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rubber, any solid substance that upon vulcanization becomes elastic; the term includes natural rubber (caoutchouc) and synthetic rubber. The term elastomer is sometimes used to designate synthetic rubber only and is sometimes extended to include caoutchouc as well.
Chemistry and Properties
All rubberlike materials are polymers, which are high molecular weight compounds consisting of long chains of one or more types of molecules, such as monomers. Vulcanization (or curing) produces chemical links between the loosely coiled polymeric chains; elasticity occurs because the chains can be stretched and the crosslinks cause them to spring back when the stress is released. Natural rubber is a polyterpene, i.e., it consists of isoprene molecules linked into loosely twisted chains. The monomer units along the backbone of the carbon chains are in a cis arrangement (see isomer) and it is this spatial configuration that gives rubber its highly elastic character. In gutta-percha, which is another natural polyterpene, the isoprene molecules are bonded in a trans configuration leading to a crystalline solid at room temperature. Unvulcanized rubber is soluble in a number of hydrocarbons, including benzene, toluene, gasoline, and lubricating oils.
Rubber is water repellent and resistant to alkalies and weak acids. Rubber's elasticity, toughness, impermeability, adhesiveness, and electrical resistance make it useful as an adhesive, a coating composition, a fiber, a molding compound, and an electrical insulator. In general, synthetic rubber has the following advantages over natural rubber: better aging and weathering, more resistance to oil, solvents, oxygen, ozone, and certain chemicals, and resilience over a wider temperature range. The advantages of natural rubber are less buildup of heat from flexing and greater resistance to tearing when hot.
Natural rubber is obtained from the milky secretion (latex) of various plants, but the only important commercial source of natural rubber (sometimes called Pará rubber) is the tree Hevea brasiliensis. The only other plant under cultivation as a commercial rubber source is guayule, a shrub native to the arid regions of Mexico and the SW United States. To soften the rubber so that compounding ingredients can be added, the long polymer chains must be partially broken by mastication, mechanical shearing forces applied by passing the rubber between rollers or rotating blades. Thus, for most purposes, the rubber is ground, dissolved in a suitable solvent, and compounded with other ingredients, e.g., fillers and pigments such as carbon black for strength and whiting for stiffening; antioxidants; plasticizers, usually in the form of oils, waxes, or tars; accelerators; and vulcanizing agents. The compounded rubber is sheeted, extruded in special shapes, applied as coating or molded, then vulcanized. Most Pará rubber is exported as crude rubber and prepared for market by rolling slabs of latex coagulated with acid into thin sheets of crepe rubber or into heavier, firmly pressed sheets that are usually ribbed and smoked.
An increasing quantity of latex, treated with alkali to prevent coagulation, is shipped for processing in manufacturing centers. Much of it is used to make foam rubber by beating air into it before pouring it into a vulcanizing mold. Other products are made by dipping a mold into latex (e.g., rubber gloves) or by casting latex. Sponge rubber is prepared by adding to ordinary rubber a powder that forms a gas during vulcanization. Most of the rubber imported into the United States is used in tires and tire products; other items that account for large quantities are belting, hose, tubing, insulators, valves, gaskets, and footwear. Uncoagulated latex, compounded with colloidal emulsions and dispersions, is extruded as thread, coated on other materials, or beaten to a foam and used as sponge rubber. Used and waste rubber may be reclaimed by grinding followed by devulcanization with steam and chemicals, refining, and remanufacture.
The more than one dozen major classes of synthetic rubber are made of raw material derived from petroleum, coal, oil, natural gas, and acetylene. Many of them are copolymers, i.e., polymers consisting of more than one monomer. By changing the composition it is possible to achieve specific properties desired for special applications. The earliest synthetic rubbers were the styrene-butadiene copolymers, Buna S and SBR, whose properties are closest to those of natural rubber. SBR is the most commonly used elastomer because of its low cost and good properties; it is used mainly for tires. Other general purpose elastomers are cis-polybutadiene and cis-polyisoprene, whose properties are also close to that of natural rubber.
Among the specialty elastomers are copolymers of acrylonitrile and butadiene that were originally called Buna N and are now known as nitrile elastomers or NBR rubbers. They have excellent oil resistance and are widely used for flexible couplings, hoses, and washing machine parts. Butyl rubbers are copolymers of isobutylene and 1.3% isoprene; they are valuable because of their good resistance to abrasion, low gas permeability, and high dielectric strength. Neoprene (polychloroprene) is particularly useful at elevated temperatures and is used for heavy-duty applications. Ethylene-propylene rubbers (RPDM) with their high resistance to weathering and sunlight are used for automobile parts, hose, electrical insulation, and footwear. Urethane elastomers are called spandex and they consist of urethane blocks and polyether or polyester blocks; the urethane blocks provide strength and heat resistance, the polyester and polyether blocks provide elasticity; they are the most versatile elastomer family because of their hardness, strength, oil resistance, and aging characteristics. They have replaced rubber in elasticized materials. Other uses range from airplane wheels to seat cushions. Other synthetics are highly oil-resistant, but their high cost limits their use. Silicone rubbers are organic derivatives of inorganic polymers, e.g., the polymer of dimethysilanediol. Very stable and flexible over a wide temperature range, they are used in wire and cable insulation.
Pre-Columbian peoples of South and Central America used rubber for balls, containers, and shoes and for waterproofing fabrics. Mentioned by Spanish and Portuguese writers in the 16th cent., rubber did not attract the interest of Europeans until reports about it were made (1736–51) to the French Academy of Sciences by Charles de la Condamine and François Fresneau. Pioneer research in finding rubber solvents and in waterproofing fabrics was done before 1800, but rubber was used only for elastic bands and erasers, and these were made by cutting up pieces imported from Brazil. Joseph Priestley is credited with the discovery c.1770 of its use as an eraser, thus the name rubber.
The first rubber factory in the world was established near Paris in 1803, the first in England by Thomas Hancock in 1820. Hancock devised the forerunner of the masticator (the rollers through which the rubber is passed to partially break the polymer chains), and in 1835 Edwin Chaffee, an American, patented a mixing mill and a calender (a press for rolling the rubber into sheets).
In 1823, Charles Macintosh found a practical process for waterproofing fabrics, and in 1839 Charles Goodyear discovered vulcanization, which revolutionized the rubber industry. In the latter half of the 19th cent. the demand for rubber insulation by the electrical industry and the invention of the pneumatic tire extended the demand for rubber. In the 19th cent. wild rubber was harvested in South and Central America and in Africa; most of it came from the Pará rubber tree of the Amazon basin.
Despite Brazil's legal restrictions, seeds of the tree were smuggled to England in 1876. The resultant seedlings were sent to Ceylon (Sri Lanka) and later to many tropical regions, especially the Malay area and Java and Sumatra, beginning the enormous East Asian rubber industry. Here the plantations were so carefully cultivated and managed that the relative importance of Amazon rubber diminished. American rubber companies, as a step toward diminishing foreign control of the supply, enlarged their plantation holdings in Liberia and in South and Central America.
During World War I, Germany made a synthetic rubber, but it was too expensive for peacetime use. In 1927 a less costly variety was invented, and in 1931 neoprene was made, both in the United States. German scientists developed Buna rubber just prior to World War II. When importation of natural rubber from the East Indies was cut off during World War II, the United States began large-scale manufacture of synthetic rubber, concentrating on Buna S. Today synthetic rubber accounts for about 60% of the world's rubber production.
See P. W. Allen, Natural Rubber and the Synthetics (1972); M. Morton, Rubber Technology (3d ed. 1987).