Synthesis of citrate-stabilized hydrocolloids of hydroxyapatite through a novel two-stage method: A possible aggregates–breakdown mechanism of colloid formation

The ligand–particle chelation induced the HA particles to loosely aggregate during low-temperature reaction (a). High-temperature aging broke some ligand–particle links, forming colloidal particles stabilized by their surface charge (b). [Display omitted] ► Citrate-stabilized hydroxyapatite (HA) hydrocolloids were synthesized through a novel two-stage method. ► The HA hydrocolloid remains stable for over 2years. ► The conformational changes in citrate ions on HA at different temperatures explain the colloid formation process. Long-term stable (>2years) hydrocolloids of hydroxyapatite (HA) were synthesized via a low-temperature (18–50°C) reaction of aqueous ammonium phosphate with calcium nitrate in the presence of citrate ions, followed by an aging process at high temperature (80–99°C) for 4h. Changing the reaction and/or aging temperature seldom yielded stable HA hydrocolloids. The as-prepared hydrocolloids were desalinated through ultrafiltration where their average particle size gradually decreased, bottomed out at 100–400μS/cm, and sharply increased in parallel with a decrease in solution conductivity. The colloid formation is most likely through a temperature-sensitive aggregates–breakdown process. During low-temperature reaction, citrate–calcium chelation bridges the growing HA particles into loose aggregates. High-temperature aging disrupts these inter-particle links and thus breaks the aggregates, imparting negative charges to the HA, forming colloidal particles stabilized by surface charge. The decrease in mean particle size during early ultrafiltration suggested that the aggregate breakdown further proceeded through desalination. In conclusion, the temperature-dependent interactions between citrate ions and calcium sites on HA particles played key roles in the synthesis and stability of the HA colloids.