Photo-cured epoxy networks reinforced with TiO2 in-situ generated by means of non-hydrolytic sol-gel process

Suspensions of titania nanoparticles in benzyl alcohol were synthesised from TiCl4 by means of non-hydrolytic sol-gel (NHSG) process. The stable suspensions were mixed with an aliphatic epoxy resin and subsequently photo-polymerised in the presence of a cationic photo-initiator to produce transparent composite films. The presence of titania didn't influence significantly the polymerisation rate, while a progressive decrease in the maximum value of epoxy groups conversion was observed by increasing the titania content. Gel content analysis demonstrated that all organic species (benzyl alcohol and corresponding by-products) were covalently linked to the epoxy network, suggesting that both 'active chain end' and 'activated monomer' mechanisms were active during the propagation step in the cationic ring-opening polymerisation. The presence of titania increased significantly both glass transition temperature and modulus (in the rubbery region) confirming the reinforcing and stiffening effect due to both the presence of inorganic nanofillers and, most importantly, a higher cross-linking density of the composite material with respect to the pristine epoxy matrix. Nano-indentation and scratch tests also showed a systematic increase of hardness and scratch resistance by increasing the filler content. © 2011 Elsevier Ltd. All rights reserved.