Physical, electrochemical and biological evaluations of spin-coated ε-polycaprolactone thin films containing alumina/graphene/carbonated hydroxyapatite/titania for tissue engineering applications.

Composite structures are at the frontier of materials science and engineering and polymeric/ceramic composites present one of their most prospective subsets. Prior studies have shown both improvements and deteriorations of properties of polymers upon the addition of ceramic phases to them, but not many studies have dealt with the direct comparison of chemically distinct inorganic additives. The goal of this study was to compare the properties of ε-polycaprolactone (PCL) thin films supplemented with alumina, graphene, carbonated hydroxyapatite or titania particles, individually, in identical amounts (12 wt%). The composite films were analyzed for their phase composition, grain size, morphology, surface roughness, porosity, cell response, mechanical properties and electrochemical performance. Each additive imparted one or more physical or biological properties onto PCL better than others. Thus, alumina increased the microhardness of the films better than any other additive, with the resulting values exceeding 10 MPa. It also led to the formation of a composite with the least porosity and the greatest stability to degradation in simulated body fluid based on open circuit potential (OCP) measurements and electrochemical impedance spectroscopy (EIS). Titania made the surface of PCL roughest, which in combination with its high porosity explained why it was the most conducive to the growth of human fibroblasts, alongside being most prone to degradation in wet, corrosive environments and having the highest Poisson's ratio. Graphene, in contrast, made the surface of PCL smoothest and the bulk structure most porous, but also most conductive, with the OCP of -37 mV. The OCP of PCL supplemented with carbonated hydroxyapatite had the highest OCP of -134 mV and also the highest mechanical moduli, including the longitudinal (781 MPa), the shear (106 MPa), the bulk (639 MPa), and the elastic (300 MPa). The only benefit of the deposition of multilayered PCL films supplemented with all four inorganic additives was to enable a relatively high resistance to degradation. This study demonstrates that the properties of thin PCL films could be effectively optimized through the simple choice of appropriate inorganic additives dispersed in them. There is no single additive that proves ideal for improving all the properties of interest in PCL thin films, but their choice should be adjusted to the actual application. One such method of compositional optimization could prove crucial in the effort to develop biocomposites for superior performance in tissue engineering applications.