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Rubber was known to the indigenous peoples of the Americas long before the arrival of European explorers. The first scientific study of rubber was undertaken by Charles de la Condamine, when he encountered it during his trip to Peru in 1735. 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. In 1815, Hancock had invented a rubber mattress and through an association with MacIntosh he produced the famous waterproof coat known as the "macintosh". Furthermore, he discovered how to cut, roll and press rubber on an industrial scale. He also noted the importance of heat during the pressing process, and built a machine for this purpose. Finally, in 1842, Hancock came into possession of vulcanized rubber produced by Goodyear. In 1845, R.W. Thomson invented the pneumatic tire, the inner tube and even the textured tread. In 1850 rubber toys were being made, as well as solid and hollow balls for golf and tennis. South America remained the main source of the limited amounts of latex rubber that were used during much of the 19th century. In 1876, Henry Wickham gathered thousands of para rubber tree seeds from Brazil, and these were germinated in Kew Gardens, England. The seedlings were then sent to India, Ceylon (Sri Lanka), Indonesia, Singapore and British Malaya. Malaya (now Malaysia) was later to become the biggest producer of rubber. In the early 1900s, the Congo Free State in Africa was also a significant source of natural rubber latex, mostly gathered by forced labor. Liberia and Nigeria also started production of rubber. In India, commercial cultivation of natural rubber was introduced by the British planters, although the experimental efforts to grow rubber on a commercial scale in India were initiated as early as 1873 at the Botanical Gardens, Calcutta. The first commercial Hevea plantations in India were established at Thattekadu in Kerala in 1902. In the 19th and early 20th century, it was often called "India rubber." In 2010, India's natural rubber consumption stood at 978 thousand tons per year, with production at 893 thousand tons; the rest was imported with an import duty of 20%.
which is native to Amazonia. because the links in the long chain are freely rotating and enable flow and distortion of material to occur under stress. Classification of rubbers Natural Rubber Natural rubber is a solid product obtained through coagulating the latex produced by certain plants. polymers behave in many ways like viscous liquids. This raw material is usually tapped from the rubber tree. Although there a large number of species that exude secretions similar to latex when the bark is cut. Materials in the class of polymers which are. and are said to be viscoelastic. predominantly organic. The structural formula for the molecule of natural rubber may be represented by the simple unit C5H8 multiplied many 1000 times. there is a fairly abrupt change to a glassy state. their molecular freedom is restricted and they show both time-dependent viscous and elastic properties. These high molecular weight polymers have a lower temperature limit to their rubbery state. which is more complex in rubbers than in ordinary low molecular weight substances crystallisation of rubbers takes place by local rearrangement of portions of molecules to form crystallites. consisting of long – chain molecules made up repeating units usually on a back bone of carbon atoms.3-butadiene with the following . At the so called glass transition temperature Tg. In rubbery state. particularly the Brazilian rubber-tree (Hevea Brasiliensis). at normal temperatures. Because of the chain length and the presence of side groups on the chain. plastics. become rubber like as the temperature is raised above their Tg.Rubber Rubber belongs to the class of substances termed ‘polymers’: high molecular weight compounds. Mention must be made of the phenomenon of crystallisation. only a few produce sufficient quantities of a quality adequate for exploitation on economic bases. Rubber is an addition polymer of a diene monomer(a hydrocarbon molecule containing two double bonds) called isoprene or 2-methyl-1.
we get polyisoprene. STRUCTURE OF SBR . styrene and butadiene. which is the chemical name of natural rubber Poly isoprene Synthetic rubbers SOME EXAMPLES FOR SYNTHETIC RUBBER: SBR(STYRENE BUTADEINE RUBBER) Styrene-butadiene or styrene-butadiene rubber (SBR) describe families of synthetic rubbers derived from styrene and butadiene. The co monomers for SBR production.formula: CH2=C(CH3)-CH=CH2 The repeating unit shown above would. be called the monomer. are today invariably produced from petroleum sources. On polymerization of isoprene. therefore.
SBR can be used to 'tank' damp rooms or surfaces.0 51. but is more expensive. . as well as being resistant to emulsification in damp conditions. Latex (emulsion) SBR is extensively used in coated papers. reduced shrinkage and increased flexibility. as a sealing and binding agent behind renders as an alternative to PVA. a process in which the rubber is painted onto the entire surface (sometimes both the walls. Properties Property S-SBR E-SBR Tensile strength (MPa) 18 19 Elongation at tear (%) 565 635 Mooney viscosity (100 ° C) 48. In the latter application. floor and ceiling) forming a continuous. It is a commodity material which competes with natural rubber.5 Glass transition temperature (° C) -65 -50 Polydispersity 2. shoe heels and soles. Copolymers prepared by use of lithium catalyst systems first came into existence in early 1960 and varieties of types are now commercially available. It is also used in building applications. gaskets and even chewing gum.5 Applications The elastomer is used widely in pneumatic tires. a typical example would be a basement. being one of the most cost-effective resins to bind pigmented coatings. Polymerization is carried out in solution and with these systems the reactivity ratios are quite different to observed with free radical polymerizations.1 4. seamless damp proof liner. it offers better durability.The bulk of SBR is produced by free radically initiated emulsion polymerisation. Solution polymerization is also used for preparation of SBR.
radical generating activators. or NBR.2-butadiene and 1. Water serves as the reaction medium within the vessel. also known as Buna-N. this form of synthetic rubber is generally resistant to oil. the . fuel. STRUCTURE OF NBR Nitrile butadiene rubber (NBR) is a family of unsaturated copolymers of 2-propenenitrile and various butadiene monomers (1. the higher the resistance to oils but the lower the flexibility of the material).3-butadiene + 1. is a synthetic rubber copolymer of acrylonitrile(ACN) and butadiene. Production Emulsifier (soap).2-butadiene → nitrile butadiene rubber Monomers are usually permitted to react for 5 to 12 hours. Once the resultant latex has “shortstopped”.NBR Nitrile rubber. Krynac and Europrene. Although its physical and chemical properties vary depending on the polymer’s composition of nitrile. The reaction for one possible portion of the polymer is shown below: 1. 2-propenenitrile. The tanks are heated to 30–40 °C to facilitate the polymerization reaction and to promote branch formation in the polymer. Perbunan. For this reason there is also no IUPAC name for the general polymer. 1. One repeating unit found throughout the entire polymer may not exist. Polymerization is allowed to proceed to ~70% conversion before a “shortstop” agent (such as dimethyldithioarbamate and diethyl hydroxylamine) is added to react with the remaining free radicals.3-butadiene + 2-propenenitrile + 1.2-butadiene). Trade names include Nipol. Because several monomers capable of propagating the reaction are involved in the production of nitrile rubber the composition of each polymer can vary (depending on the concentrations of each monomer added to the polymerization tank and the conditions within the tank). various butadiene monomers (including 1.3-butadiene + 1.3butadiene). and other chemicals (the more nitrile within the polymer. and a catalyst are added to polymerization vessels in the production of hot NBR.3-butadiene.
. For these reasons. The production process itself is not overly complex. or 2-methyl-1-propene.unreacted monomers are removed through a steam in a slurry stripper. and coagulation processes require some additives and equipment. Among the highest producers of NBR are mainland China and Taiwan. but they are typical of the production of most rubbers. is the homopolymer of isobutylene. monomer recovery. a copolymer of isobutylene with isoprene. Unlike polymers meant for ingestion. oil seals. printer's roller. The yielded polymer latex is coagulated using calcium nitrate. NBR latex can also be used in the preparation of adhesives and as a pigment binder. It is generally odourless and tasteless. hoses. also known as "PIB" or polyisobutene. BUTYL RUBBER Butyl rubber is a synthetic rubber. gaskets. less branching will form on polymers (the amount of branching distinguishes cold NBR from hot NBR). latex is sent through a series of filters to remove unwanted solids and then sent to the blending tanks where it is stabilized with an antioxidant. the polymerization. The necessary apparatus is simple and easy to obtain. automotive transmission belts. Under lower temperature conditions. The process for the production of cold NBR is very similar to that of hot NBR. synthetic leather. the general properties of NBR are not altered by minor structural/compositional differences. Recovery of unreacted monomers is close to 100%. Polyisobutylene. Polymerization tanks are heated to 5–15 °C instead of 30–40 °C. Butyl rubber is produced by polymerization of about 98% of isobutylene with about 2% of isoprene. V belts. After monomer recovery. O rings. The coagulated substance is then washed and dried into crumb rubber. Structurally. though it may exhibit a slight characteristic odour. Polyisobutylene is a colourless to light yellow viscoelastic material. (C4H8)n. and as cable jacketing. where small inconsistencies in chemical composition/structure can have a pronounced effect on the body. having two methyl groups substituted on every other carbon atom. the substance is widely produced in poorer countries where labour is relatively cheap. on which butyl rubber is based. The abbreviation IIR stands for Isobutylene Isoprene Rubber. polyisobutylene resembles polypropylene. aluminium sulfate. Applications The uses of nitrile rubber include non-latex gloves for the healthcare industry. and other coagulating agents in an aluminium tank.
Chloroprene rubber Among the speciality elastomers polychloroprene [poly(2-chloro [poly(2 chloro-1. later “Neoprene”) and since then CR has an outstanding position due to its favourable combination of technical properties.3butadiene)] is one of the most important.Butyl rubber has excellent impermeability. . APPLICATIONS Butyl rubber and halogenated butyl rubber are used for the inner liner that holds the air in the tire. First production was in 1932 by DuPont (“Duprene”. and the long polyisobutylene segments of its polymer chains give it good flex properties. The formula for PIB is: –(–CH2–C(CH3)2–)n– The formula for IIR is: It can be made from the monomer isobutylene or CH2=C(CH3)2 only via cationic addition polymerization.
The basic polymerization scheme leads to incorporation of the monomer into a polymer consisting of different structural units. polymerization aids (comonomers. chemical and rheological properties of the different grades of commercial polychloroprene are dependent on the ability to change the molecular structure by changing polymerization conditions. e. The high amount of trans-1. type and amount of molecular weight modifier and emulsifier) and conditions during finishing.g. which has crystallization as an inherent property.4-units in the polymer (about 90 % at standard polymerization conditions) leads to synthetic rubber. The physical. polymerization temperature or monomer conversion. .
oils and chemicals is not thoroughly distributed and dispersed through the mass of the compound. To develop the required level of such elastomers have to be mixed with various compounding ingredients. If each of the various components rubbers. transmission belts. It has: Good mechanical strength High ozone and weather resistance Good aging resistance Low flammability Good resistance toward chemicals Moderate oil and fuel resistance Adhesion to many substrates Polychloroprene can be vulcanized by using various accelerator systems over a wide temperature range. shaping. conveyor belts. Application areas in the elastomer field are widely spread. because they all have poor physical properties and chemical properties. then problems cascade down through the subsequent process of shaping and curing and result in less than optimum physical properties in the end product. fuel hose. These three components. The levels of properties such as resilience. PROCESSING OF RUBBER Raw elastomers as received from the manufacturer or from plantation in the case of natural rubber have few uses as such. but its balance of properties is unique among the synthetic elastomers. and curing together constitute rubber processing. hardness. Mixing Mixing is the first and most critical process. mixing. fillers. or an oil seal. shaped and cured. and tensile strength that raw elastomers possess are completely inadequate for such typical end applications such as tyre tread. .Properties CR is not characterised by one outstanding property. profiles etc. cables. radiator hose. such as moulded goods. abrasion resistance.
Before mixing. After mixing. the rubber compound is formed into the shape required by the end product. whereas in moulding. there is a mastication step. Among these. In this step. the reduction of viscosity and increase of plasticity is brought about by mechanical milling and working. particularly for large scale production. curing takes place in the mould. the compound is either stored for maturation or taken to shaping operations.A compound is formulated first to meet the requirements of the end application. The compounding ingredients are mixed and uniformly distributed though intensive shearing action of rolls. Basically. the product is either transferred to dispatch or to curing stage. whether compression. The resulting product is a non-vulcanized compound. The quantity of additives used varies for 20 to 130 percent as a percentage on the weight. Mixing process is carried out in any of the two basic machines: two roll mill and the internal mixer. Curing (Vulcanising) The final step in processing is the vulcanization or curing of the shaped product. In curing stage. The choice of the base polymer and the additives is closely linked to the type of properties to be achieved. transfer or injection. the curing or vulcanizing agents incorporated in the rubber compound reacts with rubber and forms crosslinks. calendaring and moulding. internal mixer is widely used.A technical vulcanisate is made up from the following ingredients. often an inline continuous system. the process is that of applying heat at a certain temperature for a certain time. There are three general shaping processes: extrusion. . In shaping operation. COMPOUNDING INGREDIENTS A rubber compound is obtained by mixing a base polymer or crude mixture with a series of additives. After shaping. which will convert the compound into the final product with required properties. Shaping Shaping operation is carried out after mixing. The first two are followed by a curing stage.
3. the ultimate properties like hardness and elasticity depend on the course of the vulcanization. 4. Base polymer or blend of polymers Cross linking agents Accelerators of cross linking agents Accelerator modifiers (activators and retarders) Antidegradants (antioxidants. 5. The reasons for the use of plasticizers are: improvement of flow of the rubber during processing. Plasticizers Besides fillers. Colouring materials (organic and inorganic) 10. softeners. UV light and oxygen. reinforcing and non-reinforcing fillers. and extending oils) 9. influence on . dispersing aids. protective waxes) 6. plasticizers play the biggest quantitative role in building a rubber compound. These vulcanizing agents are mostly sulphur or peroxide and sometimes other special vulcanizing agents or high energy radiation. This is also the reason why most rubbers are black. Diluents (inert mineral fillers. factice and lubricants) 8. plasticizers. tackifiers. Processing aids (chemical peptisers for polymers. Reinforcing fillers (black. Accelerators Accelerating agents increase the rate of the cross linking reaction and lower the sulphur content necessary to achieve optimum vulcanizate properties. Vulcanizing agents are necessary for the crosslink formation. Calcium carbonate is an example of non-reinforcing filler. mineral and organic) 7. Activators Like zinc-oxide and stearic acid. Carbon black is commonly used as reinforcing filler. improved filler dispersion. fibrous materials) Crosslinking agents (Vulcanising agents) Vulcanization is the conversion of rubber molecules into a network by formation of crosslinks.1. They activate the vulcanisation process and help the accelerators to achieve their full potential. Since vulcanization is the process of converting the gum-elastic raw material into the rubber-elastic end product. antiozonants. organic materials. Fillers There are two types of fillers. inhibitors of metal catalyzed oxidation. Antidegradants These agents increase the resistance to attacks of ozone. fungicides. 2.Specific additives (blowing agents.
Silicone can be coloured easily without loss of properties. Open mill (Two roll mill) An open mill consists of twin counter-rotating rolls.g. Factice are added to control die swell. Rubber compounding is generally carried out on open mills or internal mixers. After the mixing operation is complete. particularly in vulcanisation. Additives are added in carefully weighed quantities during the mixing process.: Renacit IV (Zinc salt of pentachlorothiophenol). Processing aids These are chemicals added to the compound that improve the processability. that provide additional mechanical working to the rubber. the compound is removed from the mill in the form of sheet. Ethylene oxide condensate etc. The rolls can be heated or cooled as necessary. Specific additives Blowing agents: DNPT. Colouring Materials-Pigments Organic and inorganic pigments are used to colour rubber compounds. Mineraloils and paraffins are widely used as a plasticizer. Zinc borate etc. Peptisers are used to increase the efficiency of mastication of rubbers. Each component has a different mix of ingredients according to the properties required for that component. The colour pigments are also considered inactive fillers. Sodium Carbonate etc. . Antistatic agents: Quaternary ammonium salts.the physical properties of the vulcanizate at low temperatures. improve surface quality and prevent distortion of shape. one serrated. E. Flame retardants: Antimony trioxide. RUBBER COMPOUNDING MACHINES Compounding is the operation of bringing together all the ingredients required to mix a batch of rubber compound. The rubber is placed on the rolls and mixing is achieved by the shearing action induced at the “nip” between the rolls. Only silica’s have a reinforcing effect.
so both rotor sand housing are water-cooled to maintain a temperature low enough to assure that vulcanization does not begin. The mixing can be done in three or four stages to incorporate the ingredients in the desired order. .Internalmixer Internal mixers are often equipped with two counter-rotating rotors in a large housing that shear the rubber charge along with the additives. The shearing action generates considerable heat.
equipped with a heating system. The mould is opened and the part is removed for necessary secondary operations . A pre-weighed amount of the compound is placed into the lower half of the mould. The method uses a split mould mounted in a hydraulic press Compression moulding process involves the following steps: 1. The compound may be in form of putty-like masses or pre-formed blanks. 2. The mould. pressing on the compound and forcing it to fill the mould cavity. provides curing (cross-linking) of the Compound 3. Major techniques are: Compression moulding Compression moulding is a process in which a compound is squeezed into a preheated mould taking a shape of the mould cavity and performing curing due to heat and pressure applied to the material.SHAPING OPERATIONS RUBBER MOULDING Moulded rubber parts can be produced by different manufacturing methods. The upper half of the mould moves downwards.
The screw of the injection moulding machine is called a reciprocating screw since it not only rotates but also moves forward and backward according to the steps of the moulding cycle. The main difference between the two machines is in screw operation. The mould is equipped with a heating system providing controlled heating and vulcanization of the material. The material is then conveyed forward by a feeding screw and forced into a split mould. and sheet). . The method is profitable in mass production of large number of identical parts. rod. The compound is held in the mould until the vulcanization has completed and then the mould opens and the part is removed from the mould.The rubber material in form of strips is fed into an injection moulding machine. A principal scheme of an injection moulding machine is shown here. An injection moulding machine is similar to an extruder. Injection moulding is a highly productive method providing high accuracy and control of shape of the manufactured parts. filling its cavity through a feeding system with sprue gate and runners. It acts as a ram in the filling step when the compound is injected into the mould and then it retracts backward in the moulding step. In the extruder type the screw rotates continuously providing output of continuous long product (pipe.Injection moulding Injection moulding is a process in which the compound is forced under high pressure into a mould cavity through an opening (sprue).
. The method combines features of both compression moulding (hydraulic pressing) and injection moulding (ram-plunger and filling the mould through a sprue). Scrap of vulcanized rubber is not recyclable. in the sprue and in the channels is removed.The scrap left on the pot bottom (cull). taking a shape of the mould cavity and performing curing due to heat and pressure applied to the material. The method uses a split mould and a third plate equipped with a plunger mounted in a hydraulic press. The picture below illustrates the transfer moulding process.Transfer moulding Transfer moulding is a process in which a pre-weighed amount of a compound is preheated in a separate chamber (transfer pot) and then forced into a preheated mould through a sprue.
various types of additives and fills like curing agents. the compound including polymers. antioxidants. RUBBER EXTRUSION In the extrusion process of rubber. Because of this the part cross-section becomes larger than the die cross-section. . The die is a sort of metal disk that has a machined opening in the desired shape of the part that needs to be extruded.The transfer moulding cycle time is shorter than compression moulding cycle but longer than the injection moulding cycle. The method is capable to produce more complicated shapes than compression moulding but not as complicated as injection moulding. a) soften b) mix c) pressurize the rubber as it is fed continuously to the die at the extruder exit. The extruder typically consists of a rotating screw inside a closely fitted heated barrel. pigments are fed into the extruder. The primary purpose of the extruder is to do three things. The rubber already softened by heating is then forced by the rotating screw through the die opening into the shape of the profile cut in the die. The part cross-section depending on the material may rise up to several folds over the die. A typical phenomenon called die swell takes place as the rubber shape leaves the die.
Different Calender configurations are shown below. or on the most modern calenders. an inverted L. The rolls rotate to produce sheeting and. A calendar comprises a large number of rolls or bowls held in a framework. This aids the rubber extruded profiles to maintain its shape and acquire necessary physical properties. modern three roll calenders may have an offset top roll instead of vertical configuration. hoses. The rubber industry normally uses three or four rolls and occasionally for rough gauge sheeting. While two rolls are normally vertical. Calendering is used to produce (1) sheet and film from thick polymer sections and (2) to embed polymeric materials into textile structures. by adjusting the distance apart of the rolls. strips and cords. The offset top roll assists the feeding of the calender from a feed strip. a two roll calender. a Z configuration on the rolls. Four roll calenders can have a vertical.Subsequently the processes of vulcanization or curing takes place as the last step in the extrusion process. CALENDERING The calendar is an important processing machine in polymer processing industry including both rubber and thermoplastic materials. Typical examples of extruded rubber parts are profiles. .