Basal plane reactivity of phyllosilicates studied in situ by hydrothermal atomic force microscopy (HAFM)

The basal plane reactivities of the sheet silicates apophyllite and phlogopite have been studied by hydrothermal atomic force microscopy (HAFM) in situ in aqueous solutions at temperatures from 20 to 140 degrees C. At pH 4-5.6 (T = 20-100 degrees C), the apophyllite basal surface undergoes a swelling process which forms square hillocks on the surface. The reaction comprises three sequential morphological transformations that cause swelling to increase from 0.15 to 2.5 nm. In the first two transformations, interlayer cations are replaced by hydronium ions from the solution; the third transformation involves a depolymerization and partial cross-linking of the protonated silicate sheets. The reaction of phlogopite with acidic aqueous solutions (pH 1.5-2) at high temperature (T = 100-140 degrees C) causes the nucleation of numerous monolayer etch pits on the pristine surface. Where the 2D pits recur at the same lateral position, they can accumulate to a total pit depth of up to 50 nm. The formation of an altered layer has also been detected at these conditions. The alteration affects the uppermost 4-5 layers. The layers are expanded, corrugated, highly unstable, and readily peel off the surface. Etch pit formation has been detected even underneath the altered layer. On the basis of HAFM data, dissolution rates and activation energies were calculated. The presented data show that the basal surface of phlogopite plays an important role in the dissolution process at least at elevated temperatures and that the absolute amount of released material has comparable contributions from both basal surfaces and edge surfaces. (c) 2006 Published by Elsevier Inc.