Irradiation polymeric materials

Among the various radiation-induced modifications, the EB-processing of polymers has gained special importance as it requires less energy, is simple, fast, and versatile in application. The overall properties of EB-irradiated polymeric materials are also improved compared to those induced by other ionizing radiation. 

James H. O DoimeU, ed.. Irradiation of Polymeric Materials Processes, Mechanisms and Applications, American Chemical Society, Washington, D.C., 1993. 

Cross-hnking efficiency of a polymeric material also depends whether the irradiation is carried out in the presence or absence of air, e.g., oxygen has been found to increase the... 

EB irradiation of polymeric materials leads to superior properties than the 7-ray-induced modification due to the latter having lower achievable dose rate than the former. Because of the lower dose rate, oxygen has an opportunity to diffuse into the polymer and react with the free radicals generated thus causing the greater amount of chain scissions. EB radiation is so rapid that there is insufficient time for any significant amount of oxygen to diffuse into the polymer. Stabilizers (antirads) reduce the dose-rate effect [74]. Their effectiveness depends on the abUity to survive irradiation and then to act as an antioxidant in the absence of radiation. 

Chlorinated dibenzo ip-dioxins are contaminants of phenol-based pesticides and may enter the environment where they are subject to the action of sunlight. Rate measurements showed that 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) is more rapidly photolyzed in methanol than octachlorodi-benzo-p-dioxin. Initially TCDD yields 2,3,7-trichlorodiben-zo-p-dioxin, and subsequent reductive dechlorination is accompanied by ring fission. Pure dibenzo-p-dioxin gave polymeric material and some 2,2 -dihydroxybiphenyl on irradiation. Riboflavin-sensitized photolysis of the potential precursors of dioxins, 2,4-dichlorophenol and 2,4,5-trichloro-phenol, in water gave no detectable dioxins. The products identified were chlorinated phenoxyphenols and dihydroxy-biphenyls. In contrast, aqueous alkaline solutions of purified pentachlorophenol gave traces of octachlorodibenzo-p-dioxin on irradiation. 

Polyethylene and polystyrene are examples of plastics subject to environmental stress cracking. Crack resistance tests have shown that surfactants, alcohols, organic acids, vegetable and mineral oils, and ethers provide an active environment for stress cracking of polyethylene. Table 6 lists typical sterile devices and plastic materials used to fabricate them, while Tables 7-9 list the potential effects of sterilization processes on polymeric materials. The effect of gamma irradiation on elastomeric closures has been studied by the Parenteral Drug Association [15]. 

Irradiation of cycloocta-2,4-dien-l-one (55) in pentane gives a racemic photodimer, anti-tricyclofSAO.O Jhexadeca- , 11 -diene-3,16-dione (60) in 10% yield along with polymeric materials 34). Efficient and enantioselective photodimerization of 58 was achieved by irradiation of the 2 1 inclusion complex 59 formed between 2 a and 5813). When a solution of 2a and an equimolar amount of 58 in ether-hexane (1 1) was kept at room temperature for 12 h, 59 was obtained as colorless needles of mp 105 to 108 °C. Irradiation of 59 in the solid state for 48 h gave (—)-60 of 78 % ee in 55 % yield. 

It is clear from this discussion that the dose requirement and unit cost will be lower if the material has a higher molar mass M and the reaction has a high G value. Thus, the best candidates will be a polymeric material and a chain reaction. Quite often, a free-radical irradiation is used. The radiation source of choice is usually a 60Co - y facility, although electron beam irradiation is also used. Since most radiation-chemical reactions used in industry can also be brought about by other conventional means such as thermal, or photochemical processes, the processing cost must be below 10irradiation cost one has to include the cost of operation, maintenance, and the like. (Danno, 1960). 

Ohmae and Katsui irradiated vitamin K-l (82) in alcoholic solution with UV light and obtained the hydroperoxide (85), its corresponding hydroxide and the ketone (89). Also isolated were phthiocol (90), the naphthofuran (91) and polymeric material [69], Similar irradiation in benzene gave (89) and (91) [70],... 

The U.S. - Australia Symposium on Radiation Effects on Polymeric Materials contained research presentations on fundamental radiation chemistry and physics as well as on technological applications of polymer irradiation. This paper represents a hybrid contribution of these two areas, examining a field of extensive technological importance. Spin casting of radiation sensitive polymer resists for microelectronic fabrication was studied using photophysical techniques that are sensitive to the fundamental radiation response in the ultraviolet range. 

The irradiation of polymers is widespread in many industries. For example, microlithography is an essential process in the fabrication of integrated circuits that involves the modification of the solubility or volatility of thin polymer resist films by radiation. The sterilization by radiation of medical and pharmaceutical items, many of which are manufactured from polymeric materials, is increasing. This trend arises from both the convenience of the process and the concern about the toxicity of chemical sterilants. Information about the radiolysis products of natural and synthetic polymers used in the medical industry is required for the evaluation of the safety of the process. 

ETEROAROMATics FURAN AND THIOPHENE. The chemical transformation of thiophene at high pressure has not been studied in detail. However, an infrared [441,445] study has placed the onset of the reaction at 16 GPa when the sample becomes yellow-orange and the C—H stretching modes involving sp carbon atoms are observed. This reaction threshold is lower than in benzene, as expected for the lower stability of thiophene. The infrared spectrum of the recovered sample differs from that of polythiophene, and the spectral characteristics indicate that it is probably amorphous. Also, the thiophene reaction is extremely sensitive to photochemical effects as reported by Shimizu and Matsunami [446]. Thiophene was observed to transform into a dark red material above 8 GPa when irradiated with 50 mW of the 514.5-nm Ar+ laser line. The reaction was not observed without irradiation. This material was hypothesized to be polythiophene because the same coloration is reported for polymeric films prepared by electrochemical methods, but no further characterization was carried out. 

Polymeric material that, when irradiated, undergoes a marked change in solubility in a given solvent or is ablated. 

Plastics are by far the largest group of polymeric materials being processed by electron beam irradiation. Cross-linking of polyolefins, PVC, polyesters, polyurethanes, fluoropolymers, and fiber-reinforced composites is a common practice. 

Different polymeric materials respond to irradiation by electron beam in different ways. Many will be modified by the formation of a cross-linked network, and by changing their surface properties or structure, some will be degraded. Another field applicable to polymeric systems is polymerization and grafting. An electron beam can also be used for polymerization and cross-linking of oligomers and monomers, i.e., in conversion of liquids to solids. 

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