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Efficient estimation of diffusion during dendritic solidification

A very efficient finite difference method has been developed to estimate the solute redistribution during solidification with diffusion in the solid. This method is validated by comparing the computed results with the results of an analytical solution derived by Kobayashi (1988) for the assumptions of a constant diffusion coefficient, a constant equilibrium partition ratio, and a parabolic rate of the advancement of the solid/liquid interface. The flexibility of the method is demonstrated by applying it to the dendritic solidification of a Pb-15 wt pct Sn alloy, for which the equilibrium partition ratio and diffusion coefficient vary substantially during solidification. The fraction eutectic at the end of solidification is also obtained by estimating the fraction solid, in greater resolution, where the concentration of solute in the interdendritic liquid reaches the eutectic composition of the alloy.

Yeum, K. S.↗

Structures Self-Assembled Through Directional Solidification

Nanotechnology has created a demand for new fabrication methods with an emphasis on simple, low-cost techniques. Directional solidification of eutectics (DSE) is an unconventional approach in comparison to low-temperature biomimetic approaches. A technical challenge for DSE is producing microstructural architectures on the nanometer scale. In both processes, the driving force is the minimization of Gibb's free energy. Selfassembly by biomimetic approaches depends on weak interaction forces between organic molecules to define the architectural structure. The architectural structure for solidification depends on strong chemical bonding between atoms. Constituents partition into atomic-level arrangements at the liquid-solid interface to form polyphase structures, and this atomic-level arrangement at the liquid-solid interface is controlled by atomic diffusion and total undercooling due to composition (diffusion), kinetics, and curvature of the boundary phases. Judicious selection of the materials system and control of the total undercooling are the keys to producing structures on the nanometer scale. The silicon-titanium silicide (Si-TiSi2) eutectic forms a rod structure under isothermal cooling conditions. At the NASA Glenn Research Center, directional solidification was employed along with a thermal gradient to promote uniform rods oriented with the thermal gradient. The preceding photomicrograph shows the typical transverse microstructure of a solidified Si-TiSi2 eutectic composition. The dark and light gray regions are Si and TiSi2, respectively. Preferred rod orientation along the thermal gradient was poor. The ordered TiSi2 rods have a narrow distribution in diameter of 2 to 3 m, as shown. The rod diameter showed a weak dependence on process conditions. Anisotropic etch behavior between different phases provides the opportunity to fabricate structures with high aspect ratios. The photomicrographs show the resulting microstructure after a wet chemical etch and a dry plasma etch. The wet chemical etches the silicon away, exposing the TiSi2 rods, whereas plasma etching preferentially etches the Si-TiSi2 interface to form a crater. The porous architectures are applicable to fabricating microdevices or creating templates for part fabrication. The porous rod structure can serve as a platform for fabricating microplasma devices for propulsion or microheat exchangers and for fabricating microfilters for miniatured chemical reactors. Although more work is required, self-assembly from DSE can have a role in microdevice fabrication.

Dynys, Frederick W.↗

SPAR and ASTP studies of plane-front solidification and magnetic properties of Bi/MnBi

Eutectic and off-eutectic Bi/MnBi compositions have been directionally solidified parallel, anti-parallel and perpendicular to the gravity vector in a one-g environment and in low-gravity during the ASTP flight. MnBi rod diameter and interparticle spacing distributions are similar for all gravity vector orientations when grown at high solidification rates in one-g. Previously reported ASTP results are explained by the existence of a metastable magnetic phase and off-eutectic solidification models.

Pirich, R. G.↗

Eutectic-Free Superalloy Made By Directional Solidification

By suitable control of thermal conditions in directional-solidification process, supperalloy structural and machine components (e.g., turbine blades) cast with microstructures enhancing resistance to fatigue. Specific version of process and thermal conditions chosen to reduce micro-segregation during solidification and to minimize or eliminate script carbide and eutectic-phase inclusions, which are brittle inclusions found to decrease resistance to fatigue.

Schmidt, Deborah Dianne↗

Solidifying Mn/Bi in a Magnetic Field

Report describes experiments in directional solidification of eutectic Mn/Bi in magnetic field. Study determines whether effects of gravitationally-induced convection reduced or eliminated by magnetic field. Morphological, thermal, and magnetic analyses done on samples grown at various speeds and various applied strengths. Magnetic effects similar to those of low gravity.

Decarlo, J. L.↗

Directional solidification of Pb-Sn eutectics with vibration

Pb-Sn eutectic alloy was directionally solidified at 1.4 to 3.2 cm/hr with forced convection induced by axial vibration of the growth ampoule with a frequency of 10 to 40 Hz and an amplitude of 0.5 to 1.0 mm. To determine the exact growth rate, an interface demarcation technique was applied. The lamellar spacing was increased 10 to 40 percent in ingots solidified with vibration compared to those solidified without vibration. The number of grain boundaries was increased by vibration. The average intensity of convection in the melt under axial vibration of the ampoule was estimated by comparing the experimental results with a theoretical model.

Caram, Rubens↗

Directional solidification of Pb-Sn eutectic with vibration

Pb-Sn eutectic alloy was directionally solidified at 1.4 to 3.2 cm/hr with forced convection induced by axial vibration of the growth ampoule with a frequency of 10 to 40 Hz and an amplitude of 0.5 to 1.0 mm. To determine the exact growth rate, an interface demarcation technique was applied. The lamellar spacing was increased 10 to 40 percent in ingots solidified with vibration compared to those solidified without vibration. The average intensity of convection in the melt under axial vibration of the ampoule was estimated by comparing the experimental results with a theoretical model.

Caram, Rubens↗

Directional solidification of Pb-Sn eutectic with vibration

Pb-Sn eutectic alloy was directionally solidified at 1.4 to 3.2 cm/h with forced convection induced by axial vibration of the growth ampoule with a frequency of 10 to 40 Hz and an amplitude of 0.5 to 1.0 mm. To determine the exact growth rate, an interface demarcation technique was applied. The lamellar spacing was increased 10 to 40 percent in ingots solidified with vibration, compared to those solidified without vibration. The number of grain boundaries was increased by vibration. The average intensity of convection in the melt under axial vibration of the ampoule was estimated by comparing the experimental results with a theoretical model.

Caram, Rubens↗

The influence of processing parameters on microstructural development of low-weight-percent primary, pro-eutectic, dendritic alloys during directional solidification

Alloy compositions centering about Sn- 5 to 15 wt pct Al and Pb- 4 to 20 wt pct Cu have been directionally solidified as a function of growth rate and orientation with respect to earth's gravity vector. The effect of these processing variables on macrosegregation is presented, and the consequence of a structural transition from primary columnar to equiaxed dendritic growth is examined. Effects detrimental to microstructure and attributed to density variations are shown to be minimized by a novel processing technique. In view of the ground-based results, some considerations follow regarding what might be gained by solidifying these alloys in a microgravity environment.

Grugel, R. N.↗

Containerless processing and rapid solidification of Nb-Si alloys in the niobium-rich eutectic range

Containerless processing and rapid solidification techniques were used to process Nb-Si alloys in the Nb-rich eutectic range. Electromagnetically levitated drops were melted and subsequently splat-quenched from different temperatures. A variety of eutectic morphologies was obtained as a function of the degree of superheating or undercooling of the drops prior to splatting. Metallic glass was observed only in drops quenched from above the melting temperature. Microstructures of splats deeply undercooled prior to quenching were very fine and uniform. These results are discussed in terms of classic nucleation theory concepts and the expected heat evolution at different regions of the splat during the rapid quenching process. The locations of the coupled-zone boundaries for the alpha-Nb + Nb3Si eutectic are also suggested.

Hofmeister, W. H.↗

Microstructure Of MnBi/Bi Eutectic Alloy

Collection of three reports describes studies of directional solidification of MnBi/Bi eutectic alloy. Two of the reports, "Influence of Convection on Lamellar Spacing of Eutectics" and "Influence of Convection on Eutectic Microstructure," establish theoretical foundation for remaining document. Reports seek to quantify effect of convection on concentration field of growing lamellar eutectic. Remaining report, "Study of Eutectic Formation," begins by continuing theoretical developments. New technique under development by one of the authors helps to reveal three-dimensional microstructures of alloys.

Wilcox, William R.↗

SPAR X Technical Report for Experiment 76-22 Directional Solidification of Magnetic Composites

The effects of gravity on Bridgman-Stockbarger directional solidification of off-eutectic Bi/MnBi were studied in reduced gravity aboard the SPAR X flight and compared to normal-gravity investigations and previous eutectic Bi/MnBi SPAR flight experiments. The directional solidification of off-eutectic Bi/MnBi results in either a dendritic structure connected with local cooperative growth or a coupled low volume fraction faceted/non faceted aligned rod eutectic whose Mn macrosegregation, MnBi rod size, interrod spacing, and thermal and magnetic properties are sensitive functions of the solidification processing conditions. Two hypoeutectic and two hypereutectic samples were solidified during 605 sec of furnace travel, with an initial 265 sec low-gravity interval. Comparison Earth-gravity samples were solidified in the same furance assembly under identical processing conditions. Macrosegregation in the low-g samples was consistent with a metastable increase in Mn solubility in the Bi matrix, in partial agreement with previous Bi/MnBi SPAR findings of MnBi volume reduction.

Bethin, J.↗

Orbital Processing of Eutectic Rod-Like Arrays

The eutectic is one of only three solidification classes that exist. The others are isostructural and peritectic-class reactions, respectively. Simplistically, in a binaryeutectic phase diagram, a single liquid phase isothermally decomposes to two solid phases in a cooperative manner. The melting point minimum at the eutectic composition, isothermal solidification temperature, near-isocompositional solidification and refined solidification microstructure lend themselves naturally to such applications as brazing and soldering; industries that eutectic alloys dominate. Interest in direct process control of microstructures has led, more recently, to in-situ eutectic directional solidification with applications in electro-magnetics and electro-optics. In these cases, controlled structural refinement and the high aspect ratio and regularity of the distributed eutectic phases is highly significant to the fabrication and application of these in-situ natural composites. The natural pattern formation and scaling of the dispersed phase on a sub-micron scale has enormous potential application, since fabricating bulk materials on this scale mechanically has proven to be particularly difficult. It is thus of obvious importance to understand the solidification of eutectic materials since they are of great commercial significance. The dominant theory that describes eutectic solidification was derived for diffusion-controlled growth of alloys where both solid eutectic phases solidify metallically, i.e. without faceting at the solidification interface. Both high volume fraction (lamellar) and low volume fraction (rod-like) regular metallic arrays are treated by this theory. Many of the useful solders and brazements, however, and most of the regular in-situ composites are characterized by solidification reactions that are faceted/non-faceted in nature, rather than doubly non-faceted (metallic). Further, diffusion-controlled growth conditions are atypical terrestrially since gravitationally-driven convection is pervasive. As a consequence, it is important to determine whether these faceted/non-faceted composites behave in the same manner as their doubly non-faceted counterparts, particularly in the presence of convection. Prior analytical convective sensitivity testing of this theory predicted insensitivity. Prior experimental testing of this theory offered broad-based agreement between theory and experiment, though most results were for high volume fraction lamellar eutectics that solidified without faceting at the solidification interface. Directional solidification experiments of low volume fraction rod eutectics under damped (microgravity or magnetic field) conditions, however, have demonstrated significant sensitivity, challenging this fundamental theory. More recent theories have been proposed which introduce kinetic undercooling, faceting, fluid shear of the solute redistribution zone and the possibility that the interface composition is not the same as the bulk liquid composition. This program tests the established and proposed analytical theories and addresses the origins of discrepancies between the experimental and analytical results.

Larson, David J., Jr.↗

Solidification of undercooled Ni-Sn eutectic alloy under microgravity conditions in the Space Shuttle

The Space Shuttle Columbia carried an Alloy Undercooling Experiment on its STS 61-C mission in January, 1986. The experiment was performed in an electromagnetic levitator. A sample of Ni-32.5 wt pct Sn eutectic was melted and solidified under microgravity conditions in the Space Shuttle. The specimen achieved only a fairly small undercooling, probably less than 30 K. The specimen was examined by optical and scanning electron microscopy. The surface and cross-sectional microstructures were primarily composed of normal lamellar eutectic, but showed several interesting features, including an apparent surface nucleation site, curved dendrites with nonorthogonal secondary arms, dendrite fragments with extremely fine arm spacing, submicron precipitates, and faceted crystals. The results of the space experiment are presented and compared with ground-based results obtained with the same alloy.

Piccone, T. J.↗

An approximate formula for recalescence in binary eutectic alloys

In alloys, solidification takes place along various paths which may be ascertained via phase diagrams; while there would be no single formula applicable to all alloys, an approximate formula for a specific solidification path would be useful in estimating the fraction of the solid formed during recalescence. A formulation is here presented of recalescence in binary eutectic alloys. This formula is applied to Ag-Cu alloys which are of interest in containerless solidification, due to their formation of supersaturated solutions.

Ohsaka, K.↗

NiAl-based Polyphase in situ Composites in the NiAl-Ta-X (X = Cr, Mo, or V) Systems

Polyphase in situ composites were generated by directional solidification of ternary eutectics. This work was performed to discover if a balance of properties could be produced by combining the NiAl-Laves phase and the NiAl-refractory metal phase eutectics. The systems investigated were the Ni-Al-Ta-X (X = Cr, Mo, or V) alloys. Ternary eutectics were found in each of these systems and the eutectic composition, temperature, and morphology were determined. The ternary eutectic systems examined were the NiAl-NiAlTa-(Mo, Ta), NiAl-(Cr, Al) NiTa-Cr, and the NiAl-NiAlTa-V systems. Each eutectic consists of NiAl, a C14 Laves phase, and a refractory metal phase. Directional solidification was performed by containerless processing techniques in a levitation zone refiner to minimize alloy contamination. Room temperature fracture toughness of these materials was determined by a four-point bend test. Preliminary creep behavior was determined by compression tests at elevated temperatures, 1100-l400 K. Of the ternary eutectics, the one in the NiAl-Ta-Cr system was found to be the most promising. The fracture toughness of the NiAl-(Cr, Al)NiTa-Cr eutectic was intermediate between the values of the NiAl-NiAlTa eutectic and the NiAl-Cr eutectic. The creep strength of this ternary eutectic was similar to or greater than that of the NiAl-Cr eutectic.

Johnson, D. R.↗