Degradation of epoxy coatings under gamma irradiation

Epoxy networks based on Diglycidyl ether of bisphenol A (DGEBA) and cured with Jeffamine (R) (POPA) or polyamidoamine (PM) were gamma irradiated at 25 degrees C in air. Dose rates of 50, 200 or 2000 Gy h(-1) for doses up 100 kGy were used. Structural changes were monitored by IR spectrophotometry, DSC and sol-gel analysis. Both networks display some common features: for I >= 200 Gy h(-1), reaction products grow proportionally to time and the rate is a decreasing function of dose rate. The simplest explanation is that peroxy radicals are the main precursors of these products (in the dose rate domain under study), through a unimolecular rearrangement of which an hypothetical mechanism is proposed. DGEBA-POPA are more reactive then DGEBA-PAA networks (according to IR criteria), that can be attributed to the high reactivity of tertiary CH bands in polyoxypropylene segments. The oxidation of these sites leads to methyl ketones. A simple kinetic model in which methyl ketones result from rearrangements of tertiary peroxyls and from tertiary alkoxyls was proposed. It leads to an expression of the radiochemical yield of methyl ketones (G(MK)) of the form G(MK) = a+bI(-1/2) where a and b are parameters depending of elementary rate constants. Experimental G(MK) values are reasonably well fitted by this equation. In DGEBA-PAA networks, a wide variety of oxidation products, among which amides predominate, can be observed. In these networks, chain scissions predominate over crosslinking, whereas a slight predominance of crosslinking was observed, at least for the lowest dose rate, in DGEBA-POPA. (C) 2012 Elsevier Ltd. All rights reserved.