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At least 109 records · Page 6

Real-Time X-Ray Transmission Microscopy for Fundamental Studies Solidification

High resolution real-time X-ray Transmission Microscopy, XTM, has been applied to obtain information fundamental to solidification of optically opaque metallic systems. We have previously reported the measurement of solute profile in the liquid, phase growth, and detailed solid-liquid interfacial morphology of aluminum based alloys with exposure times less than 2 seconds. Recent advances in XTM furnace design have provided an increase in real-time magnification (during solidification) for the XTM from 4OX to 16OX. The increased magnification has enabled for the first time the XTM imaging of real-time growth of fibers and particles with diameters of 5 micrometers. We have applied this system to study of the kinetics of formation and morphological evolution of secondary fibers and particles in Al-Bi monotectic alloys to observe a previously unreported velocity dependent thermo-capillary depletion mechanism for Bi rich liquid which can penetrate many fiber diameters into the solid-liquid interface. In this talk we will discuss application of the XTM to the study the fundamentals of monotectic and eutectic solidification, the enhancement of XTM data with precise solid liquid interfacial temperature and thermal gradient measurement techniques, and the application of this technology to the study of the fundamentals of solidification in microgravity,

Curreri, Peter A.↗

Effects of Heating Configuration and Operating Parameters on Heat Transfer and Interfacial Physics of Microgravity Flow Boiling With Subcooled Inlet Conditions –Experiments Onboard the International Space Station

This study is part of the Flow Boiling and Condensation Experiment (FBCE), a collaborative effort between the Purdue University Boiling and Two-Phase Flow Laboratory (PU-BTPFL) and the NASA Glenn Research Center. The FBCE fitted with the Flow Boiling Module (FBM) was launched to the International Space Station (ISS) in August 2021 and experiments were successfully performed from February to July 2022 to amass a large microgravity-flow-boiling database. This study is focused on heat transfer and flow visualization of microgravity flow boiling of n-Perfluorohexane in a rectangular channel of 5.0 mm height, 2.5 mm width (heated), and 114.6 mm length, with subcooled inlet conditions. High-speed-video photography is utilized to present flow patterns and temporal interfacial behavior. Heat transfer results are presented in the form of flow boiling curves and both parametric curves and streamwise profiles of wall temperature and heat transfer coefficient. Firstly, the parametric effects of mass velocity (199.4 – 3200.0 kg/m 2 s), inlet subcooling (0.2 – 46.0°C), and inlet pressure (124.2 – 176.7 kPa), on the aforementioned aspects are assessed for double-sided heating to establish them for a microgravity environment. Of these three parameters, mass velocity and inlet subcooling mostly determine the microgravity flow boiling behavior, while inlet pressure plays an insignificant role. Flow patterns for double-sided heating are more complex than those for single-sided heating due to interaction between the two vapor layers. Vapor interaction is minimized at high subcoolings and high mass velocities due to strong condensation offered by the subcooled bulk liquid layer separating them. Despite the different flow patterns, both single- and double-sided heating generally result in similar parametric trends and local heat transfer coefficients for similar operating conditions. Flow instabilities manifest as temporal flow anomalies and temperature oscillations, and their severity increases with increasing boiling number. Secondly, the effects of heating configuration are analyzed by comparing and contrasting several aspects of single- and double-sided heating data. The heat fluxes at which onset of nucleate boiling degradation (ONBD) and critical heat flux (CHF) occur are distinctly different for single- and double-sided heating. There exists a threshold inlet subcooling demarcating the dominance of flow acceleration and condensation effects in vapor removal from the near-wall region and replenishment of fresh liquid for boiling. Above the threshold, condensation from the near-wall region is dominant and single-sided heating yields higher heat fluxes, and below it, acceleration is dominant and double-sided yields higher heat fluxes. At mass velocity in the range of 200 – 2400 kg/m 2 s, the threshold inlet subcooling lies in the approximate range of 20 – 30°C (corresponding inlet quality of roughly -0.40 – -0.20).

Microgravity↗

Hot-Carrier Transfer at Photocatalytic Silicon/Platinum Interfaces

Interfacial charge transfer from silicon to heterogeneous catalysts plays a key role in silicon-based photoelectrochemical systems. In general, prior to interfacial charge transfer, carriers that are generated by photons with energies above the bandgap dissipate the excess kinetic energy via hot-carrier cooling, and such energy loss limits the maximum power conversion efficiency. The excess energy of hot-carriers, however, could be utilized through hot-carrier transfer from silicon to the catalysts, but such hot-carrier extraction has not yet been demonstrated. In this work, we exploit transient reflection spectroscopy to interrogate charge transfer at the interface between silicon and platinum. Additionally, quantitative modeling of the surface carrier kinetics indicates that the velocity of charge transfer from silicon to platinum exceeds 2.6 x 10 7 cm s -1 , corresponding to an average carrier temperature of extracted carriers of ~600 K, two times higher than the lattice temperature. The charge transfer velocity can be controllably reduced by inserting silica spacing layers between silicon and platinum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Energy-Resolved Femtosecond Hot Electron Dynamics in Single Plasmonic Nanoparticles

Efficient excitation and harvesting of hot carriers from nanoscale metals is central to many emerging photochemical, photovoltaic, and ultrafast optoelectronic applications. Nevertheless, direct experimental evidence of the energy-dependent femtosecond dynamics in ubiquitous tens-of-nanometer gold structures remains elusive, despite the potentially rich interplay between interfacial and internal plasmonic fields, excitation distributions, and scattering processes. To explore the effects of nanoscale structure on these dynamics, we employ simultaneous time-, angle-, and energy-resolved photoemission spectroscopy of single plasmonic nanoparticles. Photoelectron velocity and electric field distributions reveal bulk-like ballistic hot electron transport in different geometries, lacking any signatures of surface effects. Energy-resolved dynamics are measured in the 1–2 eV range and extrapolated to lower energies via Boltzmann theory, providing a detailed view of hot electron lifetimes within nanoscale gold. Here, we find that particles with relevant dimensions as small as 10 nm serve as exemplary platforms for studying intrinsic metal dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diffusive crack growth at a bimaterial interface

The diffusional microcrack growth behavior in a bimaterial system is investigated with an aim at estimating service life of advanced ceramic composites under creep-rupture conditions. The crack is assumed to grow via a coupled surface and grain-boundary diffusion under steady state conditions. The tensile stress distribution along the interface ahead of the moving crack tip is solved, and it is found that a new length parameter exists as a scaling factor for which the solution becomes identical to the single phase case when plotted on the nondimensional physical plane. In contrast to the elastic stress solution which shows singularity at the tip, together with oscillatory character away from the tip, the creep stresses have a peak value away from the tip due to a wedging effect and interfacial sliding eliminates stress oscillation resulting in a decoupling between mode I and mode II loading. This solution ties the far-field loading parameter to the crack tip conditions in terms of the unknown crack velocity to give a specific V-K(1) relationship. It is shown that an exponent of 12 in the conventional crack growth power law emerges at the higher applied stress range.

Chuang, Tze-Jer↗

Effects of Convective Transport of Solute and Impurities on Defect-Causing Kinetics Instabilities in Protein Crystallization

The objective of the proposed research is to obtain further insight into the onset and development of the defect-causing instabilities that anise due to the coupling of the bulk transport and nonlinear-interfacial kinetics during growth in the mixed regime, utilizing the reduction of the convective contribution to the bulk transport under microgravity. These studies will build upon the data on the effects of quantitative variations of the forced convection velocity on the averaged and time-dependent kinetic behavior of protein crystal growth systems that have recently been obtained in our laboratory.

Vekilov, Peter G.↗

An implicit, sharp numerical treatment of viscous terms at arbitrarily shaped liquid-gas interfaces in evaporative flows

We report a novel methodology for accurate treatment of viscous terms in evaporation problems. The proposed scheme is an extension of the sharp viscous treatment of Kang et al. (2000) [7] to 3D phase change problems. To ensure accuracy and grid converging solutions, a new implicit approach to computing viscous fluxes across the phase interfaces is proposed, which was previously unavailable in fixed grid numerical schemes. Analytical relations were derived for the jump in velocity gradients across the 2D and 3D phase interfaces, an important constituent of the proposed scheme. The relations show a non-vanishing jump in the tangential gradients across the phase interface that are associated with evaporative flux and interfacial curvature. The proposed methodology demonstrated first order accuracy in canonical test cases. It is general and applicable to arbitrarily oriented interfaces, and can be readily implemented in existing evaporation flow solvers.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Alloying induces directionally-dependent mobility and alters migration mechanisms of faceted grain boundaries

Faceted grain boundaries exhibit unusual segregation and migration tendencies. To gain a deeper understanding of how solute atoms interact with faceted interfacial structures during migration, this study probes the migration behavior of a faceted Σ11 boundary in Cu doped with Ag atoms. Furthermore, the solutes are found to segregate to the facet with more free volume and strongly reduce boundary velocity in one migration direction, but not the other, due to the presence of a directionally-dependent motion mechanism that can escape solute pinning and therefore speed up migration. Hence, a new mechanism of chemically-induced anisotropy in grain boundary mobility is uncovered by these simulations.

36 MATERIALS SCIENCE↗

Intergranular fracture of lithium fluoride-22 percent calcium fluoride hypereutectic salt at 800 K

Substantial strain-hardening was noted during the initial stages of deformation in constant-velocity compression tests conducted on as-cast samples of the LiF-22 mol pct CaF2 hypereutectic salt at 800 K. The deformed specimens exhibited extensive grain-boundary cracking and cavitation, suggesting that such cracking, in conjunction with interfacial sliding, is important for cavity nucleation at grain boundaries and at the LiF-CaF2 interfaces. Cavity growth and interlinkage occur through the preferential failure of the weaker LiF phase.

Raj, Subramanium V.↗

Numerical Simulation of Combustion and Extinction of a Solid Cylinder in Low-Speed Cross Flow

The combustion and extinction behavior of a diffusion flame around a solid fuel cylinder (PMMA) in low-speed forced flow in zero gravity was studied numerically using a quasi-steady gas phase model. This model includes two-dimensional continuity, full Navier Stokes' momentum, energy, and species equations with a one-step overall chemical reaction and second-order finite-rate Arrhenius kinetics. Surface radiation and Arrhenius pyrolysis kinetics are included on the solid fuel surface description and a parameter Phi, representing the percentage of gas-phase conductive heat flux going into the solid, is introduced into the interfacial energy balance boundary condition to complete the description for the quasi-steady gas-phase system. The model was solved numerically using a body-fitted coordinate transformation and the SIMPLE algorithm. The effects of varying freestream velocity and Phi were studied. These parameters have a significant effect on the flame structure and extinction limits. Two flame modes were identified: envelope flame and wake flame. Two kinds of flammability limits were found: quenching at low-flow speeds due to radiative loss and blow-off at high flow speeds due to insufficient gas residence time. A flammability map was constructed showing the existence of maximum Phi above which the solid is not flammable at any freestream velocity.

Tien, J. S.↗

The mechanism of growth of quartz crystals into fused silica

It is proposed that the growth of quartz crystals into fused silica is effected by a mechanism involving the breaking of an Si-O bond and its association with an OH group, followed by cooperative motion of the nonbridging oxygen and the hydroxyl group which results in the crystallization of a row of several molecules along a crystalline-amorphous interfacial ledge. This mechanism explains, at least qualitatively, all the results of the earlier experimental study of the dependence of quartz crystal growth upon applied pressure: large negative activation volume; single activation enthalpy below Si-O bond energy; growth velocity constant in time, proportional to the hydroxyl and chlorine content, decreasing with increasing degree of reduction, and enhanced by nonhydrostatic stresses; lower pre-exponential for the synthetic than for the natural silica.

Fratello, V. J.↗

Microgravity Flow Boiling Experiments With Liquid-Vapor Mixture Inlet Onboard the International Space Station

This article is part of a series of studies culminating from the multi-objective Flow Boiling and Condensation Experiment (FBCE) onboard the International Space Station, which utilized the Flow Boiling Module (FBM) for experiments between February and July 2022. This study investigates microgravity flow boiling of n-Perfluorohexane with liquid-vapor mixture (two-phase) inlet conditions to the FBM with either one or two opposite walls heated. The FBM’s channel has a rectangular cross-sectional area of 5.0 × 2.5 mm 2 and a heated length of 114.6 mm. Key parameters of interest include mass velocity (180 – 2400 kg/m 2 s), inlet quality (-0.01 – 0.87), inlet pressure (120 – 200 kPa), and heat flux (1.8 W/cm 2 to critical heat flux), and a large database is amassed. The flow is visualized via a high-speed video camera and photographs are recorded at each heating increment to assess the periodic flow patterns within the channel and the near-wall interfacial behavior. Flow patterns are complex and mainly characterized by high- and low-density fronts alternately traversing the channel to yield high- and low-density-dominant periods of boiling. At all operating conditions, high-density fronts are faster during high-density-dominant periods. At low inlet qualities, the flow is annular near the channel inlet with a central vapor core surrounded by an annular liquid layer. Each high-density front having a high liquid fraction leaves a thin liquid layer sheared onto the heated walls. Boiling occurs within the liquid layer and a vapor layer is formed next to the heated wall. Inlet quality and mass velocity most dictate the overall flow patterns followed by heating configuration, and to a much lesser extent, heat flux and inlet pressure. Heat transfer characteristics are assessed via averaged boiling curves, streamwise profiles of wall temperature and heat transfer coefficient, and parametric curves of local and averaged heat transfer coefficients. Inlet pressure has an insignificant effect on heat transfer. At similar operating conditions, both the heating configurations yield similar trends and values of heat transfer coefficient and critical heat flux (CHF, slightly higher for single-sided) even though double-sided heating adds twice the heat to the fluid and doubly raises local quality. The heat fluxes required for both onset of nucleate boiling degradation and CHF are larger at high mass velocities and low inlet qualities. For a fixed inlet quality, high mass velocities yield higher average heat transfer coefficients at both lower and higher heat fluxes, while the nucleate boiling regime at intermediate heat fluxes is unaffected. For a fixed mass velocity, higher inlet qualities yield higher and lower average heat transfer coefficients at lower and higher heat fluxes, respectively.

Microgravity↗

Ultrasonic characterization of the nonlinear elastic properties of unidirectional graphite/epoxy composites

The theoretical treatment of linear and nonlinear elasticity in a unidirectionally fiber reinforced composite as well as measurements for a unidirectional graphite/epoxy composite (T300/5208) are presented. Linear elastic properties were measured by both ultrasonic and strain gage measurements. The nonlinear properties were determined by measuring changes in ultrasonic natural phase velocity with a pulsed phase locked loop interferometer as a function of stress and temperature. These measurements provide the basis for further investigations into the relationship between nonlinear elastic properties and other important properties such as strength and fiber-matrix interfacial stength in graphite/epoxy composites.

Prosser, William H.↗

Ultrasonic characterization of the nonlinear elastic properties of unidirectional graphite/epoxy composites

The theoretical treatment of linear and nonlinear elasticity in a unidirectionally fiber reinforced composite as well as measurements for a unidirectional graphite/epoxy composite (T300/5208) are presented. Linear elastic properties were measured by both ultrasonic and strain gage measurements. The nonlinear properties were determined by measuring changes in ultrasonic natural phase velocity with a pulsed phase locked loop interferometer as a function of stress and temperature. These measurements provide the basis for further investigations into the relationship between nonlinear elastic properties and other important properties such as strength and fiber-matrix interfacial strength in graphite/epoxy composites.

Prosser, William H.↗

Visualizing pectin polymer-polymer entanglement produced by interfacial water movement

In this report, we investigated the physical conditions for creating pectin polymer-polymer (homopolymer) entanglement. The potential role of water movement in creating pectin entanglement was investigated by placing water droplets-equivalent to the water content of two gel phase films-between two glass phase films and compressing the films at variable probe velocities. Slow probe velocity (0.5 mm/sec) demonstrated no significant debonding. Furthermore, corresponding videomicroscopy demonstrated an occasional water bridge, but no evidence of stranding or polymer entanglement. In contrast, fast probe velocity (5 mm/sec) resulted in 1) an increase in peak adhesion strength, 2) a progressive debonding curve, and 3) increased work of cohesion (p < .001). Corresponding videomicroscopy demonstrated pectin stranding and delamination between pectin films. Scanning electron microscopy images obtained during pectin debonding provided additional evidence of both stranding and delamination. We conclude that water movement can supply the motive force for the rapid chain entanglement between pectin films.

59 BASIC BIOLOGICAL SCIENCES↗

Data and Modeling of Dendrites Subject to A Step Change in Pressure (TDSE)

There is considerable interest in dendritic solidification because of the influence dendrites have in the determination of microstructure, and thereby in the physical properties of cast metals and alloys. Current theories and models of dendritic growth generally couple diffusion effects in the melt with the physics of the interface. Data and subsequent analysis prior of the tip growth speed and radii of thermal succinonitrile dendrites in the near-convection free, on-orbit, free-fall environment demonstrate that these theories yield predictions that are reasonably in agreement with the results of experiment. However, data and analysis for assessing the interfacial physics component of theory are not sufficiently detailed or definitive. To study fundamental aspects of dendritic interface stability, we are measuring and modeling the kinetics and morphology of dendrites as they evolve from one well-defined steady state at a pre-set supercooling, through a transient stage, to a different well-defined steady state. More specifically, we subject succinonitrile dendrites, growing under steady-state conditions, to a rapid change in pressure. This leads to a rapid change in thermal driving force from the corresponding change in both the equilibrium melting temperature due to the Clapeyron effect, and a change in the far-field temperature due to adiabatic temperature changes in the bulk liquid and solid. Subsequently, we observe transformations from a well-characterized initial state into a new steady-state. Initial data reveal that the dendrite tip velocity changes almost as fast as the pressure charges, while the tip radius changes occur more slowly, taking from 10 60 seconds depending on the size of the step change and the final supercooling. Computer modeling of this process shows both agreements and disagreements with the experimental data. In making these observations and measurements, we are gaining new understandings of interfacial dynamics and state-selection physics.

Koss, Matthew B.↗

Dissipating Step Bunches during Crystallization under Transport Control

In studies of crystal formation by the generation and spreading of layers, equidistant step trains are considered unstable---bunches and other spatiotemporal patterns of the growth steps are viewed as ubiquitous. We provide an example to the opposite. We monitor the spatiotemporal dynamics of steps and the resulting step patterns during crystallization of the proteins ferritin and apoferritin using the atomic force microscope. The variations in step velocity and density are not correlated, indicating the lack of a long-range attraction between the steps. We show that (i) because of its coupling to bulk transport, nucleation of new layers is chaotic and occurs at the facet edges, where the interfacial supersaturation is higher; (ii) step bunches self-organize via the competition for supply from the solution; and, (iii) bunches of weakly interacting steps decay as they move along the face. Tests by numerical modeling support the conclusions about the mechanisms underlying our observations. The results from these systems suggest that during crystallization controlled by transport, with weakly or noninteracting growth steps, the stable kinetic state of the surface is an equidistant step train, and step bunches only arise during nucleation of new layers. Since nucleation only occurs at a few sites on the surface, the surface morphology may be controllably patterned or smoothened by locally controlling nucleation.

Lin, Hong↗

Understanding the Conductivity and Transference Trade-Off in Polymer Electrolytes Using a Robeson-Inspired Upper Bound

The development of high-performance electrolytes is crucial for advancing next-generation lithium and sodium battery technologies. Since the cation is the working ion in both technologies, electrolytes exhibiting the rapid cation transport are essential for making progress. Pathways to optimize electrolytes are unclear due to the inherent trade-off between conductivity and cation transference. While this trade-off is sometimes recognized, there are no well-accepted methodologies for quantifying it. Inspired by the Robeson upper bound for the permeability–selectivity trade-off in gas separation membranes, we propose an approach for quantifying the trade-off in electrolytes using Newman’s concentrated solution theory. We suggest calling this the Newman upper bound. By analyzing published data from 30 polymer electrolytes containing univalent lithium and sodium salts, the Newman upper bound is expressed as κ = 2.0­(1/ρ+ – 1) where κ (mS/cm) is conductivity and ρ+ is the current fraction measured in a symmetric cell as first described by Bruce et al. [J. Electroanal. Chem. Interfacial Electrochem. 1987, 225 (1), 1–17]. This formulation of the upper bound introduces a critical guiding metric for designing next-generation polymer electrolytes; it highlights factors underlying the trade-off, including the salt diffusion coefficient (D), cation transference number relative to solvent velocity ( t + 0 ), and thermodynamic factor (1 + (d lnγ+–)/(d lnm)), where γ+– is the mean molar activity coefficient and m is the molality. These parameters have been measured for very few electrolytes. We posit that establishing the molecular properties that govern these parameters will lead to improved electrolytes that greatly exceed the current upper bound.

He, Zirong↗