Vulcanization

In the process of vulcanization, the added sulfur allows some C-H bonds to be broken and replaced by C-S bonds. The process of vulcanization cross-links the chains or polyisoprene to each other. The cross-linked molecules create a three-dimensional network of rubber. Each cross-link is a chain of about eight sulfur atoms between two long chains of polyisoprene.

Vulcanized rubber is about 10 times stronger than natural rubber and is also about 10 times more rigid. However, it is still very elastic, which means that is can be stretched reversibly. Polymers that are elastic are sometimes called elastomers. The optimum amount of sulfur to be added to the rubber is about 10% by weight. Adding an excess of sulfur produces a very brittle and inelastic substance called ebonite. Man-made or synthetic rubber can also be vulcanized, and the process is similar.

Figure 1 shows what happens to rubber when the long chains of polyisoprene are cross-linked. In part a, the macromolecules are bent and randomly arranged. In part b, the chains are cross-linked but still randomly arranged. The molecules become aligned when the rubber is stretched. If the individual chains were not crosslinked, each chain could slide freely past each other.