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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

A Model for Tetragonal Lysozyme Crystal Nucleation and Growth

Macromolecular crystallization is a complex process, involving a system that typically has 5 or more components (macromolecule, water, buffer + counter ion, and precipitant). Whereas small molecules have only a few contacts in the crystal lattice, macromolecules generally have 10's or even 100's of contacts between molecules. These can range from hydrogen bonds (direct or water-mediated), through van der Waals, hydrophobic, salt bridges, and ion-mediated contacts. The latter interactions are stronger and require some specificity in the molecular alignment, while the others are weaker, more prevalent, and more promiscuous, i.e., can be readily broken and reformed between other sites. Formation of a consistent, ordered, 3D structure may be difficult or impossible in the absence of any or presence of too many strong interactions. Further complicating the process is the inherent structural asymmetry of monomeric (single chain) macromolecules. The process of crystal nucleation and growth involves the ordered assembly of growth units into a defined 3D lattice. We suggest that for many macromolecules, particularly those that are monomeric, this involves a preliminary solution-phase assembly process into a growth unit having some symmetry prior to addition to the lattice, recapitulating the initial stages of the nucleation process. If this model is correct then fluids and crystal growth models assuming a strictly monodisperse nutrient solution need to be revised. This model has been developed from experimental evidence based upon face growth rate, AFM, and fluorescence energy transfer data for the nucleation and growth of tetragonal lysozyme crystals.

Pusey, Marc L.↗
NASA NTRS1990

Inhomogeneous deformation in INCONEL 718 during monotonic and cyclic loadings

The paper concentrates on the relation between microstructural observations of the dislocation structures and the macroscopic deformation responses of both aged and homogenized precipitate-hardened alloys at room temperature. The deformation responses are compared to the cyclic deformation response of an aged precipitate-hardened alloy. Early in the deformation, one deformation band per grain and little evidence of work hardening are observed; with increased deformation, work hardening begins, more bands nucleate, and their spacing becomes similar to that in the aged material. It is pointed out that the degree of coarseness of inhomogeneous deformation is not a result of a softening process within the bands due to precipitate shearing, but it is a function of the amount of work hardening within the bands.

Worthem, D. W.↗
NASA NTRS1987

Solidification of undercooled Ni-Sn eutectic alloy under microgravity conditions in the Space Shuttle

The Space Shuttle Columbia carried an Alloy Undercooling Experiment on its STS 61-C mission in January, 1986. The experiment was performed in an electromagnetic levitator. A sample of Ni-32.5 wt pct Sn eutectic was melted and solidified under microgravity conditions in the Space Shuttle. The specimen achieved only a fairly small undercooling, probably less than 30 K. The specimen was examined by optical and scanning electron microscopy. The surface and cross-sectional microstructures were primarily composed of normal lamellar eutectic, but showed several interesting features, including an apparent surface nucleation site, curved dendrites with nonorthogonal secondary arms, dendrite fragments with extremely fine arm spacing, submicron precipitates, and faceted crystals. The results of the space experiment are presented and compared with ground-based results obtained with the same alloy.

Piccone, T. J.↗
NASA NTRS1987

Experimental correlation of melt structures, nucleation rates, and thermal histories of silicate melts

The theory and measurement of the structure of liquids is an important aspect of modern metallurgy and igneous petrology. Liquid structure exerts strong controls on both the types of crystals that may precipitate from melts and on the chemical composition of those crystals. An interesting aspect of melt structure studies is the problem of melt memories; that is, a melt can retain a memory of previous thermal history. This memory can influence both nucleation behavior and crystal composition. This melt memory may be characterized quantitatively with techniques such as Raman, infrared and NMR spectroscopy to provide information on short-range structure. Melt structure studies at high temperature will take advantage of the microgravity conditions of the Space Station to perform containerless experiments. Melt structure determinations at high temperature (experiments that are greatly facilitated by containerless technology) will provide invaluable information for materials science, glass technology, and geochemistry. In conjunction with studies of nucleation behavior and nucleation rates, information relevant to nucleation in magma chambers in terrestrial planets will be acquired.

Boynton, W. V.↗
NASA NTRS2024

Iridescence Reveals the Formation and Growth of Ice Aerosols in Martian Noctilucent Clouds

Water and carbon dioxide each form mesospheric clouds on Mars. At such altitudes (40–100 km), clouds may remain sunlit for part of the night. We describe a previously unreported, visually spectacular season of iridescent, noctilucent clouds visible in early southern autumn from the Curiosity rover's site in Gale crater. Ice nucleation begins near sunset with a narrow range of particle sizes, and the ice aerosols grow and precipitate. The iridescence, visible through three-color imaging, arises from locally uniform particle sizes resulting from similar growth histories. Colorful fall streaks show the clouds evolving, and a scattering corona shows size uniformity over large areas. The terminator was observed on the clouds, allowing the determination of cloud altitudes and a likely CO2 composition. This is the first observation of particle size variations within individual Martian clouds, allowing a new probe of Martian cloud physics.

M T Lemmon↗
NASA NTRS1988

P/M aluminum metal matrix composites

Development of lightweight, high specific stiffness engineered materials has been the long term goal of many investigators. Recently, this quest has focused on discontinuously reinforced aluminum metal matrix composites. This paper reviews the fabrication of powder metallurgy discontinuously reinforced metal matrix composites. Emphasis is given to the differences in heat treatment response reported between unreinforced and reinforced powder metallurgy materials. It is proposed that these observations can be rationalized by considering the effects of pre-existing heterogeneous nucleation sites, i.e., the dislocation substructure developed during rapid cooling of discontinuously reinforced aluminum metal matrix composites, on precipitation in reinforced aluminum alloys.

Rack, H. J.↗
NASA NTRS1992

FNAS/advanced protein crystal growth

A scintillation method is presented for determination of the temperature dependence of the solubility, S(T), of proteins in 50-100 micro-l volumes of solution. S(T) data for lysozyme and horse serum albumin were obtained for various combinations of pH and precipitant concentrations. The resulting kinetics and equilibrium information was used for dynamic control, that is the separation of nucleation and growth stages in protein crystallization. Individual lysozyme and horse serum albumin crystals were grown in 15-20 micro-l solution volumes contained in x-ray capillaries.

Rosenberger, Franz↗
NASA NTRS2005

Anvil Glaciation in a Deep Cumulus Updraught over Florida Simulated with the Explicit Microphysics Model. I: Impact of Various Nucleation Processes

Simulations of a cumulonimbus cloud observed in the Cirrus regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) with an advanced version of the Explicit Microphysics Model (EMM) are presented. The EMM has size-resolved aerosols and predicts the time evolution of sizes, bulk densities and axial ratios of ice particles. Observations by multiple aircraft in the troposphere provide inputs to the model, including observations of the ice nuclei and of the entire size distribution of condensation nuclei. Homogeneous droplet freezing is found to be the source of almost all of the ice crystals in the anvil updraught of this particular model cloud. Most of the simulated droplets that freeze to form anvil crystals appear to be nucleated by activation of aerosols far above cloud base in the interior of the cloud ("secondary" or "in cloud" droplet nucleation). This is partly because primary droplets formed at cloud base are invariably depleted by accretion before they can reach the anvil base in the updraught, which promotes an increase with height of the average supersaturation in the updraught aloft. More than half of these aerosols, activated far above cloud base, are entrained into the updraught of this model cloud from the lateral environment above about 5 km above mean sea level. This confirms the importance of remote sources of atmospheric aerosol for anvil glaciation. Other nucleation processes impinge indirectly upon the anvil glaciation by modifying the concentration of supercooled droplets in the upper levels of the mixed-phase region. For instance, the warm-rain process produces a massive indirect impact on the anvil crystal concentration, because it determines the mass of precipitation forming in the updraught. It competes with homogeneous freezing as a sink for cloud droplets. The effects from turbulent enhancement of the warm-rain process and from the nucleation processes on the anvil ice properties are assessed.

Phillips, Vaughan T. J.↗
NASA NTRS2000

Does Warming a Lysozyme Solution Cook Ones Data?

Chicken egg white lysozyme has a well characterized thermally driven phase transition. Between pH 4.0 and 5.2, the transition temperature, as defined by the point where the tetragonal and orthorhombic solubility are equal, is a function of the pH, salt (precipitant) type and concentration, and most likely of the buffer concentration as well. This phase transition can be carried out with protein solution alone, prior to the initiation of the crystallization process. We have now measured the kinetics of this process and investigated its reversibility. An aliquot of a stock protein solution is held at a given temperature, and at periodic intervals used to set up batch crystallization experiments. The batch solutions were incubated at 20 C until macroscopic crystals were obtained, at which point the number of crystals in each well were counted. The transition effects increased with temperature, slowly falling off at 30 C with a half time (time to approx. 1/2 the t = 0 number of crystals) of approx. 5 hours, and an estimated half time of approx. 0.5 hours at 43 C. Further, the process was not reversible by simple cooling. After holding a lysozyme solution at 37 C (prior to addition of precipitant) for 16 hours, then cooling and holding it at 4 C, no return to the pre-warmed nucleation kinetics are observed after at least 4 weeks. Thus every thermal excursion above the phase transition point results in a further decrease in the nucleation rate of that solution, the extent being a function of the time and temperature. Orthorhombic lysozyme crystals apparently do not undergo the flow-induced growth cessation of tetragonal lysozyme crystals. We have previously shown that putting the protein in the orthorhombic form does not affect the averaged face growth kinetics, only nucleation, for tetragonal crystals. We may be able to use this differential behavior to elucidate how flow affects tile lysozyme crystal growth process.

Pusey, Marc↗
NASA NTRS2004

CO2 Condensation Models for Mars

During the polar night in both hemispheres of Mars, regions of low thermal emission, frequently referred to as "cold spots", have been observed by Mariner 9, Viking and Mars Global Surveyor (MGS) spacecraft. These cold spots vary in time and appear to be associated with topographic features suggesting that they are the result of a spectral-emission effect due to surface accumulation of fine-grained frost or snow. Presented here are simulations of the Martian polar night using the NASA Ames General Circulation Cloud Model. This cloud model incorporates all the microphysical processes of carbon dioxide cloud formation, including nucleation, condensation and sedimentation and is coupled to a surface frost scheme that includes both direct surface condensation and precipitation. Using this cloud model we simulate the Mars polar nights and compare model results to observations from the Thermal Emission Spectrometer (TES) and the Mars Orbiter Laser Altimeter (MOLA). Model predictions of "cold spots" compare well with TES observations of low emissivity regions, both spatially and as a function of season. The model predicted frequency of CO2 cloud formation also agrees well with MOLA observations of polar night cloud echoes. Together the simulations and observations in the North indicate a distinct shift in atmospheric state centered about Ls 270 which we believe may be associated with the strength of the polar vortex.

Colaprete, A.↗
NASA NTRS2000

The Effect of Solution Thermal History on Chicken Egg White Lysozyme Nucleation

Proteins are highly flexible molecules and often exhibit defined conformational changes in response to changes in the ambient temperature. Chicken egg white lysozyme has been previously shown to undergo an apparent structural change when warmed above the tetragonal/orthorhombic phase transition temperature. This is reflected by a change in the habit of the tetragonal and orthorhombic crystals so formed. In this study we show that possible conformational changes induced by heating are stable and apparently non- reversible by simple cooling. Exposure of protein solutions to temperatures above the phase change transition temperature, before combining with precipitant solution to begin crystallization, reduces final crystal numbers. Protein that is briefly warmed to 37 C, then cooled shows no sign of reversal to the unheated nucleation behavior even after storage for 4 weeks at 4 C. The change in nucleation behavior of tetragonal lysozyme crystals, attributed to a structural shift, occurs faster the greater the exposure to temperature above the equi-solubility point for the two phases. Heating for 2 h at 48 C reduces crystal numbers by 20 fold in comparison to the same solution heated for the same time at 30 C. Thermal treatment of solutions is therefore a possible tool to reduce crystal numbers and increase crystal size. The effects of a protein's previous thermal history are now shown to be a potentially critical factor in subsequent macromolecule crystal nucleation and growth studies.

Burke, Michael W.↗
NASA NTRS2001

The Effect of Solution Thermal History on Chicken Egg White Lysozyme Nucleation

Proteins are highly flexible molecules and often exhibit defined conformational changes in response to changes in the ambient temperature. Chicken egg white lysozyme has been previously shown to undergo an apparent structural change when warmed above the tetragonal/orthorhombic phase transition temperature. This is reflected by a change in the habit of the tetragonal and orthorhombic crystals so formed. In this study, we show that possible conformational changes induced by heating are stable and apparently non-reversible by simple cooling. Exposure of protein solutions to temperatures above the phase change transition temperature, before combining with precipitant solution to begin crystallization, reduces final crystal numbers. Protein that is briefly warmed to 37 C, then cooled shows no sign of reversal to the unheated nucleation behavior even after storage for four weeks at 4 C. The change in nucleation behavior of tetragonal lysozyme crystals, attributed to a structural shift, occurs faster the greater the exposure to temperature above the equi-solubility point for the two phases. Heating for 2 hours at 48 C reduces crystal numbers by 20 fold in comparison to the same solution heated for the same time at 30 C. Thermal treatment of solutions is therefore a possible tool to reduce crystal numbers and increase crystal size. The effects of a protein's previous thermal history are now shown to be a potentially critical factor in subsequent macromolecule crystal nucleation and growth studies.

Burke, Michael W.↗
NASA NTRS1998

The Effect of Solution Conditions on the Nucleation Kinetics of Tetragonal Lysozyme Crystals

An understanding of protein crystal nucleation rates and the effect of solution conditions upon them, is fundamental to the preparation of protein crystals of the desired size and shape for X-ray diffraction analysis. The ability to predict the effect of supersaturation, temperature, pH and precipitant concentration on the number and size of crystals formed is of great benefit in the pursuit of protein structure analysis. In this study we experimentally examine the effect of supersaturation, temperature, pH and sodium chloride concentration on the nucleation rate of tetragonal chicken egg white lysozyme crystals. In order to do this batch crystallization plates were prepared at given solution concentrations and incubated at three different temperatures over the period of one week. The number of crystals per well with their size and dimensions were recorded and correlated against solution conditions. Duplicate experiments indicate the reproducibility of the technique. Although it is well known that crystal numbers increase with increasing supersaturation, large changes in crystal number were also correlated against solution conditions of temperature, pH and salt concentration over the same supersaturation ranges. Analysis of these results enhance our understanding of the effect of solution conditions such as the dramatic effect that small changes in charge and ionic strength can have on the number of tetragonal lysozyme crystals that form and grow in solution.

Judge, Russell A.↗
NASA NTRS1987

Growth process of gamma'-particles in a liquid-quenched Ni-15 at percent Al alloy

The growth of gamma-prime particles in a supersaturated Ni-15 at% Al alloy prepared by the liquid-quench method was studied using a magnetic mass balance, transmission electron microscopy, and field ion microscopy. Three stages in the precipitation and growth of these particles are demonstrated. In the first phase, the gamma-prime phase was produced by nucleation of spinodal decomposition of the alloy. In the second stage, spherical gamma-prime particles were arranged at random in the matrix with the size independent of aging time. Then, the Al concentration in the matrix decreased with the -1/3 power of the aging time. These results suggest that the degree of ordering increases with aging time. In the third stage, the particles were coarsened with aging time. They were arranged in the matrix (100) zone and were cubic, with the cube face lying on (100). The interfacial free energy was 28.4 mJ/sq m at 873 K and 22.4 mJ/sq m at 973 K.

Tachikake, A.↗
NASA NTRS1993

Calcified microbes in Neoproterozoic carbonates: implications for our understanding of the Proterozoic/Cambrian transition

Tidal flat and lagoonal dolostones of the Neoproterozoic Draken Formation, Spitsbergen, exhibit excellent preservation of carbonate fabrics, including heavily calcified microfossils. The crust-forming cyanobacterium Polybessurus is preserved locally by carbonate precipitated on and within sheaths in mildly evaporitic upper intertidal to supratidal environments. In contrast, calcified filaments in columnar stromatolites reflect subtidal precipitation. Filament molds in dolomicrites independently document extremely early lithification. The presence of heavily calcified cyanobacteria in Draken and other Proterozoic carbonates constrains potential explanations for the widespread appearance of calcified microorganisms near the Proterozoic-Cambrian boundary. We propose that the rarity of Proterozoic examples principally reflects the abundance and wide distribution of carbonate crystals precipitated on the sea floor or in the water column. Cyanobacterial sheaths would have competed effectively as sites for carbonate nucleation and growth only where calcitic and/or aragonitic nuclei were absent. In this view, the Proterozoic-Cambrian expansion of calcified microfossils primarily reflects the emergence of skeletons as principal agents of carbonate deposition.

Non-NASA Center↗
NASA NTRS1997

Containerless Liquid to Solid Nucleation Pathways in Two Representative Grades of Commercially Available Zirconium

Experimental measurements were conducted to determine the solid metal nucleation pathways of radiatively cooling, molten zirconium spheres of two different commercially available purity grades in a high-vacuum, high-temperature electrostatic levitator. The ensemble distribution of maximum undercooling temperatures was interpreted using Poisson statistics to determine the temperature dependence of the solid metal nucleation rate. For a sample of nominally 99.95% pure zirconium, the results are consistent with heterogeneous solid metal nucleation either on static catalyst particles at least approx. 30 nm diameter or on a surface coating. For a sample of nominally 99% pure zirconium, however, it appears that heterogeneous solid metal nucleation occurred either on a polydispersion of approx. 10 nm (mean diameter) static catalyst particles or on dynamic catalyst particles that precipitated from a solution that became supersaturated as the melt cooled.

Rulison, A. J.↗
NASA NTRS1997

Whiting events: biogenic origin due to the photosynthetic activity of cyanobacterial picoplankton

An annual whiting event occurs each year in late May to early June in Fayetteville Green Lake, New York. The initiation of this event correlates with exponential growth of the Synechococcus population within the lake. Synechococcus is the dominant (by approximately 4 orders of magnitude) autotrophic organism owing to the oligotrophic condition of the lake. The delta 13C values of the dissolved inorganic C range seasonally from -9.5% in winter to -6.2% in summer due to photosynthetic activity. Calcite precipitates principally in the microenvironment surrounding Synechococcus because of a photosynthetically driven alkalization process and the availability of the cells as nucleation sites. This calcite has a heavier delta 13C value (>4%) than does the dissolved inorganic C of the lake water owing to the cells' preferential uptake of 12C. A conceptual model suggests that photosynthetic activity and cell surface chemistry, together with the substantial surface area that arises from the great abundance of micron-sized cells, allow Synechococcus to dominate the annual whiting events in Fayetteville Green Lake.

NASA Center ARC↗
NASA NTRS1997

Liquid-Liquid Phase Separation in Supersaturated Lysozyme Solutions and Associated Precipitate Formation/Crystallization

Using cloud point determinations, the phase boundaries (binodals) for metastable liquid-liquid (L-L) separation in supersaturated hen egg white lysozyme solutions with 3%, 5%, and 7% (wlv) NaCl at pH= 4.5 and protein concentrations c between 40 and 400 mg/ml were determined. The critical temperature for the binodal increased approximately linearly with salt concentration. The coexisting liquid phases both remained supersaturated but differed widely in protein concentration. No salt repartitioning was observed between the initial and the two separated liquid phases. After the L-L separation, due to the presence of the high protein concentration phase, crystallization occurred much more rapidly than in the initial solution. At high initial protein concentrations, a metastable gel phase formed at temperatures above the liquid binodal. Both crystal nucleation and gel formation were accelerated in samples that had been cycled through the binodal. Solutions in the gel and L-L regions yielded various types of precipitates. Based on theoretical considerations, previous observations with other proteins, and our experimental results with lysozyme, a generic phase diagram for globular proteins is put forth. A limited region in the (T,c) plane favorable for the growth of protein single crystals is delineated.

Muschol, Martin↗