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At least 451 records · Page 25

Differentiating Thermal Conductances at Semiconductor Nanocrystal/Ligand and Ligand/Solvent Interfaces in Colloidal Suspensions

Infrared-pump, electronic-probe (IPEP) spectroscopy is used to measure heat flow into and out of CdSe nanocrystals suspended in an organic solvent, where the surface ligands are initially excited with an infrared pump pulse. Subsequently, the heat is transferred from the excited ligands to the nanocrystals and in parallel to the solvent. Parallel heat transfer in opposite directions uniquely enables us to differentiate the thermal conductances at the nanocrystal/ligand and ligand/solvent interfaces. Using a novel solution to the heat diffusion equation, we fit the IPEP data to find that the nanocrystal/ligand conductances range from 88 to 135 MW m –2 K –1 and are approximately 1 order of magnitude higher than the ligand/solvent conductances, which range from 7 to 26 MW m –2 K –1 . Transient nonequilibrium molecular dynamics (MD) simulations of nanocrystal suspensions agree with IPEP data and show that ligands bound to the nanocrystal by bidentate bonds have more than twice the per-ligand conductance as those bound by monodentate bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Faster ablative Kelvin–Helmholtz instability growth in a magnetic field

Shear flows along a plasma interface will quickly grow unstable due to the Kelvin–Helmholtz instability. If there is a concurrent temperature gradient across the interface, higher modes are stabilized by the thermal diffusion. These ablative effects must be considered in, for example, jet features in inertial confinement fusion hot-spots, or plasma plumes in young supernovae. We show that magnetization of the plasma can greatly affect the instability, even if magnetic pressure is small. This is because electrons are localized by their gyromotion, reducing the heat flux and material ablation. We use a two-dimensional numerical extended-magnetohydrodynamics approach to assess this effect for dense fusion conditions. In comparison with the unmagnetized case, self-generated Biermann fields make only a minor difference to growth rates. However, simulations with a large 50 kT external field found that the growth rate of the least stable mode increased by 40%. In conclusion, this has implications for mix processes in Z-pinches and magnetized inertial confinement fusion concepts.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Modeling diffusion and depletion in high-aspect-ratio atomic layer deposition processes: Process parameters and manufacturing impacts

Atomic layer deposition (ALD) is a powerful technique for modifying the surface chemistry and properties of substrates with complex and nonplanar topologies. However, achieving uniform and conformal deposition on ultrahigh-aspect-ratio substrates remains challenging, typically requiring large quantities of precursors and long exposure times. Furthermore, process optimization is often performed empirically and involves substantial trial and error. In this work, we perform a combined experimental and computational study of ALD Al 2 O 3 infiltration into silica aerogel monoliths (aspect ratio >10 5 ). A reaction-diffusion model is used to explore the effects of key processing parameters, namely, exposure time per dose, precursor source temperature, number of aerogels in the reactor, and reactor volume. The model is based on quasi-static mode ALD, where the dosed precursor is held in the chamber for a fixed period of time before purging. We analyze the trade-offs between process throughput and precursor utilization for each of these parameters. Furthermore, we investigate the co-optimization and interactions between multiple process parameters, demonstrating the potential for further improvements. Furthermore, this physics-based model can be used to identify a set of process parameters for high-aspect-ratio ALD that meet specific manufacturing objective functions, including throughput, cost, and sustainability.

Aerogel↗

Improving the damage tolerance of Si 3 N 4 by forming laminate composites with refractory metals

The objective of this research was to demonstrate that the damage tolerance of Si 3 N 4 could be significantly improved by forming laminate composites with refractory metals, providing materials that undergo graceful failure, rather than the fast-fracture mechanism exhibited by monolithic Si 3 N 4 . A damage tolerant Si 3 N 4 could be used as a ring material in an all-ceramic bearing, decreasing the chance for catastrophic failure if the ring is stressed in tension during operation. The technical approach formed a laminate composite material using alternating Si 3 N 4 -metallic layers, with both outer layers being Si 3 N 4 to take advantage of its greater wear resistance, chemical stability, and thermal stability. The metallic layers are designed to arrest any cracks in the outer layers, thus producing a toughened Si 3 N 4 and avoiding the catastrophic failure behavior exhibited by monolithic ceramics. The laminate composites were fabricated using a combination of tape-casting Si 3 N 4 and metals from slurries, as well as metal foils, followed by hot pressing at 1500°C. The metallic materials employed were chromium, titanium, and tantalum. Analysis confirmed that the interfaces were well formed, and the laminates with chromium and titanium formed intermetallic compounds more readily than the composites with tantalum. The Si 3 N 4 -Ta laminates demonstrated crack deflection and bridging behavior during failure and flexural strength of 800–900 MPa. The hardness and elastic modulus of Si 3 N 4 -Ta laminates measured by nanoindentation were similar to those reported in literature. The hardness across the interface of the Si 3 N 4 -Ta composite varied according to the composition of the interface, which displayed a profile indicative of a diffusion bond.

36 MATERIALS SCIENCE↗

Intermodule ventilation studies for the Space Station

This paper examines the ability of the Space Station intermodule ventilation system to maintain centralized control of CO2 removal and O2 supply. The resulting concentration gradients that will arise are calculated by assuming steady state, ideal gas, isothermal conditions, and perfect mixing of air within and between the pressurized elements. In order to estimate the degree of mixing actually obtained for a given ventilation scheme, a program has been developed based on a potential flow solution technique. Preliminary results from this study indicate that substantial short circuiting and recirculation air flow patterns could arise if a simple duct and diffuser air exchange method at the docking port interface were employed.

Davis, Roy G.↗

The kinetics of the Au-InP interaction

An analysis of the reaction of Au and Au-In alloys with InP has permitted the identification of the mechanisms occurring during the first two stages of the Au-InP interaction. The first stage of the interaction, during which the Au is converted to a saturated Au (In) solution, is controlled by the vacancy-generation rate at the free surface of the metallization. The activation energy for this process is the activation energy for Au self-diffusion. Evidence is presented for the existence of large localized variations in this value due to surface related effects. At the completion of stage I stage II becomes active and continues until the metallization is converted to Au3In. This process, proceeding via an interstitial interchange mechanism, is many orders of magnitude slower than stage I. The rate-limiting step, with an activation energy of 2.8 eV, is shown to be the diffusion of In from the InP-metal interface. The P atoms that are released when In enters the metallization during stage I leave the system without reacting, whereas in stage II they form a compound (Au2P3) at the InP-metal interface. The presence of the Au2P3 severely retards the stage II interaction rate.

Fatemi, Navid S.↗

Color image processing and object tracking workstation

A system is described for automatic and semiautomatic tracking of objects on film or video tape which was developed to meet the needs of the microgravity combustion and fluid science experiments at NASA Lewis. The system consists of individual hardware parts working under computer control to achieve a high degree of automation. The most important hardware parts include 16 mm film projector, a lens system, a video camera, an S-VHS tapedeck, a frame grabber, and some storage and output devices. Both the projector and tapedeck have a computer interface enabling remote control. Tracking software was developed to control the overall operation. In the automatic mode, the main tracking program controls the projector or the tapedeck frame incrementation, grabs a frame, processes it, locates the edge of the objects being tracked, and stores the coordinates in a file. This process is performed repeatedly until the last frame is reached. Three representative applications are described. These applications represent typical uses and include tracking the propagation of a flame front, tracking the movement of a liquid-gas interface with extremely poor visibility, and characterizing a diffusion flame according to color and shape.

Klimek, Robert B.↗

Ignition, Burning, and Extinction of a Strained Fuel Strip

Flame structure and ignition and extinction processes associated with a strained fuel strip are explored numerically using detailed transport and complex kinetics for a propane-air reaction. Ignition modes are identified that are similar to those predicted by one-step activation energy asymptotics, i.e., modes in which diffusion flames can ignite as independent or dependent interfaces, and modes in which single premixed or partially premixed flames ignite. These ignition modes are found to be dependent on critical combinations of strain rate, fuel strip thickness, and initial reactant temperatures. Extinction in this configuration is seen to occur due to fuel consumption by adjacent flames, although viscosity is seen to have the effect of delaying extinction by reducing the effective strain rate and velocity field experienced by the flames.

Selerland, T.↗

Ignition, Burning and Extinction of a Strained Fuel Strip with Complex Kinetics

Flame structure and ignition and extinction processes associated with a strained fuel strip are explored numerically using detailed transport and complex kinetics for a propane-air reaction. Ignition modes are identified that are similar to those predicted by one-step activation energy asymptotics, i.e., modes in which diffusion flames can ignite as independent or dependent interfaces and modes in which single premixed or partially premixed flames ignite and burn. These ignition modes have been found to be dependent on critical combinations of strain rate, fuel strip thickness and initial reactant temperatures. The formation of NO/NO2 is found to be strongly dependent on strain rate and the local molecular mixing of reactants which occurs as a consequence of strain. Extinction in this configuration is seen to occur due to fuel consumption by adjacent flames, although viscosity is seen to have the effect of delaying extinction by reducing the effective strain rate experienced by the flames. Response of the flames to oscillatory strain rates is seen to be strongly dependent on the amplitude and frequency of the oscillation.

Selerland, T.↗

Influences of Models on the Unsteady Pressure Characteristics of the NASA National Transonic Facility

Pressure fluctuations have been measured over the course of several tests in the National Transonic Facility to study unsteady phenomenon both with and without the influence of a model. Broadband spectral analysis will be used to characterize the length scales of the tunnel. Special attention will be given to the large-scale, low frequency data that influences the Mach number and force and moment variability. This paper will also discuss the significance of the vorticity and sound fields that can be related to the Common Research Model and will also highlight the comparisons to an empty tunnel configuration. The effectiveness of vortex generators placed at the interface of the test section and wind tunnel diffuser showed promise in reducing the empty tunnel unsteadiness, however, the vortex generators were ineffective in the presence of a model.

Jones, Gregory↗

Deep Chandra Observation and Numerical Studies of the Nearest Cluster Cold Front in the Sky

We present the results of a very deep (500 ks) Chandra observation, along with tailored numerical simulations, of the nearest, best resolved cluster cold front in the sky, which lies 90 kpc (19 arcmin) to the north-west of M87. The northern part of the front appears the sharpest, with a width smaller than 2.5 kpc (1.5 Coulomb mean free paths; at 99 per cent confidence). Everywhere along the front, the temperature discontinuity is narrower than 4-8 kpc and the metallicity gradient is narrower than 6 kpc, indicating that diffusion, conduction and mixing are suppressed across the interface. Such transport processes can be naturally suppressed by magnetic fields aligned with the cold front. Interestingly, comparison to magnetohydrodynamic simulations indicates that in order to maintain the observed sharp density and temperature discontinuities, conduction must also be suppressed along the magnetic field lines. However, the northwestern part of the cold front is observed to have a non-zero width. While other explanations are possible, the broadening is consistent with the presence of Kelvin-Helmholtz instabilities (KHI) on length-scales of a few kpc. Based on comparison with simulations, the presence of KHI would imply that the effective viscosity of the intracluster medium is suppressed by more than an order of magnitude with respect to the isotropic Spitzer-like temperature dependent viscosity. Underneath the cold front, we observe quasi-linear features that are approximately 10 per cent brighter than the surrounding gas and are separated by approximately 15 kpc from each other in projection. Comparison to tailored numerical simulations suggests that the observed phenomena may be due to the amplification of magnetic fields by gas sloshing in wide layers below the cold front, where the magnetic pressure reaches approximately 5-10 per cent of the thermal pressure, reducing the gas density between the bright features.

hydrodynamics↗

Diffusivities of Redox-Sensitive Elements in Basalt vs. Oxygen Fugacity Determined by LA-ICP-MS

Several diffusion experiments were conducted in a piston cylinder device across a range of oxygen fugacities (FMQ-3 FMQ-1.2, FMQ+6) at 1 GPa and 1300 C. This was done to explore the effects of oxygen fugacity (fO2) on diffusivity of redox sensitive trace elements. This allows investigation of how these elements diffuse across the fO2 range encountered in different reservoirs on planets and moons in our solar system. The University of Rochester LA-ICP-MS system was used for analysis of samples. Analyses were conducted using an Agilent 7900 quadrupole mass spectrometer connected to a Photon Machines 193 nm G2 laser ablation (LA) system equipped with a HelEx 2-volume sample chamber. Spots used were 35 micrometers circles spaced at 65 micrometers intervals. Laser fluence was 7.81 J/cm^2 with a rep rate of 10 Hz. The iolite software package was used to reduce data collected from laser ablation analysis of experiments with Si-29 used as the internal standard isotope. Iolite's global fit module was used to simultaneously fit elements' diffusivities in each experiment while keeping the Matano interface constant. Elements analysed include V, Nb, W, Mo, La, Ce, Pr, Sm, Eu, Gd, Ta, and W. Figures

Szumila, Ian↗

J-OCTA Applications to in Space Manufacturing and Nanofluidic Technologies

We consider examples of J-OCTA software application to physics-based analysis of in-space manufacturing technologies. Firstly, we consider an atomistic model of thermal welding at the polymer-polymer interface for applications to 3D manufacturing by following diffusion of polymer chains. We show that each component of the polymer blend has its own characteristic time of diffusion and that both strain–stress and shear viscosity curves agree with experimental data. Next, nonlinear shrinkage of the metal part during manufacturing by bound metal deposition under microgravity, is considered using a multi-scale physics-based approach that spans from atomistic dynamics to full-part shrinkage. At the smallest scale we use atomistic dynamics to simulated sintering of a few Ti6Al4V nanoparticles, study sintering mechanisms and estimate important parameters including grain boundary width and diffusion rates of the atoms at the surface that are used at the other scales of modelling. Finally, we analyse selective ionic conduction through an artificial nanopore in a graphene sheet motivated by applications to desalination and energy harvesting. We build distributions of the number and orientation of water molecules in the ion’s hydration shells providing novel insight into the ion-water-carbon interaction at the nanopore.

molecular dynamics↗

Modeling of a Non-Dilute Alloy Solidification Under Terrestrial and Microgravity Conditions

A general finite element model of non-dilute alloy solidification was used to simulate growth of HgCdTe from the melt. 2-D and 3-D models with and without Oberbeck-Boussinesq (O-B) approximation were used. Verification of the 3-D model was based on experimental data. The location and the shape of the interface were determined using melting temperatures obtained from the HgCdTe liquidus curve. Double-diffusive convection in the melt is caused by radial temperature gradients and by rejection at the solid-melt interface of the heavier HgTe-rich solute. Because of these complicating factors, dimensional rather than non-dimensional modeling was performed. Models based on complete set of Navier-Stokes equations for compressible media are superior to the O-B approximation in microgravity, because they provide more accurate estimation of convection.

Bune, Andris V.↗

Dendritic growth in the presence of convection

The motion of the freezing front between a dendritic crystal and a supercooled liquid is studied using an interface evolution equation derived from a boundary integral transformation of the transient convective-diffusion equation. A new steady-state theory is introduced that incorporates the effects of convection in dendritic growth. It is shown that in the absence of capillary effects the shape of the crystal-melt interface is a paraboloid of revolution, similar to that found in situations where diffusion is the sole heat transfer mechanism. A relation between the supercooling, the product of the tip velocity and tip radius, and the strength of the flow is derived which reduces to the well-known Ivantsov theory in the absence of convection. A non-linear interface-tracking algorithm is developed and used to study the temporal and spatial evolution of the dendritic interface. The important role of capillarity and convection on the interface dynamics is established and the response of the interface to finite amplitude disturbances is examined for the first time. Tip splitting is identified as the dominant destabilization mechanism in the limit of zero surface tension. Finite surface tension leads to interface stabilization, irrespective of the magnitude and structure of the external perturbations. Finally, convection significantly decreases the magnitude of the freezing velocity.

Beaghton, Pantelis John↗

Insights into Sorption and Molecular Transport of Aqueous Glucose into Zeolite Nanopores

Liquid-phase heterogeneous catalysis using zeolites is important for biomass conversion to fuels and chemicals. There is a substantial body of work on gas-phase sorption in zeolites with different topologies; however, studies investigating the diffusion of complex molecules in liquid medium into zeolitic nanopores are scarce. Here, we present a molecular dynamics study to understand the sorption and diffusion of aqueous β-d-glucose into β-zeolite silicate at T = 395 K and P = 1 bar. Through 2-μs-long molecular dynamics trajectories, we reveal the role of the solvent, the kinetics of the pore filling, and the effect of the water model on these properties. We find that the glucose and water loading is a function of the initial glucose concentration. Although the glucose concentration increases monotonically with the initial glucose concentration, the water loading exhibits a nonmonotonic behavior. At the highest initial concentration (~20 wt %), we find that the equilibrium loading of glucose is approximately five molecules per unit cell and displays a weak dependence on the water model. Glucose molecules follow a single-file diffusion in the nanopores due to confinement. Here, the dynamics of glucose and water molecules slows significantly at the interface. The average residence time for glucose molecules is an order of magnitude larger than that in the bulk solution, while it is about twice as large for the water molecules. Our simulations reveal critical molecular details of the glucose molecule’s local environment inside the zeolite pore relevant to catalytic conversion of biomass to valuable chemicals.

09 BIOMASS FUELS↗

Concentration Dependent Interfacial Chemistry of the NaOH(aq):Gibbsite Interface

Caustic conditions are often employed for dissolution of a wide variety of minerals, where ion sorption, surface diffusion, and interfacial organization impact surface reactivity. In the case of gibbsite, gamma-Al(OH)3, the chemistry at the NaOH(aq) interface is deeply intertwined with industrial processing of aluminum, including metal production and the disposition of Al-containing wastes. To date, little is known about the structure, speciation, and dynamic behavior of gibbsite interfaces (and that of many other minerals) with NaOH(aq)—particularly as a function of ionic strength. Yet concentration-dependent interfacial organization and dynamics are a critical starting point to develop a fundamental understanding of the factors that influence dissolution. This work reports equilibrium molecular dynamics simulations of the gamma-Al(OH)3:NaOH(aq) interface, revealing the sorption behavior and speciation of ions from 0.5–10 M [NaOH]. As inner-sphere complexes, Na+ primarily coordinates to the side of the gibbsite hexagonal cavities, while OH accepts hydrogen-bonding from the surface-OH groups. The mobility of inner-sphere Na+ and OH ions is significantly reduced due to a strong surface affinity in comparison to previous reports of NaCl, CaCl2, or BaCl2 electrolytes. At high [NaOH], contact ion pairing that is observed in the bulk solution is partially disrupted upon sorption to the gibbsite surface by the individual ion–surface interactions. The molecular-scale changes to surface speciation and competition between ion–surface vs. ion–ion interactions influence surface characterization of gibbsite and potential dissolution processes, providing a valuable baseline for starting conditions needed within future reactive molecular simulations.

alkaline solutions, IDREAM, gibbsite, molecular dy↗

Growth of Megaspherulites In a Rhyolitic Vitrophyre

Megaspherulites occur in the middle zone of a thick sequence of rhyolitic vitrophyre that occupies a small, late Eocene to early Oligocene volcanic-tectonic basin near Silver Cliff, Custer County, Colorado. Diameters of the megaspherulites range from 0.3 m to over 3.66 m, including a clay envelope. The megaspherulites are compound spherulites. consisting of an extremely large number (3.8 x 10(exp 9) to 9.9 x 10(exp 9)) of individual growth cones averaging 3 mm long by 1.25 mm wide at their termination. They are holocrystalline, very fine- to fine-grained, composed of disordered to ordered sanidine (orthoclase) and quartz, and surrounded by a thin K-feldspar, quartz rich rind, an inner clay layer with mordenite, and an outer clay layer composed wholly of 15 A montmorillonite. Whole rock analyses of the megaspherulites show a restricted composition from their core to their outer edge, with an average analyses of 76.3% SiO2, 0.34% CaO, 2.17% Na2O, 6.92% K2O, 0.83% H2O+ compared to the rhyolitic vitrophyre from which they crystallize with 71.07% SiO2, 0.57% CaO, 4.06% Na2O,4.l0% K2O, and 6.40% H2O+. The remaining oxides of Fe2O3 (total Fe), A12O3, MnO,MgO, TiO2, P2O5, Cr2O3, and trace elements show uniform distribution between the megaspherulites and the rhyolitic vitrophyre. Megaspherulite crystallization began soon after the rhyolitic lava ceased to flow as the result of sparse heterogeneous nucleation, under nonequilibrium conditions, due to a high degree of undercooling, delta T. The crystals grow with a fibrous habit which is favored by a large delta T ranging between 245 C and 295 C, despite lowered viscosity, and enhanced diffusion due to the high H2O content, ranging between 5% and 7%. Therefore, megaspherulite growth proceeded in a diffusion controlled manner, where the diffusion, rate lags behind the crystal growth rate at the crystal-liquid interface, restricting fibril lengths and diameters to the 10 micron to 15 micron and 3 micron and 8 micron ranges respectively. Once diffusion reestablishes itself at the crystallization front, a new nucleation event occurs at the terminated tips of the fibril cones and a new cone begins to develop with a similar orientation (small angle branching) to the earlier cones. During crystallization, these fibril cones impinge upon each other, resulting in fibril cone-free areas. These cone-free areas consist of coarser, fine-grained phases, dominated by quartz, which crystallized from the melt as it accumulated between the crystallizing K-feldspar fibrils of the cones. The anhydrous nature of the disordered to ordered sanidine (orthoclase) and quartz, suggests that water in the vitrophyre moved ahead of the crystallization front, resulting in a water rich fluid being enriched in Si, K, Na, Mg, Ca, Sr, Ba, and Y. The clay layers associated with the megaspherulites are therefore, the result of the deuteric alteration between the fractionated water and the vitrophyre, as indicated by the presence of the minerals mordenite and montmorillonite. This silica rich fluid also resulted in the total silicification of the megaspherulites within the upper 3 m of the vitrophyre.

Smith, Robert K.↗