Using phenolic polymers to control the size and morphology of calcium carbonate microparticles

Calcium carbonate (CaCO₃) is a naturally occurring mineral that occurs in biology and is used industrially. Due to its benign nature, CaCO₃ microparticles have found use in the food and medical fields, where the specific size of the microparticles determine their functionality and potential applications. We demonstrate that phenolic polymers with different numbers of hydroxy groups can be used to control the diameter of CaCO₃ microparticles in a range of 2-9 μm, and obtained particles were relatively uniform. The largest particles (∼9 μm in diameter) were obtained using poly(2,3,4,5-tetrahydroxystyrene) (P4HS), which showed the highest water solubility among the tested phenolic polymers. The polymer concentration and stirring speed influenced the size of microparticles, where the size of the obtained particles became smaller as the concentrations of phenolic polymers increased and as the stirring speed increased, both likely due to promoting the formation of a large number of individual crystal seeds by shielding seed-seed fusion and increasing the chances for precursor contact, respectively. The preparation time and temperature had a great influence on the morphology of the CaCO₃ particles, where vaterite transforms into calcite over time. Specifically, aragonite crystals were observed at preparation temperature of 80 °C and vaterite particles with rough surfaces were obtained at 40 °C. Molecular weight and scale of reaction were also factors which affect the size and morphologies of CaCO₃ particles. This research represents a facile method for producing relatively monodisperse CaCO₃ microparticles with diameters that have previously proven difficult to access.