UNIT II POLYMERS AND COMPOSITES

INTRODUCTION Polymers are generally macromolecules formed by the repeated linking of large number of small molecules. Polymers are widely used in automobiles, defence, electrical goods and computer components etc. Polymers Polymers are macromolecules (giant molecules of higher molecular weight) formed by the repeated linking of large number of small molecules called monomers. Eg: Polyethylene is a polymer formed by the repeated linking of large number of ethylene molecule. n CH2=CH2 Monomer Monomer is a micro molecule (small molecule) which combines with each other to form a polymer. POLYMERISATION Polymerisation is a process in which large number of small molecules (called monomers) combines to give a big molecule (called a polymer) with or without elimination of small molecules like water. Degree of Polymerisation (DP) The number of repeating units (n) in a polymer chain is known as the degree of polymerisation. It is represented by the following relationship. Degree of polymerization= molecular weight of the polymeric network ___________________________________ Molecular weight of the repeating unit Eg: 5CH2=CH2 -CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2Degree of polymerisation = 5. __(_CH2-CH2__)n_

In this example, five repeating units are present in the polymer chain.

(i)

Oligo Polymers Polymers with low degree of polymerisation are known as oligo polymers, their molecular

weight ranges from 500 - 5000. (ii) High Polymers Polymers with high degree of polymerisation are known as high polymers, and their molecular weight ranges from 10,000 - 2, 00,000. TYPES OF POLYMERISATION

Addition or chain growth polymerization It is a reaction that yields a polymer, which is an exact multiple of the original monomeric molecule. The original monomeric molecule, usually, contains one or more double bonds. In this addition polymerisation there is no elimination of any molecule. Eg 1: Polyethylene is produced from ethylene. Heat/pressure n CH2=CH2 Ethylene catalyst __(_CH2-CH2__)n_ Polyethylene

Eg 2: PVC is produced from vinyl chloride. Heat/pressure n CH2=CH Cl Vinyl chloride catalyst _(_ CH2-CH _)n_ Cl Polyvinyl chloride

Condensation or step wise polymerisation It is a reaction between simple polar groups containing monomers with the formation of polymer and elimination of small molecules like H2O, HCl, etc.

Eg: Hexamethylene diamine and adipic acid condense to form a polymer, Nylon 6:6 nH2N - (CH2)6 - NH2 + NHOOC - (CH2)4 COOH Hexamethylene diamine Adipic acid - (HN (CH2)6 NH C = O CH2 C =O) nNylon 6:6 Copolymerisation It is the joint polymerisation in which two (or) more different monomers combine to give a polymer. High molecular weight polymers, obtained by copolymerisation, are called copolymers. Eg:Butadiene and styrene copolymerise to give GR-S rubber. nCH2 = CH CH = CH2 + nCH2 =CH C6H5 Butadiene styrene _(_ CH2 - CH = CH - CH2 - CH2 CH_)n_ C6H5 Styrene butadiene rubber

Differences between addition (chain) polymerisation and condensation (step) polymerisation Addition polymerisation The monomer must have at least one multiple bond It is a reaction that yields a polymer, which is an exact multiple of the original monomeric molecule & no other by product is formed Condensation polymerisation The monomer must have at least two identical functional groups. It is a reaction between simple polar groups containing monomers with the formation of polymer and elimination of small

molecules like H2O, HCl, etc. Molecular weight of the polymer is an integral multiple of molecular weight of monomer. Longer reaction times give higher yield,but have a little effect on molecular weight Thermoplastics are produced Eg:polyethylene , PVC etc. Homo chain polymer is obtained

Molecular weight of the polymer need not to be an integral multiple of monomer Longer reaction times are essential to obtain high molecular weight Thermosetting plastics are produced Eg:Bakelite, urea formaldehyde Hetero chain polymer is obtained

MECHANISM OF ADDITION POLYMERISATION The mechanism of addition polymerisation can be explained by any one of the following three types. 1. 2. 3. (i) (ii) (iii) (i) (a) Free radical mechanism Ionic mechanism Co-ordination mechanism Initiation Propagation, and Termination

All the above mechanisms occur in three major steps namely,

Free radical mechanism Initiation It is considered to involve two reactions. First reaction involves production of free radicals by homolytic dissociation of an initiator (or catalyst) to yield a pair of free radicals (R.). I Intiator 2R. Free radicals

Examples of some commonly used thermal initiators

Thermal initiator is a substance used to produce free radicals by homolytic dissociation at high temperature.

70 --- 800 C (i) CH3COO OOC CH3 Acetyl peroxide 2(CH3COO) . Free radicals 80---95o C (ii) C6H5COO OOCC6H5 Benzoyl peroxide (b) 2(C6H5COO). Free radicals

Second reaction involves addition of this free radical to the first monomer to produce chain initiating species. H R. + CH2 = C Y H R CH2 C. Y Chain initiating species

Free radical (ii)

First monomer

Propagation

It involves the growth of chain initiating species by successive addition of large number of monomers. H R - CH2 - C + n CH2 = C Y Y
.

H R ( CH2 C_)n__CH2 C Y
.

H Y

Growing chain (living polymer) The growing chain of the polymer is known as living polymer. (iii) Termination Termination of the growing chain of polymer may occur either by coupling reaction or disproportionation.

a)

Coupling (or) Combination

It involves coupling of free radical of one chain end to another free radical forming a macro molecule. H Y H Y H Y H Y R CH2 C. + .C CH2 R R CH2 C C CH2 - R Dead polymer b) Disproportionation

It involves transfer of a hydrogen atom of one radical centre to another radical centre, forming two macromolecules, one saturated and another unsaturated. H H H Y H H H H Y Unsaturated macromolecule H H Y H saturated macromolecule R C C. + .C C R H Y R C =C + H- C C - R

The product of addition polymerisation is known as Dead polymer.

PLASTICS Plastics are high molecular weight organic materials that can be moulded into any desired shape by the application of heat and pressure in the presence of a catalyst. Advantages of plastics (i) (ii) They are light in weight. They possess low melting point.

(iii) They can be easily moulded and have excellent finishing. (iv) They possess very good strength and toughness. (v) They possess good shock absorption capacity. (vi) They are corrosion resistant and chemically inert. (vii) They have low co-efficient of thermal expansion and possess good thermal and electrical insulating property (viii) They are very good water-resistant and possess good adhesiveness.

Disadvantages of plastics (i) (ii) Softness. Embrittlement at low temperature.

(iii) Deformation under load. (iv) Low heat-resistant and poor ductility. (v) Combustibility. (vi) Polymers tend to degrade upon exposure to heat and uv-radiation. (vii) Polymers are non bio-degradable. CLASSIFICATION OF PLASTICS Plastics are classified in the following two ways. 1. 2. Based on structure. Based on usage.

Classification based on structure Based on the structure and type of resin used for the manufacture of plastics, plastics are classified into two main types. 1. 2. Thermoplastics. Thermosetting plastics.

A resin is a basic binding material, which undergoes polymerization reaction during moulding. I. Thermoplastic resins

Thermoplastics are prepared by addition polymerisation. They are straight chain (or) slightly branched polymers and various chains are held together by weak vanderwaals forces of attraction. Thermoplastics can be softened on heating and hardened on cooling. They are generally soluble in organic solvents. Eg: Polyethylene, Polyvinyl chloride. 2. Thermosetting resins (or) Thermosets

Thermosetting plastics are prepared by condensation polymerisation. Various polymer chains are held together by strong covalent bonds (called crosslinks). Thermosetting plastics get harden on heating and once harden, they cannot be softened again. They are almost insoluble in organic solvents.

Eg:Bakelite, Polyester. Difference between thermoplastic and thermosetting resins Thermoplastic resins They are formed by addition polymerization They consist of linear long chain polymer All the polymer chains are held together by weak vanderwaals forces They are weak, soft & less brittle They soften on heating & harden on cooling They can be remoulded They have low molecular weights They are soluble in organic solvents Classification based on usage Based on usage plastics are classified into two types 1. 2. General purpose plastics. Engineering plastics. Thermosetting resins They are formed by condensation polymerization They consist of three dimensional network structure All the polymer chains are held together by strong covalent bonds They are strong, hard & more brittle They do not soften on heating They cannot be remoulded They have high molecular weights They are insoluble in organic solvents

1. General Purpose Plastics (Commodity) General purpose plastics have low to medium mechanical properties. They are used for the manufacture of commodity items. They account for about 80 - 85% of total polymer production. Polyethylene, Polypropylene, Polyvinyl chrloride, Polystyrene. Properties of General Purpose Plastics 1. They are mostly crystalline with low glass transition temperature (T g) (or) they are glossy (or) amorphous polymers.

2. 3. 4.

They have low use temperature; therefore they cannot be used at high temperature. They have low to medium mechanical properties. Generally they have low abrasion resistance and poor dimensional stability.

ENGINEERING PLASTICS Engineering plastics are a group of materials obtained from high polymer resins. They possess high mechanical strength, toughness and higher use temperature. They are mainly used in load bearing applications, generally to replace conventional materials like metal, wood, glass and ceramics. Not only engineering plastics can replace metals, but they can also be used along with metals. Characteristics of Engineering Plastics Engineering plastics possess (i) (ii) High load bearing characteristics, High mechanical strength,

(iii) High dielectric constants, (iv) Readily moldable properties into complicated shapes, (v) High abrasion resistance, (vi) Very good rigidity, (vii) Good dimensional stability, (viii) Fairly good thermal stability, (ix) Light weight, (x) High performance properties i.e., they can be used in the same manner as metals, alloys and ceramics.

Applications (i) (ii) They can be used alone or in conjunction with metals, ceramics or glasses, etc. They find applications in demanding areas like automobiles, defence, electrical and electronics, telecommunications, textiles, satellite, robots, computer components, etc.

IMPORTANT ENGINEERING PLASTICS Polyvinyl Chloride (PVC)

Preparation Preparation of PVC involves the following two steps. 1 Step: Vinyl chloride is prepared by treating acetylene with hydrogen chloride at 60 80C in the presence of metal chloride as catalyst. II Step: Polyvinyl chloride is obtained by heating water emulsion of vinyl chloride in presence of benzoyl peroxide (or) hydrogen peroxide under pressure. Heat/pressure n CH2=CH Cl Vinyl chloride Properties (i) (ii) PVC is colourless, odourless and chemically inert powder. It is insoluble in inorganic acids and alkalis, but soluble in hot chlorinated hydrocarbons such as ethylchloride. It undergoes degradation in presence of heat (or) light. H2O2 _(_ CH2-CH _)n_ Cl Polyvinyl chloride

Uses (i) (ii) It is used in the production of pipes, cable insulations, table covers and rain-coats, etc., It is also used for making sheets, which are employed for tank-linings, light fittings, refrigerator components, etc.,

Teflon (or) Fluon (or) Polytetrafluoroethylene (PTFE) Preparation

Teflon is obtained by polymerization of water-emulsion of tetrafluoroethylene in presence of benzoyl peroxide under pressure.

CaF2 + H2SO4 CaS04+ 2HF CH4 + 3Cl2 CHCl3 + 2HF 2CHClF2 Chlorodifluoro methane nCF2 = CF2 CHCl3 + 3HCl CHClF2 + 3HCl CF2 = CF2 + 2HCl Tetrafluoro ethylene _(_CF2 CF2 _)n_

Tetrafluoro ethylene Properties i) ii) iii) iv) i) ii) iii) iv)

Teflon

Teflon is extremely tough, flexible material possess

high softening point (about 350C).

It possesses extremely good electrical and mechanical properties. It is chemically resistant towards all chemicals (except hot alkali metal and hot fluorine). It has an excellent thermal stability. It is used as a very good electrical insulating material in motors, cables, transformers, electrical fittings It is also used for making gaskets, packings, pump parts, tank linings, etc. It is also used for making non-lubricating bearings, chemical carrying pipes, etc. It is used in making non-sticking stop cocks for burettes.

Uses

Polycarbonates (PC) (Lexan, Merlan) Preparation Polycarbonates are prepared by interaction of diphenyl carbonate with bisphenol - A. CH3 _O_C=O + 2 Diphenyl carbonate Bisphenol A CH3 __O C= O O -C CH3 Lexane Properties i) ii) Polycarbonates are characterised by high impact and tensile strength over a wide range of temperature. They are soluble in organic solvents and alkalis. __ n Phenol + 2n C6H5 - OH OH__C__ CH3 -OH

iii)

They possess good dimensional stability, stiffness, transparency, etc.

Uses They are used for making electrical insulators, housing apparatus, plugs, sockets, switches, sterilizable transparent containers, camera, photographic films, hair-drier bodies, baby bottles, safety windows in prison and jewellery shops, etc. Polyurethanes (Perlon - U) Preparation It is obtained by the reaction of 1, 4-butanediol with 1,6-hexamethylene di-isocyanate. nC =O = N (CH2)6 N = C = O +n HO (CH2)4 OH 1,6 Hexamethylene di isocyanate 1,4 butane diol

___ C = O N H (CH2)6 N H C = O (CH2)4 O __n_ Polyurethane Properties i) ii) iii) iv) It possess excellent flexibility, toughness even at sub-zero temperature. It is less stable than polyamides. It is easily affected by moisture. It is characterised by excellent resistance to abrasion and solvents.

Uses i) ii) iii) Polyurethanes are used as coatings, films, foams adhesives and elastomers. They are also used in defence, oceanographic research, mountaineering. Resilient polyurethane fibre (spandex) is used for foundation garments and swim suits.

Polyethylene Terephthalate (PET) Preparation It is saturated polyester, prepared by condensation of ethylene glycol and terephthalic acid. nHO (CH2)2 OH + nHOOC C6H5 COOH Ethylene glycol Terephthalic acid

__O (CH2)2 O C= O C6H5 C = O___ n PET Properties i) ii) iii) It ix a good fibre-forming material and is converted into commercial fibres. The fibres possess high stretch-resistance, high-crease and wrinkle-resistance. It is highly resistant to mineral and organic acids, but is less resistant to alkalis.

Uses 1. 2. 3. It is mostly used for making synthetic fibres like terylene, dacron, etc. It is used for blending with wool to provide better crease and wrinkle resistance. It is also used as glass reinforcing material in safety helmets, aircrafts, battery boxes, etc.

Nylon (Polyamides) (i) Nylon - 6:6

Preparation Nylon - 6.6 is obtained by the polymerisation of adipic acid with hexamethylene diamine. nH2N - (CH2)6 - NH2 + NHOOC - (CH2)4 COOH Hexamethylene diamine Adipic acid - (HN (CH2)6 NH C = O CH2 C =O) n- +2nH2O Nylon 6:6 (polyamide)

(ii)

Nylon - 6 It is prepared by self-polymerization of caprolactam. CH2 CH2 CH2 CH2 _(__C =O (CH2)5 N H_)n_ CH2 Nylon 6

NH CO Caprolctum

(iii) Nylon - 11 It is prepared by self-condensation of w-amino undecanoic acid. Self condensation nH2N (CH2)10 COOH w- Amino undecanoic acid _(_NH (CH2)10 C = O _)n_ Nylon 11

Among the different nylons, nylon 6:6 and nylon-6 are important for fibre. The number indicates, number of carbon atoms in the material from which it is made. Properties 1. 2. 3. 1. 2. 3. Nylons are translucent, whitest, horny and high melting polymers. They possess high temperature stability and good abrasion-resistance. They are insoluble in common organic solvents and soluble in phenol and formic acid. Nylons are used for making fiiaments for ropes, bristles for tooth-brushes and films, etc. Nylon - 6 and Nylon - 11 are mainly used for moulding purposes for gears, bearings, etc. Nylon 6:6 is used for fibres, which is used in making socks, dresses, carpets, etc.

Uses

RUBBERS OR ELASTOMERS Rubbers (or) elastomers are non-crystalline high polymers (linear polymers), having elastic and other rubber - like properties. Types of Rubbers Rubbers can be obtained from two sources, which may be natural or artificial. Thus, we have 1. Natural rubber, and

2. 1.

Synthetic rubber (elastomers) Natural rubber

Natural rubber is obtained from the tree as a latex, which IS a dispersion of isoprene. During the treatment of latex, these isoprene molecules undergo polymerisation to form long coiled chain of polyisoprene.

nCH2= C CH CH2 CH3 Isoprene 2. Synthetic rubber

_( CH2 -C = CH CH2_)n_ CH3 Polyisoprene

An elastomer (synthetic rubber) is any vulcanisable man made rubber like polymer, which is superior to natural rubber in certain properties. Styrene rubber (Buna-S) Buna-S rubber is produced by copolymerization of butadiene and styrene Drawbacks of raw rubber 1. 2. 3. 4. 5. 6. 7. It is plastic in nature, ie., it becomes soft at high temperature and is too brittle at low temperature. It has poor strength. It has large water-absorption capacity. It is non-resistant to non-polar solvents like benzene, vegetable & mineral oils. It is attacked by oxidising agents like HNO3 and H2SO4 It swells and disintegrates gradually in organic solvents. It has little durability.

VULCANIZATION OF RUBBER The properties of rubber can be improved by compounding it with some chemicals like sulphur, hydrogen sulphide, benzoyl chloride, etc., But most important addition is sulphur. Objectives of vulcanization

Uncross-linked rubber products, such as natural rubber obtained from latex, are soft and have poor tensile strength and abrasion resistance. To obtain a cross-linked structure of rubber, the process of vulcanization is made. Process of vulcanization The process of vulcanization consists of heating the raw rubber with sulphur to about 100 140 C.
0

The added sulphur combines chemically at the double bonds of different long chain rubber springs. Thus the vulcanization prevents intermolecular movement of rubber springs. The extent of stiffness of vulcanized rubber depends on the amount of sulphur added.

CH3 +

CH3

.-CH2 C = CH CH2 C = CH CH2-... .-CH2 C = CH CH2 C = CH CH2-... CH3 Vulcanization +S CH3

CH3

CH3

.-CH2 C - CH CH2 C - CH CH2-... S S S S (sulphur cross links)

.-CH2 C - CH CH2 C - CH CH2-... CH3 Example (i) (ii) Tyre rubber contains 3 to 5% sulphur. Battery case rubber contains 30% sulphur.] CH3

Comparison between Raw and vulcanized rubber

Raw rubber

Vulcanized rubber Tensile strength is high(200 0kg/cm2) Water absorbing tendency is low Oxidation resistance is high It has moderateelongation(1200%) The useful temperature range 40 100 o C It is resistant to organic solvents

Tensile strength is low(200 kg/cm2) Water absorbing tendency is high Oxidation resistance is low

It has high elongation(1200%) The useful temperature range 10 60 o C It is attacked by organic solvents

IMPORTANT SYNTHETIC RUBBERS SBR (Styrene-butadiene rubber) (GR-S or Buna-S or ameripol rubber or cold rubber) SBR is the polymer of about 75% butadiene and 25% styrene. Preparation SBR is obtained by copolymerizing an aqueous emulsion of the mixture containing 75% butadiene, 25% styrene and an emulsifying agent (cumene hydroperoxide).

nCH2 = CH CH = CH2 + nCH2 =CH C6H5 Butadiene styrene _(_ CH2 - CH = CH - CH2 - CH2 CH_)n_ C6H5 Styrene butadiene rubber Properties

1. 2.

The vulcanization process is similar to that with natural rubber, but it requires less sulfur for vulcanization. Tensile strength and flexibility of these rubbers are inferior to those of natural rubber.

Uses SBR is used mainly for making light duty tyres, belts, floor tiles, gaskets, gum, hoses, adhesives and electrical insulation. Butyl rubber (GR-I rubber) Butyl rubber is the copolymer of isobutylene and a small amount of isoprene. Preparation It is obtained by copolymerizing isobutylene with 1.5 to 4.5% isoprene in methyl chloride. A catalyst solution, made by dissolving anhydrous AICl3 in methyl chloride, is added to the
reaction mixture.

Properties 1. 2. 3. 4. 5. Butyl rubber is amorphous under normal conditions. Unstabilized polyisobutylenes are degraded by light or heat to sticky low molecular weight products. It has low permeability to gases. It is soluble in hydrocarbon solvent. It possesses good electrical insulating property and resistance to heat and abrasion.

Uses 1. 2. Butyl rubber is used for making tubes, hoses, conveyor belts, etc. It is also used for wire and cable insulation.

COMPOSITES Definition A composite material may be defined as, a material system consisting a mixture of two or more micro-constituents, which are mutually insoliible, differing in form or composition

and forming distinct phases. Such a combination possesses properties different from those of any of its constituents.

Characteristics of Composites (i) (ii) They possess higher specific strength and lower specific gravity. They possess lower electrical conductivity and thermal expansIon.

(iii) They possess better creep, fatigue strength, corrosion and oxidation resistance. (iv) They maintain very good strength, even upto high temperatures. Constituents of Composites Composites consist of two important constituents. 1. 2. 1. 2. Matrix Phase Dispersed phase. Matrix Phase Matrix phase is the continuous body constituent, which encloses the composite. Dispersed Phase Dispersed phase is the structural constituent, which determines the internal structure of composite. Fibres, Particulates, Flakes, Whiskers.

TYPES OF COMPOSITES Based on the type of matrix phase, classified into three types 1. 2. 3. Polymer matrix composites. Metal matrix composites. Ceramic matrix composites.

Polymer matrix composites (or) Fibre Reinforced Polymer Composites The fibre reinforced polymer composites constitute more than 90% (by weight) of the total composites used in various industries. The advantages of using polymer in structural composites are the ease of fabrication of complex structural shapes. It can be easily manufactured.

Preparation Fibre-reinforced plastics are produced by suitably bonding a fibre material with a resin matrix and curing them under heat and pressure. The main reinforcing agents used in FRP composites are, glass, graphite, alumina, carbon, boron, etc. The reinforcement material can be in different forms such as short fibres, continuous filaments or woven fabrics. The resin matrix commonly used in FRP is polyesters, epoxy, phenolic, silicone, and polyamide polymer resins.

Characteristics (or) Properties of FRP 1. 2. 3. It possess superior properties like higher,. Yield strength, fracture strength and fatigue life. since fibre prevents slip and crack propagation, the mechanical properties of FRP gets increased. It possesses high corrosion resistance and heat resistance property. The properties of FRP mainly depends on nature of the resin matrix Polyester resin Epoxy resin ____ provides very good strength & mechanical properties _____ Imparts good mechanical strength

Silicone resins _____ Impart excellent thermal & electrical properties Phenolic resins _____ withstand high temperatures Types of FRP Composites The various types of FRP composites are 1. Glass FRP 2. Boron FRP 3. Carbon FRP 4. Aramid FRP 5. Alumina FRP Name of FRP Glass FRP Properties (i) lower densities, dielectric constants (ii)higher tensile strength Applications Automobile parts, storage tanks, plastic pipes,transportation

(iii) good corrosion resistance, chemical resistance, noninflammability Boron FRP (i)excellent stiffness & compressive strength

industries etc.

Horizontal and vertical tail in aeroplane, stiffening spares, ribs etc. Structural components of aircraft & helicopters, recreational equipments, sport materials, antenna disc, solar panel etc.,

Carbon FRP

(i)lighter density (ii) good corrosion resistance (iii)retention of desired properties even at high temperatures

Aramid FRP

(i)ductile in nature

Structural components of aircraft & helicopters

Alumina FRP

(i)good abrasion resistance, creep resistance & dimensional stability

Components of engine parts in automobile industry& turbine engine