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POLYMER SCIENCE AND TECHNOLOGY
POLYETHYLENE
TEREPHTHALATE
USES, PROPERTIES
AND DEGRADATION
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POLYETHYLENE
TEREPHTHALATE
USES, PROPERTIES
AND DEGRADATION
NAOMI A. BARBER
EDITOR

Copyright © 2017 by Nova Science Publishers, Inc.
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CONTENTS
Preface vii
Chapter 1 Poly(Ethylene Terephthalate):
Synthesis and Physicochemical Properties 1
Marija V. Pergal and Milica Balaban
Chapter 2 The Applications of Polyethylene Terephthalate
for RF Flexible Electronics 103
Tzu-Hsuan Chang, Yei Hwan Jung, Dong Liu,
Hongyi Mi, Juhwan Lee, Jiarui Gong
and Zhenqiang Ma
Chapter 3 Progress in Polyethylene Terephthalate Recycling 155
Adel Elamri, Khmais Zdiri, Omar Harzallah
and Abdelaziz Lallam
Index 187

PREFACE
Polyethylene terephthalate (PET) is an aliphatic-aromatic and

semicrystalline thermoplastic polyester of prime commercial and industrial
importance. Namely, PET is a very important industrial polymer due to its
excellent properties such as processability, chemical resistance, high
tensile impact strength, high thermal stability and clarity. Chapter One
summarizes the synthesis and physicochemical properties of PET. In
Chapter Two, the authors review the frequency-dependent parameters of
the PET substrate, developments of the flexible RF electronics on PET
substrate, and the challenges and potentials of RF applications using
flexible electronics fabricated on PET films. Chapter Three presents a
background of the current state of knowledge with respect to PET
recycling.
Chapter 1 - This chapter summarizes the synthesis and
physicochemical properties of thermoplastic polyester, poly(ethylene
terephthalate) (PET). PET, along with poly(butylene terephthalate) (PBT)
is an aliphatic-aromatic and semicrystalline thermoplastic polyester of
prime commercial and industrial importance. Namely, PET is a very
important industrial polymer due to its excellent properties such as
processability, chemical resistance, high tensile impact strength, high
thermal stability and clarity. PET is synthesized from ethylene glycol and
terephthalic acid or dimethyl terephthalate by a two-stage

viii Naomi A. Barber
polycondensation process. High molecular weight of PET can be achieved

by solid-state polymerization. This chapter presents different types of
nanoparticles, such as organoclays, carbon nanotubes and carbon black,
which are used for the improvement of the physical, mechanical, thermal
and barrier properties of PET nanocomposites. It also highlights the recent
developments in PET/layered silicate nanocomposites. The blending of
PET with other polymers, as an excellent method of preparing materials
with enhanced property/cost performance, is described. Processing,
recycling and degradation of PET are also presented. This chapter
discusses the surface modification of PET by physical treatment, chemical
treatment and grafting polymerization in order to modify its surface
properties, for enhanced surface wettability, adhesion activities and
biocompatibility improvement. Moreover, this chapter also surveys the
most relevant aspects related to the preparation and characterization of
thermoplastic copolyester elastomers, especially PET and PBT
copolyesters. The application potential of PET is discussed and selected
examples of commercially available PET are given. Future trends in PET-
based material synthesis and design are also discussed.
Chapter 2 - Polyethylene terephthalate (PET) has been one of the most
reliable and cost-efficient candidates in recent development of flexible
device applications. Flexible electronics have rapidly evolved into a variety
of applications including displays, e-papers, solar cells, sensors, wearable
electronics, etc. In particular, high-performance electronics such as radio-
frequency devices have been designed and fabricated on flexible
substrates, such as PET, with operating frequencies of up to the giga-hertz
(GHz) regime, which covers current major portable electronics, wireless
communication, and transmission units. The flexible electronics that
operate at the GHz regime are generally composed of high-performance
flexible microwave active and/or passive devices. Typically, they have
stringent requirements for substrate choice, in terms of mechanical
properties, thermal properties, and electrical parameters, which have a
significant impact on the performance at high frequencies. In this chapter,
the authors review the frequency-dependent parameters of the PET
substrate, developments of the flexible RF electronics on PET substrate,

Preface ix
and the challenges and potentials of RF applications using flexible

electronics fabricated on PET films.
Chapter 3 - In the last decade, an increasing interest has been focused
on the recycling of plastic wastes, especially on the polyethylene
terephthalate (PET). PET polymer is already being recycled and numerous
applications for recycled polyesters can be explored depending on the
properties of the resin. However, the common problem faced during
processing of recycled PET is degradation. Thus, many solutions have
been proposed in literature to undermine this problem. This chapter
presents a background of the current state of knowledge with respect to
PET recycling. In the first section, a brief theoretical background is
presented about virgin PET synthesis, thermal transitions, processing and
applications. The second section deals with the PET recycling process with
a focus on contaminations and ways to increase the molecular weight of
recycled PET (RPET). It serves as an introduction to Section Three where
the authors’ process to improve the RPET properties is described. Finally,
Section Four covers the effect of blending virgin PET (VPET) with
recycled PET on thermal and rheological behaviors.

In: Polyethylene Terephthalate ISBN: 978-1-53611-991-6
Editor: Naomi A. Barber © 2017 Nova Science Publishers, Inc.
Chapter 1
POLY(ETHYLENE TEREPHTHALATE):
SYNTHESIS AND
PHYSICOCHEMICAL PROPERTIES
Marija V. Pergal1,* and Milica Balaban2

1
Institute of Chemistry, Technology and Metallurgy (ICTM) – Centre
of Chemistry, University of Belgrade, Belgrade, Serbia
2
Faculty of Science, University of Banja Luka,
Banja Luka, Bosnia and Herzegovina
ABSTRACT
This chapter summarizes the synthesis and physicochemical

properties of thermoplastic polyester, poly(ethylene terephthalate) (PET).
PET, along with poly(butylene terephthalate) (PBT) is an aliphatic-
aromatic and semicrystalline thermoplastic polyester of prime
commercial and industrial importance. Namely, PET is a very important
industrial polymer due to its excellent properties such as processability,
*
Correspondence to M. V. Pergal; e-mail: [email protected].

2 Marija V. Pergal and Milica Balaban
chemical resistance, high tensile impact strength, high thermal stability

and clarity. PET is synthesized from ethylene glycol and terephthalic acid
or dimethyl terephthalate by a two-stage polycondensation process. High
molecular weight of PET can be achieved by solid-state polymerization.
This chapter presents different types of nanoparticles, such as
organoclays, carbon nanotubes and carbon black, which are used for the
improvement of the physical, mechanical, thermal and barrier properties
of PET nanocomposites. It also highlights the recent developments in
PET/layered silicate nanocomposites. The blending of PET with other
polymers, as an excellent method of preparing materials with enhanced
property/cost performance, is described. Processing, recycling and
degradation of PET are also presented. This chapter discusses the surface
modification of PET by physical treatment, chemical treatment and
grafting polymerization in order to modify its surface properties, for
enhanced surface wettability, adhesion activities and biocompatibility
improvement. Moreover, this chapter also surveys the most relevant
aspects related to the preparation and characterization of thermoplastic
copolyester elastomers, especially PET and PBT copolyesters. The
application potential of PET is discussed and selected examples of
commercially available PET are given. Future trends in PET-based
material synthesis and design are also discussed.
Keywords: poly(ethylene terephthalate), thermoplastic polyester, two-

stage polycondensation, physicochemical properties, surface
modification, PET blends, PET nanocomposites, applications
1. INTRODUCTION
This chapter summarizes the synthesis, physicochemical properties and

applications of the main member of the thermoplastic polyester family,
poly(ethylene terephthalate) (PET), which is the most widely recognized in
the scientific community and which has widespread commercial and
industrial applications. Polyesters are polymers containing at least one
ester linking group per repeating unit. They are obtained from the chemical
resources found mostly in petroleum and are manufactured in films, fibers
and objects with a simple or complex shape [1]. Namely, commercial
thermoplastic polyester is produced in the reaction including dimethylester
of terephthalic acid rather than terephthalic acid, owing to the faster rate of

Poly(Ethylene Terephthalate): Synthesis … 3
transesterification compared to direct polycondensation from acid, and the

fact that the diester can easily be purified and has better solubility
characteristics [1-3]. Poly(ethylene terephthalate) and poly(butylene
terephthalate) (PBT) are linear aliphatic-aromatic thermoplastic polyesters
that are commercially available engineering plastics [3]. PET and PBT
possess high mechanical strength, excellent processing characteristics and
electrical properties, and good resistance to chemical attack for a broad
range of applications [1, 2]. These characteristics make them suitable for
use in fibers, films, textiles, bottles, molding components and as housing
for home appliances [1-5].
The modern history of thermoplastic polyester goes back to 1929 with
the pioneering research of Carothers, which was based on the aliphatic
polyesters produced from aliphatic dicarboxylic acids and diols [6-10].
These aliphatic polyesters had low melting temperatures (Tm = 80-100°C),
were sensitive to hydrolysis, and thus, were not suitable for commercial
applications. Moreover, they could not compete against aliphatic
polyamide fiber (nylons) which was discovered by Carothers at DuPont in
1930 [11].
In order to increase the melting temperature of polyester and get the
thermomechanical properties obtained with nylons, it was required to
stiffen the polyester chain by using rigid aromatic monomers instead of
flexible aliphatic monomers [1]. The first aromatic polyester with a high
melting temperature, PET, was prepared between ethylene glycol (EG) and
terephthalic acid (TPA), by J.R. Whinfield and J.T. Dickson in the early
1940s [12-14]. Subsequently, in 1941, they developed the first aromatic
polyester fibers called Terylene and which were initially manufactured by
Imperial Chemical Industries (ICI). Around the same time Schlack had
commenced the synthesis of polyester from 1,4-butanediol (BD) and TPA
and patented it in 1949 [15]. Schlack found that PBT was less suitable to
be used as a fiber material in contrast to PET, which was easily melt-spun
into a fiber. PET was produced commercially in 1953 as fiber for the
textile industry (Dacron) by DuPont using modified nylon technology,
while PBT was commercialized by the Celanese Corporation in 1969,
under the trade name Celanex [1]. DuPont’s polyester research rapidly led

to a wide range of trademarked products such as a strong polyester film,

called Mylar, however PET bottles came much later (in the 1970s).
PET retains good mechanical properties, toughness and fatigue
resistance up to 150-170°C, as a result of a high melting temperature
(270°C) and rigid polymer chains. PET also exhibits a resistance to
solvents, chemicals and hydrolytic degradation under the usual
temperatures of application. The disadvantage of PET is a relatively slow
rate of crystallization, which increases the price of the processing
(extended cycle due to slow cooling) and requires nucleating agents (such
as talc, magnesium oxide, zinc-stearate, calcium-silicate, etc.) for extrusion
and injection-molding applications [2]. Conversely, PBT owes its success
to its fast crystallization rate compared to PET, which makes it suitable for
injection molding applications [3]. Due to the lower melting temperature of
PBT compared to PET, PBT can be molded at a comparatively lower
molding temperature. This permits fast processing and rapid production
cycles. However, larger production volumes and lower prices make PET a
serious competitor to PBT for many varied applications. Hence, PBT is
often used as substitute for PET if a higher crystallization rate is necessary,
but the maximum temperature of application for PBT is slightly lower as
compared to PET at 120-140°C. PET has also an advantage over
polyamides due to its much lower moisture absorption, allowing the
material to maintain excellent dimensional stability through extremes of
temperature and high humidity. Due to its low cost, superior aesthetic
appearance and better handling, PET is usually preferred over
polycarbonates.
Nowadays, a broad range of pure and modified PET grades are
available, and are found in many applications such as fibers, parts in the
automotive and electric/electronic industries, architectural glazing and
window films [2]. Due to the excellent mechanical and barrier (carbon
dioxide permeation), PET is used for food and beverage packaging
applications, even replacing traditional materials such as metals or glass.
PET is also used as a recyclable polymer, and the markets for recycled
PET (R-PET) are growing by the year [16, 17]. Commercial PET grades
can be found under the trade names of Arnite (DSM), Crastine (DuPont),

Dacron (Invista), Hostaphan Films (Mitsubishi), Impet (Ticona), Melinex

(DuPont), Mylar (DuPont Teijin Films), Terylene (ICI), Tergal (Tergal
Industries), Rynite (DuPont), Raditer (Radici Group), Petra (BASF), Pocan
(Bayer).
In considering the great versatility of PET, it is obvious time and again
that the single most important factor is the significant contribution made by
its chemical structure. This attribute, due to the foresight of PET’s
inventors, has some noteworthy properties which affect its processing
behavior and also the products obtained from it. Firstly, as previously
mentioned, PET is a polymer that is crystallizable, but is distinguished by
slow crystallization kinetics [2, 18]. Because of this combination of
properties, PET can be obtained in various states of order, such as
amorphous (transparent), “oriented mesomorphic” (transparent),
spherulitically crystallized (opaque), and oriented crystallized (transparent)
from strain-induced crystallization [1, 18]. Mechanical properties, storage
stability, gas barrier, dye ability and transparency are the properties
controlled by the nature of the degree of ordering in finished articles made
from PET. Contrary to PBT which occurs almost in partially crystalline
form, PET can also be processed into amorphous molded bodies with high
transparency; on heating to 70-100°C this transparency is lost due to
postcrystallization.
The production of PET has increased rapidly and during the two last
decades PET has become the material of choice in various applications [2].
Currently, the annual production of PET is close to 60 million tons,
registering average annual growth of over 7% [19]. PET is mainly used to
produce fibers in textile applications, and the use of PET represents 80% of
the worldwide consumption of synthetic fibers. The extensive use of PET
for food and beverage packaging and its high resistance to atmospheric and
biological agents, and accumulation in the waste stream, are of serious
concern for the environment. This issue of environmental pollution could
be overcome by applying some of the many methods which have been
developed, such as mechanical recycling, non-destructive methods, or
chemical recycling, which represent some of the great advantages of PET
[1, 2, 20, 21].

2. SYNTHESIS OF PET
2.1. Conventional Two-Stage Polycondensation Reaction
Two methods are used for the industrial manufacturing of PET. PET
can generally be produced by reacting ethylenediol with an aromatic
diester (dimethyl terephthalate – DMT) or diacid (terephthalic acid), in the
presence of a polyesterification catalyst [5]. Although polycondensation to
high conversions requires the stoichiometric balance of reacting groups,
the industrial methods for manufacturing polyesters such as PET involve
the initial use of excess ED, which is later removed and recycled in the
process.
The original industrial synthesis of PET is based on a relatively
expensive two-step melt polymerization reaction between dimethyl
terephthalate and excess ethylenediol of approximately 30-50%, in the
presence of a catalyst. The polymerization of dimethylterephthalate (DMT)
and ethylene glycol (EG) to PET proceeds in two steps: transesterification
and polycondensation [1-3, 5, 22]. The first, the transesterification step,
involves the conversion of the methyl ester groups of DMT into bis(2-
hydroxyethyl)terephthalate (bis-HET) and a small amount of oligomers are
formed in this step of the reaction. This reaction is performed at
atmospheric pressure, in an inert atmosphere to prevent oxidative side
reactions, and in a temperature range from 150 to 210°C. During the first
step methanol is distilled off and hydroxyethyl–terminated terephthalate
oligomers are produced [19]. If only one terephthalate residue exists per
molecule (x = 1 in Figure 1), the diester is usually called
bis(2-hydroxyethyl)terephthalate). In reality, the transesterification step
produces not only bis-HET, but also a decreasing number of 2-
hydroxyethyl-terminated oligomers containing 2,3,4,... terephthalate
residues. The first step is finished when the methanol stops distilling off.
In the second step of the method i.e., polycondensation, the
temperature increases to 270-280°C (well above the melting temperature of
PET) and a high vacuum is applied (10-50 Pa) [2]. bis-HET, and other low
molecular weight oligomers, formed during the transesterification step,

further react by polycondensation between the two hydroxyethyl end

groups to result in a PET homopolymer. ED is formed and is eliminated as
a by-product (Figure 1). PET with a degree of polymerization of
approximately 100 is usually obtained. In order to favor the
polycondensation, which is an equilibrium reaction, it is necessary to
efficiently remove the excess of ED. The evaporation of ED from the
reaction mixture is accelerated by the application of the high vacuum and
by intensive mixing of the melt [2]. During the polycondensation the
viscosity of the reaction mixture dramatically increases with the molecular
weight of the polymer formed. As a result, the mass transfer of the
volatiles out of the reaction mixture becomes a rate limiting process.
Heating above 300°C leads to thermal degradation of the polymer, since
the thermal stability of PET is limited at such high temperatures.
Temperature control and the choice of catalyst are very important in
performing polycondensation. The reaction time including the two steps of
the reaction is long (between 5 and 10 h) and can be decreased by a high
temperature and the addition of a metal catalyst [1]. In the production of
PET, a combination of two different catalysts is used in each of the two
polymerization phases. Catalysts such as acetates of manganese, zinc,
calcium and magnesium are used in the first step of the reaction, while
antimony trioxide is the most popular catalyst for the second stage of the
reaction, although antimony pentoxide, tetrabutoxy titanate and germanium
dioxide have also been used [3].
The monomers used for the direct polyesterification reaction for PET
synthesis are terephthalic acid and ethylenediol [1-3]. The process based
on TPA is very similar to the DMT-based route to PET, which has been
previously described in this section. In the first step, TPA esterifies with an
excess of ED, distilling water in order to shift the esterification equilibrium
towards the product, i.e., hydroxyethyl end functionalized oligo-esters of
PET (Figure 2). However, in the case of the TPA-based route, the reaction
medium is heterogeneous because it is difficult to dissolve TPA in ED at
the temperatures which are applied for the melt polymerization. The use of
a small monomer feed ratio and a high reaction temperature are important
to improve the solubility. Water formed during the reaction was collected

to estimate the conversion of the reaction. The addition of a catalyst is not

required since the acid group of TPA self-catalyzes the reaction. However,
when the concentration of acid groups decreases, metal catalysts could be
used to maintain the reaction rate [19].
Figure 1. Synthesis of PET from DMT as the starting reactant: (a) Formation of bis-
HET and other hydroxyethyl–terminated terephthalate oligomers by transesterification
of DMT with ED and (b) polycondensation of bis-HET and hydroxyethyl–terminated
oligomers resulting in PET.
One of the main advantages in production from DMT, compared with

production from TPA, is that no environmentally aggressive chemicals are
used (such as bromides or acetic acid), which eliminates the need for
expensive, high corrosion resistant reaction vessels. Moreover, at the
beginning of production of terephthalate-based polyesters, DMT was
predominantly used for their synthesis because it was relatively easily
purified in comparison with TPA. Yet, since the 1960s purified TPA has
become available due to the development of new technologies and as a

consequence, it has gained a lot of importance as a monomer in polyester

synthesis [2]. Currently, the most frequently adopted method for the
purification of TPA is commercialized by Amoco.
In both methods for producing PET, the secondary reactions that occur
during polycondensation can alter the stoichiometric ratio, and thus
terminate polycondensation or confer undesirable properties on the end
product [19, 23]. Diethylene glycol can be generated during the
polycondensation reaction and incorporated in the polymer. Other
important secondary reactions include the dehydration of ethylene glycol
to form acetaldehyde, ester pyrolysis which in the case of PET generates
carboxyl groups and olefins. Commercial PET prepared by
polycondensation contains a small amount of low molecular weight cycle
structures with high molecular weight linear macromolecules. The cyclic
oligomers can create problems during the processing of PET but the
removal of cyclic oligomers is not currently practiced in the industry.
Figure 2. Synthesis of PET from TPA as the starting reactant.

At the industrial level, PET can be made by using both batch and
continuous processes [3]. Early commercial processes were DMT-based
batch processes, which were typically run in at least two reactors. In the
batch processes, after the first step is completed (when no more methanol
is distilled off), the reaction mixture transfers to the second reactor for the
polycondensation step, where a vacuum is applied (< 1 mbar) at increased
temperatures (between 270°C and 280°C), well above the melting
temperature of PET, in order to strip off the excess ED.
Nowadays, batch processes are usually replaced by continuous
processes, which involve a series of reactors in which the pressure is
gradually reduced. Finally, so-called finishing reactors, which create a high
surface area combined with a deep vacuum, are applied to increase the
molecular weight even further. Batch processes are mainly used to produce
specialty PET grades.
3. SOLID STATE POLYMERIZATION
Solid state post-polycondensation is widely used in order to increase

the average molecular weight of polyesters [2]. The process is particularly
important for achieving large values of Mn in the case of crystalline
condensation polymers of high melting temperature, when thermal
degradation takes place in the melt. PET of a very high molecular weight
(Mn above 100000 g/mol) can be obtained by the solid state post-
polymerization of melt-synthesized material. PET has both hydroxyl and
carboxylic acid groups at the chain ends, as well as the active residual
catalyst and as a result PET is still capable of reacting, and the molecular
weight may be increased by solid state polymerization. Solid state
polymerization is carried out around 220-230°C, i.e., at a temperature
between the glass transition (Tg) and melting temperature of PET, for 10-
30 h in order to enhance the polycondensation reaction. PET obtained by
solid state polymerization has a higher melting temperature and higher
crystallinity compared to conventional PET [19]. To promote the removal
of low-molecular weight products and thus increase the molecular weight

of polymer chains, the polymer chips or pellets are heated in a vacuum or

in a steam of inert gas at a temperature approximately 20-50°C below the
melting temperature. PET of higher molecular weight can be used for
articles made by blow molding and for shock absorber elements.
4. PHYSICAL PROPERTIES OF PET
4.1. Thermal and Mechanical Properties of PET
Depending on its processing and thermal conditions, PET may exist

both as amorphous and as semicrystalline polymer. In its purest form, PET
is an amorphous glass-like material. Under the influence of modifying
additives or by heat treatment of the polymer melt, PET develops
crystallinity. The degree and quality of crystallinity have long been
recognized as having a dominant influence upon the properties of PET and
they are highly dependent on processing conditions like processing
temperature, cooling rate, stretching process etc. At glass transition
temperature of 72°C, the semicrystalline PET changes from a rigid glass-
like state into a rubbery elastic form. The polymer molecular chains in the
rubbery state can be stretched and aligned in either one direction to form
fibers, or in two directions to form films and bottles. Only a limited
amount of crystallization can occur during cooling after injection molding
of PET due to its rather high transition temperature. However, when the
PET melt is cooled quickly, while still held in the stretched state, the
chains are frozen, wherein their orientation remains intact. The resulting
material is extremely tough and suitable for the fabrication of bottles. At
temperatures above 72°C, the stretched PET slowly crystallizes and the
material gradually starts to become opaque, more rigid and less flexible.
This so-called crystalline PET or CPET is capable of withstanding higher
temperatures and can be used for trays and containers capable of
withstanding moderate oven temperatures.
The crystallization of PET has been widely investigated. Jabarin [24,
25] studied the crystallization behavior of PET under isothermal and

dynamic cooling conditions by differential scanning calorimetry (DSC), as

a function of molecular weight, polycondensation catalyst system and
polymerization conditions. Kinetic parameters of crystallization were
calculated for both cases by utilizing Avrami-type expressions. The
analysis of the crystallization kinetic data indicated that the same
mechanism was operative under isothermal and dynamic cooling
crystallization conditions. The dynamic cooling crystallization method
could establish the minimum cooling rate required to produce PET without
detectable crystallinity. The results showed that the cooling requirements
for producing noncrystalline PET were dependent on the molecular weight
of the resin, but more importantly, were dependent on the catalyst system
used in the polycondensation step. These results were in good agreement
with the results obtained under isothermal conditions.
The fabrication of PET into fibers, films and containers usually
involves molecular orientation caused by molecular strain, which may lead
to stress- or strain-induced crystallization (SIC). Jabarin [26] also
investigated the SIC of PET by the methods of birefringence, density,
thermal analysis, light scattering and wide-angle X-ray scattering (WAXS).
The results indicated that the SIC of annealed, stretched PET could
proceed in three different paths depending on the residual degree of
orientation. At a low degree of residual orientation, as indicated by the
birefringence value, annealing of stretched PET led only to molecular
relaxation, resulting in a decrease of birefringence. At intermediate
orientation levels, annealing caused an initial decrease in birefringence
followed by a gradual increase and finally a leveling off of birefringence
after a fairly long period of time. At higher orientation levels, annealing
caused a rapid increase in birefringence before leveling off.
Alves et al. [27] determined the relaxation times of the cooperative
conformational rearrangements of the amorphous phase in semicrystalline
PET and compared them with those calculated in amorphous PET. The
thermograms measured in the samples with low crystallinity clearly
showed the existence of two amorphous phases with different
conformational mobility, Phase I and Phase II. Phase I contained polymer
chains with a mobility similar to that in the purely amorphous polymer,

while Phase II showed a much more restricted mobility, probably

corresponding to conformational changes within the intraspherulitic
regions. The model simulation allowed to determine the temperature
dependence of Phase II relaxation times, which were independent from the
crystallinity fraction in the sample and around two decades longer than
those of the amorphous polymer at the same temperature.
The crystalline phase may contribute highly anisotropic behavior to the
bulk polymer due to the orientation of chains which accompanies
preferential alignment of the crystallites themselves. Such preferential
alignment may be accomplished through careful processing operations.
The noncrystalline phase is also often anisotropic, prompting investigators
to decompose this component into isotropic and oriented constituents [28].
In 1994, Fu et al. [29] proposed that, beside the crystalline phase and the
randomly oriented amorphous phase, there is an intermediate phase in
semicrystalline PET fibers. The chains of the intermediate phase are
partially oriented with respect to the fiber axis. The intermediate phase is
mainly present between the fibrils, whereas the crystallites are separated in
the fiber direction mainly by a more random amorphous phase.
Recognition of this third phase permitted the development of a simple
model for structure-insensitive properties such as modulus, density and
orientation.
PET is a typical example of polymer with complex melting behavior.
On heating, it can show three main fusion endotherms with sizes and
positions related to its thermal history. The melting behavior of PET,
crystallized and/or annealed under elevated pressure, was studied using
DSC at atmospheric pressure. The melting point of the sample crystallized
from the melt by slow cooling under elevated pressure was lower than that
of the sample crystallized at atmospheric pressure, although the former
sample had a slightly thicker lamella than the latter one. This implied that
the fold surface energy was much larger in the elevated pressure
crystallized sample. The atmospheric pressure melting point increased
greatly by annealing under elevated pressure. In particular, a remarkable
increase in melting point was observed at the early stage of the annealing
for the elevated pressure crystallized sample, which may be due mainly to

the decrease in fold surface energy in addition to lamella thickening. An

electron micrograph of the sample annealed for a long period after the melt
crystallization under elevated pressure showed a morphology of a band
structure composed of extended-chain-like crystal [30].
Medellin-Rodriguez et al. [31] studied the melting behavior of
isothermally crystallized PET using linear heating by DSC. Variables such
as crystallization temperature, crystallization time, heating rate and average
molecular weight were the main focus of the study. On the basis of several
experimental techniques, a correlation of the melting behavior of PET with
the amount of secondary crystallization was found to exist. It was observed
that the triple melting of PET was a function of programmable DSC
variables such as crystallization temperature, crystallization time and
heating rate. However, in testing the hypothesis that there is a correlation
between melting endotherms and secondary crystallization inside
spherulites, it was found necessary to use a DSC-independent variable in
order to enhance the observed effects. Therefore, on the basis of a
crystallization model that involved secondary branching along the edges of
parent lamellar structures, it was speculated that an increase in the average
molecular weight could affect the triple melting of PET due to an increase
of rejected portions of the macromolecules. It was found that the second
melting endotherm increased, apparently, at the expense of the third one as
the average molecular weight was increased. The second melting
endotherm was also found to correlate proportionally with the amount of
secondary crystallization inside spherulites. The results support a model of
crystallization which basically consists of parent crystals and at least one
population of secondary, probably metastable, crystals. This latter
structural component must involve excluded portions of the
macromolecules that did not crystallize during the isothermal
crystallization period of the parent crystals. An increase of molecular
weight gives rise to a higher entanglement density which in turn increases
the fraction of initially rejected chain sections and therefore the amount of
secondary crystallization.
Reorganization of semicrystalline polymers on heating is a fast
process. For PET heating rates of several thousand Kelvin per second are

needed to prevent reorganization of unstable crystals. Utilizing a thin film

vacuum gauge as a fast calorimeter, Minakov et al. [32] extended the
scanning rate range of commercial DSC’s (μK/s to 10 K/s) to rates as high
as 10 000 K/s on heating and cooling. Because of the fast equilibration
time, isothermal experiments can be performed after scanning at several
thousand Kelvin per second. The dead time after such a quench is in the
order of 10 ms and the time resolution is in the order of milliseconds.
These ultra-fast calorimeters allow the study of the kinetics of extremely
fast processes in semicrystalline polymers like reorganization. For the PET
crystallized at 130°C, reorganization needed less than 40 ms between
150°C and 200°C. Isothermal reorganization at 223°C was about two
orders of magnitude faster than isothermal crystallization from the
isotropic melt at the same temperature. The melt memory for the remaining
structures needed for reorganization is removed 25°C above the
equilibrium melting temperature of PET.
In isothermally crystallized samples, a small endotherm is often
observed during heating about 10-30°C above the crystallization
temperature. Song [33] used the differential of the reversing heat capacity
and nonreversing heat flow signals were used to analyze the behavior of
the glass transition and the low temperature melting endotherm. With
increasing annealing time, the increment of the heat capacity at the glass-
transition temperature decreased and the increment of the heat capacity at
the annealing temperature increased. It was suggested that the origin of the
low temperature melting endotherm mainly resulted from the transition of
the rigid amorphous fraction for the PET used. The glasslike transition of
the rigid amorphous fraction occurred between the glass transition and
melting. Recently, Di Lorenzo et al. [34] have presented the quantitative
thermal analysis of PET including details about the coupling between the
crystal and amorphous fractions. Isothermal crystallization at 190°C
followed by cooling to room temperature provides a three-phase structure
composed of a mobile amorphous, a crystalline and a rigid amorphous
fraction. A close connection between multiple melting and devitrification
of the rigid amorphous fraction in PET is revealed by conventional (DSC)
and temperature-modulated calorimetry (TMDSC). Rearrangements of

PET crystals at high temperatures involve recrystallization/

annealing/crystal perfection following partial melting, which can occur
only if the amorphous chain portions coupled to the crystal/melt phase
boundary have sufficient mobility. Such mobility can be achieved above
the glass transition of the amorphous chain segments coupled with the just-
melted crystals. Combined analysis of the reversing heat capacity
monitored during quasi isothermal modulation with the thermal properties
of the resulting structure suggested that annealing at temperatures below
210°C did not result in considerable reorganization and perfection of the
crystal phase. The temperature of 210°C seems to be the point at which the
rigid amorphous fraction coupled with the crystal phase attains sufficient
mobility to allow development of crystals with increased perfection and
thus higher thermal stability. In this study the combination of DSC,
TMDSC and fast scanning calorimetry (FSC) has proven to be a powerful
calorimetric technique to study not only crystals and amorphous polymers
but also the multiphase structures with intermediate, coupled nanophases.
The dynamic mechanical properties of PET have been studied by a
number of authors [31, 35-38]. PET exhibits at least two mechanical loss
peaks in the temperature range -180 to 200°C. One peak occurs at about -
40°C ( dispersion) and the other is near 100°C ( dispersion). The 
dispersion has been reported to be related to the degree of crystallinity,
while the  dispersion of PET has been associated with the glass transition.
In their early work, Illers and Breuer [35] studied unoriented films of
the PET samples in which the position of the  peak shifted to higher
temperatures for degree of crystallinity up to 30%. At higher degree of
crystallinity, the position of this peak shifted toward lower temperatures.
The variations of the  loss modulus peak indicated the onset of segmental
motion within the amorphous regions with increasing degree of
crystallinity. This behavior has been attributed to the effect of crystal size
on the amorphous regions. At low to medium degree of crystallinity, there
would be many small crystallites which would act like crosslinks and
restrict the motion of segments in the amorphous regions, while at high
degree of crystallinity, the crystallites would be larger and fewer in
number, which would allow the segments in the amorphous regions more

freedom. However, in all samples a very broad  peak occurs at

approximately 65°C (at a frequency of 1 Hz). Increasing crystallinity
causes a slight shift of the  peak to higher temperatures in the first stage,
followed by a lowering for the higher degree of crystallinity. This behavior
is similar to that described above the  peak.
The relationship between crystallinity and crystal size parameters and
the position of the  dispersion peak, which was developed by Dumbleton
and Murayama [39] for polyamides, has been successfully applied to PET.
Matsuo and Ishimuro [37] have reported a detailed study on effects of
moisture and solid phase polymerization on melt viscoelastic properties of
PET. They found a drying condition and an experimental procedure which
did not induce any variation of either molecular weight or molecular
weight distribution in samples during periods of sample preparation and a
short time run of viscoelastic measurements. For a long time run, η’ and G’
increased with time and especially the increase of the latter was
remarkable. The similar behavior was observed for nylon-66 but not for
PBT. It is suggested that highly branched and/or cross-linked substances
were produced in the samples besides linearly polymerized ones.
Thermal and micromechanical properties of amorphous and
semicrystalline PET are found to be dependent on ageing effects occurring
by thermal treatments below Tg. These effects are studied using two
complementary techniques: DSC and dynamic mechanic analysis (DMA)
at low frequencies (1-10-4 Hz). Experimental results can be described
through a physical model assuming diffusion and annihilation of “quasi-
point defects”. The distribution in the mobility of these defects is able to
take into account all the phenomena observed after physical ageing, in
particular the effects of low-temperature ageing. The ageing effects in the
semicrystalline material cannot be deduced from those observed for the
amorphous one by a single two-phase rule. Changes in the correlation
factor of molecular movements and changes in the distribution of defects
are necessary to describe all the observed effects, putting in evidence the
role of the crystallites to reduce the segmental mobility [38].
Thermal analysis techniques such as DSC and DMA have proved to be
suitable techniques for the quality assessment of recycled PET. Thermo-

mechanical degradation causes deep changes in the microstructure and

properties of PET under recycling. A dramatic increase in the degree of
crystallinity is observed during consecutive extrusion cycles, leading to
significant embrittlement of the recycled material and the complete loss of
its plastic deformation properties after four reprocessing cycles. Chain
scission reactions induced under thermo-mechanical degradation may
result in a heterogeneous distribution of polymeric chain lengths in the
melt state, altering the subsequent amorphous and crystalline
microstructure in recycled PET after chain rearrangement during cooling
[40].
Also, the thermal properties (glass transition, melting point and
crystallinity) and mechanical properties (Young’s modulus, elongation at
break and impact strength) of post-consumer PET bottles were compared
with those of the virgin resin. There are two types of scraps of recycled
PET: one arising from homogeneous deposits of bottles and the other of
heterogeneous deposits soiled by contaminants such as poly(vinyl
chloride), PVC, and adhesives. The presence of contaminants and residual
moisture coming in the shape of scraps facilitates the crystallization of
recycled PET compared to virgin PET and induces cleavages of chains
during the melt processing. This leads to a reduction in intrinsic viscosity
and consequently in molecular weight, and these decreases are more
significant when the recycled resin is soiled. Virgin PET exhibited a
ductile behavior (>200% of elongation at break), whereas post-consumer
PET bottles exhibited a brittle one (<10% of elongation at break). This was
a consequence of the difference in crystallinity, the presence of impurities
in the recycled PET and the different thermal and mechanical history of the
virgin and recycled materials [41].
The fibers produced from polymers with intermediate chain rigidity
like PET show relatively lower tensile strength at the present state of
technology and various attempts have been undertaken to improve the
tensile strength of PET fibers [42]. As noted above, the strain-induced
crystallization of PET is the structure change caused by tensile deformation
leading to the development of microcrystalline structure. Thus,
understanding of the structure changes of PET fibers during tensile

deformation up to fracture is of substantial importance for the

improvement of its mechanical properties. It is well established that
crystallization of PET begins when a minimum strain has been reached
[43, 44] and it could involve intermediate stages or phases [45]. Gorlier et
al. [46] studied strain induced crystallization of PET designed for stretch-
blow molding combining well-controlled tensile tests, different quenching
protocols and X-ray diffraction technique. Strain hardening can be
observed before the crystalline microstructure is totally developed,
emphasizing the fact that strain hardening is mainly controlled by first
stages of crystallization and that actual crystallization occurs during a
following relaxation step. Tensile deformation of PET also causes the
structure changes leading to the destruction of the microcrystalline
structure and macroscopic fracture. With increasing strain and
temperatures above the glass-transition, slip deformation mechanisms
become more important. The formation of microvoids was observed at
strain near to elongation at break below or in the range of glass-transition
temperature [47]. Shioya et al. [48] have conducted small-angle X-ray
scattering (SAXS) measurements during tensile deformation of a PET fiber
at room temperature. The strain of the long period structure increased in
accordance with the external fiber strain at small fiber strains, while it
deviated from the fiber strain at large fiber strains. Microvoids much larger
than the long-period structures were formed at a large fiber strain in the
regions which linked the long-period structures and the number of the
microvoids continued to increase with increasing fiber strain up to fiber
fracture. Concomitantly with the formation of microvoids, the ligaments
which continued to sustain the fiber load were formed in the linking
regions. The formation of microvoids, which depended on the strength of
the linking regions, contributed to the fracture toughness of the fiber.
Recently, Di Lorenzo et al. [34] have presented the quantitative
thermal analysis of PET including details about the coupling between the
crystal and amorphous fractions. Isothermal crystallization at 190°C
followed by cooling to room temperature provides a three-phase structure
composed of a mobile amorphous, a crystalline and a rigid amorphous
fraction, as shown in Figure 3.

Figure 3. Specific heat capacity of PET after isothermal crystallization at 190°C and
subsequent cooling to 40°C. The thick solid line is the total heat capacity by standard
DSC at 5°C/min, the solid circles represent the reversing heat capacity after 16 min of
modulation at T0, and the thin solid lines are the solid and liquid specific heat
capacities, as taken from the ATHAS Data Bank. The specific baselines heat capacity
of PET computed for a two- and three-phasemodel are shown as dashed and dotted
lines, respectively. The major endothermic peaks are numbered in order of increasing
temperatures as TI, TII and TIII, respectively [34].
Figure 4. Specific reversing heat capacity of PET after 4 h of quasi isothermal

modulation as a function of the temperature of quasi isothermal treatment [34].

A close connection between multiple melting and devitrification of the

rigid amorphous fraction in PET is revealed by DSC and TMDSC.
Rearrangements of PET crystals at high temperatures involve
recrystallization/annealing/crystal perfection following partial melting,
which can occur only if the amorphous chain portions coupled to the
crystal/melt phase boundary have sufficient mobility. Such mobility can be
achieved above the glass transition of the amorphous chain segments
coupled with the just-melted crystals. Combined analysis of the reversing
heat capacity monitored during quasi isothermal modulation with the
thermal properties of the resulting structure suggested that annealing at
temperatures below 210°C did not result in considerable reorganization
and perfection of the crystal phase. The temperature of 210°C seems to be
the point at which the rigid amorphous fraction coupled with the crystal
phase attains sufficient mobility to allow development of crystals with
increased perfection and thus higher thermal stability (Figure 4). In this
study the combination of DSC, TMDSC and fast scanning calorimetry
(FSC) has proven to be a powerful calorimetric technique to study not only
crystals and amorphous polymers but also the multiphase structures with
intermediate, coupled nanophases.
4.2. Gas Barrier Properties of PET
PET is widely used in a range of high-barrier applications because of

its low cost and good mechanical properties. Also, the gas barrier
properties of PET are acceptable for many food and beverage products.
The main reasons for its popularity are the properties of glass-like
transparency coupled with adequate gas barrier properties for retention of
carbonation. It is established that gas barrier properties depend on the
number and size of cavities in the polymer matrix (static free volume) and
the frequency of channel formation (dynamic free volume). Also, the gas
permeability of aromatic polymers and copolymers consistently decreases
when the symmetric para-phenylene linkage is replaced by an asymmetric
meta- or ortho-linkage [49]. In an early work, Michaels et al. [50] studied

diffusion of helium, oxygen, nitrogen, argon, carbon dioxide and methane

in glassy and rubbery PET in the range 25 to 130°C. A model for diffusion
in the glassy amorphous and crystalline polymers is proposed, assuming
that the driving force for diffusion is the concentration gradient of
dissolved molecules which are assumed to be in local equilibrium with
molecules in the cavities.
Various methods have been used to reduce the inherent oxygen
permeability of PET as a passive (nonreactive) polymer in order to meet
the requirements for packaging highly oxygen sensitive food and beverage
products. One approach includes structure and morphology manipulation
by changing the degree of crystallization and orientation in the material
[51, 52]. The efficient packing of chains in lamellar crystals or in the
ordered regions of oriented PET reduces the available free volume to the
extent that these regions are considered impermeable.
The improvement in the oxygen barrier properties of PET by
orientation and heat setting was examined. Orientation was carried out at
65°C by constrained uniaxial stretching to a draw ratio of about 4. Heat
setting was performed at temperatures from 90 to 160°C with the specimen
taut. Orientation decreased the permeability of PET to almost one-third
that of the unoriented, amorphous polymer because of decreases in both the
diffusion coefficient and the solubility coefficient. The proposed two-phase
model for oriented PET consisted of a permeable isotropic amorphous
phase (density = 1335 g/m3) with ethylene linkages predominately in the
gauche conformation and an impermeable oriented phase (density = 1380
g/m3) with ethylene linkages that had transformed from the gauche
conformation to the trans conformation during stretching. Chain segments
in the trans conformation did not possess crystalline order. Instead, they
were viewed as forming an ordered amorphous phase. Crystallization by
heat setting above the glass-transition temperature did not dramatically
affect the permeability. However, a decrease in the diffusion coefficient,
offset by an increase in the solubility coefficient, indicated that
crystallization affected the barrier properties of the permeable amorphous
phase. The analysis of the barrier data, assuming a two-phase model with
variable density for both the permeable and impermeable phases, revealed

that the impermeable phase density increased during crystallization,

approaching a value of 1476 g/m3. This value is consistent with previous
measurements of the density of the defective crystalline phase in PET. The
density of the permeable amorphous phase decreased concurrently to about
1.325 g/m3, indicating the appearance of additional free volume [51].
Sekelik et al. [52] studied the improvement in oxygen barrier
properties of PET by incorporation of an impermeable phase such as
crystallinity or talc platelets. Crystallinity was induced by crystallization
from the glassy state (cold crystallization), while microlayering was used
to create talc-filled structures with controlled layer architecture. The
reduction of permeability in crystallized and talc-filled PET was well
described by Nielsen’s model. Changes in permeability of crystalline PET
could not be ascribed to the filler effect of crystallites only. Data on
solubility, obtained on the basis of measurements of the oxygen transport
coefficients, confirmed a previous finding that the amorphous phase
density of PET decreases upon crystallization. The data were amenable to
interpretation by free volume theory. Talc-filled materials processed by
different methods showed the same permeability. However, much better
mechanical properties were achieved by microlayering.
In numerous papers the copolymerization was considered as a method
for the improvement of barrier properties of PET. The oxygen barrier
properties of amorphous PET based copolymers with various acid
comonomers were examined. The incorporation of increasing amounts of
isophthalate, phthalate or naphthalate gradually reduced the permeability
toward the low values obtained for the corresponding homopolymers.
Generally, comonomer affected the solubility less than the diffusivity and
therefore changes in the permeability reflected primarily changes in the
diffusivity for the polymers studied. Correlation of the diffusivity with the
magnitude of the subambient γ relaxation identified dynamic free volume
with thermally activated conformational changes and segmental motions
[53]. The solubility and diffusivity depended on copolymer composition in
accordance with static and dynamic free-volume concepts of gas
permeability in glassy polymers. The solubility correlated with the amount
of free volume, as determined by the glass-transition temperature [54].

Liu et al. [55] examined PET and a series of statistical and blocky
copolymers in which up to 30% of the terephthalate was replaced with
isophthalate by copolymerization and melt blending, respectively. The
polymers were oriented at four temperatures in the vicinity of the Tg and
characterized by oxygen transport, WAXS, positron annihilation lifetime
spectroscopy and infrared spectroscopy. Orientation of all the copolymers
resulted in property changes consistent with strain-induced crystallization.
Analysis of oxygen solubility based on free volume concepts led to a two-
phase model from which the amount of crystallinity and the amorphous
phase density were extracted.
Hu et al. [56] reported on improvement of gas barrier properties of
PET by blending with an aromatic polyamide, either poly(m-xylylene
adipamide) (MXD6) or a copolyamide based on MXD6 in which 12 mol.%
adipamide was replaced with isophthalamide (MXD6-12I). Incorporating a
small amount of sodium 5-sulfoisophthalate into the PET matrix
compatibilized the blends and reduced the polyamide domain size to 100-
300 nm. Thermal analysis showed that the polyamides had a nucleating
effect on PET crystallization, whereas crystallization of the polyamides
was inhibited especially in compatibilized blends. Without orientation,
blending with 10 wt.% MXD6 or MXD6-12I reduced oxygen permeability
of PET by a factor of about 0.8 (P/PPET) when measured at 43% relative
humidity (RH), in accordance with the Maxwell model prediction.
However, after biaxial orientation, oxygen permeability of blends with 10
wt.% MXD6 was reduced by 0.3 at 43% RH, and permeability of blends
with 10 wt.% MXD6-12I was reduced by 0.4. Even at 85% RH, oxygen
permeability was reduced by 0.4 and 0.6 for blends with MXD6 and
MXD6-12I, respectively. Blending with an aromatic polyamide was even
more effective in reducing carbon dioxide permeability of oriented PET.
Transformation of spherical polyamide domains into platelets of high
aspect ratio increased tortuosity of the diffusion pathway. The platelet
aspect ratio predicted by the Nielsen model was confirmed by atomic force
microscopy (AFM). Higher aspect ratio of MXD6 domains was ascribed to
a lower Tg compared to MXD6-12I. Similar reduction in oxygen

permeability was achieved in bottle walls blown from PET blends with
MXD6 or MXD6-12I.
The addition of an active oxygen scavenger directly into the PET
polymer can significantly improve the oxygen barrier properties of PET
films and containers. The PET active barrier system can be achieved by
blending through extrusion and reactive extrusion or by direct
polymerization of PET monomer with the incorporation of the scavenging
moiety as a copolymer. Mahajan et al. [57] synthesized copolymers of PET
by the melt polymerization of TPA with EG and with each of the active
oxygen scavengers: monoolein (MO) and 3-cyclohexene-1,1-dimethanol
(CHEDM) in separate compositions. Proton nuclear magnetic resonance
spectroscopy (1H NMR) and 2D correlation spectroscopy (COSY)
indicated that PET had reacted with both MO and CHEDM at their
hydroxyl end groups. Oxygen barrier properties of the MO and CHEDM
copolymers exhibited improvements of up to 40%, in comparison with an
unmodified commercial PET. Effects of the oxygen scavengers on the
copolymers’ physical properties were investigated in terms of their
crystallization, melting, and rheological behaviors. Both types of
copolymers showed decreases in peak melting temperatures with increased
scavenger concentrations and also crystallized more slowly as the
scavenger concentrations increased. The PET/MO copolymer showed non-
Newtonian rheological behavior with higher MO concentration; while the
PET/CHEDM copolymers showed Newtonian behavior within the studied
range of CHEDM concentrations.
Al-Jabareen et al. [58] reported on the oxygen gas barrier properties of
nanocomposites of PET containing graphite nanoplatelets (GNPs). The
effects of the structural morphology on oxygen gas permeability were
analyzed using a range of thermal, microscopic, and mechanical
characterization techniques. The investigated nanocomposite films
exhibited GNP exfoliated morphology and good mixing with PET, as well
as uniform dispersion within the polymer. All nanocomposite films were
shown to possess superior oxygen barrier properties and improved thermal
and dimensional stability compared with the plain PET films. In the best
case, for 1.5 wt.% GNP, the oxygen permeation was reduced by more than

99%. The improved barrier properties are attributed to the direct effect of
the GNPs and to their induced increase of degree of crystallinity. Also,
nanocomposites of PET and two different montmorillonite-based
organoclays were prepared by a co-rotating twin screw extruder. Both
organoclays had a good intercalation with PET and were uniformly
dispersed within the polymer. Oxygen permeability of thin films of
nanocomposites showed that the nanocomposites had better oxygen barrier
properties than the neat PET [59].
PET nanocomposites with low loading (0.1-0.5 wt.%) of graphene
oxide (GO) have been prepared by using in situ polymerization method.
Investigations of oxygen permeability of amorphous films of
nanocomposites showed that the nanocomposites had better oxygen barrier
properties than the neat PET. The improvement of oxygen permeability for
PET nanocomposite films over the neat PET is approximately factors of 2-
3.3 [60].
4.3. Electrical Properties of PET
There is a lot of interest in industrial scale applications of PET due to

its good electrical and dielectric properties. PET is often used as a
dielectric in high-performance foil capacitors and as a polymer electrode.
On the other hand, PET has attracted a lot of interest for fundamental
investigations by dielectric relaxation spectroscopy (DRS) [61]. In most
studies this interest is based on PET being the main chain polymer having
dielectrically active primary and secondary relaxation processes and a very
useful model for “low”- crystallinity polymers [9].
In his early work, Amborski [62] studied the direct current
conductivity of three different forms of PET over a wide temperature and
voltage range to determine the structural dependence of the conduction
process. From the films in the amorphous, crystallized and oriented and
crystallized forms it was determined that crystallization reduces the
conductivity by more than one order of magnitude. Orientation results in a
six-fold decrease in conductivity. The conductivity does not change over a

wide range of molecular weight or carboxyl end group concentration. As

shown from model polymers and copolymers, disruption of chain
symmetry and molecular packing, introduction of side chains or any other
modification which reduces the crystallinity and order, results in greater
conductivity. The results showed that the structural dependence of
conductivity, the temperature dependence, and the current-voltage
relationships of PET were consistent with a proposed ionic mechanism for
the conduction process.
Pop et al. [63] performed DRS measurements on the PET samples of
different microstructures (semicrystalline, amorphous, amorphous
oriented), between 80 and 300 K for frequencies ranging from 10 2 to 105
Hz. The data pertaining to the  relaxation of PET could be fitted to the
Cole-Cole phenomenological equations, from which the relaxation
strength, the average activation energies and the temperature-dependent
distribution functions of relaxation times were obtained. On the basis of
these results, the authors discussed the origin of the  relaxation and the
degree of cooperativity of the  motions.
Electrical conductivity effects in biaxially stretched PET films of 6 μm
thickness and 68% degree of crystallinity were investigated by means of
DRS in the frequency range 10-2-106 Hz and at temperatures higher than the
Tg (∼85°C) up to 190°C. The formalisms of complex permittivity, electric
modulus and impedance were employed to analyze the experimental data.
The results are discussed in terms of dc (direct current) conductivity,
conductivity current relaxation, interfacial Maxwell-Wagner-Sillars
polarization, ρ peak, space-charge polarization and electrode polarization.
They were compared with the predictions of models for the electrical and
dielectric properties of ion-conducting polymers. The dc conductivity
values determined from dc measurement, from ac (alternating current)
conductivity plots and from complex impedance plots agree well with each
other. Their temperature dependence was described by the Vogel-
Tammann-Fulcher equation and classifies PET as a fragile system [64].
PET/graphene nanocomposites with a uniform dispersion of graphene
in PET matrix were prepared by melt compounding. The incorporation of
graphene greatly improved the electrical conductivity of PET, resulting in

a sharp transition from electrical insulator to semiconductor with a low

percolation threshold of 0.47 vol.%. A high electrical conductivity of 2.11
S/m was achieved with only 3.0 vol.% of graphene. The low percolation
threshold and superior electrical conductivity are attributed to the high
aspect ratio, large specific surface area and uniform dispersion of the
graphene nanosheets in PET matrix [65].
In Table 1 are shown some physical, thermal, mechanical and electrical
properties of PET [66].
Table 1. Some physical, thermal, mechanical and electrical properties

of PET (Commercial Polyethylene Terephthalate Polyester, PETP)
[66]
Property Value
Density (ρ), g/m3 1410
Glass transition temperature (Tg),°C 69-115
Melting temperature (Tm),°C 265
Heat of fusion (ΔH), kJ/mol 24.1
Breaking strength (σB), MPa 50
Tensile (Young’s) modulus (E), MPa 1700
Flexural modulus (rigidity) (E), MPa 2000
Ultimate strain (εB), % 180
Yield strain (εY), % 4
Impact Strength (Notched Izod), J/m 90
Hardness (Rockwell) R105
Water absorption after 24 h, % 0.5
Dielectric strength, kV/mm 15.7
Dielectric constant, 106 Hz 3.2 (thermal)
3.3 (electrical)
Volume resistivity, ohm cm  1016
Power factor, 106 Hz 0.0019

5. CHEMICAL STABILITY OF PET
5.1. Chemical Resistance of PET
The chemical resistance of PET is in general very good, mainly due to

its robust chemical nature, but also because its crystalline structure. PET
shows very good resistance to alcohols, dilute acids, aliphatic
hydrocarbons, oils and greases. The resistance of PET toward dilute alkali,
aromatic hydrocarbons and halogenated hydrocarbons is moderate. Phenol,
cresol, chloroethane and nitrobenzene are good solvent for PET at elevated
temperatures.
5.2. Hydrolytic Degradation of PET
Because of its specific microstructure, PET is sensitive to humid

conditions at temperatures above Tg and usually undergoes degradation,
which means that the length of its macromolecular chains decreases. The
extent of degradation strongly depends on the polymer structure and the
environmental conditions of the polymer. Three main mechanisms of
degradation that occur during the melt processing of PET are hydrolytic,
thermal and oxidative mechanisms [67]. In their early study in 1959,
McMahon et al. [68] reported on the effect of relative humidity content,
temperature and film thickness on hydrolytic degradation of PET. They
found that the hydrolytic degradation rate is much higher than the rate of
thermal and oxidative degradation. Relationships between chemical and
physical properties such as viscosity and tensile strength, and their effect
on electrical degradation, were also discussed. Empirical equations were
derived for degradation rates and time to failure. It was concluded that PET
is quite resistant to hydrolysis when compared to other polyesters and
processing conditions such as drawing and final surface finish may alter its
resistance.
Hydrolytic degradation of a polyester includes chain scission reactions
at ester linkages and leads to the creation of one carboxyl and one hydroxyl

end group. Thus, end-group analysis can be implemented as a suitable

technique for investigating the rate of degradation in PET. The hydrolytic
degradation processes are closely encountered with the extrusion, melt
spinning and processing of PET, as well as during the washing of textiles
made from PET fibers. During degradation, it is assumed that water
diffuses into the amorphous regions of the polymer where hydrolysis
occurs at a rate which depends upon the shape, morphology, degree of
crystallinity, relative humidity and temperature. Hydrolysis mechanisms
differ in various chemical environments, i.e., acidic, neutral, and basic
conditions. Under acidic conditions, the accelerated hydrolysis involves
protonation of the in-chain oxygen atom of the ester group followed by a
reaction with water to produce equivalent amounts of hydroxyl and
carboxyl end groups. Under alkaline conditions, the hydroxide anion
attacks the carboxyl oxygen atom to produce equivalent amounts of
hydroxyl and carboxyl end groups [69]. The presence of carboxyl groups
in PET was not only a result of thermal exposure but it also had an
influence on hydrolytic stability.
The hydrolytic cleavage of polyester chains, i.e., the formation of
carboxyl groups, was found to be an autocatalytic reaction [70]. This
autocatalytic reaction is dependent upon the concentration of initial
carboxylic end groups which, in turn, controls the degree of hydrophilicity
of the polyester. PET is a semicrystalline polymer and its crystalline
fraction is nonreactive toward hydrolysis because of its impermeability to
water. With regard to PET microstructure, water molecules can diffuse into
the amorphous regions, and chain scission occurs in this area. This
provides the conditions for small chains to mobilize and realign in the
polymer media, thus increasing the polymer crystallinity. In the Fourier
transformed infrared spectroscopy (FTIR) study of the effect of hydrolytic
degradation on the structure of thin PET films, Sammon et al. [71]
confirmed the autocatalytic nature of the hydrolysis in pure water and the
occurrence of the so-called “chemicrystallization” effect, with crystallinity
increasing with degradation. The thin nature (∼100 nm) of the PET films
allowed a spectroscopic insight into the morphology of the degrading films
as a function of treatment time.

As noted above, PET is quite resistant to hydrolysis in comparison to

other polyesters, which can be attributed to its aromatic character and close
packing of macromolecular chains. However, the rate of hydrolysis
increased quite fast with temperature, wherein the extent of hydrolysis
depends strongly on particle size, crystallinity, relative humidity content
and time of exposure [72].
The degradation of amorphous PET sheet material is investigated
under various environmental conditions: dry soil, wet soil, 100% and 45%
relative humidity (RH) and UV irradiation by measuring the rate of chain
scission using viscometric analysis at several temperatures. The lifetime of
the polyester is found to be very dependent upon the environmental
conditions, with hydrolysis being a dominant process at lower
temperatures. Negligible degradation is observed at temperatures below the
glass transition (∼80°C) in dry conditions. From density measurements at
45 and 100% RH, the crystallinity exhibits an initial facile increase due to
plasticization by the moisture and annealing followed by an inflection
which increases from 26 to 40% with the severity of the degradation
conditions. This inflection is consistent under all degradation conditions at
0.5 of a chain scission and is then followed by a much lower rate due to
combined hydrolytic degradation/oxidation of the polymer chains. The
initial rapid increase is found to be faster at lower rates of chain scission
because of an annealing/plasticization effect by the moisture. This view is
confirmed by the fact that under both dry conditions and UV irradiation,
where significant rates of chain scission are observed especially at high
temperatures and prolonged times (>500 h), the crystallinity only increases
to about 5%. The implications of these results are discussed in terms of
assessing the degradation and hydrolysis of the polymer through physical
and mechanical analysis in relation to actual polymer breakdown [73].
The hydrolysis of PET (Mw = 27 kg/mol) in boiling water has been
studied by steric exclusion chromatography. It appears that both the
average molar mass and the polydispersity index decrease in a
pseudohyperbolic way and tend towards asymptotic values, respectively
Mn∞→2 kg/mol and I∞→1.50. This behavior indicates that hydrolysis is
homogeneous at dimension scales higher than lamellae thickness (Lc).

Hydrolysis occurs in the amorphous phase and at chain folds at the crystal
surface, whereas crystals are unaffected due to their impermeability to
water. The chain length decreases to tend, thus, towards Lc. Embrittlement
is expected to occur when the entanglement network is destroyed in the
amorphous phase. However, despite the above mentioned, PET hydrolysis
can be considered as a random chain scission process in kinetic studies.
[74].
Hosseini et al. [67] studied the hydrolytic degradation which occurred
at the drying of PET before processing and the loss of weight and
mechanical properties in textile materials during washing. Hydrolytic
conditions were used to expose fiber-grade PET chips in water at 85°C for
different periods of time. Solution viscometry and end-group analysis were
used as the main methods for determining the extent of degradation. The
experimental results show that PET is susceptible to hydrolysis. Also, as
the time of retention in hydrolytic condition increased, the molecular
weight decreased, while the rate of chain cleavage decreased to some
extent, at which point there was no more sensible degradation.
The effects of PET resin moisture content and temperature exposure
have been investigated in terms of material changes resulting from the
injection molding process. Two resins with initial carboxyl contents of
10 µeq/g PET and 20 µeq/g PET have been analyzed. Preforms processed
at different resin moisture contents and processing temperatures of 280,
290 and 300 °C were evaluated in terms of carboxyl end-group
concentration using a titration method. Mathematical models describing
the relationships of carboxyl end-group concentration and intrinsic
viscosity to the processing conditions were generated from the
experimental data. Carboxyl end-groups formed were compared for both
resins and shown to be dependent on initial carboxyl content in the resin.
Reducing the initial carboxyl content in the resin was shown to increase its
hydrolytic stability. The hydrolytic effect on the overall molecular weight
drop was separated from the thermal/thermal-oxidative degradation and
shown to be dependent on both the processing temperature and the resin
moisture content [75].

Thermal and hydrolytic degradation of PET (Partly Oriented Yarn

(POY), Fully Drawn Yarn (FDY) and granule) at temperatures above and
below Tg were carried out using a water bath and an electrical oven to
illustrate the extent of hydrolytic degradation of PET caused by warm
water and also to separate the influence of moisture, temperature, and
orientation in the degradation process. The results obtained from different
analysis, including determination of the moisture content, viscometric
analysis, carboxylic end group titration, and X-ray diffraction, showed that
the major portion of degradation is carried out by both moisture and heat
mutually. Degradation at lower temperatures from Tg was less prominent
and was increased noticeably above Tg. Crystallinity played a significant
role in preventing hydrolytic degradation as the extent of degradation was
increased from FDY to granule to POY. X-ray diffraction analysis showed
that crystallinity was increased from POY to granule to FDY [76].
The kinetic studies of polymer microwave depolymerization have
received much attention because of the non-thermal effects that are
observed. The facts that the polymer depolymerization could be
accelerated by microwave irradiation, and that the depolymerization
mechanism was a combination of regular and random chain scission have
generally been accepted. The kinetic processes of PET hydrolytic
depolymerization under microwave irradiation were studied in detail. The
microwave depolymerization reaction of PET occurred simultaneously in
the interior and on the exterior of PET. More than one kinetic process
occurred because of the non-thermal effects of the microwave irradiation.
The chain scission during PET depolymerization under microwave
irradiation involved regular, then random and then again regular processes.
Microwave irradiation made PET depolymerize with a higher rate of
random chain scission events, resulting in the observed non-thermal effects
of microwave irradiation. The reaction rate of PET depolymerization
increased more quickly as the temperature rose. In this experiment, the
depolymerization process was divided into two stages, that is, the stage
before random chain scission and the stage after random chain scission.
The corresponding activation energies were 142 and 378 kJ/mol,

respectively, which were much higher than that of the thermal

depolymerization of heating [77].
5.3. Thermal and Thermo-Oxidative Degradation of PET
The mechanism of PET thermal degradation has been the subject of

several studies [70, 72, 78]. It is believed that the thermal degradation of
PET occurs through random chain scission of the ester linkages, wherein
the methylene group represents the most likely point at which the
degradation begins. The quantitative estimation of the thermal degradation
extent has been done in terms of products formed such as acetaldehyde,
rate of change of molecular weight and rate of change in the concentration
of end groups.
The reactions of thermo-oxidative degradation are additionally
complicated by the participation of oxygen. It has been suggested that the
process starts with the formation of a hydroperoxide at the methylene
group, followed by homolytic chain scission. It has been concluded that
hydroperoxide groups not only play an important role in inducing the
thermal and photo-oxidative degradation of PET, but are also important
intermediates in such reactions [79].
When PET is maintained in a molten state under nitrogen at about
280°C, it decomposes slowly to gaseous and to solid, low molecular
weight products. The functional groups react with one another and the
polymer becomes colored. The composition of gaseous products varies
with temperature, whereby acetaldehyde is always the major product. A
white “dust”, formed during melt spinning of PET, consists primarily of
terephthalic acid and acidic oligomers. Cyclic oligomers (mainly the
trimer) are also formed during the thermal degradation of PET. A kind of
equilibrium between the cyclic oligomers and the polymer seems to exist.
After extracting these oligomers from PET and heating the extracted
polymer for about one hour at 280°C, the same amount of cyclic oligomer
is formed again. During thermal degradation of PET, the concentration of
hydroxyl groups tends to fall and the carboxyl group content of the

polymer increases. Anhydride groups can be formed and they begin to

accumulate when most of the hydroxyl end groups have been consumed.
The anhydride groups are formed by the reaction of vinyl end groups with
carboxyl groups and by dehydration of two carboxyl groups [72].
Discoloration is a serious problem in the production of PET since the
consumer of white polyester goods demands a brilliant white color. As
PET degrades, its color changes first to yellow, then to brown, and finally
to black. Discoloration has assumed the formation of polyenaldehydes
from acetaldehyde. On the other hand, Zimmermann and Kim [70] showed
that unsaturated, color forming molecules are formed from polyvinyl
esters. Edge et al. [80] suggested that the colored species in melt degraded
PET arise from hydroxylation of the terephthalate ring, formation of
unsaturated-ester and quinonoid species.
Jabarin and Lofgren [78] studied the kinetics of thermal and thermal-
oxidative degradation of PET as a function of melt temperature, melt
residence time, melt environment and drying environment. Rates of
thermal and thermal-oxidative degradation were measured in terms of
weight loss of volatile degradation products, decreasing inherent viscosity
and increasing of the carboxyl end groups concentration. Thermal-
oxidative degradation was also investigated by DSC. The DSC results
showed that thermal-oxidative degradation of PET is an exothermic
reaction, with an apparent activation energy of 117 kJ/mol. The authors
concluded that the time and temperature of melting play major roles in
determining the extent of PET degradation as exemplified by weight loss,
color formation, final inherent viscosity and carboxyl end group
concentration. At equivalent experimental (time and temperature)
conditions, significantly more degradation occurs when a material is
melted in an air rather than in a nitrogen environment. When melting in air,
the amount of degradation increases rapidly with increasing temperatures,
especially at temperatures above 300°C. Drying conditions of PET pellets
(temperature, time and atmosphere) can affect weight loss during melting
as well as resultant inherent viscosity and carboxyl end group
concentration. The amount of degradation in the melt is larger (at a given
melt temperature and time) when the material was previously dried in air

atmosphere rather than in a vacuum or inert atmosphere. The amount of

degradation of the PET samples dried in air followed by vacuum drying is
the same as for the samples dried in air atmosphere alone.
Botelho et al. [81] conducted a comparative study of the thermo-
oxidative degradation of PET and PBT. Degradation of the polymer films
and model compounds, ethylene dibenzoate (EDB) and butylene
dibenzoate (BDB), was carried out in an oxygen atmosphere at 160°C. On
the basis of the compounds identified by GC/MS (gas chromatography-
mass spectrometry), a mechanism is proposed for the degradation of the
model compounds that involves the oxidation at the -methylene carbon
with formation of unstable peroxides and carboxylic acids. From the
studies performed under nitrogen at 160°C, it could be concluded that
benzoic acid and esters are products of the thermal degradation, while
benzoic and aliphatic acids, anhydride and alcohols are due to thermo-
oxidative degradation. In contrast to the thermo-oxidative degradation of
other polymers, for PET and PBT, especially at the beginning, thermal
degradation plays an important role. The results clearly showed that PET is
more stable towards degradation than PBT.
1
H NMR and MALDI-TOF MS measurements were used to study the
thermo-mechanical and thermo-oxidative degradation mechanisms of
bottle-grade PET (btg-PET). In the thermo-oxidative degradation, the
concentration of low molar mass compounds increased with time and the
main products were cyclic and linear di-acid oligomers. In the thermo-
mechanical degradation, the main-chain scission reactions affected the
stability of the cyclic oligomers. One of the most important bottle-grade
PET co-monomers is diethylene glycol (DEG), which is a “reactive” site in
the thermal degradation of btg-PET. The DEG co-monomer was shown to
be the precursor to color changes in btg-PET, owing to the attack by
molecular oxygen on the methylene protons adjacent to the ether oxygen
atoms of DEG. This behavior was observed in the thermo-oxidative
degradation process in which the degradation of DEG caused the release of
hydroxyl radicals in the polymeric matrix, thereby producing mono- and
di-hydroxyl substituted species. This was also observed in the thermo-
mechanical degradation process [82].

De A. Freire et al. [83] investigated two PET samples under severe

heating conditions and analyzed oligomers and volatile substances as
potential migrants into foods. The samples were tested for migration into
water, 3% acetic acid and 15% ethanol solution for 1 hour at 95°C. Overall
migration and the specific migration of TPA, EG and DEG were all very
low. The plastics were heated at 150°C, 260°C and 270°C, for 5 minutes,
30 minutes and 60 minutes. Oligomer analysis by LC/MS (liquid
chromatography-mass spectrometry) showed that the concentration of the
second series alicyclic oligomers increased up to 15-fold on heating
whereas the major oligomer fraction, the cyclic trimer, tetramer, pentamer
and hexamer showed only minor concentration changes with heating.
Volatiles evolved by the samples were trapped on a Tenax trap and
identified by GC/MS. They were few in number and low in concentration
and none merited migration tests. It is concluded that even when tested up
to melting point, PET plastics of this type have good temperature stability
and are well suited for high-temperature food contact applications.
The thermal oxidative degradation kinetics of the PET copolymers
modified with poly(lactic acid) (PLA) were investigated by TGA. The
thermal properties of the modified products were also determined by DSC
technique. PETW (P100) obtained from postconsumer water bottles was
modified with a low-molecular-weight PLA. The PET/PLA weight ratio
was 90/10 (P90) and 50/50 (P50) in the modified samples. The thermal
oxidative degradation kinetics of the modified samples was compared with
those of the P100 sample. The segmented block and/or random copolymer
structure of the modified samples formed by a transesterification reaction
between the PLA and PET units in solution and the length of the aliphatic
and aromatic blocks were found to have a great effect on the degradation
behavior. On the basis of the results of the degradation kinetics determined
by Kissinger method, the degradation rate of the samples decreased in the
order of P50 > P90 > P100, depending on the amount of PLA in the
copolymer structure. However, the degradation activation energies of the
samples decreased in the order of P100 > P90 > P50. The authors
concluded that the degradation rate and mechanism were affected

significantly by the incorporation of PLA into the copolymer structure

[84].
Yuan et al. [85] studied thermal stability of the PET nanocomposite
based on the fibrous silicates (PT) organically modified by water-soluble
polyvinylpyrrolidone (PVP). The thermal degradation behavior of PET and
PET/PT nanocomposite was investigated by thermogravimetric analysis
(TGA) under non-isothermal conditions at various heating rates in air and
nitrogen, respectively. The apparent activation energies of the samples
were evaluated by Kissinger and Flynn-Wall-Ozawa method. It is
suggested that, during thermal decomposition in nitrogen, the clay as a
mass-transport protective barrier can slow down degradation of polymer,
but the catalytic effect of metal derivatives in clays may accelerate the
decomposition behavior of PET. The combination of these two effects
determines the final thermal stability of nanocomposite. However, in air
atmosphere, the oxidative thermal stability of PET/PT nanocomposite was
obviously superior to that of pure PET.
6. PROCESSING OF PET
6.1. PET Bottles
Production of PET bottles requires injection molding of preforms, i.e.,

PET granules, and subsequent stretching and blowing of these into bottles.
The combination of the two operations is called injection-stretch-blow
molding and was developed by Wyeth and Roseveare at Du Pont [86].
Both operations can be combined in one machine (the single-stage process)
or in two (the two-stage process). In the single-stage process, the
temperature remains constantly high for the whole process of injection
molding and blow molding, the material should continue being in an elastic
form. This method saves a lot of energy as the material has to be heated
only once, that is when it is injected into the cavity to produce the preform.
The single-stage method is commonly used in small or medium PET
production companies.

In the two-stage process, the preform is injected into shape on the first
machine and then it is reheated and blown on the second machine. The
two-stage method is not very efficient as the heat lost is considered as a
loss of energy, but this machines are fully automated and about 200% more
efficient than the one-step machine [87].
When PET is stretched, it exhibits strain-hardening properties, which
are temperature and strain-rate dependent. This provides a self-leveling
effect on the stretching preform, which is important for forming a bottle of
uniform wall thickness. It is also well known that this behavior is
temperature and strain-rate dependent. At any given strain, increasing the
temperature reduces the strain hardening properties and vice versa. In
contrast, at a fixed temperature, increasing the strain rate causes the
polymer to strain-harden, above all at large strain values. To take
advantage of the strain-hardening properties of PET, the operating
conditions during blow molding, as well as the bottle and preform designs,
must be considered in order to achieve bottles of desirable quality. Pham et
al. [88] characterized experimentally two grades of PET using biaxial tests.
A visco-hyperelastic model is used to describe the stretching behavior for
the polymer. A biaxial characterization method is employed to determine
the model parameters using a robust nonlinear curve-fitting program. This
model can represent adequately well the stretching behavior of PET. Based
on this model, the membrane finite element formulation is developed to
simulate the stretch blow molding process. Two bottles of different
designs, produced based on the single-stage injection blow molding
process, are used to validate the model. Good agreement with the bottle
thickness profile is observed.
Simulations of various stretch blow and blow moldings of
axisymmetric PET bottles have been carried out using ABAQUS software.
A creep constitutive model with material data developed for a
thermoforming process was used in the finite element analysis. Simulations
using shell and solid elements were compared with experimental moldings.
The creep material model, when combined with solid elements and a very
high coefficient of friction, provided the best predictions for bottle side
wall thickness, strains, blowing pressure, and general material movement.

It was found that the predicted wall thickness distribution of the material in
an injection blow molded bottle agreed well with the values obtained using
commercial process conditions [89].
Also, Jang et al. [90] proposed a non-isothermal finite element (FE)
model for the injection stretch-blow molding (ISBM) process of PET
bottles. The constitutive behavior of PET is modeled by the physically
based Buckley glass-rubber model in form of UMAT in ABAQUS. The
heat transfer between the stretch rod, the preform and the mold was
modeled. Extensive FE simulations were carried out to model ISBM of a
20 g - 330 ml bottle made in plant tests. Comparisons of numerical results
with the measurements demonstrated that the model could satisfactorily
predict the bottle thickness and material distributions. Significant nonlinear
differentials were found in strain, temperature and temperature reduction
rate in both bottle thickness and length direction during the process.
6.2. PET Fibers
Textile yarns, used for the production of finished fabrics, are of two
categories: filament yarns and spun yarns. Filament yarns are made of
continuous filaments which are kilometers long, while spun yarns are
composed of cut staple fibers which are a few centimeters long and are
twisted or spun to hold them together in the form of strands. For filament
and fiber applications, PET with inherent viscosity in the range 0.4 to 0.98
dL/g is used [91].
The most effective approach for the production of PET fibers with
improved mechanical properties so far is the utilization of high molecular
weight polymers, which can be obtained by solid-state polymerization.
Due to extremely high viscosity, fiber formation of high molecular weight
PET can be accomplished by solution spinning or spinning with a
plasticizer [42]. However, the melt process, without the added complexities
of chemical reaction and/or mass transfer, is the simplest, conceptually and
economically, for producing fibers suitable for textile and industrial end
uses. In the melt spinning technique, the molten polymer is extruded

through a die, called the spinneret, which has multiple capillaries to form a
slander and cylindrical jet of molten polymer. After passing a certain
distance (frost line) from the spinneret, the molten polymer jet becomes
solidified.
Lin et al. [92] studied fiber melt spinning of PET via modification of
threadline dynamics. Several techniques were implemented in the high-
speed spinning process for the judicious control of threadline dynamics.
This included a thermal conditioning zone (TCZ) for controlling the
threadline temperature profile and a hydraulic drag bath (HDB) for
controlling the threadline spinning stress. Through controlled threadline
dynamics, key factors affecting the structure development such as
temperature, tensile stress and crystallization time, were manipulated to
favor formation of a highly oriented and transversely uniform structure in
the spun fibers. The attenuation profile of the threadline is observed to be
dependent of TCZ temperature, residence time in the HDB, temperature of
the HDB, and take-up speed. It is believed that for the melt spinning
process with the TCZ and the HDB, the threadline dynamics is changed
from the one controlled by inertia and air drag forces to the one controlled
by the imposed hydraulic drag.
Bicomponent melt spinning technology is mainly used to make the
new fibers. Wool is a natural bicomponent fiber, and the side-by-side
bicomponent fibers were developed to imitate the crimp property of wool.
Hwan Oh [93] studied the crimp contraction and the thermal shrinkage in
the bicomponent fiber consisting of two different PET. Regular PET and
modified PET were selected to make a latent crimp yarn. The modified
PET was synthesized to increase thermal shrinkage. The crimp contraction
was mainly dependent on drawing conditions such as draw ratio, heat-set
temperature, and drawing temperature. Difference in shrinkage between
the PET and the modified PET caused the self-crimping of bicomponent
fibers. Although changing the heat-set temperature and the drawing
temperature could not affect dimensional change, the crimp contraction
varied with those variables. As the heat-set temperature and the drawing
temperature decreased, the crimp contraction increased. Difference in
elongation also affected the crimp contraction in the effect of draw ratio.

When the modified PET with neopentyl group was used for highly
shrinkable part, the crimp contraction was greater in comparison with
modified PET with dimethyl isophthalate.
6.3. PET Sheets and Films
Both, PET sheets (thicker than 180 μm) and films can be produced in
a melt polymerization line or by a secondary processing step from preform.
The unoriented PET sheets are made by extruding an appropriate
molecular weight PET melt through a slot die and quenching over a chill
roller. The amorphous, transparent sheets are used mainly in
thermoforming, where a sheet of polymer (50-1200 μm), is reheated
(softened) and then deformed by vacuum into a mold where it cools. The
products include clear cups, trays and blister packages for pharmaceutical
tablets [87].
A highly crystalline, but opaque PET trays are produced from a
polymer with very high inherent viscosity (1 dL/g) and high melting point
(260°C). Due to the high crystallinity, the trays can be heated with food in
a microwave oven and can withstand temperatures up to 220°C. For their
production, the transparent thermoformed PET article is transferred to a
heated mold to crystallize. Spherulite crystallization takes place because
the article formed by the initial thermoforming did not undergo much
strain-induced crystallization and it may be promoted by addition of
nucleation additives incorporated to promote fast thermal crystallization
[87].
Biaxially oriented films are much thinner (5-180 μm) than the
unoriented sheets. Their applications include video and magnetic tapes,
floppy disks, photographic products, and capacitors. A high degree of
purity is required, and clean room conditions similar to those used to
manufacture electronic or medical components are often applied. A
sequential drawing process for the production of biaxially oriented films
consists of four steps: melt extrusion through a slot die and quenching to
form an amorphous precursor film, on-line drawing in the extrusion

direction, on-line drawing in the transverse direction and on-line heat-

setting. A thick biaxially oriented PET films (75-180 μm) are used in
various photographic applications and are produced by extrusion and chill
casting.
Biaxially oriented films can be produced also by the tubular film
blowing process. The melt is extruded in the form of a tube from an
annular die and is inflated by air pressure. Kang et al. [94] reported on
double bubble-tubular film extrusion of PET. In the second bubble, the
film is passed through a hot air where it undergoes a significant increase in
inflation level. The film produced by the first bubble is largely
amorphous/glassy (5 to 7% of crystallinity), while that produced in the
second bubble can have significant levels of crystallinity (7 to 45%)
dependent upon process conditions. Crystallinity notably increases with
machine direction draw down ratio. The crystallinity levels are similar to
those of biaxially stretched films. Subsequent annealing increases and
perfects crystallinity. The surface roughness of double bubble tubular films
is similar to that of glassy polymers produced from single bubble
operations and is much smaller than for polyolefins. Biaxiality of
orientation increases with the second blowup ratio.
7. RECYCLING OF PET WASTE
As already stated, due to its excellent mechanical properties and

chemical resistance, today PET is an irreplaceable material with numerous
applications. On the other hand, a continuous increasing consumption
along with non-biodegradability of poly(ethylene terephthalate) waste
(PETW) has led to serious problem of environmental and economic
importance, wherein management of PETW has become a global social
issue. It is considered that recycling processes are the best way to
economically reduce PETW [95]. Recycling of PET represents one of the
most successful and widespread examples of polymer recycling. This
material is fully recyclable and may be used for manufacturing new

products in many industrial fields such as packaging for detergents,

cosmetics, carpets, foils, car parts or back into PET bottles [96].
The various methods of PET recycling include primary, secondary
(mechanical), tertiary (chemical) and quaternary methods [97]. Primary
recycling refers to the in-plant recycling of the scrap material of controlled
history, that is, reuse of products in their original structure. This method is
easy to perform and low cost, but dealing only with clean, uncontaminated,
single-type waste.
7.1. Mechanical Recycling of PETW
Currently, the dominant form of PETW recycling worldwide is

mechanical recycling which means the reprocessing of waste plastics by
physical means, like cutting, shredding, washing, and so on, into plastic
products. Mechanical recycling requires homogenous plastics and
relatively clean material. It is especially important to remove paper labels
and label adhesives which cause the PET to discolor and lose clarity, as
well as PVC liners in bottle caps. PVC and PET have almost the same
density and are difficult to separate from each other. PVC releases
hydrochloric acid during PET reprocessing, reducing the commercial value
of recycled PET. Also, the presence of colored PETW imparts an
undesirable gray color to the recycled PET [98]. The general process of
mechanical recycling involves a six-stage process: collection/segregation,
cleaning and drying, chipping/sizing, coloring/agglomeration, pelletizing/
extrusion and manufacturing of the end product [99]. However, the powder
obtained by mechanical recycling, due to the degradation which occurs
during each cycle, shows a decrease in physical properties compared to
virgin PET and it is not suitable for bottle products. The molecular weight
of the recycled polymer is reduced because of chain-scission reactions
caused by the presence of water and traces of acidic impurities. Through
mechanical recycling, waste PET bottles can be found in films, sheets,
strapping packaging, and fiber used for sacking and their usage for
insulation and for floor covering has also been studied [100, 101].

Strategies for maintaining the high average molecular weight of polymer

during reprocessing are also studied and include intensive drying,
reprocessing with vacuum degassing and the use of chain extender
compounds [102]. Mechanical recycling, however, does not prevent the
accumulation of PET in landfills, because the lifetime of the secondary
product is limited, and it will eventually be discharged into the landfill.
The recycled PET is chemically heterogeneous due to the presence of trace
metals from the catalyst residues and additives (such as antimony, cobalt
and manganese) which may affect the melt rheology behavior from batch
to batch [98]. Despite this fact, mechanical recycling is an inexpensive way
to reduce the buildup of waste PET into the landfills after they have been
consumed. Also, the reprocessed material can be blended with virgin PET
to improve physical properties and obtain superior results [97].
7.2. Chemical Recycling of PETW
Chemical or feedstock recycling (tertiary recycling) involves

transformation of polymer chains. It is defined as the process leading to the
total or partial degradation of the polymer backbone to the monomers (i.e.,
depolymerization) or to oligomers or larger chain fragments (i.e., random
chain scission) and other chemical substances, which are mainly gaseous
products. The chemical recycling is carried out either by solvolysis or by
pyrolysis. The solvolysis occurs through degradation by different solvents,
while the pyrolysis occurs through degradation by heat in absence of
oxygen or air or in a vacuum. Chemical recycling yields monomers,
petroleum liquids and gases [21]. Monomers are purified by distillation
and drying, and they could subsequently be repolymerized to regenerate
the original polymer [97]. Chemical recycling of PET has been the subject
of increased interest as a valuable feedstock for different chemical
processes. The solvolytic chemical recycling by chemical degradation of
waste PET is usually divided in several groups according to the reaction
mechanism involving methanolysis, glycolysis, hydrolysis, ammonolysis,

aminolysis and other processes, whereby methanolysis and glycolysis are

mainly applied on a commercial scale [103].
The techniques of tertiary recycling include hydrogenation,
gasification, chemical depolymerization, thermal cracking, catalytic
cracking and reforming, photodegradation, ultrasound degradation and
degradation in a microwave reactor. Some other technologies are also
developed in order to produce oligomeric intermediate products from
waste PET of specialized components for the chemical industry. Only
chemical recycling conforms to the principles of sustainable development
because it leads to the formation of the raw materials from which PET is
originally made. In a large collection of researches of the chemical
recycling of PET, the primary objective is to increase the monomer yield
while reducing the reaction time and/or carrying out the reaction under
mild conditions. Continuous efforts of researchers have brought about
great improvements in the chemical recycling processes [104].
7.3. Methanolysis
Methanolysis of PET consists of the degradation by methanol at

relatively high temperatures (170-280°C) and pressures (20-40 atm). The
main products of PET methanolysis are DMT and EG, which are the
monomers for the PET synthesis [105, 106]. The Kodak Co. possesses a
patent describing a process of PET methanolysis and its optimum
properties [107]. Another approach to methanolysis was presented in a
patent concerning a continuous, two stage process whose main product is
TPA [108]. Sako et al. [109] proposed an improved procedure of
methanolysis by treating PET with supercritical methanol, whereby PET
was completely depolymerized to DMT, EG and oligomers above 300°C at
11 MPa for 30 min without a catalyst. The solid products of the PET
methanolysis with supercritical methanol mainly composed of dimethyl
terephthalate and small amounts of methyl-(2-hydroxyethyl) terephthalate,
bis(hydroxyethyl)terephthalate, dimers and oligomers, and the liquid
products composed of ethylene glycol and methanol. It was found that both

the yield of dimethyl terephthalate and the degree of PET depolymerization

were seriously influenced by the temperature, weight ratio of methanol to
PET, and reaction time, whilst the pressure has insignificant influence
when it is above the critical point of methanol [110].
PET methanolysis involves both random and chain-end scission, and is
interesting from a theoretical point of view because of the secondary
reactions of the chain-end scission products. Goto et al. [111] reported the
population balance equation that governs the PET molecular weight
distribution solve with the moment method. Their work demonstrated that
conventional kinetics can be combined with distribution kinetics to analyze
complex macromolecular reactions. The methanolysis is used by large PET
manufacturers such as Hoechst and Eastman as well as lesser
manufacturers [21]. The main advantage of this method is that an
installation of methanolysis can be located in the polymer production line,
where waste PET arising in the production cycle is used and the monomers
recovered can be re-used in the manufacture of a full value polymer.
Disadvantages of the method include the high cost associated with the
separation and refining of the mixture of the reaction products (glycols,
alcohols and phthalate derivatives). The methanolysis process can tolerate
a wide range of contaminants. However, water does perturb the process
and poisons the catalyst to form various azeotropes. The main
disadvantage is associated with the trend of all of the new PET production
processes to use TPA instead of DMT as the raw material. The conversion
of the DMT produced by hydrolysis to TPA adds considerable cost to the
methanolysis process [21].
Misra and Goje [112] determined optimal reaction conditions for the
methanolysis of PETW including reaction time, reactant particle size,
percentage recovery of monomeric products, methanolysis rate constant,
condensation rate constant, equilibrium constant, Gibbs free energy,
enthalpy and entropy of reaction using zinc acetate in the presence of lead
acetate as the catalyst at 120, 130 and 140°C. Methanolysis reactions were
carried out below 150 °C to avoid oxidation/carbonization during the
reaction. Optimal percentage conversion of PETW into DMT and EG was
97.8% (at 120 °C) and 100% (at 130 and 140 °C) for the optimal reaction

time of 120 min. Yields of DMT and EG were almost equal to PET

conversion. A kinetic model was developed and the experimental data
show good agreement with the kinetic model. Rate constants, equilibrium
constant, Gibbs free energy, enthalpy and entropy of reaction were also
evaluated at 120, 130 and 140 °C. The methanolysis rate constant of the
reaction at 140 °C (10.3 atm) was 1.4 × 10−3 g PET mol-1 min-1. The
activation energy and the frequency factor for methanolysis of PETW were
95.31 kJ/mol and 107.1 g PET mol-1 min-1, respectively.
Kurokawa et al. [113] studied the use of aluminium triisopropoxide
(AIP) as a catalyst for the methanolysis of PET. The methanolysis at
200°C in methanol with an AIP catalyst gave DMT and EG in 64% and
63% yields, respectively. The yields were increased by using a
toluene/methanol mixed solvent containing 20-50 vol.% toluene.
Maximum yields, 88% for DMT and 87% for EG, were obtained at 20
vol.% toluene. These results indicate that the rate of methanolysis strongly
depends on the solubility of PET. The results of gel permeation
chromatography (GPC) suggest that the methanolysis of PET in the
absence of the catalyst includes three steps. In the first step, the
depolymerization occurred at a tie molecule connecting PET crystals and
the chain length was shortened to about 1/3. The shortened chain was
depolymerized to oligomers in the second step. The GPC curve of the
oligomers tailed to low molecular weight, clearly indicating that the
depolymerization took place at random positions on the polymer chain.
The third step, the depolymerization from the oligomers to the monomers,
was promoted only in the presence of the AIP catalyst.
7.4. Glycolysis
The simplest method of PET depolymerization, which is widely used

on a commercial scale in many companies worldwide such as DuPont,
Goodyear, Shell Polyester, Zimmer, Eastman Kodak and other, is the
glycolysis reaction [98]. The glycolysis represents the molecular
degradation of PET polymer by glycols, in the presence of typical

transesterification catalysts, mainly metal acetates, where ester linkages are

broken and replaced with terminal hydroxyl groups, either under pressure
or at atmospheric pressure [114-116]. The method involves a
transesterification reaction of PET with an excess of glycol at temperatures
in the range of 180-240°C, promoting the formation of bis-HET. The bis-
HET monomer and a low molecular mixture of oligomers from a partial
hydrolysis of the PETW with EG can be re-circulated to the PET synthesis
process or used in the synthesis of various polymers such as unsaturated
polyesters, polyurethanes, vinyl esters, epoxy resins and polymer concretes
[117].
Glycolysis of PETW proceeds through at least three stages: oligomers,
dimer and monomer. The glycol diffuses into the polymer, causing the
polymer to swell up, thus increasing the diffusion rate. The glycol
subsequently reacts with an ester bond in the chain and degrades the PET
into lower fractions [118]. Baliga and Wong reported on glycolysis of
PETW from post-consumer soft-drink bottles in excess of EG at 190°C in
the presence of a metal acetate catalyst. After 8 h the glycolyzed products
consisted mostly of the monomer, bis-HET and the dimer. After prolonged
glycolysis, equilibrium was established between the monomer and the
dimer and EG, with an equilibrium constant lying between 1.13 and 1.53.
Of the four metal acetates (lead, zinc, cobalt, and manganese) tested, zinc
acetate was found to be the best in terms of the extent of depolymerization,
that is, the relative amount of monomer formed [119]. Also, PETW was
depolymerized with ethylene glycol in the presence of different catalysts,
two conventional metal catalysts (zinc acetate and lead acetate) and two
alkalies (sodium carbonate and sodium bicarbonate). The results show that
the qualitative and quantitative yields of the monomer obtained with
alkalies as catalysts were most comparable with the conventional heavy
metal catalysts, thus providing a further advantage for the recycling of
polyester waste for the cause of environmental pollution abatement [120].
Controlled glycolysis of PET was carried out under nonaqueous alkali
conditions to obtain an enhanced hygroscopicity. This treatment
considerably enhanced the hygroscopicity of the treated PET as indicated
by instant wicking and contact angle measurement. The effectiveness of

three alkali catalysts was directly related to their alkali strength, i.e.,
sodium hydroxide > sodium carbonate > sodium bicarbonate. Both losses
of weight and strength increased at higher temperatures, but with sodium
hydroxide they leveled off at 120°C. At 2 h of treatment, the treated PET
showed instantaneous wetting in most cases. The morphological changes
that substantiated strength loss of the fabrics were confirmed by FTIR
analyses, and the effect was greater with sodium hydroxide. DSC analysis
indicated that melting peaks of the glycolyzed PET were relatively
consistent except at high temperature (120°C), which showed a significant
conformational change. These results showed that the glycolysis treatment
of PET fabric at 80°C for 1 h could be an optimal condition to obtain the
balance between high hygroscopicity and desired physical properties [121].
Various experimental factors include temperature, pressure, reaction
time, as well as stirring speed, particle size, a choice of solvent and its ratio
[122]. López-Fonseca et al. [123] studied the kinetics of glycolysis of
PETW to give highly pure bis-HET in a batch reactor using EG in excess
at atmospheric pressure. The reaction was carried out in the presence of
sodium carbonate as active catalyst. A kinetic model considering the
reaction rate to be first order with respect to PET, bis-HET and sodium
carbonate concentration satisfactorily described the kinetics of the
glycolysis with an excess of EG. The effect of particle size (0.14–3 mm)
and stirring rate (50–800 rpm) on conversion was examined. The selected
PET particle size and stirring rate were 0.25 mm and 600 rpm,
respectively. Using PET:catalyst molar ratio of 100:1 about 80% bis-HET
yield was attained at 196°C after 1 h.
The type and amount of used glycol have a significant impact on the
properties of the final products. For the glycolysis of PETW can be used
different glycols, such as EG, diethylene glycol (DEG), propylene glycol
(PG), poly(ethylene oxide) (PEO), neopentyl glycol (NPG), 1,4-butanediol,
and hexylene glycol. Also, it is possible to use the mixture of some glycols,
but EG is more suitable and brings about remarkable result in PET
depolymerization [124]. An increasing of glycol/PET ratio increases the
rate of decomposition which leads to producing lower weight oligomers,
but the high glycol/PET ratio, which is suitable for achieving lower

molecular weight of oligomers, can cause problems in the mixing process

[122]. G. Güçlü et al. [125] reported the use of xylene as the solvent for the
products of glycolysis, wherein PET and EG were insoluble in xylene,
even at high temperatures. During the multiphase reaction,
depolymerization products transferred to the xylene medium from the
dispersed PET/glycol droplets, shifting the equilibrium to glycolysis. Best
results were obtained from the EG reaction at 220°C, which yielded 80
mol. % bis-HET monomer and 20 mol.% dimer fractions in quite pure
crystalline form. Other advantages of the use of xylene in glycolysis of
PET were improvement of mixing at high PET/EG ratios and recycling
possibility of excess glycol, which separates from the xylene phase at low
temperatures.
Besides metal acetates, there are various catalysts which can be used in
PET glycolysis, such as ionic liquids [126-129], urea [130], metal oxide
nanocomposites [131, 132] or hydrotalcit [133]. Wang et al. [127] reported
on the chemical recycling of PETW by EG catalyzed by different kinds of
ionic liquids at atmospheric pressure. It was found that the purification
process of the products in the glycolysis catalyzed by ionic liquids was
simpler than that catalyzed by traditional compounds, such as metal
acetate. Qualitative analysis showed that the main product in the glycolysis
process was the bis-HET monomer. Thermal analysis of the glycolysis
products was carried out by DSC and TGA. The influences of experimental
parameters, such as the amount of catalyst, glycolysis time, reaction
temperature, and water content in the catalyst on the conversion of PET,
selectivity of bis-HET, and distribution of the products were investigated.
The results show that reaction temperature was a critical factor in this
process. The conversion of PET increased with increasing amount of
catalyst, glycolysis time and reaction temperature, but decreases with the
addition of water in the catalyst. The selectivity of bis-HET is enhanced by
increasing amount of catalyst and reaction temperature with a maximum
value for an optimum value of glycolysis time, but decreases with the
increase of water content in the ionic liquid. The glycolysis of PET was
studied using 1-butyl-3-methylimidazolium acetate [Bmim][OAc] as a
catalyst. The effects of temperature, time, ethylene glycol dosage, PET

amount and [Bmim][OAc] dosage on the glycolysis reaction were

examined. The results revealed that the [Bmim][OAc] has a PET
conversion of 100% and bis-HET yield of 58.2% under the optimum
conditions of 1.0 g of [Bmim][OAc] with 20 g of ethylene glycol in the
presence of 3.0 g of PET at 190°C after 3 h of glycolysis. The ionic liquid
could be reused up to six times with no apparent decrease in the conversion
of PET or yield of bis-HET. The pH plays a major role in explaining the
proposed mechanism of glycolysis using the Lewis base ionic liquid
[Bmim][OAc]. The kinetics of the reaction was first-order with an
activation energy of 58.53 kJ/mol [128]. The degradation of PET bottles
has been successfully achieved using hydrotalcite as catalyst and dimethyl
sulfoxide (DMSO) as solvent. The reaction was carried out at boiling point
of DMSO (190°C) and degradation was complete in 10 min. The oligomer
(tetramer) obtained was treated with NaOH at room temperature in
methanol to get DMT and EG. The hydrotalcite can be recycled again. The
oligomer (tetramer) has been found to be pure [133].
7.5. Aminolysis
Aminolysis is the reaction of PET with different primary amine

aqueous solutions such as methylamine, ethylamine, ethanolamine and
anhydrous n-butylamine in the temperature range of 20-100°C to yield the
corresponding diamides of TPA and EG [98]. PET in the form of waste
fibres and disposable soft drink bottles was subjected to depolymerization
through aminolysis using excess of ethanolamine in the presence of glacial
acetic acid, sodium acetate and potassium sulphate as catalysts. The
product bis(2-hydroxyethylene) terephthalamide (BHETA) obtained was in
its pure form with sufficiently high yields with all the catalysts. The
maximum yields of BHETA under optimized conditions were 91.1% from
PET fibrous waste and 83.2% from bottle waste. In the absence of any
catalyst, the yield was only 52%. This difference in the yields was
attributed to the molecular weight and its distribution in PET fibrous waste
and the bottle waste. For the fibre grade PET, the molecular weight is

lower and the molecular weight distribution is narrower than that for the
bottle grade PET in order to attain higher viscosity for the latter, necessary
for the blow-molding process [134]. The aminolysis reaction can be also
run successfully as uncatalyzed reaction. Soni et al. [135] reported on the
uncatalyzed degradation of PETW by hydrazine monohydrate at ambient
temperature and pressure. The end product was characterized as
terephthalic dihydrazide (TPD) and further used in PVC compounding as
secondary plasticizer. The complete degradation of PETW was achieved
after 45 days in the case of a 1:10 weight/volume ratio of PET to amine,
but with a 1:2 weight/volume ratio of PET to hydrazine monohydrate, the
degradation time was considerably reduced to 24 h at ambient conditions.
Mittal et al. [136] studied the degradation properties of the PETW
flakes by aqueous methylamine and aqueous ammonia, respectively, at
room temperature in the presence and absence of quaternary ammonium
salt as a catalyst for different periods of time. PET degraded more quickly
in the presence of the catalyst, where the long polymeric chains in the
semicrystalline PET were reduced to monodisperse rods before full
degradation into the end products, and the fissures on the surface of PET
were found to deepen with time. The amorphous portion was removed at a
faster rate, and there was a marked increase in the crystallinity of the
residue toward the completion of the reaction.
The product of aminolysis, BHETA, has the potential for further
reactions to obtain useful products. There are few reports on usage of
recycled BHETA from PETW to synthesis of novel biodegradable
polyurethanes based on polycaprolactone diol, which showed excellent
chemical, thermal and mechanical properties [137]. Also, the suitability of
BHETA obtained from the aminolyzed PET waste was assessed for use as
an ingredient in the anticorrosive paint formulations for the protection of
steel structures [138]. The synthesized BHETA possessed high hardness
and stiffness, good resistance to weathering, creep strength, and high
dimensional stability. The addition of organic BHETA into the paint
formulation barely affected the physical and mechanical properties of the
paint films.

7.6. Ammonolysis
Ammonolysis is the reaction of ammonia with PET to produce a

terephthaldiamide (TPDA). This can be converted to terephthalonitrile, and
further, to other chemical substances. Very good results were obtained
from the ammonolysis of PET waste from postconsumer bottles. The
process was carried out under a pressure of about 2 MPa in a temperature
range of 120-180°C for 1-7 h. After the reaction was completed, the amide
produced was filtered, rinsed with water, and dried at a temperature of
80°C. The TPDA amide is produced by the action of anhydrous ammonia
on PET in an ethylene glycol environment. This can be converted into
terephthalic acid nitrile and further to p-xylylenediamine or 1,4-
bis(aminoethyl)cyclohexane [97, 139].
7.7. Hydrolysis
Hydrolysis is a method of PETW recycling in which PET is reacted

with water in acidic, basic or neutral condition, leading to complete
depolymerization and resulting in its monomers, TPA and EG. The
hydrolysis reactions require the use of high temperature (200-250°C), as
well as relatively high pressure and also long time needed for complete
depolymerization. Commercially, hydrolysis is not widely used, because of
the cost associated with purification of the recycled TPA. Hydrolysis of
PET can be carried out as alkaline, acid and neutral hydrolysis [21].
Alkaline hydrolysis of PET is usually carried out with the use of an
aqueous alkaline solution of NaOH or KOH, in the concentration of 4-20
wt. % [140]. The reaction products are EG and the disodium or
dipotassium terephthalate salt. The mixture is heated up to 340°C to
evaporate and recover the EG by distillation. Pure TPA can be obtained by
neutralization of the reaction mixture with a strong mineral acid (e.g.,
H2SO4) [98, 103]. Kumar and Guria [141] studied hydrolytic
decomposition of PETW in the presence of an aqueous potassium
hydroxide solution and developed a modified shrinking core model with a

depleting product layer of waste PET under finite solution volume

conditions. This model assumes the first order depolymerization kinetics
with respect to the concentration of potassium hydroxide solution. The
conversion of PETW is determined after filtration of the unreacted PET
left after depolymerization. The conversion of PET is also compared with
the amount of terephthalic acid obtained after acidification of the filtrate.
The factors which have a great effect on the kinetics of the alkaline
depolymerization of PET in NaOH solution are temperature, time and
alkali concentration, as well as the choice of solvent [142]. The main
advantage of alkaline hydrolysis in comparison with the other methods of
the chemical recycling is that it can tolerate highly contaminated, post-
consumer PET such as magnetic recording tape, metallized PET film or
photographic film (X-ray film). The process is relatively simple and less
costly than methanolysis [98]. Karayannidis et al. [143] studied the
reaction alkaline hydrolysis of PET in an autoclave with a nonaqueous
solution of KOH in an ether alcohol, methyl Cellosolve. The ether part of
methyl Cellosolve led to swelling of the PET solid and the alcoholic part
supported the action of the OH- groups in destroying the chemical structure
of PET during depolymerization. The reaction temperature was 120°C and
the reaction time was 2.5 h.
Acid hydrolysis is performed most frequently using concentrated
sulfuric acid, although other concentrated mineral acids (e.g., phosphoric
or nitric acid) can be used. Acid hydrolysis of PET in sulfuric acid at
different temperatures and solution concentrations was reported [140].
Neutral hydrolysis is carried out with the use of water or steam in the
presence of alkali metal acetates as transesterification catalysts. Low purity
of TPA is the major drawback of this method. Hydrolysis is comparatively
slow because water is a weak nucleophile [97, 98].
7.8. Enzyme Catalyzed Hydrolysis
Recently, the recycling methods based on enzyme catalysis have been

provided with many advantages compared to classical chemical processes.

Enzyme technology could be applicable in large scale such as, in term,

improving green industries especially in dealing with production (such as
detergents) or recycling and detoxifying of daily products. Advantages of
enzymatic methods include the fact that their action under mild conditions
with low energy input without the need for expensive machinery might be
helpful in PET degradation [122]. PET is a non-natural substrate for
enzymatic reactions and therefore classically is considered as recalcitrant
to biodegradation, which results in slow enzymatic rate toward this
polymer.
Eberl et al. [144] reported on hydrolysis of PET and
bis(benzoyloxyethyl) terephthalate (3PET) endo-wise by a lipase from
Thermomyces lanuginosus and cutinases from Thermobifida fusca and
Fusarium solani and bis(benzoyloxyethyl)terephthalate (3PET) endo-wise
as shown by MALDI-Tof-MS, LC-UVD/MS, cationic dyeing and XPS
analysis. Due to interfacial activation of the lipase in the presence of Triton
X-100, a seven-fold increase of hydrolysis products released from 3PET
was measured. In the presence of the plasticizer N,N-diethyl-2-
phenylacetamide (DEPA), increased hydrolysis rates of semi-crystalline
PET films and fabrics were measured both for lipase and cutinase. The
formation of novel polar groups resulted in enhanced dye ability with
additional increase in color depth by 130% and 300% for cutinase and
lipase, respectively, in the presence of plasticizer.
Recently, Yoshida et al. [145] isolated a novel bacterium, Ideonella
sakaiensis 201-F6, that is able to use PET as its major energy and carbon
source. When grown on PET, this strain produces two enzymes capable of
hydrolyzing PET and the reaction intermediate, mono(2-
hydroxyethyl)terephthalic acid. Both enzymes are required to
enzymatically convert PET efficiently into its two environmentally benign
monomers, TPA and EG. The assimilation of PET by I. sakaiensis bacteria
may be advantageous for removing this plastic material from the
environment. However, if the terephthalic acid could be isolated and
reused, this could provide huge savings in the production of new polymer
without the need for petrol-based starting materials. To establish such a
process, it may be possible to integrate the PETase/MHETase pair into

common production strains via metabolic engineering or the use of enzyme

cascade systems. Further research in this area will hopefully provide
concepts and solutions for the degradation and recycling of other
degradation-resistant plastic materials that are currently used and disposed
[146].
7.9. Quaternary Recycling
Energy recovery or quaternary recycling refers to the recovery of

energy that is contained in a polymer, and this is currently the most
effective way to reduce the volume of organic materials together with
considerable yield of energy. However, in some aspects this method is
ecologically unacceptable owing to the health risk from airborne toxic
substances [147]. Apart from the aforementioned methods, direct reuse of
PET bottles could be considered as a zero-order recycling techniques.
However, this should be done with a great care since plastic bottles are
more likely than glass to absorb contaminants, which could be released
into the contents (especially food) when the bottle is refilled. Moreover,
refilling a PET bottle with a drink of high alcoholic content may lead to the
degradation of the macromolecular chains with unpredictable
consequences.
8. THERMOPLASTIC COPOLYESTER ELASTOMERS
Thermoplastic copolyester elastomers, poly(ester-ether)s (TPEEs) are

multiblock copolymer containing crystalline, hard segments and
amorphous, soft segments [148-150]. The thermoplastic and elastic
behavior of TPEEs can be explained by their two-phase microstructure,
which is a consequence of the chemical nature and incompatibility of the
hard and soft segments, which are built into the polymer chains. The hard
phase acts as physical crosslinks for the amorphous, rubbery regions,
imparting the material properties as an elastomer [151-154]. TPEEs

possess the mechanical properties of chemically crosslinked elastomers,

e.g., elastic recovery and good flexibility at low temperatures, and of
thermoplastics such as high modulus and impact strength. Moreover,
TPEEs can be processed as conventional thermoplastic materials above the
melting temperature of the hard segment and conventional methods for
processing are extrusion and injection-molding. TPEEs behave as
crosslinked elastomers at room temperature and as linear polymers at high
temperatures.
Over the past four decades, the commercial growth of TPEEs has been
increasing constantly due to their good physical and mechanical properties.
The properties of TPEEs depend on their molecular weight, the type and
molecular weight of the soft segment and the hard/soft segment content.
PET and PBT are very suitable for use as hard crystallizable segments
in multiblock copolymers, which belong to the class of thermoplastic
copolyester elastomers. The hard, crystalline PET or PBT segments are
dispersed in an amorphous matrix usually at lower hard segment content,
which contains the soft polyether segments and the non-crystalline parts of
the hard segments. In a molten state, TPEEs with relatively short hard
segments typically form a homogeneous mixed phase of hard and soft
segments. Upon crystallization, hard segments are ordered into domains,
creating a physical network, which provides dimensional stability and
minimizes the cold flow of the polymeric material [155-157]. It was shown
that the crystallization process is the driving force for the phase separation
causing the formation of a co-continuous two-phase morphology [158,
159].
The structure of TPEEs after crystallization can be presented by a two-
phase model: a crystalline polyester phase and a homogeneous amorphous
phase of the polyether mixed with the non-crystalline polyester part. Both
phases are considered to be continuous (Figure 5). Gabriëlse et al. [160]
reported that the crystalline structure of TPEEs is typically a lamellar or
pseudo-lamellar microstructure. The lamellar hard domains in TPEEs are
regular in size and shape, similar to the structure observed for PBT or PET
homopolymers. Transmission electron microscopy (TEM) images have
shown that the dimensions of these lamellae are 10 nm in thickness and up

to several hundred nanometers in length. The crystalline hard domains

appear as white regions, while the amorphous soft segments are visible as
black regions owing to their absorption of the staining agent. The
crystalline lamellae are probably interconnected by tie molecules as they
are in crystalline PBT homopolymer.
In 1954, Coleman [161] reported the first synthesis of thermoplastic
poly(ester-ether) elastomers based on PET as the hard segment and PEO
with up 30 wt.% as the soft segments. It was shown that the inclusion of
PEO segments into polyester chains decreased crystallinity and enhanced
hydrophilicity, which could improve the dyeability of the PET fibers. In
1959, Charch and Shivers [162] revealed that when the PEO content as the
soft segments was between 40 and 70 wt.%, then the elastic properties of
TPEEs could be observed.
Figure 5. TEM image of poly(ester-ether) films based on PBT and PTMO: (a) 35 wt.%
of PTMO soft segment and (b) 60 wt.% of PTMO soft segment [160]. Similar
morphology was observed for PET-based poly(ester-ether)s with same soft segment
content.
Commercial thermoplastic poly(ester-ether) elastomers, based on PBT

as the hard segment and poly(tetramethylene oxide) (PTMO) as the soft
segment were developed by DuPont and introduced to the market in 1972,
under the trade name of Hytrel® [163]. Lately, a large number of studies of

segmented copolymers based on PBT hard, rigid segments and different

new soft, flexible segments, such as polyethers, aliphatic polyesters,
polyolefin, polyamide, dimerized fatty acids, and polydimethylsiloxanes,
have been reported [164-176].
TPEEs are mostly synthesized from PET or PBT by step-growth
polycondensation in the molten state with ED or BD, polyether macrodiol,
DMT or terephthalic acid in two or three stages (Figure 6). These stages
are: (a) transesterification of DMT or the condensation of terephthalic acid
with hydroxyl groups of both polyether and low molecular weight diol, (b)
low-pressure melt polycondensation at a high temperature (250-300°C),
and (c) post-polycondensation in a solid state when a copolyester of higher
molecular weight is required.
Figure 6. Synthesis of PET-based poly(ester-ether)s by conventional two-stage

polycondensation.
Contrary to PBT, which generates TPEE based on PTMO with a

phase-separated microstructure, PET is not known to produce such
elastomers without additional modification of the polymer [157]. The
synthesis and properties of PET block copolymers based on PEO [177-

180], PTMO [181], and poly(ε-caprolactone) (PCL) [182-184] segments

have been described. The addition of 10 wt.% of polyether segments in
PET-based TPEEs hampers is known as the “cold crystallization” of PET,
and these block copolymers can be considered to be semicrystalline. A
reduction the melting temperature due to the presence of polyether
segments in block copolymers [185] was observed. Moreover, the
enhanced modulus and thermal properties are of great interest in
developing PET based block copolymers [3]. The introduction of any
flexible molecular repeat units, such as long-chain aliphatic diols or
diacids, large hydrocarbon phases, such as C36 dimer acid would be
expected to impart macroscopic flexibility to PET copolymers. Hence, the
primary goal of the copolymerization of PET with modifying substances is
to either accelerate or delay the ultimate degree of crystallization, to either
increase or decrease the modulus and tensile properties, to bring about
higher or lower glass transition temperature and melting temperature
values for the copolymer, and to modify the dynamic properties, such as
oxygen and carbon dioxide permeation rates – all while essentially
retaining the balance of the properties and the low manufacturing costs
which are associated with PET homopolymer.
The employees at AlliedSignal have developed a block copolymer
based on PET and PCL, which have been commercialized for use in ‘load-
leveling’ seat belt fabrics [184]. These block copolymers were obtained by
reacting a caprolactone monomer with PET a homopolymer, in the
presence of a tin catalyst, in a twin screw extruder. The reactive extrusion
produced a block copolymer of PET and PCL with domains of
poly(caprolactone) which grew from the hydroxyl end groups of the
starting PET core, with minimal randomization of the monomeric units. It
has been found that this bock copolymer in fiber form is resistant to creep
under normal usage, but it irreversibly deforms when elongated at high
strain rates, such as those encountered in an automobile accident.
It is shown that the block copolymers of PET and PEO, synthesized by
the copolymerization of terephthalate, ED and PEO macrodiol, crystallize
into two phases. Crystallization of the PEO blocks in these block
copolymers are constrained by the microstructure of the PET phases [186].

Due to the significant increase in equilibrium moisture content in the block

copolymer with an increasing content of PEO, it has been suggested that
these block copolymers are good candidates for biodegradation, especially
in the presence of lipase enzymes.
Employees at Eastman Chemical have reported that the incorporation
of 1–45 mol.% of C3–C8 aliphatic acids, such as succinic acid or adipic
acid, can lead to a significant decrease in carbon dioxide permeability
versus the PET homopolymer [187]. This improvement can be explained
by a decrease in the glass transition temperature, which leads to less
supercooling of the polymer at room temperature (the temperature of
interest in measuring the loss of carbonation in soft drinks in polyester
bottles) and lower gas solubility in the copolymer and therefore decreased
gas permeation [188]. With lower glass transition temperature values and
decreased gas permeation, the copolyesters of PET based on aliphatic
diacids are also more prone to creep under the pressure of carbonated
beverages, rendering them unsatisfactory this application.
TPEEs can replace rigid plastics when improved shock absorption,
impact resistance, flexural and compressive properties, and spring
characteristics or silent operations are required, for example for industrial
and automotive hydraulic tubing, hoses, gaskets and bellows and also for
the jacketing of electrical and fiber-optic cable. Interestingly, TPEEs can
also be used as biodegradable materials. It has been reported that the
inclusion of PEO soft segments into polyester (PET or PBT) chains has
resulted in an enhancement of the hydrolytic susceptibility that leads to the
degradation of these poly(ester-ether)s within a few months. Gilding and
Reed [179, 189] reported that the synthesis and biodegradation of block
copolymers based on PET and PEO, are suitable for temporary biomedical
application. Namely, biodegradable TPEEs based on PBT and PET –
commercialized under the trade name of PolyActive® and first developed
by HC Corporation in the Netherlands – could be used in tissue
engineering scaffolds, wound dressings, artificial skin, bone replacement
and as drug delivery systems, due to good biocompatibility and mechanical
properties which are similar to native cartilage [190].

Thermoplastic copolyester elastomers are produced by various

manufactures under the trade names: Arnitel® (DSM, Netherlands),
Ecdel® (Eastman Kodak, USA), Elitel® (Elana, Poland), Pelprene®
(Toyobo, Japan) and Lomed® (General Electric, USA).
9. PET BASED BLENDS AND NANOCOMPOSITES
9.1. PET Based Blends
The blending of two or more polymers is an excellent strategy for

obtaining a specified portfolio of physical properties. From the standpoint
of commercial applications, polymer blending represents one of the fastest
growing aspects of polymer technology to obtain new and tailored
materials with improved physical and processing properties and optimal
cost performance [1]. The primary requirement for achieving a useful set
of properties through blending is either miscibility or compatibilization
(which is frequent) of the immiscible components [2]. In the majority of
cases, the criterion of polymer-polymer miscibility is not satisfied and the
blends phase separate under such conditions, with the formation of
undesirable product morphology. In order to achieve the desired property
profile and stabilize the blend morphology, the control of compatibility at
the interface between the component polymer phases is the most important
factor. The interfacial properties of an immiscible polymer blend are
suitably modified using the compatibilization method, and the desired
morphologies and properties are obtained. Two methods that find practical
application are following: (a) incorporation of a separate chemical
compatibilizer into an immiscible polymer blend during melt compounding
and (b) “reactive” compounding to form in situ a compatibilizer.
Compatibilizers for blends are low molecular weight block or graft
copolymers which are used separately or generated in situ in blends by
reactive blending. A copolymer compatibilizer usually consists of
correspond chain segments that will interact with the component polymers
of the blends, leading to decreased interfacial tension and increased

interfacial adhesion. Since thermoplastic polyesters possess carboxyl and

hydroxyl functional groups at the chain ends, in situ or reactive
compatibilization is an effective approach for obtaining engineering
thermoplastic blends from these materials. Also, since transesterification is
often difficult to control, reactive compatibilization is normally practiced
in a modern blend system.
The most general industrial method of the preparation of blends is melt
blending in a mixer or a twin-screw extruder [2]. However, the rheological
properties of the blend components, the conditions of the melt blending,
and the method of stabilization of the morphology, e.g., by controlled
cooling, crystallization and chemical reaction as well as optimum
processing conditions, are important parameters for obtaining the desired
properties in the blends.
Generally, thermoplastic copolyester elastomers are used as modifiers,
i.e., the minor phase components, and rarely as continuous phase or matrix
of blends [1]. They can be blended with different polymers or with other
TPEEs, due to their low melt viscosity and melt stability. Most of the
blends based on TPEEs and other polymers are physical mixtures.
Moreover, during the blending of TPEEs with condensation polymers,
such as polyesters in the melt or solid state, chemical reactions can take
place at the interface of the condensation polymers.
Blends of PET with other polymers may offer an attractive balance of
processability as well as mechanical and barrier properties. Primarily, the
motivations for obtaining blends based on PET and other polymers are to:
a) enhance the solvent resistance and processability of amorphous
polymers (such as polycarbonate); b) improve toughness; and c) reduce the
mold shrinkage of PET connected with its crystallization [191]. Therefore,
the development of PET blends has mainly been market driven, motivated
by the desire to extend the applications of PET into areas where improved
solvent resistance and processability are required, while still retaining good
mechanical properties. Recent developments have resulted in blends of
PET with PBT, polyamide (PA), polycarbonate (PC), poly(propylene) (PP)
and acrylonitrile-butadiene-styrene copolymer (ABS), to improve impact
resistance at low temperatures and other mechanical properties. There are

many possibilities for blending PET with other polymers, some of which
are described below.
9.1.1. PET/PBT Blends

Blends of PET with PBT constitute an important category of
commercial blends. A commercial grade of PET and PBT were melt
blended over different composition using a twin-screw extruder [1]. There
was a transesterification reaction during the melt processing, resulting in
the formation of block copolymers in the initial stage and a random
copolymer at the end of the reaction.
PBT (Tm  220°C) and PET (Tm  250°C) are miscible in the melt, but
crystallize as separate phases upon cooling [2]. Because of the complete
miscibility of PBT and PET, only a single glass transition temperature was
observed, and the mobility of PBT molecules decreased, while that of PET
molecules increased at a particular crystallization temperature.
Consequently, the crystallization rate of PBT was reduced in the presence
of PET, and on the other hand, PET could crystallize much faster due to
enhanced mobility in the presence of PBT, compared to the neat polymer.
Therefore, the processability of PET increases in the presence of PBT
[192]. PET slightly improves the mechanical properties of PET/PBT
blends. It was observed that these blends showed enhanced crystallinity,
high elongation and impact strength compared to a PET- or PBT-
homopolymer. The good cost/performance of PET/PBT blends results
from the incorporation of PET, which is much cheaper than PBT.
PET/PBT blends can also be impact-modified and reinforced with
glass fibers [193]. The typical properties of unfilled PBT and PET/PBT
blends containing glass fibers as reinforcements (Commercial Pocan®
PBT grades) are given in Table 2 [194], while the properties of PET are
presented in Table 1. Impact-modified blends contain a third component
for the enhancement of impact strength. Commercially interesting
modifiers include acrylonitrile-butadiene-styrene elastomers, acrylic
elastomers and other styrene copolymers [193]. The Valox 800 series from
GE Plastics and the Celanex 5000 series from Hoechst-Celanese are
commercial examples of PET/PBT blends, which may be impact-modified

with elastomeric substances such as polyacrylates. PET/PBT blends, which

are commercially available in glass reinforced, injection molding grades,
find applications in household appliances [2]. The properties of these
blends – such as excellent surface appearance and gloss, high resistance to
warpage for glass-reinforced grades, high strength and high temperature
performance – are better compared to glass-reinforced PBT grade.
Table 2. Typical properties of PBT and reinforced PET/PBT blends

(Commercial Pocan® PBT grades) [194]
PBT/PET blends, PBT/PET blends,

Property PBT 15% glass fibers 15% glass fibers
(KU1-7313) (T 7331)
Density, kg/m3 1300 1430 1550
Melting temperature,°C 220 225-250 225-250
Melt viscosity (260°C), Pa s - 300 300
Tensile modulus, MPa 2700 6500 10500
Flexular strength, MPa 90 170 220
Flexular modulus, MPa 2600 5500 9000
Izod Impact strength at 23°C, 85 25 50
kJ/m2
Stress at break, % - 110 130
Stain at break, % - 3.0 2.5
Mold shrinkage (parallel)a, % 2.10 0.30 0.30
Mold shrinkage (across)a, % 2.10 1.10 0.90
a
Plaque 150x105x3 mm.
9.1.2. PET/Polyamide Blends

The reactive blending of various nylons with PET has been generally
applied as a method for the toughening of polyamides. These blends
exhibit two glass transition temperatures, but with a slight shift of both
glass transition temperatures supporting the opinion that good interfacial
grafting has been obtained in this two-phase system, which is a result of
the transesterification between the components. The PET/PA blends
possess good mechanical properties and sometimes better than those of

pure polyamides [195-197]. The target applications of PET/polyamide

blends are for automotive parts, since these blends offer an excellent
combination of mechanical and impact strength with thermal and chemical
resistance [2]. Blending PET with polyamide overcomes the drawback of
PET’s poor impact strength and helps expand its application potential.
Considerable efforts have been directed toward the compatibilization of
PET/polyamide blends because the non-compatibilized blends exhibit
brittle fracture and inferior impact strength [198]. It is known that
PET/polyamide blends are immiscible at ambient temperature [199]. In
addition to compatibilization, the blending of PET with polyamide requires
some degree of toughening, in order to meet the stringent conditions for
their use in automobiles [2]. The reason being that the faster crystallizing
polyamide acts as a nucleating agent in the blend to enhance the
crystallization rate and the degree of the crystallinity of PET, resulting in a
higher modulus, and also inadequate impact strength of the blends. Huang
et al. [199] reported that low molecular weight bisphenol A epoxy resin
was successfully used as a reactive compatibilizer in PET/polyamide 6
(PA6) blends. They found that only 5 wt.% of the epoxy compatibilizer
was used for blending, resulting in a significant improvement of the
notched impact strength and flexural strength of the blends. PA6 domains
were uniformly distributed within the PET phase in the presence of the
epoxy resin compatibilizer for the blending of PET with PA6. The grafting
during melt mixing onto PA6 by the epoxy resin was thought to impart
good compatibility to the blend components. They observed that a
crosslinking reaction took place during the blending at a high level of
epoxy, leading to the improvement of both the impact toughness and
flexural rigidity. The WAXS analysis revealed that PET and PA6
crystallized separately without the formation of any cocrystallites. The
DSC results showed that the crystallization of the blend was slowed down
by the presence of the epoxy resin. The use of other reactive couplers, such
as phosphoryl azide, polyhydroxyether of bisphenol A or phenoxy resin,
ethylene glycidyl methacrylate grafted on butylacrylate-block-
methylacrylate copolymer, has also been reported for PET/polyamide
blends [2].

A new type of polymer/polymer composite from PET/polyamide

blends (so-called microfibrillar composites, MFCs) have been developed
[200]. The MFCs were obtained by reactive extrusion ensuring an adequate
ester-amide interchange reaction between the PET and the polyamide,
followed by cold drawing of the extrude and annealing of the drawn blend.
Bundles of highly oriented microfibrils of a diameter of about 1-2 μm,
upon drawing, were formed from the minor, higher-melting PET
component, as well as from the major, lower-melting polyamide. The
microfibrillar structure of the PET was later stabilized in an isotropic,
unoriented material of polyamide via annealing, which was performed at a
temperature between the melting temperatures of the two polymer
components. The prepared microfibrils significantly enhanced the
mechanical properties, such as the tensile modulus and tensile strength of
the PET/polyamide blend.
9.1.3. PET/PC Blends

Blends of PET with amorphous engineering thermoplastic, such as
bisphenol A polycarbonate represent an important group of materials. The
motivation for choosing an amorphous engineering polymer in PET-based
blends is to increase the dimensional stability and reduce mold shrinkage
[2]. In the case of glass fiber-reinforced grades, the blending approach
helps to reduce warpage. PC provides good impact strength in addition to
dimensional stability and freedom from shrinkage or warpage, while
crystalline PET offers good mechanical properties, chemical resistance,
and ease of melt processing due to low viscosity above its melting
temperature.
Blends of PET with PC prepared in the melt with no exchange reaction
between the components, showed partial miscibility through a shift in the
glass transition and melting temperatures [1]. For compositions containing
PET higher than 70 wt.% and less than 5 wt.%, the blends are transparent,
with only one glass transition temperature [201]. One of the most
important commercial examples of PET/PC blends is Makroblend from
Mobay/Bayer. The blends are impact-modified with high-density
polyethylene (HDPE) or ABS, and are normally available in injection

molding grades as unfilled (Makroblend UT-1018) or reinforced

(Makroblend DP-4-1350) compounds [2]. Due to the superior toughness,
thermal properties and resistance to chemicals of PET/PC blends, these
blends have widespread applications, such as: (a) automotive - car
bumpers, mirror housings and brackets, rear quarter panels, (b)
telecommunications - radio housings, speaker grills, instrument housings,
(c) outdoor power equipment - tractor shrouds and consoles, lawn mower
decks, (d) sports goods - protective helmets, ski boot and binding
components.
9.1.4. PET/PP Blends

Recycling PET and PP wastes and designing novel fiber materials are
important factors for the development of PET/PP blends [2]. Blends of PP
with PET offer some advantages in comparison with the pure components.
PET can improve the stiffness of PP at higher temperatures, whereas the
PP can facilitate the crystallization of PET. It is known that PET as a polar
polymer is immiscible with PP, which is a nonpolar polymer. Non-
compatibilized and compatibilized PP/PET blends can be prepared.
Appropriate compatibilization is required to enhance the impact strength
and other mechanical properties when the dispersed phase concentration
exceeds 5-10 wt.% [202]. There are two approaches to the
compatibilization of PET with PP: (a) the addition of a suitable block or
graft copolymer containing reactive functionalities such as maleic
anhydride (MA) or glycidyl methacrylate (GMA) in styrene/ethylene-
butylene/styrene (SEBS) block copolymer, and (b) blending of a suitably
functionalized PP, such as maleic or acrylic acid-grafted PP [203]. Graft
copolymers formed in situ by the reactions between the functionalities of
the compatibilizer and the end-groups of PET assist in blend
compatibilization. In uncompatibilized PET/PP blends, the strength and
modulus increase with increasing PET content almost linearly, however
very poor impact strength results due to incompatibility. Heino et al. [204]
reported that PP/PET blends with GMA-functionalized SEBS
compatibilizer showed superior impact strength compared to those with
MA-functionalized SEBS. These blends were on a rotating twin-screw

extruder at 275°C. Reactions between the functionalized SEBS and PET

favored the good mixing of PP and PET phases, leading to smaller
dispersed phase domains. The improved interfacial adhesion in
compatibilized blends was also reflected by the shift in the glass transition
temperature of the PET phase toward that of the PP phase, which is
demonstrated by dynamic mechanical analysis (DMA). Rudin et al. [205]
observed that sheath/core filaments of PP/PET could not be oriented
because of the poor adhesion between PP and PET. However, melt-blended
compositions of 70/30 and 50/50 PET/PP produced oriented
monofilaments with useful properties. It was revealed that the blended
monofilaments have good mechanical properties and better recycling and
reuse value compared to the blended products.
9.1.5. PET/ABS Blends

The motivation for obtaining blends based on PET and tough
amorphous thermoplastic ABS is to combine the high impact strength of
ABS with the solvent resistance, good mechanical properties and ease of
processability of PET [2]. These blends can replace the more expensive
ABS/PC blends that are used in automotive applications. Makroblend
formulations based on PET/PC/ABS are available from Mobay/Bayer. PET
and ABS are immiscible and need compatibilization [206]. The grafting of
maleic anhydride-grafted ABS (ABS-g-MA) particles onto the PET matrix
lead to compatibilization, resulting in stabilization of morphology and the
desired mechanical properties [207]. Uncompatibilized blends quenched
from the melt showed good tensile properties, but these deteriorated during
storage at room temperature due to the debonding of the ABS particles.
Impact-modified PET is glass fiber-reinforced and can find applications in
injection molded automotive and industrial components such as windshield
wiper blade supports, industrial pump housings and impellers, gears and
bearings. Cook et al. [208] prepared a PET/ABS blend in an extruder
without a compatibilizer or with a commercially available compatibilizer,
namely, maleated SEBS triblock copolymer. They observed that the
uncompatibilized blends were immiscible and consisted of four phases:
styrene-acrylonitrile copolymer (SAN), grafted polybutadiene, amorphous

PET, and small amounts of crystalline PET. They observed that the two
major phases, SAN and amorphous PET, interpenetrated to result in co-
continuous structures over the compositional range of 30-70 wt.% PET.
The flexural modulus and yield stress increased in an almost linear fashion
with the increase of the PET content in the blend. However, the notched
Izod impact strength and toughness reached the highest levels at 50 wt.%
PET.
9.2. PET Nanocomposites
The development of nanocomposites with different kinds of nanofillers

has become an attractive subject in material science in recent years. PET
nanocomposites reinforced with layered silicates have been intensively
investigated as promising materials for packaging applications. Among the
diverse types of layered silicates, montmorillonite (MMT) is particularly
attractive as a reinforcement for polymer/clay nanocomposites [209-212].
It is a naturally occurring 2:1 phyllosilicate with a high surface area and its
crystal lattice is composed of two silica tetrahedral sheets and an
octahedral alumina sheet between the tetrahedrons [213]. The production
of organically modified organoclays by exchange of intragallery cations
with alkylammonium ions has attracted great interest in the last decade
[214]. As a result, the surface energy of MMT decreases, the wetting
properties of polymer–clay interface is enhanced, and the basal spacing
expands causing an easing in the intercalation of the polymers [215, 216].
Upon the loading of a small amount of clay, PET/organoclay
nanocomposites exhibit significantly improved mechanical, thermal, flame
resistant and physicochemical performance, compared to pure polymer or
conventional composites. The high aspect ratio (70–150) [217], large
surface area (750 m2/g) [217] and high strength and stiffness of nanoclays
are reasons why these materials have such an influence. In order to obtain
polymer/clay nanocomposites (NCs), aggregation of the nanolayers and
tactoids of a few nanolayers must be prevented.

Incorporation of organoclay can have a significant influence on the

applications of PET, potentially improving flame resistance for textiles,
decreasing oxygen permeability in food packaging and enhancing the
modulus in reinforcement and packaging products.
The main approaches for the preparation of PET-based
nanocomposites are in situ polymerization [218-222], solvent casting
[223], and the melt intercalation method [224, 225]. In most cases,
intercalated PET-based nanocomposites were prepared. PET/clay
nanocomposites prepared by in situ polymerization result in high levels of
dispersion and improved physical properties. However, a more
commercially viable approach with conventional melt processing leads to
relatively poorly dispersed clay in the polymer matrix. This phenomenon is
attributed to the low decomposition temperature (250°C) of the ammonium
salt modifier bound to the clay surface. In addition, the presence of
thermally stable organoclay can overcome the problem of melt
compounding and processing at high temperatures.
Imai et al. [226] prepared intercalated PET/clay nanocomposites with
different types of cationic surfactants as compatibilizers with a two-step
polymerization: a melt polymerization of bis(2-hydroxyethyl)terephthalate
followed by a solid state polymerization. The higher tensile strength of
nanocomposites was observed, compared to those prepared without
compatibilizers. Davis et al. [227] compounded PET/montmorillonite clay
nanocomposites by melt blending in a corotating mini twin-screw extruder.
They prepared PET/organoclay nanocomposites with an intercalated
structure. Nanocomposites compounded with 1,2-dimethyl-3- N-
hexadecylimidazolium treated montmorillonite had higher levels of clay
dispersion and delamination within the PET matrix compared to those
prepared with a typical quaternary ammonium salt as the modifier.
Abdallah et al. [228] carried out surface modification of the purified
bentonite with phosphonium salts which resulted in thermally stable
organoclays that can be used in the melt processing of PET. The
compatibility of the organoclay with the polymer matrix was the main
factor in the intercalation and dispersion of the organoclay within the PET
matrix. They found that the alkyl based organoclay exhibited better

dispersion and thus, higher tensile strength and elongation at break in the
PET/organoclay/elastomer ternary nanocomposites than the aryl-based
organoclay did. Upon compounding PET with alkyl and aryl phosphonium
organoclays, the onset decomposition temperature of PET increased from
413°C to 420°C and 424°C, respectively. The DSC results showed that the
use of organoclays did not significantly promote the nucleation process in
PET based nanocomposites, whereas the elastomer decreased the level of
crystallinity.
There are reports in literature of PET nanocomposites incorporating
carbon nanotubes (CNTs), such as single-walled carbon nanotubes
(SWCNTs) and multi-walled carbon nanotubes (MWCNTs). CNTs are a
good candidate for use as nanofillers for high strength polymer
nanocomposites because of their excellent mechanical, thermal and
electrical properties, high aspect ratio, and nanometer scale diameter [229,
230]. An important increase of the tensile modulus and yield strength of
polymers has been reported after the random dispersion of CNTs. It is
known that the addition of CNTs to PET not only improves the mechanical
and electrical properties of PET, but also increases the rate of
crystallization of PET by acting as a nucleating agent [231]. The chemical
modification of CNTs is a good method for overcoming the problems
related to the poor dispersion of CNTs into the polymer matrix due to
strong van der Waals interactions between the CNTs [232]. Recently,
various approaches toward enhancing the properties of PET/CNT
nanocomposites using the surfactant and chemical functionalization of
CNTs have been demonstrated, including the functionalization of CNTs
through covalent and noncovalent reactions with organic molecules and
polymers [230]. The other methods for improving the dispersion of CNTs
within the PET matrix are solution processing techniques, in situ
polymerization and melt processing [230, 233].
Gómez-del Río et al. [234] observed that, due to their large aspect ratio
and mechanical properties, SWCNT are considered to be unique candidates
for making PET-based nanocomposites. They prepared nanocomposites of
PET reinforced with small quantities of carbon nanotubes by in situ
polymerization. The results showed that the Young’s modulus increases

continuously with the volume fraction of SWCNT added, while the

Poisson ratio decreases. Regarding the plastic properties of PET and its
nanocomposites, yield stress exhibits a minor increase with the SWCNT
content, but the failure strain is dramatically reduced with the presence of
SWCNT.
Despite the superior mechanical performance of SWCNTs, MWCNTs
are the most common variety of CNTs studied and a wide variety of
surface functionalization has been investigated. Yoo et al. [229] prepared
PET nanocomposites by melt-extruding mixtures of PET and
functionalized MWCNTs with some interaction with PET molecules.
Isocyanate-attached CNTs were obtained through the covalent bonding of
the isocyanate group on the molecule and CNT. They observed that PET
nanocomposites with MWCNT-phenyl and MWCNT-benzyl showed better
dispersion of nanotubes in the PET matrix because of the increased
interaction between the PET chains and CNTs compared to the
nanocomposites of pristine MWCNT and MWCNT-COOH. The PET
nanocomposites containing isocyanate groups showed improved
mechanical properties, including tensile strength and tensile modulus,
compared to those with pristine and acid-treated MWCNTs. These
improvements were ascribed to π–π interactions between the aromatic
rings of the PET molecules and the isocyanate group in MWCNTs. The
crystallinity of the PET/functionalized MWCNT nanocomposites was
significantly higher than those of the pristine and acid-treated MWCNTs.
Fourier transformed infrared spectroscopy (FTIR) results indicated that the
presence of MWCNTs induced the trans-conformation of PET chains, and
trans-conformation was particularly dominant in the PET composites
incorporating MWCNT-phenyl.
Yesil and Byram [235] prepared PET-based conductive composites by
using functionalized CNT by melt mixing with a twin screw extruder. The
surfaces of MWCNTs were functionalized by treatment with a strong acid
mixture (purification) followed by modification with sodium dodecyl
sulfate, PEO, and diglycidyl ether of Bisphenol A (DGEBA). The amount
of carboxylic acid groups on the CNT surface increased after acid
treatment, but decreased with surface modification due to the consumption

of these groups during the chemical reactions between the surface

modifiers and the CNT surface. FTIR and nuclear magnetic resonance
analyses of the composites revealed an increase in the interactions between
the PET and CNT surface after treatment with PEO and DGEBA. The
mechanical strength of the composites prepared with modified CNT was
higher than that of the untreated CNT-filled composite owing to the
enhanced interactions between the PET and CNT.
Heeley et al. [236] observed that uniaxial deformed PET/MWCNT
films displayed improved mechanical properties compared to unfilled PET
films. The PET homopolymer was physically blended with low loadings of
MWCNTs by weight (1 and 2 wt.%), with the intention of improving the
electrical and mechanical properties of the PET. SAXS/WAXS data
revealed a well oriented lamellar structure for unfilled PET films. In
contrast, the PET-MWCNT composites revealed a nanohybrid shish-kebab
(NHSK) morphology, with reduced orientation and crystallinity. The
MWCNTs in the PET based composite increase nucleation events,
increasing the rate of crystallization of PET, but inhibit the growth of the
crystallite structure and reduce the overall crystalline orientation. The
development of these PET/CNT composite materials could potentially lead
to further industrial applications, e.g., in fuel cells and bipolar plates.
There is also a growing body of work on PET nanocomposites
incorporating carbon black (CB) nanoparticles. In the case of conductive
PET composites reinforced with carbon black, their properties depend on
the features of both, polymers (such as the degree of crystallinity, melt
viscosity, surface tension) and CB (such as species, surface area, chemical
groups, and dibutyl phthalate (DBP) absorption values). The properties of
PET based composites are also affected by the distribution of the CB
particles in the material, as well as the interaction between CB and
polymers and especially, by the percolation threshold [237, 238]. The
percolation threshold is the critical amount of CB required to build
originally continuous conductive networks, at which the drastic insulator
conductor transition appears. A reduction of the percolation threshold of
conductive polymer composites is of significance for better mechanical
properties, easier processing and a decrease in cost. Many authors [239-

242] have reported that the CB particles were first localized in the minor
phase (i.e., in PET), and then the conductive CB/PET masterbatch was
elongated in situ to form conductive in situ microfibrils in the polyethylene
(PE) matrix during melt extrusion processing. After compression molding,
a conductive three-dimensional microfibrillar network was obtained,
resulting in a relatively low percolation threshold (6.0 vol.%). Dai et al.
[243] successfully fabricated electrically conductive in situ microfibrillar
CB/PET/PE composite with the selective distribution of CB particles on
the surfaces of the PET microfibrils. The percolation threshold of the in
situ microfibrillar conductive PET composite was only ca. 3.8 vol.%,
showing a considerable decrease of percolation compared to that of the
common CB/PE composite. They found that interfacial tension, viscosity
and chemical groups on the surface of the CB particles and the processing
order, were in favor of the migration of the CB particles from the PE
matrix to the dispersed PET phases. The morphological observation
indicated that, depending on the mixing time, the CB particles gradually
migrated from the PE matrix to the surfaces initially, and then to the center
of the PET phases. They concluded that the anisotropic distribution of the
CB particles, the tunneling conduction, the geometry of the electrical
network, and the complex structure of the microfibrillar composite, are
likely to make conducting composites.
10. SURFACE MODIFICATION OF PET
PET is one of the most commonly applied polymers for textile and
biomedical applications [244]. The polyester fibers have interesting
physicochemical and mechanical properties. However, the major problems
associated with PET are related to its hydrophobic character i.e., poor
hydrophilicity, low moisture regain (0.42%) and lack of softness [245-
248]. Enhancement of the hydrophilicity of PET fibers is an important
requirement for many applications, ranging from textile production to
applications in the biomedical field.

In the textile field, increased hydrophilic properties improve comfort in

wear with better moisture management due to increased wettability and
wicking; it also improves adhesion to other materials (coating for
example), and dyeing [244]. Several approaches can be adopted to increase
the surface energy and hence the hydrophilicity of PET fibers: physical
treatment, chemical treatment and grafting polymerization [244, 249-251].
Surface treatments have been developed to obtain specific surface
properties, such as: enhanced surface wettability, adhesion activities,
surface functionalization, molecules immobilization, biocompatibility
improvement, non-fouling coating and barrier surface coating.
The surface properties of PET can be modified both chemically and
physically after its surface has been exposed to physical treatments such as
plasma, corona discharge, UV irradiation or electron and neutron beam
irradiation [252]. Plasma treatments were primarily developed in order to
modify surface characteristics of PET, such as: hydrophilicity and adhesive
properties [1]. The modification of the surface properties of PET films is of
great interest in the packaging industry in order to enhance wettability or
printability, to enhance optic characteristics and in biomedical applications
to improve biocompatibility. Plasma treatments have the advantage of
being eco-friendly by keeping the bulk properties unchanged, compared to
conventional chemical treatment cold plasma techniques. The gases used
for plasma treatments include NH3 and O2, H2O vapor, He and Ar, O2 and
CF4, SF6, and air. These plasma treatments can make the PET fabric
surface hydrophilic by introducing highly reactive species (radicals, ions,
electrons, excited molecules, photons, etc.). Plasma treatment using the
energetic ions and radiation generated in the plasma, leads to disruption of
the polymer chains as well as to the introduction of the functional groups
on the PET surface [253].
Interestingly, double plasma treatment has been used to graft
glycopolymers onto PET fibers in order to obtain a surface which is
compatible with the biological material [254]. The first step is based on
activation of the surface of the PET using argon plasma treatment leading
to the creation of radicals by scission of the chemical bonds. Furthermore,
the PET fibers are exposed to the air with the aim of forming

hydroperoxide functions. Then, the activated fibers are dipped in

glycomonomers solutions and dried. The second plasma treatment is used
to polymerize the monomers adsorbed on fibers.
Yang et al. [247] successfully modified PET film surfaces using a
glow discharge plasma treatment. The plasma treatment incorporated polar
functional groups onto the surface of the PET film (as shown by XPS
analysis) causing a decrease in the contact angle and an increase in the
surface free energy. This is due to the existence of a mass of reactive
particles (electrons, ions, radicals, etc.) in the discharge area, while in the
afterglow area and remote area there are only radicals. The AFM and
weight loss results showed moderate increased roughness in the afterglow
area and the properties of the PET film surfaces were more outstanding in
the afterglow and the remote area. The above changes in the PET surfaces
made the films more hydrophilic and increased the surface free energy
leading to PET being suitable for industrial applications.
Takke et al. [244] demonstrated that immobilizing a hydrophilic
oligomer like PEO immediately after plasma treatment would perhaps
yield a more durable hydrophilic treatment. PEO can be used for surface
modification because of its unique properties such as hydrophilicity,
flexibility, and nontoxicity. These authors activated PET fabrics with
atmospheric plasma treatment before immobilizing PEO on the polyester
fabric surface by padding. Air-plasma treatment of the PET fabrics before
PEO coating further increases the hydrophilicity of the inner fabric fiber
surface (i.e., soil-release properties) and improves adhesion of PEO-1500
to the plasma-treated PET woven fabric surface.
Jingrun et al. [255] modified the surfaces of PET by oxygen plasma-
induced and ultraviolet (UV)-assisted acrylic acid (AAc) grafting
polymerization, and using the –COOH as reacting sites, the molecules of
gelatin and bovine serum albumin (BSA) were further co-immobilized on
the PET surface. Immobilization of albumin and gelatin markedly
decreased the extent of platelet adhesion. Activation compared to the
untreated PET surface immobilization of albumin and gelatin molecules
which could improve the anticoagulation (i.e., decrease the extent the
platelet adhesion and activation on PET surface) of the PET surface, and

may enhance the endothelialization (i.e., increase endothelial cell

attachment on the PET surface) than onto that of the control PET.
Many methods of the surface modification of PET by chemical
treatment have been described [1]. Generally, these methods involve
chemical breaking of the ester bonds by reaction with low molecular
weight compounds containing hydroxyl or amine groups in order to
generate reactive functional groups on the surface. These reactions enhance
the hydrophilicity of the PET surface and generate anchored functionalities
(when difunctional compounds are used) available for subsequent
reactions.
The aminolysis of PET fibers with various diamines (such as 1,2-
diaminoethane, 1,6-diaminohexane or hydrazine) can introduce amino
groups onto the PET surface [251]. This approach leads to the formation of
a new amide group and the presence of free alcohol and amine groups on
the PET surface. This reaction is effective because amine groups are
hydrophilic; thus, aminated PET fabric exhibits excellent hydrophilicity.
The amine groups are also reactive; thus, other functional compounds can
be grafted onto the PET fabric to endow the PET macromolecules with
various functions. One of the disadvantages of this chemical treatment is
finding optimal conditions that do not lead to degradation and the loss of
the mechanical properties of the PET films or fibers. Thus, the
development of a new method to aminate PET fabric while maintaining its
tensile strength and weight is very much required. Bech et al. [251]
developed a technique based on aminolysis and sugar grafting through
which polymeric biomaterials can easily be obtained. They grafted
different diamines onto PET fibers by aminolysis reaction and observed
that factors such as temperature, solvent, diamines concentration, and
reaction time significantly affect the grafting yield. The introduction of
amino groups onto PET fibers cannot only modify the hydrophilicity but
also provide the active sites for immobilization of biocompatible
molecules. Oligosaccharides such as maltose, maltotriose, and
maltohexaose were successfully grafted onto the PET surface by reductive
amination and amidation.

Zhou et al. [256] developed a facile aminolysis method involving the

gradual concentration of diluted ethylenediamine in order to aminate PET
fibers. The results showed that the hydrophilicity of the PET fabric
substantially improved and that reactive NH2 groups were introduced onto
the PET fibers. The aminated PET fabrics retained the weight loss,
breaking strength and elongation, crease recovery angle, stiffness and
whiteness of the original PET fabrics. They reported that the aminolysis of
PET fibers via the gradual concentration of dilute ethylenediamine is a
promising method for the efficient, rapid, and eco-friendly modification of
PET fibers.
Grafting from approaches can be applied for the surface modification
of PET-based materials [1]. In this approach, the polymerization is initiated
from initiator-functionalized surfaces. Living polymerization methods are
satisfactoty for obtaining polymer brushes following the grafting from
approach. These overall methods for the preparation of polymer brushes
provide precise control over brush thickness, architecture and composition
[257]. Bech et al. [258] demonstrated the preparation of polymer brushes
on the surface of PET films, fibers and fabrics. In the first step, a primary
amine such as 1,2-diaminoethane is used to anchor the amino groups onto
the PET surface by aminolysis reaction. In the second step, atom transfer
radical polymerization initiators were grafted by reaction with
bromoisobutyryl bromide and this reaction was carried out in bulk using
styrene and the corresponding catalyst in the presence of a sacrificial
initiator. Then, the polymer brushes were prepared with good control of
polymerization.
11. APPLICATIONS OF PET
According to the Merchant Research and Consulting Ltd. website

[259], the global annual production of PET in 2012 stood at over 28
million tonnes. Asia-Pacific held about half of the overall production, with
China ranking first both in the region and throughout the globe. Europe
and North America followed after, each accounting for around 14% of the

installed capacity of PET production worldwide. During 2004-2011, the

world PET production increased from nearly 11.3 million tonnes to around
18.6 million tonnes, registering an average annual growth of over 7%. In
2012, it surpassed the 19.8 million tonnes mark. The dominant companies
engaged in the global PET industry are Indorama Ventures PCL, DAK
Americas, M&G Group, Jiangsu Sanfangxiang Group Co, China
Resources Packaging, JBF Industries Ltd, SINOPEC, Octal Holding & Co,
Shahid Tondgooyan Petrochemical Co, Lotte Chemical, Far Eastern
Textile Ltd and Nan Ya Plastics Corp. The world PET consumption was on
an upward trend during 2004-2012. In 2012, it stood at over 19.8 million
tonnes. Asia was the leading PET consumer in the world, followed by
Europe and North America. The polyester fiber industry is the major end-
user sector for PET - over 60% of the annual supply volume was used in
this application in 2012.
The main use of PET is in the textile industry, to manufacture video
and audio tapes, X-ray films, food packaging, as well as water and soft-
drink bottles. Besides, PET is used in thermoforming applications, as well
as engineering resins often in combination with glass fiber. It also used for
microwave food trays and food packaging films.
In its semicrystalline form, PET is made into a high-strength textile
fibre marketed under such trademarked names as Dacron (DuPont) and
Terylene (Imperial Chemical Industries Ltd.). PET is the most important of
the man-made fibers in weight produced and in value. The stiffness of PET
fibers makes them highly resistant to deformation, what imparts excellent
resistance to wrinkling in fabrics. They are often used in durable-press
blends with other fibers such as rayon, wool, and cotton, reinforcing the
inherent properties of those fibers while contributing to the ability of the
fabric to recover from wrinkling. PET is also made into fiber filling for
insulated clothing and for furniture and pillows. When made in very fine
filaments, it is used in artificial silk, and in large-diameter filaments it is
used in carpets. Among the industrial applications of PET are automobile
tire yarns, conveyor belts and drive belts, reinforcement for fire and garden
hoses, seat belts (an application in which it has largely replaced nylon),
nonwoven fabrics for stabilizing drainage ditches, culverts, and railroad

beds, and nonwovens for use as diaper top sheets and disposable medical
garments [260].
At a slightly higher molecular weight, PET is made into a high-
strength plastic that can be shaped by all the common methods employed
with other thermoplastics. Recording tapes and magnetic films are
produced by extrusion of PET film (often sold under the trademarks Mylar
and Melinex). Molten PET can be blow-molded into a transparent
container of high strength and rigidity that also possesses good
impermeability to gas and liquid. In this form PET has become widely
used in carbonated-beverage bottles and in jars for food processed at low
temperatures.
PET is used in the packaging sector in the form of films, trays or
bottles, its principle use being in bottles. In 2010, almost 70% of all bottled
water and soft drinks sold globally was supplied in PET bottles. Due to its
excellent mechanical and optical properties, good oxygen and carbon
dioxide barrier properties, as well as consumer trend favoring healthier
beverage options, lately the carbonated soft drink sector has been growing
more rapidly than other applications. Of the few polymers that are
potentially suitable for bottles, PET is the only plastic with a balance of
properties such as transparency (near 100% light transmission in a bottle),
gloss, lightweight and resistance to carbon dioxide permeation. This has
resulted in the nearly full replacement of glass in Europe for all but the
most demanding applications that require both an oxygen barrier and UV
resistance to protect the contents.
Recently, growing interest has been observed in the utilization of
chemically recycled PET products as raw materials for the preparation of a
rather different class of polymers such as unsaturated polyester resins,
polyurethanes, epoxy resins, vinyl esters, and alkyd resins [124]. Also,
PET is a commercially available fabric suitable for many biomedical
applications. Due to its ability to retain mechanical strength and fatigue
characteristics for a long period of time in the body, as well as considerable
biocompatiblity, PET has attracted considerable attention for many
applications such as vascular graft, sewing cuffs of mechanical heart
valves, sutures, etc. Under trademark Dacron®, PET has been used

successfully as a material for blood vessel tissue engineering in treating the

pathology of large diameter arteries [261]. The first tissue-engineered
blood vessel substitute was created by Weinberg and Bell in 1986 [262].
They generated cultures of bovine endothelial cells, smooth muscle cells
and fibroblasts in layers of collagen gel supported by a Dacron® mesh.
Although physiologic pressures were sustained for only 3-6 weeks, they
did demonstrate the feasibility of a tissue-engineered graft with human
cells. Dacron® is most commonly used for aortic replacement and to a
lesser extent as a conduit for femoropopliteal bypass surgery [263].
Numerous following studies have focused on the improvement of the
existing and development of new PET based biomaterials. Ma et al. [264]
reported on the modification of conventional polymer used in vascular
graft, which was processed into non-woven nanofiber mat (NFM) via
electrospinning. To overcome the chemical and biological inertness of the
PET surface, gelatin was covalently grafted onto the PET NFM surface to
produce a new kind of material for blood vessel tissue engineering. Also,
hybrid materials combining PET and different types of cells (endothelial
and osteoblastic cells) have been developed thanks to the covalent grafting
of different densities of rat genome database (RGD) containing peptides
onto the polymer surface. The results demonstrate that various peptides,
grafted to PET surface, act to enhance osteogenic differentiation and
mineralization of pre-osteoblastic cells, which has a potential in developing
engineered biomaterials for bone regeneration [265]. Kidane et al. [266]
developed a simple two-step procedure for covalent grafting of
poly(ethylene oxide) (PEO) onto the surface of Dacron® fabric. This
surface modification substantially reduced platelet adhesion on the PET
polymer. To improve mechanical properties of collagen, a novel porous
scaffold for bone tissue engineering was prepared with collagen sponge
reinforced by polypropylene/poly(ethylene terephthalate) (PP/PET) fibers.
Incorporation of PP/PET fibers significantly enhanced the compressive
strength of the collagen sponge. Proliferation and osteogenic
differentiation of mesenchymal stem cell in collagen sponges reinforced
with PP/PET fibers incorporation were significantly enhanced compared
with collagen sponge without PP/PET incorporation. The incorporation of

PP/PET fibers not only improves the mechanical properties of collagen

sponge, but also enables mesenchymal stem cells to positively improve
their proliferation and differentiation [267].
CONCLUSION AND FUTURE TRENDS
Since the mid-twentieth century PET has been attracting a great deal of
interest due to its excellent mechanical properties, high thermal stability
and chemical resistance, as well as processability and optical clarity.
Nowadays, a broad range of pure and modified PET grades are available,
and are found in many applications such as fibers, films and food and
beverage packaging applications.
The use of PET as a recyclable polymer has opened numerous new
markets, which are in constant growth. Through mechanical recycling,
waste PET bottles can be found in films, sheets, strapping packaging and
fiber used for sacking, insulation and floor covering. In the field of
mechanical recycling, development of the strategies for maintaining the
high average molecular weight of PET during reprocessing is of great
importance. Also, the improvement of the chemical recycling processes
will certainly still be attracting great interest, both in terms of obtaining the
monomers for the re-synthesis of PET, and of producing chemically
recycled PET products as raw materials for the preparation of different
class of polymers such as unsaturated polyester resins, polyurethanes,
epoxy resins, vinyl esters and alkyd resins.
Among various polyesters, PET and also PBT are very suitable for use
as the hard crystallizable segments in thermoplastic copolyester
elastomers, whose commercial importance has constantly been increasing
in the last four decades. One of the future trends could be the inclusion of
hyperbranched polyesters or dendritic segments into PET-based
copolymers. Moreover, some prospect has been obtained in inclusion of
liquid crystalline sequences into the backbone or as side chains.
In addition, numerous studies have so far focused on the blends of PET
with other polymers in order to achieve an attractive balance of

processability and mechanical and barrier properties of the final products.

The blends based on PET and other, mostly amorphous, polymers often
have enhanced the solvent resistance and processability in comparison with
amorphous component of the blends. On the other hand, the presence of
other polymer can improve toughness and reduce the mold shrinkage of
PET connected with its crystallization. Various type of nanofillers such as
organoclay, carbon nanotubes and carbon black are usually used in
improving physical, thermal and mechanical properties of PET.
Incorporation of nanofillers can have a significant influence on the
applications of PET, potentially improving flame resistance for textiles,
decreasing oxygen permeability in food packaging and enhancing the
modulus in reinforcement and packaging products. Future trend in
development of PET-based materials would be their reinforcement with
different nanomaterials, such as organoclays, nanoparticles and nanofibers.
Due to the wide applications of PET in many fields, it can be expected that
the volume of its production will be further enhanced in the future.
ACKNOWLEDGMENTS
This work was financially supported by the Ministry of Education,

Science and Technological Development of the Republic of Serbia and by
the Ministry of Science and Technology of the Republic of Srpska.
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3821-3830.

Chapter 2
THE APPLICATIONS OF POLYETHYLENE

TEREPHTHALATE FOR RF
FLEXIBLE ELECTRONICS
Tzu-Hsuan Chang, Yei Hwan Jung, Dong Liu,

Hongyi Mi, Juhwan Lee, Jiarui Gong
and Zhenqiang Ma
Electrical and Computer Engineering,
University of Wisconsin-Madison, Madison, US
ABSTRACT
Polyethylene terephthalate (PET) has been one of the most reliable

and cost-efficient candidates in recent development of flexible device
applications. Flexible electronics have rapidly evolved into a variety of
applications including displays, e-papers, solar cells, sensors, wearable
electronics, etc. In particular, high-performance electronics such as radio-
frequency devices have been designed and fabricated on flexible
substrates, such as PET, with operating frequencies of up to the giga-
hertz (GHz) regime, which covers current major portable electronics,
wireless communication, and transmission units. The flexible electronics

104 Tzu-Hsuan Chang, Yei Hwan Jung, Dong Liu et al.
that operate at the GHz regime are generally composed of high-

performance flexible microwave active and/or passive devices. Typically,
they have stringent requirements for substrate choice, in terms of
mechanical properties, thermal properties, and electrical parameters,
which have a significant impact on the performance at high frequencies.
In this chapter, we review the frequency-dependent parameters of the
PET substrate, developments of the flexible RF electronics on PET
substrate, and the challenges and potentials of RF applications using
flexible electronics fabricated on PET films.
1. INTRODUCTION
Radio-frequency (RF) stands for the electromagnetic wave frequencies

that are used for radio stations, radar, satellite transmission, and other
telecommunication applications. During the last few decades, the focus of
RF applications has been placed on the general frequency spectrum which
has the lowest transmission attenuation in air. The outer shell of the
atmosphere mainly contains nitrogen (N2), oxygen (O2), carbon dioxide
(CO2), water vapor (H2O), and ozone (O3). Due to different resonant
vibration frequencies of each individual gas molecules in the atmosphere, a
significant amount of electromagnetic wave energy is absorbed at certain
wavelengths. For example, H2O absorbs the electromagnetic wave with
wavelengths in the range of 5.5-7.0 μm and larger than 27 μm. CO2
primarily contributes to absorptions in the mid and far infrared portions of
the absorption spectrum. O3, which absorbs energy strongly in the
ultraviolet (UV) range, heavily covers the atmosphere and participates in
signal transmission in satellite communication. In contrast to the
absorption spectrum, the transmission spectrum shows the fraction of
electromagnetic energy that can pass through the atmosphere and
propagate at a given distance. Figure 1 shows the absorption/transmission
spectrum of the atmosphere. The intermediate bands in between the high
absorption region, open the windows for the electromagnetic waves with
certain wavelengths to transmit through the atmosphere in wireless
applications.

The Applications of Polyethylene Terephthalate … 105
Figure 1.1. Absorption/Transmission spectrum at which electromagnetic radiation will

penetrate the Earth's atmosphere. Chemical notation (CO2, O3, etc.) indicates the gas
responsible for blocking sunlight at a wavelength. Copyright 2016 NASA.
RF electronics, as indicated by the term, are electronics that operate at

high frequencies ranging from 3kHz to 300 GHz [1]. Pursuing higher
frequency in RF applications leads to the need for a broader bandwidth and
higher speed in telecommunication applications. As engineers pursue the
discovery of higher performances in RF applications, another branch of RF
electronics has gained popularity in the development of flexible
electronics, which cover anything from flexible displays, e-papers,
wearable electronics, flexible RFIDs for warehousing, to implantable or
bandage-like in situ biomedical monitoring electronics. Typically, low-
speed flexible electronics are based on organic materials [2-4] or non-
crystalline semiconductors (e.g., amorphous-Si) [5] or metal oxide
materials [6], which are enabled by related process developments including
large area printing, coating, and deposition techniques that are compatible
with the flexible substrate. On the contrary, RF flexible transistors can
extend flexible electronics applications toward wireless data transmission
and wireless power transfer with wider signal handling capability, allowing
circuits to operate with significantly lower power consumption, higher
signal-to-noise ratio, and faster operating response [7]. Nevertheless, such
organic or non-crystalline semiconductors are unsuitable for RF electronics

fabrications due to its poor intrinsic electrical properties. Thus,

semiconductors with superior intrinsic carrier mobility, such as inorganic
semiconductors, must be utilized. In parallel, the substrates in which the
active electronic components adhere to must possess certain specifications
to minimize RF loss, be compatible with electronics fabrication, and
maximize reliability.
Table 1. Available candidate plastic substrates
PET PEN PC PES PI

(Melinex) (Teonex) (Lexan) (Sumilite) (Kapton)
Tg, °C 78 121 150 223 410
Transmission
89 87 90 90 Yellow
(400-700 nm), %
Moisture
0.14 0.14 0.4 1.4 1.8
absorption, %
Young’s Modulus,
5.3 6.1 1.7 2.2 2.5
Gpa
Tensile strength,
225 275 - 83 231
Mpa
Density, gcm-2 1.4 1.36 1.2 1.37 1.43
Refractive index 1.66 1.5-1.75 1.58 1.66 -
Birefringence, nm 46 - 14 13 -
Table 2. Comparison of Organic/Inorganic Materials

for Flexible Electronics
Mobility Bandgap Young’s

Organic References
(cm2/V*s) (eV) Modulus (GPa)
P3HT 10-5 ~ 10-1 2.0 1.3 [8, 9]
Pentacene ~8.9 0.97 1.0 [10, 11]
C60 2~4.9 2.3 8-20 [12, 13]
Mobility Bandgap Young’s
Inorganic References
(cm2/V*s) (eV) Modulus (GPa)
Si 1400 1.12 185 [7, 14]
Ge 3900 0.6 103 [15, 16]
GaAs 8500 1.39 85.5 [17]

Plastic materials are perfect for flexible electronics as they are

bendable in nature. Among a variety of plastics, the quest to find the most
suitable substrate starts with comparing the physical properties. Ideally, the
substrate must be able to withstand high temperature, repel moisture, have
good mechanical strength, and have high transparency The properties of
the common candidate plastics for flexible electronics fabrication are
shown in Table 1. Polyethylene terephthalate (PET – e.g., Melenix® from
DuPont Teijin Films) [18-20], polyethylene naphthalate (PEN, e.g.,
Teonex® Q65 from DuPont Teijin Films) [19, 21, 22], poly carbonate (PC,
e.g., Lexan® from GE) [20, 23], polyethersulfone (PES, e.g., Sumilite®
from Sumitomo Bakellite) [20, 24], and polyimide (PI, e.g., Kapton® from
DuPont) [25, 26] comprise the candidate substrates. Polyimide has
excellent glass transition temperature for the process capability;
nevertheless, it absorbs visible light which is not feasible for electronics
applications that require the substrate to be transparent. Engineers have
been investigating clear plastic substrates with high process temperature
for the replacement of glass with the conventional electronics fabrication
process [27, 28]. Also, high moisture absorbing materials like PC and PES
are unsuitable for electronics fabrication as the processes generally require
chemical solvents and organic compounds. PET and PEN can repel
moisture, while at the same time exhibit high mechanical strength and
relatively high glass transition temperature (enough for electronics
processing). Out of the two, PET is the material of choice for many
applications due to its high-abundancy and low-cost.
The main challenges in the development of RF flexible electronics on
PET are: (1) the lack of high quality active channel materials with
sufficient mobility and simultaneous mechanical flexibility, and (2)
difficulties in designing a fabrication procedure that is thermally
compatible with the PET substrate [7, 14, 29, 30]. Table 2 summarizes the
mainstream organic/inorganic materials used in flexible electronics.
Organic materials typically feature a relatively low Young’s modulus that
is close to the modulus of PET film (2~2.7 GPa) compared with other
flexible substrate candidates. The high bendability and ease-of-fabrication
have enabled the organic materials-based applications to prevail in the

early development of flexible applications, but the intrinsic low carrier

mobility of the organic materials pose an inherent barrier to achieve high-
speed electronics devices that are comparable to those of its rigid
counterparts.
As an alternative, scientists and engineers have been searching for
solutions to shape bulk inorganic semiconductor materials that are superior
to organic in terms of carrier mobility into flexible formats and produce
high-performance RF electronics in practical flexible applications. Even
though inorganic materials are rigid in their bulk formats due to a high
Young’s modulus, the scaling law developed in microelectromechanical
systems (MEMS) explains that flexural rigidity decreases as the thickness
of the bulk materials decrease. As shown in Figure 1.2a, a 22 nm thick Si
nanomembrane can be bent without fracturing and thus is highly flexible.
Figure 1.2. a) SEM image of a 22 nm Si nanomembrane shows high flexibility. b)

Flexural rigidity decreases linearly with thickness and a 2 nm Si nanomembrane (dash
line) shows a ~1015 times smaller flexural rigidity than a 200μm Si bulk wafer. The
blue line represents calculations for silicon nanomembranes bonded to sheets of
polyimide at room temperature, and then heated to 300°C [31].
In Figure 1.2b, the flexural rigidity of a 2 nm-thick silicon thin-film is

on the order of ~1015 times smaller than that of a 200 μm thick Si bulk
wafer. Meanwhile, the energy release rate also decreases linearly with
thickness, enabling inorganic nanomembranes to conformably and robustly
bond onto the flexible substrates. Figure 1.3 summarizes the development
on the fast (high-speed) flexible electronics within the last decade.

Researchers have been working on replicating those rigid electronics based

on the flexible infrastructure. Significant efforts to maximize frequency
responses of RF transistors on flexible substrate have been made, with the
majority of such developments being made on PET films. These advances
are known for the ability to transfer print numerous inorganic
semiconductors on flexible plastic films, where certain conventional
electronics fabrication processes may be utilized. Other active channel
materials with exceptional properties, such as Ge, III-V group, and
complex epitaxy heterogeneous structures, have been introduced into
flexible electronics and the function of the flexible electronics has moved
from single flexible RF transistors to functional integrated circuits. In the
following sections, a generic fabrication process for building RF devices
using thin-film nanomembranes on PET films are introduced.
Figure 1.3. A short development history of flexible RF active devices (and related
passive devices) on plastic substrates using transferrable nanomembranes. Update from
[14].

2. FABRICATION PROCEDURE OF PET FOR FAST

FLEXIBLE RF ELECTRONICS
Although many approaches based on organic semiconductors have

been demonstrated with low production cost and high flexibility that can
take advantage of the flexibility of the PET substrate, these organic
materials generally have relatively low mobility in the range of below 1 to
10 cm2/Vs for electronic devices, respectively. Thus, the typical transient
response from these devices is around the order of mili-seconds that are
only suitable for the flexible display applications, but not for RF
electronics. To adapt the mature rigid applications into flexible
applications and explore its potentials, researchers have been looking for
reliable methods to prepare the large scale single crystal semiconductor
nanomembrane. The nanomembrane is thin enough to maintain the
flexibility. On the other hand, it still possessess its intrinsic mobility from
several hundreds to thousands cm2/Vs, which is generally two orders of
magnitude higher than the organic semiconductors. In the following
paragraphs, the current mainstream approaches in preparing the high-
quality free-standing single-crystalline nanomembranes are covered, which
render high speed flexible electronics possible.
2.1. Thin Film Membrane Released from Anisotropic Etching of

Bulk Wafer
The initial approach to prepare thin film Si nanomembrane is derived

from the intuitive idea of releasing the thin-film from the bulk single-
crystalline substrate. Bulk Si substrates have been the fundamental
building blocks in the current semiconductor industry and can be grown in
large-scale at low-cost. The direct release of the thin-film membrane from
the bulk substrates can significantly reduce the production cost and the
bulk substrate can be later polished and recycled.

Figure. 2.1.1. Schematic process flow of single-crystal silicon ribbon fabrication. a)

SF6 plasma etch trenches in a (111) Si surface. b) Thermal oxidation and angled
evaporation of Ti ∕Au passivate the sidewalls. c) Hot KOH ∕IPA ∕ H2O solution
undercuts the Si ribbons. d) Cross-sectional SEM image of partially undercut ribbons
[32].
Because the target thin film Si nanomembrane has similar chemical

properties as the bulk Si substrate, this approach is not unveiled until the
anisotropic wet etching of Si is discovered [33]. The atoms of single
crystalline Si are arranged in a diamond cubic lattice and the periodicity of
the lattices are organized in three orientation planes: (100), (110), and

(111). By viewing the Si lattices from these three directions, the atomic
density of the three directions are different. The plane where Si has the
lowest density, (100), is more vulnerable to chemicals such as KOH(aq)
and TMAH. Si (110) and especially Si (111), which has the highest density
of Si atoms, are not etched until the surrounding Si atoms are attacked;
thus, the etching rate is much slower compared to Si (100). This
phenomenon is identified as the anisotropic etching of Si and has been
widely used in the micro-electro-mechanical-system (MEMS) to fabricate
reliable vibration/gauge sensors. To release the thin Si nanomembrane, Si
(111) substrate is adapted as shown in Figure 2.1.1.
Before immersing the Si (111) substrate into the anisotropic KOH etchant,
a trench is formed in the Si substrate by plasma SF6 etching and the design of
the trench is to define the final thickness of the released Si nanomembrane.
After etching, thermal oxidation is applied and a Ti/Au protection layer is
deposited around the membrane area. SiO2 has high selectivity in KOH
etching and prevents the KOH from attacking the sidewalls of the membrane.
The Ti/Au layer is used as the hard-etching mask when removing the oxide in
the trench and the protection layer through the KOH wet etching process.
After immersing the structures in hot KOH/IPA/H2O solution, the exposed Si
will be etched inwards along the horizontal Si (111) plane that is protected
within the oxide. The front edge of the etching will stop at the Si (110) plane
and move towards the two sides until the etching from both sides meet. The
released Si nanomembrane is then rinsed with KI2 metal etcher to remove the
gold and is then ready for the post-transfer process.
2.2. Thin Film Membrane Released from

Si on Insulator (SOI) Substrate
Different from the anisotropic wet releasing approach, this method has
much higher controllability over the uniformity of the released
nanomembrane. The thickness of the released membrane could range from
a few nanometers to a couple of micrometers and the surface roughness
can be controlled within ~1 nm. To adapt this approach, special Si on

Insulators (SOI) substrates have been prepared by the SmartCut process.

The target Si nanomembrane is embedded on top of the handling Si
substrate with a thick SiO2 sacrificial layer as illustrated in Figure 2.2.1a.
Similar to the anisotropic releasing approach, hydrofluoride (HF) solution
was employed as the wet etchant to selectively remove the SiO 2 sacrificial
layer.
Figure 2.2.1. Generic process for Si nanomembrane release from SOI and transfer. (a)
Use SOI as the starting material; (b) Patterning top Si template layer into strips or
meshed NM and partially expose BOX; (c) Immersing SOI into aqueous HF to
undercut BOX; (d) Si template layer falls as BOX is fully undercut and gets registered
on the handling substrate. Two transfer routes exist: direct flip transfer (e1)–(f1) and
stamp-assisted transfer (e2)–(g2). (e1) Flexible substrate with adhesive coating is
attached to Si nanomembrane. (f1) Peel off the plastic substrate with NM transferred.
(e2) Si nanomembrane is first picked up by the elastomeric stamp. (f2) Bring the stamp
into contact with a (adhesive-coated) new host substrate. (g2) The stamp is slowly
peeled off, leaving the NM attached/transferred to the new host [14].

In the approach, the top Si layer is patterned with an array of holes or

strips to expose the SiO2 layer underneath, which is later removed by HF
solution. The membrane becomes suspended and falls to the top of the
bottom handling substrate due to capillary force when the sacrificial layer
is removed, as shown in Figure 2.2.1b-2.21d. The free-standing Si
nanomembrane is then picked up by the PDMS stamp and printed on to the
flexible substrate for further processing. The printing process can be
classified as direct-flip transfer, by flipping the released membrane upside
down, and stamp-assisted transfer, which maintains the original surface
direction.
The high yield and high reproducibility of the release/print top Si layer
SOI has boosted the rapid advancement in high performance flexible
electronics. The success of this approach relies heavily on the discovery of
the PDMS releasing and printing methods [34, 35]. As shown in Figure
2.2.2, the soft PDMS stamp is used to pickup (Figure 2.2.2a) and print
back (Figure 2.2.2b) the target membrane. The stamp is peeled away from
the substrate at a steady-state speed υ, which is similar to the steady-state
propagation of a crack at the same velocity. The thin film and substrate are
both elastic, while the stamp is viscoelastic. The critical energy release rate
for the film/substrate interface is denoted by , which is
considered a material property of the interface and is independent of the
peeling velocity υ since the film and substrate are elastic, while
, the energy between the stamp and the film, is a
monotonically increasing function of the release rate υ. In other words,
adjusting the release rate of the PDMS stamp at the speed above Vc which
corresponds to the Gcrit will attach the film onto the stamp, as illustrated in
Figure 2.2.2c. After the success of releasing the Si nanomembrane with the
sacrificial SiO2 layer, researchers have discovered approaches to transfer
Ge [36], GaAs [37], InP [38], GaN [39, 40], and even complex epitaxy
heterostructures [41, 42].

Figure 2.2.2 Schematic diagrams of a) the pickup and b) printing of thin film.
c) Schematic diagram of critical energy release rates for the film/substrate interface
and for the stamp/film interface. The intersection of the horizontal line in the middle
with the curve representing the critical peel velocity for kinetically controlled transfer
printing. The horizontal lines at the bottom and top represent very weak and very
strong film/substrate interfaces, respectively, corresponding to pickup only and
printing only [43].
2.3. Thermal Compatibility Issues
High speed RF electronics on PET substrate requires distinctly

different fabrication procedures from the procedure on rigid bulk Si
substrate. Unlike Si substrate with a melting point of up to 1414°C [44],
the reported melting point of PET film is as low as 254°C (Dupont Mylar).
This will prohibit most standard processes commonly used for rigid
applications, such as furnace oxidation (750°C ~1150°C), dopant
implantation, dopant activation annealing (750°C ~900°C), and PECVD
oxide/nitride (250°C ~ 350°C). Besides the low melting point, PET film
will also generate shape distortion and internal tensile strain even at lower
temperatures. For example, the basic photolithography and plasma etching
process could cause the PET film to deform and curl up, which would
significantly compromise the resolution of the lithography, feature-
alignment in following processes, and the device yield.

To resolve the distortion issues during fabrication, PET is placed on a

hot plate at 115°C for pre-process conditioning for 10-15 minutes. The film
is tightly attached to the hot plate with a backside vacuum to distribute the
heat uniformly and maintain the flatness of the film. PET film will
experience a shrinking of around 1-2% in dimension in the first few
minutes and the shape of the film will gradually become stable afterwards.
To peel off the PET film from the hot plate, the temperature of the hot
plate needs to decrease slowly to below 50°C before removing the film. In
this way, the PET film will maintain strain balance on both sides of the
film. Even though the pre-baking can greatly reduce the misalignment
caused by the distortion of PET film, fabricating devices with feature sizes
smaller than 1 μm will still require alternative procedures: transferring the
pre-fabricated electronic devices onto rigid substrates. In this approach, the
devices are pre-fabricated on rigid substrates with releasable structures.
The thermal processes are not limited only to lithography related
processes, the preparation of dielectric layer, metallization, and the post-
process capping process should all be taken into consideration. The
dielectric layer, for example, needs to be formed by a lower temperature
procedure, such as evaporation, sputtering, and atomic layer deposition to
preserve the performance of the devices. Multiple high performance
flexible RF transistors have been demonstrated using the thermal
compatible process of PET film and will be introduced in a later section of
the chapter.
2.4. Dielectric Constant and Dissipation Factor
Another consideration of designing flexible RF transistors is the

dielectric constant and the dissipation factor of the flexible substrate. The
dielectric constant characterizes the strength of a material under the electric
field, while the substrate with a higher dielectric constant can withhold a
higher breakdown voltage and qualify for high-power electronics.
However, there exists a trade-off between having a high dielectric constant
and device response, as the substrate will result in a crosstalk delay due to

the parasite capacitance. Hence, for the flexible substrate with a lower
dielectric constant can reduce the loss from the embedded electronics [40].
Different from the dielectric constant that represents the ability of
storing the energy under the applied electric field, the dissipation factor
characterizes of loss-rate of energy of a mode of oscillation electric field,
which is one of the critical parameters in designing high speed flexible RF
electronics. The dissipation constant can be interpreted by the phase angle
δ of the resistive (lossy) component and lossless (reactive) component of
an electromagnetic field in the complex plane, usually quantized by
tangent δ and named tangent loss of a material. If the tangent loss of a
substrate is large, the majority of the electromagnetic energy transport in
this material will dissipate as localized heat, thus significantly reducing the
efficiency of the RF devices. In the following paragraph, we will briefly
introduce the state-of-the-art methods of accurately measuring the
dielectric constant and tangent loss of a flexible substrate.
Figure 2.4.1. a) The schematic structure of microstrip transmission line. b) Optical

image of fabricated microstrip transmission line based on the PET film c) Equivalent
circuit model of the transmission line. The parasitic elements L, C and R were included
in this model [45].

The characterization of these two factors have been an important issue

in designing the high speed flexible electronics, since the existing
approaches cannot precisely retrieve the two parameters of PET at high
frequency. The transmission line method (TLM) approximation with a
single measurement was recently developed for characterizing microwave
dielectric properties of thin films and is applicable in a wide frequency
range [46-48]. The schematic of the TLM structures is shown in Figure
2.4.1a and the PET embedded transmission line is shown in Figure 2.4.1b.
In this method, thin-film is adopted as the substrate for microstrip
transmission lines. The dielectric properties of the thin film can be
extracted from measured scattering parameters (S-parameters). This
method is employed to characterize the microwave dielectric properties of
flexible substrates in the frequency range of 1 - 10 GHz, which covers the
wireless communication bands: the L-, S-, C- and the lower part of the X-
bands. The transmission (signal) line, made of thick copper foil tape, was
made to cover the entire length of the flexible PET film, and is designed to
be long enough for several guided wavelengths, in order to reduce the
influence of the SMA connectors and parasitic effects between the
connector and transmission line, on overall measurement accuracy. An
equivalent circuit for this microstrip transmission line was built using
Agilent/Keysight Advanced Design System (ADS). This circuit also
included the presence of an edge mounted SMA connector on each side
and illustrated parasitic effects between the connectors and microstrip
transmission line. The circuit structure is shown in Figure 2.4.1c.
The ground plane of the microstrip transmission line was made by
covering the backside of the PET substrate with conducting copper foil
tape. A flat copper sheet was then brought into contact with the copper foil
tape to facilitate mounting of the SMA connectors. Two SMA connectors
were finally soldered to the structure. As shown in Figure 2.4.1c, a series
inductance (L), a shunt capacitance (C), and a series resistance (R) on each
side between the line and connectors were included in the model to
represent the transition between coaxial connectors and the transmission
line, and assembly imperfections. Fabrication imperfections exist at the

two connection points, such as an air gap between the substrate edge and
the side of the SMA connector.
Figure 2.4.2 a) Measured and simulated transmission coefficients (S21) of the PET
based microstrip transmission line. b) Extracted microwave dielectric properties
(dielectric constant and loss tangent) [45].
Table 3. Comparison of Dielectric Constant & Tangent Loss

of Flexible Substrate and Si
Dielectric Constant Tangent Loss (1kHz) Tangent (10 GHz)

Si 11.7 0.005 0.015
PET 3.1 0.008 0.013
Kapton 3.7 0.002 0.005
Figure. 2.4.2a shows the extracted s-parameters from the designed

TLM circuits, and the average dielectric constant and loss tangent for both
the PET films are extracted from the simulation (blue line) to fit the
experimental data [48, 49]. The PET film shows an average dielectric
constant close to 3.1 and an average loss tangent between 0.008 at 1 kHz
and 0.013 at 10 GHz. 10 GHz is beyond the current prevailing 4G standard
Wi-Fi applications and more than enough for flexible applications. PET
showing an improved tangent loss over Si at high frequency will facilitate
the development of high frequency flexible electronics. Table 3 lists most

of the research representative flexible substrates and the related extracted

parameters.
3. APPLICATION OF HIGH SPEED FLEXIBLE

ELECTRONICS ON PET
Among many types of flexible electronics, high-performance devices

are especially challenging to fabricate on plastic substrates, requiring
advanced fabrication techniques that typically involve high temperatures
and organic compounds [50]. RF electronics usually comprise of such
high-performance components as they deal with the generation,
acquisition, and manipulation of high-frequency signals, mostly in the
gigahertz range. For active RF flexible components, like transistors and
diodes, inorganic semiconductors in nanomembrane forms must be
utilized, since these materials have superior mobility and wide bandgaps
compared to its organic counterparts. To fabricate one, a semiconductor
nanomembrane is usually transfer printed onto the targeted plastic
substrate and goes through all the advanced fabrication processes, such as
photolithography, plasma etching, chemical etching, metal and dielectric
deposition, etc. In conventional electronics fabrication, the substrate is
typically the semiconductor itself, which is generally not affected by the
abovementioned processes. For flexible electronics, however, the plastic
substrate typically encounters problems as it can expand or contract during
lithography, chemically react in plasma, dissolve in chemicals, and melt at
high temperatures.
In most cases, the manufacturing tools are not designed for such plastic
substrates and the expensive tools also become damaged from the adverse
reactions in a process. Only a handful of plastic types are compatible with
all processes, and the excellent mechanical properties in conjunction with
the high-abundance and low-cost of PET films have enabled various
classes of RF components on the film for flexible RF electronics. The
fabrication of flexible electronics using inorganic semiconductor

nanomembranes on PET films starts with a generic process of transfer

printing the nanomembrane using rubber stamps as shown in Figure 3.1.
Using this process, different types of vital RF components such as
transistors, diodes, and switches are fabricated on the PET film.
Figure 3.1. Illustration of Si nanomembrane transfer methods: a,b,c,d) for PDMS

assisted transfer and a,b’,d) for direct flip transfer. a) Strips are released in situ on
source substrate. b) PDMS was applied to the source substrate and the strips were
picked up. b’) A PET substrate coated with an adhesive layer was applied to the source
substrate and lifted up the released strips. c) The strips on PDMS were print transferred
to PET. d) The transferred strips were fabricated into transistors/circuits using either
PDMS or direct flip transfer method. e) Strips are picked up by a PDMS stamp.
f) Strips were picked up by PET substrate coated with SU-8 [29].

Figure 3.2. a) Cross-section illustration of the TFT on PET with the channel length and
the overlap distances between gate and source/drain shown. b) Microscope image a
two-gate-finger TFT. c) Zoomed-in view of accurate gate alignment realized with the
local gate alignment procedure. d) Image of a TFT array on a bent PET substrate.
e) Illustration of bending test for the TFT on PET. (f) Measured fT and fmax variations
under different bending radii [29].
Of most significance, transistors are the vital components in an RF

circuit. Transistors can amplify or switch electronic signals and electrical
power, and the ability to do so at high frequencies has outperformed
traditional low-frequency transistors in terms of power consumption and
signal processing capability. Also, the high-frequency transistors allow
wireless communication and power transfer capability. As flexible
electronics are mainly advantageous in mobile electronics, like wearable or
implantable devices, the wireless functionalities would dramatically
expand the applications of flexible electronics. Whereas low-frequency
transistors were readily fabricated on PET films using either organic or
inorganic semiconductors [6, 32, 35, 51, 52], one of the most important
demonstrations that proved PET films can also be utilized for high-
frequency transistors is shown in Figure 3.2 [29]. Figure 3.2a represents
the cross-section schematic illustration of the device. The transistor is
fabricated with silicon (Si) nanomembrane, a high-mobility material
mostly comprised of conventional electronics devices, as the active

material, and silicon monoxide, an insulator with a high dielectric constant,

as the gate dielectric material, all on the PET substrate. In addition, the
gate length of the device of only 1 μm to maximize the speed of the device
was achieved on the PET substrate for the first time as shown in Figure
3.2b and 3.2c. Thus, a record-breaking maximum oscillation frequency of
12 GHz was achieved in flexible format. This is a significant achievement
as it indicates that the transistor can be utilized on flexible substrates for
amplification of RF signals typically used in wireless communications.
Finally, the finished images of the flexible transistors are shown in Figure
3.2d. With this successful entry of a high-speed flexible transistor, many
improvements have been made to maximize the speed, such as the strained
transistor and nanotrench transistor, all on the same PET film as the
substrate [7, 53].
The semiconductor nanomembranes from transfer and printing
methods can further integrate different fabrication techniques to boost the
device performance by several times. The traditional lithography method
(Figure 3.3b) has limits on both the length and thickness of the channel.
Due to dopant diffusion, the length of the channel is limited at the micro-
scale, which lower the maximum-oscillation frequency. To reduce the
resistance and maintain the mechanical strength of the device, the
thickness of the channel is also limited to several hundred nanometers,
setting constraints on the on-off speed of the transistor. As an alternative
approach, nano-imprinting lithography, as shown in Figure 3.3a, can create
a sharp-and-deep-submicron channel on the Si nanomembrane, allowing to
overcome the previously mentioned limits posed by the traditional
fabrication. Instead of the traditional lateral structure, a vertical PN
structure on the Si membrane was built, which helped to overcome the
problem of dopant diffusion, making it possible to narrow down the
channel length to mechanical limit. The channel length can be narrowed
down to 100 nm, while the thickness is only 20 nm (Figure 3.4b). As a
result, the carriers of the active channel are highly confined only in the
local thin bridge-like structure, as shown in Figure 3.4c, and this unique
structure significantly improves the overall DC characteristics of the
transistors, as shown in Figure 3.4d and 3.4e. The maximum oscillation

frequency of such a device reaches an amazing 38 GHz in practice (Figure

3.4f), making it possible to realize the same performance on flexible
substrates as the best transistor on rigid substrates [7].
Figure 3.3. Comparison of the device structures (cross-sectional view) and fabrication
processes between a) 3-D nano trench Si nanomembrane flexible RF TFTs, and
b) conventional 2-D TFTs. The effective channel lengths (Lch) are marked in red in
(a3, b3). The smallest Lch of the nano trench TFT can reach down to 50 nm via NIL
and that of the conventional TFT can only reach down to about 1.5 µm. (a1) Blanket
phosphorous ion implantation and thermal anneal. (a2) Nano trench formation via
nanoimprint. (a3) Final structure of nano trench TFT where the channel length Lch is
defined by nanoimprint. (b1) Photolithography to define S/D regions for ion
implantation. (b2) Selective ion implantation and thermal anneal. (b3) Final structure
of conventional TFT where Lch is limited by gate electrode and dopant out-diffusion
during ion implantation and thermal anneal [7].

Figure 3.4. a) Optical image of arrays of the bent TFTs on a PET substrate. b) Defining
a nano trench on a phosphorus implanted p- SOI substrate using NIL. c) Simulated
current density with the 250 nm deep trench (70 nm of the trench depth extends into
the p- layer: 20 nm p- layer remains as the active channel) forms a very strong field-
effected channel without a leakage current. d) Drain current versus drain voltage.
e) Drain current versus gate voltage. f) Measured (solid lines) and simulated (dashed
lines) RF characteristics of the trench TFT [7].
Along with the transistors, diodes play a critical role in an RF

integrated circuit, as it can rectify RF signals to DC signals, as well as
switch, mix, and regulate high-speed signals. A diode is a simple two-
terminal element that conducts in one direction only, allowing current to
flow in one direction and blocks from the other direction with high
resistance. Diodes utilizing numerous types of materials were
demonstrated on the PET film for many DC or low-frequency applications.
These are relatively simple to fabricate as it involves rough doping of one
terminal and eliminates the need of low contact resistance, which is
problematic on plastic substrates. On the other hand, the high-frequency
ones are not so easy to fabricate. High-doping concentrations in the top
layer are essential to ensure low sheet resistance and low contact
resistance. Therefore, careful ion implantation, followed by high-
temperature diffusion is carried out during fabrication [54]. Figure 3.5
represents the RF diodes, as well as RF switches made using the diodes,
fabricated on a flexible PET film. As shown in Figure 3.5a, the cross-
section schematic illustration shows that the diode utilizes a heavily doped

Si nanomembrane connected with a thin-film metal on top for low

resistance. Figure 3.5b shows the final device bent using hands. Figures
3.5c and d show the optical-microscope images of the finished diodes and
a shunt-series single-pole single-throw switch containing the two diodes,
respectively. Further demonstrations of RF diodes incorporating other
semiconductor materials like germanium on PET films have been reported
[36]. These demonstrations of high-speed switches on PET films prove that
high-frequency diodes have enabled RF functionalities that were not
possible with only using low-frequency diodes on flexible substrates.
Figure 3.5. a) Schematic cross-section of lateral Si nanomembrane PIN diodes on a

flexible PET substrate. b) Optical image of finished PIN diode and switch arrays on a
bent PET substrate. c) Optical microscope image of a finished Si nanomembrane PIN
diode. Shown in the inset is the diode circuit diagram. d) Optical microscope image of
a finished shunt-series PIN diode SPST switch. The circuit diagram of the SPST RF
switch is shown in the inset. e) Illustration of the mechanical bending direction for the
SPST PIN diode switch under bending test [54].

Figure 3.6. Illustration of the fabrication process for integrated flexible spiral inductors
and MIM capacitors. a) M1 was evaporated on a PET substrate to form the bottom
electrode of MIM capacitors and the center lead metal of inductors. b) A 200 nm SiO
layer was evaporated on top of the bottom electrode as the capacitor high-k dielectric.
M2 was evaporated on top of SiO to form the top electrode for capacitors. The two
layers were lifted together to form a self-aligned structure. c) A layer of SU-8 was spun
on to act as the intermetal low-k isolation layer. Via holes were opened with
lithography and SU-8 was cured to cross link. d) M3 was evaporated to form the spiral
metals of inductors and interconnects. An optical-microscope image of e) a 4.5-turn
spiral inductor, f) an MIM capacitor, and g) the finished inductor and capacitor arrays
on a bent PET substrate. Measured (h) L values and (f) Q values of a 4.5-turn spiral
inductor as a function of frequency under flat and bending conditions. The spiral metal
line width is 15 µm and the metal line spacing is 4 µm. The inset of (h) shows the
zoomed-in graph of L values in the low frequency range. The fres is indicated by the
zero L and zero Q values. The two figures have the same X-axis scale [29].
Electronic components, like the transistors and the diodes, require

semiconductor materials, whereas some passive components, which are
components that do not require an external source of power to perform,
like inductors and capacitors, do not necessarily require semiconductors.
These two elements are the devices that store energy rather than dissipate it
and play important roles in many circuits. At high frequencies, inductors
and capacitors are extremely significant as they serve diverse purposes,
such as matching, storing, attenuating, and passing of signals. Successful
fabrication of RF inductors and capacitors on PET films would allow the

abovementioned transistors and diodes to be monolithically integrated in a

circuit. As the PET allows for electronics fabrication processing, layers of
metals and insulators can be lithographically defined and deposited to form
spiral inductors and metal-insulator-metal capacitors as presented in Figure
3.6a-f [29]. Figure 3.6g presents the image of the devices fabricated on the
PET film. Inductors and capacitors fabricated this way can reliably operate
up to 10 GHz even with bending [30]. Other than using lithography
techniques, these relatively simple devices are also demonstrated on PET
with other techniques like the screen printed passive devices, as presented
in Figure 3.7 [55]. As such, different approaches may be used to fabricate
RF devices, although using one common technique to fabricate all the
devices, including transistors and diodes is ideal, as the devices ultimately
need to be merged into a circuit.
While the demonstrated RF devices on PET films already perform well
at a few to a couple of tens of gigahertz, it is highly desirable that these
devices could perform at even higher frequencies. Because of the lack of
available bandwidths at low frequencies and the demand for a larger
bandwidth, the technology of RF devices is motivated to advance towards
higher frequencies for search of unexplored bandwidths. In addition,
devices that are capable of operating at higher frequencies are more
efficient at lower frequencies. With battery and heat issues associated with
flexible electronics becoming prominent, efficiency must be improved as
well. On the other hand, the devices operating at a certain frequency on a
conventional wafer substrate typically performs at a lower frequency on a
plastic substrate like PET. This is due to the intrinsic electrical properties
that plastics suffer from, such as low thermal conductivity and higher RF
losses. Thus, there are a lot of advancements to be made to the RF
electronics devices on PET films. Nevertheless, the remarkable
accomplishments made on the flexible RF electronics fabricated on PET
films have undoubtedly created a practical and promising path for flexible
electronics research.

Figure 3.7. (a) Photograph of screen-printed RLC circuit using a series combination of
8 μ H inductor and 0.8 nF capacitor, in parallel with a 25 kΩ resistor. (b) Model of the
circuit including inductor and capacitor series resistances. (c), (d) Impedance
magnitude (c) and phase (d) of the circuit [55].
CONCLUSION
In conclusion, we have discussed the applications of RF flexible

electronics on the plastic film, PET, as one of the applicable candidates in
terms of cost, process temperature (high glass transition temperature, Tg),
mechanical flexibility, solvent resistance, and thermal stability. Despite of
numerous studies regarding the low temperature process of conventional
TFT fabrication on plastic films, the current fabrication technology still
limits the flexible electronics application that requires high speed RF
elements. With the introduction of the alternative fabrication approach
such as membrane transfer technique on PET film, this chapter
summarized various applications available for high speed flexible RF
electronics on flexible substrates.

Releasing and transferring thin film from bulk Si wafer or silicon on

insulator (SOI) wafer onto plastic film enable high speed RF electronics in
flexible form by using active semiconductor materials with high mobility
and high saturation velocity, which is also less demanding in regards to
processing temperature during preparation of single crystal
nanomembrane. While the silicon process temperature is much higher than
1000°C, the PET film has a relatively low Tg which requires heat-treated
pre-process conditioning to avoid significant distortions in shape. The new
method can accommodate the rest of the RF element fabrication process
with high yield as well as produce various elements for RF electronic
circuitry. Successful characterization of passive elements including
capacitors, inductors, and microstrip transmission line in both low and high
frequency microwave circuits using PET as a dielectric layer has been
investigated and even active devices have been fabricated on PET film
with outstanding flexibility, while still maintaining high performance and
achieving a record-breaking maximum oscillation frequency.
Other flexible substrates for flexible RF electronic applications have
also been introduced, such as PEN, PC, PES, and PI, that can replace PET
as a flexible RF electronics substrate, which enable the devices to be
wirelessly rechargeable and promote the wireless communication
application of portable and wearable electronics. In summary, the unique
and exceptional achievements made on RF electronics in flexible form on
PET films indeed extend the applications of flexible electronics to portable
consumer electronics, wearable sensors, and even nanoscale implantable
medical devices in the near future.
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BIOGRAPHICAL SKETCHES
Tzu-Hsuan Chang
Affiliation: University of Wisconsin-Madison
Education:
B.S. in Computer and Electrical Engineering, National Taiwan
University
M.S. in Computer and Electrical Engineering, National Taiwan
University
Ph.D. in Computer and Electrical Engineering, University of
Wisconsin-Madison
Business Address:
1415 Engineering Dr., B640
Madison, WI 53706

Research and Professional Experience:

Chang was a research assistant in National Taiwan University
majoring in enhance the efficiency in automata and later pursuing the
Ph.D. degree in UW-Madison, U.S.A. In the Ph.D. degree, Chang
continued his research assistant appointment with research topic such as
self-assembly sub-10nm nanofabrication, high power fast flexible
electronics, green electronics, 2D materials, and novel renewable energy
from heterogeneous tandem solar cell and photonic applications. Chang is
currently a post-doctoral fellow in UW-Madison and continuing his
research in high power k-band flexible electronics, solar cell, and high
speed UV detectors.
Professional Appointments:
Post-Doctoral Fellow, University of Wisconsin-Madison
Honors:
Harold A. Peterson Best Dissertation Award 2016.
Publications Last 3 Years:
1) T.-H. Chang, K. Xiong, D. Liu, M.-Y. Wu, H. Mi, H. Zhang, Z. Xia, S.

H. Park, M. S. Arnold, J. Han and Z. Ma, “Fast solar-blind
AlGaN/GaN 2DEG UV detector with transparent graphene electrode,”
Government Microcircuit Applications and Critical Technology
Conference (GOMACTech), Reno, NV, March 20-23, 2017.
2) T.-H. Chang, S. Xiong, R. M. Jacobberger, S. Mikael, C.-C. Liu, D.
Geng, X. Wang, M. Arnold, Z. Ma, P. F. Nealey, “Directed self-
assembly of block copolymer films on atomically-thin graphene
chemical patterns,” Scientific Reports, 6, 31407, 2016.
3) T.-H. Chang, W. Fan, S. Liu, D. Liu, Z. Xia, L. Menon, H. Yang, J.
Berggren, M. Hammar, Z. Ma, W. Zhou, “Selective Release of InP
Heterostructures from InP Substrates,” JVSTB, 34, 041229, 2016.
4) H. Mi, C. Liu, C. Yao, T.-H. Chang, J. Seo, H. Zhang, S. Cho, S.
Gong, N. Behdad, Z. Cai and Z. Ma, “Microwave dielectric

characterization of biogradable cellulose nanofibrils (CNF) thin film

for flexible microwave applications,” Cellulose, 2016.
5) Z. Ma, Y. H. Jung, T.-H. Chang, J.-H. Seo, Z. Cai and S. Gong,
“Green Microwave Electronics for the Coming Era of Flexible
Electronics,” 2016 IEEE/MTT-S International Microwave Symposium,
San Francisco, CA, May, 2016.
6) Z. Ma, Y. Jung, J. Seo, J. Lee, S. Cho, T.-H. Chang, H. Zhang, S.
Gong and W. Zhou, “Radio-frequency flexible and stretchable
electronics,” Proceedings of CSTIC, Shanghai, China, Feb 13-17,
2016.
7) D. Liu, Z. Xia, S. Cho, D. Zhao, H. Zhang, T.-H. Chang, X. Yin, M.
Kim, J. Seo, J. Lee, X. Wang, W. Zhou and Z. Ma “Cavity enhanced
1.5 m LED with silicon as hole injector,” SPIE Photonics West, San
Francisco, CA, Feb, 2016.
8) Y. H. Jung*, T.-H. Chang*, H. Zhang, C. Yao, Q. Zheng, V. W. Yang,
H. Mi, M. Kim, S. J. Cho, D.-W. Park, H. Jiang, J. Lee, Y. Qiu, Z. Cai,
W. Zhou, S. Gong, Z. Ma, “High-Performance Green Flexible
Electronics Based on Biodegradable Cellulose Nanofibril Paper,”
Nature Communications, 6, 7170, 2015.
9) T.-H. Chang, K. Xiong, S. H. Park, H. Mi, H. Zhang, S. Mikael, Y. H.
Jung, S. Gong, J. Han, Z. Ma, “High power fast flexible electronics:
Transparent RF AlGaN/GaN HEMTs on Plastic Substrates, “ 2015
IEEE/MTT-S International Microwave Symposium, Phoenix, Arizona,
2015.
10) Y. H. Jung, T.-H. Chang, S. Gong and Z. Ma, “Towards High-
Performance Green Flexible Electronics Using Nanocellulose
Materials,” 2015 MRS Fall Meeting & Exhibit, Boston, MA,
December, 2015.
11) K. Xiong, H. Mi, T.-H. Chang, M. Wu, S. Gong, W. Zhou, M. Arnold,
H. Yuan, Z. Ma, “AlGaAs/Si dual-junction tandem solar cells
fabricated by epitaxial lift-off and print transfer-assisted bonding,” 42nd
*
Equal contribution.

IEEE Photovoltaic Specialists Conference (2015), New Orleans, June

14-19, 2015.
12) J.-H. Seo, T.-H. Chang, J. Lee, R. Sabo, W. Zhou, Z. Cai, S. Gong,
Z.Ma, “Microwave Flexible Transistors on Cellulose Nanofibrillated
Fiber Substrates,” Applied Physics Letters, 106, 2015.
13) M.-Y. Wu, J. Zhao, F. Xu, T.-H. Chang, R. M. Jacobberger, Z. Ma, M.
S. Arnold, “Highly Stretchable Carbon Nanotube Transistors Enabled
By Buckled Ion Gel Gate Dielectrics,” Applied Physics Letters, 107,
053301, 2015.
14) D.-W. Park, S. Mikael, T.-H. Chang, S. Gong and Z. Ma, “Bottom-
gate coplanar graphene transistors with enhanced graphene adhesion
on atomic layer deposition Al2O3,” Applied Physics Letters, 106,
102106, 2015.
15) J.-H. Seo, T.-H. Chang, R. Sabo, Z. Cai, S. Gong, Z. Ma, “Radio-
Frequency Flexible Transistors on Cellulose Nanofibrillated Fiber
(CNF) Substrates,” 15th Topical Meeting on Silicon Monolithic
Integrated Circuits in RF Systems, Jan. 26-28 2015, Omni San Diego
Hotel, San Diego, California, 2015.
16) F. Xu, M. Wu, N. Safron, S. S. Roy, R. M. Jacobberger, D. J. Bindl, J.-
H. Seo, T.-H Chang, Z. Ma, M. S. Arnold, “Highly stretchable carbon
nanotube transistors with ion gel gate dielectrics,” Nano Letters, 14
(2), 682-868, 2014.
Yei Hwan Jung
Education:
B.S. in electrical engineering, University of Illinois at Urbana-
Champaign
M.S. in electrical engineering, University of Wisconsin-Madison

Business Address:
Madison, WI 53706

From 2010 to 2012, Jung was a Research Associate with the
University of Illinois at Urbana-Champaign, where he focused on wireless
implantable medical devices for brain optogenetics and high-performance
flexible thin-film silicon transistors. Since 2012, he has been a Research
Assistant and since 2015, a Fellow with the University of Wisconsin-
Madison, focusing on flexible and stretchable microwave electronics,
transparent electronics and optoelectronics for neural applications, and
micro-structured implantable scaffolds.
HHMI Predoctoral Fellow, University of Wisconsin-Madison
Honors:
Jung was a recipient of the 2015 HHMI International Student Research
Fellowship and the 2012 Wisconsin Chancellor’s Opportunity Award and
has won numerous innovation competitions including the Grand First Prize
of the 2014 Qualcomm Innovation Prize and Runner-Up Prize of the 2014
G. Steven Burill Business Plan Competition.
1) Y. H. Jung, J. Lee, Y. Qiu, N. Cho, S. J. Cho, H. Zhang, S. Lee, T. J.

Kim S. Gong and Z. Ma, “Stretchable Twisted-Pair Transmission
Lines for Microwave Wearable Electronics,” Advanced Functional
Materials 26, 4635-4642 (2016).
2) Y. H. Jung, H. Zhang and Z. Ma, “Wireless Applications of Conformal
Bioelectronics,” a chapter in “Stretchable Bioelectronics for Medical
Devices and Systems,” edited by J. A. Rogers, R. Ghaffari and D.-H.
Kim, Springer (2016).

3) Y. H. Jung, J.-H. Seo, W. Zhou and Z. Ma, “High Speed, Flexible

Electronics by Use of Si Nanomembranes,” a chapter in “Silicon
Nanomembranes: Properties and Applications,” edited by J. A. Rogers
and J.-H. Ahn, Wiley-VCH (2016).
4) Y. H. Jung, Y. Qiu, S. Lee, T.-Y. Shih, Y. Xu, R. Xu, J. Lee, A. A.
Schendel, W. Lin, J. C. Williams, N. Behdad and Z. Ma, “A Compact
Parylene-Coated WLAN Flexible Antenna for Implantable
Electronics,” IEEE Antennas and Wireless Propagation Letters 15,
1382-1385 (2016).
5) Y. Qiu, Y. H. Jung, S. Lee, J. Lee, T.-Y. Shih, Y. Xu, R. Xu, W. Lin, J.
C. Williams, N. Behdad and Z. Ma, “Flexible Capacitively Loaded
Antenna with Parylene Conformal Coating,” Microwave Journal 59
(4), 134-142 (2016).
6) S. J. Cho, Y. H. Jung and Z. Ma, “X-band Compatible Flexible
Microwave Inductors and Capacitors on Plastic Substrate,” IEEE
Journal of the Electron Devices Society 3 (5), 435-439 (2015).
7) Y. H. Jung, T.-H. Chang, H. Zhang, C. Yao, Q. Zheng, V. W. Yang, H.
Mi, M. Kim, S. J. Cho, D.-W. Park, H. Jiang, J. Lee, Y. Qiu, W. Zhou,
Z. Cai, S. Gong and Z. Ma, “High-Performance Green Flexible
Nature Communications 6, 7170 (2015).
8) J. Kim, M. Lee, H. J. Shim, R. Ghaffari, H. R. Cho, D. Son, Y. H.
Jung, M. Soh, C. Choi, S. Jung, K. Chu, D. Jeon, S.-T. Lee, J. H. Kim,
S. H. Choi, T. Hyeon and D.-H. Kim, “Stretchable Silicon Nanoribbon
Electronics for Skin Prosthesis,” Nature Communications 5, 5747
(2014).
9) Y. Qiu, Y. H. Jung, S. Lee, T.-Y. Shih, J. Lee, Y. H. Xu, R. Xu, W.
Lin, N. Behdad and Z. Ma, “Compact Parylene-C-coated Flexible
Antenna for WLAN and Upper-band UWB Applications,” Electronics
Letters 50 (24), 1782-1784 (2014).
10) T.-I. Kim, M. J. Kim, Y. H. Jung, H. Jang, C. Dagdeviren, H. A. Pao,
S. J. Cho, A. Carlson, K. J. Yu, A. Ameen, H.-J. Chung, S. H. Jin, Z.
Ma and J. A. Rogers, “Thin Film Receiver Materials for Deterministic

Assembly by Transfer Printing,” Chemistry of Materials 26 (11), 3502-

3507 (2014).
11) G. Park, H.-J. Chung, K. Kim, S. A. Lim, J. Kim. Y.-S. Kim, W.-H.
Yeo, R.-H. Kim, S. S. Kim, J.-S. Kim, Y. H. Jung, T.-I. Kim, V.
Kumar, C. Yee, J. A. Rogers and K.-M. Lee, “Immunologic and Tissue
Biocompatibility of Flexible/stretchable Electronics and
Optoelectronics,” Advanced Healthcare Materials 3, 515-525 (2014).
12) J. G. McCall, T.-I. Kim, G. Shin, X. Huang, Y. H. Jung, R. Al-
Hassani, F. G. Omenetto, M. R. Bruchas and J. A. Rogers “Fabrication
and Application of Flexible, Multimodal Light-Emitting Devices for
Wireless Optogenetics,” Nature Protocols 8 (12), 2413-2428 (2013).
13) T.-I. Kim, Y. H. Jung, H.-J. Chung, K. J. Yu, N. Ahmed, C. Corcoran,
J. S. Park, S. H. Jin and J. A. Rogers, “Deterministic Assembly of
Releasable Single Crystal Silicon-Metal Oxide Field-Effect Devices
Formed from Bulk Wafers,” Applied Physics Letters 102, 182104
(2013).
14) T.-I. Kim, J. G. McCall, Y. H. Jung, X. Huang, E. R. Siuda, Y. Li, J.
Song, Y. M. Song, H. A. Pao, R.-H. Kim, C. Lu, S. D. Lee, I.-S. Song,
G. C. Shin, R. Al-Hassani, S. Kim, M. P. Tan, Y. Huang, F. G.
Omenetto, J. A. Rogers and M. R. Bruchas, “Injectable, Cellular-Scale
Optoelectronics with Applications for Wireless Optogenetics,” Science
340, 211-216 (2013).
Dong Liu
Education:
B.S. in electrical engineering, University of Electronics Science and
Technology of China
Ph. D in electrical engineering, Tsinghua University

Business Address:
Madison, WI 53706

From 2009 to 2014, Dong was a Research Assistant with the
University of Illinois at Tsinghua University, where she focused on III-V
semiconductor based optoelectronic devices, including light emitting
diode, laser, modulator and photodetectors. Since 2014, she has been a
Research Associate with the University of Wisconsin-Madison, focusing
on high performance electronics and optoelectronics devices based on
heterogeneous materials for applications in silicon photonics, deep ultra-
violet light emitting diodes and high response photodetectors.
Honors:
Dong was a recipient of the 2014 Best Doctoral Thesis upon Ph.D
graduation in Tsinghua University.
Dong Liu, Changzheng Sun, Bing Xiong, and Yi Luo, Nonlinear dynamics
in integrated coupled DFB lasers with ultra-short delay, Optics
Express, 2014, 22(5): 5614-5622.
Dong Liu, Changzheng Sun, Bing Xiong, and Yi Luo. Suppression of
chaos in integrated twin DFB lasers for millimeter-wave generation,
Optics Express, 2013, 21(2): 2444-2451.
Changzheng Sun, Dong Liu, Bing Xiong, and Yi Luo, Modulation
Characteristics Enhancement of Monolithically Integrated Laser
Diodes under Mutual Injection Locking. IEEE Journal of Selected
Topics in Quantum Electronics, 2015, 21(6): 1802008.
Cho Minkyu, Jung-Hun, Munho Jaeseong, Dong Liu, Weidong Zhou,and
Zongfu Yu,and Zhenqiang Ma,, Resonant cavity germanium
photodetector via stacked single-crystalline nanomembranes, Journal
of Vacuum Science & Technology B, 2016, 34: 040604.

Dong Liu, Zhenyang Xia, SangJune Cho, Huilong Zhang, Tzu-Hsuan

Chang et al., 1.5um InGaAsP edge-emitting laser with silicon hole
injector, SPIE Photonics West, 2016, 9767-34.
Zhenyang Xia, Ming Zhou, Munho Kim, Tzu-Hsuan Chang, Dong Liu, et
al., Ultra-thin single crystal Germanium nanomembrane
photodetecting MOSFET. CLEO2016.
Dong Liu, Changzheng Sun, Bing Xiong, and Yi Luo. Resonance
Frequency Enhancement by Mutual Injection Locking of
Monolithically Integrated Laser Diodes, Conference on Lasers and
Electro-Optics, CLEO2014, SF2G.4.
Dong Liu, Changzheng Sun, Bing Xiong, and Yi Luo, Locked and
Unlocked Behavior of Mutually Coupled Lasers with Ultra-short
Delay, 24th IEEE International Semiconductor Laser Conference,
ISLC 2014, TP7.
Dong Liu, Changzheng Sun, Bing Xiong, and Yi Luo. A Novel Method for
Photonic Generation of Millimeter-wave Signals with Optical Injection
Locked Microring Laser, Asia communications and photonics
conference, ACP2013, AW3B.4.
Dong Liu, Changzheng Sun, Bing Xiong, and Yi Luo, Suppression of
Chaos in Integrated Coupled DFB Lasers for Millimeter-wave
Generation, Conference on optical fiber communication, OFC,
2013, JTh2A.53.
Hongyi Mi
Affiliation: Department of Electrical and Computer, the University of

Wisconsin-Madison.
Education: Ph.D, Department of Electrical and Computer, the

University of Wisconsin-Madison.
Business Address: B640 Engineering Hall, 1415 Engineering Dr.,

Madison, WI 53706.

Research and Professional Experience: Research in electrical and

opto-electrical devices and materials.
Juhwan Lee
Education:
B.S. in electrical engineering, University of Illinois at Urbana-
Champaign
Business Address:
Madison, WI 53706

From 2011 to 2013, Juhwan was a Research Associate with the
University of Illinois at Urbana-Champaign, where he focused on
stretchable batteries with self-similar serpentine electrodes and integrated
wireless recharging systems. Since 2013, he has been a Research Assistant
and since 2015, a Fellow with the University of Wisconsin-Madison,
focusing on flexible and stretchable microwave electronics,
electrocardiogram monitoring with graphene electrodes and micro-
structured implantable scaffolds.
Research Assistant, University of Wisconsin-Madison
Honors:
Juhwan has been selected as one of the finalists in the 2016 Wisconsin
Alumni Research Foundation Innovation Awards

1) Y. H. Jung, J. Lee, Y. Qiu, N. Cho, S. J. Cho, H. Zhang, S. Lee, T. J.

Kim, Shaoqin Gong, and Z. Ma, “Stretchable Twisted-Pair
Transmission Lines for Microwave Frequency Wearable
Electronics,” Advanced Functional Materials, 26, 4636-4642 (2016).
2) Y. Qiu, Y. H. Jung, S. Lee, T.-Y. Shih, Y. Xu, R. Xu, J. Lee, A. A.
Schendel, W. Lin, J. C. Williams, N. Behdad, and Z. Ma, “A
Compact Parylene Coated WLAN Flexible Antenna for Implantable
Electronics,” IEEE Antennas and Wireless Propagation Letters, 15,
1382-1385 (2016).
3) Y. Qiu, Y. H. Jung, S. Lee, J. Lee, T.-Y. Shih, Y. Xu, R. Xu, W. Lin,
J. C. Williams, N. Behdad, and Z. Ma, “Flexible Capacitively Loaded
Antenna with Parylene Conformal Coating,” Microwave Journal, 59
(4), 134-142 (2016).
4) Y. H. Jung, T.-H Chang, H. Zhang, C. Yao, Q. Zheng, V. W. Yang,
H. Mi, M. Kim, S. J. Cho, D.-W. Park, H. Jiang, J. Lee, Y. Qiu, Z.
Cai, W. Zhou, S. Gong, and Z. Ma, “High-Performance Green
Flexible Electronics Based on Biodegradable Cellulose Nanofibril
Paper,” Nature Communications, 6, 7170 (2015). DOI:
10.1038/ncomms8170.
5) Y. Qiu, Y. H. Jung, S. Lee, T.-Y. Shih, J. Lee, Y. H. Xu, R. Xu, W.
Lin, N. Behdad, and Z. Ma, “Compact parylene-c-coated flexible
antenna for WLAN and upper-band UWB applications,” IET
Electronics Letters 24 (50), 1782-1784 (2014),
DOI:10.1049/el.2014.3647.
6) Y. Zhang, S. Xu, H. Fu, J. Lee, J. Su, K.-C. Hwang, J. A. Rogers and
Y. Huang, “Buckling in serpentine microstructures and applications
in elastomer-supported ultra-stretchable electronics with high areal
coverage,” Soft Matter 9, 8062-8070 (2013).
7) S. Xu, Y. Zhang, J. Cho, J. Lee, X. Huang, L. Jia, J. A. Fan, Y. Su, J.
Su, H. Zhang, H. Cheng, B. Lu, C. Yu, C. Chuang, T.-I. Kim, T.
Song, K. higeta, S. Kang, C. Dagdeviren, I. Petrov, P. V. Braun, Y.
Huang, U. Paik, and J. A. Rogers, Stretchable Batteries with Self-

Similar Serpentine Interconnects and Integrated Wireless Recharging

Systems,” Nature Communications 4, 1543 (2013). DOI:
10.1038/ncomms2553.
Jiarui Gong
Affiliation: Department of Physics

University of Wisconsin-Madison, Madison, WI, US
Education:
B.S. Physics, Peking University, Beijing, China, 2015
Business Address:
B640
1415 Engineering Drive
Madison, WI 53706
Teaching Assistant, University of Wisconsin-Madison
Zhenqiang (Jack) Ma
Affiliation:
Department of Nuclear Engineering and Engineering Physics
Department of Materials Science and Engineering
Madison, WI, USA
Education:
Ph.D. Electrical Engineering, University of Michigan, Ann Arbor,
Michigan, 2001

Business Address:
3445 EH
1415 Engineering Drive
Madison, WI 53706

Zhenqiang Ma received the B.S. degree in applied physics and the B.E.
degree in electrical engineering from Tsinghua University, Beijing, China,
in 1991, the M.S. degree in nuclear science and the M.S.E. degree in
electrical engineering from the University of Michigan, Ann Arbor, in
1997, and the Ph.D. degree in electrical engineering from the University of
Michigan, in 2001. From 2001 to 2002, he was a Member of the Research
and Development Team, Conexant Systems and later its spin-off Jazz
Semiconductor, Newport Beach, CA. In 2002, he left Jazz to join the
faculty of University of Wisconsin–Madison, as an Assistant Professor
with the Department of Electrical and Computer Engineering. He is
currently the Lynn H. Matthias Professor of Engineering and the Vilas
Distinguished Achievement Professor with affiliated appointments in four
other engineering departments/institutions/programs. His current research
interest includes high-speed electronics, optoelectronics, and
nanophotonics, semiconductor materials processing and heterogeneous
integration, flexible electronics, flexible optoelectronics, and flexible
photonics, energy conversion semiconductor devices, including power
devices, solar cells, and light emitting devices, bioelectronics, and
biomimetics, and semiconductor device physics. He has authored or co-
authored over 400 peer-reviewed technical papers and book chapters
related to the above areas and holds about 34 U.S. and international
patents. He has been featured in MIT’s Technology Review for his
research innovations four times since 2004. He was a recipient of the
Presidential Early Career Award for Scientists and Engineers and the
DARPA Young Faculty Award. He serves on the editorial boards and as a
Reviewer of 78 international journals.

Professor
Lynn H. Matthias Professor in Engineering and Vilas Distinguished
Achievement Professor
Department of Electrical and Computer Engineering
University of Wisconsin-Madison
Honors:
H. I. Romnes Fellowship, 2012.
Presidential Early Career Award for Scientists and Engineers
(PECASE) 2007
DARPA Young Faculty Award, 2008.
1) T.-H. Chang, S. Xiong, R. M. Jacobberger, S. Mikael, H. S. Suh, C.-C.

Liu, D. Geng, X. Wang, M. S. Arnold, Z. Ma, P. F. Nealey, “Directed
self-assembly of block copolymer films on atomically-thin graphene
chemical patterns,” Scientific Reports, In Press (2016).
2) M. Kim, J.-H. Seo, Z. Yu, W. Zhou, Z. Ma, “Flexible germanium
nanomembrane metal-semiconductor-metal (MSM) photodiodes,”
Applied Physics Letters, In Press (2016).
3) D.-W. Park, S. K. Brodnick, J. P. Ness, F. Atry, L. Krugner-Higby, A.
Sandberg, S. Mikael, T. J. Richner, J. Novello, H. Kim, D-H. Back, J.
Bong, S. T. Frye, S. Thongpang, K. I. Swanson, W. Lake, R. Pashaie,
J. C. William, Z. Ma, “Fabrication and utility of a transparent graphene
neural electrode array for electrophysiology, in vivo imaging,and
optogenetics,” Nature Protocols, In Press (2016).
4) M.Cho, J.-H. Seo, D.-W. Park, W. Zhou, Z. Ma, “Capacitance-voltage
characteristics of Si and Ge nanomembrane based flexible metal-oxide-
semiconductor devices under bending conditions,” Applied Physics
Letters, 108, 233505 (2016).

5) M. Kim, S. C. Liu, J. Lee, T. Kim, J.-H. Seo, W. Zhou, Z. Ma, “Light

absorption enhancement in Ge nanomembranes and its optoelectronic
application,” Optics Express, 24(15): 16894-16903 (2016).
6) D. Liu, W. Zhou, Z. Ma, “Semiconductor nanomembrane-based light-
emitting and photodetecting devices” (Invited Review), Photonics,
3(2), 40 (2016).
7) S. Mikael, J.-H. Seo, A. Javadi, S. Gong, Z. Ma, “Wrinkled Bilayer
Graphene with Wafer Scale Mechanical Strain,” Applied Physics
Letters, 108, 183101 (2016).
8) L. Menon, H. Yang, S. J. Cho, S. Mikael, Z. Ma, W. Zhou,
“Heterogeneously integrated InGaAs and Si membrane four color
photodetector arrays,” IEEE Photonics Journal, 8(2), 6801907 (2016).
9) J.-H. Seo, T. Ling, S. Gong, W. Zhou, L. J. Guo, Z. Ma, “Fast Flexible
Thin-Film Transistors with a Nanotrench Structure,” Scientific
Reports, 6, 24771, (2016).
10) Y. H. Jung, Y. Qiu, S. Lee, T.-Y. Shih, Y. Xu, R. Xu, J. Lee, A. A.
Schendel, W. Lin, J. C. Williams, N. Behdad, Z. Ma, “A Compact
Parylene-Coated WLAN Flexible Antenna for Implantable
Electronics,” IEEE Antennas and Wireless Propagation Letters, 15,
1382-1385 (2016).
11) J.-H. Seo, H. Wu, S. Mikael, H. Mi, G. Venkataramanan, J. P.
Blanchard, S. Gong, W. Zhou, D. Morgan, Z. Ma, “Thermal Diffusion
Doping of Single Crystal Natural Diamond,” Journal of Applied
Physics, 119, 205703 (2016).
12) F. Wang, J.-H. Seo, G. Luo, M. Starr, Z. Li, D. Geng, X. Yin, S.
Wang, D. Fraser, D. Morgan, Z. Ma, X. D. Wang, “Nanometre-thick
single-crystalline nanosheets grown at the water-air interface,” Nature
Communications, 7, 10444 (2016).
13) D. Zhao, S. Liu, H. Yang, Z. Ma. C. R. Hedlund, M. Hammar, W.
Zhou, “Printed Large-Area single mode photonic crystal bandedge
surface-emitting lasers on Silicon,” Scientific Reports, 6, 18860
(2016).

14) H. Yang, D. Zhao, S. Liu, Y. Liu, J.-H. Seo, Z. Ma, W. Zhou,

“Transfer Printed Nanomembranes for Heterogeneously Integrated
Membrane Photonics,” Photonics 2(4), 1081-1100 (2015).
15) H. Mi, S. Mikael, C.-C. Liu, J.-H. Seo, G. Gui, A. L. Ma, P. F. Nealey,
Z. Ma, “Creating periodic local strain in monolayer graphene with
nanopillars patterned by self-assembled block copolymer,” Applied
Physics Letters, 107, 143107 (2015).
16) J.-H. Seo, T.-H. Chang, J. Lee, R. Sabo, W. Zhou, Z. Cai, S. Gong,
Z.Ma, “Microwave Flexible Transistors on Cellulose Nanofibrillated
Fiber Substrates,” Applied Physics Letters, 106, 262101 (2015).
17) Y. H. Jung, T.-H Chang, H. Zhang, C. Yao, Q. Zheng, V. W. Yang, H.
Mi, M. Kim, S. J. Cho, D.-W. Park, H. Jiang, J. Lee, Y. Qiu, Z. Cai,
W. Zhou, S. Gong, Z. Ma, “High-Performance Green Flexible
Nature Communications, 6, 7170 (2015).
18) M. Kim, H. Mi, M. Cho, J.-H. Seo, W. Zhou, S. Gong, Z. Ma,
“Tunable biaxial in-plane compressive strain in a Si nanomembrane
transferred on a polyimide film,” Applied Physics Letters, 106,
212107106 (2015).
19) M. Cho, J.-H. Seo, J. Lee, D. Zhao, H. Mi, X. Yin, X. Wang, W. Zhou,
Z. Ma, “Ultra-thin distributed Bragg reflectors via stacked single-
crystal silicon nanomembranes,” Applied Physics Letters, 106, 181107
(2015).
20) S.-C. Liu, D. Zhao, J.-H. Seo, Y. Liu, Z. Ma, W. Zhou, “Athermal
Photonic Crystal Membrane Reflectors on Diamond,” IEEE Photonics
Technology Letters, 27, (10) 1072-1075 (2015).
21) J.-H. Seo, J. Li, J. Lee, J. Lin, Hx. Jiang, and Z. Ma, “A simplified
method of making flexible blue LEDs on a plastic substrate,” IEEE
Photonics Journal, 7(2) 8200207 (2015).
22) D.-W. Park, S. Mikael, T.-H. Chang, S. Gong and Z. Ma, “Bottom-
gate coplanar graphene transistors with enhanced graphene adhesion
on atomic layer deposition Al2O3,” Applied Physics Letters, 106,
102106 (2015).

23) G. Qin, K. Zuo, J.-H. Seo, Y. Xu, H.-C. Yuan, H. Liu, Z. Huang, J.
Ma, and Z. Ma, “On the bending characterization of flexible radio-
frequency single-crystalline germanium diodes on a plastic substrate,”
Applied Physics Letters 106, 043504 (2015).
24) G. Gui, D. Morgan, J. Booske, J. Zhong, and Z. Ma, “Local strain
effect on the band gap engineering of graphene by a first-principles
study,” Applied Physics Letters 106, 053113 (2015).
25) L. Menon, H. Yang, S. J. Cho, S. Mikael, Z. Ma, W. Zhou,
“Transferred flexible three-color silicon membrane photodetector
arrays,” IEEE Photonics Journal, Vol.7, No.1, 6800106 (2015).
26) Y. Liu, A. Chadha, D. Zhao, J. R. Piper, Y. Jia, Y. Shuai, L. Menon, H.
Yang, Z. Ma, S. Fan, F. Xia, W. Zhou, “Approaching total absorption
at near infrared in a large area monolayer graphene by critical
coupling,” Applied Physics Letters, 105, 181105 (2014).
27) D.-W. Park, A. A. Schendel, S. Mikael, S. K. Brodnick, T. J. Richner,
J. P. Ness, M. R. Hayat, Farid Atry, S. T. Frye, R. Pashaie, S.
Thongpang, Z. Ma, J. C. Williams, Graphene-based carbon-layered
electrode array technology for neural imaging and optogenetic
applications. Nature Communications, 5:5258 (2014).
28) D. Zhao, H. Yang, J.H. Seo, Z. Ma, W. Zhou, “Design and
Characterization of Photonic Crystal Membrane Reflector Based
Vertical Cavity Surface Emitting Lasers on Silicon,” Reviews in
Nanoscience and Nanotechnology, 3 (2), 77-87 (2014).
29) G. Qin, T. Cai, H. C. Yuan, J. H. Seo, J. Ma, Z. Ma, “Flexible radio-
frequency single-crystal germanium switch on plastic substrates,”
Applied Physics Letters, 104, 163501 (2014).

Chapter 3
PROGRESS IN POLYETHYLENE
TEREPHTHALATE RECYCLING
Adel Elamri1, Khmais Zdiri1, Omar Harzallah2,*

and Abdelaziz Lallam2
1
Unité de Recherche Matériaux et Polymères Textiles,
Ecole Nationale d’Ingénieurs de Monastir, Monastir, Tunisie
2
Laboratoire de Physique et Mécanique Textiles (EA 4365),
Université de Haute Alsace, Mulhouse, France
ABSTRACT
In the last decade, an increasing interest has been focused on the

recycling of plastic wastes, especially on the polyethylene terephthalate
(PET). PET polymer is already being recycled and numerous applications
for recycled polyesters can be explored depending on the properties of the
resin. However, the common problem faced during processing of
recycled PET is degradation. Thus, many solutions have been proposed in
literature to undermine this problem. This chapter presents a background
*
Corresponding Author address: Email:[email protected].

156 Adel Elamri, Khmais Zdiri, Omar Harzallah et al.
of the current state of knowledge with respect to PET recycling. In the

first section, a brief theoretical background is presented about virgin PET
synthesis, thermal transitions, processing and applications. The second
section deals with the PET recycling process with a focus on
contaminations and ways to increase the molecular weight of recycled
PET (RPET). It serves as an introduction to Section Three where our
process to improve the RPET properties is described. Finally, Section
Four covers the effect of blending virgin PET (VPET) with recycled PET
on thermal and rheological behaviors.
Keywords: PET, recycling, blends, thermal and rheological
1. INTRODUCTION
The production of plastic materials in its various declinations comes

mainly from petroleum. However, we know that the depletion of fossil
resources is inevitable. The economy of the main material, in this case oil,
becomes a goal in itself. This objective can be achieved both through the
use of renewable materials, or recycling of materials, if operations are
technically and economically feasible.
In this work, the treatment is focused on the technical aspect of
thermomechanical recycling of PET waste from mineral water bottles. The
thermomechanical recycling presents the advantage of being fast and
cheap. In contrast, thermomechanical recycling leads to loss of important
mechanical properties by thermal degradation mechanism. It is possible to
overcome the loss of these properties, either by recycling under vacuum,
which requires heavy and expensive equipment, or by the addition of
virgin material to the primary material for recycling. In this chapter, it is
the second procedure which is described.
2. VIRGIN PET
Virgin PET has come to be considered as one of the most important

engineering polymers in the past two decades. It is regarded as an excellent

Progress in Polyethylene Terephthalate Recycling 157
material for many applications and is widely used for making liquid
containers (bottles). It has excellent thermomechanical and chemical
properties [1]. Many companies produce virgin PET giving it different
trade names [2]. Some of the common trade names of commercially
available PET are summarized in Table 1.
Table 1. Trade names of common PET and their manufacturer
Trade name Manufacturer

Rynite Du Pont de Nemours & Co.
Diolen ENKA-Glazstoff
Eastapac Eastman chemical company
Arnite DSM Engineering Plastics
Mylar E. I. Du Pont de Nemours & Co.
Melinex Imperial Chemical Industries Ltd.
Commercial PET has a wide range of intrinsic viscosity [η] that varies
from 0.45 to 1.2 dL.g-1 with a polydispersity index generally equal to 2.
The PET repeating unit is shown in Figure 1.
Figure 1. PET repeating unit.
2.1. PET Synthesis
PET production process involves two different starting reactions. The

first starting reaction is an esterification reaction (Figure 2a) where
terephthalic acid (TPA) reacts with ethylene glycol (EG) at a temperature
between 240°C and 260°C and a pressure between 300 and 500 kPa. The
second reaction is a trans-esterification reaction (Figure 2b) where
dimethyl terephthalate (DMT) reacts with EG at 180 – 210°C and 100 kPa

[3]. Trans-esterification is the much preferred process due to easier

purification. The output of both these processes is bis(hydroxyethyl)
terephthalate (BHET). The pre-polymerisation step follows, in which
BHET is polymerised to a degree of polymerization (DP) of up to 30
(Figure 2c). Pre-polymerisation reactions conditions are 250–280°C and 2–
3 kPa. The third stage is the polycondensation process where the DP is
further increased to 100. The polycondensation process conditions are
280–290°C and 50–100 Pa.
Up to this stage, PET is suitable for applications that do not require
high molecular weight (Mw) or intrinsic viscosity [η] such as fibers and
sheets. A solid state polymerization (SSP) step might be required when a
high Mw PET is produced. SSP is used to increase the DP to 150, and also
increasing Mw. SSP operating conditions are 200–240°C at 100 kPa and
5–25 h [4]. Bottle grade PET that has an [η] of 0.7–0.85 dL.g-1 is normally
produced by SSP at 210°C for around 15–20 h [5-6]. Some virgin PET
manufacturers have tended in recent years to produce PET co-polymer;
such as isophthalic acid modified PET, rather than homopolymer PET.
Bottles are then made from co-polymer PET because of its lower
crystallinity, improved ductility, better process ability and better clarity [7].
(a)
(b)
Figure 2. (Continued).

(c)
Figure 2. PET synthesis reactions (a) esterification of TPA with EG (b) trans-
esterificationof DMT with EG and (c) polymerization.
The PET chain is considered to be highly stiff above the glass

transition temperature (Tg) unlike many other polymers. The low
flexibility of the PET chain is a result of the nature of the short ethylene
group and the presence of the p-phenylene group. This chain inflexibility
significantly affects PET structure-related property. The standard physical
and chemical properties of commercial PET are shown in Table 2.
Table 2. Physical and chemical properties of PET [8]
Property Test method Value (Unit)

Molecular weight - 192 (g.mol-1)
(of repeating unit)
Weight-average Mw GPC 30,000 – 80,000 (g.mol-1)
Density - 1.41 (g.cm-3)
Glass transition temperature DSC 69-115 (°C)
Melting Temperature DSC 265 (°C)
Breaking strength Tensile 50 (MPa)
Tensile strength - 1700 (MPa)
(Young’s modulus)
Yield strain Tensile 4 (%)
Water absorption (after 24h) - 0.5 (%)

2.2. PET Applications
PET is used broadly in products such as bottles, electrical and

electronic instruments, in different sectors of automotive industry,
housewares, lighting products, power tools and material handling
equipment. PET films and fibers are the oldest applications of PET. Films
are produced by biaxial orientation through heat and drawing. PET films
are used in photographic applications, x-ray sheets and in food packaging.
PET films are also reported to be used in electrical and dielectrics
applications due to the severe restriction of the electric dipole orientation at
room temperature that is well below the transition temperature [9].
PET fibers are another important application of PET and are produced
by forcing molten PET through small holes in a die. Fiber strength is
achieved by applying tension to align the chains through uniaxial
stretching. Bottle production requires the use of PET with high molecular
weight. This is explained in part by the manufacturing process (bi-
stretching, blow - extrusion), and by the need to obtain sufficient barrier
properties for this application, often related to beverage packaging. PET
chains with high molecular weight will allow a 'mesh' at most ends of the
chains after bi-stretching which will limit the diffusion of gaseous
molecules from the outside to the content and vice versa [10].
Table 3. Intrinsic viscosity of PET depending on its application [11]
PET [η] (dL.g-1)

Fibers Textiles 0.40 – 0.70
Techniques 0.72 – 0.98
bi-oriented 0.60 – 0.70
Thermoforming 0.70 – 1.00
Bottles for water 0.70 – 0.78
for soft drinks 0.78 – 0.85

Virgin PET is produced at different specifications because different

applications require various properties. Examples of PET’s [η] with respect
to the required application are shown in Table 3.
2.3. Thermal and Crystallization Behaviors
Commercial PET has a melting temperature (Tm) between 255 and

265°C and for more crystalline PET it is situated between 255 and 270°C
[4]. The Tg of virgin PET varies between 67 and 140 C. The thermal
transitions and crystallization of virgin PET with a focus on reversing
crystallization and melting have been analyzed by several researchers [12,
13]. An interesting phenomenon was reported in which the virgin PET
experiences multiple endothermic transitions during thermal analysis [14].
It was reported that this phenomenon is attributable to morphological and
structural re-organization. As the temperature increases, better crystal
structures are achieved because of the re-organization of the less perfect
crystals.
Virgin PET is well known for having a very slow crystallization rate.
The highest crystallization rate takes place between 170°C and 190°C.
Cooling PET rapidly from the melt to a temperature below Tg can produce
an amorphous, transparent PET. Semi-crystalline PET can be obtained by
heating the solid amorphous PET to a temperature above Tg where 30%
crystallinity can be achieved [15].
The rate of crystallization of virgin PET depends greatly on
temperature and reaches its maximum at a temperature of 150–180°C. The
rate of crystallization also depends on other factors such as Mw, the
presence of nucleating agents, the degree of chain orientation, the nature of
the polymerization catalyst used in the original production of PET and the
thermal history.

3. RECYCLED PET
Due to its increasing consumption and non-biodegradability, PET

waste disposal has created serious environmental and economic concerns.
Thus, management of PET waste has become an important social issue. In
view of the increasing environmental awareness in the society, recycling
remains the most viable option for the treatment of waste PET. On the
other hand, as the price of virgin PET remains stable, new and cheaper
technologies for recycling PET give an added value to the PET recycling
industry by providing industry with relatively cheaper PET.
Many researchers reported that in order to achieve successful PET
recycling, PET flakes should meet certain minimum requirements [16, 17].
Examples of the minimum requirements for the post consumer PET
(POSTC-PET) flakes are summarized in Table 4.
Table 4. Minimum requirements for POSTC-PET flakes

to be reprocessed
Property Value
Intrinsic viscosity [η] >0.7 dL.g-1
Melting temperature Tm >240 °C
Water content <0.02 wt.%
Dye content <10 ppm
Yellowing index <20
Metal content <3 ppm
PVC content <50 ppm
Polyolefin content <10 ppm
The major factor affecting the suitability of POSTC-PET flake for

recycling is the level and nature of contaminants present in the flakes.

3.1. Recycled PET Contamination
Contamination of POSTC-PET is the major cause of deterioration of

its physical and chemical properties during re-processing. Minimizing the
amount of these contaminants leads to better quality of recycled PET.
POSTC-PET is contaminated with many substances such as:
3.1.1. Acid Generating Contaminants

The most harmful acids to the POSTC-PET recycling process are
acetic acid, which is produced by poly(vinyl acetate) closures degradation,
rosin acid and abietic acid that are produced by adhesives and hydrochloric
acid that is produced by PVC. The acids act as catalysts for the chain
scission reactions during POSTC-PET melt processing [18]. Paci and La
Mantia [19] investigated the influence of small amount of PVC during the
melt processing of POSTC-PET. They reported that the presence of PVC
(as little as 100 ppm) would increase POSTC-PET chain scission due to the
catalytic effect of hydrogen chloride evolving during the degradation of
PVC. The presence of PVC also results in discoloration of POSTC-PET
during processing.
3.1.2. Water
Water reduces Mw during POSTC-PET recycling through a hydrolysis
reaction. Moisture contamination should be below 0.02% to avoid the Mw
reduction. Most water content comes from the flake washing process but
can be reduced substantially by proper drying.
3.1.3. Coloring Contaminants

Fragments of colored bottles and printed ink labels cause undesirable
colors during processing. Enhancement of sorting and washing processes
in bottle recycling may reduce coloring contaminants.
3.1.4. Acetaldehyde
Acetaldehyde is present in virgin PET and POSTC-PET. It is a by-
product of PET degradation reactions. The migration of acetaldehyde into

food products from PET containers was a major concern in the early stages
of developing the POSTC-PET recycling process. The high volatility of
acetaldehyde means that it can be minimized by processing under vacuum
or by drying. Stabilizers such as (4-aminobenzoic acid, diphenylamine and
4,5dihydroxybenzoic acid) are added to PET in order to minimize the
amount of the generated acetaldehyde [20].
3.1.5. Other Contaminants

The public use PET bottles for storing other substances such as
detergents, fuel, pesticides, etc... The remains of these substances could be
a health hazard if traces of these substances remain after POSTC-PET
recycling [21]. The increase of people’s awareness of the danger of such
practices to public health has minimized the amount of these contaminants
significantly.
3.2. Recycling Methods
PET recycling has been one of the most successful and widespread
among polymer recycling. PET recycling methods can be categorized into
three groups namely primary, secondary and tertiary recycling. There is
also a so-called ‘zero-order’ recycling technique, which involves the direct
reuse of a PET waste material [22].
3.2.1. Zero-order Recycling

This technique consists in washing of PET bottles in hot water with
detergents following the similar procedure of that practiced for glass
bottles. The collected bottles are first subjected to hot washing with
detergents and then to a control by sensors that detect and eject bottles
containing volatile or liquid pollutants. The main disadvantage of this
method is that it does not allow to effectively eliminate any contaminants
absorbed by the PET [23].

3.2.2. Primary Recycling

Primary recycling, also known as mechanical recycling, was applied
for the first time in the 1970s. It involves separating the polymer from its
contaminants and reprocessing it to granules via mechanical means.
Mechanical recycling steps include sorting and separation of wastes,
removal of contaminants, reduction of size by crushing and grinding,
extrusion by heat, and reforming. The more complex and contaminated the
waste is, the more difficult it is to recycle mechanically. Among the main
drawbacks of primary recycling are the heterogeneity of the solid waste,
and the degradation of the product properties each time it is recycled.
Mechanical recycling of PET includes 4 phases (Figure 3).
3.2.3. Secondary Recycling

Secondary recycling, more commonly known as chemical recycling,
involves the transformation of the PET polymer chain. Usually by means
of solvolytic chain cleavage, this process can either be a total
depolymerization back to its monomers or a partial depolymerization to its
oligomers and other industrial chemicals. Since PET is a polyester with
functional ester groups, it can be cleaved by some reagents such as water,
alcohols, acids, glycols, and amines. Also, PET is formed through a
reversible polycondensation reaction, so it can be transformed back to its
monomer or oligomer units by pushing the reaction to the opposite
direction through the addition of a condensation product. These low
molecular products can then be purified and reused as raw materials to
produce high quality chemical products [24].
Among the recycling methods, chemical recycling is the most
established and the only one acceptable according to the principles of
‘sustainable development’, defined as development that meets the needs of
the present generation without compromising the ability of future
generations to meet their needs, because it leads to the formation of the raw
materials (monomers) from which the polymer is originally made [25].

Figure 3. Phases of mechanical recycling of PET bottles.
As shown in Figure 4, there are three main methods in PET chemical

recycling depending on the added hydroxyl bearing molecule: glycol for

gylcolysis, methanol for methanolysis, and water for hydrolysis. Other

methods include aminolysis and ammonolysis. Over the past five decades,
since the start of PET chemical recycling research numerous researches
have been done in order to fully understand the chemical pathways of the
depolymerization methods, and improve desired products yield from these
methods.
Figure 4. Different solvolysis methods for PET chemical recycling.
3.2.4. Tertiary Recycling

Tertiary recycling represents the recovery of energy content from the
plastic waste by incineration. When the collection, sorting and separation
of plastics waste are difficult or economically not viable, or the waste is
toxic and hazardous to handle, the best waste management option is
incineration to recover the chemical energy stored in plastics waste in the
form of thermal energy. However, it is thought to be ecologically
unacceptable due to potential health risks from the airborne toxic
substances.
3.3. Increasing PET Intrinsic Viscosity
During the melt processing of recycled PET at high temperatures, R-

PET undergoes a series of thermal and hydrolytic degradation reactions in

the presence of water and contaminants, such as adhesives, poly(vinyl

chloride) (PVC), etc… This leads to the decrease in intrinsic viscosity (η)
by formation of low molecular mass PET with a significant increase of
carboxyl and hydroxyl end groups. Oligomers and volatile compounds are
produced during PET processing above its melting temperature, which
contribute to the depression of Mw [26]. Scheirs [7] reported that cyclic
and linear oligomeric compounds are formed during the reprocessing of
PET as a result of thermal degradation reactions. He also showed that the
oligomers content increased from 0.9 wt.% in virgin PET to 1.8–3.0 wt.%
in R-PET. These products also serve as a catalyst to increase the rate of
degradation reactions. Furthermore, as some of the degradation products
have carboxyl ends, this increases the overall PET carboxyl content which
leads to a decrease in PET thermal stability.
Overcoming the reduction of R-PET’s Mw or [η] has been the
objective of many investigations [27, 28]. Different methods and processes
have been reported over the past two decades to restore or maintain R-PET
properties during processing, which are outlined below.
3.3.1. Reprocessing Under Vacuum

The most recent PET recycling units are equipped with vacuum
systems. All volatile substances present or produced while processing,
including water vapor, are removed constantly during processing. Volatile
components further promote the degradation reactions and the removal of
the volatile compounds during processing has recently been regarded as
essential. Currently, intensive drying to remove moisture, as well as
vacuum degassing processing, is introduced in plastic recycling systems to
minimize the effect of degradation reactions, resulting in higher R-PET
intrinsic viscosity in comparison with normally extruded POSTC-PET.
3.3.2. Stabilizers
PET processing stabilizers mainly have the function of reducing the
effect of PVC contamination and are also associated with thermal
stabilization. The majority of the PET process stabilizers are metal based
such as butyl tin mercaptide, antimony mercaptide and lead phthalate.

Adding organic phosphate to PET during re-processing helps to stabilize it

by decomposing hydroperoxide groups to non-radical products. Scheirs [7]
reported that bis(2,4,di-tertbutylphenyl) pentaerythritol diphosphite can
prevent Mw loss, inhibit yellowing reactions and reduce the production of
acetaldehyde. The major disadvantage of using stabilizers is the significant
added cost to the PET recycling process.
3.3.3. Solid State Polymerization

The SSP is a process in which POSTC-PET is heated to above its Tg
but below the Tm. Condensation reactions occur at a temperature range of
between 200 and 240°C, which is lower than the melt processing
temperature (280°C). Degradation reactions have little effect at the low
temperature of processing leading to an increase in R-PET Mw. The SSP
by-products are removed continuously by vacuum or by applying an inert
gas stream [29].
Karayannidis et al. [30] investigated the use of SSP to increase the
POSTC-PET’s Mw. They investigated the effect of reaction temperature
and time on the resulted PET [η]. They reported that modified PET is
produced with improved Mn after solid stating at 230°C for 8 h. However,
SSP is considered too slow and expensive to be applied on an industrial
scale.
3.3.4. Chain Extension

PET or POSTC-PET chain extension is a process where a di- or poly-
functional low Mw material is reacted with PET carboxyl and/or hydroxyl
end groups to rejoin the broken chains that result from PET chain scissions
during melt processing.
The mechanism of the PET chain extension reaction was introduced by
Inata and Matsumura [31]. They suggested that for a 2,2’-bis(2-oxazoline)
chain extender there are three types of reactions with PET:
 A blocking reaction where a molecule of chain extender reacts

with one chain of PET.

 A coupling reaction where a molecule of chain extender joins two

PET chains.
 No reaction where the chain extender molecule fail to react.
Chain extenders can be classified according to the PET functional end

group that they react with. The chain extenders that react with carboxyl
end groups are effective, in addition to the chain lengthening, by reducing
the overall carboxyl content leading to high hydrolytic and thermal
stability which in turn maintains Mw during melt processing [32]. The
other type of chain extenders is hydroxyl-reactive chain extenders. They
are more effective with low Mw PET produced by melt polycondensation
because the hydroxyl content predominates over the carboxyl end groups.
The hydroxyl-reactive chain extenders will increase [η] rapidly when
reacting with PET that is produced by melt polycondensation PET [33]. An
example of hydroxyl reactive chain extenders are 2,2’-bis(3,1-benzoxanin-
4one). Many researchers reported disadvantages associated with operating
with some chain extenders. Cardi et al. [34] reported that undesired side
reactions could take place when using bis(2-oxazoline) (BO) to chain
extend PET due to the sensitivity of the oxazolinic ring to acidic
compounds. Structure of bis(2-oxazoline) is shown on Figure 5.
Figure 5. Chemical structure of BO chain extender.
Torres et al. [27] reported that diisocyanates are more effective chain
extenders than BO and diepoxides; however, they reported product
discoloration when using diisocyanates.
PMDA has previously been reported as an effcient chain extender or
branching agent. It is thermally stable, produces no side products on
reaction with PET, is tetra functional, commercially available and
economical [35].

3.3.5. Reactive Extrusion Process

Reactive extrusion processes facilitate polymer modifications greatly
in the sense of providing a modified polymer with better specifications for
different applications. Reactive extrusion is basically achieved by using an
extruder as a reactor. For the POSTC-PET modification process, reactive
extrusion has been attractive because of its advantages of combining a
reactor and an extruder in one system. Many researchers used reactive
extrusion systems to modify POSTC-PET [36] in order to achieve better
chemical and rheological properties. When applying POSTC-PET chain
extensions in a reactive extrusion system, process parameters such as the
twin-screw extruder performance and stability are closely monitored to
ensure successful operation. Awaja et al. [37] investigated a reactive
extrusion system with added chain extenders. They obtained lower
carboxylic content using different types of chain extenders. For the
POSTC-PET reactive extrusion processes, single or twin-screw extruders
can be used. Single screw extruders have the advantage over twin-screw
extruders lower capital cost which is the reason why they are used widely
in the extrusion industry. Twin-screw extruders are well known for their
high mixing ability and are used mainly in compounding and reactive
polymer processes.
As described in this section, several efforts have been made by
researchers to overcome the problem of intrinsic viscosity loss of POSTC-
PET when extruded. Nevertheless, the proposed techniques have two main
disadvantages: the high cost of required chemical products and the
complication of the process. Indeed, the application of these techniques on
the industrial scale is both relatively difficult and costly.
4. ENHANCEMENT OF RECYCLED PET PROPERTIES
Using recycled polymer blends with virgin polymer of the same nature
is a common solution for upgrading post-consumer materials. Scarfato and
La Mantia [38], have studied blends of recycled PA6 and virgin PA. They
found that the blends prepared in specific conditions show rheological and

mechanical properties close to those of the virgin polymer. Kukaleva et al.

[39], investigated blends of recycled and virgin HDPE polymers. They
stated that mechanical properties (modulus and elongation) of the blends
have predictable linear behavior. Earlier Wenguang [40], prepared and
characterised homopolymer blends of recycled/virgin PVC. He found that
the properties of the blends are between those of the pure compounds.
In many cases it is proposed to use blends of recycled PET and virgin
PET to maintain the properties of the recycled polymer sufficiently high
during the transformation processes.
4.1. Raw Polymers
In this context, the authors of this chapter conducted experiments

based on three types of polymers: two PET bottle waste polymers and a
virgin one to obtain melt spun yarns. Chips of crushed and cleaned bottles,
purchased from an industrial plastic waste collector, were used as the
source for recovered PET materials. Recycled PET (PET-A) comes from
blue post-consumer bottles and recycled PET (PET-B) arises from
heterogeneous deposits of various colored bottles (white, green, etc.). A
fiber grade PET (PET-C) was used as the virgin PET resin. The
characteristics of these three starting polymers are recapitulated in Table 5:
Table 5. Intrinsic Viscosity, molecular weight and MFI of

the three PET polymers
[] Mw Mn MWD MFI

-1
(dL.g ) (g.mol-1) (g.mol-1) (Mw/Mn) (g.10’)
PET-A 0,67 35500 17700 2,03 26
PET-B 0,63 32300 16100 2,01 30
PET-C 0,74 42100 20200 2,1 20

4.2. Melt Processing
The moisture content of PET should not exceed 0.005%. So, recycled
chips and virgin pellets were dried under vacuum during 12H at 90°C in
order to eliminate the residual moisture. Then, blends of virgin/recycled
PET (PETV/R) were obtained using a Haake-Rheocard twin screw
extruder under the following conditions: die temperature 270°C, extrusion
speed 40 rpm and residence time of 5mn. The extrudate is cooled in water
then passed through a pelletizing unit. We considered the following
compositions of blends: 90/10, 70/30, 50/50 and 25/75 (PETV/ PETR
w/w).
4.3. Methods of Analysis
Solution viscosity measurements were carried out on a Scött Gerate

viscosimeter equipped with Ubbelohde capillary in a solution of phenol
and 1,1,2,2-tetrachloroethane (60/40 w/w %) at 25°C. the intrinsic
viscosity, [η], of polymers was extrapolated using the Huggins equation.
The average molecular weights, Mw and Mn, were then computed from
the values of [η] according to the following relations, Berkowitz [41] and
Kokkalas [42]:
M w  6,58.10 4  
__
1, 54
Eq. 1
M n  3,29.10 4  
__
1, 54
Eq. 2
A TA Instruments calorimeter was used to obtain thermograms of

virgin, recycled and blended PET polymers. The swept temperature lies
between 30 and 280°C under nitrogen atmosphere and an empty capsule as
reference. The calorimeter is attached to a thermal analysis data station that
calculates glass transition temperature Tg, crystallisation temperature Tc,
melting temperature Tm, enthalpy of crystallisation Hc, enthalpy of
melting Hm of samples. The percent of crystallinity, c, for all PET

samples was calculated from equation 3 whenever a crystallisation

exotherm was present during heating:
H m - Hc
 % 
c H0m
*100 Eq. 3
0
where ΔHm  32,5cal/g , is the heat of fusion of a 100% crystalline PET
[43].
Dynamic and steady shear rheological measurements were carried out
on a dynamic rheometer MCR500 from Physica. This operates at both
controlled stress and strain modes. The rheological properties of molten
materials were determined using parallel plate geometry: 25 mm diameter
and a constant gap of 1 mm. Steady shear viscosity measurements were
carried out in a shear rate range varying from 0,1 to 300 s-1. For very
higher shear rates the data obtained were inconsistent due to the fact that
molten polymer ejected outside of measurement gap because of the
important centrifuge force that develops at high rotation speed of superior
plate.
For dynamic tests, the strain () values are chosen in order to perform
the frequency sweeps in the linear viscoelastic range (LVR) i.e., the
limiting strain under which the rheological parameters (η*, G’, G"…)
remained constant. For this purpose, preliminary strain sweeps were made,
at constant frequency (1 Hz) and temperature (270°C), and the LVR was
determined for each polymer. The frequency range investigated was 0,1-
100 Hz with a constant shear strain of 10% (within the LVR of polymers).
5. RECYCLED/VIRGIN PET BLENDS’ BEHAVIOR
5.1. Thermal Analysis of PET-V/R Blends
DSC analysis of PET-V/R blend pellets was carried out following this
experimental protocol:

 a heating step from 20 to 280°C at a rate of 10°C.mn-1

 a thermal treatment at 280°C for 3 minutes
 a crystallization step from 280°C down to 20°C at 10°C.mn-1.
The thermograms recorded during heating run of PET-C/A blends are

reported on Figure 6:
Figure 6. Thermal behavior during crystallization run of PET-C/A blends.
The same behavior was also observed for PET-C/B blends.

It can be deduced from PETV/R thermograms that:
 glass transition temperature (Tg) that remains almost constant for

all the PET-V/R blends (between 83 and 84°C).
 an exothermic peak known as “cold crystallisation” [44],
corresponding to the crystallisation of amorphous phase. This peak
is typical for semicrystalline polymers such as PET or PEEK The
phenomenon of cold crystallisation is explainable. As the frozen
chains are heated, a critical mobility for crystallisation is reached
and the material organises with an exothermic process. From the
Table 6, we observe that the values of the cold crystallisation
temperature (Tcc, min) of our blends increase with increasing
recycled PET content.

 an endothermic peak associated with the fusion of the whole

crystalline structure. We can see on Figure 5 that the values of
melting temperatures (Tm, max), that correspond to the maximum
of the melting peak, of the PET-V/R blends decrease with the
PETR concentration and are between those of the starting materials
i.e., PETR and PETV. This absence of melting depression or
synergy was explained by Fann et al. [45] by the fact that
PET/PET blends are crystalline-crystalline isomorphous polymer
blends of the same material (PET).
Table 6. Thermal characteristics of the PET-V/R blends
Tg Tm, max Hm Tcc, min Hcc  Tc, min Hc

(°C) (°C) (J.g-1) (°C) (J.g-1) (%) (°C) (J.g-1)
PET-C 83 255 55.8 - 0 41 199 36
(100%)
PET-C/A 83 257 39.5 121 26.1 10 211 44.6
(90/10)
PET-C/B 83 257,5 38,7 119 23 11,5 212 44
(90/10)
PET-C/A 84 255 38.1 124 27.1 8 213 42.9
(70/30)
PET-C/B 84 254.5 35.7 122 21.2 10.6 213.5 45.1
(70/30)
PET-C/A 84 253.5 40.6 125 25.5 11 213 44.3
(50/50)
PET-C/B 84 253 38.2 124 22.1 12 214.5 43.9
(50/50)
PET-C/A 84 252 37.5 129 23.8 10 212 43.6
(25/75)
PET-C/B 84 255 44.5 127 20.7 17.5 217.5 44.1
(25/75)
PET-A 85 251 45.5 131 21 18 217 38.6
(100%)
PET-B 85 254 44.3 129 22 16 218 37.8
(100%)
DSC curves obtained from the cooling run of PET-V/R samples are
plotted on Figure 7.

Contrary to other samples, PETC exhibits a rather broad temperature

range of crystallisation starting at a lower temperature than other materials.
However, recycled PET polymers (PETA and PETB) show higher
crystallisation temperatures Tc ( + 20°C) with a sharper and narrower
temperature range of crystallisation than PETV. This is explainable by the
lower molecular weight (Mw) of PETR polymers and the physical
contaminations that they may contain that will act as nucleation agents for
crystallisation kinetics.
On the other hand, PET-V/R blends show various degrees of
improvement of the crystallisation process. Their crystallisation is
narrower and sharper than parent polymers. We can also deduce from
Table V that minimum crystallisation temperature (Tc, min) of the blends
increases with the increase of PETR composition.
Figure 7. Thermal behavior during crystallization run of PET-C/B blends.
5.2. Rheological Behavior of PET-V/R Blends
Steady state rheological properties of virgin/recycled PET blends were

determined at shear rates ranging between 0,1-300 s-1 at constant

temperature 260°C. The flow curves obtained for different blends are
reported on Figure 8. We remark that the apparent viscosity increases with
the increase of PETR percentage for the two types of blends PET-C/A and
PET-C/B. Also the viscosities of all the blends lie between those of pure
PET materials.
.
Figure 8. Viscosity η vs shear rate  for PET-C/B blends (at 260°C).
Furthermore, it can be noted that the viscosity of the blends PET-C/B

is higher than that of the blends PET-C/A. This is probably due to the fact
that the PET-A is more likely to degrade than the PET-B. Indeed, during
the preparation of the blends the polymers undergo shearing, thermal and
mechanical stress (temperature and pressure).
The zero shear viscosity of the PET-C/A blends is plotted against the
PETV weight fraction (Figure 9). The experimental curves show a negative
deviation (ND) from the logarithmic additivity rule frequently used to
model polymer/polymer blends viscosity [46].
Dynamic rheological properties (*, G' = ''/ and G'' = '/) for the
PETV/R blends and extruded pure polymers (PETR and PETV) were
measured with constant strain of 10% at 260°C. As expected the dynamic
viscosity (*) decreases with frequency (Figure 10). Also, as for steady

state shear viscosity, the complex melt viscosity increases with virgin PET
concentration.
Figure 9. Negative deviation of η0 vs. composition for PETC/A blends.
Figure 10. Dynamic viscosity η* of PET-C/A blends at 260°C.
In order to analyse the dynamic rheological data, the Cole-Cole plot

(G' vs. G'') was used. This criterion was developed by Han and Kim [47].

In this method, if a blend is miscible the same slope is observed between

the blend compositions and pure components; otherwise it is considered to
be immiscible or a phase separated blend. On Figure 11, the plots showed
almost the same slope for all the PET-V/R blends which is a good criterion
proving the miscibility of recycled and virgin PET polymers. The
independence of composition and the absence of phase separation would
mean that PETV and PETR are miscible down to the macromolecular
level. The PET-V/R blends would thus form an isotropic medium that has
no separate domains occupied by the respective constituent components.
Figure 11. Cole-Cole analysis of viscoelastic modulus of PET-C/A blends.
CONCLUSION
In addition to the environmental incentive, recycling of PET as an

industry derives its driving force from the increasing value and
applications of virgin and modified PET. As described in the first sections,
many scientific findings have been made in the field of PET recylcing.
Particular focus in this study was given to the methods used to enhance
properties of recycled PET.

The study of thermal behavior of virgin/recycled PET blends points

out the their good microstructural morphology. The absence of melting
depression or synergy was explained by the fact that PETR/PETV blends
are crystalline-crystalline isomorphous polymer blends of the same
material. This statement was in accordance with rheological measurements.
The steady and dynamic tests showed the absence of phase separation that
would mean that PETV and PETR are miscible down to the
macromolecular level. The PET-V/R blends can be considered as forming
an isotropic medium that have no separate fields occupied by the
respective constituent components.
Thus, the study reveals that the mechanical blending of recycled PET
chips and virgin PET pellets improves the melt processing of recycled
PET.
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INDEX
alcohols, 29, 36, 47, 165

#
aliphatic polyesters, 3, 60
1H alkaline hydrolysis, 55
NMR, 25, 36
aluminium, 48
amino groups, 79, 80
A Aminolysis, 52
ammonia, 53, 54
acetaldehyde, 9, 34, 35, 163, 169 ammonium, 53, 72
acetic acid, 8, 37, 52, 163 Ammonolysis, 54
acid, vii, 2, 3, 6, 7, 8, 10, 23, 34, 36, 37, 44, amorphous phases, 12
52, 54, 55, 56, 60, 61, 62, 69, 74, 78, amorphous polymers, 16, 21, 64
157, 158, 163, 164 anisotropic, 13, 76, 111, 112
acidic, 30, 34, 44, 54, 170 annealing, 12, 13, 15, 21, 31, 43, 68, 115
acrylic acid, 69, 78 annihilation, 17, 24
acrylonitrile, 64, 65, 68, 70, 97 anticoagulation, 78
acrylonitrile-butadiene-styrene copolymer antimony, 7, 45, 168
(ABS), 64, 68, 70, 97 applications, viii, ix, 2, 3, 4, 5, 21, 26, 37,
activation energy, 35, 48, 52 40, 42, 43, 63, 64, 66, 67, 69, 70, 71, 72,
active oxygen, 25 75, 76, 77, 78, 81, 82, 84, 85, 103, 104,
active RF flexible components, 120 105, 107, 108, 110, 115, 119, 122, 125,
additives, 11, 42, 45 129, 130, 131, 134, 136, 138, 139, 141,
adhesion, viii, 2, 64, 70, 77, 78, 83, 140, 144, 147, 153, 155, 157, 158, 160, 161,
152 171, 180
adhesive properties, 77 argon, 22, 77
adhesives, 18, 44, 163, 168 aromatic hydrocarbons, 29
advancement, 114, 128 aromatic rings, 74

188 Index
atmosphere, 6, 35, 36, 38, 104, 105, 173 capillary, 114, 173
atmospheric pressure, 6, 13, 49, 50, 51 carbon black (CB), viii, 2, 75, 85
audio tapes, 81 carbon dioxide, 4, 22, 24, 61, 62, 82, 104
automotive application, 70 carbon nanotubes (CNTs), viii, 2, 73, 74, 85
awareness, 162, 164 carboxyl, 9, 27, 29, 30, 32, 34, 35, 64, 168,
169, 170
carboxylic acid, 10, 36, 74
B
Carothers, 3, 86
catalyst, 6, 7, 8, 10, 12, 45, 46, 47, 48, 49,
bacterium, 56
50, 51, 52, 53, 61, 80, 161, 168, 185
band gap, 153
catalytic effect, 38, 163
bandwidth, 105, 128
cationic surfactants, 72
base, 26, 52, 59, 60, 72, 73, 74, 80
Celanex, 3, 65
batch and continuous processes, 10
cellulose, 132, 136, 139
Beijing, 148, 149, 181
chain rigidity, 18
biaxial orientation, 24, 160
chain scission, 29, 30, 31, 32, 33, 34, 36, 45,
bicarbonate, 49, 50
163, 169
biocompatibility, viii, 2, 62, 77, 143
challenges, vii, ix, 104, 107, 183
biodegradability, 43, 162
chaos, 144
biodegradable materials, 62
chemical bonds, 77
biodegradation, 56, 62
chemical degradation, 45
biomaterials, 79, 83
chemical etching, 120
biomedical applications, 76, 77, 82
chemical functionalization, 73
birefringence, 12
chemical industry, 46
bis(2-hydroxyethyl)terephthalate (bis-HET),
chemical properties, 111, 157, 159, 163
6
Chemical Recycling, 91, 183
bisphenol, 67, 68
Chemical Stability, 29
Bisphenol A, 74
chemical treatment, viii, 2, 77, 79
blends, 2, 24, 63, 64, 65, 66, 68, 69, 70, 81,
chemicals, 4, 8, 69, 112, 120, 165
84, 86, 96, 97, 156, 171, 172, 173, 174,
China, 80, 139, 143, 148, 149, 181
175, 176, 177, 178, 179, 180, 181, 184,
chromatography, 31, 36, 37, 48
185
clarity, vii, 2, 44, 84, 158
bonding, 74, 140
cleavage, 30, 32, 165
branching, 14, 170
CO2, 104, 105
breakdown, 31, 116
cobalt, 45, 49
butadiene, 64, 65, 68, 70, 97
collagen sponges, 83
butadiene-styrene, 64, 65, 68, 70, 97
commercial, vii, 1, 2, 3, 10, 15, 25, 40, 44,
46, 48, 58, 63, 65, 68, 84, 159
C Commercial Pocan® PBT grades, 65, 66
communication, 118, 122, 130
calorimetry, 12, 15, 21 compatibility, 63, 67, 72
candidates, viii, 62, 73, 103, 107, 129 composites, 68, 71, 74, 75, 182

Index 189
composition, 23, 34, 65, 80, 177, 179, 180

compounds, 36, 45, 51, 69, 79, 107, 120,
D
135, 168, 170, 172
Dacron, 3, 5, 81, 82
condensation, 10, 47, 60, 64, 165
decomposition, 38, 50, 54, 72, 73
conditioning, 41, 116, 130
degradation, viii, ix, 2, 4, 7, 10, 18, 29, 30,
conductivity, 26, 27, 28, 128
31, 32, 33, 34, 35, 36, 37, 38, 44, 45, 46,
consumption, 5, 43, 74, 81, 105, 122, 162,
48, 52, 53, 56, 57, 62, 79, 155, 156, 163,
181
165, 167, 168, 183
containers, 11, 12, 25, 157, 164, 183
degradation mechanism, 36, 156, 183
contamination, 163, 168, 183
degradation process, 30, 33, 36
conventional composite, 71
degradation rate, 29, 37
COOH, 74, 78
degree of crystallinity, 16, 18, 26, 27, 30, 75
cooling, 4, 11, 12, 13, 15, 18, 19, 20, 64, 65,
demonstrations, 122, 126
176, 185
dendritic segments, 84
copolymer, 23, 25, 37, 57, 61, 62, 63, 64,
depolymerization, 33, 45, 46, 47, 48, 49, 50,
65, 67, 68, 69, 70, 97, 138, 150, 152
52, 54, 55, 165, 167
copolymerization, 23, 24, 61
deposition, 105, 116, 120, 140, 152
corona discharge, 77
depression, 168, 176, 181
correlation, 14, 17, 25
depth, 56, 125
cosmetics, 44
derivatives, 38, 47
cost, viii, 2, 4, 21, 44, 47, 54, 63, 65, 75,
detergents, 44, 56, 164
103, 107, 110, 120, 129, 132, 169, 171
deviation, 178, 179
covalent bond, 74
dielectric constant, 116, 117, 119, 123, 136
covalent bonding, 74
dielectric relaxation spectroscopy (DRS), 26
covering, 44, 84, 118
dielectrics, 140, 160
creep, 39, 53, 61, 62
differential scanning calorimetry, 12
crystal structure, 161
diffraction, 19, 33
crystalline, 5, 10, 11, 13, 15, 18, 19, 22, 23,
diffusion, 17, 22, 24, 49, 123, 124, 125, 160
29, 30, 42, 51, 56, 57, 58, 68, 71, 75, 84,
diffusivity, 23
105, 110, 111, 132, 134, 135, 136, 144,
diisocyanates, 170
151, 153, 161, 174, 176, 181
dimethyl terephthalate, vii, 2, 6, 46, 157
crystallinity, 10, 11, 12, 16, 17, 18, 23, 24,
diodes, 120, 121, 125, 126, 127, 135, 137,
26, 27, 30, 31, 33, 42, 43, 53, 59, 65, 67,
144, 153
73, 74, 75, 158, 161, 173, 184, 185
direct polyesterification reaction, 7
crystallisation, 173, 175, 177
dispersion, 16, 17, 25, 27, 72, 73, 74
crystallites, 13, 16, 17, 23
dissipation factor, 116, 117
crystallization, 4, 5, 11, 12, 14, 15, 18, 19,
distillation, 45, 54
20, 22, 23, 24, 25, 26, 41, 42, 58, 61, 64,
distortion issues, 116
65, 67, 69, 73, 75, 85, 161, 175, 177,
distribution, 17, 18, 27, 40, 47, 51, 52, 75,
182, 185
183
crystallization kinetics, 5
distribution function, 27
crystals, 14, 15, 16, 21, 22, 32, 48, 161

190 Index
DOI, 147, 148 engineering, 3, 57, 62, 64, 68, 81, 83, 140,
doping, 125, 151 143, 146, 149, 153, 156, 182, 185
drawing, 29, 41, 42, 68, 160 entanglement network, 32
drink bottles, 49, 52, 81, 183 entropy, 47
drug delivery systems, 62 environment, 5, 35, 54, 56, 133
drying, 17, 32, 35, 44, 45, 163, 164, 168 environmental awareness, 162
DSC, 12, 13, 14, 15, 17, 20, 21, 35, 37, 50, environmental conditions, 29, 31
51, 67, 73, 159, 174, 176 environments, 30
DSM, 157 enzyme, 55, 56, 57, 62
ductility, 158 epoxy resins, 49, 82, 84
dyeing, 56, 77 equilibrium, 7, 15, 22, 34, 47, 49, 51, 62
dynamic mechanical analysis, 70 equipment, 69, 156, 160
dynamic mechanical properties, 16 EST, 97
dynamic viscosity, 178 ester, 2, 6, 9, 29, 34, 35, 49, 57, 58, 59, 60,
61, 62, 64, 68, 79, 165
ester bonds, 79
E
ETA, 177
etching, 111, 112, 115, 120, 134, 135
Egypt, 93
ethanol, 37, 48
elastic behavior, 57
ethylene, vii, 2, 3, 6, 9, 22, 36, 43, 46, 49,
elastomer, 57, 73, 147
50, 51, 54, 67, 69, 83, 97, 157, 159, 182,
elastomers, viii, 2, 57, 58, 59, 60, 63, 64, 65,
183, 184, 185
84, 96, 182
ethylene glycol, vii, 2, 3, 6, 9, 46, 49, 51,
electric field, 116, 117
54, 157
electrical conductivity, 27
ethylene oxide, 50, 83
electrical properties, 3, 28, 73, 106, 128
extrusion, 4, 18, 25, 30, 42, 43, 44, 58, 61,
electrocardiogram, 146
68, 76, 82, 160, 165, 171, 173, 184
electrodes, 146
electromagnetic, 104, 105, 117
electromagnetic waves, 104 F
electron, 14, 58, 59, 77, 78, 132
electron microscopy, 58, 59, 132 fabrication, 11, 12, 106, 107, 109, 110, 111,
electrospinning, 83 115, 116, 118, 120, 123, 124, 125, 127,
elongation, 18, 19, 41, 65, 73, 80, 172 129, 130, 131, 135, 143, 150
encapsulation, 133 fibers, 2, 3, 4, 5, 11, 12, 13, 18, 30, 40, 41,
endothelial cells, 83 59, 65, 66, 76, 77, 79, 80, 81, 83, 84,
endothermic, 20, 161, 176 158, 160, 172, 182
endotherms, 13, 14 film thickness, 29
energy, 14, 35, 38, 39, 48, 52, 56, 57, 71, films, vii, ix, 2, 4, 11, 12, 16, 25, 26, 27, 30,
77, 78, 104, 108, 114, 115, 117, 127, 36, 42, 43, 44, 53, 56, 59, 75, 77, 78, 79,
138, 149, 167 80, 81, 82, 84, 104, 109, 118, 119, 120,

Index 191
122, 126, 127, 128, 129, 130, 132, 138, glass transition, 10, 11, 15, 16, 18, 21, 31,
150 61, 62, 65, 66, 68, 70, 107, 129, 159,
filtration, 55 173, 175
flame, 71, 72, 85 glass transition temperature, 11, 61, 62, 65,
flatness, 116 66, 68, 70, 107, 129, 159, 173, 175
flexibility, 58, 61, 78, 107, 108, 110, 129, glassy polymers, 23, 43
130 glow discharge, 78
flexible electronics, vii, viii, 103, 105, 107, glycol, vii, 2, 3, 6, 9, 36, 46, 49, 50, 52, 54,
108, 110, 114, 118, 119, 120, 122, 128, 157, 166
129, 130, 132, 133, 134, 135, 137, 138, glycolysis, 45, 48, 49, 50, 51
139, 149 GNP, 25
flexural rigidity, 67, 108 GPC, 48, 159
flow curves, 178 grades, 4, 10, 39, 65, 66, 68, 69, 84
food, 4, 5, 21, 22, 37, 42, 57, 72, 81, 82, 84, Grafting from approaches, 80
85, 160, 164 granules, 38, 165
food packaging, 72, 81, 85, 160 graph, 127
food products, 164 graphite, 25
force, 22, 24, 58, 114, 174, 180 growth, 5, 58, 60, 75, 81, 84, 136
formation, 19, 21, 30, 34, 35, 36, 40, 41, 46, growth mechanism, 136
49, 56, 58, 63, 65, 67, 79, 124, 165, 168,
183
H
fouling, 77
fracture toughness, 19
hard segments, 57, 58
free energy, 47, 78
hardness, 53
free volume, 21, 22, 23, 24
HDPE, 68, 91, 172, 184
freedom, 17, 68
health, 57, 164, 167
FTIR, 30, 50, 74, 75
health risks, 167
fuel cell, 75
heart valves, 82
functionalization, 73, 74, 77
heat capacity, 15, 20, 21
fusion, 13, 28, 174, 176, 185
heat transfer, 40
heating rate, 14, 38
G helium, 22
heterogeneity, 165
gallium, 135 high strength, 66, 71, 73, 82
gasification, 46 humidity, 4, 24, 29, 30, 31
gel, 48, 83, 140 hydrazine, 53, 79
gel permeation chromatography, 48 hydrocarbons, 29
genome, 83 hydrogen chloride, 163
geometry, 76, 174 hydrogenation, 46
germanium, 7, 126, 132, 135, 144, 150, 153 hydrolysis, 3, 29, 30, 31, 32, 45, 47, 49, 54,
glass fibers, 65, 66 55, 56, 163, 167, 183

192 Index
hydrolytic stability, 30, 32 isolation, 127

hydrophilicity, 30, 59, 76, 77, 78, 79, 80 isophthalic acid, 158
hydroxide, 30, 50, 54 isothermal crystallization, 14, 15, 20
hydroxyl, 10, 25, 29, 34, 36, 49, 60, 61, 64, issues, 116, 128
79, 166, 168, 169, 170
hydroxyl groups, 34, 49, 60
K
hyperbranched polyesters, 84
hypothesis, 14
kinetic model, 48, 50
Hytrel®, 59
kinetic studies, 32, 33
kinetics, 5, 15, 35, 37, 47, 50, 52, 55, 177
I Kissinger method, 37
KOH, 54, 111, 112
image, 59, 108, 111, 117, 122, 125, 126,
127, 128
L
immobilization, 77, 78, 79
impact strength, vii, 2, 18, 58, 65, 67, 68,
lactic acid, 37
69, 70
lakes, 53
improvements, 25, 46, 74, 123
lamella, 13
impurities, 18, 44
lamellar or pseudo-lamellar microstructure,
in situ polymerization, 26, 72, 73
58
incompatibility, 57, 69
landfills, 45
independence, 180
lasers, 144, 151
independent variable, 14
lattices, 111
inductor, 127, 129
layered silicates, 71
industrial chemicals, 165
leaching, 181
industry, 3, 9, 46, 77, 81, 110, 160, 162,
lead, 12, 47, 49, 57, 62, 70, 75, 79, 127, 168
171, 180
lending, 24, 63, 64
infrared spectroscopy, 24, 30, 74
lifetime, 24, 31, 45
infrastructure, 109
light, 12, 82, 107, 133, 144, 149, 151
injection molding, 4, 11, 32, 38, 66, 69
light emitting diode, 144
institutions, 149
light scattering, 12
integrated circuits, 109
light transmission, 82
integration, 149
linear macromolecule, 9
interface, 63, 64, 71, 114, 115, 151
linear polymers, 58
interfacial adhesion, 64, 70
liquid chromatography, 37
intrinsic viscosity, 18, 32, 157, 158, 168,
liquid crystalline sequences, 84
171, 173
lithography, 115, 116, 120, 123, 127, 128
inventors, 5
lossless (reactive) component, 117
ion implantation, 124, 125
low temperatures, 51, 58, 64, 82
ions, 71, 77, 78
lower prices, 4
irradiation, 31, 33, 77
Luo, 96, 144, 145, 151

Index 193
melting, 3, 4, 6, 10, 13, 14, 15, 18, 21, 25,

M 35, 37, 42, 50, 58, 61, 68, 115, 161, 168,
173, 176, 181, 182
machinery, 56
melting temperature, 3, 4, 6, 10, 15, 25, 58,
macromolecular chains, 29, 31, 57
61, 68, 161, 168, 173, 176
macromolecules, 9, 14, 79, 182
melting temperatures, 3, 25, 68, 176
magnesium, 4, 7
mesenchymal stem cells, 84
magnetic resonance spectroscopy, 25
metal-oxide-semiconductor, 150
magnitude, 15, 23, 26, 110, 129
metals, 4, 45, 127, 128
majority, 63, 109, 117, 168
methanol, 6, 10, 46, 48, 52, 167
MALDI-TOF MS, 36
Methanolysis, 46, 47
management, 43, 77, 162, 167
MFI, 172
manganese, 7, 45, 49
microcrystalline, 18
manipulation, 22, 120
microscope, 126, 127
manufacturing, 6, 43, 44, 61, 120, 133, 136,
microscopy, 24, 58
160
microstructure, 18, 19, 27, 29, 30, 57, 58,
mass, 7, 31, 36, 38, 40, 78, 168
60, 61, 147
mass spectrometry, 36
migration, 37, 76, 163
material handling, 160
mineral water, 156
materials, viii, 2, 4, 18, 23, 32, 46, 56, 57,
Ministry of Education, 85
58, 62, 63, 68, 69, 71, 75, 77, 80, 83, 84,
mixing, 7, 25, 51, 67, 70, 74, 76, 171
85, 105, 107, 108, 109, 110, 120, 125,
models, 27, 32
127, 130, 136, 138, 144, 146, 149, 156,
modules, 135
165, 171, 172, 174, 176, 177, 178, 182
modulus, 13, 16, 18, 27, 28, 58, 61, 66, 67,
matrix, 21, 24, 27, 36, 58, 64, 70, 72, 73, 74,
68, 69, 71, 72, 73, 74, 85, 107, 108, 132,
76, 133
159, 172, 180
measurements, 17, 19, 23, 27, 31, 36, 40,
moisture, 4, 17, 18, 31, 32, 33, 62, 76, 77,
49, 118, 136, 173, 174, 181
107, 168, 173
mechanical degradation, 18, 36
moisture content, 32, 33, 62, 173
mechanical properties, viii, 4, 16, 18, 19,
mold, 40, 42, 64, 68, 85
21, 23, 32, 40, 43, 53, 58, 62, 64, 65, 66,
molecular mass, 168
68, 69, 70, 73, 74, 75, 76, 79, 83, 84, 85,
molecular orientation, 12
104, 120, 156, 172, 184
molecular oxygen, 36
medical, 42, 82, 130, 141
molecular weight, viii, ix, 2, 6, 9, 10, 12, 14,
melt, 3, 6, 7, 10, 11, 13, 15, 16, 17, 18, 21,
17, 18, 27, 32, 34, 40, 42, 44, 47, 48, 51,
24, 25, 27, 29, 30, 34, 35, 40, 41, 42, 43,
52, 58, 60, 63, 67, 79, 82, 84, 156, 158,
45, 60, 63, 64, 65, 67, 68, 70, 72, 73, 74,
160, 172, 173, 177, 184
75, 120, 161, 163, 167, 169, 170, 172,
molecular weight distribution, 17, 47, 53
179, 181, 182
molecules, 22, 30, 35, 59, 65, 73, 74, 77, 78,
melt intercalation method, 72
79, 104, 160
monolayer, 152, 153

194 Index
monomers, 3, 7, 36, 45, 46, 47, 48, 54, 56,

78, 84, 165
O
montmorillonite (MMT), 26, 71, 72
oil, 118, 156
morphology, 14, 22, 25, 30, 58, 59, 63, 64,
oligomers, 6, 8, 9, 34, 36, 37, 45, 46, 48, 49,
70, 75, 181
50, 165, 168
motivation, 68, 70
operations, 13, 38, 43, 62, 156
multiblock copolymers, 58
optical fiber, 145
multi-walled carbon nanotubes (MWCNTs),
optical properties, 82
73, 74, 75
optoelectronics, 141, 144, 149
Mylar, 4, 5, 82, 115, 157
organ, 71, 72, 85
organic compounds, 107, 120
N organoclays, viii, 2, 26, 71, 72, 85
oscillation, 117, 123, 130
nanoclays, 71 oxidation, 31, 36, 47, 111, 112, 115
nanocomposites, viii, 2, 25, 26, 27, 51, 63, oxygen, 22, 23, 24, 25, 26, 30, 34, 36, 45,
71, 72, 73, 74, 75, 98 61, 72, 78, 82, 85, 104
nanofabrication, 138 oxygen plasma, 78
nanofibers, 85 ozone, 104
nanoimprint, 124
nanolayers, 71
nanomaterials, 85, 135
P
nanometers, 59, 73, 112, 123
parallel, 66, 106, 129, 174
nanoparticles, viii, 2, 75, 85
PDMS stamp, 114, 121
nanophases, 16, 21
PEO, 50, 59, 60, 61, 62, 74, 78, 83
nanophotonics, 149
peptides, 83
nanotube, 140
percolation, 28, 75
nanowires, 136
periodicity, 111
Netherlands, 62, 63
permeability, 21, 22, 23, 24, 25, 26, 62, 72,
neutral, 30, 54
85
NH2, 80
permeation, 4, 25, 48, 61, 62, 82
nitrobenzene, 29
PES, 106, 107, 130
nitrogen, 22, 34, 35, 36, 38, 104, 173
PET blends, 2, 25, 64, 66, 69, 176, 177, 181
NMR, 25, 36
PET Fibers, 90
nontoxicity, 78
PET nanocomposites, viii, 2, 26, 71, 73, 74,
North America, 80
75
nuclear magnetic resonance, 25, 75
PET Waste, 43
nucleating agent, 4, 67, 73, 161
PET/ABS Blends, 70
nucleation, 42, 73, 75, 177
PET/organ oclay nanocomposites, 71, 72
PET/PBT Blends, 65
PET/PC Blends, 68
PET/Polyamide Blends, 66

Index 195
PET/PP Blends, 69 110, 115, 116, 117, 118, 119, 120, 121,
petroleum, 2, 45, 156 122, 125, 126, 127, 128, 129, 130, 155,
PETW, 37, 43, 44, 45, 47, 49, 50, 51, 53, 54 156, 157, 158, 159, 160, 161, 162, 163,
photodegradation, 46 164, 165, 166, 167, 168, 169, 170, 171,
photodetector, 144, 151, 153 172, 173, 174, 175, 176, 177, 178, 179,
photodetectors, 132, 144 180, 181, 182, 183, 184, 185
photolithography, 115, 120 poly(propylene) (PP), 64, 69, 83, 91, 97,
photonics, 144, 145, 149 183
photons, 77 poly(tetramethylene oxide) (PTMO), 59, 60
physical and mechanical properties, 53, 58 poly(vinyl chloride), 18, 168
physical crosslinks, 57 poly(ε-caprolactone) (PCL), 61, 81
physical properties, 25, 29, 44, 50, 63, 72, PolyActive®, 62
107 polyamide (PA), 3, 24, 60, 64, 66, 68, 111,
physical treatments, 77 171, 184
physicochemical properties, vii, 1, 2 polyamide fiber, 3
physics, 149 polyamides, 4, 17, 24, 66
Plasma treatments, 77 polybutadiene, 70
plastic deformation, 18 polycarbonate, 64, 68
plastic products, 44 polycarbonate (PC), 4, 64, 68, 70, 91, 106,
plasticization, 31 107, 130
plasticizer, 40, 53, 56 polycondensation, viii, 2, 3, 6, 8, 9, 10, 12,
plastics, 3, 37, 44, 62, 107, 128, 167 60, 158, 165, 170, 183
platelets, 23, 24 polycondensation process, viii, 2, 158
PMDA, 170 polydimethylsiloxanes, 60
PMMA, 91 polydispersity, 31, 157
point defects, 17 polyesters, ix, 3, 6, 8, 10, 29, 31, 49, 60, 64,
Poisson ratio, 74 84, 155, 182, 184
polar, 56, 69, 78 polyether, 58, 60, 61
poly(butylene terephthalate) (PBT), vii, 1, 3, polyethylene terephthalate, ix, 155, 181,
4, 5, 17, 36, 58, 59, 60, 62, 64, 65, 66, 182, 183
84, 96 polyhydroxyether, 67
poly(ester-ether)s (TPEEs), 57, 58, 59, 60, polyimide, 107, 108, 133, 152
61, 62, 64 polymer, vii, ix, 1, 4, 5, 7, 9, 11, 12, 13, 21,
poly(ethylene terephthalate) (PET), vii, viii, 22, 25, 26, 29, 30, 31, 33, 34, 36, 38, 39,
ix, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 40, 42, 43, 44, 45, 47, 48, 49, 56, 57, 60,
14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 62, 63, 65, 68, 69, 71, 72, 73, 75, 77, 80,
25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 83, 84, 85, 98, 136, 155, 158, 164, 165,
36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 171, 172, 174, 176, 178, 181, 182, 183,
47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 185
58, 59, 60, 61, 62, 63, 64, 65, 66, 68, 69, polymer blends, 171, 176, 178, 181, 185
70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, polymer chain, 4, 11, 12, 31, 45, 48, 57, 77,
81, 82, 84, 90, 91, 103, 106, 107, 109, 165

196 Index
polymer composites, 75
polymer films, 36
R
polymer matrix, 21, 72, 73
radar, 104
polymer media, 30
radiation, 77, 105
polymer nanocomposites, 73, 98
radical polymerization, 80
polymer structure, 29
radicals, 36, 77, 78
polymeric chains, 53
radio, viii, 69, 103, 104, 153
polymerization, viii, 2, 6, 7, 10, 12, 17, 25,
rate of change, 34
26, 40, 42, 72, 73, 77, 78, 80, 158, 159,
raw materials, 46, 82, 84, 165
161, 181
reactant, 8, 9, 47
polymers, viii, 2, 10, 15, 16, 18, 21, 23, 24,
reaction mechanism, 45
26, 27, 36, 40, 43, 49, 58, 63, 64, 71, 73,
reaction medium, 7
75, 76, 82, 84, 100, 131, 156, 159, 172,
reaction rate, 8, 33, 50
173, 174, 175, 177, 178, 180, 181
reaction temperature, 7, 51, 55, 169
polyolefins, 43
reaction time, 7, 46, 47, 50, 55, 79
polypropylene, 83
reactions, 6, 9, 18, 29, 34, 36, 44, 47, 53, 54,
polyurethanes, 49, 53, 82, 84, 98
56, 64, 69, 73, 75, 79, 120, 157, 159,
polyvinylchloride, 182
163, 167, 168, 169, 170
population, 14, 47
reagents, 165
potassium, 52, 54
reality, 6
Power factor, 28
recovery, 47, 57, 58, 80, 167
preparation, iv, viii, 2, 17, 64, 72, 80, 82,
recrystallization, 16, 21
84, 116, 130, 178
recycling, v, vii, viii, ix, 2, 5, 18, 43, 44, 45,
principles, 46, 153, 165
46, 49, 51, 54, 55, 57, 70, 84, 91, 92,
processability, vii, 1, 64, 65, 70, 84, 85
155, 156, 162, 163, 164, 165, 166, 167,
Processing, viii, 2, 38, 133, 173, 182, 184
168, 169, 180, 181, 182, 183
proliferation, 84
reform, 39
propagation, 114
regenerate, 45
propylene, 50, 64, 69, 83, 91, 97, 183
regeneration, 83
protection, 53, 112
reinforcement, 71, 72, 81, 85
purification, 9, 51, 54, 74
reinforcements, 65
PVC, 18, 44, 53, 91, 162, 163, 168, 172,
relaxation, 12, 19, 23, 26, 27
184
relaxation times, 12, 27
PVP, 38
reliability, 106
pyrolysis, 9, 45
renewable energy, 138
reprocessing, 18, 44, 84, 165, 168
Q requirements, viii, 12, 22, 104, 162
researchers, 46, 110, 114, 161, 162, 170,
quantitative estimation, 34 171
quaternary ammonium, 53, 72 residue, 6, 45, 53
resins, 32, 49, 81, 82, 84

Index 197
resistance, vii, 2, 3, 4, 5, 29, 43, 53, 62, 64, signals, 15, 120, 122, 125, 127
66, 67, 68, 69, 70, 72, 81, 82, 84, 85, signal-to-noise ratio, 105
118, 123, 125, 129 silicon, 108, 111, 122, 130, 132, 133, 134,
resistive (lossy) component, 117 136, 137, 139, 141, 144, 145, 152, 153
resolution, 15, 115 simulation, 13, 119
resources, 2, 156 single-walled carbon nanotubes (SWCNTs),
response, 105, 110, 116, 133, 144 73, 74
RF applications, vii, ix, 104, 105 SiO2, 112, 113, 114
RF loss, 106, 128 small-angle X-ray scattering (SAXS), 19, 75
rheological behavior, ix, 25, 156 smooth muscle, 83
rheology, 45, 184, 185 smooth muscle cells, 83
room temperature, 15, 19, 52, 53, 58, 62, society, 162
70, 108, 160 sodium, 24, 49, 50, 52, 74
roughness, 43, 78, 112 sodium dodecyl sulfate, 74
rubber, 40, 121 sodium hydroxide, 50
rubbery state, 11 soft segments, 57, 58, 59, 62
SOI, 112, 113, 114, 125, 130
solar cells, viii, 103, 135, 139, 149
S
solid phase, 17
solid state, 10, 60, 64, 72, 158, 183
sacrificial layer, 113, 114
Solid state post-polycondensation, 10
scanning calorimetry, 12, 16, 21
solid waste, 165
scattering, 12, 19, 75, 118
solubility, 3, 7, 22, 23, 24, 48, 62
scavengers, 25
solution, 37, 40, 54, 55, 73, 111, 112, 113,
science, 71, 149, 182
114, 131, 171, 173
SCP, 97
solvent casting, 72
segregation, 44
solvents, 4, 45, 107
selectivity, 51, 112
species, 35, 36, 75, 77
self-assembly, 138, 150
specific heat, 20
semiconductor, 28, 108, 110, 120, 122, 123,
specific surface, 28, 77
126, 127, 130, 131, 134, 135, 136, 144,
specifications, 106
149, 150
spectroscopy, 24, 25, 26, 30, 74
semicrystalline polymer, 11, 14, 30, 175
spherulites, 14
sensitivity, 170
stability, vii, 2, 4, 5, 7, 16, 21, 25, 30, 32,
sensors, viii, 103, 112, 130, 131, 164
36, 37, 38, 53, 58, 64, 68, 84, 129, 168,
shape, 2, 18, 30, 39, 58, 108, 115, 116, 130
170, 171, 183
shear, 174, 177, 178, 179
stabilization, 64, 70, 168, 183
shear rates, 174, 177
stabilizers, 168
shock, 11, 62
state, vii, viii, ix, 2, 10, 11, 18, 23, 34, 40,
showing, 76, 119
58, 60, 64, 72, 114, 117, 156, 158, 177,
SIC, 12
179, 181, 183, 185
side chain, 27, 84
steel, 53

198 Index
stress, 12, 41, 71, 74, 174, 178 47, 50, 51, 52, 53, 54, 55, 58, 60, 61, 62,
stretching, 11, 22, 38, 39, 160 65, 66, 67, 68, 70, 72, 73, 79, 107, 108,
structural changes, 182 116, 125, 129, 130, 131, 157, 159, 160,
structural characteristics, 184 161, 162, 168, 169, 173, 174, 175, 177,
structure, 5, 13, 14, 15, 18, 19, 21, 22, 29, 178
30, 37, 41, 44, 55, 58, 68, 72, 75, 76, temperature dependence, 13, 27
117, 118, 123, 124, 127, 131, 159, 170, temperature-modulated calorimetry
176 (TMDSC), 15, 21
styrene, 64, 65, 69, 70, 80 tensile strength, 18, 29, 68, 72, 73, 74, 79
styrene copolymers, 65 tension, 63, 76, 160
substrate, vii, viii, 56, 104, 105, 107, 109, terephthalic acid, vii, 2, 3, 6, 7, 34, 54, 55,
110, 111, 112, 113, 114, 115, 116, 117, 56, 60, 157
118, 120, 121, 122, 123, 125, 126, 127, Terylene, 3, 5, 81
128, 130, 133, 134, 135, 136, 152, 153 test procedure, 183
Sun, 132, 134, 135, 144, 145 tetrachloroethane, 173
surface area, 10, 28, 71, 75 textile industry, 3, 81
surface energy, 13, 71, 77 textiles, 3, 30, 72, 85, 131
surface modification, viii, 2, 72, 74, 76, 78, TGA, 37, 38, 51
79, 80, 83 thermal analysis, 12, 15, 19, 161, 173
surface properties, viii, 2, 77 thermal and rheological, ix, 156
surface tension, 75 thermal behavior, 181, 184
surface wettability, viii, 2, 77 thermal decomposition, 38
susceptibility, 62 thermal degradation, 7, 10, 34, 36, 38, 156,
sustainable development, 46, 165 168
synthesis, vii, ix, 1, 2, 3, 6, 7, 8, 46, 49, 53, thermal energy, 167
59, 60, 62, 84, 156, 159, 181, 183 thermal oxidation, 112
synthesized copolymers, 25 thermal oxidative degradation, 37
synthetic fiber, 5 thermal properties, viii, 16, 18, 21, 37, 61,
69, 104
thermal stability, vii, 2, 7, 16, 21, 38, 84,
T
129, 168, 170
thermal treatment, 17, 175
target, 67, 111, 113, 114
thermodynamics, 181
techniques, 14, 17, 25, 41, 46, 57, 73, 77,
thermograms, 12, 173, 175
105, 120, 123, 128, 171
thermogravimetric analysis, 38
technology, 3, 18, 41, 56, 63, 128, 129, 133,
thermoplastic, vii, 1, 2, 3, 57, 58, 59, 64, 68,
136, 153, 162, 181
70, 84, 136, 182
telecommunications, 69
Thermoplastic copolyester elastomers, 57,
TEM, 58, 59
63
temperature, 3, 4, 6, 7, 10, 11, 13, 14, 15,
thermoplastic polyester, vii, 1, 2, 3, 64, 182
16, 17, 19, 20, 21, 22, 23, 26, 27, 28, 29,
thermoplastics, 58, 82
30, 31, 32, 33, 34, 35, 37, 38, 39, 40, 41,
thin films, 26, 118

Index 199
tissue engineering, 62, 83 vapor, 77, 104, 168

tissue engineering scaffolds, 62 variables, 14, 41
titanate, 7, 131 variations, 16, 122
toxic substances, 57, 167 velocity, 114, 115, 130
TPA, 3, 7, 8, 9, 25, 37, 46, 47, 52, 54, 55, vibration, 104, 112
56, 157, 159 vinyl chloride, 18, 168
trade, 3, 4, 59, 62, 63, 116, 157 viscoelastic properties, 17
transesterification, 3, 6, 8, 37, 49, 55, 60, viscoelastic., 114
64, 65, 66 viscosity, 7, 18, 29, 32, 35, 40, 42, 53, 64,
transformation, 45, 165, 172 66, 68, 75, 157, 158, 160, 162, 168, 171,
transformation processes, 172 173, 174, 178, 179
transistor, 122, 123, 136
transition temperature, 11, 15, 19, 22, 23,
W
28, 61, 62, 65, 66, 68, 70, 107, 129, 159,
160, 173, 175
waste, 5, 43, 44, 45, 46, 47, 49, 52, 53, 54,
transmission, viii, 82, 103, 104, 105, 117,
55, 84, 156, 162, 164, 165, 167, 172
118, 119, 130, 132
waste disposal, 162
Transmission electron microscopy (TEM),
waste management, 167
58, 59, 132
water, 7, 30, 31, 32, 33, 37, 38, 44, 47, 51,
transmission line method (TLM), 118, 119
54, 55, 81, 82, 104, 151, 156, 160, 163,
transparency, 5, 21, 82, 107
164, 165, 167, 168, 173, 181
transport, 23, 24, 38, 117, 131, 181
water vapor, 104, 168
treatment, viii, 2, 11, 20, 30, 49, 74, 77, 78,
wavelengths, 104, 118
79, 156, 162, 175
WAXS, 12, 24, 67, 75
two-phase microstructure, 57
weight loss, 35, 78, 80
two-stage polycondensation, viii, 2, 60
weight ratio, 37, 47
two-step melt polymerization reaction, 6
wettability, viii, 2, 77
Wisconsin, 103, 137, 138, 140, 141, 143,
U 144, 145, 146, 148, 149, 150
worldwide, 5, 44, 48, 81
ultrasound, 46
uniform, 25, 27, 39, 41
X
UV irradiation, 31, 77
X-axis, 127
V XPS, 56, 78
X-ray diffraction, 19, 33
vacuum, 6, 10, 11, 15, 36, 42, 45, 116, 156, X-ray films, 81
164, 168, 169, 173
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Progress in polyethylene terephtalate recycling

Chapter · October 2017

Adel Elamri Khmais Zdiri

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Polyethylene terephthalate (PET) is an aliphatic-aromatic and

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polycondensation process. High molecular weight of PET can be achieved

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and the challenges and potentials of RF applications using flexible

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Marija V. Pergal1,* and Milica Balaban2

This chapter summarizes the synthesis and physicochemical

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chemical resistance, high tensile impact strength, high thermal stability

Keywords: poly(ethylene terephthalate), thermoplastic polyester, two-

This chapter summarizes the synthesis, physicochemical properties and

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transesterification compared to direct polycondensation from acid, and the

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to a wide range of trademarked products such as a strong polyester film,

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Dacron (Invista), Hostaphan Films (Mitsubishi), Impet (Ticona), Melinex

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2.1. Conventional Two-Stage Polycondensation Reaction

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further react by polycondensation between the two hydroxyethyl end

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to estimate the conversion of the reaction. The addition of a catalyst is not

One of the main advantages in production from DMT, compared with

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consequence, it has gained a lot of importance as a monomer in polyester

Figure 2. Synthesis of PET from TPA as the starting reactant.

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3. SOLID STATE POLYMERIZATION

Solid state post-polycondensation is widely used in order to increase

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of polymer chains, the polymer chips or pellets are heated in a vacuum or

4. PHYSICAL PROPERTIES OF PET

4.1. Thermal and Mechanical Properties of PET

ISBN: H%RRN