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All sourcesNASA NTRSDOE OSTI
NASA NTRS1996

Corrosion of Mullite by Molten Salts

The interaction of molten salts of different Na2O activities and mullite is examined with furnace and burner tests. The more-acidic molten salts form small amounts of Al2O3; the more-basic molten salts form various Na2O-Al2O3-SiO2 compounds. The results are interpreted using the Na2O-Al203-SiO2 ternary phase diagram, and some possible diffusion paths are discussed. The generally higher melting points of Na2O-Al2O3-SiO2 compounds lead to better behavior of mullite in molten salts, as compared to SiO2-protected ceramics such as SiC. Mullite-coated SiC is discussed, and the corrosion behavior is evaluated.

Jacobson, Nathan S.↗
NASA NTRS1983

Conduit for high temperature transfer of molten semiconductor crystalline material

A conduit for high temperature transfer of molten semiconductor crystalline material consists of a composite structure incorporating a quartz transfer tube as the innermost member, with an outer thermally insulating layer designed to serve the dual purposes of minimizing heat losses from the quartz tube and maintaining mechanical strength and rigidity of the conduit at the elevated temperatures encountered. The composite structure ensures that the molten semiconductor material only comes in contact with a material (quartz) with which it is compatible, while the outer layer structure reinforces the quartz tube, which becomes somewhat soft at molten semiconductor temperatures. To further aid in preventing cooling of the molten semiconductor, a distributed, electric resistance heater is in contact with the surface of the quartz tube over most of its length. The quartz tube has short end portions which extend through the surface of the semiconductor melt and which are lef bare of the thermal insulation. The heater is designed to provide an increased heat input per unit area in the region adjacent these end portions.

Fiegl, George↗
NASA NTRS2010

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Shchetkovskiy, Anatoliy↗
NASA NTRS2010

Corrosion-Resistant Container for Molten-Material Processing

In a carbothermal process, gaseous methane is passed over molten regolith, which is heated past its melting point to a temperature in excess of 1,625 C. At this temperature, materials in contact with the molten regolith (or regolith simulant) corrode and lose their structural properties. As a result, fabricating a crucible to hold the molten material and providing a method of contact heating have been problematic. Alternative containment approaches use a large crucible and limit the heat zone of the material being processed, which is inefficient because of volume and mass constraints. Alternative heating approaches use non-contact heating, such as by laser or concentrated solar energy, which can be inefficient in transferring heat and thus require higher power heat sources to accomplish processing. The innovation is a combination of materials, with a substrate material having high structural strength and stiffness and high-temperature capability, and a coating material with a high corrosion resistance and high-temperature capability. The material developed is a molybdenum substrate with an iridium coating. Creating the containment crucible or heater jacket using this material combination requires only that the molybdenum, which is easily processed by conventional methods such as milling, electric discharge machining, or forming and brazing, be fabricated into an appropriate shape, and that the iridium coating be applied to any surfaces that may come in contact with the corrosive molten material. In one engineering application, the molybdenum was fashioned into a container for a heat pipe. Since only the end of the heat pipe is used to heat the regolith, the container has a narrowing end with a nipple in which the heat pipe is snugly fit, and the external area of this nipple, which contacts the regolith to transfer heat into it, is coated with iridium. At the time of this reporting, no single material has been found that can perform the functions of this combination of materials, and other combinations of materials have not proven to be survivable to the corrosiveness of this environment. High-temperature processing of materials with similar constituencies as lunar regolith is fairly common. The carbo-thermal process is commonly used to make metallurgical-grade silicon for the semiconductor and solar-cell industries.

Stern, Theodore G.↗
NASA NTRS2010

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Shchetkovskiy, Anatoliy↗
NASA NTRS2020

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↗
NASA NTRSDate not supplied

Computational Tools to Design Molten Salt Electrolytes for High-Temperature Environments

Current Li-ion batteries are designed for a small operating window of 5 °C to 55 °C. Modifications to the electrolyte for operation in Mars atmosphere extended this range on the lower bound to ~ -40 °C. These operating-temperature ranges are far from those presented in high-temperature environments, such as the Venus surface, where temperatures are around 450 °C. Protecting the state-of-the-art Li-ion batteries require insulations that decreases the volumetric capacity and limiting the operational time-window. These unique challenges require a paradigm shift in materials used for designing high-temperature batteries. Molten salt electrolyte-based batteries offer a plausible route to designing high-temperature batteries. ZEBRA batteries are known to be one of the safest energy storage devices operating at 270-350 °C. Nitrate based eutectics, operating at 150 °C have also been used in Li-O2 batteries. In this study, we will examine molten-salt electrolyte transport and electrochemical properties using first-principles computations and benchmark against experiments. Further, we will present thermodynamics-based models for designing and predicting melting point of molten salt mixtures. Based on these computational tools, new molten salt mixtures designed with desired operating temperatures and electrochemical windows will be presented. Implications of these new eutectics in the context of high-temperature environment exploration will also be discussed.

Balachandran Radhakrishnan↗
NASA NTRSDate not supplied

System Modeling of a Lunar Molten Regolith Electrolysis Plant

Introduction: In-Situ Resource Utilization (ISRU) is the process of extracting local resources to produce commodities for propulsion, life support systems, and off-planet construction rather than transporting consumables from Earth. Molten Regolith Electrolysis (MRE) is a novel ISRU method of extracting oxygen gas and metal alloy from lunar regolith. The MRE process involves placing lunar regolith between two electrodes, through which current is passed, to melt the regolith and reduce the metal oxide constituents by direct electrolysis (e.g. FeO, SiO2, MgO, Al2O3) into oxygen gas and metal alloys. The oxygen is liquefied and used as propellant for landers, while the metals (e.g. Ferro-alloys) are further processed and used in structural building materials and parts manufacturing. A system model was developed that accounted for the major processes of an MRE plant (from excavation of raw materials to storage of products) to assess the feasibility of a lunar MRE plant. The System Engineering and Integration (SE&I) ISRU Modeling and Analysis (SIMA) team utilized its previously documented system sizing model, the Mission Analysis and Integration Tool (MAIT) [1] as framework of the system model. MAIT uses MATLAB/Simulink to integrate subsystem models into a complete system model of the MRE plant. Total mass, volume, and power requirements were computed for numerous iterations of a MRE plant. System Model: Figure 1: MRE Plant Block Diagram The regolith excavation model determines the mass and power needed to excavate sufficient regolith. The preheating auger initiates the regolith heating process before regolith enters the MRE re-actor to reduce the energy required to turn the solid into a molten liquid. The MRE reactor is modeled in COMSOL Multiphysics and based on the research by Dominguez, Sibille, and Schreiner [2, 3, 4]. This preliminary reactor model provides an accurate calculation of thermal equilibrium during electrochemical operation of the reactor system to assess the optimal mass and power required to process the inlet flow of regolith. The model also computes the outlet flowrates of oxygen and molten products. For this analysis, the primary components of the metal alloy considered were iron and silicon. The oxygen is then purified using an Yttrium Stabilized Zirconia (YSZ) electrode, followed by liquefaction using a 90K cryocooler to be stored as liquid oxygen in insulated cylindrical tanks. In future iterations of the system model, the molten metal tapped from the MRE reactor will undergo additional processing or refinement. However, downstream handling of metals is currently a technology gap that is missing a high TRL subsystem model. Therefore, for this analysis, the accumulated metal alloy stream terminates after leaving the MRE reactor. Study Goals: This analysis investigates multiple input variables to the system to determine the sensitivity of a (near) complete plant at full-scale. This preliminary investigation ran parametric sweeps on the MRE reactor geometry, electrical current supply, layers of multi-layer insulation (MLI) on the reactor, size of the electrodes in the oxygen purification model, and regolith composition (based on landing site location). Three production targets of oxygen (1,000, 10,000, and 50,000 kg/yr) were investigated for this analysis. The parametric sweeps conducted in this analysis provide valuable insight into the expected impact of the various model inputs on plant size. This information can be used to identify the most critical components of the plant and guide future decisions on allocating funding for research and development, providing subsystem developers with appropriate interfaces with downstream and upstream processes, and assessing the overall feasibility of MRE when compared to other ISRU plants. References: [1] Carlson, A. et al. (2024) ICES, ICES-2024-53. [2] Dominguez, D.A., and Sibille, L. (2011) AIAA, AIAA-2011-700. [3] Schreiner, S.S. (2015) MIT, Dissertation. [4] Schreiner, S.S. et al. (2016) ASR, 57(7), pp.1585-1603.

ISRU↗
NASA NTRS1964

A Possible Regenerative, Molten-Salt, Thermoelectric Fuel Cell

Molten or fused salts have been evaluated as possible thermoelectric materials because of the relatively good values of their figures of merit, their chemical stability, their long liquid range, and their ability to operate in conjunction with a nuclear reactor to produce heat. In general, molten salts are electrolytic conductors; therefore, there will be a transport of materials and subsequent decomposition with the passage of an electric current. It is possible nonetheless to overcome this disadvantage by using the decomposition products of the molten-salt electrolyte in a fuel cell. The combination of a thermoelectric converter and a fuel cell would lead to a regenerative system that may be useful.

SALT↗
NASA NTRS1982

Electromigration process for the purification of molten silicon during crystal growth

A process for the purification of molten materials during crystal growth by electromigration of impurities to localized dirty zones. In the Czochralski crystal growing process, the impurities are electromigrated away from the crystallization interface by applying a direct electrical current to the molten silicon for electromigrating the charged impurities away from the crystal growth interface. The edge-defined film-fed crystal growth process, a direct electrical current is applied between the two faces which are used in forming the molten silicon into a ribbon. The impurities, migrated to one side only of the crystal ribbon, may be removed or left in place. If left in place, they will not adversely affect the ribbon when used in solar collectors. The migration of the impurity to one side only of the silicon ribbon is especially suitable for use with asymmetric dies which preferentially crystallize uncharged impurities along one side or face of the ribbon.

Shlichta, P. J.↗
NASA NTRS1983

The study of integrated coal-gasifier molten carbonate fuel cell systems

A novel integration concept for a coal-fueled coal gasifier-molten carbonate fuel cell power plant was studied. Effort focused on determining the efficiency potential of the concept, design, and development requirements of the processes in order to achieve the efficiency. The concept incorporates a methane producing catalytic gasifier of the type previously under development by Exxon Research and Development Corp., a reforming molten carbonate fuel cell power section of the type currently under development by United Technologies Corp., and a gasifier-fuel cell recycle loop. The concept utilizes the fuel cell waste heat, in the form of hydrogen and carbon monoxide, to generate additional fuel in the coal gasifier, thereby eliminating the use of both an O2 plant and a stream bottoming cycle from the power plant. The concept has the potential for achieving coal-pile-to-busbar efficiencies of 50-59%, depending on the process configuration and degree of process configuration and degree of process development requirements. This is significantly higher than any previously reported gasifier-molten carbonate fuel cell system.

Source record↗
NASA NTRS1985

High stress shallow moonquakes - Evidence for an initially totally molten moon

Thermoelastic stress calculations show that if the moon was initially molten only in the outer few hundred kilometers, as in the magma ocean model of the moon, the highlands crust should be aseismic. In contrast, if the moon was initially totally molten, high stress (1 to more than about 3 kbar), shallow (0 to about 6 km deep), compressional moonquakes should be occurring in the highlands crust. Calculations of the minimum stress drops made for the 28 observed shallow moonquakes suggest that 3 of them probably have stress drops in the kbar range. Thus, these very limited seismic data are consistent with the model that the moon was initially totally molten.

Binder, A. B.↗
NASA NTRS1985

Metals Electroprocessing in Molten Salts

The present study seeks to explain the poor quality of solid electrodeposits in molten salts through a consideration of the effects of fluid flow of the electrolyte. Transparent cells allow observation of electrolyte circulation by a laser schlieren optical technique during the electrodeposition of solid zinc from the molten salt electrolyte, ZnCl2 - LiCl-KCl. Experimental variables are current, density, electrolyte composition, and cell geometry. Based on the results of earlier electrodeposition studies as well as reports in the literature, these parameters are identified as having the primary influence on cell performance and deposit quality. Experiments are conducted to measure the fluid flow patterns and the electrochemical cell characteristics, and to correlate this information with the morphology of the solid electrodeposit produced. Specifically, cell voltage, cell current, characteristic time for dendrite evolution, and dendrite growth directions are noted. Their relationship to electrolyte flow patterns and the morphology of the resulting electrodeposit are derived. Results to date indicate that laser schlieren imaging is capable of revealing fluid flow patterns in a molten salt electrolyte.

Sadoway, D. R.↗
NASA NTRS1985

Tidally forced viscous heating in a partially molten Io

Models of Io that generate most of their heat by viscous dissipation in a partially molten (perhaps nearly liquid) asthenosphere are developed: a partially molten asthenosphere model and a partially molten interior model. An approximate thermal analysis is carried out, suggesting the possibility of a stable steady state. The models are consistent with observations of widely dispersed hot spots on the Io surface that radiate most of Io's heat loss. The hot spots imply that magmas carry most of the dissipative heating that is naturally accounted for in the models.

Ross, M. N.↗
NASA NTRS1985

Destabilization of yttria-stabilized zirconia induced by molten sodium vanadate-sodium sulfate melts

The extent of surface destabilization of ZrO2 - 8 wt percent Y2O3 ceramic disks was determined after exposure to molten salt mixtures of sodium sulfate containing up to 15 mole percent sodium metavanadate (NaVO3) at 1173 K. The ceramic surface was observed to transform from the cubic/tetragonal to monoclinic phase, concurrent with chemical changes in the molten salt layer in contact with the ceramic. Significant attack rates were observed in both pure sulfate and metavanadate sulfate melts. The rate of attack was found to be quite sensitive to the mole fraction of vanadate in the molten salt solution and the partial pressure of sulfur trioxide in equilibrium with the salt melt. The observed parabolic rate of attack is interpreted to be caused by a reaction controlled by diffusion in the salt that penetrates into the porous layer formed by the destabilization. The parabolic rate constant in mixed sodium metavanadate - sodium sulfate melts was found to be proportional to the SO3 partial pressure and the square of the metavanadate concentration. In-situ Raman spectroscopic measurements allowed simultaneous observations of the ceramic phases and salt chemistry during the attack process.

Nagelberg, A. S.↗
NASA NTRS1990

Composite superconducting wires obtained by high-rate tinning in molten Bi-Pb-Sr-Ca-Cu-O system

The preparation of high-T(sub c) superconducting long composite wires by short-time tinning of the metal wires in a molten Bi-Pb-Sr-Ca-Cu-O compound is discussed. The application of this method to the high-T(sub c) materials is tested, possibly for the first time. The initial materials used for this experiment were ceramic samples with nominal composition Bi(1.5)Pb(0.5)Sr2Ca2Cu3O(x) and T(sub c) = 80 K prepared by the ordinary solid-state reaction, and industrial copper wires from 100 to 400 microns in diameter and from 0.5 to 1 m long. The continuously moving wires were let through a small molten zone (approximately 100 cubic mm). The Bi-based high-T(sub c) ceramics in a molten state is a viscous liquid and it has a strongly pronounced ability to spread on metal wire surfaces. The maximum draw rate of the Cu-wire, at which a dense covering is still possible, corresponds to the time of direct contact of wire surfaces and liquid ceramics for less than 0.1 s. A high-rate draw of the wire permits a decrease in the reaction of the oxide melt and Cu-wire. This method of manufacture led to the fabrication of wire with a copper core in a dense covering with uniform thickness of about h approximately equal to 5 to 50 microns. Composite wires with h approximately equal to 10 microns (h/d approximately equal to 0.1) sustained bending on a 15 mm radius frame without cracking during flexing.

Grozav, A. D.↗
NASA NTRS1992

Chronopotentiometry of refractory metals, actinides and oxyanions in molten salts: A review

The applications of chronopotentiometry to the study of electrochemical behavior of three technologically important areas of refractory metals, actinides, and oxyanions in molten salts are critically reviewed. Chronopotentiometry is a very versatile diagnostic tool to understand the reaction mechanism of the electrode processes for the electrochemical reduction/oxidation of these electroactive species in molten salt solutions. Well adherent, compact, and uniformly thick coatings of refractory metals may be electrodeposited from their solutions in molten salts.

Bansal, Narottam P.↗
NASA NTRS1997

Measurements of Thermophysical Properties of Molten Silicon by a High-Temperature Electrostatic Levitator

Several thermophysical properties of molten silicon measured by the high-temperature electrostatic levitator at JPL are presented. They are density, constant-pressure specific heat capacity, hemispherical total emissivity, and surface tension. Over the temperature range investigated (1350 less than T(sub m) less than 1825 K), the measured liquid density (in g/cc) can be expressed by a quadratic function, pi(P) = p(sub m) - 1.69 x 10(exp -4)(T - T(sub m)) - 1.75 x 10(exp -7)((T - T(sub m))(exp 2) with T(sub m) and p(sub m) being 1687 K and 2.56 g/cc, respectively. The hemispherical total emissivity of molten silicon at the melting temperature was determined to be 0.18, and the constant-pressure specific heat was evaluated as a function of temperature. The surface tension (in 10(exp -3) N/m) of molten silicon over a similar temperature range can be expressed by sigma(T) = 875 - 0.22( T - T(sub m)).

Rhim, W. K.↗