Third Session: Preparation, properties and uses of Teflon Preparation: By polymerization of water, emulsion of tetraflouroethylene under pressure in presence

of benzoyl peroxide as catalyst. n(CF2=CF2) -(CF2 CF2)- n Tetraflouroethylene Teflon (PTFE) Properties: High Chemical resistance towards all common chemicals. The presence of the most electronegative element F atoms and the regular configuration results in a very strong attractive force between the different chains. So Teflon is resistant to chemicals making it an inert polymer. Low co efficient of friction, waxy touch (not wetted by water/oils). The molecules of Teflon are among the largest ones and its surface is so smooth and polished that no substance would stick on it. High thermal stability, good mechanical strength High density (2.3g/cc), high MP(~350C) High degree of crystillanity (93%); good electrical insulating properties. Uses: As insulating material insulation of motors, generators, transformers, cable wires, fitting. Autistic applications Non-sticking stop cocks for burettes, bakery trays, frying pans, food processing equipment. Anticorrosive coatings for making army weapons, pump parts, tank linings, chemical carrying pipes and tubings. Non Lubricating bearings Good material for bearings and artificial joints coated with PTFE. Nylon 6,6 Preparation Sequential reaction of two dysfunctional molecules nNH2-(CH2)6-NH2 + NCOOH-(CH2)4-COOH [-NH-(CH2)6-NH-CO-(CH2)4-CO-]n + nH2o Hexamethylene diamine plus Adipic acid, when heated to 280C gives polyhexamethylene adipate or Nylon 6,6 Properties: High temperature stability and high MP(~250C) Good abrasion resistance Have good mechanical strength depending on the degree of crystallinity Flexible and retain original shape after use Insoluble in common organic solvents, but soluble in phenol and formic acid It has got a long life

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Uses: For fibers to manufacture textiles, socks, shoelaces, swimsuits, raincoats, carpets) High tensile strength, water resistant non absorbent, semi elastic and dry quickly. Nylon melts on high temperature so iron from the wrong side with a press cloth. Synthetic fabrics burn faster and then melt and cling to the body in the event of a fire. For molding purposes: gears and bearings, combs, dishware and machinery parts. High impact strength and resistance to abrasion, nylon bearings and gears perform quietly and need no lubrication. Filaments for mountaineering ropes, bristles for toothbrushes, parachutes, insect screening, strings for tennis rackets etc. Molded nylon is also used for wire insulation, tyre-cods of automobiles, appliance parts. PF resin (bakelite) Preparation: By condensing phenol with formaldehyde in the presence of acidic/alkaline catalyst, the initial reaction results in the formation of ortho and para hydroxyl methyl phenol, which reacts to form linear polymer, novolac {Phenol (Xs) + formaldehyde novolacs ==.Heat TS plastic. Phenol + CH2)(X5) Resoles Heat, curing agent TS plastic}

During molding, hexamethylene tetraamine [(CH2)6N4] is added that provides HCHO. This converts the soluble fusible novolac to hard, infusible and insoluble solid ofcross linked structure

Cross linked polymer bakelite (turned resole resins) Properties It is rigid, hard, scratch-resistant, infusible, water-resistant, insoluble solid. Resistant to non-oxidizing acids, salts, organic solvents. Excellent electrical insulating properties Uses For making molded articles like telephone parts, cabinets for TVs and radios Electrical insulator parts, switches, plugs, switch boards, heater handles. As an adhesive for grinding wheels In paints and varnishes Epoxy Resins [Araldite] Preparation: Polycondensation of bisphenol and epichlorohydrin with elimination of HCl to give a 3D cross linked structure. Molecular weight reanges from 350 (a mobile liquid) to 8000 (high melting solid)

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Properties: High flexibility It is tough and heat resistant Excellent adhesive quality Uses As surface coatings, adhesives like araldite For skid resistant surfaces on highways For molding components of aircrafts, automobiles Applied over cotton, rayon for shrinkage control As laminating material

Elastomers Elastomers Polymeric material strength (large elongation 500 1000%) when force is applied. Return to their original shape upon removal of distorting force [exhibit elastic behavior when subject to stretching or bending within elastic limit] eg rubber. Relaxed state of rubber band, coiled polysoprene chains held together by cross links. Stretched state of rubber band: Polymer chains straighten out to the extent the cross links allows. Returns spontaneously to its original shape due to inverse in entropy.

Characteristics of Elastomers Have highly coiled structure unstretched rubber is amorphous Have high dergree of elasticity [>300%] can be stretched like a spring marcromolecules getpartially aligned with respect to another causing crystallization. Rubber band can be stretched to 4-10 times its original length Can retract rapidly chains get reverted back to their original coiled state and the material becomes amorphous again Cross links (inter-chain cohesive forces) connect the chain in elastomers (rubber) upon stretching. The (cross links prevent any further motion of one chain with respect to another.

Natural Rubber A resilient, elastic substance obtained from a variety of unrelated, latex producing, and tropical trees. Raw rubber is obtained from the milky latex extracted from the trees as a response to injury. Latex is collected by making series of spiral cuts halfway around the circumference of the trunk, allowing the fluid to collect in cups. Latex during treatment polymerises to form long coiled chains of cis-polyisoprene (natural rubber).

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Gutta percha obtained from the mature leaves of gutta trees. (Malaya and Sumatra) Used in the manufacture of golf balls, submarine cables, adhesives, issures for surgical purposes Malaysia worlds largest produces of rubber Drawbacks of natural rubber Hard and brittle at low temp where as soft and sticky at high temp Low TS (200kg/cm^2) and sticky, which is difficult to handle Sensitive to oxidative degradation by agents like HNO3 and chromic acid Swells considerably and gradually and disintegrates in organic solvent High water absorption capacity It undergoes permanent deformation if stretched to a great extent because of sliding and slippage of certain molecule chains over each other Virgin rubber is as useless as pure gold Both are soft and have very low strength Vulcanization Process of heating raw rubber mixed with sulfur to 100 150C for 1-4hrs to promote a certain degree of cross linking between chains. The sulfur cross links are introduced between polymer molecules of rubber. The vulcanized rubber is stiff and the extent of stiffness depends on the amount of sulfur added. The rubber would be harder and less flexible as the percentage of sulfur increases due to increased degree of cross linking. Which covalently bond the polymer chains together. Thus vulcanization is the modification of the properties of rubber by chemical treatment mainly with sulfur. Eg tyre rubber 3-5%sulfur, Ebonite hard and rigid rubber. (black material) high proportion. Vulcanization process

Application of rubber Insulating coatings on wires Rubber bands, golg balls, automobile/aero plane/bicycle tubes and tyres Shoe heals and soles, conveyer belts Rubber lined metal tanks, vessels used in chemical industry Rubber hoses for transmission of petrol, oil, water Hard rubber storage of battery cases, switch boards, panels Sponge rubbers, for shock absorption, thermal insulation Foam rubber bed pillows, mattresses, cushions Rubber gasket for sealing cookers and refrigerator doors Heart valves, transmission tuber

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Advantages of vulcanized rubber The cross linking gives good TS Have excellent resilience (elasticity) Possess low water absorption tendency Higher resistance to oxidation Higher resistance to wear and tear/ abrasion resistant Better electrical insulator and low thermal conductivity Ease of fabrication to produce desired shape Because chains are linked together, vulcanized rubber does not soften as much as normal rubber as the temp is raised useful temp range -40 to 100C Low elasticity depends on the cross linking. (High percentage of sulfur results in hardest and strongest form of rubber much more resistant to deformation when stretched, because the cross links pull it back) Resistance to the action of H2O, bases and dilute acids and organic solvents. It is more durable when exposed to the weather. (Concentrated acid reacts with rubber and destroys it) Compounding of rubber Mixing of raw rubber with other substances to impart product specific properties for particular applications 1. softeners and plasticizers: to provide greater resilience and adhesion for easy processing eg vegetable oils waxes, staric acid, ester plasticizers 2. vulcanizing agents: To give mechanical strength. Sulfur percentage varies between 0.15 to 32. other agents sulfur monochloride, h2S benzoyl chloride, trinitrobenzene, benoyl peroxide 3. Accelerators to shorten the time required for vulcanization and of cure of the compounded rubber -2- metacaprel, thiocarbonates, thiozoles 4. Antioxidants to retard the oxidation of rubber and thus check deterioration phenyl napthalamine, phosphates. 5. Reinforcing pigments: To give strength and rigidity and to lower the cost. Carbon black, zinc oxide, calcium carbonate, titanium dioxide is used 6. Coloring matter to impart the desired color. White products TiO2, colored products calcium oxide (green), ferric oxide (red), lead chromate (yellow) 7. Process: Properly weighted amounts of ingredients are mixed and then kneaded to make the final rubber uniform, soft and plastic using roll mill. The roll mill consists of parallel / horizontal hollow rolls rotating in opposite direction. Hot / cold water can be circulated in rolls to maintain the desired temp. During this process, the material is softened by continuous break down. After several passes through the mill, rubber forms a sufficient coherent, plastic and soft mass suitable for use for specific purpose.

Synthetic Rubber SBR (styrene butadiene rubber) Preparation: By copolymerization of butadiene (75 parts) and styrene (25 parts). The monomers are emulsifies in water using soap or detergent. The retain is initiated by peroxide initiators like Cr2O3 + Al2O3 Kunal Page 5 MIT-Bugz.com

n(CH2=CH-CH=CH2) + n(CH2=CH(C6H5))

-[CH2-CH=CH-CH2-CH(C6H5)]-n

ie 1,3 Butadiene plus styrene yields Polybutadie coherene Properties of SBR High abrasion resistance High load bearing capacity and resilience Heat fluid up under heavy loading Oxidized in the presence of traces of ozone in the atmosphere Swells in oil and organic solvents Uses: Manufacture of car, scooter, motorcycle tires and tuber either by itself or as high percentage of blend with natural rubber Mechanical goods, floor tiles, foot ware components, gaskets, electrical insulation(wire and cable insulators) adhesives Used in chewing gum What is silicon rubber [ SR polymer containing alternating oxygen and silicon atoms] SR is a unique synthetic elastomers made from a cross linked polymer which is reinforced with silica. It is a polymer that has a back bone of silicon oxygen required to vulcanize the silicone rubber. This is normally carried out in a two stage process at the point of manufacture into the desired shape and then in a prolonged post cure process Preparation: dimethyl silicon hydrozides polymerize to give silicon rubbers, long chains polymers arising from intermolecular condensations. They can be vulacanized by organic peroxides. (1-3%) benzoyl peroxide. To from cross links between two neighboring chains. Peroxide causes the formation of dimethyl bridges between methyl groups of adjacent chains. Free radical capture h atom from methyl group of adjacent linear molecules. Thus formation of ethylenic bridges. It is not vulcanized by normal sulfur as the reaction is extremely slow even in the presence of a catalyst. Properties High and low temp stability (thermal stability), inertness (oxidative stability), their strength and inertness are related to two factors. 1) Their stable silica like skeleton of Si-O-Si-O-Si; the Si-O bond energy is very high (502 KJ/mole) 2) The high strength of the Si-O bond Wide hardness range, chemical resistance (oils, hot water, oxygen, dilute acids and alkaline), exceptional resistance to weathering (weatherability), prolonged exposure to sunlight (UV radiation), excellent electrical insulators. Silicone rubber flows very easily and as a result can be molded using relatively low amount of energy. Extremely easy to fabricate, particularly when compared to conventional organic elastomers Complete physiological inertness (highly biocompatible polymers) and excellent water repellency

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Depending on the length of the chains and the degree of cross linking between chains, silicones can be either oils or rubber like materials. (Silicone elastomers) Silicone is non toxic. No taste or smell, translucent and easy to color.

Silicone rubber as organic rubber Silicones have many unique proper uses which most organic elastomers are unable to copy. One excellent example is the wide operating temp of -100 to 500C. In such conditions, its tensile strength, elongation and compression can be far superior to organic rubber. This makes silicones excellent for many automotive and industrial applications Unlike many organic rubbers, which may only be available in black or pastel shades, silicones can be transparent or brightly colored enabling them to properly match many applications Silicones have no taste or smell, they are nitrosamine free and many grades are suitable for food contact Organic rubber has carbon to carbon backbone. This can leave them susceptible to ozone, UV heat and other ageing factors. Silicone rubber is the best material in extreme industries Applications Once milled and coated, silicone rubber can be extruded into tubers, strips, sonic cords or custom profiles within the size restrictions. For insulating electric lining in strips and washing machines Making artificial heat valves and transfusion tubing and surgical implants. The silicones are biologically intact when exposed to body fluids, they dont coagulate blood and do not stick to body tissues Widely used as industrial sealants and greases, where their water repellent properties are useful, as adhesives in electronic industry, burette tap, car polishes Their water repellent property brings them to be used in fabrics used in rain water. Silicones are used to waterproof fabrics because their O atoms attach to fabric surface, leaving hydrophobic methyl groups to repel water Anti rubber Prepared from polymer foam compressed and heated to slightly above its softening point, then cooled to room temp and released Reclaimed rubber Its the recovered rubber in a unstable condition from worn out articles and rubber waste from factories Process Waste rubber material is sent into small pieces and powdered by using a cracker Iron containing impurities are removed by electromagnetic method The purified waste powder rubber is heated at about 200C in a closed iron vessel with aqueous solution of Na ion to remove the fabric and the rubber gets de vulcanized due to reversal of S as alkali sulphide. Kunal Page 7 MIT-Bugz.com

Rubber is washed in water and dried Mixed with small quantity of reinforcing agents, like clay, C black incorporated with a compound of fresh rubber

Properties Possesses lower TS and elasticity, lesser wear resistance Much cheaper uniform composition and better ageing properties Easily fabricated Uses Manufacture of tires and tuber, floor mats, belts, shoes etc

Corrosion Is spontaneous destruction/ deterioration of a metal or alloy by the surrounding environment through chemical or electrochemical interaction.

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