Deterioration, polymers

Chisso VCM Removal PVC slurry with unreacted VCM Stripping process for PVC plants to recover VCM from PVC slurry VCM can be reused without deteriorating polymer quality 36 2000... 

Deterioration proceeds inwards from the surface and the degree of deterioration varies with exposure time (t) and the depth from the surface (x). As the deterioration advances, deteriorated polymer molecules having infrared (IR) active functional groups as carbonyl (-CO) are created, and the degree of deterioration is reflected in... 

One of the problems generally associated with the utilization of additives is the continuous action under the engine s operating conditions. That is particularly important for polymers that are sensitive to mechanical deterioration due to shear effects. 

Environmental Aging. AH ceUular polymers are subject to a deterioration of properties under the combined effects of light or heat and oxygen. The response of ceUular materials to the action of light and oxygen is governed almost entirely by the composition and state of the polymer phase (22). Expansion of a polymer into a ceUular state increases the surface area reactions of the foam with vapors and Hquids are correspondingly faster than those of soHd polymer. 

These polymers possess enhanced solubility compared to the aromatic polyamides with no deterioration in thermal stability. Their Ts vary from... 

The actual time required for poly-L-lactide implants to be completely absorbed is relatively long, and depends on polymer purity, processing conditions, implant site, and physical dimensions of the implant. For instance, 50—90 mg samples of radiolabeled poly-DL-lactide implanted in the abdominal walls of rats had an absorption time of 1.5 years with metaboHsm resulting primarily from respiratory excretion (24). In contrast, pure poly-L-lactide bone plates attached to sheep femora showed mechanical deterioration, but Httie evidence of significant mass loss even after four years (25). 

Many antioxidants ia these classes are volatile to some extent at elevated temperatures and almost all antioxidants are readily extracted from their vulcanizates by the proper solvent. These disadvantages have become more pronounced as performance requirements for mbber products have been iacreased. Higher operating temperatures and the need for improved oxidation resistance under conditions of repeated extraction have accelerated the search for new techniques for polymer stabilization. Carpet backiag, seals, gaskets, and hose are some examples where high temperatures and/or solvent extraction can combine to deplete a mbber product of its antioxidant and thus lead to its oxidative deterioration faster (38,40). 

Catalysts in this service can deactivate by several different mechanisms, but deactivation is ordinarily and primarily the result of deposition of carbonaceous materials onto the catalyst surface during hydrocarbon charge-stock processing at elevated temperature. This deposit of highly dehydrogenated polymers or polynuclear-condensed ring aromatics is called coke. The deposition of coke on the catalyst results in substantial deterioration in catalyst performance. The catalyst activity, or its abiUty to convert reactants, is adversely affected by this coke deposition, and the catalyst is referred to as spent. The coke deposits on spent reforming catalyst may exceed 20 wt %. 

The extent of the long-chain branching of a series of ethyl xanthogen disulfide modified polymers carried to increasing conversion is shown in Table 1. No branches are found until 56% conversion. The gel point is a Htfle over 82%. Polymer rheology deteriorates between 56 and 82% conversion. 

Finally mention may be made about the influence of humidity on the electrical insulating properties of plastics. Once again the polymers may be classified into two groups, those which do not absorb water and those which do. The nonabsorbent materials are little affected by humidity whereas the insulation characteristics of the absorbent materials deteriorate seriously. These latter materials are generally certain polar materials which all appear capable of forming some sort of bond, probably a hydrogen bond, with water. Three reasons may be given for the deleterious effects of the water. 

The chemical resistance of polyethylene is, to a large measure, that expected of an alkane. It is not chemically attacked by non-oxidising acids, alkalis and many aqueous solutions. Nitric acid oxidises the polymer, leading to a rise in power factor and to a deterioration in mechanical properties. As with the simple alkanes, halogens combine with the hydrocarbon by means of substitution mechanisms. 

As with c -polyisoprene, the gutta molecule may be hydrogenated, hydro-chlorinated and vulcanised with sulphur. Ozone will cause rapid degradation. It is also seriously affected by both air (oxygen) and light and is therefore stored under water. Antioxidants such as those used in natural rubber retard oxidative deterioration. If the material is subjected to heat and mechanical working when dry, there is additional deterioration so that it is important to maintain a minimum moisture content of 1%. (It is not usual to vulcanise the polymer.)... 

Increase in the chain branching in the polychloroprene, reducing the stability in polymer viscosity and deteriorating the processing properties. 

Stabilisers. Stabilisers prevent deterioration of the polymer due to environmental factors. Antioxidants are added to ABS, polyethylene and polystyrene. Heat stabilisers are required in processing polyvinyl chloride. Stabilisers also prevent deterioration due to ultra-violet radiation. 

Weathering. This generally occurs as a result of the combined effect of water absorption and exposure to ultra-violet radiation (u-v). Absorption of water can have a plasticizing action on plastics which increases flexibility but ultimately (on elimination of the water) results in embrittlement, while u-v causes breakdown of the bonds in the polymer chain. The result is general deterioration of physical properties. A loss of colour or clarity (or both) may also occur. Absorption of water reduces dimensional stability of moulded articles. Most thermoplastics, in particular cellulose derivatives, are affected, and also polyethylene, PVC, and nylons. 

In cases when the two surfaces are non-equivalent (e.g., an attractive substrate on one side, an air on the other side), similar to the problem of a semi-infinite system in contact with a wall, wetting can also occur (the term dewetting appHes if the homogeneous film breaks up upon cooHng into droplets). We consider adsorption of chains only in the case where all monomers experience the same interaction energy with the surface. An important alternative case occurs for chains that are end-grafted at the walls polymer brushes which may also undergo collapse transition when the solvent quality deteriorates. Simulation of polymer brushes has been reviewed recently [9,29] and will not be considered here. 

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