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At least 163 records · Page 9

Skylab experiments on semiconductors and alkali halides

The space processing experiments performed during the Skylab missions included one on single crystal growth of germanium selenide and telluride, one on pure and doped germanium crystals, two on pure and doped indium antimonide, one on gallium-indium-antimony systems, and one on a sodium chloride-sodium fluoride eutectic. In each experiment, three ampoules of sample were processed in the multipurpose electric furnace within the Skylab Materials Processing Facility. All were successful in varying degrees and gave important information about crystal growth removed from the effects of earth surface gravity.

Lundquist, C. A.↗

Internal coating of air cooled gas turbine blades

Six coating systems were evaluated for internal coating of decent stage (DS) eutectic high pressure turbine blades. Sequential deposition of electroless Ni by the hydrazine process, slurry Cr, and slurry Al, followed by heat treatment provided the coating composition and thickness for internal coating of DS eutectic turbine blades. Both NiCr and NiCrAl coating compositions were evaluated for strain capability and ductile to brittle transition temperature.

Ahuja, P. L.↗

Olivine Weathering aud Sulfate Formation Under Cryogenic Conditions

High resolution photography and spectroscopy of the martian surface (MOC, HiRISE) from orbit has revolutionized our view of Mars with one of the most important discoveries being wide‐spread layered sedimentary deposits associated with sulfate minerals across the low to mid latitude regions of Mars. The mechanism for sulfate formation on Mars has been frequently attributed to playa‐like evaporative environments under prolonged warm conditions. An alternate view of the ancient martian climate contends that prolonged warm temperatures were never present and that the atmosphere and climate has been similar to modern conditions throughout most of its history. This view has had a difficult time explaining the sedimentary history of Mars and in particular the presence of sulfate minerals which seemingly need more water. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryo‐concentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars. This study seeks to test whether sulfate formation may be possible at temperatures well below 0degC in water limited environments removing the need for prolonged warm periods to form sulfates on early Mars. To test this idea we performed laboratory experiments to simulate weathering of mafic minerals under Mars‐like conditions. The weathering rates measured in this study suggest that fine grained olivine on Mars would weather into sulfate minerals in short time periods if they are exposed to H2SO4 aerosols at temperatures at or above ‐40degC. In this system, the strength of the acidic solution is maximized through eutectic freezing in an environment where the silicate minerals are extremely fine grained and have high surface areas. This provides an ideal environment despite the very low temperatures. On Mars the presence of large deposits of mixed ice and dust is undisputed. The presence of substantial sulfur‐rich volcanism, and sulfur‐rich surface deposits also makes it very likely that sulfate aerosols have also been an important component of the martian atmosphere. Thus mixtures of ice, dust, and sulfate aerosols are likely to have been common on the martian surface. Given the fact that it is not difficult to achieve surface temperatures above ‐40degC on Mars throughout its history, it seems likely that sulfate formation on Mars is controlled by the availability of sulfate aerosols and not by the martian climate. The current polar regions of Mars and Earth provide interesting analogs. Large regions of sulfaterich material have been detected on and around the modern north polar region of Mars. The prevalence of ice‐dust mixtures in this region and the existence of sulfates within the ice cap itself are strong evidence for the origin of the sulfates from inside the ice deposits. In addition sulfates have been found in ice deposits in Greenland and Mount Fuji on Earth that have been attributed to forming within the ice deposit. These sulfates can form either through interaction with dust particles in the atmosphere or through weathering inside the ice itself.

Niles, Paul B.↗

Feasibility Study of a Nuclear-Stirling Plant for the Jupiter Icy Moons Orbiter

NASA is undertaking the design of a new spacecraft to explore the planet Jupiter and its three moons Calisto, Ganymede and Europa. This proposed mission, known as Jupiter Icy Moons Orbiter (JIMO) would use a nuclear reactor and an associated electrical generation system (Reactor Power Plant-RPP) to provide power to the spacecraft. The JIMO spacecraft is envisioned to use this power for science and communications as well as Electric Propulsion (EP). Among other potential power-generating concepts, previous studies have considered Thermoelectric and Brayton Power conversion systems, coupled to a liquid metal reactor for the JIMO mission. This paper will explore trades in system mass and radiator area for a nuclear reactor power conversion system, however this study will focus on Stirling power conversion. The Stirling convertor modeled in this study is based upon the Component Test Power Convertor design that was designed and operated successfully under the Civil Space Technology Initiative for use with the SP-100 nuclear reactor i the 1980's and early 1990's. The study design is such that two of the four convertors would operate at any time to generate the 100 kWe while the others are held in reserve. For this study the Stirling convertors hot-side temperature is 1050 K, would operate at a temperature ratio of 2.4 for a minimum mass system and would have a system efficiency of 29%. The Stirling convertor would generate high voltage (400 volt), 100 Hz single phase AC that is supplied to the Power Management and Distribution system. The waste hear is removed from the Stirling convertors by a flowing liquid sodium-potassium eutectic and then rejected by a shared radiator. The radiator consists of two coplanar wings, which would be deployed after the reactor is in space. System trades were performed to vary cycle state point temperatures and convertor design as well as power output. Other redundancy combinations were considered to understand the affects of convertor size and number of spares to the system mass.

Schmitz, Paul C.↗

The promise of eutectics for aircraft turbines

The current status of the first generation eutectics, gamma/gamma transition - delta and NiTaC-13, is described in detail. Several second generation systems, such as gamma/gamma transition - alpha and NiTaC 3-116A, gamma - beta, and COTAC 74 are also reviewed with particular emphasis on their critical physical and mechanical properties, future research directions, and potential applications. Results of recent cost-benefit analyses of eutectic turbine blades are discussed.

Gray, H. R.↗

Comprehensive Data Analysis and Analytic Method Development for PBX9501 Material (FY2019 Annual Report of Aging and Lifetimes Program)

In the polymer bonded explosive (PBX) 9501, a binder consisting of 2.5 wt% nitroplasticizer (NP) and 2.5 wt% Estane R 5703 (Estane) is combined with 94.9 wt% of the high-explosive HMX and 0.1 wt% stabilizer. Because of its flexibility and tensile strength, this binder lowers the sensitivity and improves the manufacturability of PBX 9501. However, like many plasticizers comprised of low molecular weight components, NP has a tendency to diffuse out of the PBX 9501 matrix and can decompose at moderate temperatures into reactive byproducts, such as NO, NO 2 , H 2 O, and HNO x . Through oxidation and hydrolysis, these molecules can further degrade NP and Estane, ultimately degrading the properties of PBX 9501. While gaseous molecules can readily diffuse out of the PBX 9501 charges, the intermediates with lower volatility are more likely trapped in the condensed phase inside the charges and, in a closed system, will co-exist with Estane for an extended period of time creating an ongoing reactive environment. Understanding the rates of formation for these volatiles and intermediates during the NP degradation is therefore a critical prerequisite for understanding the long-term stability of polymeric binders used in munition systems. To work toward this ultimate goal, in the past year, we have conducted comprehensive studies on the physical properties of NP and finished three-year long aging experiment to understand the aging behavior of NP under thermal treatment. Important results are summarized in this annual report. Although NP is widely used in the DOE complex, their physical properties are rather scattered and inconsistent in the open literature. For example, there are at least two widely different values, 14.5°C and -15°C, for the melting point of NP. Although it is known that NP is a eutectic 50:50 mixture of BDNPA and BDNPF, their eutectic phase diagram is not well documented. Furthermore, the effect of temperature on the miscibility between water and eutectic BDNPA/F mixture is rarely reported. To fill these knowledge gaps, a large set of BDNPA/F mixtures with BDNPA concentration ranging from 0 to 100 wt% was analyzed using DSC techniques. In addition to determining the eutectic melt point as -25°C, a phase diagram of the BDNPA/F system was constructed from -30°C to 45°C. With this phase diagram, the phase transition temperatures and composition can be readily found for the BDNPA/F mixtures with various mass ratios.

36 MATERIALS SCIENCE↗

Design of a Mechanical NaK Pump for Fission Space Power Systems

Alkali liquid metal cooled fission reactor concepts are under development for mid-range spaceflight power requirements. One such concept utilizes a sodium-potassium eutectic (NaK) as the primary loop working fluid. Traditionally, linear induction pumps have been used to provide the required flow and head conditions for liquid metal systems but can be limited in performance. This paper details the design, build, and check-out test of a mechanical NaK pump. The pump was designed to meet reactor cooling requirements using commercially available components modified for high temperature NaK service.

Mireles, Omar R.↗

Ab initio molecular dynamics (AIMD) simulations of NaCl, UCl 3 molten salts

Ab initio molecular dynamics (AIMD) simulations are used to calculate select thermophysical and thermodynamic properties of NaCl, UCl and NaCl-UCl 3 molten salts. Following established approaches, the AIMD simulations include a model for Van der Waals interactions. The Langreth & Lundqvist (vDW-DF2), DFT-D3, and density-dependent energy correction (DFT-dDsC) dispersion models are first tested for molten NaCl in order to assess their accuracy for density and heat capacity predictions across a range of temperatures. Based on the NaCl results, the vdW-DF2 and DFT-dDsC methods are extended to the UCl 3 system and compared to available experimental data. Next, mixtures of NaCl-UCl 3 are investigated and analyzed with respect to the deviation from ideal solution behavior. For the DFT-dDsC simulations, density deviates by up to 2% from an ideal mixture, with the maximum occurring close to the eutectic composition. The mixing energy also deviates from an ideal solution and exhibits a minimum of about -0.074 to eV per formula unit, again close to the eutectic composition. Finally, the compressibility and species diffusivity of the pure and mixed salt systems are calculated. The diffusivities are slightly reduced in the mixed compared to the pure systems and the compressibilities loosely follow a linear correlation as a function of the UCl 3 composition. The trends observed for mixing properties are rationalized by correlating them to the coordination chemistry, which emphasizes the importance of maintaining the extended network formed by U and Cl ions as the NaCl concentration increases. The concentration at which breakdown of the extended network occurs, roughly coincides with the minimum of both the mixing energy and the deviation from ideal solution behavior for density.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electrodes for solid state devices

The invention relates to coated metal powders and to dispersions of such powders in liquid vehicles forming screenable, sinterable pastes for use in forming electrodes on photovoltaic devices. The primary nickel or copper metal particles are provided with a carrier of lower melting sintering metals such as 1-20% by weight, of a non-oxidizing metal such as lead or tin. The powdered metal systems operate on the basis of fusing together by way of eutectic alloying. As the paste is heated during firing the organic binder is first vaporized. An eutectic of the base metal (copper) and coating (tin) forms at the intersections of the base metal grains. This eutectic dissolves the grains and as the temperature is raised above the eutectic temperature, more of the base metal is dissolved. While the temperature is held at the higher value, the much smaller amount of sintering metal disappears as the eutectic dissolves and diffuses into the base metal until the composition of the eutectic is so enriched with base metal that it no longer has the eutectic properties and it solidifies. In this high temperature solidification, the base metal grains became thoroughly alloyed together and will not separate at the eutectic temperature (a lower temperature than their solidification by diffusion).

Bickler, D. B.↗

The volume change during solidification

The liquid-solid phase transformation of solidifying metallic melts is accompanied by a volume change Delta-Vm. This volume change produces a gravity-independent microscopic flow near the solidification front. In a ground-based laboratory, solidification processes are also affected by convection due to temperature and concentration gradients. A quantitative evaluation of the effects of these flows on the formation of structure requires reproducible values of Delta-Vm. Alloys with Delta-Vm = 0 would be best suited for such an evaluation, while alloys with a constant value for Delta-Vm are still usable. Another requirement is related to a solidus-liquidus interval which is as small as possible. One-phase alloys, which would be particularly well suited, could not be found. For these reasons, alloys which solidify in two phases, as for example eutectics, have been considered, taking into account the Al-Ge system. Attention is given to the volume change at the melting point, the measurement of this change, the volume change at solidification, and applications to terrestrial technology.

Rittich, M.↗

Design of a pool boiler heat transport system for a 25 kWe advanced Stirling conversion system

The overall operating temperature and efficiency of solar-powered Stirling engines can be improved by adding a heat transport system to more uniformly supply heat to the heater head tubes. One heat transport system with favorable characteristics is an alkali metal pool boiler. An alkali metal pool boiler heat transport system was designed for a 25-kW advanced Stirling conversion system (ASCS). Solar energy concentrated on the absorber dome boils a eutectic mixture of sodium and potassium. The alkali metal vapors condense on the heater head tubes, supplying the Stirling engine with a uniform heat flux at a constant temperature. Boiling stability is achieved with the use of an enhanced boiling surface and noncondensible gas.

Anderson, W. G.↗

Effect of Mn on eutectic phase equilibria in Al-rich Al-Ce-Ni alloys

Microstructural analysis of additively manufactured (AM) Al-Ce-Ni-Mn alloys has identified phases not predicted from existing ternary liquidus projections in the Al-Ce-Ni system. Because the rapid cooling rate of AM is orders of magnitude above that of traditional casting, it is unclear if these additional phases arose from the non-equilibrium processing conditions of AM, a drastic shift in phase stability in the system due to the addition of 1 wt% Mn, or some combination of these two influences. The phases and microstructure of cast samples of Al-Ce-Ni and Al-Ce-Ni-Mn alloys were characterized for several annealing conditions which revealed the equilibrium phases at different temperatures. Phase analysis confirmed that minute levels of Mn substituted for Ni in the system drastically shifts the liquidus projection in the Al-rich corner of the ternary phase diagram such that the eutectic Al 3 Ni phase is suppressed in favor of the Al 23 Ni 6 (Ce,Mn) 4 phase. Further addition of Mn promotes the formation of Al 20 Mn 2 Ce and Al 10 Mn 2 Ce phases. The phase analysis data was then used to improve the CALPHAD modeling of the liquidus projection and isothermal sections for the Al-rich Al-Ce-Ni-Mn quaternary system. Thermodynamic modeling and experimental analysis on phases in the AM sample of Al-Ce-Ni with Mn confirmed that the phases present are consistent with Mn-containing Al-Ce-Ni cast samples. Here, this investigation demonstrates the potential for using secondary alloying elements to drastically alter phase stability and microstructure in alloy systems.

36 MATERIALS SCIENCE↗

Cost/benefit studies of advanced materials technologies for future aircraft turbine engines: Materials for advanced turbine engines

Cost benefit studies were conducted on six advanced materials and processes technologies applicable to commercial engines planned for production in the 1985 to 1990 time frame. These technologies consisted of thermal barrier coatings for combustor and high pressure turbine airfoils, directionally solidified eutectic high pressure turbine blades, (both cast and fabricated), and mixers, tail cones, and piping made of titanium-aluminum alloys. A fabricated titanium fan blisk, an advanced turbine disk alloy with improved low cycle fatigue life, and a long-life high pressure turbine blade abrasive tip and ceramic shroud system were also analyzed. Technologies showing considerable promise as to benefits, low development costs, and high probability of success were thermal barrier coating, directionally solidified eutectic turbine blades, and abrasive-tip blades/ceramic-shroud turbine systems.

Stearns, M.↗

Experimental Results from the Thermal Energy Storage-2 (TES-2) Flight Experiment

Thermal Energy Storage-2 (TES-2) is a flight experiment that flew on the Space Shuttle Endeavour (STS-72), in January 1996. TES-2 originally flew with TES-1 as part of the OAST-2 Hitchhiker payload on the Space Shuttle Columbia (STS-62) in early 1994. The two experiments, TES-1 and TES-2 were identical except for the fluoride salts to be characterized. TES-1 provided data on lithium fluoride (LiF), TES-2 provided data on a fluoride eutectic (LiF/CaF2). Each experiment was a complex autonomous payload in a Get-Away-Special payload canister. TES-1 operated flawlessly for 22 hr. Results were reported in a paper entitled, Effect of Microgravity on Materials Undergoing Melting and Freezing-The TES Experiment, by David Namkoong et al. A software failure in TES-2 caused its shutdown after 4 sec of operation. TES-1 and 2 were the first experiments in a four experiment suite designed to provide data for understanding the long duration microgravity behavior of thermal energy storage salts that undergo repeated melting and freezing. Such data have never been obtained before and have direct application for the development of space-based solar dynamic (SD) power systems. These power systems will store energy in a thermal energy salt such as lithium fluoride or a eutectic of lithium fluoride/calcium difluoride. The stored energy is extracted during the shade portion of the orbit. This enables the solar dynamic power system to provide constant electrical power over the entire orbit. Analytical computer codes were developed for predicting performance of a space-based solar dynamic power system. Experimental verification of the analytical predictions were needed prior to using the analytical results for future space power design applications. The four TES flight experiments were to be used to obtain the needed experimental data. This paper will address the flight results from the first and second experiments, TES-1 and 2, in comparison to the predicted results from the Thermal Energy Storage Simulation (TESSIM) analytical computer code. An analysis of the TES-2 data was conducted by Cleveland State University Professor, Mounir Ibrahim. TESSIM validation was based on two types of results; temperature history of various points on the containment vessel and TES material distribution within the vessel upon return from flight. The TESSIM prediction showed close comparison with the flight data. Distribution of the TES material within the vessel was obtained by a tomography imaging process. The frozen TES material was concentrated toward the colder end of the canister. The TESSIM prediction indicated a similar pattern. With agreement between TESSIM and the flight data, a computerized representation was produced to show the movement and behavior of the void during the entire melting and freezing cycles.

Tolbert, Carol↗

Modulating solvation interactions of deep eutectic solvents formed by ammonium salts and carboxylic acids through varying the molar ratio of hydrogen bond donor and acceptor

Deep eutectic solvents (DESs) have gained increasing popularity in separation science due to the fact that their physico-chemical properties can be easily fine-tuned by varying the type or ratio of hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD). While it is well-known that the molar ratio of HBA/HBD affects the melting point of a eutectic mixture, much less is understood regarding its effect on the magnitude of individual solvation interactions. This is largely due to the fact that established solvatochromic dye methods lack sensitivity when the HBA/HBD ratio is varied slightly in a eutectic mixture. Herein, this study is the first to measure the variation of DES solvation interactions with small changes in the molar ratio of HBA/HBD using inverse gas chromatography (IGC). Solute-solvent interactions of three different DES systems comprised of ammonium salts and organic acids were examined. The probe molecules were studied for 18 eutectic mixtures of varied HBA and HBD composition. We report DES hydrogen bond basicity, hydrogen bond acidity, and dispersive-type interactions exhibited the greatest change when the molar ratio of HBA/HBD was varied in the eutectic mixture. Results from this study demonstrate that the HBA/HBD ratio can be used to modulate the solvation characteristics for this class of DESs in separations and that the stoichiometric ratio of the HBA/HBD is important in ensuring their reproducible preparation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A modified scheil approach for nucleation-dependent solidification pathways

As-solidified microstructures of near-eutectic alloys often contain multiple primary phases that are not expected from equilibrium phase diagrams. Such microstructures are caused by cooling-rate-dependent solidification pathways, a factor not captured by the Scheil–Gulliver model or variations thereof. Here, we present a model and algorithm that incorporate the critical nucleation undercooling for each solid phase into the Scheil–Gulliver model. We hypothesize that the non-equilibrium microstructure formation is primarily governed by a nucleation-competition mechanism. This mechanism accounts for both stable/metastable phase selection and primary-phase formation within eutectic regions driven by asymmetric nucleation barriers. The model is validated against a hypereutectic Al-Fe alloy, where it successfully reproduces the observed microstructural constituents, revealing the key dependencies of solidification microstructure on nucleation kinetics. Applicability to multicomponent systems is demonstrated through a hypereutectic Al–Fe–Si ternary alloy, where the model successfully predicts divorced eutectic microstructures and the associated oscillatory solidification pathways along univariant lines. As a result, the proposed framework establishes a nucleation-dependent computational approach for interpreting and predicting solidification microstructures.

Alloy design↗

Development of media for dynamic latent heat storage for the low-temperature range. Part 1: Thermal analyses of selected salt hydrate systems

Phase change temperatures and phase change enthalpies of seventeen salt hydrates, three double salts, and four eutectics were measured thermodynamically and the results reported herein. Good results were obtained, especially for congruently melting salt hydrates. Incongruently melting salt hydrates appear less suitable for heat storage applications. The influence of the second phase - water, acid and hydroxide - to the latent heat is described. From these results, basic values of the working temperatures and storage capabilities of various storage media compositions may be derived.

Kanwischer, H.↗

Methyl Carbamate-Lithium Salt Deep Eutectic Electrolyte for Lithium-Ion Batteries

Deep eutectic electrolytes (DEEs) represent a burgeoning field in electrolytes for energy storage applications. Compared to the more conventionally studied Li-ion electrolyte systems, these electrolytes offer numerous advantages, such as high ion concentration, costs, lower temperature operation, and safety. In this work, the formation of a novel eutectic electrolyte based on lithium salts and methyl carbamate was reported. These DEEs were formed via mixing lithium salts and low-cost methyl carbamate at ratios varying from 1:2 to 1:5 (mol:mol). Here, the DEE formed from methyl carbamate and lithium hexafluorophosphate (LiPF 6 ) at a 1:5 molar ratio generated a 4V stability window and a 25°C conductivity of up to 3.16E –3 S cm –1 . The DEE formed from methyl carbamate and lithium bis(trifluoromethane)sulfonimide (LiTFSI) at a 1:5 molar ratio generated a 3.2 V stability window and a 25°C conductivity of up to 2.87E –3 S cm –1 . The LiPF 6 DEE also demonstrated a discharge capacity of 128 mAh g –1 after 50 cycles with 93% discharge capacity retention at moderate cycling rates of 0.5C in a lithium titanate (LTO)/lithium iron phosphate (LFP) full cell. These results demonstrate the potential for methyl carbamate to generate eutectics from lithium salts and offer alternative electrolytes for use in low-temperature Li-ion battery applications.

25 ENERGY STORAGE↗