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Pyroxenes in Martian meteorites as petrogenetic indicators
Pyroxenes in Martian meteorites are important recorders of petrogenetic processes. Understanding the details of pyroxene major and minor element compositional variations can provide important insights into those processes. A combination of careful petrographic analysis of natural samples and experimental crystallization studies can lead to better understanding of the processes that gave rise to these samples on Mars. In addition, experimentally determined major, minor and trace element partition coefficients are important for using natural pyroxenes to estimate the compositions of the melts from which they crystallized and the oxidation conditions that prevailed during crystallization. We will report on minor element (Al, Ti, Cr) zoning in nakhlite pyroxenes and in synthetic pyroxenes that we have grown for the purposes of determining pyroxene/melt partition coefficients for Sr and REE. The natural pyroxenes have patchy Al zoning that, by analogy with our experimental pyroxenes, we interpret as sector zoning. The irregular patchy nature of the zoning is probably the result of the vagaries of growth kinetics and local environment during crystal growth. More slowly cooled nakhlites have the most distinct bimodal zoning, with one mode having Al2O3 around 0.5-0.6 wt%, and the other around 0.9 %. Average Al content increases with increasing cooling rate. This feature is puzzling, since the cumulus pyroxenes were almost certainly present at the time of eruption. Al and Ti are strongly correlated, but Cr is completely decoupled from those elements. The synthetic pyroxenes are distinctly sector zoned in Al and Ti, and the sector-to-sector variation in Al within a single crystal has important effects on trace element partition coefficients. Trivalent REE are strongly correlated with Al, while divalent elements (Sr, Eu+2) show a significantly weaker correlation. For example, as the Al2O3 content varies from 0.3 to 0.6 wt % from one sector to another, D(Gd) increases by approx.80% while D(Sr) and D(Eu) only increase by 20-30% at oxygen fugacities near IW. The different Al dependency of D for trivalent REE vs. divalent Eu and Sr considerably complicates the calibration of the Eu oxybarometer.
Overview of Bulk Silicon Crystal Growth
The Czochralski and float-zone techniques are reviewed and the consequences of high growth rates in the growth of electronic grade silicon are examined. Impurity segregation coefficients are defined.
Large area Czochralski silicon
The overall cost effectiveness of the Czochralski process for producing large-area silicon was determined. The feasibility of growing several 12 cm diameter crystals sequentially at 12 cm/h during a furnace run and the subsequent slicing of the ingot using a multiblade slurry saw were investigated. The goal of the wafering process was a slice thickness of 0.25 mm with minimal kerf. A slice + kerf of 0.56 mm was achieved on 12 cm crystal using both 400 grit B4C and SiC abrasive slurries. Crystal growth experiments were performed at 12 cm diameter in a commercially available puller with both 10 and 12 kg melts. Several modifications to the puller hoz zone were required to achieve stable crystal growth over the entire crystal length and to prevent crystallinity loss a few centimeters down the crystal. The maximum practical growth rate for 12 cm crystal in this puller design was 10 cm/h, with 12 to 14 cm/h being the absolute maximum range at which melt freeze occurred.
Influence of Containment on the Growth of Silicon-Germanium: A Materials Science Flight Project
This investigation involves the comparison of results achieved from three types of crystal growth of germanium and germanium-silicon alloys: (1) Float zone growth (2) Bridgman growth (3) Detached Bridgman growth crystal The fundamental goal of the proposed research is to determine the influence of containment on the processing-induced defects and impurity incorporation in germanium-silicon (GeSi) crystals (silicon concentration in the solid up to 5 at%) for three different growth configurations in order to quantitatively assess the improvements of crystal quality possible by detached growth.
Smooth periodic gauge satisfying crystal symmetry and periodicity to study high-harmonic generation in solids
Intense lasers can easily drive nonadiabatic transitions of excited electron wave packets across the Brillouin zones, thus transition dipole moments (TDM) between energy bands of solids should be continuous, satisfying crystal symmetry, and periodic at zone boundaries. While current ab initio algorithms are powerful in calculating band structures of solids, they all introduced random phases into the eigenfunctions at each crystal momentum k. In this work, we show how to choose a “smooth-periodic” gauge where TDMs can be smooth versus k, preserving crystal symmetry, as well as maintaining periodic at boundaries. The symmetry properties of TDMs with respect to k ensure the absence of even-order harmonics from MgO with inversion symmetry, while the TDM in the “smooth-periodic” gauge for broken-symmetry ZnO is responsible for even harmonics that were underestimated in previous simulations. These results reveal the importance of correctly treating the complex TDMs that satisfy crystal symmetry and continuous across zone boundaries in nonlinear laser-solid interactions, which has been elusive in most theories so far.
Reduction of Defects in Germanium-Silicon
It is well established that crystals grown without contact with a container have far superior quality to otherwise similar crystals grown in direct contact with a container. In addition to float- zone processing, detached-Bridgman growth is often cited as a promising tool to improve crystal quality, without the limitations of float zoning. Detached growth has been found to occur quite often during micro-g experiments and considerable improvements of crystal quality have been reported for those cases. However, no thorough understanding of the process or quantitative assessment of the quality improvements exists so far. This project will determine the means to reproducibly grow Ge-Si alloys in the detached mode. Specific objectives include: (1) measurement of the relevant material parameters such as contact angle, growth angle, surface tension, and wetting behavior of the GeSi-melt on potential crucible materials; (2) determination of the mechanism of detached growth including the role of convection; (3) quantitative determination of the differences of defects and impurities among normal Bridgman, detached Bridgman, and Floating Zone (FZ) growth; (4) investigation of the influence of defined azimuthal or meridional flow due to rotating magnetic fields on the characteristics of detached growth; (5) control time-dependent Marangoni convection in the case of FZ-growth by the use of a rotating magnetic field to examine the influence on the curvature of the solid-liquid interface and the heat and mass transport; and (6) grow high quality GeSi-single crystals with Si-concentration up to 10 at% and diameters up to 20 mm.
Plastic deformation of molybdenum-rhenium alloy crystals
Plastic deformation of Mo-Re single crystals produced by electron beam zone refining, investigating lattice frictional stress, activation volume temperature variation, etc
Actinide crystal-liquid partitioning for clinopyroxene and Ca3/PO4/2
Coefficients for the partitioning of the actinide elements Th, U and Pu, which are used as indicators of r-process nucleosynthesis and the ages of meteorite and lunar samples, between diopsidic clinopyroxene, whitlockite and silicate liquid at 20 kbar are measured. Fission and alpha track radiography techniques are employed to detect element concentrations in synthetic crystals made using spiked starting materials, under the assumptions of equilibrium partitioning at the crystal-liquid interface and actinide zoning. Analysis of the data indicates results to be consistent with interface equilibrium except at high cooling rates. Th/U/Pu partition coefficients of about 0.002/0.002/O.06 are measured for clinopyroxene and 1.2/0.5/3.4 for whitlockite. The greater incorporation of Pu into the crystalline phases is attributed to the importance of trivalent Pu, and the similarity of its partition coefficient into clinopyroxene to that of the light rare earths supports the concept of Pu/rare earth dating.
Early Archean tonalite gneiss in the upper peninsula of Michigan
Geochronological results on tonalite gneiss of northern Michigan that is 3.56 Ga or slightly older is presented. Tonalitic augen gneiss and structurally overlying biotite gneiss and schist are exposed in a dome near Watersmeet. They are part of an extensive gneiss terrane of southern Minnesota, Wisconsin and Michigan that includes rocks of early to late Archean ages and lies south of the Wawa volcanic subprovince. Two samples of the augen gneiss and one of the biotite gneiss show zircon grains of similar shape, zoning, color, and development of crystal faces. These zircons give Pb/U isotopic ratios that plot on a chord of 3,560 + or - 40 m.y. upper intersect and of 1,250 + or m.y. lower intersect. The 3,560 m.y. number is believed to be a minimum age because analysis of one of the least discordant zircon fractions by ion microprobe that gave a nearly concordant age of 3,650 m.y. The 1,250 m.y. lower intersect is without geological significance: it is interpreted to be a result of multiple lead loss at 2.7, 1.8, and 0.5 Ga by U/Pb in zircon. Archean rocks 10 to 25 km northwest of the Watersmeet dome give a 2.75 Ga age on zircons. Quartz monzonite here is dated at 2.65 Ga.
The Water-Fe-Pressure dependent single-crystal elastic properties of wadsleyite: Implications for the seismic anisotropy in the upper Mantle Transition Zone
Recent seismic studies suggest an anisotropic Mantle Transition Zone (MTZ) in areas adjacent to subducted slabs. Wadsleyite is the main anisotropy contributor in the upper MTZ, therefore the interpretation of these seismic observations requires the knowledge of single-crystal elastic moduli (C ij s) and the deformation-induced lattice preferred orientation (LPO) of wadsleyite. Wadsleyite can host up to 3 wt% water in its crystal structure as point defects in the form of hydroxyl groups, however, the combined effect of water content, Fe content, and pressure on the C ij s of wadsleyite remains unclear. In this study, we measured the high-pressure single-crystal elasticity of a synthetic hydrous Fe-bearing wadsleyite (0.14(5) wt% water, Fe#=9.4, Fe 3+ /ΣFe=0.3) up to 18.2 (2) GPa. In combination with previous experimental data, we separated the effects of pressure, water, and Fe contents on the Cijs and intrinsic elastic anisotropy of wadsleyite. Overall, our results suggest that the intrinsic elastic anisotropy of wadsleyite decreases with pressure, water, and Fe contents. At 15 GPa, increasing the water content by 0.1 wt% or Fe# by 1 decreases the V P and V S anisotropy of wadsleyite by ~1.1-1.3%, and ~0.8-1.3% in average, respectively. Combined with the LPO determined in previous deformation experiments, we modeled the seismic anisotropy in the upper MTZ generated by a sub-vertical mantle flow near cold subducted slabs and a sub-horizontal mantle flow in the ambient mantle. In both scenarios, the LPO of wadsleyite leads to V SV (vertically polarized shear wave velocity) > V SH (horizontally polarized shear wave velocity). Our results suggest that wadsleyite may account for a weak anisotropic MTZ (<1%) on the global scale. Considering the fact that water decreases the elastic anisotropy but promotes LPO of wadsleyite, seismic anisotropy may not be a good water sensor.
Enhanced calcium–magnesium–aluminosilicate (CMAS) resistance of GdAlO 3 (GAP) for composite thermal barrier coatings
Not provided.
Reduction of Defects in Germanium-Silicon
It is well established that crystals grown without contact with a container have far superior quality to otherwise similar crystals grown in direct contact with a container. In addition to float-zone processing, detached-Bridgman growth is often cited as a promising tool to improve crystal quality, without the limitations of float zoning. Detached growth has been found to occur quite often during microgravity experiments and considerable improvements of crystal quality have been reported for those cases. However, no thorough understanding of the process or quantitative assessment of the quality improvements exists so far. This project will determine the means to reproducibly grow Ge-Si alloys in the detached mode. Specific objectives include: (1) measurement of the relevant material parameters such as contact angle, growth angle, surface tension, and wetting behavior of the GeSi-melt on potential crucible materials; (2) determination of the mechanism of detached growth including the role of convection; (3) quantitative determination of the differences of defects and impurities among normal Bridgman, detached Bridgman, and floating zone (FZ) growth; (4) investigation of the influence of defined azimuthal or meridional flow due to rotating magnetic fields on the characteristics of detached growth; (5) control time-dependent Marangoni convection in the case of FZ-growth by the use of a rotating magnetic field to examine the influence on the curvature of the solid-liquid interface and the heat and mass transport; and (6) grow high quality GeSi-single crystals with Si-concentration up to 10 at% and diameters up to 20 mm.
Origin of Intrinsically Low Thermal Conductivity in a Garnet-Type Solid Electrolyte: Linking Lattice and Ionic Dynamics with Thermal Transport
Understanding thermal transport in solid electrolytes is essential for improving the performance, reliability, and safety of all-solid-state batteries. Garnet-type lithium-ion conductors are promising candidates for solid electrolytes, yet their thermal-transport mechanisms remain poorly understood. Here, we connect the lattice and ion dynamics of single-crystal garnet-type Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 to its intrinsically low thermal conductivity. Our study reveals that the single crystals grown by the floating-zone method exhibit remarkably low glasslike thermal conductivity. Using first-principles calculations and inelastic-neutron-scattering measurements, we identify both the acoustic and numerous optical phonon modes, which stem from the complex crystal structure of the material. Notably, a low-energy optical branch exhibits an avoided crossing with acoustic phonons near 7 meV. These optical modes can enhance the scattering of heat-carrying acoustic phonons and reduce thermal conductivity. Furthermore, the calculated Grüneisen parameters are large, especially for the vibrational modes around 6 meV, indicating strong anharmonicity, with a noticeable contribution from lithium-ion vibrations. A two-channel thermal-transport model is employed to describe the weak temperature dependence of the thermal conductivity, which can be attributed to the substantial contribution of diffuson transport facilitated by the abundance of optical phonons and intrinsic anharmonicity. These results offer valuable insights into the thermal transport in a broad class of ionic conductors of interest for energy conversion and storage applications.
Development of microchannel plate x-ray optics
The goal of this research program was to develop a novel technique for focusing x-rays based on the optical system of a lobster's eye. A lobster eye employs many closely packed reflecting surfaces arranged within a spherical or cylindrical shell. These optics have two unique properties: they have unlimited fields of view and can be manufactured via replication of identical structures. Because the angular resolution is given by the ratio of the size of the individual optical elements to the focal length, optical elements with sizes on the order of one hundred microns are required to achieve good angular resolution with a compact telescope. We employed anisotropic etching of single crystal silicon wafers for the fabrication of micron-scale optical elements. This technique, commonly referred to as silicon micromachining, is based on silicon fabrication techniques developed by the microelectronics industry. An anisotropic etchant is a chemical which etches certain silicon crystal planes much more rapidly than others. Using wafers in which the slowly etched crystal planes are aligned perpendicularly to the wafer surface, it is possible to etch a pattern completely through a wafer with very little distortion. Our optics consist of rectangular pores etched completely through group of zone axes (110) oriented silicon wafers. The larger surfaces of the pores (the mirror elements) were aligned with the group of zone axes (111) planes of the crystal perpendicular to the wafer surface. We have succeeded in producing silicon lenses with a geometry suitable for 1-d focusing x-ray optics. These lenses have an aspect ratio (40:1) suitable for x-ray reflection and have very good optical surface alignment. We have developed a number of process refinements which improved the quality of the lens geometry and the repeatability of the etch process. A significant progress was made in obtaining good optical surface quality. The RMS roughness was decreased from 110 A for our initial lenses to 30 A in the final lenses. A further factor of three improvement in surface quality is required for the production of efficient x-ray optics. In addition to the silicon fabrication, an x-ray beam line was constructed at Columbia for testing the optics.
Elastic response of (001)-oriented PWA 1480 single crystal - The influence of secondary orientation
The influence of secondary orientation on the elastic response of a zone axis (001)-oriented nickel-base single-crystal superalloy, PWA 1480, was investigated under mechanical loading conditions by applying finite element techniques. Elastic stress analyses were performed with a commercially available finite element code. Secondary orientation of the single-crystal superalloy was offset with respect to the global coordinate system in increments from 0 to 90 deg and stresses developed within the single crystal were determined for each loading condition. The results indicated that the stresses were strongly influenced by the angular offset between the secondary crystal orientation and the global coordinate system. The degree of influence was found to vary with the type of loading condition (mechanical, thermal, or combined) imposed on the single-crystal superalloy.
Oxygen isotope ratios in zircon and garnet: A record of assimilation and fractional crystallization in the Dinkey Dome peraluminous granite, Sierra Nevada, California
Abstract The 119 Ma Dinkey Dome pluton in the central Sierra Nevada Batholith is a peraluminous granite and contains magmatic garnet and zircon that are complexly zoned with respect to oxygen isotope ratios. Intracrystalline SIMS analysis tests the relative importance of magmatic differentiation processes vs. partial melting of metasedimentary rocks. Whereas δ18O values of bulk zircon concentrates are uniform across the entire pluton (7.7‰ VSMOW), zircon crystals are zoned in δ18O by up to 1.8‰, and when compared to late garnet, show evidence of changing magma chemistry during multiple interactions of the magma with wall rock during crustal transit. The evolution from an early high-δ18O magma [δ18O(WR) = 9.8‰] toward lower values is shown by high-δ18O zircon cores (7.8‰) and lower δ 18O rims (6.8‰). Garnets from the northwest side of the pluton show a final increase in δ18O with rims reaching 8.1‰. In situ REE measurements show zircon is magmatic and grew before garnets. Additionally, δ18O in garnets from the western side of the pluton are consistently higher (avg = 7.3‰) relative to the west (avg = 5.9‰). These δ18O variations in zircon and garnet record different stages of assimilation and fractional crystallization whereby an initially high-δ18O magma partially melted low-δ18O wallrock and was subsequently contaminated near the current level of emplacement by higher δ18O melts. Collectively, the comparison of δ18O zoning in garnet and zircon shows how a peraluminous pluton can be constructed from multiple batches of variably contaminated melts, especially in early stages of arc magmatism where magmas encounter significant heterogeneity of wall-rock assemblages. Collectively, peraluminous magmas in the Sierran arc are limited to small <100 km2 plutons that are intimately associated with metasedimentary wall rocks and often surrounded by later and larger metaluminous tonalite and granodiorite plutons. The general associations suggest that early-stage arc magmas sample crustal heterogeneities in small melt batches, but that with progressive invigoration of the arc, such compositions are more effectively blended with mantle melts in source regions. Thus, peraluminous magmas provide important details of the nascent Sierran arc and pre-batholithic crustal structure.
Preparation for microgravity science investigation of compound semiconductor crystal growth
Preparatory work on Bridgman directional solidification (BDS) of PbSnTe crystals prior to microgravity crystal growth experiments on Shuttle flights are reported. Gravitational effects become important in crystal growth when density gradients are present. The situation is critical in BDS of PbSnTe because of the necessity of obtaining homogeneous compositional distributions, which can be disturbed when convective processes occur. Numerical models have been defined which quantify the effects of convection in the crystal growth solution. The models were verified by earth-based crystal-growth tests in a two-zone furnace using equal concentrations of each of the elements. Data are provided to demonstrate the differences in composition among crystals grown at different orientations to the gravitational field vector.