We used atom probe tomography to complement electron microscopy for the investigation of spinodal decomposition in alkali feldspar. To this end, gem-quality alkali feldspar of intermediate composition with a mole fraction of a K = 0.43 of the K end-member was prepared from Madagascar orthoclase by ion-exchange with (NaK)Cl molten salt. During subsequent annealing at 550 • C and close to ambient pressure the ion-exchanged orthoclase unmixed producing a coherent lamellar intergrowth of Na-rich and K-rich lamellae. The chemical separation was completed, and equilibrium Na-K partitioning between the different lamellae was attained within four days, which was followed by microstructural coarsening. After annealing for 4 days, the wavelength of the lamellar microstructure was ≈ 17 nm and it increased to ≈ 30 nm after annealing for 16 days. The observed equilibrium compositions of the Na-rich and K-rich lamellae are in reasonable agreement with an earlier experimental determination of the coherent solvus. The excess energy associated with compositional gradients at the lamellar interfaces was quantified from the initial wavelength of the lamellar microstructure and the lamellar compositions as obtained from atom probe tomography using the Cahn-Hilliard theory. The capability of atom probe tomography to deliver quantitative chemical compositions at nm resolution opens new perspectives for studying the early stages of exsolution. In particular, it helps to shed light on the phase relations in nm scaled coherent intergrowth.

We present a model for multicomponent diffusion in ionic crystals. The model accounts for vacancy-mediated diffusion on a sub-lattice and for diffusion due to binary exchange of different ionic species without involvement of vacancies on the same sub-lattice. The diffusive flux of a specific ionic species depends on the self-diffusion coefficients, on the diffusion coefficients related to the binary exchanges, and on the site fractions of all ionic species. The model delivers explicit expressions for these dependencies, which lead to a set of coupled non-linear diffusion equations. We applied the model to diffusion of 23 Na, 39 K, and 41 K in alkali feldspar. To this end, gem-quality crystals of alkali feldspar were used together with 41 K doped KCl salt as diffusion couples, which were annealed at temperatures between 800 • and 950 • C. Concentration-distance data for 23 Na, 39 K, and 41 K were obtained by Time of Flight Secondary Ion Mass Spectrometry. Over the entire investigated temperature range the Na self-diffusion coefficient is by a factor of ≥ 500 higher than the K self-diffusion coefficient. Diffusion mediated by binary 39 K-41 K exchange is required for obtaining satisfactory fits of the model curves to the experimental data, and the respective kinetic coefficient is well constrained.

The microstructural and textural characteristics of a spinel corona that formed around a faceted corundum xenocrystal by reaction with the hosting basaltic melt in the Siebengebirge volcanic field demonstrate that the crystallographic and shape preferred orientation of spinel is influenced by the orientation of the reaction interface with respect to the corundum crystal lattice. The spinel roughly shows the common topotactic orientation relationships with corundum, where one of the {111}Spl planes is parallel to the (0001)Crn plane, and three of the {110}Spl planes are parallel to the {1010}Crn planes. In detail, there are subtle but systematic deviations from this topotactic relationship due to small rotations about the c-axis and/or an a-axis of corundum. The former is observed when the corundum c-axis is closely parallel to the interface plane, while the latter require a corundum a-axis orientation perpendicular to the interface. In this case, the preferred sense of rotation depends on the sign of the a-axis direction, irrespective of the spinel growth direction being parallel or antiparallel to this axis. Additionally, the selection of either one or both of two spinel twin variants that equally fulfill the topotactic orientation relationship depends on the orientation of the corundum-spinel interface with respect to the lattices of both the corundum and the spinel. Finally, also the grain boundary character is controlled by the interface orientation and the corundum lattice. Despite the differences between corona segments, the nature of these textures are persistent along and across each segment. We emphasize that all these microstructural and textural features are ascribed to the period of spinel growth in magmatic environment. The extent to which prominent slip planes in spinel are aligned parallel with the corundum-spinel interface seems to be of crucial importance for the nature of the spinel texture and microstructure, indicating that the activity of dislocations pertaining to these slip systems ease the accommodation of lattice misfit across the corundum-spinel interface. By comparison with experimentally grown spinel layers we infer predominantly interface reaction controlled growth of the studied spinel corona.