2

Types of Hydrogenated Nitrile Rubber

Polymers Available

2.1 Introduction

This chapter provides an overview of the types and grades of HNBR polymers
commercially available and their performance characteristics in the context of other
oil-resistant polymers.

2.2 Summary of Grades Available

Table 2.1 summarises the grades of HNBR polymers available from two manufacturers,
Zeon Chemicals and Lanxess. The primary sort was made by mole% ACN, a
secondary sort by approximate residual unsaturation and a tertiary sort by nominal
Mooney viscosity. It is seen that HNBR polymers are available with mole% ACN
within the range 17 to 50%, at a variety of residual unsaturation levels and bulk
viscosities. For a given mole% ACN content, a higher residual unsaturation figure
is useful for providing more rapid sulfur vulcanisation or when greater crosslink
density is required in the finished product. A lower bulk Mooney viscosity results in
improved high-shear flow in transfer or injection moulding.

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Practical Guide to Hydrogenated Nitrile Butadiene Rubber Technology

Table 2.1 HNBR grades commercially available, December 2010

Grade Manufacturer Mole% Mooney Residual %
ACN viscosity unsaturation
(nominal) ML(1+4) (approximate)
at 100C
(nominal)
Zetpol 4300EP Zeon 17 30 0.5
Zetpol 4300 Zeon 17 75 0.5
Zetpol 4310EP Zeon 17 30 5
Zetpol 4310 Zeon 17 62 5
Therban AT LT
2004 VP Lanxess 21 39 0.9
Therban LT
2007 Lanxess 21 74 0.9
Therban LT
2057 Lanxess 21 67 5.5
Therban LT
2157 Lanxess 21 70 5.5
Zetpol 3310EP Zeon 25 30 5
Zetpol 3310 Zeon 25 80 5
Therban AP A
3404 Lanxess 34 39 0.9
Therban 3406 Lanxess 34 63 0.9
Therban 3407 Lanxess 34 70 0.9
Therban AT C
3443 VP Lanxess 34 39 4

Therban 3446 Lanxess 34 61 4

Therban 3467 Lanxess 34 68 5.5
Therban VP KA
8837 Lanxess 34 55 18
Zetpol 2000EP Zeon 36 30 0.5
Zetpol 2000L Zeon 36 65 0.5
Zetpol 2000 Zeon 36 85 0.5

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 Types of Hydrogenated Nitrile Rubber Polymers Available

Therban 3607 Lanxess 36 66 0.9

Therban 3627 Lanxess 36 87 2
Zetpol2010L Zeon 36 58 4
Zetpol 2010 Zeon 36 85 4
Zetpol 2010H Zeon 36 135 4
Therban AT A
3904 VP Lanxess 39 39 0.9
Therban 3907 Lanxess 39 70 0.9
Therban AT
4304 VP Lanxess 43 39 0.9
Therban 4307 Lanxess 43 63 0.9
Therban 4309 Lanxess 43 100 0.9
Therban AT
4364 VP Lanxess 43 39 5.5
Therban 4367 Lanxess 43 61 5.5
Therban 4369 Lanxess 43 97 5.5
Zetpol 1000L Zeon 44 65 2
Zetpol 1010EP Zeon 44 29 4
Zetpol 1010 Zeon 44 85 4
Zetpol 1020EP Zeon 44 30 9
Zetpol 1020L Zeon 44 57 9
Zetpol 1020 Zeon 44 78 9
Therban AT
5005 VP Lanxess 49 55 0.9
Therban 5008
VP Lanxess 49 80 0.9
Therban AT
5065 VP Lanxess 49 55 6
Zetpol 0020EP Zeon 50 40 9
Zetpol 0020 Zeon 50 65 9
Therban is a registered trademark of Lanxess
Zetpol is a registered trademark of Zeon Chemicals

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Practical Guide to Hydrogenated Nitrile Butadiene Rubber Technology

In addition to these grades, speciality polymers are available for specific applications
and end-products. These are summarised in Table 2.2.

Table 2.2 HNBR speciality grades available

Grade Manufacturer Mole% Mooney Residual % Modification
ACN viscosity unsaturation
(nominal) ML(1+4) (approximate)
at 100 C
(nominal)
Zeoforte Zeon 36 95 9 Zinc
ZSC methacrylate
2295CX
Zeoforte Zeon 36 80 9 Zinc
ZSC methacrylate
2295L
Zeoforte Zeon 36 70 15 Zinc
ZSC methacrylate
2385
Therban Lanxess 33 77 3.5 Carboxylated
XT VP (XHNBR)
KA 8889
Therban Lanxess 34 22 5.5 Acrylate
VP KA
8796
Therban is a registered trademark of Lanxess
Zetpol and Zeoforte are registered trademarks of Zeon Chemicals

Modification with acrylates such as zinc methacrylate gives tough and mechanically
durable materials for use in power transmission belts and conveyor belts, and in
similar products requiring a high level of resistance to abrasion, cutting and wear.

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 Types of Hydrogenated Nitrile Rubber Polymers Available

2.3 HNBR Grades and Technology

One way to illustrate the position of HNBR within the elastomer market is to employ
the ASTM D2000 classification system [1]. This is illustrated in Figure 2.1, along with
a selection of other elastomers for comparison. Not only does the HNBR family fill a
gap in the properties identified, HNBR also offer tear resistance, abrasion resistance
and overall toughness that polymers such as acrylic elastomers (ACM) and ethylene
acrylic copolymer elastomers (AEM) cannot match.

ASTM D2000 Classification

% Swell in ASTM IRM903 Oil
300

Temperature resistance (C)

FKM 250

VMQ FVMQ 200

EPDM AEM ACM
150
HNBR
CR 100
NBR
NR
50

0
200 150 100 50 0
Class by Oil Swell

Figure 2.1 Graphical illustration of speciality elastomers, showing the position of

HNBR within the ASTM D2000 system

NBR are among the oldest and most widely used oil-resistant polymers and provide
an excellent combination of properties and durability, but due to their high level of
unsaturation they are prone to oxidation and to attack by sulfur. HNBR materials are
much more resistant to oxidation and sulfur attack and combine the compounding
flexibility and toughness of NBR with improved temperature and chemical resistance.
This is illustrated in Figures 2.2 and 2.3 in the case of resistance to engine oil and
automatic transmission fluids, respectively. The loss of elongation after 1008 hours
at 150 C is shown for HNBR, NBR, ACM and AEM materials [2]. An estimate
of the life of an elastomer is the time required to reduce the elongation to 50% of
its original value. Figures 2.2 and 2.3 show that HNBR materials still retain some
useful life after long-term ageing, whereas NBR and CSM materials had reached the

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Practical Guide to Hydrogenated Nitrile Butadiene Rubber Technology

end of their useful life before the end of the ageing test. The ACM material showed
excellent long-term ageing performance in these fluids, but did not have the tear and
abrasion resistance of HNBR materials.

Comparison of Oil-Resistant
Elastomers, 10W30SG engine oil at 150 C
40
30
% Elongation Loss

20
10
0 % Elongation Loss, 504 h
10
20 % Elongation Loss, 1008 h
30
40
50
60
35% ACN 25% ACN ACM AEM
HNBR HNBR
Material

Figure 2.2 Comparison of engine oil resistance of HNBR, ACM and AEM
elastomers

Comparison of Oil-resistant
Elastomers, Dexron III ATF at 150 C
25
20
% Elongation Loss

15
10
5 % Elongation Loss, 504 h
0
5 % Elongation Loss, 1008 h
10
15
20
25
30
35% ACN 25% ACN ACM AEM
HNBR HNBR
Material

Figure 2.3 Comparison of resistance to automatic transmission fluid (ATF) of

HNBR, ACM and AEM elastomers

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 Types of Hydrogenated Nitrile Rubber Polymers Available

The relative abrasion resistance of HNBR materials compared to other oil-resistant

elastomers, such as NBR, epichlorohydrinethylene oxide copolymers (ECO),
fluorocarbons (FKM) and ACM, is shown in Figure 2.4 [3]. Traditional NBR materials
are given a relative rating of 100.

Akron-type abrasion resistance rating

200
Relative resistance to

150
abrasion

100

50

0
45% ACN NBR ECO FKM ACM
HNBR
Material

Figure 2.4 Comparison of the abrasion resistance of various elastomers

The effects of abrasion, wear and friction are not well understood, but this type
of testing is valuable in providing a relative rating for a range of materials. The
combination of increased high temperature performance and improved wear resistance
emphasises the niche occupied by HNBR among the available oil-resistant elastomers.

In the remainder of this chapter the effect of HNBR and compounding ingredients
on the final properties of the compound are discussed. This is not intended to be
an exhaustive account of every compounding possibility, but the use of statistical
experimental design will be emphasised and illustrated as a cost-effective way of
studying the compounding variables.

Finally, it is important to compare the relative cost of the various oil-resistant

elastomers. The poundvolume cost is used, which is simply the cost of the compound
multiplied by its specific gravity. This gives the relative cost of the compound required
to fill a given volume such as a mould cavity. This has been shown earlier in Table
2.2, along with the upper temperature limits of the various materials. While acrylic
elastomers such as ACM and AEM are cost-effective up to 150 C, HNBR are much
tougher and more abrasion-resistant. FKM and fluorosilicones (FVMQ) have excellent
upper temperature limits, but their poundvolume cost is heavily influenced by their
relatively high specific gravity.

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Practical Guide to Hydrogenated Nitrile Butadiene Rubber Technology

Table 2.3 gives a cost comparison of oil-resistant elastomers, and a combination

of Table 2.3 and Figures 2.2 to 2.4 puts the niche filled by HNBR materials in
perspective. HNBR combine toughness, abrasion resistance, fluid resistance and good
cost effectiveness at temperatures up to 150 C.

Table 2.3 Commercial comparison of oil-resistant elastomers

Polymer SG Cost of lbvol cost ($) Operating temperature,
compound ($) upper limit (C)
NBR 1.22 $1.00 $1.22 100
ACM 1.32 $2.30 $3.04 150
AEM 1.32 $2.40 $3.17 150
HNBR 1.22 $10.40 $12.69 150
FVMQ 1.53 $23.00 $35.19 200
FKM 1.86 $16.00 $29.76 250
Note: 75 Shore A, assumes carbon black filler, except for FVMQ

2.4 Summary

This chapter has given a brief overview of the polymers currently available and how
these fit into the overall range of oil-resistant elastomers. Formulation guidelines
and examples of formulations for specific applications will be given in detail later.

References

1. Rubber, American Society of Testing and Materials, Washington, DC, USA,

2006, 9, 2, D2000-06.

2. A Comparison of Oil Resistant Elastomers in Engine Oil and ATF, Z7.3.16,

Zeon Chemicals LP, Louisville, KY, USA, 1999, p.1.

3. Zetpol Product Guide, Zeon Chemicals LP, Louisville, KY, USA, 1999.

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