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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
NASA NTRS2006

Pyroxenes in Martian meteorites as petrogenetic indicators

Pyroxenes in Martian meteorites are important recorders of petrogenetic processes. Understanding the details of pyroxene major and minor element compositional variations can provide important insights into those processes. A combination of careful petrographic analysis of natural samples and experimental crystallization studies can lead to better understanding of the processes that gave rise to these samples on Mars. In addition, experimentally determined major, minor and trace element partition coefficients are important for using natural pyroxenes to estimate the compositions of the melts from which they crystallized and the oxidation conditions that prevailed during crystallization. We will report on minor element (Al, Ti, Cr) zoning in nakhlite pyroxenes and in synthetic pyroxenes that we have grown for the purposes of determining pyroxene/melt partition coefficients for Sr and REE. The natural pyroxenes have patchy Al zoning that, by analogy with our experimental pyroxenes, we interpret as sector zoning. The irregular patchy nature of the zoning is probably the result of the vagaries of growth kinetics and local environment during crystal growth. More slowly cooled nakhlites have the most distinct bimodal zoning, with one mode having Al2O3 around 0.5-0.6 wt%, and the other around 0.9 %. Average Al content increases with increasing cooling rate. This feature is puzzling, since the cumulus pyroxenes were almost certainly present at the time of eruption. Al and Ti are strongly correlated, but Cr is completely decoupled from those elements. The synthetic pyroxenes are distinctly sector zoned in Al and Ti, and the sector-to-sector variation in Al within a single crystal has important effects on trace element partition coefficients. Trivalent REE are strongly correlated with Al, while divalent elements (Sr, Eu+2) show a significantly weaker correlation. For example, as the Al2O3 content varies from 0.3 to 0.6 wt % from one sector to another, D(Gd) increases by approx.80% while D(Sr) and D(Eu) only increase by 20-30% at oxygen fugacities near IW. The different Al dependency of D for trivalent REE vs. divalent Eu and Sr considerably complicates the calibration of the Eu oxybarometer.

McKay, Gordon↗
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 NTRS1984

The undercooling of liquids

The formation by melt quenching of such metastable structures as glassy or microcrystalline solids and highly supersaturated solutions is made possible by the extreme resistance of most melts to homophase crystal nucleation at deep undercooling. This nucleation resistance contrasts sharply with the very low kinetic resistance to the movement of crystal-melt interfaces, once formed, in metals and other fluid systems at even minute undercooling. The methods of nucleation study which have proven especially effective in bypassing nucleation by heterophase impurities thereby exposing the high resistance of melts to homophase nucleation may be summarized as follows: observation of the crystallization behavior of dispersed small droplets; drop tube experiments in which liquid drops solidify, under containerless conditions, during their fall in the tube; and observation of the crystallization of bulk specimens immersed in fluxes chosen to dissolve or otherwise deactivate (e.g., by wetting) heterophase nucleants. This method has proven to be remarkably effective in deactivating such nucleants in certain pure metals.

Turnbull, D.↗
NASA NTRS1998

The Effect of Temperature and Solution pH on Tetragonal Lysozyme Nucleation Kinetics

Part of the challenge of macromolecular crystal growth for structure determination is obtaining an appropriate number of crystals with a crystal volume suitable for x-ray analysis. In this respect an understanding of the effect of solution conditions on macromolecule nucleation rates is advantageous. This study investigated the effects of supersaturation, temperature and pH on the nucleation rate of tetragonal lysozyme crystals. Batch crystallization plates were prepared at given solution concentrations and incubated at set temperatures over one week. The number of crystals per well with their size and axial ratios were recorded and correlated with solution conditions, Duplicate experiments indicate the reproducibility of the technique, Crystal numbers were found to increase with increasing supersaturation and temperature. The most significant variable however, was pH, where crystal numbers changed by two orders of magnitude over the pH range 4.0 to 5.2. Crystal size varied also with solution conditions, with the largest crystals being obtained at pH 5.2. Having optimized the crystallization conditions, a batch of crystals were prepared under exactly the same conditions and fifty of these crystals were analyzed by x-ray techniques. The results indicate that even under the same crystallization conditions, a marked variation in crystal properties exists.

Judge, Russell A.↗
NASA NTRS1996

Nucleation and convection effects in protein crystal growth

The following activities are reported on: repartitioning of NaCl and protein impurities in lysozyme crystallization; dependence of lysozyme growth kinetics on step sources and impurities; facet morphology response to nonuniformities in nutrient and impurity supply; interactions in undersaturated and supersaturated lysozyme solutions; heterogeneity determination and purification of commercial hen egg white lysozyme; nonlinear response of layer growth dynamics in the mixed kinetics-bulk transport regime; development of a simultaneous multiangle light scattering technique; and x-ray topography of tetragonal lysozyme grown by the temperature-control technique.

Rosenberger, Franz↗
NASA NTRSDate not supplied

Vapor Growth of ZnSe-based Compound Semiconductors in Low Gravity environment on International Space Station

Six low-gravity experiments of crystal growth of ZnSe-based compound semiconductors by physical vapor transport (PVT) are scheduled to be processed inside Low Gradient Furnace (LGF) on Materials Science Research Rack (MSRR) in Material Science Laboratory (MSL) on International Space Station (ISS) starting from February 27th, 2023. The flight samples consist of three unseeded growths of ZnSe, Cr-doped ZnSe and ZnSeTe as well as growth of ZnSe on top of three single crystal ZnSe seeds with orientation of (100), (110) and (111). The main scientific objective of the flight experiments is to establish the effects of gravity-driven fluid flows on Earth to (i) the non-uniform incorporation of impurities and defects and (ii) the deviation from stoichiometry observed in the grown crystals caused by growth interface fluctuations and evolution as the results of buoyancy-driven convection and irregular fluid-flows. The investigation will also evaluate the effects of gravity on the PVT process by examining (i) the growth kinetics on various seed orientations, (ii) the dopant segregation and distribution in the Cr doped ZnSe, and (iii) the compositional segregation and distribution in the ternary ZnSeTe crystal grown by PVT. Additionally, from X-ray diffraction/topography and by measuring the density and distribution of various crystalline defects it will assess the self-induced strain effects developed during processing at elevated temperatures caused by the weight of the crystals. During the ground-based preparations, the following tasks have been accomplished: • Establish the thermodynamic properties of the ZnSe binary and related ternary systems by measuring the partial pressures of the vapor phase coexisting with the condensed phases and perform phase diagram calculations for comparison. • Evaluate the effects of gravity-driven convection in the growth process by performing experiments under various vapor transport orientations relative to gravity vector, i.e., horizontal, vertically stabilized and destabilized configurations. • Establish a quantitative correlation between growth parameters and the characteristics and properties of the grown crystals by characterizing the crystals using a variety of techniques. • Evaluate the fundamentals of the current theories on vapor transport and crystal growth kinetics by performing in-situ and real-time monitoring techniques during growth. • Develop a one-dimensional diffusion limited theory of mass transport and two- and three-dimensional numerical simulations of both mass transport and heat transfer and thus establish the microgravity requirements for the flight experiments and to predict the characteristics of the grown crystals such as the solid-vapor interface shapes… etc. and establish a fundamental understanding of the crystal growth process from the comparison with experimental results.

ZnSe↗
NASA NTRS1997

A Rationale for System-Dependent Advantages and Disadvantages of Solution Crystal Growth at Low Gravity

Protein crystallization experiments at reduced gravity have yielded crystals that, depending on the specific material, are either superior or inferior in their structural perfection compared to counterparts grown at normal gravity. A reduction of the crystals' quality due to their growth at low gravity cannot be understood from existing models. Our experimental investigations of the ground-based crystallization of the protein lysozyme have revealed pronounced unsteady growth layer dynamics and associated defect formation under steady external conditions. Through scaling analysis and numerical simulations we show that the observed fluctuations originate from the coupling of bulk transport with non-linear interface kinetics under mixed kinetics-transport control of the growth rate. The amplitude of the fluctuations is smallest when either transport or interfacial kinetics dominate the control of the crystallization process. Thus, depending on the specific system, crystal quality may be improved by either enhancing or suppressing the transport in the solution. These considerations provide, for the first time, a material-dependent rationale for the advantages, as well as the disadvantages, of reduced gravity for (protein) crystallization.

Rosenberger, Franz↗
NASA NTRS1972

Improved magnesia for thermal control coatings

Formation of radiation-generated color centers using single crystals of magnesium oxide is discussed. Crystal structure of magnesium oxide is described. Chemical processes used to produce magnesium oxide with desired color center kinetics are presented. Proton irradiation of magnesium oxide crystals was conducted to determine lattice defects.

Levin, H.↗
NASA NTRS2008

The Influence of Radiation on Ice Crystal Spectrum in the Upper Troposphere

This theoretical study is carried out to investigate the effect of radiation on ice crystal spectrum in the upper troposphere. First, an explicit expression is obtained for the ice crystal growth rate that takes account of radiative and kinetic effects. Second, the expression is used to quantitatively analyze how radiation broadens the ice crystal spectrum and then reveal a new precipitation mechanism in the upper troposphere and the stratosphere. Third, the radiative effect is used to explain the subvisual clouds near the tropopause.

Zeng, Xiping↗
NASA NTRS2002

Solutal Convection Around Growing Protein Crystal and Diffusional Purification in Space

This work theoretically addressed two subjects: 1) onset of convection, 2) distribution of impurities. Onset of convection was considered analytically and numerically. Crystal growth was characterized by slow surface incorporation kinetics, i.e. growth kinetic coefficient beta (cm/s) small as compared to the typical bulk diffusion rate, D(sub 1)/h, where D(sub 1) is diffusivity of major crystallizing protein and h is the crystal size. Scaling type analysis predicted two laws on how the convection rate, v, essentially the Peclet number, Pe exactly equal to vh/D(sub 1), depends on dimensionless kinetic coefficient a exactly equal to beta h/D(sub 1). Namely: Pe = C(sub 2/5)(aRa(sup 2/5)) and Pe = C(sub 1) aRa. Here, Reynolds number Ra = rho(sub 1)(sup 0)gh(sup 3)(rho(sub p) - rho(sub w))/rho(sup p)rho(sub 1)vD(sub 1), v being solution viscosity. The constants C(sub 2/5), exactly equal to 0.28 and C(sub 1) exactly equal to 10(exp -2) found from the full scale computer simulation for a cylindrical crystal inside big cylindrical vessel. The linear boundary conditions connecting protein and impurity concentration at the interface with the flux to/from the interface was applied. No-slip condition for Navier-Shocker equations was employed. With these conditions, flow and concentration distributions were calculated. Validity of the Pe(Ra) dependencies follows for wide range of parameters for which numerical calculations have been accomplished and presented by various points.

Chernov, A. A.↗
NASA NTRS1988

Initial conditions implied by t exp 1/2 solidification of a sphere with capillarity and interfacial kinetics

The paper explores the initial conditions implied by t exp 1/2 growth of a spherical crystal solidifying from a pure, undercooled melt, including the effects of both capillarity and interface kinetics, and relates the findings to initial conditions that would be expected on the basis of classical nucleation theory. For crystal sizes near the nucleation radius, the calculated temperature profiles show a cold region ahead of the advancing interface that is even more undercooled than the undercooled bath. This cold region acts as a local heat sink that compensates for the reduced growth speed that would otherwise result from capillarity and kinetics, leading to precisely the same t exp 1/2 growth law that would have been obtained had both capillarity and kinetics been neglected.

Sekerka, R. F.↗
NASA NTRS2014

Measurements of Protein Crystal Face Growth Rates

Protein crystal growth rates will be determined for several hyperthermophile proteins.; The growth rates will be assessed using available theoretical models, including kinetic roughening.; If/when kinetic roughening supersaturations are established, determinations of protein crystal quality over a range of supersaturations will also be assessed.; The results of our ground based effort may well address the existence of a correlation between fundamental growth mechanisms and protein crystal quality.

Gorti, S.↗
NASA NTRS1978

Growth of single crystals by vapor transport

The primary objectives of the program were to establish basic vapor transport and crystal growth properties and to determine thermodynamic, kinetic and structural parameters relevant to chemical vapor transport systems for different classes of materials. An important aspect of these studies was the observation of the effects of gravity-caused convection on the mass transport rate and crystal morphology. These objectives were accomplished through extensive vapor transport, thermochemical and structural studies on selected Mn-chalcogenides, II-VI and IV-VI compounds.

Wiedemeier, H.↗
NASA NTRS1978

The law of constant rejection

Improvements in analytical technique, study of multielement partitioning in natural systems, and improvements in ionic radius values have permitted construction of Onuma diagrams, in which the logarithm of partition coefficient is plotted versus ionic radius. The optimum radii, corresponding to crystallographic sites, do change in response to changes in major element composition for any particular mineral-type. In natural systems elements compete for sites rather than substituting for another element. It is proposed on empirical grounds, for equilibrium ionic bonding, that Onuma diagram curves for a particular lattice site are parabolic near optimum radius, linear elsewhere, parallel for different valences, and mirror images on opposite sides of optimum. Deviations may be due to overlapping peaks, liquid structure, polyvalence, bonding differences, contamination, kinetics, alteration, etc. However, dominant crystal-chemical control is indicated.

Philpotts, J. A.↗
NASA NTRS1979

Free convection about a rectangular prismatic crystal growing from a solution

Sodium chlorate crystals growing from unstirred aqueous solutions were observed by Schlieren techniques. Growth rate data were best correlated by a Sherwood number with finite interface kinetics and a characteristic length equal to the crystal height plus the inverse reciprocal sum of the horizontal dimensions. The growth rate was slightly higher when the plume was laminar than when it was irregular. The horizontal growth rate was greater than the vertical growth rate, with the ratio tending to decrease with increasing plume instability. The threshold Grashof number for plume instability was greatly decreased with decreasing height for crystals with the same horizontal dimensions. The velocity of the eddies approached a constant value with increasing distance above the crystal surface, the terminal value being roughly proportional to the ratio of the square root of the Rayleigh number to the crystal characteristic length.

Chen, P.-S.↗