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lubricants, antistatic additives, and metal soaps. ISBN:ISBN: E. Zaikov, DSc, and A. K. Haghi, PhD
978-1-77188-040-4
978-1-77188-040-4 DevrimAbbas
Balköse,
Devrim Hamrang,
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Editors PhD PhD
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ISBN:DSc, and A. K. Haghi, PhD
978-1-77188-040-4
9 0 0 0 09 0 0 0 0
Abbas Hamrang,
Devrim Balköse,
PhD PhD

ISBN: 978-1-77188-040-4
90000
Devrim Balköse, PhD
90000
9 7819
771 880404
781 771 88 040 4

9 781 771 88 040 4

www.appleacademicpress.com 9 781 771 880404

APPLIED METHODOLOGIES
IN POLYMER RESEARCH
AND TECHNOLOGY
This page intentionally left blank
APPLIED METHODOLOGIES
IN POLYMER RESEARCH
AND TECHNOLOGY

Edited by
Abbas Hamrang, PhD, and Devrim Balköse, PhD

Gennady E. Zaikov, DSc, and A. K. Haghi, PhD

Reviewers and Advisory Board Members

Apple Academic Press

TORONTO NEW JERSEY
CRC Press Apple Academic Press, Inc
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ABOUT THE EDITORS

Abbas Hamrang, PhD

Abbas Hamrang, PhD, is a professor of polymer science and technology.
He is currently a senior polymer consultant and editor and member of the
academic boards of various international journals. His research interests
include degradation studies of historical objects and archival materials,
cellulose-based plastics, thermogravemetric analysis, and accelerated age-
ing process and stabilization of polymers by chemical and non-chemical
methods. His previous involvement in academic and industry sectors at
the international level includes deputy vice-chancellor of research and
development, senior lecturer, manufacturing consultant, and science and
technology advisor.

Devrim Balköse, PhD

Devrim Balköse, PhD, graduated from the Middle East Technical Uni-
versity in Ankara, Turkey, with a degree in chemical engineering. She
received her MS and PhD degrees from Ege University, Izmir, Turkey,
in 1974 and 1977 respectively. She became associate professor in mac-
romolecular chemistry in 1983 and professor in process and reactor en-
gineering in 1990. She worked as research assistant, assistant professor,
associate professor, and professor between 1970–2000 at Ege University.
She was the Head of Chemical Engineering Department at Izmir Institute
of Technology, Izmir, Turkey, between 2000 and 2009. She is now a fac-
ulty member in the same department. Her research interests are in polymer
reaction engineering, polymer foams and films, adsorbent development,
and moisture sorption. Her research projects are on nanosized zinc borate
production, ZnO polymer composites, zinc borate lubricants, antistatic ad-
ditives, and metal soaps.
This page intentionally left blank
REVIEWERS AND ADVISORY BOARD
MEMBERS

Gennady E. Zaikov, DSc

Gennady E. Zaikov, DSc, is Head of the Polymer Division at the N. M.
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences,
Moscow, Russia, and Professor at Moscow State Academy of Fine Chemi-
cal Technology, Russia, as well as Professor at Kazan National Research
Technological University, Kazan, Russia. He is also a prolific author, re-
searcher, and lecturer. He has received several awards for his work, includ-
ing the Russian Federation Scholarship for Outstanding Scientists. He has
been a member of many professional organizations and on the editorial
boards of many international 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 engineer-
ing from North Carolina A&T State University (USA); a DEA in applied
mechanics, 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 as
well as 1000 published papers in various journals and conference proceed-
ings. Dr. Haghi has received several grants, consulted for a number of
major corporations, and is a frequent speaker to national and international
audiences. Since 1983, he served as a professor at several universities. He
is currently Editor-in-Chief of the International Journal of Chemoin-
formatics and Chemical Engineering and Polymers Research Journal and
on the editorial boards of many international journals. He is a member of
the Canadian Research and Development Center of Sciences and Cultures
(CRDCSC), Montreal, Quebec, Canada.
This page intentionally left blank
CONTENTS

List of Contributors .................................................................................... xi

List of Abbreviations ................................................................................ xiii
List of Symbols ...........................................................................................xv
Preface .................................................................................................... xvii
1. Electrospinning Process: A Comprehensive Review and Update ........... 1
S. Rafiei

2. Aluminium-Coated Polymer Films as Infrared Light Shields for

Food Packing ........................................................................................... 109
Esen Arkış and Devrim Balköse

3. Generalization of Fuels Swelling Data by Means of Linear

Free Energy Principle ............................................................................. 125
Roman Makitra, Halyna Midyana, Liliya Bazylyak, and Olena Palchykova

4. Trends on New Biodegradable Blends on the Basis of Copolymers

3-Hydroxybutyrate with Hydroxyvalerate and Segmented
Polyetherurethane ................................................................................... 151
Svetlana G. Karpova, Sergei M. Lomakin, Anatolii A. Popov, and Aleksei A. Iordanskii

5. New Biologically Active Composite Materials on the Basis of

Dialdehyde Cellulose............................................................................... 159
Azamat A. Khashirov, Azamat A. Zhansitov, Genadiy E. Zaikov, and Svetlana Yu.
Khashirova

6. Microheterogeneous Titanium Ziegler–Natta Catalysts: The Influence

of Particle Size on the Isoprene Polymerization................................... 167
Elena M. Zakharova, Vadim Z. Mingaleev, and Vadim P. Zakharov

7. The Role and Mechanism of Bonding Agents in Composite Solid

Propellants ............................................................................................... 185
S. A. Vaziri, S. M. Mousavi Motlagh, and M. Hasanzadeh
x Contents

8. A Study on Adsorption of Methane on Zeolite 13x at Various

Pressures and Temperatures .................................................................. 197
Farshid Basiri, Alireza Eslami, Maziyar Sharifzadeh, and Mahdi Hasanzadeh

9. Importance of the Phase Behavior in Biopolymer Mixtures............... 207

Y. A. Antonov and Paula Moldenaers

Index.......................................................................................................... 237
LIST OF CONTRIBUTORS

Esen Arkış
Izmir Institute of Technology Department of Chemical Engineering, Gülbahce Urla 35430, Izmir
Turkey, Email: [email protected]

Devrim Balköse
Izmir Institute of Technology Department of Chemical Engineering, Gülbahce Urla 35430 Izmir Tur-
key

Farshid Basiri
Department of Chemical Engineering, South Tehran Branch, Islamic Azad University, Tehran, Iran

Liliya Bazylyak
Chemistry of Oxidizing Processes Division; Physical Chemistry of Combustible Minerals Depart-
ment, Institute of Physical–Organic Chemistry & Coal Chemistry named after L. M. Lytvynenko,
National Academy of Science of Ukraine 79053, Ukraine, Email: [email protected]

Alireza Eslami
Department of Chemical Engineering, South Tehran Branch, Islamic Azad University, Tehran, Iran

M. Hasanzadeh
Department of Textile Engineering, University of Guilan, Rasht, Iran

Mahdi Hasanzadeh
Department of Textile Engineering, University of Guilan, Rasht, Iran, Email: hasanzadeh_mahdi@
yahoo.com

Aleksei A. Iordanskii
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia

Svetlana G. Karpova
Emmanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia

Azamat A. Khashirov
Kabardino-Balkarian State University, Nalchik 360004, Russia, Russian Federation, Email: new_
[email protected]

Svetlana Yu. Khashirova

Kabardino-Balkarian State University, Nalchik 360004, Russia, Russian Federation, Email: new_
[email protected]

Sergei M. Lomakin
Emmanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia

Roman Makitra
Chemistry of Oxidizing Processes Division; Physical Chemistry of Combustible Minerals Depart-
ment; Institute of Physical–Organic Chemistry & Coal Chemistry named after L. M. Lytvynenko,
National Academy of Science of Ukraine 79053, Ukraine; Email: [email protected]
xii List of Contributors

Halyna Midyana
Chemistry of Oxidizing Processes Division; Physical Chemistry of Combustible Minerals Depart-
ment, Institute of Physical–Organic Chemistry & Coal Chemistry named after L. M. Lytvynenko,
National Academy of Science of Ukraine 79053, Ukraine, Email: [email protected]

Vadim Z. Mingaleev
Institute of Organic Chemistry, Ufa Scientific Center of Russian Academy of Sciences, Ufa,
Bashkortostan, 450054, Russia

S. M. Mousavi Motlagh
Department of Chemical Engineering, Imam Hossien University, Tehran, Iran

Olena Palchykova
Institute of Geology and Geochemistry of Combustible Minerals; National Academy of Science of
Ukraine 79053, Ukraine

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

S. Rafiei
University of Guilan, Rasht, Iran

Maziyar Sharifzadeh
Department of Chemical Engineering, Ayatollah Amoli Branch, Islamic Azad University, Amol, Iran

S. A. Vaziri
Department of Chemical Engineering, Imam Hossien University, Tehran, Iran

Genadiy E. Zaikov
N.M. Emanuel Institute of Biochemical Physics of Russian Academy of Sciences, Moscow 119991,
Russia, Russian Federation

Vadim P. Zakharov
Bashkir State University, Ufa 450076, Bashkortostan, Russia, Email: [email protected]

Elena M. Zakharova
Institute of Organic Chemistry, Ufa Scientific Center of Russian Academy of Sciences, Ufa, Bashkor-
tostan, 450054, Russia

Azamat A. Zhansitov
Kabardino-Balkarian State University, Nalchik 360004, Russia, Russian Federation, Email: new_
[email protected]
LIST OF ABBREVIATIONS

ACs active sites

CS cuckoo search
DAC dialdehyde cellulose
DAGA diallylguanidine acetate
DAGTFA diallylguanidine trifluoroacetate
DE differential evolution
DLS dynamic light scattering
DSS dextran sulfate sodium salt
ESEM environment scanning electron microscope
FPLC fast protein liquid chromatography
MCC microcrystalline cellulose
MWD molecular weight distribution
NPBA neutral polymeric bonding agent
OM optical microscopy
PHB poly(3-hydroxybutyrate)
PMMA poly (methylmethacrylate)
PSO particle swarm optimization
SA sodium alginate
SALS small angle light scattering
SC sodium caseinate
SPEUs segmented polyetherurethanes
This page intentionally left blank
LIST OF SYMBOLS

δ1 and δ2 Hildebrand’s parameters

ρ2 density of a polymer into solution
V1 molar volume of the solvent
Tm melting temperature
Pmax maximum pressure of each isotherm
S number of point per isotherm per gas
Cexp methane concentrations (experimental)
Ccal methane concentrations (calculated)
Ue electrophoretic mobility
ε dielectric constant
η viscosity
zρ zeta potential
k Boltzmann’s constant
T temperature
n dumbbells density
p unit vector in nanoelement axis direction
ωij rotation rate tensor
γij deformation tensor
Dr rotary diffusivity
θ shape factor
l mean segment length
V velocity
h fabric thickness
m equivalent mass
α surface charge parameter
This page intentionally left blank
PREFACE

Polymers are substances that contain a large number of structural units

joined by the same type of linkage. These substances often form into a
chain-like structure. Starch, cellulose, and rubber all possess polymeric
properties. Today, the polymer industry has grown to be larger than the
aluminum, copper, and steel industries combined. Polymers already have
a range of applications that far exceeds that of any other class of material
available to man. Current applications extend from adhesives, coatings,
foams, and packaging materials to textile and industrial fibers, elastomers,
and structural plastics. Polymers are also used for most nanocomposites,
electronic devices, biomedical devices, and optical devices, and are pre-
cursors for many newly developed high-tech ceramics.
This book presents leading-edge research in this rapidly changing and
evolving field. Successful characterization of polymer systems is one of
the most important objectives of today’s experimental research of poly-
mers. Considering the tremendous scientific, technological, and economic
importance of polymeric materials, not only for today’s applications but
for the industry of the twenty-first century, it is impossible to overestimate
the usefulness of experimental techniques in this field. Since the chemical,
pharmaceutical, medical, and agricultural industries, as well as many oth-
ers, depend on this progress to an enormous degree, it is critical to be as
efficient, precise, and cost-effective in our empirical understanding of the
performance of polymer systems as possible. This presupposes our pro-
ficiency with, and understanding of, the most widely used experimental
methods and techniques. This book is designed to fulfill the requirements
of scientists and engineers who wish to be able to carry out experimental
research in polymers using modern methods.
Polymer nanocomposites are materials that possess unique properties.
These properties are enhanced properties of the polymer matrix. Some of
the improved properties are thermal stability, permeability to gases, flam-
mability, mechanical strength and photodegradability. At complete disper-
sion of the new layers in the polymer matrix, these enhanced properties
xviii Preface

are obtained. The unique properties of the material makes it suitable in

applications as, food and beverage packaging, automobile parts, furniture,
carrier bags, electrical gadgets, and so on.
CHAPTER 1

ELECTROSPINNING PROCESS:
A COMPREHENSIVE REVIEW AND
UPDATE
S. RAFIEI

CONTENTS

1.1 Introduction ...................................................................................... 2

1.2 Nanostructured Materials ................................................................. 4
1.3 Nanofiber Technology ................................................................... 13
1.4 Design Multifunctional Product by Nanostructures ...................... 23
1.5 Multifunctional Nanofiber-Based Structure .................................. 33
1.6 Concluding Remarks of Multifunctional Nanostructure Design ... 49
1.7 Introduction to Theoretical Study of Electrospinning Process ...... 49
1.8 Study of Electrospinning Jet Path .................................................. 51
1.9 Electrospinning Drawbacks ........................................................... 54
1.10 Modeling the Electrospinning Process .......................................... 56
1.11 Electrospinning Simulation............................................................ 95
Keywords ................................................................................................ 95
References ............................................................................................... 96
2 Applied Methodologies in Polymer Research and Technology

1.1 INTRODUCTION

Understanding the nanoworld makes up one of the frontiers of modern sci-

ence. One reason for this is that technology based on nanostructures prom-
ises to be hugely important economically [1–3]. Nanotechnology literally
means any technology on a nanoscale that has applications in the real
world. It includes the production and application of physical, chemical,
and biological systems at scales ranging from individual atoms or mol-
ecules to submicron dimensions, as well as the integration of the resulting
nanostructures into larger systems. Nanotechnology is likely to have a pro-
found impact on our economy and society in the early twenty-first century,
comparable with that of semiconductor technology, information technol-
ogy, or cellular and molecular biology. Science and technology research
in nanotechnology promises breakthroughs in areas such as materials and
manufacturing [4], nanoelectronics [5], medicine and healthcare [6], en-
ergy [7], biotechnology [8], information technology [9], and national se-
curity [10]. It is widely felt that nanotechnology will be the next Industrial
Revolution [9].
As far as “nanostructures” are concerned, one can view this as objects
or structures whereby at least one of its dimensions is within nanoscale.
A “nanoparticle” can be considered as a zero dimensional nanoelement,
which is the simplest form of nanostructure. It follows that a “nanotube”
or a “nanorod” is a one-dimensional nanoelement from which slightly
more complex nanostructure can be constructed of Refs. [11–12].
Following this fact, a “nanoplatelet” or a “nanodisk” is a two-dimen-
sional element which, along with its one-dimensional counterpart, is use-
ful in the construction of nanodevices. The difference between a nano-
structure and a nanodevice can be viewed upon as the analogy between
a building and a machine (whether mechanical, electrical, or both) [1]. It
is important to know that as far as nanoscale is concerned, these nanoele-
ments should not be considered only as an element that forms a structure
while they can be used as a significant part of a device. For example, the
use of carbon nanotube as the tip of an atomic force microscope (AFM)
would have it classified as a nanostructure. The same nanotube, however,
can be used as a single-molecule circuit, or as part of a miniaturized elec-
tronic component, thereby appearing as a nanodevice. Hence, the func-
tion, along with the structure, is essential in classifiying which nanotech-
Electrospinning Process: A Comprehensive Review 3

nology subarea it belongs to. This classification will be discussed in detail

in further sections [11, 13].
As long as nanostructures clearly define the solids’ overall dimensions,
the same cannot be said so for nanomaterials. In some instances, a nano-
material refers to a nanosized material; whereas in other instances, a nano-
material is a bulk material with nanoscaled structures. Nanocrystals are
other groups of nanostructured materials. It is understood that a crystal
is highly structured and that the repetitive unit is indeed small enough.
Hence, a nanocrystal refers to the size of the entire crystal itself being
nanosized, but not of the repetitive unit [14].
Nanomagnetics are the other types of nanostructured materials that are
known as highly miniaturized magnetic data storage materials with very
high memory. This can be attained by taking advantage of the electron
spin for memory storage; hence, the term “spin-electronics,” which has
since been more popularly and more conveniently known as “spintronics”
[1, 9, 15]. In nanobioengineering, the novel properties of nanoscale are
taken advantage of for bioengineering applications. The many naturally
occurring nanofibrous and nanoporous structure in the human body further
adds to the impetus for research and development in this subarea. Closely
related to this is molecular functionalization whereby the surface of an
object is modified by attaching certain molecules to enable desired func-
tions to be carried out such as for sensing or filtering chemicals based on
molecular affinity[16–17].
With the rapid growth of nanotechnology, nanomechanics are no lon-
ger the narrow field that it used to be[13]. This field can be broadly cat-
egorized into the molecular mechanics and the continuum mechanics ap-
proaches that view objects as consisting of discrete many-body system and
continuous media, respectively. As long as the former inherently includes
the size effect, it is a requirement for the latter to factor in the influence
of increasing surface-to-volume ratio, molecular reorientation, and other
novelties as the size shrinks. As with many other fields, nanotechnology
includes nanoprocessing novel materials processing techniques by which
nanoscale structures and devices are designed and constructed [18–19].
Depending on the final size and shape, a nanostructure or nanodevice
can be created from the top-down or the bottom-up approach. The for-
mer refers to the act of removing or cutting down a bulk to the desired
size; whereas, the latter takes on the philosophy of using the fundamental
building blocks—such as atoms and molecules, to build up nanostructures
4 Applied Methodologies in Polymer Research and Technology

in the same manner. It is obvious that the top-down and the bottom-up
nanoprocessing methodologies are suitable for the larger and two smaller
ends, respectively, in the spectrum of nanoscale construction. The effort
of nanopatterning—or patterning at the nanoscale— would hence fall into
nanoprocessing [1, 12, 18].

1.2 NANOSTRUCTURED MATERIALS

Strictly speaking, a nanostructure is any structure with one or more di-

mensions measuring in the nanometer (10−9m) range. Various definitions
refine this further, stating that a nanostructure should have a characteris-
tic dimension lying between 1nm and 100 nm, putting nanostructures as
intermediate in size between a molecule and a bacterium. Nanostructures
are typically probed either optically (spectroscopy, photoluminescence
...), or in transport experiments. This field of investigation is often given
the name mesoscopic transport, and the following considerations give an
idea of the significance of this term[1–2, 12, 20–21].
What makes nanostructured materials very interesting and award them
with their unique properties is that their size is smaller than critical lengths
that characterize many physical phenomena. In general, physical prop-
erties of materials can be characterized by some critical length, a ther-
mal diffusion length, or a scattering length, for example. The electrical
conductivity of a metal is strongly determined by the distance that the
electrons travel between collisions with the vibrating atoms or impurities
of the solid. This distance is called the mean free path or the scattering
length. If the sizes of the particles are less than these characteristic lengths,
it is possible that new physics or chemistry may occur [1, 9, 17].
Several computational techniques have been used to simulate and
model nanomaterials. Since the relaxation times can vary anywhere from
picoseconds to hours, it becomes necessary to employ Langevin dynam-
ics besides molecular dynamics in the calculations. Simulation of nanode-
vices through the optimization of various components and functions
provides challenging and useful task[20, 22]. There are many examples
where simulation and modeling have yielded impressive results, such as
nanoscale lubrication [23]. Simulation of the molecular dynamics of DNA
has been successful to some extent [24]. Quantum dots and nanotubes
have been modeled satisfactorily [25–26]. First principles calculations of
Electrospinning Process: A Comprehensive Review 5

nanomaterials can be problematic if the clusters are too large to be treated

by Hartree–Fock methods and too small for density functional theory [1].
In the next section various classifications of these kinds of materials are
considered in detail.

1.2.1 NANOSTRUCTURED MATERIALS AND THEIR

CLASSIFICATIONS

Nanostructure materials as a subject of nanotechnology are low-dimen-

sional materials comprising building units of a submicron or nanoscale
size at least in one direction and exhibiting size effects. The first classifica-
tion idea of NSMs was given by Gleiter in 1995 [3]. A modified classifica-
tion scheme for these materials, in which 0D, 1D, 2D, and 3D are included
suggested in later researches [21] . These classifications are given below.

1.2.1.1 0D NANOPARTICLES

A major feature that distinguishes various types of nanostructures is their

dimensionality. In the past 10 years, significant progress has been made
in the field of 0D nanostructure materials. A rich variety of physical and
chemical methods have been developed for fabricating these materials with
well-controlled dimensions[3, 18]. Recently, 0D nanostructured materials
such as uniform particles arrays (quantum dots), heterogeneous particles
arrays, core-shell quantum dots, onions, hollow spheres, and nanolenses
have been synthesized by several research groups[21]. They have been
extensively studied in light-emitting diodes (LEDs), solar cells, single-
electron transistors, and lasers.

1.2.1.2 1D NANOPARTICLES

In the past decade, 1D nanostructured materials have focused an increas-

ing interest due to their importance in research and developments and have
a wide range of potential applications [27]. It is generally accepted that
these materials are ideal systems for exploring a large number of novel
phenomena at the nanoscale and investigating the size and dimensional-
ity dependence of functional properties. They are also expected to play a
6 Applied Methodologies in Polymer Research and Technology

significant role as both interconnects and the key units in fabricating elec-
tronic, optoelectronic, and EEDs with nanoscale dimensions. The most
important types of this group are nanowires, nanorods, nanotubes, nano-
belts, nanoribbons, hierarchical nanostructures, and nanofibers [1, 18, 28].

1.2.1.3 2D NANOPARTICLES

2D nanostructures have two dimensions outside of the nanometric size

range. In recent years, synthesis of 2D nanomaterial has become a focal
area in materials research, owing to their many low-dimensional charac-
teristics different from the bulk properties. Considerable research attention
has been focused over the past few years on the development of them.
Two-dimensional nanostructured materials with certain geometries ex-
hibit unique shape-dependent characteristics and subsequent utilization as
building blocks for the key components of nanodevices[21]. In addition,
these materials are particularly interesting not only for basic understanding
of the mechanism of nanostructure growth but also for investigation and
developing novel applications in sensors, photocatalysts, nanocontainers,
nanoreactors, and templates for 2D structures of other materials. Some of
the 3D nanoparticles are junctions (continuous islands), branched struc-
tures, nanoprisms, nanoplates, nanosheets, nanowalls, and nanodisks [1].

1.2.1.4 3D NANOPARTICLES

Owing to the large specific surface area and other superior properties over
their bulk counterparts arising from quantum size effect, they have attract-
ed considerable research interest and many of them have been synthesized
in the past 10 years [1, 12]. It is well known that the behaviors of NSMs
strongly depend on the sizes, shapes, dimensionality and morphologies,
which are thus the key factors to their ultimate performance and appli-
cations. Therefore, it is of great interest to synthesize 3D NSMs with a
controlled structure and morphology. In addition, 3D nanostructures are an
important material due to its wide range of applications in the area of catal-
ysis, magnetic material and electrode material for batteries [2]. Moreover,
the 3D NSMs have recently attracted intensive research interests because
the nanostructures have higher surface area and supply enough absorption
sites for all involved molecules in a small space [58]. On the contrary, such
Electrospinning Process: A Comprehensive Review 7

materials with porosity in three dimensions could lead to a better transport

of the molecules. Nanoballs (dendritic structures), nanocoils, nanocones,
nanopillers, and nanoflowers are in this group[1–2, 18, 29].

1.2.2 SYNTHESIS METHODS OF NANOMATERIALS

The synthesis of nanomaterials includes control of size, shape, and struc-

ture. Assembling the nanostructures into ordered arrays often becomes
necessary for rendering them functional and operational. In the past de-
cade, nanoparticles (powders) of ceramic materials have been produced in
large scales by employing both physical and chemical methods. There has
been considerable progress in the preparation of nanocrystals of metals,
semiconductors, and magnetic materials by using colloid chemical meth-
ods [18, 30].
The construction of ordered arrays of nanostructures by using tech-
niques of organic self-assembly provides alternative strategies for nanode-
vices. 2D and 3D arrays of nanocrystals of semiconductors, metals, and
magnetic materials have been assembled by using suitable organic re-
agents [1, 31]. Strain directed assembly of nanoparticle arrays (e.g., of
semiconductors) provides the means to introduce functionality into the
substrate that is coupled to that on the surface[32].
Preparation of nanoparticles is an important branch of the materials
science and engineering. The study of nanoparticles relates various sci-
entific fields, for example, chemistry, physics, optics, electronics, mag-
netism, and mechanism of materials. Some nanoparticles have already
reached practical stage. To meet the nanotechnology and nanomaterials
development in the next century, it is necessary to review the preparation
techniques of nanoparticles.
All particle synthesis techniques fall into one of the three catego-
ries: vapor-phase, solution precipitation, and solid-state processes. Al-
though vapor-phase processes have been common during the early days
of nanoparticles development, the last of the three processes mentioned
above is the most widely used in the industry for production of micron-
sized particles, predominantly due to cost considerations[18, 31].
Methods for preparation of nanoparticles can be divided into physical
and chemical methods based on whether there exist chemical reactions
[33]. On the contrary, in general, these methods can be classified into the
8 Applied Methodologies in Polymer Research and Technology

gas-phase, liquid-phase, and solid-phase methods based on the state of

the reaction system. The gas-phase method includes gas-phase evapora-
tion method (resistance heating, high-frequency induction heating, plasma
heating, electron beam heating, laser heating, electric heating evaporation
method, vacuum deposition on the surface of flowing oil, and exploding
wire method), chemical vapor reaction (heating heat pipe gas reaction,
laser-induced chemical vapor reaction, plasma-enhanced chemical vapor
reaction), chemical vapor condensation, and sputtering method. Liquid-
phase method for synthesizing nanoparticles mainly includes precipita-
tion, hydrolysis, spray, solvent thermal method (high temperature and high
pressure), solvent evaporation pyrolysis, oxidation reduction (room pres-
sure), emulsion, radiation chemical synthesis, and sol-gel processing. The
solid-phase method includes thermal decomposition, solid-state reaction,
spark discharge, stripping, and milling method [30, 33].
In other classification, there are two general approaches to the synthe-
sis of nanomaterials and the fabrication of nanostructures, bottom-up and
top-down approach. The first one includes the miniaturization of material
components (up to atomic level) with further self-assembly process lead-
ing to the formation assembly of nanostructures. During self-assembly,
the physical forces operating at nanoscale are used to combine basic units
into larger stable structures. Typical examples are quantum dot formation
during epitaxial growth and formation of nanoparticles from colloidal dis-
persion. The latter uses larger (macroscopic) initial structures, which can
be externally controlled in the processing of nanostructures. Typical ex-
amples include etching through the mask, ball milling, and application of
severe plastic deformation [3, 13]. Some of the most common methods are
described in the sections that follow.

1.2.3 PLASMA-BASED METHODS

Metallic, semiconductive, and ceramic nanomaterials are widely synthe-

sised by hot and cold plasma methods. A plasma is sometimes referred to
as being “hot” if it is nearly fully ionized, or “cold” if only a small fraction,
(e.g., 1%), of the gas molecules are ionized, but other definitions of the
terms “hot plasma” and “cold plasma” are common. Even in cold plasma,
the electron temperature is still typically several thousand degrees Celsius.
In general, the related equipment consists of an arc-melting chamber and a
Electrospinning Process: A Comprehensive Review 9

collecting system. The thin films of alloys were prepared from highly pure
metals by arc melting in an inert gas atmosphere. Each arc-melted ingot
was flipped over and remelted three times. Then, the thin films of alloy
were produced by arc melting a piece of bulk materials in a mixing gas
atmosphere at a low pressure. Before the ultrafine particles were taken out
from the arc-melting chamber, they were passivated with a mixture of inert
gas and air to prevent the particles from burning up [34–35].
Cold plasma method is used for producing nanowires in large scale
and bulk quantity. The general equipment of this method consists of a con-
ventional horizontal quartz tube furnace and an inductively coupled coil
driven by a 13.56 MHz radiofrequency (RF) power supply. This method
often is called as an RF plasma method. During RF plasma method, the
starting metal is contained in a pestle in an evacuated chamber. The metal
is heated above its evaporation point using high-voltage RF coils wrapped
around the evacuated system in the vicinity of the pestle. Helium gas is
then allowed to enter the system, forming a high-temperature plasma in
the region of the coils. The metal vapor nucleates on the He gas atoms and
diffuses up to a colder collector rod where nanoparticles are formed. The
particles are generally passivated by the introduction of some gas such as
oxygen. In the case of aluminum nanoparticles, the oxygen forms a layer
of aluminum oxide about the particle [1, 36].

1.2.4 CHEMICAL METHODS

Chemical methods have played a significant role in developing materi-

als imparting technologically important properties through structuring the
materials on the nanoscale. However, the primary advantage of chemical
processing is its versatility in designing and synthesizing new materials
that can be refined into the final end products. The secondary most ad-
vantage that the chemical processes offer over physical methods is a good
chemical homogeneity, as a chemical method offers mixing at the molecu-
lar level. On the contrary, chemical methods frequently involve toxic re-
agents and solvents for the synthesis of nanostructured materials. Another
disadvantage of the chemical methods is the unavoidable introduction of
byproducts that require subsequent purification steps after the synthesis
in other words, this process is time-consuming. Despite these facts, prob-
ably the most useful methods of synthesis in terms of their potential to be
10 Applied Methodologies in Polymer Research and Technology

scaled up are chemical methods [33, 37]. There are a number of different
chemical methods that can be used to make nanoparticles of metals, and
we will give some examples. Several types of reducing agents can be used
to produce nanoparticles such as NaBEt3H, LiBEt3H, and NaBH4 where
Et denotes the ethyl (–C2Hs) radical. For example, nanoparticles of mo-
lybdenum (Mo) can be reduced in toluene solution with NaBEt3H at room
temperature, providing a high yield of Mo nanoparticles having dimen-
sions of 1–5 nm [30].

1.2.4.1 THERMOLYSIS AND PYROLYSIS

Nanoparticles can be made by decomposing solids at high temperature

having metal cations, and molecular anions or metal organic compounds.
The process is called thermolysis. For example, small lithium particles can
be made by decomposing lithium oxide, LiN3. The material is placed in
an evacuated quartz tube and heated to 400°C in the apparatus. At about
370°C, the LiN3 decomposes, releasing N2 gas, which is observed by an
increase in the pressure on the vacuum gauge. In a few minutes, the pres-
sure drops back to its original low value, indicating that all the N2 has been
removed. The remaining lithium atoms coalesce to form small colloidal
metal particles. Particles less than 5 nm can be made by this method. Pas-
sivation can be achieved by introducing an appropriate gas [1].
Pyrolysis is commonly a solution process in which nanoparticles are
directly deposited by spraying a solution on a heated substrate surface,
where the constituent react to form a chemical compound. The chemical
reactants are selected such that the products other than the desired com-
pound are volatile at the temperature of deposition. This method repre-
sents a very simple and relatively cost-effective processing method (par-
ticularly, in regard to equipment costs) as compared to many other film
deposition techniques [30].
The other pyrolysis-based method that can be applied in nanostruc-
tures production is a laser pyrolysis technique that requires the presence
in the reaction medium of a molecule absorbing the CO2 laser radiation
[38–39]. In most cases, the atoms of a molecule are rapidly heated via
vibrational excitation and are dissociated. But in some cases, a sensitizer
gas such as SF6 can be directly used. The heated gas molecules transfer
their energy to the reaction medium by collisions leading to dissociation
Electrospinning Process: A Comprehensive Review 11

of the reactive medium without, in the ideal case, dissociation of this mol-
ecule. Rapid thermalization occurs after dissociation of the reactants due
to transfer collision. Nucleation and growth of NSMs can take place in the
as-formed supersaturated vapor. The nucleation and growth period is very
short time (0.1–10 ms). Therefore, the growth is rapidly stopped as soon
as the particles leave the reaction zone. The flame-excited luminescence
is observed in the reaction region where the laser beam intersects the re-
actant gas stream. Since there is no interaction with any walls, the purity
of the desired products is limited by the purity of the reactants. However,
because of the very limited size of the reaction zone with a faster cooling
rate, the powders obtained in this wellness reactor present a low degree of
agglomeration. The particle size is small (~ 5–50 nm range) with a nar-
row size distribution. Moreover, the average size can be manipulated by
optimizing the flow rate, and, therefore, the residence time in the reaction
zone [39–40].

1.2.4.2 LASER-BASED METHODS

The most important laser-based techniques in the synthesis of nanopar-

ticles are pulsed laser ablation. As a physical gas-phase method for prepar-
ing nanosized particles, pulsed laser ablation has become a popular meth-
od to prepare high-purity and ultrafine nanomaterials of any composition
[41–42]. In this method, the material is evaporated using pulsed laser in a
chamber filled with a known amount of a reagent gas and by controlling
condensation of nanoparticles onto the support. It is possible to prepare
nanoparticles of mixed molecular composition such as mixed oxides/ni-
trides and carbides/nitrides or mixtures of oxides of various metals by this
method. This method is capable of a high rate of production of 2–3 g/min
[40].
Laser chemical vapor deposition method is the next laser-based tech-
nique in which photoinduced processes are used to initiate the chemical
reaction. During this method, three kinds of activation should be consid-
ered. First, if the thermalization of the laser energy is faster than the chem-
ical reaction, pyrolytic, and/or photothermal activation is responsible for
the activation. Second, if the first chemical reaction step is faster than the
thermalization, photolytical (nonthermal) processes are responsible for the
excitation energy. Third, combinations of the different types of activation
12 Applied Methodologies in Polymer Research and Technology

are often encountered. During this technique, a high intensity laser beam is
incident on a metal rod, causing evaporation of atoms from the surface of
the metal. The atoms are then swept away by a burst of helium and passed
through an orifice into a vacuum where the expansion of the gas causes
cooling and formation of clusters of the metal atoms. These clusters are
then ionized by UV radiation and passed into a mass spectrometer that
measures their mass: charge ratio [1, 41–43].
Laser-produced nanoparticles have found many applications in medi-
cine, biophotonics, in the development of sensors, new materials, and so-
lar cells. Laser interactions provide a possibility of chemical clean synthe-
sis, which is difficult to achieve under more conventional NP production
conditions [42]. Moreover, a careful optimization of the experimental con-
ditions can allow a control over size distributions of the produced nano-
clusters. Therefore, many studies were focused on the investigation the
laser nanofabrication. In particular, many experiments were performed to
demonstrate nanoparticles formation in vacuum, in the presence of a gas
or a liquid. Nevertheless, it is still difficult to control the properties of
the produced particles. It is believed that numerical calculations can help
explain experimental results and to better understand the mechanisms in-
volved [43].
Despite rapid development in laser physics, one of the fundamental
questions still concerns the definition of proper ablation mechanisms and
the processes leading to the nanoparticles formation. Apparently, the prog-
ress in laser systems implies several important changes in these mecha-
nisms, which depend on both laser parameters and material properties.
Among the more studied ablation mechanisms there are thermal, photo-
chemical and photomechanical ablation processes. Frequently, however,
the mechanisms are mixed, so that the existing analytical equations are
hardly applicable. Therefore, numerical simulation is needed to better un-
derstand and to optimize the ablation process [44].
Thus far, thermal models are commonly used to describe nanosecond
(and longer) laser ablation. In these models, the laser-irradiated material
experiences heating, melting, boiling, and evaporation. In this way, three
numerical approaches were used [29, 45]:
Atomistic approach based on such methods as molecular dynamics
(MD) and direct Monte Carlo (DSMC) simulation. Typical calculation
results provide detailed information about atomic positions, velocities, ki-
netic, and potential energy.
Electrospinning Process: A Comprehensive Review 13

Macroscopic approach based hydrodynamic models. These models al-

low the investigations of the role of the laser-induced pressure gradient,
which is particularly important for ultra-short laser pulses. The models are
based on a one fluid two-temperature approximation and a set of additional
models (equation of state) that determines thermal properties of the target.
Multiscale approach based on the combination of two approaches cited
above was developed by several groups and was shown to be particularly
suitable for laser applications.

1.3 NANOFIBER TECHNOLOGY

Nanofiber consists of two terms “nano” and “fiber,” as the latter term
looks more familiar. Anatomists observed fibers as any of the filament
constituting the extracellular matrix of connective tissue, or any elongated
cells or thread-like structures, muscle fiber, or nerve fiber. According to
textile industry, fiber is a natural or synthetic filament, such as cotton or
nylon, capable of being spun into simply as materials made of such fila-
ments. Physiologists and biochemists use the term “fiber” for indigestible
plant matter consisting of polysaccharides such as cellulose, that when
eaten stimulates intestinal peristalsis. Historically, the term “fiber” or
“fibre” in British English comes from Latin “fibra.” Fiber is a slender,
elongated thread-like structure. Nano is originated from Greek word “na-
nos” or “nannos” refer to “little old man” or “dwarf.” The prefixes “nan-
nos” or “nano” as nannoplanktons or nanoplanktons used for very small
planktons measuring 2–20 μm. In modern “nano” is used for describing
various physical quantities within the scale of a billionth as nanometer
(length), nanosecond (time), nanogram (weight), and nanofarad (charge)
[1, 4, 9, 46]. As mentioned earlier, nanotechnology refers to the science
and engineering concerning materials, structures, and devices, which has
at least one dimension is 100nm or less. This term also refers for a fabrica-
tion technology, where molecules, specification, and individual atoms that
have at least one dimension in nanometers or less is used to design or built
objects. Nanofiber, as the name suggests, is the fiber having a diameter
range in nanometer. Fibrous structure having at least 1D in nanometer
or less is defined as nanofiber according to National Science Foundation
(NSC). The term “nano” describes the diameter of the fibrous shape at
anything below one micron or 1,000 nm [4, 18].
14 Applied Methodologies in Polymer Research and Technology

Nanofiber technology is a branch of nanotechnology whose primary

objective is to create materials in the form of nanoscale fibers in order to
achieve superior functions [1–2, 4]. The unique combination of high spe-
cific surface area, flexibility, and superior directional strength makes such
fibers a preferred material form for many applications ranging from cloth-
ing to reinforcements for aerospace structures. Indeed, while the primary
classification of nanofibers is that of nanostructure or nanomaterial, other
aspects of nanofibers such as its characteristics, modeling, application, and
processing would enable nanofibers to penetrate into many subfields of
nanotechnology [4, 46–47].
It is obvious that nanofibers would geometrically fall into the category
of 1D nanoscale elements that include nanotubes and nanorods. However,
the flexible nature of nanofibers would align it along with other highly
flexible nanoelements such as globular molecules (assumed as 0D soft
matter), as well as solid and liquid films of nanothickness (2D). A nanofi-
ber is a nanomaterial in view of its diameter, and can be considered a nano-
structured material material if filled with nanoparticles to form composite
nanofibers [1, 48].
The study of the nanofiber mechanical properties as a result of manu-
facturing techniques, constituent materials, processing parameters, and
other factors would fall into the category of nanomechanics. Indeed, while
the primary classification of nanofibers is that of nanostructure or nanoma-
terial, other aspects of nanofibers such as its characteristics, modeling, ap-
plication, and processing would enable nanofibers to penetrate into many
subfields of nanotechnology [1, 18].
Although the effect of fiber diameter on the performance and processi-
bility of fibrous structures has long been recognized, the practical genera-
tion of fibers at the nanometer scale was not realized until the rediscovery
and popularization of the electrospinning technology by Professor Dar-
rell Reneker almost a decade ago [49–50]. The ability to create nanoscale
fibers from a broad range of polymeric materials in a relatively simple
manner using the electrospinning process, coupled with the rapid growth
of nanotechnology in recent years have greatly accelerated the growth
of nanofiber technology. Although there are several alternative methods
available for generating fibers in a nanometer scale, none of the methods
matches the popularity of the electrospinning technology due largely to
the simplicity of the electrospinning process[18]. These methods will be
discussed in the sections that follow.
Electrospinning Process: A Comprehensive Review 15

1.3.1 VARIOUS NANOFIBER PRODUCTION METHODS

As was discussed in detail, nanofiber is defined as the fiber having at least

1D in nanometer range that can be used for a wide range of medical appli-
cations for drug delivery systems, scaffold formation, wound healing and
widely used in tissue engineering, skeletal tissue, bone tissue, cartilage
tissue, ligament tissue, blood vessel tissue, neural tissue, and so on. It is
also used in dental and orthopedic implants [4, 51–52]. Nanofiber can be
formed using different techniques including drawing, template synthesis,
phases separation, self-assembly, and electrospinning.

1.3.1.1 DRAWING

In 1998, nanofibers were fabricated with citrate molecules through the

process of drawing for the first time [53]. During drawing process, the fi-
bers are fabricated by contacting a previously deposited polymer solution
droplet with a sharp tip and drawing it as a liquid fiber that is then solidi-
fied by rapid evaporation of the solvent owing to the high surface area. The
drawn fiber can be connected to another previously deposited polymer so-
lution droplet, thereby forming a suspended fiber. Here, the predeposition
of droplets significantly limits the ability to extend this technique, espe-
cially in 3D configurations and hard-to-access spatial geometries. Further,
there is a specific time in which the fibers can be pulled. The viscosity of
the droplet continuously increases with time due to solvent evaporation
from the deposited droplet. The continual shrinkage in the volume of the
polymer solution droplet affects the diameter of the fiber drawn and limits
the continuous drawing of fibers [54].
To overcome the above-mentioned limitation, it is appropriate to use
hollow glass micropipettes with a continuous polymer dosage. It provides
greater flexibility in drawing continuous fibers in any configuration. More-
over, this method offers increased flexibility in the control of key parame-
ters of drawing such as waiting time before drawing (because the required
viscosity of the polymer edge drops), the drawing speed or viscosity, thus
enabling repeatability and control on the dimensions of the fabricated fi-
bers. Thus, drawing process requires a viscoelastic material that can un-
dergo strong deformations while being cohesive enough to support the
stresses developed during pulling [54–55].
16 Applied Methodologies in Polymer Research and Technology

1.3.1.2 TEMPLATE SYNTHESIS

Template synthesis implies the use of a template or mold to obtain a de-

sired material or structure. Hence, the casting method and DNA replica-
tion can be considered as template-based synthesis. In the case of nano-
fiber creation by Feng et al. [56], the template refers to a metal oxide
membrane with through-thickness pores of nanoscale diameter. Under the
application of water pressure on the one side and restrain from the porous
membrane causes extrusion of the polymer which, upon coming into con-
tact with a solidifying solution, gives rise to nanofibers whose diameters
are determined by the pores [1, 57].
This method is an effective route to synthesize nanofibrils and nano-
tubes of various polymers. The advantage of the template synthesis meth-
od is that the length and diameter of the polymer fibers and tubes can be
controlled by the selected porous membrane, which results in more regular
nanostructures. General feature of the conventional template method is
that the membrane should be soluble so that it can be removed after syn-
thesis so as to obtain single fibers or tubes. This restricts practical applica-
tion of this method and gives rise to a need for other techniques [1, 56–57].

1.3.1.3 PHASE SEPARATION METHOD

This method consists of five basic steps: polymer dissolution, gelation,

solvent extraction, freezing, and freeze-drying. In this process, it is ob-
served that gelatin is the most difficult step to control the porous mor-
phology of nanofiber. Duration of gelation varied with polymer concen-
tration and gelation temperature. At low gelation temperature, nanoscale
fiber network is formed; whereas, high gelation temperature led to the
formation of platelet-like structure. Uniform nanofiber can be produced
as the cooling rate is increased, polymer concentration affects the proper-
ties of nanofiber, as polymer concentration is increased porosity of fiber
decreased and mechanical properties of fiber are increased [1, 58].

1.3.1.4 SELF-ASSEMBLY

Self-assembly refers to the build-up of nanoscale fibers using smaller mol-

ecules. In this technique, a small molecule is arranged in a concentric man-
Electrospinning Process: A Comprehensive Review 17

ner so that they can form bonds among the concentrically arranged small
molecules that, upon extension in the plane-s normal, give the longitudinal
axis of a nanofiber. The main mechanism for a generic self-assembly is the
intramolecular forces that bring the smaller unit together. A hydrophobic
core of alkyl residues and a hydrophilic exterior lined by peptide residues
was found in obtained fiber. It is observed that the nanofibers produced
with this technique have a diameter range of 5–8 mm approximately and
are several microns in length [1, 59].
Although there are a number of techniques used for the synthesis of
nanofiber, electrospinning represents an attractive technique to fabricate
polymeric biomaterial into nanofibers. Electrospinning is one of the most
commonly utilized methods for the production of nanofiber. It has a wide
advantage over the previously available fiber formation techniques be-
cause here electrostatic force is used instead of conventionally used me-
chanical force for the formation of fibers. This method will be debated
comprehensively in the sections that follow.

1.3.1.5 ELECTROSPINNING OF NANOFIBERS

Electrospinning is a straightforward and cost-effective method to produce

novel fibers with diameters in the range of from less than 3 nm to over 1
mm, which overlaps contemporary textile fiber technology. During this
process, an electrostatic force is applied to a polymeric solution to pro-
duce nanofiber [60–61] with diameter ranging from 50 to 1,000 nm or
greater [49, 62–63]; Due to surface tension, the solution is held at the tip
of syringe. Polymer solution is charged due to applied electric force. In the
polymer solution, a force is induced due to mutual charge repulsion that
is directly opposite to the surface tension of the polymer solution. Further
increases in the electrical potential led to the elongation of the hemispheri-
cal surface of the solution at the tip of the syringe to form a conical shape
known as “Taylor cone.” [50, 64]. The electric potential is increased to
overcome the surface tension forces to cause the formation of a jet, ejects
from the tip of the Taylor cone. Due to elongation and solvent evaporation,
charged jet instable and gradually thins in air primarily [62, 65–67]. The
charged jet forms randomly oriented nanofibers that can be collected on
a stationary or rotating grounded metallic collector [50]. Electrospinning
18 Applied Methodologies in Polymer Research and Technology

provides a good method and a practical way of producing polymer fibers

with diameters ranging from 40 to 2,000 nm [49–50].

1.3.1.5 1 THE HISTORY OF ELECTROSPINNING

METHODOLOGY

William Gilbert discovered the first record of the electrostatic attraction of

a liquid in 1,600 [68]. The first electrospinning patent was submitted by
John Francis Cooley in 1900 [69]. After that in 1914, John Zeleny studied
on the behavior of fluid droplets at the end of metal capillaries that caused
the beginning of the mathematical model the behavior of fluids under elec-
trostatic forces [65]. Between 1931 and 1944, Anton Formhals took out at
least 22 patents on electrospinning [69]. In 1938, N.D. Rozenblum and I.V.
Petryanov-Sokolov generated electrospun fibers, which they developed
into filter materials [70]. Between 1964 and 1969, Sir Geoffrey Ingram
Taylor produced the beginnings of a theoretical foundation of electrospin-
ning by mathematically modeling the shape of the (Taylor) cone formed
by the fluid droplet under the effect of an electric field [71–72]. In the
early 1990s, several research groups (such as Reneker) demonstrated elec-
trospun nanofibers. Since 1995, the number of publications about electro-
spinning has been increasing exponentially every year [69].

1.3.1.5 2 ELECTROSPINNING PROCESS

Electrospinning process can be explained in five significant steps includ-

ing the folloiwng [48, 73–75]:
1. Charging of the polymer fluid: The syringe is filled with a polymer
solution, the polymer solution is charged with a very high potential
around 10–30 kV. The nature of the fluid and polarity of the ap-
plied potential free electrons, ions, or ion pairs are generated as
the charge carriers form an electrical double layer. This charging
induction is suitable for conducting fluid, but for nonconducting
fluid charge directly injected into the fluid by the application of
electrostatic field.
2. Formation of the cone jet (Taylor cone): The polarity of the fluid
depends on the voltage generator. The repulsion between the sim-
Electrospinning Process: A Comprehensive Review 19

ilar charges at the free electrical double-layer works against the

surface tension and fluid elasticity in the polymer solution to de-
form the droplet into a conical-shaped structure, that is known as a
Taylor cone. Beyond a critical charge density Taylor cone becomes
unstable and a jet of fluid is ejected from the tip of the cone.
3. Thinning of the jet in the presence of an electric field: The jet trav-
els a path to the ground; this fluid jet forms a slender continuous
liquid filament. The charged fluid is accelerated in the presence of
an electrical field. This region of fluid is generally linear and thin.
4. Instability of the jet: Fluid elements accelerated under electric field
and thus stretched and succumbed to one or more fluid instabilities
that distort as they grow following many spiral and distort the path
before collected on the collector electrode. This region of instabil-
ity is also known as whipping region.
5. Collection of the jet: Charged electrospun fibers travel downfield
until its impact with a lower potential collector plate. The orienta-
tion of the collector affects the alignment of the fibers. Different
types of collector also affect the morphology and the properties of
producing nanofiber. Different types of collectors are used—rotat-
ing drum collector, moving belt collector, rotating wheel with bev-
elled edge, multifilament thread, parallel bars, simple mesh collec-
tor, and so on.

1.3.1.5 3 ELECTROSPINNING SETUPS

Electrospinning is conducted at room temperature with atmospheric

conditions. The typical setup of electrospinning apparatus is shown
in Figure 1.1. Basically, an electrospinning system consists of three
major components: a high-voltage power supply, a spinneret (such
as a pipette tip), and a grounded collecting plate (usually a metal
screen, plate, or rotating mandrel) and utilizes a high-voltage source
to inject charge of a certain polarity into a polymer solution or melt,
which is then accelerated toward a collector of opposite polarity [73,
76–77]. Most of the polymers are dissolved in some solvents before
electrospinning, and when it completely dissolves, forms polymer
solution. The polymer fluid is then introduced into the capillary tube
20 Applied Methodologies in Polymer Research and Technology

for electrospinning. However, some polymers may emit unpleasant

or even harmful smells; therefore, the processes should be conduct-
ed within chambers having a ventilation system. In the electrospin-
ning process, a polymer solution held by its surface tension at the
end of a capillary tube is subjected to an electric field and an electric
charge is induced on the liquid surface due to this electric field.
When the electric field applied reaches a critical value, the repulsive
electrical forces overcome the surface tension forces. Eventually, a
charged jet of the solution is ejected from the tip of the Taylor cone
and an unstable and a rapid whipping of the jet occurs in the space
between the capillary tip and collector, which leads to evaporation
of the solvent, leaving a polymer behind. The jet is only stable at the
tip of the spinneret and after that instability starts. Thus, the electro-
spinning process offers a simplified technique for fiber formation
[50, 73, 78–79].

FIGURE 1.1 Scheme of a conventional electrospinning set-up.

1.3.1.5 4 THE EFFECTIVE PARAMETERS ON ELECTROSPINNING

The electrospinning process is generally governed by many parameters

that can be classified broadly into solution parameters, process parameters,
Electrospinning Process: A Comprehensive Review 21

and ambient parameters. Each of these parameters significantly affects the

fiber morphology obtained as a result of electrospinning; and by proper
manipulation of these parameters, we can get nanofibers of desired mor-
phology and diameters. These effective parameters are sorted as below
[63, 67, 73, 76]: (a) Polymer solution parameters that includes molecular
weight and solution viscosity, surface tension, solution conductivity, and
dielectric effect of solvent and (b) processing parameters that include volt-
age, feed rate, temperature, effect of collector, and the diameter of the
orifice of the needle.

(a) Polymer solution parameters

(1) Molecular weight and solution viscosity
The higher the molecular weight of the polymer increases molecular en-
tanglement in the solution, the higher the increase in viscosity. The elec-
trospun jet eject with high viscosity during it is stretched to a collector
electrode leading to formation of continuous fiber with higher diameter,
but very high viscosity makes difficult to pump the solution and also lead
to the drying of the solution at the needle tip. As a very low viscosity lead
in bead formation in the resultant electrospun fiber; therefore, the molecu-
lar weight and viscosity should be acceptable to form nanofiber [48, 80].

(2) Surface tension

Lower viscosity leads to decrease in surface tension resulting bead forma-
tion along the fiber length because the surface area is decreased, but at
the higher viscosity effect of surface tension is nullified because of the
uniform distribution of the polymer solution over the entangled polymer
molecules. Therefore, lower surface tension is required to obtain smooth
fiber and lower surface tension can be achieved by adding of surfactants
in polymer solution [80–81].

(3) Solution conductivity

Higher conductivity of the solution followed a higher charge distribution
on the electrospinning jet which leads to increase in stretching of the solu-
tion during fiber formation. Increased conductivity of the polymer solu-
tion lowers the critical voltage for the electrospinning. Increased charge
leads to the higher bending instability leading to the higher deposition area
of the fiber being formed, as a result jet path is increased and finer fiber
22 Applied Methodologies in Polymer Research and Technology

is formed. Solution conductivity can be increased by the addition of salt

or polyelectrolyte or increased by the addition of drugs and proteins that
dissociate into ions when dissolved in the solvent formation of smaller
diameter fiber [67, 80].

4) Dielectric effect of solvent

Higher the dielectric property of the solution lesser is the chance of bead
formation and smaller is the diameter of electrospun fiber. As the dielec-
tric property is increased, there is increase in the bending instability of the
jet and the deposition area of the fiber is increased. As jet path length is
increased fine fiber deposit on the collector [67, 80].

(b) Processing condition parameters

(1) Voltage
Taylor cone stability depends on the applied voltage; at higher voltage,
greater amount of charge causes the jet to accelerate faster leading to
smaller and unstable Taylor cone. Higher voltage leads to greater stretch-
ing of the solution due to fiber with small diameter formed. At lower volt-
age, the flight time of the fiber to a collector plate increases that led to
the formation of fine fibers. There is greater tendency to bead formation
at high voltage because of increased instability of the Taylor cone, and
these beads join to form thick diameter fibers. It is observed that the better
crystallinity in the fiber obtained at higher voltage. Instead of DC if AC
voltage is provided for electrospinning, it forms thicker fibers [48, 80].

(2) Feed rate

As the feed rate is increased, there is an increase in the fiber diameter be-
cause greater volume of solution is drawn from the needle tip [80].

3) Temperature
At high temperature, the viscosity of the solution is decreased, and there
is increase in higher evaporation rate that allows greater stretching of the
solution and a uniform fiber is formed [82].
Electrospinning Process: A Comprehensive Review 23

4) Effect of collector
In electrospinning, collector material should be conductive. The collec-
tor is grounded to create stable potential difference between needle and
collector. A nonconducting material collector reduces the amount of fiber
being deposited with lower packing density. But in case of conducting
collector, there is accumulation of closely packed fibers with higher pack-
ing density. Porous collector yields fibers with lower packing density as
compared with nonporous collector plate. In porous collector plate, the
surface area is increased so residual solvent molecules gets evaporated fast
as compared with nonporous. Rotating collector is useful in getting dry fi-
bers as it provides more time to the solvents to evaporate. It also increases
fibermorphology [83]. The specific hat target with proper parameters has
a uniform surface electric field distribution, the target can collect the fiber
mats of uniform thickness and thinner diameters with even-size distribu-
tion[80].

5) Diameter of pipette orifice

Orifice with small diameter reduces the clogging effect due to less expo-
sure of the solution to the atmosphere and leads to the formation of fibers
with smaller diameter. However, very small orifice has the disadvantage
that it creates problems in extruding droplets of solution from the tip of
the orifice [80].

1.4 DESIGN MULTIFUNCTIONAL PRODUCT BY

NANOSTRUCTURES

The largest variety of efficient and elegant multifunctional materials is

seen in natural biological systems, which occur sometimes in the simple
geometrical forms in human-made materials. The multifunctionality of a
material could be achieved by designing the material from the micro- to
macroscales (bottom up design approach), mimicking the structural for-
mations created by nature [84]. Biological materials present around us
have a large number of ingenious solutions and serve as a source of in-
spiration. There are different ways of producing multifunctional materials
that depend largely on whether these materials are structural composites,
smart materials, or nanostructured materials. The nanostructure materials
are most challenging and innovative processes, introducing, in the manu-
24 Applied Methodologies in Polymer Research and Technology

facturing, a new approaches such as self-assembly and self-replication.

For biomaterials involved in surface-interface-related processes, common
geometries involve capillaries, dendrites, hair, or fin-like attachments sup-
ported on larger substrates. It may be useful to incorporate similar hierar-
chical structures in the design and fabrication of multifunctional synthetic
products that include surface sensitive functions such as sensing, reactivi-
ty, charge storage, transport property, or stress transfer. Significant effort is
being directed to fabricate and understand materials that involve multiple-
length scales and functionalities. Porous fibrous structures can behave like
lightweight solids providing significantly higher surface area compared to
compact ones. Depending on what is attached on their surfaces, or what
matrix is infiltrated in them, these core structures can be envisioned in a
wide variety of surface active components or net-shape composites. If na-
noelements can be attached in the pores, the surface area within the given
space can be increased by several orders of magnitude, thereby increasing
the potency of any desired surface functionality. Recent developments in
electrospinning have made these possible, thanks to a coelectrospinning
polymer suspension [85]. This opens up the possibility of taking a func-
tional material of any shape and size, and attaching nanoelements on them
for added surface functionality. The fast-growing nanotechnology with
modern computational/experimental methods gives the possibility to de-
sign multifunctional materials and products in human surroundings. Smart
clothing, portable fuel cells, and medical devices are some of them. Re-
search in nanotechnology began with applications outside of everyday life
and is based on discoveries in physics and chemistry. The reason for that is
need to understand the physical and chemical properties of molecules and
nanostructures in order to control them. For example, nanoscale manipu-
lation results in new functionalities for textile structures, including self-
cleaning, sensing, actuating, and communicating. Development of pre-
cisely controlled or programmable medical nanomachines and nanorobots
is great promise for nanomedicine. Once nanomachines are available, the
ultimate dream of every medical man becomes reality. The miniaturization
of instruments on micro- and nanodimensions promises to make our future
lives safer with more humanity. A new approach in material synthesis is a
computational-based material development. It is based on multiscale ma-
terial and process modeling spanning, on a large spectrum of time as well
as on length scales. Multiscale materials design means to design materials
from a molecular scale up to a macroscale. The ability to manipulate at
Electrospinning Process: A Comprehensive Review 25

atomic and molecular level is also creating materials and structures that
have unique functionalities and characteristics. Therefore it will be and
revolutionizing next-generation technology ranging from structural mate-
rials to nanoelectro-mechanical systems (NEMs), for medicine and bioen-
gineering applications. Recent research development in nanomaterials has
been progressing at a tremendous speed for it can totally change the ways
in which materials can be made with unusual properties. Such research
includes the synthetic of nanomaterials, manufacturing processes, in terms
of the controls of their nanostructural and geometrical properties, mould-
ability, and mixability with other matrix for nanocomposites. The cost of
designing and producing a novel multifunctional material can be high and
the risk of investment to be significant [12, 22].
Computational materials research that relies on multiscale model-
ing has the potential to significantly reduce development costs of new
nanostructured materials for demanding applications by bringing physi-
cal and microstructural information into the realm of the design engineer.
As there are various potential applications of nanotechnology in design
multifunctional product, only some of the well-known properties come
from by nanotreatment are critically highlighted [12, 22, 30]. This section
reviews current research in nanotechnology application of the electros-
pinning nanofiber, from fibber production, and development to end uses
as multifunctional nanostructure device and product. The electrospinning
phenomena are described from experimental viewpoint to it simulation as
multiscale problem.

1.4.1 THE MULTIFUNCTIONAL MATERIALS AND PRODUCTS

1.4.1.1 RESPONSIVE NANOPARTICLES

There are several directions in the research and development of the re-
sponsive nanoparticle (RNP) applications (Figure 1.2). Development of
particles that respond by changing stability of colloidal dispersions is the
first directions. Stimuli-responsive emulsions and foams could be very
attractive for various technologies in coating industries, cosmetic, and
personal care. The RNPs compete with surfactants; and hence, the costs
for the particle production will play a key role. The main challenge is
the development of robust and simple methods for the synthesis of RNPs
26 Applied Methodologies in Polymer Research and Technology

from inexpensive colloidal particles and suspensions. That is indeed not a

simple job since most of commercially available NPs are more expensive
than surfactants. Another important application of RNPs for tunable col-
loidal stability of the particle suspensions is a very broad area of biosen-
sors [86–87].

FIGURE 1.2 Stimuli-responsive nanoparticles.

The second direction is stimuli-responsive capsules that can release the

cargo upon external stimuli. The capsules are interesting for biomedical
applications (drugs delivery agents) and for composite materials (release
of chemicals for self-healing). The most challenging task in many cases is
to engineering systems capable to work with demanded stimuli. It is not
a simple job for many biomedical applications where signalling biomol-
ecules are present in very small concentrations and a range of changes
of many properties is limited by physiological conditions. A well-known
challenge is related to the acceptable size production of capsules. Many
medical applications need capsules less than 50 nm in diameter. Fabri-
cation of capsules with a narrow pore-size distribution and tunable sizes
could dramatically improve the mass transport control [86, 88].
A hierarchically organized multicompartment RNPs are in the focus.
These particles could respond to weak signals, multiple signals, and could
demonstrate a multiple response. They can perform logical operations
with multiple signals, store energy, absorb and consume chemicals, and
synthesize and release chemicals. In other words, they could operate as
an autonomous intelligent minidevice. The development of such RNPs
can be considered as a part of biomimetics inspired by living cells or logic
Electrospinning Process: A Comprehensive Review 27

extension of the bottom up approach in nanotechnology. The development

of the intelligent RNPs faces numerous challenges related to the coupling
of many functional building blocks in a single hierarchically structured
RNP. These particles could find applications for intelligent drug delivery,
removal of toxic substances, diagnostics in medicine, intelligent catalysis,
microreactors for chemical synthesis and biotechnology, new generation
of smart products for personal use, and others [88–89].

1.4.1.2 NANOCOATINGS

In general, the coating’s thickness is at least an order of magnitude lower

than the size of the geometry to be coated. The coating’s thickness less
than 10 nm is called nanocoating. Nanocoatings are materials that are pro-
duced by shrinking the material at the molecular level to form a denser
product. Nanostructure coatings have an excellent toughness, good cor-
rosion resistance, wear, and adhesion properties. These coatings can be
used to repair component parts instead of replacing them, resulting in sig-
nificant reductions in maintenance costs. In addition, the nanostructure
coatings will extend the service life of the component due to the improved
properties over conventional coatings [90–91].

FIGURE 1.3 Nanocoatings.

1.4.1.3 FIBROUS NANOSTRUCTURE

The nanofibers are basic building block for plants and animals. From the
structuralviewpoint, a uniaxial structure is able to transmit forces along
28 Applied Methodologies in Polymer Research and Technology

its length and reducing required mass of materials. Nanofibers serve as

another platform for multifunctional hierarchical example. The success-
ful design concepts of nature, the nanofiber, become an attractive basic
building component in the construction of hierarchically organized nano-
structures. To follow nature’s design, a process that is able to fabricate
nanofiber from a variety of materials and mixtures becomes a prerequisite
[92–93].
Control of the nanofibers arrangement is also necessary to optimize
structural requirements. Finally, incorporation of other components into
the nanofibers is required to form a complex, hierarchically organized
composite. A nanofiber fabrication technique known as electrospinning
process has the potential to play a vital role in the construction of a mul-
tilevels nanostructure [94]. In this chapter, we will introduce electrospin-
ning as a potential technology for use as a platform for multifunctional,
hierarchically organized nanostructures. Electrospinning is a method of
producing superfine fibers with diameters ranging from 10 nm to 100
nm. Electrospinning occurs when the electrical forces at the surface of a
polymer solution overcome the surface tension and cause an electrically
charged jet of polymer solution to be ejected. A schematic drawing of the
electrospinning process is shown in Figure 1.3. The electrically charged
jet undergoes a series of electrically induced instabilities during its pas-
sage to the collection surface, which results in complicated stretching and
looping of the jet [50, 60]. This stretching process is accompanied by the
rapid evaporation of the solvent molecules, further reducing the jet diam-
eter. Dry fibers are accumulated on the surface of the collector, resulting in
a nonwoven mesh of nanofibers.

FIGURE 1.4 The electrospinning process.

Electrospinning Process: A Comprehensive Review 29

Basically, an electrospinning system consists of three major compo-

nents: a high-voltage power supply, an emitter (e.g., a syringe), and a
grounded collecting plate (usually a metal screen, plate, or rotating man-
drel). There are a wide range of polymers that used in electrospinning and
are able to form fine nanofibers within the submicron range and used for
varied applications. Electrospun nanofibers have been reported as being
from various synthetic polymers, natural polymers or a blend of both in-
cluding proteins, nucleic acids [74]. The electrospinning process is solely
governed by many parameters, classified broadly into rheological, pro-
cessing, and ambient parameters. Rheological parameters include viscos-
ity, conductivity, molecular weight, and surface tension; whereas process
parameters include applied electric field, tip to collector distance, and flow
rate. Each of these parameters significantly affects the fibers morphol-
ogy obtained as a result of electrospinning, and by proper manipulation
of these parameters we can get nanofibers fabrics of desired structure and
properties on multiple material scale (Figure 1.5).
Among these variables, ambient parameters encompass the humidity
and temperature of the surroundings that play a significant role in deter-
mining the morphology and topology of electrospun fabrics. Nanofibrous
assemblies such as nonwoven fibrous sheet, aligned fibrous fabric, con-
tinuous yarn, and 3D structure have been fabricated using electrospin-
ning [51]. Physical characteristics of the electrospun nanofibers can also
be manipulated by selecting the electrospinning conditions and solution.
Structure organization on a few hierarchical levels (see Figure 1.4) has
been developed using electrospinning. Such hierarchy and multifunction-
ality potential will be described in the sections that follow. Finally, we
will describe how electrospun multifunctional, hierarchically organized
nanostructure can be used in applications such as healthcare, defence and
security, and environmental.
The slender-body approximation is widely used in electrospinning
analysis of common fluids [51]. The presence of nanoelements (nanopar-
ticles, carbon nanotube, clay) in suspension jet complicate replacement
3D axisymetric with 1D equivalent jet problem under solid–fluid interac-
tion force on nanolevel domain. The applied electric field induced dipole
moment, while torque on the dipole rotate and align the nanoelement with
electric field. The theories developed to describe the behavior of the sus-
pension jet fall (Figure 1.6) into two levels: macroscopic and microscopic.
The macroscopic-governing equations of the electrospinning are equation
30 Applied Methodologies in Polymer Research and Technology

of continuity, conservation of the charge, balance of momentum, and elec-

tric field equation. Conservation of mass for the jet requires that [61, 95].

FIGURE 1.5 Multiscale electrospun fabric.

FIGURE 1.6 Geometry of the jet flow.

For polymer suspension stress tensor τij come from polymeric τˆij and
solvent contribution tensor via constitutive equation:

߬௩ ൌ ߬Ƹ ௩ ൅ ݊௦ Ǥ ‫ݕ‬ሶ௩ (1.4.1)

where ηs is solvent viscosity and γij strain rate tensor. The polymer contri-
bution tensor τˆij depends on microscopic models of the suspension. Mi-
croscopic approach represents the microstructural features of material by
means of a large number of micromechanical elements (beads, platelet,
Electrospinning Process: A Comprehensive Review 31

rods), obeying stochastic differential equations. The evolution equations

of the microelements arise from a balance of momentum on the elemen-
tary level. For example, rheological behavior of the dilute suspension of
the carbon nanotubes (CNTs) in polymer matrix can be described as FENE
dumbbell model [96].

௖‫࣫ۃ‬Ǥ࣫‫ۄ‬
ߣ‫࣫ۃ‬Ǥ ࣫‫ ׏ۄ‬ൌ ߜ௩ െ (1.4.2)>
ଵି௧௥‫࣫ۃ‬Ǥ࣫‫ۄ‬Ȁ௕೘ಲೣ

where <Q.Q> is the suspension configuration tensor (see Figure 1.7), c is

a spring constant, and max b is maximum CNT extensibility. Subscript ∇
represent the upper convected derivative, and λ denote a relaxation time.
The polymeric stress can be obtained from the following relation:

FIGURE 1.7 FENE dumbbell model.

ఛොೡ ௖‫࣫ۃ‬Ǥ࣫‫ۄ‬
ൌ ߜ௩ െ (1.4.3)
௡௞் ଵି௧௥‫࣫ۃ‬Ǥ࣫‫ۄ‬Ȁ௕೘ಲೣ

where k is Boltzmann’s constant, T is temperature, and n is dumbbells

density. Orientation probability distribution function ψ of the dumbbell
vector Q can be described by the Fokker–Planck equation, neglecting ro-
tary diffusivity.

డట డ
൅ ሺ߰Ǥ ࣫ሻ ൌ Ͳ (1.4.4)
డ௧ డ࣫
32 Applied Methodologies in Polymer Research and Technology

Solution equations (1.4.3) and (1.4.4), with supposition that flow in

orifice is Hamel flow [97], give value orientation probability distribution
function ψ along streamline of the jet. Rotation motion of a nanoelement
(e.g., CNTs) in a Newtonian flow can be described as short fiber suspen-
sion model as another rheological model [8].

ௗ௣ ଵ ଵ ௗఊೡ ௗఊೖ೗ ଵ డట
ൌ ߱௩ ܲ௜ ൅ Ĭ ቂ ܲ௃ െ ܲ௞ ܲ௧ ܲ௟ ቃ െ ‫ܦ‬௥ (1.4.5)
ௗ௧ ଶ ଶ ௗ௧ ௗ௧ ట డ௧

where p is a unit vector in nanoelement axis direction, ωij is the rotation

rate tensor, γij is the deformation tensor, Dr is the rotary diffusivity, and θ
is shape factor. Microscopic models for evolution of suspension micro-
structure can be coupled to macroscopic transport equations of mass and
momentum to yield micro–macro multiscale flow models. The presence of
the CNTs in the solution contributes to new form of instability with influ-
ences on the formation of the electrospun mat. The high strain rate on the
nanoscale with complicated microstructure requires innovative research
approach from the computational modeling viewpoint [98].

FIGURE 1.8 The CNTs alignment in jet flow.

Electrospinning Process: A Comprehensive Review 33

By the illustrated multiscale treatment (Figure 1.8), the CNT suspen-

sion in the jet, one time as short flexible cylinder in solution (microscale),
and second time as coarse grain system with polymer chain particles and
CNT(nanoscale level).

1.5 MULTIFUNCTIONAL NANOFIBER-BASED STRUCTURE

The variety of materials and fibrous structures that can be electrospun

allow for the incorporation and optimization of various functions to the
nanofiber, either during spinning or through postspinning modifications.
A schematic of the multilevel organization of an electrospun fiber based
composite is shown in Figure 1.9.

FIGURE 1.9 Multiscale electrospun fabrics.

Based on crrent technology, at least four different levels of organiza-

tion can be put together to form a nanofiber-based hierarchically orga-
nized structure. At the first level, nanoparticles or a second polymer can
be mixed into the primary polymer solution and electrospun to form com-
posite nanofiber. Using a dual-orifice spinneret design, a second layer of
material can be coated over an inner core material during electrospinning
34 Applied Methodologies in Polymer Research and Technology

to give rise to the second-level organization. Two solution reservoirs, one

leading to the inner orifice and the other to the outer orifice will extrude
the solutions simultaneously. Otherwise, other conditions for electros-
pinning remain the same. Rapid evaporation of the solvents during the
spinning process reduces mixing of the two solutions, thereby forming
core-shell nanofiber. At the same level, various surface coating or func-
tionalization techniques may be used to introduce additional property to
the fabricated nanofiber surface. Chemical functionality is a vital compo-
nent in advance multifunctional composite material to detect and respond
to changes in its environment. Thus, various surface modifications tech-
niques have been used to construct the preferred arrangement of chemical-
ly active molecules on the surface with the nanofiber as a supporting base.
The third-level organization will see the fibers oriented and organized to
optimize its performance. A multilayered nanofiber membrane or mixed
materials nanofibers membrane can be fabricated in situ through selective
spinning or using a multiple orifice spinneret design, respectively. Finally,
the nanofibrous assembly may be embedded within a matrix to give the
fourth-level organization. The resultant structure will have various proper-
ties and functionality due its hierarchical organization. Nanofiber structure
at various levels have been constructed and tested for various applications
and will be covered in the following sections. To follow surface function-
ality and modification, jet flow must be solved on multiple scale level. All
above scale (nanoscale) can be solved by using particle method together
with coarse-grain method on supramolecular level [50–51].

1.5.1 NANOFIBER EFFECTIVE PROPERTIES

The effective properties of the nanofiber can be determined by homog-

enization procedure using representative volume element (RVE). There
is need for incorporating more physical information on microscale to pre-
cisely determine material behavior model. For electrospun suspension
with nanoelements (CNTs), a concentric composite cylinder embedded
with a caped carbon nanotube represents RVE as shown in Figure 1.10.
A carbon nanotube with a length 2l, radii 2a is embedded at the center of
matrix materials with a radii R and length 2L.
Electrospinning Process: A Comprehensive Review 35

FIGURE 1.10 The nanofiber representative volume element.

The discrete atomic nanotube structure replaced the effective (solid) fi-
ber having the same length and outer diameter as a discrete nanotube with
effective Young’s nanotube modulus determined from atomic structure.
The stress and strain distribution in RVE was determined using modified
shear-lag model [99]. For the known stress and strain distribution under
RVE, elastic effective properties quantificators can be calculated. The ef-
fective axial module E33, and the transverse module E11= E22, can be cal-
culated as follow:

‫ۃ‬ఙ೥೥ ‫ۄ‬
‫ܧ‬ଷଷ ൌ ‫ۃ‬ఌ೥೥ ‫ۄ‬
‫ۃ‬ఙೣೣ ‫ۄ‬ (1.4.6)
‫ܧ‬ଵଵ ൌ ‫ۃ‬ఌೣೣ ‫ۄ‬
where denotes a volume average under volume V as defined by

ଵ 
‫ۃ‬ȩ‫ ۄ‬ൌ ‫׬‬௏ ȩ ሺ‫ݔ‬ǡ ‫ݕ‬ǡ ‫ݖ‬ሻǤ ܸ݀Ǥ (1.4.7)
௏

The three-phase concentric cylindrical shell model has been proposed to

predict effective modulus of nanotube reinforced nanofibers. The modulus
of nanofiber depends strongly on the thickness of the interphase and CNTs
diameter [12].

1.5.2 NETWORK MACROSCOPIC PROPERTIES

Macroscopic properties of the multifunctional structure determine final

value of the any engineering product. The major objective in the determi-
36 Applied Methodologies in Polymer Research and Technology

nation of macroscopic properties is the link between atomic and continuum

types of modeling and simulation approaches. The multiscale method such
as quasicontinuum, bridge method, coarse-grain method, and dissipative
particle dynamics are some popular methods of solution [98, 100]. The
main advantage of the mesoscopic model is its higher computational ef-
ficiency than the molecular modeling without a loss of detailed properties
at molecular level. Peridynamic modeling of fibrous network is another
promising method, which allows damage, fracture, and long-range forces
to be treated as natural components of the deformation of materials [101].
In the first stage, effective fiber properties are determined by homogeniza-
tion procedure; whereas in the second stage, the point-bonded stochastic
fibrous network at mesoscale is replaced by continuum plane stress mod-
el. Effective mechanical properties of nanofiber sheets at the macroscale
level can be determined using the 2D Timoshenko beam network (figure
1.11). The critical parameters are the mean number of crossings per nano-
fiber, total nanofiber crossing in sheet and mean segment length [102].
Let us first consider a general planar fiber network characterized by fibre
concentration n and fibre angular and length distribution ψ (ϕ, 1), where
ϕ and l are fiber orientation angle and fiber length, respectively. The fibre
radius r is considered uniform and the fibre concentration n is defined as
the number of fiber per unite area.

FIGURE 1.11 The fiber contact analysis.

Electrospinning Process: A Comprehensive Review 37

The Poisson probability distribution can be applied to define the fiber

segment length distribution for electrospun fabrics, a portion of the fiber
between two neighboring contacts:

ଵ
݂ሺκሻ ൌ ‡š’൫െκȀκ൯ (1.4.8)
κ

where l is the mean segment length. The total number fiber segments Nˆ in
the rectangular region b* h:

ܰ ൌ ሼ݊Ǥ κ଴ ሺ‫ ۄߣۃ‬൅ ʹ‫ݎ‬ሻ െ ͳሽǤ ݊Ǥ ܾǤ ݄ (1.4.9)

With

థ ஶ
‫ ۄߣۃ‬ൌ න  න ߰ሺ ͻǤ κሻǤ ߣሺͻሻǤ ݀κǤ ݀ͻ (1.4.10)
଴ ଴

where the dangled segments at fiber ends have been excluded. The fiber
network will be deformed in several ways. The strain energy in fiber seg-
ments comes from bending, stretching, and shearing modes of deforma-
tion can be calculated as follows (see Figure 1.12)

ଵ ாǤ஺ ଶ
ܷ ൌ ܰǤ κ଴ Ǥ ܾǤ ݄ ‫ ׭‬ ߝ Ǥ ߰ሺ߮ǡ κሻǤ κǤ ݀κǤ ݀߮
ଶ κ ௑௑

൅݊Ǥ κ଴ Ǥ ሼሺ‫ ۄߣۃ‬൅ ʹ‫ݎ‬ሻ െ ͳሽǤ ܾǤ ݄Ǥ ቄ‫׭‬

ଵ ீǤ஺ ଶ
Ǥ Ǥ ߛ௫௬ Ǥ ߰ሺ߮ǡ κሻǤ κǤ ݀κǤ ݀߮ (1.4.11)
ଶ κ

ଷǤாǤூ ଶ
൅‫׭‬ ߛ௫௬ Ǥ ߰ሺ߮ǡ κሻǤ κǤ ݀κǤ ݀߮ሽ
κయ

where A and I are beam cross-section area and moment of inertia, respec-
tively. The first term on right-hand side is stretching mode, whereas the
second and last terms are shear-bending modes, respectively.
38 Applied Methodologies in Polymer Research and Technology

FIGURE 1.12 Fiber network 2D model.

The effective material constants for fiber network can be determined

using homogenization procedure concept for fiber network. The strain en-
ergy fiber network for representative volume element is equal to strain
energy continuum element with effective material constant. The strain en-
ergy of the representative volume element under plane stress conditions
are as follows:

ͳ
ܷ ൌ Ǥ ‫ߝۃ‬௩ ‫ۄ‬Ǥ ‫ܥ‬௩௞௟ ‫ߝۃ‬௞௟ ‫ۄ‬Ǥ ܸ (1.4.12)
ʹ
where is V. b. h. 2. r representative volume element, Cijkl are effective
elasticity tensor. The square bracket < > means macroscopic strain value.
Microscopic deformation tensor was assume of a fiber segments εij is
compatible with effective macroscopic strain <εij> of effective continuum
Electrospinning Process: A Comprehensive Review 39

(affine transformation). This is bridge relations between fiber segment

microstrain εij and macroscopic strain <εij> in the effective medium.
Properties of this nanofibrous structure on the macro scale depend on
the 3D joint morphology. The joints can be modeled as contact torsional
elements with spring and dashpot [102]. The elastic energy of the whole
random fiber network can be calculated numerically, from the local de-
formation state of the each segment by finite element method [103]. The
elastic energy of the network is then the sum of the elastic energies of
all segments. We consider here tensile stress, and the fibers are rigidly
bonded to each other at every fiber–fiber crossing points. To mimic the
microstructure of electrospun mats, we generated fibrous structures with
fibers positioned in horizontal planes, and stacked the planes on top of
one another to form a 2D or 3D structure. The representative volume
element dimensions are considered to be an input parameter that can
be used among other parameters to control the solid volume fraction
of the structure, density number of fiber in the simulations. The num-
ber of intersections/unit area and mean lengths are obtained from image
analysis of electrospun sheets. For the random point field, the stochastic
fiber network was generated. Using polar coordinates and having the
centerline equation of each fiber, the relevant parameters confined in the
simulation box is obtained. The procedure is repeated until reaching the
desired parameters is achieved [22, 95, 104].The nonload-bearing fiber
segments were removed and trimmed to keep dimensions b*h of the rep-
resentative window (see Figure 1.13).
A line representative network model is replaced by finite element beam
mesh. The finite element analyses were performed in a network of 100
fibers, for some CNTs volume fractions values. Nanofibers were modeled
as equivalent cylindrical beam as mentioned above. Effective mechanical
properties of nanofiber sheets at the macroscale level can be determined
using the 2D Timoshenko beam network.
40 Applied Methodologies in Polymer Research and Technology

FIGURE 1.13 Repesentative volume element of the network.

For a displacement-based form of beam element, the principle of vir-

tual work is assumed valid. For a beam system, a necessary and sufficient
condition for equilibrium is that the virtual work done by sum of the ex-
ternal forces and internal forces vanish for any virtual displacement δW =
0. The W is the virtual work that the work is done by imaginary or virtual
displacements.

  
ߜܹ ൌ ශ ‫ߝߜݒ‬௩ ൅ ශ ‫ܨ‬௝ ߜ‫ݑ‬௦ ܸ݀ ൅ ඾ ܶߜ‫ݑ‬௟ ݀‫ܣ‬ (1.4.13)
௩ ௩ ஺

where ε is the strain, σ is the stress, F is the body force, δu is the virtual
displacement, and T is the traction on surface A. The symbol δ is the varia-
tional operator designating the virtual quantity. Finite element interpola-
tion for displacement field [15]:

ሼ‫ݑ‬ሽ ൌ ሾܰሿሼ‫ݑ‬ොሽ (1.4.14)>

where is {u} u displacement vector of arbitrary point and {uˆ} is nodal dis-
placement point’s vector. [N] is shape function matrix. After FEM proce-
dure, the problem is reduced to the solution of the linear system of equations
Electrospinning Process: A Comprehensive Review 41

ሾ‫ܭ‬௘ ሿǤ ሼ‫ݑ‬ሽ ൌ ሼ݂ሽ (1.4.15)

where {u} is global displacement vector, {f} is the global nodal force vec-
tor, and [Ke] is the global stiffness matrix. Finite element analyses were
performed for computer generated network of 100 fibers. The comparison
of calculated data with experimental data [99] for nanotube sheet shows
some discrepancies (Figure 1.14). A rough morphological network model
for the sheets can explain this on the one hand and simple joint morphol-
ogy on the other hand [103].

ሼ‫ݑ‬ሽ ൌ ሾܰሿሼ‫ݑ‬ොሽ
FIGURE 1.14 The stress–strain curve.

1.5.3 FLOW IN FIBER NETWORK

Electrospun nanofiber materials are becoming an integral part of many

recent applications and products. Such materials are currently being used
in tissue engineering, air and liquid filtration, protective clothing’s, drug
delivery, and many others. Permeability of fibrous media is important in
many applications, therefore during the past few decades, there have been
many original studies dedicated to this subject. Depending on the fiber
diameter and the air thermal conditions, there are four different regimes of
flow around a fiber:
a) Continuum regime (KN ≤ 10−3),
b) Slip-flow regime (10−3 ≤ KN ≤ 0.25),
c) Transient regime (0.25 ≤ KN ≤ 10).
d) Free molecule regime (NK ≥10),
Here, KN=2λ /d is the fiber Knudson number, where λ= RT//√2Nˆπ.
d2p is the mean free path of gas molecules, d is fiber diameter, and Nˆ is
Avogadro number. Air flow around most electrospun nanofibers is typi-
cally in the slip or transition flow regimes. In the context of air filtration,
the 2D analytical work of Kuwabara [105] has long been used for predict-
ing the permeability across fibrous filters. The analytical expression has
been modified by Brown [106] to develop an expression for predicting
the permeability across filter media operating in the slip flow regime. The
ratio of the slip to no-slip pressure drops obtained from the simplified 2D
42 Applied Methodologies in Polymer Research and Technology

models may be used to modify the more realistic, and so more accurate,
existing 3D permeability models in such a way that they could be used to
predict the permeability of nanofiber structure. To test this supposition, for
above developed 3D virtual nanofibrous structure, the Stokes flow equa-
tions solved numerically inside these virtual structures with an appropriate
slip boundary condition that is developed for accounting the gas slip at
fiber surface.

1.5.3.1 FLOW FIELD CALCULATION

A steady-state, laminar, incompressible model has been adopted for the

flow regime inside our virtual media. Implemented in the Fluent code is
used to solve continuity and conservation of linear momentum in the ab-
sence of inertial effects [107]:

‫׏‬Ǥ ‫ ݒ‬ൌ Ͳ (1.4.16)

‫ ܲ׏‬ൌ ߤǤ οଶ ‫ݒ‬ (1.4.17)

The grid size required to mesh the gap between two fibers around their
crossover point is often too small. The computational grid used for compu-
tational fluid dynamics (CFD) simulations needs to be fine enough to re-
solve the flow field in the narrow gaps, and at the same time coarse enough
to cover the whole domain without requiring infinite computational pow-
er. Permeability of a fibrous material is often presented as a function of
fiber radius, r, and solid volume fraction α, of the medium. Here, we use
the continuum regime analytical expressions of Jackson and James [108],
developed for 3D isotropic fibrous structures given as follows:

݇ ͵‫ ݎ‬ଶ
ൌ ሾെκ݊ሺܽሻ െ ͲǤͻ͵ͳሿ (1.4.18)
‫ ݎ‬ଶ ʹͲܽ
Brown [106] has proposed an expression for the pressure drop across a
fibrous medium based on the 2D cell model of Kuwabara[105] with the
slip boundary condition:
Electrospinning Process: A Comprehensive Review 43

ͶߤܽǤ ݄ܸǤ ሺͳ ൅ ͳǤͻͻ͸‫ܭ‬ே

οܲௌ௅ூ௉ ൌ (1.4.19)
෡
‫ ݎ‬ଶ ൣ‫ܭ‬ ൅ ͳǤͻͻ͸‫ܭ‬ே ሺെͲǤͷǤ Ɛ݊ܽ െ ͲǤʹͷ ൅ ͲǤʹͷܽଶ ൧

෡ ൌ െͲǤͷǤ Ɛ݊ܽ െ ͲǤʹͷ ൅ ͲǤʹͷܽଶ

‫ܭ‬

where Kˆ = −0.5. lnα − 0.75 +α − 0.25α2, Kuwabara hydrodynamic factor,

h is fabric thickness, and V is velocity. As discussed in the some reference
[101-108], permeability (or pressure drop) models obtained using ordered
2D fiber arrangements are known for underpredicting the permeability of
a fibrous medium. To overcome this problem, if a correction factor can be
derived based on the above 2D expression, and used with the realistic ex-
pressions developed for realistic 3D fibrous structures. From Eq. (1.4.19),
we have for the case of no-slip boundary condition (KN = 0):

ସఓ௔Ǥ௛௏
οܲேைேௌ௅ூ௉ ൌ (1.4.20)
௥మ௄෡

The correction factor is defined as follows:

୼௉ಿೀಿೄಽ಺ು
Ȅൌ (1.4.21)
୼௉ೄಽ಺ು

to be used in modifying the original permeability expressions of Jackson

and James [109], and/or any other expression based on the no-slip bound-
ary condition, in order to incorporate the slip effect. For instance, the mod-
ified expression of Jackson and James can be presented as follows:

ଷ௥ మ
݇௭ ൌ ሾെ Žሺߙሻ െ ͲǤͻ͵ͳሿǤ ȩ (1.4.22)
ଶ଴ఈ

Operating pressure has no influence on the pressure drop in the continuum

region, whereas pressure drop in the free molecular region is linearly pro-
portional to the operating pressure. Although there are many equations
available for predicting the permeability of fibrous materials made up of
coarse fibers, there are no accurate “easy-to-use” permeability expressions
that can be used for nanofiber media. On Figure 1.15 are drown corrected
Jackson and James data (blue line). Points on figure are CFD numerical
data.
44 Applied Methodologies in Polymer Research and Technology

FIGURE 1.15 Permeability k/r2 dependence on solid volume fraction.

1.5.4 SOME ILLUSTRATIVE EXAMPLES

1.5.4.1 FUEL CELL EXAMPLE

Fuel cells are electrochemical devices capable of converting hydrogen or

hydrogen-rich fuels into electrical current by a metal catalyst. There are
many kinds of fuel cells, such as proton exchange mat (PEM) fuel cells, di-
rect methanol fuel cells, alkaline fuel cells, and solid oxide fuel cells [110].
PEM fuel cells are the most important ones among them because of high
power density and low operating temperature. Pt nanoparticle catalyst is
a main component in fuel cells. The price of Pt has driven up the cell cost
and limited the commercialization. Electrospun materials have been pre-
pared as alternative catalyst with high catalytic efficiency, good durability,
and affordable cost. Binary PtRh and PtRu nanowires were synthesized by
electrospinning, and they had better catalytic performance than commer-
cial nanoparticle catalyst because of the one-dimensional features [111].
Pt nanowires also showed higher catalytic activities in a polymer electro-
lyte membrane fuel cell [112]. Instead of direct use as catalyst, catalyst
supporting material is another important application area for electrospun
nanofibers. Pt clusters were electrodeposited on a carbon nanofiber mat
for methanol oxidation, and the catalytic peak current of the composite
catalyst reached 420 mA/mg compared with 185 mA/mg of a commercial
Electrospinning Process: A Comprehensive Review 45

Pt catalyst [113]. Pt nanoparticles were immobilized on polyimide-based

nanofibers using a hydrolysis process and Pt nanoparticles were also load-
ed on the carbon nanotube containing polyamic acid nanofibers to achieve
high catalytic current with long-term stability [114]. Proton exchange mat
is the essential element of PEM fuel cells and normally made of a Nafion
film for proton conduction. Because pure Nafion is not suitable for elec-
trospinning due to its low viscosity in solution, it is normally mixed with
other polymers to make blend nanofibers. Blend Nafion/PEO nanofibers
were embedded in an inert polymer matrix to make a proton conducting
mat [115], and a high proton conductivity of 0.06–0.08 S/cm at 15 °C in
water and low water swelling of 12-23 wt% at 25 °C were achieved [116].

1.5.4.2 PROTECTIVE CLOTHING EXAMPLE

The development of smart nanotextiles has the potential to revolutionize

the functionality of our clothing and the fabrics in our surroundings (Fig-
ure 1.16). This is made possible by such developments as new materials,
fibbers, and finishing; inherently conducting polymers; carbon nanotubes;
an antimicrobial nanocoatings. These additional functionalities have nu-
merous applications in healthcare, sports, military applications, fashion,
and so on. Smart textiles become a critical part of the emerging area of
body sensor networks incorporating sensing, actuation, control and wire-
less data transmission [51–52, 117].

FIGURE 1.16 Ultrathin layer for selective transport.

46 Applied Methodologies in Polymer Research and Technology

1.5.4.3 MEDICAL DEVICE

FIGURE 1.17 Cotton coated with silver.

Basic engineered nanomaterial and biotechnology products will enor-

mously be useful in future medical applications. We know nanomedicine
as the monitoring, repair, construction, and control of biological systems
at the nanoscale level, using engineered nanodevices and nanostructures.
The upper portion of the dress contains cotton coated with silver nanopar-
ticles. Silver possesses (Figure 1.17) natural antibacterial qualities that are
strengthened at the nanoscale, thus giving the ability to deactivate many
harmful bacteria and viruses. The silver infusion also reduces the need to
wash the garment, since it destroys bacteria, and the small size of the par-
ticles prevents soiling and stains [16, 118].

1.5.4.3.1 DRUG DELIVERY AND RELEASE CONTROL

Controlled release is an efficient process of delivering drugs in medical

therapy. It can balance the delivery kinetics, immunize the toxicity and
side effects, and improve patient convenience [119]. In a controlled-re-
lease system, the active substance is loaded into a carrier or device first,
and then released at a predictable rate in vivo when administered by an
Electrospinning Process: A Comprehensive Review 47

injected or noninjected route. As a potential drug delivery carrier, elec-

trospun nanofibers have exhibited many advantages. The drug loading is
very easy to implement via electrospinning process, and the high applied
voltage used in electrospinning process had little influence on the drug
activity. The high specific surface area and short diffusion passage length
give the nanofiber drug system higher overall release rate than the bulk
material (e.g., film). The release profile can be finely controlled by modu-
lation of nanofiber morphology, porosity, and composition.
Nanofibers for drug release systems mainly come from biodegradable
polymers and hydrophilic polymers. Model drugs that have been studied
include water soluble[120], poor water-soluble[121], and water insoluble
drugs [122]. The release of macromolecules, such as DNA [123] and bio-
active proteins from nanofibers was also investigated. In most cases, wa-
ter-soluble drugs, including DNA and proteins, exhibited an early-stage
burst [124]. For some applications, preventing postsurgery induced adhe-
sion for instance, and such an early burst release will be an ideal profile
because most infections occur within the first few hours after surgery. A
recent study also found that when a poorly water soluble drug was loaded
into PVP nanofibers [125], 84.9% of the drug can be released in the first
20 seconds when the drug-to-PVP ratio was kept as 1:4, which can be used
for fast drug delivery systems. However, for a long-lasting release process,
it would be essential to maintain the release at an even and stable pace,
and any early burst release should be avoided. For a water insoluble drug,
the drug release from hydrophobic nanofibers into buffer solution is dif-
ficult. However, when an enzyme capable of degrading nanofibers exists
in the buffer solution, the drug can be released at a constant rate because
of the degradation of nanofibers [122]. For example, when rifampin was
encapsulated in PLA nanofibers, no drug release was detected from the
nanofibers. However, when the buffer solution contained proteinase K, the
drug release took place nearly in zero-order kinetics, and no early burst
release happened. Similarly, initial burst release did not occur for poor
water-soluble drugs, but the release from a nonbiodegradable nanofiber
could follow different kinetics [126]. In another example, blending a hy-
drophilic but water-insoluble polymer (PEG-g-CHN) with PLGA could
assist in the release of a poor water-soluble drug Iburprofen [127]. How-
ever, when a water soluble polymer was used, the poorly soluble drug was
released accompanied with dissolving of the nanofibers, leading to a low
burst release [128]. The early burst release can be reduced when the drug
48 Applied Methodologies in Polymer Research and Technology

is encapsulated within the nanofiber matrix. When an amphiphilic block

copolymer, PEG-b-PLA was added into Mefoxin/PLGA nanofibers, the
cumulative amount of the released drug at earlier time points was reduced
and the drug release was prolonged [129]. The reason for the reduced burst
release was attributed to the encapsulation of some drug molecules within
the hydrophilic block of the PEG-b-PLA. Amphiphilic block copolymer
also assisted the dispersion and encapsulation of water-soluble drug into
nanofibers when the polymer solution used an oleophilic solvent, such
as chloroform, during electrospinning [130]. In this case, a water-in-oil
emulation can be electrospun into uniform nanofibers, and drug molecules
are trapped by hydrophilic chains. The swelling of the hydrophilic chains
during releasing assists the diffusion of drug from nanofibers to the buffer.
Coating nanofibers with a shell could be an effective way to control the
release profile.
When a thin layer of hydrophobic polymer, such as poly (p-xylylene)
(PPX), was coated on PVA nanofibers loaded with bovine serum albu-
min (BSA)/luciferase, the early burst release of the enzyme was prevented
[131]. Fluorination treatment [132] on PVA nanofibers introduced func-
tional C-F groups and made the fiber surface hydrophobic, which dramati-
cally decreased the initial drug burst and prolonged the total release time.
The polymer shell can also be directly applied via a coaxial coelectros-
pinning process, and the nanofibers produced are normally named “core-
sheath” bicomponent nanofibers. In this case, even a pure drug can be
entrapped into nanofiber as the core, and the release profile was less de-
pendent on the solubility of drug released [133]. A research has compared
the release behavior of two drug-loaded PLLA nanofibers prepared using
blend and coaxial electrospinning [134]. It was found that the blend fibers
still showed an early burst release, while the threads made of core-sheath
fibers provided a stable release of growth factor and other therapeutic
drugs. In addition, the early burst release can also be lowered via encapsu-
lating drugs into nanomaterial, followed by incorporating the drug-loaded
nanomaterials into nanofibers. For example, halloysite nanotubes loaded
with tetracycline hydrochloride were incorporated into PLGA nanofibers
and showed greatly reduced initial burst release [135].
Electrospinning Process: A Comprehensive Review 49

1.6 CONCLUDING REMARKS OF MULTIFUNCTIONAL

NANOSTRUCTURE DESIGN

Electrospinning is a simple, versatile, and cost-effective technology that

generates nonwoven fibers with high surface area to volume ratio, poros-
ity, and tunable porosity. Because of these properties, this process seems to
be a promising candidate for various applications especially nanostructure
applications. Electrospun fibers are increasingly being used in a variety of
applications, such as tissue engineering scaffolds, wound healing, drug de-
livery, immobilization of enzymes, as membrane in biosensors, protective
clothing, cosmetics, affinity membranes, filtration applications, and so on.
In summary, mother nature has always used hierarchical structures such as
capillaries and dendrites to increase multifunctional of living organs. Ma-
terial scientists are at beginning to use this concept and create multiscale
structures where nanotubes, nanofillers can be attached to larger surfaces
and subsequently functionalized. In principle, many more applications can
be envisioned and created. Despite several advantages and success of elec-
trospinning there are some critical limitations in this process such as small
pore size inside the fibers. Several attempts in these directions are being
made to improve the design through multilayering, inclusion of nanoele-
ments and blending with polymers with different degradation behavior.
As new architectures develop, a new wave of surface-sensitive devices
related to sensing, catalysis, photovoltaic, cell scaffolding, and gas storage
applications is bound to follow.

1.7 INTRODUCTION TO THEORETICAL STUDY OF

ELECTROSPINNING PROCESS

Electrospinning is a procedure in which an electrical charge to draw very

fine (typically on the micro- or nanoscale) ibers from polymer solution or
molten. Electrospinning shares characteristics of both and conventional
solution dry spinning of fibers. The process does not require the use of
coagulation chemistry or high temperatures to produce solid threads from
solution. This makes the process more efficient to produce the fibers us-
ing large and complex molecules. Recently, various polymers have been
successfully electrospun into ultrafine fibers mostly in solvent solution
and some in melt form [79, 136]. Optimization of the alignment and
50 Applied Methodologies in Polymer Research and Technology

morphology of the fibers is produced by fitting the composition of the

solution and the configuration of the electrospinning apparatus such as
voltage, flow rate, and and so on. As a result, the efficiency of this method
can be improved [137]. Mathematical and theoretical modeling and simu-
lating procedure will assist to offer an in-depth insight into the physical
understanding of complex phenomena during electrospinningand might be
very useful to manage contributing factors toward increasing production
rate [75, 138].
Despite the simplicity of the electrospinning technology, industrial ap-
plications of it are still relatively rare, mainly due to the notable problems
with very low fiber production rate and difficulties in controlling the pro-
cess [67].
Modeling and simulation (M&S) give information about how some-
thing will act without actually testing it in real. The model is a represen-
tation of a real object or system of objects for purposes of visualizing its
appearance or analyzing its behavior. Simulation is a transition from a
mathematical or computational model for description of the system behav-
ior based on sets of input parameters [104, 139]. Simulation is often the
only means for accurately predicting the performance of the modeled sys-
tem [140]. Using simulation is generally cheaper and safer than conduct-
ing experiments with a prototype of the final product. In addition, simula-
tion can often be even more realistic than traditional experiments, as they
allow the free configuration of environmental and operational parameters
and can often be run faster than in real time. In a situation with different
alternatives analysis, simulation can improve the efficiency, in particular
when the necessary data to initialize can easily be obtained from opera-
tional data. Applying simulation adds decision support systems to the tool
box of traditional decision support systems [141].
Simulation permits set up a coherent synthetic environment that allows
for integration of systems in the early analysis phase for a virtual test envi-
ronment in the final system. If managed correctly, the environment can be
migrated from the development and test domain to the training and educa-
tion domain in real systems under realistic constraints [142].
A collection of experimental data and their confrontation with simple
physical models appears as an effective approach toward the development
of practical tools for controlling and optimizing the electrospinning pro-
cess. On the contrary, it is necessary to develop theoretical and numerical
models of electrospinning because of demanding a different optimization
Electrospinning Process: A Comprehensive Review 51

procedure for each material[143]. Utilizing a model to express the effect

of electrospinning parameters will assist researchers to make an easy and
systematic way of presenting the influence of variables and by means of
that, the process can be controlled. In addition, it causes to predict the re-
sults under a new combination of parameters. Therefore, without conduct-
ing any experiments, one can easily estimate features of the product under
unknown conditions [95].

1.8 STUDY OF ELECTROSPINNING JET PATH

To yield individual fibers, most, if not all of the solvents must be evapo-
rated by the time the electrospinning jet reaches the collection plate. As a
result, volatile solvents are often used to dissolve the polymer. However,
clogging of the polymer may occur when the solvent evaporates before
the formation of the Taylor cone during the extrusion of the solution from
several needles. To maintain a stable jet while still using a volatile solvent,
an effective method is to use a gas jacket around the Taylor cone through
two coaxial capillary tubes. The outer tube that surrounds the inner tube
will provide a controlled flow of inert gas which is saturated with the
solvent used to dissolve the polymer. The inner tube is then used to de-
liver the polymer solution. For 10 wt% poly (L-lactic acid) (PLLA) solu-
tion in dichloromethane, electrospinning was not possible due to clogging
of the needle. However, when N2 gas was used to create a flowing gas
jacket, a stable Taylor cone was formed and electrospinning was carried
out smoothly.

1.8.1 THE THINNING JET (JET STABILITY)

The conical meniscus eventually gives rise to a slender jet that emerges
from the apex of the meniscus and propagates downstream. Hohman et al.
[60] first reported this approach for the relatively simple case of Newto-
nian fluids. This suggests that the shape of the thinning jet depends signifi-
cantly on the evolution of the surface charge density and the local electric
field. As the jet thins down and the charges relax to the surface of the jet,
the charge density and local field quickly pass through a maximum, and
the current due to advection of surface charge begins to dominate over that
due to bulk conduction.
52 Applied Methodologies in Polymer Research and Technology

The crossover occurs on the length scale given by [6]:

( )
1/5
LN = K 4Q 7 ρ 3 (ln X ) 2 / 8π 2 E∞ I 5ε −2 (1.6.1)

This length scale defines the “nozzle regime” over which the transition
from the meniscus to the steady jet occurs. Sufficiently far from the nozzle
regime, the jet thins less rapidly and finally enters the asymptotic regime,
where all forces except inertial and electrostatic forces cease to influence
the jet. In this regime, the radius of the jet decreases as follows:
1/4
⎛ Q3ρ ⎞
h=⎜ 2 z −1/4 (1.6.2)
⎝ 2π E∞ I ⎟⎠

Here, z is the distance along the centerline of the jet. Between the “noz-
zle regime” and the “asymptotic regime,” the evolution of the diameter of
the thinning jet can be affected by the viscous response of the fluid. Indeed
by balancing the viscous and the electrostatic terms in the force balance
equation, it can be shown that the diameter of the jet decreases:
1/2
⎛ 6 μQ 2 ⎞
h=⎜ z −1 (1.6.3)
⎝ π E I ⎟⎠
∞

In fact, the straight jet section has been studied extensively to under-
stand the influence of viscoelastic behavior on the axisymmetric instabili-
ties [93] and crystallization [60] and has even been used to extract exten-
sional viscosity of polymeric fluids at very high strain rates.
For highly strain-hardening fluids, Yu et al. [144] demonstrated that the
diameter of the jet decreased with a power-law exponent of −1/2, rather
than −1/4 or −1, as discussed earlier for Newtonian fluids. This −1/2 pow-
er-law scaling for jet thinning in viscoelastic fluids has been explained
in terms of a balance between electromechanical stresses acting on the
surface of the jet and the viscoelastic stress associated with extensional
strain hardening of the fluid. In addition, theoretical studies of viscoelastic
fluids predict a change in the shape of the jet due to non-Newtonian fluid
behavior. Both Yu et al. [144] and Han et al. [145] have demonstrated that
substantial elastic stresses can be accumulated in the fluid as a result of the
highstrain rate in the transition from the meniscus into the jetting region.
Electrospinning Process: A Comprehensive Review 53

This elastic stress stabilizes the jet against external perturbations. Further
downstream the rate of stretching slows down, and the longitudinal stresses
relax through viscoelastic processes. The relaxation of stresses following
an extensional deformation, such as those encountered in electrospinning,
has been studied in isolation for viscoelastic fluids [146]. Interestingly,
Yu et al. [144] also observed that, elastic behavior notwithstanding, the
straight jet transitions into the whipping region when the jet diameter be-
comes of the order of 10 mm.

1.8.2 THE WHIPPING JET (JET INSTABILITY)

While it is in principle possible to draw out the fibers of small diameter by

electrospinning in the cone-jet mode alone, the jet does not typically so-
lidify enough en route to the collector and succumbs to the effect of force
imbalances that lead to one or more types of instability. These instabilities
distort the jet as they grow. A family of these instabilities exists, and can be
analyzed in the context of various symmetries (axisymmetric or nonaxi-
symmetric) of the growing perturbation to the jet.
Some of the lower modes of this instability observed in electrospinning
have been discussed in a separate review [81]. The “whipping instabil-
ity” occurs when the jet becomes convectively unstable and its centerline
bends. In this region, small perturbations grow exponentially, and the jet
is stretched out laterally. Shin et al. [62] and Fridrikh et al. [63] have dem-
onstrated how the whipping instability can be largely responsible for the
formation of solid fiber in electrospinning. This is significant, since as
recently as the late 1990s, the bifurcation of the jet into two more or less
equal parts (also called “splitting” or “splaying”) were thought to be the
mechanism through which the diameter of the jet is reduced, leading to the
fine fibers formed in electrospinning. In contrast to “splitting” or “splay-
ing,” the appearance of secondary, smaller jets from the primary jet have
been observed more frequently and in situ [64, 147]. These secondary jets
occur when the conditions on the surface of the jet are such that perturba-
tions in the local field, for example, due to the onset of the slight bending
of the jet, is enough to overcome the surface tension forces and invoke a
local jetting phenomenon.
54 Applied Methodologies in Polymer Research and Technology

The conditions necessary for the transition of the straight jet to the
whipping jet has been discussed in the works of Ganan-Calvo [148], Yarin
et al. [64], Reneker et al. [66], and Hohman et al. [60].
During this whipping instability, the surface charge repulsion, surface
tension, and inertia were considered to have more influence on the jet path
than Maxwell’s stress, which arises due to the electric field and finite con-
ductivity of the fluid. Using the equations reported by Hohman et al. [60]
and Fridrikh et al. [63] obtained an equation for the lateral growth of the
jet excursions arising from the whipping instability far from the onset and
deep into the nonlinear regime. These developments have been summa-
rized in the review article by Rutledge and Fridrikh.
The whipping instability is postulated to impose the stretch necessary
to draw out the jet into fine fibers. As discussed earlier, the stretch im-
posed can make an elastic response in the fluid, especially if the fluid is
polymeric in nature. An empirical rheological model was used to explore
the consequences of nonlinear behavior of the fluid on the growth of the
amplitude of the whipping instability in numerical calculations [63, 79].
There, it was observed that the elasticity of the fluid significantly reduces
the amplitude of oscillation of the whipping jet. The elastic response also
stabilizes the jet against the effect of surface tension. In the absence of any
elasticity, the jet eventually breaks up and forms an aerosol. However, the
presence of a polymer in the fluid can stop this breakup if
1/2
⎛ ρh 3 ⎞
τ /⎜ ≥1 (1.6.4)
⎝ γ ⎟⎠
where τ is the relaxation time of the polymer, ρ is the density of the fluid, h
is a characteristic radius, and γ is the surface tension of the fluid.

1.9 ELECTROSPINNING DRAWBACKS

Electrospinning has attracted much attention both to academic research

and industry application because electrospinning (1) can fabricate con-
tinuous fibers with diameters down to a few nanometers, (2) is applicable
to a wide range of materials such as synthetic and natural polymers, metals
as well as ceramics and composite systems, (3) and can prepare nanofibers
with low cost and high yielding [47].
Electrospinning Process: A Comprehensive Review 55

Despite the simplicity of the electrospinning technology, industrial ap-

plications of it are still relatively rare, mainly due to the notable problems
of very low fiber production rate and difficulties in controlling the process
[50, 67]. The usual feedrate for electrospinning is about 1.5ml/hr. Given a
solution concentration of 0.2g/ml, the mass of nanofiber collected from a
single needle after an hour is only 0.3g. In order for electrospinning to be
commercially viable, it is necessary to increase the production rate of the
nanofibers. To do so, multiple-spinning setup is necessary to increase the
yield while at the same time maintaining the uniformity of the nanofiber
mesh [48].
Optimization of the alignment and morphology of the fibers which is
produced by fitting the composition of the solution and the configuration
of the electrospinning apparatus such as voltage, flow rate, and so on, can
be useful to improve the efficiency of this method [137]. Mathematical
and theoretical modeling and simulating procedure will assist to offer an
in-depth insight into the physical understanding of complex phenomena
uring electrospinningand might be very useful to manage contributing fac-
tors toward increasing production rate [75, 138].
At present, nanofibers have attracted the attention of researchers due
to their remarkable micro and nanostructural characteristics, high surface
area, small pore size, and the possibility of their producing 3D structure
that enables the development of advanced materials with sophisticated ap-
plications [73].
Controlling the property, geometry, and mass production of the
nanofibers is essential to comprehend quantitatively how the electrospin-
ning process transforms the fluid solution through a millimeter diameter
capillary tube into solid fibers that are four to five orders smaller in diam-
eter [74].
As mentioned earlier, the electrospinning gives us the impression of
being a very simple and easily controlled technique for the production of
nanofibers. But, in reality, the process is very intricate. Thus, electrospin-
ning is usually described as the interaction of several physical instability
processes. The bending and stretching of the jet are mainly caused by the
rapidly whipping which is an essential element of the process induced by
these instabilities. Until now, little is known about the detailed mechanisms
of the instabilities and the splaying process of the primary jet into multiple
filaments. It is thought to be responsible that the electrostatic forces over-
56 Applied Methodologies in Polymer Research and Technology

come surface tensions of the droplet during undergoing the electrostatic

field and the deposition of jets formed nanofibers [47].
Although electrospinning has been become an indispensable technique
for generating functional nanostructures, many technical issues still need
to be resolved. For example, it is not easy to prepare nanofibers with a
same scale in diameters by electrospinning; it is still necessary to inves-
tigate systematically the correlation between the secondary structure of
nanofiber and the processing parameters; the mechanical properties, pho-
toelectric properties, and other property of single fiber should be system-
atically studied and optimized; the production of nanofiber is still in labo-
ratory level, and it is extremely important to make efforts for scaled-up
commercialization; nanofiber from electrospinning has a the low produc-
tion rate and low mechanical strength which hindered its commercializa-
tion; in addition, another more important issue should be resolved is how
to treat the solvents volatilized in the process.
Until now, lots of efforts have been put on the improvement of elec-
trospinning installation, such as the shape of collectors, modified spin-
nerets, and so on. The application of multijets electrospinning provides
a possibility to produce nanofibers in industrial scale. The development
of equipments which can collect the poisonous solvents and the applica-
tion of melt electrospinning, which would largely reduce the environment
problem, create a possibility of the industrialization of electrospinning.
The application of water as the solvent for elelctrospinning provide an-
other approach to reduce environmental pollution, which is the main fact
hindered the commercialization of electrospinning. In summary, electro-
spinning is an attractive and promising approach for the preparation of
functional nanofibers due to its wide applicability to materials, low cost
and high production rate [47].

1.10 MODELING THE ELECTROSPINNING PROCESS

The electrospinning process is a fluid dynamics-related problem. Con-

trolling the property, geometry, and mass production of the nanofibers is
essential to comprehend quantitatively how the electrospinning process
transforms the fluid solution through a millimeter diameter capillary tube
into solid fibers that are four to five orders smaller in diameter [74]. Al-
though information on the effect of various processing parameters and
Electrospinning Process: A Comprehensive Review 57

constituent material properties can be obtained experimentally, theoreti-

cal models offer in-depth scientific understanding which can be useful to
clarify the affecting factors that cannot be exactly measured experimental-
ly. Results from modeling also explained how processing parameters and
fluid behavior lead to the nanofiber of appropriate properties. The term
“properties” refers to basic properties (i.e., fiber diameter, surface rough-
ness, and fiber connectivity), physical properties (i.e, stiffness, toughness,
thermal conductivity, electrical resistivity, thermal expansion coefficient,
and density) and specialized properties (i.e., biocompatibility, degradation
curve, and for biomedical applications) [48, 73].
For example, the developed models can be used for the analysis of
mechanisms of jet deposition and alignment on various collecting devices
in arbitrary electric fields [149].
Various methods formulated by researchers are prompted by several
applications of nanofibers. It would be sufficient to briefly describe some
of these methods to observed similarities and disadvantages of these ap-
proaches. An abbreviated literature review of these models will be dis-
cussed in the sections that follow.

1.10.1 MODELING ASSUMPTIONS

Just as in any other process modeling, a set of assumptions are required for
the following reasons:
a. To furnish industry-based applications whereby speed of calcula-
tion, but not accuracy, is critical
b. To simplify, hence enabling checkpoints to be made before more
detailed models can proceed
c. For enabling the formulations to be practically traceable
The first assumption to be considered as far as electrospinning is con-
cerned is conceptualizing the jet itself. Even though the most appropriate
view of a jet flow is that of a liquid continuum, the use of nodes connect-
ed in series by certain elements that constitute rheological properties has
proven successful [64, 66]. The second assumption is the fluid constitutive
properties. In the discrete node model [66], the nodes are connected in
series by a Maxwell unit, that is, a spring and dashpot in series, for quan-
tifying the viscoelastic properties.
58 Applied Methodologies in Polymer Research and Technology

In analyzing viscoelastic models, we apply two types of elements: the

dashpot element that describes the force as being in proportion to the ve-
locity (recall friction), and the spring element which describes the force as
being in proportion to elongation. One can then develop viscoelastic mod-
els using combinations of these elements. Among all possible viscoelastic
models, the Maxwell model was selected by Reneker et al. [66] due to its
suitability for liquid jet as well as its simplicity. Other models are either
unsuitable for liquid jet or too detailed.
In the continuum models a power law can be used for describing the
liquid behavior under shear flow for describing the jet flow [150]. At this
juncture, it can be noted that the power law is characterized from a shear
flow, whereas the jet flow in electrospinning undergoes elongational flow.
This assumption will be discussed in detail in the subsequent sections.
The other assumption that should be applied in electrospinning mod-
eling is about the coordinate system. The method for coordinate system
selection in electrospinning process is similar to other process modeling,
the system that best bring out the results by (i) allowing the computation
to be performed in the most convenient manner and, more importantly, (ii)
enabling the computation results to be accurate. In view of the linear jet
portion during the initial first stage of the jet, the spherical coordinate sys-
tem is eliminated. Assuming the second stage of the jet to be perfectly spi-
raling, due to bending of the jet, the cylindrical coordinate system would
be ideal. However, experimental results have shown that the bending in-
stability portion of the jet is not perfectly expanding spiral. Hence, the
Cartesian coordinate system, which is the most common of all coordinate
system, is adopted.
Depending on the processing parameters (i.e., applied voltage and vol-
ume flow rate) and the fluid properties (i.e., surface tension and viscos-
ity) as many as 10 modes of electrohydrodynamically driven liquid jet
have been identified [151]. The scope of jet modes is highly abbreviated
in this chapter because most electrospinning processes that lead to nano-
fibers consist of only two modes, the straight jet portion, and the spiraling
(or whipping) jet portion. Insofar as electrospinning process modeling is
involved, the following classification indicates the considered modes or
portion of the electrospinning jet.
1. Modeling the criteria for jet initiation from the droplet [Senador et
al. [152]; Yarin et al.[64]
Electrospinning Process: A Comprehensive Review 59

2. Modeling the straight jet portion [153–154] Spivak et al. [150,

155]
3. Modeling the entire jet [Reneker et al. [66]; Yarin et al.[156];
Hohman et al. [60–61]

1.10.2 CONSERVATION RELATIONS

Balance of the producing accumulation is, particularly, a basic source

of quantitative models of phenomena or processes. Differential balance
equations are formulated for momentum, mass, and energy through the
contribution of local rates of transport expressed by the principle of New-
ton’s, Fick’s, and Fourier laws. For a description of more complex systems
such as electrospinning that involved strong turbulence of the fluid flow,
characterization of the product property is necessary and various balances
are required [157].
The basic principle used in modeling of chemical engineering process
is a concept of balance of momentum, mass and energy, which can be ex-
pressed in a general form as follows:

A = I +G −O−C (1.8.1)

where
A is the accumulation built up within the system.
I is the input entering through the system surface.
G is the generation produced in system volume.
O is the output leaving through system boundary.
C is consumption used in system volume.
The form of expression depends on the level of the process phenom-
enon description. [157–158]
According to the electrospinning models, the jet dynamics are gov-
erned by a set of three equations representing mass, energy, and momen-
tum conservation for the electrically charge jet [159].
60 Applied Methodologies in Polymer Research and Technology

1.1.1. IN ELECTROSPINNING MODELING FOR

SIMPLIFICATION OF DESCRIBING THE PROCESS,
RESEARCHERS CONSIDER AN ELEMENT OF THE JET AND
THE JET VARIATION VERSUS TIME IS NEGLECTED.

1.1.2. MASS CONSERVATION

The concept of mass conservation is widely used in many fields such as

chemistry, mechanics, and fluid dynamics. Historically, mass conserva-
tion was discovered in chemical reactions by Antoine Lavoisier in the late
eighteenth century, and was of decisive importance in the progress from
alchemy to the modern natural science of chemistry. The concept of matter
conservation is useful and sufficiently accurate for most chemical calcula-
tions, even in modern practice [160].
The equations for the jet follow from Newton’s Law and the conserva-
tion laws obey, namely, conservation of mass and conservation of charge
[60].
According to the conservation of mass equation

π R 2υ = Q (1.8.2)

∂ ∂
∂t
( )
π R2 +
∂z
( )
π R 2υ = 0 (1.8.3)

For incompressible jets, by increasing the velocity the radius of the jet
decreases. At the maximum level of the velocity, the radius of the jet re-
duces. The macromolecules of the polymers are compacted together closer
while the jet becomes thinner as shown in Figure 1.18. When the radius
of the jet reaches the minimum value and its speed becomes maximum to
keep the conservation of mass equation, the jet dilates by decreasing its
density which is called electrospinning dilation [161–162].
Electrospinning Process: A Comprehensive Review 61

FIGURE 1.18 Macromolecular chains are compacted during the electrospinning.

1.10.3 ELECTRIC CHARGE CONSERVATION

An electric current is a flow of electric charge. Electric charge flows when

there is voltage present across a conductor. In physics, charge conserva-
tion is the principle that electric charge can neither be created nor de-
stroyed. The net quantity of electric charge, the amount of positive charge
minus the amount of negative charge in the universe, is always conserved.
The first written statement of the principle was by American scientist and
statesman Benjamin Franklin in 1747 [163]. Charge conservation is a
physical law which states that the change in the amount of electric charge
in any volume of space is exactly equal to the amount of charge in a region
and the flow of charge into and out of that region [164].
During the electrospinning process, the electrostatic repulsion between
excess charges in the solution stretches the jet. This stretching also de-
creases the jet diameter that this leads to the law of charge conservation as
the second governing equation [165].
62 Applied Methodologies in Polymer Research and Technology

In electrospinning process, the electric current that induced by electric

field included two parts, conduction, and convection.
The conventional symbol for current is I:

I = I conduction + I convection (1.8.4)

Electrical conduction is the movement of electrically charged particles

through a transmission medium. The movement can form an electric cur-
rent in response to an electric field. The underlying mechanism for this
movement depends on the material.

I conduction = J cond × S = KE × π R 2 (1.8.5)

I
J= (1.8.6)
A( s )

I = J ×S (1.8.7)

Convection current is the flow of current with the absence of an electric

field.

I convection = J conv × S = 2π R( L) × σ v (1.8.8)

J conv = σ v (1.8.9)

Therefore, the total current can be calculated as:

π R 2 KE + 2π Rvσ = I (1.8.10)

∂ ∂
∂t ∂z
(
(2π Rσ ) + π R 2 KE + 2π Rvσ = 0 ) (1.8.11)
Electrospinning Process: A Comprehensive Review 63

1.10.4 MOMENTUM BALANCE

In classical mechanics, linear momentum or translational momentum is

the product of the mass and velocity of an object. Like velocity, linear mo-
mentum is a vector quantity, possessing a direction as well as a magnitude:

P = mυ (1.8.12)

Linear momentum is also a conserved quantity, meaning that if a closed

system (one that does not exchange any matter with the outside and is not
acted on by outside forces) is not affected by external forces, its total linear
momentum cannot change. In classical mechanics, conservation of linear
momentum is implied by Newton’s laws of motion; but it also holds in
special relativity (with a modified formula) and, with appropriate defini-
tions, a (generalized) linear momentum conservation law holds in electro-
dynamics, quantum mechanics, quantum field theory, and general relativ-
ity[163]. For example, according to the third law, the forces between two
particles are equal and opposite. If the particles are numbered 1 and 2, the
second law states:

dP1
F1 = (1.8.13)
dt

dP2
F2 = (1.8.14)
dt

Therefore:

dP1 dP
=− 2 (1.8.15)
dt dt

d
( P1 + P2 ) = 0 (1.8.16)
dt
If the velocities of the particles are υ11 and υ12 before the interaction,
and afterwards they are υ21 and υ22, then
64 Applied Methodologies in Polymer Research and Technology

m1υ11 + m2υ12 = m1υ 21 + m2υ 22 (1.8.17)

This law holds no matter how complicated the force is between the par-
ticles. Similarly, if there are several particles, the momentum exchanged
between each pair of particles adds up to zero; therefore; the total change
in momentum is zero. This conservation law applies to all interactions,
including collisions and separations caused by explosive forces. It can also
be generalized to situations where Newton’s laws do not hold, for example
in the theory of relativity and in electrodynamics [153, 166]. The momen-
tum equation for the fluid can be derived as follow:

dυ dυ d γ dr σ dσ dE 2σ E
ρ( +υ ) = ρ g + [τ zz − τ rr ] + 2 . + + (ε − ε 0 )( E )+ (1.8.18)
dt dz dz R dz ε 0 dz dz r
But commonly, the momentum equation for electrospinning modeling
is formulated by considering the forces on a short segment of the jet [153,
166].

d d γ
(π R 2 ρυ 2 ) = π R 2 ρ g + ⎡⎣π R 2 ( − p + τ zz ) ⎤⎦ + .2π RR ′ + 2π R(tte − tne R ′ ) (1.8.19)
dz dz R

FIGURE 1.19 Momentum balance on a short section of the jet.

Electrospinning Process: A Comprehensive Review 65

As shown in Figure 1.19, the element’s angels could be defined as α

and β. According to the mathematical relationships, it is obvious that

π
α +β = (1.8.20)
2

sin α = tan α
(1.8.21)
cos α = 1
Due to the figure, relationships between these electrical forces are as
given below:

dR e
tne sin α ≅ tne tan α ≅ −tne tan β ≅ − tn = − R ' tne (1.8.22)
dz

tte cos α ≅ tte (1.8.23)

Therefore, the effect of the electric forces in the momentum balance equa-
tion can be presented as follows:

2π RL(tte − R ' tne )dz (1.8.24)

(Notation: In the main momentum equation, final formula is obtained by

dividing into dz)
In addition, the normal electric force is defined as follows:

1 1 σ 2 σ2 (1.8.25)
t ≅ ε En = ε ( ) =
e
n
2

2 2 ε 2ε
A little amount of electric forces is perished in the vicinity of the air.

σ
En = (1.8.26)
ε

The electric force can be presented by the following equation:

ΔWe 1
F= = (ε − ε ) E 2 × ΔS (1.8.27)
Δl 2
66 Applied Methodologies in Polymer Research and Technology

The force per surface unit is

F 1
= (ε − ε ) E 2 (1.8.28)
ΔS 2
Generally the electric potential energy is obtained by using the follow-
ing equation:

Ue = −We = − ∫ F .ds (1.8.29)

1 1
ΔWe = (ε − ε ) E 2 × ΔV = (ε − ε ) E 2 × ΔS .Δl (1.8.30)
2 2
Therefore, finally it could result in the following equation:

σ2 1
tne = − (ε − ε ) E 2 (1.8.31)
2ε 2

tte = σ E (1.8.32)

1.10.5 COULOMB’S LAW

Coulomb’s law is a mathematical description of the electric force between

charged objects, which is formulated by the eighteenth-century French
physicist Charles-Augustin de Coulomb. It is analogous to Isaac Newton’s
law of gravity. Both gravitational and electric forces decrease with the
square of the distance between the objects, and both forces act along a
line between them[167]. In Coulomb’s law, the magnitude and sign of the
electric force are determined by the electric charge, more than the mass of
an object. Thus, a charge that is a basic property matter determines how
electromagnetism affects the motion of charged targets [163].
Coulomb force is thought to be the main cause for the instability of
the jet in the electrospinning process [168]. This statement is based on the
Earnshaw’s theorem, named after Samuel Earnshaw [169] which claims
that “A charged body placed in an electric field of force cannot rest in
stable equilibrium under the influence of the electric forces alone.” This
Electrospinning Process: A Comprehensive Review 67

theorem can be notably adapted to the electrospinning process [168]. The

instability of charged jet influences on jet deposition and as a consequence
on nanofiber formation. Therefore, some researchers applied developed
models to the analysis of mechanisms of jet deposition and alignment on
various collecting devices in arbitrary electric fields [66].
The equation for the potential along the centerline of the jet can be
derived from Coulomb’s law. Polarized charge density is obtained
 
ρ p ′ = −∇.P ′ (1.8.33)

where P′ is polarization:
 
P ′ = (ε − ε ) E (1.8.34)

By substituting P′ in the previous equation:

dE
ρ P ′ = − (ε − ε ) (1.8.35)
dz '
Beneficial charge per surface unit can be calculated as follows:

Qb
ρP′ = (1.8.36)
π R2

dE
Qb = ρb .π R 2 = −(ε − ε )π R 2 (1.8.37)
dz '

d ( ER 2 )
Qb = −(ε − ε )π (1.8.38)
dz '

d
ρsb = Qb .dz ' = −(ε − ε )π ( ER 2 )dz ' (1.8.39)
dz '
The main equation of Coulomb’s law:

1 qq0
F= (1.8.40)
4πε 0 r 2
68 Applied Methodologies in Polymer Research and Technology

The electric field is:

1 q
E= (1.8.41)
4πε 0 r 2
The electric potential can be measured:

ΔV = − ∫ E.dL (1.8.42)

1 Qb
V= (1.8.43)
4πε 0 r
According to the beneficial charge equation, the electric potential could
be rewritten as follows:

1 (q − Qb )
4πε ∫
ΔV = Q( z ) − Q∞ ( z ) = dz ' (1.8.44)
r

1 q 1 Qb
4πε ∫ r 4πε ∫
Q( z ) = Q∞ ( z ) + dz '− dz ' (1.8.45)
r

d ( ER 2 )
Qb = −(ε − ε )π (1.8.46)
dz '
The surface charge density’s equation is

q = σ .2π RL (1.8.47)

r 2 = R 2 + ( z − z ') 2 (1.8.48)

r = R 2 + ( z − z ') 2 (1.8.49)

The final equation that obtained by substituting the mentioned equa-

tions is
Electrospinning Process: A Comprehensive Review 69

1 σ .2π R 1 (ε − ε )π d ( ER 2 )
4πε ∫ 4πε ∫
Q( z ) = Q∞ ( z ) + dz '− (1.8.50)
2
( z − z ') + R 2 2
( z − z ') + R 2dz '

It is assumed that β is defined as follows:

ε (ε − ε )
β= −1 = − (1.8.51)
ε ε
Therefore, the potential equation becomes

1 σ .R β 1 d ( ER 2 )
Q( z ) = Q∞ ( z ) +
2ε ∫ ( z − z ') 2 + R 2
dz '−
4∫ ( z − z ') 2 + R 2 dz '
(1.8.52)

The asymptotic approximation of χ is used to evaluate the integrals

mentioned earlier:

(
χ = − z + ξ + z 2 − 2 zξ + ξ 2 + R 2 ) (1.8.53)

where χ is “aspect ratio” of the jet (L = length, R0= initial radius)

This leads to the final relation to the axial electric field:

⎛ 1 d (σ R ) β d 2 ER 2 ⎞
E ( z ) = E∞ ( z ) − ln χ ⎜ −
( ) (1.8.54)
⎟
⎝ ε dz 2 dz 2 ⎠

1.10.6 FORCES CONSERVATION

There exists a force, as a result of charge build-up, acting on the drop-

let coming out of the syringe needle pointing toward the collecting plate
which can be either grounded or oppositely charged. Further, similar
charges within the droplet promote jet initiation due to their repulsive
forces. Nevertheless, surface tension and other hydrostatic forces inhibit
the jet initiation because the total energy of a droplet is lower than that of
a thin jet of equal volume upon consideration of surface energy. When the
forces that aid jet initiation (such as electric field and Columbic) overcome
the opposing forces (such as surface tension and gravitational), the drop-
let accelerates toward the collecting plate. This forms a jet of very small
diameter. Other than initiating jet flow, the electric field and Columbic
70 Applied Methodologies in Polymer Research and Technology

forces tend to stretch the jet, thereby contributing toward the thinning ef-
fect of the resulting nanofibers.
In the flow path modeling, we recall the Newton’s Second Law of mo-
tion:

d 2P
m =∑ f (1.8.55)
dt 2
where, m (equivalent mass) and the various forces are summed as fol-
lows:

∑ f = fC + f E + fV + f S + f A + fG + ... (1.8.56)

In which subscripts C, E, V, S, A and G correspond to the Colum-

bic, electric field, viscoelastic, surface tension, air drag, and gravitational
forces, respectively. A description of each of these forces based on the
literature [5] is summarized in Table 1.1 where
V0 = applied voltage
h = distance from pendent drop to ground collector
σV= viscoelastic stress
v = kinematic viscosity

TABLE 1.1 Description of itemized forces or terms related to them

Forces Equations

Columbic q2
fC =
l2
qV0
Electric field fE = −
h
d σ V G dl G
Viscoelastic fV = = − σV
dt l dt η

απ R 2 k
Surface tension fS = ⎡⎣i x Sin( x) + i y Sin( y ) ⎤⎦
xi2 + yi2
Electrospinning Process: A Comprehensive Review 71

−0.81
⎛ 2ν R ⎞
Air drag f A = 0.65π Rρairν ⎜2

⎝ ν ⎟⎠ air

Gravitational f G = ρ gπ R 2

1.10.7 CONSTITUTIVE EQUATIONS

In modern condensed matter physics, the constitutive equation plays a ma-

jor role. In physics and engineering, a constitutive equation or relation is
a relation between two physical quantities that is specific to a material or
substance, and approximates the response of that material to external stim-
ulus, usually as applied fields or forces [170]. There are a sort of mechani-
cal equation of state, which describe how the material is constituted me-
chanically. With these constitutive relations, the vital role of the material
is reasserted [171]. There are two groups of constitutive equations: Linear
and nonlinear constitutive equations [172]. These equations are combined
with other governing physical laws to solve problems; for example, in
fluid mechanics the flow of a fluid in a pipe, in solid-state physics the re-
sponse of a crystal to an electric field, or in structural analysis, the connec-
tion between applied stresses or forces to strains or deformations [170].
The first constitutive equation (constitutive law) was developed by
Robert Hooke and is known as Hooke’s law. It deals with the case of lin-
ear elastic materials. Following this discovery, this type of equation, often
called a “stress-strain relation” in this example, but also called a “consti-
tutive assumption” or an “equation of state” was commonly used [173].
Walter Noll advanced the use of constitutive equations, clarifying their
classification and the role of invariance requirements, constraints, and
definitions of terms such as “material,” “isotropic,” “aeolotropic,” and so
on. The class of “constitutive relations” of the form stress rate = f (veloc-
ity gradient, stress, density) was the subject of Walter Noll’s dissertation
in 1954 under Clifford Truesdell [170]. There are several kinds of consti-
tutive equations that are applied commonly in electrospinning. Some of
these applicable equations are discussed in the following.
72 Applied Methodologies in Polymer Research and Technology

1.10.7.1 OSTWALD–DE WAELE POWER LAW

Rheological behavior of many polymer fluids can be described by power

law constitutive equations [172]. The equations that describe the dynamics
in electrospinning constitute, at a minimum, those describing the conser-
vation of mass, momentum and charge, and the electric field equation.
In addition, a constitutive equation for the fluid behavior is also required
[76]. A power law fluid, or the Ostwald–de Waele —relationship, is a type
of generalized Newtonian fluid for which the shear stress, τ, is given by
m
⎛ ∂υ ⎞ (1.8.57)
τ = K′⎜
⎝ ∂y ⎟⎠
where ∂ν/∂y is the shear rate or the velocity gradient perpendicular to
the plane of shear. The power law is only a good description of fluid be-
havior across the range of shear rates to which the coefficients are fitted.
There are a number of other models that better describe the entire flow be-
havior of shear-dependent fluids, but they do so at the expense of simplic-
ity; therefore, the power law is still used to describe fluid behavior, permit
mathematical predictions, and correlate experimental data [166, 174].
Nonlinear rheological constitutive equations applicable for polymer
fluids (Ostwald–de Waele power law) were applied to the electrospinning
process by Spivak and Dzenis [77, 150, 175].

( )⎦
( m −1) 2
τˆ c = μ ⎡tr γˆ 2 ⎤ γˆ (1.8.58)
⎣
m −1
⎛ ∂υ ⎞
μ= K⎜ ⎟ (1.8.59)
⎝ ∂y ⎠
Viscous Newtonian fluids are described by a special case of equation
above with the flow index m = 1. Pseudoplastic (shear thinning) fluids are
described by flow indices 0≤m≤1. Dilatant (shear thickening) fluids are
described by the flow indices m˃1 [150].

1.10.7.2 GIESEKUS EQUATION

In 1966, Giesekus established the concept of anisotropic forces and mo-

tions in polymer kinetic theory. With particular choices for the tensors
Electrospinning Process: A Comprehensive Review 73

describing the anisotropy, one can obtain Giesekus constitutive equation

from elastic dumbbell kinetic theory [176–177]. The Giesekus equation is
known to predict, both qualitatively and quantitatively, material functions
for steady and nonsteady shear and elongational flows.
However, the equation sustains two drawbacks: it predicts that the vis-
cosity is inversely proportional to the shear rate in the limit of infinite
shear rate and it is unable to predict any decrease in the elongational vis-
cosity with increasing elongation rates in uniaxial elongational flow. The
first one is not serious because of the retardation time that is included
in the constitutive equation, but the second one is more critical because
the elongational viscosity of some polymers decreases with increasing of
elongation rate [178–179].
In the main Giesekus equation, the tensor of excess stresses depending
on the motion of polymer units relative to their surroundings was connect-
ed to a sequence of tensors characterizing the configurational state of the
different kinds of network structures present in the concentrated solution
or melt. The respective set of constitutive equations indicates [180–181]:

∂Ck
Sk + η =0 (1.8.60)
∂t
The equation below indicates the upper-convected time derivative
(Oldroyd derivative):

∂Ck DCk
= − ⎡⎣Ck ∇υ + (∇υ )T Ck ⎤⎦ (1.8.61)
∂t Dt
(Note: The upper convective derivative is the rate of change of any tensor
property of a small parcel of fluid that is written in the coordinate system
rotating and stretching with the fluid.)
Ck also can be measured as follows:

Ck = 1 + 2 Ek (1.8.62)

According to the concept of “recoverable strain” Sk may be understood

as a function of Ek and vice versa. If linear relations corresponding to
Hooke’s law are adopted.

S k = 2 μ k Ek (1.8.63)
74 Applied Methodologies in Polymer Research and Technology

Therefore,

S k = μ k (Ck − 1) (1.8.64)

Equation (1.8.60) becomes thus:

∂S k
Sk + λ k = 2ηD (1.8.65)
∂t

η
λk = (1.8.66)
μk
As a second step in order to rid the model of the shortcomings is the
scalar mobility constants Bk, which are contained in the constants η. This
mobility constant can be represented as follows:

1 (β S + S β ) + η ∂Ck = 0 (1.8.67)
2 k k k k
∂t
The two parts of equation (1.8.67) reduces to the single constitutive
equation:

 ∂Ck
βk + η =0 (1.8.68)
∂t
The excess tension tensor in the deformed network structure where the
well-known constitutive equation of a so-called Neo–Hookean material is
proposed [180, 182]:

Neo–Hookean equation

S k = 2 μ k Ek = μ k (Ck − 1) (1.8.69)

μ k = NKT
(1.8.70)
βk = 1 + α (Ck − 1) = (1 − α ) + α Ck
where K is Boltzmann’s constant.
Electrospinning Process: A Comprehensive Review 75

By substitution Eqs (1.8.69) and (1.8.70) in the Eq. (1.8.64), it can be

obtained where the condition 0≤α≤1 must be fulfilled, the limiting case α
= 0 corresponds to an isotropic mobility [183].

∂Ck
0 ≤ α ≤1 [1 + α (C k − 1) ] (Ck − 1) + λ k
∂t
=0 (1.8.71)

∂Ck (1.8.72)
α =1 Ck (Ck − 1) + λ k =0
∂t

Sk
0 ≤ α ≤1 Ck = +1 (1.8.73)
μk
By substituting equations above in Eq. (1.8.64), we obtain

⎡ α Sk ⎤ Sk ∂Ck
⎢1 + ⎥ + λk =0 (1.8.74)
⎣ μk ⎦ μk ∂t

S
∂( k μ + 1)
Sk α Sk2 (1.8.75)
+ + λk k
=0
μ k μ k2 ∂t

Sk α Sk2 λ k ∂Sk (1.8.76)

+ + =0
μ k μ k2 μ k ∂t

α Sk2 ∂S
Sk + + λk k = 0 (1.8.77)
μk ∂t
D means the rate of strain tensor of the material continuum [180].

1
D= ⎡⎣∇υ + (∇υ )T ⎤⎦ (1.8.78)
2
The equation of the upper convected time derivative for all fluid prop-
erties can be calculated as follows:

∂⊗ D⊗
= − ⎡⊗.∇υ + (∇υ )T . ⊗ ⎤⎦ (1.8.79)
∂t Dt ⎣
76 Applied Methodologies in Polymer Research and Technology

D⊗ ∂⊗
= + [ (υ.∇). ⊗ ] (1.8.80)
Dt ∂t
By replacing Sk instead of the symbol:

∂S k DS k DS k
λk = λk − λ k ⎡⎣ S k ∇υ + (∇υ )T S k ⎤⎦ = λ k − λ k (υ.∇) S k (1.8.81)
∂t Dt Dt
By simplification the equation above, we obtain

α Sk2 DS k
Sk + + λk = λ k (υ.∇) S k (1.8.82)
μk Dt

S k = 2 μ k Ek (1.8.83)

The assumption of Ek = 1 would lead to the next equation:

αλ k Sk2 DS k η
Sk + + λk = (2 μ k ) D = 2ηD = η ⎡⎣∇υ + (∇υ )T ⎤⎦ (1.8.84)
η Dt μk
In electrospinning modeling articles τ is used commonly instead of Sk
[154, 159, 161].

Sk ↔ τ
αλ k τ 2 (1.8.85)
τ+ + λ k τ (1) = η ⎡⎣∇υ + (∇υ )T ⎤⎦
η

1.10.7.3 MAXWELL EQUATION

Maxwell’s equations are a set of partial differential equations that, togeth-

er with the Lorentz force law, form the foundation of classical electrody-
namics, classical optics, and electric circuits. These fields are the bases of
modern electrical and communications technologies. Maxwell’s equations
describe how electric and magnetic fields are generated and altered by
each other and by charges and currents; they are named after the Scot-
tish physicist and mathematician James Clerk Maxwell who published an
Electrospinning Process: A Comprehensive Review 77

early form of those equations between 1861 and 1862 [184–185]. It will
be discussed further in detail.

1.10.8 MICROSCOPIC MODELS

One of the aims of computer simulation is to reproduce experiment to

elucidate the invisible microscopic details and further explain the experi-
ments. Physical phenomena occurring in complex materials cannot be en-
capsulated within a single numerical paradigm. In fact, they should be
described within hierarchical, multilevel numerical models in which each
submodel is responsible for different spatial-temporal behavior and passes
out the averaged parameters of the model, which is next in the hierar-
chy. The understanding of the nonequilibrium properties of complex flu-
ids such as the viscoelastic behavior of polymeric liquids, the rheological
properties of ferrofluids and liquid crystals subjected to magnetic fields,
based on the architecture of their molecular constituents is useful to get a
comprehensive view of the process. The analysis of simple physical par-
ticle models for complex fluids has developed from the molecular compu-
tation of basic systems (atoms, rigid molecules) to the simulation of mac-
romolecular “complex” system with a large number of internal degrees of
freedom exposed to external forces [186–187].
The most widely used simulation methods for molecular systems are
Monte Carlo, Brownian dynamics, and molecular dynamics. The micro-
scopic approach represents the microstructural features of material by
means of a large number of micromechanical elements (beads, platelet,
rods) obeying stochastic differential equations. The evolution equations of
the microelements arise from a balance of momentum at the elementary
level. The Monte Carlo method is a stochastic strategy that relies on prob-
abilities. The Monte Carlo sampling technique generates large numbers
of configurations or microstates of equilibrated systems by stepping from
one microstate to the next in a particular statistical ensemble. Random
changes are made to the positions of the species present, together with
their orientations and conformations where appropriate. Brownian dynam-
ics are an efficient approach for simulations of large polymer molecules
or colloidal particles in a small molecule solvent. Molecular dynamics is
the most detailed molecular simulation method which computes the mo-
tions of individual molecules. Molecular dynamics efficiently evaluates
78 Applied Methodologies in Polymer Research and Technology

different configurational properties and dynamic quantities which cannot

generally be obtained by Monte Carlo [188–189].
The first computer simulation of liquids was carried out in 1953. The
model was an idealized two-dimensional representation of molecules as
rigid disks. For macromolecular systems, the coarse-grained approach is
widely used as the modeling process is simplified, hence becomes more
efficient, and the characteristic topological features of the molecule can
still be maintained. The level of detail for a coarse-grained model varies
in different cases. The whole molecule can be represented by a single par-
ticle in a simulation and interactions between particles incorporate aver-
age properties of the whole molecule. With this approach, the number of
degrees of freedom is greatly reduced [190].
On the contrary, a segment of a polymer molecule can also be rep-
resented by a particle (bead). The first coarse-grained model, called the
“dumbbell” model, was introduced in the 1930s. Molecules are treated
as a pair of beads interacting via a harmonic potential. However by using
this model, it is possible to perform kinetic theory derivations and calcula-
tions for nonlinear rheological properties and solve some flow problems.
The analytical results for the dumbbell models (Figure 1.20) can also be
used to check computer simulation procedures in molecular dynamics and
Brownian dynamics [191–192].

FIGURE 1.20 The first coarse-grained models—the rigid and elastic dumbbell models.
Electrospinning Process: A Comprehensive Review 79

The bead-rod and bead-spring model (Figure 1.21) were introduced

to model chainlike macromolecules. Beads in the bead-rod model do not
represent the atoms of the polymer chain backbone, but some portion of
the chain, normally 10 to 20 monomer units. These beads are connected
by rigid and massless rods. While in the bead-spring model, a portion of
the chain containing several hundreds of backbone atoms are replaced by
a “spring,” and the masses of the atoms are concentrated on the mass of
beads [193].

FIGURE 1.21 The freely jointed bead-rod and bead-spring chain models.

If the springs are taken to be Hookean springs, the bead-spring chain

is referred to as a Rouse chain or a Rouse–Zimm chain. This approach has
been applied widely as it has a large number of internal degrees of free-
dom and exhibits orientability and stretchability. However the disadvan-
tage of this model is that it does not have a constant contour length and can
be stretched out to any length. Therefore, in many cases finitely extensible
springs with two more parameters, the spring constant and the maximum
extensibility of an individual spring, can be included so the contour length
of the chain model cannot exceed a certain limit [194–195].
The understanding of the nonequilibrium properties of complex flu-
ids such as the viscoelastic behavior of polymeric liquids, the rheological
80 Applied Methodologies in Polymer Research and Technology

properties of ferrofluids and liquid crystals subjected to magnetic fields,

based on the architecture of their molecular constituents [186].

FIGURE 1.22 Simple microscopic models for complex fluids by using dumbbell model.

Dumbbell models are very crude representations of polymer mol-

ecules. Too crude to be of much interest to a polymer chemist, since it in
no way accounts for the details of the molecular architecture. It certainly
does not have enough internal degrees of freedom to describe the very
rapid motions that contribute, for example, to the complex viscosity at
high frequencies. On the contrary, the elastic dumbbell model is orient-
able and stretchable, and these two properties are essential for the qualita-
tive description of steady-state rheological properties and those involving
slow changes with time. For dumbbell models, one can go through the
entire program of endeavor—from molecular model for fluid dynamics—
Electrospinning Process: A Comprehensive Review 81

for illustrative purposes, in order to point the way toward the task that
has ultimately to be performed for more realistic models. According to
the researches, dumbbell models must, to some extent then, be regarded
as mechanical playthings, somewhat disconnected from the real world of
polymers (Figure 1.22). However, when used intelligently , they can be
useful pedagogically and very helpful in developing a qualitative under-
standing of rheological phenomena [186, 196].
The simplest model of flexible macromolecules in a dilute solution is
the elastic dumbbell (or bead-spring) model. This has been widely used
for purely mechanical theories of the stress in electrospinning modeling
[197].
A Maxwell constitutive equation was first applied by Reneker et al. in
2000. Consider an electrified liquid jet in an electric field parallel to its
axis. They modeled a segment of the jet by a viscoelastic dumbbell (Fig-
ure 1.23). They used a Gaussian electrostatic system of units. According
to this model each particle in the electric field exerts repulsive force on
another particle [66].
He had three main assumptions [66, 198]:
1. The background electric field created by the generator is consid-
ered static.
2. The fiber is a perfect insulator.
3. The polymer solution is a viscoelastic medium with constant elas-
tic modulus, viscosity, and surface tension.

FIGURE 1.23 A schematic of one section of the model.

The researcher considered the governing equations for each bead as

follows [198]:
82 Applied Methodologies in Polymer Research and Technology

d
dt
(
π a 2l = 0 ) (1.8.86)

Therefore, the stress between these particles can be measured by using

the following equation [66]:

dσ dl G
=G − σ (1.8.87)
dt ldt η
The stress can be calculated by a Maxwell viscoelastic constitutive
equation [199]:

⎛ τ⎞
τ = G ⎜ ε ′ − ⎟ (1.8.88)
⎝ η⎠
where ε’ is the Lagrangian axial strain [199]:

∂x ˆ
ε′ ≡ .t . (1.8.89)
∂ξ
Equation of motion for beads can be written as follows[200]:

mass × acceleration = viscous drag + Brownian motion force (8.90)

+ force of one bead on another through the connector

The momentum balance for a bead is [198]:

dυ q2
m = − 2 − qE
 + π
a 2σ
dt l Electric force Mechanical forces
(1.8.91)
Coulomb forces

So the momentum conservation for model charges can be calculated as

[201] follows:

d υi ri − rj r −r r −r
mi = qi ∑ q j K + qi E + π ai2,i +1σ i ,i +1 i +1 i − π ai2−1,iσ i −1,i i i −1
dt 3  r − r ri − ri −1 (1.8.92)
i≠ j ri − rj Electric force i
+1 i

 Mechanical forces
Coulomb forces

Boundary condition assumptions: A small initial perturbation is added

to the position of the first bead, the background electric field is axial and
uniform and the first bead is described by a stationary equation. For solving
Electrospinning Process: A Comprehensive Review 83

these equations, some dimensionless parameters are defined then by sim-

plifying equations, the equations are solved by using boundary conditions
[198, 201].
Now, an example for using this model for the polymer structure is men-
tioned. For a dumbbell consists of two that are connected with a nonlinear
spring (Figure 1.24), the spring force law is given by the following equa-
tion[96]:

HQ
F=− (1.8.93)
1 − Q 2 Q02
Now if we considered the model for the polymer matrix such as carbon
nanotube, the rheological behavior can be obtained as follows [96, 201]:

τ ij = τ p + τ s (1.8.94)

τp = na Qa Fa + n f Q f Ff − nkT δ ij
   (1.8.95)
aggregated dumbbells free dumbbells

τ s = ηγ (1.8.96)

∇ c Q.Q
λ Q.Q = δ ij − (1.8.97)
1 − tr Q.Q bmax

The polymeric stress can be obtained from the following relation [96]:

τˆij c Q.Q
= δ ij − (1.8.98)
nd kT 1 − tr Q.Q bmax
84 Applied Methodologies in Polymer Research and Technology

FIGURE 1.24 Modeling of two kinds of dumbbell sets, (a) aggregate FENE dumbbell
which has lower mobility and (b) free FENE dumbbell which has higher mobility.

1.10.9 SCALING

The physical aspect of a phenomenon can use the language of differential

equation that represents the structure of the system by selecting the vari-
ables that characterize the state of it and certain mathematical constraint
on the values of those variables can take on. These equations can predict
the behavior of the system over a quantity such as time. For an instance, a
set of continuous functions of time that describe the way the variables of
the system developed over time starting from a given initial state [208]. In
general, the renormalization group theory, scaling, and fractal geometry
are applied to the understanding of the complex phenomena in physics,
economics, and medicine [203-209].
In more recent times, in statistical mechanics, the expression “scal-
ing laws” has referred to the homogeneity of form of the thermodynamic
and correlation functions near critical points, and to the resulting relations
among the exponents that occur in those functions. From the viewpoint
of scaling, electrospinning modeling can be studied in two ways: allome-
tric and dimensionless analysis. Scaling and dimensional analysis actually
Electrospinning Process: A Comprehensive Review 85

started with Newton, and allometry exists everywhere in our daily life and
scientific activity[209–210].

1.10.9.1 ALLOMETRIC SCALING

Electrospinning applies electrically generated motion to spin fibers. There-

fore, it is difficult to predict the size of the produced fibers, which depends
on the applied voltage in principal. Therefore, the relationship between
the radius of the jet and the axial distance from the nozzle is always the
subject of investigation [211–212]. It can be described as an allometric
equation by using the values of the scaling exponent for the initial steady,
instability, and terminal stages [213].
The relationship between r and z can be expressed as an allometric
equation of the following form:

r ≈ zb (1.8.99)

When the power exponent, b = 1, the relationship is isometric and when b

≠ 1 the relationship is allometric [211, 214]. In another view, b = −1/2 is
considered for the straight jet, b = −1/4 for instability jet, and b = 0 for
final stage [172, 212].
Due to high electrical force acting on the jet, it can be illustrated [211]:

d ⎛ ν 2 ⎞ 2σ E
=
dz ⎜⎝ 2 ⎟⎠
(1.8.100)
ρr
Equations of mass and charge conservations applied here as mentioned
earlier [211, 214–215]
From the above equations, it can be noted that [161, 211]

dυ 2
r ≈ z b , σ ≈ r , E ≈ r −2 , ≈ r −2 (1.8.101)
dz
Therefore, it is obtained for the initial part of jet, r ≈ z −1 / 4 for the in-
stable stage and for the final stage.
The charged jet can be considered as a 1D flow as mentioned. If the
conservation equations modified, they would change as follows [211]:
86 Applied Methodologies in Polymer Research and Technology

2π rσ α ν + K π r 2 E = I (1.8.102)

−α (1.8.103)
(α +1)
r≈z
where α is a surface charge parameter; the value of α depends on the sur-
face charge in the jet. When α = 0 no charge in jet surface, and in α = 1 use
for full surface charge.
Allometric scaling equations are more widely investigated by different
researchers. Some of the most important allometric relationships for elec-
trospinning are presented in Table 1.2.

TABLE 1.2 Investigated scaling laws applied in electrospinning model

Parameters Equation Ref.

Conductance and polymer concentration g ≈ cβ [161]

Fiber diameters and the solution viscosity d ≈ηα [212]

−α
Mechanical strength and threshold voltage σ ≈ Ethreshold [216]

Threshold voltage and the solution viscosity Ethreshold ≈ η 1/ 4 [216]

Viscosity and the oscillating frequency η ≈ ω −0.4 [216]

Volume flow rate and the current I ≈ Qb [215]

Current and the fiber radius I ≈ r2 [217]

Surface charge density and the fiber radius σ ≈ r3 [217]

Induction surface current and the fiber radius φ ≈ r2 [217]

Fiber radius and AC frequency r ≈ Ω1 / 4 [172]

Note: β, α, and b = scaling exponent

Electrospinning Process: A Comprehensive Review 87

1.10.9.2 DIMENSIONLESS ANALYSIS

One of the simplest, yet most powerful, tools in the physics is dimensional
analysis in which there are two kinds of quantities: dimensionless and di-
mensional.
In physics and all science, dimensional analysis is the analysis of the
relationships between different physical quantities by identifying their di-
mensions. The dimension of any physical quantity is the combination of
the basic physical dimensions that compose it, although the definitions of
basic physical dimensions may vary. Some fundamental physical dimen-
sions, based on the SI system of units, are length, mass, time, and electric
charge. (The SI unit of electric charge is, however, defined in terms of
units of length, mass and time, and, for example, the time unit and the
length unit are not independent but can be linked by the speed of light c.)
Other physical quantities can be expressed in terms of these fundamen-
tal physical dimensions. Dimensional analysis is based on the fact that a
physical law must be independent of the units used to measure the physical
variables. A straightforward practical consequence is that any meaningful
equation (and any inequality and inequation) must have the same dimensions
on the left and right sides. Dimensional analysis is routinely used as a
check on the plausibility of derived equations and computations. It is also
used to categorize types of physical quantities and units based on their
relationship to or dependence on other units.
Dimensionless quantities that are without associated physical dimen-
sions are widely used in mathematics, physics, engineering, economics,
and in everyday life (such as in counting). Numerous well-known quanti-
ties, such as π, e, and φ, are dimensionless. They are “pure” numbers, and
as such always have a dimension of 1 [218–219].
Dimensionless quantities are often defined as products or ratios of
quantities that are not dimensionless, but whose dimensions cancel out
when their powers are multiplied [220].
The basic principle of dimensional analysis was known to Isaac Newton
(1686) who referred to it as the “Great Principle of Similitude.” James Clerk
Maxwell played a major role in establishing modern use of dimensional
analysis by distinguishing mass, length, and time as fundamental units,
while referring to other units as derived. The nineteenth-century French
mathematician Joseph Fourier made important contributions based on the
idea that physical laws like F = ma should be independent of the units
used to measure the physical variables. This led to the conclusion that
88 Applied Methodologies in Polymer Research and Technology

meaningful laws must be homogeneous equations in their various units of

measurement, a result that was eventually formalized in the Buckingham π
theorem. This theorem describes how every physically meaningful equa-
tion involving n variables can be equivalently rewritten as an equation of
n−m dimensionless parameters, where m is the rank of the dimensional
matrix. Further, and most importantly, it provides a method for computing
these dimensionless parameters from the given variables.
A dimensional equation can have the dimensions reduced or eliminat-
ed through nondimensionalization, which begins with dimensional analysis,
and involves scaling quantities by characteristic units of a system or natural
units of nature. This gives insight into the fundamental properties of the
system, as illustrated in the examples below:
In nondimensional scaling, there are two key steps:
1. Identifying a set of physically relevant dimensionless groups
2. Determining the scaling exponent for each one
Dimensional analysis will help you with step (a), but it cannot be ap-
plicable possibly for step (b).
A good approach to systematically getting to grips with such problems
is through the tools of dimensional analysis (Bridgman, 1963). The domi-
nant balance of forces controlling the dynamics of any process depends
on the relative magnitudes of each underlying physical effect entering the
set of governing equations [221]. Now, the most general characteristics
parameters that are used in dimensionless analysis in electrospinning are
introduced in Table 1.3.

TABLE 1.3 Characteristics parameters employed and their definitions

Parameter Definition
Length R0

Velocity Q
υ0 =
πR02 K

Electric field I
E0 =
πR02 K

Surface charge density

σ 0 = ε E0
Viscous stress η 0υ 0
τ0 =
R0
Electrospinning Process: A Comprehensive Review 89

For achievement of a simplified form of equations and reduction of a

number of unknown variables, the parameters should be subdivided into
characteristic scales to become dimensionless. Electrospinning dimen-
sionless groups are shown in Table 1.4 [222].

TABLE 1.4 Dimensionless groups employed and their definitions

Name Definition Field of application

Froude number υ02 The ratio of inertial to gravitational

Fr = forces
gR0

Reynolds number ρυ0 R0 The ratio of the inertia forces of the vis-
Re = cous forces
η0

Weber number ρυ02 R0 The ratio of the surface tension forces to

We = the inertia forces
γ

Deborah number λυ0 The ratio of the fluid relaxation time to

De = the instability growth time
R0

Electric Peclet number 2ευ0 The ratio of the characteristic time for
Pe = flow to that for electrical conduction
KR0

Euler number ε0 E 2 The ratio of electrostatic forces to iner-

Eu = tia forces
ρυ02

Capillary number ηυ0 The ratio of inertia forces of viscous

Ca = forces
γ

Ohnesorge number η The ratio of viscous force to surface

oh = force
( ργ R0 ) 1/2

Viscosity ratio ηp The Ratio of the Polymer Viscosity to

rη = Total Viscosity
η0

Aspect ratio L The ratio of the length of the primary

χ= radius of jet
R0
90 Applied Methodologies in Polymer Research and Technology

TABLE 1.4 (Continued)

Name Definition Field of application

Electrostatic force pa- The relative importance of the electro-

ε E2
rameter ε = 02 static and hydrodynamic forces
ρυ0

Dielectric constant ratio ε The ratio of the field without the dielec-
β= −1 tric to the net field with the dielectric
ε

The governing and constitutive equations can be transformed into a

dimensionless form using the dimensionless parameters and groups.

1.10.10 SOME OF ELECTROSPINNING MODELS

The most important mathematical models for electrospinning process are

classified in the Table 1.5 according to the year, advantages, and disadvan-
tages of the models.

TABLE 1.5 The most important mathematical models for electrospinning

Researchers Model Year Ref.

Taylor, G. I. Leaky dielectric model 1969 [223]

Melcher, J. R. Dielectric fluid
Bulk charge in the fluid jet considered
to be zero
Only axial motion
Steady-state part of jet

Ramos Slender body 1996 [224]


Incompressible and axisymmetric and
viscous jet under gravity force
No electrical force
Jet radius decreases near zero

Velocity and pressure of jet only
change during axial direction

Mass and volume control equations
and Taylor expansion were applied to
predict jet radius.
Electrospinning Process: A Comprehensive Review 91

TABLE 1.5 (Continued)

Researchers Model Year Ref.

Saville, D. A. Electrohydrodynamic model 1997 [225]


The hydrodynamic equations of di-
electric model were modified.

Using dielectric assumption
This model can predict drop formation

Considering jet as a cylinder (ignoring
the diameter reduction)
Only for steady-state part of the jet

Spivak, A. Spivak and Dzenis model 1998 [150]

Dzenis, Y. 
The motions of a viscose fluid jet with
lower conductivity were surveyed in
an external electric field.
Single Newtonian fluid jet

The electric field assumed to be uni-
form and constant, unaffected by the
charges carried by the jet

Use asymptotic approximation was
applied in a long distance from the
nozzle.

Tangential electric force assumed to
be zero.

Using nonlinear rheological consti-
tutive equation (Ostwald–de Waele
law), nonlinear behavior of fluid jet
were investigated.

Jong Wook Droplet formation model 2000 [226]


Droplet formation of charged fluid jet
was studied in this model.

The ratio of mass, energy and electric
charge transition are the most impor-
tant parameters on droplet formation.

Deformation and breakup of droplets
were investigated too.
Newtonian and non-Newtonian fluids

Only for high conductivity and viscose
fluids
92 Applied Methodologies in Polymer Research and Technology

TABLE 1.5 (Continued)

Researchers Model Year Ref.

Reneker, D. H. Reneker model 2000 [227]

Yarin, A. L. 
For description of instabilities in vis-
coelastic jets.

Using molecular chain theory, behav-
ior of polymer chain of spring-bead
model in electric field was studied.

Electric force based on electric field
cause instability of fluid jet while re-
pulsion force between surface charges
make perturbation and bending insta-
bility.

The motion paths of these two cases
were studied

Governing equations: momentum bal-
ance, motion equations for each bead,
Maxwell tension and Columbic equa-
tions

Hohman, M. Stability Theory 2001 [60]

Shin, M. 
This model is based on a dielectric
model with some modification for
Newtonian fluids.

This model can describe whipping,
bending and Rayleigh instabilities and
introduced new ballooning instability.

Four motion regions were introduced:
dipping mode, spindle mode, oscillat-
ing mode, precession mode.

Surface charge density introduced as
the most effective parameter on insta-
bility formation.

Effect of fluid conductivity and vis-
cosity on nanofibers diameter were
discussed.

Steady solutions may be obtained
only if the surface charge density at
the nozzle is set to zero or a very low
value.
Electrospinning Process: A Comprehensive Review 93

TABLE 1.5 (Continued)

Researchers Model Year Ref.

Feng, J. J Modifying Hohman model 2002 [153]


For both Newtonian and non-Newto-
nian fluids

Unlike Hohman model, the initial sur-
face charge density was not zero, so the
“ballooning instability” did not accrue.
Only for steady-state part of the jet

Simplifying the electric field equation
which Hohman used in order to elimi-
nate ballooning instability.

Wan–Guo–Pan Wan–Guo–Pan model 2004 [175]


They introduced thermo-electro-hydro
dynamics model in electrospinning
process

This model is a modification on Spi-
vak model which mentioned before

The governing equations in this
model: Modified Maxwell equation,
Navier–Stocks equations, and several
rheological constitutive equations.

Ji-Haun AC-electrospinning model 2005 [172]


Whipping instability in this model was
distinguished as the most effective pa-
rameter on uncontrollable deposition
of nanofibers.

Applying AC current can reduce this
instability so make oriented nanofi-
bers.

This model found a relationship be-
tween axial distance from nozzle and
jet diameter.

This model also connected ac frequen-
cy and jet diameter.
94 Applied Methodologies in Polymer Research and Technology

TABLE 1.5 (Continued)

Researchers Model Year Ref.

Roozemond Combination of slender body and dielec- 2007 [228]

(Eindhoven University tric model
and Technology) In this model, a new model for viscoelas-
tic jets in electrospinning was presented by
combining these two models.
All variables were assumed uniform in
cross-section of the jet, but they changed
in during z direction.
Nanofiber diameter can be predicted.

Wan Electromagnetic model 2012 [229]


Results indicated that the electromag-
netic field which made because of
electrical field in charged polymeric
jet is the most important reason of he-
lix motion of jet during the process.

Dasri Dasri model 2012 [230]


This model was presented for descrip-
tion of unstable behavior of fluid jet
during electrospinning.

This instability causes random deposi-
tion of nanofiber on surface of the col-
lector.

This model described dynamic behav-
ior of fluid by combining assumption
of Reneker and Spivak models.

The most frequent numeric mathematical methods which were used in

different models are listed in Table 1.6:

TABLE 1.6 Applied numerical methods for electrospinning

Method Ref.

Relaxation method [153, 159, 231]

Boundary integral method (boundary element method) [199, 226]

Semi-inverse method [159, 172]

(Integral) control-volume formulation [224]

Electrospinning Process: A Comprehensive Review 95

TABLE 1.6 (Continued)

Method Ref.

Finite element method [223]

Kutta–Merson method [232]

Lattice Boltzmann method with finite difference method [233]

1.11 ELECTROSPINNING SIMULATION

Electrospun polymer nanofibers demonstrate outstanding mechanical and

thermodynamic properties as compared with macroscopic-scale structures.
These features are attributed to nanofiber microstructure [234–254]. Theo-
retical modeling predicts the nanostructure formations during electrospin-
ning. This prediction could be verified by various experimental condition
and analysis methods that called are simulation. Numerical simulations
can be compared with experimental observations as the last evidence[149,
236].
Parametric analysis and accounting complex geometries in simulation
of electrospinning are extremely difficult due to the nonlinearity nature in
the problem. Therefore, a lot of researches have done to develop an exist-
ing electrospinning simulation of viscoelastic liquids [231].

KEYWORDS

• Electrospinning
• Freeze-drying
• Laser-based techniques
• Molecular dynamics
• Momentum balance
• Nanocoatings
• Nanoparticles
• Nanostructures
• Proton exchange mat
• Quantum dots
96 Applied Methodologies in Polymer Research and Technology

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247–260.
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Bifurcat. Chaos. 1992, 2(03), 427–449.
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ential equations. Appl. Numer. Math. 1999, 31(2), 227–238.
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Kutta and General Linear Methods. Wiley-Interscience; 1987, 512 p.
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108 Applied Methodologies in Polymer Research and Technology

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CHAPTER 2

ALUMINIUM-COATED POLYMER
FILMS AS INFRARED LIGHT SHIELDS
FOR FOOD PACKING
ESEN ARKIŞ and DEVRİM BALKÖSE

CONTENTS

2.1 Introduction ...................................................................................110

2.2 Experimental .................................................................................111
2.3 Results and Discussion .................................................................112
2.4 Conclusions .................................................................................. 122
Acknowledgments................................................................................. 123
Keywords .............................................................................................. 123
References ............................................................................................. 123
110 Applied Methodologies in Polymer Research and Technology

2.1 INTRODUCTION

The protection from harmful effects caused by infrared radiation on foods

can be made by using infrared shielding packing materials. Nano-oxides
with the surface effect, small-size effect, quantum-size effect, macroscop-
ic quantum tunneling effect, and other special properties can be used in
preparation of infrared shielding coating, absorbing coatings, conductive
coatings, insulation coatings, and so on [1].
Polymer coatings on the surfaces are very easily degraded because of
the infrared light. The life of the polymer coating could be extended if
they are coated with an infrared light reflecting or absorbing layer. Alumi-
num coatings were used for this purpose in many applications [2]. Alumi-
num oxide coating on polymers is also used for protection of the polymer
layer. Covalent bonds are responsible for adhesion of aluminum oxide to
polymer surface. Nano Al2O3 particles have a wide absorption band in the
infrared band, and they have been used widely in the paint, military, sci-
entific and industrial application [2]. Resonance absorption of the infrared
radiation may take place at extremely thin metal coatings by reducing the
overall temperature of the heat shield [3].
Polymer surfaces are modified by plasma techniques for interfacial
enhancement [4–10]. Au, Ag, Pd, Cu, and Ni were coated on poly (meth-
ylmethacrylate) (PMMA) by barrel technique [11]. Coating of Al alloys
on PET was compared with Ti layer under Al alloys [12]. Thin aluminum
oxide coatings have been deposited on various uncoated papers, polymer-
coated papers, and plain polymer films using atomic layer deposition tech-
nique [13]. The isotactic polypropylene (iPP) and Al composite is widely
used as television cable electromagnetic shielding materials [14]. The
reflection of infrared light depends on geometry of the surface of alumi-
num. The reflection of infrared light was reduced when the height of the
triangular aluminum gratings were reduced [15]. Al coating obtained by
roll-to-roll coating on polypropylene was polycrystalline with a grain size
of 20–70 nm [16].
The morphology, order, light transmittance, and water vapor perme-
ability of the Al-coated polypropylene films were reported in a previous
publication [17]. The films did not transmit light in the UV and visible
region of the light spectrum, and Al coating reduced the water vapor per-
meation through the films [17].
Aluminium-Coated Polymer Films as Infrared Light Shields 111

The objective of this study is to study the absorption and reflection of

infrared light by the uncoated and Al-coated surfaces of polymer films
using transmission and reflection techniques. For this purpose, two com-
mercial biaxially oriented polypropylene film, a cast polypropylene film, a
milk cover and a chocolate coating material with their one surface coated
with a thin aluminum layer were examined by infrared spectroscopy. One
surface of the each film was coated with a thin aluminum layer.

2.2 EXPERIMENTAL

2.2.1 MATERIALS

Infrared light absorption and reflection of the uncoated and Al-coated

surfaces of polymer films were investigated in the present study. Two
commercial biaxially oriented polypropylene samples coated with Al by
physical vapor deposition technique were examined. The samples called
commercial film 1 and commercial film 2 were provided by POLINAS
and POLIBAK companies, respectively. They were 16 μm and 19 μm
thick, and their one surface was coated with Al after a corona discharge
treatment.
An aluminum-coated polypropylene film with 50 μm thickness that
was previously prepared by [17] was also examined. Al film on polypro-
pylene was deposited by the high vacuum magnetron sputtering system
having four guns. Argon gas (99.9 wt percent) was used to create plasma.
Polypropylene film fixed on glass substrates was coated by condensation
of Al atoms sputtered from an Al target. In the sputtering process, 20 W
DC power and 20 mA current were applied to pure Al target. The Al coat-
ing obtained by magnetron sputtering method was 98–131 nm thickness
and formed by small Al particles having 22–29 nm grain sizes [18]. Com-
mercial milk and chocolate packaging materials were also investigated.

2.2.2 METHODS

The surface morphology of the films was examined by scanning electron

microscopy. FEI QUANTA FEG-250 SEM was used for this purpose. The
thickness of Al coating on the surface of the films was measured from the
fractured brittle Al layer obtained by stretching the films.
112 Applied Methodologies in Polymer Research and Technology

The transmission infrared spectra of the films at 20°C were taken with
Excalibur DIGILAB FTS 3000 MX-type Fourier transform infrared spec-
trophotometer with a resolution of 4 cm–1. DTGS-type detector was used
for all measurements. The transmission spectra of the films were obtained
by placing the films in two different positions. The incident infrared light
first strikes to either Al coated or uncoated surface in these positions. In
transmission spectrum, the light that passes through the sample is mea-
sured. The grazing angle specular reflectance accessory with 80° (Pike
Technologies), in the reflection–absorption mode was used to obtain spec-
ular reflectance spectra. Gold-coated glass was used as a reference.

2.3 RESULTS AND DISCUSSION

2.3.1 MORPHOLOGIES OF AL COATINGS

SEM micrographs of the Al-coated surfaces of the films were taken to

observe the morphology of the coatings on the films. The Al coating on
the surface of the films were broken by stretching the polymer phase to
observe the thickness of Al coatings.

2.3.1.1 MORPHOLOGY OF COMMERCIAL FILM 1

The commercial polypropylene films were coated with a layer of Al by

physical vapor deposition. The coating thickness was determined from
SEM pictures of commercial film 1 as can be seen in Figure 2.1(a) as 32
nm for commercial film 1. The coating had the shape of the polymer layer.
There were parallel lines on the surface of the polymer produced during
processing of the polypropylene film in continuous film machinery.
Aluminium-Coated Polymer Films as Infrared Light Shields 113

FIGURE 2.1 SEM pictures of al-coated surface of commercial film 1: (a) the al surface
fractured to observe coating thickness and (b) the surface as produced.

2.3.1.2 MORPHOLOGY OF COMMERCIAL FILM 2

In Figure 2.2, SEM micrograph of commercial film 2 is shown. Figure

2.2(a) is fractured Al coating on the surface. Coating thickness is deter-
mined as 185 nm from Figure 2.2(a). Figure 2.2(b) is Al-coated polypro-
pylene surface. The coating was made up of Al particles condensed on the
surface of the polypropylene phase. There were uncoated regions on the
surface.

FIGURE 2.2 SEM Pictures from BOPP metalized commercial film 2(a). Fractured Al
surface (b). Coated polypropylene.
114 Applied Methodologies in Polymer Research and Technology

2.3.1.3 MORPHOLOGY OF MAGNETRON SPUTTERED FILMS

The polypropylene films were at 50 μm thickness and their one surface

was covered with 98–131 nm thick Al layer with magnetron sputtering
[18]. In Figure 2.3, SEM micrographs of magnetron sputtered film are
shown. In the Figure 2.3(a) there is fractured Al coating on the surface of
polypropylene. Figure 2.6(b). is the top view of the Al layer. From Figure
2.3(a), the coating thickness is determined to be 185 nm, close to the value
reported previously [18]. The top view of the Al layer seen in Figure 2.3(b)
indicated that the surface was covered by Al particles having nearly 30 nm
size. The surface was not very smooth. There are cracks on the surface of
the brittle Al coating.

FIGURE 2.3 SEM pictures of a. fractured Al coating on the cast polypropylene film (b).
Al coated surface of the polypropylene film.

FIGURE 2.4 The photographs of (a) Chocolate packing (b) Milk cover.
Aluminium-Coated Polymer Films as Infrared Light Shields 115

2.3.1.4 MORPHOLOGY OF MILK AND CHOCOLATE PACKAGES

The chocolate packing had an outer layer coated with aluminum. The in-
ner layer was milk cover that had the function of opening the packing
when it was pulled. The inner side of the cover that was in contact with the
milk was covered with a polymer layer.

FIGURE 2.5 The SEM micrographs Al coated surface of a. the chocolate packing (b).
Milk cover.

Photographs of chocolate packing and milk cover are shown in Figure

2.4. The SEM micrographs of their Al-coated surfaces are shown in Figure
2.5. They have an even Al coating as seen in Figure 2.5.

2.3.2 TRANSMISSION SPECTRA OF AL-COATED

POLYPROPYLENE FILMS

2.3.2.1 COMMERCIAL AL-COATED POLYPROPYLENE FILMS

The transmission infrared spectra of commercial films 1 and 2 were ob-

tained by placing the films in the path of the infrared light. Spectrum 1
and spectrum 2 in Figure 2.6 belonged to commercial film 1 and film
2, respectively. The baseline absorbance values were close to 1 for com-
mercial film 1 and were close to 4 for commercial film 2. This indicated
that 1/10000 and 1/10 of the input infrared light was transmitted from the
samples. The Al coating on the film acted as a barrier to infrared light.
The higher coating thickness of commercial film 2 (185 nm) than that of
116 Applied Methodologies in Polymer Research and Technology

commercial film 1 (30 nm) resulted higher level of shielding from infrared
radiation. The film 2 had better infrared light shielding efficiency than the
film 1.
The peaks observed at 3000–2800 cm–1 belonged to C–H asymmetric
and symmetric stretching, at 1450 cm–1 C–H bending, at 1350 cm–1 C–H
deformation bending17. The peak at 973 cm–1 belongs to amorphous CH3
rocking and C–C chain stretching vibrations and the peak at 998 cm–1 be-
longs to crystalline CH3 rocking, CH2 wagging, and CH bending vibra-
tions20.
The magnetron sputtered film’s polymer layer and Al layer were 50
μm and 185 nm, respectively. This film was nearly three times thicker
than commercial film 1 and commercial film 2. The absorbance values of
this film in transmission mode were too high, since both the Al layer and
polypropylene layer were thicker. The FTIR transmission spectrum of this
thick film coated by magnetron sputtering had very high absorbance val-
ues, indicating it was also a good shield for infrared radiation.

FIGURE 2.6 Transmittance spectra of the commercial films 1 and 2.

2.3.3 SPECULAR REFLECTANCE OF SPECTRA OF THE FILMS

2.3.3.1 COMMERCIAL AL-COATED POLYPROPYLENE FILM1

Figure 2.6 shows the specular reflectance spectra of Al-coated and un-
coated surfaces of the film 1. Al-coated surface reflected 100 percent
of the infrared rays since the absorbance values were very close to zero.
Aluminium-Coated Polymer Films as Infrared Light Shields 117

Uncoated surface had the characteristic spectrum of polypropylene. How-

ever, there were other peaks observed called fringes due to reflection of
light from both surfaces of the thin film (Figure 2.7).

FIGURE 2.7 Specular reflectance of spectra of the film 1, (1) Polypropylene surface, (2)
Al-coated surface of the film 1.

2.3.3.2 THICKNESS OF COMMERCIAL FILM 1

To count the number of fringes, select the starting and ending points both
as minima or maxima of the spectrum and then count the number of op-
posing minima or maxima. In other words, if we select minima values for
starting and ending points in the spectrum, then select maxima points to
count the number of fringes.

2.3.3.3 SPECULAR REFLECTANCE SPECTRA OF COMMERCIAL

AL-COATED POLYPROPYLENE FILM 2

The specular reflectance spectra of the surfaces of the commercial film 2

are seen in Figure 2.8; curve 1 shows the specular reflectance spectrum
of the polypropylene side of the film and curve 2 shows the specular re-
flection spectrum of the Al side of the film. Although the polypropylene
surface has the spectrum of polypropylene, the Al-coated surface reflected
the infrared rays. The absorbance values close to zero indicated that the
light was not absorbed but reflected by the Al surface.
118 Applied Methodologies in Polymer Research and Technology

FIGURE 2.8 Specular reflectance spectra of the film 2: 1, polypropylene surface and 2,
Al-coated surface of the film 1.

2.3.3.4 THICKNESS OF COMMERCIAL FILM 2

There were six refraction fringes observed in specular reflection spectrum

of commercial film 2 in Figure 2.5. Using Eq. (2.1) and inserting values of
six fringes between 1600 cm–1 and 2650 cm–1 and the film thickness was
calculated to be 19 μm.

2.3.3.5 SPECULAR REFLECTANCE SPECTRA OF MAGNETRON

SPUTTERED FILMS

The specular reflection spectra of uncoated and coated surfaces of poly-

propylene film prepared by Ozmihci et al.,5 can be seen in Figure 2.9. Both
surfaces showed the
Aluminium-Coated Polymer Films as Infrared Light Shields 119

FIGURE 2.9 Specular reflection spectra of (a) Uncoated surface and (b) Al-coated
surface of cast film.

Characteristic spectrum of polypropylene. This indicated that there

were uncoated polypropylene regions on the coated surface. However the
Al-coated surface had lower absorbance values at all wave numbers due to
reflection of infrared rays from its surface. However, the reflection extent
was not as high as the reflection extent of the commercial films. The Al
surface of this film was not a reflecting surface like commercial films.
120 Applied Methodologies in Polymer Research and Technology

2.3.3.6 SPECULAR REFLECTANCE SPECTRA OF MILK PACKAGE

Milk cardboard container has an Al lid to open it. The specular reflection
spectra of uncoated and coated surfaces of milk package can be seen in
Figure 2.10. Al coating at the upper surface has lower absorbance value
than polymer at the lower surface. Thus, Al coating reflected the infrared
light and caused light protection of milk from heat and light conditions.
The lower surface is less bright. Both surfaces appear to be covered with
different polymer layers. The shining surface had peaks at 2920 cm–1, 2860
cm–1, 1745 cm–1, 1645 cm–1, 1282 cm–1, 1070 cm–1, 997 cm–1, and 869 cm–1.
There are CH2 streching vibration peaks at 2920 and 2860 cm–1, C = O
peaks at 1745 cm–1, C = C peak at 1645 cm–1. The other surface had peaks
at 2951 cm–1, 2885 cm–1, 1734 cm–1, 1454 cm–1, 1296 cm–1, and 723 cm–1,
respectively. 2951 cm-– and 2885 cm–1 peak belonged to CH2 stretching
vibrations and 1745 cm–1 peak belonged to C = O stretching vibration.
Further characterizations are needed to determine which polymers were
coated on the surfaces.

FIGURE 2.10 Specular reflection of milk package: 1, Mat surface and 2, shining surface.

2.3.4 SPECULAR REFLECTANCE SPECTRA OF CHOCOLATE

PACKING

The chocolate packing showed that Al-coated surface had lower absor-
bance values than uncoated surface indicating that infrared light was re-
flected by the Al coating as can be seen in Figure 2.11.
Aluminium-Coated Polymer Films as Infrared Light Shields 121

FIGURE 2.11 Specular reflection spectra of chocolate package: 1, Polymer surface and
2, Al-coated surface.

2.3.5 COMPARISON OF ABSORBANCE VALUES IN

SPECULAR REFLECTANCE SPECTRA OF PACKING MATERIALS

Comparison of five different films absorbance values are given in Table

2.1. Baseline absorbance values at 920 cm–1 and maximum absorbance
values due to polypropylene band at 1450 cm–1 are reported in the table.
The baseline absorbance values of the uncoated and coated surfaces at 920
cm–1 are close to each other for all five films. The highest baseline value
was observed for magnetron sputtered films. The lowest baseline absor-
bance was observed for commercial film 1. The absorbance values of the
uncoated polypropylene surface of the five films at 1450 cm–1 are close to
each other in the range of 0.50–0.77. This peak is due to bending vibration
of the CH2 groups in polypropylene phase. FTIR light was reflected by the
Al surfaces of the films. The highest reflection and the lowest absorbance
value of –0.08 was observed for commercial film 2. Commercial film 1
also had a low absorbance value of 0.11 and high level of reflection. The
magnetron sputtered films reflection was not as high as the commercial
films, since its absorbance value at 1450 cm–1 was 0.36. The Al coating on
this film did not cover the whole surface, and there were polypropylene
phase exposed to infrared light. Chocolate packing materials’ Al-coated
surface also had low absorbance value, 0.20, indicating that it also ref-
lected strogly the infrared light. The milk cover Al-coated surface even
higher absorbance value 0.44 than other films.
122 Applied Methodologies in Polymer Research and Technology

TABLE 2.1 Absorbance values of specular reflectance spectra of uncoated and Al-coated
surfaces of packing materials

Type of film Absorbance at 1450 cm–1 Absorbance at 920 cm–1

Uncoated Al-Coated Uncoated Al-Coated

Surface Surface Surface Surface

Commercial film 1 0.50 0.11 0.12 0.11

Commercial film 2 0.66 –0.08 –0.03 –0.07

Magnetron sputtered film 0.60 0.36 0.29 0.28

Chocolate packing 0.77 0.20 0.69 0.18

Milk cover 0.75 0.44 0.63 0.38

2.4 CONCLUSIONS

Infrared spectroscopy is an efficient tool for measuring the thickness of

thin polymer films and their ability to absorb or reflect infrared lights. The
thicknesses of the commercial films coated with aluminum were deter-
mined to be 16 and 19 μm for film 1 and 2, respectively. The aluminum-
coated surface of the commercial films had the ability to reflect the infra-
red rays that strike. They can be used efficiently as infrared light shields
for the materials inside their packing. The Al coatings obtained by chemi-
cal vapor deposition were 32 nm and 185 nm for commercial film 1 and 2,
respectively. The coatings were more perfect than the coating obtained by
magnetron sputtered cast film.
The Al coating of the cast film was more brittle, and there were uncoat-
ed polypropylene regions, and the infrared light was only partially filtered.
Thus, it was a less-efficient infrared shield when compared with commer-
cial films. The magnetron sputtering method needs more investigation for
optimum results. The chocolate and milk-packing materials’ Al-coated
surfaces reflected the infrared light better than their other surfaces. They
were also good infrared light protectors. However, milk-packing material
Al surface was also coated with another polymer layer either for esthetic
or safety reasons or since it was used in contact with milk.
Aluminium-Coated Polymer Films as Infrared Light Shields 123

ACKNOWLEDGMENTS

The authors thank The POLİNAS and POLİBAK companies and the au-
thors of Ref. [19] for providing for providing commercial aluminum-coat-
ed films and magnetron sputtered film, respectively.

KEYWORDS

• Aluminum-coated polymer films

• commercial films
• quantum-size effect

REFERENCES

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tocki, K. A.; Eng, D. A.; Mehoke, D. S.; Mattix, M. P.; Thomas, M. E.; Nagle, D. C.;
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Technol. 2007, 201, 5646–5650.
5. Takano, I.; Inoue, N.; Matsui, K.; Kokubu, S.; Sasase, M.; Isobe, S.; Surf. Coat. Tech-
nol. 1994, 66, 509–513.
6. O’Hare, L.; A., Leadley, S.; Parbhoo, B.; Surf. Interface Anal. 2002, 33, 335–342.
7. Greer, J.; Street R.; A.; Acta Mater. 2007, 55, 6345–6349.
8. Fortunato, E.; Nunes, P.; Marques, A.; Costa, D.; Aguas, H.; Ferreira, I.; Costa, M.
E. V.; Godinho, M. H.; Almeida, P. L.; Borges, J. P.; Martins, R.; Surf. Coat. Technol.
2002, 151–152, 247–251.
9. Yanaka, M.; Henry, B., M.; Roberts, A. P.; Grovenor, C., R., M., Briggs, G., A., D.,
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Films. 2001, 397, 176–185.
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1999, 112, 373–378.
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1997, 11(2), 233–246.
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124 Applied Methodologies in Polymer Research and Technology

15. Qui J.; Liu L. H.; Hsu P. F.; Appl. Surf. Sci. 2005, 111, 1912–1920.
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lating Thickness- Free Standing Films-by FTIR.pdf, 2012.
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CHAPTER 3

GENERALIZATION OF FUELS
SWELLING DATA BY MEANS OF
LINEAR FREE ENERGY PRINCIPLE
ROMAN MAKITRA, HALYNA MIDYANA, LILIYA BAZYLYAK, and
OLENA PALCHYKOVA

CONTENTS

3.1 Introduction .................................................................................. 126

3.2 Methodology ................................................................................ 126
Keywords .............................................................................................. 147
Reference .............................................................................................. 147
126 Applied Methodologies in Polymer Research and Technology

3.1 INTRODUCTION

An action of the organic solvents on solid fuels, namely black and brown
coal or peat is under the active investigation for a long time. This is caused
by two reasons; specifically, this is one among successful methods of the
solid fuels structure study with the aim of their technological application
for obtaining of the so-called montan wax, or it is used for obtaining of the
low-molecular liquid extracts that can be next transformed into synthetic
liquid fuel via the hydrogenation. It is necessary to add that the interaction
of coal with the solvents is taken as a principle of the coals liquefaction
under their transformation into the liquid fuel.

3.2 METHODOLOGY

The first stage of the interaction into the systems coal solvent is their
swelling and expansion as a result of the molecules of liquid invasion into
the pores and into the structure of coal. Depending on the nature of solvent
and also on coal itself, its volume can be multiplied many times; correspond-
ingly, the increment of weight for the investigated sample can achieve 100 and
more percentage.
A review of the early works concerning coal swelling is presented in
Refs. [1–2]. It can be noted that still in 50 years, the coals swelling process
was considered as the first stage of their extraction, and it was connected
with their physical−chemical interaction with the solvents [3]. The process
itself was explained by two reasons: first is caused by the adsorption and
absorption of liquid in pores, and accordingly to the second one the swell-
ing process is connected with the change of the cohesion energy of the
solid and liquid phases of a system. Sanada and coworkers [4–6] consid-
ered that the coal represents by itself the natural three−dimensional poly-
mer, and in accordance with the Flory—Huggin’s theory, the change of a
free energy under the coal swelling represents by itself the conditional sum
of the polymer and the solvent mixing energies; this free energy change
is determined first of all by the difference in the Hildebrand’s solubility
parameters δ of both components:

ΔG = [ln(1–Ø2) + χØ2 + Ø2], (3.1)

Generalization of Fuels Swelling Data 127

where Ø2 is a volumetrical part of the netting structure (of polymer)

into the swollen system; and the parameter χ indicating the interaction of
polymer and the solvent is equal to

β + (δ1 - δ 2 ) 2 V1
χ= (3.2)
RT
where δ1 and δ2 are the Hildebrand’s parameters of the solubility for the
solvent and for the polymer, and they are equal to [(ΔHvap–RT)/Vmol]1/2, re-
spectively; the empirical term β is the correction factor taking into account
the number of the branching points into the structure of polymer.
After the insignificant transformations, it can be obtained the Flory–
Renner’s equation. Such equation helps to calculate the sizes of the poly-
mer link between the cross bonds Mc:

ρ 2V1Ø21/3 , (3.3)
Mc =
[− ln(1 − Ø2 ) − χ Ø2 2 -Ø2 ]
where ρ2 is the density of a polymer into solution; V1 is molar volume of
the solvent.
Coefficient χ is determined empirically for each solvent and, of course,
from the concentration dependence of the osmotic pressure taking into ac-
count a series of the assumptions.
In the work of Sanada [5] and subsequent works of other authors, the
swelling degree in the volumetric parts Q is represented as a function on
the δ of solvents. These data in the most cases form the parabolic, a so-
called bell-like curve with a maximum for the solvent, δ2 of which in ac-
cordance with the theory of the regular solutions is equal or is near to δ1
of a polymer (coal). In reality, in Ref. [5], it was already maintained that
only the approximated dependencies are obtained for coal since a number
of experimental data concerning to Q are visibly take one’s leaved from
the generalizing curve. Under the extraction of vitrain from the Yubary
field (the content of carbon consists of 85.2 percent) using the solvents
into Soxhlet’s apparatus it was determined in Ref. [4], that the maximal
yields of the extract are observed at their molar volume about 10 cm3/mole
(ethylendiamine, dimethylformamide, cyclohexanone 24–26 percent, ace-
tophenone 35.6 percent, pyridine 33.2 percent); this fact authors explain
by the influence of the value of cohesion energy.
128 Applied Methodologies in Polymer Research and Technology

However, there are a plenty of exclusions, for example, for butanol Vmol
= 9.5, but the yield of an extract in this case is only 0.8 per cent. The expla-
nation of this deviation as a result of the solvent association, which caused
by the presence of the hydrogen bond, seems unconvincing, since under
the experiments conditions (the extraction proceeds into Soxhlet’s appara-
tus, and, therefore under the boiling temperature) such association will be
insignificant. It was discovered in Ref. [6] that the value Mc for Japanese
coal with the carbon content less than 80 per cent is unreal low—only 10
(!), next this value, is sharply increased and achieves the maximum Mc =
175.
Authors starting from the following positions at the explanation of
this fact: firs, experimental determinations were carried out in pyridine, in
which the specific interactions can take place and, second, this deviation
can be caused by the mistakes at the determination of χ coefficient. It is
necessary to notify that although it is hardly to estimate the verisimilitude
of determined in such a way molecular weights of structural links of a
coal between the points of cross bonds, however, in a case of the syn-
thetic polymers in a same way determined masses of links visible do not
agree with the values obtained in accordance with others methods. The
same approach was discussed especially in detail in the work of Kirov
and coauthors [7] on example of swelling (and extraction) of three kinds
of bituminous Australian coal. These authors confirmed the main obser-
vations of Sanada, namely the swelling degree Q increases from ~1.4 in
hydrocarbons to ~2 in pyridine (δ–11.0) and again is decreased to ~ 1.5 in
alcohols. Calculated on this basis value δ of coal is increased steadily at
the increase of the carbon content from 70 percent till 87 percent and in a
case of more metamorphosed coal is sharply decreased again.
Data concerning to the extraction of Greta coal are evidence of the
maximal yield of extract (more than 20%) under its treatment with eth-
ylendiamine and dimethylformamide (δ–11.5); however, authors admit a
fact that this is a consequence of the specific interactions, since in alcohols
from the δ by the same order, the yield of the extract is only 1–2 percent.
But for all that authors concluded that although the swelling degree of coal
is not directly connected with the molecular characteristics of the absorbed
liquids, however the determining factor is their parameter of the solubility
despite the fact that at the detailed consideration of the dependencies Q
= f(δ) (or f(δ2)), there are a number of deviations (as same as in Ref. [5])
from the ideal curve for many solvents are observed.
Generalization of Fuels Swelling Data 129

Despite the indicated lacks, the above described approach is applied in

later works concerning the coal swelling for the results interpretation. It
is necessary to indicate a plenty of investigations devoted to the swelling
studies of coal No 6 from the Illinois State (standard in the US coal for
the carbon–chemical investigations) [8–10]. General conclusions are in
good agreement with the results of Ref. [5, 7]. Comparison of the swelling
degree for different coal in some solvents depending on the content of car-
bon has been done in Ref. [11]. Similar investigation for Kansk–Achynsk
Siberia coal was carried out in Ref. [12, 13]. In both cases, as same as in
Ref. [7], it was proved that the dependence of swelling degree of coal on
the carbon content in it.
It is logical to assume the influence of the specific interactions during
the swelling process because the values of the parameters of coal solubil-
ity δ2, which are determining accordingly to the Flory–Renner’s equation,
are differed. It depends on fact that the data for all solvents are taken into
account in calculations, or such calculations are performed with the exclu-
sion of results for the solvents that can be acceptors of the hydrogen bonds
(amines, ketones). Different results have been obtained also at the appli-
cation of other calculations methods, especially of the Van–Krevelen’s
method [14].
It is notified in Ref. [15] that the swelling of some coal does not agree
with the thesis of the regular solutions theory; that is why, to calculate the
parameter χ for them is impossible. Authors explain this fact by the pres-
ence of oxygen atoms in the investigated coal. But also the molecular mass
of separate sections (clusters) between the points of crossing for methyl-
ated or acetylated samples is equal only to 300–600 in accordance with the
calculations (i.e., unreal).It is necessary to notify that the critical analysis
of the Flory theory application for the determination of molecular mass
and the crossing density of the coal structure has been done in the Painter’s
works [16]. Authors assert that the possible formation of the hydrogen
bonds between the hydroxy groups of the low–metamorphized coal and
the basic solvents plays a significant role here; this is why even the intro-
duction of a lot of the empirical amendments into the calculations leads
to the obtaining of the understated values of molecular masses of clusters.
Taking into account the above-mentioned lacks, many authors con-
cluded that the theory of regular solutions is insufficient for adequate de-
scription of the coals swelling process in different solvents (and also for
their extraction) since such theory does not take into account the possible
130 Applied Methodologies in Polymer Research and Technology

specific solvation of the active structures of coal and first of all its hetero-
atoms [17], especially by the formation of the hydrogen bonds. To take
into account the possible acid–base interactions, it was proposed by Mar-
zec and coauthors [18, 19] to determine the swelling degree as a function
of donor number of DN solvents or as a function of their donor and accep-
tor numbers disparity accordingly to Gutmann. However, corresponding
analysis of data concerning the swelling of the Silessian bituminous coal
showed the following: although between the swelling degree Q and DN,
the visible symbasis exists and the deviations from the straight line are less
than for the function Q = f(δ), however, it is complicated to confirm about
the quantitative description of the process. The same conclusion about
only qualitative character of such dependence has been done by authors
in Ref. [13] on example of swelling the brown Kansk–Achynsk coal and
some kinds of the Donbas coal.
Above-mentioned facts and disagreements lead to the conclusions in
Ref. [20] that the sorption of solvents by coal is very complicated process
covering also the changes under the action of a solvent into the coal struc-
ture and other possible nonequilibrium phenomena. That is why an appli-
cation for coal of the theories developed for the description of thermody-
namically equilibrium process of the simple synthetic polymers swelling
is unwarranted first of all due to neglect by existing chemical (specific)
solvation interactions. As it was confirmed in many investigations, the
swelling Flory–Huggins’s model based on the theory of regular solutions
is not sufficiently consistent with the real experimental data. It is caused
by a range of simplifying assumptions putted into the base of this model
and, first of all, by the presence of full isoentalpic mixing (solution) of
two phases that is in disagreement with the reality—even in a case of the
polymers that do not contain the donor–acceptor groups into the structure
a swelling and solution processes are accompanied with a great enthalpy
effect; it is known, that even nonspecific solvation is often accompanied
by the changes of free energy and enthalpy of the system. Also, isoentalpy
will be not remained in a case of the possible donor–acceptor (acid–base)
interaction, which is often observed in a case of the synthetic polymers
with the content of heteroatoms (polyurethane, nitryle rubbers) and is ob-
served in a case of coal as a result of the presence in it of such groups as
–OH, –COOH, tertiary atom of nitrogen and etc.
The principle of the linearity of free energies (LFEs) is applied in chem-
istry of solutions over 30 years for quantitative description of the solvents
Generalization of Fuels Swelling Data 131

influence on the behavior of dissolved substances (spectral characteristics,

constants of the reaction rate). In accordance with this principle, general
change of free energy of the system consists of the separate interindepen-
dent terms and first of all consists of the nonspecific and specific solvation
effects and also needed energy for the formation of cavity in the structure
of liquid phase with the aim of allocation the exterior molecule introduc-
ing there. And only full sum of these all possible energetic effects gives the
final (equilibrium) energy of the system [21]:

ΔG = ∑ Δgi (3.4)

By taking this into account, the constants of the reaction rates are de-
termined via the equilibrium constants of the activated reactive complex
formation, and the last in part depends on the solvation processes; Koppel
and Palm [22] proposed the following equation to determine the influence
of medium properties on the reaction rates of the processes proceeding in
it:

a1 (n 2 -1) a2 (ε − 1)
lg k = a0 + 2 + + a3 B + a4 ET (3.5)
(n + 2) (2ε + 1)

The above equation takes into account the influence of the polarization
f(n2) and polarity f(ε) of the solvents determining their ability to nonspe-
cific solvation and also their basicities B, and electrophilicity accordingly
to Reichardt, ET characterizing their ability to introduce into acid–base
interactions (specific solvation). Appropriateness of this equation for the
generalization of experimental data of the dependencies of reactions rates
(and also spectral characteristics of dissolved substances) on physical–
chemical characteristics of the solvents has been proved by a number of
hundred examples.
For the processes of the phase equilibria, it was proposed by us to add
to the Koppel−Palm equation the fifth term, which takes into account the
density of the energy of solvents cohesion proportional to the squared Hil-
debrand’s solubility parameter δ2. Due to this fact, necessary energy for
the formation of cavity for the allocation of the molecule introducing into
liquid phase is taking into account:

lg K = a0 + a1 f (n 2 ) + a2 f (ε ) + a3 B + a4 ET + a5δ 2 (3.6)
132 Applied Methodologies in Polymer Research and Technology

Modified equation turned out to be effective for determining the sol-

vents’ influence on the equilibrium of such processes as solubility in dif-
ferent media of gases or solids, the distribution of substances between two
phases, and resembling equilibrium processes. Therefore, it will be logi-
cal to try to use Eq. (3.6) for the swelling processes. As a matter of fact,
it turned out that with the use of the equation, it is possible to determine
the quantitative connection between the properties of the solvents and the
equilibrium swelling degree for a number of polymers, and also for a coal
[23–25].
To achieve the satisfactorily high values of the coefficients of multiple
correlations R, it is necessary to exclude from the calculations the data
for some quantity (3–5) of the solvents. It is hard to explain this. Besides,
the model of the interactions into the system was not quite clear. In a case
when the solvation processes are energetically advantageous (∆G < 0),
the role of δ2 factor remains unclear. Such factor characterizes the energy
needed for the cavity formation into the structure of the liquid; at the same
time, unlike the evaporation process, under the swelling of substances into
liquid, the following process takes place: liquid solvent penetrates into the
structure of solid polymeric phase mostly as the whole.
At the beginning of the ninetieth century, the works of Aminabhavi ap-
peared [26]. These worked concerned the polymeric membranes swelling
into organic solvents and to the diffusion rate D of the liquids into their
structure in which these values were considered as dependencies from the
molar volume Vmol of the liquids. Generalizations obtained in Ref. [26]
are rather unsatisfactory–approximately linear dependencies lgQ or lgD
on Vmol are observed only in the homologic ranges or in the case of similar
solvents. But the approach itself must be considered as logical: it is clear
that the bigger the sizes of the introducing molecule, the more difficult it
will be to penetrate into the structure of polymer including the adsorbent
interstice. Low generalization ability of the dependencies presented in the
work [26] can be explained by fact that they do not take into account the
solvation effects that promote to liquids penetration. That is why Eq. (3.6)
has been expanded by us by the additional term taking into account the
influence of the molar volume Vmol of the solvents [27]:

lg Q = a0 + a1 f (n 2 ) + a2 f (ε ) + a3 B + a4 ET + a5δ 2 + a6VM (3.7)

Generalization of Fuels Swelling Data 133

Such equation under the stipulation that Q is represented not in the

volumetric parts accordingly to the Flory–Huggins’s model but in ac-
cordance with the interpretation of equilibrium processes in the chemical
thermodynamics as a moles of the solvent absorbed by one gram or by one
cm3 of polymer turned out to be effective under the generalization of data
for swelling degree of different synthetic polymers, for example, polyeth-
ylene, in different organic solvents depending on their physical–chemical
parameters [28]. That is s why it was necessary to check the possibility of
Eq. (3.7) application for the generalization of data concerning coal swell-
ing since this equation takes into account the following: (i) All the most
important possible energetic effects caused by possible donor–acceptor
interaction of active groups of the coal with noninert solvents including
the formation of hydrogen bonds; (ii) the effects of nonspecific coal solva-
tion with solvents, which are caused by a presence in it the cyclic aromatic
structures as a result of which the visible influence of the ability of some
solvents for the polarization can be expected; (iii) the endothermic effects
as a result of steric complications of the solvents penetration (VM); and (iv)
destruction of the liquid phase structure (δ2).
The meaningfulness of the parameter VM was confirmed in Ref. [29−30],
where it was shown that the quantity of the solvent’s moles absorbed by
the coal weight unit is decreased symbasis to the VM of the solvent; at
the same time, in Ref. [31] it was shown that under the coals swelling in
homologous series of the solvents by the same basicity (amines, alcohols,
etc.), the value lgQ is linearly decreased till the number of Carbon’s atoms,
that is, to their VM. In addition, the values of the correction parameter χ
from Eq. (3.1) can be connected with the physical−chemical characteris-
tics of the penetrants via Eq. (3.7) (see Ref. [32]).
Data concerning the swelling of the most popular coal (namely, coal Il-
linois № 6) have been considered as the main object of our investigations.
This coal is the standard object for the carbon–chemical investigations
in the United States. These data were already analyzed earlier in Refs.
[23–25] with the aim of their generalization according to Eq. (3.6), but the
results obtained were unsatisfactory. Evidently, this was caused by two
factors: (i) the influence of the molecules sizes of the solvents penetrating
into the coal structure (their molar volume) was not taken into account in
these works; (ii) starting values of the swelling degree Q were given ac-
cordingly to original works [9–11] in ml (sometimes in g) of the solvent
absorbed by 1 ml or 1 g of coal since the Flory–Huggins’s model has
134 Applied Methodologies in Polymer Research and Technology

been used by authors (this model uses the volumes of two liquids that are
mutually mixed). If to consider the coal swelling process (and generally
polymers swelling processes) as thermodynamically equilibrium process
then the free energy change at the penetration.
In this chapter, we have checked the efficiency of the factors mentioned
above, considering studying the swelling process in organic solvents. Il-
linois coals are low–metamorphized, bituminous and contain 20–31 per-
cent of volatile substances, are characterized by ash content 8–12 percent
and sulfur content 4–7.8 percent. Investigated in Ref. [8–10] sample was
characterized by following composition: C 79.8; H 5.11; N 1.8; Sorg 2.0
and O 11.2 percent. The samples were pulverized and extracted from the
soluble components with pyridine [8] and were washed by water, and after
vacuum drying, they were saturated by solvent’s steams until their full
saturation at room temperatures in the closed vessels. Authors give the
ratio of the weights for swelled samples respectively to the starting W;
they were recalculated in the quantities of solvent moles absorbed by 1 g
of coal SM (Table 1).

TABLE 1 Experimental [8] and calculated in accordance with the two-parametric Eq.
(3.8) values of the swelling degree SM of the coal Illinois № 6

Experiments Calculations
№ Solvent
W SM103 lgSM lgSM ΔlgSM Δ%

1 Pyridine 1.87 11.00 –1.959 –1.958 –0.001 0.1

2 Dioxane 1.64 7.264 –2.139 –2.143 0.005 0.2

3 CH2Cl2 1.60 7.064 –2.151 –2.179 0.028 1.3

4 Clorobenzene 1.48 4.264 –2.370 –2.364 –0.006 0.3

5 Isopropanol 1.45 7.489 –2.126 –2.136 0.010 0.5

6 Toluene 1.41 4.450 –2.352 –2.364 0.012 0.5

7 Ethanol 1.40 8.682 –2.061 –2.069 –0.008 0.4

8 Benzene 1.38 4.864 –2.313 –2.283 0.030 1.3

9 Acetonitrile 1.34 8.283 –2.082 –2.056 0.026 1.2

10 Cyclohexene* 1.11 1.307 –2.884 – – –

Note: *Data excluded from the final calculations

Generalization of Fuels Swelling Data 135

Generalization of studied data for 10 solvents in accordance with the

fifth-parameter Eq. (3.6) leads to the expression with unsatisfactory low
value of correlation coefficient R = 0.81 [23]. Exclusion from the consid-
eration of the most uncoordinated data for dioxane gives the possibility
to obtain the fifth-parameter equation with low, but acceptable degree of
connection R = 0.941. At the same time, consideration of the molar vol-
ume factor and the change of weight parts on the molar ones essentially
improve the correlation for all 10 studied solvents R = 0.940, and after the
exclusion the data concerning to cyclohexene for the rest 9 solvents we
obtain the equation with high connection degree R = 0.996 [33].
There are only two decisive parameters here the basicity that assists to
the swelling process and the molar volume, which opposites to this pro-
cess, taking into account the needed energy and the negotiation of the
cohesion forces have only insignificant influence and the exclusion of this
parameter from the calculations practically does not worsen the equation:

lg S M = −1.96 + (0.665 ± 0.074)10-3 B - (4.12 ± 0.58)10-3VM ;

R = 0,984

and

S = 0, 030 (3.8)

Obtained equations have greater predicted ability comparatively to the

fifth-parameter equation obtained in Ref. [23], which does not take into
account the factor of the molar volume.
The influence of the factor of molar volume is confirmed by fact that
between lgSM and VM the neatly marked symbasis is observed, namely
with increasing of VM the value lgSM is decreased. The action of other
decisive factor solvents basicity is opposite, in other words, with the basic-
ity increasing the symbate increasing of lgSM is observed. Evidently, this
is caused by the specific solvation of acid centers, which are in the macro-
molecule of coal and, first of all, of hydroxy groups. Their presence can be
136 Applied Methodologies in Polymer Research and Technology

assumed taking into account a great number of the oxygen in the Illinois
coal. Comparison of these two oppositely directed dependencies leads to
the conclusion, that they are mutually compensated. Although these de-
pendencies are only symbate, but the algebraic sum of the influence of
these two factors is practically linearly connected with the respective val-
ues lgSM [34]. The third factor is the density of the cohesion energy, which
is proportional to needed energy for separation of absorbed molecules
from the structure of liquid phase; this factor respectively also decreases
the swelling value. However, the influence of this value is insignificant;
this fact is confirmed by negligible decreasing of the R value at its exclu-
sion only from 0.991 to 0.984. The possible processes of nonspecific and
electrophilic solvation practically do not impact on the value SM.
In Ref. [10], authors also have been studied the swelling process of the
coal Illinois № 6 in the liquid phase. Swelling degree SV has been studied
volumetrically as the ratio of volumes of swelling sample to the starting
one. Unlike Ref. [9], the process was investigated in a range of amines
including the primary ones, which were able to form hydrogen bonds and
also alcohols. At the generalization of these data in accordance with the
fifth-parameter equation without taking into account of VM for the all 17
solvents, the equation was obtained with the low value R = 0.861; in order
to obtain the satisfactory correlation, it is necessary to exclude from the
consideration the data for the methyl and dimethylanilines [25].

TABLE 2 Experimental [10] and calculated in accordance with the Eq. (3.10) values of
swelling degree for the coal Illinois № 6

№ Solvent Experiments Calculations

SV SM103 lgSM lgSM ΔlgSM

1 2-Picoline 2.76 17.84 –1.749 –1.794 0.045

2 Pyridine 2.75 21.72 –1.663 –1.808 0.145

3 Butylamine 2.64 16.57 –1.781 –1.941 0.160

4 Propylamine 2.45 17.62 –1.754 –1.655 –0.099

5 Aniline 1.99 10.86 –1.964 –2.205 0.241

6 2-Hexanon 1.98 8.120 –2.090 –2.312 0.221

7 Methylaniline 1.44 4.052 –2.392 –2.037 –0.355

Generalization of Fuels Swelling Data 137

TABLE 2 (Continued)

№ Solvent Experiments Calculations

SV SM103 lgSM lgSM ΔlgSM

8 Propanol 1.36 4.820 –2.317 –2.240 –0.077

9 Ethanol 1.34 5.824 –2.235 –2.194 –0.041

10 Butanol 1.34 3.715 –2.430 –2.242 –0.188

11 Methanol 1.23 5.690 –2.245 –2.204 –0.041

12 Dimethylaniline* 1.10 0.789 –3.103 –– ––

13 Isopropanole* 1.06 0.784 –3.106 –– ––

14 Toluene 1.06 0.562 –3.250 –3.311 0.061

15 p-Xylene 1.06 0.487 –3.312 –3.326 0.013

16 m-Xylene 1.05 0.407 –3.390 –3.293 –0.097

17 Benzene 1.04 0.447 –3.350 –3.362 0.012

Note: *Data excluded from the calculations

In Table 3.2, the starting values of SV from Ref. [10] are presented and
calculated on the basis quantities of solvent’s moles absorbed by 1 g of
coal−SM and lgSM. In this case for 17 solvents, it was obtained by means of
the six-parametric Eq. (3.7) a relatively low value of R (only 0.884) too,
but after the exclusion of data for isopropanol and dimethylaniline, we will
obtain Eq. (3.9) with a high correlation degree:

lg S M = -2.91 + (0.454 ± 1.40) f (n 2 ) + (5.73 ± 1.22) f (ε ) + (1.43 ± 0.37)10-3

B - (29.9 ± 22.0)10-3 ET - (0.722 ± 0.947)δ 2 - (6.52 ± 4.54)10-3VM

N = 15 R = 0.981 S = 0.160 (3.9)

and after the exclusion of insignificant factors

lg S M = −4,34 + (3.42 ± 0.69) f (ε ) + (2.02 ± 0.27)10−3 B − (0.86 ± 2.55)10 −3Vmol

138 Applied Methodologies in Polymer Research and Technology

R = 0.968 and S = 0.172 (3.10)

In this case, the basicity and the molar volume of the solvents are
decisive factors too, the influence of which is oppositely directed. An ap-
pearance of the polarity as significant factor is connected with the specific
selection of high polar solvents (alcohols, amines).
Accordingly to Ref. [9], the swelling process of the Illinois coal № 6
has been carried out principally under other conditions, namely the sam-
ples were previously extracted with pyridine, dried coal was stranded till
the full saturation with vapors at 100°C in closed metallic ampoules (with
the exception of phenol, investigating temperature of which is 182°C). Au-
thors presented the results of investigations as the ratio of swelling W (in
percentages); that is, the ratio of weights of swelling sample after 1 h to the
dried sample. These data have been previously generalized in Ref. [24].
Low value R for the all 12 solvents equal to 0.876 after the exclusion from
the consideration data concerning to the phenol and tetrahydrophurane is
increased till 0.972. Essentially, better results were obtained by taken into
account the molar volume factor and after recalculation of W in SM.
The data concerning to W taken from Ref. [9] and calculated on their
basis swelling values in moles SM and lgSM are presented in Table 3.3; the
generalization of these data in accordance with the sixth-parameter Eq.
(3.7) leads to higher degree of relationship R = 0.909, and the exclusion
from the consideration of one solvent (butylamine) gives the possibility to
obtain the equation with satisfactory degree of relationship R = 0.974; an
additional exclusion of the dimethylformamide gives Eq. (3.11) with R =
0.991:

lg Q = −2, 61 + (3,50 ± 0,82) f (n 2 ) + (2.30 ± 0.46) f (ε ) − (0.33 ± 0.14)10 −3

B − (2.37 ± 6.8)10 −3 ET + (0.70 ± 0.24)10 −3 δ 2 − (1.5 ± 2.1)10 −3VM

N = 10, R = 0.991 and S = 0.055 (3.11)

and after the exclusion of insignificant factors

lg Q = −2,51 + (2, 66 ± 1, 20) f (n 2 ) + (1.80 ± 0.60) f (ε ) − (7.4 ± 5.0)10−3 ET − (2.8 ± 2.9)10−3VM

R = 0.964 and S = 0.086 (3.12)

Generalization of Fuels Swelling Data 139

TABLE 3 Experimental [9] and calculated in accordance with the Eq. (3.12) values of
swelling ratio of soluble part of coal for the coal Illinois № 6

№ Solvent Experiments Calculations

W SM103 lgSM lgSM ΔlgSM

1 Dimethylformamide 6.2 60.54 –1.218 –– ––

2 N-Methylpyrrolidone 5.7 37.17 –1.430 –1.503 0.073

3 Dimethylsulphoxide 5.5 49.19 –1.308 –1.407 0.099

4 Ethylendiamine 4.6 33.24 –1.478 –1.466 –0.012

5 Aniline 4.6 34.13 –1.467 –1.513 0.047

6 Butylamine *
3.8 29.82 –1.525 –– ––

7 Pyridine 3.7 28.67 –1.543 –1.475 –0.068

8 Phenol 3.4 22.49 –1.648 –1.512 –0.136

9 Pipyridine 3.0 19.26 –1.543 –1.475 –0.068

10 Tetrahydrofuran 2.8 22.97 –1.639 –1.615 –0.024

11 Toluene 2.6 16.65 –1.779 –1.874 0.095

12 Hexane 1.6 6.902 –2.161 –2.134 –0.027

Note: *Data excluded from the calculations

With the increase in molar volume of the solvents, the coal swelling
degree gets decreased; the same is an effect of the ability to electrophilic
solvation. Unlike both previous cases, the positive influence of the sol-
vents basicity (namely their ability to form the donor–acceptor bonds with
acid groups of the coal) here is insignificant evidently as a consequence
of especial influence of the conditions of experiment carrying out. Under
higher temperatures, the hydrogen bonds get easily decomposed. At the
same time, the possible positive influence of the factors of nonspecific sol-
vation f(n2) and f(ε) is observed. Calculated values lgSM and their discrep-
ancy with the experiment ΔlgSM are presented for comparison in Table 3.3.
Both the equilibrium swelling degree and the kinetics of this process
depend on the character of the solvent. In Ref. [10], it has been studied
that the swelling rate of the coal Illinois № 6 volumetrically in different
solvents; on the starting stages, it is ordered to the pseudo first-order reac-
140 Applied Methodologies in Polymer Research and Technology

tions kinetics as is observed in the case of polymers swelling too. It helps

in determining the respective constants rate of the process k, which are
presented in Table 3.4. In Ref. [25], we have generalized these data for 24
solvents with the use of the fifth-parameter Eq. (3.6). For the all maximal
sequence of the data, the value of correlation multiple coefficient R was
very low and equal to 0.694; and only after the exclusion from the calcula-
tion, the data for five solvents (that is practically 20 percent) the satisfacto-
ry value of R = 0.957 can be obtained. In addition, taking into account the
influence of molar volume, that is transition to sixth-parameter equation,
gives the possibility to obtain the expression with R = 0.883. And in order
to obtain the satisfactory correlation, it was enough to exclude from the
calculations data for only two solvents, namely 2–hexanone (methylbutyl
ketone) and triethylamine:

lg k = 2.20 − (2.55 ± 3.84) f (n 2 ) + (1.08 ± 4.26) f (ε ) + (4.17 ± 1.12)10−3 B − (71.7 ± 62.5)10−3 ET −

−(0.92 ± 2.45)δ 2 − (42.8 ± 9.1)10−3VM

N = 22, R = 0.959 and S = 0.448 (3.13)

The equation terms characterizing the influence of non–specific solva-

tion and also cohesion energy have a great standard deviations which are
more than the absolute values of the coefficients and that is why are evi-
dently insignificant. Checking the value R decreasing at the exclusion of
these terms confirmed this assumption and helped to obtain the equation
with lesser quantity of significant terms. This equation also adequately
characterizes the influence of the solvents properties on the rate of their
penetration into the coal structure; besides, the decisive factor in this case
as same as in a case of swelling value is the influence of molar volume of
the solvents, increasing of which leads to the process rate decreasing.

lg k = 1.12 + (4.85 ± 0.52)10−3 B − (66.0 ± 19.5)10−3 ET − (42.1 ± 6.2)10−3VM

R = 0.957 and S = 0.418 (3.14)

Significant factor as same as in a case of the swelling degree is the

solvents basicity. With the solvents basicity increasing, the process rate
is also increased. The less essential is a role the solvents ability to elec-
trophilic solvation; although this factor increases the process rate but it
Generalization of Fuels Swelling Data 141

exclusion from the consideration decreases R till 0.928. The values lgk
calculated in accordance with the Eq. (3.14) are represented in Table 3.4.

TABLE 3.4 Experimental [10] and calculated accordingly to Eq. (3.14) values of the
logarithms of the constants rate of the coals Illinois № 6 swelling

Experiments Calculations
№ Solvent
k10 , s
5 –1
lgk lgk Δlgk
1 Propylamine 1167.0 –1.933 –1.679 –0.254
2 Butylamine 614.0 –2.212 –2.974 0.763
3 Pyridine 316.7 –2.499 –2.655 0.155
4 2-Picoline 126.7 –2.897 –3.124 0.226
5 2-Hexanone *
125.0 –2.903 –– ––
6 Methanol 53.30 –3.273 –3.183 –0.091
7 Ethanol 21.30 –3.672 –3.624 –0.048
8 Aniline 20.0 –3.699 –3.962 0.263
9 Propanol 10.90 –3.963 –4.290 0.328
10 Butanol 3.84 –4.416 –4.926 0.511
11 Isopropanol 2.54 –4.595 –4.152 –0.443
12 Methylaniline 2.47 –4.607 –4.063 –0.545
13 Butanole-2 1.32 –4.879 –4.694 –0.185
14 Toluene 0.90 –5.046 –5.334 0.288
15 Isobutanol 0.833 –5.079 –4.859 –0.220
16 Dimethylaniline 0.59 –5.229 –4.578 –0.651
17 Benzene 0.45 –5.347 –4.675 –0.671
18 Pentanol 0.376 –5.425 –5.510 0.085
19 p-Xylene 0.375 –5.426 –5.924 0.498
20 m-Xylene 0.225 –5.648 –5.919 0.271
21 o-Xylene 0.118 –5.928 –5.891 –0.037
22 Ethyl benzene 0.113 –5.947 –6.032 0.086
23 Cumene 0.009 –7.046 –6.716 –0.330
24 Triethylamine *
0.00038 –8.420 –– ––
Note: *Data excluded from the calculations
142 Applied Methodologies in Polymer Research and Technology

Decisive role of the VM factor during the adsorption process of the sol-
vents by coal is in agreement with the determined in Ref. [25] propor-
tionality for the alcohols between lgk and steric factor Es of the Hammet–
Taft’s equation.
Therefore, the swelling characteristics of the Illinois coal are deter-
mined by total influence of molar volume of liquids and their ability to
specific solvation. The same conclusion has been done by authors Refs.
[35−36] explaining the adsorption growing by increasing the donor num-
ber of the solvents via the formation of hydrogen bond by OH–groups
of coal. But these authors have not done respective quantitative gener-
alization giving the possibility on the basis of the linearity of free ener-
gies principle adequately to connect the properties of the liquids with their
ability to interact with a coal; it was confirmed that the approaches based
on the theory of regular solutions equitable only at the consideration of
the swelling process in the inert (so-called low basic) solvents, mainly of
low–polar.
Correctness of the sixth-parameter Eq. (3.7) and its simplified forms
for the generalization of the swelling data was proved for other coals in-
cluding the Donbas coal [37] at the parameters B and VM, for lignites from
the Rawhile and Big Brown mines (USA) and also for the Silesian coal
(Poland). In Ref. [18] presented data concerning to the bituminous Silesian
coal swelling in 21 solvents. It can be assumed, that such coal is situated
between the cannel coals and gas coal (such assumption has been done on
the basis of the Silesian coal characteristics, namely (percent per daf): C
= 80.7; H = 5.6; N = 1.9 and S = 0.9; a content of the volatile substances
consists of 39.5 percent). The swelling degree Q has been determined vol-
umetrically at 25°C starting from the increase of the volume of coal under
the solvent excess till the equilibrium achievement (2−7 weeks). Appro-
priating values of Q are represented in Table 3.5.

TABLE 5 Experimental [8] and calculated values of the bituminous Silesian coal swelling
degree

Experiments Calculations
№ Solvent
Q SM10 3
lgSM lgSM ΔlgSM Δ%

1 Benzene* 1.00 0.00 – – – –

2 Nitrobenzene 1.10 0.98 –3.009 –3.003 0.006 0.2

Generalization of Fuels Swelling Data 143

TABLE 5 (Continued)

Experiments Calculations
№ Solvent
Q SM10 3
lgSM lgSM ΔlgSM Δ%

3 Diethyl ether* 1.15 1.44 –2.842 – – –

4 Isopropanol *
1.14 1.83 –2.738 – – –

5 1,4-Dioxane 1.16 1.88 –2.726 –2.704 –0.022 0.8

6 Ethyl acetate 1.26 2.66 –2.575 –2.481 –0.094 3.6

7 Acetonitrile 1.15 2.86 –2.544 –2.499 –0.045 1.8

8 n-Propanol 1.23 3.08 –2.511 –2.316 –0.196 7.8

9 Nitromethane* 1.18 3.36 –2.474 – – –

Methyl ac- 5.4

10 1.32 3.99 –2.399 –2.528 0.128
etate

11 Acetone 1.30 4.08 –2.389 –2.366 –0.023 1.0

12 Ethanol 1.25 4.28 –2.369 –2.316 –0.052 2.2

13 Methanol 1.19 4.70 –2.328 –2.402 0.075 3.2

Methyl ethyl 0.2

14 1.49 5.47 –2.262 –2.256 –0.006
ketone

Dimethoxy- 3.9
15 1.60 5.75 –2.240 –2.327 0.087
ethane

Tetrahydrofu- 0.0
16 1.59 7.28 –2.138 –2.138 0.000
ran

Dimethyl for- 3.3

17 1.69 8.92 –2.050 –2.118 0.069
mamide

18 Pyridine 2.08 13.40 –1.873 –1.711 –0.162 8.6

N-Methylpir- 3.6
19 2.38 14.28 –1.845 –1.912 0.067
rolidone

Dimethyl 9.8
20 2.04 14.66 –1.834 –2.014 0.180
sulfoxide

Ethylenedi- –
21 2.08 16.17 –1.791 – –
amine*

Note: *Data Excluded from the Final Calculations

144 Applied Methodologies in Polymer Research and Technology

Authors in Ref. [8] consider that inherently of the presented coal swell-
ing process is the donor−acceptor interaction of the coals’ acidic groups
with the basic ones of the solvents. However, really they determined only
the symbasis between the swelling degree Q and donor number of the
solvent DN; at that, incomprehensible sharp bend is observed at DN =
12−13 on this dependence. In a case of hydrocarbons, ethers, alcohols it is
observed only the slow increasing of Q at the DN increase, while for the
carbonyl compounds of amines and dimethyl sulfide (DMSO) the inclina-
tion of line is essentially steeper [8]. The same peculiarity is observed also
for the SM. At the same time, the dependence between Q and δ was not
determined.
In Ref. [24], we had a go to generalize the results presented in Ref. [8]
via the fifth-parametric Eq. (3.6) without taking into account a factor of
the molar volume. The obtained value R for 21 solvents was unsatisfactory
(0.887); and in order to achieve the acceptable value of R = 0.958, it was
necessary to exclude from the consideration the data for three solvents.
In accordance with the approach developed in Ref. [29], we had a go to
generalize the data from Ref. [8] by means of Eq. (3.1), that is, taking into
account of influence of the molar volume of the solvents VM; the logarithm
of the moles of solvent absorbed by 1 sm3 of coal lgSM determined based
on the W (see Table 3.5) was used as the correlated value. However, in a
case for 20 solvents (data for benzene are excluded from the consideration
since for this solvent W and, respectively, SM are equal to zero) the cor-
relation is also unsatisfactory: R = 0.818; sequential exclusion of data for
diethyl ether (№ 3), isopropanol (№ 4), nitromethane (№ 9) and ethylene-
diamine (№ 21) increases the value R till 0.877; 0.911; 0.934 and 0.969.
Thus, for the 16 solvents, the sixth-parametric Eq. (3.15) was obtained,
which with the acceptable accuracy connects the swelling degree with the
physical−chemical characteristics of the solvents:
lg S M = −2.72 − (6.07 ± 1.45) f (n) + (2.26 ± 0.55) f (ε ) + (3.53 ± 0.33)10 −3 B − (0,130 ± 0, 063) ET + n
+ (1.17 ± 0.55)10 −3 δ 2 − 9.92 ± 3.36)10 −3VM

N = 16, R = 0.969 and S = 0.104 (3.15)

By−turn exclusion of the separate terms of an equation denotes on the

lesser significance of the terms with ET (the R of the corresponding fifth-
parametric equation is equal to 0.954) and with the δ2 (R is equal to 0.951).
Generalization of Fuels Swelling Data 145

Thereby, the swelling process of the presented coal can be adequately de-
scribed with the use of the fourth−parametric equation:

lg S M = −3, 47 − (4,11 ± 1, 27) f (n) + (1.82 ± 0.51) f (ε ) + (3.50 ± 0.36)10−3 B − (6.66 ± 2.45)10−3VM
(3.16)

N = 16, R = 0.951 and S = 0.117

At the same time, the equations which do not take into account the fac-
tors of the non−specific solvation give the essentially poor results:

lg S M = n3.02 + 3.0 ⋅10 −3 B − 3.85 ⋅10 −3VM ; R = 0.872; S = 0.171.

And the three−parametric equations with taken into account of f(n) or
f(ε) give the value or R ~ 0,9.
In Table 3.5, the values of lgSM are presented, which were determined
in accordance with the above presented equation. As can be seen, the de-
viations more than ± 0.117 are observed only for the propanol, pyridine
and DMSO. Essentially, more deviations were observed also for the ex-
cluded from the calculations solvents. In a case of the isopropanol such
disagreement of the calculations and experiment was caused probably by
the steric difficulties, and in a case of the ethylene diamine–by the extreme
high basicity. It’s interesting, that in a case of the benzene, in which the
swelling practically does not proceed (SM is equal to zero), the calculation
accordingly to the Eq. (3.16) gives the values lgSM = −3,49, i. e., it is dif-
fered only insignificantly from zero by the value SM.
It is necessary to stop on a role of the separate terms into Eq. (3.16).
Between lgSM and VM the symbate decrease of the swelling degree with
the liquid molar volume increasing is observed (as same as in the previous
cases). In accordance with the earlier developed principles, it very im-
portant is also the contribution of the acid−base interaction–the swelling
degree is distinctly increased at the value of B of solvents (see Figure 3.1),
though the correlation between these values is only medium (R = 0.752
for the all points).
146 Applied Methodologies in Polymer Research and Technology

FIGURE 3.1 The correlation between the quantity of the absorbed solvent lgSM by the
bituminous silesian coal and the basicity B; ´ − data excluded from the calculation.

After the exclusion of the most deviating solvents, the value R becomes
equal to 0.870. Significantly is also the influence of the nonspecific solva-
tion. After the exclusion of one among terms f(n) or f(ε) the R is decreased
till 0.9, and in a case of the exclusion of both together terms this value is
decreased till 0.872. But if to apply Eq. (3.7) to the coal extraction data,
then the factor of molar volume VM is insignificant, and the connection
between quantities of extracted substance (in g/mole of the solvent) and
physical–chemical characteristics can be satisfactorily described by fifth
parameter Eq. (3.6) or by its simplified forms; in this case possible acid–
base interaction is the decisive factor, that is factor B [38–40]
This confirmation is in good agreement with the above–said: bigger
molecules harder introduce into the coal structure and after equilibrium
state their size does not play the role. Let us notify, that the same approach
has the positive results at the data generalization concerning to the solubil-
ity of the synthetic low–molecular coal analogous diphenylolpropane in
20 solvents [41]. This approach is also applicable for the generalization of
data concerning to the coal extraction under sub–critical conditions, but
Generalization of Fuels Swelling Data 147

the role of the specific solvation is also insignificant, evidently as a result

of its suppression at high temperatures.
Therefore, it was discovered the lack of fit the description of the coal
swelling process with the use of one–parametric dependencies including
those dependencies based on the theory of regular solutions on the solu-
bility parameter of liquids. It was shown, that the quantitative connection
between the swelling degree of coal and physical–mechanical properties
of the solvents is achieved only on the basis of principle of the linearity of
free energy under condition of taking into account the all-solvation pro-
cess. The basicity of the solvents and their molar volume are the factors
determining the swelling degree for low-metamorphized coal.

KEYWORDS

• Coal swelling
• Fuels swelling
• Linear free energy principle

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This page intentionally left blank
CHAPTER 4

TRENDS ON NEW
BIODEGRADABLE BLENDS ON
THE BASIS OF COPOLYMERS
3-HYDROXYBUTYRATE WITH
HYDROXYVALERATE AND
SEGMENTED POLYETHERURETHANE
SVETLANA G. KARPOVA, SERGEI M. LOMAKIN,
ANATOLII A. POPOV, and ALEKSEI A. IORDANSKII

CONTENTS

4.1 Introduction .................................................................................. 152

4.2 X-Ray and DSC Studies............................................................... 153
4.3 Dynamics of ESR Probe Mobility and H–D Exchange
Kinetics in D2O ........................................................................... 155
4.4 Conclusions .................................................................................. 157
Keywords .............................................................................................. 157
References ............................................................................................. 158
152 Applied Methodologies in Polymer Research and Technology

4.1 INTRODUCTION

The new biodegradable blends based on the combination of synthetic and

natural polymers are alternative option for the use of individual poly-
mers. As a result of composite production, the emergence of essentially
new exploitation characteristics is expected, which are not inherent to the
original polymer components. Biodegradable systems are widely used in
innovative technologies for the drug delivery, in tissue engineering, and
prosthetic vascular stenting, in a contemporary design of environmentally
friendly barrier materials in packaging [1–3]. When creating such sys-
tems, segmented polyetherurethanes (conventional SPEU on the basis of
multifunctional isocyanates) may be of particular interest. Because of the
unique combination between mechanical properties and biocompatibility,
they are widely and successfully applied in various fields of biomedicine
as constructional and functional materials [4, 5]. However, the low rate
of SPEU biodegradation, which is a positive factor in the case of a long-
term functioning, limits considerably their use during short-term exploita-
tion. Regulation of SPEU lifetime can be achieved by blending it with a
variety of biodegradable biopolymers, such as poly(α-hydroxyacid)s or
poly(β-hydroxyalkanoate)s and the common representatives of the latter
as poly(3-hydroxybutyrate) (PHB) and its copolymer with 3-hydroxyval-
erate (PHBV) (Refs [6, 7]).
PHB, along with valuable properties, has certain disadvantages, in par-
ticular, high cost and fragility. For overcoming such disadvantages, either
copolymers PHAs or their blends with other natural polymers, in particu-
lar, with chitosan [8] are often used.
PHB–SPEU and PHBV–SPEU polymer systems can be applied as the
basis of promising new composites, in particular, for use in cardiosurgery,
as well as for a scaffold design. By varying the blend content, and, conse-
quently, affecting the morphology of the systems, we can obtain composi-
tion with different physical and chemical characteristics such as perme-
ability, solubility in water and drugs, controlled release, and reduced rate
of degradation. The comprehensive description of PHBV–SPEU system
requires the assessment of a combination of structural and dynamic fea-
tures that allow a more complete evaluation of its structural evolution at
relatively short-term times that precede its hydrolytic decomposition as a
result of exposure to water at elevated temperatures.
Trends on New Biodegradable Blends 153

Blends comprising the copolymer of 3-hydroxybutyrate (~ 95mol per-

cent) and 3-hydroxyvalerat (~5 mol percent) PHBV (Tianan Co, Ningbo,
China), Mw = 2.4 × 105, Mn = 1.5 × 105, ρ=1.25 g/cm3) and SPEU on
the basis of MDI medical grade (Elastogran, Basf Co., Germany), Mw =
2.29×105, Mn = 5.3 × 104, ρ = 0.97 g/cm3 were studied. Mixing weight
ratio of PHBV/SPEU ranged in the following sequence: 100:0, 60:40,
50:50, 40:60, and 0:100 percent, respectively. The films were obtained
in a solvent mixture of tetrahydrofuran and dioxane. In addition, by the
DSC method, the thermophysical characteristics (melting points and endo-
thermal fusion) were studied. DSC measurements were performed with a
microcalorimeter DSC 204 F1 Netzsch Co in an inert atmosphere of argon
at a heating rate of 10°/min. Analysis of the mixtures was carried out by
dynamic (ESR probe analysis and isotope deuterium D–H exchange) and
structural (WAXS and DSC) methods. Segmental mobility was studied by
paramagnetic probe by determining the correlation time τ, characterizing
the rotational mobility of the nitroxyl probe TEMPO in accordance with
known method [9, 10].
X-ray analysis of the films was carried out using transmission tech-
nique with a diffractometer Bruker Advance D8 (Cu Kα). IR spectra of
deuterated films were recorded on a spectrophotometer Bruker IFS 48
with a Fourier transform at a resolution of 2 cm–1.

4.2 X-RAY AND DSC STUDIES

In this study, it was shown by X-ray technique (WAXS) that the original samples
of PHBV are characterized by high crystallinity. In their diffraction patterns, at
least five reflections of the orthorhombic lattice with characteristics a = 5.74 Å, b
= 13.24 Å and c = 5.98 Å were determined that well conform to the earlier studies
[11, 12]. In Figure 4.1 the WAXS diffractograms are presented as a set of curves
belonging to initial PHBV (1), PHBV treated by water at 40°C (2), PHBV/SPEU
blend with component ratio 40/60 (3), the same blend treated by water at 70°C
(4), and the PHBV/SPEU (60/40) blend also treated by water at 70°C (5). The
presence of SPEU in the system leads to an amorphous hallo in the range 22° (see
curves 1 and 3), its intensity is increased with the SPEU content.
154 Applied Methodologies in Polymer Research and Technology

FIGURE 4.1 WAXS diffractograms for initial PHB (1), PHB after water treatment at 318
K (2), initial blend PHB–SPEU 40:60 (3), blend PHB–SPEU 40:60 after water treatment at
343 K (4), and PHB–SPEU blend 60:40 after water treatment at 343 K.

The impact of the water medium causes noticeable changes in the crys-
tal structure, namely an increase in the crystallinity degree, the crystallite
size growth ,and improving their crystalline structure that manifested as a
decrease in the basic interplanar spacings d020 and d110 (Table 4.1). The
ratio of the integrated intensity of the crystalline reflections to the total
intensity is 66 percent for the initial samples and 84 percent for samples
treated with water. Crystallite sizes, the corresponding lattice parameters,
and crystallinity of PHBV are presented in Table 4.1 to summarize the
results of X-ray analysis. The above influence of water is similar for hy-
drophobic PELD with different molecular weights that are subjected to
ionizing radiation [13].

TABLE 4.1 Crystalline and thermophysical characterization of PHBV and its Blend
PHB content (%) Crystallinity (%) Interplanar Sizes of Crystallites
WAXS-DSC Spacings (A)

100 (initial) 66–58 6,640 215/160

100 (water exposition) 84–59 6,606 255/190
60 (water exposition) 68–58 6,649 183/157
40 (initial) 55–58 6,600 174/149
40 (water exposition) 53–50 6,600 173/145
Trends on New Biodegradable Blends 155

The exposure of the samples in aquatic environment affects the origi-

nal PHBV and its composition with SPEU in different ways. The parent
biocopolymer shows stability and even improving of the crystalline phase.
According to the DSC data, its crystallinity degree is kept constant after
the contact with water and approximately is equal to 60 percent. After the
water treatment for 4 h and elevated heating (70°C) simultaneously, melt-
ing temperature (Tm) shifts to higher temperatures from 175 to 177°C for
the native sample and from 172 to 174°C for the sample subjected to the
first melting–cooling cycle. These T-scale shifts as well as the analysis
by WAXS indicated more perfect organization of PHBV crystals that oc-
curred due to water impact.
For polymer compositions PHBV/SPEU exposed to water at 70°C, the
DSC curves of melting show a moderate decrease in crystallinity from 59
to 50 percent. The crystallinity reduction is accompanied by a decrease
of Tm from 174°C for the initial sample to 170°C for the PHBV/SPEU
blend with 60/40 percent ratio and then to 168°C for the blend with 40/60
percent content. Therefore, the SPEU molecules prevent the crystalliza-
tion completion of PHBV and, hence, reduce both the quality of structural
organization and the crystallinity degree.

4.3 DYNAMICS OF ESR PROBE MOBILITY AND H–D

EXCHANGE KINETICS IN D2O

Recently, we have studied the behavior of spin probes (TEMPO and TEM-
POL) in high сrystalline PHB at room and elevated temperatures [14].
Water temperature effects on molecular mobility of the ESR probe (TEM-
PO) in PHBV were studied at two different temperatures: 40°C, close to
physiological temperature and 70°C adopted in a number of studies as the
standard temperature for accelerated testing of hydrolytic stability of bio-
polymers [15, 16]. Figure 4.2 shows that the heating of polymer composi-
tions in water for 4 h at ~40°C does not significantly reduce the molecular
mobility of the probe in the mixture, as well as does not change the PHBV
crystallinity that we have shown above by DSC technique. For samples of
PHBV and its blends, the impact of the aquatic environment under more
rigorous conditions—that is, at 70°C—is accompanied by the probe mo-
bility increase in comparison with the mobility in the initial polymer sys-
tems. These results obtained from ESR spectra reveal plasticizing effect
156 Applied Methodologies in Polymer Research and Technology

of water molecules, so that segmental mobility of macromolecules in the

intercrystalline space is increased, and hence the relaxation processes pro-
ceed faster, which leads to an increase in the rotation velocity of the probe
TEMPO.
The supplemental feature of SPEU behavior in the blends is an FTIR
band intensity decrease for the–NH–fragments of urethane groups which
can be represented as a series of kinetic curves. The curves reflect the H–D
exchange rate in the PHB/SPEU blends immersed into heavy water. Only
those–NH–groups can exchange proton for deuterium that are accessible
to the attack by molecules of D2O (see Ref. [17]).
These fragments belong to the amorphous regions and are not included in the
domain structures of SPEU. For the blend films, the dependence of exchange rate
on the PHBV/SPEU composition has an extreme character (Figure 4.3), and the
position of the minimum is in the same concentration range as the minimum value
of exchange degree (not shown).

FIGURE 4.2 ESP correlation frequency of TEMPO in the parent polymers (PHB, SPEU)
and their blends (1, initial polymer systems; 2, water treatment at 40°C; and 3, water
treatment at 70°C).

It was at this ratio of PHBV/SPEU (40:60) that the most ordered struc-
ture in the blend was formed and stabilized by intermolecular hydrogen
bonds. Figure 4.3 also shows that in this concentration range, there is a
maximum oscillation frequency shift ascribed to–NH–fragments in rela-
tion to the frequency of–NH–groups in the native SPEU. Such a change in
Trends on New Biodegradable Blends 157

the dynamics of fluctuations is probably due to the formation of the previ-

ously mentioned hydrogen bonds in the system.

FIGURE 4.3 Dependences of effective constant for isotopic exchange (left y-axis) and
the shift of wavenumber for –NH–fragment in urethane groups (right y-axis) on PHBV
concentration in PHBVSPEU blends.

4.4 CONCLUSIONS

The complex dynamic and structural properties reveal the influence of

SPEU on the molecular dynamics and structure of PHBV, by forming in-
termolecular hydrogen bonds and setting up of energy and steric barriers
to PHBV crystallization. In terms of design of new biomedical compos-
ites, results presented have a scientific and practical interest to describe
their behavior at water temperature exposure.

KEYWORDS

• Biodegradable composition
• Crystallinity
• DSC
• EPR
• X-ray analysis
158 Applied Methodologies in Polymer Research and Technology

REFERENCES

1. Tian, H.; Tang, Z. et al.; Progress in Polymer Science. 2012, 37, 237. doi:10.1016/j.
progpolymsci.2011.06.004.
2. Suyatma, N. E.; Copinet, A. et al.; J Polym Environ. 2004, 12(1), 1. doi: 1566-
2543/04/0100-01/0.
3. Bonartsev, A. P.; Boskhomodgiev, A. P. et al.; Mol. Cryst. Liquid Cryst. 2012, 556 (1),
288.
4. Bagdi, K.; Molnar, K. et al.; EXPRESS Polym. Lett. 2011, 5(5), 417. doi: 10.3144/
expresspolymlett.2011.41.
5. Shi, R.; Chen, D. et al.; Int. J. Mol. Sci. 2009, 10, 4223. doi:10.3390/ijms10104223.
6. Sanche z-Garcia, M. D.; Gimene z, E. et al.; Carbohydr. Polym. 2008, 71(2), 235.
doi:10.1016/j. carbpol. 2007.05.041.
7. Yang, K-K.; Wang, X.-L. et al.; J. Ind. Eng. Chem. 2007, 13(4), 485.
8. Iordanski, A. L.; Rogovina, S. Z. et al.; Dokl. Phys. Chem. 2010, 431, Part 2, 60.
doi:10.1134/S0012501610040020.
9. Smirnov, A. I.; Belford, R. L. et al.; (Ed. Berliner, L. J.). New York: Plenum Press;
1998, Ch. 3, 83–108.
10. Karpova, S. G.; Iordanskii, A. L. et al.; Russ. J. Phys. Chem. B. 2012, 6(1), 72.
11. Bloembergen, S.; Holden, D. A. et al.; Marchessault: Macromolecules. 1989, 22,
1656.
12. Di Lorenzo, M. L.; Raimo, M. et al.; J. Macromol. Sci.-Phys. 2011, B40(5), 639.
13. Selikhova, V. I.; Shcherbina, M. A. et al.; Polym. Chem. 2002, 22(4), 605 (in Russian).
14. Kamaev, P. P.; Aliev, I. I. et al.; Polymer, 2001, 42, 515.
15. Freier, T.; Kunze, C. et al.; Biomaterials, 2002, 23(13), 2649.
16. Artsis, M. I.; Bonartsev, A. P. et al.; Mol. Cryst. Liq. Cryst. 2012, 555, 232. doi:
10.1080/15421406.2012.635549.
17. Zaikov, G. E.; Iordanskii, A. L. et al.; Diffusion of Electrolytes in Polymers. Ser. New
Concepts in Polymer Science. Utrecht-Tokyo: VSP BV; 1988, 229–231.
CHAPTER 5

NEW BIOLOGICALLY ACTIVE

COMPOSITE MATERIALS ON THE
BASIS OF DIALDEHYDE CELLULOSE
AZAMAT A. KHASHIROV, AZAMAT A. ZHANSITOV,
GENADIY E. ZAIKOV, and SVETLANA YU. KHASHIROVA

CONTENTS

5.1 Introduction .................................................................................. 160

5.2 Results and Discussion ................................................................ 161
5.3 Conclusion ................................................................................... 165
Keywords .............................................................................................. 165
References ............................................................................................. 165
160 Applied Methodologies in Polymer Research and Technology

5.1 INTRODUCTION

Formation and research of systems “polymeric carrier” biologically active

substance have recently gained great importance. Such systems find an
application as immobilized biocatalysts, bioregulators, and an active form
of medicinal substances of the prolonged action.
In this work, for the first time modification peculiarities of microcrys-
talline cellulose (MCC) and its oxidized form (dialdehyde cellulose or
DAС) guanidine-containing monomers and polymers of vinyl and diallyl
series have been studied [1–3]. The structure and some characteristics of
used guanidine-containing modifiers are shown in Table 5.1.

TABLE 5.1 Structure and some characteristics of guanidine-containing modifiers of

cellulose and dialdehyde cellulose
Modifier Molecular Melting Structure
Weight Point, °С
Acrylate guanidine (AG) 131.134 175–176
H2N H O

H2N C N + C CR=CH2

H O

R=Н

Methacrylate guanidine 145.160 161–163

H2N H O
(MAG)
H2N C N + C CR=CH2

H O

R=СН3
N,N-diallylguanidine 199.253 211–212
acetate (DAGA) H2N O N H O
N C + C CX3 C CX3
C N+
H2N O O
H2N H

IV V

X = H or F

N, N-diallylguanidine tri- 253.224 157–158

fluoroacetate (DAGTFA)
H2N O N H O
N C + C CX3 C CX3
C N+
H2N O O
H2N H

IV V

X = H or F
New Biologically Active Composite Materials 161

5.2 RESULTS AND DISCUSSION

Composite materials were received by treating the microcrystalline cel-

lulose (MCC) or dialdehyde cellulose (DAС), water-soluble monomeric
guanidine derivatives (Table 5.1), with subsequent polymerization. Quan-
tity of the monomer/polymer zwitterionic quaternary ammonium cations
acrylate and diallyl guanidine derivatives included in MСC or DAС are
determined by nitrogen content using elemental analysis.
The results of IR spectroscopic studies show the structural differences
of cellulose samples and its modified forms (Figure 5.1).

FIGURE 5.1 Comparison of the spectra PMAG (1), DAC–MAG in Situ (2), and DAC
(3).

For example, the polymerization in DAСMAG in situ (Figure 5.1,

curve 3) in the spectra varies the ratio of the intensity of stripes both cel-
lulose (within 1000–1100 cm–1) and MAG, moreover, the stripe disappears
within 860 cm–1, indicating the presence of a double tie. Splitting of the
tie C = O ties PMAG within 1250 cm–1 takes place, which clearly shows
strong mutual influence of the DAС and MAG/PMAG and formation of
bimatrix systems. Increasing the intensity of the peak 1660 cm–1 in the
162 Applied Methodologies in Polymer Research and Technology

spectrum of the DAC–MAG formation aldimine connection. Increasing

the width of the characteristic absorption stripes in DAC-–MAG within
1450–1680 cm–1, probably due to the formation of relatively strong ties
with the active MAG–DAC centers.
Comparison of the IR spectra of the composites and DAZ DAZ–DAG
and DAZ–DAGTFA demonstrates differences in the spectra of these com-
pounds and indicates the formation of new structures (Figure 5.2).

FIGURE 5.2 IR-Spectra DAC (1), DAC–DAGTFA (2), and DAGTFA (3).

In the spectra of the modified DAC, νOH observed increase in absorp-

tion from the high frequency, especially in the spectrum of DAC modified
DAG. This is due to increasing of the hydroxyls involved in weak hydro-
gen bonds. Stretching vibrations of C–H bonds of methane and methylene
groups DAC appear in 3000–2800 cm–1. In the spectra of the modified
DAG and DAGTFA dialdehyde cellulose, these valence oscillations are
superimposed on the absorption of the CH2 groups that are part of diallyl
compounds.
New Biologically Active Composite Materials 163

This leads to an increase in the intensity of the absorption bands with

a frequency of ~ 2900 cm–1. In the area of ~1650 cm–1 peaks appear ad-
sorbed water. Raising polar amino groups comprising the modifier that
increases the polarity of the substrate. Increasing the intensity of the peak
1655 cm–1 in the spectrum of DAC–DAG and DAC–DAGTFA may indicate
formation aldimine communication giving a signal in this area. In the po-
lymerization in the DAG and DAGTFA, DAC in situ peak at 1140 cm–1
present in the DAC disappears. Obviously, the terminal CHO groups DAC
and guanidine containing diallyl modifier reacted with each other.
Thus, immobilization AG, MAG, DAG and DAGTFA, DAC between
components in the formation of various types of bonds: due to van der
Waals’ forces, intra and intermolecular coordination and hydrogen bonds,
C–C bonds formed during the free radical polymerization in situ immo-
bilized AG, MAG, DAG, and DAGTFA, bonds formed during the graft
copolymerization of monomer radical salts with DAC and labile covalent
aldimine C = N bonds formed by reacting aldehyde groups with amino
DAC guanidine-containing compounds.
Composite materials obtained by polymerization and DAG, DAGTFA
in situ in the inter and intrafibrillar DAC pores dissolve well in water.
It can be assumed that the action of pulp and DAGTFA, DAG, a major
role in breaking the inter and intramolecular hydrogen bonds play anions
CH3COO– and SF3COO– that form a dialdehyde cellulose stable complex-
es through its hydroxyl groups. Simultaneously, esterification may occur
partly sterically more accessible alcohol groups dialdehyde cellulose.
SEM method shows that the dissolution of cellulose sphere-like complex
is formed between the components of the solution in which the cellulose
macromolecules have coil conformation (Figure 5.3).
164 Applied Methodologies in Polymer Research and Technology

FIGURE 5.3 SEM images dialdehyde cellulose (а) and complex of dialdehyde cellulose
with N,N-diallylguanidine trifluoroacetate (b).

In the process of dissolution of dialdehyde cellulose and DAG, DAGT-

FA also acts as acceptors of hydrogen bonds and associated solvent mol-
ecules, thereby preventing re-association of cellulose macromolecules.
New Biologically Active Composite Materials 165

The biological activity of the synthesized composite materials was investi-

gated, and it was shown that the composite synthesized materials are quite
active and have a biocidal effect against Gram-positive (Staphylococcus
aureus and Gram (Escherichia coli) microorganisms. Being the most ex-
pressed biocidal activity is shown in the composites with diallyl deriva-
tives of guanidine.

5.3 CONCLUSION

Studies of the structure of the composites by SEM showed that DAG and
DAGTFA localized in the surface layers of the composite, which increases
the availability of biocidal centers and explains a higher relative activity
of these composites.
In the case of dialdehyde cellulose, modified acrylate derivatives, gua-
nidine antibacterial active groups are in the deeper layers of the interfibril-
lar dialdehyde cellulose, which reduces their bioavailability; and therefore,
the DAC–PAG and DAC–PMAG and start to show the bactericidal activ-
ity of only 48 h. Slowing down the release rate of the bactericidal agent
opens prospect of long-acting drugs with a controlled release bactericide.

KEYWORDS

• Acrylate guanidine
• Cellulose
• IR spectroscopy
• Methacrylate guanidine
• N, N-diallylguanidine acetate
• N, N-diallylguanidine trifluoroacetate
• SEM

REFERENCES

1. Khashirova, S. Yu.; Zaikov, G. E.; Malkanduev, U. A.; Sivov, N. A.; Martinenko, A. I.;
Synthesis of new monomers on diallyl gyanidine basis and their ability to radikal (co)
166 Applied Methodologies in Polymer Research and Technology

polymerization, J. Biochemistry and Chemistry: Research and developments. New

York: Nova Science Publishers Inc; 2003, 39–48.
2. Sivov, N. A.; Martynenko, A. I. Kabanova, E. Yu.; Popova, N. I.; Khashirova, S. Yu.;
Ésmurziev, A. M.; Methacrylate and acrylate guanidines: synthesis and properties.
Petrol. Chem. 2004, 44(1), 43–48.
3. Sivov, N. A.; Khashirova, S. Yu.; Martynenko, A. I.; Kabanova, E. Yu.; Popova, N. I.;
NMR1H spectral characteristics of diallyl monomers derivatives, handbook of con-
densed phase chemistry. Nova Science Publishers; 2011, 293–301.
CHAPTER 6

MICROHETEROGENEOUS TITANIUM
ZIEGLER–NATTA CATALYSTS: THE
INFLUENCE OF PARTICLE SIZE ON
THE ISOPRENE POLYMERIZATION
ELENA M. ZAKHAROVA, VADIM Z. MINGALEEV,
and VADIM P. ZAKHAROV

CONTENTS

6.1 Introduction .................................................................................. 168

6.2 Experimental ................................................................................ 168
6.3 Results .......................................................................................... 171
6.4 Discussion .................................................................................... 176
6.5 Conclusion ................................................................................... 181
Acknowledgments................................................................................. 182
Keywords .............................................................................................. 182
References ............................................................................................. 183
168 Applied Methodologies in Polymer Research and Technology

6.1 INTRODUCTION

The formation of highly stereoregular polymers under the action of mi-

croheterogeneous Ziegler–Natta catalysts is accompanied by broadening
of the polymer MWD [1, 2]. This phenomenon is related to the kinetic
heterogeneity of active sites (АСs) [1, 3, 4]. The possible existence of
several kinetically nonequivalent ACs of polymerization correlates with
the nonuniform particle-size distribution of a catalyst [4]. At present time,
much attention is given to study the influence of microheterogeneous cata-
lysts particle size on the properties of polymers [5, 6]. However, almost
no detailed study has been made of the effect of particle-size catalysts on
their kinetic heterogeneity.
The microheterogeneous catalytic system based on TiCl4 and Al(iso-
C4H9)3 that is widely used for the production of the cis-1,4-isoprene. Our
study has shown [7] that the targeted change of the solid phase particle
size during the use of a tubular turbulent reactor at the stage of catalyst
exposure for many hours is an effective method of controlling the po-
lymerization process and some polymer characteristics of isoprene. It is
supposed that the key factor is the interrelation between the reactivity of
isoprene polymerization site and the size of catalyst particles on which
they localize.
The aim of this study is to investigate the interrelation between the
particle size of a titanium catalyst and its kinetic heterogeneity in the po-
lymerization of isoprene.

6.2 EXPERIMENTAL

Titanium catalytic systems (Table 6.1) were prepared through two meth-
ods.
Method 1: At 0 or –10°С in a sealed reactor 30–50 mL in volume with
a calculated content of toluene, calculated amounts of TiCl4 and Al(iso-
C4H9)3 toluene solutions (cooled to the same temperature) were mixed.
The molar ratio of the components of the catalyst corresponded to its max-
imum activity in isoprene polymerization. The resulting catalyst was kept
at a given temperature (Table 6.1) for 30 min under constant stirring.
 Microheterogeneous Titanium Ziegler–Natta Catalysts
TABLE 6.1 Titanium catalytic systems and their fractions used for isoprene polymerization

Range of particle diameters in fractions of

Molar ratio of catalyst com- titanium catalysts, μm
Labels ponents
Catalyst T, °С Method
Fraction I Fraction II Fraction III
Al/Ti DPO/Ti PP/Al

1 0.7−4.5 0.15−0.65 0.03−0.12

TiCl4−Al(i-C4H9)3 C-1 1 – - 0
2 − 0.20−0.7 0.03−0.18

TiCl4−Al(i-C4H9)3 1 0.7−4.5 0.15−0.65 0.03−0.12

C-2 1 0.15 – 0
−DPO 2 − 0.15−0.68 0.03−0.12

TiCl4−Al(i-C4H9)3 1 − 0.12−0.85 0.03−0.10

C-3 1 0.15 0.15 0
−DPO−PP 2 − 0.15−0.80 0.03−0.12

TiCl4−Al(i-C4H9)3 1 − 0.12−0.45 0.03−0.10

C-4 1 0.15 0.15 -10
−DPO−PP 2 − 0.12−0.18 0.04−0.11

Averaged ranges, μm 0.7−4.5 0.15−0.69 0.03−0.14

Note: DPO—diphenyloxide, PP—piperylene

169
170 Applied Methodologies in Polymer Research and Technology

Method 2: After preparation and exposure of titanium catalysts via

Method 1, the system was subjected to a hydrodynamic action via single
circulation with solvent through a six-section tubular turbulent unit of the
diffuser–confuser design [8] for 2–3 s.
The catalyst was fractionated through sedimentation in a gravitational
field. For this purpose, calculated volumes of catalysts prepared through
methods 1 and 2 were placed into a sealed cylindrical vessel filled with
toluene. In the course of sedimentation, the samples were taken from the
suspension column at different heights—a procedure that allowed the sep-
aration of fractions varying in particle size.
The titanium concentrations in the catalyst fractions were determined
via FEK colorimeter with a blue light filter in a cell with a 50 mm thick
absorbing layer. A K2TiF6 solution containing 1 × 10−4 g Ti/mL was used
as a standard. The catalyst particle-size distribution was measured via the
method of laser diffraction on a Shimadzu Sald-7101 instrument.
Before polymerization, isoprene was distilled under the flow of argon
in the presence of Al(iso-C4H9)3 and then distilled over a TiCl4–Al(iso-
C4H9)3 catalytic system, which provided a monomer conversion of 5–7
per cent. The polymerization on fractions of the titanium catalyst was con-
ducted in toluene at 25°C under constant stirring. In this case, calculated
amounts of solvent, monomer, and catalyst were successively placed into
a sealed ampoule 10–12 mL in volume. The monomer and catalyst con-
centrations were 1.5 and 5 × 10–3 mol/L, respectively. The polymerization
was terminated via the addition of methanol with 1 per cent ionol and 1
per cent HCl to the reaction mixture. The polymer was repeatedly washed
with pure methanol and dried to a constant weight. The yield was esti-
mated gravimetrically.
The MWD of polyisoprene was analyzed via GPC on a Waters GPC-
2000 chromatograph equipped with three columns filled with a Waters
microgel (a pore size of 103–106 A) at 80°С with toluene as an eluent. The
columns were preliminarily calibrated relative to Waters PS standards with
a narrow MWD (Мw/Мn = 1.01). The analyses were conducted on a chro-
matograph, which allows calculations with allowance for chromatogram
blurring. Hence, the need for additional correction of chromatograms was
eliminated.
The microstructure of polyisoprene was determined via high-resolu-
tion 1H NMR spectroscopy on a Bruker AM-300 spectrometer (300 MHz).
The MWD of cis-1,4-polyisoprene obtained under the aforementioned
Microheterogeneous Titanium Ziegler–Natta Catalysts 171

experimental conditions, qw(M), were considered through the following

equation:
qw(M) = ∫∞0 Ψ(β)Mβ2exp(–Mβ)dβ
where β is the probability of chain termination and ψ(β) is the distribution
of active site over kinetic heterogeneity, M is current molecular weight.
As shown earlier [9], Eq. (6.1) is reduced to the Fredholm integral
equation of the first kind, which yields function ψ(β) after solution via the
Tikhonov regularization method. This inverse problem was solved on the
basis of an algorithm from Ref. [9]. As a result, the function of the distri-
bution over kinetic heterogeneity in ψ(lnβ)—lnM coordinates with each
maximum related to the functioning of AC of one type was obtained.

6.3 RESULTS

After mixing of the components of the titanium catalyst, depending on its

formation conditions, particles 4.5 μm to 30 nm in diameter, which are
separated into three arbitrary fractions, are formed (Table 6.1).

FIGURE 6.1 Fractional compositions of titanium catalyst C-1−C-2 (Table 6.1).

172 Applied Methodologies in Polymer Research and Technology

During the formation of catalyst C-1 via Method 1, the fraction com-
posed of relatively coarse particles, fraction I, constitutes up to 85 per cent
(Figure 6.1). In Method 2, the hydrodynamic action on the titanium cata-
lyst formed under similar conditions results in an increase in the content
of fraction II. Analogous trends are typical of catalyst C-2. The catalyst
modification with piperylene additives, catalyst C-3, is accompanied by
the disappearance of fraction I and an increase in the content of fraction
II (Figure 6.1), as was found during the hydrodynamic action on C-1. The
hydrodynamic action on a two-component catalyst is equivalent to the ad-
dition of piperylene to the catalytic system. The preparation of catalytic
complex C-3 via Method 2 results in narrowing of the particle-size dis-
tribution of fraction II owing to disintegration of particles 0.50–0.85 μm
in diameter (Figure 6.1). The reduction of the catalyst exposure tempera-
ture to –10°С (catalyst C-4) is accompanied by further disintegration of
fraction II (Figure 6.1). In this case, the content of particles 0.19–0.50
μm in diameter decreases to 22 per cent with predominance of particles
0.15–0.18 μm in diameter. The formation of C-4 via Method 2 results in
additional dispersion of particles of fraction II, with the content of par-
ticles 0.15–0.18 μm in diameter attaining 95 per cent.
The content of the finest catalyst particles in the range 0.03–0.14 μm,
fraction III, attains 5–12 per cent and is practically independent of the
catalyst formation conditions. The most considerable changes are shown
by particles 0.18–4.50 μm in diameter. Particles of fraction I are easily
dispersed as a result of the hydrodynamic action in turbulent flows and the
addition of catalytic amounts of piperylene, and their diameter becomes
equal to that of particles from fraction II. The decrease in the catalyst ex-
position temperature from 0 to –10°С with subsequent hydrodynamic ac-
tion leads to a more significant reduction of particle size and the formation
of a narrow fraction.
Isolated catalyst fractions differing in particle size were used for iso-
prene polymerization. The cis-1,4-polymer was obtained for all fractions,
regardless of their formation conditions. The contents of cis-1, 4 and 3, 4
units were 96–97 and 3–4 per cent, respectively. Coarse particles (fraction
I) are most active in isoprene polymerization (method 1) on different frac-
tions of C-1 (Figure 6.2).
Microheterogeneous Titanium Ziegler–Natta Catalysts 173

FIGURE 6.2 cis-1,4-Polyisoprene yields U vs. polymerization times τ in the presence of

fractions particles of titanium catalysts (1) C-1, (2) C-2, (3) C-3, and (4) C-4.

As the particle size of C-1 decreases, its activity drops significantly.

The catalyst modification with diphenyloxide (C-2) has practically no ef-
fect on the fractional composition, but the activities of different catalyst
fractions change. The most marked increase in activity was observed for
fraction I. Catalyst C-3 prepared via Method 1 comprises two fractions,
with fraction II having the maximum activity. The decrease of the catalyst
exposition temperature to –10°С (C-4) result in further increase in the rate
of isoprene polymerization on particles of fraction II.
174 Applied Methodologies in Polymer Research and Technology

The hydrodynamic action increases the content of fraction II in C-1,

but its activity in isoprene polymerization does not increase (Figure 6.2).
For C-2, the analogous change in the fractional composition is accompa-
nied by an increased activity of fraction II (Method 2). The addition of
piperylene to C-3 results in a stronger effect on the activity of fraction II
under the hydrodynamic action. The change of the hydrodynamic regime
in the reaction zone does not affect the activity of fine particles of catalyst
fraction III. Isoprene polymerization in the presence of fraction III always
has a low rate and a cis-1,4-polyisoprene yield not exceeding 7–12 per
cent.
During polymerization with C-1 composed of fraction I (Method 1), the
weight-average molecular mass of polyisoprene increases with the process
time (Table 6.2). Polyisoprene prepared with catalyst fraction II has a low-
er molecular mass. A more considerable decrease in the weight-average
molecular mass is observed during isoprene polymerization on the finest
particles of fraction III, with Mw being independent of the polymerization
time. The width of the MWD for polyisoprene obtained on fraction I in-
creases with polymerization time from 2.5 to 5.1. The polymer prepared
in the presence of catalyst fraction III shows a narrow molecular mass
distribution (Mw/Mn ~ 3.5). The addition of DPO is accompanied by an
increase in the weight-average molecular mass of polyisoprene obtained
in the presence of fraction I. Under a hydrodynamic action (Method 2)
on catalysts C-1 and C-2, polyisoprene with an increased weight-average
molecular mass is formed. During the addition of piperylene to the catalyst
(C-3), Mw of polyisoprene increases to values characteristic of C-2 formed
via method 2. The formation of the catalytic system TiCl4-Al(iso-C4H9)3-
DPO-piperylene via method 1 at –10°С results in substantial increases in
the activity of the catalyst and the reactivity of the active centers of frac-
tion II. The polymerization of isoprene on catalyst fraction III, regardless
of the conditions of catalytic system formation (electrondonor additives,
exposure temperature, hydrodynamic actions), yields a low-molecular-
mass polymer with a polydispersity of 3.0–3.5.
Microheterogeneous Titanium Ziegler–Natta Catalysts 175

TABLE 6.2 Molecular-mass characteristics of cis-1,4-polyisoprene. 1 and 2 are the

methods of catalyst preparation

C τ, Fraction I Fraction II Fraction III

Min
Mw×10-4 Mw/Mn Mw×10-4 Mw/Mn Mw×10-4 Mw/Mn

1 2 1 2 1 2 1 2 1 2 1 2

3 17.1 2.6 43.2 43.6 4.6 4.8 25.4 21.4 3.7 3.8

20 56.3 4.2 46.5 57.5 4.0 5.9 23.7 22.6 3.4 3.7
C-1
40 64.9 4.6 47.4 62.7 4.1 5.8 27.6 28.9 3.6 3.6

90 72.2 5.1 54.3 61.4 4.3 6.2 26.8 22.4 3.7 3.6

3 24.3 3.3 39.5 54.8 4.3 4.9 21.1 22.3 3.8 3.7

20 69.7 3.8 41.2 67.5 3.9 4.6 24.6 24.6 3.7 3.4
C-2
40 78.4 3.7 42.6 72.8 4.4 4.3 26.3 22.4 3.3 3.5

90 84.6 4.0 58.0 73.2 4.3 4.2 24.7 24.3 3.5 3.3

3 66.2 60.5 3.9 3.8 22.4 20.0 3.8 3.6

20 75.4 71.1 3.7 3.5 28.1 21.3 3.7 3.7

C-3
40 79.6 78.8 4.1 4.0 21.5 23.6 3.8 3.8

90 81.6 79.6 3.9 3.8 23.2 26.8 3.6 3.3

3 81.2 72.7 3.6 3.7 25.4 20.3 3.8 3.6

20 62.7 51.3 3.3 3.2 24.8 21.6 3.7 3.7

C-4
40 57.6 44.3 3.1 3.2 23.2 26.8 3.6 3.6

90 61.4 48.2 3.2 3.4 19.6 21.5 3.1 3.3

The solution of the inverse problem of the formation of the MWD in

the case of cis-1,4-polyisoprene made it possible to obtain curves of the
active site distribution over kinetic heterogeneity (Figures 6.3–6.6). As a
result of averaging of the positions of all maxima, three types of polymer-
ization site that produce isoprene macromolecules with different molecu-
lar masses were found: type A (lnM = 10.7), type B (lnM = 11.6), and type
C (lnM = 13.4).
176 Applied Methodologies in Polymer Research and Technology

The polymerization of isoprene in the presence of fractions I and II of

C-1 (Method 1) occurs on site of types B and C (Figure 6.3). The polym-
erization in the presence of fraction III proceeds on active site of type A
only. The single site and low activity character of the catalyst composed
of particles of fraction III is typical of all the studied catalysts and all the
methods of their preparation. Thus, these curves are not shown in subse-
quent figures. Likewise, catalyst C-2 prepared via Method 1 features the
presence of type B and type C site in isoprene polymerization on fractions
I and II (Figure 6.4). The hydrodynamic action (Method 2) on C-1 accom-
panied by dispersion of particles of fraction I does not change the types
of site of polymerization on particles of fraction II (Figure 6.5). A similar
trend is observed during the same action on a DPO-containing titanium
catalyst in turbulent flows (Figure 6.5).
In the presence of piperylene, the main distinction of function ψ(lnβ)
relative to the distributions considered above is a significantly decreased
area of the peak due to the active site of type В (Figure 6.6). The decrease
of the catalyst exposition temperature to –10°С (C-4, Method 1) allows
the complete “elimination” of active site of type В (Figure 6.6). With al-
lowance for the low content of fraction III, it may be concluded that under
these conditions, a single-site catalyst is formed. In the case of the hydro-
dynamic action on C-4, the particles of fraction II contain active centers
of type С with some shift of unimodal curve ψ(lnβ) to smaller molecular
masses (Figure 6.6).

6.4 DISCUSSION

The particles of the titanium catalyst 0.03–0.14 μm in diameter, regard-

less of the conditions of catalytic system preparation, feature low activity
in polyisoprene synthesis, and the resulting polymer has a low molecular
mass and a narrow MWD. The molecular mass characteristics of polyiso-
prene and the activity of the catalyst comprising particles 0.15–4.50 μm in
diameter depend to a great extent on its formation conditions.
Microheterogeneous Titanium Ziegler–Natta Catalysts 177

FIGURE 6.3 Active site distributions over kinetic heterogeneity during isoprene
polymerization on fractions C-1. Method 1. Here and in figures 6.4–6.5 numbers next to
the curves are conversions (%).
178 Applied Methodologies in Polymer Research and Technology

FIGURE 6.4 Active site distributions over kinetic heterogeneity during isoprene
polymerization on fractions C-2. Method 1.
Microheterogeneous Titanium Ziegler–Natta Catalysts 179

FIGURE 6.5 Active site distributions over kinetic heterogeneity during isoprene
polymerization on particles of fraction II of C-1 and C-2. Method 2.
180 Applied Methodologies in Polymer Research and Technology

FIGURE 6.6 Active site distributions over kinetic heterogeneity during isoprene
polymerization on particles of fraction II of C-3 and C-4. Methods 1-1, Method 2-2.
Microheterogeneous Titanium Ziegler–Natta Catalysts 181

As shown earlier [10, 11], the region of coherent scattering for particles
based on TiCl3 spans 0.003–0.1 μm, a range that corresponds to the linear
size of the minimum crystallites. Coarser catalyst particles are aggregates
of these minimum crystallites. This circumstance makes it possible to sug-
gest that the fraction of catalyst particles 0.03–0.14 μm in diameter that
was isolated in this study is a mixture of primary crystallites of β-TiCl3
that cannot be separated via sedimentation. The fractions of catalyst par-
ticles with larger diameters are formed by stable aggregates of 2–1100
primary crystallites. There is sense in the suggestion that the elementary
crystallites are combined into larger structures via additional Al–Cl bonds
between titanium atoms on the surface of a minimum of two elementary
crystallites, that is (Ti)1–Cl–Al–Cl–(Ti)2.
Similar structures can be formed with the participation of AlR2Cl and
AlRCl2, which are present in the liquid phase of the catalyst. Trialkyl alu-
minum AlR3 is incapable of this type of bonding. Thus, the structure of the
most alkylated Ti atom (in the limit, a monometallic center of polymeriza-
tion), which has the minimum reactivity, should be assigned to the active
centers localized on particles 0.03–0.14 μm in diameter [9]. On particles
0.15–4.50 μm in diameter in clusters of primary crystallites, highactivity
bimetallic centers with the minimum number of Ti–C bonds at a Ti atom
are present. Thus, the experimental results obtained in this study show that
the nature of the polymerization center resulting from successive parallel
reactions between the pristine components of the catalytic system deter-
mines the size of the titanium catalyst particles and, consequently, their
activity in isoprene polymerization.

6.5 CONCLUSION

We first examined the isoprene polymerization on the fractions of the ti-

tanium catalyst particles that were isolated by sedimentation of the total
mixture. The results obtained allow considering large particle as clusters
that are composed of smaller particles. In the process of polymerization or
catalyst preparation, the most severe effects are large particles (clusters).
This result in the developing process later on substantially smaller as com-
pared with initial-size particles. These particles are fragments of clusters
which are located over the active centers of polymerization. Note that the
stereo specificity is not dependent on the size of the catalyst particles.
182 Applied Methodologies in Polymer Research and Technology

Hypothesis about clusters agrees well with the main conclusions of

this paper:
I. Isolated the fraction of particles of titanium catalyst TiCl4–Al(iso-
C4H9)3: I—0.7–4.5 μm, II—0.15–0.68 μm, III—0.03–0.13 μm.
With decreasing particle size decreases the rate of polymerization
the molecular weight and width of the molecular weight distribu-
tion. Hydrodynamic impact leads to fragmentation of large par-
ticles of diameter greater than 0.5 μm.
II. Isoprene polymerization under action of titanium catalyst is occurs
on three types active sites: type A—lnM = 10.7; type B—lnM =
11.6; and type C—lnM = 13.4. Fractions I and II particles contain
the active site of type B and C. The fraction III titanium catalyst is
represented by only one type of active sites producing low-molec-
ular-weight polymer (lnM = 10.7).
III. The use of hydrodynamic action turbulent flow, doping DPO and
piperylene, lowering temperature of preparation of the catalyst al-
lows to form single site catalyst with high reactivity type C (lnM =
13.4), which are located on the particles of a diameter of 0.15–0.18
μm.

ACKNOWLEDGMENTS

This study was financially supported by the Council of the President of the
Russian Federation for Young Scientists and Leading Scientific Schools
Supporting Grants (project no. MD-4973.2014.8).

KEYWORDS

• Active sites
• Isoprene polymerization
• Particles-size effect
• Single-site catalysts
• Ziegler–Natta catalyst
Microheterogeneous Titanium Ziegler–Natta Catalysts 183

REFERENCES

1. Kissin, Yu. V.; J. Catal. 2012, 292, 188–200.

2. Hlatky, G. G.; Chem. Rev. 2000, 100, 1347–1376.
3. Kamrul Hasan, A. T. M.; Fang, Y.; Liu, B.; Terano, M.; Polymer, 2010, 51, 3627–3635.
4. Schmeal, W. R.; Street, J. R.; J. Polym. Sci: Polym. Phys. Ed. 1972, 10, 2173–2183.
5. Ruff, M.; Paulik, C.; Macromol. React. Eng. 2013, 7, 71–83.
6. Taniike, T.; Thang, V. Q.; Binh, N. T.; Hiraoka, Y.; Uozumi, T.; Terano, M.; Macromol.
Chem. Phys. 212, 2011, 723–729.
7. Morozov, Yu. V.; Nasyrov, I. Sh.; Zakharov, V. P.; Mingaleev, V. Z.; Monakov, Yu.
B.; Russ. J. Appl. Chem., 2011, 84, 1434–1437.
8. Zakharov, V. P.; Berlin, A. A.; Monakov, Yu. B.; Deberdeev, R. Ya.; Physicochemical
fundamentals of rapid liquid phase processes. Moscow: Nauka; 2008, 348 p.
9. Monakov, Y. B.; Sigaeva, N. N.; Urazbaev, V. N.; Active sites of polymerization. Mul-
tiplicity: stereospecific and kinetic heterogeneity. Leiden: Brill Academic, 2005, 397
p.
10. Grechanovskii, V. A.; Andrianov, L. G.; Agibalova, L. V.; Estrin, A. S.; Poddubnyi, I.
Ya.; Vysokomol. Soedin., 1980, Ser. A 22, 2112–2120.
11. Guidetti, G.; Zannetti, R.; Ajò, D.; Marigo, A.; Vidali, M.; Eur. Polym. J. 1980, 16,
1007–1015.
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CHAPTER 7

THE ROLE AND MECHANISM OF

BONDING AGENTS IN COMPOSITE
SOLID PROPELLANTS
S. A. VAZIRI, S. M. MOUSAVI MOTLAGH, and M. HASANZADEH

CONTENTS

7.1 Introduction .................................................................................. 186

7.2 The Mechanism of Bonding Agents in Improving Mechanical
Properties ..................................................................................... 187
7.3 Appropriate Bonding Agents for Propellants Containing
Nitramine ..................................................................................... 189
7.4 Conclusions .................................................................................. 194
Keywords .............................................................................................. 194
References ............................................................................................. 194
186 Applied Methodologies in Polymer Research and Technology

7.1 INTRODUCTION

Composite propellants are the basic component for development and

production of modern propellants. Comparison of composite propellants
with double-base propellants indicated that composite propellants have re-
markable properties, such as high performance, high density, and superior
physical properties for producing large grain; therefore, they are excel-
lent candidates for application in military systems such as strategic bal-
listic missiles as well as space shuttle boosters in space systems. Bonding
agents, as an extremely important component in solid rocket propellants,
may affect the processability, mechanical and ballistic properties, safety,
aging, and temperature cycles of propellants. Recently, nitramine used as
an oxidizer in propellant due to its potential advantages [1].
Allen [2] investigated the application of water-soluble animal collagen
proteins for cyclotrimethylene—trinitramine (RDX) and cyclotetrameth-
ylene—tetranitramine (HMX) as a bonding agent. In the study on the ef-
fect of tensile strain rate on the mechanical properties of HTPB-based fu-
els by [3], it was demonstrated that the elongation at break increases with
increasing strain rate. However, with increasing solids, tensile strength
increases and elongation at break decreases. [4] indicated that [tris (2-hy-
droxyl) isocyanurate] can be used as bonding agent for CTPB/Al/RDX
composite propellants system. They investigated the interaction of several
bonding agents based on isocyanurate and found that the oxidizers form
hydrogen bonds with [tris (2-hydroxyl) isocyanurate] and [tris (2-carboxy-
ethyl) isocyanurate]. The investigation was performed on several isocyan-
urate bonding agents with AP and several binders by using FTIR analytics.
It is found that the oxidizers interact with bonding agent [tris (2-hydroxyl)
isocyanurate] and [tris (2-carboxy-ethyl) isocyanurate] through hydrogen
bond. Moreover, it is found that RDX interacts with both bonding agents,
whereas HTPB have only interacted with [tris (2-carboxy-ethyl) isocyan-
urate] [4].In another work, [5] studied the effect of RDX on tensile prop-
erties and elongation of the AP/HTPB composite propellants. They found
that in the presence of RDX, elongation at maximum stress has increased
about 90 per cent, at room temperature. RDX also reduces the burning rate
and improves the processability of these propellants. The result showed
that increasing the temperature from 25°C to 55°C leads to an increase in
elongation and tensile strength and slightly decreases the elastic modulus.
Moreover, the mechanical properties increase with increasing strain rate
The Role and Mechanism of Bonding Agents 187

from 1 to 1,000 mm/min [5]. [6] studied the relationship between micro-
structure and mechanical properties of HTPB-based fuels. It is found that
mechanical properties of HTPB-based fuel are closely related to its micro-
structure. They explained that the structure of composite solid propellants
and also their mechanical properties are influenced by a great number of
parameters including binder/solid interface, size, shape and distribution
of the solid particles, and the quantity of binder matrix. Composite solid
propellants containing nitramine with RDX or HMX offer many advan-
tages such as combustion with low-flame temperature and low molecular
weight. Generally, in composite propellants formulation, single-crystal-
line nitramine propellants such as HMX or RDX mixed with polymeric
binder [7].
To improve the mechanical properties of composite solid propellants
containing nitramine, the addition of plasticizer, cross-linking materials,
suitable catalyst and curing agent and also the addition of the bonding
agent have been proposed. According to literature, the bonding agents play
a significant role in increasing adhesions between the binder and the solid
phase, and therefore improving the mechanical properties of solid propel-
lants [1, 8].

7.2 THE MECHANISM OF BONDING AGENTS IN IMPROVING

MECHANICAL PROPERTIES

It is well known that the main components of the composite solid propel-
lants are oxidizer, metal fuel, and polymeric binders (Figure 7.1). Since
composite solid propellants are not homogeneous, the oxidizer and metal
fuel are suspended in the binder. Therefore, the presence of solid particles
(such as AP and Al) in composite solid propellants can lead to grain sepa-
ration [4, 8].
The addition of bonding agents increased the strength of composite by
producing chemical or physical bond between binder and oxidizer [8, 10].
The mechanism of improved mechanical performance of composite solid
propellants is based on the absorption of bonding agent on the surface of
oxidizer and its chemical reaction with binder (Figure 7.2). The compat-
ibility of bonding agent with solid particles and having suitable functional
groups for chemical bond formation are two essential features of bonding
agent [8].
188 Applied Methodologies in Polymer Research and Technology

FIGURE 7.1 Classification of composite solid propellant components [1, 9].

FIGURE 7.2 General mechanism of bonding agents [8].

The Role and Mechanism of Bonding Agents 189

7.3 APPROPRIATE BONDING AGENTS FOR PROPELLANTS

CONTAINING NITRAMINE

There are convenient bonding agents for AP such as polyamines, aziri-

dine, oxazoline and amine salts, schiff base, tetra-alkyl titanate, and vi-
nyl ethers [11–16]. For nitramine fillers (such as RDX), bonding agents
include di (2-hydroxyethyl) dimethylhydantoin (DHE), vinyltriethoxysi-
lane (VTEO), triethanolamine (TEA), maleic anhydrate–terminated poly
butadiene (MPB) [17–19]. In recent years, hydantoin are known as most
popular bonding agent for RDX and HMX in solid propellant composites.
Moreover, hydantoin has been used as bonding agent in KP, AN, and AP
oxidizers. In this section, the effective bonding agents used for improving
mechanical properties of composite solid propellants containing nitramine
are discussed in detail [18].

7.3.1 NEUTRAL POLYMERIC BONDING AGENT

Alkanolamines, alkanolamides, polyamines, Dantcol, and amine salts are

typical examples of bonding agents for propellants, with relatively non-
polar binders such as polybutadiene glycol. These small polar molecules,
due to the nonpolarity of binder matrix, undergo adsorption on polar solid
particles. However, these bonding agents are no longer effective in a sys-
tem where polar binders such as nitro and nitratoplasticizers are used. This
is because these bonding agents are too soluble in the polar submix. When
the solid particles are nitramine crystals (such as HMX), adsorption be-
comes even less likely since they have cohesive energy density close to
that of the binder matrix. However, in situations where the polarity of the
submix approaches that of the solid particles, this criterion is difficult to
satisfy [10].
The polar plasticizers not only compete with the bonding agent for
adsorption on the solid surfaces but also dissolve the bonding agent exten-
sively. In some cases, these polar plasticizers are even known to partially
dissolve the HMX particles. Although the bonding agents with acidic or
basic molecules tend to absorb more solid particles, they are usually det-
rimental to the cure or the aging stability of binders containing nitrato,
nitro, or azido groups. For such binder systems, bonding agents should not
only be neutral and polymeric, that is, a neutral polymeric bonding agent
190 Applied Methodologies in Polymer Research and Technology

(NPBA), but they should also have a high affinity for the solid particles.
Moreover, NPBA should contain many hydroxyl groups per molecules,
that are enough available to undergo crosslinking with the isocyanate and
also form primary bonds with the binder matrix. Polymers containing one
or more functionalities such as nitro, nitrato, cyano, sulfone, amide, sul-
fonamide, substituted amides such as cyanoethylated amides, and ammo-
nium salt groups are some of the most examples of such bonding agents.
This bonding agents should have an average molecular weight in the range
from 3,000 to 5,00,000 (preferably between 5,000 and 1,00,000), and have
ato 100 hydroxyl groups per polymer molecule [10, 20].
It has been proven that the strength and initial modulus of high-energy
propellant containing NG, PEG, and HMX can be improved by addition
of small amount of NBPA bonding agent during the mixing process. Al-
though deviation from neutrality often causes poor cure and/or impairs
stability of the binder components, it is known that the use of basic or
acidic bonding agents may improve the degree of adsorption [10].
Addition of a small amount (0.2–0.6 % of the propellant formulation)
of neutral polymeric bonding agent leads to filler reinforcement. For ex-
ample, it is found that HMX/PEG with 0.2 wt. per cent of NPBA will
result in a fivefold increase of elongation in comparison to their counter-
parts without NPBA. Figures (7.3) shows the stress–strain curves of HMX
particles coated by NBPA bonding agents [10].

FIGURE 7.3 The effect of NBPA coating on mechanical properties of HMX particles: (a)
uncoated HMX and (b) coated HMX [10].
The Role and Mechanism of Bonding Agents 191

Figure (7.4) shows the mechanical properties of HMX-filled and un-

filled composite. It can be noted that incorporation of 0.2 wt. per cent of
NPBA gives a material with significantly greater strength than the unfilled
binder [10].

FIGURE 7.4 Stress-strain curve of HMX-filled and unfilled composite: (a) 40 per cent
HMX without NPBA, (b) without HMX and NPBA, and (c) 40 per cent HMX and 0.2 per
cent NPBA [10].

Figure (7.5) shows another demonstration of the effectiveness of

NPBA in composite with higher plasticizer and solid contents, and also
larger particle size in comparison with that of illustrated in Figure (7.4). It
is found that the incorporation of 0.6 wt. per cent of NPBA into the PEG/
TMETN/NP composite with 50 per cent HMX, would result the stress–
strain curve approaches the curve of the composite containing coated
HMX particles [10].
192 Applied Methodologies in Polymer Research and Technology

FIGURE 7.5 Effect of NPBA on mechanical properties of composite, (a) without HMX
and NPBA, (b) 50 per cent HMX, 0.6 per cent NPBA, and (c) 50 per cent HMX without
NPBA [10].

In another study, [11] investigated the mechanisms of NPBA in a

HMX/NG/PEG composite. It is found that during the curing process,
bonding agent tied with a PEG binder, and thereby the initial modulus will
increase. The chemical reaction of NBPA and PEG binder are shown in
Figure (7.6) [10, 11].

FIGURE 7.6 The chemical reaction of NBPA bonding agent and PEG binder [11].
The Role and Mechanism of Bonding Agents 193

7.3.2 SILANE BONDING AGENTS

Silane bonding agents contain two or more functional groups that each
of them will interact with various type of molecules. These bonding
agents have potential application in surface improvement of insulating
layer. According to literature, the addition of silane bonding agents can
increase the modulus and strength of propellant [10]. For example, in the
study on the effects of silane bonding agent on the improvement of ther-
mal stability and mechanical properties of HTPB/HMX composite sys-
tem by [19], it was demonstrated that the addition of amino-silane in the
HTPB/HMX matrix improved the mechanical properties of composite.
Moreover, enhanced moisture resistance and thermal stability of com-
posite are obtained. They demonstrated that the silane bonding agents,
due to their considerable effect on tensile strength enhancement, are ex-
cellent candidates for application in HTPB/HMX composite systems. As
a result, it can be concluded that the HTPB/HMX composite with silane
bonding agent has higher mechanical properties than the ones with with-
out silane bonding agent [19].

7.3.3 HYDANTOINS BONDING AGENTS

Today, hydantoins are known to be an important bonding agent for

composite solid propellants containing nitramine. Hydantoin bond-
ing agent could bring strong interaction between the binder and filler
through covering particles as a sticky beads. DHE bonding agent, as a
most popular hydantoin bonding agent, is suitable for linking oxidants
(including RDX, HMX) in composite solid propellants. Using hydan-
toin bonding agent in composite solid propellant would make it easier
to casting, molding, extruding, or mixing processes [18, 21]. The ef-
fect of DHE percent on the mechanical properties of composite solid
propellants is illustrated in Table (7.1). It can be noted that the samples
with 0.25 per cent DHE bonding agent have better mechanical proper-
ties than the other samples.
194 Applied Methodologies in Polymer Research and Technology

TABLE 7.1 Effect of DHE percent on the mechanical properties of composite solid
propellants [21]

DHE% 293K (20°C) 223K (−50°C)

σm εm M εe ε m× σ m σm εm εe
(%) (MPa) (%) (%) (%)
(MPa) (MPa) (MPa)

0.05 0.63 20 4.9 13 8.2 1.6 13 7.4

0.15 0.87 36 5.8 15 13 1.9 18 4.8

0.25 0.74 50 2.9 26 19 1.8 30 8.9

7.4 CONCLUSIONS

This chapter summarizes the effect of bonding agent on mechanical prop-

erties of composite solid propellants containing nitramine. Bonding agents
can improve the mechanical properties of propellants by producing chemi-
cal or physical bond between binder and oxidizer. Among several bond-
ing agent described earlier, neutral polymeric bonding agent (NBPA) is
the most effective bonding agent that used in composite solid propellants
containing nitramine. For example, the results show that the addition of
0.2 wt. per cent of NBPA bonding agent to HMX/PEG, results in higher
elongation and mechanical properties.

KEYWORDS

• Bonding agents
• Composite solid propellants
• Mechanical properties
• Nitramine propellants

REFERENCES

1. Agrawal, J. P.; High Energy Materials Propellants, Explosives and Pyrotechnics.

Weinheim: WILEY-VCH Verlag GmbH & Co. KGaA; 2010.
The Role and Mechanism of Bonding Agents 195

2. Allen, H. C.; Bonding Agent for Nitramines in Rocket propellants. US Patent 4389263,
1983.
3. Chung, H. L.; Kawata, K.; Itabashi, M.; Tensile strain rate effect in mechanical proper-
ties of dummy HTPB propellants. J. Appl. Polym. Sci. 1993, 50, 57–66.
4. Uscumlic, G. S.; Zreigh, M. M.; Dusan, Z. M.; Investigation of the interfacial bond-
ing in composite propellants.1,3,5-Trisubstituted isocyanurates as universal bonding
agents, J. Serb. Chem. Soc. 2006, 71, 445–458.
5. Behera, S.; Effect of RDX on elongation properties of AP/HTPB based case bonded
composite propellants. Sci. Spectrum, 2009, 31–36.
6. Li, X.; Jiao, J.; Yao, J.; Wang, L.; Study on the relationship between microscopic
structure and mechanical properties of HTPB propellant. Adv. Mater. Res. 2011, 4,
1151–1155.
7. Duterque, G.; Lengellej, G.; Combustion mechanisms of nitramine-based propellants
with additives. J. Propul. Power, 1990, 6, 718–725.
8. Shokri, S.; Sahafian, A.; Afshani, M. E.; Bonding agents and their performance mech-
anisms in composite solid propellants. MSc Thesis, K.N. Toosi University of Technol-
ogy, Iran, 2005.
9. Davenas, A.; Solid Rocket Propulsion Technology. Oxford: Pergamon Press; 1993.
10. Kim, C. S.; Youn, C. H.; Nobel, P. N.; Gao, A.; Development of neutral polymeric
bonding agents for propellants with polar composites filled with organic nitramine
crystals. Propell. Explos. Pyrot. 1992, 17, 38–42.
11. Kim, C.; Sue, N.; Paul, N.; Youn, C. H.; Tarrant, D.; Gao, A.; The mechanism of filler
reinforcement from addition of neutral polymeric bonding agents to energetic polar
propellants. Propell. Explos. Pyrot. 1992, 5, 51–58.
12. Hamilton, R. S.; Wardle, R.; Hinshaw, J.; Oxazoline Bonding Agents in Composite
Propellants. US Patent 5366572, 1994.
13. Ducote, M. E.; Carver, J. G.; Amine Salts as Bonding Agents. US Patent 4493741,
1987.
14. Wallace, I. A.; Ambient Temperature Mix, Cast, and Cure Composite propellant For-
mulations. US Patent 5472532, 1995.
15. Allen, H. C.; Clarke, F.; Tetra-Alkyl Titanates as Bonding Agents for Thermoplastic
Propellants. US Patent 4597924, 1986.
16. Hamilton, R. S.; Wardle, R.B.; Hinshaw, J. C.; Vinyl Ethers as Nonammonia Produc-
ing Bonding Agents In Composite Propellant Formulations. US Patent 5336343, 1994.
17. Hasegawa, K.; Takizuka, M.; Fukuda, T.; Bonding Agents for AP and Nitramine/
HTPB Composite Propellants. AIAA/SAE/ASME, 19th Joint Propulsion Conference,
Washington, 1983.
18. Consaga, J. P.; Dimethyl Hydantoin Bonding Agents in Solid Propellants. US Patent
4,214,928; 1980.
19. Leu, A. L.; Shen S. M.: The effects of silane bonding agent on the improvement of
thermal stability and mechanical properties of HTPB/HMX composite system. Tech-
nol. Polym. Compd. Energ. Mater. 1990, 101–1.
20. Kim, C. S.; Filler reinforcement of polyurethane binder using a Neutral Polymeric
Bonding Agent. US Patent 4915755, 1990.
21. Perrault, G.; Lavertu, R.; Drolet, J. F; High-Energy Explosives or Propellant Composi-
tion. US Patent 4289551, 1981.
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CHAPTER 8

A STUDY ON ADSORPTION
OF METHANE ON ZEOLITE 13X
AT VARIOUS PRESSURES AND
TEMPERATURES
FARSHID BASIRI, ALIREZA ESLAMI, MAZIYAR SHARIFZADEH, and
MAHDI HASANZADEH

CONTENTS

8.1 Introduction .................................................................................. 198

8.2 Experimental ................................................................................ 199
8.3 Results and Discussion ................................................................ 200
8.4 Conclusions .................................................................................. 202
Acknowledgments................................................................................. 202
Keywords .............................................................................................. 202
References ............................................................................................. 202
198 Applied Methodologies in Polymer Research and Technology

8.1 INTRODUCTION

Natural gas, as a cleanest burning fossil fuel, has low carbon content and
negligible sulfur dioxide emissions. Therefore, it is an excellent candidate
for applications in diverse fields, and especially in heating and cooking
on a domestic level and to power generation [1]. The use of natural gas is
expected to increase in the utility, transportation, and industrial sectors in
the near future [1, 2]. In general, natural gas is primarily methane, how-
ever, depending on the source and geographical location of production; it
can contain large proportions of other compounds such as carbon dioxide,
nitrogen, and small amounts of higher molecular weight hydrocarbons [3].
It is necessary to develop technologies that will allow us to utilize the
fossil fuels while reducing the emissions of greenhouse gases [4]. There
are many approaches to separate methane from air, such as cryogenic dis-
tillation of liquefied air and adsorption processes [5]. In recent years, sepa-
ration and purification of gas mixtures by adsorption has been extensively
studied in chemical and petrochemical industries [6, 7]. Pressure swing
adsorption (PSA) attracts a growing interest due to its low energy require-
ments and low capital investment costs [7, 8]. This process was used to
separate some gas species from a mixture of gases under pressure. It oper-
ates according to the molecular characteristics of gas species and affinity
for an adsorbent material. In general, the higher the pressure, the more the
gas being adsorbed. Special adsorptive materials (e.g., zeolites) are used
as a molecular sieve, preferentially adsorbing the target gas species at high
pressure [9, 10].
There have been various approaches to develop mathematical models
for PSA process according to the literature. Several traditional adsorption
models have been used by researchers, including Langmuir, Sips, Toth,
UNILAN, and Dubinin-Astakhov [4]. In recent years, many algorithms
grow out of nature—such as particle swarm optimization (PSO), differ-
ential evolution (DE) and, more recently, the cuckoo search (CS)—have
been developed as an optimization tool for researchers. CS is a metaheuris-
tic search algorithm that was inspired by the obligate parasitism of some
cuckoo species by laying their eggs in the nests of other host birds [11].
In this chapter, adsorption of methane on zeolite 13X at various pres-
sures and temperatures by PSA process was studied. Several adsorption
isotherm models including Langmuir, Toth, Sips, UNILAN, and Dubinin-
Astakhov were used to model the adsorption process of methane on zeolite
A Study on Adsorption of Methane on Zeolite 199

13X. The parameters of these adsorption models were optimized using CS

algorithm.

8.2 EXPERIMENTAL

In this work, the data obtained from high-pressure adsorption of methane,

on zeolite 13X were used to modeling this process. The working data of
this research were obtained from the results of [12]. The data were mod-
eled by the Langmuir, Toth, Sips, UNILAN, and Dubinin-Astakhov iso-
therms. The models and the parameters used in the fits are the same and
are tabulated in Table 8.1. Fitting of the adsorption isotherm equations to
experimental data was done with MATLAB mathematical software (ver-
sion 7.6). The best fitting parameters were determined based on the mini-
mum value of objective function, square of residuals, Fobj[12]:

a Pmax n
Fobj = ∑∑∑ (Cexp − Ccal ) 2 (8.1)
T =1 P = 0 S =1

where Cexp and Ccal are the methane concentrations, experimental and cal-
culated, respectively,
Ti are the three different temperatures used, Pmax is the maximum pres-
sure of each isotherm, and S is the number of point per isotherm per gas.

TABLE 8.1 Traditional adsorption models that have been used to fit adsorption data for
zeolite 13X

Isotherm Model Adjustable Parameter

KP
Langmuir Ci = Cmi Cmi,K
KP + 1

( KP)1/ n
Toth Ci = Cmi Cmi,K,n
1 + ( KP)1/ n

KP
Sips Ci = Cmi Cmi,K,n
(1 + ( KP) n )1/ n
200 Applied Methodologies in Polymer Research and Technology

TABLE 8.1 (Continued)

Isotherm Model Adjustable Parameter

1 ⎡ 1 + KP0 exp(n) ⎤
Unilan Ci = Cmi Ln ⎢ ⎥ C ,K,n
2n ⎣1 + KP0 exp(−n) ⎦ mi

⎧ ⎡ RT ⎛ P sat ⎞ n ⎤ ⎫
⎪ ⎪
Dubinin-Astakhov Ci = Cmi exp ⎨− ⎢ ln ⎜ ⎟ ⎥C⎬mi,E,n
⎪⎩ ⎣⎢ E ⎝ P ⎠ ⎦⎥ ⎪⎭

8.3 RESULTS AND DISCUSSION

The adsorption isotherms of methane on zeolite 13X at 298, 308, and 323
K are shown in Figure 8.1, and the parameters of the fitting are reported
in Table 8.2. As illustrated in this the figure, the data were well fitted with
all models. Both the Toth and Dubinin-Astakhov models have a very good
flexibility to fit experimental data. However, Dubinin-Astakhov model
shows much lower objective function (Fobj) than the Toth model. Adsorp-
tion equilibrium of methane has been compared with previous literature
[4, 7] and showed good agreement with previously published data. Com-
paring the results obtained for this system to those obtained by [4] shows
that we get a much improved objective function by usign CS algorithm.
The improvement of both the Toth and Dubinin-Astakhov models was
0.15 and 1.47, respectively.

FIGURE 8.1 (Continued)

A Study on Adsorption of Methane on Zeolite 201

FIGURE 8.1 Methane adsorption equilibrium in zeolite 13X of (a) Langmuir, (b) Toth,
(c) Sips, (d) Unilan, and (e) Dubinin-Astakhov models.

TABLE 8.2 Optimum values for the fitting of the models

Cmi Hst K0 E
Isotherm n Fobj
(mol/kg-1) (kj/mol-1) (Mpa-1) (j/mol-1)

Longmuir 6.73 - 15.95 0.0013 - 0.76

Toth 11.99 0.526 15.33 0.0017 - 0.24

Sips 8.40 1.13 12.498 0.0036 - 0.32

UNILAN 7.45 1.34 15.52 0.0012 - 0.40

Dubinin-Astakhov 7.36 1.87 - - 0.0088 0.23

202 Applied Methodologies in Polymer Research and Technology

8.4 CONCLUSIONS

This chapter presented a study on the adsorption equilibrium isotherms of

methane on zeolite 13X at high-pressure process. The data were well fitted
with the Langmuir, Toth, Sips, UNILAN, and Dubinin-Astakhov models
according to the cuckoo search algorithm. Although all models have a very
good flexibility to fit experimental data, Dubinin-Astakhov model shows
much lower objective function (Fobj) than the other models. The data pre-
sented compare very well with previously reported values.

ACKNOWLEDGMENTS

The authors thank S. Cavenati, C. A. Grande, and A. E. Rodrigues at Uni-

versity of Porto for their data.

KEYWORDS

• Adsorption models
• Cuckoo search algorithm
• Methane
• Pressure swing adsorption

REFERENCES

1. Blaha, D.; Bartlett, K.; Czepiel, P.; Harriss, R.; Crill, P.; Natural and anthropogenic
methane sources in New England, Atmos. Environ. 1999, 33, 243–255.
2. Hui, K. S.; Chao, C. Y. H.; Kwong, C. W.; Wan, M. P.; Use of multitransition-metalion-
exchanged zeolite 13X catalysts in methane emissions abatement, Combust. Flame.
2008, 153, 119–129.
3. Wang, Y.; Hashim, M.; Ercan, C.; Khawajah, A.; Othman, R.; High Pressure Meth-
ane Adsorption on Granular Activated Carbons, 21st Annual Saudi-Japan Symposium,
November 2011, Catalysts in Petroleum Refining & Petrochemicals, Dhahran, Saudi
Arabia; 2011.
4. Behvandi, A.; Tourani, S.; Equilibrium modeling of carbon dioxide adsorption on zeo-
lites. World Acad. Sci. Eng. Technol. 2011, 76.
A Study on Adsorption of Methane on Zeolite 203

5. Salil, U.; Rege, R.; Yang, T.; Qian, K.; Buzanowski, M. A.; Air-purification by pres-
sure swing adsorption using single/layered beds. Chem. Eng. Sci. 2001, 56, 2745–
2759.
6. Jee, J. G.; Kim, M. B.; Lee, C. H.; Adsorption characteristics of hydrogen mixtures in a
layered bed: binary, ternary and five component mixtures. Ind. Eng. Chem. Res. 2001,
40, 868–878.
7. Cavenati, S.; Grande, C. A.; Rodrigues, A. E.; Adsorption equilibrium of methane,
carbon dioxide, and nitrogenon zeolite 13X at high pressures. J. Chem. Eng. 2004, 49,
1095–1101.
8. Moghadaszadeha, Z.; Towfighib, J.; Mofarahi, M.; Four-bed pressure swing adsorp-
tion for oxygen separation from air with zeolite 13X, iran international zeolite confer-
ence (IIZC’08), 29 April 2008, Tehran, Iran; 2008.
9. Mofarah, M.; Sadrameli, M.; Towfighi, J.; Four-bed vacuum pressure swing adsorp-
tion process for propylene/propane separation. Ind. Eng. Chem. 2005, 44, 1557–1564.
10. Yoshida, S.; Ogawa, N.; Kamioka, K.; Hirano, S.; Mori, T.; The study of zeolite mo-
lecular sieves for production of oxygen by using presuure swing adsorption. Kluwer
Acad. Pub. 1999, 5, 57–61.
11. Subotic, M.; Tuba, M.; Bacanin, N.; Simian, D.; Parallelized cuckoo search algorithm
for unconstrained optimization. World Sci. Eng. Acad. Soc. 2012.
12. Santos, J.C.; Cruz, P.; Regala, T.; Magalhaes, F. D.; Mendes, A.; High-purity oxygen
production by pressure swing adsorption. Ind. Eng. Chem. 2007, 46, 591–599.
This page intentionally left blank
CHAPTER 9

IMPORTANCE OF THE PHASE

BEHAVIOR IN BIOPOLYMER
MIXTURES
Y. A. ANTONOV and PAULA MOLDENAERS

CONTENTS

9.1 Introduction .................................................................................. 206

9.2 Materials and Methods................................................................. 207
9.3 Results and Discussion .................................................................211
9.4 Conclusions .................................................................................. 232
Keywords .............................................................................................. 233
References ............................................................................................. 233
206 Applied Methodologies in Polymer Research and Technology

9.1 INTRODUCTION

The importance of the phase behavior in biopolymer mixtures is evident

in many technological processes, such as isolation and fractionation of
proteins (see, e.g., Refs. [1–6]), and enzymes [7], enzyme immobilization
[8–9], encapsulation [10], and drug delivery [9, 11]. Aqueous, two-phase
systems are used in modern technological processes where clarification,
concentration, and partial purification are integrated in one step [12].
Thermodynamic incompatibility, or, in other words, segregative phase
separation determines the structure and physical properties of biopolymers
mixtures in quiescent state [13–15] and under flow [16–18] and plays an
important role in protein processing in food products [14].
From a technological viewpoint, especially important are biopolymer
systems that undergo liquid–liquid phase separation in a wide concen-
tration range, starting from low concentrations [19]. But whether phase
separation is desired or not, it is important for practical applications to
understand the underlying mechanisms and molecular interactions that
govern the phase behavior of a given system [20]. Despite the consider-
able amount of research in the field of segregating polymer mixtures,
the molecular interactions in the systems are inadequately understood,
although theoretical models have been proposed [21–28]. There have, as
of yet, been comparatively few studies on phase separation in mixtures
of similarly charged polyelectrolytes [29, 30]. Such systems may have ad-
vantages over uncharged systems in the separation of proteins due to
the tunable charge in the system arising from the dissociated counter
ions of the polyelectrolytes [29, 30]. Although the majority of biopolymer
mixtures show phase separation [14, 32], in most cases the phase separa-
tion takes places at critical total concentrations, which are much higher
(7–12 wt%) [31, 32] compared with those of synthetic polymers (less than
1–2 wt%). Unlike synthetic polymers with flexible chains, many proteins
are known to be relatively symmetric compact molecules and are usually
able to form solutions that can still be considered dilute for concentrations
tenfold higher than for synthetic polymers of the same molecular weight
[33].
The aims of this study is to induce demixing in semidilute and highly
compatible sodium caseinate/sodium alginate system (SC–SA) mixtures
in the presence of sodium salt of dextran sulfate (DSS) at pH 7.0, (above
the isoelectrical point of caseins), and to characterize phase equilibrium,
Importance of the Phase Behavior in Biopolymer Mixtures 207

intermacromolecular interactions, and structure of such systems by rheo-

small angle light scattering (SALS), optical microscopy (OM), phase anal-
ysis, dynamic light scattering (DLS), fast protein liquid chromatography
(FPLC), ESEM, and rheology. The molecular weight, charge, and topogra-
phy of the accessible surface of water-soluble complexes of proteins with
anionic polysaccharides differ markedly from the “free” proteins. There-
fore, it can be assumed that all these factors may affect the phase separa-
tion. In the present work, we focus our study on the phase transitions in
aqueous semidilute homogeneous sodium caseinate/sodium alginate (SC–
SA) systems with the total concentration of biopolymers 1, 5 wt per cent–
2.5 wt per cent, that is, much below the critical concentrations for phase
separation [17]. The phase state of the SC–SA mixtures is not sensitive to
changes in pH, ionic strength, and temperature in the quiescent state [31,
32] and under of shear flow [17]. Therefore, the effect of demixing that
can be reached for this system can be easily reproduced for other emul-
sions in which the phase equilibrium is more sensitive to physicochemical
parameters. Here, it will be explored how far this strategy of demixing
can be extended to other biopolymer pairs. For this reason, gelatin SA
and gelatin SC systems will be investigated to assess the generality of our
observations. In addition, the shear-induced behavior of the decompatibil-
ized semidilute SC–SA system will be presented and compared with that
of the “native” SC–SA system.
Alginate is an anionic polysaccharide consisting of linear chains of
(1–4)-linked ß-D-mannuronic and α-L-guluronic acid residues. These
residues are arranged in blocks of mannuronic or guluronic acid residues
linked by blocks in which the sequence of the two acid residues is predom-
inantly alternating [33, 34]. Casein is a protein composed of a heteroge-
neous group of phosphoproteins organized in micelles. These biopolymers
are well known, widely used in industry for their textural and structuring
properties [14, 31, 32, 33, 35], and the thermodynamic behavior of the
ternary water–caseinate–alginate systems is known from literature [17, 31,
32, 35].

9.2 MATERIALS AND METHODS

The caseinate at neutral pH is negatively charged, such as alginate and

DSS. The sodium caseinate sample (90% protein, 5.5% water content,
208 Applied Methodologies in Polymer Research and Technology

3.8% ash, and 0.02% calcium) was purchased from Sigma Chemical Co.
The isoelectric point is around pH = 4.7–5.2 [36]. The weight average mo-
lecular mass of the sodium caseinate in 0.15 M NaCl solutions is 320 kDa.
The medium viscosity sodium alginate, extracted from brown seaweed
(Macrocystis pirifera), was purchased from sigma. The weight average
molecular weight of the sample, Mw was 390 kDa [16]. Dextran sulfate,
DSS (MW = 500 kDa, Mn = 166 kDa, η (in 0.01 M NaCl) = 50 mL/g, 17%
sulfate content, free SO4 less than 0.5%) was produced by Fluka, Sweden
(Reg. No. 61708061 A, Lot No. 438892/1). The gelatin sample used is an
ossein gelatin type A 200 Bloom produced by SBW Biosystems, France.
The Bloom number, weight average molecular mass, and the isoelectric
point of the sample reported by the manufacturer are 207, 99.3 kDa, and
8–9, respectively.
Preparation of the protein/polysaccharide mixtures: Most experiments
were performed in the much diluted phosphate buffer (ionic strength, I =
0.002). To prepare molecularly dispersed solutions of SC, SA, gelatin, or
DSS with the required concentrations, phosphate buffer (Na2HPO4/NaH-
2
PO4, pH 7.0, I = 0.002, and 0.015) was gradually added to the weighed
amount of biopolymer sample at 298 K, and stirred, first for 1h at this
temperature and then for 1h at 318K. The solutions of SC, SA, and DSS
were then cooled to 296K and stirred again for 1h. The required pH value
(7.0) was adjusted by addition of 0.1–0.5M NaOH or HCl. The resulting
solutions were centrifuged at 60,000g for 1h at 296K or 313K (gelatin
solutions) to remove insoluble particles. Concentrations of the solutions
are determined by drying at 373K up to constant weight. The ternary wa-
ter–SC–SA systems with required compositions were prepared by mixing
solutions of each biopolymer at 296K. After mixing for 1 h, the systems
were centrifuged at 60,000 g for 1 h at 296K to separate the phases using
a temperature-controlled rotor.
Determination of the phase diagram: The effect of the presence of DSS
on the isothermal phase diagrams of the SC–SA system was investigated
using a methodology described elsewhere [36]. The procedure is adapted
from Koningsveld and Staverman [37] and [38]. The weight DSS/SC ratio
in the system, (q) was kept at 0.14. The threshold point was determined
from the plot as the point where the line with the slope−1 is tangent to the
binodal. The critical point of the system was defined as the point where
the binodal intersects the rectilinear diameter, which is the line joining the
centre of the tie lines.
Importance of the Phase Behavior in Biopolymer Mixtures 209

Rheo-optical study: A rheo-optical methodology based on small angle

light scattering (SALS) during flow, is applied to study in situ and on a
time-resolved basis the structure evolution. Light scattering experiments
were conducted using a Linkam CSS450 flow cell with a parallel-plate
geometry. A5 mW He–Ne laser (wavelength 633 nm) was used as light
source. The 2D scattering patterns were collected on a screen by semi-
transparent paper with a beam stop and recorded with a 10-bit progressive
scan digital camera (Pulnix TM-1300). Images were stored on a computer
with the help of a digital frame grabber (Coreco Tci-Digital SE). The opti-
cal acquisition set-up has been validated for scattering angles up to 18°.
The gap between the plates has been set at 1 mm, and the temperature was
kept constant by means of a thermostatised water bath. In-house developed
software was used to obtain intensity profiles and contour plots of the images
(New SALS SOFTWARE-K.U.L.). Turbidity measurements have been
performed by means of a photodiode.
Microscopy observations during flow have been performed on a Linkham
shearing cell mounted on a Leitz Laborlux 12 Pols optical microscope using
different magnifications.
Rheological measurements were performed using a Physica Rheom-
eter, type CSL2500 A/G H/R, with a cone-plate geometry CP50-1/Ti ~
diameter 5 cm, angle 0,993°, Anton Paar. The temperature was controlled
at 23°C by using a Peltier element. For each sample, flow curves were
measured at increasing shear rate ~ from 0.1 to 150s–1. The ramp mode
was logarithmic and the time between two measurements was 30s. Fre-
quency sweeps ~0.1–200 rad/s were carried out as well for a strain of 3.0
per cent, which was in the linear response regime. During the rheological
measurements, all samples were covered with paraffin oil to avoid drying.
Dynamic light scattering: Determination of intensity-weighted distri-
bution of hydrodynamic radii (RH) of SC, SA, and DSS solutions and their
mixtures was performed, using the Malvern ALV/CGS-3 goniometer. Con-
centration of the protein in protein-dextran sulfate mixtures was kept at 0.1
(w/w). For each sample, the measurement was repeated three times. The
samples were filtered before measurement through DISMIC-25cs (cellu-
lose acetate) filters (sizes hole of 0.22 μm for the binary water-casein and
water-dextran sulfate solutions and 0.80 μm for the protein–polysaccha-
ride mixtures). Subsequently, the samples were centrifuged for 30 sec at
4,000 g to remove air bubbles, and placed in the cuvette housing that was
kept at 23°C in a toluene bath. The detected scattering light intensity was
210 Applied Methodologies in Polymer Research and Technology

processed by digital ALV-5000 correlator software. The second-order cu-

mulant fit was used for the determination of the hydrodynamic radii. The
asymmetry coefficient (Z) of the complex particles was estimated by Debye
method based on determining the scattering intensity at two angles 45° and
135°, symmetrical to the angle 90°.
Zeta potential measurement: The ζ potential measurements of SC and
DSS solutions and their mixtures at different q values were performed at
23°C with a Malvern-Zetamaster S, model ZEM 5002 (England), using a
rectangular quartz capillary cell. The concentration of the protein in solu-
tions was 0.1 wt per cent, and the concentrations of DSS in the protein-
polysaccharide solutions were variable. All solutions were prepared in
phosphate buffer (Na2HPO4/NaH2PO4, pH 7.0, I = 0.002). The zeta potential
was determined at least three times for each sample. The zeta potential was
calculated automatically from the measured electrophoretic mobility, by
using the Henry equation:

Ue = εzρf/6πη, (9.1)

where Ue is electrophoretic mobility, ε is the dielectric constant, η is the

viscosity, and zρ is the zeta potential. The Smoluchowski factor, f = 1.5
was used for the conversion of mobility into zeta potential.
Environment scanning electron microscopy: Microstructural investiga-
tion was performed with the environment scanning electron microscope
Philips XL30 ESEM FEG. The instrument has the performance of a con-
ventional SEM but has the additional advantage that practically any mate-
rial can be examined in its natural state. The samples were freeze-fractured
in freon and immediately placed in the environment scanning electron mi-
croscope (ESEM). Relative humidity in the ESEM chamber (100%) was
maintained using a Peltier stage. Such conditions were applied to mini-
mize solvent loss and condensation, and control etching of the sample.
Images were obtained within less than 5 min of the sample reaching the
chamber. The ESEM images were recorded multiple times and on multiple
samples to ensure reproducibility.
Fast protein liquid chromatography or FPLC. Solutions of sodium ca-
seinate, (0.5 wt%), dextran sulfate (0.5 wt%) and their mixtures, contain-
ing 0.5 wt per cent of the protein and variable amount of dextran sulfate
were applied on a Superose 6 column (HR 10/30), Amersham Biosciences
mounted on an FPLC apparatus (Pharmacia, Uppsala, Sweden). Elution
Importance of the Phase Behavior in Biopolymer Mixtures 211

was performed at room temperature with phosphate buffer (5mM Na2H-

PO4/NaH2PO4, pH 7.0) 2 per cent (v/v) n-propanol (Riedel-de Haen, Seel-
ze, Germany) and 0.015 M NaCI. The samples and the elution buffer were
filtered through a 0.22 um sterile filter. The flow rate was 0.2 mL min-1
and the column was monitored by UV detection at 214 nm.
Determination of dextran sulfate content: The phenol-sufuric acid
method of [39]., was applied. 50 uL. 80 per cent (w/w) phenol in water and
5 mL sulfuric acid were added to the measured samples of 0.5 mL. After
30 min at room temperature, the absorbance at 485 nm was measured. A
calibration plot was constructed with D-glucose (Riedel-de Haen).

9.3 RESULTS AND DISCUSSION

9.3.1 DSS-INDUCED DEMIXING

The experimental results shown in this section have been obtained on wa-
ter (97.5 wt%)-SC (2.00 wt%)-SA (0.5 wt%) semidilute systems. This sys-
tem is located in the one-phase region far from the binodal line. To study
the effect DSS on the phase behavior, a flow history consisting of two
shear zones is used. First, a preshear of 0.5 s–1 is applied for 1,000 s (500
strain units) to ensure a reproducible initial morphology. Subsequently,
this preshear is stopped, and the sample is allowed to relax for 30 sec
leaving enough time for full relaxation of deformed droplets. Then, SALS
patterns are monitored.
The SALS patterns and the scattering intensity upon adding different
amount of DSS are shown in Figures 9.1 (a–f), and 9.2, starting from a
concentration of DSS as low as 2.08 10–3 wt per cent. In the absence of
DSS, no scattered light is observed (data are not presented). The presence
of even only 2.08 10–3 wt per cent DSS in the homogeneous system led to
appreciable increase the SALS pattern (Figure 9.1), and accordingly the
light scattering intensity (Figure 9.2). It is important to note that that the
SC-DSS system remains homogeneous in the DSS concentration range
studied here. Centrifugation of the SC-DSS systems (120 min, 60.000 g,
296 K) prepared at the same conditions did not show phase separation.
212 Applied Methodologies in Polymer Research and Technology

FIGURE 9.1 Effect of the concentration of DSS on the SALS patterns of water (97.5
wt%)-SC (2.00 wt%)-SA (0.5 wt%) single-phase systems. pH 7.0. I = 0.002 (phosphate
buffer); temperature 296 K; and concentrations of DSS in mixture, wt per cent: (a) 2.08 ×
10–3, (b) 4.10 × 10–3, (c) 1.61 × 10–2, (d) 7.50 × 10–2, (e) 0.15, (f) 0.29, and resulting DSS/
SC ratio: (a) 0.001, (b) 0.002, (c) 0.008, (d) 0.0375, (e) 0.075, and (f) 0.145.

FIGURE 9.2 Effect of the concentration of DSS on the scattering intensity of water (97.5
wt%)-SC (2.00 wt%)-SA (0.5 wt%) single-phase systems as a function of the distance from
the bean stop. The other parameters are the same as in Figure 9.1.
Importance of the Phase Behavior in Biopolymer Mixtures 213

When the DSS concentration in the SC–SA system increases, the SALS
pattern (Figure 9.1) and the scattering intensity (Figure 9.2) of the system
sharply grows. This indicates that the position of the system on the phase
diagram changes deeply into the two phase range. The corresponding mi-
croscopy images for the same concentrations of DSS and the same flow
conditions are shown in Figure 9.3. One can see that the phase separation
led to formation of liquid–liquid emulsions. At the lowest DSS concentra-
tion (2.08 10-3 wt%), the system contains ultrasmall droplets of the dis-
persed phase having a size of 2–3 μm. At higher DSS concentrations, the
size of the droplets increases significantly in agreement with SALS data
achieving more than 50 μm in diameter.

FIGURE 9.3 Microscopy images of water (97.5 wt%)-SC (2.00 wt%)-SA (0.5 wt%)
system after addition of different amounts of DSS. pH 7.0, I = 0.002 (phosphate buffer).
temperature 296 K. The other parameters are the same as in Figure 9.1.

To quantify the effect of DSS on phase equilibrium in semi-diluted

SC–SA system, the isothermal phase diagram of the system was deter-
mined in the presence of DSS, at DSS/SC weight ratio (q) = 0.14, plotted
in the classical triangular representation, and compared with that obtained
in the absence of DSS (Figure 9.4). The phase separation in the presence
of DSS has a segregative character with preferential concentrating of SC
and SA in different phases. The phase diagram of the initial system, with-
out DSS, is characterized by a high total concentration of biopolymers at
the critical point (Cct = 62.9 g/L), and a strong asymmetry (Ks = 15.5).
214 Applied Methodologies in Polymer Research and Technology

FIGURE 9.4 Isothermal phase diagrams of the W–SC–SA system. pH 7.0, I = 0.002
(phosphate buffer), 296 K. 1, In the absence of DSS and 2, in the presence of DSS, at DSS/
SC weight ratio (q) = 0.14.

The presence of DSS affects dramatically the phase separation, signifi-

cantly increasing the concentration range corresponding to two phase state
of the system. The total concentrations of biopolymers at the critical point
decreases to 10.6 g/L. The phase separation is observed at total concentra-
tions of biopolymers just above 1 wt per cent, i.e., level of compatibility of
the biopolymers after an addition of DSS seems to be one of the smallest
known for biopolymer mixtures (see, e.g., [40, 41]). The decrease in com-
patibility of casein and alginate is especially surprising when taking into
account that the phase composition of this system is weakly dependent on
many physicochemical factors, such as pH (in the pH range from 7 to 10),
ionic strength and temperature (from 5 to 60°C) [17, 32, 34].
Importance of the Phase Behavior in Biopolymer Mixtures 215

9.3.2 RHEOLOGICAL BEHAVIOR OF THE DEMIXED SYSTEMS

For the rheological investigations, the homogeneous W-SC (2.0 wt%)-SA

(0.5 wt%) system (point A on the phase diagram, Figure 9.4) was charac-
terized before, and after addition of DSS at the DSS/SC weight ratio, q =
0.045, and q = 0.15, respectively. The latter two systems were two-phase
ones with the content of the casein enriched phase 15 w/w, and 55 per cent
w/w accordingly. The experimental flow protocol applied was the same
as the one used for rheo-SALS. The mechanical spectrum and flow curve
were determined to characterize the state of the systems through their vis-
coelastic behaviors. It has been shown [42] that at moderately low-shear
rates, the biopolymer emulsions can be regarded as conventional emul-
sions and various structural models that are available in the literature for
prediction of the morphology in these emulsions can also be used for pre-
diction of the structure in aqueous biopolymer emulsions.
The evolution of the mechanical spectrum was investigated as a func-
tion of DSS concentration. These viscoelastic behaviors were monitored
and compared with the behavior of the W–SC–SA system without DSS.
The dynamic modulus G′ (elastic) and G″ (viscous) were measured with
frequency sweep experiments at a constant strain of 3 per cent, which was
checked as being in the linear regime. The obtained data are presented in
Figure 9.5.

FIGURE 9.5 Dynamic spectra of single-phase W–CS (2 wt%)-SA (0.5 wt%) system,
and two phase W–CS (2 wt%)-SA (0.5 wt%)-DSS systems. pH 7.0, I = 0.002 (phosphate
buffer), 296 K.
216 Applied Methodologies in Polymer Research and Technology

FIGURE 9.6 Flow viscosity of single-phase W–CS (2 wt%)-SA (0.5 wt%) system, and
two-phase W–CS (2 wt%)-SA (0.5 wt%)-DSS Systems, after application of increasing
shear rates. pH 7.0, I = 0.002 (phosphate buffer), 296 K.

For the single-phase system, and the system containing 0.09 wt per cent
DSS, G′ was too low to be measured accurately. Under these conditions,
the system behaves as purely viscous liquid with the curve of G″ versus
frequency displaying a slope of one on a double logarithmic graph. In the
present of DSS, the system undergoes phase separation, and this transition
leads to an appreciable increase of the moduli. The elastic properties of
the decompatibilized W–SC–SA system were mainly induced by the pres-
ence of the DSS. In the presence of high ionic strength (0.25, NaCl), when
electrostatic interactions were suppressed the mechanical spectrum of the
system (q = 0.14) becomes insensitive to the presence of DSS (data are not
presented). Flow curves determined at the same concentrations show an
increase in viscosity for the demixed systems, especially remarkable at a
low shear rates (Figure 9.6).
More detailed experiments were then carried out on the single phase
W–SC (4 wt%)-DSS (variable), and W–SA (0.5 wt%)-DSS (variable) sys-
tems to understand how DSS affects the mechanical spectrum of the casein
and alginate solutions, and accordingly the coexisting phases. The behav-
ior of these solutions in the presence of sulfated polysaccharide is clearly
different (Figures 9.7 and 9.8), the casein-enriched phase is sensitive to
the presence of DSS, whereas the viscoelastic properties of the alginate-
Importance of the Phase Behavior in Biopolymer Mixtures 217

enriched phase in the presence of DSS remain almost unaltered. As re-

ported in Figure 9.7a, the dependence of the G″ on the DSS/casein ratio
has an extreme character, with a maximum at a DSS/casein ratio around
0.14. In the presence of even small amounts of DSS (0.01–0.05 wt%), a
dramatic increase of the G″ of the emulsion takes place. Thus, in the pres-
ence of 0.5 wt per cent of DSS (at q = 0.14) and at a frequency 1 rad/s,
G″ values is more than 1,400 times, higher compared with those of the
single-phase system with almost the same composition. From theory, we
know that such dependences are typical for the formation of interpolymer
complexes [42]. Similar changes were observed for the viscosity (Figure
9.8 ab). At q = 0.14 and a shear rate of 10 s–1, the viscosity is more than 940
times higher compared with those of the single-phase system with almost
the same composition (Figure 8b). It is important to note that in the shear
rate range from 0.1 to 150 s–1, we did not find any difference in the flow
curves obtained in conditions with increasing versus decreasing shear rate
(data are not presented). It can be assumed that the dramatic changes in
rheological behavior of the casein-alginate system in the presence of DSS
are due to interactions of the casein molecules with the DSS molecule.

FIGURE 9.7 (a), G″ of W–SA(0.5 wt%),W-SA(0.5 wt%)-DSS, and W-SC(4 wt%)—

DSS, systems at different q values, (b) the dependence of G″ on q values for W–SC(4
wt%)—DSS, system at frequency 1.0 rad/s. pH 7.0, I = 0.002 (phosphate buffer), 296 K.
218 Applied Methodologies in Polymer Research and Technology

FIGURE 9.8 (a) Dependences of flow viscosity of W–SC(4 wt%), W–SA(0.5 wt%),
and W–SC (4 wt%)—DSS (var) systems (b) and the dependence of flow viscosity of the
W–SC–DSS system on q values at shear rate 1.0 s–1. pH 7.0, I = 0.002 (phosphate buffer),
296 K.

It can be suggested that casein interacts with DSS, and this interac-
tion may have an effect on the phase separation. Note that the viscosity of
the demixed system in Figure 9.8 decreased from 5.72 to 1.74 Pa s with
increasing shear rate from 0.1 to 150 sec–1, which highlights the shear
thinning behavior of the demixed system, indicating a structural change.
The result was striking since most concentrated protein–polysaccharide
mixtures can be shear thinning only due to the polysaccharide relaxations.
In the absence of structure-induced formation, the rheological behavior
of concentrated polysaccharide solutions is monotonically shear thinning;
the viscosity varies between two extremes ηo and η∞. A possible additional
mechanism would be the breakdown of structures due to the breakup of
physical bonds at high shear. This structure was most probably due to the
electrostatic interactions between SC and DSS. Indeed, in the presence of
0.25 M NaCl, when no attractive interaction took place, no shear thinning
behavior was observed (data are not shown). More detailed experiments
were then carried out to understand the mechanism of demixing.
Importance of the Phase Behavior in Biopolymer Mixtures 219

9.3.3 INTERMACROMOLECULAR INTERACTIONS AND THE

MECHANISM OF DEMIXING IN SC–SA–DSS SYSTEM

An important property of the demixed semidilute SC–SA systems de-

scribed above is their high stability against homogenization and low
sensitivity to change in temperature. Thus, for the mixtures with differ-
ent composition, we observed constancy of absorption values at 500 nm
during 6h storage, as well as in processes of their heating from +5°C to
70°C. The results obtained (Figures 9.7 and 9.8) show the presence the
intermacromolecular interactions between SC and DSS. Usually, coulomb
protein–polysaccharide complexes are formed only in the vicinity of the
isoelectric point of the protein [44]; but for several systems, formation of
soluble protein—polysaccharide complexes has been registered even at
pH 6–8.0 [45–47]. A beneficial consequence of complexation of sulfated
polysaccharide with caseins at pH values above IEP is the protection af-
forded against loss of solubility as a result of protein aggregation during
heating or following high-pressure treatment [48, 49].
The mechanism of this protection has been unclear until now. Snoeren,
Payens, Jevnink and both, assumed [50] that there is a nonstatistical dis-
tribution of positively charged aminoacid residues along the polypeptide
chain of kappa casein molecules and, as a consequence, the existence of a
dipole interacting by its positive pole with sulfur polysaccharide is respon-
sible for complex formation in such systems.
Many scientists suppose [51, 52] that nonelectrostatic forces, hydro-
phobic, and (or) hydrogen bonds play a determinant role in this process.
In the case of sulfated polysaccharides, this assumption is confirmed by
experimental data showing the capacity of the sulfate groups to form hy-
drogen bonds with the protein cationic groups [53].
Introduction of NaCl in the initial buffer results in full insensitivity
of the viscosity and the phase diagram of the SC–SA system to the pres-
ence of DSS in all the q range studied. On the other hand, an addition of
0.2 M NaCl in the SC–SA–DSS system at q = 0.14 after a 24 h storage
results in a sharp increase in the level of compatibility of SC with SA to
that of SC–SA solution alone. This shows that the complexes are formed
and stabilized via electrostatic interaction, rather than through hydrogen
bonds formation or hydrophobic interaction. The role of salt is to “soften”
the interactions, which is equivalent to making the electrostatic binding
constant smaller.
220 Applied Methodologies in Polymer Research and Technology

To study intermacromolecular interactions in the process of demixing

of the SC–SA system, at first, we focus our attention to the interaction be-
tween SC and DSS in aqueous solutions within the region of pair interac-
tion. To this aim, we have chosen SC and DSS concentrations low enough
to exclude or considerably diminish effects of possible aggregation. This
allows us to single out information on interaction processes between the
two types of macromolecules, well separated from the subsequent aggre-
gation process. DLS can provide information about the hydrodynamic ra-
dius of proteins and polysaccharides and about the binding of ligands to
these types of macromolecules. Figure 9.9 shows the intensity-weighted
distribution of hydrodynamic radii (RH) of solutions of sodium caseinate,
dextran sulfate and their mixtures with the concentration of the protein equal
to 0.1 (w/w), that is, at the total concentrations below the critical concentra-
tion of phase separation of SC–SA system (see Figure 9.4). At 296 K, mol-
ecules of SC and DSS have RH values 119 nm and 250 nm, respectively.

FIGURE 9.9 The intensity-weighted distribution of hydrodynamic radii (RH) of solutions

of sodium caseinate, dextran sulfate and their mixtures. Concentration of SC is equal to 0.1
(w/w). pH 7.0, I = 0.002 (phosphate buffer), 296 K.
Importance of the Phase Behavior in Biopolymer Mixtures 221

An addition of DSS to SC solution at DSS/SC weight ratios ranging (q)

from 0.025 to 0.05 leads to significant increase in the RH toward the values
RH for DSS solution. At higher q values = 0.14, RH of the mixed associates
achieve the values RH for DSS, and their size does not change with the
further increase of q values. This is an indication of intermacromolecular
interaction of the casein molecules with DSS and formation of complexes.
At q = 0.14, function of the intensity-weighted distribution of hydrodynamic
radii (RH) is placed completely outside that describing free SC.

FIGURE 9.10 Dependence of the ratio of the scattering intensity, R at 45° and 135° on the
concentration of casein in the SC–DSS mixture at q = 0.14. pH 7.0, I = 0.002 (phosphate
buffer), 296 K.

The asymmetry coefficient (Z) of the complex associates was estimat-

ed by Debye method based on determination of the scattering intensity,(R)
at two angles 45° and 135° symmetrical to the angle 90° and subsequent ex-
trapolation of the R45°/R/135° to zero concentration. The results obtained
are presented in Figure 9.10. The complex associates are asymmetric with
Z values equal to 0.7.
222 Applied Methodologies in Polymer Research and Technology

Figure 9.11 presents zeta potential values and the total concentration
of the biopolymer at the critical point Ctcr as a function of the DSS/SC
ratio, q. After an addition of DSS the negative value of the zeta potential
increases and Ctcr decreases achieving correspondingly the maximal and
minimal values at q = 0.14.

FIGURE 9.11 Dependence of zeta potential, and the total critical concentration of
biopolymers corresponding to phase separation of W–SC–SA–DSS system on q. SC/SA
weight ratio is 4. pH 7.0, I = 0.002 (phosphate buffer), 296 K.

Once the negative charge of a protein becomes higher in the presence

of DSS, interactions between casein molecules could be hindered by an
overall effect of electrostatic repulsion. Thus, an increase in the net charge
of casein due to DSS binding could lead to an enhancement in the extent of
such repulsions, contributing to the suppression of the further association
and aggregation. Obviously, at pH = 7.0, the total charge of the high-mo-
lecular-weight DSS molecule is higher than the total positive charge of the
relatively small SC molecule. This gives the possibility to regard complex
formation between these biopolymers (similarly to other weak-polyelectro-
lyte—strong-polyelectrolyte interactions [54, 55]) as a mononuclear
Importance of the Phase Behavior in Biopolymer Mixtures 223

association in which the DSS molecule is the nucleus and the casein mol-
ecule is a ligand. Therefore, the formation of casein—DSS complex can be
regarded as the reaction of few casein molecules successively joining one
molecule of DSS nucleus. Note that at pH = 7.0, (experimental conditions)
all the cationic groups of casein, as well as all the sulfate groups of DSS
are ionized. It easy to show that at q° = q* (0.135), the ratio of the total
amount of sulfate groups in DSS molecule and cationic groups in casein
molecule ( [S ] ) is close to unity. Actually, the total amount of cationic
−

[Cat ] +

groups in casein molecule is 0.76 mmol/g [50, 56] and the content of
sulfur groups in DSS molecule is equal to 5.43 mmol/g [57]. Therefore,
[S − ] = q 5.43 . At q* = 0.135, one can obtain [S − ] = 0.964.
[Cat + ] 0.76 [Cat + ]
Figure 9.12 presents the chromatograms of the initial solutions of SC
(0.25 wt%) and DSS (0.25 wt%), and the SC–DSS system (q = 0.14, con-
centrations of SC = 0.25 wt% and 1.0 wt%), showing distribution of the
protein, polysaccharide, and complex associates in the chromatographic
fractions.

FIGURE 9.12 Chromatograms of the initial solutions of SC and DSS, and the SC–
DSS system (q = 0.14), showing distribution of the protein, polysaccharide, and complex
associates in the chromatographic fractions at concentrations of the protein 0.1 wt per cent
and 1.0 wt per cent. pH 7.0, I = 0.015 (phosphate buffer), 296 K.
224 Applied Methodologies in Polymer Research and Technology

Free SC exhibited at pH 7.0 two unequal peaks. The first peak (83%
from the total square) presents SC molecules, and the second one (17%
from the total square) corresponds to the SC associates. Estimation of the
molecular weights of these components on the basis of known molecular
weights of alpha, beta, and gamma gelatins gave 260 kDa and 380 kDa
accordingly. The weight average molecular weight of both fractions was
about 300 kDa.
DSS exhibited at the same conditions a weak wide signal in the ex-
cluded volume. The chromatograms of the SC (0.25 wt%)-DSS systems
at q = 0.14 gave a new high-molecular-weight component corresponding
to excluded volume and the peak corresponding to the elution volume of
the free (unbounded SC). It is interesting to note that at concentration of
SC below the critical concentration of the phase separation, the degree of
conversion of the SC in water soluble complex with DSS is low (30%),
and mainly the high molecular fraction of SC interact with DSS. The in-
teraction becomes stronger when the concentration of the SC in the mix-
ture increases up to 1.0 wt% (inside two-phase range of SC–SA system
in the presence of DSS (q = 0.14). In such conditions 83 per cent of SC
form complex with DSS. Taking into account that the maximal yield of the
complex takes place at q = 0.14, knowing the weight-average molecular
weights of SC and DSS, and the degree of the protein conversion in pro-
tein–polysaccharide complex, we can roughly evaluate the SC/DSS molar
ratio in the complex in the selected conditions corresponding to demixing
of the mixed solutions of SC (2 wt%)-SA (0.5 wt%) in the presence of
DSS (q = 0.14). Simple calculation showed that about 10 molecules of
SC join to 1 DSS molecule, forming large associates with high molecu-
lar weight. Systematic experimental data concerning dependence of C*t
upon the radius, or molecular weight of synthetic or natural polymers are
unknown until now, although it is generally accepted that thermodynamic
compatibility of polymers decreases with increase in molecular weights. It
has been shown recently [58] that the total concentrations of biopolymers
at the threshold point (C*t) for casein-guar gum system changes in accor-
dance to C*t ∞ Mcasw–0.27, where Mcasw is molecular weight of caseins. This
dependence has been established in a wide range of Mcasw (from 25 kDa to
160.000 kDa). In that way, formation of large SC–DSS associates should
decrease considerably compatibility of SA with bonded SC compared with
that of “free” casein molecules that was observed in present work (Figure
9.4).
Importance of the Phase Behavior in Biopolymer Mixtures 225

9.3.4 COMMONALITY OF THE DDS-INDUCED DEMIXING

AT REST

The other question that arises from the demixing phenomenon in diluted
biopolymer systems in the presence of DSS is, what is the key factor deter-
mining complex formation between DSS and caseins at pH 7.0 (far from
the pH value corresponding to IEP of caseins)? Is the high local charge
density of the positively charged kappa casein responsible for that, or it is
mainly determined by the structural features of DSS, such as the concen-
tration of sulfate groups, charge density, and conformation of the polysac-
charide? Specific interaction between k-casein and carrageenan has been
ascribed by [50]., to an attraction between the negatively charged sulfate
groups of carrageenan and a positively charged region of κ-casein, located
between residues 97 and 112.
It does not occur with the other casein types. Since the positive patch
on κ-casein is believed to have a size of about 1.2 nm and is surrounded
by predominantly negatively charged regions, the importance of the in-
tersulfate distances is unmistakable. To extend, the Snoeren suggestion to
our system, containing more stronger polyelectrolyte than carrageenan, or
to reject it, we investigated the effect of DSS on the phase equilibrium in
semi-dilute single-phase biopolymer systems containing the protein (gela-
tin) with the statistical distribution of the positively charged functional
groups. Two systems were under consideration, gelatin type A–SA, and
gelatin-type A–SC. The former is a single-phase one in water over a wide
concentration range, and it undergoes phase separation at ionic strength
above 0.2 [59].The latter system undergoes phase separation only at a very
high ionic strength (above 0.5) [60] and is characterized by a very high
total concentration of the biopolymer (>15–20 wt%) at the critical point
[61].
The compatibility of these biopolymer pairs in water in the presence
of DSS (at q = 0.14) was studies. The phase separation of both systems in
the presence of DSS was established, and the binodal lines for them were
determined (Figure 9.13). The binodals for the systems without DSS are
placed outside the concentration range studied. In both systems the phase
separation leads to formation of water in water emulsions with liquid co-
existing phases (Figure 9.13). Two important conclusions can be made
from these data. First, the DSS-induced phase separation in semi-dilute
226 Applied Methodologies in Polymer Research and Technology

biopolymer solutions at rest is a rather general phenomenon not an excep-

tional case.

FIGURE 9.13 Shift of the Bimodal Line of the W-gelatin type A-SA, and W-SC-gelatin
Type A Systems in the Presence of DSS at DSS/Protein Weight ratio 0.14; Photo Images
and Microscopy Images of the Demixed W-gelatin type A(6 wt%)–SA (0.5 wt%), and
W-SC (16 wt%)-gelatin type A (16 wt%) systems (points A on phase diagrams). W-gelatin
type A-SA System was Prepared at pH 5.0, and W-SC-gelatin type A System was Prepared
at pH 7.0.

Second, the structural features of DSS molecules is the more impor-

tant factor determining complex formation of SC with DSS and subse-
quent demixing of the single-phase semi-dilute systems, rather than the
characteristics of the distribution of the positively charged groups in the
protein molecules. The last conclusion is in agreement with the FPLC data
(Figure 9.12). As can be seen, the degree of the protein conversion in com-
plex achieves 80 per cent, whereas the content of kappa casein in SA is only
12–14 per cent [62]. It is known that the sulfate groups of DSS are more
closely packed than that of κ-carrageenan (0.5 nm for DSS and 1.2 nm for
carrageenan [62, 63]. The latter can allow for the attractive forces to over-
come the repulsive forces acting outside the positive patch. Bowman, Ru-
binstein, and Tan, characterizing complex formation between negatively
charged polyelectrolytes and a net negatively charged gelatin by light scat-
Importance of the Phase Behavior in Biopolymer Mixtures 227

tering, suggested [64] that the protein is polarized in the presence of strong
polyelectrolyte. Junhwan and Dobrynin have recently presented the results
of molecular dynamics simulations of complexation between protein and
polyelectrolyte chains in solution [65]. They found that protein placed
near polyelectrolyte chains is polarized in such a way that the oppositely
charged groups on the protein are close to the polyelectrolyte, maximizing
effective electrostatic attraction between the two, whereas the similarly
charged groups on the protein far away from the polyelectrolyte minimize
effective electrostatic repulsion. In dilute and semi-dilute solutions, which
are subjects of our study, polyampholyte chains usually form a complex
at the end of polyelectrolyte chains resulting from the above polarization
effect by polyelectrolyte. We believe that polarization-induced attraction
is the main mechanism of complexation SC and DSS.

9.3.5 DISCUSSION ON THE STRUCTURE OF THE SC–DSS

COMPLEXES AND SC ENRICHED PHASE OF THE DEMIXED
SC–SA SYSTEM

From study of polyelectrolyte complexes, we know that interaction be-

tween oppositely charged polyelectrolyte’s leads to partial or complete
neutralization of charges, complexes remain soluble or precipitate, and
in some cases gel-like networks are formed. If neutralization of charges
is significant, the so-called “scrambled egg” compact structure will be
formed. When neutralization of charges is far from complete, a “ladder”
structure of complex can be formed [66].
The results of the zeta potential measurements, DLS, and flow experi-
ments shown that the negative charge of the SC increases during interac-
tion with DSS, and the maximal binding takes place at approx 0.14 DSS/
SC weight ratio. Such features of the intermacromolecular interactions
do not promote formation of the “scrambled egg” structure, because DSS
molecule having many combined SC molecules and considerable negative
charge can not be fold. Therefore, the ladder structure is more preferable
for the system (Figure 9.14a). The overage size of the SC–DSS complex
associates established from the DLS experiments is 0.2 um. Such a length
scale would be in line with the fact that the SC/DSS solution is slightly
turbid. This turbidity arises from a length scale in the micrometer range.
228 Applied Methodologies in Polymer Research and Technology

FIGURE 9.14 Schematic representation of the possible structures of (a) ladder-like and
(b) gel-like. The long chain represent DSS molecule and the balls represent casein chains.

Obviously, heterogeneities on a micrometer scale were formed. If SC/

DSS solution was made of a homogeneous structure of polymers on the
nanometer scale, it would be transparent. In the presence of free polymer-
SA, complex associates of SC and DSS undergo further association and
the system becomes two phasic. This suggestion finds confirmation in the
flow experiments; viscosity of the demixed SC–SA system is considerably
higher than that of undemixed SC–SA system having the same concen-
trations (Figure 9.6). This difference is even much higher in the case of
higher protein concentration in the single-phase SC–DSS system (Figure
9.8), this is a clear indication of association of the “ladder” structure of the
complex associates, and formation of network (Figure 9.14b).

9.3.6 SHEAR-INDUCED BEHAVIOR OF THE SC–SA SYSTEM

IN THE PRESENCE OF DSS

The experimental results shown in this section have been obtained on a

water (97.5 wt%)-SC (2.0 wt%)-SA (0.5 wt%)-DSS (2ּ103 wt%) system.
It contains 99 wt per cent of the SC enriched phase and 1 wt per cent of
Importance of the Phase Behavior in Biopolymer Mixtures 229

the SA enriched phase, which have been mixed by hand, typically result-
ing in a very fine morphology. This emulsion is located in the two-phase
region not far from the binodal line. The coexisting phases have Newtonian
viscosities at 296 K, of 0.03 Pa·s and 0.02 Pa·s for the SC enriched and the
SA-enriched phase, respectively.
To study the effect of flow on the phase behavior, a flow history con-
sisting of three shear zones is used (Figure 9.15). First, a preshear of 0.5 s–1
is applied for 1,000 s (500 strain units). It has been verified that this pro-
cedure leads to a reproducible initial morphology. Subsequently, this pres-
hear is stopped and the slightly deformed droplets are allowed to retract to
a spherical shape. The resulting droplet radius is of the order of 5 micron.
Finally, the shear rate is suddenly increased to a high value for 80 s, and
after stopping flow the evolution of the SALS patterns are monitored.

FIGURE 9.15 Schematic r of the shear history.

The evolution of the SALS patterns after cessation of steady-state

shear flow at 60 s–1, 100 s–1, and 150 s–1 is shown in Figure 9.17. In each
experiment, a freshly loaded sample has been used. As can be seen at all
shear rates selected, the SALS patterns become more intensive just after
cessation of flow. The higher the shear rate applied, the more intensive
the SALS pattern becomes. This is a clear indication of shear induced
demixing in SC–SA system in the presence of DSS. After cessation of
shear flow, the light intensity is slowly decreasing (Figure 9.16), but the
230 Applied Methodologies in Polymer Research and Technology

complete recovery of the initial SALS pattern takes place only after 1–2
h (data are not presented). In Figure 9.17 microscopy images correspond-
ing to the same emulsion as in SALS experiments are presented first, after
preshear of the emulsion at 0.5 s–1 for 1,000 s with subsequent cessation of
steady-state shear flow at 60 s–1(a), 100 s–1 (b), and 150 s–1. One can see an
appreciable increase of the droplet size after cessation of high shear rate
flow, in accordance with SALS data.
In Figure 9.18, the light scattering intensity of semidilute demixed
water (97.5 wt%)-SC (2.0 wt%)-SA (0.5 wt%)-DSS (2.10–3 wt%) system
after preshear (curve 1) and just after cessation of flow at 60 s–1 (curve 2)
is compared with that of water (87.8 wt%)-SC (12.2 wt%)-SA (0.1 wt%)
system, containing 1 wt per cent SA enriched phase at the same shear his-
tory (curves 3 and 4). It is seen that the increase in the light intensity after
cessation of flow takes place for both systems, however for the former
system the light intensity increased much higher that for the latter one.

FIGURE 9.16 Evolution of the SALS patterns of water (97.5 wt%)-SC (2.00 wt%)-SA
(0.5 wt%)-DSS (2 10–3 wt%) after cessation of a high shear rate flow. Shear rates and times
of the shear as indicated on the figure. pH 7.0. I = 0.002 (phosphate buffer). Temperature
296 K. The SALS pattern of water (97.5 wt%)-SC (2.00 wt%)-SA (0.5 wt%)-DSS (2·10–3
wt%) system before high shear rate is shown in Figure 9.1a.
Importance of the Phase Behavior in Biopolymer Mixtures 231

FIGURE 9.17 The evolution of microscopy images of water (97.5 wt%)-SC (2.00 wt%)-
SA (0.5 wt%)-DSS (2 10–3 wt%) system before high shear rate flow (a) and just after
cessation of a high shear rate flow. shear rate: b) 60 s–1, c) 100 s–1, and d) 150 s–1. pH 7.0. I
= 0.002 (phosphate buffer). Temperature 296 K.

FIGURE 9.18 Dependence of the scattering intensity of the demixed water (97.5 wt%)-
SC (2.00 wt%)-SA (0.5 wt%)-DSS (2ּ10–3 wt%) system after preshear (curve 1), and just
after cessation of flow at 60 s–1 (curve 2) and water (87.8 wt%)-SC (12.2 wt%)-SA (0.1
wt%) system after preshear (curves 3), and just after cessation of flow at 60 s–1, on the
distance from the bean stop. Both systems contain 1.0 wt per cent SA-enriched dispersed
phase.
232 Applied Methodologies in Polymer Research and Technology

These observations can be explained on the basis of a comparison of

the molecular weights of the “free” SC and SC, combined with DSS (see
Figure 9.12). The molecular weight of the latter one is much higher than
that of the former one. Note that the second virial coefficients on the mo-
lar scale, related to pair interactions of similar SC macromolecules, A22
depends on the molecular weight inversely [67]. Therefore, according to
conditions of the phase separation in biopolymer systems in flow [68]:

A23 > A2 A3 (9.2)

in which Aij are the second virial coefficients on the molar scale, related
to pair interactions of similar (2-protein, 3-polysaccharide) and dissimi-
lar macromolecules, the protein-polysaccharide mixture containing mac-
romolecules with lower values of A22 will be more predisposed to shear
induced demixing.

9.4 CONCLUSIONS

It well known that phase equilibrium in aqueous system containing casein

and linear acid polysaccharide is weakly sensitive to changes of the main
physico-chemical parameters, such as pH, ionic strength, and temperature.
This is the case both at rest [17, 31, 32, 34] and under shear flow [69].
The weak intermacromolecular interactions caused by the presence of a
complexing agent in two phase biopolymer mixture can affect its phase
equilibrium and morphology. In this communication, the attempt was per-
formed to induce demixing in semidilute and highly compatible sodium
caseinate/sodium alginate system (SC–SA) mixtures in the presence of so-
dium salt of dextran sulfate (DSS) at pH 7.0, (above the isoelectrical point
of caseins), and to characterize phase equilibrium, intermacromolecular
interactions, and structure of such systems by rheo-small angle light scat-
tering (SALS), optical microscopy (OM), phase analysis, dynamic light
scattering (DLS), fast protein liquid chromatography (FPLC), ESEM, and
rheology.
Addition of dextran sulfate sodium salt (DSS) to the semi-dilute single
phase SC–SA system, even in trace concentrations (10–3 wt%), leads to
segregative liquid–liquid phase separation, and a substantial increase in
storage and loss moduli of the system. The degree of the protein conver-
Importance of the Phase Behavior in Biopolymer Mixtures 233

sion in the complex grows, when the concentration of SC in the system

increases from 1 to 2 wt per cent. It is also established here that demix-
ing of semi-dilute biopolymer mixtures, induced by the minor presence
of DSS is a rather common phenomenon, because it is also was observed
here for other biopolymer pairs. At high shear rates SC becomes even less
compatible with SA in the presence of DSS than at rest. Experimental ob-
servations suggest that the approach for inducing demixing of semidilute
and highly compatible biopolymer mixtures by physical interactions of the
constituents is a promising tool for regulation of biopolymer compatibility
and achieving better predictions of phase behavior of aqueous protein-
charged polysaccharide systems.

KEYWORDS

• Biopolymer mixture
• Complex formation
• Demixing
• Rheo-optics
• Structure formation

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 Applied Methodologies in Polymer Research and Technology

Hamrang
Balköse
Applied Methodologies
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projects focusing on nanosized zinc borate production, ZnO polymer composites, zinc borate
Reviewers and Advisory Board Members: Gennady
lubricants, antistatic additives, and metal soaps. ISBN:ISBN: E. Zaikov, DSc, and A. K. Haghi, PhD
978-1-77188-040-4
978-1-77188-040-4 DevrimAbbas
Balköse,
Devrim Hamrang,
Balköse,
Editors PhD PhD
PhD
Reviewers and Advisory Board Members: Gennady E. Zaikov,
ISBN:DSc, and A. K. Haghi, PhD
978-1-77188-040-4
9 0 0 0 09 0 0 0 0
Abbas Hamrang,
Devrim Balköse,
PhD PhD

ISBN: 978-1-77188-040-4
90000
Devrim Balköse, PhD
90000
9 7819
771 880404
781 771 88 040 4

9 781 771 88 040 4

www.appleacademicpress.com 9 781 771 880404