Eco Permeability

12 Elastomers and Rubbers
An elastomer is a polymer with the property of properties that are affected by each phase can be
“elasticity,” generally having notably low Young’s generalized:
modulus and high yield strain compared with other “Hard phase”dPlastic properties:
materials.1 The term is often used interchangeably
with the term rubber. Elastomers are amorphous 1. Processing temperatures
polymers existing above their glass transition 2. Continuous use temperature
temperature, so that considerable segmental motion
is possible, so it is expected that they would also 3. Tensile strength
be very permeable. At ambient temperatures 4. Tear strength
rubbers are thus relatively soft and deformable. 5. Chemical and fluid resistance
Their primary uses are for seals, adhesives, and
6. Adhesion to inks, adhesives, and over-molding
molded flexible parts. Elastomers may be thermo-
substrates.
sets (requiring vulcanization, a form of cross-
linking) or thermoplastic, called thermoplastic “Soft phase”dElastomeric properties:
elastomer or TPE.
TPEs have two big advantages over the conven- 1. Lower service temperature limits
tional thermoset (vulcanized) elastomers. Those are
ease and speed of processing. Other advantages of 2. Hardness
TPEs are recyclability of scrap, lower energy costs 3. Flexibility
for processing, and the availability of standard, 4. Compression set and tensile set
uniform grades (not generally available in
thermosets). This chapter has data on many thermoset and
TPEs are molded or extruded on standard plas- TPEs. TPEs will be discussed first.
tics-processing equipment in considerably shorter
cycle times than those required for compression or
transfer molding of conventional rubbers. They are 12.1 Thermoplastic Polyurethane
made by copolymerizing two or more monomers, Elastomers (TPU)
using either block or graft polymerization tech-
niques. One of the monomers provides the hard, or Urethanes are a reaction product of a diisocyanate
crystalline, polymer segment that functions as and long- and short-chain polyether, polyester, or
a thermally stable component; the other monomer caprolactone glycols.2 The polyols and the short-
develops the soft or amorphous segment, which chain diols react with the diisocyanates to form linear
contributes the elastomeric or rubbery polyurethane molecules. This combination of diiso-
characteristic. cyanate and short-chain diol produces the rigid or
Physical and chemical properties can be hard segment. The polyols form the flexible or soft
controlled by varying the ratio of the monomers segment of the final molecule. Figure 12.1 shows the
and the length of the hard and soft segments. Block molecular structure in schematic form.
techniques create long-chain molecules that have The properties of the resin depend on the nature of
various or alternating hard and soft segments. Graft the raw materials, the reaction conditions, and the
polymerization methods involve attaching one ratio of the starting raw materials. The polyols used
polymer chain to another as a branch. The have a significant influence on certain properties of
Permeability Properties of Plastics and Elastomers. DOI: 10.1016/B978-1-4377-3469-0.10012-8

Copyright Ó 2012 Elsevier Inc. All rights reserved. 251
252 P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS
Figure 12.1 Molecular structure of

a thermoplastic polyurethane elastomer.
the thermoplastic polyurethane. Polyether and poly- The polyether-based TPUs have the following
ester polyols are both used to produce many products. characteristic features:
The polyester-based TPUs have the following
characteristic features: Fungus resistance
Low-temperature flexibility
Good oil/solvent resistance Excellent hydrolytic stability
Good UV resistance Acid/base resistance
Abrasion resistance
In addition to the basic components described
Good heat resistance
above, most resin formulations contain additives to
Mechanical properties facilitate production and processability. Other addi-
tives can also be included such as:
Demolding agents
Table 12.1 Permeation of Gases and Vapors
through Lubrizol EstaneÒ TPU3 Flame retardants
Heat/UV stabilizers
Permeability Coefficient
Plasticizers
Source
Document Normalized The polyether types are slightly more expensive
Units Units and have better hydrolytic stability and low-
Permeant (m3 mm/ (cm3 mm/ temperature flexibility than the polyester types.
Gas m2 day) m2 day atm) Manufacturers and trade names: Lubrizol
Air 0.00052 5200 EstaneÒ TPU, Bayer MaterialScience Texin and
Oxygen 0.00162 16,200 Desmopan, BASF ElastollanÒ (Tables 12.1e12.5).
See also Figs. 12.2e12.6.
Nitrogen 0.0004 400
Carbon 0.01023 102,300 Table 12.2 Permeation of Water Vapor at 23 C and
dioxide 50% RH through Lubrizol EstaneÒ Breathable TPU4
Helium 0.00291 29,100
EstaneÒ Water Vapor Transmission
Argon 0.00112 11,200 Code Rate (g/m2 day)
FreonÒ 12 0.00122 12,200 75AT3 380
Ò
Freon 22 0.00106 10,600 80AF3 650
Vapor Permeation Rate 90AF3 500
Permeant 2
(g/m day) 2
(g mm/m day) 58245 650
Vapor 58315 250
Water 2.0 0.1 58237 550
Thickness: 1.14 mm. Test method: ASTM E96 B.
12: E LASTOMERS AND RUBBERS 253
Table 12.3 Permeation of Solvent Vapors through Lubrizol EstaneÒ TPU2
Vapor Permeation Rate
Permeant Temperature Thickness Source Document Normalized Units

Vapor ( C) (mm) Units (cm3/m2 day) (g mm/m2 day)
Gasoline fuel B 23 0.18 117.2 15.4
Gasoline fuel B 23 0.26 16.9 3.2
Gasoline fuel B 23 0.18 19.1 4.6
JP-4 fuel 27 0.47 3.8 0.13
JP-4 fuel 48 0.47 40.1 13.8
JP-4 fuel 66 0.47 112 38.4
JP-4 fuel 70 0.47 216 74.1
JP-4 fuel 83 0.47 385 132
JP-4 fuel 121 0.47 917 315
Test method: ASTM E96 B.
Table 12.4 Permeation of Gases at 20 C through Various BASF ElastollanÒ TPUs3
Source Document Units, Permeability Coefficient (m2/s Pa) 3 10e18
ElastollanÒ Carbon
Type Argon Methane Dioxide Hydrogen Helium Nitrogen Oxygen
C 80 A 12 11 200 45 35 4 14
C 85 A 9 6 150 40 30 3 10
C 90 A 5 4 40 30 25 2 7
C 95 A 3 2 20 20 20 1 4
1180 A 14 18 230 70 50 6 21
1185 A 9 14 180 60 40 5 16
1190 A 7 9 130 50 30 4 12
1195 A 6 5 90 40 20 3 8
Normalized Units, Permeability Coefficient (cm3 mm/m2 day atm)
C 80 A 105 96 1751 394 306 35 123

C 85 A 79 53 1313 350 263 26 88
C 90 A 44 35 350 263 219 18 61
C 95 A 26 18 175 175 175 9 35
1180 A 123 158 2014 613 438 53 184
1185 A 79 123 1576 525 350 44 140
1190 A 61 79 1138 438 263 35 105
1195 A 53 44 788 350 175 26 70
Test method: DIN 53536.
Table 12.5 Water Vapor Permeation at 23 C through Various BASF ElastollanÒ

TPUs3
ElastollanÒ Type Water Vapor Permeation Rate (g mm/m2 day)
C 80 A 18
C 85 A 15
C 90 A 20
C95 A 8
1180 A 21
1185 A 17
1190 A 15
1195 A 12
Test method: DIN 53122 Part 1; RH differential of 93%.
Figure 12.2 Permeability of

nitrogen vs. temperature through
BASF ElastollanÒ 1185A TPU.5
Figure 12.3 Water vapor

transmission vs. thickness,
temperature, and relative humidity
(RH) of Bayer MaterialScience
TexinÒ 285 TPU.6
Figure 12.4 Permeability of gases

vs. thickness, temperature, and
RH of Bayer MaterialScience
TexinÒ 390 TPU.4

TexinÒ 285 TPU.4

TexinÒ 453 TPU.4
12.2 Olefinic TPEs (TPO) compounds include fillers, reinforcements, lubri-

cants, heat stabilizers, antioxidants, UV stabilizers,
Polyolefin TPE (TPO) materials are defined as colorants, and processing aids. They are character-
compounds (mixtures) of various polyolefin poly- ized by high-impact strength, low density, and good
mers, semicrystalline thermoplastics, and amorphous chemical resistance; they are used when durability
elastomers. Most TPOs are composed of poly- and reliability are primary concerns.
propylene and a copolymer of ethylene and propy- Manufacturers and trade names: Advanced Elas-
lene called ethyleneepropylene rubber (EPR).2 tomer Systems SantopreneÒ , LyondelBasell
A common rubber of this type is called EPDM Advanced Polyolefins DexflexÒ .
rubber, which has a small amount of a third mono- Applications and uses: Roofing and automotive
mer, a diene (two carbonecarbon double bonds in it). exterior parts; capping distilled water, dairy prod-
The diene monomer leaves a small amount of unsa- ucts, fruit juices, sports drinks, beer, wine; and food,
turation in the polymer chain that can be used for cosmetics, toiletries; and pharmaceutical packaging,
sulfur crosslinking. Like most TPEs, TPO products sterilized closures, seals, and liners (Tables 12.6 and
are composed of hard and soft segments. TPO 12.7).
Table 12.6 Permeation of Gases at 23 C through Advanced Elastomer Systems SantopreneÒ TPO7
SantopreneÒ Grade
201e73 201e87 203e50 201e73 201e87 203e50

Source Document Units Normalized Units

Permeant Gas (cm3 0.5mm/100 in.2 day atm) (cm3 mm/m2 day atm)
Air 31 39 18 240 302 140
Nitrogen 25 34 12 194 264 93
Oxygen 65 56 36 504 434 279
Carbon dioxide 390 260 170 3023 2015 1318
Argon 67 77 51 519 597 395
Propane 150 430 250 1163 3333 1938
Thickness: 0.5 mm. Test method: ASTM D1434.
Table 12.7 Water Vapor Transmission at 25 C through Advanced Elastomer Systems SantopreneÒ TPO7
ASTM E96, ASTM E96, ASTM E96, ASTM E96,

Procedure A Procedure BW Procedure A Procedure BW
25% RH 75% RH 25% RH 75% RH
Vapor Permeation Rate
SantopreneÒ Source Document Units

Grade (g 0.5 mm/m2 day) Normalized Units (g mm/m2 day)
201e73 0.97 0.45 0.49 0.23
201e87 0.32 0.45 0.16 0.23
203e50 0.45 1.61 0.23 0.81
Thickness: 0.5 mm. Test method: ASTM E96.
Figure 12.7 Molecular structure of

Ticona RiteflexÒ thermoplastic
copolyester elastomers.
12.3 Thermoplastic Copolyester In these polyester TPEs, the hard polyester

Elastomers (TPE-E or COPE) segments can crystallize, giving the polymer some of
the attributes of semicrystalline thermoplastics, most
Thermoplastic copolyester elastomers (TPE-E or particularly better solvent resistance than ordinary
COPE) are block copolymers.2 The chemical struc- rubbers, but also better heat resistance. Above the
ture of one such elastomer is shown in Fig. 12.7. melting temperature of the crystalline regions, these
These TPEs are generally tougher over a broader TPEs can have low viscosity and can be molded
temperature range than the urethanes described in easily in thin sections and complex structures.
Section 10.1.1. Also, they are easier and more Properties of thermoplastic polyester elastomers can
forgiving in processing. be fine-tuned over a range by altering the ratio of
hard to soft segments.
Excellent abrasion resistance In DuPont HytrelÒ polyester TPEs, the resin is
High tensile, compressive, and tear strength a block copolymer. The hard phase is polybutylene
terephthalate (PBT). The soft segments are long-
Good flexibility over a wide range of temperatures chain polyether glycols.
Good hydrolytic stability Manufacturers and trade names: Ticona
Resistance to solvents and fungus attack RiteflexÒ , DuPontÔ HytrelÒ , Eastman EcdelÒ ,
DSM engineering plastics ArnitelÒ (Tables
Selection of a wide range of hardness 12.8e12.13).
Table 12.8 Permeability of Various Gases at 21.5 C
through DuPontÔ HytrelÒ 4056 Thermoplastic Table 12.9 Permeability of Various Gases at 21.5 C
Copolyester Elastomer8 through DuPontÔ HytrelÒ 5556 Thermoplastic
Copolyester Elastomer2
Source
Document Normalized Source
Units Units Document Normalized
[cm3(STP) (cm3 mm/ Units Units
Gas mm/m2 s Pa] m2 day atm) [cm3(STP) (cm3 mm/
Air 2.4 108 210 Gas mm/m2 s Pa] m2 day atm)
Nitrogen 1.7 10 8
150 Air 1.8 108 160
8
Carbon 3.5 107 3100 Nitrogen 1.4 10 120
7
dioxide Carbon 1.8 10 1600
Helium 1.57 10 7
1370 dioxide
Propane <2.0 10 9
<18 Helium 9.9 108 870
9
Water 3.1 105 270,000 Propane <2.0 10 <18
5
FreonÒ 1.4 108 120 Water 2.4 10 210,000
Ò 8
12 Freon 1.2 10 105
Freon Ò
4.7 10 9
41 12
22 FreonÒ 5.9 109 52
Freon Ò
4.1 10 7
3600 22
114 FreonÒ 2.8 107 2500
Thickness: 0.5 mm. Test method: ASTM E96. 114
Table 12.10 Permeability of Various Gases at 21.5 C through DuPontÔ HytrelÒ 6346
Thermoplastic Copolyester Elastomer2

Gas [cm3(STP) mm/m2 s Pa] (cm3 mm/m2 day atm)
Propane <0.2 108 <18
Ò 8
Freon 12 1.20 10 105
Ò 8
Freon 22 <0.2 10 <18
Ò 8
Freon 114 4.60 10 400
Table 12.11 Permeability of Various Gases at 21.5 C through DuPontÔ HytrelÒ 7246

Gas [cm3(STP) mm/m2 s Pa] (cm3 mm/m2 day atm)
Helium 3.20 108 280
Ò 9
Freon 12 8.20 10 72
Ò 8
Freon 114 2.70 10 240
Table 12.12 Permeability of Oxygen at 23 C through Ticona RiteflexÒ 663


Test Conditions (cm3/100 in.2 day atm) (cm3 mm/m2 day atm)
Film cast at temperature 38 C 93 C 38 C 93 C
0% RH 68.4 63.0 37.1 34.2
50% RH 68.4 64.0 37.1 34.7
100% RH 71.7 65.9 38.9 35.8
Cast film thickness: 0.035 mm.
Table 12.13 Permeability of Oxygen and Carbon Dioxide through Eastman EcdelÒ 9966
Normalized Units, Permeability
Gas Temperature ( C) Coefficient (cm3 mm/m2 day atm)
Carbon dioxide 23 >1000
Oxygen 30 130
RH: 50%. Test method: ASTM D1434.
12.4 Thermoplastic Polyether Light weight

Block Polyamide Elastomers Great flexibility (extensive range)
(PEBA) Resiliency
Polyether block amides are plasticizer-free TPEs.2 Very good dynamic properties
The soft segment is the polyether and the hard High strength
segment is the polyamide (nylon). For example, Outstanding impact resistance properties at low
Arkema PEBAXÒ 33 series products are based on temperature
nylon 12 (see Section 8.4) and polytetramethylene
Easy processing
glycol segments (PTMG). They are easy to process
by injection molding and profile or film extrusion. Good resistance to most chemicals
Often they can be easily melt-blended with other
polymers, and many compounders will provide Manufacturers and trade names: Arkema
custom products by doing this. Their chemistry PEBAXÒ , EMS-Grivory GrilflexÒ .
allows them to achieve a wide range of physical and Applications and uses: Medical. Surgical garments
mechanical properties by varying the monomeric and sheeting; Textile. Sports, leisure, and workwear;
block types and ratios. Construction. Membranes, housewrap; and food and
agriculture packaging (Tables 12.14e12.21).
See also Figs. 12.8 and 12.9.
Table 12.14 Water Vapor Permeation at 38 C and 50% RH through Arkema PEBAXÒ Films11
Vapor Transmission Rate

PEBAX (g/m2 day) (g mm/m2 day)
Thickness (mm) 0.012 0.025 0.050 0.012 0.025 0.050
MX1205 3000 1800 1400 36 45 70
MV1041 18,000 12,000 7000 216 300 350
MV3000 28,000 22,000 18,000 336 550 900
MV1074 30,000 25,000 21,000 360 625 1050
MV6100 6000 150
Test method: ASTM E96 E.
Table 12.15 Water Vapor Permeation at 38 C and 90% RH through Arkema PEBAXÒ Films10
PEBAX Source Document Units (g/m2 day) Normalized Units (g mm/m2 day)
Thickness (mm) 0.012 0.025 0.050 0.012 0.025 0.050
MX1205 3000 1800 1400 36 45 70
MV1041 3500 2700 1800 42 68 90
MV3000 4500 3300 2200 54 82 110
MV1074 4800 4300 3600 57 107 180
Test method: ASTM E96 E.
Table 12.16 Permeability of Oxygen at 23 C and Table 12.18 Permeability of Nitrogen at 23 C and
0% RH through Arkema PEBAXÒ Films10,12 0% RH through Arkema PEBAXÒ Films10
Permeability Coefficient Permeability Coefficient
Source Normalized Source

Document Units Units Document Normalized
(cm3 mm/ (cm3 mm/ Units Units
PEBAX cm2 s cm Hg) cm2 day atm) (cm3 mm/ (cm3 mm/
3533 131 1010 860 PEBAX cm2 s cm Hg) cm2 day atm)
2533 150 1010 985 3533 100 1010 657

10
5533 35 1010 230 2533 170 10 1116
10
4033 59 1010 387 5533 11 10 72
10
6333 31 1010 204 4033 39 10 256
10
(cm3 25 mm/cm2 (cm3 mm/cm2 6333 5 10 33
day atm) day atm) (cm 25 mm/
3 3
(cm mm/
MV3000 18,500 463 cm2 day atm) cm2 day atm)
MV6100 6500 163 MV3000 3000 75
MV1205 24,000 600 MV6100 650 17
PEBD 6000 150 MV1205 3900 98

PEBD 2800 70
Table 12.17 Permeability of Carbon Dioxide at 23 C

and 0% RH through Arkema PEBAXÒ Films10
Source
Document Normalized
Units Units
(cm3 mm/ (cm3 mm/ Table 12.19 Permeability of Helium at 23 C and 0%
PEBAX cm2 s cm Hg) cm2 day atm) RH through Arkema PEBAXÒ Films10
3533 1790 1010 11,800
10 Permeability Coefficient
2533 2600 10 17,100
5533 500 1010 3280 Source
Document Normalized
4033 780 1010 5122
Units Units
6333 420 1010 2760 (cm3 mm/ (cm3 mm/
(cm 25 mm/
3
(cm3 mm/ PEBAX cm2 s cm Hg) cm2 day atm)
cm2 day atm) cm2 day atm) 3533 174 1010 1142
10
MV3000 177,000 4425 2533 235 10 1543
10
MV6100 72,000 1800 5533 70 10 460
10
MV1205 175,000 4375 4033 147 10 965
10
PEBD 27,000 675 6333 46 10 302
Table 12.20 Permeability of Propane at 23 C and 0% RH through Arkema PEBAXÒ Films10

PEBAX (cm3 mm/cm2 s cm Hg) (cm3 mm/cm2 day atm)
5533 120 1010 789
10
6333 36 10 236
Table 12.21 Water Vapor Permeability at 38 C and 100% RH through Arkema PEBAXÒ Films10
PEBAX Normalized Units, Vapor Transmission Rate (g mm/m2 day)
6333 31
5533 34
4033 38
3533 67
2533 89
Figure 12.8 Water vapor permeation vs. film thickness at 38 C and 50% RH through Arkema PEBAXÒ breath-
able PEBA films per ASTM E96.13
Figure 12.9 Water vapor perme-

ation vs. film thickness at 38 C
and 90% RH through Arkema
PEBAXÒ breathable PEBA films
per ASTM E96.11
12.5 Styrenic Block Copolymer Applications and uses: Primarily food packaging,
(SBC) TPEs packed fruits and vegetables, fresh pasta and cheese,
as thermoformed cups and lids, and also in applica-
Styrenic block copolymer (SBC) TPEs are multi- tions including shrink film, must stay fresh as long
phase compositions in which the phases are chemi- as possible. Styrolux co-extruded with other ther-
cally bonded by block copolymerization (see Section moplastics, provides transparent barrier-layer
2.2). At least one of the phases is a hard styrenic composites (Tables 12.22e12.24).
polymer. This styrenic phase may become fluid when
the TPE composition is heated. Another phase is Table 12.23 Permeability of Nitrogen at 23 C
a softer elastomeric material that is rubber-like at through BASF StyroluxÒ Films12
room temperature. The polystyrene blocks act as
cross-links, tying the elastomeric chains together in Permeability Coefficient
a three-dimensional network. SBC TPEs have no Source Normalized
commercial applications when the product is just Document Units
a pure polymer. They must be compounded with Units (cm3/ (cm3 mm/
other polymers, oils, fillers, and additives to have any StyroluxÒ m2 day bar) cm2 day atm)
commercial value. 684 D 700 70.9
Manufacturers and trade names: BASF
656 C 350 35.5
StyroluxÒ .
Thickness: 0.1 mm.
Table 12.22 Permeability of Oxygen at 23 C Table 12.24 Permeability of Carbon Dioxide at 23 C

through BASF StyroluxÒ Films14 through BASF StyroluxÒ Films12
Permeability Coefficient Permeability Coefficient
Source Normalized Source Normalized

Document Units Document Units
Units (cm3/ (cm3 mm/ Units (cm3/ (cm3 mm/
StyroluxÒ m2 day bar) cm2 day atm) StyroluxÒ m2 day bar) cm2 day atm)
684 D 2600 263 684 D 15,000 1520
656 C 1600 162 656 C 8000 811
Thickness: 0.1 mm. Thickness: 0.1 mm.
12.6 Ethylene Acrylic Elastomers

(AEM)
AEM is mainly a copolymer of ethylene and
methyl acrylate. These copolymers are generally
cured with peroxides. Some AEM polymers add
small amounts of a third carboxylic monomer to
provide cure sites reactive to certain amines. AEM Figure 12.10 Structural units that are in DuPont
Elastomers VamacÒ AEM.
polymers do not have any crystallinity and the
properties are related to the ratio of ethylene to Good mechanical strength
methyl acrylate monomers used to make the poly-
mer. The ethylene imparts good low-temperature Very good compression set resistance
properties, while the methyl acrylate content Good flex resistance
provides oil resistance (see Fig. 12.10). Vibration-damping consistency
Cured properties of AEM include:
Low permeability to many gases
High-temperature durability Colorability
Good oil resistance with service lubricants Nonhalogen, low-smoke emissions
Excellent water resistance
Manufacturers and trade names: Ferrod
Good low-temperature flexibility Advanced Polymer Alloys, AlcrynÒ ; DuPont
Outstanding ozone/weather resistance VamacÒ (Tables 12.25e12.28).
Table 12.25 Permeation of Various Gases at 0 C through FerrodAdvanced Polymer Alloys AlcrynÒ 1170BK
AEM15

Permeant Gas [cm3 (STP) 0.5 mm/m2 atm day] (cm3(STP) mm/m2 atm day)
Air 64 32
Nitrogen 48 24
Oxygen 598 299
Propane 192 96
Butane 174 87
Table 12.26 Permeation of Various FreonÒ Gases at 0 C through FerrodAdvanced Polymer Alloys AlcrynÒ
AEM14

[cm3(STP) 1010/s cm2 cm Hg] (cm3 mm/m2 day atm)
Product Code FreonÒ 12 FreonÒ 22 FreonÒ 12 FreonÒ 22

AlcrynÒ 1060BK 5.3 32.3 348 2121
AlcrynÒ 1070BK 7.27 23.6 477 1550
Ò
Alcryn 1080BK 7.07 39.9 464 2620
Table 12.27 Permeation of Various Liquids at 23 C through FerrodAdvanced Polymer Alloys AlcrynÒ AEM14

Liquids (g 30 mil/day m2) (g mm/m2 day)
Distilled water (0e5 days) 2.4 1.8288
Distilled water (5e8 days) 6.8 5.1816
Reference fuel B 1820 1386.84
Exxon unleaded gasoline 1795 1367.79
Diesel fuel 70 53.34
ASTM #3 Oil 0 0
Test method: ASTM E96.
Table 12.28 Permeation of Various Gases at 23 C through DuPont Elastomers VamacÒ AEM16
Permeation Coefficient

Permeant Gas (108 cm3 cm/cm2 atm s) (cm3 mm/m2 atm day)
Air 0.3 25.9
Nitrogen 0.3 25.9
Methane 1 86
Ò
Freon 12 1 86
Oxygen 1 86
Ò
Freon 22 5 432
Carbon dioxide 7 605
Hydrogen 2.9 251
Helium 2.7 233
12.7 Bromobutyl Rubber conveyor belts for high-temperature resistance, tank

linings for chemical resistance, and pharmaceutical
Bromobutyl rubber is a isobutyleneeisoprene closures and adhesives (Tables 12.29 and 12.30).
copolymer (halogenated butyl) containing reactive See also Figs. 12.13 and 12.14.
bromine replacing one of the hydrogens on some of
the isoprene units, which are shown in Fig. 12.11.
Bromobutyl rubber has a CAS number of 68441-14-5.
The bromine provides a crosslinking site. Cross-
linking occurs by reaction of the bromines on
different polymer chains or within the same polymer
chain.2 See Fig. 12.12 and the reference for chem-
istry details.
Manufacturers and trade names: Lanxess
Bromobutyl.
Applications and uses: It is mainly used in tubeless Figure 12.11 Bromobutyl rubber is a random mixture
tire inner liners. Nontire applications include of the following isoprene-based structural units.
Figure 12.12 Bromobutyl rubber crosslinking (vulcanization) occurs through the bromine atoms on adjacent
polymer chains.
Table 12.29 Permeation of Oxygen Gas through ExxonMobil Chemical Model Formula Compounds17
Source Document Units, Normalized Units, Permeability
Grade Transmission Rate (cm3/m2 day) Coefficient (cm3 mm/m2 day atm)
At 40 C
Butyl Grade 065 120.0 135
Butyl Grade 0268 121.0 136
Butyl Grade 0269 118.0 129

At 60 C
Butyl Grade 2222 593
Ò
Test method: Mocon permeability test, ExxonMobil method, oxygen 21% concentration.
Table 12.30 Permeation of Oxygen Gas at 60 C through ExxonMobil Chemical Model Formulations for Auto-
mobile Tire Innerliners18
Normalized Units, Permeability
Grade Coefficient (cm3 mm/m2 day atm)
100% Butyl Grade 2222 530
90% Butyl Grade 2222 þ 10% Natural Rubber TSR20 760
Test method: Mocon permeability test, ExxonMobil method, oxygen 21% concentration.
Figure 12.13 Permeation of air vs.

bromobutyl concentration through
bromoisobutyleneeisoprene
copolymer.19
Figure 12.14 Permeation of

moisture vapor vs. bromobutyl
concentration through
bromoisobutyleneeisoprene
copolymer.18
12.8 Butyl Rubber

Butyl is an elastomeric copolymer of isobutylene
with small amounts of isoprene (1e2.5 mol%). Its
structure is shown in Fig. 12.15 and its CAS Number
is 9010-85-9.
Manufacturers and trade names: Lanxess Butyl,
ExxonMobil Chemical (Polysar is obsolete).
Applications and uses: Major application area is
the tire industry, mainly used for inner tubes and tire-
curing bladders. Nontire applications include phar-
maceutical closures, roof membranes, body mounts,
and tank linings (Tables 12.31e12.34).
See also Fig. 12.16. Figure 12.15 Chemical structure of butyl rubber.
Table 12.31 Permeation of Air vs. Temperature through Butyl

Rubber20,21
(cm3 mm/m2 day atm)
Temperature ( C) Polysar Butyl 301a Exxon Butyl 268

24 36.4
40 51.8
60 155
66 375
80 3974
93 1195
Table 12.32 Permeation of Various Gases at 0 C through Butyl Rubber15
Source Document Units
[cm3(STP) Normalized Units

Permeant 0.5 mm/ [1010 cm3 (STP) cm/ (cm3 mm/
Gas m2 day atm] cm2 s cm Hg] m2 day atm)
Air 45 23
Nitrogen 50 25
Oxygen 195 98
Propane 475 238
Butane 4360 2180
Ò
Freon 12 22.8 1497
Ò
Freon 22 33.6 2206
Table 12.33 Permeation of Oxygen at 40 C through EXXONÔ Butyl Rubber

Material Grade (cm3 mm/m2 day mm Hg) (cm3 mm/m2 day atm)
EXXONÔ Butyl Grade 268 0.179 136
Oxygen concentration: 21%. Test method: Mocon Permeability Test, ExxonÔ procedure.
Table 12.34 Permeability of Gas vs. Temperature through Bayer Lanxess ButylÒ Butyl Rubber22
Temperature Source Document Units Normalized Units

Permeant Gas ( C) (cm2/s bar) 3 109 (cm3 mm/m2 day atm)
Air 60 20 176
80 50 438
Nitrogen 60 15 131
80 35 306
Carbon dioxide 60 130 1138
80 290 2539

temperature through butyl rubber.23
12.9 Chlorobutyl Rubber the more common sulfur modified “GN” types.
(Polychloroprene) Polychloroprene is known for its resistance to oil,
gasoline, sunlight, ozone, and oxidation though there
Chlorobutyl rubber or polychloroprene is elasto- are other polymers that have better resistance to these
meric isobutyleneeisoprene copolymer (halogenated same elements. Polychloroprene’s advantage is its
butyl) containing reactive chlorine. Polychloroprene ability to combine these properties moderately into
was developed in 1930 by DuPontÔ and is best one all-purpose polymer.
known under the name neoprene. The polymer is
made from chloroprene and its structure is given in
Fig. 12.17. Its CAS number is 9010-98-4. The poly-
mer is often modified to permit some degree of
polymerization. Sulfur is a common modifier and the
compounds are often called vulcanizates.
DuPont elastomer neoprene is available in many
varieties including nonsulfur modified “W” and Figure 12.17 Polymerization of chloroprene.
Table 12.35 Permeation of Gases through Lanxess BayprenÒ Polychloroprene Rubber

Vulcanizate24
Permeant Temperature Source Document Units Normalized Units

Gas ( C) (cm2/s bar) 3 109 (cm3 mm/m2 day atm)
Air 60 70 613
80 120 1051
Nitrogen 60 40 350
80 80 700
Carbon 60 580 5078
dioxide 80 760 6653
Manufacturers and trade names: DuPontÔ inner tubes. Other applications include conveyor
Performance Elastomers Neoprene (discontinued), belts requiring high-temperature resistance, tank
ExxonÔ Chlorobutyl, Lanxess BayprenÒ . linings for chemical resistance, and pharmaceu-
Applications and uses: Chlorobutyl’s major tical closures and adhesives, gloves, adhesives,
application area is the tire industry. It is mainly binders, coatings, dipped goods, elasticized
used in tubeless tire inner liners, sidewalls, and asphalt, and concrete (Tables 12.35e39).
Table 12.36 Permeation of gases at 23 C through DuPontÔ Performance Elastomers Neoprene

Polychloroprene Rubber Vulcanizate15

Permeant Gas [cm3(STP)/m2 day atm] (cm3 mm/m2 day atm)
Air 210 105
Nitrogen 170 85
Oxygen 595 298
Methane 380 190
Propane 2100 445
Butane 6150 3075
Hydrogen 2185 1093
Helium 1800 900
Ammonia 26,350 13,175
Sulfur dioxide 40,120 20,060
Ò
Freon 12 1155 578
Ò
Freon 22 2415 1208
Thickness: 0.5 mm.
Table 12.37 Permeation of Vapors at 23 C through DuPontÔ Performance Elastomers Neoprene Poly-
chloroprene Rubber Vulcanizate22
Permeant Vapor Source Document Units (g/m2 day) Normalized Units (g mm/m2 day)
Water (0e5 days) 1.2 0.7
Water (0e5 days) 3.4 2.6
Reference fuel B 2875 2191
Exxon unleaded gasoline 2960 2256
Diesel fuel 215 164
ASTM #3 oil 0 0
Thickness: 0.762 mm.
Table 12.38 Permeability of Various Gases at 23 C and One Atmosphere Pressure Differential through
Chlorobutyl Rubber25
Source Document Units, 3108$ Normalized Units

Permeant Gas (cm3 cm/cm2 s atm) (cm3 mm/m2 day atm)
Air 1.1 95
Nitrogen 1.0 86
Methane 2.9 248
Ò
Freon 12 6.7 576
Oxygen 3.2 273
Ò
Freon 22 14.2 1224
Carbon dioxide 22.5 1940
Hydrogen 12.6 1086
Helium 10.5 905
Table 12.39 Permeability of Air vs. Temperature through ExxonÔ Chlorobutyl 1068 Chlorobutyl Rubber21
Temperature ( C) 23.9 65.6 93.3
3 2
Source document units, permeability coefficient (ft mil/ft day psi) 0.00034 0.0032 0.0104
3 2
Normalized units, permeability coefficient (cm mm/m day atm) 38.7 364 1183
Test apparatus: Aminco permeability apparatus.
12.10 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.
Manufacturers and trade names: ExxonÔ ply roofing sheet, window gaskets, sound deadening,
VistalonÔ and Lanxess BunaÒ EP. solar pool panels, and face respirators (Tables 12.40
Applications and uses: Impact modification, hose, and 12.41).
tubing, weather strips, insulation, jacketing, single- See also Fig. 12.18.
Table 12.40 Permeation of Various Gases at 0 C and One Atmosphere Pressure Differential through EPDM
Rubber15

Permeant Gas [cm3(STP) 0.5 mm/m2 day atm] (cm3 mm/m2 day atm)
Air 1615 808
Oxygen 3470 1735
Nitrogen 1180 590
Carbon dioxide 15,385 7693
Helium 2720 1360
Table 12.41 Permeability of Air vs. Temperature through Exxon VistalonÔ EthyleneePropyleneeDiene
Copolymer (EPM) Rubbers21
Product Code VistalonÔ 404 VistalonÔ 4608

Temperature ( C) 23.9 65.6 93.3 23.9 65.6 93.3
Source document 0.00405 0.0225 0.0637 0.00587 0.029 0.0619
units, permeability
coefficient (ft3 mil/
ft2 day psi)
Normalized units, 461 2560 7247 668 3299 7043
permeability
coefficient
(cm3 mm/
m2 day atm)
Test apparatus: Aminco permeability apparatus.
Figure 12.18 Air vs. temperature

through ethyleneepropylenee
diene copolymer rubber.20
12.11 Epichlorohydrin Rubber oxide. There is also a terpolymer of epichlorohydrin,

(CO, ECO) ethylene oxide, and a monomer to introduce a carbon
double bond to the chain that functions as a cure site.
Epichlorohydrin rubbers include homopolymer of CO is the ISO designation for the homopolymer and
epichlorohydrin and a copolymer with ethylene ECO is the ISO designation for the ethylene oxide
copolymer. GECO is the designation for
the terpolymer (usually allyl glycidyl ether). The
monomers and polymer structures are given in Figs
12.19e12.21.
The ratios of the monomers are tailored to provide
the desired properties. The epichlorohydrin mono-
Figure 12.19 Epichlorohydrin homopolymer (CO) mer provides heat and ozone resistance, fuel and oil
monomer and polymer structure. resistance, and gas permeation resistance.
Figure 12.20 Epichlorohydrin copolymer

(ECO) monomers and polymer structure.
Figure 12.21 Epichlorohydrin terpolymer (GECO) monomers and polymer structures.
Table 12.42 Permeability of Various Gases at Room Temperature through Zeus Chemicals HydrinÒ
Epichlorohydrin Polymers26
HydrinÒ Homopolymer HydrinÒ Copolymer
Permeation Coefficient
Source Document Normalized Source Normalized

Units, 3108 Units Document Units
Permeant (cm3 cm/ (cm3 mm/ Units, 3108 (cm3 mm/
Gas cm2 s atm) m2 day atm) (cm2/s atm) m2 day atm)
Air 0.105 9 0.525 45
Nitrogen 0.048 4
Oxygen 0.255 22
Helium 1.97 170
Carbon dioxide 2.6 225
Table 12.43 Water Vapor Transmission Rate at 38 C through Zeus

Chemicals HydrinÒ Epichlorohydrin Polymers26
Polymer Type Vapor Transmission Rate (g/m2 day)
HydrinÒ homopolymer 15.5
Ò
Hydrin copolymer 85.9
Thickness not known.
Table 12.44 Comparison of Air and Nitrogen Permeability through

Different Types of Zeon Chemicals HydrinÒ Epichlorohydrin
Polymers27
(cm3 mm/m2 day atm)
Polymer Type Air Nitrogen

Homopolymer HydrinÒ H 15 12
Copolymer HydrinÒ C2000 43 38
Ò
Terpolymer Hydrin T3102 26 30
Figure 12.22 Permeation vs.

temperature of gases through
epichlorohydrin rubber.28
The ethylene monomer lowers the glass transition boots, closed-cell sponge, and fabric coatings/belting
temperature, reduces heat resistance, and imparts (Tables 12.42e12.44).
static dissipative properties. The unsaturated mono- See also Fig. 12.22.
mer introduces a site for sulfur and peroxide curing.
Manufacturers and trade names: Hercules, Inc.
Herclor, B.F. Goodrich Co., and Zeon Chemicals, 12.12 Fluoroelastomers (FKM)
HydrinÒ .
Applications and uses: Fuel hoses/liners (cells), air A fluoroelastomer is a special-purpose fluoro-
ducts, emissions tubing, electrostatic dissipative carbon-based synthetic rubber. When compared with
rolls, low-temperature fuel handling curb hose, dia- most other elastomers, it has wide chemical resis-
phragms, gaskets/O-rings, vibration dampers, dust tance and superior performance, especially in high-
used throughout the chemical processing and

power generation industries. “B” types are spec-
ified for gaskets sealing mineral acids such as
sulfuric acids and other aggressive chemicals
that are hauled by rail and bulk tankers. “B”
types can be formulated with peroxide cure
systems to resist strong acids, hot water, and
steam.
“F ” Type: This terpolymer is the latest generation
Figure 12.23 Monomers used to make of “high” fluorine elastomers, with the addition of
fluoroelastomers. 2% more fluorine (70%). This is considered an
excellent elastomer for sealing today’s oxygenated
automotive fuels and lubricants. “F” types can be
temperature application in different media. Fluo- formulated to resist concentrated aqueous inor-
roelastomers are categorized under the ASTM ganic acids, hot water, and steam.
D1418 & ISO 1629 designation of FKM. The four VitonÒ GF fluorocarbons are tetrapolymers
main monomers that are used to make fluoroelas- composed of TFE, VF2, HFP, and small amounts
tomers are shown in Fig. 12.23. of a cure site monomer. Presence of the cure site
The fluorine content is an important parameter of monomer allows peroxide curing of the
each fluoroelastomer and is frequently reported in compound, which is normally 70% fluorine. As
fact sheets. Most common grades have fluorine the most fluid resistant of the various FKM types,
content that varies between 66 and 70%. Generally VitonÒ GF compounds offer improved resistance
more fluorine means higher chemical resistance. to water, steam, and acids.
There are a number of types of fluoroelastomers. VitonÒ GFLT fluorocarbons are similar to VitonÒ
GF, except that perfluoromethylvinyl ether
“A” Type: FKM-A is the most widely used poly- (PMVE) is used in place of HFP. The “LT” in
mer in industry today, and it is the most cost-effec- VitonÒ GFLT stands for “low temperature.” The
tive polymer in relationship to performance. It has combination of VF2, PMVE, TFE, and a cure
a fluorine level around 66%. This elastomer was site monomer is designed to retain both the supe-
designed in the late 1950s for the space program rior chemical resistance and high-heat resistance
and today is widely used as a general-purpose of the G-series fluorocarbons. In addition, VitonÒ
FKM offering excellent fluid resistance to auto- GFLT compounds (typically 67% fluorine) offer
motive fuels and lubricants, as well as elevated the lowest swell and the best low-temperature
service temperatures. properties of the types discussed here VitonÒ
“B” Type: FKM-B is a terpolymer with an GFLT can seal in a static application down to
increased fluorine (68e69%) content is widely approximately 40 F.
Table 12.45 Curing Chemistry of Fluoroelastomers

Recommended
FKM Type Monomers Curable By Curative
Copolymer VF2, HFP Amine and bisphenol Bisphenol
Terpolymer VF2, HFP, TFE Amine and bisphenol Bisphenol
Peroxide curable VF2, HFP, TFE, CSM Amine, bisphenol, and Peroxide
peroxide
Low temperature VF2, HFP, TFE, PMVE, Amine, bisphenol, and Peroxide
CSM peroxide
FVMQ is a fluorosilicone and is covered in the The fluoroelastomers are cured by several
chapter on polysiloxanes/silicones. chemical means as described in Tables 12.45 and
FFKM (perfluoronated elastomers): This family of 12.46.
elastomers is widely known by the trade name that Manufacturers and trade names: Dyneon Fluo-
its inventors gave it, KalrezÒ . It is essentially an relÔ, Solvay Solexis TecnoflonÒ , DuPont VitonÒ ,
elastomeric form of PTFE and retains the extreme KalrezÒ , Daikin Dai-elÔ, Asahi Glass AFLASÒ .
chemical resistance at a temperature of PTFE up Applications: Seals, caulks, coatings, vibration
to 327 C. dampeners, expansion joints, gaskets, 0-rings, piston
seals, custom shapes, and stock rod and sheet (Tables
AFLASÒ , made by Asahi Glass Co., Ltd, is 12.47e12.51).
a copolymer of tetrafluoroethylene and propylene. See also Figs. 12.24e12.26.
The fluorine content is typically 57%.
Table 12.46 The Curing Chemistry Used by Solvay Solexis TecnoflonÒ Fluoroelastomer Products
Grade Fluorine Content (%) 10% Temperature of 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.
Table 12.47 Permeation of Air, Carbon Dioxide, Helium, Nitrogen, and Oxygen through DuPont
VitonÒ Fluoroelastomer29
Carbon
Penetrant Air Dioxide Helium Nitrogen Oxygen
Temperature 24 30 24 121 204 24 30
( C)
Source 9.9 5.9 8.92 1.74 6.7 5.4 1.1
document 1010 108 108 106 106 1010 108
gas
permeability
(cm3 cm/
cm2 s atm)
Normalized 8.55 508 771 15,034 57,888 4.67 95.0
permeability
coefficient
(cm3 mm/
m2 day atm)
Pressure: 1 atm. Sample size: 1cm2 1cm thick.
Table 12.48 Average Permeation Rates (Over 28 Days) of

Fuel C, Ethanol 90:10 for Solvay Solexis TecnoflonÒ FKM
Fluoroelastomers30
Permeation Rate (g mm/m2 day)
Fuel C, Ethanol Fuel C, Ethanol

Grade 90:10 85:15
N-535 2.2 40.7
T 636 2.7 45.5
P 757 0.9 21.9
P 959 NM 4.6
P 958 3.4 16.0
PL 855 10.2 68.2
Table 12.49 Oxygen Permeation through Dyneon FluorelÔ Fluoroelastomer

Grades
Permeability
Coefficient
% (cm3 mm/
Grade Type Fluorine m2 day atm)
22 Copolymer, 22% 66 98
carbon
35 Copolymer, 35% 66 98
carbon
FC- Copolymer 65.9 98
2110Q
FC-2110 Copolymer 65.9 98
Table 12.50 Permeation of Fuel Vapors through Various DuPontÔ Elastomer VitonÒ
Elastomers31
Vapor Permeation Rate (g mm/m2 day)
VitonÒ Type Fuel C CE-10 CE-25 CE-50 CE-85 Ethanol

GLT-S 24.4 85.0 101.8 94.1 35.9 18.0
GBLT-S 20.1 52.4 64.8 56.0 20.1 9.8
GFLT-S 17.2 42.8 52.8 44.0 16.9 8.4
GF-S 4.9 11.3 13.7 8.4 3.7 1.7
F605C 5.5 14.0 16.1 9.9 4.6 1.7
VTR-9209-NPC 8.5 25.8 29.1 18.8 10.0 3.8
Table 12.51 Additional Permeation of Fuel Vapors through Various DuPontÔ Elastomer VitonÒ Elastomers32
Vapor Permeation Rate (g mm/m2 day)
Fuel C at 90% Fuel C, 10% 85% Fuel C, 15% Toluene at

Material 23 C Ethanol Methanol 40 C
Fluorosilicone 455 584 635
Ò
Viton GLT 2.6 14 60
Ò
Viton AL 0.8 6.7 32
Ò
Viton A 0.8 7.5 36 49
Ò
Viton GFLT 1.8 6.5 14
Ò
Viton B 0.7 4.1 12
Ò
Viton GF 0.7 1.1 3.0 7
Ò
Viton ETP 14
Figure 12.24 Permeation of water,

helium, argon, and oxygen vs.
temperature through DuPontÔ
advanced elastomers VitonÒ
fluoroelastomer.28,33
Figure 12.25 Permeation of carbon

dioxide, hydrogen and nitrogen vs.
temperature through DuPontÔ
advanced elastomers VitonÒ
Figure 12.26 Permeation of

gases vs. temperature through
Asahi Glass AFLASÒ
12.13 Natural Rubber

Natural rubber is polyisoprene. The structure of
the monomer and polymer are given in Fig. 12.27. Its
CAS number is 9006-04-6. Chemical and environ-
mental resistance and mechanical properties are
improved through crosslinking (vulcanizing),
usually through treatment with sulfur. Figure 12.27 Structure of isoprene and polyisoprene.
Table 12.52 Relative Permeation of Various Gases through Natural Rubber34

Penetrant Oxygen Hydrogen Carbon Dioxide Nitrogen
Relative gas permeability (based on 46 100 260 17
hydrogen as 100)
Table 12.53 Permeability of Gas vs. Temperature through Natural Rubber15

Permeant Gas
Temperature ( C) (cm2/s bar) 3 109 (cm3 mm/m2 day atm)
Air 60 250 2189
80 400 3502
Nitrogen 60 180 1597
80 330 2889
Carbon dioxide 60 1600 14,007
80 2100 18,384
Natural rubber is more unsaturated and has fewer an increase in damping

methyl groups than butyl rubber causing it to be a reduction in swelling in hydrocarbon oils
20 times more permeable to air. The presence of
methyl groups generally serves to reduce the a decrease in gas permeability
permeability of polymers. an increase in silica reinforcement; improved
Epoxidized natural rubber (ENR) is derived from compatibility with polar polymers like polyvinyl
the partial epoxidation of the natural rubber mole- chloride
cule, resulting in a totally new type of elastomer. The reduced rolling resistance and increased wet
epoxide groups are randomly distributed along the grip
natural rubber molecule.
Epoxidation results in a systematic increase in the Applications and uses: Tire and other automotive
polarity and glass transition temperature. Property (Tables 12.52e12.54).
changes with increasing level of epoxidation include: See also Figs. 12.28e12.30.
Table 12.54 Permeation of Air vs. Temperature through Formulated Natural Rubber
Polysar Formulation20 Exxon Formulation21
Temperature ( C) 40 60 80 23.9 65.6 93.3

Source document 0.00436 0.0237 0.0402
units, gas
permeability (ft3 mil/
ft2 day psi)
Source document 11.8 26.8 43.9
units, gas 108 108 108
permeability (cm3 cm/
cm2 s atm)
Normalized units, 1020 2316 3793 496 2696 4574
permeability
coefficient (cm3 mm/
m2 day atm)

temperature through natural
rubber.22
Figure 12.29 Permeation of various gases vs. mineral filler through natural rubber.15
Figure 12.30 Permeation of oxygen and nitrogen vs. mol% epoxidation through natural rubber.35
12.14 AcrylonitrileeButadiene typically used in molded parts to provide sufficient

Copolymer (NBR) molding forces, or back pressure, to eliminate
trapped air. Another use is to provide increased
Acrylonitrileebutadiene copolymers (NBR) or dimensional stability or shape retention for
more common nitrile rubbers are copolymers of extruded goods and calendered goods. This leads
butadiene and acrylonitrile. The monomers and to more efficient extruding and vulcanization of
polymer structure are shown in Fig. 12.31. The CAS intricate shaped parts as well as improved release
number is 9003-18-3. from calender rolls. These NBRs also add dimen-
NBR is commonly considered the workhorse of sional stability, impact resistance, and flexibility
the industrial and automotive rubber products for PVC modification.
industries. NBR is actually a complex family of Carboxylated Nitrile (XNBR)dAddition of
unsaturated copolymers of acrylonitrile and buta- carboxylic acid groups to the NBR polymer’s
diene. The amount of acrylonitrile in the polymer is backbone significantly alters processing and cured
used to manipulate the balance of NBR properties. properties. The result is a polymer matrix with
Acrylonitrile content may range from 18 to 50%. significantly increased strength, measured by
Increasing acrylonitrile content leads to higher improved tensile, tear, modulus, and abrasion
hardness, strength, abrasion resistance, heat resis- resistance. The negative effects include reduction
tance, and oil/fuel resistance, and lower resilience, in compression set, water resistance, resilience,
and low-temperature flexibility. and some low-temperature properties.
There are several general types of NBR:
Bound Antioxidant NBRdAn antioxidant is poly-
merized into the polymer chain. The purpose is to
Cold NBRdAcrylonitrile content ranges from 15
provide additional protection for the NBR during
to 51%. Cold polymers are polymerized at
prolonged fluid service or in cyclic fluid and air
a temperature range of 5 Ce15 C, depending
exposure. When compounding with highly rein-
on the balance of linear-to-branched configuration
forcing furnace carbon black the chemical reac-
desired. The lower-polymerization temperatures
tivity between the polymer and the pigment can
yield more-linear polymer chains.
limit hot air aging capability. Abrasion resistance
Hot NBRdPolymers are polymerized at the is improved when compared with conventional
temperature range of 30 Ce40 C. This process NBR, especially at elevated temperatures. They
yields highly branched polymers. Branching have also been found to exhibit excellent dynamic
supports good tack and a strong bond in adhesive properties.
applications. The physically entangled structure of
this kind of polymer also provides a significant Manufacturers and trade names: Lanxess
improvement in hot tear strength compared with PerbunanÒ , KrynacÒ and BaymodÒ N, Girsa,
a cold-polymerized counterpart. The hot poly- Hyundai, JSR Corporation, Kumho, Nantex, Nitri-
mers’ natural resistance to flow makes them excel- flex, PetroChina, Petroflex, Polimeri Europa Euro-
lent candidates for compression molding and prene, Zeon Chemicals.
sponge. Other applications are thin-walled or Applications and uses: Nonlatex gloves for the
complex extrusions where shape retention is healthcare industry, automotive transmission belts,
important. hoses, O-rings, gaskets, oil seals, V-belts, synthetic
Crosslinked Hot NBRdThese are branched poly- leather, printer’s roller, and as cable jacketing
mers that are further cross-linked by the addition (Tables 12.55e12.58).
of a difunctional monomer. These products are See also Fig. 12.32.
Figure 12.31 Monomers and polymer

structure of NBR.
Table 12.55 Permeability of Air vs. Temperature through Bayer Lanxess KrynacÒ 800 Nitrile Rubber21
Temperature ( C) 40 60 80
8 8
Source document units, permeability coefficient 1.1 10 4.1 10 9.9 108
(cm3 cm/cm2 s atm)
Normalized units, permeability coefficient 95 354 855
(cm3 mm/m2 day atm)
Table 12.56 Permeability of Gas vs. Temperature through Bayer Lanxess KrynacÒ and PerbunanÒ Nitrile
Rubber22

Permeant Gas Temperature ( C) (cm2/s bar) 3 109 (cm3 mm/m2 day atm)
Air 60 25e75 219e657
80 55e210 481e1838
Nitrogen 60 10e40 88e350
80 25e70 219e613
Carbon dioxide 60 300e580 2626e5077
80 480e970 4202e8492
Table 12.57 Permeability of Gases at 23 C through High-Nitrile Content Nitrile Rubber15

Permeant Gas [cm3(STP)/m2 day atm] (cm3 mm/m2 day atm)
Air 220 110
Oxygen 145 78
Hydrogen 920 460
Nitrogen 45 23
Carbon dioxide 1165 583
Helium 950 475
Table 12.58 Permeation of Vapors at 23 C through Low- and High-Nitrile Content Nitrile Rubber5
Low-Nitrile Content NBR High-Nitrile Content NBR

Document Units Units Document Units Units
Permeant Vapor (g/m2 day) (g mm/m2 day) (g/m2 day) (g mm/m2 day)
Water (0e5 days) 4.5 3.4 3.3 2.5
Water (0e5 days) 5.4 4.1 5.4 4.1
Table 12.58 (Continued )
Low-Nitrile Content NBR High-Nitrile Content NBR

Document Units Units Document Units Units
Permeant Vapor (g/m2 day) (g mm/m2 day) (g/m2 day) (g mm/m2 day)
Reference fuel B 1750 1333 390 297
Exxon unleaded 1930 1471 275 210
gasoline
Diesel fuel 95 72 20 15
ASTM #3 oil 0 0 0 0
Thickness: 0.762 mm.
Figure 12.32 Air vs. temperature

through Lanxess KrynacÒ 800
nitrile rubber.15
12.15 StyreneeButadiene Rubber

(SBR)
Styreneebutadiene or styreneebutadiene rubber
(SBR)2 is a synthetic rubber copolymer consisting of
styrene and butadiene, its structure is shown in
Fig. 12.33.
Manufacturers and trade names: Lanxess
KryleneÒ and KrynolÒ and many others.
Applications and uses: Employed extensively in
almost all sectors of the rubber industry. Used mainly
for tires, often in blends with NR; conveyor and
transmission belting, footwear soles and heels;
technical goods of all kinds, for example, seals,
membranes, hose, and rolls (Table 12.59).
See also Fig. 12.34. Figure 12.33 Structure of SBR.
Table 12.59 Permeability of Gas vs. Temperature through Bayer Lanxess KryleneÒ StyreneeButadiene
Rubber15

Permeant Gas Temperature ( C) (cm2/s bar) 3 109 (cm3 mm/m2 day atm)
Air 60 150 1313
80 260 2276
Nitrogen 60 110 963
80 200 1751
Carbon dioxide 60 1200 10,505
80 1500 13,132

temperature through styrenee
butadiene rubber.20
References 8. HytrelÒ design guidedmodule V, H-81098.

DuPontÔ; 2000.
1. McKeen LW. The effect of temperature and other 9. RiteflexÒ brochure RF-001. Ticona; 2006.
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William Andrew Publishing; 2008. industry. PPM-201B Eastman; 1999.
2. Drobny JG. Handbook of thermoplastic elasto- 11. PebaxÒ , supplier design guide. Atochem; 1987.
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3. Estane thermoplastic polyurethane for film and 14. Styrolux product line, properties, processing,
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4. Estane breathabledhigh moisture vapor trans- BASF Aktiengesellschaft; 1992.
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6. Texin and Desmopan. A guide to engineering 1997.
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7. SantopreneÒ rubber physical properties guide. elastomers. DuPont Performance Elastomers;
Advanced Elastomer Systems; 2005. 2008.
17. ExxonMobil Chemical. Model formulation 28. Laurenson L, Dennis N. Permeability of

property sheets; 2008. common elastomers for gases over a range of
18. ExxonMobil Chemical. ExxonÔ bromobutyl temperatures. J Vacuum Science & Technology
rubber compounding and applications manual; 1985;3:1707e10.
2009. 29. The engineering properties of viton fluoroelas-
19. Bromobutyl rubber optimizing key properties. tomer. Supplier design guide (E-46315e1).
Supplier marketing literature. Exxon Chemicals, DuPont Company; 1987.
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12 Elastomers and Rubbers

Permeability Properties of Plastics and Elastomers. DOI: 10.1016/B978-1-4377-3469-0.10012-8

Figure 12.1 Molecular structure of

Table 12.3 Permeation of Solvent Vapors through Lubrizol EstaneÒ TPU2

Vapor Permeation Rate

Permeant Temperature Thickness Source Document Normalized Units

Table 12.4 Permeation of Gases at 20 C through Various BASF ElastollanÒ TPUs3

Source Document Units, Permeability Coefficient (m2/s Pa) 3 10e18

C 80 A 105 96 1751 394 306 35 123

Table 12.5 Water Vapor Permeation at 23 C through Various BASF ElastollanÒ

Figure 12.2 Permeability of

Figure 12.3 Water vapor

Figure 12.4 Permeability of gases

Figure 12.5 Permeability of gases

Figure 12.6 Permeability of gases

12.2 Olefinic TPEs (TPO) compounds include fillers, reinforcements, lubri-

201e73 201e87 203e50 201e73 201e87 203e50

Source Document Units Normalized Units

ASTM E96, ASTM E96, ASTM E96, ASTM E96,

SantopreneÒ Source Document Units

Figure 12.7 Molecular structure of

12.3 Thermoplastic Copolyester In these polyester TPEs, the hard polyester

Source Document Units Normalized Units

Source Document Units Normalized Units

Table 12.12 Permeability of Oxygen at 23 C through Ticona RiteflexÒ 663

Source Document Units Normalized Units

12.4 Thermoplastic Polyether Light weight

Vapor Transmission Rate

Source Document Units Normalized Units

Vapor Transmission Rate

Permeability Coefficient Permeability Coefficient

Source Normalized Source

2533 150 1010 985 3533 100 1010 657

MV6100 6500 163 MV3000 3000 75

MV1205 24,000 600 MV6100 650 17

PEBD 6000 150 MV1205 3900 98

Table 12.17 Permeability of Carbon Dioxide at 23 C

Table 12.20 Permeability of Propane at 23 C and 0% RH through Arkema PEBAXÒ Films10

Source Document Units Normalized Units

Figure 12.9 Water vapor perme-

Table 12.22 Permeability of Oxygen at 23 C Table 12.24 Permeability of Carbon Dioxide at 23 C

Permeability Coefficient Permeability Coefficient

Source Normalized Source Normalized

12.6 Ethylene Acrylic Elastomers

Source Document Units Normalized Units

Source Document Units Normalized Units

Product Code FreonÒ 12 FreonÒ 22 FreonÒ 12 FreonÒ 22

Vapor Transmission Rate

Source Document Units Normalized Units

Source Document Units Normalized Units

12.7 Bromobutyl Rubber conveyor belts for high-temperature resistance, tank

Figure 12.13 Permeation of air vs.

Figure 12.14 Permeation of

12.8 Butyl Rubber

Table 12.31 Permeation of Air vs. Temperature through Butyl

Temperature ( C) Polysar Butyl 301a Exxon Butyl 268

Table 12.32 Permeation of Various Gases at 0 C through Butyl Rubber15

Source Document Units

[cm3(STP) Normalized Units

Table 12.33 Permeation of Oxygen at 40 C through EXXONÔ Butyl Rubber

2533 150 1010 985 3533 100 1010 657

Source Document Units, 3108$ Normalized Units