Rapid and topotactic transformation from octacalcium phosphate to hydroxyapatite (HAP): A new approach to self-organization of free-standing thin-film HAP-based nanohybrids

Abstract

Biomineralization-inspired processing is attractive for the preparation of functionalized inorganic/organic polymer hybrid materials because the materials are obtained under mild conditions and by using organic templates. As for the formation processes of ordered nanocrystalline hydroxyapatite (HAP), the preparation of self-standing hybrid films based on HAP has not yet been established. In the present study, self-standing thin-film hybrids composed of HAP and poly(vinyl alcohol) (PVA) are obtained by rapid and topotactic transformation of thin films based on octacalcium phosphate (OCP) as a precursor in the organic polymer matrix. Bioinspired crystallization of calcium phosphate on the PVA matrix in the presence of poly(acrylic acid) leads to the formation of nanocomposite structures with oriented OCP nanorod crystals 2-4 nm in width and 10-30 nm in length. The nanostructures allow the composites to transform rapidly into a HAP/PVA hybrid thin film in water. The transformation proceeds without a change in the original OCP/PVA nanostructures, resulting in the formation of a HAP/PVA hybrid thin film with oriented HAP nanorod crystals 5-6 nm in width and 20-50 nm in length. The HAP/PVA hybrids have been obtained as self-standing films with submicrometer scale thickness. The ratio of organic to inorganic components in the self-standing hybrid thin films is similar to that in bones of vertebrates.