Polyethylene degradation resistance

Despite its oxygen content, polyester (i.e., the aromatic polyethylene terephthalate) is degradation-resistant probably because of its rigid, rod-like chains. The same is true for polyamides in spite of their nitrogen content. 

In the presence of light, halogens attack both vulcanised and unvulcanised butyl rubber. Whether vulcanised or unvulcanised the effect of the reaction is to produce rapid deterioration in molecular weight. A strip of butyl vulcanisate suspended in bromine gas degrades rapidly. In a few minutes the specimen becomes fluid enough to drip to the bottom of the vessel. Chlorosulfonated polyethylene is resistant to ozone being better than Neoprene and butyl rubber compounds [18]. 

A. Lustiger, Understanding Environmental Stress Cracking in Polyethylene, in Medical Plastics Degradation, Resistance Failure Analysis ed. R.C. Portnoy (SPE, Plastic Design Library, Rice RC, Tritsch DE, 1998), pp. 66-71... 

There is much evidence that weak links are present in the chains of most polymer species. These weak points may be at a terminal position and arise from the specific mechanism of chain termination or may be non-terminal and arise from a momentary aberration in the modus operandi of the polymerisation reaction. Because of these weak points it is found that polyethylene, polytetrafluoroethylene and poly(vinyl chloride), to take just three well-known examples, have a much lower resistance to thermal degradation than low molecular weight analogues. For similar reasons polyacrylonitrile and natural rubber may degrade whilst being dissolved in suitable solvents. 

Since acetal resins are degraded by ultra violet light, additives may be included to improve the resistance of the polymer. Carbon black is effective but as in the case of polyethylene it must be well dispersed in the polymer. The finer the particle size the better the ultra violet stability of the polymer but the poorer the heat stability. About 1.5% is generally recommended. For white compounds and those with pastel colours titanium dioxide is as good in polyacetals as most transparent ultraviolet absorbers, such as the benzophenone derivatives and other materials discussed in Chapter 7. Such ultraviolet absorbers may be used for compounds that are neither black, white nor pastel shade in colour. 

All polyethylenes are soft, flexible and resistant to acids and alkalis up to 60°C. They retain this flexibility down to —40°C. Hence they have good resistance to impact even at low temperatures. However, unless correctly formulated they can suffer from environmental stress cracking (ESC), poor adhesion and UV degradation. ESC is the phenomenon which occurs when a thermoplastic is put under stress, e.g. bent, in a particular environment and prematurely cracks or crazes. Alcohol and detergent are examples of agents that can cause ESC in polyethylenes. 

Compared with tar, which has a relatively short lifetime in the marine environment, the residence times of plastic, glass and non-corrodible metallic debris are indefinite. Most plastic articles are fabricated from polyethylene, polystyrene or polyvinyl chloride. With molecular weights ranging to over 500,000, the only chemical reactivity of these polymers is derived from any residual unsaturation and, therefore, they are essentially inert chemically and photochemically. Further, since indigenous microflora lack the enzyme systems necessary to degrade most of these polymers, articles manufactured from them are highly resistant or virtually immune to biodegradation. That is, the properties that render plastics so durable... 

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