Polymeric Materials

Asma Ashraf

Contents
The history of plastics Introduction Additives General properties of polymeric materials Properties and applications of elastomers Properties and application of typical thermoplastics Properties and applications of typical thermosetting plastics
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History
Plastics do not exist naturally Their manufacturing started after the development of chemical industry and in particular the oil refining industry which provided raw materials for many of these plastics. The first man-made plastic was Parkesene which was a substitute of traditional bone ware (1854). The second plastic was Bakelite which expanded the electrical engineering industry (1907). A mass production of many different polymers started after 1930 till the present modern and fully developed polymer industry.
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Polymers
There is an ever increasing number of synthetic, polymeric materials available under the popular name of Plastics. The name plastic comes from the fact that during the moulding process by which they are shaped, they are reduced to a plastic condition by heating them. There are three main groups of polymeric or plastic materials:
Thermosetting plastics (thermosets) Thermoplastics Elastomers
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Thermosetting plastics (Thermosets)

This group of polymeric materials undergoes chemical change during the moulding process and can never be softened again by reheating. These materials are generally hard, rigid and brittle. Example is melamine formaldehyde. The strength of Thermosetting plastics can be greatly increased by reinforcing them with fibrous materials.

Thermoplastics
They become soft and can be reheated each time they are heated. They are not so rigid as thermosetting plastics but they are tough. For example PVC

Elastomers
The elastomers or rubbers are cross-linked polymeric materials in which there are not sufficient cross links to make them as rigid as the thermosetting plastics, but just sufficient to make them return to their original dimensions when the deforming load is removed. Thermosets show little elongation under stress but elastomers are capable of extreme elastic deformation at low levels of stress (upto 1000%). Unlike metals strain is not proportional to stress.
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Crystallinity in Polymers
Most polymers are amorphous The crystallinity of a polymeric material is defined as the ratio between the mass of crystallites and the total mass of the material being considered. For example a material having 80% crystallinity will consists of 80% crystallite structure and 20% amorphous structure. A material with high crystallinity will be more dense than the material with a low crystallinity.
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Crystallinity in Polymers
Increasing the crystallinity of a material:
Increase, the melting point of material and, instead of softening gradually with increasing temperature, it will exhibit a sharp melting point. Increases the resistance of material to the absorption of water and solvent attack. Prevents the penetration of plasticizers and this reduces the ultimate elongation of the material. Makes the material more impervious to gases and this may be useful in food packaging nd protective coatings
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 Effect of crystallinity on ultimate tensile strength and percentage elongation of a polyethylene

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Glass Transition Temperature

The temperature at which a polymeric material changes from being rigid and brittle to being flexible and rubbery is called glass transition temperature (Tg). It is less well defined than the melting temperature (Tm) and is difficult to determine. Below the glass transition temperature the polymeric materials show a relatively high tensile modulus, with little extension and a high level of rigidity. Above the glass transition temperature the tensile modulus is lower and the extension is very considerably increased. Glass transition temperature is unaffected by crystallinity.
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 Effect of glass transition temperature on the mechanical properties of a typical thermoplastic material.

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Effect of temperature on polymer application

Since polymeric materials with a high crystallinity have a well defined melting point, they can be hot formed (moulded) above this temperature and cold formed between their Tg and Tm , when they will be solids but soft and flexible. For example polyethylene with 95% crystallinity has a Tg of -120OC and a Tm of +138OC. Thus it is soft and flexible over a wide temperature range. The maximum service temperature is usually taken as approximately 85% of the melting point, which in this case is 120OC.
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For amorphous polymeric materials

Amorphous polymeric materials are usually moulded or formed above glass transition temperature where they are soft, but are used below this temperature where they are rigid. For example rigid PVC is an amorphous polymer with a Tg of 87OC. It is normally softened by hot blast of air. Amorphous plastics do not have a well-defined melting temperature, the service temperature is taken as 85% of the Tg.
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Additives
The appearance and performance of most plastics and elastic polymers can be improved by the use of various additives. Some types of additives are:
Plasticizers Fillers Stabilizers Colorants Antistatic agents
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Plasticizers
These are added to polymeric material to:
reduce their rigidity and brittleness And to improve their flow properties

There are two main groups of plasticizers:

Primary plasticizers Secondary plasticizers

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 Primary plasticizers
These are used to reduce the Vander Waals force between adjacent molecular chains and allow greater mobility between adjacent polymer chains.

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 Secondary plasticizers
These are monomers of a compatible but inert material without polar groups. These are added to provide mechanical separation of the polymer chains in the same way that a lubricant separates a shaft from its bearing. Separation of the polymer chain in this manner reduces the Vander Waals force of attraction between them
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Secondary plasticizers
Internal Plasticization
Small amounts of plasticizers are added during polymerization. Separation of polymer chain is achieved during polymerization process. PVC is a rigid and brittle plastic material. But it can be made flexible for raincoats, insulation of electric cables etc by the addition of 15% of vinyl acetate as a secondary plasticizer during polymerization.
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Secondary plasticizers
External plasticization
This is more common method of plasticization. The plasticizer is added after polymerization. The plasticizer acts as a lubricant and fills the voids between the polymer chains. Only amorphous zones will be treated in this way because crystalline materials will not absorb sufficient plasticizer. However in case of crystalline polymers the presence of plasticizer reduces the degree of crystallinity and also reduces the glass transition Temperature Tg
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Fig

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Fillers
They have influence on the properties of moldings produced for any given polymeric material. They increase the impact strength and reduce shrinkage during molding. Fillers are essential in thermosetting molding powders and may be present in quantities up to 80% by weight. In thermoplastics their amount is up to 25% by weight. The exceptions are thermoplastic floor tiles which may contain up to 40% calcium carbonate as filler.
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Some filler materials and their properties

Filler Material
Glass fiber
Wood flour; calcium carbonate Asbestos Aluminium powder Shredded paper/cloth

Properties
Good electrical insulation properties
Low cost, low strength Heat resistant ( health hazards) High mechanical strength Good strength, electrical insulation properties

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Selection of filler Material

A filler material is selected according to the properties required. However all fillers must:
Have a low moisture absorption rate Not adversely affect the color or surface finish of the product Not cause abrasive wear in the processing equipment Be capable of being wetted by the resin.

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Stabilizers
Stabilizers reduce degradation of polymeric material and prevent it from environmental attack. They are used in plastics where the material have to withstand environmental attack over a long period of time such as window frames etc. Degradation of polymeric materials occurs when they are exposed to heat, sunlight or weathering. Such degradation is usually accompanied by
color change Deterioration of mechanical properties Cracking and surface crazing
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Colorants
Three categories of colorants are:
Dyestuffs Organic pigments Inorganic pigments

Dyestuffs
Are usually aromatic organic chemicals which are soluble in variety of solvents. they absorb light selectively to produce their characteristic colors. They are suitable for coloring transparent and translucent polymers such as polystyrene Organic dyestuffs have only a limited color stability when exposed to sunlight, and they may also degrade at molding temperatures of some high temperature polymers.
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Colorants
Organic pigments
They are opaque and cannot be used to color transparent plastic materials. They are usually used in opaque plastic products. Their light and heat stability is superior to dyestuffs

Inorganic pigments
They are based on metal oxides and salts Have greatest opacity Superior light and heat stability. e.g. Titanium oxide used in non-toxic white plastics and paints Iron oxides used to provide yellows and red colors Carbon black used to produce black color and is also used as ultraviolet radiation absorber
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Antistatic Agents
These are included to increase surface conductivity so that static charges can leak away. This prevents the attraction of dust particles They reduce the risk of explosion in hazardous environments caused by the spark associated with an electric discharge. It also prevents electric shocks when synthetic fabric materials are handled in very dry climate.
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General properties of Polymeric Materials

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 Electrical Insulation
All polymeric materials exhibit good electrical insulation properties. But they have low heat resistance and are soft.

Strength/weight Ratio
Polymeric materials vary in strength considerably Some polymers e.g. Nylon are comparable with Weak metals. All polymeric materials are much lighter than any of the metals used for engineering purpose. Some polymeric materials are being used in place of metals because of their comparable strength/weight ratio.
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 Corrosion Resistance
All polymeric materials are inert to most inorganic chemicals and can be used in environments which are hostile even to most corrosion-resistant metals. Synthetic rubber is superior to natural rubber since it os not attacked by oils and greases.

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Degradation of Polymers
Temperature has much greater effect on polymeric materials than it has on metals and substantially reduces the fatigue resistance of material. Polymeric materials heat up internally when subjected to rapidly alternating stresses. The greater the stress and the more rapidly it alternates, the greater will be the temperature rise. The fatigue resistance of polymeric materials and their general strength and toughness can be adversely affected by presence of organic substances such as soaps, detergents and alcohols. UV radiation and the presence of ozone can cause some polymeric materials to degrade and fail in fatigue at a lower then normal value.
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Properties and applications of elastomers

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 Elastomers are substances which allow extreme reversible extensions to take place at normal temperatures. Natural rubber is an example of elastomers. Applications of rubbers
Resilient floor coverings Footwear Vehicle tires Joint sealants Expansion joints
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 Vibration insulation and isolation

Shock absorbers Anti-vibration machines and engine mountings Sound insulation

Distortional systems
Changing shapes such as belts, rollers and tires Seals and gaskets

Protective systems
Protection against abrasion Protection against corrosion Electrical insulations Protective clothing, gloves, aprons, boots etc.
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Some commercials Elastomers

Acrylic rubbers
excellent resistance to oils, oxygen, ozone and UV radiation

Butyl rubber
Impervious to gases and is used as a vapor barrier. Highly resistant to outdoor weathering and UV radiations

Nitrile rubber
excellent resistance to oils and solvents Used for hose linings air craft fuel tank linings Resistant to Refrigerant gases

Polychloropren rubbers
Resistant to oils, solvents, abrasion and elevated temperatures. fire resistant
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Some commercials Elastomers

Polyisoprene
high tensile strength Easily attacked by solvents, oils and ozone Degrades rapidly in sunlight

Polysulfide rubber
Low mechanical strength High weathering resistance Good bonding properties

Silicone rubbers
Low tensile strength Working temperature range is -80OC to +235OC Used for high temperature seals Space vehicles and aircraft satellites
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Properties and application of Thermoplastics

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Polyethylene
Most versatile and widely used plastic material Remains tough and flexible over a wide temperature range and has good dimensional stability Easily molded and is used in a wide range of domestic goods Used commercially for water piping, chemical equipment and electrical insulation Resistant to most solvents and has good weathering properties It degrades when exposed to strong sunlight unless it contains UV filter such as carbon black.
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Polystyrene
Tough, dense plastic which is hard and rigid and has good dimensional stability High surface gloss Good mechanical properties but it tends to be brittle Attacked by petrol and other solvents Used for ceiling tiles and refrigerator trays

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Polyvinyl Chloride (PVC)

Unplasticized PVC is hard and tough To form and mold rigid PVC, it has to be heated above its glass transition Temperature (87OC) to make it soft and flexible When plasticized, it becomes flexible and rubbery and is used for water proof clothing
Hose pipes Electric cables insulation Chemical tank lining

It offers good resistance to attack by water, acids, alkalis and most chemicals but it becomes brittle with age.
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Polytetraflouroethylen (PTFE)
High cost Suitable for manufacturing tough moldings and as a non-stick, anti-friction coating It doesnt burn and is neither attacked by any known reagent Good electrical insulator and it has lowest co-efficient of friction of any known solid widely used for fuel hoses, gaskets and tapes and as a non-stick coating for cooking utensils Also used as a lining for chemical equipment because of its resistance to chemical attack
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Nylons
Strong, tough and flexible Good resistance to abrasion Their dimensional stability and electrical insulation properties are affected by water absorption Good resistance to most common solvents but are not good weather resistant Nylons are easily extruded and drawn into fibers.
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Polyesters
They can be thermoplastic or thermosetting Thermoplastic polyesters have good dimensional stability
resistant to most organic solvents but they are attacked by acids and alkalis. Excellent insulation properties and are used as dielectric in capacitor

Polyester films and fibers are used in textiles

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Polycarbonates
Good impact strength Good heat resistance Good dimensional stability Good electrical insulation properties Good optical properties high scratch resistance Applications are: Electrical insulators Capacitor dielectrics Lightweight spectacle lenses Aircraft components
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Properties and Applications of Thermosetting Plastics

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Phenol-formaldehyde
Phenolic resins are never used by themselves but in conjunction with fillers and other additives which reduce the inherent brittleness, improve the mechanical and electrical properties Applications are:
Electrical insulators Electrical plugs and sockets Handles Clutch and brake lining
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Urea-formaldehyde
Hard, brittle, rigid and scratch resistant Never used by itself but in conjunction with fillers and additives Resistant to most solvents and detergents Good electrical insulation properties

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Epoxides
Used for bonding glass fiber fillers Resistant to water and most reagents Have excellent insulation properties

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