The transformation of vaterite to calcite: effect of the conditions of the solutions in contact with the mineral phase

The transformation of the thermodynamically unstable vaterite into the stable calcite was investigated during the precipitation of calcium carbonate, under conditions of constant supersaturation at 25, 35 and 45 degrees C and pHs 8.5, 9.0 and 10.0. The calcite content in the solid precipitates was determined quantitatively by the X-ray diffraction technique (XRD) using the appropriate mixed standards of known composition. Scanning electron microscopy (SEM) and particle number and size measurements were also used for the characterisation of the solid precipitates. It was found that the transformation of vaterite into calcite does not depend on pH and temperature in the range 25-45 degrees C. It depends only on the supersaturation, and this, only at relatively high supersaturation ratios (1.5-1.9). Specifically, the rate of transformation decreases as supersaturation increases. It was suggested on the basis of the kinetics results, that the transformation takes place through dissolution of vaterite, preferably of the small crystals followed by the crystallisation of calcite. At relatively high supersaturation ratios (1.5-1.9) the transformation is controlled by the dissolution of vaterite, whereas at lower supersaturation ratios (1.2-1.5) the rate of dissolution of vaterite is similar with that of crystallisation of calcite. Finally, a model equation which predicts a linear dependence of the rate of transformation on supersaturation ratio has been derived at relatively high supersaturation ratios. (C) 1998 Elsevier Science B.V. All rights reserved.