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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
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Devrim Balköse,
PhD PhD

ISBN: 978-1-77188-040-4
90000
Devrim Balköse, PhD
90000
9 7819
771 88
781 04088
771 4 040 4

9 781 771 88 040 4

www.appleacademicpress.com 9 781 771 88 040 4

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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8 8. A Study on Adsorption of Methane on
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Hydrocolloids. 2009, 23, 262– 270. This page intentionally
left blank Applied Methodologies in Polymer Research and
Technology Editors PhD PhD Abbas Hamrang, Devrim Balköse, A
p p l i e d M e t h o d o l o g i e s i n a n d P o l y m e
r R e s e a r c h T e c h n o l o g y

Applied Methodologies in Polymer Research and Technology

This book covers a broad range of polymeric materials and

presents the latest developments

and trends in advanced polymer materials and structures. It

discusses the developments of

advanced polymers and respective tools to characterize and

predict the material properties

and behavior. This book has an important role in advancing

polymer materials in macro and

nanoscale. Its aim is to provide original, theoretical, and

important experimental results that

use non-routine methodologies. It also includes chapters on

novel applications of more familiar

experimental techniques and analyses of composite problems

that indicate the need for new

experimental approaches.

This new book:

• highlights some important areas of current interest in

key polymeric materials and

technology

• gives an up-to-date and thorough exposition of the

present state of the art of key

polymeric materials and technology

• describes the types of techniques now available to the

engineers and technicians and

discusses their capabilities, limitations, and applications

• provides a balance between materials science and

chemical aspects and basic and

applied research

• focuses on topics with more advanced methods

• explains modification methods for changing of different

materials properties

ABOUT THE EDITORS

Abbas Hamrang, PhD, is a professor of polymer science and

technology. He is currently a

senior polymer consultant and editor and a member of the

academic board of various
international journals. 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. His research interests

include degradation studies of historical objects and

archival materials, cellulose-based

plastics, thermogravemetric analysis, and accelerated

ageing processes and stabilization of

polymers by chemical and non-chemical methods.

Devrim Balköse, PhD, is a retired Professor and Head of the

Chemical Engineering

Department of Izmir Polytechnic Institute in Turkey. She

has been an associate professor in

macromolecular chemistry and a professor in process and

reactor engineering. She has also

worked as research assistant, assistant professor,

associate professor, and professor at Ege

University in İzmir, Turkey. Her research interests are in

polymer reaction engineering,

polymer foams and films, adsorbent development, and

moisture sorption, with her research

projects focusing on nanosized zinc borate production, ZnO

polymer composites, zinc borate

lubricants, antistatic additives, and metal soaps.

Reviewers and Advisory Board Members: Gennady E. Zaikov,

DSc, and A. K. Haghi, P hD H a m r a n g B a l k ö s e
ISBN: 978-1-77188-040-4 9 781771 880404 00009

www.appleacademicpress.com Applied Methodologies in

Polymer Research and Technology Editors PhD PhD Abbas
Hamrang, Devrim Balköse, A p p l i e d M e t h o d o l o g
i e s i n a n d P o l y m e r R e s e a r c h T e c h n o l
o g y
Applied Methodologies in Polymer Research and Technology

This book covers a broad range of polymeric materials and

presents the latest developments

and trends in advanced polymer materials and structures. It

discusses the developments of

advanced polymers and respective tools to characterize and

predict the material properties

and behavior. This book has an important role in advancing

polymer materials in macro and

nanoscale. Its aim is to provide original, theoretical, and

important experimental results that

use non-routine methodologies. It also includes chapters on

novel applications of more familiar

experimental techniques and analyses of composite problems

that indicate the need for new

experimental approaches.

This new book:

• highlights some important areas of current interest in

key polymeric materials and technology

• gives an up-to-date and thorough exposition of the

present state of the art of key polymeric materials and
technology

• describes the types of techniques now available to the

engineers and technicians and d scusses their
capabilities, limit tions, and applicat ons

• provides a bal nce between materials science a d

chemical aspects and basic and applied research

• focuses on topics with more advanced methods

• explains modification methods for changing of different

materials properties

ABOUT THE EDITORS

Abbas Hamrang, PhD, is a professor of polymer science and

technology. He is currently a

senior polymer consultant and editor and a member of the

academic board of various

international journals. 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. His research interests

include degradation studies of historical objects and

archival materials, cellulose-based

plastics, thermogravemetric analysis, and accelerated

ageing processes and stabilization of

polymers by chemical and non-chemical methods.

Devrim Balköse, PhD, is a retired Professor and Head of the

Chemical Engineering

Department of Izmir Polytechnic Institute in Turkey. She

has been an associate professor in

macromolecular chemistry and a professor in process and

reactor engineering. She has also

worked as research assistant, assistant professor,

associate professor, and professor at Ege

University in İzmir, Turkey. Her research interests are in

polymer reaction engineering,

polymer fo ms and films, adsorb nt dev lopment, and

moisture sorption, with her research

projects focusing on nanosized zinc bo ate pr duction, ZnO

poly er composites, zinc borate

lubricants, an istatic additives, and metal soaps.

Reviewers and Advisory Board Memb rs: Gennady E. Zaikov,

DSc, and A. K. Haghi, P hD H a m r a n g B a l k ö s e
ISBN: 978-1-77188-040-4 9 781771 880404 00009 Applied
Methodologies in Polymer Research and Technology Editors
PhD PhD Abbas Hamrang, Devrim Balköse, A p p l i e d M e t
h o d o l o g i e s i n a n d P o l y m e r R e s e a r c h
T e c h n o l o g y Applied Methodolog e in Polymer Re
arch and Technology This bo k covers a broad range of
polymeric materials and pres nts the latest devel pments
and tr ds in advanc d polymer materials and structures. It
discusses the developments of advanced polymers and
respective tools to characterize and predict the material
properties and behavior. This book has an important role
in advancing polymer materials in macro and nanoscale. Its
aim is to provide original, theoretical, and important
experimental results that use non-routine methodologies.
It also includes chapters on novel applications of more
familiar experimental techniques and analyses of composite
problems that indicate the need for new experimental
approaches. This new book: • highlights some important
areas of current interest in key polymeric materials and
technology • gives an up-to-date and thorough exposition
of the present state of the art of key polymeric materials
and technology • describes the types of techniques now
available to the engineers and technicians and discusses
their capabilities, limitations, and applications •
provides a balance between materials science and chemical
aspects and basic and applied research • focuses on
topics with more advanced methods • explains modification
methods for changing of different materials properties
ABOUT THE EDITORS Abbas Hamrang, PhD, is a professor of
polymer science and technology. He is currently a senior
polymer consultant and editor and a member of the academic
board of various international journals. 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. His
research interests include degradation studies of
historical objects and archival materials, cellulose-based
plastics, thermogravemetric analysis, and accelerated
ageing processes and stabilization of polymers by chemical
and non-chemical methods. Dev im Balköse, PhD, is a
retired Professor and Head of the Chemical Engineering
Department of Izmir Polytechnic Institute in Turkey. She
has been an associate prof ssor in macromolecular
chemistry and a professor in process and reactor
engineering. She has also worked as research assistant,
assistant professor, associate professor, and professor at
Ege University in İzmir, Turkey. Her research interests
are in polymer reaction engineering, polymer foams and
films, adsorbent development, and moisture sorption, with
her research projects focusing on nanosized zinc borate
production, ZnO polymer composites, zinc borate
lubricants, antistatic additives, and metal soaps.
Reviewers and Advisory Board Members: Gennady E. Zaikov,
DSc, and A. K. Haghi, P hD H a m r a n g B a l k ö s e
ISBN: 978-1-77188-040-4 9 781771 880404 00009 Applied
Methodologies in Polymer Research and Technology Editors
PhD PhD Abbas Hamrang, Devri Balköse, A p p l i e d M e t
h o d o l o g i e s i n a n d P o l y m e r R e s e a r c h
T e c h n o l o g y Appli d Methodologies in Polym r
Research and Technology This book covers a broad range of
polymeric materials and presents the latest developments
and trends in advanced polymer materials and structures. It
discusses the developments of advanced polymers and
respective tools to characterize and predict the material
properties and behavior. This book has an important role
in advancing polymer materials in macro and nanoscale. Its
aim is to provide original, theoretical, and important
experimental results that use non-routine methodologies.
It also includes chapters on novel applications of more
familiar experimental techniques and analyses of composite
problems that indicate the need for new experimental
approaches. This new book: • highlights some important
areas of current interest in key polymeric materials and
technology • gives an up-to-date and thorough exposition
of the present state of the art of key polymeric materials
and technology • describes the types of techniques now
available to the engineers and technicians and discusses
their capabilities, limitati ns, and applications •
provides a balance betw en materials science and chemical
aspects and basic and applied res arch • focuses on
topics with more dvanced methods • explains modification
methods for changing of different materials properties
ABOUT THE EDITORS Abbas Hamrang, PhD, is a professor of
polymer science and technology. He is currently a senior
polymer consultant and editor and a member of the academic
bo rd of various international journals. 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. His
research interests include degradation studies of
historical objects and archival materials, cellulose-based
plastics, thermogravemetric analysis, and accelerated
ageing processes and stabilization of polymers by chemical
an non-chemical m thods. Devrim Balköse, PhD, is a
retired Professor and Head of the Chemical Engineering
Department of Izmir Polytechnic Institute in Turkey. She
has been an associate professor in macromolecular
chemistry and a professor in process and reactor
engineering. She has also worked as research assistant,
assistant professor, associate professor, and professor at
Ege University in İzmir, Turkey. Her research interests
are in polymer reaction engineering, p lymer foams and
films, adsorbent development, and moisture sorption, with
her res arch proj cts focusing on nanosized zinc bora
productio , ZnO polymer composit s, zinc borate
lubricants, antistat c additives, an m tal soaps.
Reviewers and Advisory Board Members: Gennady E. Zaikov,
DSc, and A. K. Haghi, P hD H a m r a n g B a l k ö s e
ISBN: 978-1-77188-040-4 9 781771 880404 00009