In situ AFM study of the dissolution and recrystallization behaviour of polished and stressed calcite surfaces

Abstract

We investigated the dissolution behaviour of polished calcite surfaces in situ using a fluid-cell atomic force microscope. Polished calcite surfaces enabled us to study the effects of applied surface stress and crystallographic orientation on calcite dissolution pattern formation. Thin-sections of Iceland spar single-crystals polished either parallel or with a 5° miscut angle to { 10 1 ¯ 4 } cleavage planes were studied. Compressive surface stresses of up to 50 MPa were applied to some of the thin-section samples by means of elastic concave bending. Experiments were carried out in semi-stagnant deionized water under mainly transport limited dissolution conditions. Samples polished parallel to { 10 1 ¯ 4 } cleavage planes dissolved by the formation of etch-pits originating from polishing defects. The dissolution behaviour of 5° miscut surfaces was relatively unaffected by polishing defects, since no etch-pits developed in these samples. Dissolution of the miscut samples led to stepped or rippled surface patterns on the nanometer scale that coarsened during the first 30–40 min of the experiments. Possible reasons for the pattern-coarsening were: (i) progressive bunching of retreating dissolution steps and (ii) surface energy driven recrystallization (Ostwald ripening) under transport limited dissolution conditions. A flat polished miscut surface in calcite may recrystallize into a hill-and-valley structure in a (near-)saturated solution so as to lower its total surface free energy in spite of a larger surface area. No clear effect of applied stress on dissolution pattern formation has been observed.