Irradiation with poly , influence

For low radiation doses, peroxides accumulate almost linearly with dose. However, after a certain dose has been reached, their concentration tends to level off. This conclusion can be derived from the observed change in the rate of graft copolymerization initiated by polymers subjected to increasing doses of preirradiation in air. Figure 2 illustrates this effect in the case of grafting acrylonitrile onto polyethylene (2). The drop in the yield of peroxide production presumably results from the efficient radiation-induced decomposition of these peroxides. Peroxides are known to decompose under free radical attack, and selective destruction of peroxides under irradiation has been established experimentally (8). This decomposition can become autocatalytic, and sometimes the concentration of peroxides may reach a maximum at a certain dose and decrease on further irradiation. Such an effect was observed in the case of poly (vinyl chloride). Figure 3 shows the influence of preirradiation dose on the grafting ratio obtained with poly (vinyl chlo-... 

H.P. Brack, H.G. Buhrer, L. Bonorand, and G.G. Scherer. Grafting of pre-irradiated poly(ethylene-alt-tetrafluoroethylene) films with styrene Influence of base polymer film properties and processing parameters. Journal of Materials Chemistry 10, 1795-1803 2000. 

Tiwari and Prabaharan (2010) develop amphiphilic guar gum grafted with poly (epsilon-caprolactone) using microwave irradiation technique. Under the influence of microwave, guar gum with high poly (epsilon-caprolactone) grafting... 

These pioneer studies laid dormant until 1977 and, influenced by Kondo and colleagues [59] reports on the synthesis of po]y(vinylsulfonium yiide) with a trivaient sulfur attached directly to the polymer chain, poly[ethyl-vinylsulfonium bis-(methoxycarbonyl) methylide] (Scheme 25) was prepared by irradiation of a benzene... 

Maleimides Alkyl and aryl maleimides in small concentrations, e.g., 5-10 wt% significantly enhance yield of cross-link for y-irradiated (in vacuo) NR, cw-l,4-polyisoprene, poly(styrene-co-butadiene) rubber, and polychloroprene rubber. A-phenyhnaleimide and m-phenylene dimaleimide have been found to be most effective. The solubihty of the maleimides in the polymer matrix, reactivity of the double bond and the influence of substituent groups also affect the cross-fink promoting ability of these promoters [82]. The mechanism for the cross-link promotion of maleimides is considered to be the copolymerization of the rubber via its unsaturations with the maleimide molecules initiated by radicals and, in particular, by allyfic radicals produced during the radiolysis of the elastomer. Maleimides have also been found to increase the rate of cross-linking in saturated polymers like PE and poly vinylacetate [33]. 

Effect of Polyhalogenated Additives. We (36) have also observed that the rate of bleaching of solid polysilane films upon irradiation is considerably slower than that observed for solutions at comparable optical densities. Although this result is consistent with the observed decrease in the quantum yields for scission, 4>(s), in going from solution to the solid state (24) (vide infra), this decreased sensitivity is inconvenient for imaging processes. For this reason, a search was made for compatible additives that might influence the bleaching rate of poly silane derivatives in the solid state. 

Also, the method how the ablation parameters are acquired can have a pronounced influence on the results. The ablation rate can be defined either as the depth of the ablation crater after one pulse at a given fluence, or as the slope of a linear fit of a plot of the ablation depth versus the pulse number for a given fluence. Very different ablation rates can result from the two different measurement methods. This is especially the case for materials where ablation does not start with the first pulse, but after multiple pulses, or if the ablation crater depth after one pulse is too small to be measured. The process that occurs if ablation does not start with the first laser pulse is called incubation. It is related to physical or chemical modifications of the material by the first few laser pulses, which often results in an increase of the absorption at the irradiation wavelength [32,33], for example, the formation of double bonds in poly (methylmethacrylate) (PMMA). Incubation is normally observed only for polymers with low absorption coefficients at the irradiation wavelength. 

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