FILE 20191029 153218 Mckeen2013

12 Elastomers and Rubbers
12.1 Elastomers and Rubbers “Hard-Phase” - Plastic properties:
An elastomer is a polymer with the property of Processing temperatures

“elasticity”, generally having notably low Young’s Continuous use temperature
modulus and high yield strain compared with other
materials.1 The term is often used interchangeably Tensile strength
with the term rubber. Elastomers are amorphous Tear strength
polymers existing above their glass transition tem- Chemical and fluid resistance
perature so that considerable segmental motion is
possible, so it is expected that they would also be very Adhesion to inks, adhesives and over-molding
permeable. At ambient temperatures, rubbers are thus substrates
relatively soft and deformable. Their primary uses are
for seals, adhesives and molded flexible parts. Elas- “Soft-Phase” - Elastomeric properties:
tomers may be thermosets (requiring vulcanization,
a form of cross-linking) or thermoplastic, called Lower service temperature limits
thermoplastic elastomer (TPE). Hardness
TPEs have two big advantages over the conven- Flexibility
tional thermoset (vulcanized) elastomers. Those
Compression set and tensile set
are ease and speed of processing. Other advantages
of TPEs are recyclability of scrap, lower energy
costs for processing, and the availability of stan- 12.2 Thermoplastic Polyurethane
dard, uniform grades (not generally available in Elastomers
thermosets).
TPEs are molded or extruded on standard plastics- Urethanes are a reaction product of a diisocyanate
processing equipment in considerably shorter cycle and long- and short-chain polyether, polyester, or
times than those required for compression or transfer caprolactone glycols.2 The polyols and the short-
molding of conventional rubbers. They are made by chain diols react with the diisocyanates to form linear
copolymerizing two or more monomers, using either polyurethane molecules. This combination of diiso-
block or graft polymerization techniques. One of the cyanate and short-chain diol produces the rigid or
monomers provides the hard, or crystalline, polymer hard segment. The polyols form the flexible or soft
segment that functions as a thermally stable segment of the final molecule. Figure 12.1 shows the
component; the other monomer develops the soft or molecular structure in schematic form.
amorphous segment, which contributes the elasto- There are three main chemical classes of
meric or rubbery characteristic. thermoplastic polyurethane elastomers (TPU):
Physical and chemical properties can be polyester, polyether and a smaller class known as
controlled by varying the ratio of the monomers polycaprolactone.3
and the length of the hard and soft segments. Block
techniques create long-chain molecules that have Polyester TPUs are compatible with PVC and
various or alternating hard and soft segments. Graft other polar plastics. Offering value in the form
polymerization methods involve attaching one of enhanced properties they are unaffected by
polymer chain to another as a branch. The prop- oils and chemicals, provide excellent abrasion
erties that are affected by each phase can be resistance, offer a good balance of physical prop-
generalized: erties and are perfect for use in polyblends.
The Effect of UV Light and Weather on Plastics and Elastomers, 3e. http://dx.doi.org/10.1016/B978-1-4557-2851-0.00012-8
Copyright Ó 2013 Elsevier Inc. All rights reserved. 299
300 T HE E FFECT OF UV L IGHT AND W EATHER ON P LASTICS AND E LASTOMERS
Figure 12.1 Molecular structure of a thermoplastic polyurethane elastomer.
Polyether TPUs are slightly lower in specific ratio of the starting raw materials. The polyols used
gravity than polyester and polycaprolactone have a significant influence on certain properties of
grades. They offer low-temperature flexibility the thermoplastic polyurethane. Polyether and poly-
and good abrasion and tear resilience. They are ester polyols are both used to produce many
also durable against microbial attack and provide products.
excellent hydrolysis resistancedmaking them The polyester-based TPUs have the following
suitable for applications where water is characteristic features:
a consideration.
Polycaprolactone TPUs have the inherent tough- Good oil/solvent resistance;
ness and resistance of polyester-based TPUs
Good UV resistance;
combined with low-temperature performance and
a relatively high resistance to hydrolysis. They Abrasion resistance;
are an ideal raw material for hydraulic and pneu- Good heat resistance; and
matic seals.
Mechanical properties.
TPUs can also be subdivided into aromatic and
The polyether-based TPUs have the following
aliphatic varieties: characteristic features:
Aromatic TPUs based on isocyanates like
4,40 -methylenediphenyl diisocyanate (MDI) are Fungus resistance;
workhorse products and can be used in applications Low-temperature flexibility;
that require flexibility, strength and toughness.
Excellent hydrolytic stability; and
Aliphatic TPUs based on isocyanates like
Acid/base resistance.
methyldicyclohexyl-diisocyanate (H12 MDI),
1,6-hexamethylene-diisocyanate and isophorone
In addition to the basic components described
diisocyanate are light stable and offer excellent
above, most resin formulations contain additives to
optical clarity. They are commonly employed in
facilitate production and processability. Other addi-
automotive interior and exterior applications and
tives can also be included such as:
as laminating films to bond glass and polycarbonate
together in the glazing industry. They are also used
in projects where attributes like optical clarity, adhe- Demolding agents;
sion and surface protection are required. Flame retardants;
The properties of the resin depend on the nature of Heat/UV stabilizers; and
the raw materials, the reaction conditions and the Plasticizers.
12: E LASTOMERS AND RUBBERS 301
The polyether types are slightly more expensive Manufacturers and trade names: Lubrizol
and have better hydrolytic stability and low- EstaneÒ TPU, Bayer MaterialScience Texin and
temperature flexibility than the polyester types. Desmopan, BASF ElastollanÒ .
Data for TPU elastomers may be found in Tables
12.1e12.4 and Figs 12.2e12.6.
12.2.1 UV Radiation Resistance
Aromatic TPUs can yellow with exposure to
UV radiation. In applications where a TPU will 12.3 Olefinic Thermoplastic
be exposed to sunlight, the best course of action is Elastomers
to employ an aliphatic TPU, which will not yellow
or degrade to the same extent with outdoor Polyolefin thermoplastic elastomer (TPO) materials
exposure. are defined as compounds (mixtures) of various
Table 12.1 Properties after Accelerated QUVÒ Weathering of Huntsman Krystalflex PE399, a High-Performance
Aliphatic Polyether TPU Film3
Exposure Hours
Properties 0 500 1000 1500 2000

Tensile Strength at Break, psi 4000 4000 3900 3500 4300
100% Tensile Modulus, psi 400 380 440 420 370
300% Tensile Modulus, psi 3500 2800 2500 2400 2000
Ultimate Elongation % 300 300 280 280 360
Tear Resistance, pli 140 125 125 125 170
Yellowness Index 042 1.73 2.08 1.86 2.52
Note: (1) Extruded film thickness: 25 5mils. (2) Test methods: ASTM G53; D412; D-624. (3) Light source: UVA 340
bulb, cycle: 4 h UV light at 60 C, 4 h condensation at 45 C, specimen preparation: without glass.
Table 12.2 Properties Retained after Fade-OmeterÒ -Accelerated Weathering for Noveon EstaneÒ 58202 and
EstaneÒ 58300 TPU Elastomer4
Material Grade Estane 58202 Nat 023 Estane 58300 Nat 021
Features Natural Resin, Flame Retardant Natural Resin, Extrusion Grade
Material Characteristics
Shore A Hardness 82 82 82 82 80 80 80 80
Exposure Conditions
Exposure Time (Days) 0.83 2.5 42 8.3 0.83 2.5 4.2 8.3
Properties Retained (%)
100% Modulus 100 100 88.9 88.9 100 107.1 100 114.3
300% Modulus 109.1 104.5 100 100 97.6 107.3 102.4 97.6
Tensile Strength 92.8 89.2 84.3 77.1 101.1 101.1 84.3 77.5
Ultimate Elongation 101.6 101.6 104.8 100 97.2 95.8 95.8 100
Note: (1) Exposure test method: ASTM D1499.
Table 12.3 Properties Retained after Fade-OmeterÒ and QUVÒ -Accelerated Weathering for Noveon EstaneÒ
58,315 Natural TPU Elastomer4
Exposure Conditions
Exposure Apparatus Fade-OmeterÒ QUVÒ
Exposure Time 2.5 42 8.3 12.5 8.3 20.8
(Days)
100% Modulus 90.9 106.1 105.1 104.5 104 105
300% Modulus 95.4 105.1 99.7 100 98.3 94.9
Tensile Strength 100.9 104.9 99.9 91.7 81.6 71
Ultimate Elongation 101.8 101.8 104.4 100 102.6 101.8
Note: (1) Exposure test method: ASTM D149. (2) Shore A hardness: 85.
Table 12.4 Properties Retained after Fade-OmeterÒ -Accelerated Weathering for Noveon EstaneÒ 58,315 and
EstaneÒ 58,863 Natural TPU Elastomer4
Material Grade Estane 58315 Estane 58863 Nat 025
Sample Thickness (mm) 0.38 0.38 0.38
Sample Length (mm) 152 152 152
Sample Width (mm) 12.7 12.7 12.7
Shore A Hardness (Units) 85 85 85 85 85 85 85
Exposure Conditions
Exposure Time (Days) 4.2 8.3 12.5 0.83 2.5 4.2 8.3
100% Modulus 107.2a 115.7a 125.3a 105 110 100 105
a a a
300% Modulus 102.8 105.6 102.1 103.2 106.5 106.5 106.5
a a a
Tensile Strength 92.3 96.4 262 109.1 107.3 100 74.5
a a a
Ultimate Elongation 103.6 101.8 55.4 203.2 206.4 213 190.4
Photovolt Reflectance 100 100 91.3
Note: (1) Exposure test method: ASTM D149. (2) Shore A hardness: 85.
a
Test method: ASTM D882; strain rate: 508 mm/min; test note: jawspace is 50.8 mm, benchmark is 25.4 mm; test direction:
transverse.
polyolefin polymers, semicrystalline thermoplastics (two carbonecarbon double bonds in it). The diene
and amorphous elastomers. Most TPOs are composed monomer leaves a small amount of unsaturation in the
of polypropylene and a copolymer of ethylene and polymer chain that can be used for sulfur cross-linking.
propylene called ethyleneepropylene rubber (EPM).7 Like most TPEs, TPO products are composed of
A common rubber of this type is called EPDM rubber, hard and soft segments. TPO compounds include
which has a small amount of a third monomer, a diene fillers, reinforcements, lubricants, heat stabilizers,
Figure 12.2 Elongation after

QUVÒ exposure of Dow Pellet-
haneÒ 2103-80 AEF TPU
elastomer.5
Figure 12.3 Tensile strength

after QUVÒ exposure of Dow
PellethaneÒ 2103-80 AEF
TPU elastomer.5
Figure 12.4 Yellowness index

after QUVÒ exposure of Dow Pel-
lethaneÒ 2103-80 AEF TPU
elastomer.5
Figure 12.5 Yellowness index

after QUVÒ exposure of BASF
ElastollanÒ 1185A-10 TPU
elastomer.6

after xenon Weather-OmeterÒ
exposure of BASF ElastollanÒ
1185A-10 TPU elastomer.6
antioxidants, UV stabilizers, colorants and processing Applications and uses: Roofing and automo-
aids. They are characterized by high impact strength, tive exterior parts, capping distilled water, dairy
low density and good chemical resistance; they are used products, fruit juices, sports drinks, beer, wine,
when durability and reliability are primary concerns. and food, cosmetics, toiletries, and pharma-
Manufacturers and trade names: Advanced ceutical packaging, sterilized closures, seals and
Elastomer Systems SantopreneÒ , LyondellBasell liners.
Advanced Polyolefins DexflexÒ . Data for TPO are found in Tables 12.5e12.15.
Table 12.5 Retention of Mechanical Properties after Xenon Arc Exposure for Black UV Grades of Advanced
Elastomer Systems SantopreneÔ TPV Olefinic Thermoplastic Elastomer1
Grades 121-67 121-73 121-80
Shore A Hardness 67 73 80
Shore D Hardness
Exposure Time (h) 3000 5000 3000 5000 3000 5000
Tensile Strength 91 83 78 73 81 74
Elongation 98 93 75 72 78 74
100% Modulus 107 110 105 102 102 97
Grades 121-87 123-40 123-50
Shore A Hardness 87
Shore D Hardness 40 50
Exposure Time (h) 3000 5000 3000 5000 3000 5000
Tensile Strength 88 87 94 96 92 95
Elongation 89 84 92 89 93 91
100% Modulus 99 104 99 109 105 107
Note: (1) Xenon arc exposure, SAE J1885.
Table 12.6 Material Properties after Arizona Outdoor Exposure for Black UV Grades of Advanced Elastomer
Systems SantopreneÔ TPV Olefinic Thermoplastic Elastomer8
Grades 121-67 121-73 121-80 121-40 101-64 103-40
Shore A Hardness 67 73 80 40 64
Shore D Hardness 40
Color Change (DE)
6 Months 3.6 4.6 1.6 0.3 5.2 3
12 Months 2.9 3.3 1.1 1.4 3.1 7.3
24 Months 1.4 2 1.4 2.7 1.7 8.3
48 Months 1.2 1.6 1.7 2.8 1.5 11.9
Change in Hardness
Shore A (6 Months) 1 2 3 2
Shore D (6 Months) 5 4
(Continued )
Table 12.6 (Continued)

Grades 121-67 121-73 121-80 121-40 101-64 103-40
Tensile Strength Retained (%)
6 Months 88 85 80 97 75 95
12 Months 83 78 77 94 74 98
24 Months 87 79 76 99 75 92
48 Months 76 77 63 97 75 96
Elongation Retained (%)
6 Months 83 84 80 94 69 95
12 Months 84 81 79 92 72 95
24 Months 86 80 75 98 74 91
48 Months 93 83 77 94 73 94
Note: (1) Arizona outdoor exposure, SAE J1545. (2) Hardness test method ASTM D2240. (3) Tensile strength test method
ASTM D412. (4) Elongation test method ASTM D412.
Table 12.7 Material Properties after Arizona Outdoor Exposure with Spray for Black UV Grades of Advanced
Grades 121-67 121-73 121-80 121-40 101-64 103-40
Shore A Hardness 67 73 80 40 64
Shore D Hardness 40
Color Change (DE)
6 Months 1 4 3 5 1 3
12 Months 1 4 4 5 1 1
24 Months 1 2 5 6 2 2
48 Months 4 5 9 2 7
Change in Hardness
Table 12.7 (Continued )

Grades 121-67 121-73 121-80 121-40 101-64 103-40
Shore A (48 Months) 4 5 2
6 Months 83 58 76 96 74 92
12 Months 89 77 76 97 77 93
24 Months 90 82 79 101 70 97
48 Months 84 80 100 75 99
6 Months 77 75 79 87 72 93
12 Months 88 78 82 85 74 91
24 Months 89 82 83 96 73 97
48 Months 87 87 98 76 97
Note: (1) Arizona outdoor exposure with spray, SAE J1545. (2) Tensile strength test method ASTM D412. (3) Elongation
test method ASTM D412. (4) Hardness test method ASTM D2240.
Table 12.8 Material Properties after Florida Outdoor Exposure for Black UV Grades of Advanced Elastomer
Systems SantopreneÔ TPV Olefinic Thermoplastic Elastomer8
Grades 121-67 121-73 121-80 123-40 101-64 103-40
Shore A Hardness 67 73 80 64
Color Change (DE)
6 Months 5.4 5.6 2.3 1.2 6.3 2.7
12 Months 4.8 5 2.1 0.9 4.4 9.1
24 Months 1.1 1.5 0.4 0.9 1.2 11.2
48 Months 1 1.3 2.4 3.2 1.7 11.7
Change in Hardness
(Continued )
Table 12.8 (Continued)

Grades 121-67 121-73 121-80 123-40 101-64 103-40
6 Months 89 82 84 97 78 98
12 Months 93 85 81 97 80 97
24 Months 82 81 78 98 69 95
48 Months 93 88 87 96 73 98
6 Months 87 86 88 98 78 100
12 Months 92 87 83 99 80 96
24 Months 80 86 84 96 75 97
48 Months 96 93 92 94 78 99
Note: (1) Exposure conditions Florida outdoor exposure. (2) Tensile strength test method ASTM D412. (3) Elongation test
method ASTM D412. (4) Hardness test method ASTM D2240.
Table 12.9 Material Properties after Florida Outdoor Exposure with Spray for Black UV Grades of Advanced
Grades 121-67 121-73 121-80 123-40 101-64 103-40
Color Change (DE)
6 Months 3.2 3.9 1.4 1.5 6.6 4.8
24 Months 3 3.4 6.5 1.3 2.6 8.5
48 Months 1.8 1.6 2.1 2.6 1.43 16.2
Change in Hardness
6 Months 89 77 84 99 79 96
24 Months 85 81 80 101 71 97
48 Months 93 84 87 103 71 65

Grades 121-67 121-73 121-80 123-40 101-64 103-40
6 Months 90 80 89 99 83 98
24 Months 86 82 82 97 69 97
48 Months 93 86 90 100 75 48
Note: (1) Exposure conditions Florida outdoor exposure with spray. (2) Hardness test method ASTM D2240. (3) Tensile
strength test method ASTM D412. (4) Elongation test method ASTM D412.
Table 12.10 Material Properties after EMMA-Accelerated Exposure with Spray for Black UV Grades of Advanced
Grades 121-73 123-40 101-73 103-40
Shore A Hardness 73 73
Color Change (DE)
6 Months 3.4 8.3 5.8 15
12 Months 2.3 8.9 5.5 14.6
24 Months 2.5 8.7 5.2 12.2
Change in Hardness
Shore A (6 Months) 2 8
6 Months 82 94 82 86
12 Months 85 100 84 82
24 Months 95 101 85 58
6 Months 72 80 67 69
12 Months 81 79 67 65
24 Months 52 76 50 6
Note: (1) EMMA-accelerated exposure, SAE J1545. (2) Hardness test method ASTM D2240. (3) Tensile strength test
method ASTM D412. (4) Elongation test method ASTM D412.
Table 12.11 Material Properties after EMMAQUAÒ -Accelerated Exposure for Black UV Grades of Advanced
Grades 121-73 123-40 101-73 103-40
Color Change (DE)
6 Months 3.6 9.5 6.8 15
12 Months 3 8.4 5.5 14.9
24 Months 2.1 7.3 5.2 9.5
Change in Hardness
6 Months 88 98 87 88
12 Months 87 114 90 75
24 Months 55 31 57 11
6 Months 85 82 77 75
12 Months 66 73 62 61
24 Months 68 2 49 1
Note: (1) EMMAQUAÒ -accelerated exposure, SAE J1545. (2) Hardness test method ASTM D2240. (3) Tensile strength
test method ASTM D412. (4) Elongation test method ASTM D412.
Table 12.12 Material Properties after Xenon Arc Exposure for Black UV Grades of Advanced Elastomer Systems
SantopreneÔ TPV Olefinic Thermoplastic Elastomer8
Grades 121-67 121-73 121-80 123-40 101-64 103-40
Color Change (DE)
3000 h 1.5 2 2.3 2.7 7.8 5.3
5000 h 2 2.1 6.5 2.1 2.5 9.5
Change in Hardness
Shore A (3000 h) 3 2 4 1
Shore D (3000 h) 5 3

Grades 121-67 121-73 121-80 123-40 101-64 103-40
Shore A (5000 h) 2 2 5 1
Shore D (5000 h) 7 3
3000 h 91 78 81 94 61 88
5000 h 83 73 74 96 64 84
3000 h 98 75 78 93 57 88
5000 h 93 72 74 90 67 84
Note: (1) Xenon arc exposure, SAE J1885. (2) Hardness test method ASTM D2240. (3) Tensile strength test method ASTM
D412. (4) Elongation test method ASTM D412.
Table 12.13 Material Properties after Xenon Arc SAE J1960 Exterior Automotive Testing for Advanced
Elastomer Systems SantopreneÔ TPV High-Flow Grades Olefinic Thermoplastic Elastomer8
Grades 121-50 M100 121-62 M100 121-75 M100
Shore A Hardness 50 62 75
Property/Exposure Energy
Color Change (DE)
600 kJ/m2 0.7 0.8 0.9
2
1240 kJ/m 1.0 0.4 1.3
2
1800 kJ/m 0.7 1.3 1.2
2
2500 kJ/m 2.4 1.8 1.8
Change in Hardness (Shore A)
600 kJ/m2 2 3 4
2
1240 kJ/m 3 4 5
2
1800 kJ/m 2 5 4
2
2500 kJ/m 2 4 5
Tensile Strength (%Loss)
600 kJ/m2 12 11 8
2
1240 kJ/m 12 16 5
2
1800 kJ/m 14 21 11
2
2500 kJ/m 11 19 7
Elongation Change (%Loss)
600 kJ/m2 14 13 10
2
1240 kJ/m 12 22 7
2
1800 kJ/m 12 26 12
2
2500 kJ/m 7 24 12
Note: (1) Exposure conditions SAE J1960 exterior automotive. (2) Hardness test method ASTM D2240. (3) Tensile strength
test method ASTM D412. (4) Elongation test method ASTM D412. (5) Color test method SAE J1545.
Table 12.14 Material Properties after UV-CON-Accelerated Indoor Exposure of SO.F.TER. SPA ForpreneÒ Olefinic Thermoplastic Elastomer2
ForpreneÒ
312
Grade 630 631 632 633 634 635 636 637 638 639 640 641 642 643
Shore A 55 60 65 70 75 80 85 90
Hardness
Shore D 40 45 50 55 60 65
Hardness
Tensile 95 95 93 94 94 95 95 97 96 96 96 98 98 99
Strength
Elongation 94 93 93 93 92 92 93 93 95 96 96 97 97 98
T HE E FFECT
Change in Physical Characteristics
Shore A 3 3 2 2 2 2 2 2
Hardness
Change
OF
Shore D 1 1 1 0 0 0
UV L IGHT AND W EATHER

Hardness
Change
Note: (1) Exposure apparatus UV-CON. (2) Exposure test method ASTM D4329. (3) UV cycle: 4 h on, 4 h off. (4) Condensation cycle: 4 h on, 4 h off. (5) Exposure
temperature 60 C. (6) Exposure time 7 days.
Table 12.15 UV Resistance after Accelerated UV Light Exposure of SO.F.TER. SPA ForpreneÒ Olefinic Thermoplastic Elastomer9
ForpreneÒ
Grade 630 631 632 633 634 635 636 637 638 639 640 641 642 643
ON
P LASTICS
Shore A 55 60 65 70 75 80 85 90
Hardness
AND
Shore D 40 45 50 55 60 65
Hardness
E LASTOMERS
Results Of Exposure
UV Excellent Excellent
resistance
Note: (1) Exposure apparatus xenon lamp. (2) Exposure temperature 40 C. (3) Exposure time 41.7 days.
These TPEs are generally tougher over a broader

12.4 Thermoplastic Copolyester temperature range than the urethanes described in
Elastomers Section 12.2. Also, they are easier and more
forgiving in processing.
Thermoplastic copolyester elastomers are block
copolymers.10 The chemical structure of one such Excellent abrasion resistance
elastomer is shown in Fig. 12.7. High tensile, compressive and tear strength
Figure 12.7 Molecular structure

of Ticona RiteflexÒ thermo-
plastic copolyester elastomers.
Table 12.16 Material Properties Retained and Surface and Appearance after Florida Outdoor Weathering for
DuPont HytrelÒ Polyester Thermoplastic Elastomer11
DuPont DuPont
Hytrel Hytrel DuPont Hytrel
Material Grade HT-X-3803 HT-X-3803 DuPont Hytrel 4056 4056
Shore D Hardness 63 63 63 63
Material Composition
Carbon Black (wt%) 0 0
SAF Black (Masterbatch 0.5 0.5 0.5 0.5 0.5 1 1 1
Form) (wt%)
Exposure Conditions
Exposure Time (Days) 182 365 182 365 182 365 730 182 365 730
Tensile Strength 70 58 94 97 96 100 80 97 106 99
Elongation at Break 13 0.5 93 75 104 112 102 104 110 104
Surface and Appearance
Surface Appearance Note Good for all Good for all black Good for all black
black specimens with loss of specimens with
specimens gloss at extended loss of gloss at
with loss of exposures, but no extended
gloss at surface crazing exposures, but no
extended surface crazing
exposures,
but no
surface
crazing
Note: (1) Sample thickness 1.9 mm, exposure 45 south.
Good flexibility over a wide range of temperatures terephthalate. The soft segments are long-chain
Good hydrolytic stability polyether glycols.
Weathering Properties: For outdoor applications,
Resistance to solvents and fungus attack HytrelÒ should be protected from UVattack. The most
Selection of a wide range of hardness efficient method is the incorporation of low levels of
carbon black. Where nonblack products are desired,
weather protection is most efficiently obtained by
In these polyester TPEs, the hard polyester incorporation of UV stabilizers alone (natural) or in
segments can crystallize, giving the polymer some of combination with low levels of colored pigments.11
the attributes of semicrystalline thermoplastics, most Manufacturers and trade names: Ticona
particularly better solvent resistance than ordinary RiteflexÒ , DuPontÔ HytrelÒ , Eastman EcdelÒ ,
rubbers, but also better heat resistance. Above the DSM Engineering plastics ArnitelÒ .
melting temperature of the crystalline regions, these Data for thermoplastic polyester elastomers are
TPEs can have low viscosity and can be molded found in Tables 12.16e12.25.
easily in thin sections and complex structures.
Properties of thermoplastic polyester elastomers can 12.5 Butyl Rubber
be fine-tuned over a range by altering the ratio of
hard to soft segments. Butyl is an elastomeric copolymer of isobutylene
In DuPont HytrelÒ polyester TPEs, the resin is with small amounts of isoprene (1e2.5 mol %). Its
a block copolymer. The hard phase is polybutylene structure is shown in Fig. 12.8.
Table 12.17 Material Properties Retained and Surface and Appearance after Florida Outdoor Weathering for
DuPont HytrelÒ 40D Polyester Thermoplastic Elastomer with Carbon Black3
Material Dupont Hytrel Dupont Hytrel
Grade 40D 40D
SAF Black 0.5% 0.5% 0.5% 0.5% 1% 1% 1% 1%
(Masterbatch
Form, wt%)
Exposure Conditions
Exposure Time 182 365 730 1826 182 365 730 1826
(Days)
Tensile 95.5a 100a 79.9a 60.4a 977a 107a 99a 68.2a
Strength
Elongation at 104a 113a 102a 136a 104a 111a 104a 119a
Break
Surface And Appearance
Surface Very good with Very good
Appearance loss of gloss but with loss of
Note no surface gloss but no
crazing surface
crazing
Note: (1) Sample thickness 1.9 mm. (2) Shore D hardness 40. (3) Exposure 45 south.
a
Strain rate: 50.8 mm/min.
Table 12.18 Material Properties Retained after Delaware Outdoor Weathering for DuPont HytrelÒ 5556 Polyester Thermoplastic Elastomer with Carbon
12: E LASTOMERS
Black12
SAF (N110) Black (Masterbatch 0.5 0.5 0.5 0.94 0.94 1.5 1.5 3 3 3
Form, 0.018e0.020 microns, wt%)
AND
Exposure Conditions
Exposure Time (Days) 182 730 1278 182 730 182 730 182 730 1278
RUBBERS
Tensile Strength 42.3 Too brittle to Too brittle to 67.4 18.4 73 33 83.3 45.6 40.6
test test
Elongation at Break 52.1 Too brittle to Too brittle to 80.6 3.5 86.5 49 87.7 61.6 54.8
test test
Note: (1) Compression molded film. (2) Sample thickness 0.25 mm.
Table 12.19 Material Properties Retained and Surface and Appearance after Florida Outdoor Weathering for Varying Thicknesses of DuPont HytrelÒ
6345 Polyester Thermoplastic Elastomer Films with Carbon Black11
Sample Thickness (mm) 0.15 0.13 0.13 0.13 0.13 0.19 0.19 0.19 0.19 0.25 0.25 0.25 0.25
Carbon Black (Masterbatch 0.80 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9
Form, wt%)
Exposure Conditions
Exposure Time (Days) 182 182 365 730 1096 182 365 730 1096 182 365 730 1096
Tensile Strength 21 53 71 39 34 56 64 51 36 72 73 67 62
Elongation at Break 6.2 108 104 40 26 96 100 56 36 91 100 91 87
Surface And Appearance
Surface Appearance Note Good for all black specimens with loss of gloss at extended exposures, but no surface crazing
315
Note: (1) Extruded film, black color. (2) Shore hardness 63. (3) Hytrel 10MS (polycarbodiimide moisture stabilizer, 1.9 wt%).
Table 12.20 Material Properties Retained after Carbon Arc-Accelerated Weathering for DuPont HytrelÒ 40D
Polyester Thermoplastic Elastomer12
SAF Black (Masterbatch Form, wt%) 0.5 0.5 1 1
Exposure Conditions
Exposure Time (Days) 20.8 41.7 20.8 41.7
Tensile Strength 97.8a 84.3a 104a 104a
Elongation at Break 113a 109a 111a 106a
Note: (1) Product form injection molded slab. (2) Shore D hardness 40. (3) Sample thickness 1.9 mm.
a
Strain rate: 50.8 mm/min.
Table 12.21 Material Properties Retained after Carbon Arc-Accelerated Weathering for DuPont HytrelÒ 5556
Polyester Thermoplastic Elastomer with Varying Levels of Carbon Black12
SAF (N110) Black (Masterbatch 0.5 0.5 0.94 0.94 1.5 1.5 1.5 3 3 3
form, 0.018e0.020 microns, wt%)
Exposure Conditions
Exposure Time (Days) 42 10.9 4.2 10.9 42 12.5 25 4.2 12.5 25
Tensile Strength 35 26 69.5 28.5 66.4 38 27 82.8 65.7 46
Elongation at Break 42.5 14.5 90.3 18.1 97 54 5.4 94.5 822 63
Note: (1) Compression molding film. (2) Sample thickness 0.25 mm.
Table 12.22 Material Properties Retained and Surface and Appearance after Carbon Arc-Accelerated Weathering
for DuPont Hytrel HT-X-3803 and 4056 Polyester Thermoplastic Elastomers with Varying Levels of Carbon Black11
HytrelÒ
Material Grade HT-X-3803 Hytrel HT-X-3803 Hytrel 4056 Hytrel 4056
Carbon Black (wt%) 0% 0%
SAF Black (Masterbatch 0.5 0.5 0.5 0.5 0.5 0.5 1 1
Form, wt%)
Exposure Conditions
Exposure Time (Days) 20.8 41.7 20.8 41.7 83.3 166.7 20.8 41.7 20.8 41.7
Tensile Strength 73 30 96 99 100 86 se 84 104 103
Elongation at Break 2.6 2.6 88 81 93 96 112 108 110 106
Surface Appearance Good for all black specimens Good for all black specimens
Note with loss of gloss at extended with loss of gloss at extended
exposures, but no surface exposures, but no surface
crazing crazing
Note: (1) Injection-molded slab. (2) Shore D hardness 63. (3) Sample thickness 1.9 mm.
Table 12.23 HytrelÒ 20UV Extends Serviceability of HytrelÒ During Weather-OmeterÒ Exposure13
Composition (Parts)
Parts HytrelÒ 5556 100 100 100
Ò
Parts Hytrel 20UV e 2.5 4
a
Letdown Ratio e 40:1 25:1
b
Original
Tensile Strength at Break, MPac 50.8 53.4 41.6
c
Elongation at Break , % 720 750 730
Exposure Time, h 48 300 300
Tensile Strength at Break, MPa 16.8 19.8
Elongation at Break, % 410 460
Exposure Time, h e 658 1000
Tensile Strength at Break, MPa e 11.2 10.8
Elongation at Break, % e 30 50
a
Pellets dried, extrusion blended, pelletized and dried again. Compression molded film, 0.275 mm (0.011 in.) thick.cTensile
b
and elongation measurements were carried out using a head speed of 50 mm/min (2 in./min).
Table 12.24 Effect of Level of Carbon Black on 2.5 mm Films of HytrelÒ 5556 after Weatheringa 13
HytrelÒ 5556
Composition
HytrelÒ 5556:HytrelÒ 40CB e 16:1 7:1
Total Carbon Black, % 0 1.47 3.13
Originalb
Tensile Strength at Break, MPa 31.4 36.4 38.8
Elongation at Break, % 430 535 535
Exposure Time, h 50 50 50
Exposure Time, h 150 150
a Ò Ò
Pellets of Hytrel 40CB and Hytrel 5556 were tumble blended and extruder melt blended prior to film preparation; film
was made by compression molding; Weather-OmeterÒ carbon arc.bProperties determined at a crosshead speed of 50.8 mm/
min (2 in./min).
Table 12.25 Effect of Level of Carbon Black on 2.5 mm Films of HytrelÒ Exposed in Floridaa
13
HytrelÒ 5556
Composition
(HytrelÒ 5556/HytrelÒ 40CB) d 16:1 7:1
Total Carbon Black, % 0 1.47 3.13
b
Original
Tensile Strength at Break, 31.4 36.4 38.8
MPa
Elongation at Break, % 430 535 535
Exposure Time, Month 3 3 3
Tensile Strength at Break, 26.0 30.4
MPa
Exposure Time, Month 6 6
MPa
Exposure Time, Month 9 9
MPa
a
Pellets of HytrelÒ 40CB and HytrelÒ 5556 were tumble blended and extruder melt blended prior
to film preparation; film was made by compression molding; outdoor aging in Florida, 5 south.
b
Properties determined at a crosshead speed of 50.8 mm/min (2 in./min).
Manufacturers and trade names: Lanxess Butyl, pharmaceutical closures, roof membranes, body
ExxonMobil Chemical, (Polysar is obsolete). mounts and tank linings.
Applications and uses: major application area is Data for butyl rubber are shown in Figs
the tire industry, mainly used for inner tubes and 12.9e12.13.
tire-curing bladders. Nontire applications include
Figure 12.8 Chemical structure of butyl rubber.

Figure 12.9 Micro-IRHD hardness

change vs. QUVÒ exposure of two
Lanxess butyl rubber compounds.2
Note: Test pieces were exposed in
QUVÒ fluorescent tube apparatus
using UVA 340A lamps with a black
panel temperature of 45 C and
a cycle of 4 h condensation and
4 h drying (3 cycles per day).

change vs. QUVÒ exposure of
two Lanxess butyl rubber
compounds.2
Note: Test pieces were
exposed in QUVÒ fluorescent
tube apparatus using UVA
340A lamps with a black panel
temperature of 45 C and
a cycle of 4 h condensation
and 4 h drying (3 cycles per
day).
Figure 12.11 Modulus at 100%

vs. QUVÒ exposure of two Lanx-
ess butyl rubber compounds.2
Note: Test pieces were exposed
in QUVÒ fluorescent tube appa-
ratus using UVA 340A lamps
with a black panel temperature
of 45 C and a cycle of 4 h
condensation and 4 h drying (3
cycles per day).
Figure 12.12 Modulus at 300%

vs. QUVÒ exposure of two Lanx-
ess butyl rubber compounds.2
using UVA 340A lamps with
a black panel temperature of
45 C and a cycle of 4 h conden-
sation and 4 h drying (3 cycles
per day).
Figure 12.13 Elongation at

break vs. QUVÒ exposure of
two Lanxess butyl rubber
compounds.2
cycles per day).
12.6 Chlorobutyl Rubber Polychloroprene was developed in 1930 by

(Polychloroprene) DupontÔ and is best known under the name
neoprene. The polymer is made from chloroprene
Chlorobutyl rubber or polychloroprene is elasto- and its structure is given in Fig. 12.14. Its CAS
meric isobutyleneeisoprene copolymer (haloge- number is 9010-98-4. The polymer is often modified
nated butyl) containing reactive chlorine. to permit some degree of polymerization. Sulfur is
Figure 12.14 Polymerization of chloroprene.

a common modifier and the compounds are often other polymers that have better resistance to these
called vulcanizates. same elements. Polychloroprene’s advantage is its
DuPont Elastomer Neoprene is available in many ability to combine these properties moderately into
varieties including nonsulfur-modified “W” and the one all-purpose polymer.
more common sulfur-modified “GN” types. Poly- Manufacturers and trade names: DuPontÔ
chloroprene is known for its resistance to oil, gaso- Performance Elastomers Neoprene (discontinued),
line, sunlight, ozone and oxidation though there are ExxonÔ Chlorobutyl, Lanxess BayprenÒ .
Table 12.26 Mechanical Properties Retained and Color Change after Arizona Outdoor Weathering, Accelerated
Outdoor Weathering by EMMAQUAÒ and Xenon Arc-Accelerated Outdoor Weathering for Black DuPont Neo-
preneÒ W Neoprene Rubber14
Exposure Conditions
Exposure Type Outdoor Accelerated outdoor Accelerated weathering
weathering weathering
Exposure Location Arizona Arizona
Exposure Apparatus EMMAQUA Xenon arc Weather-
OmeterÒ
Exposure Time 365 365 216
(Days)
Exposure Note Water spray added
Tensile Strength 79.5 60.1 70.4
Elongation 77.9 28.2 15.3
DE Color Change 7.7 9.5 92.
Table 12.27 Material Properties Retained, Hardness Change, and Color Change after Arizona and Florida
Outdoor Weathering for Black DuPont NeopreneÒ W Neoprene Rubber15
Exposure Conditions
Exposure Location Arizona Arizona Arizona Arizona Florida
Exposure Time (Days) 183 365 730 1461 730
Tensile Strength 71a
Elongation 70a
Hardness Change (Units) 4b
DE Color Change (Samples Washed) 9.6 10.18 3.2 11.0
Note: (1) Black color, commercially available grade.
a
Test method: ASTM D412.
b
Applications and uses: Chlorobutyl’s major chemical resistance and pharmaceutical closures and
application area is the tire industry. It is mainly used adhesives, gloves, adhesives, binders, coatings, dip-
in tubeless tire inner liners, sidewalls and inner tubes. ped goods, elasticized asphalt and concrete.
Other applications include conveyor belts requiring Data for polychloroprene rubber are found in
high-temperature resistance, tank linings for Tables 12.26 and 12.27 and Figs 12.15e12.19.
Figure 12.15 Micro-IRHD hardness change vs. QUVÒ exposure of several DuPont polychloroprene
compounds.16
Note: Test pieces were exposed in QUVÒ fluorescent tube apparatus using UVA 340A lamps with a black panel
temperature of 45 C and a cycle of 4 h condensation and 4 h drying (3 cycles per day).
Figure 12.16 Tensile strength change vs. QUVÒ exposure of several DuPont polychloroprene compounds.16
temperature of 45 C and a cycle of 4 h condensation and 4 h drying (3 cycles per day).
Figure 12.17 Elongation at break

vs. QUVÒ exposure of several
DuPont polychloroprene
compounds.16
cycles per day).
Figure 12.18 Modulus at 100% vs.

QUVÒ exposure of several DuPont
polychloroprene compounds.16
4 h drying (3 cycles per day).
Figure 12.19 Modulus at

300% vs. QUVÒ exposure of
several DuPont polychloro-
prene compounds.16
and 4 h drying (3 cycles per
day).
12.7 EthyleneePropylene this classification there are two basic kinds of eth-
Rubbers (EPM, EPDM) yleneepropylene rubber:
There are two basic types of ethyleneepropylene EPM, the copolymer of ethylene and propylene.
rubber available. ASTM classifies this synthetic EPDM, the terpolymer of ethylene, propylene and
elastomer as “EPM”, meaning that it has a saturated a nonconjugated diene with residual unsaturation
polymer chain of the polymethylene type. Within in the side chain.
Table 12.28 Mechanical Properties Retained after Outdoor and Accelerated Outdoor Weathering of White,
Randomly Selected, Unstrained EPDM Terpolymer17
Exposure Conditions
Exposure Type Accelerated outdoor weathering Outdoor weathering
Exposure Location New River, Arizona Homestead, Florida
Exposure Apparatus EMMA, Fresnel concentrator with 10 mirrors
Exposure Note Water spray at night only; specimens 45 angle south; specimens
mounted on kiln dried white oak boards; mounted on kiln-dried white oak;
unstrained specimens unstrained specimens
Exposure Time (Days) 19 44 61 132 182 365 730
2
Total Irradiation (MJ/m ) 4000 8000 12,000 20,000 4290 6276 12,505
2
UV Irradiation (MJ/m ) 110 242 394 462 144 282 562
Tensile Strength 96.3 96.3 88.8 88.8 102 81.4 76.2
Elongation at Break 104 104 98 96 104 106 98
Note: (1) White color; randomly selected samples from different manufacturers.
Table 12.29 Mechanical Properties Retained after Outdoor and Accelerated Outdoor Weathering of Black,
Weather Resistant, Unstrained EPDM Terpolymer17
Exposure Conditions
mounted on kiln-dried white oak boards; mounted on kiln-dried white oak
unstrained specimens boards; unstrained specimens
2
2
Tensile Strength 106.5a 107.1a 109.5a 106.9a 103.7a 106.5a 109.5a
Elongation at Break 100a 100a 100a 86.7a 90a 96.6a 82.2a
Note: (1) Known formulation with a 20-year history of proven weather performance.
a
Manufacturers and trade names: ExxonÔ Data for EPDM rubbers are found in Tables
VistalonÔ, Lanxess BunaÒ EP. 12.28e12.48 and Figs 12.20e12.27.
Applications and uses: Impact modification,
hose, tubing, weather strips, insulation, jacketing, 12.8 Epichlorohydrin Rubber
single-ply roofing sheet, window gaskets, and
sound deadening, solar pool panels and face Epichlorohydrin rubbers (CO, ECO) include
respirators. homopolymer of epichlorohydrin and a copolymer
Table 12.30 Mechanical Properties Retained after Outdoor and Accelerated Outdoor Weathering of Black,
Randomly Selected, Unstrained EPDM Terpolymer17
Exposure Conditions
unstrained specimens boards; unstrained specimens
2
2
Tensile Strength 96 92.7 97 97 97.8 992 100.3
Elongation at Break 105.8 962 92.3 83.7 98.1 92.3 82.7
Note: (1) Randomly selected samples from different manufacturers.
Table 12.31 Mechanical Properties Retained and Color Change after Outdoor Weathering, Accelerated Outdoor
Weathering by EMMAQUA, and Accelerated Weathering with a Xenon Arc Weather-OmeterÒ for Black Exxon
VistalonÔ EPDM Terpolymer14
Exposure Conditions
Exposure Type Outdoor weathering Accelerated outdoor Accelerated weathering
weathering
Exposure Location Arizona Arizona
Exposure Apparatus EMMAquaÒ Xenon arc Weather-
OmeterÒ
Exposure Time (Days) 365 365 216
Exposure Note Water spray added
Tensile Strength 98.2 90.9 87.9
Elongation 66.8 34.4 20.8
DE Color Change 6.5 10.5 8.6
Table 12.32 Material Properties Retained and Color Change after Arizona Outdoor Weathering with and Without
Water Spray Added for Black Exxon VistalonÔ 5600 EPDM Terpolymer4
Material Composition (phr)

VistaIon 5600 100 100 100 100 100 100 100 100
DPTTS 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
Flectol H (Monsanto) 1 1 1 1 1 1 1 1
Stearic Acid 2 2 2 2 2 2 2 2
TDEDC 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
Thiotax (Monsanto) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Thiurad (Monsanto) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
Naphthenic Process Oil 100 100 100 100 100 100 100 100
Sulfur 2 2 2 2 2 2 2 2
Zinc Oxide 5 5 5 5 5 5 5 5
N-550 Carbon Black 100 100 100 100 100 100 100 100
N-774 Black 100 100 100 100 100 100 100 100
Exposure Conditions
Exposure Note 5 angle 5 angle; with water spray (distilled water
sprayed for 4 h proceeding
Sunrise and Then 20 Times
during the Day in 15 s
Bursts
Exposure Time (Days) 182 365 730 1461 182 365 730 1461
Tensile Strength, ASTM 97 100 111 99 94 98 109 87
D412
Elongation, ASTM D412 65 67 48 47 60 67 49 52
Hardness Change (Units) 6 6 11 11 6 6 11 14
ASTM D2240
DE Color Change 7 9.9 5.4 10.5 7.5 6.5 9.2 8.7
Note: (1) Outdoor weathering in Phoenix Arizona, test lab DSET Laboratories. (2) Shore A hardness 76. (3) Sample
thickness (mm) 0.76.
Table 12.33 Mechanical Properties Retained and Color Change after Arizona Outdoor Weathering of Black
Exxon VistalonÔ 5600 EPDM Terpolymer5
VistalonÔ 5600 100 100 100 100
DPTTS 0.8 0.8 0.8 0.8
Flectol H (Monsanto) 1 1 1 1

Stearic Acid 2 2 2 2
TDEDC 0.8 0.8 0.8 0.8
Thiotax (Monsanto) 1.5 1.5 1.5 1.5
Thiurad (Monsanto) 0.8 0.8 0.8 0.8
Naphthenic Process Oil 100 100 100 100
Sulfur 2 2 2 2
Zinc Oxide 5 5 5 5
N-550 Carbon Black 100 100 100 100
N-774 Black 100 100 100 100
Exposure Conditions
Exposure Time (Days) 182 365 182 365
Exposure Note 5 south latitude 5 south latitude; water spray added
100% Modulus 132 134 138 134
Tensile Strength 98 100 95 99
Elongation at Break 66 68 60 66
DE Color Change, ASTM 7 10.1 7.4 6.5
D412
Note: (1) Outdoor weathering in Phoenix Arizona, test lab DSET Laboratories. (2) Shore A hardness 76. (3) Sample
thickness (mm) 0.76.
Table 12.34 Mechanical Properties Retained after Florida Outdoor Weathering and Accelerated Outdoor
Weathering by EMMA for Black, Weather Resistant, Strained EPDM Terpolymer17
Exposure Conditions
Exposure Apparatus EMMA, Fresnel concentrator with 10
mirrors
specimens strained at 50% boards; specimens strained at
50%
2
(Continued )

Exposure Conditions
UV Irradiation (MJ/m2) 110 242 394 462 144 282 562
Tensile Strength, ASTM 117.5 112.6 125.5 120.6 116.3 116.9 104
D412
Elongation at Break, ASTM 91.1 70 67.8 722 72.2 65.6 46.7
D412
Table 12.35 Material Properties Retained and Color Change after Florida Outdoor Weathering with and Without
Water Spray Added for Black Exxon VistalonÔ 5600 EPDM Terpolymer18

VistalonÔ 5600 100 100 100 100 100 100 100 100
OPUS 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
Stearic Acid 2 2 2 2 2 2 2 2
TDEDC 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
Sulfur 2 2 2 2 2 2 2 2
Zinc Oxide 5 5 5 5 5 5 5 5
N-550 Carbon Black 100 100 100 100 100 100 100 100
N-774 Black 100 100 100 100 100 100 100 100
Exposure Conditions
Exposure Note 5 angle 5 angle; with water spray (distilled water sprayed
for 4 h preceding sunrise and then 20 times during
the day in 15 s bursts)
Tensile Strength, ASTM 90 94 110 97 109 95
D412
Elongation, ASTM D412 720 71 62 77 67 61
Hardness Change (Units), 1 1 9 13 6 8
ASTM D2240
DE Color Change, FMC-2 5.3 5.8 4.5
Hunterlab; Test Method:
SAE J1545
Note: (1) Outdoor weathering in Homestead, FL, test lab DSET Laboratories. (2) Shore A hardness 76. (3) Sample thickness
(mm) 0.76.
Table 12.36 Material Properties Retained and Surface and Appearance after Florida Outdoor Weathering of
Black, Medium Gloss Weatherable EPDM Terpolymer6
Exposure Conditions
Exposure Note Direct exposure; 5 south Under glass exposure; 5 south
Exposure Time (Days) 730 730
100% Modulus 115 132
Tensile Strength 101 103
Elongation at Break 86 67
Shore A Hardness Change 8 13
(Units)
Gloss at 60 Retained 57 14.3
(%);Gardner Gloss; Test
Method: ASTM D3134
DE Color 0.8 0.5
Visual Observation Slight chancing Severe mildew
(As Weathered)
Visual Observation (Washed) No chalking, no cracks Spotted, no cracks
Note: (1) Outdoor weathering in FL. (2) Shore A hardness 65. (3) Sample thickness (mm) 32.
Weathering by EMMA for Black, Randomly Selected, Strained EPDM Terpolymer17
Exposure Conditions
Exposure Apparatus EMMA, Fresnel concentrator with 10 mirrors Outdoor weathering
specimens strained 0 50% boards; specimens strained 0 50%
2
2
Tensile Strength 110 107.8 117.5 115.4 112.1 110.5 105.7
Elongation at Break 88.5 81.7 76.9 75 83.7 76 59.6
Weathering by EMMA for White, Randomly Selected, Strained EPDM Terpolymer17
Exposure Conditions
specimens strained at 50% boards; specimens strained at
50%
Total Irradiation (MJ/m2) 4000 8000 12,000 20,000 4290 6276 12,505
UV Irradiation (MJ/m2) 110 242 394 462 144 282 562
Tensile Strength 112.9 107 108.9 105.4 121.8 102 92.3
Elongation at Break 92 90 82 73 82 80 68
with ethylene oxide. There is also a terpolymer of for the homopolymer and ECO is the ISO desig-
epichlorohydrin, ethylene oxide and a monomer to nation for the ethylene oxide copolymer. Epichlo-
introduce a carbon double bond to the chain that rohydrin terpolymer is the designation for the
functions as a cure site. CO is the ISO designation terpolymer (usually allyl glycidyl ether). The
Table 12.39 Material Properties Retained and Color Change after Florida Outdoor Weathering of Black EPDM
Terpolymer15
Exposure Conditions
Exposure Location Arizona Arizona Arizona Arizona Florida
Exposure Time (Days) 183 365 730 1461 730
Tensile Strength, ASTM 148
D412
Elongation, ASTM D412 44
Hardness Change (Units), 24
ASTM D2240
DE Color Change 7.02 9.9 5.4 10.53
(Samples Washed)
Table 12.40 Material Properties Retained and Color Change after Accelerated Outdoor Weathering by EMMA
and EMMAQUAÒ and Accelerated Weathering in a Xenon Arc Weather-OmeterÒ for Black Exxon VistalonÔ 5600
EPDM Terpolymer18

VistalonÔ 5600 100 100 100 100 100 100 100 100
DPTTS 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
Stearic Acid 2 2 2 2 2 2 2 2
TDEDC 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
Sulfur 2 2 2 2 2 2 2 2
Zinc Oxide 5 5 5 5 5 5 5 5
N-550 Carbon Black 100 100 100 100 100 100 100 100
N-774 Black 100 100 100 100 100 100 100 100
Exposure Conditions
Exposure Type Accelerated weathering Accelerated outdoor Accelerated outdoor
weathering weathering
Exposure Apparatus Xenon arc Weather-OmeterÒ EMMA EMMAQUA
Exposure Note 89 C; 3.8 h in light at 50%
Relative Humidity (RH), 1 h in
dark at 100% RH; test method:
SAE J1885; GM TM30-2
2
Energy at 340 nm (kJ/m ) 4703 7838
Energy 01 <380 nm 403 672
(MJ/m2)
Tensile Strength, ASTM 85 88 93 89 83 91 91 69
D412
Elongation, ASTM D412 23 21 38 28 17 47 34 14
Hardness Change (Units), 16 16 1 12 19 15 13 22
ASTM D2240
DE Color Change, FMC-2 5.3 8.6 74 9.71 9.84 7.6 10.5 8.74
Hunterlab; Test Method:
SAE J1545
Note: (1) Shore A hardness 76. (2) Sample thickness (mm) 0.76.
Table 12.41 Mechanical Properties Retained and Color Change after Arizona Accelerated Outdoor Weathering
by EMMA and EMMAQUAÒ for Black Exxon VistalonÔ 5600 EPDM Terpolymer19

VistalonÔ 5600 100 100 100 100
DPTTS 0.8 0.8 0.8 0.8
Flectol H 1 1 1 1
(Monsanto)
Stearic Acid 2 2 2 2
TDEDC 0.8 0.8 0.8 0.8
Thiotax 1.5 1.5 1.5 1.5
(Monsanto)
Thiurad 0.8 0.8 0.8 0.8
(Monsanto)
Naphthenic 100 100 100 100
Process Oil
Sulfur 2 2 2 2
Zinc Oxide 5 5 5 5
N-550 Carbon 100 100 100 100
Black
N-774 Black 100 100 100 100
Exposure Conditions
Exposure EMMA EMMA EMMAquaÒ EMMAquaÒ
Apparatus
Exposure Time 182 365 182 365
(Days)
Exposure Note Correlates to Correlates to Correlates to Correlates to
approximately 2.5 approximately 5 approximately 2.5 approximately 5
years of actual years of actual years of actual years of actual
Florida aging Florida aging Florida aging Florida aging
100% Modulus 156
Tensile Strength 95 92 92 92
Elongation at 38 29 47 35
Break
DE Color 5.3 8.6 74 9.71
Change
Note: (1) Shore A hardness 76. (2) Sample thickness (mm) 0.76.
12: E LASTOMERS
Table 12.42 Mechanical Properties Retained after Accelerated Weathering in a UV-CON and a Xenon Arc Weather-Ometer for White, Randomly
Selected, Strained EPDM Terpolymer17
Exposure Conditions
Exposure Xenon arc Weather-OmeterÒ UV-CON
Apparatus
AND
Exposure Filter type: borosilicate inner and outer, spray nozzle: F-80; Lamp type: fluorescent UVB-313 (UVB-B)
Apparatus Note exposure: 0.35 W/m2 0340 nm
RUBBERS
Exposure Cycle 690 min light, 30 min light and deionized water spray 20 h UV at 80 C, 4 h condensation at 50 C
Note
Exposure Test ASTM 026 ASTM G53
Method
Exposure Specimens mounted on exterior grade plywood covered with Specimens mounted on exterior grade plywood covered with
aluminum foil; specimen rotation every 250 h; specimens aluminum foil; specimens strained at 50%
strained at 50%
Exposure 45e55 45e55 45e55 45e55 45e55
Relative
Humidity (%)
Exposure 77e83 77e83 77e83 77e83 77e83
Temperature
( C, Black
Panel)
Exposure Time 20.8 41.7 83.3 125 166.6 20.8 41.7 83.3 125 166.6
(Days)
Total Irradiation 711 1422 2844 4266 5688 53 106 213 319 425
(MJ/m2) (calculated) (calculated)
UV Irradiation 72 144 288 432 576 52 103 206 310 413
Tensile Strength 105.4 102 96.9 10.9 (sample 105.4 86.5 85.4 64.8 21.8
(sample broke) (sample (sample
broke) broke) broke)
Elongation at 91 80 79 32 (sample (sample 99 87 90 48 (sample 16 (sample
Break broke) broke) broke) broke)
333
334
Table 12.43 Mechanical Properties Retained after Accelerated Weathering in a UV-CON and a Xenon Arc Weather-OmeterÒ for White, Randomly
Selected, Unstrained EPDM Terpolymer17
Exposure Conditions
Exposure Apparatus Xenon arc Weather-OmeterÒ UV-CON
Exposure Apparatus Filter type: borosilicate inner and outer; spray nozzle: Lamp type: fluorescent UVB-313 (UVB-8)
Note F-80; exposure: 0.35 W/m2 at 340 nm
Exposure Cycle Note 690 min light, 30 min light and deionized water spray 20 h UV at 80 C, 4 h condensation at 50 C
T HE E FFECT
Exposure Test Method ASTM G26 ASTM G53
Exposure Note Specimens mounted on exterior grade plywood covered Specimens mounted on exterior grade plywood covered with
with aluminum foil; specimen rotation every 250 h; aluminum foil; unstrained specimens
unstrained specimens
OF
Exposure Relative 45e55 45e55 45e55 45e55 45e55

Humidity (%)
Exposure Temperature 77e3 77e83 77e83 77e83 77e83
( C, Black Panel)
Exposure Time (Days) 20.8 41.7 83.3 125 166.6 20.8 41.7 83.3 125 166.6
Total Irradiation 711 1422 2844 4266 5688 53 106 213 319 425
UV Irradiation 72 144 288 432 576 52 103 206 310 413
ON
P LASTICS
Tensile Strength 91.7 86.5 76.8 64.2 29.8 92.8 84.8 86.5 48.1 31 (wide spread in test
results)
Elongation at Break 101 106 100 102 86 100 88 98 62 28 (wide spread in test
AND
results)
E LASTOMERS
12: E LASTOMERS
Table 12.44 Mechanical Properties Retained after Accelerated Weathering in a UV-CON and a Xenon Arc Weather-OmeterÒ for Black, Weather
Resistant, Strained EPDM Terpolymer17
AND
Exposure Conditions
RUBBERS
Exposure Apparatus Note Filter type: borosilicate inner and outer, spray nozzle: F-80; Lamp type: fluorescent UVB-313 (UVB-B)
exposure: 0.35 Wm, at 340 nm
Exposure Note Specimens mounted on exterior grade plywood covered with Specimens mounted on exterior grade plywood
aluminum foil; specimen rotation every 250 h; specimens covered with aluminum foil; specimens strained ay
strained at 50% 50%
Humidity (%)
( C, Black Panel)
Exposure Time (days) 20.8 41.7 83.3 125 166.6 20.8 41.7 83.3 125 166.6
2
Total Irradiation (MJ/m ) 711 (calculated) 1422 2844 4266 5688 53 (calculated) 106 213 319 425
2
UV Irradiation (MJ/m ) 72 (calculated) 144 288 432 576 52 (calculated) 103 206 310 413
Tensile Strength, ASTM 133.2 136 128 94.8 94.8 120 114.5 118.2 112 108.3
D412
Elongation at Break, ASTM 77.8 67.8 46.7 36.7 37.8 88.9 72.2 66.7 36.7 37.8
D412
335
336
Table 12.45 Mechanical Properties Retained after Accelerated Weathering in a UV-CON and a Xenon Arc Weather-OmeterÒ for Black, Randomly
Selected, Unstrained EPDM Terpolymer17
Exposure Conditions
Exposure Apparatus Note Filter type: borosilicate inner and outer; spray nozzle: F-80; Lamp type: fluorescent UVB-313 (UVB-B)
exposure: 0.35 W/m2 at 340 nm
T HE E FFECT
Exposure Note Specimen rotation every 250 h; unstrained specimens Unstrained specimens
OF
Exposure Relative 45e55 45e55 45.55 45e55 45e55

Humidity (%)
( C) (Black Panel Temp.)
2
(calculated)
UV Irradiation (MJ/m2) 72 (calculated) 144 288 432 576 52 (calculated) 103 206 310 413
ON
P LASTICS
Tensile Strength 97 99.2 97 90.1 78.7 952 99.7 105.7 90 79.8
Elongation at Break 83.7 76 66.3 58.7 62.5 74 80.8 69.2 55.8 48
Note: (1) Randomly selected samples from different manufacturer; specimens mounted on exterior grade plywood covered with aluminum foil.
AND
E LASTOMERS
Table 12.46 Mechanical Properties Retained and Color Change after Accelerated Weathering in a Xenon Arc
Weather-OmeterÒ of Black Exxon VistalonÔ 5600 EPDM Terpolymer19
Exposure Conditions

Exposure Temperature ( C) 89 89
DE Color Change 5.3a 8.8a
Note: (1) Sample thickness (mm) 0.76. (2) Shore A hardness 76. (3) Material composition (phr): VistalonÔ 5600 ¼ 100,
DPTTS ¼ 0.8, Flectol H (Monsanto) ¼ 1, stearic acid ¼ 2, TDEDC ¼ 0.8, Thiotax (Monsanto) ¼ 1.5, Thiurad
(Monsanto) ¼ 0.8, naphthenic process oil ¼ 100, sulfur ¼ 2, zinc oxide ¼ 5, N-550 carbon black ¼ 100, N-774 black ¼ 100.
(4) Exposure test method: GM TM30. (5) Exposure Note: 3.8 h in light at 50% RH, 1 h in dark at 100% RH.
a
Test apparatus: Hunter colorimeter; test note: samples washed with water.
monomers and polymer structures are given in Figs The fluorine content is an important parameter of
12.28e12.30. each FKM and is frequently reported in fact sheets.
The ratios of the monomers are tailored to provide Most common grades have fluorine content that
the desired properties. The epichlorohydrin monomer varies between 66% and 70%. Generally more fluo-
provides heat and ozone resistance, fuel and oil rine means higher chemical resistance.
resistance and gas permeation resistance. The There are a number of types of FKMs.
ethylene monomer lowers the glass transition
temperature, reduces heat resistance and imparts “A” type: FKM-A is the most widely used polymer
static dissipative properties. The unsaturated mono- in industry today, and it is the most cost-effective
mer introduces a site for sulfur and peroxide curing. polymer in relationship to performance. It has a fluo-
Manufacturers and trade names: Hercules, Inc. rine level around 66%. This elastomer was designed
Herclor, B.F. Goodrich Co. and Zeon Chemicals, in the late 1950s for the space program and today is
HydrinÒ . widely used as a general purpose FKM offering
Applications and uses: Fuel hoses/liners (cells), excellent fluid resistance to automotive fuels and
air ducts, emissions tubing, electrostatic dissipative lubricants, as well as elevated service temperatures.
rolls, low-temperature fuel handling curb hose,
“B” type: FKM-B is a terpolymer with an
diaphragms, gaskets/O-rings, vibration dampers,
increased fluorine (68e69%) content is widely
dust boots, closed-cell sponge and fabric coatings/
used throughout the Chemical Processing and
belting.
Power Generation Industries, “B” types are speci-
Data for ECO are found in Figs 12.31e12.34.
fied for gaskets sealing mineral acids such as
sulfuric acids and other aggressive chemicals
12.9 Fluoroelastomers that are hauled by rail, and bulk tankers. “B” types
A fluoroelastomer (FKM) is a special-purpose can be formulated with peroxide cure systems to
fluorocarbon-based synthetic rubber. When resist strong acids, hot water and steam.
compared to most other elastomers, it has wide “F” types: This terpolymer is the latest generation
chemical resistance and superior performance, of “high” fluorine elastomers, with the addition of
especially in high temperature application in 2% more fluorine, (70%) This is considered an
different media. FKMs are categorized under the excellent elastomer for sealing today’s oxygenated
ASTM D1418 & ISO 1629 designation of FKMs. automotive fuels and lubricants. “F” types can be
The four main monomers that are used to make formulated to resist concentrated aqueous inor-
FKMs are shown in Fig. 12.35. ganic acids, hot water, and steam.
338
Table 12.47 Mechanical Properties Retained after Accelerated Weathering in a UV-CON and a Xenon Arc Weather-OmeterÒ for Black, Weather
Resistant, Unstrained EPDM Terpolymer17
Exposure Conditions
Exposure Apparatus Xenon arc Weather-OmeterÒ IN-CON
T HE E FFECT
OF
Exposure Note Specimen rotation every 250 h; unstrained specimens Unstrained specimens

Exposure Temperature 77e83 77e83 77-83 77e83 77e83
2
2
Tensile Strength 104 100.3a 105.8 89.8 83.7 103.4 103.4 105.5 93.5 85.5
83.3a 75.13 74.4 48.9 40 88.9 82.2 71.1 48.9 422
ON
Elongation at Break
P LASTICS
Note: (1) Known formulation with a 20-year history of proven weather performance; specimens mounted on exterior grade plywood covered with aluminum foil. (2)
Relative humidity (%) ¼ 45e55.
a
AND
E LASTOMERS
12: E LASTOMERS
Table 12.48 Mechanical Properties Retained after Accelerated Weathering in a UV-CON and a Xenon Arc Weather-OmeterÒ of Black, Randomly
AND
Selected, Strained EPDM Terpolymer17
RUBBERS
Exposure Conditions
Exposure Type Accelerated weathering Accelerated weathering
Exposure Note Specimen rotation every 250 h; specimens strained at 50% Specimens strained at 50%
Humidity (%)
2
2
Tensile Strength 118.6 119.1 114.3 101.9 105.1 114 116.2 112.9 110 98
Elongation at Break 71.7 64.5 55.8 52.9 49 73.1 76 61.5 51.9 442
Note: (1) Specimens mounted on exterior grade plywood covered with aluminum foil.
339
Figure 12.20 Carbonyl formation

after xenon arc Weather-
OmeterÒ exposure of EPDM
terpolymer.20
Figure 12.21 Decrease in molec-

ular weight after xenon arc
Weather-OmeterÒ exposure of
EPDM terpolymer.20
Figure 12.22 Relative change in

elongation at break vs. exposure
in xenon test DIN 53387 for
a typical EPDM resin.21
Figure 12.23 Micro-IRHD hard-

ness change vs. QUVÒ exposure
of EPDM compound.16
4 h dry (3 cycles per day).

EPDM compound.16
using UVA 340A lamps with
a black panel temperature of
45 C and a cycle of 4 h condensa-
tion and 4 h dry (3 cycles per day).

vs. QUVÒ exposure of EPDM
compound.16
condensation and 4 h dry (3
cycles per day).
Figure 12.26 Modulus at 100% vs. QUVÒ exposure of EPDM compound.16

temperature of 45 C and a cycle of 4 h condensation and 4 h dry (3 cycles per day).
Figure 12.27 Modulus at 300% vs. QUVÒ exposure of EPDM compound.16

Figure 12.28 Epichlorohydrin homopolymer (CO) monomer and polymer structure.

Figure 12.29 Epichlorohydrin copolymer (ECO) monomers and polymer structure.
Figure 12.30 Epichlorohydrin terpolymer (GECO) monomers and polymer structures.
Figure 12.31 Micro-IRHD hardness change vs. QUVÒ exposure of typical epichlorohydrin rubber compound.16

change vs. QUVÒ exposure of typical
epichlorohydrin rubber compound.16
a cycle of 4 h condensation and 4 h
dry (3 cycles per day).

vs. QUVÒ exposure of typical epi-
chlorohydrin rubber compound.16

QUVÒ exposure of typical epichlo-
rohydrin rubber compound.16
ether (PMVE) is used in place of HFP. The

“LT” in VitonÒ GFLT stands for “low tempera-
ture.” The combination of VF2, PMVE, TFE,
and a cure site monomer is designed to retain
both the superior chemical resistance and high
heat resistance of the G-series fluorocarbons. In
addition, VitonÒ GFLT compounds (typically
67% fluorine) offer the lowest swell and the
best low-temperature properties. VitonÒ GFLT
can seal in a static application down to approxi-
mately 40 F.
Fluorosilicone (FVMQ) is covered in the section
Figure 12.35 Monomers used to make on polysiloxanes/silicones.
fluoroelastomers.
Perfluorinated elastomers (FFKM): This family of
Ò
Viton GF fluorocarbons are tetrapolymers elastomers is widely known by the trade name that
composed of TFE (tetrafluoroethylene), VF2 its inventors gave it, KalrezÒ . It is essentially an
(vinyl fluoride), HFP (hexafluoropropylene), and elastomeric form of PTFE and retains the extreme
small amounts of a cure site monomer. Presence chemical resistance at temperature of PTFE up to
of the cure site monomer allows peroxide curing 327 C.
of the compound, which is normally 70% fluorine. AFLASÒ , made by Asahi Glass Co., Ltd, is
As the most fluid resistant of the various FKM a copolymer of tetrafluoroethylene and propylene.
types, VitonÒ GF compounds offer improved resis- The fluorine content is typically 57%.
tance to water, steam, and acids.
VitonÒ GFLT fluorocarbons are similar to The FKMs are cured by several chemical means as
VitonÒ GF, except that perfluoromethylvinyl described in Tables 12.49 and 12.50.
Table 12.49 Curing Chemistry of Fluoroelastomers

FKM Type Monomers Curable By: Recommended Curative
Copolymer VF2, HFP Amine, bisphenol Bisphenol
Terpolymer VF2, HFP, TFE Amine, bisphenol Bisphenol
Peroxide Curable VF2, HFP, TFE, CSM Amine, bisphenol, peroxide Peroxide
Low Temperature VF2, HFP, TFE, PMVE, Amine, bisphenol, peroxide Peroxide
CSM
Table 12.50 The Curing Chemistry Used by Solvay Solexis TecnoflonÒ Fluoroelastomer Products
10% Temperature of
Grade Fluorine Content (%) Retractiona ( C) Cure Type
T 636 66 19 Bisphenol A
L636 65 21 Bisphenol A
PL 458 67 24 Peroxide
a
An industry standard for determining the ability of an elastomer to seal.
Manufacturers and trade names: Dyneon An increase in silica reinforcement; improved

FluorelÔ, Solvay Solexis TechnoflonÒ , DuPont compatibility with polar polymers like polyvinyl
VitonÒ , KalrezÒ , Daikin Dai-elÔ, Asahi Glass chloride
AFLASÒ . Reduced rolling resistance and increased wet grip
Applications: Seals, caulks, coatings, vibration
dampeners, expansion joints, gaskets, O-rings, piston Applications and uses: Tire and other automotive.
seals, custom shapes, and stock rod and sheet. The natural rubber data are found in Figs
The FKM data are found in Figs 12.36e12.39. 12.41e12.50.
12.10 Natural Rubber 12.11 AcrylonitrileeButadiene

Natural rubber is polyisoprene. The structure of Copolymer
the monomer and polymer are given in Fig. 12.40. Its
CAS number is 9006-04-6. Chemical and environ- Acrylonitrileebutadiene copolymers (NBR) com-
mental resistance and mechanical properties are monly called nitrile rubbers are copolymers of
improved through cross-linking (vulcanizing), butadiene and acrylonitrile. The monomers and
usually through treatment with sulfur. polymer structure are shown in Fig. 12.51. The CAS
Natural rubber is more unsaturated and has fewer number is 9003-18-3.
methyl groups than butyl rubber causing it to be 20 times NBR is commonly considered the workhorse of
more permeable to air. The presence of methyl groups the industrial and automotive rubber products
generally serves to reduce the permeability of polymers. industries. NBR is actually a complex family of
Epoxidized natural rubber is derived from the unsaturated copolymers of acrylonitrile and
partial epoxidation of the natural rubber molecule, butadiene. The amount of acrylonitrile in the
resulting in a totally new type of elastomer. The polymer is used to manipulate the balance of
epoxide groups are randomly distributed along the NBR properties. Acrylonitrile content may range
natural rubber molecule. from 18% to 50%. Increasing acrylonitrile
Epoxidation results in a systematic increase in the content leads to higher hardness, strength, abra-
polarity and glass transition temperature. Property sion resistance, heat resistance, and oil/fuel
changes with increasing level of epoxidation include: resistance, and lower resilience and low-tempera-
ture flexibility.
An increase in damping There are several general types of NBR:
A reduction in swelling in hydrocarbon oils Cold NBRdAcrylonitrile content ranges from
A decrease in gas permeability 15% to 51%. Cold polymers are polymerized at
Figure 12.36 Micro-IRHD hard-

ness change vs. QUVÒ exposure
of DuPont VitonÒ A200C fluoroe-
lastomer.16

DuPont VitonÒ A200C fluoroelasto-
mer.16

vs. QUVÒ exposure of DuPont
VitonÒ A200C fluoroelastomer.16

QUVÒ exposure of DuPont VitonÒ
A200C fluoroelastomer.16
Figure 12.40 Structure of isoprene and polyisoprene.
Figure 12.41 Micro-IRHD hardness change vs. QUVÒ exposure of Natural Rubber.16
Figure 12.42 Tensile strength change vs. QUVÒ exposure of natural rubber.16

natural rubber.16
condensation and 4 h dry
(3 cycles per day).

natural rubber.16
(3 cycles per day).

natural rubber.16
(3 cycles per day).
Figure 12.46 Micro-IRHD

hardness change vs. QUVÒ
exposure of mineral-filled
natural rubber.16
and 4 h dry (3 cycles per day).

mineral-filled natural rubber.16

vs. QUVÒ exposure of mineral-
filled natural rubber.16
Figure 12.49 Modulus at 100% vs. QUVÒ exposure of mineral-filled natural rubber.16
Figure 12.50 Modulus at 300% vs. QUVÒ exposure of mineral-filled natural rubber.16
Figure 12.51 Monomers and polymer structure of NBR.

a temperature range of 5e15 C, depending on the Hydrogenated nitrile butadiene rubber (HNBR),
balance of linear-to-branched configuration also known as highly saturated nitrile, is special
desired. The lower polymerization temperatures class of nitrile rubber (NBR) that has been hydro-
yield more-linear polymer chains. genated to increase saturation of the butadiene
Hot NBRdPolymers are polymerized at the segment of the carbon polymer backbone. This
temperature range of 30e40 C. This process means that many of the carbonecarbon double
yields highly branched polymers. Branching bonds are changed to single bonds with the addi-
supports good tack and a strong bond in adhesive tion of hydrogens to those carbons. Carbone
applications. The physically entangled structure carbon single bonds are more flexible that double
of this kind of polymer also provides a significant bonds. Subsequent improvements to the material
improvement in hot tear strength compared with properties, over that of a nitrile rubber (NBR),
a cold-polymerized counterpart. The hot polymer’s include greater thermal stability, broader chemical
natural resistance to flow makes them excellent resistance and greater tensile strength.
candidates for compression molding and sponge.
Other applications are thin-walled or complex Manufacturers and trade names: Lanxess
extrusions where shape retention is important. PerbunanÒ , KrynacÒ and BaymodÒ N, Girsa,
Hyundai, JSR Corporation, Kumho, Nantex, Nitri-
Cross-linked hot NBRdThese are branched poly-
flex, PetroChina, Petroflex, Polimeri Europa Euro-
mers that are further cross-linked by the addition
prene, Zeon Chemicals ZetpolÒ .
of a difunctional monomer. These products are
Applications and uses: nonlatex gloves for the
typically used in molded parts to provide sufficient healthcare industry, automotive transmission belts,
molding forces, or back pressure, to eliminate
hoses, O-rings, gaskets, oil seals, V-belts, synthetic
trapped air. Another use is to provide increased leather, printer’s roller and as cable jacketing.
dimensional stability or shape retention for
The NBR rubber data are found in Table 12.51 and
extruded goods and calendered goods. This leads Figs 12.52e12.61.
to more efficient extruding and vulcanization of
intricate shaped parts as well as improved release
from calender rolls. These NBRs also add dimen-
sional stability, impact resistance and flexibility 12.12 StyreneeButadiene Rubber
for PVC modification.
Styreneebutadiene or styreneebutadiene rubber
Carboxylated nitriledAddition of carboxylic acid (SBR)22 is a synthetic rubber copolymer consisting
groups to the NBR polymer’s backbone signifi- of styrene and butadiene, and its structure is shown in
cantly alters processing and cured properties. Fig. 12.62.
The result is a polymer matrix with significantly Manufacturers and trade names: Lanxess
increased strength, measured by improved tensile, KryleneÒ and KrynolÒ and many others.
tear, modulus and abrasion resistance. The nega- Applications and uses: Employed extensively in
tive effects include reduction in compression set, almost all sectors of the rubber industry. Used mainly
water resistance, resilience and some low-temper- for tires, often in blends with natural rubber; con-
ature properties. veyor and transmission belting, footwear soles and
Bound antioxidant NBRdan antioxidant is poly- heels; technical goods of all kinds, e.g. seals,
merized into the polymer chain. The purpose is membranes, hose and rolls.
to provide additional protection for the NBR SBR 1500 is a high-molecular-weight SBR
during prolonged fluid service or in cyclic fluid combining good extrusion behavior and superior
and air exposure. When compounding with highly compound properties. It has relatively wide molec-
reinforcing furnace carbon black the chemical ular weight distribution and the butadiene compo-
reactivity between the polymer and the pigment nent has an average about 9% Cis-1,4; 54.5% trans
can limit hot air-aging capability. Abrasion resis- and 13% 1,2 vinyl structure. SBR 1500 contains
tance is improved when compared with conven- antioxidant to avoid product degradation. The high
tional NBR, especially at elevated temperatures. strength and great toughness of rubber permit the use
They have also been found to exhibit excellent of its elastic qualities. The properties of rubber show
dynamic properties. excellent resistance to cutting, tearing and abrasion.
Table 12.51 Material Properties after Florida Outdoor Weathering of Eliokem ChemigumÒ TPE 2175 Nitrile
Thermoplastic Elastomer21
Sample Thickness (mm) 32 32
Exposure Conditions
Exposure Note Direct exposure; 5 south Under glass exposure; 5
south
100% Modulus 97 97
Shore A Hardness Change 0 0
(Units)
Gloss at 60 Retained (%) 12.6a 301a
DE Color 2.28b 1.46b
Visual Observation Slight chalking No blemish
(As Weathered)
Visual Observation No chalking, no cracks Clean, no cracks
(Washed)
Note: (1) Black color, medium gloss. (2) Compression molding.
a
Test name: Gardner gloss; test method: ASTM D3134.
b
Test method: SAE J545.

exposure of NBR rubbers.16

NBR rubbers.16

NBR rubbers.16

NBR rubbers.16

NBR rubbers.16

exposure of Zeon Chemicals
ZetpolÒ HNBR rubbers.16

Zeon Chemicals ZetpolÒ
16
HNBR rubbers.

HNBR rubbers.16

16
HNBR rubbers.

16
HNBR rubbers.
It has a relatively long, useful life under a wide

variety of conduction.
The SBR rubber data are found in Figs
12.63e12.72.
12.13 EthyleneeVinyl Acetate

Copolymer
Ethyleneevinyl acetate copolymer (EVA) is
Figure 12.62 Structure of SBR. a copolymer of ethylene and vinyl acetate as shown
in Fig. 12.73. These polymers have several “short-
hand” identifiers including EVAC, EVA, E/VA,
E/VAC and EVM. Its CAS number is 24937-78-8.

exposure of SBR 1500
rubber.16

SBR 1500 rubber.16

SBR 1500 rubber.16

Zeon Chemicals SBR 1500
rubber.16

rubber.16

rubber.16
Figure 12.69 Tensile

strength change vs. QUVÒ
rubber.16
340A lamps with a black
panel temperature of 45 C
and a cycle of 4 h condensa-
tion and 4 h dry (3 cycles per
day).

SBR 1710 rubber.16

rubber.16

rubber.16
Figure 12.73 Structure of EVA

polymers.
Commercial resins range in vinyl acetate content EVA properties vary depending on vinyl acetate
from 7.5 wt% to 33 wt%. Some grades are available content:
with antiblock and slip additives. DuPontÔ ElvaxÒ Higher vinyl acetate content:
grades vary by vinyl acetate content. Increased gas permeability
Increased impact strength-toughness Phenolic antioxidant: such as pentaerythritol tet-

Improved optical qualities-clarity rakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)
propionate);
Increased flex-crack resistance
Amine: such as benzenamine, N-phenyl-, reaction
Increased cling products with 2,4,4-trimethylpentene;
Increased solubility Optical brightener: 2,20 -(1,2-ethylenediyldi-4,1-
Increased coefficient of friction phenylene)bisbenzoxazole, C.I.F.B. 3671;
Decreased sealing temperature-softening point Manufacturers and trade names: DuPontÔ
Increased crystallinity AppeelÒ and ElvaxÒ , Celanese EVA Performance
Polymers AtevaÒ , Lanxess LevaprenÒ ,
Reduced stiffness
Baymond L and Levamelt , Arkema EvataneÒ .
Ò Ò
Reduced surface hardness
Applications and uses: automotive, machinery,
building/construction, wire and cable, sporting
Weathering: The major decomposition reactions
goods and photovoltaic modules.
are deacetylation or what is called a Norrish II
reaction (shown at the top of Fig. 12.74) and hemo-
Data for EVA elastomers are found in Figs
lytic dissociation or what is called a Norrish I reac-
12.75e12.79.
tion (shown at the bottom for Fig. 12.74). Increased
concentration of vinyl acetate in the EVA polymer
contributes to a long-term increased stability of 12.14 Polysulfide Rubber
unstabilized copolymer.
Products of photodegradation include hydroper- Polysulfide rubber is a synthetic rubber that is
oxides, hydroxyl groups, polyene sequences, alde- a product of the polycondensation of dihalides of
hyde and acetic acid. Typical results of aliphatic compounds (for example, ethylene
photodegradation are yellow-brown discoloration dichloride or propyl dichloride) with polysulfides of
and loss of mechanical properties. alkali metals (for example, Na2Sx, where x ¼ 2e4).
Stabilization: Most important stabilizers: Polysulfide rubbers are divided into polytetrasulfides
and polydisulfides, with the general formulas
Ultraviolet Absorber (UVA): such as 2-hydroxy-4- [eReSeSeSeSe]n and [eReSeSe]n, shown in
octyloxybenzophenone; more detail in Fig. 12.80.
Hindered Amine Stabilizer: such as 1,3,5- The curing of liquid polysulfide polymers to high-
triazine-2,4,6-triamine, N,N000 [1>,2-ethane-diyl-bis molecular-weight elastomers is normally accom-
[[[4,6-bis[butyl(1,2,6,6-pentamethyl-4-piperidinyl) plished by oxidizing the polymer’s thiol(eSH)
amino]-1,3,5-triazine-2-yl]imino]-3,1-propanediyl] terminals to disulfide (eSeSe) bonds as shown in
bis[N0 ,N00 -dibutyl-N0 ,N00 -bis(1,2,2,6,6-pentamethyl- Fig. 12.81. H2O the curing agents most commonly
4-piperidinyl)-; used are oxygen-donating materials such as
Figure 12.74 Major EVA polymer degradation pathways.

Figure 12.75 Relative change

of elongation at break (%) of
Lanxess Levapren Ò EVA.24
Note: Xenon Test DIN 53, 387.

exposure of Lanxess
LevaprenÒ 400 EVA rubber.16
Figure 12.77 Tensile Strength

Lanxess LevaprenÒ 400 EVA
rubber.16

rubber.16
340A lamps with a black
panel temperature of 45 C
and a cycle of 4 h condensa-
tion and 4 h dry (3 cycles per
day).

rubber.16
Figure 12.80 Structure of a typical polysulfide rubber resin.
molecular-weight rubbers, respectively), and also as

aqueous dispersions, or lattices.
Figure 12.81 Cure/cross-linking reaction of polysul- Polysulfide rubbers are special-purpose polymers
fide resin with oxygen.
characterized by high resistance to swelling in solvents,
fuels and oils; resistance to sunlight; moisture and gas
manganese dioxide, calcium peroxide, cumenehy- impermeability; and stability during storage. These
droperoxide and p-quinone dioxime. properties result from the high sulfur content and the
Polysulfide rubbers are produced in solid and absence of unsaturated bonds in the macromolecules.
liquid forms (high-molecular-weight and low- The molecular weight of solid rubbers is (200e500)
103; density, 1.27e1.60 g/cm3; glass transition point, commercial polysulfide rubbers are Thiokol DA
e23 C to e57 C. Zinc oxide, p-quinone dioxime, and (USSR) and Thiokol A, FA and ST (USA).
a mixture of Altax and diphenylguanidine are used to Data for polysulfide rubbers are found in Figs
vulcanize polysulfide rubbers. Vulcanized polysulfide 12.82e12.85.
rubbers are inferior in mechanical properties to those
made from other synthetic rubbersdfor example, their
tensile strength is 6e10 MN/m2; relative elongation, 12.15 Polysiloxane/Silicone
200e400 percent. Rubber
Polysulfide rubbers are used in rubberizing fuel
storage tanks and in the manufacture of oil- and Silicones are also known as siloxanes, poly-
gasoline-resistant tubing and of gastight diaphragms organosiloxanes, or polysiloxanes. Silicone rubber is
for gas meters. Sealing compounds are prepared a semi-organic synthetic. Its polymer backbone
from liquid Thiokols. The most important structure consists of a chain of silicon and oxygen

exposure of polysulfide
rubber.16

polysulfide rubber.16


atoms rather than carbon and hydrogen atoms, as in

the case with other types of rubber. The molecular
structure of silicone rubber results in a very flexible-
dbut weakdchain. Silicones are very stable at low
and high temperatures. Although fillers may improve
properties somewhat, tear and tensile strengths remain
relatively low. Figure 12.86 shows four of the primary Figure 12.86 Structure of groups that make up poly-
groups that make up a typical polysiloxane. To simply siloxanes, “M” stands for Me3SiO, “D” for Me2SiO2,
the discussion of polysiloxane composition, the “T” for MeSiO3, “Q” for SiO4 “P” for replace Me with
monomers are identified by letters: phenyl side groups “V” for replace Me with vinyl
Some common abbreviations for the polymers side groups (typically <1%) “F” for replace Me with
include: MQ, VMQ, PMQ, PVMQ, PDMS fluorine.
(polydimethylsiloxane). See Figure 12.86 for most Platinum-cured high-consistency rubber (platinum-
letter designations. cured HCR), Wacker Chemie AG ElastosilÒ
The curing chemistry affects the properties of R4000/50; and
silicone rubbers. Three common curatives used in Peroxide-cured high-consistency rubber (peroxide-
Figs 14.25e14.39 are: cured HCR), GE Bayer Silicones GmbH & Co.
KG HV3 622, cured by Di-2,4-dichlorobenzoylper-
Platinum-cured liquid silicone rubber (LSR), oxide with 1% loading.
Wacker Chemie AG ElastosilÒ LR3003/50 LSR,
Part A & B liquid system;
Table 12.52 Change in Mechanical Properties after Florida and Michigan Outdoor Weathering for Dow Corning
SilasticÒ Silicone Rubber23
Exposure Location Michigan Michigan Michigan Florida
Exposure Time 1 year 2 years 5 years 20 years
Property Change
Tensile Strength (%) þ8 to 25 þ4 to 22 þ22 to 27 31
Elongation (%) þ4 to 28 þ14 to 34 55
Hardness (Point Change) þ3 to 6 þ2 to 6 þ8 to 9 þ7
Note: (1) Exposure conditions ASTM D518, method A.
Table 12.53 Change in Mechanical Properties after Florida and Michigan Outdoor Weathering for Dow Corning
SilasticÒ Silicone Rubber23
Exposure Location Michigan Michigan Michigan Florida
Exposure Time 1 year 2 years 5 years 20 years
Property Change
Tensile Strength (%) 0 to 23 8 to 42 14 to 54 41
Elongation (%) þ4 to 40 0 to 45 24 to 50 60
Hardness (Point Change) þ1 to 8 3 to 16 þ5 to 8 þ2
Note: (1) Exposure conditions ASTM D518, method B.

exposure of silicone rubber.16
Peroxide curing gives an end product that is more Corning Corp. SilasticÒ ; General Electric SilplusÒ ,
rigid, more resilient with methyl and vinyl cross- TufelÒ , SE; Rhone-Poulenc Inc. Rhodorsil, Wacker
links. Platinum curing gives an end product that is Chemie AG ElastosilÒ .
more flexible with better tear with vinyl/hydride Data for Polysiloxanes are found in Tables 12.52
cross-links. and 12.53 and Figs 12.87e12.94.
Manufacturers and trade names: Bayer Corpo-
ration BaysiloneÒ ; Shincor Silicones KEÒ ; Dow
Figure 12.88 Tensile strength change vs. QUVÒ exposure of silicone rubber.16
Figure 12.89 Elongation at break vs. QUVÒ exposure of silicone rubber.16


silicone rubber.16

exposure of silicone FVMQ
rubber.16

silicone FVMQ rubber.16


References technical report (306-00439-1293 SMG). Dow

Chemical Company; 1993.
1. McKeen LW. The effect of temperature and other 6. Elastollan design and processing guide, supplier
factors on plastics, plastics design library. Wil- design guide. BASF Corporation; 1993.
liam Andrew Publishing; 2008. 7. Drobny Jiri George. Handbook of thermoplastic
2. Drobny Jiri George. Handbook of thermoplastic elastomers. William Andrew; 2007. p. 191e199.
elastomers. William Andrew; 2007. p. 215e234. 8. Weathering of Santoprene thermovulcanizate
3. A guide to thermoplastic polyurethanes (TPU). black ultraviolet grades, Santoprene specialty
Huntsman Chemical; 2010. products. Exxon Mobil Chemical Co.; 1992.
4. Estane thermoplastic polyurethane product data 9. Forprene by S.O.F.TER., supplier marketing
sheets, supplier technical report (BFG-15512-J). literature (RDS 049/9240). Evode Plastics.
The BFGoodrich Company. 10. Drobny Jiri George. Handbook of thermo-
5. UV stabilization of aromatic pellethane ther- plastic elastomers. William Andrew; 2007.
moplastic polyurethane elastomers, supplier p. 249e264.
11. Hytrel technical notesdWeather protection of conference proceedings. National Bureau of

Hytrel with carbon black, supplier technical Standards and NRCA; 1987.
report (1e48). DuPont Company. 18. Weathering of Santoprene thermoplastic rubber
12. Pigmentation and weathering protection of black ultraviolet grades, supplier technical report
Hytrel, supplier technical report (HYT-303(R1)/ (TCD00592). Advanced Elastomer Systems;
E-73191). DuPont Company; 1985. 1992.
13. Hytrel design guidedModule V. DuPont; 2000. 19. Weathering data of Santoprene thermoplastic
14. Weatherability of Santoprene rubber compared rubber (black grades) versus standard thermoset
to other materials, supplier technical report rubbers, supplier technical report (TCD03787).
(TCD01588). Advanced Elastomer Systems; 1988. Monsanto Company; 1987.
15. Set a new standard of performance for your 20. Engage polyolefin elastomers, supplier marketing
non-residential glazing seals, supplier marketing literature (305-01995-1293 SMG). Dow Chemical
literature. Advanced Elastomer Systems; 1993. Company; 1993.
16. Brown RP, Butler T, Hawley SW. Ageing of 21. LEVAPRENÒ ethylene vinyl acetate (EVM) the
rubberdAccelerated weathering and ozone test cost-effective specialty rubber. Lanxess; 2005.
results. Smithers Rapra Technology; 2001. 22. Drobny Jiri George. Handbook of thermoplastic
17. Gish BD, Jablonowski TL. Weathering tests for elastomers. William Andrew; 2007. p. 161e177.
EPDM rubber sheets for use in roofing appli- 23. Rubber physical and chemical properties. Dow
cations, 8th Conference on Roofing Technology, Corning Corporation; 2005.

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12 Elastomers and Rubbers

12.1 Elastomers and Rubbers “Hard-Phase” - Plastic properties:

An elastomer is a polymer with the property of Processing temperatures

Figure 12.1 Molecular structure of a thermoplastic polyurethane elastomer.

Properties 0 500 1000 1500 2000

Material Grade Estane 58315 Estane 58863 Nat 025

Figure 12.2 Elongation after

Figure 12.3 Tensile strength

Figure 12.4 Yellowness index

Figure 12.5 Yellowness index

Figure 12.6 Tensile strength

Table 12.6 (Continued)

Table 12.7 (Continued )

Table 12.8 (Continued)

Table 12.9 (Continued )

Table 12.12 (Continued )

UV L IGHT AND W EATHER

These TPEs are generally tougher over a broader

Figure 12.7 Molecular structure

Figure 12.8 Chemical structure of butyl rubber.

Figure 12.9 Micro-IRHD hardness

Figure 12.10 Tensile strength

Figure 12.11 Modulus at 100%

Figure 12.12 Modulus at 300%

Figure 12.13 Elongation at

12.6 Chlorobutyl Rubber Polychloroprene was developed in 1930 by

Figure 12.14 Polymerization of chloroprene.

Figure 12.17 Elongation at break

Figure 12.18 Modulus at 100% vs.

Figure 12.19 Modulus at

Material Composition (phr)

Table 12.33 (Continued )

Table 12.34 (Continued )

Material Composition (phr)

Material Composition (phr)

Material Composition (phr)

UV L IGHT AND W EATHER

UV L IGHT AND W EATHER

UV L IGHT AND W EATHER

Figure 12.20 Carbonyl formation

Figure 12.21 Decrease in molec-

Figure 12.22 Relative change in

Figure 12.23 Micro-IRHD hard-

Figure 12.24 Tensile strength

Figure 12.25 Elongation at break

Figure 12.26 Modulus at 100% vs. QUVÒ exposure of EPDM compound.16

Figure 12.27 Modulus at 300% vs. QUVÒ exposure of EPDM compound.16

Figure 12.28 Epichlorohydrin homopolymer (CO) monomer and polymer structure.

Figure 12.29 Epichlorohydrin copolymer (ECO) monomers and polymer structure.

Figure 12.30 Epichlorohydrin terpolymer (GECO) monomers and polymer structures.

Figure 12.32 Tensile strength

Figure 12.33 Elongation at break

Figure 12.34 Modulus at 100% vs.

ether (PMVE) is used in place of HFP. The

Table 12.49 Curing Chemistry of Fluoroelastomers

Manufacturers and trade names: Dyneon An increase in silica reinforcement; improved

12.10 Natural Rubber 12.11 AcrylonitrileeButadiene

Figure 12.36 Micro-IRHD hard-

Figure 12.37 Tensile strength