Orientation and Mg Incorporation of Calcite Grown on Functionalized Self-Assembled Monolayers: A Synchrotron X-ray Study

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Seo-Young Kwak, Elaine DiMasi, Yong-Jin Han, Joanna Aizenberg, Ivan Kuzmenko

Abstract:
Calcite crystals were nucleated from MgCl2/CaCl2 solutions onto functionalized self-assembled monolayers adsorbed onto E-beam evaporated Au films. Synchrotron X-ray scattering studies of the crystals reveal new information about preferred orientation and Mg incorporation. The Au [111] axis is distributed within 2.6 degrees of the film surface normal, but the oriented crystals may be tilted up to 6 degrees away from this axis. For low Mg2+ content, SO3--functionalized films nucleated primardy near the (106) calcite face, odd-chain-length carboxylic acid terminated alkanethiol films nucleated near the (012) face, and even-chain-length carboxylic acid terminated alkanethiol films nucleated near the (113) face. [Mg2+]/[Ca2+] concentration ratios (n) of 2 and greater defeated this preferred orientation and created a powder texture. Diffraction patterns within the layer plane from the coarse calcite powders indicated a shift to higher 2 theta accompanied by peak broadening with increasing n. For 0.5 < n < 3.5, a double set of calcite peaks is observed, showing that two distinct Mg calcite phases form: one of comparatively lower Mg content, derived from the templated crystals, and a Mg-rich phase derived from amorphous precursor particles. According to the refinement of lattice parameters, Mg incorporation of up to 18 mol % occurs for n = 4, independent of film functionality. We discuss the differences between the differently functionalized monolayers and also introduce the hypothesis that two separate routes to Mg calcite formation occur in this system.