Specialty Elastomers for Automotive Applications

SPECIALTY ELASTOMERS FOR AUTOMOTIVE
APPLICATIONS
Kinro Hashimoto, Akio Maeda, Kiyoshi Hosoya,∗ and Yoshihiro Todani
Nippon Zeon Co., Ltd. Rubber Laboratory, 1-2-1 Yako, Kawasaki-ku, Kawasaki, Japan 210
CONTENTS
Page
I. General/Historical discussion of the use of speciality elastomers for
automotive applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
A. General introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
B. Oil-resistant elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
C. Automotive engine applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
1. Synchronous belts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
2. Seals and gaskets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
3. Oil cooler hose and air duct hose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
4. Vibration isolation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
D. Fuel and hydraulic systems applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
1. Hoses for fuel systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
a. Fuel hose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
b. Filler neck hose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
c. Evaporation hose (connecting the canister and the fuel
tank) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
d. Control hose (connecting the vacuum control valve and the
intake manifold) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
2. Seals and diaphragms for fuel systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
3. Rubber devices for power steering systems . . . . . . . . . . . . . . . . . . . . . . . . . 460
a. Power steering hose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460
b. Seals for power steering systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
4. Rubber devices for air conditioning systems . . . . . . . . . . . . . . . . . . . . . . . 461
a. Air conditioning hoses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
b. Air conditioning seals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
II. Synthesis, characteristics and properties of speciality elastomers . . . . . . . . . . 461
A. Nitrile elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
2. Manufacturing method of NBR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
3. Manufacturing method of HNBR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 462
4. Grades of NBR and HNBR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 462
a. Acrylonitrile content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 462
b. Polymerization temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
c. Mooney viscosity of NBR and HNBR . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
d. Conversion of polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
e. Stabilizers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
f. Terpolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
g. Physical form of products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
h. Polymer blend and carbon wet masterbatch . . . . . . . . . . . . . . . . . . . . . 464
i. After reaction of NBR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
∗
Corresponding author. Tel.: 81-44-276-3733, 3734; fax: 81-44-276-3730; e-mail: hosoya@zeon.co.jp
449
450 RUBBER CHEMISTRY AND TECHNOLOGY Vol. 70
5. Formulation and processing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464

a. Compounding of NBR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
b. Compounding of HNBR. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465
6. Structure and properties of NBR and HNBR . . . . . . . . . . . . . . . . . . . . . . 465
a. Structure and analytical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
b. Basic properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
c. Unvulcanized NBR characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
d. Characteristics of vulcanized NBR, HNBR . . . . . . . . . . . . . . . . . . . . . . 468
7. Applications of NBR and HNBR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
a. Automotive uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
b. Hoses and tubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
c. Seals, packing and O-rings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
d. Rolls. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
e. Belts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471
f. Miscellaneous applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471
B. Epichlorohydrin elastomers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
2. Manufacturing method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
3. Grades of epichlorohydrin elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
4. Formulation and processing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
a. Selection of the cure system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
b. Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
c. Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
d. Antioxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
e. Processing aids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
f. Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
5. Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 476
a. Heat resistance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 476
b. Oil resistance and low temperature flexibility . . . . . . . . . . . . . . . . . . . . 476
c. Temperature dependency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 476
d. Air impermeability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 476
e. Miscellaneous properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 476
6. Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 476
C. Polyacrylic elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
2. Method of manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 478
3. Grades of ACM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 480
4. Compounding formulations and processing. . . . . . . . . . . . . . . . . . . . . . . . . 481
a. Curatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
b. Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
c. Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
d. Antioxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
e. Processing aids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
f. Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
5. Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
a. Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
b. Heat resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
c. Oil resistance and low-temperature properties . . . . . . . . . . . . . . . . . . . 486
d. Ozone, fluid and chemicals resistance. . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
6. Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
III. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
IV. Appendix A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 490
V. Appendix B . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
A. Glossary of abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
SPECIALTY ELASTOMERS FOR AUTOMOTIVE APPLICATIONS 451
I. GENERAL/HISTORICAL DISCUSSION OF THE USE OF SPECIALITY ELASTOMERS

FOR AUTOMOTIVE APPLICATIONS
A. GENERAL INTRODUCTION
Various elastomers are used for automotive components because of their physical properties,
chemical properties, durability, etc. There are belts to transmit energy, seals to support radial or
reciprocating parts, gaskets and O-rings to seal in oils and fuels, hoses to deliver liquid and gases
and diaphragms to control them.
Figure 1 shows one example of elastomers for gasoline engines reported by Akema and Yoshida.1
Rubbers are soft polymeric materials having generally 100 MPa of Young’s modulus (shown in
Figure 22 ) for the normally applied temperature range. They are widely used for the buffer posi-
tion between high modulus materials such as metals, plastics, glasses, etc., in energy transmission,
liquid delivery, and energy isolation positions. The materials are selected for their resistance to
fuels, oils, and heat; as well as their cold flexibility and sealing ability. However, different materials
are sometimes selected for the same device depending upon such factors as applied temperature,
class of fuels and oils, and the engineering design of the car.
The many problems confronting the automotive industry these days are shown in Table A–I.23
They are roughly classified into two areas: environmental and safety.
Elastomers for automotive applications have been changing to solve many kinds of problems.
Table A–II24 shows the trends of rubber materials being used for automotive parts. High perfor-
mance rubbers, which have heat resistance, long life, low permeability, good abrasion resistance,
and so on, are all being adopted.
B. OIL-RESISTANT ELASTOMERS
In 1934, nitrile rubber (NBR) was first manufactured by IG in Germany.3 NBR is an oil-
resistant elastomer similar to chloroprene (CR), both of which are widely used. NBR elastomers
are used for 70% of the automotive applications in Japan where oil resistance is required. Much
of the synthesis and processing technology for NBR elastomers was developed in response to the
needs of the automotive industry. Nominal production capacity of major synthetic suppliers is
listed in Table A–III.7
Fig. 1.—Rubber devices for automotive gasoline engines.

Fig. 2.—Young’s modulus of organic and inorganic materials.
Since 1960, the automotive industry has been subjected to the regulation of exhaust gas,
evaporation, noise, waste disposal, and environmental hazards. The industry must also adapt to
new considerations such as fuel economy, development of maintenance-free automobiles, durabil-
ity, high-class trend stability of products, high performance engines, and driving comfort. Also
important is the processability of the elastomer and a lower purchase price.4
The classification system of SAE J200 is intended for use with rubber products for automo-
tive applications. Rubber materials are designated on the basis of “Type” indicating their heat
resistance and “Class” designating their oil resistance. Type is based on change in tensile strength
of not more than ±30%, elongation of not more than 50%, and hardness of not more than ±15
points after heat aging for 70 hours at the appropriate temperature. Class is based on the resistance
of the materials to swelling in IRM 903 oil after immersion for 70 h at the appropriate temperature
up to 150 ◦ C.8 Figure 3 shows classified elastomers and elastomers that will be classified in the
near future.
C. AUTOMOTIVE ENGINE APPLICATIONS
1. Synchronous belts.—These belts synchronize crankshafts and camshafts. They were first
made under a Uniroyal patent in 1946; GM initially adopted the rubber synchronous belt in the
mid 1960s. In Japan, synchronous belts came into general use in the 1970s.9 Synchronous belts are
superior to metal chains in several respects: reduced noise when in contact with the sprocket, no
lubrication needed, lighter weight because of low density, multi-axle drives are an option because
of flexibility. The synchronous belt is used in more than 70% of the cars in Japan and 80% of the
Fig. 3.—Classification on SAE J 200.
cars in Europe.10 In North America, the large overhead valve engine is still widely used but the
small overhead camshaft engine is becoming more popular and synchronous belt use is expanding.
As synchronous belts replace metal chains, certain differences should be kept in mind. Since
belts are made of organic materials such as rubber and textiles, special consideration should be
given to mechanical load and degradation in ambient temperature. A synchronous belt and its
structure are shown in Figure 4.11 There are two flaws in belts composed of a fiberglass reinforcing
element and synthetic rubber matrix covered with a polyamide fabric. One is the cracking of the
back cover and the other is the loss of teeth. Table A–IV briefly explains the relationship between
the primary requirements of belts for the automotive industry and required characteristics of
rubber agreed upon by belt manufacturers and polymer suppliers.
To satisfy the first requirement—high transmission power—the lag between the rotation of the
sprocket and belt must be minimal. Therefore, high rigidity of the belt teeth is necessary to pre-
vent or reduce their deformation and deflection. This rigidity depends not only on hardness and
modulus, but also on dynamic complex modulus, because the teeth actually pulse during opera-
tion. As is indicated by the second quality requirement, the rigidity characteristics must perform
satisfactorily over a wide temperature range. High performance over a wide temperature range re-
quires high hardness, high modulus, excellent dynamic complex modulus with constancy of these
properties over the temperature range. These properties enable the belt to provide exceptional
power transmission performance.
One element of the third requirement—slower rate of crack growth of the back cover—relates
to heat, ozone and flex-crack resistance of the elastomer. Another—no breakage of the teeth—
Fig. 4.—Structure of synchronous belts.

relates to failure of the fabric, change of shape of the teeth, and adhesive strength of fabric and
cord to rubber. To prevent fabric fatigue, a minimal deformation of fabric is important. Hence,
the rubber teeth should be rigid. The reported phenomenon that the strength of the teeth in a CR
belt reaches a maximum after a short heat aging period supports this analysis.11 The change in
shape of the teeth is caused primarily by dynamic compression and, to a lesser extent, by volume
swell due to oil splashing onto the belt.
Twelve properties of an elastomer regarded as significant for synchronous belts are shown in
Figure 513 that, for simplification, we call a radar chart. The farther the location of the point on
each arm from the center of the circle, the better the property. The elastomer that has the greatest
area enclosed by connecting the individual point on the twelve arms of the chart is the best for the
application. It can be seen that HNBR has a much better balance of properties than CR because
of its stable complex modulus over a wide temperature range, low-temperature properties, better
heat and ozone resistance, much better resistance to flex crack initiation after aging, and good
oil resistance.
Fig. 5.—Quality requirements of synchronous belt and performance of CR and HNBR.

A belt for a taxi actually encounters higher temperature because of long idling during traffic
jams or waiting time. So it strongly needs a higher heat-resistance type belt. Compared with
CR for the back cover in belt functional tests, HNBR provides a 40 ◦ C improvement at the
same running time.11 HNBR can provide double the life of CR that has more than 100,000 km
durability as shown in Figure 6.11 Due to its superior characteristics, today approximately 90%
of all synchronous belts in Japan are made of HNBR. In Europe the figure is 60% and increasing.
Manufacturers are also beginning to use HNBR in the V-belt which serves the cooler fan
and the alternator. Continuous variable transmission belts made of rubber have been used in
motorcycles and these belts will soon be used in passenger cars if development progress continues.
New grades of HNBR were successfully developed in response to a variety of market needs. A wide
variety of HNBR grades are available such as easy processing grades, low-temperature grade, and
a grade reinforced with zinc methacrylate that gives exceptionally high tensile values.
2. Seals and gaskets.—A seal is a system used to stop the flow of liquids or other materials.
Metals, plastics, and fabrics are sometimes used to manufacture seals but rubber is preferred
because it maintains appropriate modulus against the sealing surface by using the viscoelastic
characteristics of rubber.15 As the lubricating oil for automotive engines and transmissions is
crude-petroleum oil, sealing materials are usually NBR, polyacrylate (ACM), silicone rubber
(VMQ), and fluoroelastomer (FKM).15 The basic physical properties and oil resistance of these
elastomers are shown in Table A–V.
Automotive engine oils are being required to have longer life between oil change intervals,
lower viscosity for fuel economy, and smoother lubrication and better performance at elevated
engine temperatures.16,17 SG grade engine oil of the American Petroleum Institute specification
was developed in 1980 and SH grade has been sold in Japan since 1994, but a lower viscosity
lubricant targeting fuel economy and high lubrication still needs to be developed. In an attempt
to find a high-performance oil, a synthetic lubricant oil has been developed, but its use is limited
because of its expensive cost and damage to rubber parts. Generally, engine oil is designed from
basic oil with additives added from 5 to 25% to work constantly at 120 ◦ C and even occasionally
at 150 ◦ C.18 These oil additives have mixed effects on rubber as some of them have a minimal
effect while others attack rubber aggressively.
A more detailed study was made of the influence of 22 different oil additives in ASTM No. 2 oil
and on several oil- and heat-resistant elastomers. The list of additives tested including dispersants,
detergents, antioxidants, viscosity improvers, antiwear agents, extreme pressure additives and
additives packages are shown in Table A–VI.
Fig. 6.—Belt running test.

The retained tensile strength of HNBR, FKM, ACM, and NBR immersed in oil with additive
after 168 hours at 150 ◦ C is shown in Figure 7.19 After immersion in various media, the actual
retained tensile strength is indicated on each of the arms of the circular radar chart, with zero
at the center and the greatest tensile strength value at the outer perimeter. The greater the area
enclosed by joining the points on each arm of the chart for various polymers, the better the overall
properties.
NBR is seriously deteriorated by detergents, antioxidants and anti-wear agents. Although
ACM has lower tensile strength, it was stable when exposed to all additives except for alkylphos-
phate and lead naphthanate. FKM also has low physical properties, but is one of the excellent
heat and oil resistant polymers. It was, however, adversely affected by succinicimide, alkyl phos-
phate and sulfur-containing olefins. HNBR has the highest tensile strength among them, and
was also resistant to all the oil additives, except for minor deterioration in the presence of zinc
dithiophosphate.
FKM is usually cured by bisphenol, amine, or peroxide; therefore, a detergent based on an
amine can react with and harden FKM. A new peroxide cured FKM has been developed. The
elastomer does not easily experience dehydrofluorination by amines as shown in Figure 8.20,21
NBR and cork rubber had been used as engine gaskets for a long time, but now ACM and
VMQ are mainly used for these gaskets to satisfy heat resistance, sealability and compression
set requirements. VMQ shows better cold flexibility and heat resistance under normal conditions
than ACM. VMQ is, however, significantly softened after long-term immersion in engine oil in
contrast to no degradation of FKM and ACM, as shown in Figure 9.22
3. Oil cooler hose and air duct hose.—Transmission-oil cooler hose and engine-oil cooler hose
had been made using an NBR tube and a CR cover. To improve heat resistance, epichlorohydrin
(ECO) and CM were selected, and now ACM and AEM are widely used. Air duct hose and
air intake hose must have flexibility, weathering resistance, vibration isolation, vacuum collapse
resistance, and oil resistance. Various elastomers (such as CR, NBR/PVC, ethylene propylene
diene rubber (EPDM), ECO, chlorinated polyethylene (CM), ACM, and thermoplastic elastomers
such as polyester, polypropylene blended with EPDM) are selected due to differing requirements
for vehicle engineering.
4. Vibration isolation.—Natural rubber (NR) has been used for quite some time for vibration
isolation in engine mounts. EPDM, IIR, and propylene oxide rubber (GPO) were tried to replace
NR; they provide better heat resistance, but because of the inferior fatigue resistance and dynamic
Fig. 7.—Lubricating oil additive resistance tensile strength at break after 168 h immersed
in ASTM #2 oil including various additives at 150 ◦ C.
Fig. 8.—Amine resistance of FKM.
properties of these materials when compared to NR, they hold only a small portion of this engine
mount market. An ideal material which provides a smooth ride should have a higher damping and
a lower stiffness ratio. Such a material is not currently available. A hydraulic damping isolator
(fluidized motor mount) had been developed which exhibits ideal damping properties by using a
sealed liquid containing reservoir inside the mount extending the dynamic properties beyond that
of the elastomer alone.
D. FUEL AND HYDRAULIC SYSTEMS APPLICATIONS
1. Hoses for fuel systems.—Fuel systems generally contain a tank, filter, pump and connecting
tubes. The fuel tubes are either steel, thermoplastic (generally polyamide, PA) or reinforced
rubber hose.
a. Fuel hose.—There are currently two fuel feed systems, i.e., carburetor and fuel injection.
The fuel hoses for the carburetor system were made from NBR or NBR/PVC(PB) for inner and
CR for outer until gasoline with a high aromatic fraction began to be used. This caused solvent
cracking of the inner NBR. Liquid NBR acting as a nonextractable plasticizer was found to resolve
this problem.
The outer layers of the fuel hoses have changed from CR to chlorosulfonated polyethylene
(CSM) or a terpolymer of epichlorohydrin, ethyleneoxide and allyl-glycidilether (GECO) because
Fig. 9.—SG grade engine oil resistance for gasket material.

Fig. 10.25 —Ozone resistance vs. AGE con- Fig. 11.25 —Heat Resistance vs. AGE Con-
tent. ∗ Sequential conditions were: immersed tent. ∗ Hardness change after air aging 288 h
in Fuel C for 48 h at 40 ◦ C, dryed for 24 h at 150 ◦ C.
at 23 ◦ C, then air aged for 72 h at 100 ◦ C.
Dynamic ozone conditions were: exposed in
50 pphm O, 0–30%, 1 Hz extention at 40 ◦ C.
of the elevated temperatures in the engine compartment. Ozone and heat resistance are improved
with increasing AGE content in GECO as shown in Figures 1025 and 11.25 GECO is extensively
used for the outer layer of current fuel hoses, because of excellent sequential dynamic ozone
resistance after test fuel extraction to compare with CR and CSM as shown in Figure 12.26
There are two types of hoses used in the fuel injection system: 1) high pressure hose between
the fuel pump and injection valve and 2) low pressure hose between the pressure regulator and
fuel tank. FKM is used for the inner layer of the high pressure type because FKM has low gasoline
permeability, good oxidized gasoline resistance and high heat resistance.
The inner layer of the low pressure hose uses FKM or HNBR. Compared to FKM, HNBR has
inferior fuel impermeability, but is less expensive. And compared with NBR, HNBR has higher
Fig. 12.26 —Sequential dynamic ozone crack rat- Fig. 13.27 —Oxidized fuel resistance of
+
HNBR
ing. ∗ Sequential conditions were: immersed in and NBR. ∗ Test fuel is: 0.1 ppm Cu2 in Fuel
test fuel (toluene 60 wt % and iso-octane 40 wt C with organic peroxide (peroxide number is 25),
%) for 48 h at 40 ◦ C, dryed for 24 h at 23 ◦ C, immersion at 60 ◦ C.
then air aged for 72 h at 100 ◦ C. Dynamic ozone
conditions were: exposed in 50 pphm O, 0–30%,
1 Hz extention at 40 ◦ C (•, GECO, ◦; CSM, 4;
CR).
tensile strength after immersion testing in oxidized gasoline as shown in Figure 13.27 In addition,
it has a good balance of physical properties as shown in Figure 14.28
b. Filler neck hose.—The filler neck hose that connects the filler cap and fuel tank has been
made from PB. Recently filler neck hoses made from FKM terpolymer for inner and GECO for
outer have been developed to further decrease gasoline permeability. This is necessary because
of stricter emission regulations such as the SHED TEST introduced in 1995 in California, USA.
Thermoplastic type fluorinated liners are one of the future material in this application.
c. Evaporation hose (connecting the canister and the fuel tank).—Evaporation hose is made
from the same materials as the carburetor fuel hose system, i.e., generally NBR for inner and CR
for outer.
d. Control hose (connecting the vacuum control valve and the intake manifold).—Three rub-
ber materials are used for control hoses depending on the service temperature. With increasing
temperature requirements these go from NBR/CR to GECO to ACM. New ACM formulations
have been developed to provide a good balance of physical properties for this application as shown
in Figure 15.29
2. Seals and diaphragms for fuel systems.—The fuel pump diaphragm is a typical fuel pump
mechanism for the carburetor system. This diaphragm sees heat from the engine so it is necessary
to have high heat resistance and long durability in gasoline. NBR and PB were used for this but
HNBR and FKM are now used because of the need for oxidized gasoline resistance. For seals
NBR, PB, HNBR and FKM are all used for damper, insulator and oil sealing depending on the
service temperature.
Fig. 14.28 —Physical properties of several elastomer for fuel applications.

Fig. 15.29 —Comparison of cure system for ACM53.
3. Rubber devices for power steering systems.—Oil pressure power steering systems (PS) consist
of a control valve, power cylinder, oil pump, and attached equipment. Power steering fluid is a
mixture of lubricating oil, antioxidant, rust preventor, defoaming agent, and other additives.
a. Power steering hose.—Power steering hoses connect the oil tank, oil pump, control valve
and power cylinder. The power steering hoses need to have high pressure resistance, high pulse
absorption, fast oil cooling, no cavitation, and low pressure loss.
Power steering systems have two different hoses: 1) a high pressure hose between the oil pump
and gear box and 2) a low pressure hose between the gear box and oil tank. Traditionally, both
hoses were made from NBR for inner and CR for outer layers. Inner layer materials for the low
pressure hoses are now changing to ACM or CSM to improve heat resistance. New high pressure
hoses made from HNBR for inner and CSM for outer have higher heat resistance than the past
hoses. Figure 1627 shows improved hoses have three times longer life at 140 ◦ C and 20 ◦ C higher
heat resistance for equivalent life.
Fig. 16.27 —Heat resistance of power steering hoses.

b. Seals for power steering systems.—Power steering systems need high pressure oil and use
many seals. Materials for these seals are changing from NBR to more heat resistant elastomers
(ACM or HNBR) due to increasing engine compartment temperatures.
4. Rubber devices for air conditioning systems.—Air conditioning systems use fluorinated re-
frigerants and consist of a compressor, condenser, receiver tank, expansion valve, and evaporator.
Dichlorodifluoromethane (CFC-12) has been replaced with tetrafluoroethane (HFC-134a) as the
refrigerant for automotive systems. The lubricating oil has also been changed from mineral to
polyalkyeleneglycol (PAG).
a. Air conditioning hoses.—Hoses with NBR for inner layers and CR for outer layers were used
with CFC-12 which absorb the vibration between the engine and chassis. However, the changing
of refrigerant and lubricating oil required improved materials, and a three layer hose. The inner
layer has high heat resistance and low permeability, the middle layer has low permeability, and
the outer layer has high heat and weathering resistance. Currently PA blended with EPDM, IIR
and EPDM or modified PA, IIR and chlorinated IIR(CIIR) three layer hoses are used in this
application.
b. Air conditioning seals.—Rubber materials for air conditioning compressor seals need to
have high solvent resistance to both refrigerants, CFC-12 and HFC-134a. Table A–VII30 shows
no rubber material alone meets requirements for both refrigerants. However, a properly blended
material can match both requirements and is described as RBR (rubber for both refrigerants) in
Table A–VIII.30
II. SYNTHESIS, CHARACTERISTICS AND PROPERTIES OF

SPECIALITY ELASTOMERS
A. NITRILE ELASTOMERS
1. Introduction.—Acrylonitrile–butadiene rubber is a synthetic rubber of copolymerized acry-

lonitrile and butadiene. Called nitrile rubber, it is abbreviated NBR and one of typical oil-resistant
elastomers.31 33 Nitrile rubber which is selectively hydrogenated, is named hydrogenated nitrile
rubber, abbreviated to HNBR.34
NBR was born through the study of copolymerization of butadiene and other monomers using
a free radical catalyst from IG in Germany. In 1930, it was found that a synthetic rubber based
on butadiene and acrylonitrile showed good properties against oil and fuels and it was named
“Buna N.”35
In Japan, NBR has been manufactured since 1959. HNBR was developed to improve its heat
and weathering resistance. In 1984 Nippon Zeon started commercial production of HNBR using
their own technology.37 There are many applications of NBR and HNBR such as fuel hoses, oil
hoses, oil seals, packing, diaphragms, printing rolls, blankets, brake shoes, adhesives, belts, safety
shoes, etc.
2. Manufacturing method of NBR.—NBR has been manufactured by an emulsion polymer-
ization system the same as SBR. To start emulsion polymerization, butadiene and acrylonitrile
monomer are charged into the polymerization vessel and mixed with deionized or softened water
and emulsifier, and then catalysts and control agents are added.
For cold polymerization, redox catalyst systems are used which consist of inorganic peroxides
such as hydrogen peroxide or potassium persulfate, or organic hydroperoxide such as cumene hy-
droperoxide, di-isopropyl benzene hydroperoxide or paramenthane hydroperoxide, and a reducing
agent such as ferric salt or tetraethylenepentamine. A pH control agent such as sodium phosphate
is also used. When the appropriate conversion from 60 to 90% is reached, the polymerization re-
action is shortstopped by hydroquinone or carbamates.3,38 (Table A–IX)
After removing and recovering nonreacted monomers from the latex by heating, reduction
of pressure, and/or steam distillation, stabilizers are added to maintain the polymers’ storage
stability. The latex is coagulated by calcium chloride, aluminum sulfate, sodium chloride with
sulfuric acid or polymeric coagulants. The product is filtered, washed and dried into its final
form.3,31 (Figure 17)
In the case of manufacturing NBR without metallic iron or with a relatively small amount of
metallic iron, emulsion, solution, suspension, or bulk polymerization can be used.39
Fig. 17.—NBR manufacturing process.
3. Manufacturing method of HNBR.—Selective hydrogenation of C=C double bonds while

maintaining the cyano group in the side chain is one of the effective methods to improve heat
resistance of NBR. After dissolving NBR in an appropriate solvent, catalysts and hydrogen are
added to produce HNBR through a hydrogenation reaction, the catalyst and solvent are recovered,
and the product is coagulated and dried.40
4. Grades of NBR and HNBR.—The manufacturers of NBR and HNBR are listed in the
elastomer manual from IISRP.41 (Table A–X) There are no unified grade numbers for NBR and
HNBR as there are for emulsion SBR. Numbering of these elastomers is done by the supplier.
NBRs are classified by acrylonitrile content, Mooney viscosity, polymerization temperature, stabi-
lizer, third monomer, and appearance of product. In addition, HNBRs are classified also by degree
of hydrogenation. Degree of hydrogenation indicates iodine value and degree of unsaturation.
a. Acrylonitrile content.—Grades of NBR with acrylonitrile content of 15 to 53% are available
on the market. There is no standardization of acrylonitrile content. However, NBRs are generally
categorized as “low,” “medium,” “medium high,” “high,” and “ultra high” in acrylonitrile content
as shown in Table A–XI. Oil resistance is determined by acrylonitrile content in NBR. Increasing
acrylonitrile content improves oil resistance, but causes poorer cold flexibility. Thus there is a
trade-off relationship between oil resistance and cold flexibility. Glass transition temperature
(T g) of NBR is estimated by the following equation.33
T g(◦ C) = −85 + 1.4A (1)

where A denotes the acrylonitrile content (%).

b. Polymerization temperature.—Polymerization temperatures from 5 to 50 ◦ C are used for
NBR. NBR reacted at higher than 25 ◦ C is called “hot NBR” which provides high tensile and
cohesive strength. Generally, high-temperature polymerization gives a faster reaction, lower degree
of polymerization, higher branching, and higher gel which makes for poorer processability.
NBR polymerized at lower than 25 ◦ C is called “cold NBR”—generally reacted at 10 ◦ C
maximum—which features better mixing, extrusion, calendering, processability and slightly lower
physical properties compared with hot NBR. More than 80% of the grades of NBR are manufac-
tured by cold polymerization.
c. Mooney viscosity of NBR and HNBR.—NBR is manufactured as a liquid having 3000 molec-
ular weight and as a solid having up to 106 molecular weight and from 25 to 140 Mooney viscosity.
A product with a high Mooney viscosity provides high tensile strength and low compression set,
and is used for high-pressure applications. When combined with high levels of plasticizer, the
compounds are useful for fuel devices and ink rolls. NBR compounds with low Mooney viscosities
show relatively low mechanical properties, but better flowability. Therefore they are suitable for
injection molding, calendering and extrusion with only small amounts of plasticizer.
d. Conversion of polymerization.—Conversion of polymerization is decided by the economics
of production and requirements for polymer properties. Generally high conversion improves pro-
ductivity because of the cost of recovering monomers. But high conversion tends to promote
self-crosslinking and branching in the polymer, which causes higher swelling in an extrusion pro-
cess. Conversion of polymerization is commonly from 60 to 90% commercially. Bound acrylonitrile
content in NBR is influenced not only by the charge ratio of butadiene and acrylonitrile, but also
final conversion. Because the reaction rates of the two monomers differ, polymer composition is
different at different conversions.
Figure 18 shows bound acrylonitrile and butadiene content in polymers being formed at dif-
ferent conversions during polymerization. The so-called azeotropic mixture is at 37% acrylonitrile
content, which produces the same composition of acrylonitrile and butadiene at any conversion.
e. Stabilizers.—Stabilizers are added to maintain Mooney viscosity during storage of raw NBR.
Seventy-five percent of NBRs contain hindered-phenol and/or phosphonium derivatives as non-
staining stabilizers. Slightly staining NBR contains amine stabilizers such as alkyldiphenylamine,
which provide better bin stability and heat resistance. The use of NBR with staining stabilizers
is declining.
f. Terpolymers.—NBR terpolymers are widely known. Typical terpolymer is called XNBR
which contains carboxylic acid in a side chain from terpolymerized acrylic or methacrylic acid.
Fig. 18.—Polymer composition generated at each moment in polymerization.

Polymerization temperature 5 ◦ C.
XNBR features excellent tensile strength and abrasion resistance. Zinc peroxide or surface treated
zinc oxides are used as cure activators of XNBR to improve scorch times.43,44
NBIR acrylonitrile–butadiene–isoprene terpolymer is available commercially which features
relatively higher tensile strength and elongation especially for light color compounds.
For improved heat resistance of NBR, bound antioxidant NBR with copolymerized amino or
phenol function group in the polymer,45 and NBAR acrylonitrile–butadiene–acrylic ester are also
on the market.46 48
Self-crosslinked NBR is manufactured by terpolymerizing with multi functional monomers
such as divinyl benzene, ethylene-glycol dimethacrylate, and so on. Its purpose is to improve the
dimensional stability of NBR compounds during the extrusion and calendering processes. Usu-
ally, self-crosslinked NBRs are blended with conventional NBR because of their inferior physical
properties. They are also applied as a nonextractable plasticizer, softener and impact modifier in
phenolic resin, epoxy resin, polyvinyl chloride, ABS, and so on.
Liquid NBRs terminated or functionalized by hydroxide, amino or carboxylic acid groups are
also available as hardeners or modifiers for epoxy resin, or as plasticizers for NBR to improve
solvent crack resistance.
g. Physical form of products.—Standard NBR is a bale or sheet. Crumb type is also used for
solution applications, to easily dissolve in solvents for adhesives. Powder NBR is mainly used for
blending with thermoplastics such as PVC, EVA, ABS, AS, and phenolic resin. There are two
ways to manufacture powder NBR. One is mechanically grinding from bale NBR, and the other
is spray drying directly from NBR latex.
h. Polymer blend and carbon wet masterbatch.—NBR is a good oil-resistant elastomer but not
good for ozone resistance because of the double bonds in the polymer backbone. One solution to
improve ozone resistance of NBR is blending with PVC, which has good compatibility.49 Seventy
parts of NBR blended with 30 parts of PVC is commonly used. There are two methods used to
disperse PVC in NBR. One is to latex blend, co-coagulate and dry. The other is to mechanically
blend by means of a Banbury mixer or kneader. The former provides better properties because
of the fine dispersion of PVC in NBR.51
NBR wet carbon black masterbatch is available and is manufactured by co-coagulating NBR
latex with a carbon black dispersion.52 Bale forms of NBR preblended with DOP plasticizer and
liquid NBRs are also available for easy processing and mixing.41
i. After reaction of NBR.—NBR has double bonds in the main chain so that its chemical
stability, heat resistance, and ozone resistance are limited. To improve the heat resistance of NBR,
there are a number of ideas to develop highly saturated nitrile elastomers (HSN). Acrylonitrile–
ethylene copolymer or terpolymer (NEM) was studied. However, no commercial grades are on the
market. Selective hydrogenation of NBR was developed and commercialized by holding the cyano
group in the polymer to maintain oil resistance and hydrogenating C=C double bonds which
are the weak point for heat resistance. These polymers were initially abbreviated HSN or NEM,
however, they are now called HNBR to designate “H” for hydrogenation.
Physical properties and processability of HNBR are influenced by the acrylonitrile content
and Mooney viscosity. Additionally, the degree of unsaturation in the polymer is a key property
of HNBR, indicated by its iodine value. Manufacturers and grades of HNBR are listed in Tables
A–XII and A–XIII.82,99,124 126 There are HNBR commercial grades with Mooney viscosity values
from 57 to 137 and acrylonitrile content from 17 to 50 weight percent. Fully hydrogenated grades
are defined as 99% hydrogenation, in which unsaturation is 1% or less, with indicated iodine
values up to 4. Partially hydrogenated grades with iodine values between 10 and 28 are widely
used. HNBR blended with PVC is used for gasohol, oxidized fuel or dynamic ozone resistance is
required. HNBR blended with zinc methacrylate provides high tensile strength (up to 50 MPa)
and is used for high abrasion resistance.109 111
5. Formulation and processing.—Compounding technology for NBR resembles NR or SBR
except for plasticizers. NBR can be vulcanized by sulfur or peroxide.
a. Compounding of NBR.—Fine particle carbon black, high structure carbon black and fine
particle silica are useful to make high strength and abrasion-resistant compounds. In the case
of high loadings, soft carbon black, calcium carbonate, clay, and talc are added. Nonstaining
antioxidants can be selected from phenols, phosphites and/or hydroquinoline. To improve heat
resistance, a combination of radical catchers such as an amine antioxidant with a hydroperoxide
decomposer (i.e., such as imidazole salt) is more useful.
Nonextractable antioxidants such as phenylenediamine and metal salts of dithiocarbamate are
effective for fuel application. Antiozonants are generally selected from paraffin wax and para-
phenylene diamine. In the case of peroxide cure systems, antioxidants and antiozonants can be
strong retarders so one must be careful to add a minimum level.
Ozone resistance can be obtained through blending techniques with other polymers such as
PVC or EPDM. NBR blended with PVC from 15 to 50 parts is commonly used not only to
improve ozone resistance, but also oil resistance. Thirty parts is a usual level of PVC. EPDM
blends can improve ozone resistance. However, their compatibility and differences in cure speed
have to be considered.54
Plasticizer is added to NBR and HNBR to reduce viscosity, control volume swell in fuel
and lubricant, and improve low-temperature properties. Compatibility of plasticizer relates to
acrylonitrile content of NBR and HNBR. The solubility of plasticizer in NBR can be estimated
from the solubility parameter (SP value). Selection of plasticizers for NBR is quite similar to that
of PVC. To avoid a bleeding problem which will occur from excess plasticizer in NBR, it is very
useful to know the maximum absorption level of a plasticizer in NBR. This can be measured by
immersion of cured NBR in plasticizer as shown in Figure 19 and Table A–XIV.55,56
Low molecular weight or liquid NBR can provide a nonvolatile, nonextractable and nonmi-
gration formulation. Curing systems for NBR generally use sulfur a sulfur donor or a peroxide.
Typical systems are shown in Figure 20.37,46 Use of TMTD is limited. TMTD is one of the most
popular accelerators to provide fast cure. During vulcanization, TMTD reacts with zinc oxide and
forms the zinc salt of dithiocarbamate, which is an antioxidant. However, it is limited in solubility
in NBR, and blooming will occur if exceeded.
b. Compounding of HNBR.—HNBR reacts to filler and plasticizer loadings in almost the same
way as NBR, except for the higher physical properties obtained. Mixing, milling, calendering, and
molding characteristics are similar to those of NBR or EPDM. As with these polymers, either a
peroxide- or sulfur-cure system may be employed. For polymers with greater than 96% saturation,
a peroxide-cure system would be required to provide a good balance of properties. The level of
peroxide needed is 4 to 15 phr, combined with 1 to 20 phr of either trimethylol propane triacrylate,
triallyl isocyanurate, or N ,N 0 -m-phenylenedimaleimide. Sulfur-cure or sulfur-donor-cure systems
have been commonly used for the 90% hydrogenated grades of HNBR.57 59
6. Structure and properties of NBR and HNBR.—Table A–XV shows an example of raw
polymer characteristics for an NBR having a Mooney viscosity of 50 and acrylonitrile content of
Fig. 19.—Absorption of plasticizer in NBR.

Fig. 20.—NBR typical curing system.
35%.49 The characteristics include bound acrylonitrile content, chemical composition distribution,
microstructure of the butadiene unit, sequencing, and branching.
a. Structure and analytical methods.—Qualitative analysis of NBR is measured by infrared
spectrum or pyrolysis gas chromatography (PGC). Quantitative analysis of bound acrylonitrile
content is determined from nitrogen and/or PGC. Microstructure and sequencing analysis re-
quires NMR. Compound formulation of cured NBR can be estimated by thermogravimetric anal-
ysis (TGA).
The first step in analyzing raw polymer NBR is to remove small volumes of polymerization
ingredients and antioxidant by Soxhlet extraction in methanol solvent, or by immersion at high
temperature. Solubility of NBR differs with acrylonitrile content. NBR or HNBR is soluble in
benzene, toluene, tetrahydrofuran, and acetone, and insoluble in water, alcohols, hexane, and
so on. Combinations of good solvent and poor solvent can be used to clean up the polymer by
the reprecipitation method. Figure 21 shows an infrared absorption spectrum of NBR, which
demonstrates typical peaks at 970 and 910 cm−1 based on trans-1,4-butadiene and 1,2-butadiene
and a peak of 2240 cm−1 determined by stretch and shrinkage vibrations of C≡N. Acrylonitrile
content can be measured by the ratio of the peak value at 2244 to 970 cm−1 , but generally the
Kjeldahl method of nitrogen determination is more precise.
An infrared absorption spectrum of HNBR is shown in Figure 22. In comparison to NBR, the
peak at 720 cm−1 from methylene chains increases. Table A–XVI shows the infrared spectrum of
NBR decomposed by pyrolysis.61
The iodine value indicates the degree of hydrogenation of HNBR. It is reported that the degree
of hydrogenation can be obtained from NMR and infrared spectrum.62,63 Number average molec-
ular weight (M n) is obtained by osmometer and so on, weight average molecular weight (M w)
is measured by the sedimentation equilibrium method, light scattering method, etc. Viscosity av-
erage molecular weight is traditionally calculated by the equation shown in Table A–XVII, after
measuring the intrinsic viscosity. Molecular weight distribution is measured by gel permeation
chromatography compared to standard polystyrene. Gel and insoluble material are measured by
paper filter, mesh or glass filter.
Fig. 21.—Infrared spectrum of NBR (acrylonitrile content 37%, iodine value 280).
b. Basic properties.—Basic characteristics of NBR are demonstrated in Table

A–XVIII.31,35,41,67 76 With increasing acrylonitrile content, glass transition and brittleness tem-
peratures rise as shown in Table A–XIX.35 Typical properties of NBR are influenced by acryloni-
trile content. Other factors are molecular weight, molecular weight distribution, polymerization
temperature, third monomer, and blending with other materials, which influence physical prop-
erties as shown in Table A–XX.3,31 33,35,46
Table A–XXI demonstrates HNBR properties compared with NBR. The glass transition tem-
perature (T g) of HNBR is slightly higher than conventional NBR and differs depending upon
manufacturing method, catalyst, and microstructure as shown in Figure 23.57,76 79 Figure 24
shows the relationship between the T g of HNBR with acrylonitrile from 18 to 50% and iodine
value.80,81 The T g of HNBR is strongly influenced by its iodine value. The T g of NBR before
hydrogenation is decided by its acrylonitrile content, but the T g of HNBR changes during hydro-
genation. Below 34% acrylonitrile content, the T g passes a minimum point and gradually increases
through the hydrogenation reaction. Above 34%, the opposite occurs. The T g of HNBRs on the
market is shown in Table A–XXII.82,83
Fig. 22.—Infrared spectrum of HNBR (acrylonitrile content 36%, iodine value 28).
Fig. 23.—Glass transition temperature of NBR, HNBR Fig. 24.—The effect of the degree of
and Ethylene–acrylonitrile copolymer57,75 79 ; E/AN; hydrogenation on T g of HNBR.
ethylene–acrylonitrile copolymer; Therban, Tean and
Zetpol; HNBR.
c. Unvulcanized NBR characteristics.—Characteristics of unvulcanized NBR are estimated by

Mooney viscosity, molecular weight distribution, branching, and gel. Lowering Mooney viscosity
improves the flowability and mixing processability. For the same polymer, the Mooney viscosity of
the polymer doesn’t always match the Mooney viscosity of the compound because of differences in
the molecular weight distribution and branching. When the polymer has a wide molecular weight
distribution, the Mooney viscosity of the compound tends to be low.
d. Characteristics of vulcanized NBR, HNBR.—Fuel resistance is the most important char-
acteristic of NBR, and it depends on the acrylonitrile content. The effect of higher acrylonitrile
content is summarized in Table A–XXIII and leads to the following characteristics:
1. High tensile strength, modulus, and hardness
2. Improved fuel resistance (lower volume change in oil or fuels)
3. Poorer cold flexibility
4. Low rebound and poor heat buildup resistance under vibration
5. High compression set
HNBR has improved heat resistance and weatherability compared to NBR. HNBR character-
istics depend not only on acrylonitrile content but also on hydrogenation degree. Hydrogenation
degree is measured by iodine value. Lower iodine value leads to the following characteristics as
shown in Figure 25:
1. Improved heat resistance
2. High compression set with sulfur cure but no effect with peroxide cure
3. Poor cold flexibility in case of less than 10 iodine value
4. Slightly larger volume change in ASTM #3 oil84
Table A–XXIV shows the volume change of rubbers by solvent. Few rubbers have low volume
changes to all oils, solvents, and liquids. Generally speaking, oil resistance means resistance to
oils made from petroleum, such as lubricating oil and engine oil. NBR has a low volume change
in these. The solubility parameter (SP value) is used as an index of volume change. NBR hardly
swells in gasoline or ASTM oil whose SP value is different from the NBR SP value but swells
significantly in MEK whose SP value is close to NBR SP value. Another index for volume change
is the aniline point. The lower the aniline point, the larger the volume change.3,31,35,47,85
Figure 26 shows a balance between oil resistance and cold flexibility. Generally, the more
improved oil resistance, the poorer cold flexibility. Compared at the same volume change, the
brittleness temperature of HNBR is lower than that of NBR.8
Fig. 25.—Properties vs. iodine-value of HNBR (AN 37).
Fuel resistance of NBR and HNBR depends on acrylonitrile content. NBR and HNBR have
been tried for use in fuel containing ethanol or methyl-t-butylether.86,87 But the volume change
of NBR in fuel containing 15 to 20% methanol is too large. (Figure 27)
Mineral lubricating oil contains added dispersant, detergent, antioxidant, extreme pressure
additive, antiwear agent, and so on. Lubricating oil life is lengthened by these additives, so
improved resistance to lubricating oil additives is needed. HNBR has excellent lubricating oil
additives resistance and higher tensile strength than other rubbers when they are measured after
swelling in oil as shown in Figure 7 and Table A–VI.108,111 High acrylonitrile content NBR has
improved gas impermeability as shown in Table A–XXV.31,59,91 Table A–XXVI92 shows solvent
impermeability of various rubbers.
Figure 28 shows strain–stress curves of NBR measured at various temperatures. At a tempera-
ture under the glass transition, the curve is like a resin that has a yield point. At temperatures over
Fig. 26.—Volume change vs. brittleness Fig. 27.—Alcohol contained fuel resistance of
temperature: • HNBR, + NBR, ⊗ ECO. FKM (), FMVQ () and NBR (N).
the glass transition, it has a typical rubber-like S curve. At high temperatures, tensile strength
and elongation are low.31,93
There are some indexes for the heat resistance, tensile strength, elongation, the product of
strength and elongation, and compression set of rubber. These are different for different kinds of
rubber products.49,94,95 For example, we used the temperature at which the change in elongation
is 80% after 1000 hours. For CR cured by ethylene thiourea (ETU), the temperature change is 100
◦
C. NBR cured by sulfur is 106 ◦ C. HNBR cured by sulfur is 126 ◦ C. HNBR cured by peroxide
is 150 ◦ C. ACM cured by ammonium benzoate is 159 ◦ C, as shown in Figure 29.96
7. Applications of NBR and HNBR.—NBR, XNBR and HNBR are widely used in industrial
products for their oil resistance, solvent resistance, and chemical resistance. Their function is
sealing and delivering oil, fuel, water, and chemicals in the automotive, aerospace, chemical, food,
machinery, oil-drilling, marine, railroad, textile, and printing industries.3,32
a. Automotive uses.—NBR and HNBR are mainly used for automobiles. Automotive elas-
tomers are classified by type of heat resistance and class of oil resistance.97,98 Figure 3 demon-
strates the elastomers classified by the Society of Rubber Specification Committee (CARS) in
the Society of Automotive Engineers (SAE), adding some candidate elastomers that might be
registered in the near future.28,97 102 NBR is classified BF, BG, BK at 100 ◦ C application and
CH at 125 ◦ C. HNBR is classified as a DH and will be proposed to be DK.
b. Hoses and tubes.—NBR is typically used as the liner in hoses reinforced by fabrics or
steel wire and covered by metal, textile, or weather-resistant rubbers. NBR is used for fuel,
transmission, brake, and steering hoses for automobiles. In industrial applications, hydraulic hose;
delivery hose for crude oil, heavy oil, fuels, acid, and alkali; and dairy hoses are also made of NBR.
HNBR has been adopted for fuel hose as shown in Figure 30.89 HBNR has also been used for
power steering and air conditioning hoses for longer life.27,107,108
c. Seals, packing and O-rings.—Various elastomers are used for sealing of oils, water, fuel,
and chemicals. One of the main applications of NBR and HNBR is in seals and gaskets because
of their resistance to oils, lubricants, and greases.3,32,87 Typical specifications for seals and O-
rings in Japan are listed on JIS B2401-1 grades A and B, B2402 grade B of seals and JIS K6380
of industrial packing BI, BII, BIII materials.103 105 HNBR is used in high-pressure and heat-
resistance applications.39
d. Rolls.—NBR covered rolls are widely used in the paper, dyeing, textile, fabric, leather, steel,
printing, chemical and polymer processing industries.3 NBR rolls are resistant to oils, surface-
active agents, dyes, ink, solvent, acid, alkali, and so on. Polyurethane rubber is widely used for
high-load roller applications. However, HNBR and HNBR blended with zinc methacrylate are
recently being used in heavy-duty roller applications such as paper, steel, and textile rollers
because of their long life at high temperature.108,111
Fig. 28.—NBR stress–strain curves at various temperature.

Fig. 29.—Service temperature and service life.
e. Belts.—NBR and XNBR are widely used in conveyor belts carrying ore, coke, sand, and
oil sand and in flat belts for conveying paper money or train tickets. NBR blended with PVC is
often employed for textile and food applications requiring ozone resistance.3 Synchronous belts,
which transmit power from the crank shaft to cam shaft in automobiles, are mainly made of
HNBR having well-balanced properties of high modulus at high temperature, abrasion resistance,
flexibility, and oil resistance as shown in Figure 6.13,107,112
f. Miscellaneous applications.—Nitrile rubbers including NBR, XNBR and HNBR are widely
used for products such as pump valves, diaphragms, bushings, grommets, adhesives,113,114 brake
shoes,115 clutch facings, sponges, isolation insulators,116 cables,118 and so on. Oil drilling devices
such as blowout preventors, downhole packers, drill pipe protectors, snake pumps, accumulators,
pump stators, and rotary drilling hoses are made of conventional NBR. HNBR is applied in prod-
ucts which require resistance to hydrogen sulfide, steam, methane gas at high pressure, corrosion
inhibition in deep wells, and extrusion resistance. Figure 31 shows that HNBR demonstrates good
resistance to sulfide mixtures.119 121 Examples of HNBR latex applications are gaskets, paints
and adhesives to metal, ceramics, and textiles.113,123
Fig. 30.—Oxidized fuel resistance: • HNBR 1020, + NBR, × ECO.

Fig. 31.—Sour environment test for tensile strength in liquid phase.
B. EPICHLOROHYDRIN ELASTOMERS
1. Introduction.—Epichlorohydrin elastomers have a good balance of the following properties:

low temperature flexibility, oil and fuel resistance, and heat and ozone resistance. These elastomers
were first introduced in 1965127 130 and were manufactured by the B.F. Goodrich Co. and Hercules
Powder, Inc., in the United States. Manufacture of these polymers by two Japanese companies,
Nippon Zeon Co., Ltd., and Daiso Co., Ltd., followed. Currently, there are three suppliers of
epichlorohydrin elastomers: Zeon Chemicals Incorporated, Nippon Zeon, and Daiso. (Table A–
XXVII)
2. Manufacturing method.—Epichlorohydrin polymers are obtained by ring-opening poly-
merization of cyclic ether monomers. The most commonly used monomers are epichlorohydrin
(ECH), ethylene oxide (EO), and allylglycidyl ether (AGE). The structures of these monomers
are shown in Figure 32. Various polymers are available, including epichlorohydrin homopoly-
mer (CO), epichlorohydrin/ethylene oxide copolymer (ECO), epichlorohydrin/allylglycidyl ether
copolymer (GCO), and epichlorohydrin/ethylene oxide/allylglycidyl ether terpolymer (GECO).
These polymer structures are shown in Figure 33.
An example of polymerization using the aluminum alkyl-water catalyst system developed by
Vandenberg is shown in Table A–XXVIII.131 Further study132 of this catalyst system led to the
Fig. 33.—Polymer type and structure

Fig. 32.— Monomers for epichlorohydrin elastomer.
of epichlorohyde elastomers.
Fig. 34.—Slurry polymerization process.
development of the aluminum alkyl-phosphoric acid133 and the aluminum alkyl-polyphosphoric

acid ester134 catalyst systems.
For the aluminum alkyl-phosphoric acid catalyst system, a solution polymerization process
similar to that of BR and SBR is employed. For the polyphosphoric acid ester system, an econom-
ical slurry polymerization process has been developed which gives a powdered polymer product.
This process is shown in Figure 34.135
3. Grades of epichlorohydrin elastomers.—Raw polymer properties of CO and ECO (ECH/
EO 50:50 mol %) are shown in Table A–XXIX.136 ECO was developed to improve low temperature
flexibility. The relationship between the EO content and low temperature flexibility is shown in
Figure 35.137 As the EO content increases, the low temperature flexibility improves, with only a
slight loss in heat resistance. (Figure 36137 ) To obtain a good balance of low temperature flexibility
and heat resistance, ECO is manufactured using a 50:50 molar ratio of ECH/EO.
CO and ECO have better heat resistance and weathering resistance than diene-based rub-
bers which contain carbon–carbon double bonds. Nevertheless, the ether linkage in the polyether
elastomers is subject to degradation from thermal softening and ozone cracking under severe
conditions. To address these problems, polymers containing AGE were developed.
The relationship between the AGE content and hardness change is shown in Figure 11.138 It
was found that the higher the AGE content, the smaller the reduction in hardness values. The
relationship between AGE content and ozone resistance is shown in Figure 10.138 As the AGE
content increases, so does ozone resistance. The types of epichlorohydrin elastomers commercially
available are shown in Table A–XXX; their composition is shown in Figure 37.
Fig. 35.—Gehman low temperature Fig. 36.—Heat resistance vs. EO content

vs. EO content. (aged 144 hours at 150 ◦ C).
Fig. 37.—Composition of epichlorohydrin elastomers (the numbers 1–7 correspond

to the grouping number in Table A–XXX).
4. Formulation and processing.—For the most part, curing of epichlorohydrin elastomers uti-
lizes the chloromethyl group of the polymer side chain, which makes these elastomers different
from the diene-based rubbers. The curing mechanism and polymer structure must be carefully
considered when choosing a cure formulation. Some chemical agents present in a given cure pack-
age may cause loss of properties, such as heat resistance.25
a. Selection of the cure system.—The various kinds of cure systems available are shown in
Table A–XXXI.139 Previously, the most widely used cure system was ethylene thiourea (ETU)
with lead (Pb3 O4 ). However, this system often yields problems with excessive mold fouling and
poses potential health risks. The lead compounds are toxic when inhaled or ingested and ETU
has been shown to be carcinogenic.
After extensive study, a cure system containing 2,4,6-trimercapto-s-triazine (Zisnet-F) was
developed.13 This cure system eliminated the problems inherent with the ETU/Pb package. Other
new cure systems, ECHOP140 and XL-21,141 were also announced. A comparison of these systems
is shown in Table A–XXXII.142 Each cure system provides a similar balance between oil resistance
and low temperature flexibility. The proposed mechanisms by which curing occurs are listed in
Figure 38.
Since GCO and GECO contain carbon–carbon double bonds on their side chains, a sulfur
or peroxide cure may be applied.142 When compared with other cure systems, sulfur provides a
similar balance between oil resistance and low temperature flexibility but gives relatively poor
heat and compression set resistance. Peroxide cures provide the best cure/scorch balance and
excellent compression set and heat aging. A suitable acid acceptor must be selected for each cure
system. (See Table A–XXXII.)
b. Fillers.—Epichlorohydrin elastomers, like diene-based types, respond to filler reinforcement.
As the particle size of the carbon black decreases, the effect of filler reinforcement increases. The
effect of carbon black on hardness and tensile strength of ECO is shown in Figure 39.139
Results of white filler studies using silica are listed in Table A–XXXIII.142 When compared
with carbon black, silica reinforcement yields improved tensile strength and elongation but poorer
compression set. In general the most widely used formulations employ carbon black.
c. Plasticizers.—Plasticizers are used to improve compound flow, low temperature flexibility,
and oil resistance. The solubility parameters of CO and ECO are similar to those of NBR which
allows for the use of the same plasticizers. Care must be taken to avoid the addition of an excess
amount of low molecular weight plasticizer as this will affect heat aging properties. The evaluation
of some plasticizers is shown in Table A–XXXIV.142
d. Antioxidants.—Antioxidants are used to improve heat and ozone resistance of epichlorohy-
drin elastomers. Amine derivative antioxidants are to be avoided, however, because they accelerate
ozone degradation.143 Better choices include 2-mercaptobenzimidazole (MBI), 2,2,4-trimethyl-1,2-
Fig. 38.—Vulcanization model of epichlorohydrin elastomer MeO: metal oxide.
dihydroquinoline polymer (TMDQ), and nickel dibutyl dithiocarbamate (NBC). Recently, it was
reported that phenol derivative antioxidants improve oxidized fuel resistance of CO.144
e. Processing aids.—Processing aids for epichlorohydrin elastomers are stearic acid, stearic
acid esters, and low molecular weight fluoropolymers. Sorbitan monostearate is the best choice.
Zinc compounds have been shown to be prodegradants.
f. Processing.—The relationship between Mooney viscosity and mill roll mastication condition
is given in Figure 40.139 A larger mastication effect is observed as the roll temperature is lowered.
Fig. 39.—Effect of carbon black on hardness and tensile strength of ECO.

Fig. 40.—Change in Mooney viscosity by mastication: Roll temperatures:

◦ cooled by water, • 50 ◦ C, 80 ◦ C, × before mastication.
Mixing of epichlorohydrin rubbers may be done in an internal mixer (Banbury). Mixing may
also be accomplished using an intermixer and mill, the same as for other rubbers. Since typical
compounds are relatively fast curing, it is often recommended that the curatives be added in a
second pass or on a cold mill, thus avoiding mixing the curatives and fillers simultaneously in the
Banbury.
The recommended temperature is 50–70 ◦ C (roll temperature) for mill mixing and 100–110
◦
C (die temperature) for extrusion. When calendering, the roll temperature should be between 50
and 60 ◦ C. Epichlorohydrin elastomers are usually cured at 150–200 ◦ C. To improve compression
set, a post cure may be employed.
5. Characteristics.—The characteristics and properties of epichlorohydrin elastomers are dis-
cribed below.
a. Heat resistance.—Changes in crosslink density of ECO, GECO, NBR, and ACM after air
aging are shown in Figure 41. At longer aging times, ECO undergoes thermal softening and the
crosslink density decreases. In contrast, at longer aging times, the crosslink density of NBR and
ACM increases, causing the rubber to become hard.
The heat resistance of selected rubbers is shown in Figure 42. ECO has poorer heat resis-
tance than ACM but better heat resistance than NBR.138 The balance of heat and oil resistance
properties of selected rubbers is shown in Figure 3.145 ECO exhibits a good balance of these
properties.
b. Oil resistance and low temperature flexibility.—ECO shows a good balance of oil resistance
and low temperature flexibility when compared with NBR, ACM, and CR as shown in Figure
43.130
c. Temperature dependency.—Tensile strength and elongation of ECO and GECO measured
from 25 to 150 ◦ C are plotted in Figure 44. Even after heat aging, the properties of epichlorohydrin
rubber show a relatively small temperature dependence.139
d. Air impermeability.—CO shows very good air impermeability properties, less than one
third that of IIR as shown in Table A–XXXV.139
e. Miscellaneous properties.—Epichlorohydrin rubber has excellent ozone resistance, flame
resistance, and dry cleaning solvent resistance.
6. Applications.— Table A–XXXVI shows the applications and requirements for epichlorohy-
drin used in automotive parts. Main automotive applications include fuel hoses, air ducts and
control hoses made of GECO as this elastomer imparts good weathering resistance and low tem-
perature flexibility. ECO is used for diaphragms because of its low temperature flexibility. The
low air permeability of CO makes it a candidate for the inner liners of tires.
Fig. 41.—Change of crosslinking density by air aging.
C. POLYACRYLIC ELASTOMERS
1. Introduction.—Polyacrylic rubbers are special synthetic rubbers which have superior re-
sistance to heat and oils. Since the BFGoodrich Chemical Company developed and marketed
Fig. 42.—Heat resistance of ECO. Service Fig. 43.—Brittle point vs. volume
life/temperature of ECO: minimum tensile of change. ∗ ASTM no. 3 oil-70 hours at
5 MPa; others minimum 50% elongation. 150 ◦ C.
Fig. 44.—Temperature dependence of tensile strength. Normal conditions. ◦ ECO and ◦– GECD. Aged
500 hours @ 125 ◦ C: • ECO and •– GECO.
the first polyacrylic rubber (Hycar 4021) in 1948, many improvements have been made to meet
changing performance requirements. Recently in the industrial world, especially the automotive
industry, progress in the development of high-performance, maintenance-free engines has increased
the performance required of the rubber parts. These include, for example, the development of the
front-engine-front-wheel-drive system, the turbo charged and DOHC engines, and regulations for
the exhaust gas. These have raised the requirement level for the heat and the oil resistance of
lubricant oil hoses, torque converter oil hoses, gaskets and seals. The performance of polyacrylic
rubber meets these requirements, and therefore, the demand has increased year by year. The 1992
production is estimated to be about 7000 metric tons. The automotive industry, particularly in
Japan, consumed over 50% of the world demand.
Polyacrylic rubber is a synthetic rubber composed of acrylates. The backbone of the polyacry-
late polymers is saturated. The saturated backbone is responsible for superior heat resistance,
resistance to weathering, and ozone resistance. The side chains are composed of ester groups
which are responsible for the oil resistance of the polymer. The ester groups give the polymer
resistance to lubricant oils such as engine oil and gear oil, and to operating oils such as auto-
matic transmission fluid.146 The polyacrylate polymers are not resistant to gasoline. Polyacrylate
rubber is superior to silicone rubber with respect to oil resistance and follows fluoro and silicone
rubbers when the polymers are classified by heat. Per ASTM nomenclature, polyacrylic rubbers
are defined as ACM and are covered by ASTM D2000/SAE J200 DH, DF, and EH classifications.
Similarly, copolymers of methyl acrylate and ethylene are defined as AEM and covered under an
EE classification.
2. Method of Manufacture.— The flow sheet of manufacturing ACM is shown in Figure 45.147
Examples of the major monomers used in manufacturing of polyacrylate elastomer are ethyl-
acrylate (EA), butylacrylate (BA) and methoxyethylacrylate (MEA). Their chemical structures
are shown in Figure 46. Commonly, the ACMs may be polymerized with one or more of the
above mentioned monomers. In addition, a curesite monomer selected for required performance
is copolymerized to facilitate crosslinking.
The polymerization of ACMs can be accomplished by the use of several different free radical
reaction methods. Examples of the methods are emulsion, suspension, and bulk polymerization
techniques. The emulsion technique is the method of choice because this type of polymerization
Fig. 45.—The manufacturing process of ACMs.
allows easy control of the polymerization and the formation of a high MW polymer. Polymerization
initiators include peroxide, persulfate, benzoylperoxide, azoderivatives, and redox systems. The
redox systems include an oxidizing agent such as persulfate or hydroperoxide and a reducing
agent such as a sulfite. (Polymerization temperatures range from a low of 5 ◦ C to a high of 80
◦
C). After polymerization a latex is formed. The solid polymer is recovered by adding salts to the
latex (coagulation). The polymer is washed and goes through dewatering and is dried by hot air,
vacuum or extrusion.
Fig. 46.—Major monomer of ACMs.

Fig. 47.—The structure and performance of ACMs.
3. Grades of ACM.— The function and structure of ACM monomer units are shown in Figure
46 and 47.29 The low temperature capability, oil resistance and heat resistance are determined by
the choice of alkyl- and/or alkoxy-side chain. For instance, the balance of oil resistance and low-
temperature capability are shown in Figures 48 and 49 with combinations of three typical acrylate
monomers. It is possible to design ACM beyond the limits given here by using acrylonitrile,148
ethoxyethylacrylate or other monomers. Commercial ACM products are designed by selecting the
combination of these monomers carefully. Generally, ACMs are divided into two groups, i.e., one
group for maximum heat resistance (EA homopolymer grade) and oil resistance, and another
group for improved low-temperature properties (copolymer grades of EA, BA and MEA).
ACMs have no double bonds, therefore, functional side groups are added for crosslinking (Ta-
ble A–XXXVII). Some typical functional groups and corresponding crosslinking curatives are
shown in Table A–XXXVIII.149 Key characteristics, advantages and disadvantages of each com-
bination are shown in the same table. Commercial ACMs currently available are shown in Table
A–XXXIX. Many kinds of products are marketed to meet the varying rubber part requirements
of oil resistance, low temperature, and processability.
Fig. 48.—Oil swell–low temperature balance.

Fig. 49.—Oil swell–low temp. balance.
4. Compounding formulations and processing.— Practical formulations for ACMs are simple
when compared to other rubbers which typically have higher loadings and more components. An
example formulation is shown in Table A–XL.
a. Curatives.—Curatives for ACMs are specific to the functional group incorporated into the
polymer as mentioned in the previous section. Generally, it is difficult to control the curing speed
utilizing a retarding agent for any ACM curing system. For those containing epoxy groups, the
curing speed is controllable by the amount of curing agent such as ammonium benzoate. For
chlorine containing ACMs with a “soap/sulfur” cure package, the amount of stearic acid, alkali
metal carboxylic salt (soap) and sulfur are all used to control the speed of curing. The speed of
the triazine cures system may be adjusted by the use of N -(cyclohexylthio) phthalimide or the
sulfenamide derivative as retarding agents.
Fig. 50.—Carbon black vs. T − B and Cs.

Fig. 51.—Carbon black grade vs. ACMs performance.
b. Fillers.—Of the various carbon black grades, N550 is most popular as it is generally superior
for processing and molding. The smaller the black particle size relative to N550, the poorer the
compound processing but higher tensile strengths result. ACM has low gum tensile strength
because a large percentage of the polymer structure is in the side groups versus the backbone.
Carbon black, therefore, is needed to improve tensile strength. The influence of carbon black type
on ACM physical properties is shown in Figures 50 and 51. Since N330 and N550 types give a
good balance of processing, tensile strength and compression set, they are most often used.
In oil seal applications, white fillers are commonly used. However, in the case of the ACM
with epoxy curesite groups, the curing behavior of the compound with white fillers is relatively
poor. Properties as good as those obtained with carbon black cannot be expected. Therefore,
Fig. 52.—Physical property with silica compounds.

Fig. 53.—Curing behavior at 170 ◦ C.
ACMs with chlorine curesites are principally used. The noncarbon–black fillers used are mainly
silica, clay and talc with a soap/backslash sulfur curing system in a chlorine curesite containing
polymer. The pH value of these white fillers affect the curing reaction. Care must be taken in the
selection of white fillers.150 The higher the pH of the white filler, the faster the curing reaction
takes place, resulting in increased crosslink density. The influence of the silica pH is shown in
Figures 52 and 53.151
c. Plasticizers.—Plasticizers are used not only for improving low temperature but also for
improving oil resistance and flow properties of the compound. For the selection of plasticizers, it
is important to consider the effect of plasticizer extraction by test oils, volatility in hot air and
Fig. 54.—Low temperature property after heat aging.

Fig. 55.—Influence of antioxidants on the heat aging resistance of ACM-42.
viscosity drop. It is not good practice to add low molecular weight volatile plasticizer as property
changes are large after heat aging. The results of an evaluation152 using plasticizers are shown in
Tables XLI and XLII and Figure 54.
d. Antioxidants.—To maximize the usefulness of ACMs in long-term aging in the 150 to
170 ◦ C region, it is necessary to add an antioxidant. Antioxidants are generally divided into two
groups, i.e., phenol derivative and amine derivative types. The amine-like antioxidants are usually
recommended for ACM. They are most effective in retarding the normal hardening during heat
aging. In unusual cases, an antioxidant is selected to prevent softening behavior early in the heat
aging, e.g., with ACM chlorine curesite types cured with a soap/sulfur system. The effect of some
antioxidants are shown in Figure 55151 when evaluated with epoxy group site ACMs.
e. Processing aids.—Processing aids are used mainly for preventing the sticking of ACMs to
processing equipment. Typical processing aids are stearic acid, fatty acid esters and sorbitan
Fig. 56.—Dump temperature.

Fig. 57.—Compound mooney vs. BBR mixing.
monostearates. Metal salts of soap can also function as anti-sticks. One point to consider is to
avoid chemicals which inhibit or accelerate the curing reaction. The effect of some processing aids
on demolding is shown in Table A–XLIII.153
f. Processing.—Mixing of ACMs can be accomplished by the use of a Banbury mixer, inter-
mixer, kneader, or roll mill just like other rubber. ACM compounds tend to be scorchy. Adding
the curatives in the second pass is recommended. The roll mill preferred mixing temperature is 20
to 50 ◦ C. The effects of wall temperature and mixing time on the dump temperature and Mooney
viscosity of the compound in a lab Banbury mixer are shown in Figures 56 and 57.154
ACM can be processed by compression molding, extruding and injection molding. The curing
temperatures involved range typically from 150 to 200 ◦ C. In general, a post cure is given after
curing to improve compression set.
5. Characteristics.—The characteristics and properties of polyacrylic elastomers are described
below.
a. Physical properties.—The physical properties of ACMs are not outstanding. The compari-
son of physical properties among ACM, NBR and ECO is shown in Table A–XLIV. This weakness
can be attributed to the relatively long ester side groups.148 The physical properties of typical
ACMs are shown in Table A–XLV and the effect of carbon black loading in Table A–XLVI.
b. Heat resistance.—The heat resistance of the ACMs follows that of fluoro rubber and sili-
cone rubber. In SAE and ASTM, ACMs are classified as DH, DF, or EH capable. Commercial
compounds are available to service the 150 to 170 ◦ C temperature range. That heat resistance is
affected primarily by the backbone monomer type and to a lesser extent by the curesite group
and curatives. The heat resistance (as judged by hardness increase in a standard compound) of
EA, BA and MEA homopolymers respectively are shown in Figure 58. Aging is significantly
Fig. 58.—Backbone structure vs. heat resistance.

Fig. 59.—Polymer grade vs. heat resistance.
poorer for MEA versus EA and slightly poorer for BA versus EA. Many commercial ACMs are
copolymers of these monomers, and the ratio of BA and MEA vs. EA increases to gain improved
low temperature performance. Consequently, the heat resistance is reduced (Figure 59).
c. Oil resistance and low-temperature properties.—The balance between oil resistance and
low temperature properties is affected by the monomer composition as mentioned previously
(Figures 48 and 49). Adding some plasticizer will improve low temperature. On the other hand,
the plasticizer may be extracted by fluids and lubricating oils in actual service, resulting in poorer
low-temperature properties after immersion versus the original property. It is very important to
design a compound for the actual service conditions.
The lubricating oils have many kinds of additives for improving the oil function.155 These
additives can have significant effects on the rubber (shown in Table A–XLVII150 ). ACMs have
excellent resistance to these additives.
Fig. 60.—Ozone resistance of ACM.

d. Ozone, fluid and chemicals resistance.—ACMs have superior resistance to ozone because
they have no double bonds in their backbone. In static and dynamic ozone tests, ACM changes
little and exhibits no damage after 1000 hours. Typical results are shown in Figure 60.156
For fluids, ACMs have excellent resistance to fatty alkanes that show weak polarity, less
resistance to aromatic derivatives, alcohol, ester, and haloalkanes (see Table A–XLVII157 ); and
have no practical use in gasoline or steam applications.
6. Applications.—The major applications are automotive parts for sealing or conveying oils
and greases. The main type of rubber used in today’s autos are shown in Tables I–II.24 ACMs are
used in hoses, seals, gaskets, and packing around engine oil and ATF. Miscellaneous applications
include grommets for battery terminals, hot air ducts, and recirculation tubing.
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133
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[Received November 1, 1995; revised October 21, 1996 ]
IV. APPENDIX A
Table A-II
Material Trends of Automotive Elastomer Parts24
Parts Name Current Materials Needs New Materials Trend
Hoses Engine Fuel hose FKM/ECO/GECO low cost

Emission control NBR/CR, ECO,
hose ACM
Air duct NBR + PVC heat resist. TPO, ACM
Water hoses EPDM heat resist. EPDM (aramid) heat resistance
(Radiator, etc.) (polyester) heat resist.
Body Fuel hose NBR/CR permeability FKM/ECO/ECO
Filler hose NBR + PVC low permeability
Air conditioning NBR/CR permeability PA6/CIIR
hose
Chassis A/T oil cooler ACM heat resist.
hose
Power steering NBR/CR heat resist. ACM heat resist.
hose
Brake hose SBR/NR/CR water EPDM
+ EPDM permeability
Clutch hose SBR/NR/CR water EPDM
+ EPDM permeability
Master vacuum NBR/CR heat resist. ECO
hose
Seals Engine Crank VMQ long-life FKM

shaft-rear
Crank ACM long-life FKM
shaft-front
Diaphragms ECO, NBR,
FVMQ
Valve stem FKM
seal
Valve cover NBR heat resist. ACM
gasket
Body Weather strip EPDM long-life
Glass run EPDM low abrasion
Filler cap NBR + PVC
O-ring
Chassis Transmission NBR heat resist. ACM
oil seal
Power steering NBR heat resist.
oil seal
Ball joint CR, U
dust cover
Constant velocity CR heat, ozone TPEE
joint boot
Rack & pinion CR heat, ozone TPO, TPEE
boot
Brake master SBR heat resist., EPDM
cup life
Caliper piston SBR heat resist., EPDM
seal life
Others Engine Synchronous belt CR heat resist., life HNBR long-life

Accessory drive CR heat resist.
belt
Body In-tank pump NBR + PVC
cushion
Muffler hanger EPDM
rubber
Wiper blade CR, NR long-life
Chassis Engine mount NR(SBR, BR) heat resist.
Table A-III
Synthetic Rubber Production Capacity
Major Producers
Total Number of
Polymer capacity Zeon Bayer DuPont JSR Eni Goodyear producers
NBR 467 85 88 40 30 39 23
HNBR 5 3 2 2
ACM 17 6 NAc 2 8
ECO, CO 12 9 3
FKM 15 Sales 6 6
CR 448 87 189 40 7
CSM 60 53 2
CM 48 3
EPDM 1,054 52 77 65 85 16
PNBR NA
NSX 5 Sales 1
ZSC 1
S 11 2
Q 27 NA 22
IB 22 NA 8
EVA 194 NA 12
U, TPU 33 NA 25
SIS, IR modified 6 NA NA 8
TPEE 36 30 5
TPO 127 19
SB block 654 NA 20 105 17
BR modified 28 12 6
E-SBR 4,056 200 110 215 295 305 36
S-SBR 583 20 20 35 15 10 19
BR 2,109 78 274 91 125 200 31
IR 1,394 37 215 30 61 7
IIR 758 105 8
a IISRP. b World Wide Rubber Statistics 1993. c NA; Not Accepted.
Table A-IV
Quality Function Deployment Table For Synchronous Belt
Key Quality Requirement
1. High Transmission Power Elastomer Characteristics
11. Less deflection of the teeth 111. Dynamic complex modulus
112. Hardness
2. Wide Operating Temperature
21. Rigidity at high temperature 211. Temperature dependence of hardness
22. Flexibility at low temperature 221. Brittleness dependence of modulus
3. Longer Life
31. Slower rate of crack growth of 311. Heat resistance
back cover 312. Ozone resistance
313. Flex crack resistance
32. Less breakage of teeth 321. Hardness
322. Dynamic complex modulus
323. Dynamic permanent set
324. Oil resistance
Table A-V
Basic Properties of Oil Resistant Elastomers
HNBR FKM VMQ ACM NBR
Hardness, Shore A 72 70 71 70 70
Tensile strength (MPa) 25.9 17.2 7.6 13.2 19.5
Elongation (%) 380 200 150 200 370
100% Modulus (MPa) 3.6 4.7 5.7 6.9 43
Gehman’s T-10 (◦ C) −31 −6 −51 −22 −28
Volume change (%)
ASTM #1 oil −0 −0 +4 −0 −0
ASTM #2 oil +12 +1 +10 +7 +12
ASTM #3 oil +20 +2 +53 +19 +21
Engine oil 5W-30 +4 +1 +25 +25 +5
Auto transmission fluid +1 +1 NMa +7 +2
Power steering fluid +6 +2 NM +5 +4
Long life coolant +1 +26 −2 NM +1
a NM: Not Measured
Table A-VI
Lubricating Oil Additives Used in the Evaluation
No. Type of Additive Main Chemical Composition Concentrationa
A-1 — Original tensile strength —

B-1 — ASTM #2 oil with no additive —
C-1 Polyalkenyl succinimide 10
2 Dispersant Polyalkenyl succinimide/borate 10
3 Polyalkenyl succinic ester 10
4 Polyalkenyl succinimide/succinic ester 10
D-1 Calcium sulfonate-Basicity 24 10
2 Detergent Calcium sulfonate-Basicity 300 10
3 Magnesium sulfonate-Basicity 400 10
4 Calcium phenate-Basicity 205 10
E-1 Antioxidant Primary dialkyl zinc dithiophosphate 5
2 Secondary dialkyl zinc dithiophosphate 5
F-1 Viscocity index improver Polyalkyl methacrylate 10
G-1 Anti-wear agent Olefin sulfide for gear oil 10
2 Olefin sulfide (Technical grade) 10
H-1 Dialkyl phosphoric ester 10
2 Extreme pressure Dialkyl phosphoric ester 2
3 additive Zinc dibutyl dithiocarbamate 1
4 Molybdenum compound 0.3
5 Lead naphthenate 10
I-1 Package #1 for gear oil 10
2 Additive package Package #2 for gear oil 10
3 Package for automobile engine oil 10
4 Package for ATF (Dexiron IID) oil 10
a gram/100 cc of ASTM #2 oil
Table A-VII
CFC Resistance30
NBR HNBR FKM EPDM IIR
Refrigerant CFC fair fair poor good good

HFC-134a resistance
System Oil resistance good good good good good
(PAG)
Refrigerant CFC good good poor poor poor

CFC-12 resistance
System Oil resistance good good good poor poor
(mineral oil)
Table A-VIII
Characteristics of RBR30
RBRa HNBRb NBRb
Refrigerant CFC Volume change (%) 8 14 13

HFC-134a resistance Blister good poor poor
System Oil resistance Volume change (%) 5 5 5
(PAG)
Refrigerant CFC Volume change (%) 9 9 9

CFC-12 resistance Blister good good good
System Oil resistance Volume change (%) 5 5 5
(mineral oil)
Heat resistance, life at 150 ◦ C 250 h 250 h 60 h
aA properly blended material. b Current material for CFC-12 system.
Table A-IX
A Example of Polymerization Recipe of NBR
Butadiene 67
Acrylonitrile 33
Water 230
Sodium oleate 5
KOH 0.05
KCl 0.30
Condensed sodium naphthalene sulfonate and formaldehyde 0.20
EDTA·Na4 ·4H2 O 0.02
t-Dodecyl mercaptan 0.38
FeSO4 0.01
SFS (NaSO2 ·CH2 OH·2H2 O) 0.05
p-Menthanehydroperoxide 0.04
Table A-X
NBR Producers
Producer Nationality Trade Name
Nippon Zeon Co., Ltd. Japan Nipol

Zeon Chemicals Europe, Ltd. UK Breon, Nipol
Zeon Chemicals Incorporated USA Nipol
Bayer AG Germany Perbunan N
Bayer Polymers France Krynac
Bayer Rubber Inc. Canada Krynac
Buna GmbH Germany Buna
DSM Copolymer, Inc. USA Nysyn
DSM Elastomers Europe B.V. Netherlands Nysyn
EniChem Elastomeri S.r.l. Italy Europrene N
Goodyear Tire & Rubber Co. USA Chemigum
Goodyear Chemicals Europe France Chemigum
Industrias Negromex, S.A. de C.V. Mexico Emulprene
Japan Synthetic Rubber Japan JSR
Korea Kumho Petrochemical Co. Korea Kosyn
Krasnoyarsk SR Plant Co. Russia
Nitriflex S.A. Industria e Comercio Brazil Nitriflex N
PASA S.A. Argentina Arnipol
Synthetics & Chemicals Ltd. India Chemaprene
Takeda Chemical Industries Japan Croslene
Uniroyal Chemical Co., Inc. USA Paracril
Zaklady Chemiczne Oswiecim Poland Ker
Table A-XI
NBR Classification32
Classification Acrylonitrile content (%)
Low nitrile 24% maximum

Medium nitrile 25–30%
Medium-high nitrile 31–35%
High nitrile 36–42%
Ultra-high nitrile 43% minimum
Table A-XII
HNBR Production Capacity41,125
Producer Location Capacity
Nippon Zeon Toyama Japan 2,800 MT/year

Bayer Polysar Texas USA 1,600 MT/year
Zeon Chemicals Texas USA 1,500 MT/year
Table A-XIII
HNBR Commercial Grades82,99,124 126
Grade Acrylonitrile content (%) Mooney viscositya Iodine valueb Unsaturation (%)c
0020 49 66 23 10
A4555 45 90 e 1f
C4550 45 90 e 5.5
1010 44 85 10 4
1020 44 78 25 10
1907 38 80 e 1f
B3850 38 85 e 2
2000 36 85 4 1
2000L 36 65 4 1
2010H 36 135 11 4
2010 36 85 11 4
2010L 36 58 11 4
2020 36 78 28 10
2020L 36 58 28 10
2030L 36 58 57 20
1706 34 60 e 1f
1707 34 75 e 1f
1746 34 60 e 4
1747 34 70 e 4
1767 34 70 e 5.5
3110 25 85 15 7
4110 17 90 15 6
PBZ123g 44 48j 25 10
ZSC2295h 36 95 28 10
a ML−1 + 4 at 100 ◦ C. b g/100 g. c Double bond content. d Trade name: Zeon-Zetpol; Bayer:-Therban,
Tornac. e Not reported. f Maximum value. g PVC blend. h Zinc-methacrylate alloy. Trade name: Zeoforte.
j ML−1 + 4 at 125 ◦ C.
Table A-XIV
Plasticizer Adsorption into HNBR56
Plasticizer HNBR(AN36%) (phr) HNBR(AN44%) (phr)
DMP Dimethyl phthalate 235 285

DEP Diethyl phthalate 254 271
DBP Dibutyl phthalate 246 213
DOP Dioctyl phthalate 105 28
DIDP Diisodecyl phthalate 58 12
DOA Dioctyl adipate 36 11
DOS Dioctyl cebacate 20 4
TOP Trioctyl phosphate 27 4
TCP Tricresil phosphate 215 188
DBEEA Dibutoxy ethoxy ethyl adipate 50 33
EBO Epoxidized soybean oil 17 4
Table A-XV
Raw Polymer Characteristics of Medium High NBR49
1. Copolymerization component
Bound acrylonitrile content, average 35%
Composition distribution, tolerance 11%
2. Microstructure of butadiene unit (13C-NMR)
trans-1,4 83%
cis-1,4 8%
1,2 9%
3. Frequency (13C-NMR)
BBB 20%
BBA 53%
ABA 27%
AAA 4%
AAB 6%
BAB 90%
4. Molecular weight and molecular weight distribution
[η] 30 ◦ C, MEK 1.36
M n × 103 (osmometer) 69
M w × 103 (GPC) 226
M w/M n (GPC) 4.1
5. Branch
λ × 105 3.7
Table A-XVI
Infrared Spectrum of Decomposed NBR by Pyrolysis61
Wave number (cm−1 ) Group
2260 small –C≡N

1645–1603 broad —
1450 small –CH2 –
1380 –CH3
1073 weak —
1045 weak —
990 RHC=CH2
965 small RHC=CHR0 trans
908 small R(CH)C=CH2
890 weak —
Table A-XVII
A and K Value of NBR for Estimation of Molecular Weight from Intrinsic Viscosity35
Solvent a K
Toluene 0.64 4.9 × 10−4

Benzene 0.55 1.3 × 10−4
Chloroform 0.68 5.4 × 10−4
Acetone 0.64 5.0 × 10−4
Table A-XVIII
NBR Raw Polymer Properties31,35,41,67 76
Property Value
Specific gravity Ha 0.999, MHb 0.978, Mc 0.968

Linear expansion H 150, MH 170, M 175
coefficient (×10−6 ◦ C−1 ) H 220, M 230, Ld 240
[below T g H 73, M 70, L 80]
Specific heat (cal/g·deg) H 0.471
Adiabatic compressibility H 35
(×10−12 cm2 /dyn)
Thermal conductivity H 0.220, MH 0.215, M 0.215
(kcal/m·h·deg)
Glass transition temperature (◦ C) H −22, MH −38, M −46, L −56
frequency
H M L
1000 cycle/min −20 −36 −45
100 −24 −39 −48
10 −26 −41 −51
1 −27 −45 −55
Speed of sound (cm/sec) 6.6 − 8.2 × 103
Volume resistivity (Ω·cm) 1017 − 1011
Power factor (%) 5−6
Dielectric constant (1000 hertz) 7 − 12
Breaking voltage (kV/mm) 20
Solubility parameter H 10.36, MH 9.64, M 9.38, L 8.7
aH High nitrile. b MH medium high nitrile. c M Medium nitrile. d L Low nitrile.
Table A-XIX
Glass Transition Temperature T g and Brittleness Temperature BT of NBR35
Acrylonitrile (%) T g (◦ C) BT (◦ C)
0 — −80
20 −56 −55
22 −52 −49.5
26 −52 −47
29 −46 −46
30 −41 −38
31 −43 —
33 −37 ∼ −39 −33
37 −34 −26.5
39 −26 ∼ −33 −23
40 −22 —
52 −16 −16.5
Table A-XX
Factor, Properties and Characteristics of NBR3,31 33,35,46
Factor/Property Characteristics
Higher acrylonitrile content:

Oil resistance better; lower volume change
Abrasion resistance better; less abrasion loss
Gas impermeability better; less permeation volume
Cold flexibility inferior; higher brittleness temperature
Rebound inferior; lower rebound
Density higher
Hardness slightly higher
Tensile modulus higher
Tensile strength slightly better; higher
Compression set slightly inferior; higher
Heat resistance slightly better; lower properties change
Heat built up inferior; higher heat built up
Flowability slightly better; higher flow rate
Extrusion die swell slightly better; lower die swell
Higher molecular weight/higher Mooney viscosity:
Tensile strength slightly better; higher
Compression set slightly better; lower compression set
Extrusion die swell slightly better; lower die swell
Wider molecular distribution:
Filler loading better;
Extrusion die swell inferior; slightly higher swell
Compared with conventional NBR
Terpolymerized crosslinking monomer:
Extrusion die swell better; lower and smooth surface
Compatibility with better; higher loading
plasticizer
Tensile strength slightly inferior; lower
Elongation lower; lower
Terpolymerized with carboxylic acid:
Abrasion resistance better; lower abrasion loss
Friction coefficient higher
Tensile strength better; higher
Scorch inferior; shorter scorch time
Flowability inferior; lower flow rate
Blended with PVC:
Weathering resistance better; longer initial time of
ozone crack observed
Oil resistance better; lower volume swell
Hardness higher
Cold flexibility inferior; higher brittleness temperature
Extrusion die swell better; lower and smooth surface
Higher polymerization temperature:
Cohesive strength better; higher
Extrusion die swell inferior; higher
Powder and particulated compared with conventional bale:
Solubility better; faster solving time
Storage stability inferior; easily blocking
Table A-XXI
Factor, Properties and Characteristics of HNBR64 66
Factor/Property Characteristics
Hydrogenated NBR compared with NBR:

Oxidized fuel resistance better; lower properties change after immersion
Hydrogen sulfide resistance better; lower properties change after immersion
High temperature properties better; higher tensile strength and modulus
Heat resistance better; lower properties change after agings
Weathering resistance better; longer initial time of ozone crack observed
Brittleness temperature better; lower
Oil resistance slightly inferior; higher volume change
Heat built up slightly inferior; higher
Physical relaxation slightly inferior; higher
Higher hydrogenation ratio:
Heat resistance better; lower properties change after agings
Weather resistance better; longer initial time of ozone crack observed
Physical relaxation slightly inferior; higher
Tear resistance better; higher
Oil resistance slightly inferior; higher volume change
Heat built up slightly inferior; higher
Table A-XXII
Glass transition temperature82,83
H MH MH −MH M L
Polymer 1020 2020 2010 2000 3110 4110
Acrylonitrile content, % 44 36 36 36 25 17
Iodine value, g/100 g 24 28 11 4 15 15
Mooney viscosity, ML−1 + 4, 100 ◦ C 78 78 85 85 95 90
Glass transition temperature, ◦ C −24 −31 −29 −28 −35 −45
Table A-XXIII
Physical Properties of NBR
DN401 DN302H 1042 1043 DN003
Raw polymer properties :

Acrylonitrile content, % 18 28 33 41 50
Mooney viscosity, ML−1 + 4 82 80 77 78 78
Uncured properties:
Oscillating disk rheometer at 160 ◦ C
T − 5, min 4 4 4 4 4
T − 95, min 7 8 10 10 18
Maximum torque, dN/m 39 42 34 45 37
Cured 20 min at 160 ◦ C :
Physical properties
Tensile strength, MPa 16.0 18.0 19.2 19.5 19.6
Elongation, % 370 380 430 440 440
100% Modulus, MPa 2.5 2.9 2.9 3.6 4.1
Hardness, JIS A 64 68 68 72 74
Tear strength, die C, kN/m 42 43 47 48 56
Volume change, %
JIS #1 oil, 70 h at 120 ◦ C +4 −2 −4 −5 −5
JIS #3 oil, 70 h at 120 ◦ C +55 +27 +16 +10 +5
Fuel B, 48 h at 40 ◦ C +71 +43 +30 +23 +15
Cold flexibility, Gehman tortional stiffness
T − 5, ◦ C −44 −26 −24 −13 −5
T − 10, ◦ C −46 −28 −25 −14 −6
T − 100, ◦ C −52 −34 −29 −19 −13
Cured 30 min at 160 ◦ C :
Rebound, % 61 54 43 23 7
Goodrich Flexometer
Heat bullet up, ◦ C +27 +31 +30 +32 +32
Compression set, %, 70 h at 120 ◦ C 16 16 18 20 26
Picco abrasion index 89 95 100 113 159
Table A-XXIV
Volume Change of Rubbers by Solvents (%)
Temp. NBR NBR NBR
Solvent (◦ C) 28% 33% 38% CR NR SBR IIR VMQ CSM
Gasoline 50 15 10 6 55 250 140 240 260 85

ASTM #1 oil 50 −1 −5 .5 −2 5 60 12 20 4 4
ASTM #3 oil 50 10 3 0 .5 65 200 130 120 40 65
Diesel oil 50 20 12 5 70 250 150 250 150 120
Olive oil 50 −2 −2 −2 27 100 50 10 4 40
Lard 50 0 .5 1 1 .5 30 110 50 10 4 45
Formaldehyde 50 10 10 10 25 6 7 0 .5 1 1 .2
Ethanol 50 20 20 18 7 3 −5 2 15 5
Glycol 50 0 .5 0 .5 0 .5 2 0 .5 0 .5 −0 .2 1 0 .5
Diethyl ether 50 50 30 20 95 170 135 90 270 85
Methyl ethyl ketone 50 250 250 250 150 85 80 15 150 150
Trichloromethane 50 290 230 230 380 420 400 300 300 600
Tetrachloromethane 50 110 75 55 330 420 400 275 300 350
Benzene 50 250 200 160 300 350 350 150 240 430
Aniline 50 360 380 420 125 15 30 10 7 70
Phenol 50 450 470 510 85 35 60 3 10 80
Cyclohexanol 50 50 40 25 40 55 35 7 25 20
Silicon oil 50 −1 .5 −2 −2 .5 −1 −2 −2 .5 −0 .5 30 −0 .5
Distilled water 100 10 11 12 12 10 25 5 2 4
Sea water 50 2 3 3 5 27 7 0 .5 0 .5 0 .5
Table A-XXV
Gas Permeabilitya of NBR and Other Rubbers
Rubber Temp. ◦ C H−2 O−2 N−2 CO−2 CH−4 He
NR 25 37 18 6.1 100 – 24
50 91 47 19 221 – 52
BR 25 32 14 4.9 105 – –
50 77 36 14 200 – –
SBR 25 31 13 4.8 94 16 17
50 74 35 14 195 43 42
NBR 25 12 2.9 0.8 23 2.4 9.3
27% 50 34 10.5 3.6 68 10 23
NBR 25 5.4 0.7 0.18 5.7 – 5.2
39% 50 17 3.5 1.1 22 – 14
CR 25 10 3 0.9 19 2.5 6
50 28 10 3.5 56 10 –
IIR 25 5.5 1 0.25 3.9 – 6.4
50 17 4 1.3 14 – 17
T 25 1.2 6.2 2.4 – –
a unit: 10 cm2 /sec/atm. Table A-XXVI
Effect of Temperature on Various Rubbers
Solubility of Liquid
in Rubber
Specific (ml/ml)
Test Liquid Permeability Permeability
and Temp. (◦ C·) (kg/h·m2 ) (kg·m/h·m2 ) 1 day 14 days
STYRENE RUBBER
Di isobutylene
25.0 9.12E + 00 6.98E − 01 1.42 1.38
54.4 1.36E + 01 1.00E + 00 1.50 1.48
82.2 1.60E + 01 1.17E + 00 1.67 2.28
SR-6
25.0 3.51E + 01 2.56E + 00 2.40 2.37
54.4 5.59E + 01 3.97E + 00 2.37 2.40
82.2 7.18E + 01 5.45E + 00 2.47 3.82
Methyl ethyl ketone
25.0 1.10E + 01 8.15E − 01 0.88 0.85
54.4 1.95E + 01 1.36E + 00 0.99 0.98
82.2 3.12E + 01 2.24E + 00 1.10 1.19
Bezene
25.0 5.35E + 01 3.93E + 00 3.05 2.88
54.4 9.04E + 01 6.04E + 00 2.91 3.02
82.2 1.02E + 02 7.71E + 00 2.89 3.63
Ethyl acetate
25.0 1.21E + 01 9.38E − 01 0.93 0.88
54.4 2.53E + 01 1.95E + 00 1.02 1.00
82.2 3.57E + 01 2.72E + 00 1.11 1.29
Methyl alcohol
25.0 5.85E − 02 4.31E − 03 0.02 0.05
54.4 6.47E − 01 4.62E − 02 0.05 0.16
82.2 1.30E + 00 9.73E − 02 — —
Carbon tetrachloride
25.0 3.34E + 01 2.38E + 00 2.36 3.20
54.4 5.25E + 01 3.97E + 00 3.33 3.37
82.2 7.45E + 01 5.70E + 00 3.36 4.73
PARACRIL 18
Di isobutylene
25.0 2.24E − 01 2.39E − 02 0.30 0.34
54.4 9.31E − 01 6.79E − 02 0.43 0.69
Table XXVI
(continued from previous page)
in Rubber
Specific (ml/ml)
and Temp. (◦ C) (kg/h·m2 ) (kg·m/h·m2 ) 1 day 14 days
82.2 2.61E + 00 1.96E − 01 0.49 0.44

SR-6
25.0 7.12E + 00 5.40E − 01 1.07 1.03
54.4 1.69E + 01 1.22E + 00 1.09 ?
82.2 2.62E + 01 1.91E + 00 1.20 1.29
Methyl ethyl ketone
25.0 3.75E + 01 6.88E + 00 2.32 2.04
54.4 5.73E + 01 1.09E + 01 1.89 2.07
82.2 8.30E + 01 1.52E + 01 2.02 2.74
Benzene
25.0 4.41E + 01 8.01E + 00 2.43 2.41
54.4 5.73E + 01 1.22E + 01 2.40 2.44
82.2 1.02E + 02 1.84E + 01 2.36 2.64
Ethyl acetate
25.0 2.34E + 01 4.49E + 00 1.65 1.62
54.4 3.62E + 01 6.78E + 00 1.59 1.65
82.2 4.48E + 01 8.46E + 00 1.60 1.81
Methyl alcohol
25.0 2.66E − 01 4.97E − 02 0.14 0.14
54.4 1.96E + 00 3.58E − 01 0.18 0.15
82.2 7.97E + 00 1.43E + 00 — —
25.0 1.08E + 01 2.04E + 00 1.72 1.66
54.4 2.03E + 01 3.94E + 00 1.65 1.64
82.2 2.63E + 01 4.84E + 00 1.63 1.86
PARACRIL 35
Di isobutylene
25.0 Negligible Negligible 0.07 0.18
54.4 6.48E − 02 1.29E − 02 0.22 0.20
82.2 9.66E − 01 1.71E − 01 0.27 0.23
SR-6
25.0 2.58E + 00 4.91E − 01 0.68 0.66
54.4 4.63E + 00 8.72E − 01 0.70 0.70
82.2 6.59E + 00 1.19E + 00 — —
Methyl ethyl ketone
25.0 3.92E + 01 7.56E + 00 2.39 2.51
54.4 5.48E + 01 1.03E + 01 2.42 2.70
82.2 7.07E + 01 1.31E + 01 2.61 3.38
Benzene
25.0 3.55E + 01 6.56E + 00 2.22 2.15
54.4 4.51E + 01 8.53E + 00 2.16 2.18
82.2 5.87E + 01 1.11E + 01 2.14 2.41
Ethyl acetate
25.0 2.21E + 01 1.64E + 00 1.73 1.69
54.4 3.03E + 01 2.17E + 00 1.63 1.70
82.2 3.85E + 01 2.77E + 00 1.61 1.92
Methyl alcohol
25.0 1.31E + 00 9.66E − 02 0.18 0.17
54.4 2.31E + 00 1.74E − 01 0.23 0.22
82.2 4.92E + 00 3.59E − 01 — —
25.0 3.41E + 00 2.40E − 01 1.06 1.03
54.4 5.75E + 00 4.08E − 01 1.06 1.04
82.2 1.06E + 01 7.55E − 01 1.09 1.11
THIOKOL
Di isobutylene
Table XXVI
in Rubber
Specific (ml/ml)
and Temp. (◦ C) (kg/h·m2 ) (kg·m/h·m2 ) 1 day 14 days

82.2 Negligible Negligible 0.08 a
SR-6
54.4 4.87E − 01 5.14E − 02 0.22 0.22
82.2 1.31E + 00 1.04E − 01 0.27 0.37
Methyl ethyl ketone
25.0 4.40E + 00 3.32E − 01 0.60 0.61
54.4 5.28E + 00 5.37E − 01 0.65 0.70
82.2 1.22E + 01 8.88E − 01 0.77 0.77
Benzene
25.0 8.60E + 00 6.50E − 01 1.22 1.25
54.4 1.60E + 01 1.20E + 00 1.29 1.41
82.2 2.92E + 01 2.17E + 00 1.46 2.31
Ethyl acetate
25.0 2.11E + 00 1.64E − 01 0.48 0.48
54.4 5.76E + 00 4.25E − 01 0.50 0.52
82.2 8.25E + 00 6.27E − 01 0.53 0.58
Methyl alcohol
54.4 4.45E − 01 3.26E − 02 0.09 0.09
82.2 2.14E + 00 1.55E − 01 — —
25.0 6.93E − 01 1.25E − 01 0.36 0.54
54.4 1.95E + 00 3.94E − 01 0.64 0.65
82.2 3.56E + 00 7.14E − 01 0.75 a
NEOPRENE
Di isobutylene
54.4 1.10E + 00 2.39E − 01 0.48 0.47
82.2 2.23E + 00 4.68E − 01 0.57 0.57
SR-6
25.0 7.48E + 00 1.66E + 00 1.54 1.59
54.4 1.25E + 01 2.78E + 00 1.84 1.90
82.2 1.72E + 01 3.33E + 00 2.06 2.41
Methyl ethyl ketone
25.0 1.06E + 01 2.44E + 00 1.39 1.42
54.4 1.55E + 01 3.91E + 00 1.41 1.52
82.2 2.31E + 01 5.33E + 00 1.71 2.02
Benzene
25.0 2.61E + 01 5.85E + 00 2.94 2.98
54.4 4.79E + 01 1.03E + 01 3.59 3.75
82.2 6.19E + 01 1.41E + 01 3.61 4.12
Ethyl acetate
25.0 5.62E + 00 1.31E + 00 1.25 1.20
54.4 1.43E + 01 3.26E + 00 1.15 1.16
82.2 1.27E + 01 2.85E + 00 1.24 1.27
Methyl alcohol
25.0 1.21E − 01 2.87E − 02 0.02 0.04
54.4 b b 0.09 0.26
82.2 b b — —
25.0 1.75E + 01 3.62E + 00 3.09 3.44
54.4 2.40E + 01 5.13E + 00 3.20 3.69
82.2 b b 3.24 3.41
a Samples dissolved. b Could not be measured due to leakage.
Table A-XXVII
Demand and Producing Capacity of Epichlorohydrin Elastomers
Demand Producing Capacity of Supplier
U.S.A. 6000MT/y Zeon Chemical 7500MT/y

JAPAN 3000MT/y Nippon Zeon 2000MT/y
Europe 2500MT/y Daiso 4000MT/y
Others 1000MT/y
Total 12500MT/y Total 13500MT/y
Table A-XXVIII
Polymerization of ECO
Monomer composition ECH EO ECH EO
Weight fraction (%) 51 49 90 10
Polymerization time (hour) —6— —27—

Yield (%) —22— —18—
Polymer composition
Weight fraction (%) 14 86 60 40
η sp/C(dl/g)a —11.4— —9.2—
Acetone soluble part (%) —100— —83—
Water soluble part (%) —75— —insoluble—
Appearance —hard rubber like— —elastic rubber like—
Catalyst preparation: (iso-butyl)3Al/Acetylacetone/H20 = 1.0/0.5/0.5 (mol ratio)
Solvent: n-pentane/diethylether = 70/30
Polymerization condition: monomer/toluene = 10/40
Temperature: 30 ◦ C
a 0.1% α-chloronaphthalene solution: 100 ◦ C.
Table A-XXIX
Properties of Epichlorohydrin Elastomers
Polymer Type CO ECO
Epichlorohydrin (wt %) 100 68

Chlorine (wt %) 38 26
Oxygen (wt %) 17 23
Specific gravity 1.36 1.27
SP value 9.35 9.05
Solvent Toluene, Methylethylketone, Benzene
Tetrahydrofuran, Cyclohexanone
Refractive index: nD 20 1.5160 1.4980
T g (by DSC) −23 ◦ C −41 ◦ C
Linear expansion coefficient
(×10−5 ◦ C−1 ) 16.4 16.4
Volume inherent resistivity
(Ohm-cm) 1010 108
Oxygen index (%) 21.5 19.5
Table A-XXX
Trade Name of Epichlorohydrin Elastomers
Supplier Trade name Abbreviation Grouping numbera
Zeon Chemical Hydrin H CO 1

C ECO 2
T GECO 7
TX-1 GECO 4
TX-2 GECO 5
Nippon Zeon Gechron 1000 CO 1
1100 GCO 3
2000 ECO 2
2101 GECO 7
3100 GECO 4
3102 GECO 5
Daiso Epichlomer H CO 1
HG GCO 3
C ECO 2
CG GECO 6
CG-104 GECO 5
a Grouping numbers corresponde to Figure 37.
Table A-XXXI
ECO Cure Systems
Cure system Cure Temp. (◦ C)
NaSH/sulfur/amines 40 ∼ 90
. . .2.S/sulfur/amines
Na ....................................................................................................
Triethylene tetramine/dipentamethylenethiuram tetrasulfide

Trimene Base/sulfur 50 ∼ 100
2-alkylamino-4,6-dimercapto-S-triazine/amines
........................................................................................................
Polyalkylamine 130 ∼ 150

2-Alkylamino-4,6-dimercapto-S-triazine
........................................................................................................
Ethylenethiourea/red lead 150 ∼ 160

2,4,6-Trimercapto-S-triazine/amines/magnesium oxide
Dialkylthioureas/sulfur
. . . . . . . . . . . . . . . . . . . . . . . .or
. . .thiurams/magnesium
. . . . . . . . . . . . . . . . . . . . . .oxide
.......................................................
Thioureas/thiurams
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .155
. . . .∼
. . .165
......
Thioureas/magnesium oxide 160 ∼ 180

Lead
. . . . . .cyanide/sorbitol/magnesium
. . . . . . . . . . . . . . . . . . . . . . . . . . . . .oxide
.....................................................................
Thiurams 180 ∼ 190

2,4,6-Trimercapto-S-triazine
Table A-XXXII
Cure System Study of ECO
Curative F ETU XL-21 ECHOP
ECO C-85 100 100 100 100

Sorbitan monostearate 3 3 3 3
N550 40 40 40 40
MgO 1.5 — — —
CaCO3 5 — 5 —
Pb3 O4 — 5 — —
Ca(OH)2 — — 4 —
BaCO3 — — — 5
ZISNET-F 0.9 — — —
ETU — 1.2 — —
DAISONET XL-21 — — 1.4 —
ECHOP — — — 2.8
NBC 1 1 1 1
N -(cyclohexylthio)phthalamide 1 — — —
Pentaerithritol — — 0.7 —
Original properties (cured 30 min. at 160 ◦ C):
Tensile strength (MPa) 12.4 13.8 13.4 11.6
Elongation (%) 550 450 490 820
Hardness (Shore A) 65 67 67 56
Aged in air—72 hours at 150 ◦ C:
Tensile strength change (%) −9 −1 −10 −21
Elongation change (%) −53 −47 −43 −70
Hardness change (point) +1 +1 −2 +2
JIS #3 Oil—70 hours at 135 ◦ C:
Volume swell (%) +12 +13 +14 +11
Fuel C—70 hours at 40 ◦ C:
Volume swell (%) +39 +37 +37 +41
Tensile strength change (%) −36 −33 −34 −40
Elongation change (%) −49 −51 −43 −38
Hardness change (point) −14 −12 −14 −26
Gehman low temperature:
T100 (◦ C) −43 −43 −43 −42
Table A-XXXIII
White Filler Studies
Formulation: Ingredients phr
GECO 3102 100 100 100 100 100

Sorbitan monostearate 3 3 3 3 3
MgO 3 3 3 3 3
CaCO3 5 5 5 5 5
ZISNET-F 0.9 0.9 0.9 0.9 0.9
N -(cyclohexylthio)phthalimide 1.5 1.5 1.5 1.5 1.5
NBC 1.5 1.5 1.5 1.5 1.5
N550 40 — — — —
Silica 200a — 40 — — —
Silica 67b — — 40 — —
Silica 80c — — — 40 —
Silica VN-3d — — — — 40
Original properties (cured 30 min at 160 ◦ C):
Tensile strength (MPa) 12.0 21.4 13.6 13.4 16.8
Elongation (%) 410 820 410 560 570
Hardness (Shore A) 68 79 72 76 74
Aged in air (144 hours at 150 ◦ C):
Tensile strength change (%) −12 −35 −24 −24 −27
Elongation change (%) −59 −60 −46 −48 −49
Hardness change (point) +4 +6 0 +3 +3
ASTM #3 Oil (70 hours at 135 ◦ C):
Volume swell (%) +14 +12 +12 +12 +12
Fuel C (70 hours at 40 ◦ C):
Volume swell (%) +44 +46 +44 +45 +46
Tensile strength change (%) −37 −64 −50 −68 −71
Elongation change (%) −54 −43 −54 −54 −61
Hardness change (point) −13 −24 −19 −21 −20
Cold impact brittleness test:
Brittle point (◦ C) −34 −31 −31 −31 −31
a Fumed Silica 16 µ, pH 4.0, SiO2 99%. b Precipitated
hydrated amorphous silica, pH 7.5, SiO2
93%. c Precipitated hydrated amorphous silica, pH 6.0, SiO2 95%. d Precipitated hydrated amorphous
silica, 16 µ, pH 6.0, SiO2 94%.
Table A-XXXIV
Plasticizer Study of GECO
Formulation NONE DBP DOP DOA TP95 TCP W-320 TP759
GECO 3102 100 100 100 100 100 100 100 100
Sorbitan monostearate 3 3 3 3 3 3 3 3
N550 60 60 60 60 60 60 60 60
MgO 3 3 3 3 3 3 3 3
CaCO3 5 5 5 5 5 5 5 5
ZISNET-F 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9
N -(cyclohexylthio)phthalimide 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
NBC 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
DBP — 20 — — — — — —
DOP — — 20 — — — — —
DOA — — — 20 — — — —
Plasticizer TP-95 — — — — 20 — — —
TCP — — — — — 20 — —
Plasticizer W-320 — — — — — — 20 —
Plasticizer TP759 — — — — — — — 20
........................................................................................................
Compound Mooney viscosity, 129 63 62 60 82 70 68 65
ML1+4 at 100 ◦ C
Original properties
(cured 30 min at 160 ◦ C):
Tensile strength (MPa) 13.9 10.8 10.9 10.7 10.5 11.0 11.3 10.2
Elongation (%) 170 290 320 290 280 300 350 290
Hardness (Shore A) 85 74 72 74 75 75 70 74
Post-cured (4 hours at 150 ◦ C):
Tensile strength (MPa) 15.2 14.0 12.4 12.6 11.7 12.3 12.5 11.7
Elongation (%) 130 210 220 210 210 200 220 200
Hardness (Shore A) 87 82 76 79 78 77 75 76
Weight loss (%) 0 −9 −2 −4 0 0 0 0
Aged in air (360 hours at 135 ◦ C):
Tensile strength change (%) 0 +17 +11 +5 +14 +21 +4 +2
Elongation change (%) −53 −66 −63 −66 −61 −67 −63 −62
Hardness change (point) +4 +15 +19 +17 +14 +!& +10 +10
Weight loss (%) 0 −10 −10 −10 −7 −8 −2 −2
ASTM #3 Oil (70 hours at 135 ◦ C):
Volume swell (%) +13 0 −1 −2 0 +2 +1 0
Fuel C (70 hours at 40 ◦ C):
Volume swell (%) +36 +22 +21 +19 +22 +25 +25 +22
Tensile strength change (%) −35 −23 −25 −27 −21 −25 −27 −20
Elongation change (%) −41 −41 −41 −38 −36 −40 −51 −45
Hardness change (point) 0 −10 −10 −10 −7 −14 −8 −11
Cold impact brittleness test:
Brittle point (◦ C) −27 −39 −39 −41 −42 −32 −37 −41
Table A-XXXV
Air Permeability of CO and ECO
Carbon black Air permeability
Polymer (phr) (cm2 sec−1 atm−1 × 10−9 )
ACM 4021 36.7 28

ACM 4042 36.7 44
NBR1041 40.0 3.9
NBR 1042 40.8 7.5
NBR 1043 41.2 11
CO 100 29.4 1.3
ECO 200 31.5 6.0
IIR 44.0 4.8
Condition: room temperature.
Table A-XXXVI
Applications and Requirements of Epichlorohydrin Elastomer
Application Requirements Polymer Type
Automotive application :
Fuel hoses Heat resistance GECO, ECO
Fuel resistance
Weathering resistance
Air intake hoses Heat resistance ECO
Oil resistance
Low temperature resistance
Control hoses Heat resistance GECO
Oil resistance
Diaphragms Heat resistance GECO, ECO
Oil resistance
Industrial application :
LPG hoses Low temperature resistance ECO
Low gas permeability
Diaphragms for gases Oil resistance ECO
Low temperature resistance
Table A-XXXIX
Polyacrylate Rubbers in Market
Zeon
Nippon Nihon Chemicals
Low Temp. Zeon Mektron Tohpe USA Enichem DuPont
Curesite Property Nipol NOXTITE TOAACRON HyTemp ELAPRIM Vamac
Chlorine −10 A-1095

−20 PA-212
−30
−40
Active −10 AR71 PA-401 AR-801 AR71 R
chlorine AR715 L
−20 AR72LS, PA-402 AR72LF C
AR72LF,
AR72HF
−30 PA-403 AR-840 #35
AR74 PA-404 AR-860 #40
−40
A-5098
Epoxide −10 AR31, AR51 PA-301 AR-601
PA-302
−20 AR32, AR42, PA-312
AR42W
AR53L PA-303
−30 AR-740
AR54 AR-760
−40
Others −10 PA-501 4051 AR153
−20 PA-502 4052 AR152
AR155
−30 4053 AR156 G, HG, D,
DLS
AR157 B-124,
N-123
−40 4054
Table A-XL
Practical Compounding Formulation
Ingredient phr
Nipol AR 100
Stearic acid 1
Gregg G-8205 2
Carbon (HAF or FEF) 60–80
Antioxidant 445 2
Plasticizer 0–5
Curatives recommended
Table A-XLI
Comparison among the Typical Grade Plasticizers
Sample No. A B C D E F G H I J
Plasticizer none DOP DOS RS-107 RS-700 TP-95 PN-160 RS-735 P-200 PN-350
Chemical name diocthyl diocthyl ether- poly- ether- poly- poly- poly- poly-
phtalate sebacate ester- ether- ester- ester- etherester- ester-
adipate ester adipate adipate ester adipate adipate
Molecular weight 391 426 434 550 435 800 850 2000 3000
Compatibility P G G G G G G G G
Amount of adding 15 15 15 15 15 15 15 15 15
(phr)
Tensile test
(Cure condition
press cured
for 10 min at
180 ◦ C &
post cured
for 4 h at
170 ◦ C)
Tensile strength 13.0 12.3 9.6 10.5 10.1 9.6 10.4 10.1 10.7 10.4
(MPa)
Elongation (%) 130 130 155 160 160 155 160 165 170 165
100% Modulus 10.7 10.5 6.2 7.5 7.0 7.6 7.1 6.9 6.7 6.6
(MPa)
Hardness (JIS A) 75 74 72 67 66 68 66 66 65 65
Weight change −0.7 −7.8 −5.6 −3.3 −2.1 −4.5 −1.8 −0.9 −0.9 −0.7
at post (%)
Cold impact
brittleness test
(Cure condition
press cured
for 10 min at
180 ◦ C &
post cured
for 4 h at
170 ◦ C)
Tb (◦ C) −23 −25 −28 −40 −37 −38 −31 −36 −30 −29
Tb (◦ C) after aging −19 −20 −22 −31 −22 −30 −35 −28 −28
for 70 h
at 170 ◦ C
Tb (◦ C) after −19 −20 −21 −22 −21 −26 −23 −28 −28
immersion in
JI #1 oil for
70 h at 150 ◦ C
Table XLI
Sample No. A B C D E F G H I J
Aging test in air

(Cure condition
press cured
for 10 min at
180 ◦ C &
post cured
for 4 h at
170 ◦ C)
(after 70 h
at 170 ◦ C)
Tensile strength −1 21 15 3 16 −2 7 −14 −8
change (%)
Elongation change −23 −39 −47 −25 −52 −25 −24 −30 −24
(%)
Hardness change 7 9 14 10 14 8 7 8 7
(point)
Weight change (%) −2.2 −9.5 −9.0 −6.2 −9.0 −3.7 −2.7 −2.5 −2.2
Immersion test
(Cure condition
press cured
for 10 min at
180 ◦ C &
post cured
for 4 h at
170 ◦ C)
(after 70 h at
at 150 ◦ C,
JIS #1 oil)
Volume change (%) 1.0 −4.9 −5.1 −6.5 −4.7 −2.9 −5.3 −0.9 −0.2
(after 70 h
at 150 ◦ C,
JIS #3 oil)
Volume change (%) 17.7 10.5 11.1 9.2 11.5 10.6 8.2 13.4 14.9
Table A-XLII
The Loss Weight After Aging
None RS-107 RS-700 RS-735
NBR 120 ◦C × 70 h −1.2% −3.1% −2.1% −1.2%

170 ◦C × 4 h −0.6 −2.9 −1.7 −0.7
ACM 150 ◦C × 70 h −1.1 −7.8 −4.2 −1.4
175 ◦C × 70 h −0.8 −8.2 −5.3 −1.2
Table A-XLIV
Comparison among the Typical Synthetic Rubbers
Rubber Name ACM NBR ECO
Product Name Nipol AR71 Nipol 1042 Gechron 2000
Tensile test
Cure condition (press cured) 170 ◦ C × 10 min 160 ◦ C × 20 min 160 ◦ C × 30 min
(post cured) 170 ◦ C × 4 h 150 ◦ C × 4 h
Tensile Strength (MPa) 12.3 19.6 17.1
Elongation (%) 340 430 250
100% Modulus (MPa) 3.6 3.0 6.5
Hardness (JIS A) 62 68 72
Table A-XLV
Comparison among the Typical Grade ACMs
Sample No. 1 2 3
Product Name AR71 AR72LS AR74
Nipol AR 100 100 100

Stearic acid 1 1 1
Gregg G8205 1 1 1
Antioxidant 445 2 2 2
MAF Carbon 50 60 60
Potasium stearate 3.0 3.0 3.0
Sodium stearate 0.5 0.5 0.5
Sulfur 0.3 0.3 0.3
Tensile test
(Cure condition press cured
for 10 min at
170 ◦ C &
post cured
for 4 h at
170 ◦ C)
Tensile strength (MPa) 12.3 10.8 10.0
Elongation (%) 340 240 180
100% Modulus (MPa) 3.6 5.1 4.5
Tear strength (kN/m) 28 22 15
Compression set test
(Cure condition press cured for
10 min at 170 ◦ C &
post cured for 4 h at 170 ◦ C)
C.S (%) (after 70 h at 150 ◦ C) 35 37 35
Aging test in air
10 min at 170 ◦ C &
(after 70 h at 150 ◦ C)
Tensile strength change (%) 2 2 4
Elongation change (%) 6 0 0
Hardness change (point) 2 2 2
Immersion test
10 min at 170 ◦ C &
(after 70 h at 150 ◦ C, JIS #3 oil)
Volume change (%) 13 21 26
Tensile strength change (%) −2 −10 −27
Elongation change (%) 6 4 −11
Hardness change (point) −12 −19 −19
Cold impact brittleness test
10 min at 170 ◦ C
Brittle point (◦ C) −11 −22 −34
Table A-XLVI
Influence of Amount of Carbon Black
Sample No. 1 2 3
Nipol AR71 100 100 100

Stearic acid 1 1 1
Polycizer W-320 5 5 5
Antioxidant 630F 1.5 1.5 1.5
FEF Carbon 35 45 60
Potasium stearate 2.5 2.5 2.5
Sodium stearate 1.0 1.0 1.0
Sulfur 0.3 0.3 0.3
Tensile test
20 min at 170 ◦ C &
Tensile strength (MPa) 12.9 13.4 14.4
Elongation (%) 340 310 240
100% Modulus (MPa) 2.2 3.4 6.7
Tear strength (kN/m) 17 19 20
Table A-XLVII
Resistance of Speciality Rubbers against Engine-oil Additives (Elongation at Break)
(after immersion for 7 days at 150 ◦ C)
Amount of
Additives Name Additives (vol. %) NBR ECO ACM VMQ FKM
Dispersant polyisobutenyl-
succinimid/boricsalt 10 510 100(20)b 180 180 160
polyisobutenyl-
succinicacid ester 10 730 200 210 140 240
polyisobutenyl-
succinimid 10 520 70(10)b 100 160 150(0)b
..............................................................................................................
Detergent basic
Ca sulfonate 10 470 170 200 130 250
basic
Mg sulfonate 10 200 120 190 150 190
basic
Ca phenate 10 240 90(40) 240 140 220
..............................................................................................................
Antioxidant Zn-DTP-
secondary-alcohol 5 230(80)a,c 70(40)c 180 harden 170
Zn-DTP-
primary-alcohol 5 120(50)c 70(0)b 150 harden 230
..............................................................................................................
Extreme diphenyldisulfide 10 240 220 200 150 270
Pressure dialkylphosfate 10 510 220 130 disolution 190
Additive dibuthyldithio-
carbamicacid Zn salt 10 440 harden 210 130 collapse
naphtenacid-
Pb salt 10 420 150 harden harden 260
..............................................................................................................
Original ASTM #2 oil — 490 210 200 190 250
a bad smoothness. b cracking by bending 180◦ . c ( ) elongation at cracking.
Table A-XLVIII
Chemicals resistance of ACM (immersion for 7 days at 40 ◦ C)
Chemical Chemical Hardness Volume State of
kind name change change surface
Inorganic hydrochloric acid 5% −5 11.7 Ea

acid sulfuric acid 5% −5 21.8 E
nitric acid 5% −10 43.7 Gb
sulfurous acid −21 100 G
phosphoric acid 85% 0 0.2 E
chromic acid −5 18 E
Alkarine anmonia 10% −16 86.2 G
sodium hydroxide 10% −10 1.5 G
Ca(OH)2 (saturation) −4 30.2 G
Mg(OH)2 (saturation) −5 39.5 G
Salts CaCl2 (saturation) 1 0.5 E
NaCl (saturation) 5 2.9 E
FeCl2 (saturation) −5 41.6 E
KHOCl (saturation) 4 12.7 E
(NH4)2CO3 (saturation) −14 57.4 G
Na2SO4 (saturation) −7 12.4 E
Organic acetic acid 10% −10 50.5 G
acid oleic acid −4 15.8 E
phtal acid −4 37.6 G
monochloroacetic acid 30% −6 42.5 Pc
oxalic acid (saturation) −9 30 G
iso-octan −8 8.1 E
Hydro- cherocine −5 8.9 E
carbon gasoline −19 25.1 E
styren −39 252.4 E
diphenyl −20 51.2 E
benzene −27 277 E
aniline −46 290 G
methylethylketone −27 138.6 E
acetoaldehide −31 58.3 E
trichrene −33 221.7 E
carbontetrachloride −13 191 E
monochlorobenzene −39 131.3 E
Alcohol methylalcohol −32 46.2 E
ethylalcohol −29 50.6 E
buthylalcohol −12 58 E
isopropylalcohol −18 57.7 E
ethylenglycol −20 18.1 E
glyceline −5 2.9 E
Ester methylacetate −39 210.5 G
ethylacetate −25 102.1 G
buthylacetate −32 12.9 G
dibuthylphtalate −29 153.4 E
Others urea −9 9.2 E
carbondisulfide −11 47.7 E
boldo-fluid −9 29.6 E
chlorine-water −8 54.7 E
hydrogen sulfide −11 47.7 E
a E—exellent. b G—good. c P—poor.
V. APPENDIX B
A. GLOSSARY OF ABBREVIATIONS
ABS acrylonitrile butadiene stylene resin FKM fluoro rubber

ACM polyacrylic rubber GCO epichrolohydrin/allylglycidyl ether co-
AEM copolymer of acrylate and ethylene polymer
AGE allyl-glycidilether GECO epichrolohydrin/ethyleneoxide/allyl-
AS acrylonitrile stylene resin glycidyl ether terpolymer
ATF automatic transmission fluid GPO propylene oxide rubber
BA butylacrylate HFC-134a tetrafluoroethane
BR butadiene rubber HNBR hydrogenated nitrile rubber
CBS N -cyclohexyl-2-benzothiazyl sulfenamide IIR butyl rubber
CFC-12 dichlorodifluoromethane MBI 2-mercaptobenzimidazole
CIIR chlorinated butyl rubber MBT 2-mercaptobenzothiazole
CM chlorynated polyethylene MBTS dibenzothiazyl disulfide
CO epichrolohydrin homopolymer MEA methoxyethylacrylate
CR chloroprene NBC nickel dibutyl dithiocarbamate
CSM chlorosulfonated polyethylene NBR nitrile rubber
DBEEA dibutoxy ethoxy ethyl adipate NR natural rubber
DBP dibutyl phthalate PA polyamide
DCP dicumyl peroxide PAG polyalkyleneglycol
DEP diethyl phthalate PB blended polymer of NBR and PVC
DIDP diisodecyl phthalate PVC polyvinylchloride
DMP dimethyl phthalate SBR stylene butadiene rubber
DOA dioctyl adipate TCP tricresil phosphate
DOHC double over head camshaft TETD tetraethylthiuram disulfide
DOP dioctyl phthalate TMDQ polymer of 2,2,4-trimethyl-1,2-dihy-
DOS dioctyl sebacate droquinoline
EA ethylacrylate TMTD tetramethylthiuram disulfide
EBO epoxidized soybean oil TMTM tetramethylthiuram monosulfide
ECH epichlorohydrin TOP trioctyl phosphate
ECO epichlorohydrin rubber TP95 etherester adipate
EO etylene oxide VMQ silicone rubber
EPDM ethylene propylene diene rubber W320 polyester adipate
ETU ethylene thiourea ZnMDC zinc dimethyl dithiocarbamate
EVA ethylene vinylacetate polymer

Specialty Elastomers for Automotive Applications

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SPECIALTY ELASTOMERS FOR AUTOMOTIVE

5. Formulation and processing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464

I. GENERAL/HISTORICAL DISCUSSION OF THE USE OF SPECIALITY ELASTOMERS

Fig. 1.—Rubber devices for automotive gasoline engines.

Fig. 2.—Young’s modulus of organic and inorganic materials.

C. AUTOMOTIVE ENGINE APPLICATIONS

Fig. 3.—Classification on SAE J 200.

Fig. 4.—Structure of synchronous belts.

Fig. 5.—Quality requirements of synchronous belt and performance of CR and HNBR.

Fig. 6.—Belt running test.

Fig. 8.—Amine resistance of FKM.

D. FUEL AND HYDRAULIC SYSTEMS APPLICATIONS

Fig. 9.—SG grade engine oil resistance for gasket material.

Fig. 14.28 —Physical properties of several elastomer for fuel applications.

Fig. 15.29 —Comparison of cure system for ACM53.

Fig. 16.27 —Heat resistance of power steering hoses.

II. SYNTHESIS, CHARACTERISTICS AND PROPERTIES OF

1. Introduction.—Acrylonitrile–butadiene rubber is a synthetic rubber of copolymerized acry-

Fig. 17.—NBR manufacturing process.

3. Manufacturing method of HNBR.—Selective hydrogenation of C=C double bonds while

T g(◦ C) = −85 + 1.4A (1)

where A denotes the acrylonitrile content (%).

Fig. 18.—Polymer composition generated at each moment in polymerization.

Fig. 19.—Absorption of plasticizer in NBR.

Fig. 20.—NBR typical curing system.

b. Basic properties.—Basic characteristics of NBR are demonstrated in Table

c. Unvulcanized NBR characteristics.—Characteristics of unvulcanized NBR are estimated by

Fig. 25.—Properties vs. iodine-value of HNBR (AN 37).

Fig. 28.—NBR stress–strain curves at various temperature.

Fig. 29.—Service temperature and service life.

Fig. 30.—Oxidized fuel resistance: • HNBR 1020, + NBR, × ECO.

Fig. 31.—Sour environment test for tensile strength in liquid phase.

1. Introduction.—Epichlorohydrin elastomers have a good balance of the following properties:

Fig. 33.—Polymer type and structure

Fig. 34.—Slurry polymerization process.

development of the aluminum alkyl-phosphoric acid133 and the aluminum alkyl-polyphosphoric

Fig. 35.—Gehman low temperature Fig. 36.—Heat resistance vs. EO content

Fig. 37.—Composition of epichlorohydrin elastomers (the numbers 1–7 correspond

Fig. 38.—Vulcanization model of epichlorohydrin elastomer MeO: metal oxide.

Fig. 39.—Effect of carbon black on hardness and tensile strength of ECO.

Fig. 40.—Change in Mooney viscosity by mastication: Roll temperatures:

Fig. 41.—Change of crosslinking density by air aging.

Fig. 45.—The manufacturing process of ACMs.

Fig. 46.—Major monomer of ACMs.

Fig. 47.—The structure and performance of ACMs.

Fig. 48.—Oil swell–low temperature balance.

Fig. 49.—Oil swell–low temp. balance.

Fig. 50.—Carbon black vs. T − B and Cs.

Fig. 51.—Carbon black grade vs. ACMs performance.

Fig. 52.—Physical property with silica compounds.

Fig. 53.—Curing behavior at 170 ◦ C.

Fig. 54.—Low temperature property after heat aging.

Fig. 55.—Influence of antioxidants on the heat aging resistance of ACM-42.

Fig. 56.—Dump temperature.

Fig. 57.—Compound mooney vs. BBR mixing.

Fig. 58.—Backbone structure vs. heat resistance.

Fig. 59.—Polymer grade vs. heat resistance.

Fig. 60.—Ozone resistance of ACM.

[Received November 1, 1995; revised October 21, 1996 ]

Hoses Engine Fuel hose FKM/ECO/GECO low cost

Seals Engine Crank VMQ long-life FKM

Others Engine Synchronous belt CR heat resist., life HNBR long-life

A-1 — Original tensile strength —