Mechanochemical synthesis of hydroxyapatite using cuttlefish bone and chicken eggshell as calcium precursors

This work explores the possibility of synthesising hydroxyapatite via mechanochemical route using biogenic calcium carbonate sources, namely calcite in chicken eggshell and aragonite in cuttlebone. The calcium source and orthophosphoric acid in ratio complying with Ca/P = 1.67 were submitted to high-energy ball milling with transferred energy values in the 1.6 to 123.0 kWh/g range, in the presence of 6.4 wt% water. Results show that increasing transferred energy results in CaCO3 -> DCPD -> HA reaction sequence when the used calcium source is cuttlebone, and in CaCO3 -> DCPD -> DCPA -> HA when eggshell is used. The produced calcium orthophosphates exist in delimited energy transfer ranges; HA forms monophasic regions at the highest transferred energy ranges tested. 52.5 kWh/g is the minimum energy value for hydroxyapatite formation starting from eggshell, while only 6.2 kWh/g is required starting from cuttlebone. Calcium orthophosphate dimensionality depends on the supplied energy and on the starting CaCO3 polymorph, and includes nanospheres and nanoplates, and more complex flower-like geometries built from individual nanoparticles. Milling maps were built to systematise the effect of initial CaCO3 polymorph and transferred milling energy on the conditions for hydroxyapatite mechanochemical formation. Obtained results demonstrate the potential of chicken eggshell and cuttlefish bone as natural precursors to produce hydroxyapatite, and the ability of high-energy milling as the corresponding processing route. This indicates an opportunity window for the development of reliable, scalable, fast and cost-effective HA production method.