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VULCANIZATION - A PRONE INT TO THE COMPLEX PROCESS

Vulcanization, also known as cross-linking or curing, is the process where the rubber chains are joined together, increasing strength and elasticity, and reducing the tendency of the rubber to creep when extended. On a molecular level, elastomers exist as single polymer chains. A measure of strength and elasticity is present, through entanglement of the chains, but this strength and elasticity is not high. Vulcanization introduces crosslinks to tie the separate polymer chains together, and this can greatly enhance strength and elasticity. Table 1 shows typical results for an unfilled natural rubber (NR) compound, before and after vulcanization. As can be seen both the tensile strength and tensile modulus are increased significantly, whilst the elongation is only slightly reduced.

Discovery of accelerators
Vulcanization is named after Vulcan, the Roman God of Fire, as the original vulcanization processes involved mixing the rubber with sulphur and heating for a long time. Although this did introduce crosslinks into the rubber, it also degraded it to some extent, so the finished properties were not very good. A big step forward in vulcanization was the discovery of rubber accelerators in the early 20th Century, initially based on compounds derived from aniline. These accelerators greatly increased the speed with which sulphur could be combined with rubbers, opening up not just the rubber industry to greater development, but also starting the rubber accelerator industry which now can provide hundreds of compounds, some specifically tailored to particular applications.

A complex process
So how does sulphur vulcanization of a latex elastomer occur? The picture is complex, and not yet fully understood. Natural rubber has been the most studied, and here vulcanization is thought to occur as follows. First an active sulphurating agent is formed, through the reaction of the S8 sulphur molecule with the accelerator. This reaction is facilitated by the presence of ammonia or other amines. The active sulphurating agent can then react with a rubber molecule to insert a short sulphur chain into the polymer chain, forming what is called a rubber-bound intermediate. This rubber-bound intermediate then can react with other rubber molecules to form the initial cross-linked network. At the same time, the residues from the accelerator can react with zinc oxide to regenerate the accelerator, which can then continue the reactions. We are not at the end of the process yet, however. This initial crosslinked network continues to react in various ways. The sulphur chains can break and reform, leading to crosslink shortening, lengthening or additional crosslinks being formed. The main polymer chain can be broken or modified, there can be sulphur-sulphur bond interchange, cyclization and many other reactions. These will all be influenced by the vulcanization conditions, temperature, vulcanization components, and their concentrations. The crosslinked network thus changes considerably with time, and this can be seen by the way the properties of the dipped products change over the first few days and weeks. The network is changed again by aging, so as you can see the picture is very complicated. An article such as this cannot do justice to the complexity of the sulphur vulcanization process, but there are many excellent descriptions in the scientific literature.

Vulcanization conditions in latex


I am sometimes asked about the use of the so-called efficient vulcanization (EV) and semi-efficient vulcanization (semi-EV) conditions in latex. These systems are characterized by having a high accelerator concentration and a low sulphur concentration. In dry rubber, these conditions lead to a network having a

high proportion of crosslinks containing only one (mono-sulphidic) or two (di-sulphidic) sulphur atoms. Networks of this type have a much better aging resistance than those where the crosslinks contain a greater number of sulphur atoms (polysulphidic crosslinks). However, the conditions required to create this type of network require high vulcanizing temperature, whereas latex articles are usually vulcanized at much lower temperatures latex article tend to be thin, and have a high surface to volume ration, and are thus more prone to oxidation at high temperatures. As a consequence dipped latex articles will have a network structure which is predominantly polysulphidic. This type of network will give good physical properties, but the aging resistance will be less than for an EV or semi EV system. Of course, there are other differences between the vulcanization of latex systems and dry rubber, not least the fact that the vulcanizing ingredients (sulphur, accelerator, zinc oxide) have to migrate from their solid phase, through the aqueous phase to the rubber phase. In addition the aqueous phase contains ammonia and other materials such as proteins which can aid the vulcanization.

Other ways of cross-linking


Whilst sulphur vulcanization is the major mechanism by which elastomers are cross-linked, it is not the only one. Elastomers which contain carboxylic groups, such as carboxylated nitrile rubber (XNBR) latex, can also be cross-linked through the carboxyl group by metal oxides or alkalis. This type of mechanism gives ionic cross links, which can be very strong, but can also be broken and reformed. Thus articles cross-linked in this way will have high strength and modulus, but can also be prone to creep. Polychloroprene rubber (CR, or Neoprene) can also be cross-linked with metal oxides, this time reacting through one of the chlorine atoms on the polymer chain. Of course, both CR and XNBR can also be cross-linked with a sulphur/accelerator system, and frequently a mixed vulcanization system will be used with these elastomers to fine tune the physical properties. Cross-linking of some elastomers can also be carried out by peroxides or radiation which give carbon-carbon crosslinks. However, at present these methods are of little significance in the industry. NR latex (and some of the other latices) can be prevulcanized (the crosslinks are put in before the article is made) or postvulcanized (the crosslinks are put in after the article is made), and owing to the ease with which prevulcanization can take place many latices will dipped with at least some degree of prevulcanization. Unless the degree of prevulcanization is taken to extreme levels, the physical properties of goods made from prevulcanized latices will be usually be entirely adequate, and frequently close to those dipped from a latex which is subsequently postvulcanized.

Measuring methods
The extent of vulcanization or prevulcanization in a latex system can be measured in several ways. For NR latex, probably the most common is the Chloroform test, where a spoonful of the latex is mixed with a small amount of Chloroform. The latex coagulates, and the appearance and properties of the coagulum are a guide to the extent of cross-linking in the rubber. However this method, although quick and easy, is subjective and not very accurate. A better method is a swelling test, where an air-dried film of the elastomer is swollen in a suitable solvent. The more cross-links there are in the sample, the less it will swell. The extent of swelling can be measured by changes in dimensions or weight. This method can be used on finished products as well as latices, and can be used with elastomers other than NR, by choosing an appropriate solvent or solvent mixture. However, a swelling method takes longer than the Chloroform test, owing to the time needed to air-dry and swell the film. Whilst an accurate and sensitive test at low levels of cross-link density, it is less accurate at higher levels of vulcanization. A third method is to measure the tensile modulus of the air-dried film or product. This can be correlated

closely with cross-link density. Finally the relaxed modulus where the stress of a dried sample or product is measured after being held at a constant strain for a controlled time can also be used to measure the extent of vulcanization. A particular version of this test the prevulcanizate relaxed modulus or PRM test has been advocated for NR latices (1).

Effects of vulcanization
The extent of vulcanization can have various effects on a rubber product. Generally, increasing the crosslinking will increase the modulus and decrease the elongation at break. Both tensile strength and tear strength pass through a maximum as the cross-linking is increased. Typically, the cross-link density which gives the maximum property is different one can either have the maximum tensile strength, or the maximum tear strength, usually not both. As always a satisfactory compromise has to be found. It is usually the amount of sulphur in the formulation which controls the extent of cross-linking. As was pointed out earlier, the accelerator is regenerated by reaction with zinc oxide, so the vulcanization is not usually controlled by exhaustion of the accelerator.

Accelerators commonly used


The accelerators commonly seen in latex chemistry are usually dithiocarbamate salts, either as the zinc salts or the soluble sodium salt, although the ammonium salt, also soluble, has been used occasionally. The most commonly used dithiocarbamatesare either the dibutyl or diethyl, although other organic groups can be used for specific applications, such as the di-isononyl group or the di-benzyl group for low nitrosamine applications. Zinc 2-mercaptobenzthiazolate (or the soluble sodium salt) is also sometimes used, as it has a synergistic action with dithiocarbamates. However, the 2-mercaptobenzthiazolates have a very bitter taste, and would be unsuitable for any products which could go into the mouth, such as baby bottle teats or balloons. CR is often vulcanized using a thiocarbanalide or guanidine accelerators, and the very rapid xanthates have also been used in latices on occasion. There are many rubber accelerators available to the industry, and the manufacturers will have extensive databases to help determine the best one for the purpose. However, it is worth noting that most rubber accelerators are toxic to some degree, and any potential health and safety concerns must be considered when using them. I have only skimmed the surface of a very complex topic in this article, but as I said earlier, there is a wealth of information in the technical literature for those who want to know more. Reference. 1. Gorton, A.D.T. and Pendle T.D. (1976) NR Technology, 7, 77.

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