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Initial hydrate formation conditions for selected mixtures of argon-methane and argon-nitrogen determined through measurements of equilibrium pressures and temperature
It is well known that in the liquid state eutectic alloys are theoretically homogeneous under 1 g conditions. However, the homogeneous solidified structure of this alloy is not obtained because thermal convection and non-equilibrium solidification occur. The present investigators have clarified the solidification mechanisms of the eutectic system alloys under 1 g conditions by using the in situ observation method; in particular, the primary crystals of the eutectic system alloys never nucleated in the liquid, but instead did so on the mold wall, and the crystals separated from the mold wall by fluid motion caused by thermal convection. They also found that the equiaxed eutectic grains (eutectic cells) are formed on the primary crystals. In this case, the leading phase of the eutectic must agree with the phase of the primary crystals. In space, no thermal convection occurs so that primary crystals should not move from the mold wall and should not appear inside the solidified structure. Therefore no equiaxed eutectic grains will be formed under microgravity conditions. Past space experiments concerning eutectic alloys were classified into two types of experiments: one with respect to the solidification mechanisms of the eutectic alloys and the other to the unidirectional solidification of this alloy. The former type of experiment has the problem that the solidified structures between microgravity and 1 g conditions show little difference. This is why the flight samples were prepared by the ordinary cast techniques on Earth. Therefore it is impossible to ascertain whether or not the nucleation and growth of primary crystals in the melt occur and if primary crystals influence the formation of the equiaxed eutectic grains. In this experiment, hypo- and hyper-eutectic aluminum copper alloys which are near eutectic point are used. The chemical compositions of the samples are Al-32.4mass%Cu (Hypo-eutectic) and Al-33.5mass%Cu (hyper-eutectic). Long rods for the samples are cast by the Ohno Continuous Casting Process and they show the unidirectionally solidified structure. Each flight and ground sample was made of these same rods. The dimensions of all samples are 4.5 mm in diameter and 23.5 mm in length. Each sample is put in a graphite capsule and then vacuum sealed in a double silica ampoule. Then the ampoule is put in the tantalum cartridge and sealed by electron beam welding. For onbard experiments, a Continuous Heating Furnance (CHF) will be used for melting and solidifying samples under microgravity conditions. Six flight samples will be used. Four samples are hypo-eutectic and two are hyper-eutectic alloys. The surface of the two hypo-eutectic alloy samples are covered with aluminum oxide film to prevent Marangoni convection expected under microgravity conditions. Each sample will be heated to 700 C and held at that temperature for 5 min. After that the samples will be allowed to cool to 500 C in the furnace and they will be taken out of the furnace for He gas cooling. The heating and cooling diagrams for the flight experiments are shown. After collecting the flight samples, the solidified structures of the samples will be examined and the mechanisms of eutectic solidification under microgravity conditions will be determined. It is likely that successful flight experiment results will lead to production of high quality eutectic alloys and eutectic composite materials in space.
Recent models for accretion of terrestrial bodies involve metal-silicate equilibrium as the metallic core formed during growth. Most elements considered are either refractory or well studied elements for which effects of pressure, temperature, oxygen fugacity, and metallic liquid composition are well known. There are a large number of elements that are both siderophile and volatile, whose fate in such models is unknown, largely due to a lack of data at comparable conditions and com-positions (FeNi core with light elements such as S, C, Si, and O). We have focused on Ge, In, As, Sb and determined the effect of Si and C on metal-silicate partitioning, and developed a thermo-dynamic model that allows application of these new data to a wide range of planetary bodies. New experiments: We have previously carried out experiments with FeSi metallic liquid at C-saturated conditions at 1600 and 1800 C [4]. In a new series of experiments we investigate the effect of Si in carbon-free systems at 1600 C for comparison. Experiments were carried out at 1 GPa in MgO capsules using the same basaltic starting composition as in previous studies. The MgO capsule reacts with the silicate melt to form more MgO-rich liquids that have 22-26 wt% MgO. Experimental met-als and silicates were analyzed using a combination of electron microprobe analysis and laser ablation ICP-MS. Results: The new results can be interpreted by considering Ge as an example, in the simple exchange equilibrium Fe + GeO = FeO + Ge, where the equilibrium constant Kd can be examined as a function of Si content of the metal. The slope of lnKd vs. (1-XSi) for this new series allows derivation of the epsilon interaction parameter for each of these four elements and Si (both C-saturated and C-free).All four elements have positive epsilon values, indicating that Si causes a decrease in the partition coefficients; values are 6.6, 6.5, 27.8 and 25.2 for In, Ge, As, and Sb, respectively, at 1 GPa and 1600 C. As an example of how large the effect of Si can be, these epsilon values correspond to activity coefficients (gamma) for As of 0.01 when XSi = 0, and up to gamma = 23 when XSi = 0.2. Combining these new results with previous determinations [5,6] of epsilon parameters for S and C for these elements allows us calculate activity of Ge, In, As, and Sb in Fe-Ni-Si-S-C-O metallic liquids. We apply this new model to sever-al terrestrial bodies such as Earth (Si-rich core), Mars (S-rich core), Moon (S-, C-, and Si-poor core), and Vesta, and examine the resulting core and mantle concentrations of these elements. Mantle concentrations of these four elements are well explained for Earth and Mars in models that call for mid-mantle equilibration between Si-bearing and S-bearing FeNi cores, respectively. Modeling results for the Moon and Vesta will also be presented.
Chemical and mineralogical data (e.g. [1]) from Mars suggest that the history of liquid water on the planet was more sporadic in nature than long-lived. The non-equilibrium chemical and isotopic compositions of the carbonates preserved in the martian meteorite ALH84001 are direct evidence of ancient secondary minerals that have not undergone significant diagenesis or stabilization processes typical of long-lived aqueous systems on Earth. Thus secondary minerals and sediments on Mars may primarily record the characteristics of the aqueous environment in which they formed without being significantly overprinted by subsequent diagenetic processes during burial.
Previous experiments indicate that the bubble point pressure of spacecraft liquid hydrogen acquisition devices is reduced substantially when the ullage is pressurized with heated hydrogen vapor. The objective is to determine whether the two-phase thermocapillary convection arising from thermodynamic non-equilibrium along the porous surfaces of such devices could lead to this observed degradation in retention performance. We also examine why retention capability appears to be unaffected by pressurization with heated helium or direct heating through the porous structure. Computational assessments based on coupled solution of the flowfield and liquid free surface indicate that for highly wetting fluids in small pores, dynamic pressure and vapor recoil dictate surface morphology and drive meniscus deformation. With superheating, the two terms exert the same influence on curvature and promote mechanical equilibrium, but with subcooling, the pressure distribution produces a suction about the pore center-line that degrades retention. This result points to thermocapillary-induced deformation arising from condensation as the cause for retention loss. It also indicates that increasing the level of non-equilibrium by reducing accommodation coefficient restricts deformation and explains why retention failure does not occur with direct screen heating or helium pressurization.
Cadmium sulfide (Cu2s - CdS) solar cells were tested under simulated space environmental conditions. Some cells were thermally cycled with illumination from a Xenon-arc solar simulator. A cycle was one hour of illumination followed immediately with one-half hour of darkness. In the light, the cells reached an equilibrium temperature of 60 C (333 K) and in the dark the cell temperature dropped to -120 C (153 K). Other cells were constantly illuminated with a Xenon-arc solar simulator. The equilibrium temperature of these cells was 55 C (328 K). The black vacuum chamber walls were cooled with liquid nitrogen to simulate a space heat sink. Chamber pressure was maintained at 0.000001 torr or less. Almost all of the solar cells tested degraded in power when exposed to a simulated space environment of either thermal cycling or constant illumination. The cells tested the longest were exposed to 10.050 thermal cycles.
Design features of a tested catalytic converter for altering vented cryogenic parahydrogen used as a coolant on spacecraft into a para-ortho equilibrium for channeling to other cooling functions are described. The hydrogen is expected to be stored in either liquid or solid form. A high surface area Ni-on-Si catalyst was selected for tests at an operating pressure of 2 torr at a ratio of 1000 gr catalyst for a gr/sec hydrogen flow. Cylindrical and radial flow geometries were tried and measurements centered on the converter efficiencies at different operating temperatures when the converter was placed in the vent line of the H2 cooler. Efficiencies ranging from 10-100 percent were obtained for varying flow rates. Further testing is necessary to characterize the converter performance under a wider range of operating temperatures and environments.
When a two-component system is cooled below the minimum temperature for its stability, it separates into two or more immiscible phases. The initial nucleation produces grains (if solid) or droplets (if liquid) of one of the phases dispersed in the other. The dynamics by which these nuclei proceed toward equilibrium is called Ostwald ripening. The dynamics of growth of the droplets depends upon the following factors: (1) The solubility of the droplet depends upon its radius and the interfacial energy between it and the surrounding (continuous) phase. There is a critical radius determined by the supersaturation in the continuous phase. Droplets with radii smaller than critical dissolve, while droplets with radii larger grow. (2) The droplets concentrate one component and reject the other. The rate at which this occurs is assumed to be determined by the interdiffusion of the two components in the continuous phase. (3) The Ostwald ripening is constrained by conservation of mass; e.g., the amount of materials in the droplet phase plus the remaining supersaturation in the continuous phase must equal the supersaturation available at the start. (4) There is a distribution of droplet sizes associated with a mean droplet radius, which grows continuously with time. This distribution function satisfies a continuity equation, which is solved asymptotically by a similarity transformation method.
A formula for the free energy difference between the undercooled liquid phase and the stable solid phase is derived for off-eutectic binary alloys in which the equilibrium solid/liquid transition takes place over a certain temperature range. The free energy change is then evaluated numerically for a Bi-25 at. pct Cd alloy modeled as a sub-subregular solution.
A thermodynamic framework (UNIQUAC model with temperature dependent parameters) is applied to model the salt-induced protein crystallization equilibrium, i.e., protein solubility. The framework introduces a term for the solubility product describing protein transfer between the liquid and solid phase and a term for the solution behavior describing deviation from ideal solution. Protein solubility is modeled as a function of salt concentration and temperature for a four-component system consisting of a protein, pseudo solvent (water and buffer), cation, and anion (salt). Two different systems, lysozyme with sodium chloride and concanavalin A with ammonium sulfate, are investigated. Comparison of the modeled and experimental protein solubility data results in an average root mean square deviation of 5.8%, demonstrating that the model closely follows the experimental behavior. Model calculations and model parameters are reviewed to examine the model and protein crystallization process. Copyright 1999 John Wiley & Sons, Inc.
The chemical activities of Al and Ni in gamma(prime)-Ni3Al-containing systems were measured using the multi-cell Knudsen effusion-cell mass spectrometry technique (multi-cell KEMS), over the composition range 8 - 32 at.%Al and temperature range T = 1400 - 1750 K. From these measurements a better understanding of the equilibrium solidification behaviour of gamma(prime)-Ni3Al-containing alloys in the Ni-Al-O system was established. Specifically, these measurements revealed that (1) gamma(prime)-Ni3Al forms via the peritectiod reaction, gamma + Beta (+ A12O3) = gamma (prime) (+ Al2O3), at 1633 +/- 1 K, (2) the {gamma + Beta + Al2O3} phase field is stable over the temperature range 1633 through 1640 K, and (3) equilibrium solidification occurs by the eutectic reaction, L (+ Al2O3) = gamma + Beta (+ Al2O3), at 1640 +/- 1 K and a liquid composition of 24.8 +/- 0.2 at.%Al (at an unknown oxygen content). When projected onto the Ni-Al binary, this behaviour is inconsistent with the current Ni-Al phase diagram and a new diagram is proposed. This new Ni-Al phase diagram explains a number of unusual steady-state solidification structures reported previously and provides a much simpler reaction scheme in the vicinity of the gamma(prime)-Ni3Al phase field.
Chemical weathering on Mars is examined theoretically from the standpoint of thermodynamic equilibrium between primary rock-forming minerals and the atmospheric gases O2, H2O, and CO2. The primary minerals considered are those common to mafic igneous rocks and include olivine, pyroxene, plagioclase, magnetite, troilite, pyrrhotite, and apatite. The importance of kinetics and reaction mechanisms in controlling possible weathering processes on Mars is discussed within the limits of currently available data, and the possible influence of liquid water on Martian weathering processes is evaluated where appropriate. For gas-solid weathering of mafic igneous rocks at the Martian surface, it is concluded that upon attainment of thermodynamic equilibrium: (1) oxides and carbonates should dominate the mineral assemblage of weathering products; (2) hematite rather than goethite should be the stable mineral form of Fe (III); (3) FeSO4 or FeSO4.H2O could be the stable weathering product of iron sulfides in the absence of liquid water; and (4) kaolinite is apparently the only clay mineral that should be thermodynamically stable over all ranges of temperature and water-vapor abundance at the Martian surface.
Instantaneous thickness of a frozen layer is a function of specific heat, heat of fusion, temperatures, the frozen layer thickness at equilibrium, the thermal conductivity, and heat transfer coefficient. The equation can be evaluated on a desk calculator.
Dynamics of a single bubble moving in a quiescent liquid is analyzed for single and binary component systems. The transport of energy and/or mass at thermodynamic-phase equilibrium governs the dynamics of the bubble at its interface.
The conditions under which ordinary chondrites containing iron in three different chemical states can form in thermodynamic equilibrium with a gas phase are calculated. Hydrogen depletion factors of 100-1000 are obtained and the formation of liquid condensates from residual gases occurs at pressures (prior to hydrogen depletion) of roughly equal to or greater than 1 atm.
The paper describes a theoretical investigation of the stability under gravitational and surface forces of a liquid in a circular cylindrical container with a concave spheroidal bottom for the case in which the volume of the liquid is sufficiently small so that the bottom is not covered completely. The gravitational field is assumed to be directed along the symmetry axis of the container, and for a specific container shape the critical Bond number is calculated as a function of liquid volume for contact angles of gamma = 0, 1, 2, and 4 deg. For gamma = 0 deg, some critical equilibrium configurations and corresponding perturbation modes are presented.
The paper compares dynamic crystallization techniques used on Apollo 15 quartz normative basalts which show differences related to their method. The variation of pyroxene core major element chemistry with cooling rate is confirmed, and it is shown that the Fe loss from liquid is shifted toward the En-Di joint; it is suggested that the nucleation temperature and breakdown of equilibrium partitioning as a function of cooling rate dictate the core composition. It is concluded that the different crystallization behavior that results from the Fe-capsule and Fe-loop container methods is related to the nucleation kinetics.
Chemical engineering analysis of the HSC process (Hemlock Semiconductor Corporation) for producing silicon from dichlorosilane in a 1,000 MT/yr plant was continued. Progress and status for the chemical engineering analysis of the HSC process are reported for the primary process design engineering activities: base case conditions (85%), reaction chemistry (85%), process flow diagram (60%), material balance (60%), energy balance (30%), property data (30%), equipment design (20%) and major equipment list (10%). Engineering design of the initial distillation column (D-01, stripper column) in the process was initiated. The function of the distillation column is to remove volatile gases (such as hydrogen and nitrogen) which are dissolved in liquid chlorosilanes. Initial specifications and results for the distillation column design are reported including the variation of tray requirements (equilibrium stages) with reflux ratio for the distillation.