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NASA NTRS2002

A Proposed Pathway for the Nucleation and Crystal Growth of the Tetragonal Form of Lysozyme

A number of factors, the shape and charge distribution anisotropy, multiple components in the solution (buffer + counter ion, precipitant, protein, and water), conformational flexibility, and large numbers of intermolecular contacts, all serve as complicating variables in understanding the nucleation and growth mechanism for macromolecules. Intermolecular contacts include hydrogen bonds, van der Waals, hydrophobic, salt bridges, and ion-mediated contacts. The latter interactions are stronger and give specificity while the others are weaker, more prevalent, and more promiscuous, i.e., can lead to a range of possible molecular interactions. We propose that for tetragonal lysozyme, and by extension many other monomeric proteins, there is a solution-phase assembly process to form 4(sub 3) helix structures that are the basic unit for nucleation. The formation of these structures is continuous and concentration dependent. They subsequently also servc as growth units, with that process then being a recapitulation of the nucleation process. The advantages of solution phase assembly are the immediate burying of the strongest interactions, removing them from subsequent participation in the nucleation and growth process, and the introduction of symmetry into the system, which also assists in the assembly process.

Pusey, Marc L.↗

NASA NTRS2023

Magnetic Anisotropy and Stress Dependent Epoxy Wetting in FeNi-based Metal Amorphous Nanocomposite

Recently developed FeNi-based metal amorphous nanocomposites (MANCs) used in high-speed motors (HSMs) exhibit reduced eddy current losses while maintaining good mechanical properties and glass-forming abilities. Magnetic anisotropy in (Fe 70 Ni 30 ) 80 Nb 4 B 14 Si 2 amorphous magnetic ribbon (AMR) in the as-cast state and upon conventional (T CA ) and strain (T SA ) annealing heat treatment is investigated. From ribbon samples in as-cast condition, quenched in stress from planar flow casting (PFC) induced as-cast curvature derived uniaxial magnetic anisotropy. Stress relief by conventional furnace annealing at T CA > 350 °C achieved isotropic properties in the bulk. Annealing about the primary crystallization temperature, T CA ~ 450 °C, resulted in the formation of both FCC and BCC nanocrystallites and evolution to isotropic bulk magnetic properties confirming the random anisotropy model. In samples strain annealed at T SA = 440 °C at various tensions, relatively large controlled induced uniaxial anisotropy is achieved. The largest magnetic anisotropy occurs in annealing under the stress of 250 MPa yielding an anisotropy field of 7.1 x 10 4 A/m. Surface anisotropy observed by MOKE differs from bulk anisotropy due to image contrast from closure domains. Epoxy coatings are important for improved bonding, mechanical properties, and resistivity in tape-wound MANC cores for HSMs. Using a sessile droplet method, the equilibrium contact angle of an epoxy droplet on a tensile stress annealed MANC exhibits stress dependent surface energies. Anisotropic wetting in FeNi-based MANC heat treated at T CA = 440 °C mimics surface magnetic anisotropy observed by MOKE.

soft magnetic materials↗

NASA NTRS2004

The Crystallization of Canavalin as a Function of pH and NaCl Concentration

We posed the question of what happens to a protein that is known to grow as an n-mer when it is placed in solution conditions where it is monomeric. The trypsin-treated, or cut, form of the protein canavalin (CCAN) has been shown to nucleate and grow crystals as a trimer from neutral to slightly acidic solutions. Under these conditions the solution is composed almost wholly of trimers. The crystalline protein can be readily dissolved by weakly basic solution, which has been proposed to result in a solution that is monomeric. There are three possible outcomes to an attempt at crystallization of the protein under monomeric (high pH) conditions: 1) we will obtain the same crystals as under trimer conditions, but at different protein concentrations governed by the self association equilibria; 2) we will obtain crystals having a different symmetry, based upon a monomeric growth unit; 3) we will not obtain crystals. Obtaining the first result would be indicative that the solution-phase self-association process is critical to the crystal nucleation and growth process. The second result would be less clear, as it may also reflect a pH-dependent shift in the trimer-trimer molecular interactions. The third result, particularly for experiments in the transition pH's between trimeric and monomeric CCAN, would indicate that the monomer does not crystallize, and that solution phase self association is not part of the crystal nucleation and growth path. Results are presented for crystallization experiments of CCAN over the pH 6.4 to 9.6 range. Fluorescence anisotropy, light scattering, and gel filtration experiments show that the solutions are primarily trimers, with association to form larger species occurring as a function of protein concentration.

Forsythe, Elizabeth L.↗

NASA NTRS1987

Life prediction and constitutive models for engine hot section anisotropic materials

The results are presented of a program designed to develop life prediction and constitutive models for two coated single crystal alloys used in gas turbine airfoils. The two alloys are PWA 1480 and Alloy 185. The two oxidation resistant coatings are PWA 273, an aluminide coating, and PWA 286, an overlay NiCoCrAlY coating. To obtain constitutive and fatigue data, tests were conducted on uncoated and coated specimens loaded in the CH76 100 CH110 , CH76 110 CH110 , CH76 111 CH110 and CH76 123 CH110 crystallographic directions. Two constitutive models are being developed and evaluated for the single crystal materials: a micromechanic model based on crystallographic slip systems, and a macroscopic model which employs anisotropic tensors to model inelastic deformation anisotropy. Based on tests conducted on the overlay coating material, constitutive models for coatings also appear feasible and two initial models were selected. A life prediction approach was proposed for coated single crystal materials, including crack initiation either in the coating or in the substrate. The coating initiated failures dominated in the tests at load levels typical of gas turbine operation. Coating life was related to coating stress/strain history which was determined from specimen data using the constitutive models.

Swanson, G. A.↗

NASA NTRS1990

Interpretation of satellite-measured bidirectional reflectance from Cirrus cloudy atmospheres

The interpretation of the observed bidirectional reflectance from cirrus cloudy atmospheres is presented. A theoretical model was developed for the computation of the transfer of solar radiation in an anisotropic medium with particular applications to oriented ice crystals in cirrus clouds. In this model, the adding principle for radiative transfer was used with modifications to account for the anisotropy of scattering particles and the associated scattering phase matrix. The single-scattering properties, including the phase function, single-scattering albedo, and extinction cross sections, were used for randomly and horizontally oriented hexagonal ice crystals in radiative transfer computations. The radiative transfer model developed for the cirrus clouds was modified to account for the scattering contributions from the atmosphere and the surface. In order to test the relevance and significance of the ice crystal model for the interpretation of observed bidirectional reflectance from satellites, visible radiances collected on the half hour by the GOES series were selected. The data are calibrated and corrected with the proper filter functions, then navigated to match selected landmark data. A number of clear and cloudy cases during the cirrus IFO of the Fire experiment were chosen for theoretical analyses. The cloud particle shape and size distributions that were taken during satellite overpasses are used in radiative transfer calculations. The sensitivities of the shape, orientation, and size distribution of ice crystals on the reflected intensities at the top of the atmosphere are investigated. Finally, the relative importance of these cloud microphysical properties in the interpretation of satellite bidirectional reflectance are assessed and presented.

Takano, Y.↗

NASA NTRS1993

Magneto-optic superlattice thin films: Fabrication, structural and magnetic characterization

During this quarter studies were extended to determine the electronic contribution to the perpendicular interface anisotropy in Co-based multilayers. Using in situ Kerr effect measurements, the influences of different transition metals (TM = Ag, Au, Cu, and Pd) on the magnetic properties of single-crystal Co films grown on Pd (111) and Au (111) surfaces are investigated. Last quarter the discovery of a large peak in the perpendicular anisotropy when approximately one monolayer of Cu or Ag is deposited on the Co surface was reported. We now have added a computer-controlled stepper-motor drive to our MBE sample transfer mechanism. The motor allows us to move the sample at a constant velocity from behind a shutter during deposition. The film, therefore, is deposited as a wedge with a linear variation of thickness across the substrate. In this way, a continuous range of coverage on a single sample is studied. The stepper motor also provides the necessary control for precisely positioning the sample in the laser beam for Kerr effect measurements at the different coverages.

Falco, C. M.↗

NASA NTRS2001

Dendritic Alloy Solidification Experiment (DASE)

A space experiment, and supporting ground-based research, is proposed to study the microstructural evolution in free dendritic growth from a supercooled melt of the transparent model alloy succinonitrile-acetone (SCN-ACE). The research is relevant to equiaxed solidification of metal alloy castings. The microgravity experiment will establish a benchmark for testing of equiaxed dendritic growth theories, scaling laws, and models in the presence of purely diffusive, coupled heat and solute transport, without the complicating influences of melt convection. The specific objectives are to: determine the selection of the dendrite tip operating state, i.e. the growth velocity and tip radius, for free dendritic growth of succinonitrile-acetone alloys; determine the growth morphology and sidebranching behavior for freely grown alloy dendrites; determine the effects of the thermal/solutal interactions in the growth of an assemblage of equiaxed alloy crystals; determine the effects of melt convection on the free growth of alloy dendrites; measure the surface tension anisotropy strength of succinon itrile -acetone alloys establish a theoretical and modeling framework for the experiments. Microgravity experiments on equiaxed dendritic growth of alloy dendrites have not been performed in the past. The proposed experiment builds on the Isothermal Dendritic Growth Experiment (IDGE) of Glicksman and coworkers, which focused on the steady growth of a single crystal from pure supercooled melts (succinonitrile and pivalic acid). It also extends the Equiaxed Dendritic Solidification Experiment (EDSE) of the present investigators, which is concerned with the interactions and transients arising in the growth of an assemblage of equiaxed crystals (succinonitrile). However, these experiments with pure substances are not able to address the issues related to coupled heat and solute transport in growth of alloy dendrites.

Beckermann, C.↗

NASA NTRS1989

The low cycle fatigue deformation response of a single-crystal superalloy at 650 C

The cyclic stress-strain response and the associated deformation structure of the single crystal nickel-base superalloy PWA 1480 were investigated. Specimens of various crystallographic orientations were tested in low-cycle fatigue (LCF) at 650 C, resulting in a significant tension-compression anisotropy in initial yield strength associated with the shearing of gamma-prime precipitates by dislocation pairs, and a LCF cyclic hardening of the crystals associated with dislocation interactions occurring in the gamma phase. In specimens deforming by slip on a single slip system, dislocations of the primary slip system accumulated in the gamma matrix and formed seesile entanglements. In specimens deforming by slip on several slip systems, the dislocations of the different operative slip systems intersected in the gamma matrix and formed sessile arrangements.

Gabb, T. P.↗

NASA NTRS1974

Crystallization behavior of anorthite

The growth rate of anorthite crystals from the melt is studied as a function of temperature with undercooling in the ranges 52-152 and 402-652 degrees C. The triclinic form is invariably observed as the crystallization product, growth is preferentially in the c direction, and the interface morphology is faceted. Significant growth rate anisotropy is indicated. The maximum growth rate of anorthite from the melt is higher than for anorthite-rich lunar compositions. Recent computer studies are combined with experimental data to estimate the heat of fusion of anorthite as 28000-45000 cal/mol; the corresponding range for entropy of fusion is (7.8-12)R (where R is the gas constant). The observations and kinetic data support Jackson's predictions concerning materials with large entropies of fusion and his suggestion that entropy of fusion is an important parameter for characterizing the crystal-liquid interface and the nature of the crystallization process.

Klein, L.↗

NASA NTRS1983

Piezoelectricity and pyroelectricity in polyvinylidene fluoride - Influence of the lattice structure

Piezoelectric and pyroelectric responses of beta-phase (Phase I) polyvinylidene fluoride are predicted for a model system of polarizable point dipoles. The model incorporates the influence of the orthorhombic crystal structure by including the dependence of the internal electric field on the lattice parameters. Strong anisotropy in the piezoelectric response under uniaxial stress is predicted as a consequence of the orthorhombic lattice structure. Predictions are found to be in reasonable agreement with room-temperature experimental data.

Purvis, C. K.↗

NASA NTRS1988

Constitutive and life modeling of single crystal blade alloys for root attachment analysis

Work to develop fatigue life prediction and constitutive models for uncoated attachment regions of single crystal gas turbine blades is described. At temperatures relevant to attachment regions, deformation is dominated by slip on crystallographic planes. However, fatigue crack initiation and early crack growth are not always observed to be crystallographic. The influence of natural occurring microporosity will be investigated by testing both hot isostatically pressed and conventionally cast PWA 1480 single crystal specimens. Several differnt specimen configurations and orientations relative to the natural crystal axes are being tested to investigate the influence of notch acuity and the material's anisotropy. Global and slip system stresses in the notched regions were determined from three dimensional stress analyses and will be used to develop fatigue life prediction models consistent with the observed lives and crack characteristics.

Meyer, T. G.↗

NASA NTRS2012

Comparison of PARASOL Observations with Polarized Reflectances Simulated Using Different Ice Habit Mixtures

Insufficient knowledge of the habit distribution and the degree of surface roughness of ice crystals within ice clouds is a source of uncertainty in the forward light scattering and radiative transfer simulations required in downstream applications involving these clouds. The widely used MODerate Resolution Imaging Spectroradiometer (MODIS) Collection 5 ice microphysical model assumes a mixture of various ice crystal shapes with smooth-facets except aggregates of columns for which a moderately rough condition is assumed. When compared with PARASOL (Polarization and Anisotropy of Reflectances for Atmospheric Sciences coupled with Observations from a Lidar) polarized reflection data, simulations of polarized reflectance using smooth particles show a poor fit to the measurements, whereas very rough-faceted particles provide an improved fit to the polarized reflectance. In this study a new microphysical model based on a mixture of 9 different ice crystal habits with severely roughened facets is developed. Simulated polarized reflectance using the new ice habit distribution is calculated using a vector adding-doubling radiative transfer model, and the simulations closely agree with the polarized reflectance observed by PARASOL. The new general habit mixture is also tested using a spherical albedo differences analysis, and surface roughening is found to improve the consistency of multi-angular observations. It is suggested that an ice model incorporating an ensemble of different habits with severely roughened surfaces would potentially be an adequate choice for global ice cloud retrievals.

Cole, Benjamin H.↗

NASA NTRS1990

Growth morphology with anisotropic surface kinetics

The morphological evolution of crystals growing from an incongruent vapor phase is studied using a Monte Carlo model, and the full range of growth morphologies is recovered. The diffusion in the bulk nutrient and the anisotropy in the interface kinetics are morphologically destabilizing and stabilizing, respectively. For a given set of simulation parameters and lattice symmetries there is a critical size, which scales linearly with the mean free path in the vapor, beyond which a crystal cannot retain its stable, macroscopically faceted growth shape. Surface diffusion stabilizes faceted growth on the shorter scale of the mean surface diffusion length. In simulations with a uniform drift superimposed on the random walk nutrient transport, crystal faces oriented toward the drift show enhanced morphological stability compared to the purely diffusive situation. Rotational drifts with periodic reversal of direction are morphologically stabilizing for all crystal facets.

Xiao, Rong-Fu↗

NASA NTRS1992

Melting of the Abrikosov flux lattice in anisotropic superconductors

It has been proposed that the Abrikosov flux lattice in high-Tc superconductors is melted over a significant fraction of the phase diagram. A thermodynamic argument is provided which establishes that the angular dependence of the melting temperature is controlled by the superconducting mass anisotropy. Using a low-frequency torsional-oscillator technique, this relationship has been tested in untwinned single-crystal YBa2Cu3O(7-delta). The results offer decisive support for the melting proposal.

Beck, R. G.↗

NASA NTRSDate not supplied

Thermophysical Property Measurements of Indium Iodide Crystals

InI single crystals are a promising room temperature detector material for X-rays and γ-rays. To improve crystal growth of the material by simulations, knowledge of thermophysical properties is essential, and since InI is orthorhombic, the anisotropy has to be taken into account. The temperature dependence of several thermophysical properties have been measured for InI, including the anisotropic thermal expansion, specific heat, and the thermal diffusivity in the b direction. The anisotropic thermal expansion coefficients, determined by X-ray diffraction, were α11=1.03·10-5 K-1, α22= 3.77·10-5 K-1, and α33 = 6.26·10-5 K-1. The specific heat, measured by DSC, was 0.226 J g-1 K-1 at 335K, with a temperature dependence of 9.582·10-5 J g-1 K-2. In the course of the X-ray diffraction and DSC measurements, it was shown that supposed phase changes, reported in older literature, are actually not phase changes but oxidation effects. The thermal diffusivity in the b direction, measured by the Xenon Flash method, was 0.288·10-6 m2s-1 at RT, decreasing to 0.253·10-6 m2 s-1 at 450K. In addition, the volume increase upon melting and the thermal expansion of the melt have been determined.

Martin Volz↗

NASA NTRS1993

Properties of Semiconducting Ru_2Ge_3

Transport properties of large single crystalline samples of Ru_2Ge_3 grown from the melt have been investigated in a 25-1000 C temperature range. A diffusionless transition between 500 and 550C from a high temperature tetragonal structure to a low temperature orthorhombic structure was clearly observed. Results showed that both the low temperature orthorhombic and the high temperature structural tetragonal phase are semiconductors. Some anisotropy of the transport coefficients was determined by measuring the samples in orientations parallel and perpendicular to the preferential direction of crystal growth. Large Seebeck coefficient (up to 400 microVK^(-1)) and low thermal conductivity (as low as 20x10^(-3) Wcm^(-1)K^(-1)) were achieved for the low temperature orthorhombic phase. Difficulties in preparing heavily doped samples and low Hall mobilities have limited values for the maximum figure of merit to 0.5 x 10^(-3) K^(-1) at 500 C.

Fleurial, Jean-Pierre↗

NASA NTRS1991

Microwave response of high transition temperature superconducting thin films

We have studied the microwave response of YBa2Cu3O(7 - delta), Bi-Sr-Ca-Cu-O, and Tl-Ba-Ca-Cu-O high transition temperature superconducting (HTS) thin films by performing power transmission measurements. These measurements were carried out in the temperature range of 300 K to 20 K and at frequencies within the range of 30 to 40 GHz. Through these measurements we have determined the magnetic penetration depth (lambda), the complex conductivity (sigma(sup *) = sigma(sub 1) - j sigma(sub 2)) and the surface resistance (R(sub s)). An estimate of the intrinsic penetration depth (lambda approx. 121 nm) for the YBa2Cu3O(7 - delta) HTS has been obtained from the film thickness dependence of lambda. This value compares favorably with the best values reported so far (approx. 140 nm) in single crystals and high quality c-axis oriented thin films. Furthermore, it was observed that our technique is sensitive to the intrinsic anisotropy of lambda in this superconductor. Values of lambda are also reported for Bi-based and Tl-based thin films. We observed that for the three types of superconductors, both sigma(sub 1) and sigma(sub 2) increased when cooling the films below their transition temperature. The measured R(sub s) are in good agreement with other R(sub S) values obtained using resonant activity techniques if we assume a quadratic frequency dependence. Our analysis shows that, of the three types of HTS films studied, the YBa2Cu3O(7 - delta) thin film, deposited by laser ablation and off-axis magnetron sputtering are the most promising for microwave applications.

Miranda, Felix Antonio↗

NASA NTRS1990

Grain orientation studies in superconductors

Grain oriented fabrication of ceramics utilizes the presence of some form of anisotropy in the particles of the starting material to obtain textured microstructures. The molten salt, or flux method, a popular technique for growing crystals and particles with anisotropic morphology, is utilized in this study. The formation of Ba2YCu3O(7-x) in the presence of molten salts of Na, K, Li belonging to chloride and sulfate systems does not appear feasible in the temperature range up to 900 C. Researchers also present the results of studies in using BaY2CuO5 as seed crystals in the formation of Ba2YCu3O(7-x) wherein BaY2CuO5 has been observed to have better stability in water and against most of the salts as compared to Ba2YCu3O(7-x). Additional results of molten salt processing of bismuth systems are also presented.

Gopalakrishnan, Sudhakar↗