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At least 379 records · Page 21

The effect of an electric field on the morphological stability of the crystal-melt interface of a binary alloy. III - Weakly nonlinear theory

The effect of a constant electric current on the crystal-melt interface morphology during directional solidification at constant velocity of a binary alloy is considered. A linear temperature field is assumed, and thermoelectric effects and Joule heating are neglected; electromigration and differing electrical conductivities of crystal and melt are taken into account. A two-dimensional weakly nonlinear analysis is carried out to third order in the interface amplitude, resulting in a cubic amplitude equation that describes whether the bifurcation from the planar state is supercritical or subcritical. For wavelengths corresponding to the most dangerous mode of linear theory, the demarcation between supercritical and subcritical behavior is calculated as a function of processing conditions and material parameters. The bifurcation behavior is a sensitive function of the magnitude and direction of the electric current and of the electrical conductivity ratio.

Wheeler, A. A.↗

Process modelling for materials preparation experiments

The main goals of the research under this grant consist of the development of mathematical tools and measurement techniques for transport properties necessary for high fidelity modelling of crystal growth from the melt and solution. Of the tasks described in detail in the original proposal, two remain to be worked on: development of a spectral code for moving boundary problems, and development of an expedient diffusivity measurement technique for concentrated and supersaturated solutions. We have focused on developing a code to solve for interface shape, heat and species transport during directional solidification. The work involved the computation of heat, mass and momentum transfer during Bridgman-Stockbarger solidification of compound semiconductors. Domain decomposition techniques and preconditioning methods were used in conjunction with Chebyshev spectral methods to accelerate convergence while retaining the high-order spectral accuracy. During the report period we have further improved our experimental setup. These improvements include: temperature control of the measurement cell to 0.1 C between 10 and 60 C; enclosure of the optical measurement path outside the ZYGO interferometer in a metal housing that is temperature controlled to the same temperature setting as the measurement cell; simultaneous dispensing and partial removal of the lower concentration (lighter) solution above the higher concentration (heavier) solution through independently motor-driven syringes; three-fold increase in data resolution by orientation of the interferometer with respect to diffusion direction; and increase of the optical path length in the solution cell to 12 mm.

Rosenberger, Franz↗

Fundamentals of Scalable Nanoparticle Assembly in Engineering Polymres

Systematically improving the properties of polymer nanocomposites is contingent on effectively controlling nanoparticle (NP) dispersion; further, it is necessary to attain this at scale if these methods are to impact practical applications. While most past work has focused on amorphous polymers, ≈ 70% of all polymers sold annually are semicrystalline. Inspired by this apparent disconnect, our work in the current DOE funded grant and this renewal proposal employs a novel handle, polymer crystallization, to organize NPs into the various amorphous zones of the lamellar semicrystalline morphology (interlamellar, interfibrillar and interspherulitic domains) of stereoregular polymers. We hypothesize that the isothermal crystallization rate of a polymer host, G, and NP diffusivity, are the two relevant control parameters in this context. In the case where the NPs are miscible in the melt, they remain spatially well-dispersed when the polymer is crystallized at a rate that is fast relative to NP diffusion. In contrast, monolayer-thick NP sheets with intersheet spacing of ~10-100nm form in slowly crystallized samples. This sheet stacking is remarkably similar to that seen in natural materials, e.g., Nacre. There is also ordering of the NPs at the larger interfibrillar scale. Importantly, the relative fraction of engulfed, interlamellar and interfibrillar NPs is determined by G. Further, the modulus of these materials can increase by a factor of 2-3 due to the organization state of the NPs, while leaving fracture toughness unaffected. We have established the broad applicability of this approach in two polymers, polyethylene (PE) and polyethyleneoxide (PEO). To achieve this goal we developed a method for grafting long PE chains from NPs with controlled graft density and molecular weight, giving us the ability to tailor their dispersion in the PE melt prior to crystallization. In this renewal proposal, we will develop the fundamental, quantitative understanding that will allow us to independently tailor polymer crystallization rate, NP diffusivity and NP agglomeration state in semicrystalline polymers so as to facilely control NP ordering and hence properties. A program that tightly integrates experiment and theory is proposed, and a key outcome of this research will be a three-dimensional design map for different regimes of NP organization (and hence properties) that can be achieved by polymer crystallization. A second independent outcome is the role of directional solidification and how it competes with the rates of polymer crystallization and NP mobility to affect the organization of the NP.

36 MATERIALS SCIENCE↗

Processing eutectics in space

Experimental work is reported which was directed toward obtaining interface shape control while a numerical thermal analysis program was being made operational. An experimental system was developed in which the solid-liquid interface in a directionally solidified aluminum-nickel eutectic could be made either concave to the melt or convex to the melt. This experimental system provides control over the solid-liquid interface shape and can be used to study the effect of such control on the microstructure. The SINDA thermal analysis program, obtained from Marshall Space Flight Center, was used to evaluate experimental directional solidification systems for the aluminum-nickel and the aluminum-copper eutectics. This program was applied to a three-dimensional ingot, and was used to calculate the thermal profiles in axisymmetric heat flow. The results show that solid-liquid interface shape control can be attained with physically realizable thermal configurations and the magnitudes of the required thermal inputs were indicated.

Douglas, F. C.↗

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.↗

Feasibility investigation of growing gallium arsenide single crystals in ribbon form

Polycrystalline GaAs ribbons have been grown in graphite boats by passage of a wide zone through B2O3 encapsulated feed stock, confined by a quartz cover plate. By controlling the heat flow in the graphite boat and controlling the zoning rate, large grained, single phase polycrystalline samples with directional solidification and good thickness control were achieved. Arsenic vaporization was effectively suppressed at the melting point of GaAs by the B2O3 moat and 3 atmospheres of pressure. A vertical constrained-zone-melting apparatus with a B2O3 moat seal, rf heating, and water cooling on the bottom will be used to control the heat flow and temperature patterns required for growth of single crystal ribbons.

Richardson, D. L.↗

Processing eutectics in space

The investigations of directional solidification have indicated the necessity of establishing a secure foundation in earth-based laboratory processing in order to properly assess low-gravity processing. Emphasis was placed on evaluating the regularity of microstructure of the rod-like eutectic Al-Al3Ni obtained under different conditions of growth involving the parameters of thermal gradient, solidification rate, and interfacial curvature. In the case of Al-Al3Ni, where the Al3Ni phase appears as facets rods, solidification rate was determined to be a controlling parameter. Zone melting of thin eutectic films showed that for films of the order of 10 to 20 micrometers thick, the extra surface energy appears to act to stabilize a regular microstructure. The results suggest that the role of low-gravity as provided in space-laboratory processing of materials is to be sought in the possibility of generating a higher thermal gradient in the solidifying ingot for a given power input-output arrangement than can be obtained under normal one-g processes.

Douglas, F. C.↗

Halide eutectic growth experiment MA-131

Fiberlike sodium chloride/lithium fluoride eutectic mixtures have been produced on earth and in space by the directional solidification technique. Macroscopic and microscopic examinations were made on longitudinal and transverse sections of Apollo Soyuz Test Project space grown and earth grown ingots. It was found that samples grown in space have a higher percentage of fibers alined with the growth axis. The enhanced alinement of fibers is attributed to the absence of convection currents in the liquid during solidification. Optical transmittance measurements of transverse sections of the space grown and earth grown ingots were performed with an infrared spectrometer. For a given sample thickness, the highest transmittance was obtained from ingots grown in space. For samples of different thicknesses, grown either in space or on earth, it was found that the thinner the sample, the higher the transmittance. This is in agreement with the general optical property of transparent materials.

Yue, A. S.↗

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.↗

Quantitative determination of zero-gravity effects on crystal growth from the melt (experiment MA-060)

The purpose of experiment MA-060 was to investigate quantitatively the effects of near-zero gravity conditions on crystal growth and dopant segregation during directional solidification from the melt. Gallium-doped germanium single crystals were successfully grown from the melt with simultaneous interface demarcation during the Apollo Soyuz Test Project mission. The analysis of the experimental data indicates striking differences of dopant segregation and growth behavior in the presence and absence of gravity. The results obtained are believed to have far-reaching implications on materials processing under zero-gravity conditions and on the theory of crystal growth and segregation in general.

Gatos, H. C.↗

Quantitative determination of zero-gravity effects on electronic materials processing germanium crystal growth with simultaneous interface demarcation. Experiment MA-060

Experiment MA-060 was designed to establish the crystal growth and segregation characteristics of a melt in a directional solidification configuration under near zero-g conditions. The interface demarcation technique was incorporated into the experiment since it constitutes a unique tool for recording the morphology of the growth rate throughout solidification, and for establishing an absolute time reference framework for all stages of the solidification process. An extensive study was performed of the germanium crystals grown during the Apollo-Soyuz Test Project mission. It was found that single crystal growth was achieved and that the interface demarcation functioned successfully. There was no indication that convection driven by thermal or surface tension gradients was present in the melt. The gallium segregation, in the absence of gravity, was found to be fundamentally different in its initial and its subsequent stages from that of the ground-based tests. None of the existing theoretical models for growth and segregation can account for the observed segregation behavior in the absence of gravity.

Gatos, H. C.↗

Cost analysis of advanced turbine blade manufacturing processes

A rigorous analysis was conducted to estimate relative manufacturing costs for high technology gas turbine blades prepared by three candidate materials process systems. The manufacturing costs for the same turbine blade configuration of directionally solidified eutectic alloy, an oxide dispersion strengthened superalloy, and a fiber reinforced superalloy were compared on a relative basis to the costs of the same blade currently in production utilizing the directional solidification process. An analytical process cost model was developed to quantitatively perform the cost comparisons. The impact of individual process yield factors on costs was also assessed as well as effects of process parameters, raw materials, labor rates and consumable items.

Barth, C. F.↗

Silicon ribbon growth by a capillary action shaping technique

Substantial improvements in ribbon surface quality are achieved with a higher melt meniscus than that attainable with the film-fed (EFG) growth technique. A capillary action shaping method is described in which meniscus shaping for the desired ribbon geometry occurs at the vertex of a wettable die. As ribbon growth depletes the melt meniscus, capillary action supplies replacement material. Topics discussed cover experimental apparatus and growth procedures; die materials investigations, fabrication and evaluation; process development for 25 mm, 38 mm, 50 mm and 100 mm silicon ribbons; and long grain direct solidification of silicon. Methods for the structural and electrical characterization of cast silicon ribbons are assessed as well as silicon ribbon technology for the 1978 to 1986 period.

Schwuttke, G. H.↗

Development of Mullite Substrates and Containers

The mullite-molten silicon interaction was evaluated through fabrication of a series of bodies made with variations in density, alumina-silica ratio, and glass-crystalline ratio. The materials were tested in a sessile drop technique. None of the variations stood up to extended exposure to molten silicon sufficiently to be recommended as a container material. However, directional solidification experiments suggest that, under proper conditions, contamination of the silicon by mullite containers can be minimized. To improve an already good thermal expansion match between mullite and silicon, compositional variations were studied. Altering of the alumina-silica ratio was determined to give a continuously varying thermal expansion. A standard mullite composition was selected and substrates 40 x 4 x .040 inches were fabricated. Slotted substrates of various configurations and various compositions were also fabricated.

Sibold, J. D.↗

Eutectic alloys. Citations from the International Aerospace Abstracts data base

These 250 abstracts from the international literature provide summaries of the preparation, treatments, composition and structure, and properties of eutectic alloys. Techniques for directional solidification and treatments including glazing, coating, and fiber reinforcement are discussed. In addition to the mechanical and thermal properties, the superconducting, corrosion, resistance, and thermionic emission and adsorption properties are described.

Moore, P.↗

Development of exothermically cast single-crystal Mar-M 247 and derivative alloys

A low-cost, exothermic directional-solidification (DS) process was developed to produce single-crystal (SC) Mar-M 247 high-pressure turbine blades. Stress-rupture data indicated that SC Mar-M 247 provides only marginal improvements in longitudinal strength relative to the columnar grained DS material. Removal of grain boundary strengthening elements (B, C, Zr, Hf) from the Mar-M 247 composition (which are also melting point depressants) permitted the alloy to be solutioned at significantly higher temperatures. An order of magnitude improvement in rupture life relative to SC Mar-M 247 was observed for several derivative alloys at 103.5 MPa (15 KSI) and 1093 C. Rupture lives of the modified SC alloys were significantly affected by both alloy purity and heat treatment. Critical aspects of vacuum induction refining, exothermic casting technology, alloy development and heat treatment, which contributed to this new class of turbine blades, are reviewed

Strangman, T. E.↗

The effect of thermal cycling to 1100 degree C on the alpha (Mo) phase in directionally solidified gamma/gamma prime-alpha alloys

In gamma/gamma prime - alpha eutectic alloys (Ni-Mo-Al), the resistance of the alpha phase to morphological changes during thermal cycling was found to be dependent on the structure formed during directional solidification. Fine, smooth alpha fibers survived up to 1000 five minute cycles to 1100 C with minor microstructural contour changes, while coarser and irregularly shaped alpha fibers tended to spheroidize. A mechanism to explain this phenomenon is proposed. It is suggested that on heating to 1100 C, the alpha phase is likely to undergo morphological changes, until differential thermal expansion creates a stress free interface between the alpha phase and the gamma/gamma prime matrix.

Harf, F. H.↗