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At least 217 records · Page 12

Alkoxysilane adsorption on metal oxide substrates

Reflection-absorption infrared and inelastic electron tunneling spectroscopies have been used to study adsorption of liquid phase mono-, di-, and trialkoxysilanes on evaporated Al and Cu substrates. Spectral evidence shows that substrate properties influence the chemical and physical nature of trialkoxysilane films and that silane functionality plays a role in molecular orientation. Results show that dialkoxysilane films contain structural gradients, with adsorption at the monomolecular level influenced by surface morphology, and with organofunctionality and dosing procedure affecting the formation of thicker films. Evidence is presented that monoalkoxysilanes react with alumina surfaces, and a broad, multipeaked band from 1600 to 1900/cm has been interpreted as characteristic of the silylated AlO(x)Pb interface.

Ramsier, R. D.↗

The unusual X-ray collision morphology of NGC 4782/4783 (3C 278)

Deep Rosat high resolution imager (HRI) observations of the X-ray emitting gas associated with the colliding elliptical galaxy pair NGC 4782 and NGC 4783 reveals the gas distribution in a pair of close interacting ellipticals. The HRI image shows hot gas around each galaxy pair and a sheet of gas at the interaction interface between the two galaxies. The hot gas distributions do not peak at the optical centers of the galaxies, but are displaced in the same sense as the tidal distensions seen in the optical luminosity distributions.

Borne, Kirk↗

Surface Processes of Faceted Growth

Atomic force microscopy and high precision optical interferometry allow to analyze the processes that are in the core of our present understanding of faceted crystal growth. Some of these processes will be reviewed. Recent experiments suggest that the Gibbs-Thomson Law (GTL) may not be applicable to the weakly fluctuating strongly polygonized steps, with low kink density. Propagation rate of a straight short step segment changes with the segment length much steeper than predicted by GTL. If the step fluctuations are still well developed, the typical transition length may be determined just by the radius of rounded comers of the polygonized step. If fluctuations do not have enough time to develop, the kinetic effects may be essential. Indeed, 'communications' between comers of a short straight step segment may occur and, thus, the GTL may be implemented only via kink exchange. E.g., dissolutions of this short segment at macroscopic equilibrium occurs as follows: The kinks are split from one comer as a result of fluctuations, and annihilate with kinks of the opposite sign generated by another comer. Similarly, an exchange via chain of kinks on a rough step is the mechanism to implement the GT Law. If there is a supersaturation with respect to a large crystal, the kinks not only diffuse along the step, but move back the generating comers. This 'wind' prevents communication between the comers and places upper limit supersaturation only below which GTL is applicable. Steps replace kinks in the 3D case, though, of course, another dimensionality brings about another physics. Another specific problem to think about is if fluctuations are always fast enough to provide enough kinks for linear dependence of step rate on supersaturation. Increasing azimuthal polygonization of growth hillocks is a sign of insufficient fluctuation rate. Morphological stability of vicinal faces is usually considered on the basis of mutually parallel steps. Azimuthal anisotropy and interlacing of step bunches inducing the well known bunch splitting is another challenge. Among other challenging problems are: existence of surface diffusion on the crystal/so1ution interface, step interaction in solutions, achievement of step flow modes from liquids, impurity effects. New phenomena essential in biomacromolecular crystallization is another interesting area.

Chernov, A.↗

Simulation of triglycine sulfate crystal growth in space

Consideration is given to the numerical simulation of the solution growth of triglycine sulfate in space, with heat transfer, mass transfer, buoyancy-driven convection, the dependence of solubility on temperature, and finite interface kinetics taken into account. In the bulk solution, weak thermal convection was established quickly. The thermal convection then becomes dominated by solutionally driven motion. The convection due to the steady background g is predicted to influence both the growth rate and the crystal morphology. The time required for buoyancy-driven convection to influence the growth rate depends on the magnitude of g, i.e., more time for smaller g. Under the same cooling condition, the average growth rate increases as the magnitude of g increases. A steady average growth rate of 1.0 mm/d can be obtained when a properly designed cooling rate is applied to the sting. The most uniform growth is obtained when the g vector is aligned such that the solution flows normal towards the center of the crystal surface.

Sun, Jianhua↗

Deformation and fracture of a directionally solidified NiAl-28Cr-6Mo eutectic alloy

A directionally solidified alloy based on the NiAl-(Cr, Mo) eutectic was examined by transmission and scanning electron microscopy to characterize the microstructure and room temperature deformation and fracture behavior. The microstructure consisted of a lamellar morphology with a group of zone axes (111) growth direction for both the NiAl and (Cr, Mo) phases. The interphase boundary between the eutectic phases was semicoherent and composed of a well-defined dislocation network. In addition, a fine array of coherent NiAl precipitates was dispersed throughout the (Cr, Mo) phase. The eutectic morphology was stable at 1300 K with only coarsening of the NiAl precipitates occurring after heat treatment for 1.8 ks (500 h). Fracture of the aligned eutectic is characterized primarily by a crack bridging/renucleation mechanism and is controlled by the strength of the semicoherent interface between the two phases. However, contributions to the toughness of the eutectic may arise from plastic deformation of the NiAl phase and the geometry associated with the fracture surface.

Chen, X. F.↗

A Structural and Molecular Approach for the Study Biomarkers

Investigation of the nucleation and growth of crystals in both abiotic and biotic systems is critical to seemingly diverse disciplines of geology, biology, environmental science, and astrobiology. While there are abundant studies devoted to the determination of the structure and composition of inorganic crystals, as well as to the development of thermodynamic and kinetic models, it is only recently that research efforts have been directed towards understanding mineralization in biological systems (i.e., biomineralization). Biomineralization refers to the processes by which living organisms form inorganic solids. Studies of the processes of biomineralization under low temperature aqueous conditions have focused primarily on magnetite forming bacteria and shell forming marine organisms. Many of the biological building materials consist of inorganic minerals (calcium carbonate, calcium phosphate, silica or iron oxide) intricately combined with organic polymers (like proteins). More recently, efforts have been undertaken to explore the nature of biological activities in ancient rocks. In the absence of well-preserved microorganisms or genetic material required for the polmerase chain reaction (PCR) method in molecular phylogenetic studies, using biominerals as biomarkers offers an alternative approach for the recognition of biogenic activity in both terrestrial and extraterrestrial environments. The primary driving force in biomineralization is the interaction between organic and inorganic phases. Thus, the investigation of the ultrastructure and the nature of reactions at the molecular level occurring at the interface between inorganic and organic phases is essential to understanding the processes leading to the nucleation and growth of crystals. It is recognized that crystal surfaces can serve as the substrate for the organization of organic molecules that lead to the formation of polymers and other complex organic molecules, and in discussions of the origins of life, is referred to as organic synthesis on mineral surfaces. Furthermore, it is suggested that the interaction between mineral surfaces and simple organic molecules resulted in the formation of amino acids, RNA, and perhaps other more complex molecules such as proteins. On the other hand, in natural systems, it is recognized that functional groups on cell walls or membranes of microorganisms serve as sites of nucleation and crystallization. The precise replication of biominerals with controlled structure, morphology, size and texture is not confined to higher organisms as it also occurs in primitive prokaryotic cells such as magnetotactic bacteria and cyanobacteria. This suggests that the principal strategies of biomineralization were established early on in the evolutionary history of organisms. It is critical, therefore, to search for common mechanisms within diverse biological systems. One such common factor is the capability for organization and self-assembly. Organic macromolecules such as proteins and lipids can aggregate and polymerize forming membranes or extracellular matrix. At the organic-inorganic interface, several factors such as lattice geometry, polarity, stereochemistry and topography may act in concert to control nucleation and growth of crystals. Although several models have been proposed that discuss the significance of these factors for biomineralization, no comprehensive experimental data are available. In contrast to crystallization in exclusively inorganic systems, the kinetics of reaction and structural relationships between organic and inorganic phases in biominerals or biomimetic material is poorly understood. For example, it is not clear if the concept of epitactic growth (geometrical matching of unit cells at the interface of a secondary crystal growing on a primary crystal) applies to organic-inorganic systems. In contrast to inorganic templates that often have a smooth and rigid surface that promotes epitactic growth, biological substrates are usually rough and result in a large degree of mismatch. It is apparent that factors controlling the reaction at the crystal-matrix interface are strongly dependent upon the nature of the substrate. Therefore, characterization of the assembled organic surface and surface structure of the inorganic phase is crucial to understanding the processes of biomineralization. The focus of our research is the investigation of the processes leading to the nucleation and growth of crystals on both natural and synthetic systems through an interdisciplinary approach that integrates molecular biology, morphology and mineralogy using advanced preparation and analytical techniques. We have studied run-products, particularly magnetite, siderite and other carbonates, that resulted from extracellular biomineralization by extremophiles isolated from a variety of extreme environments ranging from permafrost to hydrothermal vent systems. The results of this study are critical to recognizing biomarkers in terrestrial and extraterrestrial environments.

Thomas-Keprta, Kathie↗

Spatiotemporal chaos near the onset of cellular growth during thin-film solidification of a binary alloy

Thin-film solidification experiments with a succinonitrile-acetone alloy are used to observe the long time-scale dynamics of cellular crystal growth at growth rates only slightly above the critical value VC = Vc(lambda sub c) for the onset of morphological instability. Under these conditions only very small amplitude cells are observed with wavelengths near the value predicted by linear stability theory lambda = lambda sub c. At long times, microstructures with wavelengths significantly finer than lambda suc c form by nucleation at defects across the interface. These interfaces do not have a unique microstructure, but seem to exhibit spatiotemporal chaos on a long time scale caused by the continual birth and death of cells by tip splitting and cell annihilation in grooves.

Lee, J. T. C.↗

Shear stabilization of solidification fronts

A linear-stability analysis is performed on the interface formed during the directional solidification of a dilute binary alloy in the presence of a time-periodic flow. In general, the flow is generated by the elliptical motion of the crystal parallel to the interface. The presence of the flow can either stabilize or destabilize the system relative to the case without flow with the result depending on the frequency and amplitude of the oscillations as well as the properties of the material. In the particular, we find that the morphological instability present in the absence of flow can be entirely suppressed with respect to disturbances of the same frequency as the oscillation.

Davis, Stephen H.↗

Convective flow effects on protein crystal growth

During the fifth semi-annual period under this grant we have pursued the following activities: (1) Characterization of the purity and further purification of lysozyme solutions, these efforts are summarized in Section 2; (2) Crystal growth morphology and kinetics studies with tetragonal lysozyme, our observation on the dependence of lysozyme growth kinetics on step sources and impurities has been summarized in a manuscript which was accepted for publication in the Journal of Crystal Growth; (3) Numerical modelling of the interaction between bulk transport and interface kinetics, for a detailed summary of this work see the manuscript which was accepted for publication in the Journal of Crystal Growth; and (4) Light scattering studies, this work has been summarized in a manuscript that has been submitted for publication to the Journal of Chemical Physics.

Rosenberger, Franz↗

Effects of Tantalum on the Temporal Evolution of a Model Ni-Al-Cr Superalloy During Phase Decomposition

The effects of a 2.0 at.% addition of Ta to a model Ni-10.0Al-8.5Cr (at.%) superalloy aged at 1073 K are assessed using scanning electron microscopy and atom-probe tomography. The gamma'(Ll2)-precipitate morphology that develops as a result of gamma-(fcc)matrix phase decomposition is found to evolve from a bimodal distribution of spheroidal precipitates, to {001}-faceted cuboids and parallelepipeds aligned along the elastically soft {001}-type directions. The phase compositions and the widths of the gamma'-precipitate/gamma-matrix heterophase interfaces evolve temporally as the Ni-Al-Cr-Ta alloy undergoes quasi-stationary state coarsening after 1 h of aging. Tantalum is observed to partition preferentially to the gamma'-precipitate phase, and suppresses the mobility of Ni in the gamma-matrix sufficiently to cause an accumulation of Ni on the gamma-matrix side of the gamma'/gamma interface. Additionally, computational modeling, employing Thermo-Calc, Dictra and PrecipiCalc, is employed to elucidate the kinetic pathways that lead to phase decomposition in this concentrated Ni-Al-Cr-Ta alloy.

Booth, Morrison, Christopher↗

Reaction of iron with hydrogen chloride-oxygen mixtures at 550 C

The reaction of iron with 1 percent HCl/0-50 percent O2/Ar has been studied at 550 C with thermogravimetry to monitor kinetics and scanning electron microscopy to characterize product morphologies. In addition, the volatile species were identified with an atmospheric pressure sampling mass spectrometer. The reaction of 1 percent HCl/Ar produces FeCl2. The reactions of 1 percent HCl/1, 10, 50 percent O2/Ar produce Fe2O3, Fe3O4, FeCl2, and FeCl3. In each case condensed phase chlorides form at the oxide/metal interface where the oxygen potential is low. The 10 and 50 percent oxygen mixtures have kinetics in the first 3 hr similar to pure oxidation with some deviations due to iron-chloride formation. The 1 percent oxygen mixture shows enhanced reaction rates over oxidation, very likely due to the formation of a porous scale.

Jacobson, N. S.↗

Optimization of residual stresses in MMC's through the variation of interfacial layer architectures and processing parameters

The objective of this work was the development of efficient, user-friendly computer codes for optimizing fabrication-induced residual stresses in metal matrix composites through the use of homogeneous and heterogeneous interfacial layer architectures and processing parameter variation. To satisfy this objective, three major computer codes have been developed and delivered to the NASA-Lewis Research Center, namely MCCM, OPTCOMP, and OPTCOMP2. MCCM is a general research-oriented code for investigating the effects of microstructural details, such as layered morphology of SCS-6 SiC fibers and multiple homogeneous interfacial layers, on the inelastic response of unidirectional metal matrix composites under axisymmetric thermomechanical loading. OPTCOMP and OPTCOMP2 combine the major analysis module resident in MCCM with a commercially-available optimization algorithm and are driven by user-friendly interfaces which facilitate input data construction and program execution. OPTCOMP enables the user to identify those dimensions, geometric arrangements and thermoelastoplastic properties of homogeneous interfacial layers that minimize thermal residual stresses for the specified set of constraints. OPTCOMP2 provides additional flexibility in the residual stress optimization through variation of the processing parameters (time, temperature, external pressure and axial load) as well as the microstructure of the interfacial region which is treated as a heterogeneous two-phase composite. Overviews of the capabilities of these codes are provided together with a summary of results that addresses the effects of various microstructural details of the fiber, interfacial layers and matrix region on the optimization of fabrication-induced residual stresses in metal matrix composites.

Pindera, Marek-Jerzy↗

Diagenetic Crystal Growth in the Murray Formation, Gale Crater, Mars

The Pahrump region (Gale Crater, Mars) marks a critical transition between sedimentary environments dominated by alluvial-to-fluvial materials associated with the Gale crater rim, and depositional environments fundamentally linked to the crater's central mound, Mount Sharp. At Pahrump, the Murray formation consists of an approximately 14-meter thick succession dominated by massive to finely laminated mudstone with occasional interbeds of cross-bedded sandstone, and is best interpreted as a dominantly lacustrine environment containing tongues of prograding fluvial material. Murray formation mudstones contain abundant evidence for early diagenetic mineral precipitation and its subsequent removal by later diagenetic processes. Lenticular mineral growth is particularly common within lacustrine mudstone deposits at the Pahrump locality. High-resolution MAHLI images taken by the Curiosity rover permit detailed morphological and spatial analysis of these features. Millimeter-scale lenticular features occur in massive to well-laminated mudstone lithologies and are interpreted as pseudomorphs after calcium sulfate. The distribution and orientation of lenticular features suggests deposition at or near the sediment-water (or sediment-air) interface. Retention of chemical signals similar to host rock suggests that original precipitation was likely poikilotopic, incorporating substantial amounts of the primary matrix. Although poikilotopic crystal growth is common in burial environments, it also occurs during early diagenetic crystal growth within unlithified sediment where high rates of crystal growth are common. Loss of original calcium sulfate mineralogy suggests dissolution by mildly acidic, later-diagenetic fluids. As with lenticular voids observed at Meridiani by the Opportunity Rover, these features indicate that calcium sulfate deposition may have been widespread on early Mars; dissolution of depositional and early diagenetic minerals is a likely source for both calcium and sulfate ion-enrichment in burial fluids that precipitated in ubiquitous late-stage hydrofracture veins

Kah, L. C.↗

Morphological and convective instabilities during solidification

Linear stability theory is employed in the present analysis of flow stability between two vertical, infinite, rigid coaxial cylinders at different temperatures. These calculations have been prompted by, and are found to be in general agreement with, experiments on succinonitrile. A long, vertical cylinder sample of this material was heated so that a vertical melt annulus formed between the coaxial heater and the surrounding crystal/melt interface. Above a critical Grashof number of about 200, a helical crystal/melt interface formed which steadily rotated about the cylinder axis and whose wave speed was several orders of magnitude lower than the base flow velocity.

Coriell, S. R.↗

In Situ Monitoring of Crystal Growth Using MEPHISTO, Mission STS 87-Program USMP-4: Experimental Analysis

This report summarizes the results of the In situ Monitoring of Crystal Growth Using MEPHISTO (Material por l'Etude des Phenomenes Interessant de la Solidification sur Terre et en Orbite) experiment on USMP-4. The report includes microstructural and compositional data obtained during the first year of the post flight analysis, as well as numerical simulation of the flight experiment. Additional analyses are being continued and will be reported in the near future. The experiments utilized MEPHISTO hardware to study the solidification and melting behavior of bismuth alloyed with 1 at% tin. The experiments involved repeated melting and solidification of three samples, each approximately 90 cm long and 6mm in diameter. Half of each sample also included a 2 mm. diameter growth capillary, to assist in the formation of single grain inside. One sample provided the Seebeck voltage generated during melting and freezing processes. Another one provided temperature data and Peltier pulsed demarcation of the interface shape for post flight analysis. The third sample provided resistance and velocity measurements, as well as additional thermal data. The third sample was also quenched at the end of the mission to preserve the interface composition for post flight determination. A total of more than 45cm of directionally solidified alloy were directionally solidified at the end of the flight for post mission structural and compositional characterization. Metallurgical analysis of the samples has shown that the interfacial kinetics play a key role in controlling the morphological stability of faceted alloys. Substantial differences were observed in the Seebeck signal between the ground-based experiments and the space-based experiments. The temperature gradient in the liquid for the ground-based experiments was also significantly lower than the temperature gradient in the liquid for the space-based experiments. Both of these observations indicate significant influence of liquid convection for the ground-based experiments.

Abbaschian, Reza↗

Simulating the Clamped Tapered Beam Specimen Under Quasi-Static and Fatigue Loading Using Floating Node Method

As part of the NASA Advanced Composites Project (ACP), a sub-element has been designed to provide validation data for progressive damage analysis models. The clamped tapered beam is a cross-ply laminated composite specimen designed to validate the simulation of the onset of matrix cracks and their interaction with delaminations, including delamination migration. A tapered geometry was used to localize the first damage occurrence in the tapered region, without prescribing an initial crack. The boundary and loading conditions were chosen to favor delamination growth and subsequent migration after the first damage occurrence. The typical sequence of events consists of a matrix crack located at the tapered region, leading to delamination onset, followed by delamination growth and subsequent delamination migration to a different interface via a dominant matrix crack. The Clamped Tapered Beam (CTB) was tested in both quasi-static and fatigue regimes. The results obtained are used in this study to assess and validate a methodology based on the Floating Node Method (FNM) implemented as an Extended Interface Element. In this methodology, quasi-static and fatigue damage formation and development are modeled by combining FNM to represent crack networks, with Directional Cohesive Zone Elements (DCZE) and Virtual Crack Closure Technique (VCCT), respectively. Qualitatively, the methodology is capable of predicting the sequence of events and overall failure morphology. Quantitatively, the simulation results generally bound the experimental data, based on the range of the characterization data used. In this paper, the results from quasi static and fatigue simulations are compared and correlated with experimental data.

Seshadri, B. R.↗

Immiscible phase incorporation during directional solidification of hypermonotectics

Solidification processes in immiscible samples were investigated by directly observing the events taking place at the solid-liquid interface during directional solidification. Visualization of these events was made possible through the use of a transparent metal analog system and a temperature gradient stage assembly fitted to an optical microscope. The immiscible transparent analog system utilized was the succinonitrile-glycerol system. This system has been shown to exhibit the same morphological transitions as observed in metallic alloys of monotectic composition. Both monotectic and hypermonotectic composition samples were directionally solidified in order to gain an improved understanding of the manner in which the excess hypermonotectic liquid is incorporated into the solidifying structure. The processing conditions utilized prevented sedimentation of the excess hypermonotectic liquid by directionally solidifying the samples in very thin (13 microns), horizontally oriented cells. High thermal gradient to growth rate ratios (G/R) were used in an effort to prevent constitutional supercooling and the subsequent formation of L(sub 2) droplets in advance of the solidification front during the growth of fibrous composite structures. Results demonstrated that hypermonotectic composites could be produced in samples up to two weight percent off of the monotectic composition by using a G/R ratio greater than or equal to 4.6 x 10(exp 4) C(s)/mm(sup 2) to avoid constitutional supercooling. For hypermonotectic samples processed with G/R ratios below 4.6 x 10(exp 4) C(s)/mm(sup 2), constitutional supercooling occurred and resulted in slight interfacial instability. For these samples, two methods of incorporation of the hypermonotectic liquid were observed and are reported. The correlation between the phase spacing, lambda, and the growth rate, R, was examined and was found to obey a relationship generally associated with a diffusion controlled coupled growth process. For samples with compositions ranging from the monotectic composition up to 2 percent off of the monotectic composition, data indicated that the square of the phase spacing (lambda) varied linearly with the inverse of the growth rate (R).

Andrews, J. Barry↗

In-Situ Monitoring of a Bismuth-Tin Alloy Solidification Using MEPHISTO

Experiments were carried out to study the morphological stability of Bi- 1 atomic % Sn alloys using the MEPHISTO directional solidification apparatus aboard Space Shuttle Columbia (STS-87, launched Nov. 19, 1997) and in ground-based studies. The Seebeck signal and temperature measurements indicate that convection was significant for ground-based studies. In the space-based experiments, interface breakdown was observed at growth velocities of 6.7, 27, and 40 microns/sec, but not at 1.8 and 3.3 microns/sec.

Abbaschian, Reza↗