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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Hydrogen and Ferric Iron in Mars Materials

Knowledge of oxygen and hydrogen fugacity is of paramount importance in constraining phase equilibria and crystallization processes of melts, as well as understanding the partitioning of elements between the cope and silicate portions of terrestrial planets. H and Fe(3+) must both be analyzed in order to reconstruct hydrogen and oxygen fugacities on Mars. To date, SIMS data have elucidated D/H and H contents of hydrous phases in SNC meteorites, but until now anhydrous martian minerals have not been systematically examined for trace hydrogen. Ferric iron has been quantified using XANES in many martian phases, but integrated studies of both Fe(3+) and H on the same spots are really needed to address the H budget. Finally, the effects of shock on both Fe(3+) and H in hydrous and anhydrous phases must be quantified. Thus, the overall goal of this research was to understand the oxygen and hydrogen fugacities under which martian samples crystallized. In this research one-year project, we approached this problem by 1) characterizing Fe(3+) and H contents of SNC meteorites using both bulk (Mossbauer spectroscopy and uranium extraction, respectively) and microscale (synchrotron micro-XANES and SIMS) methods; 2) relating Fe(3+) and H contents of martian minerals to their oxygen and hydrogen fugacities through analysis of experimentally equilibrated phases (for pyroxene) and through study of volcanic rocks in which the oxygen and hydrogen fugacities can be independently constrained (for feldspar); and 3) studying the effects of shock processes on Fe(3+) and H contents of the phases of interest. Results have been used to assess quantitatively the distribution of H and Fe(3+) among phases in the martian interior, which will better constrain the geodynamic processes of the interior, as well as the overall hydrogen and water budgets on Mars. There were no inventions funded by this research.

Dyar, Melinda D.↗
DOE OSTI2023

Thermodynamic modeling of KCl-PrCl 3 and KCl-LiCl-PrCl 3 systems

Molten salt electrolysis can recover the actinides from spent nuclear fuels, and it involves a eutectic LiCl-KCl in molten form as an electrolyte. During reprocessing, the concentration of fission products such as La, Nd, Pr, etc., increases and affects the recovery efficiency of the electrolyte. In this work, thermodynamic modeling of KCl-PrCl 3 and KCl-LiCl-PrCl 3 systems was carried out using the CALPHAD (Calculation of Phase Diagrams) approach for the first time. The thermodynamic functions for the pure salts were taken from the SGTE (Scientific Group Thermodata Europe) Substances (SSUB) database. The experimental thermochemical and phase equilibria data available in the literature were used as input for the assessment of KCl-PrCl 3 and KCl-LiCl-PrCl 3 systems. The model parameters for the KCl-LiCl system were adjusted to include the new Gibbs energy descriptions for the pure salts. In addition, the sublattice model for the liquid phase in the LiCl-PrCl 3 system was modified and reassessed to ensure the model compatibility for higher-order extrapolation. There is a good agreement between the experimental and calculated thermochemical and phase diagram data for all the optimized constituent binaries and the ternary system. Furthermore, this work will be beneficial for determining the solubility limit of PrCl 3 in molten LiCl-KCl electrolytes and their thermodynamic properties for improving the efficiency of the pyrochemical process.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1984

High pressure cosmochemistry applied to major planetary interiors: Experimental studies

Progress is reported on a project to determine the properties and boundaries of high pressure phases of the H2-He-H2O-NH3-CH4 system that are needed to constrain theoretical models of the interiors of the major planets. This project is one of the first attempts to measure phase equilibria in binary fluid-solid systems in diamond anvil cells. Vibrational spectroscopy, direct visual observations, and X-ray diffraction crystallography of materials confined in externally heated cells are the primary experimental probes. Adiabats of these materials are also measured in order to constrain models of heat flow in these bodies and to detect phase transitions by thermal anomalies. Initial efforts involve the NH3-H2O binary. This system is especially relevant to models for surface reconstruction of the icy satellites of Jupiter and Saturn. Thermal analysis experiments were completed for the P-X space, p4GPa:0 or = 0.50, near room temperature. The cryostat, sample handling equipment, and optics needed to extend the optical P-T-X work below room temperature was completed.

Nicol, M. F.↗
NASA NTRS1976

Superalloy eutectic composites with the VI A refractory elements - Cr, Mo and W

The paper discusses the phase equilibria for the ternary systems NiAlCr, NiAlMo, and NiAlW, with emphasis on reactions from the liquid state, although some of the solid state reactions are mentioned. It is shown that eutectics in the Ni-Al-refractory element (Cr, Mo, W) systems offer the potential for high-temperature turbine blade and vane applications. In particular, it is shown that the phase diagrams of these ternary systems can be manipulated to alter the eutectic phases and morphologies by simple quaternary alloying modifications. The resultant combination of chemistry and structure can be controlled to ensure a behavior that is well-matched to hot section component materials requirements.

Jackson, M. R.↗
DOE OSTI2020

Critical evaluation and thermodynamic modeling of the Pd–Sn system

The single crystalline material PdSn 4 , a homologue of the Dirac nodal arc semimetal PtSn 4 , is a promising candidate to search for new topological states with fascinating quantum physical properties. In the present work, the thermochemistry and phase diagram information of the Pd–Sn system published in the literature was collected and critically reviewed, two thermodynamic reassessments of the Pd–Sn system were carried out in the frame of the CALPHAD approach to optimize the Gibbs free energy of each phase presented in the system. The liquid phase was described using respectively the Bragg-Williams random mixing model and the associate solution model. All the reliable thermodynamic property and phase equilibria data can be generally described using the presently obtained thermodynamic descriptions of the Pd–Sn system. Issues related to the further improvement of the thermodynamic descriptions of the Pd–Sn system are discussed.

36 MATERIALS SCIENCE↗
NASA NTRS2012

Electrostatic Levitation: A Tool to Support Materials Research in Microgravity

Containerless processing represents an important topic for materials research in microgravity. Levitated specimens are free from contact with a container, which permits studies of deeply undercooled melts, and high-temperature, highly reactive materials. Containerless processing provides data for studies of thermophysical properties, phase equilibria, metastable state formation, microstructure formation, undercooling, and nucleation. The European Space Agency (ESA) and the German Aerospace Center (DLR) jointly developed an electromagnetic levitator facility (MSL-EML) for containerless materials processing in space. The electrostatic levitator (ESL) facility at the Marshall Space Flight Center provides support for the development of containerless processing studies for the ISS. Apparatus and techniques have been developed to use the ESL to provide data for phase diagram determination, creep resistance, emissivity, specific heat, density/thermal expansion, viscosity, surface tension and triggered nucleation of melts. The capabilities and results from selected ESL-based characterization studies performed at NASA's Marshall Space Flight Center will be presented.

Rogers, Jan↗
DOE OSTI2020

Impact of fission product inclusion on phase development in U 3 Si 2 fuel

Due to its high thermal conductivity and uranium density, U 3 S i2 has been considered as a candidate for use as an accident tolerant fuel (ATF). In order to fully assess its suitability and performance as a fuel, the impact of fission products (FPs) on the stability and performance of U 3 Si 2 must be investigated. The interactions of FPs and U 3 Si 2 have had relatively little study until now and require experimental and computational examination. U 3 Si 2 was doped with individual FPs to explore U-Si-FP interactions and phase equilibria that may impact the performance of the ATF during irradiation. Elemental Ce, Mo, Y, or Zr were used to individually dope U 3 Si 2 at a concentration of 5 wt% FP. A diffusion couple of a 1:1 Mo:Zr alloy and U 3 Si 2 was heated to 1200 °C in order to consider the impacts of multiple FPs on the stability and structure of the fuel. Samples were characterized for FP solubility and secondary phase formation using electron microscopy, energy dispersive spectroscopy, and x-ray diffraction. First principles density functional theory calculations complemented the experimental effort to understand FP behavior. Experimental and computational findings were used in the development of a thermodynamic database containing 8 major FPs and their associated silicide phases. Finally, fuel compositions generated from depletion calculations were used to thermodynamically model the equilibrium phases of the fuel undergoing burnup.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1980

The role of P2O5 in silicate melts

Phase equilibria data in the systems SiO2-P2O5, P2O5-M(x)O(y), and P2O5-M(x)O(y)-SiO2 are employed in conjunction with chromatographic and spectral data to investigate the role of P2O5 in silicate melts. P2O5 depolymerizes pure SiO2 melts by entering the network as a four-fold coordinated cation, but polymerizes melts in which an additional metal cation other than silicon is present. In this complex system P2O5 acts to increase phase separation by further enrichment of the high charge density cations Ti, Fe, Mg, Mn, Ca, in the ferrobasaltic liquid. The dual behavior of P2O5 is explained in a model which requires complexing of phosphate anions and metal cations in the melt. This interaction destroys Si-O-M-O-Si bonds polymerizing the melt. The higher concentration of Si-O-M-O-Si bond complexes in immiscible ferrobasaltic liquids relative to their conjugate immiscible granite liquids explains the partitioning of P2O5 into the ferrobasaltic liquid.

Ryerson, F. J.↗
NASA NTRS1995

Ca-Rich Carbonate Melts: A Regular-Solution Model, with Applications to Carbonatite Magma + Vapor Equilibria and Carbonate Lavas on Venus

A thermochemical model of the activities of species in carbonate-rich melts would be useful in quantifying chemical equilibria between carbonatite magmas and vapors and in extrapolating liquidus equilibria to unexplored PTX. A regular-solution model of Ca-rich carbonate melts is developed here, using the fact that they are ionic liquids, and can be treated (to a first approximation) as interpenetrating regular solutions of cations and of anions. Thermochemical data on systems of alkali metal cations with carbonate and other anions are drawn from the literature; data on systems with alkaline earth (and other) cations and carbonate (and other) anions are derived here from liquidus phase equilibria. The model is validated in that all available data (at 1 kbar) are consistent with single values for the melting temperature and heat of fusion for calcite, and all liquidi are consistent with the liquids acting as regular solutions. At 1 kbar, the metastable congruent melting temperature of calcite (CaCO3) is inferred to be 1596 K, with (Delta)bar-H(sub fus)(calcite) = 31.5 +/- 1 kJ/mol. Regular solution interaction parameters (W) for Ca(2+) and alkali metal cations are in the range -3 to -12 kJ/sq mol; W for Ca(2+)-Ba(2+) is approximately -11 kJ/sq mol; W for Ca(2+)-Mg(2+) is approximately -40 kJ/sq mol, and W for Ca(2+)-La(3+) is approximately +85 kJ/sq mol. Solutions of carbonate and most anions (including OH(-), F(-), and SO4(2-)) are nearly ideal, with W between 0(ideal) and -2.5 kJ/sq mol. The interaction of carbonate and phosphate ions is strongly nonideal, which is consistent with the suggestion of carbonate-phosphate liquid immiscibility. Interaction of carbonate and sulfide ions is also nonideal and suggestive of carbonate-sulfide liquid immiscibility. Solution of H2O, for all but the most H2O-rich compositions, can be modeled as a disproportionation to hydronium (H3O(+)) and hydroxyl (OH(-)) ions with W for Ca(2+)-H3O(+) (approximately) equals 33 kJ/sq mol. The regular-solution model of carbonate melts can be applied to problems of carbonatite magma + vapor equilibria and of extrapolating liquidus equilibria to unstudied systems. Calculations on one carbonatite (the Husereau dike, Oka complex, Quebec, Canada) show that the anion solution of its magma contained an OH mole fraction of (approximately) 0.07, although the vapor in equilibrium with the magma had P(H2O) = 8.5 x P(CO2). F in carbonatite systems is calculated to be strongly partitioned into the magma (as F(-)) relative to coexisting vapor. In the Husereau carbonatite magma, the anion solution contained an F(-) mole fraction of (approximately) 6 x 10(exp -5).

Treiman, Allan H.↗
NASA NTRS1998

Differential Thermal Analysis of Hg(1-x)Mn(x)Te Alloys in the X=0 to 0.3 Range

Understanding the experimental conditions necessary for the development of radial and axial compositional homogeneity in directionally solidified Hg(0.89)Mn(0.11)Te(MMT) crystals has been difficult due to the lack of segregation coefficient data on the Hg(1-x)Mn(x)Te alloy system in the X = 0 to 0.3 composition range. Determining segregation coefficient data from the available Hg(1-x)Mn(x)Te alloy phase equilibria data is not practical due to discrepancies in the shape of the reported solidus and liquidus curves in the X = 0 to 0.3 range. To resolve these discrepancies and to obtain segregation coefficient data which can be used to understand homogeneity in directionally solidified MMT crystals, the solidus and liquidus temperatures of seven Hg(1-x)Mn(x)Te alloys in the X = 0 to 0.3 range were determined using differential thermal analysis (DTA). The Hg(1-x)Mn(x)Te phase diagram constructed for the X = 0 to 0.3 range of this alloy system from the DTA measurements clarifies the shape of the solidus and liquidus curves in this range. The segregation coefficient for the Hg(1-x)Mn(x)Te system was found to vary from 5 to 4.4 as the solidus composition increased from 0-30 atomic percent MnTe. This information will be useful in the analysis of axial and radial homogeneity of directionally solidified MMT crystals.

Price, M. W.↗
NASA NTRS1989

Origin of opaque assemblages in C3V meteorites - Implications for nebular and planetary processes

The results of analyses of meteoritic opaque assemblages (OAs) are presented and used in conjunction with literature data on phase equilibria and diffusion to further develop the hypothesis of Blum et al. (1989) for the origin of OAs in Ca,Al-rich inclusions (CAIs). Based on the results of the analyses, it is suggested that OAs formed after the crystallization of host CAIs by exsolution, sulfidation, and oxidation of precursor alloys at low temperatures (about 770 K) and higher than solar gas sulfur and oxygen fugacities. This model contrasts with previous models that call upon the formation of CAI OAs by aggregation of previously formed phases in the solar nebula prior to the crystallization of CAIs.

Blum, Joel D.↗
DOE OSTI2022

Comparison of Na 2 SO 4 , K 2 SO 4 and Na 2 SO 4 -K 2 SO 4 deposit induced hot corrosion of a β-NiAl coating

Here, hot corrosion behaviour of a β-NiAl coating induced by Na 2 SO 4 , K 2 SO 4 , and Na 2 SO 4 -K 2 SO 4 deposits was investigated at 700 °C in air + 300 ppm SO 2 . To provide an insight into the corrosion mechanisms, phase equilibria of the Na 2 SO 4 -K 2 SO 4 -NiO-SO 3 system were calculated using an in-house developed thermodynamic database. The attack rates and morphologies could be correlated with the deposit compositions and their reactions with oxides. K 2 SO 4 and Na 2 SO 4 -K 2 SO 4 deposits are more corrosive than Na 2 SO 4 . This is attributed to a reduction of the melting temperature of the deposit and the formation of Ni-containing mixed sulphate phases in the presence of K 2 SO 4 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2013

The W-W02 Oxygen Fugacity Buffer at High Pressures and Temperatures: Implications for f02 Buffering and Metal-silicate Partitioning

Oxygen fugacity (fO2) controls multivalent phase equilibria and partitioning of redox-sensitive elements, and it is important to understand this thermodynamic parameter in experimental and natural systems. The coexistence of a metal and its oxide at equilibrium constitutes an oxygen buffer which can be used to control or calculate fO2 in high pressure experiments. Application of 1-bar buffers to high pressure conditions can lead to inaccuracies in fO2 calculations because of unconstrained pressure dependencies. Extending fO2 buffers to pressures and temperatures corresponding to the Earth's deep interior requires precise determinations of the difference in volume (Delta) V) between the buffer phases. Synchrotron x-ray diffraction data were obtained using diamond anvil cells (DAC) and a multi anvil press (MAP) to measure unit cell volumes of W and WO2 at pressures and temperatures up to 70 GPa and 2300 K. These data were fitted to Birch-Murnaghan 3rd-order thermal equations of state using a thermal pressure approach; parameters for W are KT = 306 GPa, KT' = 4.06, and αKT = 0.00417 GPa K-1. Two structural phase transitions were observed for WO2 at 4 and 32 GPa with structures in P21/c, Pnma and C2/c space groups. Equations of state were fitted for these phases over their respective pressure ranges yielding the parameters KT = 190, 213, 300 GPa, KT' = 4.24, 5.17, 4 (fixed), and αKT = 0.00506, 0.00419, 0.00467 GPa K-1 for the P21/c, Pnma and C2/c phases, respectively. The W-WO2 buffer (WWO) was extended to high pressure by inverting the W and WO2 equations of state to obtain phase volumes at discrete pressures (1-bar to 100 GPa, 1 GPa increments) along isotherms (300 to 3000K, 100 K increments). The slope of the absolute fO2 of the WWO buffer is positive with increasing temperature up to approximately 70 GPa and is negative above this pressure. The slope is positive along isotherms from 1000 to 3000K with increasing pressure up to at least 100 GPa. The WWO buffer is at a higher fO2 than the IW buffer at pressures lower than 40 GPa, and the magnitude of this difference decreases at higher pressures. This qualitatively indicates an increasingly lithophile character for W at higher pressures. The WWO buffer was quantitatively applied to W metal-silicate partitioning by using the WWO-IW buffer difference in combination with literature data on W metal-silicate partitioning to model the exchange coefficient (KD) for the Fe-W exchange reaction. This approach captures the pressure dependence of W metal-silicate partitioning using the WWO-IW buffer difference and models the activities of the components in the silicate and metallic phases using an expression of the Gibbs excess energy of mixing. Calculation of KD along a peridotite liquidus predicts a decrease in W siderophility at higher pressures that supports the qualitative behavior predicted by the WWO-IW buffer difference, and agrees with findings of others. Comparing the competing effects of temperature and pressure on W metal-silicate partitioning, our results indicate that pressure exerts a greater effect.

Shofner, G. A.↗
NASA NTRS1975

Origin of titaniferous lunar basalts

Delineation of low pressure phase equilibria in the composition space relevant to titaniferous lunar basalts demonstrates a significant degree of control by those equilibria on the compositions of the basalts. The existence of two distinct chemical groups of basalts (high and low K) which cannot be related one to the other by fractional crystallization at any pressure, suggests that melting is responsible for the two groups. Consideration of the pressure shift required to produce the differences between groups constrains magma segregation to have occurred in the outer 150 km of the moon. It is difficult to relate low-Ti and high-Ti basalts to the same source region. The preferred source region of high-Ti basalts, based on phase equilibrium considerations, is a late ilmenite-rich cumulate produced from the residual liquid of the primordial differentiation of the outer portions of the moon. This ilmenite-rich layer is sandwiched between the lunar feldspathic crust and a complementary mafic cumulate.

Walker, D.↗
DOE OSTI2021

NaCl aggregation in water at elevated temperatures and pressures: Comparison of classical force fields

The properties of water vary dramatically with temperature and density. This can be exploited to control its effectiveness as a solvent. Thus, supercritical water is of keen interest as solvent in many extraction processes. The low solubility of salts in lower density supercritical water has even been suggested as a means of desalination. The high temperatures and pressures required to reach supercritical conditions can present experimental challenges during collection of required physical property and phase equilibria data, especially in salt-containing systems. Molecular simulations have the potential to be a valuable tool for examining the behavior of solvated ions at these high temperatures and pressures. However, the accuracy of classical force fields under these conditions is unclear. We have, therefore, undertaken a parametric study of NaCl in water, comparing several salt and water models at 200 bar–600 bar and 450 K–750 K for a range of salt concentrations. We report a comparison of structural properties including ion aggregation, hydrogen bonding, density, and static dielectric constants. All of the force fields qualitatively reproduce the trends in the liquid phase density. An increase in ion aggregation with decreasing density holds true for all of the force fields. The propensity to aggregate is primarily determined by the salt force field rather than the water force field. This coincides with a decrease in the water static dielectric constant and reduced charge screening. While a decrease in the static dielectric constant with increasing NaCl concentration is consistent across all model combinations, the salt force fields that exhibit more ionic aggregation yield a slightly smaller dielectric decrement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Mixture Model for Refrigerant Pairs R-32/1234yf, R-32/1234ze(E), R-1234ze(E)/227ea, R-1234yf/152a, and R-125/1234yf

In this work, thermodynamic models based on the corresponding states framework with departure terms are developed for the refrigerant pairs R-32/1234yf, R-32/1234ze(E), R-1234ze(E)/227ea, R-1234yf/152a, and R-125/1234yf. These models are based on new measurements of density, speed of sound, and phase equilibria, combined with the data available in the literature. The model for R-32/1234yf is most comprehensive in its data coverage, with speed of sound deviations within 1%, density deviations within 0.1%, and bubble- and dew-point pressure deviations within 1%. In conclusion, the other mixtures have generally more limited data availability but a similar goodness of fit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Thermodynamic modeling of CsF with LiF-NaF-KF for molten fluoride-fueled reactors

Gibbs energy models were developed to describe the thermochemical behavior of CsF in molten FLiNaK (46.5LiF-11.5NaF-42KF mol%), a proposed molten salt reactor (MSR) fuel solvent and coolant, as cesium is of concern due to its high radiotoxicity and volatility. Initially, it was necessary to obtain a more accurate Gibbs energy function for CsF which required fitting parameters to reported vapor pressures over condensed phase CsF. The pseudo-binary systems CsF-LiF, CsF-NaF and CsF-KF were then evaluated utilizing phase equilibria and enthalpy of mixing (Δ mix H) values, together with original differential scanning calorimetry (DSC) measurements performed for the CsF-LiF and CsF-KF systems. The CsF-LiF-NaF, CsF-LiF-KF and CsF-NaF-KF pseudo-ternary system representations were obtained by interpolation of the constituent pseudo-binary systems, with DSC measurements performed for the CsF-LiF-NaF system to corroborate the calculated liquidus temperature. Ultimately, the pseudo-ternary systems were interpolated to obtain Gibbs energy models for the pseudo-quaternary CsF-LiF-NaF-KF system, supported by DSC measurements at low CsF compositions (1–10 mol%), yielding computed equilibria and cesium-containing vapor pressures that compare favorably with reported values. In conclusion, the Molten Salt Thermal Properties Database – Thermochemical (MSTDB-TC) was subsequently expanded to include these Gibbs energy models allowing description of the thermochemical behavior of the CsF-LiF-NaF-KF system.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Interactive Exploration of High-Dimensional Phase Diagrams

High-dimensional thermodynamic phase stability databases are becoming increasingly common due to the convergence of three recent trends: (i) the widespread interest in so-called “high-entropy” alloys, (ii) the availability of high-throughput computational assessments of phase stability in broad composition spaces and (iii) the ongoing development of ever-increasingly broad, multicomponent, multiphase CALPHAD databases. Although automated computational tools can readily process such high-dimensional data, scientists are often unable to visualize the relevant phase relations, an ability that is crucial to gaining an intuitive understanding of the stability constraints governing materials design. The present work addresses this need by providing algorithms that enable the interactive exploration of phase equilibria in high-dimensional spaces. These algorithms concentrate the complex nonlinear nonsmooth optimization needed into a preprocessing step that generates a large number of high-dimensional yet elementary graphical primitives. Furthermore, these primitives can then be cross-sectioned to yield 3-dimensional views in a computationally efficient manner that enables an interactive exploration of high-dimensional spaces. All of these operations are highly parallelizable, thus facilitating scaling of this method to large data sets.

36 MATERIALS SCIENCE↗