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Introduction
A polymer is a macromolecule composed of a large number of repeating units called monomers connected by covalent bonds. Examples of natural polymers are cellulose, rubber, wool, resins, silk and proteins. Man-made polymers include plastics such as polyethylene, polystyrene, nylon, Perspex and synthetic rubbers. Polymer degradation is a change in the properties- tensile strength, colour shape of a polymer under theinfluence of one or more environmental factors, such as heat, light, chemicals and in some cases, galvanic action.
The chemistry and technology of polymer degradation relates to the engineering issues: Material durability - mechanical and aesthetic qualities Polymer stabilization - antioxidant and UV stabilizer choices Recycling - breakdown reactions of packaging and vulcanizates
Oznolysis
Cracks can be formed in many different polymers and elastomers by ozone attack. It is characterized by form of cracks in mostly vulnerable rubber (tires) or rubber like plastic. Ozone cracks form in products under tension, but the critical strain is very small. Such cracks are very dangerous when they occur in fuel pipes because the cracks will grow from the outside exposed surfaces into the bore of the pipe, so fuel leakage and fire may follow.
Susceptible elastomers: Tiny traces of ozone in air will attack double bonds in rubber chains. Most susceptible elastomers are natural rubber, polybutadiene , styrene and nitrile rubber.
Thermal degradation
At high temperature, polymers such as poly(methyl methacrylate) become thermally unstable, leading to degradation by depolymerisation to yield a mixture of monomer and polymer. The components of the long chain backbone of the polymer separate (molecular scission) and react with one another to change the properties of the polymer. Characteristics of thermal degradation; mechanical failure i.e. possible loss in mechanical properties; ductility, malleability and brittleness is altered. Other properties altered: colour change, crack formation and molecular weight distribution.
The backbone breaks down randomly at any possible position of the backbone, forming chain molecule radicals reacting with one another in a disproportionate manner.
When the polymer is being heated, the side groups are stripped off from the backbone into small monomers, e.g. PVC.
Chlorine-induced cracking
Chlorine gas is highly reactive and attacks susceptible polymers such as acetal resin and polybutylene pipe work. Essentially the gas attacks sensitive parts of the chain molecules (especially secondary, tertiary carbon atoms), oxidising the chains and ultimately causing chain cleavage. Sometimes chlorine reduces the lining of the pipes joints carrying water thereby causing leakage & domestic flood..
Radical attacks
Radical from external, foreign to the structure polymer attacks the polymer chains .initiation starts followed by propagation and ends with termination. Radical chemistry is very disorder chemistry. So, it leads to unknown possibilities of change in the polymer properties.
Hydrolysis
Some polymers such as nylon is sensitive to degradation by acids, a process known as hydrolysis, and nylon mouldings will crack when attacked by strong acids.
Oxidative degradation
Polymer degradation is almost always faster in the presence of oxygen (air), due primarily to the auto accelerating nature of reactions between oxygen and carbon centered radicals; especially at elevated temperatures encountered during processing to shape.
Plastic degradation can occur aerobically or anaerobically. In this case aerobically is considered. It is characterized by physical disintegration and drastic reduction in molecular weight. Plastic becomes like flakes .Conversion of carbon into monomers and carbon dioxide gradually happens.
New Plastic
later on
Other agents of degradation include micro organism leading to biological attack & ionizing radiation leading to radiolysis.
Photo-oxidation
Photo-oxidation is the oxidation of a polymer surface in the presence of oxygen or ozone that is facilitated by radiant energy such as UV or artificial light. This process is often the most significant component of weather degradation of polymers. Photo-oxidation results in chemical changes and normally a reduction in the polymer's molecular weight. Consequently, the material becomes more brittle coinciding with a reduction in tensile strength, impact strength, elongation at break. Often discoloration and loss of gloss accompany photo-oxidation. High temperature and stress concentration are significant factors to increase reaction rate of photooxidation. Graph of hardness v/s deepness
Material becomes less ductile at surface compared to inside the material cracks can be encouraged as a result on the surface hardness.