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 gure is useful for providing more rapid sulfur vulcanisation or when greater crosslink density is required in the nished product. A lower bulk Mooney viscosity results in improved high-shear ow 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% ACN (nominal) Mooney viscosity ML(1+4) at 100C (nominal) 30 75 30 62 39 74 67 70 30 80 39 63 70 39 61 68 55 30 65 85 Residual % unsaturation (approximate)

Zetpol 4300EP Zetpol 4300 Zetpol 4310EP Zetpol 4310 Therban AT LT 2004 VP Therban LT 2007 Therban LT 2057 Therban LT 2157 Zetpol 3310EP Zetpol 3310 Therban AP A 3404 Therban 3406 Therban 3407 Therban AT C 3443 VP Therban 3446 Therban 3467 Therban VP KA 8837 Zetpol 2000EP Zetpol 2000L Zetpol 2000

Zeon Zeon Zeon Zeon Lanxess Lanxess Lanxess Lanxess Zeon Zeon Lanxess Lanxess Lanxess Lanxess Lanxess Lanxess Lanxess Zeon Zeon Zeon

17 17 17 17 21 21 21 21 25 25 34 34 34 34 34 34 34 36 36 36

0.5 0.5 5 5 0.9 0.9 5.5 5.5 5 5 0.9 0.9 0.9 4 4 5.5 18 0.5 0.5 0.5

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Types of Hydrogenated Nitrile Rubber Polymers Available

Therban 3607 Therban 3627 Zetpol2010L Zetpol 2010 Zetpol 2010H Therban AT A 3904 VP Therban 3907 Therban AT 4304 VP Therban 4307 Therban 4309 Therban AT 4364 VP Therban 4367 Therban 4369 Zetpol 1000L Zetpol 1010EP Zetpol 1010 Zetpol 1020EP Zetpol 1020L Zetpol 1020 Therban AT 5005 VP Therban 5008 VP Therban AT 5065 VP Zetpol 0020EP Zetpol 0020

Lanxess Lanxess Zeon Zeon Zeon Lanxess Lanxess Lanxess Lanxess Lanxess Lanxess Lanxess Lanxess Zeon Zeon Zeon Zeon Zeon Zeon Lanxess Lanxess Lanxess Zeon Zeon

36 36 36 36 36 39 39 43 43 43 43 43 43 44 44 44 44 44 44 49 49 49 50 50

66 87 58 85 135 39 70 39 63 100 39 61 97 65 29 85 30 57 78 55 80 55 40 65

0.9 2 4 4 4 0.9 0.9 0.9 0.9 0.9 5.5 5.5 5.5 2 4 4 9 9 9 0.9 0.9 6 9 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 specic applications and end-products. These are summarised in Table 2.2.

Table 2.2 HNBR speciality grades available Grade Manufacturer Mole% ACN (nominal) Mooney viscosity ML(1+4) at 100 C (nominal) 95 Residual % unsaturation (approximate) Modication

Zeoforte ZSC 2295CX Zeoforte ZSC 2295L Zeoforte ZSC 2385 Therban XT VP KA 8889 Therban VP KA 8796

Zeon

36

Zinc methacrylate Zinc methacrylate Zinc methacrylate Carboxylated (XHNBR) Acrylate

Zeon

36

80

Zeon

36

70

15

Lanxess

33

77

3.5

Lanxess

34

22

5.5

Therban is a registered trademark of Lanxess Zetpol and Zeoforte are registered trademarks of Zeon Chemicals

Modication 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 classication system [1]. This is illustrated in Figure 2.1, along with a selection of other elastomers for comparison. Not only does the HNBR family ll a gap in the properties identied, 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
FKM VMQ AEM CR NR FVMQ ACM HNBR NBR

250 200 150 100 50 0

EPDM

200

150

100
Class by Oil Swell

50

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 exibility 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 uids, 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

Temperature resistance (C)

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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 uids, 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 20 10 0 10 20 30 40 50 60 35% ACN 25% ACN HNBR HNBR ACM AEM % Elongation Loss

% Elongation Loss, 504 h % Elongation Loss, 1008 h

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 15 10 5 0 5 10 15 20 25 30 35% ACN 25% ACN HNBR HNBR ACM AEM % Elongation Loss

% Elongation Loss, 504 h % Elongation Loss, 1008 h

Material

Figure 2.3 Comparison of resistance to automatic transmission uid (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), uorocarbons (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 abrasion 150 100 50 0 45% ACN HNBR NBR ECO Material FKM ACM

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 nal 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 specic gravity. This gives the relative cost of the compound required to ll 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 uorosilicones (FVMQ) have excellent upper temperature limits, but their poundvolume cost is heavily inuenced by their relatively high specic gravity. 19

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 lled by HNBR materials in perspective. HNBR combine toughness, abrasion resistance, uid resistance and good cost effectiveness at temperatures up to 150 C.

Table 2.3 Commercial comparison of oil-resistant elastomers

Polymer
NBR ACM AEM HNBR FVMQ FKM

SG
1.22 1.32 1.32 1.22 1.53 1.86

Cost of compound ($)

$1.00 $2.30 $2.40 $10.40 $23.00 $16.00

lbvol cost ($)

$1.22 $3.04 $3.17 $12.69 $35.19 $29.76

Operating temperature, upper limit (C)

100 150 150 150 200 250

Note: 75 Shore A, assumes carbon black ller, except for FVMQ

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

References
1. 2. 3. Rubber, American Society of Testing and Materials, Washington, DC, USA, 2006, 9, 2, D2000-06. A Comparison of Oil Resistant Elastomers in Engine Oil and ATF, Z7.3.16, Zeon Chemicals LP, Louisville, KY, USA, 1999, p.1. Zetpol Product Guide, Zeon Chemicals LP, Louisville, KY, USA, 1999.

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