Rubber Industry

Rubber Rubber is a tough elastic polymeric substance made from the latex of a tropical plant or synthetically. The most common chemical elements in rubber are carbon (C) and hydrogen (H). The polymers of natural rubber are mainly built of these elements. In synthetic rubber these elements are products from the petrochemical industry. Rubber is a specific type of polymer called an elastomer: a large molecule that can be stretched to at least twice its original length and returned to its original shape. Early forms of rubber had many gluelike properties, especially in hot weather. In cold temperatures, rubber became hard and brittle. It was only after an accidental discovery by Charles Goodyear in 1839 that modern rubber became possible. Since that time, rubber has become an important natural polymer in society. We make rubber from rubber trees (natural latex) and from oil (synthetic rubber). We use both types of rubber in many products. Like the Mesoamericans (Aztecs and Mayans) before them, athletes and children today play with rubber balls. Of course, the most common use for rubber is in automotive tires. But pencil erasers, shoes, gloves, dental dams and condoms contain the ubiquitous substance, too. In many products, rubber is added as a protective coating for either weatherproofing or shockproofing.

History
1525: Padre d'Anghieria reported that he had seen Mexican tribes people playing with elastic balls. 1735: The 1st scientific study of rubber was undertaken by Charles de la Condamine, when he encountered it during his trip to Peru The first use for rubber was an eraser. It was Magellan, a descendent of the famous Portuguese navigator, who suggested this use. In England, Priestley popularized it to the extent that it became known as India Rubber. The word for rubber in Portuguese - borracha - originated from one of the first applications for this product, when it was used to make jars replacing the leather borrachas that the Portuguese used to ship wine. 1820: British industrialist Nadier produced rubber threads and attempted to use them in clothing accessories. 1832: Rosburg factory was set up. 1840: Goodyear discovered vulcanization, quite by accident. 1815: Hancock - became one of the leading manufacturers in the UK. He had invented a rubber mattress and through an association with MacIntosh he produced the famous waterproof coat known as the "macintosh".

 MacIntosh discovered the use of benzene as a solvent, while Hancock discovered that prior chipping and heating were required in order to ensure that the rubber dissolved completely. Hancock also discovered how to manufacture elastic balls. Charles Goodyear accidentally discovered that by mixing sulfur and rubber, the properties of the rubber improved in being tougher, resistant to heat and cold, and increased in elasticity. This process was later called vulcanization after the Roman god of fire. Vulcanization causes shorter chains to cross link through the sulfur to longer chains. The development of vulcanized rubber for automobile tires greatly aided this industry. 1845: R.W. Thomson invented the pneumatic tire, the inner tube and even the textured tread. 1850 : Rubber toys were being made, as well as solid and hollow balls for golf and tennis. 1830: 1st bicycle tire. 1895 : Michelin had the daring idea of adapting the tire to the automobile.

History of Natural and Synthetic Rubber

Natural Rubber -Natural rubber is a solid product obtained through coagulating the latex produced by certain plants, particularly the Brazilian rubber-tree (HeveaBrasiliensis). This raw material is usually tapped from the rubber tree, which is native to Amazonia. Thanks to its multiple applications, particularly in the expanding automobile industry, rubber produced from latex tapped from rubber-trees became a product in demand worldwide. And there was no lack of rubber-trees in the Brazilian Amazon. This brought a boom to Northern Brazil - which at that time was one of the poorest and least-inhabited parts of the country. Synthetic Rubber -synthetic rubber had been known since 1875, its production had been expensive and almost negligible. 1941: total output of synthetic rubber barely topped 8,000 tons, consisting largely of products not suitable for tires. The nation's survival depended on its capacity to manufacture over 800,000 tons of products that had barely begun to be developed. There were few detailed instructions on how the factories should organize themselves to produce this vast amount. No facilities had been built, nor was there any way of producing enough raw materials to produce rubber

GENERAL RUBBER MANUFACTURING

Rubber manufacturing generally comprises the following operations:

1. 2. 3. 4. 5. 6. 7.

Weighing and mixing (raw materials handling) Milling Extruding and calendering Component assembly and building Curing or vulcanizing Inspection and finishing Storage and dispatch

1. Raw Materials Handling, Weighing and Mixing All the materials required for the manufacture of the finished product are assembled. The raw polymer, either natural or synthetic is brought together at this stage with a variety of compounding chemical additives before being introduced into a mixer. The extensive range of chemicals required and the volume of raw material handled can give rise to substantial quantities of airborne dust. 2. Milling From the mixer, the uncured rubber compound usually passes to one or more milling machines, where it is thoroughly blended to ensure an even dispersion of its chemical constituents. At this stage, considerable heat is generated, and, although many technical improvements have been introduced in recent years, the job of mill operator still involves a considerable degree of physical exertion and exposure to fumes arising from the heated compound.

3. Extruding and Calendering The extruders force the rubber compound through a die into various forms, which are then cut to appropriate lengths. Strips of softened rubber compounds are fed into multiple-roll milling machines (calenders) to form rubber sheeting, or to apply the rubber directly onto woven textile fabric, which can then be wound of onto a roll. During such manufacturing operations, fumes are often generated. 4. Curing or Vulcanizing Heat is applied to the product, usually by use of steam, in a curing mould, press, or autoclave. Operators working in the area are exposed both to heat from the presses and to fumes from the heated rubber products. Chemical reactions take place throughout the manufacturing process, and may give rise to new, more volatile chemicals

5. Inspection and Finishing This involves the handling of cured rubber products, often while still hot. It usually involves direct and extensive skin-contact with the surface of the finished article (during inspection) and may also involve exposure to vulcanizing fumes. Grinding, trimming, repair, painting and cleaning may also entail exposure to rubber dust, fumes and solvents. 6. Storage and Dispatch Large quantities of stored rubber goods may release considerable amounts of toxic substances, either as vapours or as constituents of the bloom on the surface of finished goods.

2 Main Types Of Rubber

1. Natural rubber (NR) -an elastic material obtained from the latex sap of trees (especially trees of the genera Hevea and Ficus) that can be vulcanized and finished into a variety of products. Natural rubber, coming from latex of Heveabrasiliensis, is mainly cis-1,4polyisoprene containing traces of impurities like protein, dirt etc that when stretched, the molecules crystallize producing a superior form of reinforcement. Although it exhibits many excellent properties in terms of mechanical performance, natural rubber is often inferior to certain synthetic rubbers, especially with respect to its thermal stability and its compatibility with petroleum products.It contains 6 to 8% nonrubber materials and has an outstanding heatbuildup resistance. -Foam rubber is a spongy rubber; made by introducing air bubbles before vulcanization and used for cushioning or upholstery. Latex is a milky exudate from certain plants that coagulates on exposure to air Crepe Rubber is a crude natural rubber; used mainly for shoe soles. Cold rubber is a rubber made at low temperatures (5 degrees Centigrade) which is tougher than conventional rubber and is often used in car tires. Ebonite, hard rubber, vulcanite are a hard nonresilient rubber formed by vulcanizing natural rubber. -Para rubber - a type of natural rubber obtained from tropical South American trees.

- When tapping the tree, a cut is made through the bark and the latex drips down into a cup. -A tree with a good yield can give 30-35 grams of rubber per day. The contents of the cups are emptied into containers and transported to a rubber factory. Acetic acid is added to promote coagulation. To manufacture smoked sheets, the rubber is made into sheets in a mill, washed, dried, smoked and finally classified. With the exception of butadiene rubber, natural rubber has the best elasticity of all rubber types. It has very good resistance to abrasion and fatigue. Among the drawbacks are the materials poor resistance to ozone (weather) and oils and fuels. -Natural rubber is mainly used in the production of heavy-duty tires, vibration dampers, springs and bearings. For special purposes it is used in hoses seals, conveyor belts, coated fabrics and other products.

Natural Rubber Manufacturing

Preparation of Raw Materials Coagulation Drying Softening

Vulcanizing

Shaping the Rubber

Compounding

A. Preparation of Raw Materials Latex is obtained by tapping the tree in such a manner as to allow the liquid to accumulate in small cups, which must be collected frequently to avoid putrefaction or contamination. It is carried to a collection stations where it is strained and a preservative (NH3) added. B. Coagulation The rubber is separated. Coagulation occurs when various acids or salts are added and the rubber separates from the liquid as a white, doughlike mass, which is then milled and sheeted to remove contaminants and to allow drying. A newer method is to form the coagulated latex into granules by cutting with rotating knives or by shear between two rollers running at different speeds. C. Drying The granules are dried in mechanical dryers in hours, instead of the days that air or wood-smoke dryers required. Either the drier sheet or granules are compressed into bales weighing 33 kg. Some natural rubber is marketed as a latex, concentrated after stabilization with ammonia and centrifugation to about 60% rubber.

D. Softening
Rubber must be softened before it can be compounded with various necessary additives. This may be done with a two-roll mill whose rolls revolve at different speeds, or a mixer in which an eccentrically shaped rotor works the rubber against the walls of the mixer.

E. Compounding
Compounding materials such as Carbon black (filler), sulfur or sulfur compounds (for vulcanization), vulcanizing accelerator, protective antioxidant, and oil, are mixed either in the same mixer or rolls.

F. Shaping the Rubber

The rubber is shaped into the desired product by extruding, or molding.

G. Vulcanizing
Vulcanization leads to a cross-linked thermoset polymer that cannot be softened or melted by reheating to the original melting point. It is important to carefully control the heat of vulcanization (140C and more) to obtain optimum properties in the finished rubber. As the vulcanization is a chemical reaction, its speed increases with temperature and care must be taken to ensure that it does not take place prematurely.

1.

Synthetic Rubber -Synthetic rubbers are any of several substances similar to natural rubber in properties anduses, produced by the polymerization of an unsaturated hydrocarbon, as butylene, or isoprene, or by the copolymerization of such hydrocarbons with styrene, butadiene, or the like. They have been classified into vulcanizable and non-vulcanizable and also by the chemical composition of the polymer chain.

Chemical structure of cis-polyisoprene, the main constituent of natural rubber. Synthetic cis-polyisoprene and natural cis-polyisoprene are derived from different precursors by different chemical pathways.

-Styrene-butadiene rubber (SBR) is the most common type of synthetic rubber. Styrene-butadiene rubber, the most common and cheapest synthetic rubber, serves as an example of the manufacturing principles. The basic material is derived from petroleum (oil) which is a fossil formation from organisms that have been dead for millions of years. In the distillation process at the oil refineries, styrene and butadiene are produced, which are then used as raw materials for the production or styrene-butadiene rubber.

-Isoprene rubber (IR) is very much as natural rubber. Isoprene rubber has the same chemical structure as natural rubber (polyisoprene). However, it does not contain proteins, fatty acids and the other substances that are present in natural rubber. The physical properties of isoprene rubber are in general somewhat inferior to those of natural rubber but, in principle, the two types are very alike. Isoprene rubber is used in the same type of products as natural rubber. -Butadiene rubber (BR) is the most elastic rubber type. Butadiene rubber is polymerized butadiene. It is used in blends with other rubber types for improved elasticity, wear resistance and low temperature properties. A typical application is a blend of butadiene rubber and natural rubber in truck tires.

-Special rubber types the above mentioned rubber types are so-called general purpose. Many other types are available, each with its own special properties. The most common special types in our products are ethylenepropylene, butyl, chloroprene and nitrile rubber. Ethylene-propylene rubber (EDM/EPDM) is for many purposes. For manufacture of the sheeting used at high temperatures, ethylenepropylene rubber, with the abbreviation EPDM, is used. The first two letters mean that the rubber consists of ethylene and propylene, but the letter D tells us that a diene is also present. That third monomer makes it possible to cure the rubber with sulfur since it introduces double bonds in the structure, thereby changing the structure to an unsaturated polymer.Since ethylene-propylene rubber does not crack outdoors (good ozone resistance) it is widely used for seals in buildings and in the automotive industry. Steam hose, high temperature-resistant seals and roll covers are other applications.

-Special rubber typesthe above mentioned rubber types are so-called general purpose. Many other types are available, each with its own special properties. The most common special types in our products are ethylenepropylene, butyl, chloroprene and nitrile rubber. Ethylene-propylene rubber (EDM/EPDM) is for many purposes. For manufacture of the sheeting used at high temperatures, ethylene-propylene rubber, with the abbreviation EPDM, is used. The first two letters mean that the rubber consists of ethylene and propylene, but the letter D tells us that a diene is also present. That third monomer makes it possible to cure the rubber with sulfur since it introduces double bonds in the structure, thereby changing the structure to an unsaturated polymer.Since ethylene-propylene rubber does not crack outdoors (good ozone resistance) it is widely used for seals in buildings and in the automotive industry. Steam hose, high temperatureresistant seals and roll covers are other applications. Butyl rubber (IIR) is when low gas permeation is needed. Products used to prevent gases from passing through the material are based. The polymer consists of isobutene with a minor part of isoprene. The isoprene makes the rubber unsaturated and possible to vulcanizeon butyl rubber.

 Chloroprene rubber (CR) is resistant to oil and weather. Most chloroprene rubber types consist solely of polymerized chloroprene monomers. The polymer has a good resistance to the outdoor climate and reasonable oil resistance. It is therefore used in products exposed to oil-based fuels and weather. Nitrile rubber (NBR) is for use with oil. Nitrile rubber is a copolymer of acrylonitrile and butadiene. It is the common polymer for products that are in contact with oil and fuel.

Synthetic Rubber Manufacturing

A. Monomer Production The monomer/s that will be used in the polymerization process will be synthesized or obtained as a byproduct. Styrene is a monomer but is mainly used in the production of polysterene plastics. The predominant route to the production of styrene is via ethylbenzene, which is made by alkylating benzene with ethylene and subsequently dehydrogenating to styrene over an aluminum chloride, solid phosphoric acid, or silica-alumina catalyst. Isobutylene is recovered from refinery light-end operations by distillation. It is the monomer for butyl rubber. Isoprene may be produced by the dehydrogenation of isopentane. Ethylene and propylene are readily available from refinery light-end cuts or may be produced by the steam cracking of propane or heavier fractions. The potential low cost of these materials as monomers for rubber and the very favorable results obtained, indicate a considerable future for rubbers produced from these petrochemicals.

B. Synthetic Rubber Polymerization The various methods of production of synthetic rubbers have much in common. The monomers are not particularly difficult to handle at reasonable pressures, and suitable inhibitors have been developed to impart storage ability. C. Monomer Recovery The rubber quality and rate of reaction both fall off as polymerization proceeds, and it is customary to stop the reaction short of complete conversion to rubber. Recovery of the unreacted monomers and purification is an essential step in economical synthetic-rubber production. Methods of recovery by steam stripping from aqueous lattices or by distillation from solvent systems are employed. In some cases, recovery of the monomer can be accomplished during the drying step in devolatilizing extruder dryer. Water or solvent is removed by a combination of mechanical squeezing and by passage through a vacuum section.

D. Coagulation and Drying The finishing process usually consists of precipitating the rubber from the latex emulsion or from the solvent solution in crumb form; it is then dried and compressed. Ordinary lattices may be easily coagulated by the addition of of NaCl and dilute H2SO4, alum, or virtually any combination of electrolyte and dilute acid. The rubbers which result from solution polymerization can be precipitated into crumb form by adding the solution to a tank of hot water under violent agitation, with or without the addition of wetting agents, to control crumb size and prevent reagglomeration. The coagulated crumb is separated from the serum and washed on vibrating screens or rotating filters and dried at appropriate temperatures. Rubber is a difficult material to dry, and care must be taken not to overheat it or otherwise cause its deterioration. E. Packaging Most rubber is now wrapped in polyethylene film as 34-kg bale of reasonably standard dimensions. In most cases, it is possible to throw bale and polyethylene wrapping into the rubber mill or internal mixer, since the polyethylene melts at a temperature lower than the usual rubber-processing temperature.

F. Rubber Compounding Pure rubber (natural or synthetic) is usually not suitable for use. The desirable properties of plasticity, elasticity, toughness, hardness or softness, abrasion resistance, impermeability, and the myriad combinations possible are achieved by the art of the rubber compounder.

The chemicals are divided into groups according to use:

a. Vulcanizing Agents They are usually sulfur compounds which react with the polymer to produce a cross-linked material in which the linkages are C-Sx-C-. The cross links may be mono-, di-, or polysulfidic. The type of linkage is determined by the concentrations of sulfur, accelerators, and retarders, and temperature. b. Accelerators They reduce the time required for the vulcanization of rubber from several hours to a few minutes. UB addition, less sulfur is needed and a more uniform product is obtained. Presumably, it involves the formation of an activated form of sulfur, whichforms a sulfur bridge at reactive sites within the rubber molecule, linking the large molecules into a tight network. Most accelerators contain sulfur and nitrogen. Two-thirds of all the accelerators made consist of mercaptobenzothiazole (MBT) and its derivatives. c. Age Resistors or Antioxidants They protect rubber goods from attack by oxygen and ozone in the atmosphere. They are classified as antioxidants, antiozonants, or anti-flex cracking agents. They function by combining with, and thus interrupting, freeradical chain reactions and thus prevent further chain degradation.

d. Catalytic Plasticizer or Peptizers They serve to reduce the viscosity of rubber to permit easier processing. When milled into the rubber, they cause chain scission, with a consequent lowering of the molecular weight. They are useful both in reclaiming vulcanized rubber and in softening high-molecular-weight crudes. e. Inert Filling Materials They may be added to the rubber. Some merely serve to harden or to dilute the mix. Others exert a profound influence called reinforcement, which is chemophysical in nature. f. Processibility It is improved by the use of reclaimed rubber, waxes, oils, factices (vulcanized vegetable oils), and mineral rubbers (asphalts, pitches, and vulcanized unsaturated hydrocarbons) or by chemical attack on the molecule, as well as by work breakdown, heat, and mastication. g. Sponge Culture It is obtained by adding sodium bicarbonate, ammonium carbonate and bicarbonate, urea, or organic gas-generating chemicals. h. Hard Rubber It may be made by greatly increasing the sulfur content and by the use of large amounts of filter. i. Rubber Fabrication As a plastic material, rubber may be spread, cemented, calendered, molded, extruded, caulked, puttied, or wrapped into virtually any shape: coated on cloth, plastic, or metal; and sandwiched or forced into cracks.

Important Terms
Latex Compounds -Concentrated lattices permit the use of the rubber as a liquid which may be spread, painted dipped, or whipped into a foam. Suspensions of compounding ingredients provide cure, but reinforcement is not nearly as effective. The use of latex is increasing, although the foam mattress, pillow, and upholstering trades have veered polyurethane and polyether rubbers for their supply. Reclaimed Rubber - Reclaim is a useful compounding ingredient produced from scrap rubber goods. It is partially depolymerized and contains a high percentage of carbon black (or other pigment), ash, and solvent oils. It imparts some desirable processing character to rubber compounds but it usually used as a cheap scrap material for very cheap products. Rubber Derivatives - Rubber, particularly natural rubber, has been used as a raw material for chemical reactions to yield various derivatives of altered nature. Plastic technology is replacing these rubber-based chemicals, for rubber I obviously an expensive raw material.

Overall
Natural rubber has a high tensile strength and is resistant to fatigue from wear such as chipping, cutting or tearing. On the other hand, natural rubber has only moderate resistance to damage from exposure to heat, light and the ozone in the air. Natural rubber also has tack, which means it can adhere to itself as well as other materials. It adheres particularly well to steel cord, which makes it an excellent material for use in tires. In general, synthetic rubber offers better resistance to abrasion than natural rubber, as well as superior resistance to heat and the effects of aging. Many types of synthetic rubber are flame-resistant, so it can be used as insulation for electrical devices. It also remains flexible at low temperatures and is resistant to grease and oil. Overall, the combined properties of natural rubber outweigh synthetic rubbers or combinations of synthetic rubbers available. However, synthetic rubber is advantageous because it is easier to produce. Natural rubber is a crop able to grow only in tropical climates and it doesnt age well, so for many countries it is easier to use synthetic rubber. Synthetic rubber may also be useful in certain applications because of their resistance to extreme temperatures and corrosive environments.