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At least 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
NASA NTRS2001

Crystal Growth of ZnSe and Related Ternary Compound Semiconductors by Vapor Transport

Crystal growth by vapor transport has several distinct advantages over melt growth techniques. Among various potential benefits from material processing in reduced gravity the followings two are considered to be related to crystal growth by vapor transport: (1) elimination of the crystal weight and its influence on the defect formation and (2) reduction of natural buoyancy-driven convective flows arising from thermally and/ or solutally induced density gradient in fluids. The previous results on vapor crystal growth of semiconductors showed the improvements in surface morphology, crystalline quality, electrical properties and dopant distribution of the crystals grown in reduced gravity as compared to the crystals grown on Earth. But the mechanisms, which are responsible for the improvements and cause the gravitational effects on the complicated and coupled processes of vapor mass transport and growth kinetics, are not well understood.

Su, Ching-Hua↗
NASA NTRS2001

Crystallization of bFGF-DNA Aptamer Complexes Using a Sparse Matrix Designed for Protein-Nucleic Acid Complexes

The Sparse Matrix approach for obtaining lead crystallization conditions has proven to be very fruitful for the crystallization of proteins and nucleic acids. Here we report a Sparse Matrix developed specifically for the crystallization of protein-DNA complexes. This method is rapid and economical, typically requiring 2.5 mg of complex to test 48 conditions. The method was originally developed to crystallize basic fibroblast growth factor (bFGF) complexed with DNA sequences identified through in vitro selection, or SELEX, methods. Two DNA aptamers that bind with approximately nanomolar affinity and inhibit the angiogenic properties of bFGF were selected for co-crystallization. The Sparse Matrix produced lead crystallization conditions for both bFGF-DNA complexes.

Cannone, Jaime J.↗
NASA NTRS2001

Characterization and In-Situ Monitoring of ZnSe Crystal Growth by Seeded PVT for Microgravity Applications

Crystal growth from the vapor phase continues to play a significant role in the production of II-VI semiconductor compounds (ZnO, ZnTe, CdTe, etc.) and SiC. As compared to melt growth methods (where available) the advantages are: (1) lower growth temperature(s); (2) reduction in defect concentration; (3) additional purification; and (4) enhanced crystal perfection. A powerful tool in determining the mechanism of PVT is microgravity. Under normal gravity conditions the transport mechanism is a superposition of diffusive and convective fluxes. Microgravity offers the possibility of studying the transport properties without the influence of convective effects. Research on the crystal growth of ZnSe by PVT (P.I.: Su of NASA/MSFC) will help to clarify the effects of convection on crystal growth. A crystal growth furnace with in-situ and real time optical monitoring capabilities was constructed and used to monitor the vapor composition and growing crystal surface morphology during the PVT growth of ZnSe. Using photoluminescence and SIMS, ex-situ, the incorporation of point defects (Zn vacancy) and impurities was found to be correlated to the gravity vector due to the influence of the convective flow. A summary of the results to date will be presented.

Feth, Shari T.↗
NASA NTRS2001

A Model for Macromolecular Crystallization

Macromolecular crystallization is a complex process. involving a system which typically has 5 or more components (macromolecule, water, buffer + counter ion, and precipitant). Whereas small molecules have only several well defined 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 often be readily broken and reformed between other sites. Formation of a consistent, ordered, 3D structure may be 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. Experimental evidence, based upon face growth rate, AFM, and fluorescence energy transfer data, for a postulated model of the nucleation of tetragonal lysozyme crystals and how it transitions into crystal growth will be presented.

Pusey, Marc L.↗
NASA NTRS2002

Generalized Reliability Methodology Applied to Brittle Anisotropic Single Crystals

A generalized reliability model was developed for use in the design of structural components made from brittle, homogeneous anisotropic materials such as single crystals. The model is based on the Weibull distribution and incorporates a variable strength distribution and any equivalent stress failure criteria. In addition to the reliability model, an energy based failure criterion for elastically anisotropic materials was formulated. The model is different from typical Weibull-based models in that it accounts for strength anisotropy arising from fracture toughness anisotropy and thereby allows for strength and reliability predictions of brittle, anisotropic single crystals subjected to multiaxial stresses. The model is also applicable to elastically isotropic materials exhibiting strength anisotropy due to an anisotropic distribution of flaws. In order to develop and experimentally verify the model, the uniaxial and biaxial strengths of a single crystal nickel aluminide were measured. The uniaxial strengths of the <100> and <110> crystal directions were measured in three and four-point flexure. The biaxial strength was measured by subjecting <100> plates to a uniform pressure in a test apparatus that was developed and experimentally verified. The biaxial strengths of the single crystal plates were estimated by extending and verifying the displacement solution for a circular, anisotropic plate to the case of a variable radius and thickness. The best correlation between the experimental strength data and the model predictions occurred when an anisotropic stress analysis was combined with the normal stress criterion and the strength parameters associated with the <110> crystal direction.

Salem, Jonathan A.↗
NASA NTRS2002

About Small Streams and Shiny Rocks: Macromolecular Crystal Growth in Microfluidics

We are developing a novel technique with which we have grown diffraction quality protein crystals in very small volumes, utilizing chip-based, microfluidic ("LabChip") technology. With this technology volumes smaller than achievable with any laboratory pipette can be dispensed with high accuracy. We have performed a feasibility study in which we crystallized several proteins with the aid of a LabChip device. The protein crystals are of excellent quality as shown by X-ray diffraction. The advantages of this new technology include improved accuracy of dispensing for small volumes, complete mixing of solution constituents without bubble formation, highly repeatable recipe and growth condition replication, and easy automation of the method. We have designed a first LabChip device specifically for protein crystallization in batch mode and can reliably dispense and mix from a range of solution constituents. We are currently testing this design. Upon completion additional crystallization techniques, such as vapor diffusion and liquid-liquid diffusion will be accommodated. Macromolecular crystallization using microfluidic technology is envisioned as a fully automated system, which will use the 'tele-science' concept of remote operation and will be developed into a research facility aboard the International Space Station.

vanderWoerd, Mark↗
NASA NTRS2002

Characterization of Surface Features in Detached Grown GeSi Crystals

The growth of detached crystals by the Bridgman technique, in which the growing crystal is not in contact with the crucible wall, has been observed both on earth and in microgravity conditions. At present, the mechanisms contributing to the detachment are not completely understood and until recently detachment has not been reproducibly obtained. It is commonly understood that the main factors that promote the occurrence of detached growth include: high contact angle between the melt and the crucible material, high growth angle, and a pressure difference between the annular gap around the solid below the melt and the volume above the melt along the meniscus. These parameters were varied in Bridgman growth experiments to determine the conditions required to achieve detached growth terrestrially in Ge and GeSi alloys. These experiments are in preparation for experiments on the International Space Station (ISS). The detailed objectives of the flight experiments and a description of the growth methods employed are the subject of another presentation at this Conference. Detached crystals were achieved repeatedly in pyrolytic boron nitride ampoules when a pressure difference was employed. All crystals, except for those grown in fused silica ampoules, were easily removed from their containers, however, this fact alone is not sufficient to infer detached growth. Detachment was verified by comparing profilometer measurements of the radius of the samples with observations of the sample surfaces using optical and electron microscopy. The surfaces of the attached areas of the crystals had the same shape and surface texture as the interior crucible wall. Regions of detached growth contained many unique features and crystal facets could usually be observed. Several of these surface features have been correlated with mechanisms of detachment or free-surface growth and others to processing events or conditions.

Cobb, S. D.↗
NASA NTRS2002

A Proposed Model for Protein Crystal Nucleation and Growth

How does one take a molecule, strongly asymmetric in both shape and charge distribution, and assemble it into a crystal? We propose a model for the nucleation and crystal growth process for tetragonal lysozyme, based upon fluorescence, light, neutron, and X-ray scattering data, size exclusion chromatography experiments, dialysis kinetics, AFM, and modeling of growth rate data, from this and other laboratories. The first species formed is postulated to be a 'head to side' dimer. Through repeating associations involving the same intermolecular interactions this grows to a 4(sub 3) helix structure, that in turn serves as the basic unit for nucleation and subsequent crystal growth. High salt attenuates surface charges while promoting hydrophobic interactions. Symmetry facilitates subsequent helix-helix self-association. Assembly stability is enhanced when a four helix structure is obtained, with each bound to two neighbors. Only two unique interactions are required. The first are those for helix formation, where the dominant interaction is the intermolecular bridging anion. The second is the anti-parallel side-by-side helix-helix interaction, guided by alternating pairs of symmetry related salt bridges along each side. At this stage all eight unique positions of the P4(sub3)2(sub 1),2(sub 1) unit cell are filled. The process is one of a) attenuating the most strongly interacting groups, such that b) the molecules begin to self-associate in defined patterns, so that c) symmetry is obtained, which d) propagates as a growing crystal. Simple and conceptually obvious in hindsight, this tells much about what we are empirically doing when we crystallize macromolecules. By adjusting the growth parameters we are empirically balancing the intermolecular interactions, preferentially attenuating the dominant strong (for lysozyme the charged groups) while strengthening the lesser strong (hydrophobic) interactions. In the general case for proteins the lack of a singularly defined association pathway may lead to formation of multiple species, i.e., amorphous precipitation. Weak interactions, such as hydrogen bonds, are promiscuous, serving to strengthen rather than define specific interactions. Participation in an interaction sequesters that surface from subsequent interactions, and we expect the strongest bonds to form first. This model, its basis, how it fits into the currently understood osmotic second virial coefficient approach to crystallization, and what it suggests will be discussed.

Pusey, Marc↗
NASA NTRS2002

Morphology and the Strength of Intermolecular Contact in Protein Crystals

The strengths of intermolecular contacts (macrobonds) in four lysozyme crystals were estimated based on the strengths of individual intermolecular interatomic interaction pairs. The periodic bond chain of these macrobonds accounts for the morphology of protein crystals as shown previously. Further in this paper, the surface area of contact, polar coordinate representation of contact site, Coulombic contribution on the macrobond strength, and the surface energy of the crystal have been evaluated. Comparing location of intermolecular contacts in different polymorphic crystal modifications, we show that these contacts can form a wide variety of patches on the molecular surface. The patches are located practically everywhere on this surface except for the concave active site. The contacts frequently include water molecules, with specific intermolecular hydrogen-bonds on the background of non-specific attractive interactions. The strengths of macrobonds are also compared to those of other protein complex systems. Making use of the contact strengths and taking into account bond hydration we also estimated crystal-water interfacial energies for different crystal faces.

Matsuura, Yoshiki↗
NASA NTRS2002

Transport and Growth Kinetics in Microgravity Protein Crystal Growth

The dynamic coupling between mass transport and incorporation of growth units into the surface of a crystal growing from solution in microgravity is used to derive quantitative information on the crystal growth kinetics. To this end, new procedures for experiment preparation, interferometric data processing and model fitting have been developed. The use of experimental data from the bulk diffusive maw transport together with a model for steady state stagnant crystal growth allows the detailed quantitative understanding of the kinetics of both the concentration depletion zone around the crystal and the growth of the crystal interface. The protein crystal used in the experiment is shown to be growing in the mixed kinetic regime (0.2 x 10(exp -6) centimeters per second less than beta R/D less than 0.9 x 10(exp -6) centimeters per second).

Otalora, F.↗
NASA NTRS2002

AFM Studies of Salt Concentration Effects on the (110) Surface Structure of Tetragonal Lysozyme Crystals

Previous high resolution AFM studies of the (110) surface of tetragonal chicken egg white lysozyme crystals had shown that only one of two possible molecular surfaces is present, those constituting the completed 43 helices. These suggested that the crystal growth process was by the solution-phase assembly of the growth units, which then attach to the surface. However, the best fit for the imaged surfaces, vs. those predicted based upon the bulk crystallographic coordinates, were obtained when the packing about the 43 helices was "tightened up", while maintaining the underlying crystallographic unit cell spacing. This results in a widening of the gap between adjacent helices, and the top- most layer(s) may no longer be in contact. We postulated that the tightened packing about the helices is a result of the high salt concentrations in the bulk solution, used to crystallize the protein, driving hydrophobic interactions. Once the crystal surface is sufficiently buried by subsequent growth layers the ratio of salt to protein molecules decreases and the helices relax to their bulk crystallographic coordinates. The crystal surface helix structure is thus a reflection of the solution structure, and the tightness of the packing about the 43 helices would be a function of the bulk salt concentration. AFM images of the (110) surface of tetragonal lysozyme crystals grown under low (2%) and high (5%) NaCl concentrations reveal differences in the packing about the 43 helices consistent with the above proposal.

Pusey, Marc Lee↗
NASA NTRS2003

RNA Crystallization

RNA molecules may be crystallized using variations of the methods developed for protein crystallography. As the technology has become available to syntheisize and purify RNA molecules in the quantities and with the quality that is required for crystallography, the field of RNA structure has exploded. The first consideration when crystallizing an RNA is the sequence, which may be varied in a rational way to enhance crystallizability or prevent formation of alternate structures. Once a sequence has been designed, the RNA may be synthesized chemically by solid-state synthesis, or it may be produced enzymatically using RNA polymerase and an appropriate DNA template. Purification of milligram quantities of RNA can be accomplished by HPLC or gel electrophoresis. As with proteins, crystallization of RNA is usually accomplished by vapor diffusion techniques. There are several considerations that are either unique to RNA crystallization or more important for RNA crystallization. Techniques for design, synthesis, purification, and crystallization of RNAs will be reviewed here.

Golden, Barbara L.↗
NASA NTRS2003

Modeling Tetragonal Lysozyme Crystal Growth Rates

Tetragonal lysozyme 110 face crystal growth rates, measured over 5 orders of magnitude in range, can be described using a model where growth occurs by 2D nucleation on the crystal surface for solution supersaturations of c/c(sub eq) less than or equal to 7 +/- 2. Based upon the model, the step energy per unit length, beta was estimated to be approx. 5.3 +/- 0.4 x 10(exp -7) erg/mol-cm, which for a step height of 56 A corresponds to barrier of approx. 7 +/- 1 k(sub B)T at 300 K. For supersaturations of c/c(sub eq) > 8, the model emphasizing crystal growth by 2D nucleation not only could not predict, but also consistently overestimated, the highest observable crystal growth rates. Kinetic roughening is hypothesized to occur at a cross-over supersaturation of c/c(sub eq) > 8, where crystal growth is postulated to occur by a different process such as adsorption. Under this assumption, all growth rate data indicated that a kinetic roughening transition and subsequent crystal growth by adsorption for all solution conditions, varying in buffer pH, temperature and precipitant concentration, occurs for c/c(sub eq)(T, pH, NaCl) in the range between 5 and 10, with an energy barrier for adsorption estimated to be approx. 20 k(sub B)T at 300 K. Based upon these and other estimates, we determined the size of the critical surface nucleate, at the crossover supersaturation and higher concentrations, to range from 4 to 10 molecules.

Gorti, Sridhar↗
NASA NTRS2003

Kinetic Roughening and Energetics of Tetragonal Lysozyme Crystal Growth

Lysozyme crystal growth rates over 5 orders of magnitude in range can be described using a layer-by-layer model where growth occurs by 2D nucleation on the crystal surface. Based upon the 2D nucleation model of layer growth, the effective barrier for growth was determined to be gamma = 1.3 plus or minus 0.3 x 10(exp -13) erg/molecule, corresponding to a barrier of 3.2 plus or minus 0.7 k(sub B)T, at 22 C. For solution supersaturation, In c/c(sub eq) greater than or equal to 1.9 plus or minus 0.2, the nucleation model would not predict or consistently estimate the highest observable crystal growth rates. As such, a kinetic roughening hypothesis where crystal growth occurs by a continuous mode was implemented for all growth rate data obtained above In c(sub r)/c(sub eq) greater than or equal to 2. That is, independent of the solution conditions that vary with either buffer pH, temperature or precipitant concentration, crystal growth occurs by the continuous addition of molecules anywhere on the crystal surface, above a roughening solution supersaturation. The energy barrier, E(sub c), for the continuous growth process is determined as 6.1 plus or minus 0.4 x 10(exp -13) erg/molecule or 15 plus or minus 1 k(sub B)T at 22 C.

Gorti, Sridhar↗
NASA NTRS2004

Structure and Dynamics of Freely Suspended Liquid Crystals

Smectic liquid crystals are phases of rod shaped molecules organized into one dimensionally (1 D) periodic arrays of layers, each layer being between one and two molecular lengths thick. In the least ordered smectic phases, the smectics A and C, each layer is a two dimensional (2D) liquid. Additionally there are a variety of more ordered smectic phases having hexatic short range translational order or 2D crystalline or quasi long range translational order within the layers. The inherent fluid-layer structure and low vapor pressure of smectic liquid crystals enables the long term stabilization of freely suspended, single component, layered fluid films as thin as 30A, a single molecular layer. The layering forces the films to be an integral number of smectic layers thick, quantizing their thickness in layer units and forcing a film of a particular number of layers to be physically homogeneous with respect to its layer structure over its entire area. Optical reflectivity enables the precise determination of the number of layers. These ultrathin freely suspended liquid crystal films are structures of fundamental interest in condensed matter and fluid physics. They are the thinnest known stable fluid structures and have the largest surface-to-volume ratio of any stable fluid preparation, making them ideal for the study of the effects of reduced dimensionality on phase behavior and on fluctuation and interface phenomena. Their low vapor pressure and quantized thickness enable the effective use of microgravity to extend the study of basic capillary phenomena to ultrathin fluid films. Freely suspended films have been a wellspring of new LC physics. They have been used to provide unique experimental conditions for the study of condensed phase transitions in two dimensions. They are the only system in which the hexatic has been unambiguously identified as a phase of matter, and the only physical system in which fluctuations of a 2D XY system and Kosterlitz Thouless phase transition has been observed and 2D XY quasi long range order verified. Smectic films have enabled the precise determination of smectic layer electron density and positional fluctuation profiles and have been used to show that the interlayer interactions in antiferroelectric tilted smectics do not extend significantly beyond nearest neighbors. Freely suspended films played a pivotal role in the recent discovery of macroscopic chiral-polar ordering in fluids of achiral molecules. The interactions which are operative in liquid crystals are generally weak in comparison to those in crystalline phases, leading to the facile manipulation of the order in liquid crystals by external agents such as applied fields and surfaces. Effects arising from weak ordering are significantly enhanced in ultrathin free films and filaments, in which the intermolecular coupling is effectively further reduced by loss of neighbors. Over the past four years this research, which we now detail, has produced a host of exciting new discoveries and unexpected results, maintaining the study of freely suspended liquid crystal structures as one of most exciting and fruitful areas of complex fluid physics. In addition, a class of experiments on the behavior of 1D interfaces in 2D films have been pursued with results that point to potentially quite interesting effects in microgravity.

Clark, Noel A.↗
NASA NTRS2003

Effect of Viscosity on the Crystallization of Undercooled Liquids

There have been numerous studies of glasses indicating that low-gravity processing enhances glass formation. NASA PI s are investigating the effect of low-g processing on the nucleation and crystal growth rates. Dr. Ethridge is investigating a potential mechanism for glass crystallization involving shear thinning of liquids in 1-g. For shear thinning liquids, low-g (low convection) processing will enhance glass formation. The study of the viscosity of glass forming substances at low shear rates is important to understand these new crystallization mechanisms. The temperature dependence of the viscosity of undercooled liquids is also very important for NASA s containerless processing studies. In general, the viscosity of undercooled liquids is not known, yet knowledge of viscosity is required for crystallization calculations. Many researchers have used the Turnbull equation in error. Subsequent nucleation and crystallization calculations can be in error by many orders of magnitude. This demonstrates the requirement for better methods for interpolating and extrapolating the viscosity of undercooled liquids. This is also true for undercooled water. Since amorphous water ice is the predominant form of water in the universe, astrophysicists have modeled the crystallization of amorphous water ice with viscosity relations that may be in error by five orders-of-magnitude.

Source record↗
NASA NTRS2004

Deformation, Stress Relaxation, and Crystallization of Lithium Silicate Glass Fibers Below the Glass Transition Temperature

The deformation and crystallization of Li(sub 2)O (center dot) 2SiO2 and Li(sub 2)O (center dot) 1.6SiO2 glass fibers subjected to a bending stress were measured as a function of time over the temperature range -50 to -150 C below the glass transition temperature (Tg). The glass fibers can be permanently deformed at temperatures about 100 C below T (sub)g, and they crystallize significantly at temperatures close to, but below T,, about 150 C lower than the onset temperature for crystallization for these glasses in the no-stress condition. The crystallization was found to occur only on the surface of the glass fibers with no detectable difference in the extent of crystallization in tensile and compressive stress regions. The relaxation mechanism for fiber deformation can be best described by a stretched exponential (Kohlrausch-Williams-Watt (KWW) approximation), rather than a single exponential model.The activation energy for stress relaxation, Es, for the glass fibers ranges between 175 and 195 kJ/mol, which is considerably smaller than the activation energy for viscous flow, E, (about 400 kJ/mol) near T, for these glasses at normal, stress-free condition. It is suspected that a viscosity relaxation mechanism could be responsible for permanent deformation and crystallization of the glass fibers below T,

Ray, Chandra S.↗
NASA NTRS2004

Solutal Convection Around Growing Protein Crystal and Diffusional Purification in Space

At least some protein crystals were found to preferentially trap microheterogeneous impurities. The latter are, for example, dimmer molecules of the crystallizing proteines (e.g. ferritin, lysozyme), or the regular molecules on which surfaces small molecules or ions are adsorbed (e.g. acetilated lysozyme) and modi@ molecular charge. Impurities may induce lattice defects and deteriorate structural resolution. Distribution of impurities between mother solution and gorwing crystal is defined by two interrelated distribution coefficients: kappa = rho(sup c, sub 2) and K = (rho(sup c, sub 2)/rho(sup c, sub 1)/rho(sub 2)/rho(sub 1). Here, rho(sub 2), rho(sub 1) and rho(sup c, sub 2) are densities of impurity (2) and regular protein (1) in solution at the growing interface and within the crystal ("c"). For the microheterogeneous impurities studied, K approx. = 2 - 4, so that kappa approx. - 10(exp 2) - 10(exp 3), since K = kappa (rho(sub 1)/rho(sup c, sub 1) and protein solubility ratio rho(sub 1)/rho(sub=p c, sub 2) much less than 1. Therefore, a crystal growing in absence of convection purifies mother solution around itself, grows cleaner and, probably, more perfect. If convection is present, the solution flow permanently brings new impurities to the crystal. This work theoretically addressed two subjects: 1) onset of convection, 2) distribution of impurities.

Lee, Chun P.↗