Phosphonic Acid Coupling Agent Modification of HAP Nanoparticles: Interfacial Effects in PLLA/HAP Bone Scaffold

In order to improve the interfacial bonding between hydroxyapatite (HAP) and poly-l-lactic acid (PLLA), 2-Carboxyethylphosphonic acid (CEPA), a phosphonic acid coupling agent, was introduced to modify HAP nanoparticles. After this. the PLLA scaffold containing CEPA-modified HAP (C-HAP) was fabricated by selective laser sintering (frittage). The specific mechanism of interfacial bonding was that the PO32− of CEPA formed an electrovalent bond with the Ca2+ of HAP on one hand, and on the other hand, the –COOH of CEPA formed an ester bond with the –OH of PLLA via an esterification reaction. The results showed that C-HAP was homogeneously dispersed in the PLLA matrix and that it exhibited interconnected morphology pulled out from the PLLA matrix due to the enhanced interfacial bonding. As a result, the tensile strength and modulus of the scaffold with 20% C-HAP increased by 1.40 and 2.79 times compared to that of the scaffold with HAP, respectively. In addition, the scaffold could attract Ca2+ in simulated body fluid (SBF) solution by the phosphonic acid group to induce apatite layer formation and also release Ca2+ and PO43− by degradation to facilitate cell attachment, growth and proliferation.