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POLYMERS AND PLASTICS

Introduction
Polymerisation:
Polymers are macromolecules of high molecular weight which are formed by linkage between large
numbers of small molecules called monomers, eg. Polyethylene is made up of the monomers ethylene.
H H H H H H
| | | | | |
n C = C →− − − C − C − C − C − − −
| | | | | |
H H H H H H
ethylene polythene

There is no limit to theoretical length of the polymer, but the polymer ceases to grow for many
practical reasons. The number of repeating units in a polymer is called the “degree of polymerization”.
Classification of Polymers:

1. Classification based on source of availability : They are classified as
a. Natural polymers
b. Synthetic polymers
c. Semi-synthetic polymers

(a) Natural polymers : The polymers obtained from nature (plants and animals) are called natural
polymers. These polymers are very essential for life. They are as under.
i. Starch: It is polymer of glucose and it is food reserve of plant.
ii. Cellulose: It is also a polymer of glucose. It is a chief structural material of the plant both
starch and cellulose are made by plants from glucose produced during photosynthesis.
iii. Proteins: These are polymers of a-amino acids, they have generally 20 to 1000 a amino
acid joined together in a highly organized arrangement. These are building blocks of
animal body and constitute an essential part of our food.
iv. Nucleic acids: These are polymers of various nucleotides. For example RNA and DNA
are common nucleotides.

It may be noted that polymers such as polysaccharides (starch, cellulose), proteins and nucleic acids etc.
which control various life processes in plants and animals are also called biopolymers.

(b) Synthetic polymers : The polymers which are prepared in the laboratories are called synthetic
polymers. These are also called man made polymers. For example polyethene, PVC nylon,
teflon, bakelite terylene, synthetic rubber etc.
(c) Semisynthetic polymers : These polymers are mostly derived from naturally occurring
polymers by chemical modifications. For example cellulose is naturally occurring polymers,
cellulose on acetylation with acetic anhydride in the presence of sulphuric acid forms cellulose
diacetate polymers. It is used in making thread and materials like films glasses etc. Vulcanized
rubber is also an example of semisynthetic polymers used in making tyres etc. gun cotton which
is cellulose nitrate used in making explosive.

Semi-synthetic polymers : Rayon and other cellulose derivatives like cellulose nitrate, cellulose acetate
etc., are semi-synthetic polymers. These are thermoplastic polymers. Viscose rayon in the form of a thin
transparent film is known as cellophane. Cellophane is softened with glycerol. Unlike plastic sheets it
absorbs water.
Rayon : Rayon is a man made material which consists of purified cellulose in the form of long fibres.
Cellulose is treated with cold NaOH solution to purify it and then treated with CS2 to form a viscose
solution. This is why rayon is sometimes called viscose rayon. This solution is allowed to pass through
fine pores in metal cylinder, into a dilute solution of H2SO4. This results in the formation of long fibres.
Rayon fibre is chemically identical to cotton but has a shine like silk. As such rayon is also known as
artificial silk. Rayon is used on a large scale for making textiles, tyre-chord, carpets and surgical
dressings. Unlike fully synthetic polymers, it absorbs moisture and is bio-degradable.

Tacticity

Polymers with regular substituents on the polymer chain possess a property known as tacticity (from the
Latin tacticus, fit for arranging). Tacticity results from the different ways in which the substituents can be
arranged on the polymer backbone (see figure below).

Atactic
polypropylene

no arrangement). Eraser rubber. the same arrangement). are highly crosslinked in order to reduce the leaking of air out of the tire and to toughen their durability. Among other applications. When the substituents are all on the same side of the chain. Higher functionality yields branched or even crosslinked or networked polymer chains. the polymer is syndiotactic. the polymer is atactic (literally. Crosslinking tends to increase Tg and increase strength and toughness. for example. A polymer molecule with a high degree of crosslinking is referred to as a polymer network. the polymer is isotactic (literally. Car tires. A cross-link suggests a branch point from which four or more distinct chains emanate. The basic functionality required for forming even a linear chain is two bonding sites. If the substituents alternate regularly from one side of the chain to the other. this process is used to strengthen rubbers in a process known as vulcanization. is not crosslinked to allow flaking of the rubber and prevent damage to the paper. in which networks of chains are of unlimited extent—essentially all chains have linked into one molecule. on the other hand.Sufficiently high crosslink concentrations may lead to the formation of an infinite network. . also known as a gel. This property of a monomer is defined as the number of reaction sites at which may form chemical covalent bonds. Syndiotactic polystyrene Isotactic poly(vinyl chloride) When the substituents are arranged in an irregular. An effect related to branching is chemical crosslinking the formation of covalent bonds between chains. Functionality of Polymer The architecture of the polymer is often physically determined by the functionality of the monomers from which it is formed. random fashion. which is based on crosslinking by sulfur.

e. CHZZCHY (YZX. Head to head type —CHYCH2—CH2CHY.CH2 CH2CHYCH2 CHY ---— Mechanism of addition polymerization: (a) Free radical polymerization is the first type which involves the following steps: Initiation: The first step of which involves two reactions. M* + CH2 = CHY —+ M-CH2CHY* Continuous addition of new monomer in this manner will finally produce a polymer chain in which the substituents are located on alternate atoms. (iii) Collision between a growing chain with impurities. − CH − C • + •C − → − CH − C + C − CH 2 | | 2 | | 2 H H H H (ii) Collision of a growing chain with an initiator radical when the latter is proportionately in excess. Propagation: The mechanism of propagation is the reaction of the radical M* with its own monomer M. 2R● + M → M* Free radical + Monomer The M* is the initiator radical or primary radical. A variety of peroxides act as initiator such as benzoyl peroxide. There are three ways of addition polymerization: 1. COZR.e. Terminations: The most common terminations are the effect of (i) Collision between two growing chains H H H H | | | | i. The first is the spontaneous decomposition of an initiator into free radicals. these monomers having double or triple bonds polymerize without the liberation of small molecules. The next part of initiation involves the addition of this radical to the monomer molecule (M) to initiate the chain. Sometimes the chain length of the polymer is . Random type —CHYCH2 CHY... Head to tail type —CH2CHY—CH2CHY—CH2CHY --- 2. i. CN etc.) undergo polymerization. tertiary butyl hydro peroxide etc.CHYCH2CH2 ---- 3.Polymerisation Processes: Mechanism of Addition Polymerisation: Monomers (M) having the general formula.

H H H H H | | | | | • • − CH − C + C − CH − → CH − C + C = C − 2 | | 2 2 | | H H Y Y (b) Ionic polymerization is an important class of addition polymerization which also involves the steps of initiation. Presence of polar groups along the chain length also increases the intermolecular forces and increases the strength of polymer. Solubility and chemical resistance Polymers containing polar groups are more soluble in polar solvents like water. brittleness and strength of the polymer. Polymers of low mol. thermoplastic and thermosetting qualities of polymer depend on structure of the polymers. alcohol but are . Very long chain polymers having free rotating groups form irregularly coiled and entangled snorts. Artificially creating crosslinking converts thermoplastic material into thermosetting. But higher-chain length polymers are tougher and more heat resistant. are soft and gummy but brittle. propagation and termination but here. Hence. The amorphous nature of polymer provides flexibility. the unstable intermediates are either cations or anions. greater rigidity. The regular arrangement increases the intermolecular forces of attraction and leads to higher softening point. three dimensional structure and they are strong and tough as the movement of inter molecular chains are totally restricted. by disproportionation an H atom of one radical is transferred to another resulting in two polymers—one saturated and the other unsaturated. More rarely. wt. Influence of structure of polymer on its properties Strength of polymer In cross-linked polymer. even for very high molecular weight. instead of free radicals. which can be stretched and again returned back to its original state giving rise to elastic character to the polymer. Three-dimensional polymer molecules are insoluble in any conventional solvent and are thcrmosetting. Plastic deformation Polymers consisting of linear-chain molecules are always soluble and thermoplastic. Strength of straight chain polymers depends on the chain length. Physical state Random arrangement of molecules in the polymer leads to amorphous state whereas regular arrangements of molecules or chains in a polymer lead to crystalline state.controlled by deliberately adding inhibitors. the units are linked by interchain covalent bonds forming giant.

particularly the greater the degree of cross-linking. PLASTICS Plastics are a class of high polymers which can be moulded into any desired form by heat and pressure.1. . molecules become bulky. 4. Similarly. form random arrangement and show rubbery character. fibres. Effect of heat Behaviour of polymer is controlled by the temperature. On increasing strain continuously ultimately the polymer chains are uncoiled and fully stretched called necking and after this point the polymer reaches its break point and yields. less is the solubility of the polymer in a solvent. Fig 4. Amorphous polymers. Shapes and forms—mechanical properties The internal arrangement of the long-chain molecules provides the forms in which the polymer may form i. the glass transition temperature is reached (Tg) after which they soften..e. lf the internal forces between the molecules are low.1: Four types of stress—strain curves illustrating how polymers of different types behave (the lines end where the sample breaks) The strength of the polymer is controlled by the length of the polymer chains and its cross-linking. Strength of a polymer is estimated from typical stress-strain curves for different polymers as shown in Fig. toluene. But the crystalline polymer on heating above T g shows thermoplastic behaviour and finally liquefies.chemically resistant to non-polar solvents like benzene. non·polar group containing polymers are chemically resistant to polar solvents but are soluble in non·polar solvents. If the internal forces are high they ultimately give rise to orderly arrangement and form fibrous nature. CCl 4 etc. Amorphous polymer becomes rubbery and then gummy and on further heating it liquefies. which do not have melting point have softening points. At very low temperature both the crystalline and amorphous polymers behave like glass and on heating. plastics and rubbers. Intermediate forces lead to plastic nature.

Thermoset. FRP is very strong and can be used to make gates of dam. tensile strength. corrosion-resistant pipes and tanks. c. hence repeated heating and cooling also does not alter its nature. colours are added to them. The process of mixing these additives to virgin plastics is called Compounding. Thus. Plasticizers: Plasticizers are small molecules which penetrate into the polymer matrix and neutralize a part of the intermolecular forces of attraction between macro. jeep bodies. There are two classes of plastics or resins. Thermoplastic resins soften on heating and harden on cooling and this change is not chemical but physical in nature. d. finish and workability.Resins are actually the binders used for plastics and these two terms are used synonymously. which binds all the additives together. Fillers: Fillers can modify the properties of plastics to give the final plastic. Resin is the binding constituent. 2. Soluble organic dyes are added to the transparent variety and inorganic pigments are added to the nontransparent plastics. hence the setting is permanent and irreversible.molecules and increase the mobility of the polymer segments so that chains can slide over each other. To give UV protection to the colours some . cotton fibre. which actually form crosslinking during the moulding process in presence of catalyst. Percentage of fillers may vary and can be upto 50%. plasticizers act as an internal lubricant and improve the plasticity and flexibility of the polymer. stearates and soaps are used to improve the finish and reduce the sticking tendency of the plastic to the moulds. camphor. chopped rags impart improved mechanical strength to the plastic. Thermosetting resins are those which are heated during moulding and heating is continued until is set and hardened. safety helmets. Colouring materials: To improve the appeal and to impart beauty to the finished materials. Plastics embedded with these mats are known as fibre reinforced plastics (FRP). Fibrous fillers such as wood flour. PVC laminated to steel or aluminium are called ‘Composites’. This hardened material cannot be softened again. Compounding Plastics for manufacturing of finished articles are always mixed with 4-10% of other materials. asbestos increases heat resistance. which impart some durable properties to the moulded material. compressed to produce a glass mat. b. Additives and their functions are discussed below: a. Waxes. oils. better hardness. Solidified filaments of glass are bundled into strands.ting resins are added as linear low molecular Weight polymers. Commonly used plasticizers include vegetable oils. 1. dibutyl/dioctyl phthalate etc. e. mica or slate powder improves electrical properties. These materials are known as additives which not only impart some properties to plastics but also make the processing easy.

Polyethylene is manufactured by gas-phase polymerization. LDPE has a branched structure and hence is flexible and tough. Two types of polyethylenes are available—LDPE (Low density polyethylene) and HDPE (high density polyethylene). Pb chromate etc. f. Important Thermoplastic resins Polyethylene Polythene is polymerised ethylene. Cu. benzoyl peroxide. Other additives: Sometimes antioxidants are added to prevent oxidative degradation of polymers. insulator parts. white. translucent non-polar material. greater rigidity but low impact strength and it is opaque and relatively brittle. gr. caps. are added to accelerate the cross-linking of the thermosetting plastics while they are in the moulds. . are added to improve the thermal stability of polymers during processing. HDPE is a completely linear polymer. Ethylene is colorless gas at ordinary temperature. Catalysts like HZOZ. Uses: Polythene sheets. waxy. HDPE is produced by using low pressure methods (31 kgf/c 2) using ionic catalysts whereas LDPE is produced by using high pressure methods (1050-2000 kgf/cm2) using free radical initiator. lndustrially dehydration of ethyl alcohol is the process for ethylene production*. It is prepared in the lab by dehydration of ethyl alcohol at 160°C with concentrated H ZSO4. Polyethylene has highly symmetrical structure so it crystalizes easily. Properties: Polyethylene is a rigid. It has low sp. It has low hardnessie. lt is also used to prepare toys. are added to dissipate the electric charge developed by conducting it away. coated—wires and cables. bags for packing. Ag. which are used for domestic purpose. particularly kerosene. which comes out from the perforated bottom of the vessel.. Pb-silicate. it has better chemical resistance. The ethylene gas is compressed to 1500 atmosphere and passed through a reactor maintained at 200°c in the upper and 120°C in the lower parts. Antistatic agents like amines. tubes are manufactured. Pb etc.01%) or peroxides act as catalyst. about 1/10th of bakelite.. Stabilizers like Pb.. O2 (0. higher softening point. The degree of crystallinity varies from 40-95% depending on degree of branching. alkalies and salt solutions. Ethylene is polymerised into polythene. amides etc. NH 3. The unreacted gas is recycled. a waxy solid. ZnO. good insulating property but it is susceptible to organic solvents. It has good chemical resistance against acids. compounds are added which preferentially absorb UV light. bottles.

Polymerize nCH 2 = CHCl → − ( CH 2 CHCl) n − PVC Properties: PVC is a colorless. The polymer is obtained in the form of fine powder and is soluble only in special solvents like dibutyl phthalate. apparels etc. Polypropylene is also an isotactic.t. for making sterilizable hospital equipments. moulded luggage. under pressure and in presence of benzoyl peroxide as catalyst. rexin. Uses: Fibres of polypropylene are very strong and hence fibres are used for making ropes.r. odorless.. It is also used for packing of pharmaceutical and cosmetic products. It is lightest among all high polymers. It has high rigidity and chemical resistance but brittle. its use is mainly in making cables. It is superior to polyethylene w. refrigerator components. .9°C) can be done in solution. organo- metallic halide with transition metal halide. It is resistant to water. emulsion and in suspension. toys. hardness. resistance to chemicals. chemically-inert powder. non-flammable. Polytetrafluoroethylene (TEFLON) It is obtained by polymerization of water-emulsion of tetrafluoro ethylene. O2. benzyl benzoate etc. moisture proofing quality etc. tyres. cycles and motor cycle mudguards etc.Polypropylene Polypropylene is obtained by polymerizing propylene in presence of Ziegler-Natta Catalyst i. Uses: It is the most widely used plastic. pipes of petroleum industry. radios. blankets. carpets. washing machine parts.e. Polymerize CH3CH = CH2 → [CH3CHCH2]--n Properties. 13. oil. petrol etc. bags.p. water hoses. so. highly crystalline polymer. inorganic acids and alkalies.. It contains 53-55% Clz and softens at around 80°C. TV. HgCl CH ≡ CH + HCl → CH 2 = CHCl The polymerization of the gaseous monomer (b. rain coats. light. pipes. colorful furniture etc. Increased solubility of the polymer is also attained by solution polymerization at high pressure and temperature. strength. but soluble in hot chlorinated hydrocarbons. floor covering. Polyvinyl Chloride (PVC) Vinyl chloride is the monomer for PVC and the monomer is produced by direct addition of HCl to acetylene at 60°C-80°C.

wires etc. lt softens at about 350°C. It can also be used for making gaskets. non-lubricating bearings and to make non-reactive coating. the polymeric material can be machined. cables. Due to all these qualities. is soft. pipes and tubes for chemical industry. Due to the presence of highly electronegative fluorine in the regular polymer structure of TEFLON strong interchain forces are present which give the material extraordinary properties like extreme toughness. tank linings. Properties. transformers. Uses: It can be used for insulating motor. high softening point (350°C). high chemical resistance. pump parts. good mechanical and electrical properties. spongy known as ‘U-foam`. It . low coefficient of friction and waxy touch.Properties. hence at this high temperature it can be moulded applying high pressure. It can he foamed like polystyrene but unlike thermocoal. Polyurethane Polyurethanes are a varied range of crosslinked polymers made from two liquids—a polyol and an isocynate. Non-stick cookware coatings are made of TEFLON.

which improves the appearance and quality of the leather and hence the bags made of these look attractive and the shoes feel comfortable. A coating of polyurethane is applied over leather. Adipic acid is commercially produced by oxidation of cyclohexane derived from either benzene or petroleum. Nylon can be extruded as a heavy ribbon. Hexamethylene is made by final hydrogenation of the adiponitrile. which have a structure similar to that of polypeptides. Adipic acid and hexamethylene diamine mixed in equirnolecular proportions in aqueous solution in an autoclave and heated at 100°C. Its greatest advantage lies in the fact that it can be made where they are needed without any complex machinery—the two liquid ingredients can be mixed and moulded. It is also used to make chairs etc. Nylon fibre is obtained by melt spinning process. The compounds react to form nylon salt in solution. Due to its spongy nature. it is used for making pillows and matresses. Nylon 66 is obtained by the polymerization of adipic acid with hexamethylene diamine. Nylon salt is then heated at 265°C with Dow therm vapours to remove water and molten nylon results. Nylon-66 Polyamides are synthetic polymers. The polymer can be remelted to spin into fibre and can be used for extrusion of molded objects.has low thermal conductivity. having recurring amide groups. Uses. lt is used as insulating material in refrigerators. in an atmosphere of nitrogen which is chilled and chipped. . Nylon belonging to this class is used for making fibres.

Natural rubber Natural rubber is polymerized isoprene. Smoked rubber sheets are made from thicker sheets than crepe rubber. The tough slabs are passed through rollers (embossed or ribbed) to obtain ribbed pattern. undergarments. Rubber coagulates as soft white mass which is washed and further processed. and by allowing the latex stream to collect in a pot attached below the cuts. carpets etc. Elastomers or rubber. Coagulation of the latex: Latex is diluted to contain between 15-20% of rubber. The latex is collected from the mature Havea tree by making deep cuts on the bark. elastic and can be dyed easily. The molecular weight of raw rubber is about 100. which find use in making socks. In releasing the stress the chains revert back to their original coiled state. The crude rubber obtained is translucent and amber in colour . silicone-glass laminates for high temperature application. high temperature insulating foams. The unstretched rubber is amorphous and the polymer chains are in a coiled state. Coagulation is then effected by adding acetic acid (1 to 2% on weight basis). Uses: The polymer can be run directly to spinning machines to produce fibre. The coagulum is converted to a sheet with uneven rough surface resembling crepe paper and called crepe rubber. Coagulation is carried out in large tanks and finally allowed to settle for 16 hours. Smoking is done at a temperature of 45°C-50°C. Nylon possesses high abrasion resistance and is chemically stable.Properties: Nylon is strong.000 and is made from the latex of different plants like Havea brasillians and gangule found in tropical and subtropical countries. hence nylon 66 is primarily used for fibres. It possesses high temperature stability and also high melting (160°C- 264°C). It is insoluble in common organic solvents but soluble in phenol. Tapping is done at intervals of about 6 months.000-150. which on stretching gets aligned causing crystallization. which have elastic properties and can be stretched upto about 300 percent. Silicone resins They are highly cross-linked polymers. Natural rubber came into market first in early 19 Lb century. possess good insulating properties. formic acid. The coagulum is allowed to drain and the absorbed serum is squeezed out through steel rollers upon which water is sprayed. Uses: Used for high voltage insulators. RUBBER Rubbers are high polymers. heat resistance and good dielectric properties. wood or coconut husk is burnt to produce heat. where on the floor. for different electrical and electronic equipment parts manufacturing. which occurs in the latex of various trees. tough. dresses. filtered to make it free from dirt. The embossed sheets are then hung up in a smoking house. whereby the sheets get dried within 4 days.

. Properties. The process of this adhesion is called bonding and the bodies are called adherends. But for decomposition product of rubber i. Limitations of natural rubber Natural rubber softens at high temperature and becomes brittle at low temperature.e. impervious to gases. . When the destructive distillation is carried out at higher temperature the condensate contains mostly the isoprene dimers. metal and plastic etc. 3. For each C5H8 unit in rubber molecule. one molecule each of Br2. On heating it softens and liquifies. Also on excessive streteching it gets permanently deformed. Bonding has several advantages 1. reacts with HCl. isoprene there is two double bonds During the process of linking. quickly and economically. Strong HNQ attacks rubber. It is actually polymerized cis-isoprene. forms ozonide with ozone. O3 and HCl reacts. it is oxidised by air.and is not attacked by micro-organisms. 2. Rubber slowly oxidises when exposed to air. translucent. Natural rubber is an amorphous solid. it is attacked by acids. To overcome these limitations rubber is vulcanized.The common feature of all adhesive joints is the highly uniform distribution of forces over the entire joint area and free from any residual stresses which leads to optimal utilization of material strength compared to rivet and screw joints. It burns to form CO2 and H2O. oxidising agents. head and tail linking of isoprene molecule occurs Rubber is attacked by strong alkalies and oxidising agents. On destructive distillation rubber first softens and then decomposes producing white fumes. thus there is only one double bond. Raw rubber powder catalytically reacts with H2 gas. Adhesives Adhesive is defined as a material that is capable ofjoining bodies together by surface adhesion and internal strength without the structures of the bodies undergoing any changes. elastic in nature.Adhesives are capable of joining numerous materials which cannot be joined by other techniques even those differing widely in type such as glass and metal. non-polar solvents. it decolorizes bromine water.The process of adhesion can be carried out very rationally.

4.Some adhesives set even in relatively thick layers. welding etc. 4. soldering etc. 3. properties and their bond strength decreases with rise in temperature. 6. Adhesion Theories Several different theories have been developed that explain the mechanism of adhesion. so any unevenness of the adherends can be smoothed out during bonding.Adhesives are generally susceptible to higher humilities. Electrostatic theory explains that by contact of the adherend and the adhesive.. 5. metal-faced plywood. 7. Bonding of dissimilar metals with adhesives prevents galvanic corrosion as the metal to metal contact is avoided.Bonding strength is low compared to other joining methods like riveting.The adhesive layer of an adhesive joint can have a vibration—dampening effect. Better composite materials having improved properties than the adherends can be designed by the adhesive bonding ag. 9. 8. Adhesives can introduce electrical and heat insulating layers between the adherends. 5.The usability of adhesives can be restricted when stringent requirements are imposed on the thermal stability on adhesive point. 11.Many adhesives can be applied at room temperature hence the adherends are not exposed to high temperature as in the welding of plastics with metals.There is not available any single adhesive for joining all types of materials and hence judicial selection is of great importance in bonding process. 2.Adhesives require appreciable time for developing their full strength bonding for better performance. 10. transfer potentials are build up which sets up an electrical double layer and the corresponding coulombic attraction forces develop between the two components.Adhesives based on organic polymers show a dependence on temperature in their strength. 6.Some adhesives when subjected to heavy static stress for long periods show a tendency to creep even at room temperature.The after-finishing process in case of bonding is not required as in the case of welding. Mechanical theory of adhesion is based on the anchorage of the adhesive in the porous rough surface of the adherends and hold the surface by interlocking action. The . 7.Adhesive bonding can be utilised to make the material leak-proof for liquids and gases. Adsorption theory regards adhesion as essentially a special property of phase interfaces. Limitation and Restrictions of Adhesive Bonding 1.

By chemical reaction: The reactive low molecular wt. This bond strength can be improved by applying pressure.. None of the above theories explain all the aspects of bonding..Thickness of the adhesive film: Very viscous adhesives produce thick film but do not wet the surfaces properly leaving many voids and hence the bonding becomes weak. In the case of other porous materials like paper. leather etc. 3. The bonding strength can also be increased by adding solvent and/or plasticizer to decrease the viscosity.forces that are responsible for adhesion are the so called secondary valence or van der Waal’s forces. 2. Physical characters of the adhesive film: The bonding strength of the adhesive film is influenced by the following physical characteristics . Diffusion theory explains that adhesion is obtained by the mutual penetration of adhesive and substrate. Adhesive Strength Development 1. permanent adhesion occurs. When this tension becomes minimum.By cooling: Thermoplastic materials are applied to the adherend surfaces in a molten and hot condition which on cooling solidifies developing bonding strength. the large number of capillaries preferentially enclose the liquid portion of the adhesive and disturb the equilibrium distribution of the adhesive on the adherend surface leading to weak joint formation 2. contact in molecular dimensions takes place. 4. By wetting the surface of the adherend with the adhesive. crosslinked three- dimensional polymers with high bond strength. only under pressure. 4. Surface tension: The wetting characteristics of an adhesive depend on its (a) viscosity and (b) surface tension. The solvent gets evaporated and thereby gelling and finally hardening takes place leading to strong bonding between the surfaces.By solvent evaporation: The adhesive is dissolved or dispersed in a solvent and applied to the surfaces to be bonded and they are brought in contact with each other.Smoothness of the adherend surfaces: For wood surfaces smoothness of the surfaces adds to the bonding strength of adhesives. The bonding between the surfaces is better when the surfaces can be uniformly wetted by the adhesive sol which is guided by the interfacial tension between the two. the surface is better wetted. wt. Latest theories consider that bonding of adherend and adhesives takes place due to the chemical or physical forces of attraction. mono and/or oligomeric ingredients of thermosetting adhesives are converted by chemical reaction into high mol. 3.By pressure application: Tacky substances in solvent-free form adhere spontaneously to the surfaces of most materials. Physical factors iniiuencing adhesive strength: 1. when the interfacial boundary energy is lower than the sum of the surface energies of the adhesive and the adherend.

wt. Degree of polymerization best suited for adhesive action is different for different adhesives e. Creep rate—Highly plasticized adhesives have higher creep rates under stress conditions than the rigid thermosetting materials. Less pressure is required in case the adherend surfaces are smooth but in the case of porous surfaces.. temperature and time are the factors that affect this strength after the application of the adhesive. Similarly. addition of polar molecules to the non-polar adhesives increases the adhesive power. But the effects of pH are different in the case of different type of adhesiveseg.When this difference is high the bonding strength weakens under temperature variations. b. products have greater adhesive action. Chemical Factors Affecting the Adhesive Strength 1. 2.. a. Sufficient time is to be allowed so that the curing time be enough to establish a strong bonding. whereas acidic pH increases the bond strength of vulcanized rubber. temperature also affects the process of bonding by allowing the solvent to evaporate. for cellulose derivatives partially degraded low molecular weight products give higher adhesive action. pressure should be applied to join the surfaces together.pH· Strong acids and strong alkalies affect the bond strength of adhesives negatively. Application modes of adhesives: The mode of application of adhesive on the surface to be joined also influences the bonding strength. slightly alkaline pH gives better bond strength in the case of Glue which are protein in nature. Creep rate under stressed condition should be lower for better adhesives. Tensile strength. 3.g. Substance can be added to the adhesive to alter the thermal coefficient of expansion to match with that of the adherend and hence increasing the bond strength. d. 4. of the film. c. In the case of phenol-aldehyde resin the higher mol. Thus. Similarly. .Degree of polymerization: Bond strength of the adhesive is affected by the extent of polymerization of the monomers. Pressure. shear strength and compressive strength of the film: These three characteristics influence the bonding strength in a positive way. in the case of cellulose esters the optimum chain length of fatty acid is from 6 to 14 for better bond strength.Complexity of the adhesive molecule: Complexity and chain length influence the adhesive action.Polarity of adhesives: For organic contacting surfaces polar-group containing adhesives provide better bond strength than non-polar adhesives. Difference in thermal coefficients of expansion of adherends and adhesive.

oil and lubricant are removed by solvent washing or immersion in acid or alkali bath or electrolytic methods. Adhesive Application Adhesives are dissolved in proper solvents. There are certain general steps involved in common bonding processes. (d) Highly viscous adhesives applied as coatings. the adherend surfaces are machined to bring smoothness for better bond strength. one component is the thermosetting resin. added in proper proportion. 4. different methods of application are used as follows: (a) By manual application with brushes. different type of adhesives. For certain plastics. For plastics which are difficult to bond. blades etc. For metals. (g) For immediately reacting and hardening of adhesives. casting knives. catalysts.2) (c) By rollers. (e) Dry adhesives are laid as film or sheet. which is applied to one surface and the other being the catalyst applied to the other surface to be bonded. Developing on the size and nature of the surface and rheologic properties of the adhesive. For wooden surfaces. (b) Thin-flowing sprayable adhesives are distributed uniformly over large areas with spray guns (Fig.Technique of Bonding Different type of adherend surfaces. pretreatment processes are used to increase the affinity for bonding. spatulas. Very uneven surfaces and others are rubbed with emery paper or sand blasted to remove firmly anchored layers that may interfere with the bonding process. plasticizers. Sometimes pressure and temperature are also used for these plastics. hardners etc. Cleaning and Pretreatment of Adherend Surfaces Layers of grease. (h) Cyanoacrylate adhesives and anaerobic reactive Fig 4. Uniform addition of calculated quantity of adhesive is required for proper bonding strength. differing bonding processes give rise to different types of bonding. Solid adhesives are melted. surfaces are modified by chemical treatment to increase the surface tension and wettability. very viscous adhesives are thinned with solvent. the components are applied to the adherend surfaces immediately before joining by double spray.2: Adhesive application by means adhesives are applied by means of special metering units of Spray gun (a) Adhesive (b)- that delivers small metered quantities at specified time compressed air (c)atomized . (f) For chemically reactive systems. Loose dirt and oxide layers can be removed by brushing. so the method of application is very important. acidic pickling baths are used to remove low cohesive strength materials.

drying cabinets. cooling under pressure is required. the adherends are joined by different methods which vary with the type of adhesive applied and the surfaces to be joined. (b) For pressure sensitive adhesives. (a) For slow reacting and setting adhesives the time of application of pressure is longer to ensure completion of the chemical reaction or complete evaporation of the solvent to develop bond strength. (d) For chemically reacting adhesives the adherend surfaces are kept in contact and the joint is allowed to remain for the required period to allow the chemical reaction to be complete to obtain high bond strength. (a) For immediately drying type of adhesives the adherends are held close to each other immediately completing the assembly. Classification of Adhesives Adhesives may be classified on the basis of chemical nature. (c) For bonding of the metal surfaces. the assembly of the adherend metal surfaces is required to be heated in an oven which is called ‘pre-curing’. (b) Adhesives or rubber solutions in organic solvents require longer period for air-drying. setting mechanisms. heating-presses etc. heat treatment is also necessary for selective adhesives. radiant heaters. Joining. For molten adhesive. pressure rolls. The necessary pressure is generally applied by using presses. Polycondensation adhesives must be heated with the application of external pressure higher than the vapour pressure of the cleavage products formed during condensation. This class has high adhesive properties by forming a network of . For warm-setting adhesives heating is required for a specified period. adhesion mechanism etc. intervals. the applied pressure is to be released immediately after the bonding. Here we classify them on the basis of their chemical nature: 1. Thus to allow the time for evaporation of the solvent and tackiness to develop the assembly is to be kept for a long period. Drying and Hardening After assembling the adhesive·applied adherend surfaces some pressure is to be applied to ensure the uniform distribution of the adhesive on the whole surface and also to keep the whole surface in close contact for the appropriate time to develop highest bond strength. Thermosetting synthetic resins. Fixing of Adherends Following application of adhesives. Similarly. The heat required for the hardening processes are supplied by recirculating-air ovens.

They set under the effect of atmospheric moisture. rubbers. The adhesive film developed by cellulose nitrate is resistant to water but affected by strong acids and alkalies and aging. Uses. Used for making laminated glass and cloth. resistant to temperature. syrupy compound. Though this adhesive forms bond which is resistant to temperature. insects and chemicals.. Uses. They possess good moisture resistance but low heat resistance. moisture etc. As multipurpose adhesive. generally with acid hardness to improve reactivity for bonding. for aircraft and in ship industries. Cellulose nitrate mixed with alcohol is well known as ‘collodion’. For bonding of silicate containing materials. Modified urea resins are important for labeling adhesives. lt can also be cured without the application of heat. Cellulose acetate has less adhesive strength than cellulose nitrate but it is more resistant to heat. dicarboxylic acid anhydrides etc. (c) Polyesters: Unsaturated polyesters dissolved in styrene or methacrylates are used as reactive adhesives. (e) Silicon resins. Cellulose nitrate is used as a raw material for solvent adhe- sives. particularly to produce plywood and chipboard. used in the form of aqueous solution or spray dried powders. fungi. Araldite which is available in the market comes under this class of resin. Addition of water to this resin helps in forming continuous film with cross linkages and with rapid setting properties. Epoxy resins are also combined with phenolic resins and poly vinyl acetate resins and used as adhesion promoters. Use: This is available as solid. The bonding of these are moisture. It is inflammable and in recent years it is replaced by others. Cellulose ethers ond cellulose esters. Usually they are used in combination with amines. it deteriorates by acids and alkalies. Used for bonding metal in aircraft industry and also for silicate containing materials and plastics. The adherend surfaces after being coated with this adhesive is subjected to curing by heat and pressure. shoe adhesive. On frequent contact with skin liquid epoxy resin causes irritation and allergies. Uses. (b) Urea-formaldehyde resin: lt is a transparent. Thermoplotstic synthetic resins: (a) Cellulose derivatives. 2. three dimensional cross-linked structures. The thin film of epoxy resin remaining after the evaporation of the solvent acts as good adhesive having good chemical and electrical resistance. Uses. Uses. Bonding wood. laminates. . liquid or impregnated film and used for bonding wood and metal. metals etc. (d) Epoxy resins: Epoxy compounds are available both in liquid and solid forms. Some members of this class are: (a) Phenol-formaldehyde resins: This is a pressure sensitive type of adhesive. plastics. heat and fungi proof.

The oily or the fatty matter is extracted or precipitated from soyabean or milk and then the protein is treated with lime and the Water solution form a jelly-like adhesive. albumin etc. Polyvinyl acetate. They are stable to all conditions but costly. books etc. paper etc. (b) Acrylics. casein. stamps. and hide scraps from leather industries are degreased with solvent. modifiers. (b) Asphalt—Used for bonding metal. Uses. The product obtained is hydrolysed with hot water to form liquid glue. . For making conveyer belts. Uses. leather etc. This is bleached and mixed with preservatives and concentrated to form solid glue. which are utilized for cross- linking and form better adhesives. Animal wastes obtained from slaughterhouses etc. 4. smooth surfaces and also in sealing of food materials. 3. polyvinyl propionate form hard films resistant to atmospheric conditions and chemicals. Similar to starch adhesive. The bonding strength of the adhesive is high but susceptible to heat and moisture. can be applied in cold and hot states but bond strength is low and susceptible to moisture. metals etc.. polyvinyl chloride. Use. The raw materials used for various types of starch and dextrin based adhesives are potato starch. polybutyl—acrylate) contain functional groups like —NH2. For manufacturing cardboard boxes and furnitures. Uses. OH etc. Natural resin adhesives: (a) Shellac—Hot shellac sol is an oldest known adhesive. Vegetable glue. Animal glue. These protein glues are obtained from soyabean. For bonding of glass. Copolymers of various esters (polymethyl. Polyvinyl acetate in combination with phenolic resins forms special adhesives. 5. A suspension of starch is heated for sometime to obtain the adhesive which is cheap. Uses. 6.Ethyl cellulose/methyl cellulose are used as aqueous solution with plasticizers. The solid cake or powder is boiled with water to form the adhesive solution. (c) Polyvinyl. Uses. Uses: For wall paper paste and also as thickener. corn. treated with lime. Polyacrylates are used both in the form of solutions and in the form of synthetic resin emulsions and are important raw materials for pressure sensitive adhesives. For bonding of paper. glass. which is hard. polyethyl. —COOH. For making envelopes. The film is moisture resistant but inflammable. They are very cheap but of poor bond strength. Starch and dextrin adhesives. corn starch etc.

breaking elongation of the films or test specimens made with the adhesives. For cardboard boxes making. 7. transport and electronics. Testing of Adhesives Testing of adhesives mainly encompasses: • Solid content • Rheologic properties • Shelf life • Flammability and inflammability • Risks involved in transport and application • Measurement of the mechanical properties like tensile strength. The bond is moisture and high temperature sensitive but fungus resistant. Uses. Inorganic adhesives. Sodium silicate alongwith litharge (lead monoxide) and MnO 2 etc. forms gel when suspended in water. This gel has adhesive properties. Continued growth is expected in construction adhesives. solvent free adhesives whereas reduction in demand is expected for solvent containing adhesives and animal and vegetable glues. Growth Rates of Different Adhesives The highest growth rate is expected in automotive industry. .

4.Explain the terms with example (i) addition polymerization (ii) co-polymerization (iii) condensation polymerization. 7. Discuss briefly the application of plastic in engineering and industry. PVC. . 1. (b) What is the effect of polymer structure on the strength and crystalline nature of polymer? (c) Give four uses of rubber. ( ii) Co-polymerization. 6. condensation polymerization c. Write the structures of five addition polymers and five condensation polymers. 10. (iii) vulcanization of rubber. 2. Discuss various methods of plastic processing. (b) Give the preparation and properties of (i) Nylon 6. addition polymerization b. Write short notes on: (i) Rayon ( ii) Synthetic rubber ( iii) Types of plastics. two properties and uses of: a. a. e. number average and molecular weight. Write the structures. with their respective monomers. (d) What are silicones? Draw the polymer obtained by hydrolysing dichlorodimethyl silicone and give its use. PTFE.Write short notes on (i) free radical polymerization ( ) cationic polymerization (iii) silicone resin. c. Write short notes on a. Give an account of one ( i) Crepe rubber. Explain with example: (i) addition polymerization. PP. Nylon 66. b. (ii) co-polymerization. 9. (ii) butyl rubber. thermoplastic and thermosetting plastics d. d. (a) Define the terms (i) Degree of polymerization. 5. (a) Discuss the effect of structure of polymers on their physical properties in detail. 8. 3. ( ii) Neoprene rubber ( iii) SBR ( iu) Silicone rubber. HDPE.

Write preparation. (a) Give a brief account of vulcanization of rubber. 17. Outline the general method of preparation of urethanes and state their applications.(a) What do you understand by vulcanization of rubber'? What are the advantages and disadvantage? Give the structural unit of vulcanised rubber. properties and uses of (i) Phenol—f0rmaldehyde resin.Define the term crystallinity of polymer. 24. 16. What is an adhesive? 22. How is it related to the chemical structure? 15. List out the difference between HDPE and LDPE. Discuss the preparation of natural rubber. c. ( ii) Silicone rubber (iii) Polyethylene. Write note on glass reinforce plastic. Give the structure of bakelite. What is meant by compounding of plastic? 14. Discuss the mechanism of addition polymerization. Write note on thermoplastic and thermosetting resin.What is vulcanization? How does it improve the property of natural rubber? 18. (c) What is an Epoxy group? Give the preparation and uses of a common Epoxy resin. 11. 19. Mention the types of adhesives used for joining (i)Wooden su rfaces (ii) Glass and cloth (iii) Metals . b. explain each. What is an elastomer? 21. a. b. 20. Explain Adhesion theory 23. 13.(b) Give the manufacture and uses of (i) teflon (ii) nylon 66. How are the following produced: ( i) Buna S (ii) thiokolsil Mention their properties and uses. Write the types of Adhesives. 12.

Discuss the physical and chemical factors that influence adhesive action. 27. Mention a few important advantages and limitations of adhesives. Describe the different steps of the bonding processes of adhesives. . (iv) Papers (v) Plastics and rubbers 25. 26.