ABSTRACT
Molecular dynamics simulations were conducted to elucidate the effects of Mg(2+) and H2O additives on the structure of amorphous calcium carbonate (ACC). New potential parameters for Mg(2+) ions were developed. The distribution function of the angle formed by three nearest-neighbor atoms was introduced to analyze the short-range local structure of ACC. The simulation indicated that ACC had a weakly ordered local structure resembling the local structure of a CaCO3 crystal. The local structure of pure ACC resembled that of vaterite. The formation of the vaterite-like local structure was hindered by Mg(2+) ions, whereas H2O molecules did not significantly influence the structure of ACC when the fraction of H2O molecules was low. However, when the fraction of H2O was high, the formation of a monohydrocalcite-like local structure was promoted. The effects of the additives on the structure of ACC were verified using the size of the additives and the interaction between the additives and CaCO3. The simulated structure of ACC was compared with the structure of CaCO3 crystals nucleated through the formation of ACC particles in real systems.
ABSTRACT
Thin-film growth of aragonite CaCO3 on annealed poly(vinyl alcohol) (PVA) matrices is induced by adding Mg(2+) into a supersaturated solution of CaCO3. Both the growth rate and surface morphology of the aragonite thin films depend upon the concentration of Mg(2+) in the mineralization solution. In the absence of PVA matrices, no thin films are formed, despite the presence of Mg(2+). Molecular dynamics simulation of the CaCO3 precursor suggests that the transition of amorphous calcium carbonate to crystals is suppressed in the presence of Mg(2+). The role for ionic additives in the crystallization of CaCO3 on organic templates obtained in this study may provide useful information for the development of functional hybrid materials.
