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At least 217 records · Page 12

The origin of chromitic chondrules and the volatility of Cr under a range of nebular conditions

We characterize ten chromatic chondrules, two spinelian chondrules andd one spinel-bearing chondrule and summarize data for 120 chromitic inclusions discovered in an extensive survey of ordinary chondrites. Compositional and petrographic evidence suggests that chromitic chondrules and inclusions are closely related. The Cr/(Cr + Al) ratios in the spinal of these objects range from 0.5 to 0.9 and bulk Al2O3 contents are uniformly high (greater than 10 wt%, except for one with 8 wt%). No other elements having comparable solar abundances are so stongly enriched, and alkali feldspar and merrillite are more common than in normal chondrules. The Cr/Mg ratios in chromitic chondrules are 180-750 times the ratios in the bulk chondrite. With the possible exception of magnetic clumping of chromite in the presolar cloud, mechanical processes cannot account for this enrichment. Examination of nebular equilibrium processes shows that 50%-condensation temperatures of Cr at pH2/pH2O of 1500 are several tens of degrees below those of Mg as Mg2SiO4; the condensation of Cr is primarily as MgCr2O4 dissolved in MgAl2O4 at nebular pressures of 10(exp -4) atm or below. At pH2 = 10(exp -3) atm condesation as Cr in Fe-Ni is favored. Making the nebula much more oxidizing reduces the difference in condensation temperatures but Mg remains more refractory. We conclude that nebular equilibrium processes are not responsible for the enhanced Cr/Mg ratios. We propose that both Cr and Al became enriched in residues formed by incomplete evaporation of presolar lumps. We suggest that spinals remained as solid phases when the bulk of the silicates were incorporated into the evaporating melt; vaporization of Al and Cr were inhibited by the slow kinetics of diffusion. Subsequent melting and crystallization of these residues fractionated Cr from Al. The resulting materials constituted major components in the precursors of chromitic chondrules. Our model implies that chromitic chondrules and inclusions preserve the Cr isotopic record of presolar sources.

Krot, Alexander↗

Interpretable Tree-Based and Graph Neural Network Approaches for Novel Solid State Electrolyte Design

All-solid-state batteries with Li metal anode can address the safety issues surrounding traditional Li-ion batteries as well as the demand for higher energy densities. However, the development of solid electrolytes simultaneously possessing high ionic conductivity and good chemical and electrochemical stabilities has proven to be a challenge. I will present our informatics approach to explore the Li compound space for promising solid electrolytes using high-throughput multi-property screening and interpretable machine learning. This is accomplished through the generation of a large database of battery-related materials properties of Li compounds. We use tree-based ensemble learning methods and graph neural network approaches to accurately learn relationships between crystal structures and corresponding thermodynamic and kinetic properties, with interpretability being a major focus. Our models give us the ability to enable rapid discovery and design of novel solid-state battery chemistries.

Materials discovery↗

Interpretable ML Approaches for Novel Solid State Electrolyte Design

All-solid-state batteries with Li metal anode can address the safety issues surrounding traditional Li-ion batteries as well as the demand for higher energy densities. However, the development of solid electrolytes simultaneously possessing high ionic conductivity and good chemical and electrochemical stabilities has proven to be a challenge. I will present our informatics approach to explore the Li compound space for promising solid electrolytes using high-throughput multi-property screening and interpretable machine learning. This is accomplished through the generation of a large database of battery-related materials properties of Li compounds. We use tree-based ensemble learning methods and graph neural network approaches to accurately learn relationships between crystal structures and corresponding thermodynamic and kinetic properties, with interpretability being a major focus. Our models give us the ability to enable rapid discovery and design of novel solid-state battery chemistries.

Shreyas J Honrao↗

The formation of lunar glasses

The work investigates experimentally the conditions required to form glasses out of a number of lunar compositions. Viscous flow and crystallization behavior of several compositions were studied over a wide range of temperature. These data exhibit the form generally found for glass-forming liquids. Combining growth rate with viscosity data, the fraction of preferred growth sites on the crystal-liquid interfaces is found to increase with increasing undercooling for all lunar compositions. The detailed forms of the kinetic data are predicted by recent computer simulations of crystal growth. Calorimetry studies indicate that lunar orange soil was formed under conditions of much slower cooling rate than 1000 deg K per sec.

Uhlmann, D. R.↗

Role of Transport and Kinetics in Growth of Renal Stones

Renal stone disease is not only a concern on earth but could conceivably pose as a serious risk to the astronauts health and safety in Space. In this paper, a combined transport-kinetics model for growth of calcium oxalate crystals is presented. The model is used to parametrically investigate the growth of renal calculi in urine with a focus on the coupled effects of transport and surface reaction on the ionic concentrations at the surface of the crystal and their impact on the resulting growth rates. It is shown that under nominal conditions of low solution supersaturation and low Damkohler number that typically exist on Earth, the surface concentrations of calcium and oxalate approach their bulk solution values in the urine and the growth rate is most likely limited by the surface reaction kinetics. But for higher solution supersaturations and larger Damkohler numbers that may be prevalent in the microgravity environment of Space, the calcium and oxalate surface concentrations tend to shift more towards their equilibrium or saturation values and thus the growth process may be limited by the transport through the medium. Furthermore, parametric numerical studies suggest that changes to the renal biochemistry of astronauts due in space may promote development of renal calculi during long duration space expeditions.

Kassemi, Mohammad↗

Kinetics of phase transformations in glass forming systems

In crystallization measurements of nonisothermal nucleation for Li2O.2SiO2 (LS2) glass, using DTA, the glass sample is scanned at different constant heating rates until it is crystallized. This means that the temperature range where nucleation can occur for the glass is scanned also at different rates which allows the glass to be nucleated for different time prior to crystallization. Consequently, the concentration of nuclei developed in the glass may be different for different heating rates and the DTA peak height which has shown to be sensitive to the number of nuclei present in the sample, is expected to change with heating rate. DTA peak height depends strongly on the overlap between the nucleation rate and growth rate curves, assuming the peak height is directly proportional to the total number of nuclei present in the glass sample under investigation, which, in turn, should be proportional to the volume or weight of the sample. To verify this assumption, DTA measurements were made using a LS2 glass to determine the peak height as a function of the sample weight. Using the DTA peak height technique, a nucleation rate like curve was determined for the BaO.2SiO2 (BS2) glass which showed that the temperature for nucleation ranged from 650 to 750 C for this glass and the temperature for maximum nucleation was approximately 705 C. These values are in excellent agreement with those determined by the conventional technique. There was international collaboration with Japan and Germany on this project.

Ray, Chandra S.↗

Direct solar-pumped iodine laser amplifier

The improvement on the collection system of the Tarmarack Solar Simulator beam was attemped. The basic study of evaluating the solid state laser materials for the solar pumping and also the work to construct a kinetic model algorithm for the flashlamp pumped iodine lasers were carried out. It was observed that the collector cone worked better than the lens assembly in order to collect the solar simulator beam and to focus it down to a strong power density. The study on the various laser materials and their lasing characteristics shows that the neodymium and chromium co-doped gadolinium scandium gallium garnet (Nr:Cr:GSGG) may be a strong candidate for the high power solar pumped solid state laser crystal. On the other hand the improved kinetic modeling for the flashlamp pumped iodine laser provides a good agreement between the theoretical model and the experimental data on the laser power output, and predicts the output parameters of a solar pumped iodine laser.

Han, Kwang S.↗

A Structural and Molecular Approach for the Study Biomarkers

Investigation of the nucleation and growth of crystals in both abiotic and biotic systems is critical to seemingly diverse disciplines of geology, biology, environmental science, and astrobiology. While there are abundant studies devoted to the determination of the structure and composition of inorganic crystals, as well as to the development of thermodynamic and kinetic models, it is only recently that research efforts have been directed towards understanding mineralization in biological systems (i.e., biomineralization). Biomineralization refers to the processes by which living organisms form inorganic solids. Studies of the processes of biomineralization under low temperature aqueous conditions have focused primarily on magnetite forming bacteria and shell forming marine organisms. Many of the biological building materials consist of inorganic minerals (calcium carbonate, calcium phosphate, silica or iron oxide) intricately combined with organic polymers (like proteins). More recently, efforts have been undertaken to explore the nature of biological activities in ancient rocks. In the absence of well-preserved microorganisms or genetic material required for the polmerase chain reaction (PCR) method in molecular phylogenetic studies, using biominerals as biomarkers offers an alternative approach for the recognition of biogenic activity in both terrestrial and extraterrestrial environments. The primary driving force in biomineralization is the interaction between organic and inorganic phases. Thus, the investigation of the ultrastructure and the nature of reactions at the molecular level occurring at the interface between inorganic and organic phases is essential to understanding the processes leading to the nucleation and growth of crystals. It is recognized that crystal surfaces can serve as the substrate for the organization of organic molecules that lead to the formation of polymers and other complex organic molecules, and in discussions of the origins of life, is referred to as organic synthesis on mineral surfaces. Furthermore, it is suggested that the interaction between mineral surfaces and simple organic molecules resulted in the formation of amino acids, RNA, and perhaps other more complex molecules such as proteins. On the other hand, in natural systems, it is recognized that functional groups on cell walls or membranes of microorganisms serve as sites of nucleation and crystallization. The precise replication of biominerals with controlled structure, morphology, size and texture is not confined to higher organisms as it also occurs in primitive prokaryotic cells such as magnetotactic bacteria and cyanobacteria. This suggests that the principal strategies of biomineralization were established early on in the evolutionary history of organisms. It is critical, therefore, to search for common mechanisms within diverse biological systems. One such common factor is the capability for organization and self-assembly. Organic macromolecules such as proteins and lipids can aggregate and polymerize forming membranes or extracellular matrix. At the organic-inorganic interface, several factors such as lattice geometry, polarity, stereochemistry and topography may act in concert to control nucleation and growth of crystals. Although several models have been proposed that discuss the significance of these factors for biomineralization, no comprehensive experimental data are available. In contrast to crystallization in exclusively inorganic systems, the kinetics of reaction and structural relationships between organic and inorganic phases in biominerals or biomimetic material is poorly understood. For example, it is not clear if the concept of epitactic growth (geometrical matching of unit cells at the interface of a secondary crystal growing on a primary crystal) applies to organic-inorganic systems. In contrast to inorganic templates that often have a smooth and rigid surface that promotes epitactic growth, biological substrates are usually rough and result in a large degree of mismatch. It is apparent that factors controlling the reaction at the crystal-matrix interface are strongly dependent upon the nature of the substrate. Therefore, characterization of the assembled organic surface and surface structure of the inorganic phase is crucial to understanding the processes of biomineralization. The focus of our research is the investigation of the processes leading to the nucleation and growth of crystals on both natural and synthetic systems through an interdisciplinary approach that integrates molecular biology, morphology and mineralogy using advanced preparation and analytical techniques. We have studied run-products, particularly magnetite, siderite and other carbonates, that resulted from extracellular biomineralization by extremophiles isolated from a variety of extreme environments ranging from permafrost to hydrothermal vent systems. The results of this study are critical to recognizing biomarkers in terrestrial and extraterrestrial environments.

Thomas-Keprta, Kathie↗

Solidification of undercooled liquids

During rapid solidification processing (RSP) the amount of liquid undercooling is an important factor in determining microstructural development by controlling phase selection during nucleation and morphological evolution during crystal growth. While undercooling is an inherent feature of many techniques of RSP, the deepest undercoolings and most controlled studies have been possible in carefully prepared fine droplet samples. From past work and recent advances in studies of nucleation kinetics it has become clear that the initiation of crystallization during RSP is governed usually by heterogeneous sites located at surfaces. With known nucleant sites, it has been possible to identify specific pathways of metastable phase formation and microstructural development in alloys. These advances have allowed for a clearer assessment of the interplay between undercooling, cooling rate and particle size statistics in structure formation. New approaches to the examination of growth processes have been developed to follow the thermal behavior and morphology in small samples in the period of rapid crystallization and recalescence. Based upon the new experimental information from these studies, useful models can be developed for the overall solidification process to include nucleation behavior, thermodynamic constraints, thermal history, growth kinetics, solute redistribution and resulting structures. From the refinement of knowledge concerning the underlying factors that govern RSP a basis is emerging for an effective alloy design and processing strategy.

Perepezko, J. H.↗

Physics of Biocrystals and Their Growth

Recent results on binding between protein molecules in crystal lattice, crystal-solution surface energy, elastic properties and strength and spontaneous crystal cracking are reviewed and discussed in the first half of the paper (Sections 2-5). In the second part, some basic approaches to solubility of proteins is followed by overview on crystal nucleation and growth (Section 6). It is argued that variability of mixing in batch crystallization may be a source scattering of crystal number ultimately appearing in the batch (Section 7). Frequency at which new molecules join crystal lattice is related to the observable crystal growth rate. Numerical criteria to discriminate diffusion and kinetic limited growth are discussed on this basis in Section 8. In Section 9, creation of defects is discussed with the emphasis on the role of impurities and convection in macromolecular crystal perfection.

Chernov, A.↗

Electron microprobe study of lunar and planetary zoned plagioclase feldspars: An analytical and experimental study of zoning in plagioclase

Natural and experimentally grown zoned plagioclase feldspars were examined by electron microprobe. The analyses revealed discontinuous, sector, and oscillary chemical zoning superimposed on continuous normal or reverse zoning trends. Postulated mechanisms for the origin of zoning are based on either physical changes external to the magma (P, T, H2O saturation) or kinetic changes internal to the magma (diffusion, supersaturation, growth rate). Comparison of microprobe data on natural zoned plagioclase with zoned plagioclase grown in controlled experiments show that it may be possible to distinguish zonal development resulting from physio-chemical changes to the bulk magma from local kinetic control on the growth of individual crystals.

Smith, R. K.↗

An analytical and experimental study of zoning in plagioclase

A detailed electron microprobe study has been conducted on natural and experimentally grown zoned plagioclase feldspars. Discontinuous, sector, and oscillatory chemical zoning are observed superimposed on continuous normal or reverse zoning trends. The relative accuracy of 3 element (Na, Ca, K) microprobe traverses was found statistically to be 2 mole percent. Comparison of microprobe data on natural zoned plagioclase with zoned plagioclase grown in controlled experiments has shown that it may be possible to distinguish zonal development resulting from physio-chemical changes to the bulk magma from zoning related to local kinetic control on the growth of individual crystals.

Smith, R. K.↗

Soft X-ray polychromator for the Solar Maximum Mission

The XRP was designed to measure the following temporal and spatial properties of the active and flaring Sun: electron temperature, departures from steady state, ion kinetic temperatures, and electron density. The Bent Crystal Spectrometer (BCS) is capable of measuring the broadening and blue shifts often observed in the impulsive phase of flares. The six simultaneous line fluxes indicative of six different temperatures of formation observable by the Flat Crystal Spectrometer (FCS) allows the derivation of the differential emission measure of the plasma at each raster point. During the operational periods of the XRP hundreds of flares of C-level (GOES classification) were observed and brighter in both the FCS and BCS, including 5 X-flares. Associated theoretical work in atomic physics, stimulated in part by the promise of XRP measurements, has benefitted from the experimental data on solar plasmas which the XRP has provided in abundance.

Haisch, B. M.↗

Kinetics of mineral condensation in the solar nebula

A natural extension of the type of gas-mineral-melt condensation experiments is to study the gas-mineral-melt reaction process by controlling the reaction times of appropriate gas compositions with silicate materials. In a condensing and vaporizing gas-solid system, important processes that could influence the composition of and speciation in the gas phase are the kinetics of vaporization of components from silicate crystals and melts. The high vacuum attainable in the space station would provide an environment for studying these processes at gas pressures much lower than those obtainable in experimental devices operated at terrestrial conditions in which the gas phase and mineral or melt would be allowed to come to exchange equilibrium. Further experiments would be performed at variable gas flow rates to simulate disequilibrium vapor fractionation. In this type of experiment it is desirable to analyze directly the species in the gas phase in equilibrium with the condensed silicate material. This analytical method would provide a direct determination of the species present in the gas phase. Currently, the notion of gas speciation is based on calculations from thermodynamic data. The proposed experiments require similar furnace designs and use similar experimental starting compositions, pressures, and temperatures as those described by Mysen.

Grove, T. L.↗

Numerical studies of convective transport associated with crystal growth in mirrogravity

Information on numerical studies of convective transport associated with crystal growth in microgravity is given in viewgraph form. Inferences drawn from the research are that protein crystals seem to grow at much larger relative supersaturations than small molecule crystals; growth rate is limited by attachment kinetics more than by transport; attachment kinetics are apparently influenced by convective flows, although the mechanism is uncertain; acceleration levels required to achieve D/L growth within Space Station Freedom specifications may not be achievable on manned vehicles; and D/L transport can help minimize incorporation of impurities, but growth cessation cannot be explained.

Ramachandran, N.↗

Evolution of a terrestrial magma ocean: Thermodynamics, kinetics, rheology, convection, differentiation

The evolution of an initially totally molten magma ocean is constrained on the basis of analysis of various physical problems in the magma ocean. First of all an equilibrium thermodynamics of the magma ocean is developed in the melting temperature range. The equilibrium thermodynamical parameters are found as functions only of temperature and pressure and are used in the subsequent models of kinetics and convection. Kinematic processes determine the crystal size and also determine a non-equilibrium thermodynamics of the system. Rheology controls all dynamical regimes of the magma ocean. The thermal convection models for different rheological laws are developed for both the laminar convection and for turbulent convection in the case of equilibrium thermodynamics of the multiphase system. The evolution is estimated on the basis of all the above analysis.

Solomatov, V. S.↗

High-temperature oxidation behavior of reaction-formed silicon carbide ceramics

The oxidation behavior of reaction-formed silicon carbide (RFSC) ceramics was investigated in the temperature range of 1100 to 1400 C. The oxidation weight change was recorded by TGA; the oxidized materials were examined by light and electron microscopy, and the oxidation product by x-ray diffraction analysis (XRD). The materials exhibited initial weight loss, followed by passive weight gain (with enhanced parabolic rates, k(sub p)), and ending with a negative (logarithmic) deviation from the parabolic law. The weight loss arose from the oxidation of residual carbon, and the enhanced k(sub p) values from internal oxidation and the oxidation of residual silicon, while the logarithmic kinetics is thought to have resulted from crystallization of the oxide. The presence of a small amount of MoSi, in the RFSC material caused a further increase in the oxidation rate. The only solid oxidation product for all temperatures studied was silica.

Ogbuji, Linus U. J. T.↗

Low Energy Sputtering Experiments for Ion Engine Lifetime Assessment

The sputtering yield of molybdenum under xenon ion bombardment was measured using a Quartz Crystal Microbalance. The measurements were made for ion kinetic energies in the range 100-1keV on molybdenum films deposited by magnetron sputtering in conditions optimized to reproduce or approach bulk-like properties. SEM micrographs for different anode bias voltages during the deposition are compared, and four different methods were implemented to estimate the density of the molybdenum films. A careful discussion of the Quartz Crystal Microbalance is proposed and it is shown that this method can be used to measure mass changes that are distributed unevenly on the crystal electrode surface, if an analytical expression is known for the differential mass-sensitivity of the crystal and the erosion profile. Finally, results are presented that are in good agreement with previously published data, and it is concluded that this method holds the promise of enabling sputtering yield measurements at energies closer to the threshold energy in the very short term.

Duchemin Olivier B.↗