Process
Vulcanization is generally irreversible, similar to other thermosets and in contrast to thermoplastic processes (the melt-freeze process) that characterize the behavior of most modern polymers. The cross-linking is usually done with sulfur, but other technologies are known, including peroxide-based systems.
The main polymers subjected to vulcanization are polyisoprene (natural rubber) and styrene-butadiene rubber (SBR), which are used for most passenger tires. The "cure package" is adjusted specifically for the substrate and the application. The reactive sites—"cure sites"—are allylic hydrogen atoms. These C-H bonds are adjacent to carbon-carbon double bonds. During vulcanization, some of these C-H bonds are replaced by chains of sulfur atoms that link with a cure site of another polymer chain. These bridges contain between one and eight atoms. The number of sulfur atoms in the crosslink strongly influences the physical properties of the final rubber article. Short crosslinks give the rubber better heat resistance. Crosslinks with higher number of sulfur atoms give the rubber good dynamic properties but with lesser heat resistance. Dynamic properties are important for flexing movements of the rubber article, e.g., the movement of a side-wall of a running tire. Without good flexing properties these movements rapidly form cracks and, ultimately, make the rubber article fail.
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