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At least 109 records · Page 6

Analysis of Advanced Thermoelectric Materials and Their Functional Limits

The world's demand for energy is increasing dramatically, but the best energy conversion systems operate at approximately 30% efficiency. One way to decrease energy loss is in the recovery of waste heat using thermoelectric (TE) generators. A TE generator is device that generates electricity by exploiting heat flow across a thermal gradient. The efficiency of a TE material for power generation and cooling is determined by the dimensionless Figure of Merit (ZT): ZT = S(exp. 2)sigmaT/κ: where S is the Seebeck coefficient, sigma is the electrical conductivity, T is the absolute temperature, and κ is the thermal conductivity. The parameters are not physically independent, but intrinsically coupled since they are a function of the transport properties of electrons. Traditional research on TE materials has focused on synthesizing bulk semiconductor-type materials that have low thermal conductivity and high electrical conductivity affording ZT values of 1. The optimization of the σ/κ ratio is difficult to achieve using current material formats, as these material constants are complementary. Recent areas of research are focusing on using nanostructural artifacts that introduce specific dislocations and boundary conditions that scatter the phonons. This disrupts the physical link between thermal (phonon) and electrical (electron) transport. The result is that κ is decreased without decreasing σ. These material formats give ZT values of up to 2 which represent approximately 18% energy gain from waste heat recovery. The next challenge in developing the next generation of TE materials with superior performance is to tailor the interconnected thermoelectric physical parameters of the material system. In order to approach this problem, the fundamental physics of each parameter S, sigma, and κ need to be physically understood in their context of electron/phonon interaction for the construction of new high ZT thermoelectric devices. Is it possible to overcome the physical limit imposed by of the effect of phonon lattice oscillation and energetic electrons towards thermal conductivity? Is the Seebeck coefficient, based on the difference in voltage over temperature gradient ( deltaV/deltaT), an intrinsic parameter of each material? All these parameters were manipulated using nano-bridge and twin-lattice structural concepts at the NASA Langley Research Center. This talk will review the current trend of TE research to optimize the ZT and discuss about new approaches on increasing ZT within functional limits of each parameter.

Kim, Hyun Jung↗

High Performance Materials Applications to Moon/Mars Missions and Bases

Two classes of material processing scenarios will feature prominently in future interplanetary exploration: in situ production using locally available materials in lunar or planetary landings and high performance structural materials which carve out a set of properties for uniquely hostile space environments. To be competitive, high performance materials must typically offer orders of magnitude improvements in thermal conductivity or insulation, deliver high strength-to-weight ratios, or provide superior durability (low corrosion and/or ablative character, e.g., in heat shields). The space-related environmental parameters of high radiation flux, low weight, and superior reliability limits many typical aerospace materials to a short list comprising high performance alloys, nanocomposites and thin-layer metal laminates (Al-Cu, Al-Ag) with typical dimensions less than the Frank-Reed-type dislocation source. Extremely light weight carbon-carbon composites and carbon aerogels will be presented as novel examples which define broadened material parameters, particularly owing to their extreme thermal insulation (R-32-64) and low densities (<0.01 g/cu cm) approaching that of air itself. Even with these low-weight payload additions, rocket thrust limits and transport costs will always place a premium on assembling as much structural and life support resources upon interplanetary, lunar, or asteroid arrival. As an example, for in situ lunar glass manufacture, solar furnaces reaching 1700 C for pure silica glass manufacture in situ are compared with sol-gel technology and acid-leached ultrapure (<0.1% FeO) silica aerogel precursors.

Noever, David A.↗

High Performance Materials Applications to Moon/Mars Missions and Bases

Two classes of material processing scenarios will feature prominently in future interplanetary exploration- in situ production using locally available materials in lunar or planetary landings and high performance structural materials which carve out a set of properties for uniquely hostile space environments. To be competitive, high performance materials must typically offer orders of magnitude improvements in thermal conductivity or insulation, deliver high strength-to-weight ratios, or provide superior durability (low corrosion and/or ablative character, e.g. in heat shields). The space-related environmental parameters of high radiation flux, low weight and superior reliability limits many typical aerospace materials to a short list comprising high performance alloys, nanocomposites and thin-layer metal laminates (Al-Cu, Al-Ag) with typical dimensions less than the Frank-Reed-type dislocation source. Extremely light weight carbon-carbon composites and car on aerogels will be presented as novel examples which define broadened material parameters, particularly owing to their extreme thermal insulation (R-32-64) and low densities (less than 0.01 g/cc) approaching that of air itself. Even with these low weight payload additions, rocket thrust limits and transport costs will always place a premium on assembling as much structural and life support resources upon interplanetary, lunar or asteroid arrival. As an example for in situ lunar glass manufacture, solar furnaces reaching 1700 C for pure silica glass manufacture in situ are compared with sol-gel technology and acid-leached ultrapure (less than 0.1% FeO) silica aerogel precursors.

Noever, David A.↗

Investigation of Strain Aging in the Ordered Intermetallic Compound beta-NiAl

The phenomenon of strain aging has been investigated in polycrystalline and single crystal NiAl alloys at temperatures between 300 and 1200 K. Static strain aging studies revealed that after annealing at 1100 K for 7200 s (i.e., 2h) followed by furnace cooling, high purity, nitrogen-doped and titanium-doped polycrystalline alloys exhibited continuous yielding, while conventional-purity and carbon-doped alloys exhibited distinct yield points and Luders strains. Prestraining by hydrostatic pressurization removed the yield points, but they could be reintroduced by further annealing treatments. Yield points could be reintroduced more rapidly if the specimens were prestrained uniaxially rather than hydrostatically, owing to the arrangement of dislocations into cell structures during uniaxial deformation. The time dependence of the strain aging events followed at t(exp 2/3) relationship suggesting that the yield points observed in polycrystalline NiAl were the result of the pinning of mobile dislocations by interstitials, specifically carbon. Between 700 and 800 K, yield stress plateaus, yield stress transients upon a ten-fold increase in strain rate, work hardening peaks, and dips in the strain rate sensitivity (SRS) have been observed in conventional-purity and carbon-doped polycrystals. In single crystals, similar behavior was observed; in conventional-purity single crystals, however, the strain rate sensitivity became negative resulting in serrated yielding, whereas, the strain rate sensitivity stayed positive in high purity and in molybdenum-doped NiAl. These observations are indicative of dynamic strain aging (DSA) and are discussed in terms of conventional strain aging theories. The impact of these phenomena on the composition-structure-property relations are discerned. Finally, a good correlation has been demonstrated between the properties of NiAl alloys and a recently developed model for strain aging in metals and alloys developed by Reed-Hill et al.

Weaver, Mark Lovell↗

Preliminary Work in Obtaining Site-Directed Mutants of Hen Egg White Lysozyme

Protein crystal growth studies are recognized as a critical endeavor in the field of molecular biotechnology. The scientific applications of this field include the understanding of how enzymes function and the accumulation of accurate information of atomic structures, a key factor in the process of rational drug design. NASA has committed substantial investment and resources to the field of protein crystal growth and has conducted many microgravity protein crystal growth experiments aboard shuttle flights. Crystals grown in space tend to be larger, denser and have a more perfect habit and geometry. These improved properties gained in the microgravity environment of space result largely from the reduction of solutal convection, and the elimination of sedimentation at the growing crystal surface. Shuttle experiments have yielded many large, high quality crystals that are suitable for high resolution X-ray diffraction analysis. Examples of biologically important macromolecules which have been successfully crystallized during shuttle missions include: lysozyme, isocitrate lyase, gamma-interferon, insulin, human serum albumin and canavalin. Numerous other examples are also available. In addition to obtaining high quality crystals, investigators are also interested in learning the mechanisms by which the growth events take place. Crystallization experiments indicate that for the enzyme HEWL, measured growth rates do not follow mathematical models for 2D nucleation and dislocation-led growth of tetragonal protein crystals. As has been suggested by the laboratory of Marc L. Pusey, a possible explanation for the disagreement between observation and data is that HEWL tetraconal crystals form by aggregated units of lysozyme in supersaturated solutions. Surface measurement data was shown to fit very well with a model using an octamer unit cell as the growth unit. According to this model, the aggregation pathway and subsequent crystal growth is described by: monomer < ------ > dimer < ------- > tetramer < ------ > octamer < ------ > higher order. It is believed that multimer aggregation of lysozyme occurs by interaction at specific binding sites on the surface of the protein crystals. If the presence of discrete binding sites and the aggregation hypothesis is true, then it follows that the alteration of the binding site(s) should have significant effect on the measurements obtained during growth experiments. Site-directed mutagenesis allows the specific alteration of proteins by replacement, deletion or addition of specific amino acid residues. This report outlines the approach for this strategy and the progress made thus far toward that end.

Holmes, Leonard D.↗

Phase Transformation and Creep Behavior in Ti50Pd30Ni20 High Temperature Shape Memory Alloy in Compression

The creep behavior and the phase transformation of Ti50Pd30Ni20 High Temperature Shape Memory Alloy (HTSMA) is investigated by standard creep tests and thermomechanical tests. Ingots of the alloy are induction melted, extruded at high temperature, from which cylindrical specimens are cut and surface polished. A custom high temperature test setup is assembled to conduct the thermomechanical tests. Following preliminary monotonic tests, standard creep tests and thermally induced phase transformation tests are conducted on the specimen. The creep test results suggest that over the operating temperatures and stresses of this alloy, the microstructural mechanisms responsible for creep change. At lower stresses and temperatures, the primary creep mechanism is a mixture of dislocation glide and dislocation creep. As the stress and temperature increase, the mechanism shifts to predominantly dislocation creep. If the operational stress or temperature is raised even further, the mechanism shifts to diffusion creep. The thermally induced phase transformation tests show that actuator performance can be affected by rate independent irrecoverable strain (transformation induced plasticity + retained martensite) as well as creep. The rate of heating and cooling can adversely impact the actuators performance. While the rate independent irrecoverable strain is readily apparent early in the actuators life, viscoplastic strain continues to accumulate over the lifespan of the HTSMA. Thus, in order to get full actuation out of the HTSMA, the heating and cooling rates must be sufficiently high enough to avoid creep.

Kumar, Parikshith K.↗

Ultrasonic characterization of plastic deformation in metals

Acoustic tone burst spectroscopy is used to examine the effect of plastic deformation on higher order elastic properties of specimens of AISI 1016, 1045, 1095 and 8620 steel rods by measuring the stress acoustic constants (SACs). The SAC is found to be influenced by prestraining, and prestrain SAC measurements on 8620 steel demonstrate similar behavior to previously measured steels even though the composition of 8620 steel is significantly different. It is suggested from bias stress measurements that the stress acoustic response of prestrained 8620 steel is sensitive to the sign of the applied stress due to the different directions is which dislocations move under tension as opposed to compression, providing an approach to nondestructive testing of residual stress in steels.

Allison, S. G.↗

An experimental investigation of fatigue damage in aluminum 2024-T3 alloys

Aluminum alloys are finding increasing use in the aerospace and automobile industries due to their attractive low density-high modulus and low density-high strength characteristics. Unfortunately, cyclic stress-strain deformation alters the microstructure of the material. These structural changes can lead to fatigue damage and ultimately service failure. Therefore, in order to assess the integrity of the alloy, a correlation between fatigue damage and a measurable microstructural property is needed. Aluminum 2024-T3, a commonly used commercial alloy, contains many grains (individual crystals) of various orientations. The sizes and orientations of these grains are known to affect the strength, hardness, and magnetic permeability of polycrystalline alloys and metals; therefore, perhaps a relationship between a grain property and the fatigue state can be established. Tension-compression cycling in aluminum alloys can also induce changes in their dislocation densities. These changes can be studied from measurements of the electrical resistivities of the materials. Consequently, the goals of this investigation were: to study the grain orientation of aluminum 2024-T3 and to seek a correlation between the grain orientation and the fatigue state of the material; and to measure the electrical resistivities of fatigued samples of aluminum 2024-T3 and to interpret the findings.

Ferguson, Milton W.↗

Atomic-scale Modeling of the Structure and Dynamics of Dislocations in Complex Alloys at High Temperatures

We report on the progress made during the first year of the project. Most of the progress at this point has been on the theoretical and computational side. Here are the highlights: (1) A new code, tailored for high-end desktop computing, now combines modern Accelerated Dynamics (AD) with the well-tested Embedded Atom Method (EAM); (2) The new Accelerated Dynamics allows the study of relatively slow, thermally-activated processes, such as diffusion, which are much too slow for traditional Molecular Dynamics; (3) We have benchmarked the new AD code on a rather simple and well-known process: vacancy diffusion in copper; and (4) We have begun application of the AD code to the diffusion of vacancies in ordered intermetallics.

Daw, Murray S.↗

Structure of transient oxides formed on NiCrAl alloys

It is one of the three objectives of the present study to document the fine internal structure of the transient scales in order to clarify the development of the stable alpha-Al2O3 from a structural point of view. Another objective is concerned with the origin of features found in the mature alpha-Al2O3 scales, such as voids, taking into account an examination in the early stages of oxidation. The third objective is to relate any difference in scale structure caused by oxide adherence additives (Y or Zr) to the current oxide adherence theories. The primary effect of short-time oxidation on the NiCrAl substrate structure is found to be production of dislocations and aluminum-depleted phases. The random alpha-Al2O3 scale is the primary oxide phase observed in contact with the metal.

Smialek, J. L.↗

Flow and fracture behavior of NiAl in relation to the brittle-to-ductile transition temperature

NiAl has only three independent slip systems operating at low and intermediate temperatures whereas five independent deformation mechanisms are required to satisfy the von Mises criterion for general plasticity in polycrystalline materials. Yet, it is generally recognized that polycrystalline NiAl can be deformed extensively in compression at room temperature and that limited tensile ductility can be obtained in extruded materials. In order to determine whether these results are in conflict with the von Mises criterion, tension and compression tests were conducted on powder-extruded, binary NiAl between 300 and 1300 K. The results indicate that below the brittle-to-ductile transition temperature (BDTT) the failure mechanism in NiAl involves the initiation and propagation of cracks at the grain boundaries which is consistent with the von Mises analysis. Furthermore, evaluation of the flow behavior of NiAl indicates that the transition from brittle to ductile behavior with increasing temperature coincides with the onset of recovery mechanisms such as dislocation climb. The increase in ductility above the BDTT is therefore attributed to the climb of the 001 line type dislocations which in combination with dislocation glide enable grain boundary compatibility to be maintained at the higher temperatures.

Noebe, R. D.↗

The effect of strain rate and temperature on the tensile properties of NiAl

Tensile testing of cast and extruded binary NiAl was performed from 300 to 900 K at strain rates of 0.00014 to 0.14/s. The brittle-to-ductile transition temperature (BDTT) was dependent on strain rate, with a three-order-of-magnitude increase in strain rate resulting in approximately a 200-K increase in transition temperature. Regardless of strain rate, at temperatures just above the BDTT the fracture strength increased significantly and the fracture morphology changed from mostly intergranular to predominantly transgranular. It was also determined that the mechanism responsible for the brittle-to-ductile transition in NiAl had an apparent activation energy of approximately 118 kJ/mol. These results support the argument that the mechanism for the brittle-to-ductile transition in NiAl is associated with the onset of thermally activated deformation process. This process is probably dislocation climb controlled by short circuit diffusion.

Noebe, R. D.↗

Transient Creep of a Composite Lower Crust: A Polymineralic Basis for Rapidly Evolving Postseismic Deformation Modes - 2

Postseismic horizontal strain and displacement following the June 28, 1992, Landers, California, earthquake (M(sub W) 7.3) is broad scale and cannot be explained solely by delayed afterslip located at the rupturing fault trace. Both the observed strain at Pifion Flat Observatory (PFO) and observed Global Positioning System receiver velocities evolve rapidly after the Landers-Big Bear earthquake sequence. The observed exponential decay of these motions, with timescales of 4-34 days, may reflect a soft creep rheology in the lower crust and brittle-ductile transition zone or even within the seismogenic crust itself. Here a simple model of a two-dimensional screw dislocation in a layered Maxwell viscoelastic Earth is employed in conjunction with a composite rheology to demonstrate that the short timescale transient response modes (approx. = 4-34 days) are consistent with the behavior of a biviscous lower crust. The lowest viscosity of this system is derivable from laboratory experimental data on the long-term creep of natural quarztites, and the highest viscosity is consistent with isostasy-related lower crustal flow in a continental extensional tectonic environment. The model predicts significant stress relaxation at the base of the seismogenic crust. Near the base of the seismogenic zone, and about 4 km away from the mainshock, the rate of predicted relaxation is of the order of 0.01 MPa/ d during the first 20 days of postseismic flow. Oblate spheroidal inclusions at 5% concentration levels that are both aligned and fairly flat in shape and that have a viscosity of 3-4 x 10(exp 15) Pa s are consistent with both the amplitude and decay time of horizontal crustal strain observed at PFO after the Landers mainshock. It is speculated that the structures exposed in cross sections and in seismic reflection profiles of the lower crust that have mylonitic associations are, in part, the cause of such rapid postseismic evolution in southeastern California. Unmylonitized quartz-rich rock at sufficiently elevated temperatures could also contribute to the rapid decay modes.

Ivins, Erik R.↗

Computer Code for Nanostructure Simulation

Due to their small size, nanostructures can have stress and thermal gradients that are larger than any macroscopic analogue. These gradients can lead to specific regions that are susceptible to failure via processes such as plastic deformation by dislocation emission, chemical debonding, and interfacial alloying. A program has been developed that rigorously simulates and predicts optoelectronic properties of nanostructures of virtually any geometrical complexity and material composition. It can be used in simulations of energy level structure, wave functions, density of states of spatially configured phonon-coupled electrons, excitons in quantum dots, quantum rings, quantum ring complexes, and more. The code can be used to calculate stress distributions and thermal transport properties for a variety of nanostructures and interfaces, transport and scattering at nanoscale interfaces and surfaces under various stress states, and alloy compositional gradients. The code allows users to perform modeling of charge transport processes through quantum-dot (QD) arrays as functions of inter-dot distance, array order versus disorder, QD orientation, shape, size, and chemical composition for applications in photovoltaics and physical properties of QD-based biochemical sensors. The code can be used to study the hot exciton formation/relation dynamics in arrays of QDs of different shapes and sizes at different temperatures. It also can be used to understand the relation among the deposition parameters and inherent stresses, strain deformation, heat flow, and failure of nanostructures.

Filikhin, Igor↗

New AFM Techniques for Investigating Molecular Growth Mechanisms of Protein Crystals

Atomic Force Microscopy (AFM) has emerged as a powerful technique for investigating protein crystal growth. Earlier AFM studies were among the first to demonstrate that these crystals grew by dislocation and 2D nucleation growth mechanisms [1]. These investigations were restricted to the micron range where only surface features, such as dislocation hillocks and 2D islands are visible. Most AFM instruments can scan at higher resolutions and have the potential to resolve individual protein molecules at nanometer ranges. Such scans are essential for determining the molecular packing arrangements on crystal faces and for probing the growth process at the molecular level. However, at this resolution the AFM tip influences the image produced, with the resulting image being a convolution of the tip shape and the surface morphology [2]. In most studies this problem is resolved by deconvoluting the image to obtain the true surface morphology. Although deconvolution routines work reasonably well for simple one- dimensional shapes, for complex surfaces this approach does not produce accurate results. In this study we devised a new approach which takes advantage of the precise molecular order of crystal surfaces, combined with the knowledge of individual molecular shapes from the crystallographic data of the protein and the AFM tip shape. This information is used to construct expected theoretical AFM images by convoluting the tip shape with the constructed crystal surface shape for a given surface packing arrangement. By comparing the images from actual AFM scans with the constructed ones for different possible surface packing arrangements, the correct packing arrangement can be conclusively determined. This approach was used in this study to determine the correct one from two possible packing arrangements on (I 10) faces of tetragonal lysozyme crystals. Another novel AFM technique was also devised to measure the dimension of individual growth units of the crystal faces. Measuring these units was not attempted before and most studies have assumed that the growth unit consisted of individual protein molecules. The linescan mode of AFM instruments allows the crystal surface to be scanned along a single line. By scanning across a growth step an image showing the motion of the step is obtained. Normally such an image shows a straight line for continuous and constant step velocity. In this study by increasing the scan rate and by decreasing the step velocity (by decreasing the supersaturation), we were able to capture images of individual growth events, shown by jump discontinuities in the step line. By suitable integration of the image the growth unit dimension in the scanned direction can be obtained. Since multiple units can be involved in the growth process it is necessary to collect a statistically relevant sample before drawing conclusions about the growth mechanism. This technique was successfully employed to obtain the dimensions of growth units for the (110) face, showing that they consisted of various aggregates corresponding to the 43 helices in the crystal structure.

Li, Huayu↗

Phase Sensitive X-Ray Diffraction Imaging Study of Protein Crystals

The study of defects and growth of protein crystals is of importance in providing a fundamental understanding of this important category of systems and the rationale for crystallization of better ordered crystals for structural determination and drug design. Yet, as a result of the extremely weak scattering power of x-rays in protein and other biological macromolecular crystals, the extinction lengths for those crystals are extremely large and, roughly speaking, of the order of millimeters on average compared to the scale of micrometers for most small molecular crystals. This has significant implication for x-ray diffraction and imaging study of protein crystals, and presents an interesting challenge to currently available x-ray analytical techniques. We proposed that coherence-based phase sensitive x-ray diffraction imaging could provide a way to augment defect contrast in x-ray diffraction images of weakly diffracting biological macromolecular crystals. I shall examine the principles and ideas behind this approach and compare it to other available x-ray topography and diffraction methods. I shall then present some recent experimental results in two model protein systems-cubic apofemtin and tetragonal lysozyme crystals to demonstrate the capability of the coherence-based imaging method in mapping point defects, dislocations, and the degree of perfection of biological macromolecular crystals with extreme sensitivity. While further work is under way, it is intended to show that the observed new features have yielded important information on protein crystal perfection and nucleation and growth mechanism otherwise unobtainable.

Hu, Z. W.↗

Glennan Microsystems Initiative

During the 2001-2002 award period, we performed research on Pt/Ti/bare 6H-SiC and bare 4H-SiC interfaces in order to identify their electronic properties as a function of surface preparation. The overall aim of this work is to optimize the electronic properties of metal contacts to SiC as well as the active SiC material itself as a function of surface preparation and subsequent processing. Initially, this work has involved identifying bare surface, subsurface, and metal induced gap states at the metal-SiC contact and correlating energies and densities of deep levels with Schottky barrier heights. We used low energy electron-excited nanoluminescence (LEEN) spectroscopy, X-ray photoemission spectroscopy (XPS), and Secondary Ion Mass Spectrometry (SIMS) in order to correlate electronic states and energy bands with chemical composition, bonding, and crystal structure. A major development has been the discovery of polytype transformations that occur in 4H-SiC under standard microelectronic process conditions used to fabricate SiC devices. Our results are consistent with the stacking fault generation, defect formation, and consequent degradation of SiC recently reported for state-of-the-art ABB commercial diodes under localized electrical stress. Our results highlight the importance of -optimizing process conditions and material properties - anneal times, temperatures and doping to control such structural changes within epitaxial SiC layers. Thus far, we have established threshold times and temperatures beyond which 4H-SiC exhibits 3C-SiC transformation bands for a subset of dopant concentrations and process conditions. On the basis of this temperature time behavior, we have been able to establish an activation energy of approximately 2.5 eV for polytype transformation and dislocation motion. Work continues to establish the fundamental mechanisms underlying the polytype changes and its dependence on material parameters.

Brillson, Leonard J.↗

Coseismic Excitation of the Earth's Polar Motion

Apart from the "shaking" near the epicenter that is the earthquake, a seismic event creates a permanent field of dislocation in the entire Earth. This redistribution of mass changes (slightly) the Earth's inertia tensor; and the Earth's rotation will change in accordance with the conservation of angular momentum. Similar to this seismic excitation of Earth rotation variations, the same mass redistribution causes (slight) changes in the Earth's gravitational field expressible in terms of changes in the Stokes coefficients of its harmonic expansion. In this paper, we give a historical background of the subject and discuss the related physics; we then compute the geodynamic effects caused by earthquakes based on normal-mode summation scheme. The effects are computed using the centroid moment tensor (CMT) solutions for 15,814 major earthquakes from Jan., 1977, through Feb., 1999, as provided in the Harvard CMT catalog. The computational results further strengthens these findings and conclusions: (i) the strong tendency for earthquakes to make the Earth rounder and more compact (however slightly) continues; (ii) so does the trend in the seismic "nudging" of the rotation pole toward the general direction of approx. 140 E, roughly opposite to that of the observed polar drift, but two orders of magnitude smaller in drift speed.

Chao, B. F.↗