title: Tetrahedral calcite crystals facilitate self-assembly at the air-water interface.
abstract: Calcite crystals often nucleate and grow in solutions of calcium carbonate, and these crystallites can become trapped at the air water interface, where they form unusual structures. The most common is a fractal structure, which can extend over a large fraction of the interface, and whose origin is understood in terms of the aggregation of the particles. Much more rarely, a different and entirely unexpected structure is observed: the particles remain well separated on the interface, forming an ordered phase reminiscent of a two-dimensional colloidal crystal. The structure of the crystallites that form this ordered phase is always observed to be tetrahedral, in contrast to the much more common rhombohedral structure of the crystallites that form the fractal phase. We show that the interparticle interaction potential that leads to this ordered phase is a balance between a long-range attractive interaction and a long-range repulsive interaction. The attraction results from gravity-induced capillary forces, while the repulsion results from a dipole-dipole interaction due to the charged surface of the tetrahedral crystals. The interaction potential is estimated from the thermal motion of the particles, and fits to the theoretically expected values suggest that the effective surface charge on the tetrahedral crystals is sigma approximately 0.01 charges/nm2.
authors.affiliation: Division of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: S M
authors.initials: SM
authors.lastname: Hashmi
authors.forename: H H
authors.initials: HH
authors.lastname: Wickman
authors.forename: D A
authors.initials: DA
authors.lastname: Weitz