Two Modes of Transformation of Amorphous Calcium Carbonate Films in Air

Abstract

Large-area amorphous calcium carbonate (ACC) films in air are shown to be transformed into crystalline calcium carbonate (CaCO₃) films via two modesdissolution−recrystallization and solid−solid phase transitiondepending on the relative humidity of the air and the temperature. Moisture in the air promotes the transformation of ACC into crystalline forms via a dissolution−recrystallization process. Increasing the humidity increases the rate of ACC crystallization and gives rise to films with numerous large pores. As the temperature is increased, the effect of moisture in the air is reduced and solid−solid transition by thermal activation becomes the dominant transformation mechanism. At 100 and 120 °C, ACC films are transformed into predominantly (110) oriented crystalline films. Collectively, the results show that calcium carbonate films with different morphologies, crystal phases, and structures can be obtained by controlling the humidity and temperature. This ability to control the transformation of ACC should assist in clarifying the role of ACC in the biomineralization of CaCO₃ and should open new avenues for preparing CaCO₃ films with oriented and fine structure.