Certain additives confer resistance to heat, sunlight, oxygen, and ozone. Amines, particularly paraphenylene diamines, are powerful retarders of oxidation, or antioxidants. Added to rubber compounds in small amounts (1–2 percent), they appear to disrupt the free-radical oxidation reactions that lead either to molecular rupture and softening or to increased interlinking and hardening as rubber ages. Hindered phenols, another antioxidant class, are less powerful than amines but have less tendency to stain light-coloured rubber compounds. Small amounts of certain metals, notably copper, manganese, and iron, act as powerful catalysts of oxidation; sequestering agents are therefore used to block the action of these elements if their presence is unavoidable.
Atmospheric ozone reacts readily with elastomers containing C=C double bonds, leading to breakage of molecules lying in the surface. As a result, small, deep fissures, termed ozone cracks, are formed if the rubber is stretched slightly (by more than about 10 percent). Cracks one millimetre long appear in unprotected rubber after only a few weeks of exposure to a typical outdoor concentration of ozone, about 5 parts per 100 million. However, certain diamines (e.g., alkyl-aryl paraphenylene diamines) prevent cracking, probably by competing with the C=C bonds in rubber for reaction with ozone. These antiozonants “bloom” to the surface and react there, protecting the rubber. A few percent of an antiozonant is therefore commonly included in the mix formulation of rubber compounds based on unsaturated elastomers. An alternative method of protection, often employed simultaneously, is to include a few percent of a microcrystalline paraffin wax in the mix formulation. Because it is incompatible with the elastomer, the wax blooms to the surface and forms a protective skin.
Plasticizers and processing aids
Liquids are added to elastomer mixes in order to soften and plasticize the compound, either in processing or later in use. For example, elastomers with high glass transition temperatures (and correspondingly slow molecular motions) can be improved by adding low-temperature plasticizers—i.e., compatible liquids that act as internal lubricants. Plasticizers must have low vapour pressure and a high boiling point in order to be retained within the compound over long periods of service. Examples are aliphatic esters and phthalates. Phosphate plasticizers also confer a measure of flame resistance. Other liquids are added to rubber compounds as processing aids in order to make mixing and extrusion easier. Typically, 5 percent of a petroleum oil is used.
Processing
Rubber processing consists of four basic steps: (1) mastication, when the elastomer is sheared and the molecules are broken down to give easier flow, (2) mixing, usually carried out immediately after mastication, when additives are incorporated, (3) shaping of the viscous mass, for example, by extrusion or molding, and (4) curing, when the polymer molecules become interlinked and the shape is fixed.
Mastication
Mastication and softening are usually carried out in batches. The operation is done either in large enclosed mixing machines or on rubber mills. The preeminent example of an enclosed machine is the Banbury (registered trademark) mixer, consisting of heavy steel counterrotating paddles in an hourglass-shaped chamber, holding up to one-half ton of rubber. Rubber mills have two large horizontally opposed, closely spaced steel cylinders, up to 3 metres (10 feet) long, that are rotated slowly in opposite directions and at somewhat different speeds. Rubber is sheared and softened in the gap between the paddles and wall of the Banbury mixer and in the gap between the two cylinders in the roll mill.
Mixing
Mixing is carried out on machines similar to those used in mastication, sometimes immediately after softening. Reactive materials, fillers, oils, and protective chemicals of various kinds, as described above, are incorporated into the base elastomer by a combined shearing and mixing action. An enclosed Banbury-type mixer can produce up to one-half ton of mixed compound in a few minutes. The compound is then sheeted out, coated with a release soap to prevent sticking, and stored until use on steel pallets that can hold up to one ton of rubber.
Shaping
Shaping of the mixture into the desired form takes place in several ways. Extruders are used to produce long continuous products such as tubing, tire treads, and wire coverings. They are also used to produce various profiles that can later be cut to length. Multiroll calenders are used to make wide sheeting. In transfer and injection molds, the rubber mix is forced through channels into a mold chamber of the required shape, where it is cured under pressure. Tires are made of several components: bead wire, sidewall compound, inner liner, cord plies, belt package, and tread; these are brought together and assembled as a complete tire before being transferred to the curing press.
Curing
Curing is carried out in pressurized steel molds, which are heated by steam or electricity to temperatures at which the interlinking reaction takes place. Typical cure conditions are several minutes at a temperature of 160 °C (320 °F). Because heat penetrates rubber slowly, thick articles must be allowed longer curing times, up to several hours, at lower temperatures. Pressures of 1 megapascal (145 pounds per square inch) or more are normally imposed in order to maintain the desired shape and to force trapped air to dissolve in the compound. Other methods of curing the rubber mix after it has been shaped include steam heating in autoclaves, microwave irradiation, and passage through a heated bath of molten metal salts or a fluidized bed. In these cases curing is carried out at near-atmospheric pressure.
