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This work attempts to introduce polyhedral oligomeric silsesquioxane compounds as a novel toughening agent for thermosetting systems. For this purpose, an acrylic/melamine thermosetting system was modified by OH-functional silsesquioxane nano-cage. Mechanical and thermo-mechanical behavior of resultant nanocomposites were studied by tensile and DMTA techniques. It was found that low content of silsesquioxane building blocks is sufficient to shift the mechanical behavior of the matrix from a brittle character to a flexible tough one. Various morphological techniques (SEM and TEM equipped with elemental analyzer together with XRD) were also utilized to clarify how nano-cages have been oriented within the matrix. It was revealed that nano-cages have been well dispersed in a molecular scale within the thermosetting network. The good dispersion of silsesquioxane compounds was assigned to the high compatibility within the matrix owing to their compact structure and OH-functional groups available on the cage.

Magnetite nanoparticles in the range 7–10.5 nm were prepared by non hydrolytic sol–gel (NHSG) process in the presence of benzyl alcohol in different concentrations. The suspensions were mixed with bisphenol A diglycidyl ether (DGEBA) and cured in the presence of ytterbium(III) trifluoromethanesulfonate as cationic initiator. Magnetite nanoparticles and epoxy nanocomposites were characterized by structural, chemical and magnetic techniques. A procedure of data analysis is proposed to determine value, sign and surface contribution of the magnetic anisotropy of nanoparticles by comparing the information gained from field-cooled/zero-field-cooled magnetization curves and TEM images. Above blocking temperature, the nanoparticles dispersed in the epoxy resin give rise to an interacting superparamagnetic system and follow the corresponding scaling law. A model explains why the magnetic interaction energy depends not only on nanoparticle concentration in the epoxy but also on concentration fluctuations, being larger in samples where the nanoparticle dispersion is not uniform.

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.

α,ω-triethoxysilane terminated poly(ethylene oxide) (PEO-Si) was prepared and used to produce organic/inorganic hybrids by the sol–gel approach. These hybrids were used as coatings for flexible PVC tubes in order to reduce the plasticizer leaching from PVC medical devices. Extraction tests carried out with hexane indicated that all coating composition investigated are able to strongly reduce (about one order of magnitude) the leaching of di-ethylhexyl phthalate in hexane. The best results were obtained by an accurate balance of organic and inorganic phases content. XPS analysis showed a preferential segregation of silica onto the outer surface suggesting that a high inorganic content at the coating–extraction medium interface was present.

An exhaustive study of the co-catalytic activity of phosphates on titanium and titanium/hafnium based catalytic systems in poly(butylene terephthalate) synthesis was conducted in order to investigate any improvement in the process and/or in the properties of the final polymer with respect to the industrially used titanium based catalyst. Small scale polymerisation and subsequent scale up in higher capacity reactors showed a strong co-catalytic effect of phosphates. A screening on model compounds showed NaH 2 PO 4 to be the most active co-catalyst. The co-catalysts had a stronger effect on titanium with respect to hafnium. Decreases in polymerisation time and tetrahydrofuran formation were observed, which in turn can improve the productivity of the whole process. Moreover, the use of phosphate improved the thermal stability of the final polymers.

A complete study of the catalytic activity of lanthanide- and hafnium acetylacetonate catalysts in PBT synthesis was conducted in order to investigate any improvement in the process and/or in the properties of the final polymer with respect to the industrially used titanium tetrabutoxide (TBT) catalyst. Small scale polymerization and subsequent scale up in higher capacity reactors showed that TBT-Hf(acac) 4 and TBT-La(acac) 3 mixed catalysts were more active with respect to TBT as single catalyst. Decreases in polymerization time and THF formation were also observed, which in turn can improve the productivity of the whole process. Furthermore, for similar values of molecular weight, a lower melt viscosity (and thus better processability and crystallizability) was obtained by using mixed catalysts, presumably due to weaker interactions of the polymer terminal groups to lanthanum and hafnium metals with respect to titanium.