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Characterization of Ultra-fine Grained and Nanocrystalline Materials Using Transmission Kikuchi Diffraction

One of the challenges in microstructure analysis nowadays resides in the reliable and accurate characterization of ultra-fine grained (UFG) and ...

Macquarie University

Investigations of the Mantle Transition Zone (MTZ; 410-660 km deep) by deformation experiments and geophysical methods suggest that the MTZ has distinct rheological properties, but their exact cause is still unclear due to the lack of natural samples. Here we present the first direct evidence for crystal-plastic deformation by dislocation creep in the MTZ using a chromitite from the Luobusa peridotite (E. Tibet). Chromite grains show exsolution of diopside and SiO2, suggesting previous equilibration in the MTZ. Electron backscattered diffraction (EBSD) analysis reveals that olivine grains co-existing with exsolved phases inside chromite grains and occurring on chromite grain boundaries have a single pronounced crystallographic preferred orientation (CPO). This suggests that olivine preserves the CPO of a high-pressure polymorph (wadsleyite) before the high-pressure polymorph of chromite began to invert and exsolve. Chromite also shows a significant CPO. Thus, the fine-grained high-pressure phases were deformed by dislocation creep in the MTZ. Grain growth in inverted chromite produced an equilibrated microstructure during exhumation to the surface, masking at first sight its MTZ deformation history. These unique observations provide a window into the deep Earth, and constraints for interpreting geophysical signals and their geodynamic implications in a geologically robust context.

Messengers from the deep: Fossil wadsleyite-chromite microstructures from the Mantle Transition Zone.

Trace elements diffuse negligible distances through the pristine crystal lattice in minerals: this is a fundamental assumption when using them to decipher geological processes. For example, the reliable use of the mineral zircon (ZrSiO4) as a U-Th-Pb geochronometer and trace element monitor requires minimal radiogenic isotope and trace element mobility. Here, using atom probe tomography, we document the effects of crystal-plastic deformation on atomic-scale elemental distributions in zircon revealing sub-micrometre-scale mechanisms of trace element mobility. Dislocations that move through the lattice accumulate U and other trace elements. Pipe diffusion along dislocation arrays connected to a chemical or structural sink results in continuous removal of selected elements (for example, Pb), even after deformation has ceased. However, in disconnected dislocations, trace elements remain locked. Our findings have important implications for the use of zircon as a geochronometer, and highlight the importance of deformation on trace element redistribution in minerals and engineering materials.

Deformation-induced trace element redistribution in zircon revealed using atom probe tomography.

Diamonds and their inclusions are unique probes into the deep Earth, tracking the deep carbon cycle to >800 km. Understanding the mechanisms of carbon mobilization and freezing is a prerequisite for quantifying the fluxes of carbon in the deep Earth. Here we show direct evidence for the formation of diamond by redox reactions involving FeNi sulfides. Transmission Kikuchi Diffraction identifies an arrested redox reaction from pyrrhotite to magnetite included in diamond. The magnetite corona shows coherent epitaxy with relict pyrrhotite and diamond, indicating that diamond nucleated on magnetite. Furthermore, structures inherited from h-Fe3O4 define a phase transformation at depths of 320-330 km, the base of the Kaapvaal lithosphere. The oxidation of pyrrhotite to magnetite is an important trigger of diamond precipitation in the upper mantle, explaining the presence of these phases in diamonds.

Redox-freezing and nucleation of diamond via magnetite formation in the Earth's mantle.

Geochemical signatures throughout the layered Earth require significant mass transfer through the lower crust, yet geological pathways are under-recognized. Elongate bodies of basic to ultrabasic rocks are ubiquitous in exposures of the lower crust. Ultrabasic hornblendite bodies hosted within granulite facies gabbroic gneiss of the Pembroke Valley, Fiordland, New Zealand, are typical occurrences usually reported as igneous cumulate hornblendite. Their igneous features contrast with the metamorphic character of their host gabbroic gneiss. Both rock types have a common parent; field relationships are consistent with modification of host gabbroic gneiss into hornblendite. This precludes any interpretation involving cumulate processes in forming the hornblendite; these bodies are imposter cumulates. Instead, replacement of the host gabbroic gneiss formed hornblendite as a result of channeled high melt flux through the lower crust. High melt/rock ratios and disequilibrium between the migrating magma (granodiorite) and its host gabbroic gneiss induced dissolution (grain-scale magmatic assimilation) of gneiss and crystallization of mainly hornblende from the migrating magma. The extent of this reaction-replacement mechanism indicates that such hornblendite bodies delineate significant melt conduits. Accordingly, many of the ubiquitous basic to ultrabasic elongate bodies of the lower crust likely map the 'missing' mass transfer zones.

Hornblendite delineates zones of mass transfer through the lower crust.

Deformation microstructures are widely used for reconstructing tectono-metamorphic events recorded in rocks. In crustal settings deformation is often accompanied and/or succeeded by fluid infiltration and dissolution-precipitation reactions. However, the microstructural consequences of dissolution-precipitation in minerals have not been investigated experimentally. Here we conducted experiments where KBr crystals were reacted with a saturated KCl-H2O fluid. The results show that reaction products, formed in the absence of deformation, inherit the general crystallographic orientation from their parents, but also display a development of new microstructures that are typical in deformed minerals, such as apparent bending of crystal lattices and new subgrain domains, separated by low-angle and, in some cases, high-angle boundaries. Our work suggests that fluid-mediated dissolution-precipitation reactions can lead to a development of potentially misleading microstructures. We propose a set of criteria that may help in distinguishing such microstructures from the ones that are created by crystal-plastic deformation.

Deformation-resembling microstructure created by fluid-mediated dissolution-precipitation reactions.

The application of atom probe tomography to the study of minerals is a rapidly growing area. Picosecond-pulsed, ultraviolet laser (UV-355 nm) assisted atom probe tomography has been used to analyze trace element mobility within dislocations and low-angle boundaries in plastically deformed specimens of the nonconductive mineral zircon (ZrSiO4), a key material to date the earth's geological events. Here we discuss important experimental aspects inherent in the atom probe tomography investigation of this important mineral, providing insights into the challenges in atom probe tomography characterization of minerals as a whole. We studied the influence of atom probe tomography analysis parameters on features of the mass spectra, such as the thermal tail, as well as the overall data quality. Three zircon samples with different uranium and lead content were analyzed, and particular attention was paid to ion identification in the mass spectra and detection limits of the key trace elements, lead and uranium. We also discuss the correlative use of electron backscattered diffraction in a scanning electron microscope to map the deformation in the zircon grains, and the combined use of transmission Kikuchi diffraction and focused ion beam sample preparation to assist preparation of the final atom probe tip.

Sandra Piazolo

Department of Earth and Planetary Sciences

Macquarie University

Characterization of Ultra-fine Grained and Nanocrystalline Materials Using Transmission Kikuchi Diffraction

Sandra Piazolo

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Department of Earth and Planetary Sciences

Macquarie University

Characterization of Ultra-fine Grained and Nanocrystalline Materials Using Transmission Kikuchi Diffraction

Department of Earth and Planetary Sciences