Oriented crystallization of CaCo3under compressed monolayers. Part 1.—Morphological studies of mature crystals

Abstract
The crystallization of CaCO3 under compressed Langmuir monolayers of stearic acid [CH3(CH2)16CO2H], octadecylamine [CH3(CH2)17NH2], octadecanol [CH3(CH2)17OH] and cholesterol (C27H45OH) has been studied over a range of supersaturation conditions by optical and scanning electron microscopy and X-ray diffraction. At total [Ca]= 9 mmol dm–3, negatively charged stearate monolayes induced the oriented nucleation of calcite. The crystals were of two related morphological types, one of which was formed through the physical realignment of the oriented crystals at the organic surface during growth. Reducing the total [Ca] to 4.5 mmol dm–3, resulted in oriented vaterite nucleation on the stearate monolayers. Vaterite was the major product on positively charged octadecylamine films, independent of [Ca]. Unlike the vaterite crystals of stearate films, these crystals were of two distinct morphological forms which represented two specific nucleation orientations. Neutral monolayers of octadecanol inhibited crystallization and those of cholesterol gave random non-oriented calcite deposition analogous to the control experiments. Morphological analyses indicated that the crystals were oriented with their [1 text-decoration:overline1.0](calcite) and [00.1] and [11.0](vaterite) axes perpendicular to the monolayer surface.