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At least 1,135 records · Page 63
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

A simple method for obtaining heat capacity coefficients of minerals

Abstract Heat capacity data are unavailable or incomplete for many minerals at geologically relevant temperatures. Despite the availability of entropy and enthalpy values in numerous thermodynamic tables (even sometimes at elevated temperatures), there remains need for extrapolation beyond, or interpolation between, temperatures. This approach inevitably results in estimates for entropy and enthalpy values because the heat capacity coefficients required for optimal thermodynamic treatment are less frequently available. Here we propose a simple method for obtaining heat capacity coefficients of minerals. This method requires only the empirically measured temperature-specific heat capacity for calculation via a matrix algorithm. The system of equations solver is written in the Python computing language and has been made accessible in an online repository. Thermodynamically, the solution to a system of equations represents the heat capacity coefficients that satisfy the mineral-specific polynomial. Direct coefficient calculation will result in more robust thermodynamic data, which are not subject to fitting uncertainties. Using hematite as an example, this method provides results that are comparable to conventional means and is applicable to any solid material. Coefficients vary within the traditional large 950 K temperature interval, indicating that best results should instead utilize a smaller 400 K temperature interval. Examples of large-scale implications include the refinement of geothermal gradient estimation in rapidly subsiding sedimentary basins or metamorphic and hydrothermal evolution.

Geochemistry & Geophysics↗
NASA NTRS1989

Collision integrals and high temperature transport properties for N-N, O-O, and N-O

Accurate collision integrals are reported for the interactions of N(4 S 0) + N(4 S 0), O(3 P), and N(4 S 0) + O(3 P). These are computed from a semiclassical formulation of the scattering using the best available representations of all of the potential energy curves needed to describe the collisions. Experimental RKR curves and other accurate measured data are used where available; the results of accurate ab initio electronic structure calculations are used to determine the remaining potential curves. The high-lying states are found to give the largest contributions to the collision cross sections. The nine collision integrals, needed to determine transport properties to second order, are tabulated for translational temperatures in the range 250 K to 100,000 K. These results are intended to reduce the uncertainty in future predictions of the transport properties of nonequilibrium air, particularly at high temperatures. The viscosity, thermal conductivity, diffusion coefficient, and thermal diffusion factor for a gas composed of nitrogen and oxygen atoms in thermal equilibrium are calculated. It was found that the second order contribution to the transport properties is small. Graphs of these transport properties for various mixture ratios are presented for temperatures in the range 5000 to 15000 K.

Levin, E.↗
NASA NTRS1997

Kinetics of the Reactions of Cl((sup 2)P(sub J)) and Br((sup 2)P(sub 3/2)) with O3

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the important stratospheric reactions Cl((sup 2)P(sub J)) + O3 yields ClO + O2 and Br((sup 2)P(sub 3/2)) + O3 yields BrO + O2 as a function of temperature. The temperature dependence observed for the Cl((sup 2)P(sub J)) + O3 reaction is nonArrhenius, but can be adequately described by the following two Arrhenius expressions (units are cu cm/(molecule.s), errors are 2 sigma and represent precision only): k(sub 1)(T) = (1.19 +/- 0.21) x 10(exp -11) exp[(-33 +/- 37)/T] for T = 189-269 K and k(sub 1)(T) = (2.49 +/- 0.38) x 10(exp -11) exp[(-233 +/- 46)/T] for 269-385 K. At temperatures below 230 K, the rate coefficients determined in this study are faster than any reported previously. Incorporation of our values for k(sub 1)(T) into stratospheric models would increase calculated ClO levels and decrease calculated HCI levels; hence the calculated efficiency of ClO catalyzed ozone destruction would increase. The temperature dependence observed for the Br((sup 2)P(sub 3/2)) + O3 reaction is adequately described by the following Arrhenius expression (units are cu cm/(molecule.s), errors are 2 sigma and represent precision only): k(sub 2)(T) = (1.50 +/- 0.16) x 10(exp -11)exp[(-775 +/- 30)/T for 195-392 K. While not in quantitative agreement with Arrhenius parameters reported in most previous studies, our results almost exactly reproduce the average of all earlier studies and therefore will not affect the choice of k(sub 2)(T) for use in modeling stratospheric BrO2 chemistry.

Nicovich, J. M.↗
DOE OSTI2024

Low-Temperature Characterization of a Nonaqueous Liquid Electrolyte for Lithium Batteries

Rechargeable batteries exhibit poor performance at low temperatures due to sluggish ion transport through the electrolytic phase. Ion transport is governed by three transport parameters—conductivity, diffusion coefficient, and the cation transference number with respect to the solvent velocity—and the thermodynamic factor. Understanding how these parameters change with temperature is necessary for designing improved electrolytes. In this work, we combine electrochemical techniques with electrophoretic NMR to determine the temperature dependence of these parameters for a liquid electrolyte, LiTFSI salt dissolved in tetraglyme between −20 and 45 °C. At colder temperatures, all species in the electrolyte tend to move more slowly due to increasing viscosity, which translates to a monotonic decrease in conductivity and diffusion coefficient with decreasing temperature. Surprisingly, we find that the field-induced velocity of solvent molecules at a particular salt concentration is a nonmonotonic function of temperature. The cation transference number with respect to the solvent velocity thus exhibits a complex dependence on temperature and salt concentration. The measured thermodynamic and transport properties are used to predict concentration gradients that will form in a lithium-lithium symmetric cell under a constant applied potential as a function of temperature using concentrated solution theory. The calculated steady current at −20 °C is lower than that at 45 °C by roughly two orders of magnitude.

25 ENERGY STORAGE↗
NASA NTRS1980

Secondary electron emission from sodium chloride, glass and aluminum oxide at various temperature

The method of single impulses was used to measure the coefficients of the secondary electronic emission for 2 types of Al2O2, monocrystalline NaCl and glass at different temperatures and for different values of the energy of the primary electrons. The value of the secondary electron emission does not depend upon temperature. The effect of a gas film on the value of the secondary electron emission was detected.

Shulman, A. R.↗
DOE OSTI2023

Thermal expansion of 4H and 6H SiC from 5 K to 340 K

The first thermal expansion measurements of the 4H and 6H polytypes of SiC below room temperature are reported. The measurements were carried out on single-crystal specimens using high-resolution capacitive-based dilatometry. For both polytypes, the thermal expansion coefficient is below 2.4 × 10 -6 1/K near room temperature. No phase transitions are observed over the 5 K to 340 K temperature range of the measurements. The thermal expansion coefficient α of 4H SiC is slightly anisotropic for measurements parallel and perpendicular to the crystallographic c axis with α ∥ about 2.2 × 10 -7 1/K larger than α ⟂ near room temperature. For 6H SiC no discernible anisotropy is observed. The differences in anisotropy can be understood by considering the ratio of hexagonal to cubic bonds of each polytype. Narrow regions with negative thermal expansion that are within the limits of our resolution (~ 1 x 10 -8 ) are observed in the vicinity of 30 K for both specimens. In conclusion, tabulated data, polynomial fits, fit parameters, and comparison to data based on lattice-parameter measurements are provided.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Effect of Pressure on Trace Element Activity Coefficients in Metal-Silicate Systems

The partitioning of trace elements between metal and silicate melts serves as the foundation for understanding the differentiation of a planetary body into a metallic core and silicate mantle. Element activity influences metal-silicate partitioning behavior. Activity coefficients are directly dependent on composition and temperature, and can be indirectly dependent on oxygen fugacity and pressure. Distinguishing the effect of pressure from other variables on the activity coefficients and partitioning is important for understanding the chemical evolution of different planetary bodies during differentiation. In this study, we investigated the influence of pressure on the activity coefficients of Cu, Mo, Pd, Pt, As, Sb, and Bi in Fe-Si metallic liquids. All of these elements exhibit moderate to high activity coefficients in Fe-Si liquids at low pressure, which significantly controls their metal-silicate partitioning behavior. Identifying whether this strong dependence persists at higher pressures is critical to modeling and understanding the chemical consequences of core formation. New experiments at 10 GPa were used to derive activity coefficients for these metals which can be compared to activity coefficients determined at 1 GPa. Experiments were conducted at 10 GPa and 2373K using a 10/5 assembly in the 880-ton multi-anvil press at NASA Johnson Space Center. The standard 10/5 COMPRES assembly was slightly modified to accommodate a sample capsule machined from single-crystal MgO that minimizes melt percolation out of the sample volume during the experiment. Experiment starting materials were comprised of 70 wt.% Knippa basalt and 30 wt.% metal. The metal mixture (~85 wt.% Fe) was created by adding the elements of interest (Cu, Mo, Pd, Pt, As, Sb, Bi) to Fe metal powder. Varied amounts of Si metal (0-10 wt.% Si) were added to the metal-silicate mixtures to generate a systematic series of starting materials. For each element, an epsilon interaction parameter in Fe-Si liquid was derived from the results of our 0-10 wt.% Si metal series. To investigate whether pressure influences the trace element activity coefficients in the 1-10 GPa pressure range, we compared our results at 10 GPa to those at 1-4 GPa [1-3]. Our results can also be directly compared to interaction parameters for Au, P, V, Mn, Ga, Zn, Cd, Sn, W, Pb, and Nb previously determined at 10 GPa and 2373K following the same methods [4]. Combined, this suite of interaction parameters will directly inform metal-silicate partitioning between 1 and 10 GPa, and assess whether these values can be extrapolated to modeling differentiation processes at pressures >10 GPa.

Kelsey Prissel↗
NASA NTRSDate not supplied

Effect of Pressure and Oxidation State on Pnictogen Metal-Silicate Partitioning

The partitioning of trace elements between metal and silicate melts serves as the foundation for understanding the differentiation of a planetary body into a metallic core and silicate mantle. Element activity influences metal-silicate partitioning behavior. Activity coefficients are directly dependent on composition and temperature, and can be indirectly dependent on oxygen fugacity and pressure. Distinguishing the effect of pressure from other variables on the activity coefficients and partitioning is important for understanding the chemical evolution of different planetary bodies during differentiation. In this study, we investigated the influence of pressure on the activity coefficients of Cu, Mo, Pd, Pt, As, Sb, and Bi in Fe-Si metallic liquids. All of these elements exhibit moderate to high activity coefficients in Fe-Si liquids at low pressure, which significantly controls their metal-silicate partitioning behavior. Identifying whether this strong dependence persists at higher pressures is critical to modeling and understanding the chemical consequences of core formation. New experiments at 10 GPa were used to derive activity coefficients for these metals which can be compared to activity coefficients determined at 1 GPa. Experiments were conducted at 10 GPa and 2373K using a 10/5 assembly in the 880-ton multi anvil press at NASA Johnson Space Center. The standard 10/5 COMPRES assembly was slightly modified to accommodate a sample capsule machined from single-crystal MgO that minimizes melt percolation out of the sample volume during the experiment. Experiment starting materials were comprised of 70 wt.% Knippa basalt and 30 wt.% metal. The metal mixture (~85 wt.% Fe) was created by adding the elements of interest (Cu, Mo, Pd, Pt, As, Sb, Bi) to Fe metal powder. Varied amounts of Si metal (0-10 wt.% Si) were added to the metal-silicate mixtures to generate a systematic series of starting materials. For each element, an epsilon interaction parameter in Fe-Si liquid was derived from the results of our 0-10 wt.% Si metal series. To investigate whether pressure influences the trace element activity coefficients in the 1-10 GPa pressure range, we compared our results at 10 GPa to those at 1-4 GPa [1-3]. Our results can also be directly compared to interaction parameters for Au, P, V, Mn, Ga, Zn, Cd, Sn, W, Pb, and Nb previously determined at 10 GPa and 2373K following the same methods [4]. Combined, this suite of interaction parameters will directly inform metal- silicate partitioning between 1 and 10 GPa, and assess whether these values can be extrapolated to modeling differentiation processes at pressures >10 GPa. [1] Righter et al. (2018) GCA 232, 101-123 [2] Righter et al. (2019) MaPS 54, 1379-1394 [3] Steenstra et al. (2020) Icarus, 335, 113391 [4] Righter et al. (2020) Geochem. Persp. Let. 15, 44-49

Kelsey Prissel↗
NASA NTRS1977

The rate coefficient for the O/+/ + N2 reaction in the ionosphere

The rate coefficient for the reaction O(+) + N2 yields NO(+) + N is determined as a function of temperature from the photochemistry of NO(+) for both day and night conditions by using a large sample of simultaneous measurements of ion and neutral concentrations and temperatures made by the Atmosphere Explorer C satellite. The results cover the ion temperature range from 500 to 1200 K. Using recent flow-drift-tube results, the rate coefficient is calculated as a function of ion temperature and mean ion drift velocity for ionospheric conditions. The satellite and laboratory determinations are found to be in good agreement. Using this temperature dependence, an earlier determination of the dissociative recombination coefficient of NO(+) with electrons is refined.

Torr, M. R.↗
DOE OSTI2022

Real-time measurement of parametric influences on the refractive index and length changes in silica optical fibers

In this paper, we present a simple cascaded Fabry-Perot interferometer (FPI) that can be used to measure in real-time the refractive index (RI) and length variation in silica optical fibers caused due to external physical parameters, such as temperature, strain, and radiation. As a proof-of-concept, we experimentally demonstrate real-time monitoring of temperature effects on the RI and length and measure the thermo-optic coefficient (TOC) and thermal expansion coefficient (TEC) by using the cascaded FPI within a temperature range of 21–486°C. The experimental results provide a TEC of 5.53 × 10 −7 /°C and TOC of 4.28 × 10 −6 /°C within the specified temperature range. Such a simple cascaded FPI structure will enable the design of optical sensors to correct for measurement errors by understanding the change in RI and length of optical fiber caused by environment parameters.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS1985

Trends in upper stratospheric temperatures as observed by rocketsondes (1965-1983)

Recent interest in possible anthropogenically induced changes in stratospheric ozone has led to a number of modeling studies. These studies indicate that stratospheric temperature changes would be related to stratospheric ozone changes. Therefore, this study was motivated by a concern to find out whether or not any significant trend in upper stratospheric temperatures could be ascertained from available observational data. June monthly mean values for 40 to 45 km layer were calculated for all Western Hemisphere rocketsonde stations for which data was available. Mean temperatures for each June were then used to calculate linear least squares regression coefficients with latitude of the stations as the independent variable. The resulting coefficients were used to calculate area-weighted mean temperatures for 25 deg N to 55 deg N. A two-to-three degree temperature drop in the early 1970s is indicated. It was noted, however, that this temperature decline coincides with a change in the principal observing system from the Arcasconde system to the Datasonde system. In order to study this temperature decrease more closely, similar mean temperatures were calculated for the 25 to 30 km layer using both rocketsondes and support radiosondes.

Johnson, K. W.↗
DOE OSTI2022

Initial study on cross-section generation requirements for a PBR equilibrium core

A Serpent model of the equilibrium core HTR-PM small modular nuclear reactor in China, was developed for use in cross-section preparation studies in order to guide methods development for the Griffin reactor multiphysics application. The model includes detailed isotopics for 10 distinct pebble burnup groups in 126 core zones with unique fuel and moderator temperatures obtained from a coupled neutronics-thermal-fluids equilibrium core calculation using Griffin-Pronghorn. A sensitivity study of the fuel and moderator temperatures for various core regions was performed with the MOOSE stochastic tools. The results show that the uncertainties are, not unexpectedly, dominated by the value of the fluid temperature and that the power level, heat transfer coefficient and effective conduction to neighboring pebbles and fluid constitute, at best, second order effects. The temperature uncertainty range varies from 28 K to 57 K between the core entry and exit planes, respectively, but these values are probably higher. We still have to quantify the significance of these uncertainties in the preparation of cross-sections in future work. In addition, we verified that the effective pebble approximation used in the PEBBED and V.S.O.P. computer codes works well for the preparation of region averaged cross-sections. Nevertheless, there are some discrepancies in the cross-sections when compared to the multi-pebble model, which could affect the prediction of peak values and the depletion calculation. We conclude that is highly desirable for future studies with Griffin to be able to handle both the 'effective' pebble approximation and the multi-pebble approach for various pebble burnup groups. This enables Griffin users with the flexibility to perform higher-fidelity studies. Finally, we initiated the preparation of cross-sections for various core regions from the full core Serpent reference model. We quantified the differences in 26 group cross-sections from infinite domain models versus the full core approach. These reference cross-sections will serve to verify the double heterogeneity, self-shielding, and spectrum-correction methods in Griffin. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
NASA NTRS1976

Recombination of NO/+/ in the ionosphere

Simultaneous nighttime measurements of ion and neutral concentrations and temperatures made by the Atmosphere Explorer-C satellite were used to determine the recombination rate coefficient of NO(+) as a function of electron temperature. The results agree in shape and absolute magnitude to within one standard deviation with those of Walls and Dunn (1974), indicating that NO(+) ions in the ionosphere may be in the ground vibrational state.

Torr, D. G.↗
NASA NTRS1959

Lubricating Properties of Lead-Monoxide-Base Coatings of Various Compositions at Temperatures to 1250 F

A number of ceramic coatings of different compositions containing lead monoxide (PbO) were studied to determine their relative merits as dry-film lubricants. Lead monoxide is known to be an effective solid lubricant at elevated temperatures, and this oxide was the main component in all compositions studied. Friction and wear properties were determined at temperatures from 750 to 1250 F, at a sliding velocity of 430 feet per minute, and at a normal load of 1 kilogram. In all of the coatings, PbO was the component primarily responsible for the lubricating properties. Oxides other than PbO had an indirect effect on lubrication by influencing such properties as adhesion, hardness, vitrifying or glaze-forming tendency, melting or softening point, and chemical stability of the coatings. Notable among these oxides were magnetite (Fe3O4.), which had generally a beneficial influence on ceramic- to-metal adhesion, and silica (SiO2), which inhibited the oxidation of PbO and enhanced the tendency for glaze formation on the sliding surfaces. Several of the compositions studied provided protection against metal-to-metal adhesive wear, galling, or seizure at test temperatures from 750 to 1250 F. Coating friction coefficients ranged from 0.20 to 0.37 at 75 F but were around 0.08 to 0.20 at temperatures of 1250 F.

Sliney, Harold E.↗
DOE OSTI2024

Climatic Drivers for the Variation of Gross Primary Productivity Across Terrestrial Ecosystems in the United States

Abstract Temperature and water stress are important factors limiting the gross primary productivity (GPP) in terrestrial ecosystems, yet the extent of their influence across ecosystems remains uncertain. This study examines how surface air temperature, soil water availability (SWA) and vapor pressure deficit (VPD) influence ecosystem light use efficiency (LUE), a critical metric for assessing GPP, across different ecosystems and climatic zones at 80 flux tower sites based on in situ measurements and data assimilation products. Results indicate that LUE increases with temperature in spring, with higher correlation coefficients in colder regions (0.79–0.82) than in warmer regions (0.68–0.78). LUE reaches a plateau earlier in the season in warmer regions. LUE variations in summer are mainly driven by SWA, exhibiting a positive correlation indicative of a water‐limited regime. The relationship between the daily LUE and daytime temperature shows a clear seasonal hysteresis at many sites, with a higher LUE in spring than in fall under the same temperature, likely resulting from younger leaves being more efficient in photosynthesis. Drought stress influences LUE through SWA in all ranges of water availability; VPD variation under moderate conditions does not have a clear influence on LUE, but extremely high VPD (exceeding the threshold of 1.6 kPa, often observed during extreme drought‐heat events) causes a dramatic reduction of LUE. Our findings provide insight into how ecosystem productivities respond to climate variability and how they may change under the influence of more frequent and severe heat and drought events projected for the future.

Environmental Sciences & Ecology↗
NASA NTRS1989

On the diurnal variation of noctilucent clouds

The relationship between nuctilucent clouds (NLC), which are observed from the ground usually within 2 or 3 hrs of local midnight, and the polar mesospheric clouds (PMC), which are observed by satellites in full daylight, as well as the reason for the differences in their optical properties and their observed heights are investigated. Based on a suggestion that these differences can be attributed to a diurnal variation in the properties of a single type of cloud, two published models of the diurnal and semidiurnal variations of temperature, vertical wind speed, and eddy diffusion coefficient at high latitude to simulate the evolution of ice clouds over a 24-hr period. The results show that the minimum in temperature at about 2000 hours LT causes a sharp maximum in scattered brightness to occur about 1 hour before local midnight, with up to a factor of 7 variation in cloud brightness between noon and midnight. It is noted, however, that considerable uncertainties exist in these tidal models.

Jensen, Eric↗
NASA NTRS1988

Electron-temperature dependence of the recombination of electrons with O4(+) ions

The coefficient for recombination of O4(+) ions with electrons has been measured as a function of Te by analyzing electron- and ion-density decays in microwave-generated afterglow plasmas in neon-oxygen mixtures. Te values in the afterglow were elevated above those of the neutral species and ions by continuous application of microwave power. The data analysis included effects on the Te arising from inelastic collisions of electrons with the minority oxygen molecules and spatial nonuniformities of Te due to the spatially nonuniform microwave heating field. Over the temperature range Te = 143-5500 K the recombination coefficients were found to have a Te exp -z dependence, with z = 0.48 + 0.1 or - 0.05. While the values of the recombination coefficients for this dimer ion are an order of magnitude larger than those of the monomer ions, the temperature dependence is close to the Te exp -0.5 dependence predicted and often observed for diatomic ions.

Dulaney, J. L.↗
NASA NTRS1991

The temperature dependence of collision-induced absorption by oxygen near 6 microns

Coefficients for oxygen absorption in the infrared induced by collisions with O2 and N2 are reported over the range 1400-1800/cm and 225-356 K. These coefficients are used to calculate the absorption for O2 in air as a function of temperature and wavenumber, and comparisons are made with previous determinations. In addition, structured absorption features superimposed on the broad collision-induced absorption band, which were observed at all temperatures studied, are interpreted in terms of the presence of (O2)2 and O2-N2 van der Waals molecules.

Orlando, John J.↗