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NASA NTRS1995

Numerical modeling of Bridgman growth of PbSnTe in a magnetic field

In this work we study heat and mass transport, fluid motion, and solid/liquid phase change in the process of steady Bridgman growth of Pb(.8)Sn(.2)Te (LTT) in an axially-imposed uniform magnetic field under terrestrial and microgravity conditions. In particular, this research is concerned with the interrelationships among segregation, buoyancy-driven convection, and magnetic damping in the LTT melt. The main objectives are to provide a quantitative understanding of the complex transport phenomena during solidification of the nondilute binary of LTT, to provide estimates of the strength of magnetic field required to achieve the desired diffusion-dominated growth, and to assess the role of magnetic damping for space and earth based control of the buoyancy-induced convection. The problem was solved by using FIDAP and numerical results for both vertical and horizontal growth configurations with respect to the acceleration of gravity vector are presented.

Yao, Minwu↗

NASA NTRS2001

Effects of Traveling Magnetic Field on Dynamics of Solidification

TMF is based on imposing a controlled phase-shift in a train of electromagnets, forming a stack. Thus, the induced magnetic field can be considered to be travelling along the axis of the stack. The coupling of this traveling wave with an electrically conducting fluid results in a basic flow in a form of a single axisymmetric roll. The magnitude and direction of this flow can be remotely controlled. Furthermore, it is possible to localize the effect of this force field though activating only a number of the magnets. This force field generated in the fluid can, in principle, be used to control and modify convection in the molten material. For example, it can be used to enhance convective mixing in the melt, and thereby modify the interface shape, and macrosegregation. Alternatively, it can be used to counteract thermal and/or solutal buoyancy forces. High frequency TMF can be used in containerless processing techniques, such as float zoning, to affect the very edge of the fluid so that Marangoni flow can be counter balanced. The proposed program consists of basic fundamentals and applications. Our goal in conducting the following experiments and analyses is to establish the validity of TMF as a new tool for solidification processes. Due to its low power consumption and simplicity of design, this tool may find wide spread use in a variety of space experiments. The proposed ground based experiments are intended to establish the advantages and limitations of employing this technique. In the fundamentals component of the proposed program, we will use theoretical tools and experiments with mercury to establish the fundamental aspects of TMF-induced convection through a detailed comparison of theoretical predictions and experimental measurements of flow field. In this work, we will conduct a detailed parametric study involving the effects of magnetic field strength, frequency, wave vector, and the fluid geometry. The applications component of this work will be focused on investigating the effect of TMF on the following solidification and pre-directional solidification processes: (1) Bridgman growth of Ga:Ge with the goal of counteracting the buoyancy-driven convection; (2) Mixing of Pb-Ga and Pb-Sn alloys with the aim of initiating and maintaining a uniform melt prior to solidification processing; and (3) Float Zone growth with the aim of identifying, through simulations and model experiments, conditions needed to counteract Marangoni flow in a microgravity environment. The proposed research has strong relevance to microgravity research and the objectives of the NRA. TMF can provide a unique and accurate mechanism for generation and control of desirable flow patterns for microgravity research. These attributes have significant relevance to 1) Alloy mixing prior to solidification in a microgravity environment. TMF can provide this mixing with a low level of power consumption; (2) TMF can offset the deleterious effects of Marangoni convection in microgravity containerless processing. Thus, TMF can be instrumental in further understanding this phenomena; (3) Generation of controlled flows will allow the investigation of the effect of these flows on growth morphology and growth kinetics; and (4) On Earth, TMF has the potential to significantly counter-balance thermosolutal convection, thereby creating conditions similar to those obtained in microgravity. Once demonstrated, this new tool for use in solidification has the strong potential to find applications in a host of microgravity material research projects.

Mazuruk, Konstantin↗

NASA NTRS1981

Template-directed synthesis of oligoguanylic acids - Metal ion catalysis

The effects of Zn(2+), Pb(2+) and other metal ions on the efficiency and stereo-selectivity of the template-directed oligomerization of guanosine 5'-phosphorimidazolide are investigated. Reactions were run in the presence of a polyC template in a 2,6-lutidine buffer, and products analyzed by high-performance liquid chromatography on an RPC-5 column. The presence of the Pb(2+) ion is found to lead to the formation of 2'-5' linked oligomers up to the 40-mer, while Zn(2+) favors the formation of predominantly 3'-5' linked oligomers up to the 35-mer. When amounts of uracil, cytidine or adenosine 5'-phosphorimidazole equal to those of the guanosine derivative are included in the reaction mixture, the incorrect base is incorporated into the oligomer about 10% of the time with a Pb(2+) catalyst, but less than 0.5% of the time with Zn(2+). The Sn(2+), Sb(3+) and Bi(3+) ions are also found to promote the formation of 2'-5' oligomers, although not as effectively as Pb(2+), while no metal ions other than Zn(2+) promote the formation of the 3'-5' oligomers. The results may be important for the understanding of the evolution of nucleic acid replication in the absence of enzymes.

Bridson, P. K.↗

NASA NTRS2003

Investigation of Dynamic Oxygen Adsorption in Molten Solder Jetting Technology

Surface tension forces play a critical role in fluid dynamic phenomena that are important in materials processing. The surface tension of liquid metals has been shown to be very susceptible to small amounts of adsorbed oxygen. Consequently, the kinetics of oxygen adsorption can influence the capillary breakup of liquid-metal jets targeted for use in electronics assembly applications, where low-melting-point metals (such as tin-containing solders) are utilized as an attachment material for mounting of electronic components to substrates. By interpreting values of surface tension measured at various surface ages, adsorption and diffusion rates of oxygen on the surface of the melt can be estimated. This research program investigates the adsorption kinetics of oxygen on the surface of an atomizing molten-metal jet. A novel oscillating capillary jet method has been developed for the measurement of dynamic surface tension of liquids, and in particular, metal melts which are susceptible to rapid surface degradation caused by oxygen adsorption. The experimental technique captures the evolution of jet swells and necks continuously along the jet propagation axis and is used in conjunction with an existing linear, axisymmetric, constant-property model to determine the variation of the instability growth rate, and, in turn, surface tension of the liquid as a function of surface age measured from the exit orifice. The conditions investigated so far focus on a time window of 2-4ms from the jet orifice. The surface properties of the eutectic 63%Sn-37%Pb solder alloy have been investigated in terms of their variation due to O2 adsorption from a N2 atmosphere containing controlled amounts of oxygen (from 8 ppm to 1000 ppm). The method performed well for situations where the oxygen adsorption was low in that time window. The value of surface tension for the 63Sn-37Pb solder in pure nitrogen was found to be 0.49 N/m, in good agreement with previously published work. A characteristic time of O(1ms) or less was determined for the molten-metal surface to be saturated by oxygen at 1000 ppm concentration in N2.

Megaridis, Constantine M.↗

NASA NTRS1975

Preferential concentration of certain elements in smaller aerosols emitted from aircraft engines

Aerosols from aircraft engines were collected with an eight-stage cascade sampler for a period of 24 h. The aerosol samples from each stage were analyzed for their elemental composition using the proton-induced X-ray emission (PIXE) technique. Seventeen elements (Si, P, S, Cl, K, Ca, Ti, V, Fe, Ni, Cu, Zn, Br, Sr, Nb, Sn, and Pb) were positively identified and quantitated at each stage. Six elements (S, Ca, Fe, Zn, Sn, and Pb) showed a fractional concentration increase with decreasing aerosol size. Similar, but less well-defined, trends were also observed for V and Ni. Silicon and chlorine, on the other hand, showed an opposite trend. Neutron-activation analysis of bulk aerosol samples collected every 2 h over the same period showed a correlation between concentration of Si, Ca, V, Ti, Zn, Br, and Sn and the density of air traffic at the airport. Analysis of the aviation-fuel samples by PIXE indicates that major fractions of Pb, Sn, Br, Zn, Ni, Fe, V, Ca, and S observed in these aerosol studies come from the aircraft engine exhaust.

Jolly, R. K.↗

NASA NTRS2012

Volatile Siderophile Elements in Shergottites: Constraints on Core Formation and Magmatic Degassing

Volatile siderophile elements (e.g., As, Sb, Ge, Ga, In, Bi, Zn, Cd, Sn, Cu, Pb) can place constraints both on early differentiation as well as the origin of volatiles. This large group of elements has been used to constrain Earth accretion [1,2], and Earth-Moon geochemistry [3]. Application to Earth has been fostered by new experimental studies of these elements such as Ge, In, and Ga [4,5,6]. Application to Mars has been limited by the lack of data for many of these elements on martian meteorites. Many volatile elements are considered in the pioneering work by [7] but for only the small number of martian samples then available. We have made new measurements on a variety of martian meteorites in order to obtain more substantial datasets for these elements using the analytical approach of [8]. We use the new dataset, together with published data from the literature, to define martian mantle abundances of volatile siderophile elements. Then, we evaluate the possibility that these abundances could have been set by mid-mantle (14 GPa, 2100 C) metal-silicate equilibrium, as suggested by the moderately and slightly siderophile elements [9]. Finally, we examine the possibility that some elements were affected by volatility and magmatic degassing.

Righter, Kevin↗

NASA NTRSDate not supplied

Effect of Pressure and Oxidation State on Pnictogen Metal-Silicate Partitioning

The partitioning of trace elements between metal and silicate melts serves as the foundation for understanding the differentiation of a planetary body into a metallic core and silicate mantle. Element activity influences metal-silicate partitioning behavior. Activity coefficients are directly dependent on composition and temperature, and can be indirectly dependent on oxygen fugacity and pressure. Distinguishing the effect of pressure from other variables on the activity coefficients and partitioning is important for understanding the chemical evolution of different planetary bodies during differentiation. In this study, we investigated the influence of pressure on the activity coefficients of Cu, Mo, Pd, Pt, As, Sb, and Bi in Fe-Si metallic liquids. All of these elements exhibit moderate to high activity coefficients in Fe-Si liquids at low pressure, which significantly controls their metal-silicate partitioning behavior. Identifying whether this strong dependence persists at higher pressures is critical to modeling and understanding the chemical consequences of core formation. New experiments at 10 GPa were used to derive activity coefficients for these metals which can be compared to activity coefficients determined at 1 GPa. Experiments were conducted at 10 GPa and 2373K using a 10/5 assembly in the 880-ton multi anvil press at NASA Johnson Space Center. The standard 10/5 COMPRES assembly was slightly modified to accommodate a sample capsule machined from single-crystal MgO that minimizes melt percolation out of the sample volume during the experiment. Experiment starting materials were comprised of 70 wt.% Knippa basalt and 30 wt.% metal. The metal mixture (~85 wt.% Fe) was created by adding the elements of interest (Cu, Mo, Pd, Pt, As, Sb, Bi) to Fe metal powder. Varied amounts of Si metal (0-10 wt.% Si) were added to the metal-silicate mixtures to generate a systematic series of starting materials. For each element, an epsilon interaction parameter in Fe-Si liquid was derived from the results of our 0-10 wt.% Si metal series. To investigate whether pressure influences the trace element activity coefficients in the 1-10 GPa pressure range, we compared our results at 10 GPa to those at 1-4 GPa [1-3]. Our results can also be directly compared to interaction parameters for Au, P, V, Mn, Ga, Zn, Cd, Sn, W, Pb, and Nb previously determined at 10 GPa and 2373K following the same methods [4]. Combined, this suite of interaction parameters will directly inform metal- silicate partitioning between 1 and 10 GPa, and assess whether these values can be extrapolated to modeling differentiation processes at pressures >10 GPa. [1] Righter et al. (2018) GCA 232, 101-123 [2] Righter et al. (2019) MaPS 54, 1379-1394 [3] Steenstra et al. (2020) Icarus, 335, 113391 [4] Righter et al. (2020) Geochem. Persp. Let. 15, 44-49

Kelsey Prissel↗

NASA NTRS1988

Ostwald ripening in a system with a high volume fraction of coarsening phase

The coarsening of Sn-rich and Pb-rich solid phases in contact with eutectic liquid in the volume fraction solid range above approximately 0.6, where the development of a solid skeletal structure inhibits sedimentation, is investigated. Particle intercept distributions are shown to be time independent when scaled by the average intercept. It is noted that the coarsening rate constants obtained exceed the values calculated from theory by factors ranging from about 2 to 5.

Hardy, S. C.↗

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 NTRS2004

Thermally Conductive Metal-Tube/Carbon-Composite Joints

An improved method of fabricating joints between metal and carbon-fiber-based composite materials in lightweight radiators and heat sinks has been devised. Carbon-fiber-based composite materials have been used in such heat-transfer devices because they offer a combination of high thermal conductivity and low mass density. Metal tubes are typically used to carry heat-transfer fluids to and from such heat-transfer devices. The present fabrication method helps to ensure that the joints between the metal tubes and the composite-material parts in such heat-transfer devices have both (1) the relatively high thermal conductances needed for efficient transfer of heat and (2) the flexibility needed to accommodate differences among thermal expansions of dissimilar materials in operation over wide temperature ranges. Techniques used previously to join metal tubes with carbon-fiber-based composite parts have included press fitting and bonding with epoxy. Both of these prior techniques have been found to yield joints characterized by relatively high thermal resistances. The present method involves the use of a solder (63 percent Sn, 37 percent Pb) to form a highly thermally conductive joint between a metal tube and a carbon-fiber-based composite structure. Ordinarily, the large differences among the coefficients of thermal expansion of the metal tube, solder, and carbon-fiber-based composite would cause the solder to pull away from the composite upon post-fabrication cooldown from the molten state. In the present method, the structure of the solder is modified (see figure) to enable it to deform readily to accommodate the differential thermal expansion.

Copeland, Robert J.↗

NASA NTRS2004

Volatile Element Geochemistry in the Lower Atmosphere of Venus

We computed equilibrium abundances of volatile element compounds as a function of altitude in Venus lower atmosphere. The elements included are generally found in volcanic gases and sublimates on Earth and may be emitted in volcanic gases on Venus or volatilized from its hot surface. We predict: 1) PbS, Bi2S3, or possibly a Pb-Bi sulfosalt are the radar bright heavy metal frost in the Venusian highlands; 2) It should be possible to determine Venus' age by Pb-Pb dating of PbS condensed in the Venusian highlands, which should be a representative sample of Venusian lead; 3) The gases HBr, PbCl2, PbBr2, As4O6, As4S4, Sb4O6, BiSe, InBr, InCl, Hg, TlCl, TlBr, SeS, Se2-7, HI, I, I2, ZnCl2, and S2O have abundances greater than 0.1 ppbv in our nominal model and may be spectroscopically observable; 4) Cu, Ag, Au, Zn, Cd, Ge, and Sn are approx. 100 % condensed at the 740 K (0 km) level on Venus.

Schaefer, L.↗

NASA NTRS2003

Minimizing Segregation during the Controlled Directional Solidification of Dendric Alloys

Gravity-driven convection induced in the liquid by density gradients of temperature or composition disrupts uniform dendritic growth during controlled directional solidification and promotes severe macrosegregation. The solute-rich region about the dendrite tip appears to play a pivotal role in channel initiation. Allen and Hunt referred to this region as an "initial transient" or dynamic region constituting steep concentration gradients. Experimental investigation also point to the role the tip region plays in developing microstructure. Hellawell and co-workers showed that flow-through dendritic channels could be effectively disrupted, and segregation minimized, during the gradient freezing of bulk castings by rotating the melt through a slight angle with respect to Earth's gravity vector. Adapting this principle to controlled directional solidification, it has been shown" that segregation in dendritic alloys can be minimized, and properties improved, by processing the sample near horizontal in conjunction with a slow axial rotation of the crucible. It is postulated that the observed microstructural uniformity arises by maintaining the developing solute field about the dendrite tip. Solute rejected during vertical directional solidification will rise or sink parallel to the primary dendrite arms during axial rotation setting the stage for accumulation, instabilities, and segregation. In contrast, during horizontal growth, the rejected solute will sink or rise perpendicular to the primary dendrite. Now, in the presence of a slight axial rotation, solute that was initially sinking (or rising) will find itself above (or below) its parent dendrite, i.e., still about the tip region. The following is intended to experimentally demonstrate the viability of this concept in coordination with a model that gives predictive insight regarding solute distribution about growing dendrites. Alloys based on the lead-tin eutectic system were used in this study. The system is well characterized, the constituent metals are available in a very pure form, and the thermophysical properties are well known. During solidification of hypoeutectic alloys, e.g., 55 wt pct Pb, the primary dendrites reject the less dense tin, and for the hypereutectic alloys, e.g., 75 wt pct Sn, the primary dendrites reject denser lead. Alloys were prepared by melting appropriate amounts of lead and tin in a glass crucible after which the homogeneous liquid was sucked directly into 5-mm i.d. glass tubes. The sample tube, containing approximately 30 cm of alloy, was then mechanically driven into the directional solidification furnace assembly and positioned such that approx. 20 cm of the sample was remelted. Subsequently, directional solidification was initiated by withdrawing the sample through a water-cooled jacket at a constant growth velocity of 2 ,microns/s. After 5 to 6 cm of growth, the sample was quickly removed from the furnace and quenched in a water bath to preserve the solid-liquid interface. Samples were directionally solidified vertically upward, nearly horizontally, and some in conjunction with an applied axial rotation of the crucible. Temperature gradients at the solid-liquid interface were measured with an in-siru K-type thermocouple. Solidified samples were cut perpendicular and parallel to the growth direction and conventionally prepared for microscopic examination.

Grugel, Richard N.↗

NASA NTRS1990

Superconductivity in the Sn-Ba-Sr-Y-Cu-O system

Since Bednorz and Muller discovered high-T(sub c) superconductivity in the La-Ba-Cu-O compound, several families of superconducting oxides have been synthesized. Here, researchers report the results of search for superconductivity in the compounds based on tin, which has a lone electron pair like Bi, Tl, Pb. The following compounds were synthesized: Sn1Ba1Sr1Cu3Ox, Sn1Ba1Ca1Cu3Ox, Sn1Ba1Mg1Cu3Ox, Sn1Sr1Ca1Cu3Ox, Sn1Sr1Mg1Cu3Ox, Sn1Ca1Mg1Cu3Ox. The initial components were oxides and carbonates of the appropriate elements. Standard firing-grinding procedure was used. Final heating was carried out at 960 C during 12 hours. Then the samples were cooled inside the furnace. All the synthesis cycles were carried out in air atmosphere. Among the synthesized compounds only Sn1Ba1Sr1Cu3Ox showed remarkable conductivity. Other compounds were practically dielectrics. Presence of a possible superconductivity in Sn1Ba1Sr1Cu3Ox was defined by using the Meissner effect. At low temperature a deviation from paramagnetic behavior is observed. The hysteresis loops obtained at lower temperatures undoubtly testify to the presence of a superconductive phase in the sample. However, the part of the superconductive phase in the Sn1Ba1Sr1Cu3Ox ceramic turned out to be small, less than 2 percent, which agrees with the estimation from magnetic data. In order to increase the content of the superconductive phase two-valent cations Ba, Sr were partially substituted by univalent (K) and three-valent ones (Y).

Aleksandrov, K. S.↗

NASA NTRS1991

Superconductivity in the Sn-Ba-Sr-Y-Cu-O system

After the discovery of high-T(sub c) superconductivity in the La-Ba-Cu-O compound, several families of superconducting oxides were synthesized. Here, researchers report the results of the search for superconductivity in the compounds based on tin which has a lone electron pair like Bi, Tl, and Pb. The following compounds were synthesized: Sn1Ba1Sr1Cu3O(sub x), Sn1Ba1Ca1Cu3O(sub x), Sn1Ba1Mg1Cu3O(sub x), Sn1Sr1Ca1Cu3O(sub x), Sn1Sr1Mg1Cu3O(sub x), and Sn1Ca1Mg1Cu3O(sub x). The initial components were oxides and carbonates of the appropriate elements. A standard firing-grinding procedure was used. Final heating was carried out at 960 C during 12 hours. Then the samples were cooled inside the furnace. All the synthesis cycles were carried out in air atmosphere. Among the synthesized compounds only Sn1Ba1Sr1Cu3O(sub x) showed remarkable conductivity. Other compounds were practically dielectrics. Presence of a possible superconductivity in Sn1Ba1Sr1Cu3O(sub x) was defined by using the Meissner effect. At low temperature a deviation from paramagnetic behavior is observed. The hysteresis loops obtained at lower temperature undoubtly testify to the presence of a superconductive phase in the sample. However, the part of the superconductive phase in the Sn1Ba1Sr1Cu3O(sub x) ceramic turned out to be small, less than 2 percent, which agrees with the estimation from magnetic data. In order to increase the content of the superconductive phase, two-valent cations Ba and Sr were partially substituted by univalent (K) and three-valent ones (Y).

Aleksandrov, K. S.↗