Gerlinde Habler

TiO2 exsolution from garnet by open-system precipitation: evidence from crystallographic and shape preferred orientation of rutile inclusions

We investigated rutile needles with a clear shape preferred orientation in garnet from (ultra) high-pressure metapelites from the Kimi Complex of the Greek Rhodope by electron microprobe, electron backscatter diffraction and TEM techniques. A definite though complex crystallographic orientation relationship between the garnet host and rutile was identified in that Rt[001] is either parallel to Grt<111> or describes cones with opening angle 27.6° around Grt<111>. Each Rt[001] small circle representing a cone on the pole figure displays six maxima in the density plots. This evidence together with microchemical observations in TEM, when compared to various possible mechanisms of formation, corroborates a precipitate origin. A review of exchange vectors for Ti substitution in garnet indicates that rutile formation from garnet cannot occur in a closed system. It requires that components are exchanged between the garnet interior and the rock matrix by solid-state diffusion, a process we refer to as “open-system precipitation” (OSP). The kinetically most feasible reaction of this type will dominate the overall process. The perhaps most efficient reaction involves internal oxidation of Fe2+ to Fe3+ and transfer from the dodecahedral to the octahedral site just vacated by

Sodium-potassium interdiffusion in potassium-rich alkali feldspar II: Composition- and temperature-dependence obtained from cation exchange experiments

{\text{Ti}}^{ 4+ }: 6\,{\text{M}}^{ 2+ }_{ 3} {\text{TiAl}}\left[ {{\text{AlSi}}_{ 2} } \right]{\text{O}}_{ 1 2} + 6\,{\text{M}}^{ 2+ }_{ 2, 5} {\text{TiAlSi}}_{ 3} {\text{O}}_{ 1 2} = 10\,{\text{M}}^{ 2+ }_{ 3.0} {\text{Al}}_{ 1. 8} {\text{Fe}}_{0. 2} {\text{Si}}_{ 3} {\text{O}}_{ 1 2} + {\text{M}}^{2+} + 2 {\text{e}}^{-} + 1 2\,{\text{TiO}}_{ 2} .

Rb/Sr isotopic and compositional retentivity of muscovite during deformation

OSP is likely to occur at conditions where the transition of natural systems to open-system behaviour becomes apparent, as in the granulite and high-temperature eclogite facies.

Reliability of chemical microanalyses for solid waste materials

Nanocomposite thin films comprised of metastable metal carbides in a carbon matrix have a wide variety of applications ranging from hard coatings to magnetics and energy storage and conversion. While their deposition using nonequilibrium techniques is established, the understanding of the dynamic evolution of such metastable nanocomposites under thermal equilibrium conditions at elevated temperatures during processing and during device operation remains limited. Here, we investigate sputter-deposited nanocomposites of metastable nickel carbide (Ni3C) nanocrystals in an amorphous carbon (a-C) matrix during thermal postdeposition processing via complementary in situ X-ray diffractometry, in situ Raman spectroscopy, and in situ X-ray photoelectron spectroscopy. At low annealing temperatures (300 °C) we observe isothermal Ni3C decomposition into face-centered-cubic Ni and amorphous carbon, however, without changes to the initial finely structured nanocomposite morphology. Only for higher temperatures (400–800 °C) Ni-catalyzed isothermal graphitization of the amorphous carbon matrix sets in, which we link to bulk-diffusion-mediated phase separation of the nanocomposite into coarser Ni and graphite grains. Upon natural cooling, only minimal precipitation of additional carbon from the Ni is observed, showing that even for highly carbon saturated systems precipitation upon cooling can be kinetically quenched. Our findings demonstrate that phase transformations of the filler and morphology modifications of the nanocomposite can be decoupled, which is advantageous from a manufacturing perspective. Our in situ study also identifies the high carbon content of the Ni filler crystallites at all stages of processing as the key hallmark feature of such metal–carbon nanocomposites that governs their entire thermal evolution. In a wider context, we also discuss our findings with regard to the much debated potential role of metastable Ni3C as a catalyst phase in graphene and carbon nanotube growth.

Crystallographic orientation relationships in host–inclusion systems: New insights from large EBSD data sets

Na-K interdiffusion in disordered potassium-rich alkali feldspar was studied experimentally using cation exchange between gem quality sanidine from the Eifel and alkali-halide melt at temperatures of 800 °C to 1000 °C and at close to ambient pressure. Sodium-potassium interdiffusion coefficient DNaK was determined for potassium mole fractions in the range 0.65 ≤ XOr ≤ 0.99. At 0.65 ≤ XOr ≤ 0.95 the sodium-potassium interdiffusion coefficient is largely independent of composition. At XOr ≥ 0.95, it rises sharply with increasing potassium mole fraction. Diffusion perpendicular to (001) is about one order of magnitude faster and less strongly temperature dependent than perpendicular to (010). The parameters of the Arrhenius equation describing the temperature dependence of the sodium-potassium interdiffusion coefficient DNaK = D0Exp (−EA/RT) were estimated as The results of our direct determinations are compared with theoretical calculations using the corresponding sodium- and potassium tracer-diffusion coefficients, and the processes underlying the observed composition- and temperature dependence of sodium-potassium interdiffusion are discussed.

Interlayer growth kinetics of a binary solid-solution based on the thermodynamic extremal principle: Application to the formation of spinel at periclase-corundum contacts

Anisotropic diffusion is described by a tensor of diffusivities, Dαβ, which may be composition dependent leading to nonlinear anisotropic diffusion. In this work the practical problem of reconstructing such a tensor for Na-K interdiffusion in potassium-rich alkali feldspar in the composition range 0.85 ≤ XOr ≤ 1.00 is addressed. Gem quality sanidine with an initial composition of XOr = 0.85 was exchanged with KCl salt melt at 850 °C and ≈1 bar. The diffusivity tensor Dαβ(XOr) and its composition dependence was reconstructed from composition profiles produced by cation exchange in six different crystallographic directions using a generalization of the Boltzmann approach. Na-K interdiffusion in potassium-rich alkali feldspar is considerably anisotropic and composition dependent. The principal axes of the diffusivity tensor representing the directions of highest and lowest diffusivity lie in the a-c plane with highest diffusivity parallel to the [101] direction, lowest diffusivity perpendicular to the (101̄) plane, and the direction with intermediate diffusivity parallel to the crystallographic b-axis. All diffusivities Dαβ(XOr) increase as XOr tends to unity. Our main result is given in the form of numerical values for all components of the Dαβ(XOr) tensor for 0.85 ≤ XOr ≤ 1.

Microstructure and texture evolution during growth of magnesio-aluminate spinel at corundum-periclase interfaces under uniaxial load: The effect of stress concentration on reaction progress

Permian metapegmatite muscovite from the Upper-Austroalpine Matsch Unit in Southern Tyrol (Italy) was investigated regarding its Rb/Sr and compositional retentivity during Cretaceous Upper-greenschist facies deformation. The data imply that microstructurally relic Permian magmatic muscovite largely maintained its major and trace element compositions during deformation, whereas the Rb/Sr geochronometer is strongly affected by a net loss of Sr. Lower Sr concentrations of muscovite correlate with higher 87Rb/86Sr and 87Sr/86Sr ratios. In most samples, the muscovite grain size- and magnetic-fractions with the lowest 87Rb/86Sr and 87Sr/86Sr ratios preserve a Permo-Triassic muscovite–whole rock Rb/Sr apparent age interpreted as to reflect formation during or cooling after pegmatite emplacement. Contrastingly, muscovite fractions with higher 87Rb/86Sr and 87Sr/86Sr ratios are arranged along a roughly linear array with a positive correlation of the 87Rb/86Sr and 87Sr/86Sr ratios in the 87Rb/86Sr vs 87Sr/86Sr space. They yield successively lower muscovite–whole rock Rb/Sr apparent ages. We explain the variations in the Rb/Sr isotopic character of microstructurally relic muscovite by a, presumably deformation-related, loss of Sr during the Cretaceous event. Contemporaneously, only very limited amounts of isotopically different Sr from the matrix reservoir might possibly have entered the muscovite. Consequently, the Rb/Sr of the relic muscovite is affected by a net loss of Sr. The results imply that at temperatures of < 500 °C, deformation is supposed to be the predominant factor in controlling the Rb/Sr geochronometer of relic muscovite, by significantly reducing the characteristic length scale for volume diffusion. However, variations of the major and trace element compositions within Permian relic muscovite are interpreted to rather reflect primary compositional instead of deformation-related variations.

Oriented feldspar-feldspathoid intergrowths in rocks of the Khibiny massif: genetic implications

The investigation of solid speciation of metals and metalloids is required for accurate assessment of the hazardous properties of solid waste materials from high-temperature technologies (slag, bottom ash, fly ash, air-pollution-control residues). This paper deals with the problem of reliability of microanalyses using a combination of electron microprobe analysis (EPMA) and scanning electron microscopy (SEM) only. These methods do not permit to detect nanophases in host-crystals and lead to erroneous interpretation of analytical results, considering the elements of nanophases as belonging to the crystal structure of the main phase. More detailed analysis using transmission electron microscopy (TEM) on foils prepared by focused ion beam (FIB) can be used to solve this analytical problem. In this study, lamellar aggregates of potassium-rich clinopyroxenes were detected in copper smelting slags by a combination of SEM and EPMA. However, FIB-TEM indicated the presence of leucite inclusions (tens to hundreds nm in size) within the clinopyroxene lamellae. Based on examples from smelting slags and other solid waste materials, recommendations for standard SEM and EPMA applications and the need for methods with higher resolution for mineralogical investigation of waste materials are discussed.