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At least 37 records · Page 2

Understanding Thermal Transport in Polymer –Silver Nanowire Composites

Understanding thermal transport across filler-polymer interfaces and filler-filler contacts within polymer composites is of great importance for better thermal design of the composites that are widely used in high-performance heat exchangers, energy storage devices, and flexible electronics. Over the past several decades, considerable progress has been made in improving the thermal conductivity of polymer composites, but several key questions concerning the influence of interfacial thermal resistance, or Kapitza resistance, still remain. Firstly, the thermal properties of these composites are highly dependent on thermal transport through the filler network and its contacts. For metallic nanofillers, the thermal conductivity is often estimated using the Wiedemann-Franz law based on electrical conductivity; however, it remains a question whether the Wiedemann-Franz law still holds at nanoscale contacts. Through investigation of silver nanowires of varying sizes, we were able to demonstrate that the Lorenz number for silver nanowire increases with decreasing nanowire diameter. Examination of the corresponding electrical and thermal conductivities indicate that these changes are due to that the relative contribution of phonons becomes more significant as a result of elastic stiffening. Furthermore, we show that for silver nanowires, the contact thermal resistance is ~8 times lower than that of multi-walled carbon nanotube (MWCNT) of similar diameters. Additionally, through systematic studies of electrospun polymer-silver nanowire composite nanofibers, we investigated the impact of interface morphology on the thermal conductivity enhancement of the composite system and probed the value of the Kapitza resistance for individual polymer-filler interfaces. For polymer nanofibers containing continuous, single silver nanowires, the thermal conductivity increases linearly with increasing volume fraction of silver, which is consistent with the prediction of percolation theory for samples above the percolation limit. By comparing this linear trend to the measured thermal conductivities of composite nanofibers with more complex structures, we were able to determine the resistance associated with any additional polymer-filler boundaries. In doing so we find that the thermal boundary resistance for polyvinylpyrrolidone (PVP)–silver interfaces is significantly lower than that of comparable polymer-MWCNT composite systems.Together our studies provide new insights into thermal transport in polymer nanocomposites and should help facilitate the design of high performance polymeric thermal interface material.

Thermal transport↗

Understanding Thermal Transport in Polymer - Silver Nanowire Composites

Understanding thermal transport across filler-polymer interfaces and filler-filler contacts within polymer composites is of great importance for better thermal design of the composites that are widely used in high-performance heat exchangers, energy storage devices, and flexible electronics. Over the past several decades, considerable progress has been made in improving the thermal conductivity of polymer composites, but several key questions concerning the influence of interfacial thermal resistance, or Kapitza resistance, still remain. Firstly, the thermal properties of these composites are highly dependent on thermal transport through the filler network and its contacts. For metallic nanofillers, the thermal conductivity is often estimated using the Wiedemann-Franz law based on electrical conductivity; however, it remains a question whether the Wiedemann-Franz law still holds at nanoscale contacts. Through investigation of silver nanowires of varying sizes, we were able to demonstrate that the Lorenz number for silver nanowire increases with decreasing nanowire diameter. Examination of the corresponding electrical and thermal conductivities indicate that these changes are due to that the relative contribution of phonons becomes more significant as a result of elastic stiffening. Furthermore, we show that for silver nanowires, the contact thermal resistance is ~8 times lower than that of multi-walled carbon nanotube (MWCNT) of similar diameters. Additionally, through systematic studies of electrospun polymer-silver nanowire composite nanofibers, we investigated the impact of interface morphology on the thermal conductivity enhancement of the composite system and probed the value of the Kapitza resistance for individual polymer-filler interfaces. For polymer nanofibers containing continuous, single silver nanowires, the thermal conductivity increases linearly with increasing volume fraction of silver, which is consistent with the prediction of percolation theory for samples above the percolation limit. By comparing this linear trend to the measured thermal conductivities of composite nanofibers with more complex structures, we were able to determine the resistance associated with any additional polymer-filler boundaries. In doing so we find that the thermal boundary resistance for polyvinylpyrrolidone (PVP)–silver interfaces is significantly lower than that of comparable polymer-MWCNT composite systems. Together our studies provide new insights into thermal transport in polymer nanocomposites and should help facilitate the design of high performance polymeric thermal interface material.

Matthew L. Fitzgerald↗

Visualizing diverse lithium growth and stripping behaviors in anode-free solid-state batteries with operando X-ray tomography

Anode-free solid-state batteries (SSBs), which eliminate the need for lithium metal use during cell assembly, have the potential to enable high energy densities and simplified manufacturing. However, the factors that control lithium growth/stripping at the anode current collector are not well understood. Here, we use operando X-ray microcomputed tomography to comprehensively image and quantify lithium deposition and stripping under various conditions in three different Li|Li 6 PS 5 Cl|current collector cells, revealing diverse behavior that depends on interface morphology, cell resistance, and solid-state electrolyte (SSE) microstructure. A cell with high resistance exhibits extensive lithium filament growth across the entire current collector interface, with filaments that grow around pre-existing pores in the SSE rather than lithium filling these pores. Lithium filament formation is partially reversible, with the cracks shrinking as lithium metal is stripped. Uniform lithium deposition is achievable at low current densities in low-resistance cells, whereas higher current densities in these cells cause an increase in interfacial roughness, which is correlated with subsequent filamentary growth at the edges of the cell. These results provide insight into filamentary vs. planar lithium growth and highlight that the evolution of lithium is sensitively dependent on SSE microstructure and electrochemical processes.

25 ENERGY STORAGE↗

Petrov-Galerkin methods for natural convection in directional solidification of binary alloys

A Petrov-Galerkin finite element method is presented for calculation of the steady, axisymmetric thermosolutal convection and interface morphology in a model for vertical Bridgman crystal growth of nondilute binary alloys. The Petrov-Galerkin method is based on the formulation for biquadratic elements developed by Heinrich and Zienkiewicz and is introduced into the calculation of the velocity, temperature and concentration fields. The algebraic system is solved simultaneously for the field variables and interface shape by Newton's method. The results of the Petrov-Galerkin method are compared critically with those of Galerkin's method using the same finite element grids. Significant improvements in accuracy are found with the Petrov-Galerkin method only when the mesh is refined and when the formulation of the residual equations is modified to account for the mixed boundary conditions that arise at the solidification interface. Calculations for alloys with stable and unstable solute gradients show the occurrence of classical flow transitions and morphological instabilities in the solidification system.

Adornato, Peter M.↗

Cellular Spacing Selection During the Directional Solidification of Binary Alloys. A Numerical Approach

The evolution of cellular solid/liquid interfaces from an initially unstable planar front was studied by means of a two-dimensional computer simulation. The developed numerical model makes use of an interface tracking procedure and has the capability to describe the dynamics of the interface morphology based on local changes of the thermodynamic conditions. The fundamental physics of this formulation was validated against experimental microgravity results and the predictions of the analytical linear stability theory. The performed simulations revealed that in certain conditions, based on a competitive growth mechanism, an interface could become unstable to random perturbations of infinitesimal amplitude even at wavelengths smaller than the neutral wavelength, lambda(sub c), predicted by the linear stability theory. Furthermore, two main stages of spacing selection have been identified. In the first stage, at low perturbations amplitude, the selection mechanism is driven by the maximum growth rate of instabilities while in the second stage the selection is influenced by nonlinear phenomena caused by the interactions between the neighboring cells. Comparison of these predictions with other existing theories of pattern formation and experimental results will be discussed.

Catalina, Adrian V.↗

Real-Time X-Ray Transmission Microscopy of Solidifying Al-In Alloys

Real-time observations of transparent analog materials have provided insight, yet the results of these observations are not necessarily representative of opaque metallic systems. In order to study the detailed dynamics of the solidification process, we develop the technologies needed for real-time X ray microscopy of solidifying metallic systems, which has not previously been feasible with the necessary resolution, speed, and contrast. In initial studies of Al-In monotectic alloys unidirectionally solidified in an X-ray transparent furnace, in situ records of the evolution of interface morphologies, interfacial solute accumulation, and formation of the monotectic droplets were obtained for the first time: A radiomicrograph of Al-30In grown during aircraft parabolic maneuvers is presented, showing the volumetric phase distribution in this specimen. The benefits of using X-ray microscopy for postsolidification metallography include ease of specimen preparation, increased sensitivity, and three-dimensional analysis of phase distribution. Imaging of the solute boundary layer revealed that the isoconcentration lines are not parallel (as is often assumed) to the growth interface. Striations in the solidified crystal did not accurately decorate the interface position and shape. The monotectic composition alloy under some conditions grew in an uncoupled manner.

Curreri, Peter A.↗

Protein Crystal Growth Under Forced Solution Flow: Experimental Setup and General Response of Lysozyme

We have experimentally studied the effects of solution flow on the growth kinetics of the protein lysozyme. To this end, we have expanded our interferometry setup by a novel crystallization cell and solution recirculation system. This combination permits monitoring of interface morphology and kinetics with a depth resolution of 200 A at bulk flow rates of up to 2000 micron/s. Particular attention was paid to the prevention of protein denaturation that is often associated with the pumping of protein solutions. We found that at bulk flow rates it less than 250 microns/s the average growth rate and step velocity, R(sub avg) and upsilon(sub avg) increase with increasing it. This can be quantitatively understood in terms of the enhanced, convective solute supply to the interface. With high-purity solutions, it u greater than 250 microns/s lead to growth deceleration, and, at low supersaturations sigma, to growth cessation. When solutions containing approx. 1% of other protein impurities were used, growth deceleration occurred at any u greater than 0 and cessation in the low sigma experiments was reached at about half the it causing cessation with pure solution. The flow-induced changes in R(sub avg) and upsilon(sub avg) including growth cessation, were reversible and reproducible, independent of the direction of the u-changes and solution purity. Hence, we attribute the deceleration to the convection-enhanced supply of impurities to the interface, which at higher flow rates overpowers the effects of enhanced interfacial solute concentration. Most importantly, we found that convective transport leads to a significant reduction in kinetics fluctuations, in agreement with our earlier expectations for the lysozyme system. This supports our hypothesis that these long-term fluctuations represent an intrinsic response feature of the coupled bulk transport-interfacial kinetics system in the mixed growth control regime.

Vekilov, P. G.↗

Failure Morphologies of Cyclically Oxidized ZrO2-Based Thermal Barrier Coatings

Plasma-sprayed thermal barrier coatings (TBC s) were thermal cycle tested in air at 1163 C until spallation of the top coat. Each thermal cycle consisted of a 45 minute exposure at the elevated temperature followed by a 15 minute cool to ambient temperature. The TBC s consisted of a ZrO2-based top coat containing various amounts of Y2O3, and/or Yb2O3, Gd2O3, and Nd2O3 applied by air plasma spraying and an MCrAlY bond coat applied by low pressure plasma spraying. The substrate was a single-crystal, Ni-based superalloy. The time to failure of the top coat varied from tens to hundreds of thermal cycles based on composition and spray parameters. The bond coat/top coat interface morphology and sample cross sections were examined by SEM and optical microscopy. The failure morphology following the cyclic oxidation testing will be discussed in relationship to the properties of the ceramic top coats.

Nesbit, James A.↗

Crystallization behavior of anorthite

The growth rate of anorthite crystals from the melt is studied as a function of temperature with undercooling in the ranges 52-152 and 402-652 degrees C. The triclinic form is invariably observed as the crystallization product, growth is preferentially in the c direction, and the interface morphology is faceted. Significant growth rate anisotropy is indicated. The maximum growth rate of anorthite from the melt is higher than for anorthite-rich lunar compositions. Recent computer studies are combined with experimental data to estimate the heat of fusion of anorthite as 28000-45000 cal/mol; the corresponding range for entropy of fusion is (7.8-12)R (where R is the gas constant). The observations and kinetic data support Jackson's predictions concerning materials with large entropies of fusion and his suggestion that entropy of fusion is an important parameter for characterizing the crystal-liquid interface and the nature of the crystallization process.

Klein, L.↗

Some observations on the characteristics of low-cost silicon sheets

To meet the need for low cost silicon sheet material in the ERDA/JPL photovoltaics program, JPL has initiated a wide ranging technology development effort in crystal growth that includes several different technology thrusts. They range in scope from innovative ingot growth and multislice wafering, to shaped growth techniques, substrate-related processes and hot forming techniques. In this paper, some salient observations on materials resulting from these processes are reported. Included are multiblade wafering-induced damage studies, interface morphology studies on the heat exchanger cast silicon, some diffusion length measurements in thin silicon layers on ceramic substrates, and results on the equilibrium structure found in laser zone ribbon growth.

Digges, T. G., Jr.↗

Rates and processes of crystal growth in the system anorthite-albite

The growth rates and interface morphologies of crystals of synthetic compositions in the anorthite (CaAl2Si2O8)-albite (NaAlSi3O8) plagioclase feldspar system are measured in an investigation of the crystallization of igneous rocks. Mixed plagioclase glasses with compositions of 75% and 50% anorthite were observed using the microscope heating technique as they crystallized at temperatures near the liquidus, and 75%, 50% and 20% anorthite crystals were treated by resistance heating and observed at greater degrees of undercooling. Growth rates were found to be independent of time and to decrease with increasing albite content, ranging from 0.5 to 2 x 10 to the -5th cm/min. The crystal morphologies for all compositions are faceted near the liquidus and become progressively skeletal, dendritic and fibrillar with increasing undercooling.

Kirkpatrick, R. J.↗

A new furnace for high gradient directional growth

A new design furnace for high gradient solidification of in-situ composites is presented. Its essential feature is the direct addition of heat to one side of a thin, pancake-like layer of liquid, and continuous withdrawal of a solid crystal from the other side. Liquid in the thin layer is continuously replenished by solid or liquid feed, and the thinness of the layer permits a large heat throughput with a high temperature gradient without excessive metal superheat. The commercial advantages of this design are improved process efficiency in scale-up, lower melt temperatures, and control of interface morphology by adjusting heater position and temperature. The furnace was tested on Sn-Pb and Al-Cu alloys, obtaining 100C/mm gradients for 6 mm specimens of Al-31.5 % Cu alloy.

Flemings, M. C.↗

Analysis of inclined growth of silicon sheet

A general-purpose finite element program was developed for analysis of silicon sheet growth in inclined configurations. This program will be used to study parametric sensitivity of various growth geometries with respect to thermal control and growth rate, dopant segregation, thermal stress and interface morphology and instability.

Brown, R. A.↗

Fluid Flow in Crystal Growth: Analysis of the Verticle Bridgman and Floating Zone Process

Research is aimed at the fundamental understanding of the interactions of heat and mass transport and fluid mechanics in crystal growth from the melt, especially in how it pertains to experiments supported by the Microgravity Science and Applications program. Emphasis has been on studies of the vertical Bridgman system, on small-scale floating zone systems proposed for space flight, and on quantitative prediction of nonlinear transitions in melt/solid interface morphologies leading to the formation of dendrites in directional solidification. The analysis of vertical Bridgman growth has lead to the complete numerical analysis of transport phenomena in directional solidification and to a detailed comparison of calculations to the GaGe growth experiments of Wang and Witt. Calculations show the central role of the ampoule material in determining the radial temperature gradients in the melt and thus, the intensity of convection. Results indicate that diffusion-controlled growth can not be achieved on Earth with conventional growth systems, but are feasible in microgravity

Brown, R. A.↗

The effect of metal surface passivation on the Au-InP interaction

The effect of SiO2 encapsulation on reaction rates in the Au-InP system was studied. Scanning electron microscopy and x-ray photoelectron spectroscopy were used to investigate surface and/or interface morphologies and in-depth compositional profiles. It was found that the rate of dissolution of InP into Au and subsequent phase transformations are largely dependent on the condition of the free surface of the metalization. SiO2 capping of Au is reported for the first time to suppress the Au-InP reaction rate. The Au-InP interaction is shown to be quite similar to the Au-GaAs interaction despite differences in behavior of the group-V elements.

Fatemi, Navid S.↗

Instability during directional solidification - Gravitational effects

After an elementary introduction to solidification, recent research that attempts to understand the interaction of fluid flow with a crystal-melt interface under gravitational influence using linear stability analysis is reviewed. Recent numerical calculations of fluid flow and interface morphology during alloy solidification are briefly discussed.

Coriell, S. R.↗

Convective Influence on Radial Segregation During Unidirectional Solidification of the Binary Alloy HgCdTe

In order to simulate the space environment for basic research into the crystal growth mechanism, Hg(0.8)Cd(0.2)Te crystals were grown by the vertical Bridgman-Stockbarger method in the presence of an applied axial magnetic field. The influence of convection, by magneto hydrodynamic damping, on mass transfer in the melt and segregation at the solid-liquid interface was investigated by measuring the axial and radial compositional variations in the grown samples. The reduction of convective mixing in the melt through the application of the magnetic field is found to have a large effect on radial segregation and interface morphology in the grown crystals. Direct comparisons are made with a Hg(0.8)Cd(0.2)Te crystal grown without field and also in the microgravity environment of space during the second United States Microgravity Payload Mission (USMP-2).

Watring, D. A.↗

Experiment 2: Vapor Transport Crystal Growth of Mercury Cadmium Telluride in Microgravity- USML-2

The new epitaxial growth experiments of Hg(l-x)Cd(x)Te on (100) CdTe substrates by chemical vapor transport (CVT), using HgI2 as a transport agent, were performed in the transient growth regime of this ternary, heteroepitaxial system at normal and reduced gravity during the USML-2 flight. The surface and interface morphology, the compositional and structural uniformity, and carrier mobility of the epitaxial layer and islands grown in microgravity are measurably improved relative to ground specimens. These observations demonstrate the effects of convective flow on the transport, deposition, and growth processes of this solid-vapor system even in the transient growth regime. The properties of the Hg(l-x)Cd(x)Te layer grown in a microgravity environment compare quite favorably to those of layers obtained by other techniques.

Wiedemeier, H.↗