IRRADIATION DEGRADATION

Ketone photolysis in an inert atmosphere has been widely studied--ft 5-Q. Apart from polymer photooxidation studies, however, little work has been done on their degradative irradiation in an oxidizing medium51 53. 

Degradation of materials is less desirable, but controlled scission can be of industrial importance like e.g. the use of degraded irradiated polytetrafluoro-ethylene as lubricating agent. For polypropylene an attractive feature could be to polymerize one base-grade of polymer and to produce numerous subgrades via controlled degradation. 

Radiation Effects. Polytetrafluoroethylene is attacked by radiation. In the absence of oxygen, stable secondary radicals are produced. An increase in stiffness in material irradiated in vacuum indicates cross-linking (84). Degradation is due to random scission of the chain the relative stabiUty of the radicals in vacuum protects the materials from rapid deterioration. Reactions take place in air or oxygen and accelerated scission and rapid degradation occur. 

Heat stabilizers protect polymers from the chemical degrading effects of heat or uv irradiation. These additives include a wide variety of chemical substances, ranging from purely organic chemicals to metallic soaps to complex organometaUic compounds. By far the most common polymer requiring the use of heat stabilizers is poly(vinyl chloride) (PVC). However, copolymers of PVC, chlorinated poly(vinyl chloride) (CPVC), poly(vinyhdene chloride) (PVDC), and chlorinated polyethylene (CPE), also benefit from this technology. Without the use of heat stabilizers, PVC could not be the widely used polymer that it is, with worldwide production of nearly 16 million metric tons in 1991 alone (see Vinyl polymers). 

Polydioxanone (PDS) is completely elirninated from the body upon absorption. The mechanism of polydioxanone degradation is similar to that observed for other synthetic bioabsorbable polymers. Polydioxanone degradation in vitro was affected by gamma irradiation dosage but not substantially by the presence of enzymes (39). The strength loss and absorption of braided PDS, but not monofilament PDS, implanted in infected wounds, however, was significantly greater than in noninfected wounds. 

Water-soluble sdanols such as (1) were found to undergo successive oxidative demethylations with tropospheric ultraviolet irradiation in the presence of suitable chromophores, such as nitrogen oxides (516). The water-soluble methylated sdicones did not promote diatom (Nap cu/apelliculosd) growth but the demethylated photo products did. The sequence of sod-induced degradation of sdicones to water-soluble species such as (1), followed by light-induced conversion to sdicate, suggests a pathway, conceptually at least, for the mineralization of sdicones. 

Degradation of carbon tetrachloride by photochemical, x-ray, or ultrasonic energy produces the trichloromethyl free radical which on dimeri2ation gives hexachloroethane. Chloroform under strong x-ray irradiation also gives the trichloromethyl radical intermediate and hexachloroethane as final product. 

An algorithm has been developed to predict the thermal conductivity degradation for a high thermal conductivity composite ( 555 W/m-K at room temperature) as a function of radiation dose and temperature [33]. The absence of irradiation data on CFCs of this type required the use of data from intermediate thermal conductivity materials as well as pyrolitic graphite to derive an empirical radiation damage term [14, 17, 19, 25, 26]. 

Fig. 7. Irradiation induced thermal conductivity degradation of selected graphite materials.

To illustrate the usefulness of such an algorithm, and the seriousness of the issue of thermal conductivity degradation to the design and operation of PFCs, the algorithm discussed above has been used to construct Fig. 9 [34], which shows the isotherms for a monoblock divertor element in the unirradiated and irradiated state and the "flat plate" divertor element in the irradiated state. In constmcting Fig. 9, the thermal conductivity saturation level of 1 dpa given in Fig. 8 is assumed, and the flat plate and monoblock divertor shown are receiving a steady state flux of... 

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