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At least 127 records · Page 7

Theoretical study of production of unique glasses in space

The potential of producing the glassy form of selected materials in the weightless, containerless nature of space processing is examined through the development of kinetic relationships describing nucleation and crystallization phenomena. Transformation kinetics are applied to a well-characterized system (SiO2), an excellent glass former (B2O3), and a poor glass former (Al2O3) by conventional earth processing methods. Viscosity and entropy of fusion are shown to be the primary materials parameters controlling the glass forming tendency. For multicomponent systems diffusion-controlled kinetics and heterogeneous nucleation effects are considered. An analytical empirical approach is used to analyze the mullite system. Results are consistent with experimentally observed data and indicate the promise of mullite as a future space processing candidate.

Larsen, D. C.↗

Synthesis and thermal evolution of structure in alkoxide-derived niobium pentoxide gels

Niobium pentoxide gels in the form of transparent monoliths and powder have been synthesized from the controlled hydrolysis and polycondensation of niobium pentaethoxide under different experimental conditions using various mole ratios of Nb(OC2H5)5:H2O:C2H5OH:HCl. Alcohol acted as the mutual solvent and HCl as the deflocculating agent. In the absence of HCl, precipitation of colloidal particles was encountered on the addition of any water to the alkoxide. The gels were subjected to various thermal treatments and characterized by differential thermal analysis, thermogravimetric analysis, x-ray diffraction, and infrared spectroscopy. After drying at 400 C, the gels were amorphous to x-rays. The amorphous powder crystallized into the low-temperature orthorhombic form of Nb2O5 at approximately 500 C, which transformed irreversibly into the high-temperature monoclinic alpha-Nb2O5 between 900 to 1000 C. The kinetics of crystallization of the amorphous niobium pentoxide have been investigated by non-isothermal differential scanning calorimetry. The crystallization activation energy was determined to be 399 kJ/mol.

Bansal, Narottam P.↗

The glass transition, crystallization and melting in Au-Pb-Sb alloys

The glass transition, crystallization and melting of Au(55)Pb(22.5)Sb(22.5) alloys have been studied by differential scanning calorimetry DSC. Crystallization on heating above the glass transition temperature Tg (45 C) begins at 64 C. Further crystallization events are observed at 172 C and 205 C. These events were found to correspond to the formation of the intermetallic compounds AuSb2, Au2Pb, and possibly AuPb2, respectively. Isothermal DSC scans of the glassy alloy above Tg were used to monitor the kinetics of crystallization. The solidification behavior and heat capacity in the glass-forming composition range were determined with droplet samples. An undercooling level of 0.3T(L) below the liquidus temperature T(L) was achieved, resulting in crystallization of different stable and metastable phases. The heat capacity C(P) of the undercooled liquid was measured over an undercooling range of 145 C.

Lee, M. C.↗

Viscous flow and crystallization behavior of selected lunar compositions

The flow characteristics of lunar compositions 15555 and 68502 have been determined over a wide range of viscosity. The temperature ranges covered by the measurements are 1201-1410 and 622-695 C for the 15555 composition and 1261-1515 and 725-840 C for 68502 composition. Reliable data could not be obtained over the intermediate ranges of temperature because of the occurrence of crystallization. The experimental data in the high temperature regions are found to be in close agreement with predictions of the semiempirical model of Bottinga and Weill. The results on these compositions are compared with previous data on other lunar compositions and on anorthite; and the importance of the flow behavior in interpreting lunar flows and phase morphologies is emphasized. Data are also reported on the kinetics of crystallization of the 15555 composition over the temperature interval from 700 to 1020 C.

Cukierman, M.↗

Effect of Gravity Level on the Particle Shape and Size During Zeolite Crystal Growth

A microscopic diffusion model is developed to represent solute transport in the boundary layer of a growing zeolite crystal. This model is used to describe the effect of gravity on particle shape and solute distribution. Particle dynamics and crystal growth kinetics serve as the boundary conditions of flow and convection-diffusion equations. A statistical rate theory is used to obtain the rate of solute transport across the growing interface, which is expressed in terms of concentration and velocity of solute species. Microgravity can significantly decrease the solute velocity across the growing interface compared to its earth-based counterpart. The extent of this reduction highly depends on solute diffusion constant in solution. Under gravity, the flow towards the crystal enhances solute transport rate across the growing interface while the flow away from crystals reduces this rate, suggesting a non-uniform growth rate and thus an elliptic final shape. However, microgravity can significantly reduce the influence of flow and obtain a final product with perfect spherical shape. The model predictions compare favorably with the data of space experiment of zeolites grown in space.

Song, Hong-Wei↗

Effect of fast neutron, gamma-ray and combined radiations on the thermal decomposition of ammonium perchlorate single crystals

The thermal decomposition kinetics have been determined for ammonium perchlorate crystals subjected to a fast neutron irradiation or to a fast neutron irradiation followed by a gamma-ray irradiation. Qualitatively, the radiation induced changes are similar to those obtained in this and in previous studies, with samples exposed only to gamma rays. The induction period is shortened and the rate constants, obtained from an Avrami-Erofeyev kinetic analysis, are modified. The acceleratory period constant increases and the decay period constant decreases. When compared on an equal deposited energy basis, the fast neutron induced changes are appreciably larger than the gamma-ray induced changes. Some, or all, of the fast neutron induced effects might be attributable to the introduction of localized regions of concentrated radiation damage ('spikes') by lattice atom recoils which become thermal decomposition sites when the crystals are heated.

Herley, P. J.↗

High modulus high temperature glass fibers

The search for a new high-modulus, high-temperature glass fiber involved the preparation of 500 glass compositions lying in 12 glass fields. These systems consisted primarily of low atomic number oxides and rare-earth oxides. Direct optical measurements of the kinetics of crystallization of the cordierite-rare earth system, for example, showed that the addition of rare-earth oxides decreased the rate of formation of cordierite crystals. Glass samples prepared from these systems proved that the rare-earth oxides made large specific contributions to the Young's modulus of the glasses. The best glasses have moduli greater than 21 million psi, the best glass fibers have moduli greater than 18 million psi, and the best glass fiber-epoxy resin composites have tensile strengths of 298,000 psi, compressive strengths of at least 220,000 psi, flexural strengths of 290,000 psi, and short-beam shear strengths of almost 17,000 psi.

Bacon, J. F.↗

The metal to metal interface and its effect on adhesion and friction

The paper considers the interface between two bulk metals and the effect of this interface on adhesive bonding, resistance to tangential displacements, friction and the interfacial transport from one surface to another. Using Auger emission spectroscopy, field ion microscopy, and low energy electron diffraction techniques, the influence of surface orientation, lattice registry, crystal lattice structure and defects, metal surface chemistry and alloying on the characteristics of the interface was studied for noble, platinum, transition, and Group 4B metals. With dissimilar metals in contact, epitaxial transfer of the cohesively weaker to the cohesively stronger metal has been observed. Surface chemical activity of the noble and platinum metals is shown to affect interfacial behavior as does a valence bonding in the transition metals, and the degree of metallic nature in the Group 4B elements. Alloying elements, e.g., Si and Fe, can alter interfacial behavior by segregation to the surface of metals or by altering bulk properties such as crystal transformation kinetics.

Buckley, D. H.↗

Advanced methods for preparation and characterization of infrared detector materials

Mercury cadmium telluride crystals were prepared by the Bridgman method with a wide range of crystal growth rates and temperature gradients adequate to prevent constitutional supercooling under diffusion-limited, steady state, growth conditions. The longitudinal compositional gradients for different growth conditions and alloy compositions were calculated and compared with experimental data to develop a quantitative model of the crystal growth kinetics for the Hg(i-x)CdxTe alloys, and measurements were performed to ascertain the effect of growth conditions on radial compositional gradients. The pseudobinary HgTe-CdTe constitutional phase diagram was determined by precision differential thermal analysis measurements and used to calculate the segregation coefficient of Cd as a function of x and interface temperature. Computer algorithms specific to Hg(1-x)CdxTe were developed for calculations of the charge carrier concentrations, charge carrier mobilities, Hall coefficient, optical absorptance, and Fermi energy as functions of x, temperature, ionized donor and acceptor concentrations, and neutral defect concentrations.

Lehoczky, S. L.↗

Pressure-Reduction Technique for Crystal Growth

Large crystals grown by varying pressure rather than temperature. In constant temerature pressure-reduction process crystal growth promoted as solubility decreases by factor of more than 10. Technique used to study crystal growth kinetics by "pressure wave"" analog of conventional "thermal wave" experiments. Technique has advantages of faster response and freedom from convective interference.

Shlichta, P. J.↗

Superconducting ceramics in the Bi1.5SrCaCu2O sub x system by melt quenching technique

Bi sub 1.5 SrCaCu sub 2 O sub x has been prepared in the glassy state by rapid quenching of the melt. The kinetics of crystallization of various phases in the glass have been evaluated by a variable heating rate differential scanning calorimetry method. The formation various phases on thermal treatments of the glass has been investigated by powder X-ray diffraction and electrical resistivity measurements. Heating at 450 C formed Bi sub 2 Sr sub 2 CuO sub 6, which disappeared on further heating at 765 C, where Bi sub 2 Sr sub 2 CaCu sub 2 O sub 8 formed. Prolonged heating at 845 C resulted in the formation of a small amount of a phase with T sub c onset of approx. 108 K, believed to be Bi sub 2 Sr sub 2 Ca sub 2 Cu sub 3 O sub 10. This specimen showed zero resistivity at 54 K. The glass ceramic approach could offer several advantages in the fabrication of the high-T sub c superconductors in desired practical shapes such as continuous fibers, wires, tapes, etc.

Bansal, Narottam P.↗

Lack of Evidence for Prenucleation Aggregate Formation in Lysozyme Crystal Growth Solutions

There have been numerous claims of large concentrations of prenucleation aggregates in supersaturated as well as undersaturated lysozyme solutions at high salt concentrations. The presence of these aggregates was derived from measurements of the light or neutron scattering intensity, ultracentrifugation and dialysis behavior, as well as over-simplified crystal growth kinetics considerations. In all these interpretations it has been assumed that lysozyme solutions are either ideal or that protein interactions are independent of salt concentration. Contrary to these presumptions, our static and dynamic light scattering experiments provide evidence that lysozyme forms highly non-ideal, strongly interacting solutions. At low salt concentrations, the scattering intensities fall well below the values expected for an ideal, monomeric solution at the same protein concentration, while diffusivities increase with increasing protein concentration. Upon increase in salt concentration, these trends are eventually reversed. This enhancement in scattering intensity and decrease in diffusivity was widely interpreted as sign of aggregate formation. Yet, a quantitative interpretation of the scattering behavior over the whole salt concentration range can only be given in terms of a transition from net repulsion to net attraction between lysozyme monomers. Increased salt screening of the electrostatic repulsion among the protein macro-ions, together with attractive protein interactions, such as van der Waals, hydrophobic and hydration forces, provide an unambiguous mechanism for the observed transition and a more physical interpretation of the various observations.

Muschol, Martin↗

Acetylated Lysozyme as Impurity in Lysozyme Crystals: Constant Distribution Coefficient

Hen egg white lysozyme (HEWL) was acetylated to modify molecular charge keeping the molecular size and weight nearly constant. Two derivatives, A and B, more and less acetylated, respectively, were obtained, separated, purified and added to the solution from which crystals of tetragonal HEWL crystals were grown. Amounts of the A or B impurities added were 0.76, 0.38 and 0.1 milligram per millimeter while HEWL concentration were 20, 30 and 40 milligram per milliliter. The crystals grown in 18 experiments for each impurity were dissolved and quantities of A or B additives in these crystals were analyzed by cation exchange high performance liquid chromatography. All the data for each set of 18 samples with the different impurity and regular HEWL concentrations is well described by one distribution coefficient K = 2.15 plus or minus 0.13 for A and K = 3.42 plus or minus 0.25 for B. The observed independence of the distribution coefficient on both the impurity concentration and supersaturation is explained by the dilution model described in this paper. It shows that impurity adsorption and incorporation rate is proportional to the impurity concentration and that the growth rate is proportional to the crystallizing protein in solution. With the kinetic coefficient for crystallization, beta = 5.10(exp -7) centimeters per second, the frequency at which an impurity molecule near the growing interface irreversibly joins a molecular site on the crystal was found to be 3 1 per second, much higher than the average frequency for crystal molecules. For best quality protein crystals it is better to have low microheterogeneous protein impurity concentration and high supers aturation.

Thomas, B. R.↗

Growth of (101) faces of tetragonal lysozyme crystals: measured growth-rate trends

Previous extensive measurements of the growth rates of the (110) face of tetragonal lysozyme crystals have shown unexpected dependencies on the supersaturation. In this study, similar growth-rate measurements were performed for the (101) faces of the crystals. The data show a similar dependence on the supersaturation, becoming appreciable only at high supersaturations, reaching a maximum value and then decreasing. The (101) growth rates are larger at low supersaturations than the (110) growth rates under the same conditions and are smaller at high supersaturations. These trends suggest that the growth mechanism of the (101) face is similar to that of the (110) face: both processes involve the addition of multimeric growth units formed in solution, but the average size of the units for the (101) face is likely to be smaller than for the (110) face.

Egg Proteins/chemistry↗

Atomic-Scale Structure and Non-Stoichiometry of Meteoritic Hibonite: A Transmission Electron Microscope Study

Hibonite (CaAl_12O_19) is a common refractory mineral in Ca-Al-rich inclusions (CAIs) in primitive meteorites. Transmission electron microscope (TEM) studies have identified enigmatic planar defects in different occurrences of hibonite in the Allende meteorite that give rise to strong streaking along c* in electron diffraction patterns. Atomic resolution high-angle annular dark-field (HAADF) imaging and energy-dispersive X-ray (EDX) analyses were used to determine the nature and origin of these planar features. HAADF images of hibonite grains reveal lamellar intergrowths of common 1.6 nm spacing, and less commonly 2.0 and 2.5 nm spacings, interspersed in stoichiometric hibonite showing 1.1 nm (002) spacing. Stoichiometric hibonite consists of alternating Ca-containing (“R”) and spinel-structured (“S”) blocks stacked in a sequence RS. In contrast, the 1.6 nm layers result from a doubled S block such that the stacking sequence is RSS, while in the widest defect observed, the stacking sequence is RSSSS. These intergrowths are epitaxial and have coherent, low-strain boundaries with the host hibonite Meteoritic hibonite shows common Ti and Mg substitution for Al in its structure. Atomic-resolution EDX maps of hibonite grains in the Allende CAI confirm the preferred site occupancy of Mg on tetragonal M3 sites in S blocks and of Ti on trigonal bipyramidal M2 and octahedral M4 sites in R blocks. Mg is highly concentrated, but Ti is absent in the planar defects where wider S blocks show Al-rich compositions compared to stoichiometric MgAl_2O_4 spinel. Therefore, Mg likely played the major role in the formation and metastability of planar defects in hibonite. Electron energy loss spectroscopy data from the Ti L_2,3 edge show the presence of mixed Ti oxidation states with ~ 15–20% of Ti as Ti^(3+) in hibonite, suggesting a direct substitution of Ti^(3+) ↔ Al^(3+) in hibonite. The remaining ~ 80–85% of Ti is present as Ti^(4+) and corresponding EDX analyses are consistent with the well-known coupled substitution 2Al^(3+) ↔ Ti^(4+) + Mg^(2+) being the major mechanism for Ti and Mg substitution in hibonite. The formation of planar defects in hibonite occurred during high-temperature nebular condensation or melting/crystallization processes. The occurrence of non-stoichiometric hibonite in the Allende CAI deviates from the mineral formation sequence predicted from equilibrium condensation models. Overall, our atomic resolution TEM observations signify non-equilibrium, kinetic-controlled crystal growth during the high-temperature formation of refractory solids in the early solar nebula.

hibonite↗

Integrated Process-Structure-Property Simulations for Additive Manufacturing Using the Open-Source Materialite Package

The microstructure and properties of additively manufactured (AM) metals are strongly dependent on process conditions. Therefore, process-structure-property (PSP) simulations are a useful tool for exploring process parameter space, studying process variations, and quantifying uncertainty in material properties. However, integrating process-structure and structure-property simulations often involves connecting multiple software packages. Each package may use unique data structures and require substantial domain knowledge. This presentation demonstrates PSP simulation capabilities of Materialite, an open-source package developed at NASA Langley Research Center. Materialite simplifies model linkages by using a common data structure and model interface, enabling straightforward simulation across a PSP model chain. Physics-based models, including kinetic Monte Carlo and crystal plasticity, are implemented within the package. The model interface is also intended to simplify implementation of new models and enable integration with external simulation tools. Example use cases include uncertainty quantification with PSP models and GPU-accelerated powder bed fusion AM process models.

additive manufacturing↗