The novel biodegradable poly(ϵ-caprolactone)/titanium dioxide hybrid materials were prepared via in situ sol-gel process of tetrabutyl titanate (TBT) as inorganic precursor in the presence of PCL. The relationships between morphology, microphase separation, crystalline structure, and properties were investigated by means of XPS, SEM, XRD, DSC, and in vitro degradation test. The microstructures of the bulk hybrids display two-phase microscopic separation on the nanometer scale, which domain is 20–80 nm. The surface morphology and intermolecular bonding interaction are significantly dependent on inorganic component. The relative crystalline degrees of PCL/TiO₂ hybrid nanocomposite materials were controlled by both inorganic component and hydrogen bonding special interaction. The hybrid nanocomposite materials with TiO₂ showed faster biodegradation rate than that of pure PCL itself, and the transparency corresponding to microstructure increase with increase of inorganic component content. © 2007 Wiley Periodicals, Inc. J Biomed Mater Res 2007

Some hydrogen-bonding-interactions-mediated poly(ε-caprolactone) (PCL)/silica (SiO₂) polymeric-inorganic hybrids were prepared by the sol–gel process. The non-isothermal crystallization kinetics of PCL in the hybrids was investigated by means of differential scanning calorimetry. The results show that the Jeziorny method, together with the combination of the Avrami and Ozawa equations, is applicable to describe the non-isothermal crystallization kinetics of the PCL in the hybrid system, while the Ozawa theoretical method can be used just for the pure PCL and the 70/30 TEOS/PCL hybrids. Depending on the composition of the PCL/silica, the hybrids displayed microphase separation at various scales, which in turn affect the crystallization behavior and mechanism of PCL in the hybrids. On the one hand, the inorganic component (viz SiO₂) could act as the nucleating agent to facilitate the crystallization of PCL in the hybrids. On the other hand, the SiO₂ networks also confine the crystallization of PCL. Copyright © 2004 Society of Chemical Industry

Inorganic–organic hybrids mediated by hydrogen-bonding interactions involving silicon oxide network and poly(ε-caprolactone) (PCL) were prepared via an in situ sol–gel process of tetraethoxysilane in the presence of PCL. Fourier transform infrared spectroscopy indicated that there were hydrogen-bonding interactions between carbonyls of PCL and silanol hydroxyls that were formed by incomplete polycondensation in the sol–gel process. In terms of the frequency shift of the hydroxyl stretching vibration bands, it is concluded that the strength of the interassociation between PCL and silicon oxide networks is weaker than that of the self-association in the control silica network. The phenomenon of equilibrium melting point depression was observed for the PCL/silica system. The hybridization of PCL with silica network causes a considerable increase in the overall crystallization rate and dramatically influences the mechanism of nucleation and growth of the PCL crystallization. The analysis of isothermal crystallization kinetic data according to the Hoffman-Lauritzen theory shows that with increasing silica content in the hybrids, the surface energy of extremity surfaces increases dramatically for the hybrids. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2594–2603, 2005