Moderate temperature Na cells. IV - VS2 and NbS2Cl2 as rechargeable cathodes in molten NaAlCl4
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Abraham, K. M.↗
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Molten Slag Would Boost Coal Conversion
Reactor increases residence time of uncovered char. Near-100percent carbon conversion achievable in reactor incorporating moltenslag bath. Slag maintains unconverted carbon impinging on surface at high temperatures for longer period of time, enhancing conversion.
Ferrall, J. F.↗
Bubble behavior in molten glass in a temperature gradient
Gas bubble motion in a temperature gradient was observed in a sodium borate melt in a reduced gravity rocket experiment under the NASA SPAR program. Large bubbles tended to move faster than smaller ones, as predicted by theory. When the bubbles contacted a heated platinum strip, motion virtually ceased because the melt only imperfectly wets platinum. In some cases bubble diameter increased noticeably with time.
Meyyappan, M.↗
Molten-Salt Electrolysis
Concept of electrolytic decomposition of gaseous hydrogen sulfide to yield gaseous sulfur at anode and hydrogen gas at cathode considered.
Cubicciotti, D.↗
Moderate temperature sodium cells. V - Discharge reactions and rechargeability of NiS and NiS2 positive electrodes in molten NaAlCl4
NiS2 and NiS have been characterized as high energy density rechargeable positive electrodes for moderate-temperature Na batteries of the configuration, Na(1)/beta double prime-Al2O3/NaAlCl4(1), NiSx. The batteries operate in the temperature range 170 - 190 C. Positive electrode reactions during discharge/charge cycles have been characterized. Excellent rechargeability of the batteries has been demonstrated by extended cell cycling. A Na/NiS2 cell, operating at 190 C, exceeded 600 deep discharge/charge cycles with practically no capacity deterioration. The feasibility of secondary Na/NiSx batteries with specific energies equal to or greater than 50 Wh/lb and cycle lifes exceeding 1000 deep discharge/charge cycles has been demonstrated.
Abraham, K. M.↗
Molten salt corrosion of SiC: Pitting mechanism
Thin films of Na2SO4 and Na2CO3 at 1000 C lead to severe pitting of sintered alpha-SiC. These pits are important as they cause a strength reduction in this material. The growth of product layers is related to pit formation for the Na2CO3 case. The early reaction stages involve repeated oxidation and dissolution to form sodium silicate. This results in severe grain boundary attack. After this a porous silica layer forms between the sodium silicate melt and the SiC. The pores in this layer appear to act as paths for the melt to reach the SiC and create larger pits.
Jacobson, N. S.↗
Kinetics and mechanism of corrosion of SiC by molten salts
Corrosion of sintered alpha-SiC under thin films of Na2CO3/CO2, Na2SO4/O2, and Na2SO4/SO3 was investigated at 1000 C. Chemical analysis was used to follow silicate and silica evolution as a function of time. This information coupled with morphology observations leads to a detailed corrosion mechanism. In all cases the corrosion reactions occur primarily in the first few hours. In the Na2CO3/CO2 case, rapid oxidation and dissolution lead to a thick layer of silicate melt in about 0.25 h. After this, silica forms a protective layer on the carbide. In the Na2SO4/O2 case, a similar mechanism occurs. In the Na2SO4/SO3 case, a porous nonprotective layer of SiO2 grows directly on the carbide, and a silicate melt forms above this. In addition, SiO2 and regenerated Na2SO4 form at the melt/gas interface due to reaction of silicate with SO3 and SO2 + O2. The reaction slows when the lower silica layer becomes nonporous.
Jacobson, N. S.↗
Analysis of molten metal
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Corrosion pitting of SiC by molten salts
The corrosion of SiC by thin films of Na2CO3 and Na2SO4 at 1000 C is characterized by a severe pitting attack of the SiC substrate. A range of different Si and SiC substrates were examined to isolate the factors critical to pitting. Two types of pitting attack are identified: attack at structural discontinuities and a crater-like attack. The crater-like pits are correlated with bubble formation during oxidation of the SiC. It appears that bubbles create unprotected regions, which are susceptible to enhanced attack and, hence, pit formation.
Jacobson, N. S.↗
Molten-salt corrosion of silicon nitride. I - Sodium carbonate. II - Sodium sulfate
An experimental study of the corrosion of Si3N4 under thin films of Na2CO3 at 1000 C has been conducted using both pure Si3N4 and Si3N4 with various additives. The reaction mechanism is shown to consist of: (1) the decomposition of Na2CO3 and the formation of Na2SiO3; (2) rapid oxidation; and (3) the formation of a protective silica layer below the silicate. In the second part, the corrosion mechanism of Si3N4 + Na2SO4/O2 at 1000 C was studied for both pure and additive-containing Si3N4. The reaction of Si3N4 + Na2SO4 was found to involve an initial period of slow weight loss (due to Na2SO4 vaporization and oxidation-dissolution) followed by further oxidation or the near termination of the reaction, depending on the Si3N4 additive.
Fox, Dennis S.↗
Molten salt corrosion of SiC and Si3N4
Industrial systems such as heat engines and heat exchangers involve harsh environments. The structural materials are subjected to high temperatures as well as corrosive gases and condensed phases. Past experience with metal alloys has shown that these condensed phases can be particularly corrosive and are often the limiting factor in the operation of these systems. In a heat engine the most common condensed corrodent is Na2SO4 whereas in a heat exchanger an oxide slag may be present. The primary emphasis is on Na2SO4 induced corrosion, however, similarities and differences to oxide slag are also discussed. The extensive research on corrosion of metal alloys has led to understanding and controlling corrosion for these materials. Currently silicon based ceramics are prime candidates for the applications discussed. Therefore it is important to understand the effects of condensed phase deposits on this emerging class of high temperature materials. Both the thermodynamic and strength of the ceramic is also examined. Finally some control strategies for corrosion of silicon based ceramics are explored.
Jacobson, Nathan S.↗
Densities of some molten fluoride salt mixtures suitable for heat storage in space power applications
Liquid densities were determined for a number of fluoride salt mixtures suitable for heat storage in space power applications, using a procedure that consisted of measuring the loss of weight of an inert bob in the melt. The density apparatus was calibrated with pure LiF and NaF at different temperatures. Density data for safe binary and ternary fluoride salt eutectics and congruently melting intermediate compounds are presented. In addition, a comparison was made between the volumetric heat storage capacity of different salt mixtures.
Misra, Ajay K.↗
Identification of relict phases in a once-molten Allende inclusion
Fassaite rims around spinel grains that are enclosed entirely by normally zoned cores of melilite crystals are interpreted as relict grains which predate the melting of Allende type B1 refractory inclusions. Nonrelict subliquidus fassaite did not begin crystallizing from melts of these compositions until the onset of precipitation of the reversely zoned melilite mantles around the same melilite crystal cores. Relict fassaite is fractionated and highly enriched in REE and other refractory lithophiles compared to subliquidus fassaite in the same inclusion. Mass balance suggests that the relict fassaite represents only 3 percent of the original premelt amount of fassaite, and that melilite and at least one other phase were additional condensate precursors of these inclusions.
Kuehner, Scott M.↗
Molten (Mg0.88Fe0.12)2SiO4 at lower mantle conditions - Melting products and structure of quenched glasses
Infrared spectra of quenched magnesium silicate glasses synthesized by fusing olivine at pressures in excess of 50 GPa and temperatures greater than 2500 K demonstrate that silicon is dominantly present in four-fold coordination with respect to oxygen within these quenched glasses. This low coordination is attributed, by analogy with the structural behavior of glasses compressed at 300 K, to the instability of higher coordinations in glasses of these compositions on decompression. Spectra of glasses formed in a hydrous environment document that water is extensively soluble in melts at these high pressures and temperatures. Also, these results are consistent with the melting of (Mg0.88Fe0.12)2SiO4 compositions to liquids near pyroxene in stoichiometry under these conditions, with iron-rich magnesiowuestite being the liquidus phase.
Williams, Quentin↗
Oxygen production by electrolysis of molten lunar regolith
The goal of this study was threefold. First, the theoretical energy requirements of the process were to be defined. This includes studies of the relevant oxidation-reduction reactions in the melt, their kinetics and energies of reaction, and experimental determination of production efficiencies and melt resistivities as functions of melt composition and applied potential. Second, the product(s) of silicate electrolysis were to be characterized. This includes: (1) evaluating the phase relationships in the systems SiO2-TiO2-Al2O3-MgO-FeO-CaO and Fe-Si; (2) estimating the compositions of the metal products as a function of applied potential and feedstock composition based on phase equilibria in the Fe-Si system and free energy values for SiO2 and FeO reported in the literature; (3) definition of compositions of products in actual experiments; and (4) definition of the form the product takes (whether phases separate or remain fixed, whether crystals settle or float in the remaining melt, and how large crystals form). Third, materials for these highly corrosive high-temperature silicate melts were to be identified. This includes identifing materials that may be either inert or thermodynamically stable in these melts, and experimental testing of the materials to confirm that they do not deteriorate. The results are discussed within this framework.
Haskin, Larry A.↗
Pulsed power molten salt battery
It was concluded that carbon cathodes with chlorine work well. Lithium alloy chlorine at 450 C, 1 atm given high power capability, high energy density, DC + pulsing yields 600 pulses, no initial peak, and can go to red heat without burn-up. Electrochemical performance at the cell and cell stack level out under demanding test regime. Engineering and full prototype development for advancing this technology is warranted.
Argade, Shyam D.↗
The electrodynamic and hydrodynamic phenomena in magnetically-levitated molten droplets. I - Steady state behavior
A mathematical formulation is given and computed results are presented describing the behavior of electromagnetically-levitated metal droplets under the conditions of microgravity. In the formulation the electromagnetic force field is calculated using a modification of the volume integral method and these results are then combined with the FIDAP code to calculate the steady state melt velocities. The specific computational results are presented for the conditions corresponding to the planned IML-2 Space Shuttle experiment, using the TEMPUS device, which has separate 'heating' and 'positioning' coils. While the computed results are necessarily specific to the input conditions, some general conclusions may be drawn from this work. These include the fact that for the planned TEMPUS experiments to positioning coils will produce only a weak melt circulation, while the heating coils are like to produce a mildly turbulent recirculating flow pattern within the samples. The computed results also allow us to assess the effect of sample size, material properties and the applied current on these phenomena.
Zong, Jin-Ho↗
The electrodynamic and hydrodynamic phenomena in magnetically-levitated molten droplets. II - Transient behavior and heat transfer considerations
Computed results are presented describing the transient evolution of the velocity and the temperature fields in a levitation-melted, electromagnetically-positioned metallic sample under microgravity, for conditions, when the heating current is switched off. Thus the calculations trace the evolution from one steady state corresponding to the simultaneous operation of both the heating and the positioning coils to that corresponding to the operation of the positioning coils only. The calculations have shown that the velocity field will decay much more rapidly than the temperature field, so that the cooling and subsequent undercooling and recalescence of the samples should take place from an essentially stagnant melt, meeting the original objectives of the experiment. The computed results for the velocity decay appear to agree with asymptotic calculations and also appear to follow the scaling laws.
Zong, Jin-Ho↗