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NASA NTRS1987

Polyphase alloys as rechargeable electrodes in advanced battery systems

The rechargeability of electrochemical cells is often limited by negative electrode problems. These may include loss of capacity, increased impedance, macroscopic shape change, dendrite growth, or a tendency for filamentary or whisker growth. In principle, these problems can be reduced or eliminated by the use of alloys that undergo either displacement or insertion reactions at reactant species activities less than unity, rather than pure elements. The fundamental reasons for some of these problems with elemental electrodes, as well as the basic principles involved in the different behavior of alloys, are briefly discussed. More information is now available concerning the thermodynamic and kinetic properties of a number of alloys of potential interest for use as electrodes in elevated temperature lithium battery systems. Recent results have extended these results down to ambient temperatures, indicating that some such materials may be of interest for use with new low temperature molten salt electrolytes, or with organic solvent electrolytes. The all solid mixed conductor matrix concept is also reviewed.

Huggins, Robert A.↗

NASA NTRS1986

Dynamic crystallization of chondrule melts of porphyritic and radial pyroxene composition

Dynamic crystallization experiments in which heterogeneous nucleation is an important variable have been completed on four melts of chondrule composition. Compositions were chosen to best represent chondrules with porphyritic pyroxene and radial pyroxene textures. Experimental results show that heterogeneous nucleation is essential for the formation of porphyritic textures. Without preexisting nuclei, too much supercooling is established before crystallization is initiated and the textures are more likely to be dendritic or radial. In the near total absence of nuclei, radial textures can form at cooling rates as slow as 5 C/hr in this study. By varying the heterogeneous nucleation conditions and having a melt in which the appropriate phases are stable or metastable, analogs to most of the recognized chondrule textures can be produced in a single melt composition.

Lofgren, G.↗

NASA NTRS1986

Microstructural variations induced by gravity level during directional solidification of near-eutectic iron-carbon type alloys

The effects of gravity on the microstructure of directionally solidified near-eutectic cast irons are studied, using a Bridgman-type automatic directional solidification furnace aboard a NASA KC-135 aircraft which flies parabolic arcs and generates alternating periods of low-g (0.01 to 0.001 g, 30 seconds long) and high-g (1.8 g, 1.5 minutes long). Results show a refinement of the interlamellar spacing of the eutectic during low-g processing of metastable Fe-C eutectic alloys. Low-g processing of stable Fe-C-Si eutectic alloys (lamellar or spheroidal graphic) results in a coarsening of the eutectic grain structure. Secondary dendrite arm spacing of austenite increases in low-g and decreases in high-g. The effectiveness of low-gravity in the removal of buoyancy-driven graphite phase segregation is demonstrated.

Stefanescu, Doru M.↗

NASA NTRS1987

Microstructures of undercooled germanium droplets

Undercoolings at crystal nucleation onset of liquid Ge droplets are measured and the microstructures of the droplets are examined. Undercooling values ranging from 150-415 + or 20 C were obtained. It is observed that for the samples undercooled less than 300 C prior to solidification the grain size was greater than 100 microns; for samples undercooled between 300-400 C the grain size was between 50-100 microns; and for samples undercooled greater than 400 C the grain size was 10-20 microns. Consideration is given to dendritic growth and interfacial undercooling. It is noted that there is a correlation between undercooling and as-crystallized grain structure.

Devaud, G.↗

NASA NTRS1987

Rate limits in silicon sheet growth - The connections between vertical and horizontal methods

Meniscus-defined techniques for the growth of thin silicon sheets fall into two categories: vertical and horizontal growth. The interactions of the temperature field and the crystal shape are analyzed for both methods using two-dimensional finite-element models which include heat transfer and capillarity. Heat transfer in vertical growth systems is dominated by conduction in the melt and the crystal, with almost flat melt/crystal interfaces that are perpendicular to the direction of growth. The high axial temperature gradients characteristic of vertical growth lead to high thermal stresses. The maximum growth rate is also limited by capillarity which can restrict the conduction of heat from the melt into the crystal. In horizontal growth the melt/crystal interface stretches across the surface of the melt pool many times the crystal thickness, and low growth rates are achievable with careful temperature control. With a moderate axial temperature gradient in the sheet a substantial portion of the latent heat conducts along the sheet and the surface of the melt pool becomes supercooled, leading to dendritic growth. The thermal supercooling is surpressed by lowering the axial gradient in the crystal; this configuration is the most desirable for the growth of high quality crystals. An expression derived from scaling analysis relating the growth rate and the crucible temperature is shown to be reliable for horizontal growth.

Thomas, Paul D.↗

NASA NTRS1987

Dislocation dynamics of web type silicon ribbon

Silicon ribbon grown by the dendritic web process passes through a rapidly changing thermal profile in the growth direction. This rapidly changing profile induces stresses which produce changes in the dislocation density in the ribbon. A viscoplastic material response function (Haasen-Sumino model) is used herein to calculate the stresses and the dislocation density at each point in the silicon ribbon. The residual stresses are also calculated.

Dillon, O. W., Jr.↗

NASA NTRS1987

Oxygen measurements in thin ribbon silicon

The oxygen content of thin silicon ribbons grown by the dendritic web technique was measured using a modification of the ASTM method based on Fourier transform infrared spectroscopy. Web silicon was found to have a high oxygen content, ranging from 13 to 19 ppma, calculated from the absorption peak associated with interstitial oxygen and using the new ASTM conversion coefficient. The oxygen concentration changed by about 10 percent along the growth direction of the ribbon. In some samples, a shoulder was detected on the absorption peak. A similar shoulder in Czochralski grown material has been variously interpreted in the literature as due to a complex of silicon, oxygen, and vacancies, or to a phase of SiO2 developed along dislocations in the material. In the case of web silicon, it is not clear which is the correct interpretation.

Hyland, S. L.↗

NASA NTRS1987

Effect of undercooling on the microstructure of Ni-35 at. pct Mo (eutectic) and Ni-38 at. pct Mo (hypereutectic) alloys

Ni-35 at. pct Mo and Ni-38 at. pct Mo alloy specimens have been solidified from various levels of undercooling in the differential thermal analysis and the electromagnetic levitation units in a pyrex/vycor bed. The evolution of the microstructure in the solified specimens has been examined in terms of the degree of undercooling, the nature of the first phase to nucleate from the melt, and the specimen cooling rate. The melt has been observed to undercool more in the presence of intermetallic NiMo (beta) phase as compared to that in the presence of nickel-rich solid solution (gamma). The 'anomalous eutectic' type of microstructure has been shown to result from the initial formation of the dendritic skeleton of either of the two phases, its segmentation due to convection and ripening, and the subsequent nucleation of the other phase in the interdendritic liquid regions. The recalescence behavior has been examined as a function of undercooling and the nature of the phase nucleating first in the melt.

Tewari, S. N.↗

NASA NTRS1987

Experimental measurement of solutal and thermal layers in unidirectional solidification

An experimental study to evaluate and characterize the effects and causes of convection in the directional solidification of metal alloys is described. The temporal history of the inverted density layers in front of a dendritic interface for directionally solidified ammonium chloride-(72 wt pct) water is presented based on photographic data taken using a laser schlieren system. Data are given for both 1-g and low-g solidification runs, and the stability of the layer is discussed. The reduction of buoyancy effects is shown to be significant, and the possible impact of reducing gravity level on freckling in metal alloys is considered.

Mccay, M. H.↗

NASA NTRS1987

Cellular microstructure of chill block melt spun Ni-Mo alloys

Chill block melt spun ribbons of Ni-Mo binary alloys containing 8.0 to 41.8 wt pct Mo have been prepared under carefully controlled processing conditions. The growth velocity has been determined as a function of distance from the quench surface from the observed ribbon thickness dependence on the melt puddle residence time. Primary arm spacings measured at the midribbon thickness locations show a dependence on growth velocity and alloy composition which is expected from dendritic growth models for binary alloys directionally solidified in a positive temperature gradient. Microsegregation across cells and its variation with distance from the quench surface and alloy composition have been examined and compared with theoretical predictions.

Tewari, S. N.↗

NASA NTRS1988

Coatings Boost Solar-Cell Outputs

Efficiencies increased by more-complete utilization of incident light. Electrical outputs of thin solar photovoltaic cells made of dendritic-web silicon increased by combination of front-surface, antireflective coatings and back-surface, reflective coatings. Improvements achieved recently through theoretical and experimental studies of ways to optimize coatings for particular wavelengths of incident light, cell thicknesses, and cell materials.

Rohatgi, Ajeet↗

NASA NTRS1988

Solidification-Rate Effects In MAR-M-246+Hf Alloy

Under slower solidification, primary-dendrite-arm spacing increases. Report discusses experiments on influence of solidification rates on crystallographic orientation and mechanical properties of superalloy MAR-M-246+Hf. Specimens grown in directional-solidification furnace, visually examined for microstructure, and stretched to failure in tensile-testing machine. Back-reflection Laue x-ray photographs taken to determine growth orientations.

Hamilton, David↗

NASA NTRS1988

Growing Wider Silicon Ribbons

New lid design makes larger withdrawal opening feasible. Wider silicon ribbons grown by dendritic-web method with proposed modification of furnace lid. Modification increases by about 22 percent size of portion of lid that limits ribbon width, potentially increasing area of single-crystal silicon ribbon and productivity.

Duncan, C. S.↗

NASA NTRS1988

Ultrasonic Measurement Of Silicon-Growth Interface

Position of interface between silicon melt and growing ribbon of silicon measured with aid of reflected ultrasound, according to proposal. Reflections reveal characteristics of ribbon and melt. Ultrasound pulses travel through rods to silicon ribbon growing by dendritic-web process. Rods return reflections of pulses to sonic transducers. Isolate transducers thermally, but not acoustically, from hot silicon melt.

Heyser, Richard C.↗

NASA NTRS1988

Automatic Replenishment Of Dopant In Silicon Growth

Dopant incorporated feed pellets to maintain required concentration. Technique of continuous replenishment of dopant in silicon melt helps ensure correct resistivity in solid silicon grown from melt. Technique used in dendritic-web growth process in which ribbon of silicon continously pulled from molten material. Providing uniform doping and resistivity in ribbon technique enables production of high-quality silicon ribbon at high yields for use in semiconductor devices.

Kochka, E. L.↗

NASA NTRS1988

Forming n/p Junctions With An Excimer Laser

Compact equipment yields high-quality solar cells. Computer controls pulses of excimer laser and movement of silcon wafer. Mirrors direct laser beam to wafer. Lenses focus beam to small spot on surface. Process suitable for silicon made by dendritic-web-growth process.

Alexander, Paul, Jr.↗

NASA NTRS1988

Stabilizing Silicon-Ribbon Growth At Early Stages

Device mechanically stabilizes buttons from which silicon ribbons grown by dendritic-web process. Eliminates tendency for button to tip and interrupt pull because of asymmetry. Silicon seed hangs from holder through stabilizing tube. While button growing, tube elevated above melt surface. When ready for pulling of ribbon, tube comes to rest on button and prevents tipping. Large button used. Even if button assumes highly-asymmetrical weight distrubtion in early stages of growth, little danger of tipping and breakage of nascent ribbon.

Henry, Paul K.↗

NASA NTRS1984

Structure and recalescence behavior of undercooled nickel-tin alloys

The effects of undercooling on the thermal behavior and structure of Ni-Sn alloys are investigated. Hypoeutectic (Ni-25 wt pct Sn) and eutectic (Ni-32.5 wt pct Sn) compositions of the Ni-Sn alloy were undercooled using a levitation melting with glass encasement technique, and the recalescence of these alloys was measured using a high speed temperature sensing device and a digital oscilloscope. It is observed that in both samples the total solidification and recalescence times decrease with increasing undercooling; the volume fraction of normal lamellar eutectic decreases with increasing undercooling; and in the hypoeutectic sample, the morphology of the primary phase changes from dendritic to spherical with increasing undercooling.

Wu, Yanzhong↗