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The parameters and requirements for growing single crystals of relatively high melting point metals in a zero gravity environment are studied. The crystal growth of metals such as silver, copper, gold, and alloys with a melting point between 900-1100 C is examined.
Hafnium and zirconium are very similar, with almost identical sizes and chemical bonding characteristics. However, they behave differently when alloyed with Ti and Ni. A sharp phase formation boundary near 18-21 at.% Hf is observed in rapidly-quenched and as-cast Ti45Zr38-xHfxNi17 alloys. Rapidly-quenched samples that contain less than 18 at.% Hf form the icosahedral quasicrystal phase, whiles samples containing more than 21 at.% form the 3/2 rational approximant phase. In cast alloys, a C14 structure is observed for alloys with Hf lower than the boundary concentration, while a large-cell (11.93 ) FCC Ti2Ni-type structure is found in alloys with Hf concentrations above the boundary. To better understand the role of Hf on phase formation, the structural evolution with supercooling and the solidification behavior of liquid Ti45Zr38-xHfxNi17 alloys (x=0, 12, 18, 21, 38) were studied using the Beamline Electrostatic Levitation (BESL) technique using 125keV x-rays on the 6ID-D beamline at the Advanced Photon Source, Argonne National Laboratory. For all liquids primary crystallization was to a BCC solid solution phase; interestly, an increase in Hf concentration leads to a decrease in the BCC lattice parameter in spite of the chemical similarity between Zr and Hf. A Reitveld analysis confirmed that as in the cast alloys, the secondary phase that formed was the C14 below the phase formation boundary and a Ti2Ni-type structure at higher Hf concentrations. Both the liquidus temperature and the reduced undercooling change sharply on traversing the phase formation boundary concentration, suggesting a change in the liquid structure. Structural information from a Honeycutt-Anderson index analysis of reverse Monte Carlo fits to the S(q) liquid data will be presented to address this issue.
A study was performed to select candidate lithium alloy anode materials and establish selection criteria. Some of the selected alloy materials were evaluated for their electrochemical properties and performance. This paper describes the criteria for the selection of alloys and the findings of the studies. Li-Si and Li-Cd alloys have been found to be unstable in the EC+2-MeTHF-based electrolyte. The Li-Al alloy system was found to be promising among the alloy systems studied in view of its stability and reversibility. Unfortunately, the large volume changes of LiAl alloys during charge/discharge cycling cause considerable 'exfoliation' of its active mass. This paper also describes ways how to address this problem. The rate of disintegration of this anode would probably be surpressed by the presence of an inert solid solution or a uniform distribution of precipitates within the grains of the active mass. It was discovered that the addition of a small quantity of Mn may improve the mechanical properties of LiAl. In an attempt to reduce the Li-Al alloy vs. Li voltage, it was observed that LiAlPb(0.1)Cd(0.3) material can be cycled at 1.5 mA/sq cm without exfoliation of the active mass.
Study of Mo-Re alloys aimed at examining the effects of small rhenium additions on the low-temperature ductility of molybdenum and determining the mechanical properties of dilute Mo-Re alloys. The results obtained indicate that high-purity Mo-Re alloys have ductile-brittle transition temperatures considerably lower than those for unalloyed molybdenum and that rhenium promotes normal solid-solution strengthening in molybdenum at elevated temperatures.
Hypoeutectic, eutectic, and hypereutectic nickel-molybdenum alloys were rapidly solidified by both bulk undercooling and melt spinning techniques. Alloys were undercooled in both electromagnetic levitation and differential thermal analysis equipment. The rate of recalescence depended upon the degree of initial undercooling and the nature (faceted or nonfaceted) of the primary nucleating phase. Alloy melts were observed to undercool more in the presence of primary Beta (NiMo intermetallic) phase than in gamma (fcc solid solution) phase. Melt spinning resulted in an extension of molybdenum solid solubility in gamma nickel, from 28 to 37.5 at % Mo. Although the microstructures observed by undercooling and melt spinning were similar the microsegregation pattern across the gamma dendries was different. The range of microstructures evolved was analyzed in terms of the nature of the primary phase to nucleate, its subsequent dendritic growth, coarsening and fragmentation, and final solidification of interfenderitic liquid.
Hypoeutectic, eutectic, and hypereutectic nickel-molybdenum alloys were rapidly solidified by both bulk undercooling and melt spinning techniques. Alloys were undercooled in both electromagnetic levitation and differential thermal analysis equipment. The rate of recalescence depended upon the degree of initial undercooling and the nature (faceted or nonfaceted) of the primary nucleating phase. Alloy melts were observed to undercool more in the presence of primary Beta (NiMo intermetallic) phase than in gamma (fcc solid solution) phase. Melt spinning resulted in an extension of molybdenum solid solubility in gamma nickel, from 28 to 37.5 at. pct Mo. Although the microstructures observed by undercooling and melt spinning were similar, the microsegregation pattern across the gamma dendries was different. The range of microstructures evolved was analyzed in terms of the nature of the primary phase to nucleate, its subsequent dendritic growth, coarsening and fragmentation, and final solidification of interfenderitic liquid.
This research applies a state of the art X-ray Transmission Microscope, XTM, to image (with resolutions up to 3 micrometers) the solidification of metallic or semiconductor alloys in real-time. We have successfully imaged in real-time: interfacial morphologies, phase growth, coalescence, incorporation of phases into the growing interface, and the solute boundary layer in the liquid at the solid-liquid interface. We have also measured true local growth rates and can evaluate segregation structures in the solid; a form of in-situ metallography. During this study, the growth of secondary phase fibers and lamellae from eutectic and monotectic alloys have been imaged during solidification, in real-time, for the first time in bulk metal alloys. Current high resolution X-ray sources and high contrast X-ray detectors have advanced to allow systematic study of solidification dynamics and the resulting microstructure. We have employed a state-of-the-art sub-micron source with acceleration voltages of 10-100 kV to image solidification of metals. One useful strength of the XTM stems from the manner an image is formed. The radiographic image is a shadow formed by x-ray photons that are not absorbed as they pass through the specimen. Composition gradients within the specimen cause variations in absorption of the flux such that the final image represents a spatial integral of composition (or thickness). The ability to image these features in real-time enables more fundamental and detailed understanding of solidification dynamics than has previously been possible. Hence, application of this technique towards microgravity experiments will allow rigorous testing of critical solidification models.
The following definitions were sought in the research on single crystals of metal solid solutions: (1) the influence of convection and/or gravity present during crystallization on the substructure of a metal solid solution; (2) the influence of a magnetic field applied during crystallization on the substructure of a metal solid solution; and (3) requirements for a space flight experiment to verify the results. Growth conditions for the selected silver-zinc alloy system are described, along with pertinent technical and experimental details of the project.
Bridgman and Float-zone crystal growth experiments are planned for NASA's First Materials Science Research Rack using the European Space Agency's Materials Science Laboratory with the Low Gradient Furnace (LGF) and Float Zone Furnace with Rotating Magnetic Field (FMF) inserts, respectively. Samples will include germanium and germanium-silicon alloys with up to 10 atomic percent silicon. The Bridgman part of the investigation includes detached growth samples and so there will be a solid-liquid-gas tri-junction in those experiments just as there will be in all float-zone experiments. There are other similarities as well as significant differences between the types of growth that will be discussed. The presentation will call attention to the reasons that experiments in microgravity will provide information unattainable from Earth-based experiments.
A fully time-dependent linear stability analysis of the morphological stability of a planar interface during directional solidification of a binary alloy at constant velocity in the presence of an electric field, is performed. The electromigration of solute and the differing electrical conductivities of solid and liquid for a model in which the temperature gradient is constant are taken into account. The present results are compared with the constitutional supercooling criterion, and it is shown there may be substantial differences. A modified constitutional supercooling criterion which is valid over a large range of conditions is derived. It is also found under certain conditions that the onset of instability may be time dependent.
This paper considers the unidirectional solidification of a binary alloy for which the liquid and solid phases are bounded by endwalls. In order to account for the transport of latent heat and solute, thermal and solutal boundary layers must be placed at the solidifying interface. Further, under the assumption of fixed temperature gradients, the presence of the endwalls leads to a velocity of solidification that decreases with time, and hence to an unsteady basic state having a planar interface. From a stability analysis of this state, a nonlinear long-wave evolution equation of Sivashinsky type is derived, with modified coefficients, that shows how the onset of cellular structure is delayed by the presence of endwalls.
The BFS (Bozzolo-Ferrante-Smith) method for alloys is applied to the study of the Cu-Pd system. A variety of issues are analyzed and discussed, including the properties of pure Cu or Pd crystals (surface energies, surface relaxations), Pd/Cu and Cu/Pd surface alloys, segregation of Pd (or Cu) in Cu (or Pd), concentration dependence of the lattice parameter of the high temperature fcc CuPd solid solution, the formation and properties of low temperature ordered phases, and order-disorder transition temperatures. Emphasis is made on the ability of the method to describe these properties on the basis of a minimum set of BFS universal parameters that uniquely characterize the Cu-Pd system.
A series of Cu-based alloys containing 2 to 10 a/o Cr and 1 to 5 a/o Nb were produced by chill block melt spinning (CBMS). The melt spun ribbons were consolidated and hot rolled to sheet to produce a supersaturated Cu-Cr-Nb solid solution from which the high melting point intermetallic compound Cr2Nb could be precipitated to strengthen the Cu matrix. The results show that the materials possess electrical conductivities in excess of 90 percent that of pure Cu at 200 C and above. The strengths of the Cu-Cr-Nb alloys were much greater than Cu, Cu-0.6 Cr, NARloy-A, and NARloy-Z in the as-melt spun condition. The strengths of the consolidated materials were less than Cu-Cr and Cu-Cr-Zr below 500 C and 600 C respectively, but were significantly better above these temperatures. The strengths of the consolidated materials were greater than NARloy-Z, at all temperatures. The GLIDCOP possessed similar strength levels up to 750 C when the strength of the Cu-Cr-Nb alloys begins to degrade. The long term stability of the Cu-Cr-Nb alloys was measured by the microhardness of aged samples and the growth of precipitates. The microhardness measurements indicate that the alloys overage rapidly, but do not suffer much loss in strength between 10 and 100 hours which confirms the results of the electrical resistivity measurements taken during the aging of the alloys at 500 C. The loss in strength from peak strength levels is significant, but the strength remains exceptionally good. Transmission electron microscopy (TEM) of the as-melt spun samples revealed that Cr2Nb precipitates formed in the liquid Cu during the chill block melt spinning, indicating a very strong driving force for the formation of the precipitates. The TEM of the aged and consolidated materials indicates that the precipitates coarsen considerably, but remain in the submicron range.
The solidification of a solid solution semiconductor, having a wide separation between liquidus and serious has been extensively studied in ground based, high magnetic field and Spacelab experiments. Two alloys of mercury cadmium telluride have been studied; mercury cadmium telluride with 80.0 mole percent of HgTe and 84.8 mole percent respectively. These alloys are extremely difficult to grow by directional solidification on earth due to high solutal and thermal density differences that give rise to fluid flow and consequent loss of interface shape and composition. Diffusion controlled growth is therefore impossible to achieve in conventional directional solidification. The ground based experiments consisted of growing crystals in several different configurations of heat pipe furnaces, NASA's Advanced Automated Directional Solidification Furnace (AADSF), and a similar furnace incorporated in a superconducting magnet capable of operating at up to 5T. The first microgravity experiment took place during the flight of STS-62 in March 1994, with the AADSF installed on the second United States Microgravity Payload (USMP-2). The alloy was solidified at 3/4 inch per day over a 9 day period, and for the first time a detailed evaluation was performed of residual acceleration effects. The second flight experiment took place in the fourth United States Microgravity Payload Mission (USMP-4) in November 1997. Due to contamination of the furnace system by a previously processed sample, the sample was not received until May 1998, and the preliminary analysis shows that the conditions prevailing during the experiment were quite different from the requirements requested prior to the mission. Early results are indicating that the sample may not accomplish the desired objectives. As with the USMP-2 mission, the results of the ground based experiments were compared with the crystal grown in orbit under microgravity conditions. On the earth, it has been demonstrated that the application of the magnetic field leads to a significant reduction in fluid flow, with improved homogeneity of composition. The field strength required to suppress flow increases with diameter of the material. The 8 mm diameter sample used here was less than the upper diameter limit for a ST magnet. The configuration for USMP-4 was changed so that the material was seeded and other processing techniques were also modified. It was decided to examine the effects of a strong magnetic field under the modified configuration and parameters. A further change from USMP-2 was that a different composition of material was grown, namely with 0.152 mole fraction of cadmium telluride rather than the 0.200 of the USMP-2 experiment. The objective was to grow highly homogeneous, low defect density material of a composition at which the conduction band and the valence band of the material impinge against each other. As indicated, the furnace was contaminated during the mission. As a result of solid debris remaining in the furnace bore, the cartridge in this experiment, denoted as SL1-417, was significantly bent during the insertion phase. During translation the cartridge scraped against the plate which isolates the hot and cold zones of the furnace. Thermocouples indicated that a thermal assymetry resulted. The scraping in the slow translation or crystal growth part of the processing was not smooth and it is probable that the jitter was sufficient to give rise to convection in the melt. Early measurements of composition from the surface of the sample have shown that the composition varies in an oscillatory manner.
Interrupted growth experiments on Hg(0.8)Cd(0.2)Se alloys were performed in an attempt to estimate the actual internal temperature gradient in the melt during directional solidification. The results have been analyzed in terms of a theoretical model which assumes an axial composition profile characteristic of diffusion controlled solute redistribution during growth. A comparison of the calculated and measured values suggests a reduction in the applied (empty furnace) temperature gradient by about a factor of three. Values of the interface segregation coefficient (k) determined from the phase diagram, predict values of solute concentration build up in the solid during growth interruptions which are inconsistent with measured results. It appears that the k values used tend to underestimate the actual k values for higher alloy compositions and overestimate k for the lower alloy compositions.
Directional solidification of pure materials and binary alloys with a planar crystal-metal interface in the presence of a time-dependent electric current is considered. For a variety of time-dependent currents, the temperature fields and the interface velocity as functions of time are presented for indium antimonide and bismuth and for the binary alloys germanium-gallium and tin-bismuth. For the alloys, the solid composition is calculated as a function of position. Quantitative predictions are made of the effect of an electrical pulse on the solute distribution in the solidified material.
As a solid solution semiconductor having, a large separation between liquidus and solidus, mercury cadmium telluride (MCT) presents a formidable challenge to crystal growers desiring an alloy of high compositional uniformity. To avoid constitutional supercooling during Bridgman crystal growth it is necessary to solidify slowly in a high temperature gradient region. The necessary translation rate of less than 1 mm/hr results in a situation where fluid flow induced by gravity on earth is a significant factor in material transport. The Advanced Automated Directional Solidification Furnace (AADSF) is equipped to provide the stable thermal environment with a high gradient, and the required slow translation rate needed. Ground based experiments in AADSF show clearly the dominance of flow driven transport. The first flight of AADSF in low gravity on USMP-2 provided an opportunity to test theories of fluid flow in MCT and showed several solidification regimes which are very different from those observed on earth. Residual acceleration vectors in the orbiter during the mission were measured by the Orbital Acceleration Research Experiment (OARE), and correlated well with observed compositional differences in the samples.
Nickel-base superalloys are the current choice for high-temperature jet engine applications such as turbine blades and vanes. However, after more than five decades of use, nickel-base superalloys have reached their limit, since the operating temperatures in gas turbine engines are now approaching the melting temperature of these alloys. Thus alternative materials, such as lightweight NiAl intermetallic alloys with superior properties, (e.g., high melting temperature, high thermal conductivity, and excellent chemical stability and oxidation resistance) are required for the next generation of high-temperature structural materials for more efficient 21st century civil transport systems. The two major disadvantages that have historically prevented the application of NiAl as a high-temperature structural material are its poor creep resistance and low room-temperature ductility. Alloying strategies similar to those used for nickel-base superalloys are being used to improve the high-temperature strength via solid-solution and precipitate-hardening effects. This study highlights the potent role of Ti and Hf as potential solid-solution strengtheners in NiAl and also the added effect of second-phase particles when Ti and Hf are both used.