In this study, we used the minute gas-liquid interfaces around CO
2/NH
3 micro-bubbles as new reaction fields where the crystal nucleation progresses and developed a crystallization technique to control the crystal structure (polymorph) of calcium carbonate (CaCO
3). At the minute gas-liquid interfaces, numerous local supersaturation regions are generated due to minimizing bubble size and mixing of NH3 gas with CO
2 gas; hence, the polymorph change of CaCO
3 is expected to occur. CaCO
3 was crystallized at 298K by a semi-batch type reaction in which CO
2/NH
3/N
2 bubbles were continuously supplied to an aqueous Ca(NO
3)
2 solution using a self-supporting bubble generator. The solution pH during crystallization was maintained constant at 9.7 by adding HNO
3 and NH
4OH solution. The average bubble size (
dbbl) was varied within the range of 40 – 1000μm by controlling the N
2 flow rate, and the molar ratio of CO
2/NH
3 (α
CO2/NH3) was set at a specified value of 0.20 – 1.00 at a constant CO
2 flow rate. By varying
dbbl and α
CO2/NH3, the effects of minimizing bubble size and mixing of NH
3 with CO
2 on the polymorphism of CaCO
3 were examined. Consequently, during reactive crystallization of CaCO
3 using CO
2/NH
3 micro-bubbles, the crystallized polymorph was changed from vaterite to aragonite when
dbbl was decreased, and the production of aragonite with minimizing bubble size was accelerated markedly with a decrease in α
CO2/NH3.
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