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At least 199 records · Page 11

Coarsening in Solid-Liquid Mixtures Studied on the Space Shuttle

Ostwald ripening, or coarsening, is a process in which large particles in a two-phase mixture grow at the expense of small particles. It is a ubiquitous natural phenomena occurring in the late stages of virtually all phase separation processes. In addition, a large number of commercially important alloys undergo coarsening because they are composed of particles embedded in a matrix. Many of them, such as high-temperature superalloys used for turbine blade materials and low-temperature aluminum alloys, coarsen in the solid state. In addition, many alloys, such as the tungsten-heavy metal systems, coarsen in the solid-liquid state during liquid phase sintering. Numerous theories have been proposed that predict the rate at which the coarsening process occurs and the shape of the particle size distribution. Unfortunately, these theories have never been tested using a system that satisfies all the assumptions of the theory. In an effort to test these theories, NASA studied the coarsening process in a solid-liquid mixture composed of solid tin particles in a liquid lead-tin matrix. On Earth, the solid tin particles float to the surface of the sample, like ice in water. In contrast, in a microgravity environment this does not occur. The microstructures in the ground- and space-processed samples (see the photos) show clearly the effects of gravity on the coarsening process. The STS-83-processed sample (right image) shows nearly spherical uniformly dispersed solid tin particles. In contrast, the identically processed, ground-based sample (left image) shows significant density-driven, nonspherical particles, and because of the higher effective solid volume fraction, a larger particle size after the same coarsening time. The "Coarsening in Solid-Liquid Mixtures" (CSLM) experiment was conducted in the Middeck Glovebox facility (MGBX) flown aboard the shuttle in the Microgravity Science Laboratory (MSL-1/1R) on STS-83/94. The primary objective of CSLM is to measure the temporal evolution of the solid particles during coarsening.

Caruso, John J.↗

Non-Additive Voltametric Currents From a Mixture of Two, Three and Four Redox-Active Compounds and Electroanalytical Implications

We have published recently the effect of dissimilar diffusion coefficients on the size of the voltammetric waves from a mixture of two redox-active compounds. Similarly, at the potential range where three redox-active species, decamethylferrocene (dMeFc), ferrocene (Fc) and N-methylphenothiazine (MePTZ), are oxidized simultaneously with rates controlled by linear diffusion, electrogenerated radicals diffusing outwards from the electrode react with the original species diffusing towards the electrode from the bulk; thus, Fc(+) reacts with dMeFc producing Fc and dMeFc(+), while MePTZ(+) reacts both with dMeFc producing MePTZ and dMeFc(+), and with Fc producing MePTZ and Fc(+). These reactions replace dMeFc with Fc at the second plateau, and both dMeFc and Fc with MePTZ at the third plateau. Since the diffusion coefficients of the three species are not equal, the mass-transfer limited currents of the second and the third oxidation wave plateaus change by approx. 10%. Numerical simulations of the experimental voltamograms support this mechanism. Similar results were also obtained for a mixture of four redoxactive compounds. The implications of this non-additive nature of currents on: (a) the use of internal voltammetric standards for quantitative analysis of a mixture of redox-active compounds; and, (b) the half wave potentials (E1/2) of the 2nd, 3rd and 4th waves for qualitative analysis, will be discussed.

Dass, Amala↗

Simulation Analysis of Computer-Controlled pressurization for Mixture Ratio Control

A procedural code (C++) simulation was developed to investigate potentials for mixture ratio control of pressure-fed spacecraft rocket propulsion systems by measuring propellant flows, tank liquid quantities, or both, and using feedback from these measurements to adjust propellant tank pressures to set the correct operating mixture ratio for minimum propellant residuals. The pressurization system eliminated mechanical regulators in favor of a computer-controlled, servo- driven throttling valve. We found that a quasi-steady state simulation (pressure and flow transients in the pressurization systems resulting from changes in flow control valve position are ignored) is adequate for this purpose. Monte-Carlo methods are used to obtain simulated statistics on propellant depletion. Mixture ratio control algorithms based on proportional-integral-differential (PID) controller methods were developed. These algorithms actually set target tank pressures; the tank pressures are controlled by another PID controller. Simulation indicates this approach can provide reductions in residual propellants.

Alexander, Leslie A.↗

Heat Transfer and Pressure Drop in Concentric Annular Flows of Binary Inert Gas Mixtures

Studies of heat transfer and pressure drop of binary inert gas mixtures flowing through smooth concentric circular annuli, tubes with fully developed velocity profiles, and constant heating rate are described. There is a general lack of agreement among the constant property heat transfer correlations for such mixtures. No inert gas mixture data exist for annular channels. The intent of this study was to develop highly accurate and benchmarked pressure drop and heat transfer correlations that can be used to size heat exchangers and cores for direct gas Brayton nuclear power plants. The inside surface of the annular channel is heated while the outer surface of the channel is insulated. Annulus ratios range 0.5 < r* < 0.83. These smooth tube data may serve as a reference to the heat transfer and pressure drop performance in annuli, tubes, and channels having helixes or spacer ribs, or other surfaces.

Reid, R. S.↗

Negative Ion Drift Velocity and Longitudinal Diffusion in Mixtures of Carbon Disulfide and Methane

Negative ion drift velocity and longitudinal diffusion has been measured for gas mixtures of carbon disulfide (CS2) and methane (CH4)' Measurements were made as a function of total pressure, CS2 partial pressure and electric field. Constant mobility and thermal-limit longitudinal diffusion is observed for all gas mixtures tested. Gas gain for some of the mixtures is also included.

Dion, Michael P.↗

Comparison of PARASOL Observations with Polarized Reflectances Simulated Using Different Ice Habit Mixtures

Insufficient knowledge of the habit distribution and the degree of surface roughness of ice crystals within ice clouds is a source of uncertainty in the forward light scattering and radiative transfer simulations required in downstream applications involving these clouds. The widely used MODerate Resolution Imaging Spectroradiometer (MODIS) Collection 5 ice microphysical model assumes a mixture of various ice crystal shapes with smooth-facets except aggregates of columns for which a moderately rough condition is assumed. When compared with PARASOL (Polarization and Anisotropy of Reflectances for Atmospheric Sciences coupled with Observations from a Lidar) polarized reflection data, simulations of polarized reflectance using smooth particles show a poor fit to the measurements, whereas very rough-faceted particles provide an improved fit to the polarized reflectance. In this study a new microphysical model based on a mixture of 9 different ice crystal habits with severely roughened facets is developed. Simulated polarized reflectance using the new ice habit distribution is calculated using a vector adding-doubling radiative transfer model, and the simulations closely agree with the polarized reflectance observed by PARASOL. The new general habit mixture is also tested using a spherical albedo differences analysis, and surface roughening is found to improve the consistency of multi-angular observations. It is suggested that an ice model incorporating an ensemble of different habits with severely roughened surfaces would potentially be an adequate choice for global ice cloud retrievals.

Cole, Benjamin H.↗

Vapor Pressure and Evaporation Coefficient of Silicon Monoxide over a Mixture of Silicon and Silica

The evaporation coefficient and equilibrium vapor pressure of silicon monoxide over a mixture of silicon and vitreous silica have been studied over the temperature range (1433 to 1608) K. The evaporation coefficient for this temperature range was (0.007 plus or minus 0.002) and is approximately an order of magnitude lower than the evaporation coefficient over amorphous silicon monoxide powder and in general agreement with previous measurements of this quantity. The enthalpy of reaction at 298.15 K for this reaction was calculated via second and third law analyses as (355 plus or minus 25) kJ per mol and (363.6 plus or minus 4.1) kJ per mol respectively. In comparison with previous work with the evaporation of amorphous silicon monoxide powder as well as other experimental measurements of the vapor pressure of silicon monoxide gas over mixtures of silicon and silica, these systems all tend to give similar equilibrium vapor pressures when the evaporation coefficient is correctly taken into account. This provides further evidence that amorphous silicon monoxide is an intimate mixture of small domains of silicon and silica and not strictly a true compound.

Ferguson, Frank T.↗

Near-Infrared Band Strengths of Molecules Diluted in N2 and H2O Ice Mixtures Relevant to Interstellar and Planetary Ices

The relative abundances of ices in astrophysical environments rely on accurate laboratory measurements of physical parameters, such as band strengths (or absorption intensities), determined for the molecules of interest in relevant mixtures. In an extension of our previous study on pure-ice samples, here we focus on the near-infrared absorption features of molecules in mixtures with the dominant components of interstellar and planetary ices, H2O and N2. We present experimentally measured near-infrared spectral information (peak positions, widths, and band strengths) for both H2O- and N2-dominated mixtures of CO (carbon monoxide), CO2 (carbon dioxide), CH4 (methane), and NH3 (ammonia). Band strengths were determined during sample deposition by correlating the growth of near-infrared features (10,000-4000 per centimeter, 1-2.5 micrometers) with better-known mid-infrared features (4000-400 per centimeter, 2.5-25 micrometers) at longer wavelengths.

Strengths↗

The Investigation of Chlorate/Iron-Phase Mixtures as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument on board the Curiosity Rover has detected oxygen and HCl gas releases from all analyzed Gale Crater sediments. The presence of perchlorate ClO4(sup-) and/or chlorates ClO3(sup-) are potential sources of the aforementioned O2 releases. The detections of O2 and HCl gas releases and chlorinated hydrocarbons by SAM coupled with the detection of perchlorates by Phoenix Lander's 2008 Wet Chemistry Laboratory all suggest that perchlorates, and possibly chorates, may be present in the Gale Crater sediments. Previous laboratory studies have attempted to replicate these O2 releases by heating perchlorates and chlorates in instruments operated similarly to those in the SAM instrument. Early studies found that pure perchlorates release O2 at temperatures higher than those observed in SAM data. Subsequently, studies were done to test the effects of mixing iron-phase minerals, analogous to those detected on Mars by ChemMin, with perchlorates. The iron in these minerals acts as a catalyst and causes O2 to be released from the perchlorate at a lower temperature. These studies found that perchlorate solutions mixed with either Hawaii palagonite or ferrihydrite produce O2 releases at temperatures similar to the Rocknest (RN) windblown deposit and the John Klein (JK) drill sample from the Sheepbed mudstone. The study also determined that perchlorate mixtures with magnetite, hematite, fayalite-magnetite, ilmentite, and pyrrhotite produce O2 releases at temperatures similar to the Confidence Hills (CH) drill sample from the Murray mudstone. Oxygen re-leases from pure chlorates were recently compared with the SAM data. Laboratory analyses determined that Ca-chlorate produces O2 and HCl peaks that are similar to those detected in RN and JK materials. Currently, no perchlorate/chlorate mixture with iron-phase minerals can explain the O2 releases from either the Cumberland (CB) drill sample from the Sheepbed mudstone or Windjana (WJ) drill sample from the Kimberly sandstone. Mixtures of chlorate solutions with iron-phase minerals may produce O2 peaks at temperatures that match those from CB and WJ materials. The goal of this work is to determine if heating chlorate solutions mixed with iron-phase minerals will produce O2 and HCl peak temperatures similar to O2 and HCl peak temperatures of sediments analyzed by SAM, particularly the WJ and CB materials.

Clark, J.↗

Computational Design of Eutectic Molten Salt Mixtures: What Can Thermodynamic Models Do?

In the search for efficient energy storage battery technologies, designing stable electrolytes has been a long-standing challenge. Electrolytes based on molten salt eutectics are known for their stability with minimum parasitic reactions when compared to their widely used organic counterparts. However, the operating temperatures of these molten salt electrolyte-based batteries are dictated by the melting point of the eutectic mixtures. Design and high throughput screening of low melting temperature eutectic molten salt mixtures have been hindered by the lack of computational models. In this work, we develop thermodynamic models to predict the eutectic points of several molten salt mixtures. The framework of the COSMO-SAC model is used for the predictions and is compared with experimental data and other thermodynamic approaches. Rapid thermodynamics-based approaches, as shown in this study, can accelerate the discovery of new materials, complementing experimental techniques.

Ashwin Ravichandran↗

Characterization of CO 4th Positive Radiation in CO2-Ar Mixtures

This paper presents measurements and simulations of CO 4th Positive spectra obtained in NASA Ames Research Center's Electric Arc Shock Tube (EAST) and CentraleSupelec's Plasma Torch. The experiments were aimed at measuring optically thin emission for the main band features of CO 4th Positive by using test gas mixtures of CO2 and Ar. By using mixtures of CO2 and Ar, the temperature of the flow (and consequently black-body curve) is increased compared to using pure CO2 (or CO2 / N2 mixtures). This temperature increase allows for emission spectroscopy of features that would nominally be black-body limited for conditions relevant to Mars entry. The CO 4th Positive system is the focus of this study as it accounts for a large percentage of the emitted radiation for Martian entry, and also due to the difficulties of obtaining experimental validation data due to the emission appearing in the Vacuum Ultraviolet (VUV) spectral range. The focus of this paper is to provide a comprehensive comparison between the EAST and plasma torch data along with various CO 4th Positive databases available in the literature. Previously reported VUV CO2 / N2 EAST data required a larger temperature than would be predicted based upon equilibrium shock relations. The need for the temperature increase implies that the EAST experiment did not fully equilibrate. Thus, it is presumed that the EAST data did not obtain an equilibrium condition. The plasma torch data, on the other hand, is very consistent with equilibrium assumptions. Thus, the equilibrium data obtained in the plasma torch is utilized to construct the CO 4th Positive emission model, which is then applied to the EAST data with a non-equilibrium interpretation.

A. M. Brandis↗

Thermal-hydraulic Performance of Emerging Low GWP Refrigerant Mixture under Flow Boiling in Brazed Plate Heat Exchangers

The hydrofluorocarbon (HFC) refrigerants used in the current refrigeration systems are facing a phase-down due to their higher greenhouse effect resulting in global warming, and thus HVAC&R industry has undergone a transition to low Global Warming Potential (GWP) refrigerants. Refrigerant mixtures are attractive alternatives since their composition can be tailored to comply with environmental regulations while preserving favorable thermophysical properties. However, the new low-GWP zeotropic mixture refrigerants have two or more components with different saturation temperatures at the same pressure level, known as temperature glide, which can cause the degradation of the overall heat transfer performance. The brazed plate heat exchangers (BPHX) provide excellent heat transfer performance due to a compact design and are used in several air-conditioning and refrigeration applications. In this study, flow boiling heat transfer and the associated pressure drop of the refrigerant mixture in a vertical BPHX were experimentally investigated. The single-phase water-to-water experiments were conducted in the tested heat exchanger with a counter-flow configuration. The flow boiling experiments charged with R-134a and R-454C were then performed in a pumped refrigerant loop to evaluate its thermal-hydraulic performance. Furthermore, parametric studies of various heat fluxes, mass fluxes, vapor qualities, and saturation temperatures were also conducted.

Yang, Cheng-Min↗

Hydrochlorination of Uranium Dioxide in a Molten Salt Mixture - Phase 1: Tube Furnace Cross Flow Experiments

In 2023, Metatomic® Inc., a South Carolina based company, was awarded a Gateway for Advanced Innovation in Nuclear (GAIN) research voucher for a proposed series of experiments aimed at demonstrating the viability of a spent nuclear fuel (SNF) recycling process patented by Met atomic® Inc. For the GAIN voucher, Metatomic® Inc. selected Savannah River National Laboratory (SRNL) as a partner in executing the proposed proof-of-concept experiments. This report outlines the proof-of-concept experiments performed by SRNL for Metatomic® Inc. during Phase 1 (of 2) experimentation. The Phase 1 hydrochlorination experiments consisted of weighing UO2 into alumina crucibles with a eutectic mixture of NaCl and CsCl, heating the uranium/salt mixture to a varied temperature (550, 650, or 750 °C), and flowing anhydrous hydrogen chloride (AHCl) gas across the surface of the uranium-bearing molten salt mixture. The hydrochlorination process conditions were maintained for 4-5 hours and the percent conversion for each batch of UO2 was determined using a suite of analytical characterization techniques. The degree of UO2 conversion was found to be greatest at the highest tested temperature, ultimately achieving 32.9% conversion of UO2 to water soluble uranium-chloro species (e.g., UO2Cl2, UCl4) after exposure to AHCl for 4.25 hours at 750 °C.

Nguyen, Vinh T. [Savannah River National Laborator↗

Speed of Sound Measurements of Binary Mixtures of trans -1,2-Difluoroethylene (R-1132(E)) with Difluoromethane (R-32) or 2,3,3,3-Tetrafluoropropene (R-1234yf)

The speed of sound of two binary mixtures containing 0.336 mole fraction trans-1,2- difluoroethylene (R-1132(E)) with difluoromethane (R-32) and 0.435 mole fraction R-1132(E) with 2,3,3,3-tetrafluoropropene (R-1234yf) were measured with a dual-path pulse-echo instrument. The speed of sound was measured along several pseudo-isochores for each blend at temperatures ranging from 230 K to 325 K for blends with R-32 and to 342 K for blends with R- 1234yf. Measurements started at pressures just above each mixtures bubble point pressure and were limited to 8 MPa to avoid potential disproportionation reactions of the R-1132(E). The data were compared to multi-fluid models incorporating Helmholtz-energy-explicit equations of state (EOS) for each pure fluid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Density Measurements of Molten LiF–BeF 2 and LiF–BeF 2 –LaF 3 Salt Mixtures by Neutron Radiography

The densities of eutectic (LiF) 2 –BeF 2 and mixtures of this salt (FLiBe) with LaF 3 were measured by dilatometry and by neutron attenuation from 673 K to 1,073 K. Because LaF 3 has a limited solubility in FLiBe, it was necessary to determine the amount of LaF 3 in solution before the density could be determined. The FLiBe density determination was favorably benchmarked against the literature data. A simple comparison was not available for the LaF 3 –FLiBe mixtures, so extrapolation of published data was necessary based on analysis using the Molten Salt Thermal Properties Database-Thermochemistry, or MSTDB-TC, developed by the US Department of Energy. Solubilities for LaF 3 in FLiBe ranged from 1 to 4 mol % over 673 to 1,073 K. The salt system was heated and cooled over 24 h to evaluate potential changes in composition and hysteresis during the measurement. Changes in the meniscus were observed, and these were included in the correction for density determinations. Salt surface tension may have led to supersaturation of LaF 3 in the salt because the solubility curve was nonlinear with respect to the inverse temperature, as would be expected for an ideal system. Surface tension measurements are currently underway to test this hypothesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic Deconstruction of Ethylene Vinyl Acetate Copolymer and Polyethylene Mixtures via Hydroconversion: Challenges and Solutions

We explore hydrogenolysis over ruthenium supported on zirconia (Ru/ZrO 2 ) and hydrocracking over platinum (Pt) supported on zeolites as an effective end-of-life strategy for ethylene vinyl acetate (EVA)–a widely used performance heat sealant in hard-to-recycle multilayer packaging. For Ru/ZrO 2 hydrogenolysis, EVA reacts slower than low-density polyethylene (LDPE) and the catalyst deactivates due to carbonaceous deposits originating from polyenes generated in situ during EVA thermal degradation. High H 2 pressures and temperatures can overcome catalyst deactivation; however, CH 4 yields are excessive due to cascade hydrogenolysis stemming from strong C=C/metal interactions. Polyene hydrogenation allows chains anchored by C=C to desorb from Ru, shifting product selectivity from CH 4 to higher-value liquids. Hydrogenolysis of mixed EVA and linear low-density polyethylene (LLDPE), mirroring typical frozen food packaging formulations, results in comparable catalyst activity and CH 4 yield as the pure EVA resin. For Pt/zeolite hydrocracking, pure EVA and EVA:LLDPE mixtures are deconstructed to propane or light naphtha with minimal CH 4 production. Among catalysts tested, Pt/HY gives the highest liquid productivity (g C5+products /g cat ·h). Furthermore, these findings showcase the recalcitrant nature of EVA and its associated mixtures for Ru/ZrO 2 hydrogenolysis, highlighting that hydrocracking catalysts may be superior for complex packaging waste.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identifying Green Solvent Mixtures for Bioproduct Separation Using Bayesian Experimental Design

Liquid–liquid extraction (LLE) is a widely used technique for the separation and purification of liquid-phase products with applications in various industries, including pharmaceuticals, petrochemicals, and renewable chemistry. A critical step in the design of an LLE process is the selection of appropriate solvents. This study presents a new methodology for identifying solvent mixtures for bioproduct separation using Bayesian experimental design (BED). Motivated by the need for environmentally friendly and effective separation methods, we address the challenge of selecting solvent systems that balance separation efficiency, selectivity, and environmental impact while also tackling the difficulty of separating multiple bioproducts using complex solvent systems. Our approach specifically seeks to predict product partition coefficients (log10 Kp values) as thermodynamic parameters underlying solvent selection. The iterative approach integrates Bayesian optimization with experimental measurements to guide solvent selection and leverages COSMO-RS simulations to enhance high-throughput experimentation. Using the design of solvent systems for the separation of lignin-derived aromatic products via centrifugal partition chromatography (CPC) as a case study, we show that within seven iterations/cycles of the methodology, we can identify new mixtures of green solvents that align with CPC design principles. Furthermore, these results demonstrate the efficacy of the BED framework in optimizing green solvent systems for complex separations, highlighting the potential of this method to advance the field of green chemistry and contribute to the development of sustainable industrial processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Maximum Cruise-power Operation at Ultra-lean Mixture and Increased Spark Advance on the Mechanical Condition of Cylinder Components

A continuous 50-hour test was conducted to determine the effect of maximum cruise-power operation at ultra-lean fuel-air mixture and increased spark advance on the mechanical conditions of cylinder components. The test was conducted on a nine-cylinder air-cooled radial engine at the following conditions:brake horsepower, 750; engine speed, 1900 rpm; brake mean effective pressure, 172 pounds per square inch; fuel-air ratio, 0.052; spark advance, 30 deg B.T.C.; and maximum rear-spark-plug-bushing temperature, 400 F. In addition to the data on corrosion and wear, data are presented and briefly discussed on the effect of engine operation at the conditions of this test on economy, knock, preignition, and mixture distribution. Cylinder, piston, and piston-ring wear was small and all cylinder component were in good condition at the conclusion of the 50-hour test except that all exhaust-valve guides were bellmouthed beyond the Army's specified limit and one exhaust-valve face was lightly burned. It is improbable that the light burning in one spot of the valve face would have progressed further because the burn was filled with a hard deposit so that the valve face formed an unbroken seal and the mating seat showed no evidence of burning. The bellmouthing of the exhaust-valve guides is believed to have been a result of the heavy carbon and lead-oxide deposits, which were present on the head end of the guided length of the exhaust-valve stem. Engine operational the conditions of this test was shown to result In a fuel saving of 16.8 percent on a cooled-power basis as compared with operation at the conditions recommended for this engine by the Army Air Forces for the same power.

ENGINE CYLINDERS-WEAR↗