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190 records · Page 11

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NASA NTRS1982

Solidification mechanism of highly undercooled metal alloys

Experiments were conducted on metal droplet undercooling, using Sn-25wt%Pb and Ni-34wt%Sn alloys. To achieve the high degree of undercooling, emulsification treatments were employed. Results show the fraction of supersaturated primary phase is a function of the amount of undercooling, as is the fineness of the structures. The solidification behavior of the tin-lead droplets during recalescence was analyzed using three different hypotheses; (1) solid forming throughout recalescence is of the maximum thermodynamically stable composition; (2) partitionless solidification below the T sub o temperature, and solid forming thereafter is of the maximum thermodynamically stable composition; and (3) partitionless solidification below the T sub o temperature with solid forming thereafter that is of the maximum thermodynamically metastable composition that is possible. The T sub o temperature is calculated from the equal molar free energies of the liquid solid using the regular solution approximation.

Shiohara, Y.↗

NASA NTRS1988

Diapirs of the Mediterranean ridge: The tectonic regime of an incipient accreted terrane

The occurrence of diapirs in the Mediterranean ridge stems mostly from the massive deposition of salt and gypsum in the Mediterranean basin during the late Miocean. The diapiric emplacement of the evaporitic sequence is not obvious, because the mobilization of the salt beds and the initiation of the diapiric upward flow are constrained by the relatively shallow thickness of the Plio-Pleistocene sedimentary overburden and by the low heat flow that prevails in the eastern Mediterranean. The diapirs consist also of early Cretaceous shales as well as other gravitationally metastable strata which are less mobile than salt. Studies of subduction trenches and their surroundings show that shallow ridges occur seaward of the trenches in many places. The collisional motion between the African and the Eurasian plates would further enhance accretion of sediments in the Mediterranean ridge, which would attain subaerial exposure, and eventually would become a mountain range accreted to southern Europe. The numerous diapirs of salt and shales that occur in the ridge would be common features in the future accreted terrane, indicating an intermediate extensional phase in the tectonic history of the development of crustal growth.

Mart, Y.↗

NASA NTRS1992

An analytical approach for the prediction of gamma-to-alpha phase transformation of aluminum oxide (Al2O3) particles in the Space Shuttle ASRM and RSRM exhausts

The analytical approach developed here utilizes the flow-field output from industry standard nozzle and plume codes as input into a particle phase conversion code which predicts the amount of gamma-to-alpha conversion in SRM exhausts. Sixty different cases were considered which varied such parameters as particle size, degree of undercooling, motor type, and altitude. On-centerline calculations were made for both the ASRM and RSRM at an altitude of 100,000 feet with particle sizes varying from 3.5 to 9.1 micron radius and undercooling varying from 0 to 20 percent. Additional calculations were made for the ASRM at 100,000 feet off centerline and at an altitude of 60,000 feet on centerline. The results indicate that significant amounts of metastable alumina will be present in ASRM and RSRM exhausts. Though not significant to motor performance, this may be important in such issues as environmental effects of rocket exhausts, plume radiative heating predictions, and particle size determination by laser scattering.

Oliver, S. M.↗

NASA NTRS1993

The gabbro-eclogite phase transition and the elevation of mountain belts on Venus

The hypothesis is explored that the crust-mantle boundary of Venus is not in phase equilibrium but rather is rate-limited by the temperature-dependent volume diffusion of the slowest ionic species. The 1D thermal evolution problem is solved assuming that the mountains formed by uniform horizontal shortening of the crust and the lithospheric mantle at a constant rate. The time-dependent density structure and surface elevation are calculated by assuming a temperature-dependent reaction rate and local Airy isostatic compensation. For a horizontal strain rate of 10 exp -15/s or greater, the temperature increase at the base of the crust during mountain formation is modest to negligible, the deepening lower crust is metastable, and the surface elevation increases as the crust thickens. For strain rates less than 10 exp -16/s, crustal temperature increases with time because of internal heat production and the lower crust is more readily transformed to the dense eclogite assemblage. For such models, a maximum elevation is reached during crustal shortening.

Namiki, Noriyuki↗

NASA NTRS1995

Nucleation and growth of crystals under cirrus and polar stratospheric cloud conditions

Laboratory studies examine phase changes of hygroscopic substances which occur as aerosol in stratosphere and troposphere (sodium chloride, ammonium sulfate, ammonium bisulfate, nitric acid, sulfuric acid), under controlled conditions, in samples volume 1 to 10(exp -4) ml. Crystallization of salts from supersaturated solutions is examined by slowly evaporating a solution drop on a substrate, under controlled relative humidity, until self nucleation occurs; controlled nucleation of ice in a mm capillary U-tube gives a measured ice crystallization velocity at known supercooling. Two states of crystallization occur for regions where hydrates exist. It is inferred that all of the materials readily exist as supersaturated/supercooled solutions; the degree of metastability appears to be slightly enhanced by inclusion of aircraft produced soot. The crystallization velocity is taken as a measure of viscosity. Results suggest an approach to a glass transition at high molality, supersaturation and/or supercooling within the range of atmospheric interest. It is hypothesized that surface reactions occur more readily on solidified particles - either crystalline or glass, whereas volume reactions are more important on droplets with sufficiently low viscosity and volume diffusivity. Implications are examined for optical properties of such particles in the atmosphere. In a separate experiment, crystal growth was examined in a modified thermal vapor diffusion chamber over the range of cirrus temperature (-30 to -70 C) and under controlled supersaturation and air pressure. The crystals grew at a velocity of 1-2 microns/s, thickness 60-70 micron, in the form of thin column crystals. Design criteria are given for a system to investigate particle growth down to -100 C, (PSC temperatures) where nitric acid particles can be grown under similar control and in the form of hydrate crystals.

Hallett, John↗

NASA NTRS1999

Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate

The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.

Non-NASA Center↗

NASA NTRS1999

Containerless, Low-Gravity Undercooling of Ti-Ce Alloys in the MSFC Drop Tube

Previous tests of the classical nucleation theory as applied to liquid-liquid gap miscibility systems found a discrepancy between experiment and theory in the ability to undercool one of the liquids before the L1-L2 separation occurs. To model the initial separation process in a two-phase liquid mixture, different theoretical approaches, such as free-energy gradient and density gradient theories, have been put forth. If there is a large enough interaction between the critical liquid and the crucible, both models predict a wetting temperature (T(sub w)) above which the minority liquid perfectly wets and layers the crucible interface, but only on one side of the immiscibility dome. Materials with compositions on the other side of the dome will have simple surface adsorption by the minority liquid before bulk separation occurs when the coexistence (i.e., binoidal) line in reached. If the interaction between the critical liquid and the crucible were to decrease, T(sub w) would increase, eventually approaching the critical consolute temperature (T(sub cc)). If this situation occurs, then there could be large regions of the miscibility gap where non-perfect wetting conditions prevail resulting in droplets of L1 liquid at the surface having a non-zero contact angle. The resulting bulk structure will then depend on what happens on the surface and the subsequent processing conditions. In the past several decades, many experiments in space have been performed on liquid metal binary immiscible systems for the purpose of determining the effects that different crucibles may have on the wetting and separation process of the liquids. Potard performed experiments that showed different crucible materials could cause the majority phase to preferentially wet the container and thus produce a dispersed microstructure of the minority phase. Several other studies have been performed on immiscibles in a semi-container environment using an emulsion technique. Only one previous study was performed using completely containerless processing of immiscible metals and the results of that investigation are similar to some of the emulsion studies. In all the studies, surface wetting was attributed as the cause for the similar microstructures or the asymmetry in the ability to undercool the liquid below the binoidal on one side of the immiscibility dome. By removing the container completely from the separation process, it was proposed that the loss of the crucible/liquid interaction would produce a large shift in T(sub w) and thus change the wetting characteristics at the surface. By investigating various compositions across the miscibility gap, a change in the type and amount of liquid wetting at the surface of a containerless droplet should change the surface nucleating behavior of the droplet - whether it be the liquid-liquid wetting or the liquid-to-solid transition. Undercooling of the liquid into the metastable region should produce significant differences in the separation process and the microstructure upon solidification. In this study, we attempt to measure these transitions by monitoring the temperature of the sample by optical pyrometry. Microstructural analysis will be made to correlate with the degree of undercooling and the separation mechanisms involved.

Robinson, M. B.↗

NASA NTRS2000

An abiotic origin for hydrocarbons in the Allan Hills 84001 martian meteorite through cooling of magmatic and impact-generated gases

Thermodynamic calculations of metastable equilibria were used to evaluate the potential for abiotic synthesis of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in the martian meteorite Allan Hills (ALH) 84001. The calculations show that PAHs and normal alkanes could form metastably from CO, CO2, and H2 below approximately 250-300 degrees C during rapid cooling of trapped magmatic or impact-generated gases. Depending on temperature, bulk composition, and oxidation-reduction conditions, PAHs and normal alkanes can form simultaneously or separately. Moreover, PAHs can form at lower H/C ratios, higher CO/CO2 ratios, and higher temperatures than normal alkanes. Dry conditions with H/C ratios less than approximately 0.01-0.001 together with high CO/CO2 ratios also favor the formation of unalkylated PAHs. The observed abundance of PAHs, their low alkylation, and a variable but high aromatic to aliphatic ratio in ALH 84001 all correspond to low H/C and high CO/CO2 ratios in magmatic and impact gases and can be used to deduce spatial variations of these ratios. Some hydrocarbons could have been formed from trapped magmatic gases, especially if the cooling was fast enough to prevent reequilibration. We propose that subsequent impact heating(s) in ALH 84001 could have led to dissociation of ferrous carbonates to yield fine-grain magnetite, formation of a CO-rich local gas phase, reduction of water vapor to H2, reequilibration of the trapped magmatic gases, aromatization of hydrocarbons formed previously, and overprinting of the synthesis from magmatic gases, if any. Rapid cooling and high-temperature quenching of CO-, H2-rich impact gases could have led to magnetite-catalyzed hydrocarbon synthesis.

Non-NASA Center↗

NASA NTRS2003

Creep Resistance of ZrO2 Ceramic Improved by the Addition of a Small Amount of Er2O3

Zirconia (ZrO2) has great technological importance in structural, electrical, and chemical applications. It is the crucial component for state-of-the art thermal barrier coatings and an enabling component as a solid electrolyte for solid-oxide fuel cell systems. Pure ZrO2 is of limited use for industrial applications because of the phase transformations that occur. Upon the addition of stabilizers, cubic (c-ZrO2) and tetragonal (t-ZrO2) forms can be preserved. It is the stabilized and partially stabilized forms of zirconia that function as thermal barrier coatings, solid electrolytes, and oxygen sensors and that have numerous applications in the electrochemical industry. The cubic form of ZrO2 is typically stabilized through Y2O3 additions. However, Y2O3-stabilized zirconia is susceptible to deformation at high temperatures (greater than 900 C) because of the large number of slip systems and the high oxygen diffusion rates, which result in high creep rates at high temperatures. Successful use of ZrO2 at high temperatures requires that new dopant additives be found that will retain or enhance the desirable properties of cubic ZrO2 and yet produce a material with lower creep rates. At the NASA Glenn Research Center, erbium oxide (Er2O3) was identified as a promising dopant for improving the creep resistance of. ZrO2. The selection of Er2O3 was based on the strong interactions of point defects and dislocations. Single crystals of 5 mol% Er2O3- doped ZrO2 rods (4 mm in diameter) and monofilaments (200 to 300 mm in diameter and 30 cm long) were grown using the laser-heated float zone technique, and their creep behavior was measured as a function of temperature. The addition of 5 mol% Er2O3 to single-crystal ZrO2 improved its creep resistance at high temperatures by 2 to 3 orders of magnitude over state-of-the-art Y2O3-doped crystals. Detailed microstructural characterization of ZrO2-Er2O3 single crystals has identified new mechanisms for improving the creep resistance of this class of materials. Adding Er2O3 to ZrO2 results in microstructure of stable and metastable tetragonal precipitates that with thermal treatment evolve to a tweed structure of nanosize tetragonal lamellae. The superior high-temperature creep resistance of Er2O3-doped ZrO2 is attributed to nanoscale precipitation hardening. Doping with Er2O3 will significantly increase the upper-use temperature limit of ZrO2. Potential applications include using Er2O3-doped ZrO2 as a high-temperature fiber for structural applications and adding Er2O3 to reduce the sintering rates of ZrO2 thermal barrier coatings. This work was conducted at Dpto. de F sica de la Materia Condensada, Universidad de Sevilla, Spain, and at NASA Glenn.

Martinez-Fernandez, Julian↗

NASA NTRS2000

Thermophysical Property Measurement and Materials Research in the NASA/MSFC Electrostatic Levitator

Containerless processing is an important tool for thermophysical property measurements and materials research. The freedom from a crucible allows processing of liquid materials in a metastable undercooled state, as well as allowing processing of high temperature and highly reactive melts. Electrostatic levitation (ESL) is a containerless method which provides a number of unique advantages, including the decoupling of positioning force from sample heating, the ability to operate in ultra-high vacuum or at moderate gas pressure (approximately 3 atm), and the ability to process non-conducting materials. ESL also has the potential to reduce internal flow velocities below those possible with electromagnetic, acoustic, or aero-acoustic techniques. The ESL facility at NASA's Marshall Space Flight Center (MSFC) is in use for thermophysical property measurements and materials research by a number of different internal and external investigators. The methods for obtaining access to the facility, as well as a summary of current capabilities and some future directions will be discussed. In electrostatic levitation, the acceleration of gravity (or residual acceleration in reduced gravity) is opposed by the action of an applied electric field on a charged sample. This positioning method is applicable to any material which can be electrically charged, whether solid or liquid, conducting, or insulating. Because the position of the sample is unstable, a 3-dimensional active control loop rapidly adjusts the applied field to maintain levitation and minimize motion of the sample. Heating lasers melt the sample, and may be adjusted to maintain specified thermal profiles. Microgravity allows electrostatic levitation to work even more effectively. With the need to cancel less than 1 milli-g, the applied field required is reduced from approximately 10 MV/m to approximately 10 kV/m. Alternatively, a microgravity ESL can position larger samples than is possible on the ground, or it can position samples which maintain their charge poorly. Microgravity also reduces the effects of buoyant convection and sedimentation. In the MSFC ESL, many different classes of experiments and measurements have been demonstrated in collaboration with many investigators. These capabilities include heat capacity measurement, phase diagram determination, and nucleation and growth experiments including nucleation rate, TTT curves, and phase selection. We have demonstrated the capability of triggering recalescence of an undercooled liquid sample without loss of levitation. Currently under development are techniques for measuring the surface tension, viscosity, and density of levitated samples, as well as other thermophysical properties. Expanded levitation capabilities including various gas environments for sample processing, sample rotation control and management of thermal gradients are under development for the MSFC ESL. Containerless processing allows research on materials which may not be processed any other way. Electrostatic levitation extends the range of containerless processing to include many materials and classes of materials which cannot be processed by conventional electromagnetic, acoustic, or aerodynamic levitation techniques.

Rogers, Jan↗