiya Publishers; 2012, 190
p. (in Russian).
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