RUBBER

Flexible material that can recover its shape after considerable

deformation.The best-known rubber is natural rubber, made from
the milky latex of the rubber tree (Hevea brasiliensis). Natural
rubber is still important industrially, but it now competes with
synthetic alternatives (e.g., neoprene, silicone) derived from
petroleum, natural gas, and other source materials. Rubber's
usefulness is based on the unique elasticity of its constituent
polymer molecules (built of thousands of isoprene monomers; see
isoprenoid), which are capable of returning to their original coiled
shape after being stretched to great extents; it is made more
durable by vulcanization with sulfur or another agent that
establishes chemical cross-links between the polymers. Fillers and
other additives allow tailoring of properties to the desired use (e.g.,
by foaming, shaping, and curing). More than half of all rubber goes
into making tires; the rest is used principally in belts, hoses,
gaskets, shoes, clothing, furniture, and toys.
Originally, a natural or tree rubber, which is a hydrocarbon
polymer of isoprene units. With the development of synthetic
rubbers having some rubbery characteristics but differing in
chemical structure as well as properties, a more general
designation was needed to cover both natural and synthetic
rubbers. The term elastomer, a contraction of the words elastic and
polymer, was introduced, and defined as a substance that can be
stretched at room temperature to at least twice its original length
and, after having been stretched and the stress removed, returns
with force to approximately its original length in a short time.
Three requirements must be met for rubbery properties to be
present in both natural and synthetic rubbers: long thread like
molecules, flexibility in the molecular chain to allow flexing and
coiling, and some mechanical or chemical bonds between
molecules.

Natural rubber and most synthetic rubbers are also commercially

available in the form of latex, a colloidal suspension of polymers in
an aqueous medium. Natural rubber comes from trees in this form;
many synthetic rubbers are polymerized in this form; some other
solid polymers can be dispersed in water. See also Polymer.

Latexes are the basis for a technology and production methods

completely different from the conventional methods used with
solid rubbers.

In the crude state, natural and synthetic rubbers possess certain

physical properties which must be modified to obtain useful end
products. The raw or unmodified forms are weak and adhesive.
They lose their elasticity with use, change markedly in physical
properties with temperature, and are degraded by air and sunlight.
Consequently, it is necessary to transform the crude rubbers by
compounding and vulcanization procedures into products which
can better fulfill a specific function.

Although natural rubber may be obtained from hundreds of

different plant species, the most important source is the rubber tree
(Hevea brasiliensis). Natural rubber is cis-1,4-polyisoprene,
containing approximately 5000 isoprene units in the average
polymer chain.

Styrene-butadiene rubber (SBR) is the most important synthetic

rubber and the most widely used rubber in the entire world.
Formerly designated GR-S, SBRs are obtained by the emulsion
polymerization of butadiene and styrene in varying ratios.
However, in the most commonly used type, the ratio of butadiene
to styrene is approximately 78:22. Unlike natural rubber, SBR does
not crystallize on stretching and thus has low tensile strength
unless reinforced. The major use for SBR is in tires and tire
products. Other uses include belting, hose, wire and cable coatings,
flooring, shoe products, sponge, insulation, and molded goods.

Butyl rubber is essentially a polyisobutylene except for the

presence of diolefin, usually isoprene, to provide the unsaturation
necessary for vulcanization. Butyl rubbers have excellent
resistance to oxygen, ozone, and weathering. In addition, these
rubbers exhibit good electrical properties and high impermeability
to gases. The high impermeability to gases results in use of butyl
as an inner liner in tubeless tires. Other widespread uses are for
wire and cable products, injection-molded and extruded products,
hose, gaskets, and sealants, and where good damping
characteristics are needed.

Ethylene-propylene polymers are produced by the

copolymerization of ethylene and propylene. These copolymers
exhibit outstanding resistance to heat, oxygen, ozone, and other
aging and degrading agents. Abrasion resistance in tire treads is
excellent. The mechanical properties of their vulcanizates are
generally approximately equivalent to those of SBR.

One of the first synthetic rubbers used commercially in the rubber

industry is neoprene, a polymer of chloroprene, 2-chlorobutadiene-
1,3. The neoprenes have exceptional resistance to weather, sun,
ozone, and abrasion. They are good in resilience, gas
impermeability, and resistance to heat, oil, and flame. They are
fairly good in low temperature and electrical properties. This
versatility makes them useful in many applications requiring oil,
weather, abrasion, or electrical resistance or combinations of these
properties, such as wire and cable, hose, belts, molded and
extruded goods, soles and heels, and adhesives.
Nitrile-type rubbers are copolymers of acrylonitrile and a diene,
usually butadiene. The nitrile rubbers can be blended with natural
rubber, polysulfide rubbers, and various resins to provide
characteristics such as increased tensile strength, better solvent
resistance, and improved weathering resistance.

Fluoroelastomers are basically copolymers of vinylidene fluoride

and hexafluoropropylene. Because of their fluorine content, they
are the most chemically resistant of the elastomers and also have
good properties under extremes of temperature conditions. They
are useful in the aircraft, automotive, and industrial areas.

Polyurethane elastomers are of interest because of their versatility

and variety of properties and uses. They can be used as liquids or
solids in a number of manufacturing methods. The largest use has
been for making foam for upholstery and bedding. See also
Polyurethane resins.

Polysulfide rubbers have a large amount of surlfur in the main

polymer chain and are therefore very chemically resistant,
particularly to oils and solvents. They are used in such applications
as putties, caulks, and hose for paint spray, gasoline, and fuel.
Polyacrylate rubbers are useful because of their resistance to oils at
high temperatures, including sulfur-bearing extreme-pressure
lubricants. See also Polysulfide resins.

Proper choice of catalyst and order of procedure in polymerization

have led to development of thermoplastic elastomers. The leading
commercial types are styrene block copolymers having a structure
which consists of polystyrene segments or blocks connected by
rubbery polymers such as polybutadiene, polyisoprene, or
ethylene-butylene polymer. Thermoplastic elastomers are very
useful in providing a fast and economical method of producing a
variety of products. One of the disadvantages for many
applications is the low softening point of the thermoplastic
elastomers.
Although rubber-yielding plants are native to Africa and Asia as
well as to the Americas, the first mention of rubber in the West
was made by Pietro Martire d'Anghiera, the Italian representative
to the court of Spain (De Rebus Oceanicis et Novo Orbe, 1516). In
the early seventeenth century, Juan de Torquemada (Monarquía
Indiana, 1615) described how the Mexican Indians used a milk-
like fluid drawn from a tree for religious rites and sport, and for
making crude footwear, waterproof bottles, and garments.
Although a little rubber was used in Europe in the eighteenth
century to make erasers—it derived its name "rubber" for its
property of rubbing out (erasing) pencil marks—along with elastic
thread, surgical tubes, and experimental balloons, the rubber
manufacturing industry was not established until the nineteenth
century.

The first record of rubber in the United States is a patent for gum
elastic varnish for footwear issued to Jacob F. Hummel in 1813.
This was followed by a patent for a grinding and mixing machine
granted to John J. Howe in 1820. Prompting these first steps was
the profitable trade in crude rubber shoes imported into Boston and
New York City from Brazil. By 1833, America's pioneering rubber
factory was established at Roxbury, Massachusetts. Other rubber
shoe and clothing factories soon appeared elsewhere in
Massachusetts, as well as in New Jersey, Rhode Island,
Connecticut, New York, and Pennsylvania. By 1840, the infant
industry had experienced a speculative boom (about $2 million in
stock was issued) and a disastrous collapse. The primary cause for
the loss of confidence was that rubber products had not proven
reliable—they softened in the heat and stiffened in the cold—but
the downturn in general business conditions that began in the fall
of 1837 only added to the industry's distress. So great were the
industry's troubles that in 1843 the Roxbury Rubber Company sold
the "monster" spreading machine (built by Edwin Marcus Chaffee
in 1837) for $525; it had been purchased for $30,000.
Although experiments to cure rubber have been attributed to the
eighteenth-century Swedish physician and pharmacist Petter-Jonas
Bergius, it remained for Charles Goodyear to solve the basic
technical problem confronting early rubber manufacturers. He did
so in 1839, at Woburn, Massachusetts, when he developed the
"vulcanization process," which gives rubber durability and
consistent qualities across a broad range of temperatures by
treating it with sulfur and white lead at a high temperature. His
samples of "cured" rubber, with which he tried to raise funds in
England, prompted the English inventor Thomas Hancock to make
his own "discovery" of vulcanization. The "elastic metal" provided
by these two inventors would soon prove indispensable to the
Western world.

Nowhere was this more marked than in the development of the

Automobile Industry. Yet long before the automobile appeared at
the end of the nineteenth century, America's consumption of raw
rubber had grown twenty fold—from 1,120 short tons in 1850 to
23,000 tons in 1900 (two-fifths of the world total of 59,000 short
tons). Wherever elastic, shock-absorbing, water-resistant,
insulating, and air-and steam-tight properties were required,
vulcanized rubber was used. Most of the raw rubber came from
Brazil, with Africa the second-most important source. The problem
was not to find rubber but to find the labor to collect it in the
almost inaccessible forests and ship it to the factories of the
Northern Hemisphere. Until the systematic development of
plantation rubber in Southeast Asia in the twentieth century made
collection and transportation a comparatively easy task, the
growing demand for crude rubber could only be met at increased
cost. In 1830, Para rubber was 20 cents a pound; in 1900 the
annual average wholesale price had risen to about a dollar.

Between 1849 and 1900, the industry's output of manufactured

goods—chiefly footwear, mechanicals (for use with machinery),
proofed and elastic goods, surgical goods, bicycle tires, and toys—
increased in value from $3 million to $53 million. In the same
years, the industry's workforce grew from 2,500 to 22,000.
Because of the economies of scale and the absence of product
differentiation, the market for rubber products was fiercely
competitive—hence the tendency for the early rubber
manufacturers to band together. Before the Civil War, marketing
arrangements were already in existence to control the sale of
footwear and other products. By the eve of World War I,
production had come to be dominated by the "Big Four": Goodyear
Tire and Rubber Company, United States Rubber Company, B. F.
Goodrich Company, and Firestone Tire and Rubber Company.
Partly to be close to the carriage-making industry—at the time the
rubber industry's major consumer—the center of rubber
manufacture had shifted from the towns of New England to Akron,
Ohio. The industry's first branch factories were established in
Western Europe in the 1850s.

The most dramatic phase of the industry's growth followed the

introduction of the internal combustion engine, cheap petroleum,
and the widespread use of the pneumatic tire in the early 1900s.
Between 1900 and 1920, consumption of raw rubber increased
tenfold—to 231,000 short tons. Even the world depression of the
early 1930s only temporarily halted the industry's rapid expansion.
By 1940, the United States was consuming 726,000 tons of a world
total of 1,243,000 tons of crude rubber. Between 1900 (when the
first four tons of Southeast Asia plantation rubber had reached the
market) and 1910, the annual average wholesale price per pound of
crude rubber doubled from $1 to $2. By 1915, more than twice as
much rubber was coming from the plantations of Southeast Asia
than from America and Africa combined, and prices had fallen to a
quarter of their 1910 level; on 2 June 1932, the price was just three
cents a pound.

Partly because of the great fluctuations in the price of crude rubber,

and partly because the plantation industry of the Far East was
largely in British hands, the industry began a search for rubber
substitutes in the 1920s. In the next decade, manufacturers
produced a few hundred tons a year of a special type of synthetic
rubber. As Japan seized the rubber lands of Southeast Asia during
World War II, U.S. production of synthetic rubber increased a
hundredfold—from 9,000 short tons in 1941 to 919,000 tons in
1945, at which point synthetic rubber met four-fifths of America's
needs. By 1973, of a world output of 6.3 million metric tons, the
United States produced about 40 percent, almost three times more
than the next greatest producer, Japan. That year, the United States
had consumed only 696,000 metric tons of a world output of
approximately 3.5 million tons of natural rubber.

Chemists succeeded in not only synthesizing rubber by making a

wide range of elastomers and plastomers available, they changed
the character of the industry until it was no longer possible to
distinguish between rubber and rubber substitutes. The price of the
synthetic compared favorably with that of the natural product, and
for some uses synthetic rubber was preferable.

The rise of other industrialized nations in the twentieth century

reduced America's domination of the industry; even so, its output
in 1970 (including plastics) was worth about $15 billion and the
industry employed more than half a million workers. In 1987, the
American rubber industry shipped $24.9 billion in goods, of which
automobile tires accounted for $10.5 billion of that amount.
According to the Environmental Protection Agency, more than
230,000 people were employed in the rubber industry in the United
States in 1987. Although rubber was used in thousands of ways,
automobile tires—with which the major technical developments in
manufacture have been associated—continued to account for more
than one-half of the industry's consumption of raw materials. The
overwhelming size of the major rubber corporations (a fifth giant
was added to the Big Four in 1915 when the General Tire and
Rubber Corporation was formed at Akron) did not lessen the
industry's competitive nature. After World War II, the tendency
toward global expansion increased, and, in the late twentieth
century, the major rubber manufacturers were worldwide in scope
and operation.

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
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 (Parthenium argentatum), 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.

Synthetic rubber

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.