Mckeen2014 PDF

8 Thermoplastic Elastomers
An elastomer is a polymer with the property of • Tensile strength

“elasticity,” generally having a notably low Young’s • Tear strength
modulus and high yield strain compared with other
materials [1]. The term is often used interchangeably • Chemical and fluid resistance
with the term rubber. Elastomers are amorphous poly- • Adhesion to inks, adhesives, and over-molding
mers existing above their glass transition temperature, substrates
so that considerable segmental motion is possible; so
it is expected that they would also be very permeable. “Soft Phase”—elastomeric properties:
At ambient temperatures rubbers are thus relatively
soft and deformable. Their primary uses are for seals, • Lower service temperature limits
adhesives, and molded flexible parts. Elastomers • Hardness
may be thermosets (requiring vulcanization, a form of
cross-linking) or thermoplastic, called thermoplastic
• Flexibility
elastomers (TPEs). • Compression set and tensile set
TPEs have two big advantages over the conven-
tional thermoset (vulcanized) elastomers, which are
ease and speed of processing. Other advantages of 8.1 Thermoplastic Polyurethane
TPEs are recyclability of scrap, lower energy costs
for processing, and the availability of standard, uni- Elastomers (TPUs)
form grades (not generally available in thermosets). Urethanes are a reaction product of a diisocya-
TPEs are molded or extruded on standard plastics- nate and long- and short-chain polyether, polyester,
processing equipment in considerably shorter cycle or caprolactone glycols [2]. The polyols and the
times than those required for compression or transfer short-chain diols react with the diisocyanates to
molding of conventional rubbers. They are made form linear polyurethane molecules. This combina-
by copolymerizing two or more monomers, using tion of diisocyanate and short-chain diol produces the
either block or graft polymerization techniques. One rigid or hard segment. The polyols form the flexible
of the monomers provides the hard, or crystalline, or soft segment of the final molecule. Figure 8.1
polymer segment that functions as a thermally stable shows the molecular structure in schematic form.
component; the other monomer develops the soft or There are three main chemical classes of TPUs:
amorphous segment, which contributes the elasto- polyester, polyether, and a smaller class known as
meric or rubbery characteristic. polycaprolactone [3].
Physical and chemical properties can be controlled
by varying the ratio of the monomers and the length 1. Polyester TPUs are compatible with PVC and
of the hard and soft segments. Block techniques create other polar plastics. Offering value in the form
long-chain molecules that have various or alternating of enhanced properties, they are unaffected by
hard and soft segments. Graft polymerization methods oils and chemicals, provide excellent abrasion
involve attaching one polymer chain to another as a resistance, offer a good balance of physical
branch. The properties that are affected by each phase properties, and are perfect for use in polyblends.
can be generalized:
“Hard Phase”—plastic properties: 2. Polyether TPUs are slightly lower in specific
gravity than polyester and polycaprolactone
• Processing temperatures grades. They offer low temperature flexibility
and good abrasion and tear resilience. They
• Continuous use temperature are also durable against microbial attack and
McKeen: The Effect of Temperature and other Factors on Plastics and Elastomers.
DOI: http://dx.doi.org/10.1016/B978-0-323-31016-1.00008-8
© 2014 Elsevier Inc. All rights reserved. 371
372 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
provide excellent hydrolysis resistance— the ratio of the starting raw materials. The polyols
making them suitable for applications where used have a significant influence on certain proper-
water is a consideration. ties of the thermoplastic polyurethane. Polyether
3. Polycaprolactone TPUs have the inherent and polyester polyols are both used to produce
toughness and resistance of polyester-based many products.
TPUs combined with low temperature perfor- The polyester-based TPUs have the following
mance and a relatively high resistance to characteristic features:
hydrolysis. They are an ideal raw material for
hydraulic and pneumatic seals. • Good oil/solvent resistance
• Good UV resistance
TPUs can also be subdivided into aromatic and • Abrasion resistance
aliphatic varieties:
• Good heat resistance
• Aromatic TPUs based on isocyanates like 4,4 - 0 • Mechanical properties
methylenediphenyl diisocyanate (MDI) are work-
horse products and can be used in applications The polyether-based TPUs have the following
that require flexibility, strength, and toughness. characteristic features:
• Aliphatic TPUs based on isocyanates like
methyldicyclohexyl diisocyanate (H12 MDI), • Fungus resistance
1,6-hexamethylene diisocyanate (HDI) and • Low temperature flexibility
isophorone diisocyanate (IPDI) are light • Excellent hydrolytic stability
stable and offer excellent optical clarity. They
are commonly employed in automotive interior
• Acid/base resistance
and exterior applications and as laminating
In addition to the basic components described
films to bond glass and polycarbonate together
above, most resin formulations contain additives to
in the glazing industry. They are also used in
facilitate production and processability. Other addi-
projects where attributes like optical clarity,
tives can also be included such as:
adhesion, and surface protection are required.
The properties of the resin depend on the nature

• Demolding agents
of the raw materials, the reaction conditions, and • Flame retardants
Figure 8.1 Molecular structure of a TPU.

8: THERMOPLASTIC ELASTOMERS 373
• Heat/UV stabilizers Elastollan®, Huntsman IROGRAN®, AVALON®,

• Plasticizers KRYSTALGRAN®, and IROSTIC®.
Applications and uses: medical thin walled,
The polyether types are slightly more expen- flexible tubing, catheters, connectors, luers and
sive and have better hydrolytic stability and stopcocks, films and fabric coatings, component
low temperature flexibility than the polyester housings, soft touch grips, dental parts, automotive
types. battery cables, ski goggles, ski boot shells, snow-
Manufacturers and trade names: Lubrizol board surfaces, and sports shoe soles.
Advanced Materials Estane® TPU, Bayer Data for TPU elastomers are found in
MaterialScience Texin® and Desmopan®, BASF Figures 8.28.25.
Figure 8.2 Stress vs. strain at

various temperatures for BASF
Elastollan® 1164 D—polyether
resin, Shore hardness 64D
TPU resin [4].

Elastollan® 1185 A—polyether
resin, Shore hardness 85A
TPU resin [4].

Elastollan® C 64 D—polyester
resin, high crystallinity, Shore
hardness 64D TPU resin [4].

Elastollan® C 85 A—polyester
hardness 85A TPU resin [4].

Elastollan® C 95 A—polyester
hardness 95A TPU resin [4].
Figure 8.7 Stress vs. strain

at various high temperatures
for Bayer Desmopan®
453—polyester resin, Shore
hardness 53D TPU resin [5].

at various low temperatures
for Bayer Desmopan®
453—polyester resin, Shore
hardness 53D TPU resin.

Elastollan® R 1000—20% glass
fiber, Shore hardness 60D TPU
resin [4].

resin [4].

resin [4].

various low temperatures for
Bayer Texin® 285—polyester
resin, Shore hardness 85A TPU
resin [5].

various high temperatures for
resin [5].

various high temperatures for
resin [5].

at various low temperatures for
resin [5].
Figure 8.16 Elastic modulus vs.

temperature for BASF
Elastollan® R glass fiber filled
TPU resins [4].

temperature for BASF Elastollan®
polyester TPU resins [4].

polyether TPU resins [4].
Figure 8.19 Tear strength vs.

Figure 8.20 Tear strength vs.

polyether TPU resins [4].
Figure 8.21 Tensile strength vs.

temperature for Bayer TPU
resins.
Figure 8.22 Tensile strength vs.

temperature (different
temperature range) for Bayer
TPU resins [5].
Figure 8.23 Tensile set vs.

temperature for Bayer TPU
resins [5].
Figure 8.24 Hardness vs.

Figure 8.25 Coefficient of

linear thermal expansion vs.
temperature for BASF
Elastollan® TPU resins [4].
8.2 Olefinic Thermoplastic 8.3 Thermoplastic Copolyester

Elastomers (TPO) Elastomers (TPE-Es or COPEs)
TPO materials are defined as compounds TPE-Es or COPEs are block copolymers [2]. The
(mixtures) of various polyolefin polymers, semi- chemical structure of one such elastomer is shown
crystalline thermoplastics, and amorphous elasto- in Figure 8.40.
mers. Most TPOs are composed of polypropylene These TPEs are generally tougher over a broader
and a copolymer of ethylene and propylene called temperature range than the urethanes described in
ethylenepropylene rubber (EPR) [2]. A common Section 8.1. Also, they are easier and more forgiving
rubber of this type is called ethylene propylene in processing.
diene monomer rubber (EPDM), which has a small
amount of a third monomer, a diene (two car- • Excellent abrasion resistance
boncarbon double bonds in it). The diene monomer • High tensile, compressive, and tear strength
leaves a small amount of unsaturation in the polymer
chain that can be used for sulfur cross-linking. Like • Good flexibility over a wide range of
most TPEs, TPO products are composed of hard and temperatures
soft segments. TPO compounds include fillers, rein- • Good hydrolytic stability
forcements, lubricants, heat stabilizers, antioxidants, • Resistance to solvents and fungus attack
UV stabilizers, colorants, and processing aids. They
are characterized by high impact strength, low den-
• Selection of a wide range of hardness
sity, and good chemical resistance; they are used
In these polyester TPEs, the hard polyester
when durability and reliability are primary concerns.
segments can crystallize, giving the polymer some of
Manufacturers and trade names: ExxonMobil
the attributes of semicrystalline thermoplastics, most
Santoprene®, LyondellBasell Advanced Polyolefins
particularly better solvent resistance than ordinary rub-
Dexflex®.
bers, and also better heat resistance. Above the melting
Applications and uses: roofing and automotive
temperature of the crystalline regions, these TPEs can
exterior parts, capping distilled water, dairy products,
have low viscosity and can be molded easily in thin
fruit juices, sports drinks, beer, wine and food,
sections and complex structures. Properties of thermo-
cosmetics, toiletries and pharmaceutical packaging,
plastic polyester elastomers can be fine-tuned over a
sterilized closures, seals, and liners.
range by altering the ratio of hard to soft segments.
Data for TPOs are found in Figures 8.268.39.
Figure 8.26 Tensile stress vs.

strain for ExxonMobil
Santoprene® 55 Shore A grades
of TPO elastomers
(per ASTM D 412) [6].

of TPO elastomers (per ASTM D
412) [6].

412) [6].

412) [6].

412) [6].

Santoprene® 40 Shore D grades
412) [6].

Santoprene® 50 Shore D grades
412) [6].
Figure 8.33 Elastic and loss

modulus vs. temperature for
ExxonMobil Santoprene®
55 Shore A grades of TPO
elastomers (per ASTM D 412) [6].





40 Shore D grades of TPO
1000
Elastic modulus
Loss modulus
100
Modulus (MPa)
10
1
0.1
50 Shore D grades of TPO –80 –60 –40 –20 0 20 40 60 80 100 120 140 160
elastomers (per ASTM D 412) [6]. Temperature (°C)
Figure 8.40 Molecular

structure of Ticona
Riteflex® TPE-Es.
In DuPont Hytrel® polyester TPEs, the resin is Applications and uses: seals, belts, bushings, pump
a block copolymer. The hard phase is polybutylene diaphragms, gears, protective boots, hose and tubing,
terephthalate (PBT). The soft segments are long-chain springs, and impact-absorbing devices, sporting goods,
polyether glycols. footwear, wire and cable.
Manufacturers and trade names: Ticona Data for thermoplastic polyester elastomers are
Riteflex®, DuPont Hytrel®, Eastman Ecdel®, DSM found in Figures 8.418.64.
Engineering Plastics Arnitel®.

various temperatures (low strain)
for DuPont Hytrel® G4075—
general purpose, low modulus,
Shore D40 thermoplastic
polyester elastomer resin [7].

at various temperatures
(high strain) for DuPont Hytrel®
G4075—general purpose,
low modulus, Shore D40
thermoplastic polyester
elastomer resin [7].

for DuPont Hytrel® 7246—high
performance, high modulus,

various temperatures (high
strain) for DuPont Hytrel® 7246—
high performance, high modulus,

performance, medium-high
modulus, Shore D63

various temperatures (high
strain) for DuPont Hytrel® 6356—
high performance, medium-high
modulus, Shore D63

performance, medium-high
modulus, Shore D55

5556—high performance,
medium-high modulus, Shore
D55 thermoplastic polyester

performance, low modulus,


at various temperatures in
compression for DuPont Hytrel®
G4075—general purpose,

high modulus, Shore D72



Figure 8.56 Typical stress vs.

strain curves for DSM Arnitel®
EM400 and Arnitel® EM550 TPE
elastomer resins [8].
Figure 8.57 Elastic modulus in

compression vs. temperature for
DuPont Hytrel® thermoplastic
polyester elastomer resins [7].

temperature for DuPont Hytrel®
Figure 8.59 Flexural modulus

vs. temperature for DuPont
Hytrel® thermoplastic polyester
Figure 8.60 Dynamic modulus

vs. temperature for DSM Arnitel®
PL 380 TPE [8].
Figure 8.61 Dropped weight

impact failure energy vs.

impact failure energy vs.

impact failure load vs.
Figure 8.64 Dissipation factor

vs. temperature for DuPont
Hytrel® thermoplastic polyester
8.4 TPEs—Polyether Block • Very good dynamic properties

Amide (PEBA) • High strength
• Outstanding impact resistance properties at
PEBAs are plasticizer-free TPEs. The soft segment
low temperature
is the polyether and the hard segment is the polyamide
(nylon). They are easy to process by injection molding • Easy processing
and profile or film extrusion. Often they can be easily • Good resistance to most chemicals
melt-blended with other polymers, and many com-
pounders will provide custom products by doing this. Manufacturers and trade names: Arkema
Their chemistry allows them to achieve a wide range Pebax®, Evonik Vestamid® E.
of physical and mechanical properties by varying the Applications and uses: noiseless gears and func-
monomeric block types and ratios. tional elements of sports shoes, as well as for high-
performance extrusion components like paint spray
• Light weight hoses, vacuum brake booster lines.
• Great flexibility (extensive range) Data for PEBA elastomers are found in
Figure 8.658.73.
• Resiliency

various temperatures for Arkema
Pebax® 2533 SN 01—Shore
hardness 25 TPEs—PEBA resin.


Figure 8.68 Shear modulus vs.

temperature for Arkema Pebax®
TPEs—PEBA resins.
Figure 8.69 Relationship

between tensile modulus and
Shore hardness of Evonik
Corporation Vestamid® PEBA
resins [9].
Figure 8.70 Temperature

dependence of the dynamic
shear modulus of Evonik
Corporation Vestamid® PEBA
resins determined with torsional
vibration analyses according to
ISO 6721-2 [9].

dependence of Shore hardness
using Evonik Corporation
Vestamid® E 40 and Vestamid®
E55 PEBA resins [9].
Figure 8.72 Specific volume vs.

temperature for Arkema Pebax®
3533 SN 01—Shore hardness
35 TPEs—PEBA resin.
0.20
Vestamid® E62-S3
0.18 Vestamid® E55-S3
Vestamid® E47-S3
0.16 Vestamid® E40-S3
0.14
Loss factor (tan δ)

0.12
0.10
0.08
0.06
dependence of the loss factor
tan δ of Evonik Corporation 0.04
Vestamid® PEBA resins 0.02

determined with torsional
0.00
vibration analyses according –200 –150 –100 –50 0 50 100 150
to ISO 6721-2 [9]. Temperature (°C)
References [5] Texin® and Desmopan®: a guide to engineering

properties. Bayer MaterialScience; 2004.
[1] McKeen LW. The effect of temperature and [6] Santoprene® rubber physical properties guide.
other factors on plastics, Plastics Design Advanced Elastomer Systems; 2005.
Library. Waltham, MA: William Andrew; 2008. [7] Hytrel® design guide—module V. DuPont;
[2] Drobny JG. Handbook of thermoplastic elasto- 2000.
mers. Waltham, MA: William Andrew; 2007. [8] Arnitel® TPE general information on proper-
p. 21534. ties. DSM; 2007.
[3] A guide to thermoplastic polyurethanes (TPU). [9] Vestamid® E polyamide 12 elastomers. Evonik
Huntsman Chemical; 2010. Industries; 2012.
[4] Thermoplastic polyurethane elastomers (TPU),
Elastollan® Material Properties. BASF; 2009.

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8 Thermoplastic Elastomers

An elastomer is a polymer with the property of • Tensile strength

The properties of the resin depend on the nature

Figure 8.1 Molecular structure of a TPU.

• Heat/UV stabilizers Elastollan®, Huntsman IROGRAN®, AVALON®,

Figure 8.2 Stress vs. strain at

Figure 8.3 Stress vs. strain at

Figure 8.4 Stress vs. strain at

Figure 8.5 Stress vs. strain at

Figure 8.6 Stress vs. strain at

Figure 8.7 Stress vs. strain

Figure 8.8 Stress vs. strain

Figure 8.9 Stress vs. strain at

Figure 8.10 Stress vs. strain at

Figure 8.11 Stress vs. strain at

Figure 8.12 Stress vs. strain at

Figure 8.13 Stress vs. strain at

Figure 8.14 Stress vs. strain at

Figure 8.15 Stress vs. strain

Figure 8.16 Elastic modulus vs.

Figure 8.17 Elastic modulus vs.

Figure 8.18 Elastic modulus vs.

Figure 8.19 Tear strength vs.

Figure 8.20 Tear strength vs.

Figure 8.21 Tensile strength vs.

Figure 8.22 Tensile strength vs.

Figure 8.23 Tensile set vs.

Figure 8.24 Hardness vs.

Figure 8.25 Coefficient of

8.2 Olefinic Thermoplastic 8.3 Thermoplastic Copolyester

Figure 8.26 Tensile stress vs.

Figure 8.27 Tensile stress vs.

Figure 8.28 Tensile stress vs.

Figure 8.29 Tensile stress vs.

Figure 8.30 Tensile stress vs.

Figure 8.31 Tensile stress vs.

Figure 8.32 Tensile stress vs.

Figure 8.33 Elastic and loss

Figure 8.34 Elastic and loss

Figure 8.35 Elastic and loss

Figure 8.36 Elastic and loss

Figure 8.37 Elastic and loss

Figure 8.38 Elastic and loss

Figure 8.40 Molecular

Figure 8.41 Stress vs. strain at

Figure 8.42 Stress vs. strain

Figure 8.43 Stress vs. strain at

Figure 8.44 Stress vs. strain at

Figure 8.45 Stress vs. strain at

Figure 8.46 Stress vs. strain at

Figure 8.47 Stress vs. strain at

Figure 8.48 Stress vs. strain

Figure 8.49 Stress vs. strain at

Figure 8.50 Stress vs. strain

Figure 8.51 Stress vs. strain

Figure 8.52 Stress vs. strain

Figure 8.53 Stress vs. strain

Figure 8.54 Stress vs. strain

Figure 8.55 Stress vs. strain

Figure 8.56 Typical stress vs.

Figure 8.57 Elastic modulus in

Figure 8.58 Elastic modulus vs.

Figure 8.59 Flexural modulus