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While much progress has been made in electron-probe microanalysis (EPMA) to improve the accuracy of point analysis, the same level of attention has not always been applied to the quantification of wavelength-dispersive spectrometry (WDS) X-ray intensity maps at the individual pixel level. We demonstrate that the same level of rigor applied in traditional point analysis can also be applied to the quantification of pixels in X-ray intensity maps, along with additional acquisition and quantitative processing procedures to further improve accuracy, precision, and mapping throughput. Accordingly, X-ray map quantification should include pixel-level corrections for WDS detector deadtime, corrections for changes in beam current (beam drift), changes in standard intensities (standard drift), high-accuracy removal of background intensities, quantitative matrix corrections, quantitative correction of spectral interferences, and, if required, time-dependent corrections (for beam and/or contamination sensitive materials). The purpose of quantification at the pixel level is to eliminate misinterpretation of intensity artifacts, inherent in raw X-ray intensity signals, that distort the apparent abundance of an element. Major and minor element X-ray signals can contain significant artifacts due to absorption and fluorescence effects. Trace element X-ray signals can contain significant artifacts where phases with different average atomic numbers produce different X-ray continuum (bremsstrahlung) intensities, or where a spectral interference, even an apparently minor one, can produce a false-positive intensity signal. The methods we propose for rigorous pixel quantification require calibration of X-ray intensities on the instrument using standard reference materials, as we already do for point analysis that is then used to quantify multiple X-ray maps, and thus the relative time overhead associated with such pixel-by-pixel quantification is small. Moreover, the absolute time overhead associated with this method is usually less than that required for quantification using manual calibration curve methods while resulting in significantly better accuracy. Applications to geological, synthetic, or engineering materials are numerous as quantitative maps not only show compositional 2D variation of fine-grained or finely zoned structures but also provide very accurate quantitative analysis, with precision approaching that of a single point analysis, when multiple-pixel averaging in compositionally homogeneous domains is utilized.

The degradation of thermal barrier coatings (TBCs) by molten silicates (CMAS) represents a fundamental barrier to progress in gas turbine technology, requiring a mechanistic understanding of the problem to guide the development of improved coatings. This article investigates the dissolution of yttria-stabilized zirconia (7YSZ and 20YSZ) into two model silicate melts at 1300–1400 °C. The approach involves the 1D dissolution of YSZ into a semi-infinite melt, characterizing the dissolution rates of YSZ and the diffusion rates of Zr4+ and Y3+ therein. The assessed kinetics of YSZ dissolution and diffusion were then applied to modeling the same phenomena on TBC-relevant length scales. These findings provide fundamental insight into (i) the dissolution mechanism of YSZ, (ii) the subsequent reprecipitation upon saturation, (iii) the quantitative effects of temperature and melt composition on the dissolution and diffusion kinetics, and (iv) how the measured kinetics manifests on the scale of flow channels present in TBCs.

We report the major-element, trace-element, and 87 Sr/ 86 Sr compositions of six plagioclase crystals from two Samoan lavas with extreme EM2 isotopic compositions (ALIA-115-18 with whole-rock 87 Sr/ 86 Sr of 0.718592, and ALIA-115-21 with whole-rock 87 Sr/ 86 Sr of 0.720469). We employed laser-ablation split-stream mass spectrometry (LASS) to simultaneously measure 87 Sr/ 86 Sr ratios, major-element concentrations, and trace-element concentrations in the same plagioclase crystal volume. We find that two plagioclase crystals have extreme 87 Sr/ 86 Sr heterogeneity in excess of 5000 ppm (where ppm of 87 Sr/Sr variability86=10 6 ⋅[Sr/8687Sr max − 87 Sr/ 86 Sr min ]/ 87 Sr/ 86 Sr avg ). In two of the plagioclase crystals, we identify the highest 87 Sr/ 86 Sr ratios (0.7224) ever measured in any fresh, mantle-derived ocean island basalt (OIB) or OIB-hosted mineral phase. We find that in 87 Sr/ 86 Sr-versus-Sr concentration space, the six plagioclase crystals overlap in a “common component” region with higher 87 Sr/ 86 Sr than has been previously identified in whole-rock Samoan lavas or mineral separates. We use the occurrence of olivine mineral inclusions (Fo=74.5±0.8, 2 SD) in the high- 87 Sr/ 86 Sr zone of one plagioclase crystal to infer the bulk composition (Mg#=46.8±0.8, 2 SD) of the extreme EM2 magma from which the olivine and high- 87 Sr/ 86 Sr plagioclase crystallized. We argue that a relatively evolved EM2 endmember magma mixed with at least one lower- 87 Sr/ 86 Sr melt to generate the observed intra-crystal plagioclase isotopic heterogeneity. By inferring that subducted terrigenous sediment gives rise to EM2 signatures in Samoan lavas, we estimate that the quantity of sediment necessary to generate the most-elevated 87 Sr/ 86 Sr ratios observed in the Samoan plagioclase is ∼7% of the mantle source. We also estimate that sediment subduction into the mantle over geologic time has generated a sediment domain that constitutes 0.02% of the mass of the mantle, a much lower proportion than required in the EM2 mantle source. Even if subducted sediment is concentrated in large low-shear-velocity provinces (LLSVPs) at the base of the mantle (which constitute up to 7.7% of the mantle's mass), then only 0.25% of the LLSVPs are composed of sediment. This requires that the distribution of subducted sediment in the mantle is heterogeneous, and the high relative abundance of sediment in the Samoan EM2 mantle is an anomalous relic of ancient subduction that has survived convective attenuation.

U–Pb petrochronology of deep crustal xenoliths and outcrops across northeastern Tanzania track the thermal evolution of the Mozambique Belt and Tanzanian Craton following the Neoproterozoic East African Orogeny (EAO) and subsequent Neogene rifting. At the craton margin, the upper–middle crust record thermal quiescence since the Archean (2.8–2.5 Ga zircon, rutile, and apatite in granite and amphibolite xenoliths). The lower crust of the craton documents thermal pulses associated with Neoarchean ultra-high temperature metamorphism (ca. 2.64 Ga, > 900 °C zircon), the EAO (600–500 Ma rutile), and fluid influx during rifting ( 650 °C (above Pb closure of rutile and apatite) at the time of eruption. Zoned titanite records growth during cooling of the lower crust at 550 Ma, followed by fluid influx during slow cooling and exhumation (0.1–1 °C/Myr after 450 Ma). Permissible lower-crustal temperatures for the craton and orogen suggest variable mantle heat flow through the crust and reflect differences in mantle lithosphere thickness rather than advective heating from rifting.

Lavas erupted at hotspot volcanoes provide evidence of mantle heterogeneity. Samoan Island lavas with high 87Sr/86Sr (>0.706) typify a mantle source incorporating ancient subducted sediments. To further characterize this source, we target a single high 87Sr/86Sr lava from Savai’i Island, Samoa for detailed analyses of 87Sr/86Sr and 143Nd/144Nd isotopes and major and trace elements on individual magmatic clinopyroxenes. We show the clinopyroxenes exhibit a remarkable range of 87Sr/86Sr—including the highest observed in an oceanic hotspot lava—encompassing ~30% of the oceanic mantle’s total variability. These new isotopic data, data from other Samoan lavas, and magma mixing calculations are consistent with clinopyroxene 87Sr/86Sr variability resulting from magma mixing between a high silica, high 87Sr/86Sr (up to 0.7316) magma, and a low silica, low 87Sr/86Sr magma. Results provide insight into the composition of magmas derived from a sediment-infiltrated mantle source and document the fate of sediment recycled into Earth’s mantle., Subduction of oceanic crust and sediments contributes to heterogeneities in the mantle, which are sampled by mantle plumes. Here, the authors find that extreme isotopic heterogeneity in Samoan clinopyroxenes can help constrain the composition of mantle sources containing sediment recycled into the Earth’s mantle.

Additive manufacturing promises a major transformation of the production of high economic value metallic materials, enabling innovative, geometrically complex designs with minimal material waste. The overarching challenge is to design alloys that are compatible with the unique additive processing conditions while maintaining material properties sufficient for the challenging environments encountered in energy, space, and nuclear applications. Here we describe a class of high strength, defect-resistant 3D printable superalloys containing approximately equal parts of Co and Ni along with Al, Cr, Ta and W that possess strengths in excess of 1.1 GPa in as-printed and post-processed forms and tensile ductilities of greater than 13% at room temperature. These alloys are amenable to crack-free 3D printing via electron beam melting (EBM) with preheat as well as selective laser melting (SLM) with limited preheat. Alloy design principles are described along with the structure and properties of EBM and SLM CoNi-base materials., Additive manufacturing promises a major transformation of the production of high economic value metallic materials. Here, the authors describe a new class of 3D printable superalloys that are amenable to crack-free 3D printing via electron beam melting as well as selective laser melting.

Successful application of selective electron beam melting to a novel CoNi-based superalloy named SB-CoNi-10 is demonstrated. Crack-free as-printed microstructures exhibit excellent ductilities above 30% and ultimate tensile strengths above 1.1 GPa at room temperature in tension. Conventional post-processing consisting of a super-solvus hot isostatic pressing (HIP), a solution heat treatment (SHT), and a low-temperature aging has been applied to remove microstructural inhomogeneities present in the as-printed microstructure. The microstructures of the as-printed and HIP+SHT+Aged alloys have been investigated to determine the effect of post-processing heat treatments on the nanoscale \(\gamma \)/\(\gamma ^{\prime }\) microstructure and the mesoscale grain structure. Tensile tests have been conducted at room temperature and elevated temperatures above 850 \(^{\circ }\)C to investigate mechanical properties in both the as-printed and HIP+SHT+Aged conditions. The high-temperature ductility and strength are strongly affected by the microstructure, with a mostly columnar-grained microstructure in the as-printed condition exhibiting superior ductility to the fully recrystallized microstructure in the HIP+SHT+Aged condition.

The genesis of seamount chains along fossil spreading ridges reflects the mantle melting dynamics of dying spreading center. The South China Sea developed a seamount chain along its fossil ridge shortly after cessation of spreading. International Ocean Discovery Program Expedition 349 has recovered three volcanic layers, a shallow volcanic breccia layer and two deeper (upper and lower sections) basalt layers, at Site U1431 near the fossil ridge of the South China Sea. Despite the mid-ocean ridge basalt (MORB)-like geochemistry of the lower and upper section basalts, they show distinct geochemical differences that indicate a change of mantle source and a transition from spreading to intraplate volcanism. While the lower section basalts could reflect the last stage volcanism before the cessation of ridge spreading, the upper section basalts with whole-rock MgO up to 20wt.% were formed by intraplate volcanism with significant olivine accumulation once the spreading center had become inactive. The MORB type basalts at Site U1431 have Hawaii-like high olivine Ni and Fe/Mn and low olivine Ca and Mn and bulk-rock low CaO that are distinctly different from normal global MORBs, suggesting an anomalous mantle source in lithology. We suggest that an eclogite-/pyroxenite-rich component, possibly sourced from the Hainan hot spot, played a fundamental role in the transition from spreading to intraplate volcanism of the dying spreading ridge of the South China Sea.

Rapid preparation utilizing assisted microwave heating permits significantly shorter preparation times for magnetocaloric compounds in the (Mn,Fe)2(P,Si) family, specifically samples of (Mn,Fe)2−δP0.5Si0.5 with starting compositions of δ = 0, 0.06, and 0.12. To fully understand the effects of processing and composition changes on structure and properties, these materials are characterized using synchrotron powder diffraction, neutron powder diffraction, electron microprobe analysis (EMPA), X-ray fluorescence (XRF), and magnetic measurements. The diffraction analysis reveals that increasing δ results in decreasing amounts of the common Heusler (Mn,Fe)3Si secondary phase. EMPA shows (Mn,Fe)2(P,Si) in all three samples to be Mn and P rich, whereas XRF demonstrates that the bulk material is Mn rich yet P deficient. Increasing δ brings the Mn/Fe and P/Si ratios closer to their starting values. Measurements of magnetic properties show an increase in saturation magnetization and ordering temperature with increas...

A few years after the theoretical prediction of magnetic MAX phases, a number of such materials have been experimentally reported, especially in the form of thin films. Yet, due to a relatively small number of studies, we have only just begun to discover the intriguing magnetic properties that are associated with this class of materials. The preparation of bulk MAX phases with later transition metals has been proven to be particularly challenging. Consequentially, there is a great need to develop synthetic strategies to obtain the respective materials in suitable quantities for magnetic investigations. Here, bulk Mn- and Fe-substituted Cr2AlC are prepared using non-conventional synthesis methods such as microwave heating and spark plasma sintering. Synchrotron X-ray diffraction coupled with detailed elemental analyses is used to confirm the successful doping of the MAX phase with the later transition metals as well as to elucidate the microstructure of the obtained dense materials. 57Fe Mossbauer spectroscopy data are presented showing signals of the doped MAX phase and Fe-containing secondary phases. Based on PPMS and SQUID measurements the non-trivial magnetic behavior of the obtained samples is discussed in the context of the existing studies.

Length scales of compositional heterogeneity in titanite from 750 to 1000 °C metamorphic rocks from southern Madagascar were measured to provide empirical constraints on elemental diffusivities. The calculated Pb diffusivity is comparable to experimental estimates of Sr diffusivity; because of this, U–Pb dates from rocks that reached peak temperatures 900 °C; thus, Zr-in-titanite thermobarometry should not be reset by diffusion in all but the smallest grains in the hottest rocks. Al and Nb diffuse at similar rates to Zr. Ce and Fe diffuse slower than Pb, but faster than Zr. Differences in empirical and experimental estimates of elemental diffusivities might be related to the complexity of most natural titanite solid solutions compared to the near-end-member titanite used in experiments.

We use an electron beam to induce and directly observe dislocation glide in strained GaAs thin films on silicon substrates at room temperature using electron channeling contrast imaging (ECCI). Plastic behavior in this brittle material is kinetically facilitated by a lowering of the Peierls barrier for glide due to recombination of cathodogenerated electron-hole pairs at dislocations. The high residual strain in the GaAs film provides the overall driving force for motion. The dynamics of a variety of previously inaccessible dislocation interactions are studied by tracking individual threading dislocations with high spatial and temporal resolution. The ECCI technique has an inherently high resolution and was conducted in a convenient scanning electron microscope environment. The results and methods described in this Rapid Communication provide insight into dislocation-filtering processes and failure mechanisms in technologically important III-V devices on silicon, as well as other mismatched heteroepitaxial systems.

Room-temperature non-radiative recombination is studied at single dislocations in Ga0.5In0.5P quantum wells grown on metamorphic templates using cathodoluminescence and electron channeling contrast imaging. An analysis of the light emission intensity profiles around single dislocations reveals that the average recombination strength of a dislocation decreases by a factor of four and seven as a result of decreasing growth temperature of the GaInP quantum well from 725 to 675 and 625 °C, respectively. This reduction occurs despite little change in the diffusion length, precluding the prospect of inducing carrier localization by ordering and phase separation in GaInP at lower growth temperatures. These observations are rationalized by the premise that point defects or impurities are largely responsible for the recombination activity of dislocations, and the extent of decoration of the dislocation core decreases with temperature. Preliminary evidence for the impact of the Burgers vector is also presented. The lowest growth temperature, however, negatively impacts light emission away from dislocations. Carrier recombination in the bulk and at dislocations needs to be considered together for metamorphic devices, and this work can lead to new techniques to limit non-radiative recombination.

This study investigated the influence of YbO1.5 concentration on the reactivity between YbO1.5–HfO2 thermal barrier coating (TBC) materials and silicate melts [calcium–magnesium aluminosilicate (CMAS), specifically 33CaO–9MgO–13AlO1.5–45SiO2, all in mol%]. Three thermal barrier oxides (TBO) with YbO1.5 concentration between 30 and 80 mol% were tested at 1300°C and 1500°C. Porous pellets were used to study reaction layer growth and the behavior within infiltrated porosity. Complementary experiments examined the phase equilibria in melts containing varying quantities of the candidate TBOs. The effectiveness of reactive crystallization to limit interaction depth increased with the YbO1.5 concentration in the TBO. The results indicate that the TBO must contain sufficient YbO1.5 to satisfy the equilibrium between the melt and HfO2-based fluorite phase before YbO1.5-bearing silicates can precipitate. Increasing the YbO1.5 availability leads to the crystallization of apatite, garnet, silicocarnotite, and/or cuspidine (alumino)silicates. Apatite was observed at 1300°C and 1500°C, garnet and silicocarnotite only appeared at 1300°C, and cuspidine was only evident at 1500°C. The implications for the design of CMAS-resistant coatings are discussed in the context of the experimental results.

Garnets record subduction earthquakes., Large earthquakes occur in rocks undergoing high-pressure/low-temperature metamorphism during subduction. Rhythmic major-element zoning in garnet is a common product of such metamorphism, and one that must record a fundamental subduction process. We argue that rhythmic major-element zoning in subduction zone garnets from the Franciscan Complex, California, developed in response to growth-dissolution cycles driven by pressure pulses. Using electron probe microanalysis and novel techniques in Raman and synchrotron Fourier transform infrared microspectroscopy, we demonstrate that at least four such pressure pulses, of magnitude 100–350 MPa, occurred over less than 300,000 years. These pressure magnitude and time scale constraints are most consistent with the garnet zoning having resulted from periodic overpressure development-dissipation cycles, related to pore-fluid pressure fluctuations linked to earthquake cycles. This study demonstrates that some metamorphic reactions can track individual earthquake cycles and thereby opens new avenues to the study of seismicity.

Sample localities, details of the analytical methods, data tables and the full discussion of the results of electron back-scatter diffraction studies of quartz lattice preferred orientations.

The electronic and thermal properties of thermoelectric materials are highly dependent on their microstructure and therefore on the preparation conditions, including the initial synthesis and, if applicable, densification of the obtained powders. Introduction of secondary phases on the nano- and/or microscale is widely used to improve the thermoelectric figure of merit by reduction of the thermal conductivity. In order to understand the effect of the preparation technique on structure and properties, we have studied the thermoelectric properties of the well-known half-Heusler TiNiSn with addition of a small amount of nickel nanoparticles. The different parameters are the initial synthesis (levitation melting and microwave heating), the amount of nickel nanoparticles added and the exact pressing profile using spark plasma sintering. The resulting materials have been characterized by synchrotron X-ray diffraction and microprobe measurements and their thermoelectric properties are investigated. We found the lowest (lattice) thermal conductivity in samples with full-Heusler TiNi2Sn and Ni3Sn4as secondary phases. © 2013 Elsevier Masson SAS. All rights reserved.

We report electron backscatter diffraction (EBSD) measurements of antigorite crystal preferred orientations (CPOs) from 7 samples of antigorite schist from serpentinite melanges adjacent to the Motagua fault system in central Guatemala. The CPOs range from diffuse girdle to point distributions of (001) atg . Girdle distributions of (001) atg are not expected from deformation theory or experiments, suggesting that they are a result of growth rather than deformation, and may thus be topotactically related to the CPO of the olivine from which the antigorite grew. The calculated seismic anisotropy ranges from 6% to 28% in V P , and 5% to 33% in V S , and is highest for samples with a point maximum of (001) atg . For all samples the minimum V P corresponds to the pole to (001) atg , and the maximum V P occurs within the foliation for samples with a clearly defined foliation. Trench-parallel shear-wave splitting observations for subduction zones can best be explained by a combination of olivine B-type CPO and antigorite oriented with (001) parallel to the foliation; only a relatively thin (~20 km) zone of hydrated mantle is required to explain the observed splitting times.

U–Pb dates of titanite from > 150 samples of chiefly quartzofeldspathic gneiss and leucosomes were measured across the Western Gneiss Region of Norway to understand deformation and metamorphism of typical crustal rocks during ultrahigh-pressure (UHP) subduction and exhumation. Titanite is unstable at these high temperatures and pressures, and, indeed, most of the titanite yielded post-UHP dates. A modest number of titanites sampled across large areas, however, have pre-UHP U–Pb dates, indicating that they survived their excursion to and return from mantle depths metastably. This has three important implications. 1. Titanite grains can remain closed to complete Pb loss during regional metamorphism at temperatures as high as 750 °C and pressures as high as 3 GPa. 2. Phase transformations in quartzofeldspathic rocks can be inhibited at the same conditions. 3. Quartz-bearing rocks can remain undeformed even at high temperature and pressure. Both of the latter were previously recognized; the present study simply presents a new method for evaluating both using titanite U–Pb dates.

The interaction of molten calcium-magnesium alumino-silicate (CMAS) with yttrium monosilicate (YMS), a candidate environmental barrier coating (EBC) for SiC-based ceramic matrix composites, was investigated. YMS monoliths were exposed to CMAS melts at 1300°C for times ranging from 1 to 100 h and characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy/electron microprobe analysis, and electron back-scattered diffraction. YMS is dissolved into CMAS and reprecipitates as a Ca 2 Y 8 (Si0 4 ) 6 0 2 oxyapatite phase. A nominally continuous layer of apatite is readily established at the interface, but its effectiveness as a diffusion barrier is compromised by the presence of thin amorphous films along the grain boundaries that enhance chemical transport between the bulk melt and the YMS. Moreover, the growth mechanism involves continuous renucleation that eventually leads to separation of the crystals formed previously from the interface and their subsequent coarsening. The latter results in widening of the amorphous boundary films, enhancing interdiffusion. The significance of these findings on the viability of YMS as a durable EBC is discussed.

The Ama Drime Massif is a north–south trending antiformal structure located on the southern margin of the Tibetan Plateau that is bound by the Ama Drime and Nyonno Ri detachments on the western and eastern sides, respectively. Detailed kinematic and vorticity analyses were combined with deformation temperature estimates on rocks from the Ama Drime detachment to document spatial and temporal patterns of deformation. Deformation temperatures estimated from quartz and feldspar microstructures, quartz [c] axis fabrics, and two-feldspar geothermometry of asymmetric strain-induced myrmekite range between ∼400 and 650 °C. Micro- and macro-kinematic indicators suggest west-directed displacement dominated over this temperature range. Mean kinematic vorticity estimates record early pure shear dominated flow (49–66% pure shear) overprinted by later simple shear (1–57% pure shear), high-strain (36–50% shortening and 57–99% down-dip extension) dominated flow during the later increments of ductile deformation. Exhumation of the massif was accommodated by at least ∼21–42 km of displacement on the Ama Drime detachment. Samples from the Nyonno Ri detachment were exhumed from similar depths. We propose that exhumation on the Nyonno Ri detachment during initiation of orogen-parallel extension (11–13 Ma) resulted in a west-dipping structural weakness in the footwall that reactivated as the Ama Drime detachment.

Kinematic, kinematic vorticity (Wm), and deformation-temperature analyses were performed to test the hypothesis that mid-crustal rocks exposed in Mabja Dome, southern Tibet, were penetratively deformed within a southward-flowing mid-crustal channel during the late Eocene/early Oligocene to early Miocene. Outcrop and thin-section kinematic indicators show a downward transition from mixed top-N and top-S shear in chloritoid- and garnet-zone rocks, through dominantly top-S shear in garnet- and kyanite-zone rocks, to solely top-S shear in staurolite-zone and deeper rocks. Along mineral elongation lineation-parallel transects, Wm in schists and orthogneisses decreases with structural depth from w0.80 (w40% pure shear) to w0.55 (w63% pure shear). Deformation temperature increases from w450 � Ci n

Experiments in which the microstructural development can be observed at the same time as the crystallography is described fully opens up new, powerful ways to advance our understanding of microstructural processes such as grain growth, primary and secondary recrystallization and phase transformations. In addition, comparison of results of experiments in different materials can be used to develop general laws for the investigated processes. In this study, we briefly review and compare the results from various ongoing studies undertaken in a variety of materials with emphasis on highlighting (a) the scientific potential of such experiments and (b)similarities and differences in their microstructural evolution. Materials studied include metals e.g. Ti, Ni, Al, Mg, Ti-SULC steel and geological materials such as rocksalt (NaCl), hematite and magnetite. Here, we present experimental results and their interpretation in terms of subgrain to grain-scale processes.

This study presents in situ observations of the hcp (α) to bcc (β) phase transformation in commercially pure titanium at 882 °C using SEM imaging concurrent with crystal orientation determination using EBSD. Direct observations of the onset of the phase transformation are presented showing the early stages of the growth of β plates within α grains and allotriomorphic β along α–α grain boundaries. Intragranular β plates have a Burgers orientation relationship (OR) with the parent α grain and are lenticular in shape. These plates also have a tent surface relief and surface-traces consistent with habit planes predicted by the phenomenological theory of martensitic crystallography for pure titanium. These features suggest a military component to the growth mechanism. The β allotriomorphs have a Burgers OR with one of the α grains abutting at the boundary, but do not have surface relief characteristic of a military transformation. These are likely to grow by a civilian mechanism. The final stage of the transformation is a process of competitive growth of the two β forms, with the allotriomorphic β dominating by virtue of its faster moving α–β interfaces. Grain growth in the β stability field is more than an order of magnitude faster than that in the α field at temperatures near the phase transformation.

The 18-electron ternary intermetallic systems TiNiSn and TiCoSb are promising for applications as high-temperature thermoelectrics and comprise earth-abundant, and relatively nontoxic elements. Heusler and half-Heusler compounds are usually prepared by conventional solid state methods involving arc-melting and annealing at high temperatures for an extended period of time. Here, we report an energy-saving preparation route using a domestic microwave oven, reducing the reaction time significantly from more than a week to one minute. A microwave susceptor material rapidly heats the elemental starting materials inside an evacuated quartz tube resulting in near single phase compounds. The initial preparation is followed by a densification step involving hot-pressing, which reduces the amount of secondary phases, as verified by synchrotron X-ray diffraction, leading to the desired half-Heusler compounds, demonstrating that hot-pressing should be treated as part of the preparative process. For TiNiSn, high thermoelectric power factors of 2 mW/mK^2 at temperatures in the 700 to 800 K range, and zT values of around 0.4 are found, with the microwave-prepared sample displaying somewhat superior properties to conventionally prepared half-Heuslers due to lower thermal conductivity. The TiCoSb sample shows a lower thermoelectric figure of merit when prepared using microwave methods because of a metallic second phase.

[1] New electron backscatter diffraction measurements show that the Papua New Guinea (PNG) ultrahigh-pressure (UHP) terrane is dominated by rocks with weakly oriented quartz and feldspar and less abundant strongly oriented hornblende, clinopyroxene, and mica. Velocities measured at high pressures (600 MPa) show that VP is 5.8–6.3 km/s for gneiss samples, 6.5–7.7 km/s for amphibolite, and 7.7–8.2 km/s for eclogite and VS is 3.4–3.9 km/s for gneiss, 4.0–4.4 km/s for amphibolite, and 4.5–4.6 km/s for eclogite. Velocities and anisotropies calculated from mineral crystal preferred orientations (CPOs) are equivalent to within 5% of the measured values. The highest seismic anisotropy for the PNG terrane is in amphibolite at 8% and 7% for VP and VS, respectively. Calculations of seismic velocities at depth based on predicted mineral assemblages indicate that the exhuming UHP terrane is of dominantly mafic composition below ∼20 km depth. Anisotropy in the PNG terrane is expected to be quite low and is controlled by the orientation of the foliation. If observable, changes in anisotropy across the exhuming body may be used to differentiate among the different proposed mechanisms of UHP exhumation.

[1] Structural analysis of two key exposures reveals the architecture of the brittle-ductile transition (BDT) of the subvertical, strike-slip Salzachtal fault. At Lichtensteinklamm, the fault zone is dominantly brittle, with a ∼70 m wide, high-strain fault core highlighted by a 50 m thick, highly foliated gouge zone. In contrast, at Kitzlochklamm, deformation is dominantly ductile, albeit with relatively low strain indicated by weak lattice-preferred orientations (LPOs). The marked contrast in structural style indicates that these sites span the BDT. The close proximity of the outcrops, coupled with Raman spectroscopy indicating similar maximum temperatures of ∼400°C, suggests that the difference in exhumation depth is small, with a commensurately small difference in total downdip width of the BDT. The small strains indicated by weak LPOs at Kitzlochklamm, coupled with evidence for brittle slip at the main fault contact and along the sides of a 5 m wide fault-bounded sliver of Klammkalk exposed 30 m into the Grauwacken zone rocks, suggest the possibility that this exposure may record hybrid behavior at different times during the earthquake cycle, with ductile deformation occurring during slow interseismic slip and brittle deformation occurring during earthquakes, as dynamic coseismic stresses induced a strain rate–dependent shift to brittle fault behavior within the nominally ductile regime in the lower part of the BDT. A key aspect of both outcrops is evidence of a high degree of strain localization through the BDT, with high-strain fault cores no wider than a few tens of meters.

[1] Kinematic, kinematic vorticity (Wm), and deformation temperature analyses were completed to test the hypothesis that midcrustal rocks exposed in the core of the Kangmar gneiss dome, southern Tibet record ductile deformation patterns of a “frozen” segment of a southward flowing midcrustal channel. Microscopic and mesoscopic kinematic indicators exhibit a downward transition from a subequal mix of top-north and top-south shear in garnet zone rocks to dominantly top-north shear in staurolite/kyanite zone and deeper rocks. Kinematic vorticity values indicate an increase in pure shear component with depth from ∼48% pure shear in chloritoid zone rocks through ∼62% in garnet zone to staurolite/kyanite zone rocks to ∼68% pure shear in an orthogneiss, the deepest exposed rocks. Deformation temperatures inferred from grain-scale microstructures and quartz lattice preferred orientations increase from ∼300°C–400°C in chloritoid zone rocks to ≥600°C in the deepest exposed rocks. These temperatures are equivalent to temperatures derived from garnet-biotite thermobarometry, indicating that Wm was recorded during peak metamorphism. This ductile deformation zone was cut by the brittle southern Tibetan detachment system (STDS) that juxtaposed metasedimentary rocks upon the orthogneiss. On the basis of these relations, midcrustal rocks in the core of Kangmar Dome record: (1) general shear (vertical thinning and N–S horizontal extension) with a component of top-north shear during peak metamorphism within a ductile shear zone corresponding to the northern and deeper portion of the STDS, (2) an increase in pure shear with structural depth, a consequence of an increase in lithostatic load, and (3) displacement of the high-temperature shear zone by the brittle STDS. Our data are compatible with the deformation patterns predicted for the top part of a southward flowing midcrustal channel.

[1] Global studies of metamorphic core complexes and low-angle detachment faults have highlighted a fundamental problem: Since detachments excise crustal section, the relationship between the mylonitic rocks in their footwalls and the brittle deformation in their hanging walls is commonly unclear. Mylonites could either reflect ductile deformation related to exhumation along the detachment fault, or they could be a more general feature of the extending middle crust that has been “captured” by the detachment. In the first case we would expect the kinematics of the mylonite zone to mirror the sense of movement on the detachment; in the second case both the direction and sense of shear in the mylonites could be different. The northern Snake Range decollement (NSRD) is a classic Basin and Range detachment fault with a well-documented top-east of displacement. We present structural, paleomagnetic, geochronological, and geothermometric evidence to suggest that the mylonite zone below the NSRD locally experienced phases of both east- and west-directed shear, inconsistent with movement along a single detachment fault. We therefore propose that the footwall mylonites represent a predetachment discontinuity in the middle crust that separated localized deformation above from distributed crustal flow below (localized-distributed transition (LDT)). The mylonites were subsequently captured by a moderately dipping brittle detachment that soled down to the middle crust and exhumed them around a rolling hinge into a subhorizontal orientation at the surface, producing the present-day NSRD. In this interpretation the brittle hanging wall represents a series of rotated upper crustal normal faults, whereas the mylonitic footwall represents one or more exhumed middle crustal discontinuities (LDTs).

[1] The Miocene Salzachtal-Ennstal-Mariazell-Puchberg (SEMP) strike-slip fault in Austria allows study of the internal structure of a fault zone from the near surface to � 30 km depth. As it enters the Tauern Window along the Rinderkarsee shear zone, the SEMP fault passes from a dominantly brittle to a dominantly ductile structure. The shear zone consists of three 1- to 100-m-wide zones of brittle-ductile and ductile deformation separated by 500-m-wide zones of less deformed rocks. The southern shear zone is mylonitic, with ductile amphibole and plagioclase; weak crystal preferred orientations imply that the main deformation mechanism was dislocation-accommodated grain boundary sliding. The northern and central shear zones are characterized by discrete millimeter-wide shear zones with ductile quartz, muscovite, and biotite and brittle feldspar. Shear zone nucleation at the grain scale involved dislocation creep and the transformation of plagioclase to muscovite; strain then localized in muscovite-rich grain boundary shear zones that linked to form throughgoing shear zones.

Extended abstract of a paper presented at Microscopy and Microanalysis 2013 in Indianapolis, Indiana, USA, August 4 – August 8, 2013.

In-situ heating experiments have been conducted at temperatures of approximately 1200 K utilising a new design of scanning electron microscope, the CamScan X500. The X500 has been designed to optimise the potential for electron backscatter diffraction (EBSD) analysis with concomitant in-situ heating experimentation. Features of the new design include an inclined field emission gun (FEG) column, which affords the EBSD geometrical requirement of a high (typically 160 degrees) angle between the incoming electron beam and specimen surface, but avoids complications in heating-stage design and operation by maintaining it in a horizontal orientation. Our studies have found that secondary electron and orientation contrast imaging has been possible for a variety of specimen materials up to a temperature of at least 900 degrees C, without significant degradation of imaging quality. Electron backscatter diffraction patterns have been acquired at temperatures of at least 900 degrees C and are of sufficient quality to allow automated data collection. Automated EBSD maps have been produced at temperatures between 200 degrees C and 700 degrees C in aluminium, brass, nickel, steel, quartz, and calcite, and even at temperatures >890 degrees C in pure titanium. The combination of scanning electron microscope imaging techniques and EBSD analysis with high-temperature in-situ experiments is a powerful tool for the observation of dynamic crystallographic and microstructural processes in metals, semiconductor materials, and ceramics.

Half-Heusler thermoelectrics offer the possibility to choose from a variety of non-toxic and earth-abundant elements. TiNiSn is of particular interest and - with its relatively high electrical conductivity and Seebeck coefficient - allows for optimization of its thermoelectric figure of merit, reaching values of up to 1 in heavily-doped and/or phase-segregated systems. In this contribution, we used an energy- and time-efficient process involving solid-state preparation in a commercial microwave oven and a fast consolidation technique, Spark Plasma Sintering, to prepare a series of Ni-rich TiNi1+xSn with small deviations from the half-Heusler composition. Spark Plasma Sintering plays an important role in the process by being a part of the synthesis of the material rather than solely a densification technique. Synchrotron powder X-ray diffraction and microprobe data confirm the presence of a secondary TiNi2Sn full-Heusler phase within the half-Heusler matrix. We observe a clear correlation between the amount of full-Heusler phase and the lattice thermal conductivity of the samples, resulting in decreasing total thermal conductivity with increasing TiNi2Sn fraction. This trend shows that phonons are scattered effectively as a result of the microstructure of the materials with full-Heusler inclusions in the size range of microns to tens of microns. The best performing samples with around 5% of TiNi2Sn phase exhibit maximum figures of merit of almost 0.6 between 750 K and 800 K which is an increase of ca. 35% compared to the zT of the parent compound TiNiSn.