Polymer degradation
Polymer degradation is a change in the properties—tensile strength, color, shape, etc.—of a polymer or polymer-based product under the influence of one or more environmental factors such as heat, light or chemicals such as acids, alkalis and some salts. These changes are usually undesirable, such as cracking and chemical disintegration of products or, more rarely, desirable, as in biodegradation, or deliberately lowering the molecular weight of a polymer for recycling. The changes in properties are often termed "aging".
In a finished product such a change is to be prevented or delayed. Degradation can be useful for recycling/reusing the polymer waste to prevent or reduce environmental pollution. Degradation can also be induced deliberately to assist structure determination.
Polymeric molecules are very large, and their unique and useful properties are mainly a result of their size. Any loss in chain length lowers tensile strength and is a primary cause of premature cracking.
Commodity polymers
Today there are primarily seven commodity polymers in use: polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, polycarbonate, and poly. These make up nearly 98% of all polymers and plastics encountered in daily life. Each of these polymers has its own characteristic modes of degradation and resistances to heat, light and chemicals. Polyethylene, polypropylene, and poly are sensitive to oxidation and UV radiation, while PVC may discolor at high temperatures due to loss of hydrogen chloride gas, and become very brittle. PET is sensitive to hydrolysis and attack by strong acids, while polycarbonate depolymerizes rapidly when exposed to strong alkalis.For example, polyethylene usually degrades by random scission—that is by a random breakage of the linkages that hold the atoms of the polymer together. When this polymer is heated above 450 Celsius it becomes a complex mixture of molecules of various sizes that resemble gasoline. Other polymers—like polyalphamethylstyrene—undergo 'specific' chain scission with breakage occurring only at the ends; they literally unzip or depolymerize to become the constituent monomers.
Photoinduced degradation
Most polymers can be degraded by photolysis to give lower molecular weight molecules. Electromagnetic waves with the energy of visible light or higher, such as ultraviolet light, X-rays and gamma rays are usually involved in such reactions.Thermal degradation
like poly can be degraded by thermolysis at high temperatures to give monomers, oils, gases and water. The degradation takes place by:| Thermolysis type | Added material | Temperature | Pressure | Final product |
| Pyrolysis | Around 500 °C | Reduced pressure | ||
| Hydrogenation | Dihydrogen | Around 450 °C | Around 200 bars | |
| Gasification | Dioxygen and/or water | Under pressure | Carbon monoxide, Carbon dioxide and hydrogen |
Chemical degradation
Solvolysis
like polyesters, polyamides and polycarbonates can be degraded by solvolysis and mainly hydrolysis to give lower molecular weight molecules. The hydrolysis takes place in the presence of water containing an acid or a base as catalyst.Polyamide is sensitive to degradation by acids and polyamide mouldings will crack when attacked by strong acids. For example, the fracture surface of a fuel connector showed the progressive growth of the crack from acid attack to the final cusp of polymer. The problem is known as stress corrosion cracking, and in this case was caused by hydrolysis of the polymer. It was the reverse reaction of the synthesis of the polymer:
Ozonolysis
Cracks can be formed in many different elastomers by ozone attack. Tiny traces of the gas in the air will attack double bonds in rubber chains, with Natural rubber, polybutadiene, Styrene-butadiene rubber and NBR being most sensitive to degradation. Ozone cracks form in products under tension, but the critical strain is very small. The cracks are always oriented at right angles to the strain axis, so will form around the circumference in a rubber tube bent over. Such cracks are dangerous when they occur in fuel pipes because the cracks will grow from the outside exposed surfaces into the bore of the pipe, and fuel leakage and fire may follow. The problem of ozone cracking can be prevented by adding anti-ozonants to the rubber before vulcanization. Ozone cracks were commonly seen in automobile tire sidewalls, but are now seen rarely thanks to these additives. On the other hand, the problem does recur in unprotected products such as rubber tubing and seals.Oxidation
The polymers are susceptible to attack by atmospheric oxygen, 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. For example, a forearm crutch suddenly snapped and the user was severely injured in the resulting fall. The crutch had fractured across a polypropylene insert within the aluminium tube of the device, and infra-red spectroscopy of the material showed that it had oxidized, possible as a result of poor moulding.Oxidation is usually relatively easy to detect owing to the strong absorption by the carbonyl group in the spectrum of polyolefins. Polypropylene has a relatively simple spectrum with few peaks at the carbonyl position. Oxidation tends to start at tertiary carbon atoms because the free radicals formed here are more stable and longer lasting, making them more susceptible to attack by oxygen. The carbonyl group can be further oxidised to break the chain, this weakens the material by lowering its molecular weight, and cracks start to grow in the regions affected.