An Introduction to Rubber Technology 6.3.3 Effects of low temperature - glass transition An elastomer is envisioned as a coiled polymer chain. Applied deformation results in movement of the molecular chain, such as stretching. This is possible due to open spaces within the coil. As the temperature is lowered, this open space (free volume) becomes smaller, restricting chain mobility. In our “macro” world this reveals itself as a stiffening of the elastomer. Eventually a temperature is reached at which there is insutficient free volume to allow any mobility and a significant (thousandfold) increase in stiffness occurs. With continued cooling, a temperature is eventually reached where if some rubbers are hit with a hammer, ir ean shatter like glass. This state is the glass transition temperature or the glass transition point, although it is more a region than a point. The stiffening isa purely physical phenomenon and is totally reversible. The glass transition temperature (Tg), will depend primarily on the raw gum elastomer, although there is the possibility of modifying it with plasticizers. Tg can be explained by considering chemical entities attached to the elastomer’s main backbone. Thermal energy allows them to rotate around this main chain. If the rubber is cooled, then as the Tg is reached, rotation stops. If these chemical monomer groups ate large (bulky), and if there are many of them, the Tg will be reached sooner, ie., at a higher temperature. For nitrile rubber, the ACN group is somewhat large. The number of ACN monomer groups polymerized in the main chain can also vary, depending on the grade of NBR rubber purchased. A low ACN nitrile (a low percentage of acrylonitrile groups) therefore has fewer bulky groups, which permits its Tg to be lower. Thus a nitrile with a 25% ACN content, will have a Ty around -48 °C, compared to a high ACN content of 45% with a Te about -14 °C. The use of dioctyl sebacate, and similar plasticizers, can lower the Tg of NR, CR and NBR. Speed of deformation (strain rate in dynamic deformation) of the rubber vulcanizate also has an effect on Tg (see section 7.7). 6.3.4 Effects of low temperature - crystallization Certain elastomers undergo a less dramatic stiffening at low temperatures, for reasons other than glass transition. The effect occurs at warmer temperatures than Tg, and is also fully reversible; it might be equivalent to a 20 point increase on the IRHD scale. As the temperature is lowered, the polymer chain takes on a more ordered orientation, and a phenomenon called crystallization occurs. Crystallization requires a regular structure, and the best known elastomers which demonstrate this phenomenon are CR and NR. Crystallization may take days or months to reach maximum stiffness. The rate at which 112Chemistry crystallization occurs in vulcanizates is maximal at -25 °C for NR and at around -10 °C. for CR. Addition of plasticizers may increase the crystallization rate. The level of sulfur in an NR formulation significantly alters the crystallization rate of the vulcanizate. A sulfur level of 2.5 phr in the compound will substantially reduce the rate compared to a level of 0.5 phr. The grade of raw gum elastomer used in CR can also affect the crystallization rate. The stiffening effect may not be too much of a concern in some applications, since dynamic movement of the vulcanizate quickly ‘dissolves’ the crystalline regions removing the problem. Effects of low temperatures on NR are discussed in MRPRA literature [1]. 6.3.5 Stretching - strain induced crystallization The term crystallization is also used to describe the behavior of CR and NR when a vulcanizate is stretched at room temperature. Upon stretching, an ordered alignment ‘occurs in the polymer chain and crystalline regions form, Here it occurs extremely rapidly and is called strain induced crystallization. The crystalline regions ‘dissolve’ just as rapidly ‘when the strain (stretching) is removed. The cured gum elastomer becomes very strong, when stretched, as shown by a high tensile strength. Most elastomers do not demonstrate strain induced crystallization and are mechanically weak as a vulcanized gum. This gives NNR and CR an advantage where soft vulcanizates are needed in certain engineering applications. 6.3.6 Aging Like the human body, rubber is subject to the ravages of aging and some of the reasons might be similar. Aging can be caused through attack by oxygen, ozone, and constant flexing. Surprisingly, ot maybe not, the means of protection from aging for both people and rubber sometimes coincide. Antioxidants in vegetables and vitamin supplements provide resistance to free radicals, while antioxidants and antiozonants provided by the industrial chemise protect rubber. The double bonds, so important for vulcanization, have an ‘achilles heel’. They can be the site for attack by ozone, even in concentrations as low as 10 parts per hundred million. If the cured rubber is kept stretched, even slightly, the rate of ozone attack dramatically increases. Cracks appear perpendicular to the stretched direction, with the potential to cause destructive tearing, which could be catastrophic in a thinner product. ‘Oxygen can cause the chains to break, softening the rubber, or in many cases providing sites for further cross-linking, thus making the vulcanizate hard and brittle. NR, as well 113An Introduction to Rubber Technology as the other unsaturated elastomers, are prone to damage by oxygen and ozone. EPDM. however has no unsaturation in its main chain and is far more resistant. Ultraviolet light, as well as copper and manganese compounds soluble in rubber, can all accelerate oxygen attack (oxidation). Asa rule, heat tends to increase chemical reactions, which means, all of the above aging processes will tend to be much faster as the temperature rises. Carbon black is an excellent UV absorber and will give good protection from the effects of UV light. If the double bonds are chemically removed from the rubber, it becomes less vulnerable to heat aging and ‘weathering’. Thus if the double bonds in nitrile are mostly or totally used up, by adding hydrogen atoms (hydrogenation), during the manufacture of the raw gum elastomer, it still retains its oil resistance and in addition, like EPDM, gains heat aging, oxygen and o7one resistance. Such a rubber is highly saturated nitrile (HSN, HNBR), described in Chapter 2. References 1. Rubber Products - Effects of Low Temperatures, Natural Rubber Technical Information Sheet No. D29, The Malaysian Rubber Research and Development Board, Brickendonbury, Hertford, SG13 8NL, UK, 1977. ‘Suggested Further Reading J. A. Brydson, Rubber Chemistry, Chapman & Hall, London, 1979. E, Files, Rubber & Plastics News, 1991, 20, 24, 39. H. Kuan, Rubber World, 1985, 192, 5, 20. L, R. Treolar, The Physics of Rubber Elasticity, 3rd Edition, Clarendon Press, Oxford, UK, 1975, Rubber & Plastics News, 1984, 14, 2, 18. 14