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Solidification kinetics and metastable phase formation in binary Ti-Al

Electromagnetic levitation was used to solidify near-equiatomic alloys of Ti-Al at various bulk undercoolings. Detailed thermal histories were acquired during experiments using optical pyrometry with sampling rates as fast as 500 KHz. Solidification and other high-temperature transformation pathways were deduced from the thermal data and microstructural analysis. Recalescence rise times were employed to determine semiquantitative primary solidification kinetics for the different phases. Primary beta solidification was observed at compositions well into the equilibrium alpha regime; this is presented as part of a near-equiatomic nucleation domain diagram that shows the primary solidification phase that results for each combination of nucleation temperature and composition. Solidification kinetics are faster for primary beta than they are for primary alpha. For undercoolings less than about 150 K, the primary solidification kinetics are about an order of magnitude slower for gamma than for alpha.

Anderson, C. D.↗

Nial and Nial-Based Composites Directionally Solidified by a Containerless Zone Process

A containerless electromagnetically levitated zone (CELZ) process has been used to directionally solidify NiAl and NiAl-based composites. The CELZ processing results in single crystal NiAl (HP-NiAl) having higher purity than commercially pure NiAl grown by a modified Bridgman process (CP-NiAl). The mechanical properties, specifically fracture toughness and creep strength, of the HP-NiAl are superior to binary CP-NiAl and are used as a base-line for comparison with the composite materials subsequently studied. Two-phase composite materials (NiAl-based eutectic alloys) show improvement in room temperature fracture toughness and 1200 to 1400 K creep strength over that of binary HP-NiAl. Metallic phase reinforcements produce the greatest improvement in fracture toughness, while intermetallic reinforcement produces the largest improvement in high temperature strength. Three-phase eutectic alloys and composite materials were identified and directionally solidified with the intent to combine the improvements observed in the two-phase alloys into one alloy. The room temperature fracture toughness and high temperature strength (in air) serve as the basis for comparison between all of the alloys. Finally, the composite materials are discussed in terms of dominant fracture mechanism observed by fractography.

Joslin, Steven M.↗

Correction factors for on-line microprobe analysis of multielement alloy systems

An on-line correction technique was developed for the conversion of electron probe X-ray intensities into concentrations of emitting elements. This technique consisted of off-line calculation and representation of binary interaction data which were read into an on-line minicomputer to calculate variable correction coefficients. These coefficients were used to correct the X-ray data without significantly increasing computer core requirements. The binary interaction data were obtained by running Colby's MAGIC 4 program in the reverse mode. The data for each binary interaction were represented by polynomial coefficients obtained by least-squares fitting a third-order polynomial. Polynomial coefficients were generated for most of the common binary interactions at different accelerating potentials and are included. Results are presented for the analyses of several alloy standards to demonstrate the applicability of this correction procedure.

Unnam, J.↗

Interactions Between Solidification and Compositional Convection in Alloys

This project combined theoretical and experimental ground-based studies of the interactions between convection and solidification of binary melts. Particular attention was focused on the alteration of the composition and microstructure of castings caused by convective flows through the interstices of mushy layers. Two different mechanisms causing convection were investigated. (i) Compositional, buoyancy driven convection is known to cause chimneys and freckles in directionally cast alloys on Earth. The analytical studies provide quantitative criteria for the formation of chimneys that can be used to assess the expediency of producing alloys in Space. (ii) Flow of the melt is also driven by the contraction (expansion) that typically occurs during change of phase. Such convection will occur even in the absence of gravity, and may indeed be the primary cause of macrosegregation during the production of alloys in Space. The studies will employed asymptotic methods in order to determine conditions for the stability of various states of solidifying systems. Further, simple macroscopic models of complete systems were developed and solved. These analytical studies were augmented by laboratory experiments using aqueous solutions, in which the convective flows could be easily observed and the effects of convection could be readily measured. These y experiments guided the development of the theoretical models and provided data against which the predictions of the models can be tested.

Davis, S. H.↗

Magnetization of small iron-nickel spheres

Magnetic properties of small iron-nickel alloy spheres, having compositions which cover the entire Fe-Ni binary, are presented. The spheres were formed during solidification in free fall following the melting of electropolished wires of appropriate composition. The spheres with Ni not greater than 25% acquired a martensitic thermal remanence while those with Ni not less than 30% acquired a thermoremanent magnetization. A magnetic remanence-composition diagram and a coercive force-composition diagram are constructed. Magnetic hysteresis loops and derived parameters demonstrate the difference between metal-bearing and oxide-bearing natural samples. The magnetic remanence varies as the sphere size in conjunction with the microstructure. These results help to explain why coercive force is generally low, remanent coercive force is generally high, and their ratio (R/C) is always large in fine metal dispersions, such as lunar samples and chondrite meteorites.

Wasilewski, P.↗

Surface Segregation in Multicomponent Systems: Modeling of Surface Alloys and Alloy Surfaces

The study of surface segregation, although of great technological importance, has been largely restricted to experimental work due to limitations associated with theoretical methods. However, recent improvements in both first-particle and semi-empirical methods are opening, the doors to an array of new possibilities for surface scientists. We apply one of these techniques, the Bozzolo, Ferrante and Smith (BFS) method for alloys, which is particularly suitable for complex systems, to several aspects of the computational modeling of surfaces and segregation, including alloy surface segregation, structure and composition of alloy surfaces, and the formation of surface alloys. We conclude with the study of complex NiAl-based binary, ternary and quaternary thin films (with Ti, Cr and Cu additions to NiAl). Differences and similarities between bulk and surface compositions are discussed, illustrated by the results of Monte Carlo simulations. For some binary and ternary cases, the theoretical predictions are compared to experimental results, highlighting the accuracy and value of this developing theoretical tool.

Bozzolo, Guillermo↗

Calculation of Gallium-metal-Arsenic phase diagrams

Electrical contacts and metallization to GaAs solar cells must survive at high temperatures for several minutes under specific mission scenarios. The determination of which metallizations or alloy systems that are able to withstand extreme thermal excursions with minimum degradation to solar cell performance can be predicted by properly calculated temperature constitution phase diagrams. A method for calculating a ternary diagram and its three constituent binary phase diagrams is briefly outlined and ternary phase diagrams for three Ga-As-X alloy systems are presented. Free energy functions of the liquid and solid phase are approximated by the regular solution theory. Phase diagrams calculated using this method are presented for the Ga-As-Ge and Ga-As-Ag systems.

Scofield, J. D.↗

Microstructure Formations in the Two-Phase Region of the Binary Peritectic Organic System TRIS-NPG

In order to prepare for an onboard experiment on the International Space Station (ISS), systematic directional solidification experiments with transparent hypoperitectic alloys were carried out at different solidification rates around the critical velocity for morphological stability of both solid phases. The investigations were done in the peritectic region of the binary transparent organic TRIS-NPG system where the formation of layered structures is expected to occur. The transparent appearance of the liquid and solid phase enables real time observations of the dynamic of pattern formation during solidification. The investigations show that frequently occurring nucleation events govern the peritectic solidification morphology which occurs at the limit of morphological stability. As a consequence, banded structures lead to coupled growth even if the lateral growth is much faster compared to the growth in pulling direction.

Mogeritsch, Johann↗

Effects of gravity reduction on phase equilibria. Part 1: Unary and binary isostructural solids

Analysis of the Skylab II M553 Experiment samples resulted in the hypothesis that the reduced gravity environment was altering the melting and solidification reactions. A theoretical study was conducted to define the conditions under which such alteration of phase relations is feasible, determine whether it is restricted to space processing, and, if so, ascertain which alloy systems or phase reactions are most likely to demonstrate such effects. Phase equilibria of unary and binary systems with a single solid phase (unary and isomorphous) were considered.

Larson, D. J., Jr.↗

Phase equilibrium modeling for high temperature metallization on GaAs solar cells

Recent trends in performance specifications and functional requirements have brought about the need for high temperature metallization technology to be developed for survivable DOD space systems and to enhance solar cell reliability. The temperature constitution phase diagrams of selected binary and ternary systems were reviewed to determine the temperature and type of phase transformation present in the alloy systems. Of paramount interest are the liquid-solid and solid-solid transformations. Data are being utilized to aid in the selection of electrical contact materials to gallium arsenide solar cells. Published data on the phase diagrams for binary systems is readily available. However, information for ternary systems is limited. A computer model is being developed which will enable the phase equilibrium predictions for ternary systems where experimental data is lacking.

Chung, M. A.↗

Observations Of A Cast Cu-Cr-Zr Alloy

The calculated phase diagram and observations of Zeng et al were confirmed. 1) Additional X-ray diffraction peaks for aged sample indicates possibility that additional metastable phases may form; 2) Cu5Zr was observed rather than the Cu9Zr2 proposed for the binary Cu-Zr phase diagram. Despite similarities between Zr and Nb, Cu-Cr-Zr does not appear to be a good candidate alloy system for rocket engine applications.

Ellis, David L.↗

Directionally solidified pseudo-binary eutectics of Ni-Cr-(Hf, Zr)

A pseudo-binary eutectic, in which the intermetallic Ni7Hf2 reinforces the Ni-Cr solid solution phase, was previously predicted in the Ni-Cr-Hf system by a computer analysis. The experimental determination of pseudo binary eutectic compositions and the directional solidification of the Ni-Cr-Hf, Zr, and Ni-Cr-Zr eutectic alloys are discussed. To determine unknown eutectics, chemical analyses were made of material bled from near eutectic ingots during incipient melting. Nominal compositions in weight percent of Ni-18.6Cr-24.0HF, Ni19.6Cr-12.8Zr-2.8Hf, and Ni-19.2Cr-14.8Zr formed aligned pseudo-binary eutectic structures. The melting points were about 1270 C. The reinforcing intermetallic phases were identified as noncubic (Ni,Cr)7Hf2 and (Ni,Cr)7(Hf,Zr)2, and face centered cubic (Ni,Cr)5Zr. The volume fraction of the reinforcing phases were about 0.5.

Kim, Y. G.↗

Some possible filler alloys with low vapor pressures for refractory-metal brazing

A compilation of eutectics and melting-point minima for binary combinations of metals having vapor pressures below 10 to the minus 10th power torr at 1500 degrees K and .00005 torr at 2000 degree K is presented. These compositions and others near them on their phase diagrams are potential special brazing fillers for refractory metals. Some possible problems and advantages for fusion bonds of such mixtures are indicated. Evaluations of brazing fillers containing refractory metals are reported.

Morris, J. F.↗

Directionally solidified pseudo-binary eutectics of Ni-Cr-/Hf,Zr/

This report is concerned with the experimental determination of pseudo binary eutectic compositions and the directional solidification of the Ni-Cr-Hf,Zr, and Ni-Cr-Zr eutectic alloys. To determine unknown eutectics, chemical analyses were made of material bled from near eutectic ingots during incipient melting. Nominal compositions in weight per cent of Ni-18.6Cr-24.0Hf, Ni-19.6Cr-12.8Zr-2.8Hf, and Ni-19.2Cr-14.8Zr formed aligned pseudo-binary eutectic structures. The melting points were about 1270 C. The reinforcing intermetallic phases were identified as noncubic (Ni,Cr)7Hf2 and (Ni,Cr)7(Hf,Zr)2, and face centered cubic (Ni,Cr)5Zr. The volume fraction of the reinforcing phases were about 0.5.

Kim, Y. G.↗

Some properties of low-vapor-pressure braze alloys for thermionic converters

Density, dc electrical resistivity, thermal conductivity, and linear thermal expansion are measured for arc-melted rod-shaped samples of binary eutectics of Zr, Hf, Ru, Nb, Ir, Mo, Ta, Os, Re, and W selected as very-low-pressure braze fillers for thermionic converters. The first two properties are measured at 296 K for Zr-21.7 at% Ru, Zr-13 wt% W, Zr-19 wt% W, Zr-22.3 at% Nb, Nb-66.9 at% Ru, Hf-25.3 wt% Re, Zr-25.7 at% Ta, Hf-22.5 at% W, and Nb-35 wt% Mo. The last property is measured from 293 K to 2/3 melting point for specified alloys of different compositions. Resistivities of 0.000055 to 0.000181 ohm-cm are observed with the alloys having resistivities about ten times that of the less resistive constituent metal and about three times that of the more resistive constituent metal, except for Zr-19 wt% W and Nb-35 wt% Mo (greater resistivities). Thermal expansion coefficients vary from 0.000006 to 0.0000105/K. All brazes exhibit linear thermal expansion near that of their constituent metals.

Bair, V. L.↗

Empirical Study of the Multiaxial, Thermomechanical Behavior of NiTiHf Shape Memory Alloys

An empirical study was conducted to characterize the multiaxial, thermomechanical responses of new high temperature NiTiHf alloys. The experimentation included loading thin walled tube Ni(sub 50.3)Ti(sub 29.7)Hf(sub 20) alloy samples along both proportional and nonproportional axial-torsion paths at different temperatures while measuring surface strains using stereo digital image correlation. A Ni(sub 50.3)Ti(sub 33.7)Hf(sub 16) alloy was also studied in tension and compression to document the effect of slightly depleting the Hf content on the constitutive responses of NiTiHf alloys. Samples of both alloys were made from nearly texture free polycrystalline material processed by hot extrusion. Analysis of the data shows that very small changes in composition significantly alter NiTiHf alloy properties, as the austenite finish (Af) temperature of the 16-at Hf alloy was found to be approximately 60 C less than the 20-at Hf alloy (approximately 120 C vs. 180 C). In addition, the 16-at Hf alloy exhibited smaller compressive transformation strains (2 vs. 2.5 percent). Multi-axial characterization of the 20-at % Hf alloy showed that while the random polycrystal transformation strains in tension (4 percent) and compression (2.5 percent) are modest in comparison with binary NiTi (6 percent, 4 percent), the torsion performance is superior (7 vs. 4 shear strain width to the pseudoelastic plateau).

tensile deformation↗

Deformation mechanisms of NiAl cyclicly deformed near the brittle-to-ductile transformation temperature

One of the ongoing challenges of the aerospace industry is to develop more efficient turbine engines. Greater efficiency entails reduced specific strength and larger temperature gradients, the latter of which means higher operating temperatures and increased thermal conductivity. Continued development of nickel-based superalloys has provided steady increases in engine efficiency and the limits of superalloys have probably not been realized. However, other material systems are under intense investigation for possible use in high temperature engines. Ceramic, intermetallic, and various composite systems are being explored in an effort to exploit the much higher melting temperatures of these systems. NiAl is considered a potential alternative to conventional superalloys due to its excellent oxidation resistance, low density, and high melting temperature. The fact that NiAl is the most common coating for current superalloy turbine blades is a tribute to its oxidation resistance. Its density is one-third that of typical superalloys and in most temperature ranges its thermal conductivity is twice that of common superalloys. Despite these many advantages, NiAl requires more investigation before it is ready to be used in engines. Binary NiAl in general has poor high-temperature strength and low-temperature ductility. On-going research in alloy design continues to make improvements in the high-temperature strength of NiAl. The factors controlling low temperature ductility have been identified in the last few years. Small, but reproducible ductility can now be achieved at room temperature through careful control of chemical purity and processing. But the mechanisms controlling the transition from brittle to ductile behavior are not fully understood. Research in the area of fatigue deformation can aid the development of the NiAl system in two ways. Fatigue properties must be documented and optimized before NiAl can be applied to engineering systems. More importantly though, probing the deformation mechanisms operating in fatigue will lead to a better understanding of NiAl's unique characteristics. Low cycle fatigue properties have been reported on binary NiAl in the past year, yet those studies were limited to two temperature ranges: room temperature and near 1000 K. Eventually, fatigue property data will be needed for a wide range of temperatures and compositions. The intermediate temperature range near the brittle-to-ductile transition was chosen for this study to ascertain whether the sharp change occurring in monotonic behavior also occurs under cyclic conditions. An effort was made to characterize the dislocation structures which evolved during fatigue testing and comment on their role in the deformation process.

Antolovich, Stephen D.↗

Alloy Design Data Generated for B2-Ordered Compounds

Developing alloys based on ordered compounds is significantly more complicated than developing designs based on disordered materials. In ordered compounds, the major constituent elements reside on particular sublattices. Therefore, the addition of a ternary element to a binary-ordered compound is complicated by the manner in which the ternary addition is made (at the expense of which binary component). When ternary additions are substituted for the wrong constituent, the physical and mechanical properties usually degrade. In some cases the resulting degradation in properties can be quite severe. For example, adding alloying additions to NiAl in the wrong combination (i.e., alloying additions that prefer the Al sublattice but are added at the expense of Ni) will severely embrittle the alloy to the point that it can literally fall apart during processing on cooling from the molten state. Consequently, alloying additions that strongly prefer one sublattice over another should always be added at the expense of that component during alloy development. Elements that have a very weak preference for a sublattice can usually be safely added at the expense of either element and will accommodate any deviation from stoichiometry by filling in for the deficient component. Unfortunately, this type of information is not known beforehand for most ordered systems. Therefore, a computational survey study, using a recently developed quantum approximate method, was undertaken at the NASA Glenn Research Center to determine the preferred site occupancy of ternary alloying additions to 12 different B2-ordered compounds including NiAl, FeAl, CoAl, CoFe, CoHf, CoTi, FeTi, RuAl, RuSi, RuHf, RuTi, and RuZr. Some of these compounds are potential high temperature structural alloys; others are used in thin-film magnetic and other electronic applications. The results are summarized. The italicized elements represent the previous sum total alloying information known and verify the computational method used to establish the table. Details of the computational procedures used to determine the preferred site occupancy can be found in reference 2. As further substantiation of the validity of the technique, and its extension to even more complicated systems, it was applied to two simultaneous alloying additions in an ordered alloy.

Noebe, Ronald D.↗