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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

A Method for Rapid and Precise Triple Oxygen Isotope Measurements via High-Temperature Conversion to CO Followed by Nickel-Catalyzed CO to CO 2 Conversion and Laser Spectroscopy

Triple oxygen isotopic compositions ( 16 O, 17 O, 18 O) have conventionally been measured via isotope ratio mass spectrometry using O 2 as an analyte. Conversion of sample oxygen to O 2 typically utilizes fluorination chemistry or catalytic equilibration between CO 2 and O 2 . Recently, laser spectroscopy has become a viable alternative for triple oxygen isotope (Δ' 17 O) measurements due to its ease and rapid throughput. Laser spectrometers are currently available for Δ' 17 O analysis of either H 2 O or CO 2 as the analyte gas. So far, these instruments have been used to measure Δ' 17 O of water, carbonate (CO 2 liberated by acid digestion), and atmospheric CO 2 samples. Here, we present a new method for high-precision Δ' 17 O analysis of CO 2 via tunable infrared laser direct absorption spectroscopy that is compatible with a wider range of geochemically important materials. This approach involves converting sample oxygen to CO 2 in two steps. First, the sample oxygen is liberated and reduced to CO by high-temperature conversion at 1450 °C in the presence of excess elemental carbon. Then, CO is catalytically converted to CO 2 over hot nickel at 350 °C. The conversion process is rapid (10 to 30 min) and quantitative. Spectroscopic Δ' 17 O analysis of the resulting CO 2 takes approximately 45 min. By measuring several oxygen isotope standards, we demonstrate that the method is precise (1σ = 12 per meg for procedural replicates) and accurate (within 11 per meg of previously reported values). The method can be applied to most pyrolytic materials where quantitative oxygen conversion is attainable, such as sulfate, phosphate, nitrate, and oxide minerals, water, and organic molecules.

Ellis, Nicholas M. [University of California, Berk↗
NASA NTRS1983

Materials for high-temperature thermoelectric conversion

High boron materials of high efficiency for thermoelectric power generation and capable of prolonged operation at temperatures over 1200 C are discussed. Background theoretical studies indicated that the low carrier mobility of materials with beta boron and related structures is probably associated with the high density of traps. Experimental work was mainly concerned with silicon borides in view of promising data from European laboratories. A systematic study using structure determination and lattice constant measurements failed to confirm the existence of an SiBn phase. Only SiB6 and a solid solution of silicon in beta boron with a maximum solid solubility of 5.5-6 at % at 1650 C were found.

Feigelson, R. S.↗
NASA NTRS1984

Materials for high-temperature thermoelectric conversion

The development of materials for high temperature thermoelectric energy conversion devices was investigated. The development of new criteria for the selection of materials which is based on understanding of the fundamental principles governing the behavior of high temperature thermoelectric materials is discussed. The synthesis and characterization of promising new materials and the growth of single crystals to eliminate possible problems associated with grain boundaries and other defects in polycrystalline materials are outlined.

Feigelson, R. S.↗
NASA NTRS1987

High-Temperature Thermoelectric Energy Conversion

Theory of thermoelectric energy conversion at high temperatures and status of research on conversion materials reviewed in report. Shows highest values of thermoelectric figure of merit, Z, found in semiconductor materials. Semiconductors keep wide choice of elements and compounds. Electrical properties tailored to particular application by impurity doping and control of stoichiometry. Report develops definition of Z useful for comparing materials and uses it to evaluate potentials of different classes of materialsmetals, semiconductors, and insulators.

Wood, C.↗
NASA NTRS1977

Low to high temperature energy conversion system

A method for converting heat energy from low temperature heat sources to higher temperature was developed. It consists of a decomposition chamber in which ammonia is decomposed into hydrogen and nitrogen by absorbing heat of decomposition from a low temperature energy source. A recombination reaction then takes place which increases the temperature of a fluid significantly. The system is of use for the efficient operation of compact or low capital investment turbine driven electrical generators, or in other applications, to enable chemical reactions that have a critical lower temperature to be used. The system also recovers heat energy from low temperature heat sources, such as solar collectors or geothermal sources, and converts it to high temperatures.

Miller, C. G.↗
NASA NTRS1984

High-temperature thermoelectric energy conversion. II - Materials survey

The current status of materials research for high-temperature thermoelectric energy conversion is reviewed. Two general classes of materials show promise for high temperature figure of merit (Z) values, viz, the rare-earth chalcogenides and the boron-rich borides. The electronic transport properties of the rare-earth chalcogenides are explicable on the basis of degenerate or partially degenerate n-type semiconductors. Boron and boron-rich borides exhibit p-type hopping conductivity, with detailed explanations proposed for the transport differing from compound to compound. Some discussion is presented on the reasons for the low thermal conductivities in these materials. Also, ZTs greater than one appear to have been realized at high temperature in many of these compounds.

Wood, C.↗
NASA NTRS1987

High temperature thermoelectric energy conversion

The theory and current status of materials research for high-temperature thermoelectric energy conversion are reviewed. Semiconductors are shown to be the preferred class of materials for this application. Optimization of the figure of merit of both broadband and narrow-band semiconductors is discussed as a function of temperature. Phonon scattering mechanisms are discussed, and basic material guidelines are given for reduction of thermal conductivity. Two general classes of materials show promise for high temperature figure of merit (Z) values, namely the rare earth chalcogenides and the boron-rich borides. The electronic transport properties of the rare earth chalcogenides are explicable on the basis of degenerate or partially degenerate n-type semiconductors. Boron and boron-rich borides exhibit p-type hopping conductivity, with detailed explanations proposed for the transport differing from compound to compound. Some discussion is presented on the reasons for the low thermal conductivities in these materials. Also, ZTs greater than one appear to have been realized at high temperature in many of these compounds.

Wood, Charles↗
NASA NTRS1984

High Temperature Thermoelectric Energy Conversion

The electronic and thermal transport properties of the most promising material systems for high temperature thermoelectric energy conversion are discussed from a theoretical and experimental viewpoint. Rare earth chalcogenides and boron-rich borides are considered in terms of thermal conductivity and transport mechanisms. Rare earth chalcogenides are generally n-type semiconductors and boron-rich borides are generally p-type semiconductors.

Wood, C.↗
NASA NTRS1992

Advanced materials for high-temperature thermoelectric energy conversion

A number of refractory semiconductors are under study at the Jet Propulsion Laboratory for application in thermal to electric energy conversion for space power. The main thrust of the program is to improve or develop materials of high figure of merit and, therefore, high conversion efficiencies over a broad temperature range. Materials currently under investigation are represented by silicon-germanium alloys, lanthanum telluride, and boron carbide. The thermoelectric properties of each of these materials, and prospects for their further improvements, are discussed. Continued progress in thermoelectric materials technology can be expected to yield reliable space power systems with double to triple the efficiency of current state of the art systems.

Vining, Cronin B.↗
NASA NTRS2014

Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas‐ and liquids‐rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC‐separated products was sent to a DSQ II quadrupole MS to make qualitative and semi‐quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II‐S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis‐GC‐MS‐TC‐IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from ~0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = ‐215.2 per mille (V‐SMOW), ranging from ‐ 271.8 per mille for the Marcellus Shale to ‐51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of ‐89.7 per mille, ranging from ‐156.0 per mille for the Barnett Shale to ‐50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas‐water or oil‐water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analyses. Understanding the role that these H‐bearing compounds play in terrestrial shale paleo‐environmental reconstruction may also prove useful as analogs for understanding the interactions of water and potential kerogen/organic compounds on the planet Mars.

Socki, Richard A.↗
NASA NTRS2013

Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleo-environmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analysis. More experiments are planned to discern these two or other possible scenarios.

Socki, Richard A.↗
NASA NTRS2013

Photo-Induced Deuterium Enrichment in Residues Produced from the UV Irradiation of Pyrimidine in H2O and H2O+NH3 Ices

Organic compounds found in meteorites often show isotopic signatures of their interstellar/protosolar heritage as enrichments in D and 15N. Meteoritic organics found to be enriched in D include amino acids, hydroxy and dicarboxylic acids, as well as polycyclic aromatic hydrocarbons (PAHs). Processes that can produce isotopic enrichments in presolar/protosolar materials include gas-phase ion-molecule reactions, gas-grain surface reactions, and unimolecular photo-dissociation reactions involving PAHs. Because many molecules in interstellar clouds are enriched in D, the presence of D anomalies in meteorites is thought to originate from preserved or slightly altered interstellar/protostellar materials. However, the link between isotopic enrichments seen in space and those in meteoritic compounds and their relationship remain unclear. In this work, we present results of hydrogen isotopic fractionation for compounds in organic residues produced from the UV irradiation using an H2- discharge UV lamp of H2O:pyrimidine = 20:1 and H2O:NH3:pyrimidine = 20:2:1 ice mixtures at low temperature (is less than 20 K). After irradiation, the resulting residues are dissolved in H2O and analyzed with gas chromatography-mass spectrometry coupled with isotope ratio mass spectrometry (GC-MS/IRMS) [1], following a protocol similar to that used for previous analyses of comparable samples [2,3]. We used this technique to measure compound-specific D/H isotopic ratios for the initial pyrimidine and for two photo-products present in the residues, namely, 2,2'-bipyrimidine and an unidentified bipyrimidine isomer [2-4]. Measuring D enrichments in bipyrimidines has the advantage that the H atoms on these molecules are not easily exchangeable with other compounds, in particular the H2O and NH3 present in the ices or the solvents used to extract the samples for GC-MS/IRMS measurements. The δD value for the initial pyrimidine, measured with a high-temperature conversion elemental analyzer connected to the IRMS, was found to be -30% per mille. Preliminary measurements made on a residue produced from the UV irradiation of an H2O:NH3:pyrimidine = 20:2:1 ice mixture indicate δD values of +118% per mille for 2,2'- bipyrimidine and +92% per mille for the other bipyrimidine isomer, and therefore show a significant D enrichment during the photo-processing and warm-up that lead to their formation [5]. New measurements are currently being performed on a number of residues produced from simpler H2O:pyrimidine = 20:1 ice mixtures under different experimental conditions and will be presented here.

Laboratory Astrochemistry↗
NASA NTRS1983

Refractory materials for high-temperature thermoelectric energy conversion

Theoretical work of two decades ago adequately explained the transport behavior and effectively guided the development of thermoelectric materials of high conversion efficiencies of conventional semiconductors (e.g., SiGe alloys). The more significant contributions involved the estimation of optimum doping concentrations, the reduction of thermal conductivity by solid solution doping and the development of a variety of materials with ZT approx. 1 in the temperature range 300 K to 1200 K. ZT approx. 1 is not a theoretical limitation although, experimentally, values in excess of one were not achieved. Work has continued with emphasis on higher temperature energy conversion. A number of promising materials have been discovered in which it appears that ZT 1 is realizable. These materials are divided into two classes: (1) the rare-earth chalcogenides which behave as itinerant highly-degenerate n-type semiconductors at room-temperature, and (2) the boron-rich borides, which exhibit p-type small-polaronic hopping conductivity.

Wood, C.↗
NASA NTRS1984

Refractory materials for high-temperature thermoelectric energy conversion

Theoretical work of two decades ago adequately explained the transport behavior and effectively guided the development of thermoelectric materials of high conversion efficiencies of conventional semiconductors (e.g., SiGe alloys). The more significant contributions involved the estimaiation of optimum doping concentrations, the reduction of thermal conductivity by solid solution doping and the development of a variety of materials with ZT approx. 1 in the temperature range 300 K to 1200 K. ZT approx. 1 is not a theoretical limitation although, experimentally, values in excess of one were not achieved. Work has continued with emphasis on higher temperature energy conversion. A number of promising materials have been discovered in which it appears that ZT 1 is realizable. These materials are divided into two classes: (1) the rare-earth chalcogenides which behave as itinerant highly-degenerate n-type semiconductors at room-temperature, and (2) the boron-rich borides, which exhibit p-type small-polaronic hopping conductivity.

Wood, C.↗
NASA NTRS1978

Thermal optical surface properties and high-temperature solar energy conversion

The effects of thermal surface properties on the performance of representative point focusing solar power plants are assessed in this paper. The tradeoff relationships are presented in terms of normalized system performance as a function of thermal optical design parameters. Crucial surface properties include solar reflectance, specular spreading due to microscopic roughness, surface error due to manufacturing slope tolerance or waviness and concentrator pointing accuracy. Two representative power conversion systems, a Rankine steam cycle and an open air Brayton cycle, are considered.

Wen, L.↗
NASA NTRS1987

Refractory semiconductors for high temperature thermoelectric energy conversion

Thermoelectric energy conversion utilizing nuclear heat sources has been employed for several decades to generate power for deep space probes. In the past, lead telluride and, more recently, silicon-germanium alloys have been the prime choices as thermoelectric materials for this application. Currently, a number of refractory semiconductors are under investigation at the Jet Propulsion Laboratory in order to produce power sources of higher conversion efficiency and, thus, lower mass per unit of power output. Included among these materials are improved Si-Ge alloys, rare earth compounds and boron-rich borides. The criteria used to select thermoelectric materials, in general, and the above materials, in particular, will be discussed. The current state of the art and the accomplishments to date in thermoelectric materials research will be reviewed.

Wood, Charles↗
NASA NTRSDate not supplied

Thermoradiative Conversion for Space Power Systems

The thermoradiative cell is a new method for converting heat energy to electrical power, first detailed by Strandberg in 2015. The cell is structurally similar to a photovoltaic cell, in that it is a p-n junction semiconductor device, but thermodynamically operates in the reverse direction, converting the thermal dark current into electrical power by utilizing the recombination radiation from thermally-generated electron hole pairs to radiate waste heat to space. This technology may have application for space missions in converting thermal energy produced by a radioisotope source or from a nuclear reactor into power. The power and efficiency can be calculated as a function of bandgap in the detailed-balance case (the Shockley-Queisser limit), in which all of the thermal emissivity of the cell is due to the recombination of thermally generated electron-hole pairs, and all other recombination losses are ignored. The current produced is directly proportional to the recombination radiation, and thus the more thermally generated pairs, the higher the current. The voltage is proportional to the external bias. These two constraints allow optimization of the optimum bias point for maximum power, and allow calculation of the efficiency at maximum power point. Unlike photovoltaic cells, the maximum power operating point is not the same as the maximum efficiency point, and higher efficiency can be achieved at a higher (negative) bias in the ideal case. Incorporating non-ideal losses, however, shifts the maximum efficiency point toward lower bias. Since a thermoradiative cell operates by radiating directly to space, the current produced by a themoradiative cells will increase with the Stefan-Boltzman radiative efficiency; roughly the fourth power of the temperature. Thus, in contrast to a photovoltaic converter, the power produced is highest at high operating temperatures. Likewise, in contrast to conventional thermal conversion, high radiator temperature increases, rather than decreases the efficiency. Thus, the thermoradiative conversion may fill a mission niche in which small radiator size is required. The basic operation will be summarized, applications to space power discussed, and the requirements for further research outlined.

Photovoltaic Cell↗
NASA NTRS1991

The use of low power dual mode nuclear thermal rocket engines to support space exploration missions

The evolution of dual mode concepts is presented, focusing on advantages and problems associated with both low and high temperature dual mode conversion systems. It is concluded that dual mode nuclear thermal rocket (NTR) systems using high temperature Brayton cycle conversion technology offer a high payoff enhancement of conventional NTR, with a comparatively minor increase of technological challenge. It is recommended that NTR engines be designed so that dual mode conversion systems can be attached to them in a modular way, thus enabling the production of electric power on all missions where it is needed.

Zubrin, Robert M.↗