The effect of crystal morphology, such as the crystallinity and lamellar structure, on the radiation-induced graft polymerization of styrenesulfonate ethyl ester (E4S) onto poly(ether ether ketone) PEEK films was evaluated. The PEEK films possessing crystallinities ranging from 11 to 32% were irradiated with 30-150 kGy, and the graft polymerization was performed in an E4S/1,4-dioxane solution at 80 degrees C. For the PEEK films with crystallinities between 11 and 26%, the graft polymerization proceeded and reached grafting degrees of up to 70%, whereas for those having crystallinities higher than 26%, the reaction barely proceeded. The concentration of phenoxy radicals that initiated the graft polymerization in the irradiated PEEK films was constant over the entire range of crystallinity (11-32%). On the other hand, in the small-angle X-ray scattering (SAXS) profiles, a discontinuous change in the peak intensity at Q = 0.44 nm(-1), which corresponds to a lamellar spacing of 14 nm, was observed at a crystallinity of approximately 26%; namely, the PEEK films with a crystallinities greater than 26% exhibited prominent anisotropic scattering in the drawing direction. Judging from the above results, it can be concluded that the graft polymerization of styrene derivatives onto the PEEK films was affected by the formation of oriented lamellar structures that inhibited monomer diffusion into the films. (c) 2013 Elsevier Ltd. All rights reserved.