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Microstructural Development during Directional Solidification of Peritectic Alloys

A thorough understanding of the microstructures produced through solidification in peritectic systems has yet to be achieved, even though a large number of industrially and scientifically significant materials are in this class. One type of microstructure frequently observed during directional solidification consists of alternating layers of primary solid and peritectic solid oriented perpendicular to the growth direction. This layer formation is usually reported for alloy compositions within the two-phase region of the peritectic isotherm and for temperature gradient and growth rate conditions that result in a planar solid-liquid interface. Layered growth in peritectic alloys has not previously been characterized on a quantitative basis, nor has a mechanism for its formation been verified. The mechanisms that have been proposed for layer formation can be categorized as either extrinsic or intrinsic to the alloy system. The extrinsic mechanisms rely on externally induced perturbations to the system for layer formation, such as temperature oscillations, growth velocity variations, or vibrations. The intrinsic mechanisms approach layer formation as an alternative type of two phase growth that is inherent for certain peritectic systems and solidification conditions. Convective mixing of the liquid is an additional variable which can strongly influence the development and appearance of layers due to the requisite slow growth rate. The first quantitative description of layer formation is a model recently developed by Trivedi based on the intrinsic mechanism of cyclic accumulation and depiction of solute in the liquid ahead of the interface, linked to repeated nucleation events in the absence of convection. The objective of this research is to characterize the layered microstructures developed during ground-based experiments in which external influences have been minimized as much as possible and to compare these results to the current the model. Also, the differences between intrinsic and externally influenced layer formation were explored. The choice of alloy system is critical to a study of the formation of layered microstructures. The ideal system would have a well-characterized phase diagram, equal densities of both elements in the liquid state to minimize compositionally-driven convective flows, a low peritectic temperature to simplify directional solidification and the achievement of a high temperature gradient in the liquid, a broad composition range for the peritectic reaction, and a reasonable hardness at room temperature to facilitate handling and metallographic preparation. The In-Sn system was selected initially due to a very low peritectic temperature and the nearly equal densities of In and Sn in the liquid state. Since the In-rich peritectic reaction had apparently not been utilized previously for solidification research, experiments were conducted to check the phase diagram in the region of interest. The alloys in this system proved to be difficult to handle and prepare in bulk form with the equipment available, so experiments were initiated with the Sn-Cd system. Layered microstructures had been observed previously in Sn-Cd.

Lograsso, Thomas A.

Macrosegregation during plane front directional solidification of Csl-1 wt. percent Tll alloy

Macrosegregation produced during vertical Bridgeman directional solidification of Csl-1 wt. pct. Tll in crucibles of varying diameter, from 0.5 to 2.0 cm, was examined. Gravity driven convection is present in the melt even in the smallest crucible diameter of 0.5 cm. Observed solutal profiles are in agreement with the analytical boundary layer model of Favier which describes macrosegregation in the presence of convection. The scintillation efficiency of Csl decreases along the specimen length as the thallium iodide content of the alloy increases.

Sidawi, I. M. S.

Directional Solidification of Mercury Cadmium Telluride in Microgravity

Mercury cadmium telluride (MCT) has been directionally solidified for ten days in the Advanced Automated Directional Solidification Furnace (AADSF) on the second United States Microgravity Payload Mission (USMP-2). A second growth experiment is planned for the USMP-4 mission in November 1997. Results from USMP-2 demonstrated significant changes between microgravity and ground-based experiments, particularly in the compositional homogeneity. Changes were also observed during the microgravity mission which were dependent on the attitude of the space shuttle and the relative magnitudes of axial and transverse residual accelerations with respect to the growth axis of the crystal. Issues of shuttle operation, especially those concerned with safety and navigation, and the science needs of other payloads dictated the need for changes in attitude. One consequence for solidification of MCT in the USMP4 mission is the desire for a shorter growth time to complete the experiment without subjecting the sample to shuttle maneuvers. By using a seeded technique and a pre-processed boule of MCT with an established diffusion layer quenched into the solid, equilibrium steady state growth can be established within 24 hours, rather than the three days needed in USMP-2. The growth of MCT in AADSF during the USMP-4 mission has been planned to take less than 72 hours with 48 hours of actual growth time. A review of the USMP-2 results will be presented, and the rationale for the USMP-4 explained. Pre-mission ground based tests for the USN4P-4 mission will be presented, as will any available preliminary flight results from the mission.

Lechoczhy, Sandor L.

Texturing of high T(sub c) superconducting polycrystalline fibers/wires by laser-driven directional solidification in an thermal gradient

This paper summarizes the technique of laser-driven directional solidification in a controlled thermal gradient of yttria stabilized zirconia core coated Y-Ba-Cu-O materials to produce textured high T(sub c) superconducting polycrystalline fibers/wires with improved critical current densities in the extended range of magnetic fields at temperatures greater than 77 K. The approach involves laser heating to minimize phase segregation by heating very rapidly through the two-phase incongruent melt region to the single phase melt region and directionally solidifying in a controlled thermal gradient to achieve highly textured grains in the fiber axis direction. The technique offers a higher grain growth rate and a lower thermal budget compared with a conventional thermal gradient and is amenable as a continuous process for improving the J(sub c) of high T(sub c) superconducting polycrystalline fibers/wires. The technique has the advantage of suppressing weak-link behavior by orientation of crystals, formation of dense structures with enhanced connectivity, formation of fewer and cleaner grain boundaries, and minimization of phase segregation in the incongruent melt region.

Varshney, Usha

Controlled Parametric Forcing During Directional Solidification of a Bulk Organic Alloy Under Microgravity

The response of dendritic microstructures to step-like pulling velocity conditions is investigated using microgravity directional solidification experiments conducted on DECLIC-DSI combined with phase-field simulations. Under a constant pulling velocity of 1.5 µm/s, the evolution toward steady-state growth is characterized in terms of primary spacing, dendrite drift, and tip dynamics. For the first time, side-view observations enabled direct measurement of tip radius and sidebranching frequency. When step-like oscillations of the pulling velocity are imposed, the dendritic array exhibits a strongly period-dependent response: short periods lead to rapid tip adaptation, whereas longer periods induce a phase lag between tip position and morphology, resulting in progressive tip flattening and, above a critical period, interface destabilization and dendrite splitting. Quantitative phase-field simulations, including a realistic thermal field and stochastic noise, reproduce the experimental observations and provide insight into the governing mechanisms, highlighting the role of characteristic relaxation times, sequence-dependent effects, and the irreversible reorganization of the microstructure following splitting.

Microgravity

Growth of HgZnTe alloy crystals by directional solidification

A series of Hg(1-x)Zn(x)Te crystals were grown by directional solidification with x ranging from 0.15 to 0.22. The axial and radial compositional variations were determined by precision density measurements, infrared (IR) transmission spectra, and energy dispersive X-ray spectroscopy (EDX). Comparison between the axial compositional profiles and the calculated results of a one-dimensional diffusion model gives a value for the effective diffusion coefficient in the HgZnTe melt of 2 to 4 x 10 to the -6th sq cm/s.

Su, Ching-Hua

Effect of gravity on coupled convective and interfacial instabilities during directional solidification

Instabilities occurring during the directional constant-rate solidification of a dilute solution of tin in lead are investigated as a function of gravity with particular emphasis on small constant gravitational accelerations. Two types of instabilities have been identified: (1) convective type that corresponds to long wavelengths, and (2) morphological type that corresponds to short wavelengths. These instabilities are coupled but while the convective instabilities depend strongly on gravity, the morphological instabilities are practically independent of gravity. For low velocities, the convective instabilities occur at much lower solute concentrations than the morphological instabilities, whereas at high velocities the reverse is true.

Coriell, S. R.

BUNDLE: A Novel Furnace for Performing Controlled Directional Solidification Experiments in a Microgravity Environment

NASA Marshall Space Flight Center has developed a novel directional solidification furnace prototype for processing metals and alloys experiments in a microgravity environment. The BUNDLE (Bridgman Unidirectional Dendrite in Liquid Experiment) furnace is intended to accommodate the science requirements of Flight Definition Principle Investigators studying cellular/dendritic growth in aluminum and lead alloys at processing temperatures up to 1200 C. The furnace implements a number of innovative features to achieve high thermal gradients and quench rates in a low-power, light-weight design. These include a pyrolytic boron nitride/graphite composite heating element surrounded by layers of self-supporting refractory metal shielding, and a graphite fiber enhanced cold zone allowing high levels of heat extraction from the sample crucible. Novel to the BUNDLE design is an in-situ helium gas quench capability that ensures rapid freezing of the solidifying region (mushy zone) of the metal sample within the furnace without sample disturbance prior to quenching; this is a stringent requirement for subsequent analysis and understanding of microstructural development. The experiment hardware concept features multiple furnaces that may be "bundled" together so many samples, currently up to eight, can be processed at one time. The design of BUNDLE is flexible enough to be implemented on the Shuttle and Space Station in a number of locations (SpaceHab, Express Rack, MPESS, ISPR, etc). BUNDLE prototype furnaces have directionally solidified and quenched 1cm diameter lead - 5.8 weight percent antimony and aluminum - 4 weight percent copper alloys. Quenching of the mushy zone, as recorded by in-situ thermocouples, occurred on the order of 0.5 seconds or less, a rate within the PI's requirements. Subsequent metallographic examination revealed the solidified microstructure to be, as expected, unidirectional. Both the dendrite tips and the eutectic reaction were planar in nature indicating uniform axial heat flow. Delineation between the growing dendrites and eutectic structure with the "quenched-in" liquid was sharp, attesting to the efficacy of the helium quench. BUNDLE's conception, development, capability, and adaptability are presented (in view of Flight PI's needs and science requirements) through viewgraphs depicting actual hardware, generated thermal analysis, and micrographs prepared from BUNDLE processed, flight-like samples.

Carrasquillo, Edgar J.

BUNDLE - A Novel Furnace for Performing Controlled Directional Solidification Experiments in a Microgravity Environment

NASA Marshall Space Flight Center has developed a novel directional solidification furnace prototype for processing metals and alloys experiments in a microgravity environment. The BUNDLE (Bridgman Unidirectional Dendrite in Liquid Experiment) furnace is intended to accommodate the science requirements of Flight Definition Principle Investigators studying cellular/dendritic growth in aluminum and lead alloys at processing temperatures up to 1200 C. The furnace implements a number of innovative features to achieve high thermal gradients and quench rates in a low-power, light-weight design. These include a pyrolytic boron nitride/graphite composite heating element surrounded by layers of self-supporting refractory metal shielding, and a graphite fiber enhanced cold zone allowing high levels of heat extraction from the sample crucible. Novel to the BUNDLE design is an in-situ helium gas quench capability that ensures rapid freezing of the solidifying region (mushy zone) of the metal sample within the furnace without sample disturbance prior to quenching; this is a stringent requirement for subsequent analysis and understanding of microstructural development. The experiment hardware concept features multiple furnaces that may be "bundled" together so many samples, currently up to eight, can be processed at one time. The design of BUNDLE is flexible enough to be implemented on the Shuttle and Space Station in a number of locations (SpaceHab, Express Rack, MPESS, ISPR, etc). BUNDLE prototype furnaces have directionally solidified and quenched 1cm diameter lead - 5.8 weight percent antimony and aluminum - 4 weight percent copper alloys. Quenching of the mushy zone, as recorded by in-situ thermocouples, occurred on the order of 0.5 seconds or less, a rate within the PI's requirements. Subsequent metallographic examination revealed the solidified microstructure to be, as expected, unidirectional. Both the dendrite tips and the eutectic reaction were planar in nature indicating uniform axial heat flow. Delineation between the growing dendrites and eutectic structure with the "quenched-in" liquid was sharp, attesting to the efficacy of the helium quench. BUNDLE's conception, development, capability, and adaptability are presented (in view of Flight PI's needs and science requirements) through viewgraphs depicting actual hardware, generated thermal analysis, and micrographs prepared from BUNDLE processed, flight-like samples.

Carrasquillo, Edgar J.

Preliminary science report on the directional solidification of hypereutectic cast iron during KC-135 low-G maneuvers

An ADSS-P directional solidification furnace was reconfigured for operation on the KC-135 low-g aircraft. The system offers many advantages over quench ingot methods for study of the effects of sedimentation and convection on alloy formation. The directional sodification furnace system was first flown during the September 1982 series of flights. The microstructure of the hypereutectic cast iron sample solidified on one of these flights suggests a low-g effect on graphite morphology. Further experiments are needed to ascertain that this effect is due to low-gravity and to deduce which of the possible mechanisms is responsible for it.

Curreri, P. A.

Directional Solidification Of Monotectic Alloys

Conditions promoting formation of aligned fibers sought. Report describes experiments in directional solidification of Cu/Pb and Bi/Ga monotectic alloys. Study motivated by need to understand physical mechanism governing formation of rodlike or fiberlike aligned structures in solidifying alloy and to determine process conditions favoring such structures.

Dhindaw, B. K.

Directional solidification of a planar interface in the presence of a time-dependent electric current

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.

Brush, L. N.

Modeling Directional Solidification

The objective of the research is to develop tools of use in explaining the results of directional solidification experiments in space. These tools consist of mathematical and experimental models. Experiments are also being flown at low-g to validate the ground-based results. Many metals and semiconductors directionally solidified in space had a diameter less than that of the containing ampoule. In fact this occurred whenever the ampoule contained a gas space. This phenomenon has been attributed in a vague way to lack of wetting of the ampoule wall by the melt. The actual liquid behavior by use of low temperature analogs is being observed aboard the KC-135. In the first flight, water was placed in plastic ampoules (not wet) with ceramic end plugs which were wet by the water to simulate a solid-liquid interface. Unfortunately during storage prior to the flight the water began to wet the ampoule wall. Discrete bubbles formed down the axis of the ampoules. New ampoule materials are being used now, with testing for stability prior to the next flight. A theoretical model has also been developed for this phenomenon.

Wilcox, W. R.

Thermosolutal convection during directional solidification. II - Flow transitions

The influence of thermosolutal convection on solute segregation in crystals grown by vertical directional solidification of binary metallic alloys or semiconductors is studied. Finite differences are used in a two-dimensional time-dependent model which assumes a planar crystal-melt interface to obtain numerical results. It is assumed that the configuration is periodic in the horizontal direction. Consideration is given to the possibility of multiple flow states sharing the same period. The results are represented in bifurcation diagrams of the nonlinear states associated with the critical points of linear theory. Variations of the solutal Rayleigh number can lead to the occurrence of multiple steady states, time-periodic states, and quasi-periodic states. This case is compared to that of thermosolutal convection with linear vertical gradients and stress-free boundaries.

Mcfadden, G. B.

Modelling directional solidification

The long range goal is to develop an improved understanding of phenomena of importance to directional solidification, to enable explanation and prediction of differences in behavior between solidification on Earth and in space. Emphasis during the period of this grant was on experimentally determining the influence of convection and freezing rate fluctuations on compositional homogeneity and crystalline perfection in the vertical Bridgman-Stockbarger technique. Heater temperature profiles, buoyancy-driven convection, and doping inhomogeneties were correlated using naphthalene doped with azulene. In addition the influence of spin-up/spin-down on compositional homogeneity and microstructure of indium gallium antimonide and the effect of imposed melting-freezing cycles on indium gallium antimonide are discussed.

Wilcox, William R.

The effect of compositionally-generated elastic stresses on morphological instability during directional solidification

The effect of compositionally-generated elastic stresses on the conditions for morphological instability during directional solidification of a dilute, ideal binary alloy is investigated using the Gibbs-Thomson equations for an elastically-stressed solid with zero surface stress in equilibrium with a liquid. It is found that these stresses lead to a small stabilization of the Mullins and Sekerka cellular mode of instability. The steady mode is stabilized by a stress-induced modification to the interfacial concentration of the solid, which in turn alters the amount of solute rejected to inhibit the growth of perturbations. The presence of elastic stresses could generate a new oscillatory instability which is most likely to be found in experiments near absolute stability for materials with segregation coefficients near unity and large solute expansion coefficients.

Spencer, B. J.

Cellular instability in rapid directional solidification - Bifurcation theory

Merchant and Davis performed a linear stability analysis on a model for the directional solidification of a dilute binary alloy valid for all speeds. The analysis revealed that nonequilibrium segregation effects modify the Mullins and Sekerka cellular mode, whereas attachment kinetics has no effect on these cells. In this paper, the nonlinear stability of the steady cellular mode is analyzed. A Landau equation is obtained that determines the amplitude of the cells. The Landau coefficient here depends on both nonequilibrium segregation effects and attachment kinetics. This equation gives the ranges of parameters for subcritical bifurcation (jump transition) or supercritical bifurcation (smooth transition) to cells.

Braun, R. J.

Thermoelectric and morphological effects of Peltier pulsing on directional solidification of eutectic Bi-Mn

Extensive in situ thermal measurements using Peltier Interface Demarcation (PID) during directional solidification of eutectic Bi/MnBi were carried out. Observations indicate that significant thermal transients occur throughout the sample as a result of the Peltier pulsing. The contributions of the Peltier, Thomson, and Joule heats were separated and studied as a function of pulse intensity and polarity. The Joule and the combined Peltier and Thomson thermal contributions were determined as a function of time during and after the current pulses, close to the solid/liquid interface. Variations of the Bi/MnBi particle morphology clearly reveal the interface shape, changes in interface velocity, meltback, and temporary loss of cooperative growth, as a result of the pulsing.

Silberstein, R. P.