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High-temperature ordered intermetallic alloys II; Proceedings of the Second Symposium, Boston, MA, Dec. 2-4, 1986

The papers presented in this volume provide on overview of recent theoretical and experimental research in the field of high-temperature ordered intermetallic alloys. The papers are gouped under the following headings: ordering behavior and theory, microstructures, mechanical behavior, alloy design and microstructural control, and metallurgical properties. Specific topics discussed include antiphase domains, disordered films and the ductility of ordered alloys based on Ni3Al; kinetics and mechanics of formation of Al-Ni intermetallics; deformability improvements of L1(2)-type intermetallic compounds; B2 aluminides for high-temperature applications; and rapidly solidified binary TiAl alloys.

Stoloff, N. S.↗

NiAl alloys for structural uses

Alloys based on the intermetallic compound NiAl are of technological interest as high temperature structural alloys. These alloys possess a relatively low density, high melting temperature, good thermal conductivity, and (usually) good oxidation resistance. However, NiAl and NiAl-base alloys suffer from poor fracture resistance at low temperatures as well as inadequate creep strength at elevated temperatures. This research program explored macroalloying additions to NiAl-base alloys in order to identify possible alloying and processing routes which promote both low temperature fracture toughness and high temperature strength. Initial results from the study examined the additions of Fe, Co, and Hf on the microstructure, deformation, and fracture resistance of NiAl-based alloys. Of significance were the observations that the presence of the gamma-prime phase, based on Ni3Al, could enhance the fracture resistance if the gamma-prime were present as a continuous grain boundary film or 'necklace'; and the Ni-35Al-20Fe alloy was ductile in ribbon form despite a microstructure consisting solely of the B2 beta phase based on NiAl. The ductility inherent in the Ni-35Al-20Fe alloy was explored further in subsequent studies. Those results confirm the presence of ductility in the Ni-35Al-20Fe alloy after rapid cooling from 750 - 1000 C. However exposure at 550 C caused embrittlement; this was associated with an age-hardening reaction caused by the formation of Fe-rich precipitates. In contrast, to the Ni-35Al-20Fe alloy, exploratory research indicated that compositions in the range of Ni-35Al-12Fe retain the ordered B2 structure of NiAl, are ductile, and do not age-harden or embrittle after thermal exposure. Thus, our recent efforts have focused on the behavior of the Ni-35Al-12Fe alloy. A second parallel effort initiated in this program was to use an alternate processing technique, mechanical alloying, to improve the properties of NiAl-alloys. Mechanical alloying in the conventional sense requires ductile powder particles which, through a cold welding and fracture process, can be dispersion strengthened by submicron-sized oxide particles. Using both the Ni-35Al-Fe alloys to contain approx. 1 v/o Y2O3. Preliminary results indicate that mechanically alloyed and extruded NiAl-Fe + Y2O3 alloys when heat treated to a grain-coarsened condition, exhibit improved creep resistance at 1000 C when compared to NiAl; oxidation resistance comparable to NiAl; and fracture toughness values a factor of three better than NiAl. As a result of the research initiated on this NASA program, a subsequent project with support from Inco Alloys International is underway.

Koss, D. A.↗

Alteration of the UV-visible reflectance spectra of H2O ice by ion bombardment

Satellite in the Jovian and Saturnian system exhibit differences in reflectivity between their 'leading' and 'trailing' surfaces which can affect the local vapor pressure. Since these differences are thought to be due to differences in the flux of bombarding magnetospheric ions, the influence of ion impact on the UV-visible reflectance of water ice surfaces (20-90 K) by keV ion bombardment was studied. An observed decrease in reflectance in the UV is attributed to rearrangement processes that affect the physical microstructure and surface 'roughness'. The ratio in reflectance of bombarded to freshly deposited films is compared to the ratio of the reflectance of the leading and trailing hemispheres for Europa and Ganymede.

Sack, N. J.↗

Evolution of Local Microstructures: Spatial and Temporal Correlation in Clusters Undergoing 2-Dimensional Diffusion

Diffusion-limited, capillarity-driven, coarsening of precipitates is an important and intensively studied phenomenon. Coarsening can occur among several microstructural constituents ranging from the primary phases to widely dispersed precipitates. Moreover, coarsening of three-dimensional (3-D) phase domains, occurring via mass transport through a two-dimensional (2-D) diffusion field (called mixed-dimensional phase coarsening) is a cooperative phenomenon that is of practical importance, especially in thin film technologies and catalysis. A primary objective of our current work is to focus on the details of evolving microstructures through a study of 'island' formation in heteroepitaxial film/substrate systems. Whereas this work has been designed for space-based coarsening studies, which require long-duration quality microgravity to observe 3-D Ostwald ripening, a significant amount of work has been performed during ground-based studies to observe diffusional coarsening in a liquid-liquid two-phase system. We have performed the experiment at an isopycnic point to maximize exclusion of gravity-based system disturbance. This has allowed observations of 3-D droplets, immobilized by container wall contact, undergoing coarsening by 2-D diffusion for the required long times (approximately 4 months) using a holographic imaging technique. Although such systems may not be as reliant on long-duration microgravity processing as 3-D systems are, they are of direct relevance to so-called mixed-dimensional coarsening and to the study of heterostructures grown by thin-film technique

Curreri, Peter A.↗

Effects of space environment on structural materials

A preliminary study of materials exposed in space in a low Earth orbit for nearly six years has revealed a wide range of micrometeorite or microparticle impact craters ranging in size from 1 to 1000 micron in diameter, debris particles from adjacent and distant materials systems, reaction products, and other growth features on the specimen surfaces, and related phenomena. The exposed surface features included fine grained and nearly amorphous materials as well as a large array of single crystal particles. A replication type, lift off technique was developed to remove reaction products and debris from the specimen surfaces in order to isolate them from the background substrate without creating microchemical or microstructural artifacts or alterations. This resulted in surface features resting on a carbon support film which was virtually invisible to observation by electron microscopy and nondispersive x ray analysis. Some evidence for blisters on leading edge aluminum alloy surfaces and a high surface region concentration of oxygen determined by Auger electron spectrometry suggests oxygen effects where fluences exceed 10(exp 21) atoms/sq cm.

Miglionico, C.↗

Techniques for Achieving Zero Stress in Thin Films of Iridium, Chromium, and Nickel

We examine techniques for achieving zero intrinsic stress in thin films of iridium, chromium, and nickel deposited by magnetron sputter deposition. The intrinsic stress is further correlated to the microstructural features and physical properties such as surface roughness and optical density at a scale appropriate to soft X-ray wavelengths. The examination of the stress in these materials is motivated by efforts to advance the optical performance of light-weight X-ray space telescopes into the regime of sub-arcsecond resolution through various deposition techniques that rely on control of the film stress to values within 10-100 MPa. A characteristic feature of the intrinsic stress behavior in chromium and nickel is their sensitivity to the magnitude and sign of the intrinsic stress with argon gas pressure and deposition rate, including the existence of a critical argon process pressure that results in zero film stress which scales linearly with the atomic mass of the sputtered species. While the effect of stress reversal with argon pressure has been previously reported by Hoffman and others for nickel and chromium, we report this effect for iridium. In addition to stress reversal, we identify zero stress in the optical functioning iridium layer shortly after island coalescence for low process pressures at a film thickness of approximately 35nm. The measurement of the low values of stress during deposition was achieved with the aid of a sensitive in-situ instrument capable of a minimum detectable level of stress, assuming a 35nm thick film, in the range of 0.40-6.0 MPa for <111> oriented crystalline silicon substrate thicknesses of 70-280 microns, respectively.

X-ray optical thin films↗

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.↗

Surface film effects on drop tube undercooling studies

The effects of various gaseous atmospheric constituents on drop-tube solidified samples of elemental metals were examined from a microstructural standpoint. All specimens were prepared from the purest available elements, so effects of impurities should not account for the observed effects. The drop-tube gas has a definite effect on the sample microstructure. Most dramatically, the sample cooling rate is effected. Some samples receive sufficient cooling to solidify in free fall while others do not, splating at the end of the drop tube in the sample catcher. Gases are selectively absorbed into the sample. Upon solidification gas can become less soluble and as a result forms voids within the sample. The general oxidation/reduction characteristics of the gas also affect sample microstructures. In general, under the more favorable experimental conditions including reducing atmospheric conditions and superheatings, examination of sample microstructures indicates that nucleation has been suppressed. This is indicated by underlying uniform dendrite spacings throughout the sample and with a single dendrite orientation through most of the sample. The samples were annealed yielding a few large grains and single or bi-crystal samples were commonly formed. This was especially true of samples that were inadvertently greatly superheated. This is in contrast with results from a previous study in which surface oxides were stable and contained numerous sites of nucleation. The number of nucleation events depends upon the surface state of the specimen as determined by the atmosphere and is consistent with theoretical expectations based upon the thermodynamic stability of surface oxide films. Oxide-free specimens are characterized by shiny surfaces, with no observable features under the scanning electron microscope at 5000X.

Ethridge, E. C.↗

Microtextured Surfaces for Turbine Blade Impingement Cooling

Gas turbine engine technology is constantly challenged to operate at higher combustor outlet temperatures. In a modern gas turbine engine, these temperatures can exceed the blade and disk material limits by 600 F or more, necessitating both internal and film cooling schemes in addition to the use of thermal barrier coatings. Internal convective cooling is inadequate in many blade locations, and both internal and film cooling approaches can lead to significant performance penalties in the engine. Micro Cooling Concepts, Inc., has developed a turbine blade cooling concept that provides enhanced internal impingement cooling effectiveness via the use of microstructured impingement surfaces. These surfaces significantly increase the cooling capability of the impinging flow, as compared to a conventional untextured surface. This approach can be combined with microchannel cooling and external film cooling to tailor the cooling capability per the external heating profile. The cooling system then can be optimized to minimize impact on engine performance.

Fryer, Jack↗

Microstructure and mechanical properties of multiphase NiAl-based alloys

The effect of the gamma-prime phase on the deformation behavior and fracture resistance of melt-spun ribbons and consolidated bulk specimens of a series of Nial-based alloys with Co and Hf additions has been examined. The morphology, location, and volume fraction of the gamma-prime phase are significant factors in enhancing the fracture resistance of the normally brittle NiAl-based alloys. In particular, the results indicate that a continuous-grain-boundary film of gamma-prime can impart limited room-temperature ductility regardless of whether B2 or L10 NiAl is present. Guidelines for microstructure control in multiphase NiAl-based alloys are also presented.

Pank, D. R.↗

Analysis of Plasma-Sprayed Thermal Barrier Coatings With Homogeneous and Heterogeneous Bond Coats Under Spatially Uniform Cyclic Thermal Loading

This report summarizes the results of a numerical investigation into the spallation mechanism in plasma-sprayed thermal barrier coatings observed under spatially-uniform cyclic thermal loading. The analysis focuses on the evolution of local stress and inelastic strain fields in the vicinity of the rough top/bond coat interface during thermal cycling, and how these fields are influenced by the presence of an oxide film and spatially uniform and graded distributions of alumina particles in the metallic bond coat aimed at reducing the top/bond coat thermal expansion mismatch. The impact of these factors on the potential growth of a local horizontal delamination at the rough interface's crest is included. The analysis is conducted using the Higher-Order Theory for Functionally Graded Materials with creep/relaxation constituent modeling capabilities. For two-phase bond coat microstructures, both the actual and homogenized properties are employed in the analysis. The results reveal the important contributions of both the normal and shear stress components to the delamination growth potential in the presence of an oxide film, and suggest mixed-mode crack propagation. The use of bond coats with uniform or graded microstructures is shown to increase the potential for delamination growth by increasing the magnitude of the crack-tip shear stress component.

Arnold, Steven M.↗

Pretreatment effects on the morphology and properties of aluminum oxide thermally grown on NiCoCrAlY

The effect of pretreatments on the morphology and properties of aluminum oxide thermally grown from NiCoCrAlY was investigated. The goal was to optimize process steps to produce a highly adherent, continuous, and insulating aluminum oxide. Two pretreatments were carried out, one in vacuum (about 0.0001 Torr) at 1350 K for 5 h, and the other consisting of deposition of a 1-micron thick Al2O3 film by activated reactive evaporation. Samples were subsequently oxidized thermally at 1000 C for 50 h at 0.5 Torr oxygen pressure. The two pretreatments were carried out on electron-beam evaporation NiCoCrAlY, about 120 microns thick, deposited on a superalloy turbine blade substrate. The results showed that the thermally grown oxide was significantly different in microstructure, surface topography and in its adherence to the NiCoCrAlY for the two pretreatments. Optimum results were obtained by combining the two pretreatments to produce an adherent, continuous, and insulating oxide film on the NiCoCrAlY-coated superalloy substrate.

Prakash, S.↗

The Features of Self-Assembling Organic Bilayers Important to the Formation of Anisotropic Inorganic Materials in Microgravity Conditions

There is a growing need for inorganic anisotropic particles in a variety of materials science applications. Structural, optical, and electrical properties can be greatly augmented by the fabrication of composite materials with anisotropic microstructures or with anisotropic particles uniformly dispersed in an isotropic matrix. Examples include structural composites, magnetic and optical recording media, photographic film, certain metal and ceramic alloys, and display technologies including flat panel displays. While considerable progress has been made toward developing an understanding of the synthesis of powders composed of monodispersed, spherical particles, these efforts have not been transferred to the synthesis of anisotropic nanoparticles. The major objective of the program is to develop a fundamental understanding of the growth of anisotropic particles at organic templates, with emphasis on the chemical and structural aspects of layered organic assemblies that contribute to the formation of anisotropic inorganic particles.

Talham, Daniel R.↗

The features of self-assembling organic bilayers important to the formation of anisotropic inorganic materials in microgravity conditions

Materials with directional properties are opening new horizons in a variety of applications including chemistry, electronics, and optics. Structural, optical, and electrical properties can be greatly augmented by the fabrication of composite materials with anisotropic microstructures or with anisotropic particles uniformly dispersed in an isotropic matrix. Examples include structural composites, magnetic and optical recording media, photographic film, certain metal and ceramic alloys, and display technologies including flat panel displays. The new applications and the need for model particles in scientific investigations are rapidly out-distancing the ability to synthesize anisotropic particles with specific chemistries and narrowly distributed physical characteristics (e.g. size distribution, shape, and aspect ratio).

Talham, Daniel R.↗

Large area polysilicon films with predetermined stress characteristics and method for producing same

Multi-layer assemblies of polysilicon thin films having predetermined stress characteristics and techniques for forming such assemblies are disclosed. In particular, a multi-layer assembly of polysilicon thin films may be produced that has a stress level of zero, or substantially so. The multi-layer assemblies comprise at least one constituent thin film having a tensile stress and at least one constituent thin film having a compressive stress. The thin films forming the multi-layer assemblies may be disposed immediately adjacent to one another without the use of intermediate layers between the thin films. Multi-layer assemblies exhibiting selectively determinable overall bending moments are also disclosed. Selective production of overall bending moments in microstructures enables manufacture of such structures with a wide array of geometrical configurations.

Heuer, Arthur H.↗

Multi-layer assemblies with predetermined stress profile and method for producing same

Multi-layer assemblies of polysilicon thin films having predetermined stress characteristics and techniques for forming such assemblies are disclosed. In particular, a multi-layer assembly of polysilicon thin films may be produced that has a stress level of zero, or substantially so. The multi-layer assemblies comprise at least one constituent thin film having a tensile stress and at least one constituent thin film having a compressive stress. The thin films forming the multi-layer assemblies may be disposed immediately adjacent to one another without the use of intermediate layers between the thin films. Multi-layer assemblies exhibiting selectively determinable overall bending moments are also disclosed. Selective production of overall bending moments in microstructures enables manufacture of such structures with a wide array of geometrical configurations.

Heuer, Arthur H.↗

Environmental fatigue of an Al-Li-Cu alloy. Part 2: Microscopic hydrogen cracking processes

Based on a fractographic analysis of fatigue crack propagation (FCP) in Al-Li-Cu alloy 2090 stressed in a variety of inert and embrittling environments, microscopic crack paths are identified and correlated with intrinsic da/dN-delta K kinetics. FCP rates in 2090 are accelerated by hydrogen producing environments (pure water vapor, moist air, and aqueous NaCl), as defined in Part 1. For these cases, subgrain boundary fatigue cracking (SGC) dominates for delta K values where the crack tip process zone, a significant fraction of the cyclic plastic zone, is sufficiently large to envelop 5 micron subgrains in the unrecrystallized microstructure. SGC may be due to strong hydrogen trapping at T1 precipitates concentrated at sub-boundaries. At low delta K, the plastic zone diameter is smaller than the subgrain size and FCP progresses along (100) planes due to either local lattice decohesion or aluminum-lithium hydride cracking. For inert environments (vacuum, helium, and oxygen), or at high delta K where the hydrogen effect on da/dN is small, FCP is along (111) slip planes; this mode does not transition with increasing delta K and plastic zone size. The SGC and (100) crystallographic cracking modes, and the governing influence of the crack tip process zone volume (delta K), support hydrogen embrittlement rather than a surface film rupture and anodic dissolution mechanism for environmental FCP. Multi-sloped log da/dN-log delta K behavior is produced by changes in process zone hydrogen-microstructure interactions, and not by purely micromechanical-microstructure interactions, in contradiction to microstructural distance-based fatigue models.

Robert S Piascik↗

High temperature strain gages

A ceramic strain gage based on reactively sputtered indium-tin-oxide (ITO) thin films is used to monitor the structural integrity of components employed in aerospace propulsion systems operating at temperatures in excess of 1500.degree. C. A scanning electron microscopy (SEM) of the thick ITO sensors reveals a partially sintered microstructure comprising a contiguous network of submicron ITO particles with well defined necks and isolated nanoporosity. Densification of the ITO particles was retarded during high temperature exposure with nitrogen thus stabilizing the nanoporosity. ITO strain sensors were prepared by reactive sputtering in various nitrogen/oxygen/argon partial pressures to incorporate more nitrogen into the films. Under these conditions, sintering and densification of the ITO particles containing these nitrogen rich grain boundaries was retarded and a contiguous network of nano-sized ITO particles was established.

Gregory, Otto J.↗