Modes of degradation of polymers

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 Degradation reactions include: 1. 2. 3. 4. 5. Thermal degradation Oxidative degradation Photo-degradation Hydrolysis (esters, amides) Chlorine-induced cracking

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. Thermal degradation generally involves changes to the molecular weight of the polymer and typical property changes include reduced ductility and embrittlement, chalking, colour changes, cracking, general reduction in most other desirable physical properties.

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 centred radicals; especially at elevated temperatures encountered during processing to shape. Many process methods such as extrusion and injection moulding involve pumping molten polymer into tools, and the high temperatures needed for melting may result in oxidation unless precautions are taken. Interactions with oxygen lead to an increase in the concentration of polymer alkyl radicals (R), and therefore to higher levels of scission and crosslinking products. Additionally, fragmentation reactions of oxygen-centred radicals (RO) yield new species (oxidation products), not found in polymers processed under air-free conditions.

Photo-degradation Photo-oxidation is the oxidation of a polymer surface in the presence of oxygen or ozone that is facilitated radiant energy such as UV or artificial light. This proces is often the 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-oxidaiton. High temperature and stress concentration are significant factors to increase reaction rate of photo-oxidation. Effect of UV irradiation on the mechanical and physical properties of low-density polyethylene during the early stages of exposure: Dynamic modulus Elongation at break Gel content Density Oznolysis Cracks can be formed in many different elastomers by ozone attack. Tiny traces of the gas in the air attack double bonds in rubber chains, with natural rubber, styrene-butadiene rubber being most sensitive to degradation. 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.

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. Chlorine-induced cracking Chlorine gas is highly reactive and attacks susceptible polymers such as acetal resin and polybutylene pipework. Essentially the gas attacks sensitive parts of the chain molecules (especially secondary, tertiary carbon atoms), oxidising the chains and ultimately causing chain cleavage.