1 Engineering Thermoplastics—Materials,
Properties, Trends
1.1 Introduction
Plastics are one of the indispensable materials
of modern life that has changed the way we live.
Throughout history we have witnessed trends where
one material has elevated to replace another for per-
formance, or economic reasons. Advancement in
materials has been coeval with the spread of civiliza-
tion. Early man used available metals in their natu-
rally occurring state. The progress of civilization was
literally determined by man’s ability to discover new
materials, allowing mankind to induce the proper-
ties necessary for increasingly sophisticated tools
and implements of destruction. Indeed, societies that
learned to exploit new materials developed distinct
advantages over their neighbors. This was broadly
exemplified in terms of key materials where mankind
advanced from the Stone Age, to the Bronze Age, the
Iron Age, and the age of steel.
The age of synthetic plastics began in 1909 with
the discovery by Leo Baekeland of synthetic phenol-
formaldehyde resin. In general, plastic materials are
arbitrarily placed into three categories commodity
thermoplastic, engineering thermoplastics (ETP),
and advanced engineering thermoplastics (AETP),
which are also referred to as specialty, advanced, or
ultrapolymers. The commodity plastics constitute
the highest volume of usage, their consumption ex-
ceeding 1 million tons per annum on global scale.
ETP comprise a special, high-performance segment
of synthetic plastic materials that offer premium
properties. When properly formulated, ETP may
be shaped into mechanically functional, semipreci-
sion parts or structural components. The term “me-
chanically functional” implies that the parts will
continue to function even if they are subjected to
factors such as mechanical stress, impact, flexure,
vibration, sliding friction, temperature extremes,
and hostile environments [1]. The ETP age began
75 years ago.
Applied Plastics Engineering Handbook. http://dx.doi.org/10.1016/B978-0-323-39040-8.00001-8
Copyright © 2017 Elsevier Inc. All rights reserved.
Edward N. Peters
SABIC, Selkirk, NY, United States
AETP are distinguished by their unmatched ther-
mal, mechanical, and chemical properties and are at
the top position in the plastics performance pyramid.
These materials have also been among the fastest
growing segment of plastics giving way to new ap-
plications driven by innovation.
Innovation in new plastic materials exploded in
the 1950s and 1960s. Continuing technological ad-
vances have resulted in an even greater impact on our
lives and ETP have further penetrated markets domi-
nated by metals.
As substitutes for metal in the construction of
mechanical apparatus, ETP offer advantages such
as corrosion resistance, transparency, lightness, self-
lubrication, and economy in fabrication and decorat-
ing. Replacement of metals by plastics is favored as
the physical properties and operating temperature
ranges of plastics improve and the cost of metals and
their fabrication increases [2]. Plastic applications
in transportation, a major growth opportunity, have
been greatly accelerated by the current awareness
of the interplay of vehicle weight and fuel require-
ments. The ability to replace metals in many areas
has resulted in tremendous growth in ETP.
A significant driving force behind the growth in ETP
is the continuing expansion of electrical/electronic mar-
kets, which demands smaller, lighter components that
operate at higher speeds. In addition, the same require-
ments are driving the automotive market segment.
Original Equipment Manufacturers strive toward low-
er production cost, style flexibility, lower maintenance
and more efficient, lower polluting vehicles that utilize
better performing materials under the hood and in ex-
terior components.
The global consumption of ETP in 2012 is esti-
mated at 19.6 million metric tons. ETP are the fastest
growing segment of the plastics industry. It is esti-
mated that the use of ETP will reach 29.1 million
metric tons by 2020. This chapter focuses on the de-
velopment of ETP during the past 75 years.
3
4 Applied Plastics Engineering Handbook
1.2 Aliphatic Polyamides
Polyamides, commonly called nylons, were the
first commercial thermoplastic engineering poly-
mers. In 1928 Wallace Carothers at DuPont began
polymer experiments on polyamide 66. Nylon 66,
PA66, is prepared from condensation polymeriza-
tion of hexamethylene diamine (HMDA) and adipic
acid. The structure is shown in Fig. 1.1. PA66 made
its commercial debut as a fiber in 1938 with its first
use in bristles for toothbrushes and later in women’s
hosiery. PA66 was the exemplar for the whole family
of polyamides. The first use of nylon as a molding
compound was in 1941. In 1953 the 4536 metric tons
of PA66 molding compound represented the entire
annual volume of ETP [3,4].
Polyamides was a new concept in plastics for
several reasons. It was semicrystalline polymer that
underwent a sharp transition from solid to melt. In
­addition, it had a relatively high service temperature.
The combination of toughness, rigidity, and “lubrica-
tion-free” performance made PA66 peculiarly suited
for mechanical bearing and gear applications. Poly-
amides acquired the reputation of a quality material
by showing that a thermoplastic could be tough, as
well as stiff, and perform better than metals in some
cases. This performance gave nylon the label “an
engineering thermoplastic.”
PA66 exhibits a glass transition temperature, Tg, of
78°C and a crystalline melting point, Tm, of 269°C.
The crystallinity and polarity of the molecule permit
dipole association that conveyed to relatively low
molecular weight polymers the properties normally
associated with much higher molecular weight amor-
phous polymers. At its Tm, the polymer collapsed into
a rather low-viscosity fluid in a manner resembling the
melting of paraffin wax. It lacked the typical familiar
broad thermal plastic range that is normally encoun-
tered in going from a glassy solid to a softer solid
to a very viscous taffy stage. This factor led to some
­complications in molding because very close toleranc-
es were required in mold construction, and very precise
temperature and pressure monitoring was necessary to
prevent flash or inadvertent leaking of the mobile melt.
Early molders of nylon were highly skilled—they had
to be because the industry was young.
Nylon based on w-aminocarboxylic acids, although
briefly investigated by Carothers, was commercialized
Figure 1.1 Structure of polyamide 66.
Figure 1.2 Structure of polyamide 6.
first in Germany around 1939 [4]. Of particular inter-
est to the plastic industry is Nylon 6, PA6, based on
caprolactam, which became available in Europe in
1946. Allied Chemical Company initially introduced
PA6 to the United States for fiber purposes in 1954.
Polycaprolactam is semicrystalline and has been suc-
cessfully applied as a molding compound. Its Tm of
228°C is lower than PA66. The structure of PA6 ap-
pears in Fig. 1.2, Nylon 46, PA46, was developed and
commercialized in 1990 by DSM Engineering Plas-
tics to address the need for a polyamide with higher
heat and chemical resistance for use in automotive
and electrical/electronic applications. PA46 is pre-
pared from 1.4-diaminobutane and adipic acid. PA46
has a Tm of 295°C and has higher crystallinity than
PA6 or 6,6 [3].
In general, the key features of polyamides are
fast crystallization, which means fast molding cy-
cling; high degree of solvent/chemical resistance,
toughness, lubricity, fatigue resistance, and excellent
flexural-mechanical properties that varies with de-
gree of plasticization by absorbed water. Deficiencies
include a tendency to creep under applied load and
very high moisture absorption, which will plasticize
the polyamide and lower some properties.
Varying the monomer composition has produced
many different varieties of polyamides. Variations in-
clude PA69, PA610, and PA612 (made from HMDA
and the 9-, 10-, and 12-carbon dicarboxylic acids, re-
spectively); and Nylon 11 and Nylon 12 (via the self-
condensation of 11-aminoundecanoic acid and lauryl
lactam, respectively). These specialty nylons exhibit
lower Tms and lower moisture absorption to one-third
or one-fourth that of PA6 or PA66.
When unsymmetrical monomers are used, the
normal ability of the polymer to crystallize can be
disrupted; amorphous (transparent) nylons can then
be formed. These amorphous nylons are not as tough
as PA6 or 66 but they do offer transparency, good
chemical resistance in some environments, and lower
moisture absorption.
For example, the polyamide prepared from the
condensation of terephthalic acid with a mixture of
2,2,4- and 2,4,4-trimethylhexamethylenediamines
(PA6-3-T) was developed at W.R. Grace and Com-
pany, later produced under license by Dynamit Nobel
AG, and currently available from Evonik Industries
1: Engineering Thermoplastics—Materials, Properties, Trends
under the trade name Trogamid TR. This amorphous
polyamide exhibits a Tg of 148°C, high clarity, stiff-
ness, toughness, resistance to chemicals, and very
good resistance to UV damage. It is used in water
filter housings, flow meters, grease containers, and
spectacles frames.
Another amorphous nylon is based on aliphatic
amines, cycloaliphatic amines, and terephthalic acid.
It is marketed under the Grilamid trade name by
EMS-Chemie. This amorphous nylon exhibits a Tg of
155°C, high transparency, stiffness, and resistance to
chemicals. It is used in viewing glasses, transparent
housings, and high-quality spectacle frames.
1.3 Aromatic Polyamides, Aramids
Nylons prepared from aromatic diamines and aro-
matic dicarboxylic acids can lead to very high-heat
aromatic nylons (aramids). Poly (m-phenyleneisoph-
thalamide), MPIA, is made from the condensation
polymerization of m-phenylenediamine and isoph-
thaloyl chloride and has a Tg of 280°C. Its structure is
shown in Fig. 1.3. W. Sweeny, a scientist at DuPont
was responsible for discoveries leading to the com-
mercialization of MPIA and is available under the
Nomex trade name. MPIA is used in fibers to make
heat-resistant and flame-retardant apparel, electrical
insulation, and composites.
Poly (p-phenyleneterephthalamide), PPTA, was in-
vented by S. Kwolek at DuPont in 1965 (first marketed
in 1971) [5]. It is made from p-phenylenediamine and
terephthaloyl chloride. It exhibits a Tg of 425°C and
Tm of >500°C. It was the first commercialized liquid
crystalline polymer. Fibers were spun from a lyotropic
sulfuric acid solution. Its structure is shown in Fig. 1.4
and is available under the Kevlar trade name. PPTA
is used to make highly oriented crystalline fibers de-
rived from liquid-crystalline technology. PPTA fibers
exhibit a very high modulus and its uses include com-
posites for sporting goods, bullet resistant apparel, au-
tomotive transmission parts, and tires.
Figure 1.3 Structure of MPIA.
Figure 1.4 Structure of PPTA.
5
1.4 SemiAromatic Polyamides
Several semiaromatic polyamides are based on the
reaction of HMDA and terephthalic acid. The structure
of poly (hexamethylene terephthalate), PA6T, appears
in Fig. 1.5. However, pure PA6T exhibits a Tg of 180°C
and a very high Tm of 370°C. The high Tm results in
expensive polymerization processes and difficulty in
molding. Therefore, modified copolymers based on
PA6T have been examined extensively because of use
of inexpensive monomers and enhanced properties over
aliphatic polyamides. For example, terpolymers using
an inexpensive, third monomer such as isophthalic
acid, adipic acid, caprolactam, or HMDA have led to
the commercialization of semiaromatic polyamides
by Amoco, BASF, and DuPont under the trademarks
Amodel R, Ultramid T, and Zytel HTN, respectively.
These terpolymers exhibit Tgs from 100 to 125°C and
Tms from 290 to 320°C and offer enhanced performance
over PA66 or 6—such as, higher stiffness, increased
strength, greater thermal, and dimensional stability.
Polyamide 9T (PA9T) is a semiaromatic polyam-
ide commercialized under the name of Genestar by
Kuraray Co [6]. PA9T uses a long, flexible aliphatic
diamine consisting of nine methylene groups in a se-
quence as part of the polyamide backbone. This melt
processible polyamide exhibits a Tg of 125°C and Tm
of 300°C. The structure of PA9T appears in Fig. 1.6.
Features include low water absorption, high heat
resistance, high chemical resistance, hydrolysis resis-
tance, low friction coefficient, high impact strength
good fuel barrier properties, and dimensional preci-
sion. It offers an alternative to materials such as PA612
and PA12. Its applications range from friction and wear
application, automotive parts to electronic/electrical.
1.5 Polyacetals
After nylon, the next engineering polymers to
be commercially introduced were polyacetals [7,8].
Polyacetals are polymerized from formaldehyde and
Figure 1.5 Structure of polyamide 6T.
Figure 1.6 Structure of polyamide 9T.
6 Applied Plastics Engineering Handbook
are also referred to as polyoxymethylenes (POM).
Staudinger explored the basic polyformaldehyde
structure rather thoroughly in the late 1920s and early
1930s, but he was unable to synthesize sufficiently
high molecular weight polymer with requisite thermal
stability to permit melt processing [9]. Pure formal-
dehyde could be readily polymerized, but the poly-
mer readily unzips (spontaneously depolymerizes).
In 1947, researchers at DuPont began a development
program on the polymerization of formaldehyde
and stabilization of the polymer. Twelve years later,
DuPont brought the unzipping tendency under con-
trol with proprietary stabilization technology and
commercially announced POM under the Delrin trade
name. The key to the stabilization of POM was to cap
the terminal hydroxyl groups that participate in, or
trigger unzipping reactions. Postetherification or es-
terification capped or blocked the hydroxyl groups.
This material has a Tg of –75°C and Tm of 181°C. The
structure of capped POM is depicted in Fig. 1.7.
Celanese joined DuPont in the market with their
proprietary polyacetal polymer under the Celcon
trademark within a year. Celanese managed to obtain
basic patent coverage, despite DuPont’s prior filing.
The Celanese POM was a copolymer that resulted in
stabilization against thermal depolymerization. POM
copolymer has a Tm of 170°C. The structure of POM
copolymer is depicted in Fig. 1.8.
Both Celanese and DuPont aimed their products
directly at metal replacement. Items such as plumbing
hardware, pumps, gears, and bearings were immedi-
ate targets. In many respects, the acetals resemble
nylons. POMs are highly crystalline, rigid, cold-flow
resistant, solvent resistant, fatigue resistant, mechan-
ically tough and strong, and self-lubricating. They
also tend to absorb less water and are not plasticized
by water to the same degree as the polyamides. Rapid
crystallization of acetals from the melt contributes to
fast mold cycles.
Key areas of use for POMs are industrial and me-
chanical products that include molded or machined
rollers, bearing, gear, conveyor chains, and housings.
POMs are widely used in plumbing and irrigation be-
cause they resist scale build up, and have excellent
Figure 1.7 Structure of capped POM.
Figure 1.8 Structure of POM copolymer.
thread strength, creep resistance, and torque retention.
A deficiency of polyacetals is a tendency to thermally
unzip and an essentially unmodifiable flammability.
1.6 Polycarbonates
The aromatic polycarbonates, PC, were the next
engineering polymers to be introduced. In 1953,
D.W. Fox at General Electric Company and H.
Schnell at Bayer AG independently discovered the
same unique super tough, heat-resistant, transpar-
ent, and amorphous polymer [7,10–13]. When the
companies became aware of each other’s activities,
agreements were reached that enabled both parties
to continue independent commercialization activi-
ties without concern for possible subsequent adverse
patent findings. General Electric Company (now
SABIC) introduced their PC into the United States
under the Lexan trademark in 1959 at about the same
time as the polyacetals, and a commercial plant was
brought on stream in 1960.
PCs of numerous bisphenols have been exten-
sively studied. However, most commercial PCs are
derived from bisphenol A (BPA) and is depicted in
Fig. 1.9. Both solution and solvent free, melt-trans-
esterification processes are used to manufacturer
polycarbonates.
In the solvent processes, PC is produced by an
interfacial polymerization process [14]. The BPA
and 1–3 m% monofunctional phenol, which controls
molecular weight, are dissolved or slurried in aque-
ous sodium hydroxide; methylene chloride is added
as a polymer solvent; a tertiary amine is added as a
catalyst, and phosgene gas is dispersed in the rapidly
stirred mixture. Additional caustic solution is added
as needed to maintain basicity. The growing polymer
dissolves in the methylene chloride, and the BPA and
phenolic content of the aqueous phase diminishes.
In the solvent free, melt-transesterification, diphe-
nyl carbonate reacts with BPA to regenerate phenol
for recycle and molten, solvent-free polymer.
BPA based PC is an amorphous polymer with a Tg
of 150°C. It offers outstanding impact strength, glass-
like transparency, heat resistance, excellent electrical
properties, intrinsic flame retardancy, and high dimen-
sional stability up to just below its Tg. This outstanding
Figure 1.9 Structure of polycarbonate.
1: Engineering Thermoplastics—Materials, Properties, Trends
combination of properties and processing versatility
have made PCs the ideal resin for many applications.
In addition, transparency gave polycarbonates another
dimension and has led to applications in safety glaz-
ing, light covers, automotive headlamp lenses, water
bottles, compact discs, and ophthalmic applications.
The PCs, like the nylons and acetals, were directed
toward metal replacement applications. Glass-fiber
filled versions of PCs are available, and this combina-
tion is particularly well suited to compete with metal
parts. As in the case of other amorphous polymers,
glass fibers act as stiffening and strengthening agents
but do not raise operating temperatures significantly. In
semicrystalline polymers, fillers tend to act as a crutch
to bridge the soft, amorphous regions that have Tg-
dependent properties, thereby permitting the plastic to
maintain structural integrity up to its crystalline melting
point. Without filler, crystalline polymers tend to creep
under static load at relatively low temperatures because
their Tg values are generally comparatively low.
PCs are readily modified via copolymerization with
long chain aliphatic dicarboxylic acids to give a resin
with improved flow; other bisphenols or phthalates to
increase Tg and give PCs with higher heat resistance;
and trisphenols to give a branched PC with improved
melt strength for blow molding/extrusion. In addition,
PC is amenable for the development of many different
commercial polyblends [10,15]. Blending PC with
other thermoplastics widens the performance window
and will be discussed later in this chapter.
Unique high heat PC copolymers have been de-
veloped that offers greater thermal resistance than
standard PC. These high Tg PCs have been achieved
through combining BPA monomer with a high-heat
comonomer. The resulting copolymers have a glass
transition temperature of 185°C or higher. These
copolymers form a family of clear, tough, high heat
PCs. In addition, their high flow enables greatly ex-
panded design options for molding thin-wall parts.
These materials are offered under the Lexan XHT
trademark by SABIC [16,17].
Application opportunities include automotive light-
ing reflectors and bezels, industrial lighting, protective
face shields, heat resistant helmets, heat shields elec-
trical components, residential fuses, landscape light-
ing, flashlight lenses, and fluorescent lighting covers.
1.7 Poly (phenylene ether)
In 1956, A. Hay of the General Electric Compa-
ny (now SABIC) discovered a convenient catalytic
oxidative coupling route to high molecular weight
7
Figure 1.10 Structure of poly(2,6-dimethyl-1,4-phen-
ylene ether).
aromatic ethers [18–20]. Polymers were made by
bubbling oxygen through a copper-amine-catalyzed
solution of phenolic monomer at ambient tempera-
tures. A wide variety of phenolic compounds were
explored, but the cleanest reactions resulted from
those that contained small, electron-donor substitu-
ents in the two ortho positions. Hence, research fo-
cused on the use of 2,6-dimethylphenol. In 1964
General Electric Co. introduced the PPE homopoly-
mer, poly(2,6-dimethyl-1,4-phenylene ether), under
the PPO trademark. PPE had excellent hydrolytic
resistance and an extremely high Tg of 215°C. The
structure is shown in Fig. 1.10.
The very high Tg, high melt viscosity, and a pro-
nounced tendency for PPE to oxidize at process-
ing temperatures made it very difficult to process.
However, in 1965 Westlake Plastics Co. started
production of extruded rods, sheets, and tubing of
PPE under the Alphalux trademark. Also in 1965
Richardson Co. marketed a miscible blend of PPE
with crystal polystyrene, PS. In spite of the PPE/PS
miscibility, the single-phase blend was not a com-
mercial success [21].
In mid-1966 GE introduced a family of PPE
blends with high impact polystyrene, HIPS, under
the Noryl trademark. This combination of total com-
patibility with PS and the added toughness from the
polybutadiene in HIPS were the keys to commercial
success. Varying the PPE/HIPS ratio results in a wide
range of high temperature, easy to process, tough, di-
mensionally stable plastics [22].
The first applications were those requiring au-
toclaving (medical equipment) and outstanding
electrical properties at elevated temperatures. As
compounding, stabilization, and processing skills
improved, markets for PPE blends expanded to in-
clude office equipment, electronic components, auto-
motive parts, water distribution systems, and general
metal replacement.
PPE-based resins are relatively resistant to burn-
ing, and judicious compounding can increase their
burn resistance without the use of halogenated flame
retardants. In addition, these blends could be modi-
fied with glass fiber and mineral fillers. Because
of low moisture absorption, dimensional stability,
8 Applied Plastics Engineering Handbook
and ability to be used over a wide temperature
range, PPE-based resins are especially adaptable to
metallization.
After expiration of the original patent on PPE, sev-
eral manufacturers (e.g., BASF, Huls, Borg-Warner,
Asahi, Engineering Plastics Ltd., Mitsubishi) be-
gan sales of their own blends based on PPE or its
copolymers.
PPE is a versatile material and is used in alloys
with PAs to enhance the performance and decrease
the moisture absorbance of the PAs. These alloys are
described in later in this chapter.
1.8 Polysulfones
Polyarylsulfones are a class of high-use tempera-
ture thermoplastics that characteristically exhibit
excellent thermal-oxidative resistance, good solvent
resistance, hydrolytic stability, and creep resistance
[23,24]. Routes to polysulfones were discovered in-
dependently and almost simultaneously in the labo-
ratories of Union Carbide Corporation, ICI, and 3M
Corporation.
In 1965 A.G. Farnham and R.N. Johnson of Union
Carbide (this business was acquired by Amoco
Polymers in 1986 and is currently part of Solvay
Advanced Polymers) announced the preparation
of thermoplastic polysulfones, PSU [25]. The first
commercially available polysulfone was prepared
by the nucleophilic aromatic displacement of the
chlorides on 4,4’-dichlorodiphenyl sulfone, DCDPS,
by the anhydrous di-sodium salt of BPA. The reac-
tion is conducted in a dipolar aprotic solvent, such
as dimethyl sulfoxide. This polysulfone, PSU, was
commercialized in 1966 under the Udel trademark.
This amorphous polymer exhibits a Tg of 186°C. The
structure of PSU is shown in Fig. 1.11.
In 1967 3M introduced polybiphenyldisulfones
under the Astrel 360 trade name. This polymer was
made by the Friedel-Crafts reaction of biphenyl-4,4’-
disulfonyl chloride with diphenyl ether and exhibited
a very high Tg of 277°C [26]. The structure is shown
in Fig. 1.12. The price was very high, it was diffi-
cult to melt process, and had limited availability. This
resin is no longer commercially available.
Figure 1.11 Structure of polysulfone.
Figure 1.12 Structure of polyarylsulfone.
Figure 1.13 Structure of polyethersulfone.
Figure 1.14 Structure of polyphenylsulfone.
In 1972 ICI started market development of poly-
ethersulfone, PES. This amorphous polymer has a Tg
of 225°C. Compared to PSU, it exhibits higher ther-
mal stability, better chemical and solvent resistance,
and improved toughness [27]. The structure appears
in Fig. 1.13.
In 1976 Union Carbide introduced a second-
generation polysulfone resin under the Radel R
polyphenylsulfone, PPSU, trade name. This higher
performing PPSU was prepared from 4,4’-biphe-
nol and DCDPS [28]. PPSU has a Tg of 225°C. Its
structure is shown in Fig. 1.14. The biphenyl moiety
imparts enhanced chemical/solvent resistance, out-
standing toughness, greater resistance to combustion,
and enhanced thermo-oxidative stability.
In general, aromatic polysulfones are somewhat
polar, aromatic ethers that offer outstanding oxida-
tion resistance, hydrolytic stability and very high
thermal endurance in conjunction with a good bal-
ance of mechanical properties which are suitable for
hot water and food handling equipment, range com-
ponents, TV applications, alkaline battery cases, and
film for hot transparencies. The unmodified prod-
ucts are transparent with a slightly yellow tint. Low
flammability and low smoke suit it for aircraft and
transportation applications. In addition, it can with-
stand rigorous handling and repeated steam steriliza-
tion cycles and is used in medical application. Thus,
polyarylsulfones are used in surgical equipment, lab-
oratory equipment, life support parts, and autoclav-
able tray systems. Blow molding polyarylsulfones
produces suction bottles, tissue culture bottles and
surgical hollow shapes.
1: Engineering Thermoplastics—Materials, Properties, Trends
1.9 High-Temperature Sulfone
Polymers (HTS)
There have been several attempts to commercial-
ize high-temperature sulfone polymers, HTS, with
performance greater than PES and PPSU. HTS was
based on the nucleophilic aromatic displacement of
the chlorides on 4,4”-bis (4-chlorophenylsulfonyl)
biphenyl with hydroquinone under basic conditions
in a dipolar aprotic solvent. In the mid-1970s and
again in the mid-1980s, ICI had unsuccessful mar-
keting efforts for polyetherbiphenyldisulfones (Vic-
trex 720P) [29].
In 2004 Solvay Advanced Polymers introduced
these HTS under the Supradel trademark. In 2007
the trademark was changed to EpiSpire. The struc-
ture appears in Fig. 1.15. HTS is a high-temperature
amorphous polymer. The more rigid biphenyldisul-
fone unit results in polymer with a Tg of 265°C, which
is noticeably higher than Tgs other sulfone polymers
[30,31]. The structure of HTS appears in Fig. 1.15.
HTS is transparent and completely amorphous
and can be melt processed by injection molding and
extrusion. HTS exhibits high thermal performance
capabilities, good strength, stiffness, resistance to hy-
drolysis by hot water and steam, excellent resistance
to acids and bases, and inherent flame resistance.
The material’s thermal performance combined with
its good strength and stiffness, dimensional stability,
and creep resistance suggests opportunities in high-
temperature injection molding applications that tra-
ditionally have been limited to filled, semicrystalline
polymers. Applications for HTS include opportuni-
ties in metal and high-performance thermoset resins
replacement in a wide range of engineering applica-
tions, which includes automotive, aerospace, electri-
cal, electronic, and industrial product applications.
1.10 Thermoplastic Polyesters
In the late 1920s W. Carothers and his research
group at DuPont investigated the formation of
polyesters from the condensation polymerization
of aliphatic dicarboxylic acids with diols. These
aliphatic polyesters were found to be inadequate as
Figure 1.15 Structure of high-temperature sulfone
polymer.
9
Figure 1.16 Structure of poly (ethylene terephthalate).
fiber precursors because of their low melting points.
The aliphatic polyesters were bypassed for polyam-
ides with much higher Tms. Semiaromatic thermo-
plastic polyesters had their beginning in 1941 when
J.R. Whinfield and J.T. Dickson at DuPont substitut-
ed terephthalic acid for the previously investigated
aliphatic dibasic acids and discovered high melting
crystalline polymers [7,32,33]. Whinfield and Dick-
son quickly realized that the polymer poly(ethylene
terephthalate), PET, based on ethylene glycol and
terephthalic acid was the best suited for fibers. ICI,
DuPont, and others developed PET into the familiar
polyester fibers and films. PET exhibits a Tg of 70°C
and Tm of 265°C. The structure appears in Fig. 1.16.
In addition, other semiaromatic polyesters includ-
ing poly (butylene terephthalate), PBT, were de-
scribed. PBT prepared by the transesterification re-
action of dimethyl terephthalate and butanediol. PBT
exhibits a Tg of 45°C and a Tm of 225°C. The struc-
ture is shown in Fig. 1.17. Many years later a num-
ber of polyester fiber producers became interested in
PBT because it resembled nylon.
While the fiber producers were busily expanding
their fiber activities, a number of companies were si-
multaneously trying to adapt PET as a molding com-
pound. In 1966, the first injection molding grades of
PET were introduced; however, these early materials
were not very successful. The primary problem was
that PET does not crystallize very rapidly. A molded
object composed of a crystallizable polymer caught
in an amorphous or partially crystallized state would
have limited utility. In service, such a part could
crystallize further, shrink, distort, crack, or fail. The
obvious solution was to use hot molds and hold the
parts in the mold until the crystallization process was
completed. Postannealing also permits continued
crystallization. These approaches, especially with
glass fiber incorporation, led to acceptable parts.
However, the molding cycles were economically
unacceptable. Alternately, some developers tried to
use very low molecular weight PET-glass products
that crystallized more rapidly. However, because of
Figure 1.17 Structure of poly (butylene terephthalate).
10
their low molecular weights, these products lacked
essential properties. A very broad search has been
conducted for such things as nucleating agents and
crystallization accelerators. An improved PET injec-
tion-molding compound was introduced by DuPont
in 1978 under the trade name Rynite. A number of
other companies have followed DuPont into the mar-
ket. The PET-based molding compounds are gaining
acceptance, but actual volume is relatively small.
Other companies look for alternative routes to faster
crystallizing polyesters. Celanese researchers focused
on PBT and found that it met all the requirements for a
molding compound. Compared to PET, PBT had very
fast molding cycles even with a cold to moderately
heated molds. The basic composition of matter patents
had long since expired on PBT when Celanese sam-
pled the market in 1970 with a glass-fiber reinforced
PBT product designated X-917. This PBT molding
compound was subsequently available under the Cel-
anex trade name. Eastman Kodak followed Celanese
early in 1971, and General Electric (now SABIC) fol-
lowed Eastman Kodak later in the same year with a
PBT polyester resin under the Valox trade name. Since
that time a dozen or more additional companies around
the world have entered the business.
Basically, PBT seems to have a unique and favor-
able balance of properties between nylons and POM
resins. It has relatively low moisture absorption, ex-
tremely good self-lubrication, fatigue resistance, sol-
vent resistance, and good maintenance of mechanical
properties at elevated temperatures. When PBT was
reinforced with glass fiber it has excellent mainte-
nance of properties up to its crystal melting point.
Key markets include under-the-hood automotive ap-
plications, which require thermal and solvent resis-
tance, electrical and electronic applications, power
tools, small and large appliance components, and
athletic goods.
Although PET and PBT are widely used, better
thermal and mechanical properties are desired for
some applications. Higher performance in semiaro-
matic polyesters was obtained from polyalkene naph-
thalates. These semicrystalline polyesters are prepared
by the condensation polymerization of naphtha-
lene-2,6-dicarboxylic acid and flexible aliphatic diols.
The naphthalene moiety imparts stiffness to the linear
polymer backbone, leading to improved physical and
mechanical, barrier, chemical resistance properties,
and UV-ray screening performance. Poly(ethylene
naphthalene-2,6-dicarboxylate), PEN, became com-
mercially available from Teijin Ltd. in the early 1970s.
PEN has a Tg and Tm of 125 and 268°C, respectively
[34]. Its structure appears in Fig. 1.18.
Applied Plastics Engineering Handbook
Figure 1.18 Structure of poly(ethylene naphtha-
lene-2,6-dicarboxylate).
PEN is a slow crystallizing polymer. PEN has
good transparency, enhanced deflection tempera-
ture under load compared to PET, very low gas and
water permeation. Targeted applications are in areas
that requires transparency, heat resistance, or chemi-
cal resistance. These include returnable bottles, cos-
metic containers, plastic dinnerware, and health-care
product containers. In addition, PEN can be blended
with PET to enhance the performance of PET to give
a good balance of cost and performance, improved
moisture and gas barrier, heat resistance, increased
UV-ray absorption.
Poly(butylene naphthalene-2,6-dicarboxylate),
PBN, is prepared from naphthalene-2,6-dicarboxylic
acid and 1,4-butsnediol. It exhibits a Tg of 78°C and
Tm of 243°C [35]. Its structure appears in Fig. 1.19.
PBN, like PBT, shows fast crystallization rates com-
pared with other polyesters. The interchain interac-
tions due to the naphthalene rings and the flexibility
of the butylene groups can give rise to fast nucleation
and spherulitic growth from the melt. PBN exhibits
the following unique features: excellent abrasion re-
sistance, excellent in chemical resistance, low gas
and water vapor barrier properties, excellent chemi-
cal resistance, and good mechanical, thermal and in-
sulating properties.
PBN exhibits much less abrasion in the Taber test
than POM and PPS at room temperature, leading to
use in gears and gear-change levers. Its gas-barrier
properties have been applied as a back-sheet material
for solar battery chargers where back-sheets are nor-
mally comprised of multilayer structures. Additional
applications include cable encapsulation for mass
transportation, where the PBN provides resistance to
abrasion between individual cables.
Figure 1.19 Structure of poly(butylene naphtha-
lene-2,6-dicarboxylate).
1: Engineering Thermoplastics—Materials, Properties, Trends
Figure 1.20 Structure of polyester of CHDM.
Figure 1.21 Structure of polyester copolymer of
CHDM and TMCD.
Another class of polyesters are based on cycloali-
phatic diols. Eastman Chemical has a broad portfo-
lio of copolyesters where the combination of cyclo-
aliphatic diols, ethylene glycol, iso- and terephthalic
moieties are varied. Two will be discussed here. The
copolyester poly(1,4-cyclohexylene-dimethylene
terephthalate/isophthalate), PCT, is produced from
1,4-cyclohexanedimethanol (CHDM) and a mixture
of terephthalic and isophthalic acid. PCT exhibits a
Tg of 91°C and Tm of 261°C. The structure of PCT
is depicted in Fig. 1.20. It has good hydrolytic and
heat stability. PCT is intended primarily for extrusion
into film and sheeting for packaging. Applications in-
clude blister packaging, food packaging, food-con-
tact applications, meat and poultry packaging.
Another copolyester is prepared from two diols,
CHDM and 2,4,4-tetramethyl-1,3-cyclobutanediol
(TMCD). These diols, which have cis and trans con-
figurations, are reacted with dimethyl terephthalate
to give an amorphous, transparent copolyester [36].
This amorphous copolyester features good chemi-
cal and heat resistance, which make this copolyester
suitable for hot-fill cosmetics packaging, personal
care and fragrance packaging. These polymers are
available from Eastman Chemical under that Tritan
trade name. The structure of CHDM/TMCD copoly-
ester is depicted in Fig. 1.21.
1.11 Liquid Crystalline Polymers
(Polyesters)
Liquid crystalline polymers are termed liquid
crystal from the fact that the polymers exhibit crys-
talline properties as a liquid. In LCPs there is little
entwining of molecules. LCPs are polymers hav-
ing a degree of molecular order either in solution
(lyotropic) or in a melt (thermotropic) intermediate
between those of a solid crystals and those of iso-
tropic liquids and are called liquid crystalline. Most
11
LCPs exhibit multiple thermal transitions. The tran-
sitions of greatest interest are those of the crystalline
to nematic phase (three dimensional order to two di-
mensional order) and nematic to isotropic phase (two
dimensional order to disorder).
In the molten state the molecules readily slide over
one another giving the resin very high flow under
shear. Hence, melt viscosities decrease significantly
as shear rates increase. In general, the melt viscosity
of LCPs are lowered by increasing injection velocity
rather than temperature. The rod-like molecules ar-
range themselves in parallel domains in the molten
state in the direction of flow and retain this ordered
condition in the solid state.
LCPs have anisotropic properties, that is, properties
are different in the direction of flow and perpendicular
to the flow direction. This generates a self-reinforcing
effect in the direction of flow, thereby resulting in
extremely high strength and elastic modulus in the
direction of flow. Moreover, the coefficient of linear
expansion in the flow direction in is very small—
exhibiting values an order of magnitude less than
conventional plastics. The thinner the molded item,
a higher the proportion of the oriented molecules re-
sults in greater strength and elastic modulus can be
achieved the thinner the product.
In general, LCPs are classified according to their
thermal performance in three categories. Type I LCPs
have the lowest thermal performance with heat de-
flection temperatures (HDTs) in the 80–210°C range;
Type II LCPs have HDTs in the 175–240°C range and
are typically all aromatic. Type III LCPs have HDT
values in the 260–355°C or higher and are all aromatic.
Most commercially important polyester LCPs are
based on p-hydroxy benzoic acid, HBA. Thermoplas-
tic liquid crystalline polyesters generally have rigid,
rod-like structures, for example, aromatic rings at-
tached to parapositions via ester linkages. The homo-
polymer of HBA has a rigid, rod-like structure. The
earliest reports on making polyesters from HBA was
in the 1880s where dimers, trimers, and oligomers
were prepared [37]. In the 1960s J. Economy of Car-
borundum Company prepared high molecular weight
poly(1,4-benzoate), PHBA. Parts were fabricated by
metal forming techniques such as plasma spray and
high-energy rate forging. It was commercialized in
early 1970 under the Ekanol trade name [38–40]. The
structure appears in Fig. 1.22.
PHBA exhibits a melting point of ∼600°C. This
material was not easy to melt process and probably
did not form a liquid crystalline melt. However, mod-
ifications of the rigid, rod-like structure can decrease
the melting temperature to below 400°C, and render
12
Figure 1.22 Structure of poly(1,4-benzoate).
Figure 1.23 Structure of HBA/biphenol/TTA based
LCP.
the polyesters liquid crystalline and melt processible.
In the mid-1960s work was initiated to prepare melt-
processible copolymers of PHBA with biphenol tere-
phthalate (BPT). Indeed, copolymerizing HBA with
4,4’-biphenol and terephthalic acid (TTA) resulted in
melt processible liquid crystalline polyesters, which
were commercialized in early 1971 under the Ekkcel
trade name. Properties are a function of the monomer
ratios. Typically the Tg is around 180°C and the Tm
340–400°C. Its structure appears in Fig. 1.23. These
polymers were difficult to manufacture and process.
In 1979 Carborundum sold the business to Sumitomo
Chemical and the technology to Dartco. Dartco intro-
duced their Xydar product line in the fall of 1984 for
use in dual ovenable cookware. Their LCP was based
on an improved HBA, biphenol, and terephthalic
acid-based resin. This technology was later sold to
Amoco Polymers (now Solvay Advanced Polymers).
In the 1970s G.W. Calundann of Celanese was
developing LCPs based on copolymers of HBA
with 6-hydroxy-2-naphthoic acid (HNA) or with
2,6-dihydroxynaphthalene and 2,6-naphthylene di-
carboxylic acid. The structure of the HBA and HNA
copolyester is depicted in Fig. 1.24. In the fall of
1985 their LCP was commercialized under the Vectra
trade name [41].
Principal US and European suppliers of polyester
LCPs are Celanese, Solvay, and DuPont with prod-
ucts under the Vectra, Xydar, and Zenite trademarks,
respectively.
LCPs offer high strength and rigidity, reduced
mold shrinkage, dimensional stability, excellent sol-
vent/chemical resistance, wear resistance, high heat
resistance, and inherent flame retardancy. Polyester
Figure 1.24 Structure of naphthalene based LCPs.
Applied Plastics Engineering Handbook
LCPs are used in electronic connectors and sockets,
surgical devices, and other parts where thin walls are
essential.
1.12 Poly(phenylene sulfide)
The first poly(phenylene sulfide), PPS, was made
in 1897 by the Friedel–Crafts reaction of sulfur and
benzene [42]. Various other early attempts have been
reported, all of which resulted in amorphous resinous
materials that decomposed between 200 and 300°C.
These materials were probably highly branched and
even partially cross-linked.
In 1967, J.T. Edmonds and H.W. Hill at Phillips
Petroleum (now Solvay Advanced Polymers) de-
veloped the first commercially viable process for
the synthesis of PPS by reacting 1,4-dichloroben-
zene with sodium sulfide in a dipolar aprotic solvent
[43,44]. The polymer exhibits a Tg of 85°C and Tm
of 280°C. The structure appears in Fig. 1.25. The
polymer precipitates out of solution as a crystalline
powder. However, this limited the molecular weight
of the PPS. Hence, thermal treatment under an oxy-
gen atmosphere was used to advance the molecular
weight. This could result in branching or slight cross-
linking which would lower the ultimate performance.
In 1973, Phillips Petroleum (Solvay Advanced
Polymers) introduced linear and branched products
under the Ryton trade name [45].
Branched PPS exhibits high heat resistance, ex-
cellent chemical resistance, low friction coefficient,
good abrasion resistance, and good electrical prop-
erties. Physical characteristics include high flexural
modulus, very low elongation, and generally poor
impact strength. Moreover, branched or slightly
crosslinked PPS is reported to be somewhat difficult
to process because of their very high melting tem-
peratures, relatively poor flow characteristics, and
because some chemistry appears to continue during
the fabrication step. Molded pieces have limited use
as regrind. Annealing of molded parts enhances me-
chanical properties but leads to almost total loss of
thermoplastic character.
In 1986, a linear, high molecular weight PPS was
developed. Linear PPS overcomes the weak points of
branched or cross-linked PPS, and exhibited several
performance advantages over branched PPS products.
Figure 1.25 Structure of polyphenylene sulfide.
1: Engineering Thermoplastics—Materials, Properties, Trends
These include faster cycle times, higher elongation
and impact strength, more consistent melt viscosity,
higher weld line strength, and lighter color. Linear PPS
is available under the Fortron trade name (Celanese).
Glass fiber, glass-mineral, and carbon fiber–re-
inforced grades that have high strength and rigidity
are available. The unreinforced resin is used only in
coatings. The reinforced materials are finding ap-
plications in aerospace technology, pump systems,
electrical and electronic equipment, appliances, and
automotive vehicles and machines.
1.13 Polyetherimide
In the early 1970s a research team headed by J.G.
Wirth developed polyetherimides, PEI. The early
laboratory process was costly and difficult. Further
development resulted in a number of breakthroughs
that led to a simplified, cost-effective production
process. The process involves the imidization of
a dicarboxylic acid anhydride with m-phenylene
diamine. PEI has a Tg of 217°C. The structure of
PEI is depicted in Fig. 1.26. PEI was formally an-
nounced by General Electric Company (SABIC) in
1982 [46,47].
PEI offers an impressive collection of attributes
such as high heat resistance, stiffness, impact strength,
transparency, high mechanical strength, good electri-
cal properties, high flame resistance, low smoke gen-
eration, and broad chemical resistance. In addition to
its unique combination of properties matching those
of high-priced specialty polymers, PEI exhibits the
processability of traditional ETPs, although higher
melt temperatures are required. The excellent ther-
mal stability is demonstrated by the maintenance of
stable melt viscosity after multiple regrinds and re-
molding. The processing window is nearly 100°C,
and PEI can be processed on most existing equip-
ment. Furthermore, this excellent flow resin can be
used for the molding of complicated parts and thin
sections (as thin as 5 mil). PEI is suitable for use in
internal components of microwave ovens, electrical
and electronic products, and automotive, appliance,
and aerospace, and transportation applications.
A new higher heat PEI has been developed by
SABIC. It is available under the Extem XH trade
Figure 1.26 Structure of polyetherimide.
13
Figure 1.27 Structure of thermoplastic imide.
name [48,49]. This amorphous thermoplastic imide,
TPI, features a Tg of 249°C, exceptional dimensional
stability, high strength, stiffness, and creep resistance
at elevated temperatures. In addition, it offers broad
chemical resistance including chlorinated solvents
and it is inherently flame retardant. TPI exhibits
good melt flow and can be processed in conventional
methods such as injection molding, film and profile
extrusion, thermoforming, extrusion blow mold-
ing, and extrusion into stock shapes. The structure
appears in Fig. 1.27. Potential applications include
thermoplastic composites, fibers, and high heat pow-
der coatings, TPI resins meet the material require-
ments for the optoelectronics industry.
1.14 Polyimides
Polyimides are a class of polymers prepared from
the condensation reaction of a dicarboxylic acid an-
hydride with a diamine [50]. Aromatic, ultrahigh
heat-resistant polymers exhibit useful mechanical
characteristics through a wide temperature range,
high tensile strength and modulus, outstanding elec-
tric properties, flame resistance, creep resistance,
high toughness, and excellent wear resistance, and
outstanding long-term heat resistance in air or inert
atmosphere. Another advantage inherent in poly-
imides is high resistance to hydrolysis. Polyimides
have excellent resistance to a broad range of chemi-
cals. However, it will be attacked by 10% and stron-
ger solutions of sodium hydroxide.
Poly(pyromellitimde-1,4-diphenyl ether), PD-
MA-ODA, is prepared from pyromellitic anhydride
(PMDA) and 4,4’-oxydianiline (ODA). The structure
is shown in Fig. 1.28. PMDA-ODA has a Tg around
360–400°C. The very high Tg of this material does
not lend itself to standard melt processing tech-
niques. PMDA-ODA resins are available as films and
Figure 1.28 Structure of poly(pyromellitimde-1,4-
diphenyl ether).
14
Figure 1.29 Structures of biphenyl tetra carboxylic
dianhydride-based polyimides.
direct-formed parts from formulated resin. Films and
molded parts are available from DuPont under the
Kapton and Vespel trade names, respectively.
Another family of aromatic polyimides is produced
from the condensation reaction between biphenyl
tetra carboxylic dianhydride (BPDA) and aromatic
diamines such as ODA and p-phenylene diamine,
PDA. The polyimides BPDA-ODA and BPDA-PDA
are available from Ube Industries under the Upilex R
and S trademarks, respectively. Their Tgs are reported
to be >400°C. Structures appear in Fig. 1.29.
Polyimides based on PMDA and 4,4’-bis(3-amin-
ophenoxy)biphenyl is available from Mitsui Chemi-
cal under the Aurum trademark [51]. This semicrys-
talline polymer has a Tg of 250°C and a Tm of 390°C.
Aromatic polyimides have been the subject of
much attention as a material for use in the electron-
ics and other leading-edge industries. Films are used
in flexible printed circuit boards, as wire and cable
wrap, motor-slot liners, transformers and capaci-
tors. Molded parts are used in applications requiring
resistance to thermally harsh environments such as
automotive transmission parts, thermal and electrical
insulators, valve seats, rotary seal rings, thrust wash-
ers and discs, bushings.
1.15 Polyamide Imides
Polyamide imides, PAI, were first developed at
DuPont in 1955. In the early 1960s they became
commercially available from Standard Oil of Indi-
ana (Amoco; now Solvay Advanced Polymers) un-
der the Torlon trade name [52]. PAIs are prepared
from trimellitic anhydride chloride and various aro-
matic diamines such as ODA and methylene diani-
line, MDA [53]. PAIs are amorphous thermoplastics
that offer Tgs around 275°C. Structures are shown in
Fig. 1.30. PAIs offer long-lasting performance in se-
vere service environments and a distinct combination
Applied Plastics Engineering Handbook
Figure 1.30 Structure of polyamide imide.
of properties, which include toughness, high con-
tinuous use temperatures, inherent flame resistance,
high-modulus, and very high strength. PAIs contain
amide groups, which will increase moisture absorp-
tion. PAIs have very broad chemical resistance but
are attacked by aqueous caustic and amines. PAIs re-
quire very high processing temperatures.
Typical uses of PAI include injection-molded au-
tomotive parts such as housings, connectors, switch-
es, relays, thrust washers, valve seats, bushings, wear
rings, ball bearings, rollers, and thermal insulators.
1.16 Aromatic Polyketones
Polyetherketone (PEK), polyetheretherketone
(PEEK), polyaryletherketone (PAEK), and poly-
etherketoneketone (PEKK) are thermoplastics that
belong to the family of polyaryletherketones. These
aromatic polyketones are semicrystalline high-
performance thermoplastics with a combination of
ketone, aryl ether, and aromatic moieties, which im-
parts outstanding high-temperature properties com-
bined with exceptional thermal stability [54]. Indeed,
aromatic polyketones are regarded as among the
highest performing materials. In addition, aromatic
polyketones offer excellent environmental resistance,
high mechanical properties, resistance to chemical
environments at high temperatures, inherent flame
retardancy, excellent friction and wear resistance,
and impact resistance.
Aromatic polyketones were first produced in the
1960s and 1970s by W.H. Bonner at DuPont. Low
molecular weight PEKK by Friedel–Crafts acylation
diphenyl ether using isophthaloyl chloride or tere-
phthaloyl chloride were reported [55]. The insolu-
bility of these polymers presented a major synthetic
problem as it limited the molecular weight that could
be obtained before the growing polymer chains crys-
tallized out from the solution.
In the early- to mid-1970s Raychem Corp. intro-
duced a high molecular weight PEK under the Stilan
trade name. This semicrystalline, aromatic polyether
was developed by K. Dahl [56,57]. Friedel–Crafts
chemistry required drastic conditions to make high
molecular weight PEK. Very strong solvents such as
1: Engineering Thermoplastics—Materials, Properties, Trends
Figure 1.31 Structure of polyetherketone.
hydrogen fluoride or an excess of aluminum chloride
were required to keep the polymer in solution so the
polymerization would continue. PEK was expensive
to manufacture and was mostly made for captive use.
PEK has a Tg of 166°C and Tm of 364°C. The structure
is shown in Fig. 1.31. In the 1980s Raychem licensed
their patents to BASF and discontinued production.
The best-known and mostly widely used
polyaryletherketone is PEEK. It prepared under
milder conditions via nucleophilic aromatic substitu-
tion reaction of the dipotassium salt of hydroquinone
and 4,4’-difluorobenzophenone. Several companies
conducted early work on PEEK, which resulted in
low molecular weight polymer, again owning to crys-
tallization and precipitation from solution. However,
Rose and coworkers at ICI (now Victrex Co.) was
able to obtain high molecular weight PEEK by using
a very high boiling solvent such as diphenylsulfone
at temperatures close to the melting point of the poly-
mer. In 1980 PEEK was commercialized under the
Victrex PEEK trade name. PEEK has a Tg of 145°C
and Tm of 335°C. The structure of PEEK is shown in
Fig. 1.32.
Applications are in the chemical process indus-
try (compressor plates, valve seats, pump impellers,
thrust washers, bearing cages), aerospace (aircraft
fairings, radomes, fuel valves, ducting), and elec-
trical (wire coating, semiconductor wafer carriers)
industries.
The latest generation of PEKK polymers are high
molecular weight made by Friedel-Crafts chemistry.
Depending on the isophthalyl and terephthalyl con-
tent, PEKKs can be amorphous or semicrystalline
[58]. When all the linkages are terephthalyl, PEKK
exhibits a Tg of 165°C and Tm of 391°C. The structure
appears in Fig. 1.33. PEKK exhibits up to 80% great-
er compression strength than PEEK and a wider pro-
cessing window of parameters than PEEK. Thanks to
its unique mechanical, physical and chemical proper-
ties, it is reported that PEKK lends itself to a broader
range of uses than PEEK.
Figure 1.32 Structure of polyetheretherketone.
15
Figure 1.33 Structure of polyetherketoneketone.
1.17 Polyarylates
Polyarylates, PARs, are a family of aromatic poly-
esters derived from aromatic dicarboxylic acids and
bisphenols. They have been under investigation since
the late 1950s. The polyarylates that have received
the most attention are based on BPA and isophthalic
or terephthalic acids. The homopolymers of bisphe-
nol A and isophthalic acid or terephthalic acids are
semicrystalline [59]. These polymers have Tgs of 183
and 206°C and Tms of 270 and 370°C, respectively.
These semicrystalline polyarylates were not com-
mercialized because of their high crystalline melting
points and very slow crystallization rates. However,
amorphous PARs are prepared from a mixture of
isophthalic and terephthalic acids and BPA and can
be melt-processed without difficulty. The structure
appears in Fig. 1.34. Unitika of Japan (1974), Union
Carbide Corporation (now Solvay Advanced Poly-
mers) (1978), Hooker Chemical Company (1979),
and DuPont (1986) commercialized PARs under the
trade names U-polymer, Ardel, Durel, and Arylon,
respectively. PARs exhibit Tgs of 180–185°C.
These amorphous PARs are transparent, slightly
yellow in color, dimensionally stable, resistant to
creep, excellent electrical properties, rigid, and have
good impact strength. PARs have poor chemical re-
sistance to ketones, esters, aromatic, and chlorinated
hydrocarbons. Typical uses include electrical/elec-
tronic and automotive applications, which require
higher heat deflection temperature than PC.
1.18 Aliphatic Polyketones
Aliphatic polyketones are produced from olefin
monomers and carbon monoxide. Basic patents on
catalyst and composition appeared in the early 1970s
[60]. However, these early resins were not easy to
process due to residual catalyst. In 1982 J. Dent of
Royal Dutch/Shell discovered a new class of catalyst
Figure 1.34 Structure of polyarylates.
16
Figure 1.35 Structure of aliphatic polyketone.
systems that were capable of copolymerizing carbon
monoxide and ethylene into linear, perfectly alternat-
ing polyketone polymers of high molecular weight.
In 1996 Shell commercialized terpolymers of carbon
monoxide, ethylene, and a small amount of propyl-
ene under the Carilon trade name. The semicrystal-
line, ethylene/propylene/CO terpolymers had a Tg of
around 15°C and Tm of 200°C. The structure appears
in Fig. 1.35.
Aliphatic polyketones offer toughness, chemical
resistance, and wear resistance and was targeted to
compete with polyamides, thermoplastic polyesters,
and syndiotactic polystyrene in the electrical connec-
tor market and POM in gear and barring applications.
The material had limited success and was with-
drawn from the marketplace in 2000.
1.19 Syndiotactic Polystyrene
Advancements in metallocene catalyst technology
resulted in the production of syndiotactic polystyrene,
SPS. General purpose polystyrene or atactic PS has
no stereo-regularity, is amorphous with a Tg around
100°C, is relatively brittle, and has poor chemical re-
sistance. In contrast, SPS has high stereo regularity,
in the syndiotactic configuration the phenyl groups
lie on alternating sides of the polymer backbone. SPS
has a Tg of 100°C and a Tm of 270°C. SPS exhibits
good high heat resistance, excellent electric proper-
ties, good chemical/solvent resistance, excellent hy-
drothermal stability, and low specific gravity [61].
The structure of SPS appears in Fig. 1.36.
Dow Chemical commercialized SPS in 1997 un-
der the Questra trade name. SPS was targeted for
automotive under-the-hood and specialty electronic
applications. It was competing for applications that
Figure 1.36 Structure of syndiotactic polystyrene.
Applied Plastics Engineering Handbook
used polyamides, thermoplastic polyesters, aliphatic
polyketones, and PPS.
However, SPS grades suffered from poor me-
chanical properties relative to other ETPs. Glass-re-
inforced grades were handicapped by no interfacial
attraction between the glass fiber and the nonpolar,
nonfunctional SPS. Besides lower strength and stiff-
ness, the weld lines were very poor. In 2005, Dow
Chemical discontinued the SPS product line. SPS
plastics are available from Indemitsu Kosan, Co. and
LG Chemicals under the Xarec SPS and LUSEP SP
trade names, respectively.
1.20 Self-Reinforcing
Polyphenylene
Poly(p-phenylene) is a highly crystalline, rigid
rod polymer that is insoluble and infusible. Proper
modification of poly(p-phenylene) can result in an
amorphous, transparent, and melt-processible poly-
mer. The modified polymer is based on a string of
substituted and unsubstituted phenylene units pro-
ducing a highly rigid chain structure. The substi-
tuted phenylene units have pendant benzoyl groups.
These benzoyl substituted phenylene units along
with some meta phenylene units were sufficient to
prevent crystallization. These polymers are prepared
by carbon-carbon coupling polymerization reactions
of 1,4-dichlorobenzene, 2,5-dichloroacetophenone,
and 1,3-dichlorobenzene. The self-reinforcing phen-
ylenes, SRP, is amorphous and has a Tg of 165°C.
The structure is depicted in Fig. 1.37.
SRP retains the rigid rod characteristics and are
self-reinforcing, which results in very high, isotropic
mechanical properties. They are one of the stiffest
unreinforced thermoplastics that are commercially
available and provide exceptional strength and stiff-
ness without fillers. Indeed, SRP exhibits two to four
times the stiffness and two to three times the strength
of most thermoplastics. In addition, there are no is-
sues the orientation of glass- or carbon fibers within
the plastic matrix—and the resulting directional dif-
ferences in strength.
Figure 1.37 Structure of self-reinforcing polyphen-
ylene.
1: Engineering Thermoplastics—Materials, Properties, Trends
The highly aromatic polymer is inherently flame
resistant. The high surface hardness results in excel-
lent scratch and wear resistance. Coefficient of fric-
tion is very low and has high compressive strength.
Mechanical performance is maintained across a
wide range of temperatures. For example, mechani-
cal properties are retained all the way down to liquid
Helium temperatures (4°K). Other characteristics in-
clude broad chemical resistance.
SRP can be processed by using standard melt pro-
cessing techniques. The polymer is soluble in com-
mon solvents and can be cast into films and coat-
ings. In addition, machinable stock plastic shapes are
available. In 2003 Mississippi Polymer Technolo-
gies (MPT) introduced modified poly(p-phenylene)
under the Parmax trade name [62]. In 2006 Solvay
Advanced Polymers acquired MPT and offers amor-
phous para-phenylene copolymers under the Primo-
Spire trademark.
SRP is suitable for applications that have histori-
cally relied on ceramic, composites, and metals for
superior mechanical performance. Market potential
includes: aerospace/defense (inherent flame resis-
tance, lightweight, superior ablation properties, high
compressive strength), health care (strength without
fibers, autoclavability, X-ray transparency, chemi-
cal resistance), semiconductor/electronic (chemical
resistance, low moisture absorption, high purity, di-
mensional stability, low CTE).
1.21 Poly(p-xylylene)
Poly(p-xylylene), PPX, was first prepared via
the reactive intermediate p-xylylene by Szwarc in
the 1940s. In the 1960s Union Carbide developed
a synthetic route based on the dimer di-p-xylylene
([2.2]paracyclophane). These PPXs are commonly
referred to as parylene and are available under the
GALXYL trade name from Specialty Coating Sys-
tems, Inc [63,64]. A general structure of PPX is de-
picted in Fig. 1.38.
Most PPX polymers are prepared by a unique
chemical vapor deposition (CVD) polymerization
method that was developed for coating components.
In the CVD process the paracyclophane dimer is va-
porized and the coating forms from a gaseous mono-
mer without an intermediate liquid stage. As a result,
Figure 1.38 Structure of poly(p-xylylene).
17
the monomeric vapor has the ability to cover every
nook and cranny and can successfully coat even the
most complex structures. Even component configu-
rations with sharp edges, points, flat surfaces, crevic-
es or exposed internal surfaces are coated uniformly
without voids. An advantage of the CVD process is
that there are no by-products from the polymeriza-
tion. Union Carbide commercialized a PPX coating
system in 1965.
There are various modified PPXs available. Three
common variations are PPX-N, PPX-C, and PPX-
D, which have zero, one, and two chloro groups at-
tached to the phenyl ring and exhibit Tms of 420, 290,
and 380°C, respectively. PPX-N offers high dielec-
tric strength and a stable dielectric properties over
a wide frequency range. PPX-C is the most widely
used an exhibited very low permeability to moisture,
chemicals, and corrosive gases. PPX-D maintains its
physical strength and electrical properties at higher
temperatures.
Features of PPX include light weight stress-free
coatings, low coefficient of friction, transparent, no
out-gassing, biocompatible, very low permeability
to moisture and gases, excellent fungus and bacteria
resistance, high tensile and yield strength, insoluble
in common solvents, acid and base resistance, and
extremely high dielectric strength.
Because of its precision application and enduring
features, PPX films have been used in various appli-
cations, including hydrophobic coatings (moisture
barriers, e.g., for biomedical hoses), barrier layers
(e.g., for filter, diaphragms, valves), microwave elec-
tronics, implanted medical devices, sensors in hostile
environments (automotive fuel/air sensors), electron-
ics for aerospace and military, corrosion protection
for metallic surfaces, reinforcement of microstruc-
tures, friction reduction (e.g., for guiding catheters,
acupuncture needles and microelectromechanical
systems) and protection of plastics and rubbers from
harmful environmental conditions.
1.22 Polybenzimidazole
Aliphatic polybenzimidazoles were first synthe-
sized by scientists in the 1950s. However, it was
not until the 1960s that H. Vogel and C.S. Marvel
first synthesized aromatic polybenzimidazoles and
discovered that these unique, highly stable linear
heterocyclic rigid-rod polymers exhibited excep-
tional thermal and oxidative stability [65]. Poly[2,2’-
(m-phenylene)-5,5’-bibenzimidazole], PBI, was
prepared by the condensation polymerization of
18
Figure 1.39 Structure of poly[2,2-(m-phenylene)-5,5-
bibenzimidazole].
3,3’,4,4’-tetraaminobiphenyl and diphenyl isophthal-
ate in poly(phosphoric) acid, or in a hot molten non-
solvent such as sulfolane or diphenyl sulfone [66,67].
PBI exhibits a glass Tg of 427°C. The structure of PBI
is shown in Fig. 1.39.
PBI research was supported by the National Aero-
nautics and Space Administration (NASA) and Air
Force Materials Laboratory (AFML). There was in-
terest in possible use for aerospace and defense ap-
plications as a nonflammable and thermally stable
textile fiber and as high-temperature matrix resins,
adhesives and foams. Celanese Corporation became
involved in PBI research through contracts with
NASA and AFML and developed polymerization
and fiber-spinning technology for a high-temperature
resistant PBI fiber in 1963. Process and application
development focused on PBI films, fibrils, papers,
microporous resin, sizing, coatings and molding
resins. In 1983 PBI fiber was commercialized. PBI
has a continuous service temperature around 400°C.
PBI exhibits excellent tensile and flexural strength,
a decomposition temperature ≥700°F, excellent
chemical resistance, good fatigue properties, excel-
lent hardness, low coefficient of friction, low coef-
ficient of thermal expansion, high volume resistivity,
and very good plasma resistance. It will not burn,
melt, or contribute fuel to flames and has interesting
electrical and nonlinear optical properties. It has one
of the highest compressive strengths of any unfilled
polymer.
In 2005 PBI Performance Products, Inc. acquired
the PBI fiber and polymer business. Grades of PBI
are available under the Celazole trade name. PBI fi-
bers are used in firefighters’ gear, thermal-protective
clothing, industrial protective clothing, fire-blocking
layers for aircraft seats, braided pump packings, and
other high-performance applications. Parts molded of
PBI are being used in the manufacture of electronic
(semiconductor, flat panel display, photovoltaic), oil
and gas recovery, and industrial applications (cham-
ber seals, wafer transportation devices, electrical in-
sulating parts, glass handling, plasma cutting torch
insulators, valve seats, seals, bearings, bushings, and
thrust washers).
Applied Plastics Engineering Handbook
Figure 1.40 Structure of poly(2,5-benzimidazole).
Another polymer containing the benzimidazole
group is poly(2,5-benzimidazole). It is prepared by
the self-polymerization of 3,4-diaminobenzoic acid
[68]. It is referred to as ab-PBI where the ab indicates
that the polymer is formed in head-tail manner. It
is available from Gharda Chemicals LTD under the
Gazole trade name. The structure appears in Fig. 1.40.
Features of ab-PBI are a Tg of 485°C, low coeffi-
cient of friction, high wear resistance properties, very
high limiting oxygen index (LOI), very high heat
deflection temperature (HDT), and extended high-
temperature mechanical performance and excellent
chemical resistance. Indeed, ab-PBI offers high heat
resistance and mechanical property retention over
300°C. Potential uses are PBI areas mentioned ear-
lier and in membranes in fuel cells, which operate at
elevated temperatures.
1.23 Comparison of Physical
Properties
Some performance attributes of ETPs and AETPs
are summarized in Tables 1.1–1.5. Properties are tak-
en from product data sheets and published technical
literature [2]. Data were chosen from grades that did
not contain any additives for these tables. Since pro-
cessing and test conditions can play an important role
in defining optimum performance, the data should be
viewed as a qualitative summary.
Properties of semicrystalline thermoplastics are
normally enhanced via reinforcing filler. However,
the type and amount of such fillers would compli-
cate any comparison. Hence, properties of various
unfilled semicrystalline resins are compared shown
in Tables 1.1–1.3. For comparison two commodity
semicrystalline polymers, high density polyethylene
(HDPE) and polypropylene (PP), are included in
Table 1.1. Table 1.1 summarizes properties of HDPE,
PP, POM, and polyesters. Table 1.2 contains proper-
ties of polyamides and SPS. Table 1.3 lists proper-
ties of the highly aromatic, semicrystalline polymers.
Clearly, semicrystalline ETPs exhibit very broad per-
formance enhancements over commodity semicrys-
talline polymers.
1: Engineering Thermoplastics—Materials, Properties, Trends 19

Table 1.1 Properties of Semicrystalline Polymers: HDPE, PP, POM, and Polyesters

Property HDPE PP POM PET PBT PEN PBN PCT

Tg (°C) –120 –15 –75 69 40 125 78 91
Tm (°C) 134 164 170 267 230 268 243 261
HDT @ 0.45 MPa,(°C) 60 90 170 72 154 125 — —
HDT @ 1.8 MPa (°C) — — 136 — 58 — 77 –
Density (g/cm3) 0.96 0.90 1.42 1.34 1.30 1.33 1.31 1.2
Tensile modulus (MPa) 965 1793 2620 2206 2344 — — 1600
Tensile strength (MPa) 30 34.5 69 55 55 74 65 43
Notched Izod (J/m) — 27 74 — 53 39 34 —

Table 1.2 Properties of Semicrystalline Polymers: Polyamides and SPS

Property PA6 PA66 PA46 PA6T/6 PA6T/6I PA9T SPS

Tg (°C) 47 47 75 100 100 125 100
Tm (°C) 225 265 295 300 290 300 270
HDT @ 0.45 MPa, (°C) 165 235 280 100 — — 110
HDT @ 1.8 MPa, (°C) 66 70 190 120 140 120 99
Density (g/cm )
3
1.13 1.14 1.18 1.16 1.21 1.34 1.01
Tensile modulus (MPa) 2944 3300 3300 3200 2440 2206 3440
Tensile strength (MPs) 76 86 100 100 108 55 41
Notched Izod (J/m) 53 59 96 70 49 — 11

Table 1.3 Properties of High-Performance, Semicrystalline Polymers

PMDA- Type II Type III

Property PPS ODA LCP LCP PEK PEEK PEKK
Tg (°C) 90 ∼400 120 — 158 150 175
Tm (°C) 280 >400 280 408 360 340 390
HDT @ 1.8 MPa, (°C) 115 360 187 293 165 160 194
Density (g/cm )
3
1.35 1.43 1.40 1.40 1.30 1.30 1.3
Tensile modulus (MPa) 4,000 — 10,600 2,400 4,000 3,600 4,000
Tensile strength (MPa) 66 86 182 96.5 104 96.5 110
Notched Izod (J/m) 139 43 750 — 100 91 45

Properties of various amorphous polymers appear
in Tables 1.4 and 1.5. For comparison, the properties
of two commodity amorphous polymers, high-im-
pact polystyrene (HIPS) and acrylonitrile/butadiene/
styrene (ABS), are included in Table 1.4. Since HIPS
and ABS are multicomponent resins, their average
property values are shown. Properties of the highly
aromatic high-performance amorphous polymers
are summarized in Table 1.5. The amorphous ETPs
exhibit very broad performance enhancements over
HIPS and ABS with higher HDT, tensile proper-
ties and enhanced resistance to burning. Moreover,
PEI, PES, and the high-performance thermoplastics
exhibit enhanced chemical resistance. Among
the ETPs and AETP there are very wide ranges in
performance.
20 Applied Plastics Engineering Handbook

Table 1.4 Properties of Amorphous Polymers

Property HIPS ABS PC PPE PAR PSU PES PEI

Tg (°C) <100 — 150 215 180 186 225 217
Density (g/cm3) 1.04 1.05 1.20 1.07 1.21 1.24 1.37 1.27
Notched Izod (J/m) 220 200 905 65 220 80 75 53
HDT @ 1.8 MPa (°C) 75 81 132 175 174 173 203 201
Oxygen index (%) 18 18 25 29 34 30 38 48
UL-94 Burns Burns V-2 V-2 V-0 V-2 V-0 V-0
Tensile modulus (MPa) 1560 2280 2380 2690 2060 2480 2410 3590
Tensile strength (MPa) 15 43 69 80 66 70 82 110
Chemical resistance – – – – – – + +

Table 1.5 Properties of High-Performance, Amorphous Polymers

Property PI PPSU TPI HTS PAI SRP PBI ab-PBI

Tg (°C) 360– 220 249 265 277 168 427 467
410
Density (g/cm3) 1.43 1.29 1.30 1.35 1.38 1.19 1.30 1.3
Notched Izod J/m) 43 690 69 91 136 59 46 21
HDT @ 1.84 MPa (°C) 360 207 230 255 254 159 435 440
Oxygen index (%) 53 38 — 41 55 58 48 —
UL-94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
Tensile modulus (MPa) — 2340 — 2500 5200 5520 5900 5900
Tensile strength (MPa) 86 69.6 97 94 117 152 160 160
Chemical resistance + + + + + + + +

Table 1.6 Properties of PPE.PS Blends

PPE (wt.%) 0 20 40 60 80 100

PS (wt.%) 100 80 60 40 20 0
Tg (°C) 98 115 135 156 181 215
Density (g/cm3) 1.048 1.057 1.064 1.068 1.069 1.07
Notched Izod (J/m) 11 18 24 34 48 65
HDT @ 1.84 MPa (°C) 95 107 123 140 159 175
Tensile strength (MPa) 46 66 83 91 90 80

1.24 Trends in Engineering 1.24.1 Copolymers

Thermoplastics
A major trend the ETPs is enhancing performance
by various routes such as modification via copoly-
mers, blends and alloys, thermoplastic composites,
and specialty additives.
An important route to modify performance of
polymers is making copolymers of an existing ther-
moplastic. This can be important if existing assets can
be used to manufacture the copolymer. Copolymers
of amorphous resins are increasing in popularity. PC,
1: Engineering Thermoplastics—Materials, Properties, Trends
PEI, and polyester copolymers, mentioned earlier
in the chapter, offer a combination of higher HDT,
increased flow, and better resistance to burning
[15–17]. Also as previously mentioned, semicrystal-
line polymers like polyphenylene, PA6T, and PHBA
have been polymerized with comonomers to lower
their extremely high crystalline melting points i to
facilitate melt processing.
A special class of copolymers are functional-
ized thermoplastics (FTPs) that contain functional
groups. FTPs typically have linear backbones, and
functionalization is introduced at the chain-ends or
on the polymer chain via block and graft copolymer-
izations. The functional groups allow the polymer to
be more interactive and have the ability to form inter-
molecular and intramolecular bonds [69,70].
Functionalization can result in intrinsic, electrical-
ly conductive thermoplastics that also possesses op-
tical properties. These electrically conductive FTPs
have advantages over conventional plastics made
conductive via the addition of conductive fillers and
can offer controlled electrical conductivity. In addi-
tion, FTPs can offer enhanced phase compatibility in
polymer blends.
Functionalized ETPs such as PC, LCP, PSU,
PEEK, PPS, PI, and polyaramids are reported to have
utility in high-temperature applications in the aero-
space, automotive, under-the-hood, electronic, and
optic-magnetic storage devices.
1.24.2 Blends and Alloys
Polymer blends and alloys are another method to
modify and tailor the performance of thermoplastics
[71,72]. Thus, two or more different polymers are
blended together to give a new product. The goal is
to leverage key properties of each material to get a
unique combination of performance that neither of
the individual polymers offers.
Blends and alloys can be economically more at-
tractive than preparing copolymers or developing a
totally new polymer. New products can be developed
more rapidly by combining available polymers to
produce desirable and novel polymers. The avail-
able degrees of freedom provide almost infinite pos-
sibilities and make the opportunity challenging. In
general, blends and alloys of thermoplastics have an
annual growth rate of 8–10% and constitute greater
than 50% of the sales of plastics. Alloys and blends
of ETPs are of major importance.
In this chapter the term blend is used to denote a
simple mixture of two mutually soluble components.
21
On the other hand, alloy refers to a nonsoluble mix-
ture, which is mixed together in such a way to give a
unique combination of properties.
A polymer blend or alloy can have a single phase
or multiple phases. The number of phases of the
blend depends on the miscibility or solubility of the
individual polymers with each other. In a single-
phase blend the polymers dissolve in each other when
mixed together, creating a single, continuous phase.
Thus, the two different polymer chains are uniformly
interdispersed with one another. In general, this is an
uncommon occurrence.
The best known example of miscible blends are PPE
with polystyrene (PS) and high impact polystyrene
(HIPS). These were mentioned earlier in this chapter
[19,20]. A truly unique feature of PPE/PS blends is
that the PPE and PS forms a miscible, single-phased
blends over the entire compositional range. Properties
of PPE/PS blends are shown in Table 1.6. The Tgs,
HDTs, and impact strengths increase with increasing
levels of PPE. The tensile strength and density exhibit
positive nonlinear behavior. The use of HIPS can give
more significant increases impact strength.
Multiphase alloys have two or more discrete phas-
es. Multiphase systems can have some interfacial
attraction between phases, have partial miscibility
between phases, or have no significant attraction be-
tween the phases.
In two-phase systems, the polymers can be co-
continuous, or one phase can be continuous phase or
matrix while the other is the discrete phase, which is
dispersed in the continuous phase. The morphology
depends on the amount of each polymer, the chemical
nature of the polymers, and processing conditions.
Properties of alloys are dependent on the nature of
the polymers, interfacial attraction between the phas-
es and the morphology. Properties can be additive
(linear behavior) and based on the linear contribution
from each polymer fraction. Properties can exhibit a
synergistic combination of properties (positive non-
linear behavior) where the properties are better than
those predicted by linear behavior.
A multiphase alloy where there is good interfacial
attraction between phases is exemplified by alloys of
PC and ABS (terpolymers of acrylonitrile, butadiene,
and styrene). PC/ABS alloys offer a balance of prop-
erties that combines the most desirable properties of
both resins [2]. The ABS improves the melt process-
ing of PC, which facilitates filling large, thin-walled
parts. In addition, the ABS enhances the toughness of
PC—especially at low temperatures, while maintain-
ing the high strength and rigidity of the PC. The PC
increases the HDT of the alloy. Moreover, PC/ABS
22
Table 1.7 Properties of PC/ABS Alloys
Property ABS PC/ABC (50/50)
Density (g/cm )3
1.06 1.13
Notched Izod (25°C, J/m) 300 690
Notched Izod (-20°C, J/m) 110 320
HDT @ 1.84 MPa (°C) 80 100
Tensile modulus (MPa) 1800 1900
Tensile strength (MPa) 40 57
Elongation @ break (%) 20 70
offers good UV stability, high dimensional stability
at ambient and elevated temperatures, and the abil-
ity for chlorine/bromine-free flame retardance [2,10].
PC/ABS alloys were first introduced by Borg-Warner
(now SABIC) under the Cycoloy trade name in 1971.
In 1977 Bayer (née Mobay) with a license from Borg-
Warner launched PC/ABS resins under the Bayblend
trade name. PC/ABS is used in interior and exterior
automotive applications, lap- and desk-top comput-
ers, copiers, printers, telecommunications, electrical,
and appliances. Typical properties of PC/ABS alloys
appear in Table 1.7.
In immiscible system with very little to no inter-
facial adhesion between phases, the properties can
be unpredictable and sometimes can exhibit an an-
tagonistic effect (negative nonlinear behavior) and
be worse than those predicted by linear behavior. In
addition to having poor and unpredictable proper-
ties, the morphology or microstructure of immiscible
mixture is unstable. The discrete phases can coalesce
into larger domains in the molten state. Moreover,
there could be delamination in the solid state when a
stress is applied to the material.
Compatibilization technology is used to circum-
vent these adverse characteristics of immiscible al-
loys [73,74]. One method of compatibilization is the
use of a graft or block copolymer, which contains
segments of each of the individual polymers to im-
prove the interfacial adhesion between the two phas-
es and lead to enhanced properties.
A prime example of an immiscible system a mix-
ture of the polar, aliphatic PA66 and the nonpolar,
aromatic PPE [74–76]. There is no significant inter-
facial attraction between PA66 and PPE.
Compatibilization technology is essential for en-
hancing interfacial adhesion and the development of
useful properties. PA66/PPE alloys are examples of
a multiphase alloy. The morphology of PA66/PPE al-
loys shows the PA66 as the continuous phase, which
gives the alloy easy of processing and chemical
Applied Plastics Engineering Handbook
PC/ABC (80/20) PC
1.17 1.20
750 905
640 150
113 132
2500 2380
60 69
150 110
resistance. The PPE is the dispersed phase and con-
tributes special properties such as reduced moisture
uptake, increase toughness, and higher properties at
elevated temperatures.
Properties of PA66, uncompatibilized PA66/PPE,
and compatibilized PA66/PPE appear in Table 1.8.
Compatibilization results in major increases in
notched Izod toughness and multiaxial impact
strength. The alloy features increase heat resistance
and better retention of properties at elevated temper-
atures and in humid environments.
PA66/PPE alloys were developed for use in ex-
terior automotive parts. It was the first injection
moldable thermoplastic with both the strength and
rigidity needed for large vertical body panels, along
with the high heat resistance for inline or online
painting. PA/PPE alloys can provide a 50% weight
savings over traditional materials. Blends were in-
troduced in 1984 under the Noryl GTX trade name
(SABIC) [20,75].
1.24.3 Additives
When properly formulated, ETPs may be modified
to tailor performance for mechanically functional,
semiprecision parts or structural components. Clearly
property enhancing additives are a key part of ex-
panding the performance windows of ETPs through
judicious blending.
Additives include processing aids, stabilizers, per-
formance enhancing additives, aesthetic additives,
and many other. Processing aids facilitate the melt
processing of plastics and fabrication of plastic parts.
Stabilizers and antioxidants extend service life and
increase the stability during melt processing. Perfor-
mance enhancing additives increase key physical and
mechanical properties of plastics. Reinforcing ma-
terials—such as glass fiber, carbon fiber, mica, talc,
and clays—are inert solids that increase the stiffness
1: Engineering Thermoplastics—Materials, Properties, Trends 23

Table 1.8 Properties of PA66, PA66/PPE

PA66/PPE PA66/PPE
Property PA66 No Compatibilization Compatibilized
Notched Izod (J/m) 55 10 570
Multiaxial impact:
Total energy (J) — 2.3 55
Maximum load (N) — 734 5093
HDT @ 1.84 MPa (°C) 70 190 190
Flexural modulus:
25°C (MPa) 96 92 92
150°C (MPa) 50 11 140
100% relative humidity (MPa) 26 60 60
H2O uptake at equilibrium (%) 8.5 3.0 3.0

and strength of the plastics. Aesthetics additives are
colorants that impart hue (shade), brightness (value),
and intensity (color strength) to plastics.
Some specific examples of performance enhance-
ment from additives include increased thermal con-
ductivity, EMI/RFI shielding, decreased coefficient
of linear thermal expansion, improved wear resis-
tance, and increased strength and rigidity
Thermally conductive materials can conduct heat
away from devices into a heat sink or the surround-
ing air and extend product life. Thermal conductive
ETP can increase the electrical efficiency of encapsu-
lated motors by lowering the operating temperature,
resulting in more power and torque and longer device
life than hotter-running devices.
ETPs can be formulated to give coefficient of lin-
ear thermal expansion (CLTE) of comparable to many
metals. The lower CLTE would decrease stresses
from differences in thermal expansion and potentially
reduce product failure and extend product life.
ETPs can be formulated to provide electromag-
netic and radio frequency interference (EMI/RFI) at-
tenuation in applications from electronics to material
handling. The EMI/RFI shielding results from con-
ductive fibers which form the conductive network.
Various internal lubricants can be used in ETPs to
improved wear resistance and lower friction. These
materials can help extend product life and reduce or
eliminate squeaks and other noise from moving parts.
Fiber reinforcement is a standard way to greatly
increase strength and stiffness. Both glass and car-
bon fibers are used extensively. Performance increas-
es with fiber length. Long fiber ETPs are available,
which offer exceptional mechanical performance,
combining rigidity with outstanding strength and re-
sistance to impact failure.
A comparison between chopped glass and long
glass fiber in PA66/PPE alloys is shown in Table 1.9
[76]. At 40 wt.% glass fiber, the strength and rigidity
are significantly higher for the long glass. In addition,

Table 1.9 Comparison of Chopped Glass and Long Glass Fiber in PA66/PPE

Chopped glass fiber, (wt.%) 40 0 0 0

Long glass fiber, (wt.%) 0 40 50 60
Density (g/cm )
3
1.44 1.43 1.52 1.69
Tensile modulus (MPa) — 12,000 15,520 21,450
Tensile strength (MPa) 161 195 207 228
Flexural modulus (MPa) 10,345 11,175 13,520 19,450
Flexural strength (MPa) 231 273 285 340
Notched Izod (J/m) 69 288 290 294
HDT @ 1.84 MPa (°C) 246 256 257 259
24
there is a substantial increase in impact strength.
Strengths and moduli continue to increase as the long
glass content increases.
Thermoplastic nanocomposites (TPNCs) are
based on the use of nanoparticle fillers. Nanoparti-
cles have greatly increased surface area and hence
can have increase interaction with the matrix resin.
Nanoparticles can revolutionize the plastics indus-
try. With careful processing, low levels (≤5 wt.%)
of nanofillers can increase the mechanical and other
properties of thermoplastics to yield a new group of
materials referred to as TPNCs [77,78]. TPNCs fea-
ture enhancements in modulus, strength, toughness,
chemical resistance, gas permeability resistance,
thermal stability, and dimensional stability. TPNCs
are exemplified by carbon nanotubes and graphene
in ETPs with promising applications in electronics,
packaging, and medical technology.
1.25 Processing
A unique versatility of ETPs are their ability to
be processed by multiple methods such as extrusion,
injection, blow molding, pultrusion. In recent years
additive manufacturing (AM) has emerged as a po-
tentially highly disruptive processes to conventional
methods of fabricating parts out of ETPs [79]. AM
refers to a process by which digital 3D design data
is used to build up a component in layers by deposit-
ing material. The term “3D printing” is increasingly
used as a synonym for AM. However, AM is more
accurate in that it describes a fabrication technique,
which builds up materials layer by layer using mate-
rials that are available in fine solid, liquid, or pow-
der forms. Rapid growth in AM is transitioning this
technology from rapid prototyping to mass markets
in automotive, electronics, aerospace, and medical
applications.
1.26 Conclusions
The future of ETP is bright. The industries served
by these plastics and many others, who use tradition-
al materials such as metals, glass, and ceramics, will
look to the benefits of engineering polymers to pro-
vide with cost-effective solutions to develop unique,
sophisticated products. Key drivers are the demands
for lighter weight, better performing materials for
transportation, increased performance for consumer
electronics, and sports/recreational equipment, and
cost-effective solutions for the challenges of the
Applied Plastics Engineering Handbook
health-care industry. The commercialization of any
new engineering polymers based on a new mono-
mer, although not impossible, is unlikely. Rather,
the major thrust will take place in molecular shuf-
fling with existing monomers, alloying activity, fur-
ther advanced is performance enhancing additives,
and innovative processing techniques. Competition
between end users, resin providers, and formulators
will raise ETP to new heights.
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[3] Kohan MI, editor. Nylon plastics handbook:
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