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Natural rubber

Natural rubber, also called India rubber or caoutchouc, as initially produced,

consists of polymers of the organic compound isoprene, with minor impurities of other
organic compounds, plus water. Thailand and Indonesia are two of the leading rubber
producers. Forms of polyisoprene that are used as natural rubbers are classified as

Currently, rubber is harvested mainly in the form of the latex from the rubber tree or
others. The latex is a sticky, milky colloid drawn off by making incisions in the bark and
collecting the fluid in vessels in a process called "tapping". The latex then is refined into
rubber ready for commercial processing. In major areas, latex is allowed to coagulate in
the collection cup. The coagulated lumps are collected and processed into dry forms for
Latex being collected from
Natural rubber is used extensively in many applications and products, either alone or in a tapped rubber tree,
combination with other materials. In most of its useful forms, it has a large stretch ratio Cameroon
and high resilience, and is extremely waterproof.[1]

Hevea brasiliensis
Congo rubber
History Rubber tree plantation in Thailand
Pre-World War II
Chemical makeup
Vulcanized rubber
Allergic reactions
Microbial degradation
See also
External links


Hevea brasiliensis
The major commercial source of natural rubber latex is the Pará rubber tree (Hevea brasiliensis), a member of the spurge
family, Euphorbiaceae. This species is preferred because it grows well under cultivation. A properly managed tree
responds to wounding by producing more latex for several years.

Congo rubber
Congo rubber, formerly a major source of rubber, came from vines in the genus Landolphia (L. kirkii, L. heudelotis, and L.

Dandelion milk contains latex. The latex exhibits the same quality as the natural rubber from rubber trees. In the wild
types of dandelion, latex content is low and varies greatly. In Nazi Germany, research projects tried to use dandelions as a
base for rubber production, but failed.[3] In 2013, by inhibiting one key enzyme and using modern cultivation methods
and optimization techniques, scientists in the Fraunhofer Institute for Molecular Biology and Applied Ecology (IME) in
Germany developed a cultivar that is suitable for commercial production of natural rubber.[4] In collaboration with
Continental Tires, IME began a pilot facility.

Many other plants produce forms of latex rich in isoprene polymers, though not all produce usable forms of polymer as
easily as the Pará.[5] Some of them require more elaborate processing to produce anything like usable rubber, and most
are more difficult to tap. Some produce other desirable materials, for example gutta-percha (Palaquium gutta)[6] and
chicle from Manilkara species. Others that have been commercially exploited, or at least showed promise as rubber
sources, include the rubber fig (Ficus elastica), Panama rubber tree (Castilla elastica), various spurges (Euphorbia spp.),
lettuce (Lactuca species), the related Scorzonera tau-saghyz, various Taraxacum species, including common dandelion
(Taraxacum officinale) and Russian dandelion (Taraxacum kok-saghyz), and perhaps most importantly for its
hypoallergenic properties, guayule (Parthenium argentatum). The term gum rubber is sometimes applied to the tree-
obtained version of natural rubber in order to distinguish it from the synthetic version.[1]

The first use of rubber was by the indigenous cultures of Mesoamerica. The earliest archeological evidence of the use of
natural latex from the Hevea tree comes from the Olmec culture, in which rubber was first used for making balls for the
Mesoamerican ballgame. Rubber was later used by the Maya and Aztec cultures – in addition to making balls Aztecs used
rubber for other purposes such as making containers and to make textiles waterproof by impregnating them with the latex
The Pará rubber tree is indigenous to South America. Charles Marie de La Condamine is credited with introducing
samples of rubber to the Académie Royale des Sciences of France in 1736.[9] In 1751, he presented a paper by François
Fresneau to the Académie (published in 1755) that described many of rubber's properties. This has been referred to as the
first scientific paper on rubber.[9] In England, Joseph Priestley, in 1770, observed that a piece of the material was
extremely good for rubbing off pencil marks on paper, hence the name "rubber". It slowly made its way around England.
In 1764 François Fresnau discovered that turpentine was a rubber solvent. Giovanni Fabbroni is credited with the
discovery of naphtha as a rubber solvent in 1779.

South America remained the main source of latex rubber used during much of the 19th century. The rubber trade was
heavily controlled by business interests but no laws expressly prohibited the export of seeds or plants. In 1876, Henry
Wickham smuggled 70,000 Pará rubber tree seeds from Brazil and delivered them to Kew Gardens, England. Only 2,400
of these germinated. Seedlings were then sent to India, British Ceylon (Sri Lanka), Dutch East Indies (Indonesia),
Singapore, and British Malaya. Malaya (now Peninsular Malaysia) was later to become the biggest producer of rubber.[10]

In the early 1900s, the Congo Free State in Africa was also a significant source of natural rubber latex, mostly gathered by
forced labor. King Leopold II's colonial state brutally enforced production quotas. Tactics to enforce the rubber quotas
included removing the hands of victims to prove they had been killed. Soldiers often came back from raids with baskets
full of chopped-off hands. Villages that resisted were razed to encourage better compliance locally. See Atrocities in the
Congo Free State for more information on the rubber trade in the Congo Free State in the late 1800s and early 1900s.
Liberia and Nigeria started production.

In India, commercial cultivation was introduced by British planters, although the experimental efforts to grow rubber on a
commercial scale were initiated as early as 1873 at the Calcutta Botanical Gardens. The first commercial Hevea
plantations were established at Thattekadu in Kerala in 1902. In later years the plantation expanded to Karnataka, Tamil
Nadu and the Andaman and Nicobar Islands of India. India today is the world's 3rd largest producer and 4th largest

In Singapore and Malaya, commercial production was heavily promoted by Sir Henry Nicholas Ridley, who served as the
first Scientific Director of the Singapore Botanic Gardens from 1888 to 1911. He distributed rubber seeds to many planters
and developed the first technique for tapping trees for latex without causing serious harm to the tree.[12] Because of his
fervent promotion of this crop, he is popularly remembered by the nickname "Mad Ridley".[13]

Pre-World War II
Charles Goodyear developed vulcanization in 1839, although Mesoamericans used stabilized rubber for balls and other
objects as early as 1600 BC.[14][15]

Before World War II significant uses included door and window profiles, hoses, belts, gaskets, matting, flooring and
dampeners (antivibration mounts) for the automotive industry. The use of rubber in car tires (initially solid rather than
pneumatic) in particular consumed a significant amount of rubber. Gloves (medical, household and industrial) and toy
balloons were large consumers of rubber, although the type of rubber used is concentrated latex. Significant tonnage of
rubber was used as adhesives in many manufacturing industries and products, although the two most noticeable were the
paper and the carpet industries. Rubber was commonly used to make rubber bands and pencil erasers.

Rubber produced as a fiber, sometimes called 'elastic', had significant value to the textile industry because of its excellent
elongation and recovery properties. For these purposes, manufactured rubber fiber was made as either an extruded round
fiber or rectangular fibers cut into strips from extruded film. Because of its low dye acceptance, feel and appearance, the
rubber fiber was either covered by yarn of another fiber or directly woven with other yarns into the fabric. Rubber yarns
were used in foundation garments. While rubber is still used in textile manufacturing, its low tenacity limits its use in
lightweight garments because latex lacks resistance to oxidizing agents and is damaged by aging, sunlight, oil and
perspiration. The textile industry turned to neoprene (polymer of chloroprene), a type of synthetic rubber, as well as
another more commonly used elastomer fiber, spandex (also known as elastane), because of their superiority to rubber in
both strength and durability.

Rubber exhibits unique physical and chemical properties. Rubber's stress–
strain behavior exhibits the Mullins effect and the Payne effect and is often
modeled as hyperelastic. Rubber strain crystallizes.

Due to the presence of weakened allylic C-H bonds in each repeat unit, natural
rubber is susceptible to vulcanisation as well as being sensitive to ozone

The two main solvents for rubber are turpentine and naphtha (petroleum).
Because rubber does not dissolve easily, the material is finely divided by Rubber latex
shredding prior to its immersion.

An ammonia solution can be used to prevent the coagulation of raw latex.

Rubber begins to melt at approximately 180 °C (356 °F).

On a microscopic scale, relaxed rubber is a disorganized cluster of erratically changing wrinkled chains. In stretched
rubber, the chains are almost linear. The restoring force is due to the preponderance of wrinkled conformations over more
linear ones. For the quantitative treatment see ideal chain, for more examples see entropic force.

Cooling below the glass transition temperature permits local conformational changes but a reordering is practically
impossible because of the larger energy barrier for the concerted movement of longer chains. "Frozen" rubber's elasticity is
low and strain results from small changes of bond lengths and angles: this caused the Challenger disaster, when the
American Space Shuttle's flattened o-rings failed to relax to fill a widening gap.[16] The glass transition is fast and
reversible: the force resumes on heating.

The parallel chains of stretched rubber are susceptible to crystallization. This takes some time because turns of twisted
chains have to move out of the way of the growing crystallites. Crystallization has occurred, for example, when, after days,
an inflated toy balloon is found withered at a relatively large remaining volume. Where it is touched, it shrinks because the
temperature of the hand is enough to melt the crystals.

Vulcanization of rubber creates di- and polysulfide bonds between chains, which limits the degrees of freedom and results
in chains that tighten more quickly for a given strain, thereby increasing the elastic force constant and making the rubber
harder and less extensible.

Raw rubber storage depots and rubber processing can produce malodour that is serious enough to become a source of
complaints and protest to those living in the vicinity.[17]
Microbial impurities originate during the processing of block rubber. These impurities break down during storage or
thermal degradation and produce volatile organic compounds. Examination of these compounds using gas
chromatography/mass spectrometry (GC/MS) and gas chromatography (GC) indicates that they contain sulphur,
ammonia, alkenes, ketones, esters, hydrogen sulphite, nitrogen, and low molecular weight fatty acids (C2-C5).[18][19]

When latex concentrate is produced from rubber, sulphuric acid is used for coagulation. This produces malodourous
hydrogen sulphide.[19]

The industry can mitigate these bad odours with scrubber systems.[19]

Chemical makeup
Latex is the polymer cis-1,4-polyisoprene – with a molecular weight of 100,000
to 1,000,000 daltons. Typically, a small percentage (up to 5% of dry mass) of
other materials, such as proteins, fatty acids, resins, and inorganic materials
(salts) are found in natural rubber. Polyisoprene can also be created
synthetically, producing what is sometimes referred to as "synthetic natural Chemical structure of cis-
polyisoprene, the main constituent
rubber", but the synthetic and natural routes are different.[1] Some natural
of natural rubber. Synthetic cis-
rubber sources, such as gutta-percha, are composed of trans-1,4-polyisoprene,
polyisoprene and natural cis-
a structural isomer that has similar properties. polyisoprene are derived from
different precursors, isopentenyl
Natural rubber is an elastomer and a thermoplastic. Once the rubber is
pyrophosphate and isoprene.
vulcanized, it is a thermoset. Most rubber in everyday use is vulcanized to a
point where it shares properties of both; i.e., if it is heated and cooled, it is
degraded but not destroyed.

The final properties of a rubber item depend not just on the polymer, but also on modifiers and fillers, such as carbon
black, factice, whiting and others.

Rubber particles are formed in the cytoplasm of specialized latex-producing cells called laticifers within rubber plants.[20]
Rubber particles are surrounded by a single phospholipid membrane with hydrophobic tails pointed inward. The
membrane allows biosynthetic proteins to be sequestered at the surface of the growing rubber particle, which allows new
monomeric units to be added from outside the biomembrane, but within the lacticifer. The rubber particle is an
enzymatically active entity that contains three layers of material, the rubber particle, a biomembrane and free monomeric
units. The biomembrane is held tightly to the rubber core due to the high negative charge along the double bonds of the
rubber polymer backbone.[21] Free monomeric units and conjugated proteins make up the outer layer. The rubber
precursor is isopentenyl pyrophosphate (an allylic compound), which elongates by Mg2+-dependent condensation by the
action of rubber transferase. The monomer adds to the pyrophosphate end of the growing polymer.[22] The process
displaces the terminal high-energy pyrophosphate. The reaction produces a cis polymer. The initiation step is catalyzed by
prenyltransferase, which converts three monomers of isopentenyl pyrophosphate into farnesyl pyrophosphate.[23] The
farnesyl pyrophosphate can bind to rubber transferase to elongate a new rubber polymer.

The required isopentenyl pyrophosphate is obtained from the mevalonate pathway, which derives from acetyl-CoA in the
cytosol. In plants, isoprene pyrophosphate can also be obtained from the 1-deox-D-xyulose-5-phosphate/2-C-methyl-D-
erythritol-4-phosphate pathway within plasmids.[24] The relative ratio of the farnesyl pyrophosphate initiator unit and
isoprenyl pyrophosphate elongation monomer determines the rate of new particle synthesis versus elongation of existing
particles. Though rubber is known to be produced by only one enzyme, extracts of latex host numerous small molecular
weight proteins with unknown function. The proteins possibly serve as cofactors, as the synthetic rate decreases with
complete removal.[25]

More than 28 million tons of rubber were produced in 2017, of which
approximately 47% was natural. Since the bulk is synthetic, which is derived
from petroleum, the price of natural rubber is determined, to a large extent, by
the prevailing global price of crude oil.[26][27][28] Asia was the main source of
natural rubber, accounting for about 94% of output in 2005. The three largest
producers, Thailand, Indonesia (2.4 million tons)[29] and Malaysia, together
account for around 72% of all natural rubber production. Natural rubber is not
cultivated widely in its native continent of South America due to the existence
of South American leaf blight, and other natural predators.
Rubber is generally cultivated in
large plantations. The image shows
a coconut shell used in collecting
latex, in plantations in Kerala, India.
Rubber latex is extracted from rubber trees. The economic life period of rubber
trees in plantations is around 32 years — up to 7 years of immature phase and
about 25 years of productive phase.

The soil requirement is well-drained, weathered soil consisting of laterite, lateritic types, sedimentary types, nonlateritic
red or alluvial soils.

The climatic conditions for optimum growth of rubber trees are:

Rainfall of around 250 centimetres (98 in) evenly distributed without any marked dry season and with at least 100
rainy days per year
Temperature range of about 20 to 34 °C (68 to 93 °F), with a monthly mean of 25 to 28 °C (77 to 82 °F)
Atmospheric humidity of around 80%
About 2000 hours sunshine per year at the rate of six hours per day throughout the year
Absence of strong winds
Many high-yielding clones have been developed for commercial planting. These clones yield more than 2,000 kilograms
per hectare (1,800 lb/acre) of dry rubber per year, under ideal conditions.

In places such as Kerala and Sri Lanka where coconuts are in abundance, the half shell of coconut was used as the latex
collection container. Glazed pottery or aluminium or plastic cups became more common in Kerala and other countries.
The cups are supported by a wire that encircles the tree. This wire incorporates a spring so it can stretch as the tree grows.
The latex is led into the cup by a galvanised "spout" knocked into the bark. Tapping normally takes place early in the
morning, when the internal pressure of the tree is highest. A good tapper can tap a tree every 20 seconds on a standard
half-spiral system, and a common daily "task" size is between 450 and 650 trees. Trees are usually tapped on alternate or
third days, although many variations in timing, length and number of cuts are used. "Tappers would make a slash in the
bark with a small hatchet. These slanting cuts allowed latex to flow from ducts located on the exterior or the inner layer of
bark (cambium) of the tree. Since the cambium controls the growth of the tree,
growth stops if it is cut. Thus, rubber tapping demanded accuracy, so that the
incisions would not be too many given the size of the tree, or too deep, which
could stunt its growth or kill it."[30]

It is usual to tap a pannel at least twice, sometimes three times, during the
tree's life. The economic life of the tree depends on how well the tapping is
carried out, as the critical factor is bark consumption. A standard in Malaysia
for alternate daily tapping is 25 cm (vertical) bark consumption per year. The
latex-containing tubes in the bark ascend in a spiral to the right. For this
reason, tapping cuts usually ascend to the left to cut more tubes.

The trees drip latex for about four hours, stopping as latex coagulates naturally
on the tapping cut, thus blocking the latex tubes in the bark. Tappers usually
rest and have a meal after finishing their tapping work, then start collecting the
liquid "field latex" at about midday.

Field coagula
A woman in Sri Lanka harvesting
The four types of field coagula are "cuplump", "treelace", "smallholders' lump"
rubber, circa 1920
and "earth scrap". Each has significantly different properties.[31] Some trees
continue to drip after the collection leading to a small amount of "cup lump"
that is collected at the next tapping. The latex that coagulates on the cut is also
collected as "tree lace". Tree lace and cup lump together account for 10–20% of
the dry rubber produced. Latex that drips onto the ground, "earth scrap", is
also collected periodically for processing of low-grade product.

Cup lump
Cup lump is the coagulated material found in the collection cup when the
tapper next visits the tree to tap it again. It arises from latex clinging to the Mixed field coagula.
walls of the cup after the latex was last poured into the bucket, and from late-
dripping latex exuded before the latex-carrying vessels of the tree become
blocked. It is of higher purity and of greater value than the other three types.

Tree lace
Tree lace is the coagulum strip that the tapper peels off the previous cut before
making a new cut. It usually has higher copper and manganese contents than
cup lump. Both copper and manganese are pro-oxidants and can damage the
physical properties of the dry rubber.
Smallholder's lump at a remilling
Smallholders' lump factory

Smallholders' lump is produced by smallholders who collect rubber from trees

far from the nearest factory. Many Indonesian smallholders, who farm paddies in remote areas, tap dispersed trees on
their way to work in the paddy fields and collect the latex (or the coagulated latex) on their way home. As it is often
impossible to preserve the latex sufficiently to get it to a factory that processes latex in time for it to be used to make high
quality products, and as the latex would anyway have coagulated by the time it
reached the factory, the smallholder will coagulate it by any means available, in
any container available. Some smallholders use small containers, buckets etc.,
but often the latex is coagulated in holes in the ground, which are usually lined
with plastic sheeting. Acidic materials and fermented fruit juices are used to
coagulate the latex — a form of assisted biological coagulation. Little care is
taken to exclude twigs, leaves, and even bark from the lumps that are formed,
which may also include tree lace. Cup lump rubber coagula in a
Myanmar road stall.

Earth scrap
Earth scrap is material that gathers around the base of the tree. It arises from latex overflowing from the cut and running
down the bark, from rain flooding a collection cup containing latex, and from spillage from tappers' buckets during
collection. It contains soil and other contaminants, and has variable rubber content, depending on the amount of
contaminants. Earth scrap is collected by field workers two or three times a year and may be cleaned in a scrap-washer to
recover the rubber, or sold to a contractor who cleans it and recovers the rubber. It is of low quality.

Latex coagulates in the cups if kept for long and must be collected before this
happens. The collected latex, "field latex", is transferred into coagulation tanks
for the preparation of dry rubber or transferred into air-tight containers with
sieving for ammoniation. Ammoniation preserves the latex in a colloidal state
for longer periods of time.

Latex is generally processed into either latex concentrate for manufacture of

dipped goods or coagulated under controlled, clean conditions using formic
acid. The coagulated latex can then be processed into the higher-grade, Removing coagulum from
coagulating troughs.
technically specified block rubbers such as SVR 3L or SVR CV or used to
produce Ribbed Smoke Sheet grades.

Naturally coagulated rubber (cup lump) is used in the manufacture of TSR10 and TSR20 grade rubbers. Processing for
these grades is a size reduction and cleaning process to remove contamination and prepare the material for the final stage
of drying.[32]

The dried material is then baled and palletized for storage and shipment.

Vulcanized rubber
Natural rubber is often vulcanized - a process by which the rubber is heated and sulfur, peroxide or bisphenol are added to
improve resistance and elasticity and to prevent it from perishing. Carbon black is often used as an additive to rubber to
improve its strength, especially in vehicle tires, which account for about 70% (~9 million tons) of carbon black production.

Natural rubber latex is shipped from factories in south-east Asia, South America, and West and Center Africa to
destinations around the world. As the cost of natural rubber has risen significantly and rubber products are dense, the
shipping methods offering the lowest cost per unit weight are preferred. Depending on destination, warehouse availability,
and transportation conditions, some methods are preferred by certain buyers.
In international trade, latex rubber is mostly shipped in 20-foot ocean
containers. Inside the container, smaller containers are used to store the

Uncured rubber is used for cements;[34] for
adhesive, insulating, and friction tapes; and
Torn latex rubber dry suit wrist seal
for crepe rubber used in insulating blankets
and footwear. Vulcanized rubber has many
more applications. Resistance to abrasion makes softer kinds of rubber valuable for the
treads of vehicle tires and conveyor belts, and makes hard rubber valuable for pump
housings and piping used in the handling of abrasive sludge.

The flexibility of rubber is appealing in hoses, tires and rollers for devices ranging from
domestic clothes wringers to printing presses; its elasticity makes it suitable for various
kinds of shock absorbers and for specialized machinery mountings designed to reduce
vibration. Its relative gas impermeability makes it useful in the manufacture of articles
Compression molded such as air hoses, balloons, balls and cushions. The resistance of rubber to water and to
(cured) rubber boots before the action of most fluid chemicals has led to its use in rainwear, diving gear, and
the flashes are removed
chemical and medicinal tubing, and as a lining for storage tanks, processing equipment
and railroad tank cars. Because of their electrical resistance, soft rubber goods are used
as insulation and for protective gloves, shoes and blankets; hard rubber is used for articles such as telephone housings,
parts for radio sets, meters and other electrical instruments. The coefficient of friction of rubber, which is high on dry
surfaces and low on wet surfaces, leads to its use for power-transmission belting and for water-lubricated bearings in
deep-well pumps. Indian rubber balls or lacrosse balls are made of rubber.

Around 25 million tonnes of rubber are produced each year, of which 30 percent is natural.[35] The remainder is synthetic
rubber derived from petrochemical sources. The top end of latex production results in latex products such as surgeons'
gloves, condoms, balloons and other relatively high-value products. The mid-range which comes from the technically
specified natural rubber materials ends up largely in tires but also in conveyor belts, marine products, windshield wipers
and miscellaneous goods. Natural rubber offers good elasticity, while synthetic materials tend to offer better resistance to
environmental factors such as oils, temperature, chemicals and ultraviolet light. "Cured rubber" is rubber that has been
compounded and subjected to the vulcanisation process to create cross-links within the rubber matrix.

Allergic reactions
Some people have a serious latex allergy, and exposure to natural latex rubber products such as latex gloves can cause
anaphylactic shock. The antigenic proteins found in Hevea latex may be deliberately reduced (though not eliminated)[36]
through processing.

Latex from non-Hevea sources, such as Guayule, can be used without allergic reaction by persons with an allergy to Hevea

Some allergic reactions are not to the latex itself, but from residues of chemicals used to accelerate the cross-linking
process. Although this may be confused with an allergy to latex, it is distinct from it, typically taking the form of Type IV
hypersensitivity in the presence of traces of specific processing chemicals.[36][38]
Microbial degradation
Natural rubber is susceptible to degradation by a wide range of bacteria.[39][40][41][42][43][44][45][46] The bacteria
Streptomyces coelicolor, Pseudomonas citronellolis, and Nocardia spp. are capable of degrading vulcanized natural

See also
Akron, Ohio, center of the United States rubber industry
Condoms, also called "rubbers"
Crepe rubber
Emulsion dispersion
Fordlândia, failed attempt to establish a rubber plantation in Brazil
Reinforced rubber
Resilin, a rubber substitute
Rubber seed oil
Rubber technology
Stevenson Plan, historical British plan to stabilize rubber prices
Charles Greville Williams, researched natural rubber being a polymer of the monomer isoprene


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