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Ray, C. S.

Publications and source records attributed to Ray, C. S..

At least 19 records

Hydrogen Reduction of Ilmenite from Lunar Regolith

Each ascent vehicle returning from the lunar surface with a crew vehicle will require several tons of fuel. Most architecture studies of lunar exploration vehicles use liquid oxygen for fuel, either for LOX/LH2 or LOX/methane. Utilization of oxygen generated on the lunar surface saves mass launched from Earth, with a multiplication factor on the order of 4-5, e.g. production and utilization of 4 tons of lunar oxygen for the ascent vehicle saves 16-20 tons of initial mass in low Earth orbit (IMLEO). The paper discusses ongoing MSFC activity on oxygen production by hydrogen reduction of Ilmenite. Specifically the important project milestone is to develop the Technology Readiness Level for the generation of lunar oxygen for propellant production from 3 to 5. The paper will provide an overview of the processes for Oxygen Generation, Complete Systems Architecture for a pilot lunar plant, experimental apparatus development and initial experimental results, and future directions.

Ramachandran, N.↗

XRD, TEM, IR, Raman and NMR Spectroscopy of In Situ Crystallization of Lithium Disilicate Glass

The structure of a Li2O-2SiO2 (LS2) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 C respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si-O-Si bond angle approx.7deg lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa a new high pressure form of lithium metasilicate crystallizes. The new phase, while having lithium metasilicate crystal symmetry, contains at least 4 different Si sites. NMR results for 6 GPa sample indicate the presence of Q4 species with (Q(sup 4))Si-O-Si(Q(sup 4)) bond angles of approx.157deg. This is the first reported occurrence of Q(sup 4) species with such large bond angles in alumina free alkali silicate glass. No five- or six- coordinated Si are found.

Fuss, T.↗

Determining Kinetic Parameters for Isothermal Crystallization of Glasses

Non-isothermal crystallization techniques are frequently used to determine the kinetic parameters for crystallization in glasses. These techniques are experimentally simple and quick compared to the isothermal techniques. However, the analytical models used for non-isothermal data analysis, originally developed for describing isothermal transformation kinetics, are fundamentally flawed. The present paper describes a technique for determining the kinetic parameters for isothermal crystallization in glasses, which eliminates most of the common problems that generally make the studies of isothermal crystallization laborious and time consuming. In this technique, the volume fraction of glass that is crystallized as a function of time during an isothermal hold was determined using differential thermal analysis (DTA). The crystallization parameters for the lithium-disilicate (Li2O.2SiO2) model glass were first determined and compared to the same parameters determined by other techniques to establish the accuracy and usefulness of the present technique. This technique was then used to describe the crystallization kinetics of a complex Ca-Sr-Zn-silicate glass developed for sealing solid oxide fuel cells.

Ray, C. S.↗

Isothermal Analysis of the Crystallization Kinetics in Lithium Disilicate Glass using Trans Temp Furnace

Crystallization kinetics for lithium disilicate, Li2O2SiO2, (LS2) glass has been studied extensively by nonisothermal methods, but only a few studies on the isothermal crystallization kinetics of LS2 are available. In the present research, isothermal crystallization experiments or the LS2 glass were conducted in a Trans Temp furnace between 600 and 635 C, and selected properties such as the activation energy for crystallization (E), crystal growth index or Avrami parameter (n), the concentration of quenched-in nuclei in the starting glass (Ni) and the crystal nucleation rate (I) were measured. The crystal nucleation rate (I) was measured at only one selected temperature of 452 C, at this time. This commercial furnace has a 13 cm long isothermal heating zone (+/- 1 C) that allows precise heat treatment of relatively large samples. By placing a thermocouple within approx. 2 mm of the sample, it was possible to detect the heat of crystallization in the form of an isothermal crystallization exotherm during isothermal heat treatment of the sample. The values of E (318 plus or minus 10 kJ/mol), n (3.6 plus or minus 0.l), and N(sub i) (1.6 x 10(exp l2) m(sup -3)) calculated by analyzing these isotherms using the standard Johnson-Mehl-Avrami (JMA) equation were reproducible and in agreement with the literature values. The value of I, 1.9 x 10(exp 10) m(sup -3) s(sup -1) at 452 C, is an order of magnitude higher than the reported value for LS2.

Fuss, T.↗

Containerless Processing of a Lithium Disilicate Glass

Glasses of Li2O.2SiO2 (LS2) and LS2 doped with 0.001 wt% platinum (LS2 + 0.001 wt% Pt) compositions were melted, cooled and re-heated at controlled rates while levitated (containerless) inside an Electrostatic Levitator (ESL) furnace at NASA Marshall Space Flight Center. The experiments were conducted in vacuum using spherical 2.5 - 3.0 mm diameter glass samples. The measured critical cooling rate for glass formation, Rc, for the LS2 and LS2 + 0.001 wt% Pt glasses processed at ESL were 14 plus or minus 2 C/min and 130 plus or minus 5 C/min, respectively. The values of Rc for the same LS2 and LS2 + 0.001 wt% Pt glasses processed in a container were 62 plus or minus 3 C/min and 162 plus or minus 5 C/min, respectively. The effective activation energy for crystallization, E, for the LS2 glass processed without a container at ESL was higher than that for an identical glass processed in a container. These results suggest that the glass formation tendency for a containerless LS2 melt is significantly increased compared to an identical melt in contact with a container. The absence of heterogeneous nucleation sites that are inherently present in all melts held in containers is believed to be the reason for the increased glass forming tendency of this containerless melt.

Ranasinghe, K. S.↗

In-Situ Crystallization of a Lithium Disilicate Glass--Effect of Pressure on Crystal Growth Rate

Crystallization of a Li2O.2SiO2 (LS2) glass subjected to a uniform hydrostatic pressure of 4.5 GPa and 6 GPa was investigated up to a temperature of 750 C. The density of the compressed glass is about 2% greater at 4.5 GPa than at 1 atm and, depending upon the processing temperature, up to 10% greater at 6 GPa. Crystal growth rates investigated as a function of temperature and pressure show that lithium disilicate crystal growth is an order of magnitude slower at 4.5 GPa than 1 atm resulting in a shift of +45 C (plus or minus 10 C) in the growth rate curve at high pressure compared to 1 atm condition. At 6 GPa lithium disilicate crystallization is suppressed entirely, while a new high pressure lithium metasilicate crystallizes at temperatures 95 C (plus or minus 10 C) higher than those reported for lithium disilicate crystallization at 1 atm. The decrease in crystal growth rate with increasing pressure for lithium disilicate glass up to 750 C is related to an increase in viscosity with pressure associated with fundamental changes in glass structure accommodating densification.

Fuss, T.↗

A Viable Scheme for Elemental Extraction and Purification Using In-Situ Planetary Resources

NASA's new strategic direction includes establishing a self-sufficient, affordable and safe human and robotic presence outside the low earth orbit. Some of the items required for a self-sufficient extra-terrestrial habitat will include materials for power generation (e.g. Si for solar cells) and habitat construction (e.g. Al, Fe, and Ti). In this paper we will present a viable elemental extraction and refining process from in-situ regolith which would be optimally continuous, robotically automated, and require a minimum amount of astronaut supervision and containment facilities, The approach is based on using a concentrated heat source and translating sample geometry to enable simultaneous oxide reduction and elemental refining. Preliminary results will be presented to demonstrate that the proposed zone refining process is capable of segregating or refining important elements such as Si (for solar cell fabrication) and Fe (for habitat construction). A conceptual scheme will be presented whereby such a process could be supported by use of solar energy and a precursor robotic mission on the surface of the moon.

Sen, S.↗

Glass and Glass-Ceramic Materials from Simulated Composition of Lunar and Martian Soils: Selected Properties and Potential Applications

In-situ resource processing and utilization on planetary bodies is an important and integral part of NASA's space exploration program. Within this scope and context, our general effort is primarily aimed at developing glass and glass-ceramic type materials using lunar and martian soils, and exploring various applications of these materials for planetary surface operations. Our preliminary work to date have demonstrated that glasses can be successfully prepared from melts of the simulated composition of both lunar and martian soils, and the melts have a viscosity-temperature window appropriate for drawing continuous glass fibers. The glasses are shown to have the potential for immobilizing certain types of nuclear wastes without deteriorating their chemical durability and thermal stability. This has a direct impact on successfully and economically disposing nuclear waste generated from a nuclear power plant on a planetary surface. In addition, these materials display characteristics that can be manipulated using appropriate processing protocols to develop glassy or glass-ceramic magnets. Also discussed in this presentation are other potential applications along with a few selected thermal, chemical, and structural properties as evaluated up to this time for these materials.

Ray, C. S.↗

Processing of Lunar Soil Simulant for Space Exploration Applications

NASA's long-term vision for space exploration includes developing human habitats and conducting scientific investigations on planetary bodies, especially on Moon and Mars. Processing and utilization of planetary in-situ resources is recognized as an important element of this vision since it can minimize the level of up-mass that will have to be transported from earth to the planetary bodies. Within this scope and context, we have undertaken a general effort aimed primarily at extracting and refining metals, developing glass, glass-ceramic, or traditional ceramic type materials using lunar soil simulants. In this paper we will present preliminary results on our effort on simultaneous carbothermal reduction of oxides for elemental extraction and zone refining for obtaining high purity metals. In additions we will demonstrate the possibility of developing glass fibers as reinforcement agents for planetary habitat construction, glasses for fixing nuclear waste from potential nuclear power generators, and glasses for magnetic applications. The paper will also include initial thermal characterization of the glasses produced from lunar simulant. Compositional analysis of processed samples will be presented.

Sen, Subhayu↗

Crystallization of a Li2O2SiO2 Glass under High Hydrostatic Pressures

The crystallization behavior of a Li2O.2SiO2 (LS2) glass subjected to a uniform hydrostatic pressure of 4.5 or 6 GPa was investigated between 550 and 800 C using XRD, IR, Raman, TEM, NMR, and DTA. The density of the glass subjected to 6 GPa was between 2.52 plus or minus 0.01 and 2.57 plus or minus 0.01 grams per cubic centimeters, depending upon the processing temperatures, and was higher than that of the stoichiometric LS2 crystals, 2.46 plus or minus 0.01 grams per cubic centimeter. Thus, crystallization in 6 GPa glass occurred in a condition of negative volume dilatation, deltaV = V(sub glass) - V(sub crystal), while that for the 4.5 GPa glass occurred in the condition deltaV greater than 0. For deltaV greater than 0, which also includes the control glass at ambient (one atmosphere) pressure, the glasses always crystallize Li2Si2O5 (orthorhombic, Ccc2) crystals, but for deltaV less than 0 (6 GPa), the glasses crystallize Li2SiO3 crystals with a slightly deformed structure. The crystal growth rate vs. temperature curve moved to higher temperature with increasing pressure, and was independent of the sign of deltaV. These results for the effect of hydrostatic pressure on the crystallization of LS2 glass were discussed from thermodynamic considerations.

Fuss, T.↗

Verification of an Analytical Method for Measuring Crystal Nucleation Rates in Glasses from DTA Data

A recently proposed analytical (DTA) method for estimating the nucleation rates in glasses has been evaluated by comparing experimental data with numerically computed nucleation rates for a model lithium disilicate glass. The time and temperature dependent nucleation rates were predicted using the model and compared with those values from an analysis of numerically calculated DTA curves. The validity of the numerical approach was demonstrated earlier by a comparison with experimental data. The excellent agreement between the nucleation rates from the model calculations and fiom the computer generated DTA data demonstrates the validity of the proposed analytical DTA method.

Ranasinghe, K. S.↗

Developing Glassy Magnets from Simulated Composition of Martian Soil for Exploration Applications

The long-term exploration goals of NASA include developing human habitation on Mars and conducting scientific investigations on Mars and other planetary bodies. In situ resource processing is a key objective in this area. We focus on the possibility of making magnetic glasses in situ for potential applications development. The paper will focus on ongoing work at NASA Marshall Space Flight Center on making magnetic glass from Mars soil simulants and its characterization. Analysis of the glass morphology, strength, chemistry and resulting magnetic properties will provide a fundamental understanding of the synthesized material that can be used for potential applications development. in an effort to characterize the magnetic properties of the Mars glasses, a series of tests were performed at NASA MSFC. Preliminary tests indicated that the glasses were attracted to a magnet and also had a small amount of residual magnetism. They were opaque (almost black in color). As the first step, a sample of Mars 1 glass (approx.1 mm x 1 mm x 5 mm length) was machined, weighed and its hysteresis curve was measured using a Vibration Sample Magnetometer (VSM). Next, a small furnace was designed and built and the sample was baked in a graphite (reducing agent) crucible at 800 C in an Argon atmosphere for 3 hours in the presence of a uniform, transverse (transverse to the 5mm length of the sample) magnetic field of 0.37 Tesla. The treated sample showed reddening on the outside and showed substantially increased residual magnetism. This sample was again analyzed in the VSM. The data clearly showed that some chemical change occurred during the heat treatment (color change) and that both the glasses have useful magnetic properties. Although no orientation effects of the magnetic field were considered, the data showed the following: 1. Both glass samples are primarily soft magnets and display ferromagnetic behavior (hysteresis, saturation, etc.) 2. The treated glass has improved saturation magnetism (order of magnitude increase), retentivity (factor of 6 increase) and susceptibility (order of magnitude increase) compared to the untreated glass 3. The untreated sample has higher coercivity (approx.50% that of Nickel) than the treated sample 4. Both samples have similar energy density. Results from a systematic study to quantify the effects of processing conditions such as heat treatment, atmosphere, containerless processing (by electrostatic levitation), and applications of external magnetic fields of different strengths will be discussed. Efforts on optimizing the magnetic properties of the product and the feasibility of using it for a couple of specific magnetic applications such as heat generation using an ac field and for electro forming will also be covered. The latter is an in situ manufacturing technique being studied for in-space fabrication applications at MSFC.

Ramachandran, N.↗

Effect of Pt Doping on Nucleation and Crystallization in Li2O.2SiO2 Glass: Experimental Measurements and Computer Modeling

Heterogeneous nucleation and its effects on the crystallization of lithium disilicate glass containing small amounts of Pt are investigated. Measurements of the nucleation frequencies and induction times with and without Pt are shown to be consistent with predictions based on the classical nucleation theory. A realistic computer model for the transformation is presented. Computed differential thermal analysis data (such as crystallization rates as a function of time and temperature) are shown to be in good agreement with experimental results. This modeling provides a new, more quantitative method for analyzing calorimetric data.

Narayan, K. Lakshmi↗

Non-Isothermal Calorimetric Studies of the Crystallization of Lithium Disilicate Glass

The influence of preannealing treatments on the polymorphic crystallization of lithium disilicate glasses is examined. As expected, glasses heated at different rates through the temperature range where there is significant nucleation develop widely different numbers of nuclei. This can dramatically influence the stability and transformation characteristics of the annealed glass. Non-isothermal differential scanning calorimetry (DSC) and differential thermal analysis (DTA) measurements are demonstrated to be useful to probe the nucleation behavior. The first systematic investigations of particle size effects on the non-isothermal transformation behavior are presented and discussed. Based on DTA and microscopy experiments, we show that small particles of lithium disilicate glasses crystallize primarily by surface crystallization. The relative importance of surface versus volume crystallization is examined by varying particle size, by introducing nucleating agents and by exposing glasses to atmospheres of different water content. These data are analyzed quantitatively using a numerical model developed in a second paper following in this volume.

Ray, C. S.↗

Computer Modeling of Non-Isothermal Crystallization

A realistic computer model for simulating isothermal and non-isothermal phase transformations proceeding by homogeneous and heterogeneous nucleation and interface-limited growth is presented. A new treatment for particle size effects on the crystallization kinetics is developed and is incorporated into the numerical model. Time-dependent nucleation rates, size-dependent growth rates, and surface crystallization are also included. Model predictions are compared with experimental measurements of DSC/DTA peak parameters for the crystallization of lithium disilicate glass as a function of particle size, Pt doping levels, and water content. The quantitative agreement that is demonstrated indicates that the numerical model can be used to extract key kinetic data from easily obtained calorimetric data. The model can also be used to probe nucleation and growth behavior in regimes that are otherwise inaccessible. Based on a fit to data, an earlier prediction that the time-dependent nucleation rate in a DSC/DTA scan can rise above the steady-state value at a temperature higher than the peak in the steady-state rate is demonstrated.

Kelton, K. F.↗

Containerless processing of glass forming melts in space

The near weightlessness of a material in the reduced gravity environment of space offers the opportunity of melting and cooling glass forming compositions without a container. This reduces the heterogeneous nucleation/crystallization which usually occurs at the walls of the container, thereby, extending the range of glass forming compositions. Based primarily on this idea, containerless glass forming experiments, which used a single axis acoustic levitator/furnace (SAAL), were conducted on SPAR rocket flights, 6 and 8, and on Space Shuttle mission, STS-7 and STS-61A. The experiments on the Space Shuttle were designed to include other studies related to melt homogenization and mixing, development of techniques for preparing uncontaminated preflight samples, and simple shaping experiments.

Day, D. E.↗

Glass formation in microgravity

An account is given of containerless glass-forming experiments conducted aboard the Space Shuttle in 1985, using a single-axis acoustic levitator furnace apparatus. An attempt was made to obtain quantitative evidence for the suppression of heterogeneous nucleation/crystallization in containerless melts under microgravity conditions, as well as to study melt homogenization in the absence of gravity-driven convection and assess the feasibility of laser fusion target glass microsphere preparation with a microgravity apparatus of the present type. A ternary calcia-gallia-silica glass thus obtained indicated a 2-3-fold increase in glass-formation tendency for this material composition in microgravity, by comparison with 1g.

Ray, C. S.↗

Containerless processing of glass forming melts: D-1, MEA/A-2 experiment 81F01 conducted on STS-61A flight, October 1985

Results of experiment 81F01, which was conducted in the Material Experiment Assembly MEA/A-2 on the D-1 Spacelab Mission (STS-61A), are presented. The general plan of the experiment was to heat, melt, and quench six spherical samples of different glass forming compositions while they were levitated in a single axis acoustic levitator furnace (SAAL). In addition, two non-melting sintered alumina samples were used to check the operational characteristics of the SAAL under reduced gravity conditions. Three of the eight samples were levitated between 1250 and 1500 C before the lack of coolant created an over-temperature condition that caused the SAAL to shut down prematurely. Two of the three samples processed were calcia-gallia-silica and soda-lime-silica glass forming compositions. Evidence of a two to three times increase in the tendency for glass formation was obtained for the calcia-gallia-silica. The final glass appeared reasonably homogeneous even though it was made from hot pressed powders containing deliberate heterogeneities. A photographic record was obtained of the microgravity sample processing sequences.

Day, D. E.↗