The influence of cation size on the misfit between the tetrahedral and the octahedral sheets of serpentine layers, and thus on the curvature of serpentine minerals, has been studied using an experimental approach, based on scanning and high-resolution transmission electron microscopies (SEM and HRTEM, respectively) coupled with analytical electron microscopy (AEM), and a theoretical approach, based on the elastic theory of thin plates and the surface stress concept.
Various Ni3(Si,Ge)2O5(OH)4 serpentine syntheses were prepared, with progressive tetrahedral substitution for Si by the larger Ge ion, the ratio Ge/(Si + Ge) ranging from 0 to 100%. Other parameters (temperature, time duration, water pressure) were fixed. From SEM-HRTEM observations and AEM analyses of all samples, two types of serpentine minerals were characterized: (1) curved structures of tubular or ‘roman-tile’ shape (curvature radius of 10 nm for 0% Ge, increasing with the Ge content), when the Ge tetrahedral content is <25%; (2) perfectly plane structures, with hexagonal or triangular shape (view normal to the layers), for greater Ge contents. These results prove the direct influence of cation size on the crystal curvature.
From a theoretical point of view, a single serpentine layer with a misfit between its tetrahedral and octahedral sheets can be considered as an elastic thin plate subjected to two different surface stresses, σ+ and σ−, on its two faces. The difference σ+ – σ − between these two surface stresses was calculated from the above geometrical misfit, and the curvature of the serpentine layer was related to σ+ – σ −, according to the elastic theory of thin plates. The calculated curvature radii, and the Ge content of transition from curved to plane structures, are in agreement with the above observed values. Curved serpentine crystals may then be considered as a stacking of such elastically curved single serpentine layers.