Epitaxial growth of celestite on barite (0 0 1) face at a molecular scale

• Published in: Surface science Vol. 581; no. 2; pp. 225 - 235
• Main Authors: Sánchez-Pastor, Nuria, Pina, Carlos M., Astilleros, José Manuel, Fernández-Díaz, Lurdes, Putnis, Andrew
• Format: Journal Article
• Language: English
• Published: Lausanne Elsevier B.V 01.05.2005; Amsterdam Elsevier Science; New York, NY
• Subjects: Atomic force microscopy; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Epitaxy; Exact sciences and technology; Physics; Solid–liquid interfaces; Surface topography; Atomic force microscopy; Solid–liquid interfaces; Surface topography; Epitaxy; Liquid solid interface; Solid-liquid interfaces
• ISSN: 0039-6028; 1879-2758
• DOI: 10.1016/j.susc.2005.02.051

In situ AFM experiments have been conducted in order to obtain information about kinetics of celestite epitaxial growth on barite. Growth has been promoted by passing aqueous solutions supersaturated with respect to celestite over freshly cleaved barite (0 0 1) surfaces. Solution supersaturation, β celestite, was varied from 1 to 45.7 ( β celestite = a ( Sr 2 + ) · a ( SO 4 2 - ) / K sp , cel ) . At supersaturations below 10 neither two-dimensional nucleation neither step advancement are observed on barite (0 0 1) surfaces. However, once the two-dimensional nucleation barrier is overcome ( β celestite > 10), nuclei preferentially form on cleavage steps parallel to [1 0 0], [1 1 0] and [1 2 0] directions and more scarcely on terraces. The subsequent growth of two-dimensional nuclei leads to the development of celestite “islands”. Their morphology is defined by (0 0 1) face and {2 1 0} and {1 0 0} forms and can be explained on the basis of PBC theory. The coalescence of such islands results in the formation of a homogeneous SrSO 4 layer. Growth rates along [0 0 1] direction have been measured for the whole supersaturation range. The growth rate equation for “Birth and Spread” crystal growth mechanism has been successfully fitted to our experimental data. The fitting process has provided basic growth parameters in a good agreement with theoretical ones. Both the high transitional supersaturation required for two-dimensional nucleation and the high interfacial energy value obtained from the fitting of the “Birth and Spread” equation ( σ 001 cel – bar = 0.137 J / m 2 ) indicate low affinity of SrSO 4 growth units for barite (0 0 1) faces. This is consistent with the relative high mismatch between celestite and barite structure. The behaviour of the epitaxial growth described in this work can help to interpret the oscillatory zoning frequently occurring in both natural and synthetic crystals of the Ba x Sr 1− x SO 4 solid solution.