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Possible Mars brines - Equilibrium and kinetic considerations

To determine the fate of postulated near surface brines on Mars, the rate of H2O mass loss from subsurface brines was calculated as a function of latitude, depth, regolith porosity, eutectic temperature, and pore size. A model for a chemically reasonable brine that could reproduce Martian radar results was developed, and the escape rate of H2O molecules from such a brine was estimated. It is suggested that the presence of a low-permeability duricrust may be required to preserve such a brine for reasonable periods, and to prevent detection of an extensive subsurface system by the Viking MAWD instrument.

Zent, A. P.↗

An Iron-Rain Model for Core Formation on Asteroid 4 Vesta

Asteroid 4 Vesta is differentiated into a crust, mantle, and core, as demonstrated by studies of the eucrite and diogenite meteorites and by data from NASA's Dawn spacecraft. Most models for the differentiation and thermal evolution of Vesta assume that the metal phase completely melts within 20 degrees of the eutectic temperature, well before the onset of silicate melting. In such a model, core formation initially happens by Darcy flow, but this is an inefficient process for liquid metal and solid silicate. However, the likely chemical composition of Vesta, similar to H chondrites with perhaps some CM or CV chondrite, has 13-16 weight percent S. For such compositions, metal-sulfide melting will not be complete until a temperature of at least 1350 degrees Centigrade. The silicate solidus for Vesta's composition is between 1100 and 1150 degrees Centigrade, and thus metal and silicate melting must have substantially overlapped in time on Vesta. In this chemically and physically more likely view of Vesta's evolution, metal sulfide drops will sink by Stokes flow through the partially molten silicate magma ocean in a process that can be envisioned as "iron rain". Measurements of eucrites show that moderately siderophile elements such as Ni, Mo, and W reached chemical equilibrium between the metal and silicate phases, which is an important test for any Vesta differentiation model. The equilibration time is a function of the initial metal grain size, which we take to be 25-45 microns based on recent measurements of H6 chondrites. For these sizes and reasonable silicate magma viscosities, equilibration occurs after a fall distance of just a few meters through the magma ocean. Although metal drops may grow in size by merger with other drops, which increases their settling velocities and decreases the total core formation time, the short equilibration distance ensures that the moderately siderophile elements will reach chemical equilibrium between metal and silicate before metal drop merger becomes important. In this model, there must be at least 30 percent melting of the silicate phase when metal melting is complete, corresponding to a crust thickness of at least 30 kilometers on Vesta, consistent with Dawn gravity observations. Greater degrees of silicate melting and a correspondingly thicker crust are possible if Vesta accreted sufficiently rapidly.

Kiefer, Walter S.↗

The Scientific Case for Sample Return from a Primitive Near-Earth Asteroid

This paper is predicated on the recent experimental findings that the smallest structural ferromagnesiosilica entities in collected chondritic aggregate interplanetary dust particles (IDPs) have a predictable metastable eutectic composition. Kinetically controlled gas to solid condensation of MgFe-SiO-O2-H2 vapors does NOT produce stoichiometric crystalline solids (i.e. minerals) such as predicted by equilibrium condensation models but instead yields amorphous solids that are chemically ordered at metastable eutectics in the binary phase diagrams. Therefore these condensed dust grains will have a considerable amount of 'internal free energy' that will make them highly responsive to changes in their environments. Their inherent high energy-content 'buys' time and energy for mineralogical modification and chemical readjustment in response to changing environmental conditions. The activation energy barrier for reactions in metastable eutectic solids will be lower than for crystalline solids. As a result the reactions can take place at much lower temperatures and on much shorter time scales. That is, they will also occur much earlier in the evolution of a parent body wherein heat-producing sources may either be immature or inefficient. The ensuing reaction chains from metastable equilibrium to full thermodynamic equilibration with the local environment will be a chaotic 'Ostwald cascade' but from a well defined starting point to a predictable end result. Here we will discuss the implications of metastable eutectic dust as we see them for dust properties in icy and ice-free parent bodies wherein circumstellar dust is still recognizable because of the primitive nature of these parent bodies. We point to potential engineering constraints on sample acquisition and storage during Earth transit. Among the scientific goals of a primitive Near Earth Asteroid (NEA) sample return mission will be verification of the nature of dust forming and modification processes during hierarchical accretion in the earliest protoplanets. We propose sampling an infrared P- or D-class NEA or an object showing cometary activity such as 2201 Oljato that could be an asteroid or evolved comet. Additional information is contained in the original extended abstract.

Rietmeijer, Frans J. M.↗

Dendritic growth of undercooled nickel-tin. I, II

A comparison is made between high speed cinematography and optical temperature measurements of the solidification of an undercooled Ni-25 wt pct Sn alloy. The first part of this study notes that solidification during the recalescence period at all undercoolings studied occurred in the form of a dendritelike front moving across the sample surface, and that the growth velocities observed agree with calculation results for the dendrite growth model of Lipton et al. (1986); it is concluded that the coarse structure observed comprises an array of much finer, solute-controlled dendrites. In the second part, attention is given to the solidification of levitated metal samples within a transparent glass medium for the cases of two undercooled Ni-Sn alloys, one of which is eutectic and another hypoeutectic. The data obtained suggest a solidification model involving dendrites of very fine structure growing into the melt at temperatures near the bulk undercooling temperature.

Wu, Y.↗

Lamellar Spacing Selection in Al-Si Eutectic System: a Theoretical Investigation

It is well known that irregular eutectics such as Al-Si and Fe-C exhibit larger lamellar spacings and undercoolings compared to the predictions made by the Jackson and Hunt (JH) theory. In this paper, we reexamine the JH theory and relax some of the assumptions used in that treatment. The modified theoretical model has enhanced capabilities to predict the lamellar spacing in both regular and irregular eutectics. For the Al-Si system in particular we identified two different spacing selection mechanisms:a) for a particular growth rate, a nearly isothermal interface can be achieved at a unique minimum spacing lambda(sub I); b) the average spacing in the microstructure (lambda(sub av) greater than lambda(sub I)) is essentially dictated by the undercooling of the faceted phase. Based on the modified theoretical model a semi-empirical expression has been developed to account for the influence of the temperature gradient. Application of a Mullin and Sekerka type stability analysis for eutectics will also be presented and the results compared to the modified JH model. It will be shown that the both theoretical approaches are in good agreement with each other and also with the published experimental measurements.

Catalina, Adrian V.↗

Origin of Domes on Europa: The Role of Thermally Induced Compositional Buoyancy,

The surface of Jupiter's moon Europa is peppered by topographic domes, interpreted as sites of intrusion and extrusion. Diapirism is consistent with dome morphology, but thermal buoyancy alone cannot produce sufficient driving pressures to create the observed dome elevations. Instead, diapirs may initiate by thermal convection that induces compositional segregation. Exclusion of impurities from warm upwellings allows sufficient buoyancy for icy plumes to create the observed surface topography, provided the ice shell has a small effective elastic thickness (0.2 to 0.5 km) and contains low-eutectic point impurities at the few percent level. This model suggests that the ice shell may be depleted in impurities over time.

Pappalardo, R. T.↗

Finite element simulations of thermosolutal convection in vertical solidification of binary alloys

Dendritic vertical solidification of a binary alloy is modeled using the finite element method to assess the effect of thermosolutal convection in macrosegregation. The mathematical model assumes steady-state solidification with a planar, undeformable surface defined by the dendrite tips and the eutectic isotherm. The dendritic region is assumed to advance at a constant solidification velocity v. The stability of the modeled system has been investigated and nonlinear calculations performed that show finger-like convection when the system is unstable. Results for lead-tin alloys show that when the system is unstable, convection is only significant in the uppermost part of the mush and is entirely driven by convection in the bulk fluid.

Heinrich, J. C.↗

Influence of convection on microstructure

In eutectic growth, as the solid phases grow they reject atoms to the liquid. This results in a variation of melt composition along the solid/liquid interface. In the past, mass transfer in eutectic solidification, in the absence of convection, was considered to be governed only by the diffusion induced by compositional gradients. However, mass transfer can also be generated by a temperature gradient. This is called thermotransport, thermomigration, thermal diffusion or the Soret effect. A theoretical model of the influence of the Soret effect on the growth of eutectic alloys is presented. A differential equation describing the compositional field near the interface during unidirectional solidification of a binary eutectic alloy was formulated by including the contributions of both compositional and thermal gradients in the liquid. A steady-state solution of the differential equation was obtained by applying appropriate boundary conditions and accounting for heat flow in the melt. Following that, the average interfacial composition was converted to a variation of undercooling at the interface, and consequently to microstructural parameters. The results obtained show that thermotransport can, under certain circumstances, be a parameter of paramount importance.

Wilcox, William R.↗

Multi-dimensional modeling of a thermal energy storage canister

The Solar Dynamic Power Module being developed for Space Station Freedom uses a eutectic mixture of LiF-CaF2 phase change material (PCM) contained in toroidal canisters for thermal energy storage. Presented are the results from heat transfer analyses of a PCM containment canister. One and two dimensional finite difference computer models are developed to analyze heat transfer in the canister walls, PCM, void, and heat engine working fluid coolant. The modes of heat transfer considered include conduction in canister walls and solid PCM, conduction and pseudo-free convection in liquid PCM, conduction and radiation across PCM vapor filled void regions, and forced convection in the heat engine working fluid. Void shape, location, growth or shrinkage (due to density difference between the solid and liquid PCM phases) are prescribed based on engineering judgment. The PCM phase change process is analyzed using the enthalpy method. The discussion of the results focuses on how canister thermal performance is affected by free convection in the liquid PCM and void heat transfer. Characterizing these effects is important for interpreting the relationship between ground-based canister performance (in 1-g) and expected on-orbit performance (in micro-g). Void regions accentuate canister hot spots and temperature gradients due to their large thermal resistance. Free convection reduces the extent of PCM superheating and lowers canister temperatures during a portion of the PCM thermal charge period. Surprisingly small differences in canister thermal performance result from operation on the ground and operation on-orbit. This lack of a strong gravity dependency is attributed to the large contribution of container walls in overall canister energy redistribution by conduction.

Kerslake, Thomas W.↗

Experimental and Theoretical Investigations of the Solidification of Eutectic Al-Si Alloy

The eutectic alloys have a wide spectrum of applications due to their good castability and physical and mechanical properties. The interphase spacing resulting during solidification is an important microstructural feature that significantly influences the mechanical behavior of the material. Thus, knowledge of the evolution of the interphase spacing during solidification is necessary in order to properly design the solidification process and optimize the material properties. While the growth of regular eutectics is rather well understood, the irregular eutectics such as Al-Si or Fe-graphite exhibit undercoolings and lamellar spacings much larger than those theoretically predicted. Despite of a considerable amount of experimental and theoretical work a clear understanding of the true mechanism underlying the spacing selection in irregular eutectics is yet to be achieved. A new experimental study of the solidification of the eutectic Al-Si alloy will be reported in this paper. The measured interface undercoolings and lamellar spacing will be compared to those found in the literature in order to get more general information regarding the growth mechanism of irregular eutectics. A modification of the present theory of the eutectic growth is also proposed. The results of the modified mathematical model, accounting for a non-isothermal solid/liquid interface, will be compared to the experimental measurements.

Sen, S.↗

A lunar core of Fe-Ni-S.

It has been proposed that lunar samples were magnetized by a field created by a lunar core of molten Fe. Low abundances of siderophile elements in lunar rocks are compatible with formation of a metallic lunar core. A molten Fe core requires that the bulk of the moon was above, or close to, the melting point, a requirement which disagrees with most models of the lunar thermal regime. A core (or perhaps a layer or pockets) of molten Fe-Ni-S, at or close to the eutectic composition would act as a lunar dynamo, and be at a temperature (approximately 1000 C) consistent with some reasonable models of lunar thermal history. The existence of a Fe-Ni-S core would also partly explain the depletion in volatile elements in lunar basalts. Such a core, occupying up to 20% of the moon's radius, requires a bulk S content for the moon of only 0.3 wt %.

Brett, R.↗

Two-dimensional model of a Space Station Freedom thermal energy storage canister

The Solar Dynamic Power Module being developed for Space Station Freedom uses a eutectic mixture of LiF-CaF2 phase change salt contained in toroidal canisters for thermal energy storage. Results are presented from heat transfer analyses of the phase change salt containment canister. A 2-D, axisymmetric finite difference computer program which models the canister walls, salt, void, and heat engine working fluid coolant was developed. Analyses included effects of conduction in canister walls and solid salt, conduction and free convection in liquid salt, conduction and radiation across salt vapor filled void regions and forced convection in the heat engine working fluid. Void shape, location, growth or shrinkage (due to density difference between the solid and liquid salt phases) were prescribed based on engineering judgement. The salt phase change process was modeled using the enthalpy method. Discussion of results focuses on the role of free-convection in the liquid salt on canister heat transfer performance. This role is shown to be important for interpreting the relationship between ground based canister performance (in l-g) and expected on-orbit performance (in micro-g). Attention is also focused on the influence of void heat transfer on canister wall temperature distributions. The large thermal resistance of void regions is shown to accentuate canister hot spots and temperature gradients.

Kerslake, Thomas W.↗

Two-dimensional model of a Space Station Freedom thermal energy storage canister

The Solar Dynamic Power Module being developed for Space Station Freedom uses a eutectic mixture of LiF-CaF2 phase change salt contained in toroidal canisters for thermal energy storage. Results are presented from heat transfer analyses of the phase-change salt containment canister. A 2-D, axisymmetric finite-difference computer program which models the canister walls, salt, void, and heat engine working fluid coolant was developed. Analyses included effects of conduction in canister walls and solid salt, conduction and free convection in liquid salt, conduction and radiation across salt vapor filled void regions, and forced convection in the heat engine working fluid. Void shape, location, and growth or shrinkage (due to density difference between the solid and liquid salt phases) were prescribed based on engineering judgement. The salt phase change process was modeled using the enthalpy method. Discussion of results focuses on the role of free-convection in the liquid salt on canister heat transfer performance. This role is shown to be important for interpreting the relationship between groundbased canister performance (in 1-g) and expected on-orbit performance (in micro-g). Attention is also focused on the influence of void heat transfer on canister wall temperature distributions. The large thermal resistance of void regions is shown to accentuate canister hot spots and temperature gradients.

Kerslake, Thomas W.↗

Use of Microgravity to Control the Microstructure of Eutectics

This grant began in June of 1996. Its long term goal is to be able to control the microstructure of directionally solidified eutectic alloys, through an improved understanding of the influence of convection. The primary objective of the present projects is to test hypotheses for the reported influence of microgravity on the microstructure of three fibrous eutectics (MnBi-Bi, InSb-NiSb, Al3Ni-Al). A secondary objective is to determine the influence of convection on the microstructure of other eutectic alloys. Two doctoral students and a masters student supported as a teaching assistant were recruited for this research. Techniques were developed for directional solidification of MnBi-Bi eutectics with periodic application of current pulses to produce an oscillatory freezing rate. Image analysis techniques were developed to obtain the variation in MnBi fiber spacing, which was found to be normally distributed. The mean and standard deviation of fiber spacing were obtained for several freezing conditions. Eighteen ampoules were prepared for use in the gradient freeze furnace QUELD developed at Queen's University for use in microgravity. Nine of these ampoules will be solidified soon at Queen's in a ground-based model. We hope to solidify the other nine in the QUELD that is mounted on the Canadian Microgravity Isolation Mount on MIR. Techniques are being developed for directional solidification of the Al-Si eutectic at different freezing rates, with and without application of accelerated crucible rotation to induce convection. For the first time, theoretical methods are being developed to analyze eutectic solidification with an oscillatory freezing rate. In a classical sharp-interface model, we found that an oscillatory freezing rate increases the deviation of the average interfacial composition from the eutectic, and increases the undercooling of the two phases by different amounts. This would be expected to change the volume fraction solidifying and the fiber spacing. Because of difficulties in tracking the freezing interfaces of the two solid phases, a phase-field model is also being developed. A paper demonstrating application of phase field methods to periodic structures has been submitted for publication.

Wilcox, William R.↗

Modeling of the Orbital Debris Population of RORSAT Sodium-Potassium Droplets

A large population resident in the orbital debris environment is composed of eutectic sodium-potassium (NaK) droplets, released during the reactor core ejection of 16 nuclear-powered Radar Ocean Reconnaissance Satellites (RORSATs) launched in the 1980s by the former Soviet Union. These electrically conducting RORSAT debris objects are spherical in shape, generating highly polarized radar returns. Their diameters are mostly in the centimeter and millimeter size regimes. Since the Space Surveillance Network catalog is limited to objects greater than 5 cm in low Earth orbit, our current knowledge about this special class of orbital debris relies largely on the analysis of Haystack radar data. This paper elaborates the simulation of the RORSAT debris populations in the new NASA Orbital Debris Engineering Model ORDEM2010, which replaces ORDEM2000. The estimation of the NaK populations uses the NASA NaK-module as a benchmark. It follows the general statistical approach to developing all other ORDEM2010-required LEO populations (for various types of debris and across a wide range of object sizes). This paper describes, in detail, each major step in the NaK-population derivation, including a specific discussion on the conversion between Haystack-measured radar-cross-sections and object-size distribution for the NaK droplets. Modeling results show that the RORSAT debris population is stable for the time period under study and that Haystack data sets are fairly consistent over the observations of multiple years.

Xu, Y.-L.↗

Influence of convection on microstructure

The primary motivation for this research was to determine the cause for space processing altering the microstructure of some eutectics, especially the MnBi-Bi eutectic. Four primary hypotheses were to be tested under this current grant: (1) A fibrous microstructure is much more sensitive to convection than a lamellar microstructure, which was assumed in our prior theoretical treatment. (2) An interface with one phase projecting out into the melt is much more sensitive to convection than a planar interface, which was assumed in our prior theoretical treatment. (3) The Soret effect is much more important in the absence of convection and has a sufficiently large influence on microstructure that its action can explain the flight results. (4) The microstructure is much more sensitive to convection when the composition of the bulk melt is off eutectic. These hypotheses were tested. It was concluded that none of these can explain the Grumman flight results. Experiments also were performed on the influence of current pulses on MnBi-Bi microstructure. A thorough review was made of all experimental results on the influence of convection on the fiber spacing in rod eutectics, including results from solidification in space or at high gravity, and use of mechanical stirring or a magnetic field. Contradictory results were noted. The predictions of models for convective influences were compared with the experimental results. Vigorous mechanical stirring appears to coarsen the microstructure by altering the concentration field in front of the freezing interface. Gentle convection is believed to alter the microstructure of a fibrous eutectic only when it causes a fluctuating freezing rate with a system for which the kinetics of fiber branching differs from that for fiber termination. These fluctuations may cause the microstructure to coarsen or to become finer, depending on the relative kinetics of these processes. The microstructure of lamellar eutectics is less sensitive to freezing rate fluctuations and to gentle convection.

Wilcox, William R.↗

Containerless processing of undercooled melts

Containerless drop tube processing allows for significant levels of liquid undercooling through control of parameters such as sample size, surface coating and cooling rate. A laboratory scale (3 m) drop tube has been developed which allows the undercooling and solidification behavior of powder samples to be evaluated under low gravity free-fall conditions. The level of undercooling obtained in an InSb-Sb eutectic alloy has been evaluated by comparing the eutectic spacing in drop tube samples with a spacing/undercooling relationship established using thermal analysis techniques. Undercoolings of 0.17 and 0.23 T(e) were produced by processing under vacuum and He gas conditions respectively. Alternatively, the formation of an amorphous phase in a Ni-Nb eutectic alloy indicates that undercooling levels of approximately 500 C were obtained by drop tube processing. The influence of droplet size and gas environment on undercooling behavior in the Ni-Nb eutectic was evaluated through their effect on the amorphous/crystalline phase ratio. To supplement the structural analysis, heat flow modeling has been developed to describe the undercooling history during drop tube processing, and the model has been tested experimentally.

Shong, D. S.↗