Deciphering osteoconductive surface charge effects in sintered hydroxyapatite via piezoresponse force microscopy

Hydroxyapatite (HAp), a main constituent of the cortical bone, retains a large surface charge that plays a critical role in the regeneration of bones, whose source remains an enigma. Here, we used multi-eigenmode piezoresponse force microscopy via Pearson correlation and conducted multiscale material analysis to independently measure the piezoelectric coefficient and the surface charge density of HAp. Quantitative comparison was conducted between the measured surface charge density and the conceptual values computed for all possible candidates of the surface charging such as piezoelectricity, chemically induced surface charging, flexoelectricity, and defect dipole moment. The results presented Ca2+ ions released during local calcium orthophosphate phase transition at the surface as the main source of the surface charging. Further analysis showed that the ion concentration was modulable using a charged conductive tip, implying that the interstitial ions are mobile within the HAp matrix. In this work, we developed a novel method to measure the effective surface charge density of arbitrary material systems, thereby facilitating the investigation of biophysical phenomena related to surface electromechanics. Most importantly, the research promotes a new understanding of the origin of osteoconduction observed in past works conducted on HAp.