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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,135 records · Page 63

Long lifetime of thermally excited magnons in bulk yttrium iron garnet

Spin currents are generated within the bulk of magnetic materials due to heat flow, an effect called intrinsic spin Seebeck. This bulk bosonic spin current consists of a diffusing thermal magnon cloud, parametrized by the magnon chemical potential (μ m ), with a diffusion length of several microns in yttrium iron garnet (YIG). Transient optothermal measurements of the spin-Seebeck effect (SSE) as a function of temperature reveal the time evolution of μ m due to intrinsic SSE in YIG. The interface SSE develops at times <2 ns while the intrinsic SSE signal continues to evolve at times >500 μs, dominating the temperature dependence of SSE in bulk YIG. Time-dependent SSE data are fit to a multitemperature model of coupled spin/heat transport using the finite-element method (FEM), where the magnon spin lifetime (τ) and magnon-phonon thermalization time (τ mp ) are used as fit parameters. From 300 to 4 K, τ mp ) varies from 1 to 10 ns, whereas tau varies from 2 to 60 μ s with the spin lifetime peaking at 90 K. At low temperature, a reduction in τ is observed consistent with impurity relaxation reported in ferromagnetic resonance measurements. Finally, these results demonstrate that the thermal magnon cloud in YIG contains extremely low-frequency magnons (similar to 10 GHz), providing spectral insight to the microscopic scattering processes involved in magnon spin/heat diffusion.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Suppressing proximity effects during rapid serial two-photon lithography through tuning of reaction–diffusion kinetics

The ability of two-photon lithography (TPL) to print deterministic nanoporous 3D structures is highly valuable for many applications. However, it is challenging to print such structures rapidly due to the proximity effects that cause closely spaced features to enlarge and merge. A key challenge is the limited understanding of the origins and spatiotemporal dynamics of the long-range proximity effects that extend beyond the optical focal spot. Here, we empirically investigate these proximity effects in serial TPL using custom-made acrylate-based photoresists. We demonstrate that the complex spatiotemporal dynamics of the proximity effects can be explained through the kinetics of the reaction–diffusion photopolymerization mechanisms that underlie the curing process. Specifically, we show that the proximity effects arise due to comparable timescales of reaction and diffusion of oxygen. Furthermore, we demonstrate that long-range proximity effects can be suppressed by introducing phenolic inhibitors, which reduce oxygen consumption through non-inhibiting side reactions and promote faster termination of curing reactions. These insights enabled improving the linewidths from >400 to 260 nm during printing of nanoporous 3D woodpiles at scanning speeds of 50 mm s −1 . Thus, the knowledge generated here can be applied to deterministically tune the proximity effects and enable rapid printing of high-resolution nanoporous 3D structures.

36 MATERIALS SCIENCE↗

Electrochemical mechanisms of leakage‐current in photovoltaic modules

Abstract This paper analyzes the mechanisms and pathways for leakage current flow observed in Si photovoltaic modules subjected to high temperature and humidity and a large voltage bias with respect to ground. The current inside of the frame is in the form of electron motion, but in the glass and polymer, it is in at least a large part attributable to the movement of ions. When the mode of current flow changes from electronic to ionic conduction, electrochemical reactions will take place at the interface. This can include reactions that produce volatile chemical species like H 2 , CO x , and O 2 , along with ionic species such as OH − and H 3 O + . Here, we see evidence of the importance of different charge carriers with different diffusion rates and the influence of electrochemical processes involved. The application of negative voltage to the cell circuit affects the resistivity of glass producing surfaces with poor conductivity but with some increases in the electrochemical potential producing complicated interactions that are important when the voltage is changed. In the polymer, there is the development of a space charge region and a chemical gradient providing two oppositional forces to current flow, which when released create a complicated discharge process. Here, we give a basic understanding of the charge/discharge of PV cells highlighting how the specific mechanisms are important in understanding some of the degradation processes in PV modules. We find that there is evidence of multiple significant charge carrier species with different diffusion time scales. The glass/polymer interface forms a depleted region of higher resistance after prolonged exposure to current. Charge also builds up at the polymer to cell antireflective coating interface and mostly flows to the gridlines to experience electrochemical reactions. These complexities result in non‐linear behavior where the apparent resistivities of the different layers change during charge/discharging processes, making the modeling of the current flow extremely difficult.

14 SOLAR ENERGY↗

Jupiter radio bursts and particle acceleration

Particle acceleration processes are important in understanding many of the Jovian radio and plasma wave emissions. However, except for the high-energy electrons that generate synchrotron emission following inward diffusion from the outer magnetosphere, acceleration processes in Jupiter's magnetosphere and between Jupiter and Io are poorly understood. We discuss very recent observations from the Ulysses spacecraft of two new Jovian radio and plamas wave emissions in which particle acceleration processes are important and have been addressed directly by complementary investigations. First, radio bursts known as quasi-periodic bursts have been observed in close association with a population of highly energetic electrons. Second, a population of much lower energy (keV range) electrons on auroral field lines can be shown to be responsible for the first observation of a Jovian plasma wave emission known as auroral hiss.

Desch, Michael D.↗

A mechanistic modeling framework for gas-phase adsorption kinetics and fixed-bed transport

Adsorption is a complex physicochemical process involving interparticle transport, interphase mass-transfer, intraparticle diffusion, and surface reactions. Although the exact description of the adsorption process will inevitably vary from system to system, it will always be governed by those primary mechanisms. Thus, by devising a model framework that can inherently include those mechanisms, it would be possible to create a modeling platform on which many different adsorption problems could be solved numerically. In order to accomplish this task, a generalized 1-D conservation law model was created to include the necessary mechanisms of adsorption on several different geometrical domains. Specific model applications for adsorption were developed under that framework and validated using experimental data available in literature or obtained in this work. This modeling platform makes it easier to model various adsorption problems and develop new adsorption models because of the common treatment of the mathematics governing the physical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A New Framework for the Attribution of Air‐Sea CO 2 Exchange

Abstract The air‐sea transfer of carbon dioxide can be viewed as a dynamic system through which atmospheric and oceanic processes push surface waters away from thermodynamic equilibrium, while diffusive gas transfer pulls them back toward local equilibrium. These push/pull processes drive significant sub‐seasonal, seasonal, and interannual variability in air‐sea carbon fluxes, the quantification of which is critical both for diagnosing the ocean response to fossil fuel emissions and for attempts to mitigate anthropogenic climate disruption through intentional modification of surface ocean biogeochemistry. In this study, we present a new approach for attributing air‐sea carbon fluxes to specific mechanisms. The new framework is first applied to a two‐box ocean nutrient and carbon cycle model as an illustrative example. Next, outputs from a regional eddy‐resolving model of the Southern Ocean are analyzed. The roles of multiple physical and biogeochemical processes are identified. The decomposition of the seasonal air‐sea carbon flux shows the dominant role of biological carbon pumps that are partially compensated by the transport convergence. Finally, the framework is used to diagnose the response to mesoscale iron and alkalinity release, explicitly quantifying transport feedback and eventual impacts on net air‐sea carbon flux. Ocean carbon transport has divergent influences between iron and alkalinity release, due to opposing near‐surface gradients of dissolved inorganic carbon. We suggest that our attribution framework may be a useful analytical technique for monitoring natural ocean carbon fluxes and quantifying the impacts of human intervention on the ocean carbon cycle.

Ito, Takamitsu [School of Earth and Atmospheric Sc↗

Analysis of furnace contamination on superconducting radio frequency niobium using secondary-ion mass spectrometry

Detection of surface contamination on niobium materials used in superconducting radio frequency (SRF) applications is difficult due to quantitative sensitivity and near-atomic depth resolution needed. Inspection of samples known to have experienced surface contamination was found to have inconsistent nitride coverage after high-temperature nitrogen gas exposure (“doping”). Here we compare contaminating species found on samples treated in several different vacuum furnaces, both “exposed” directly in the chamber and “protected” by containment shielding from evaporative sources with “furnace caps.” Typically, furnace caps are used to impede contamination from reaching the interior surface of cavities during the high-temperature vacuum bake that immediately precedes exposure to nitrogen gas. Although, to date, little is known about the effectiveness of these caps, SIMS results showed that they were effective in limiting contamination arising from the furnace environment. Inspection of sample surfaces by SEM showed a lack of nitrides present on contaminated specimens. TEM with energy dispersive spectroscopy performed on these samples revealed that a carbon-rich layer now existed, indicating that a relatively high contaminant load prevents the nucleation and growth of surface nitrides, while thus inhibiting interstitial nitrogen uptake. Except in extreme cases, subsequent removal of the top several micrometers of the surface via electropolishing appears to effectively eliminate any strong influence on the subsequent SRF cavity performance. With the absence of furnace cleaning, carbon contamination was found to be nearly 10× higher for protected nitrogen-doped and electropolished samples, with minimal metallic contamination detected for both processes. SIMS analysis was also performed to compare the cleanliness of samples fully prepared by such nitrogen “doping” with those prepared by a related process, involving the dissolution of niobium surface oxide and diffusion of oxygen into the surface. This oxygen doping or alloying process offers attractive advantages.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Chemical vapor deposition growth

The objective was to investigate and develop chemical vapor deposition (CVD) techniques for the growth of large areas of Si sheet on inexpensive substrate materials, with resulting sheet properties suitable for fabricating solar cells that would meet the technical goals of the Low Cost Silicon Solar Array Project. The program involved six main technical tasks: (1) modification and test of an existing vertical-chamber CVD reactor system; (2) identification and/or development of suitable inexpensive substrate materials; (3) experimental investigation of CVD process parameters using various candidate substrate materials; (4) preparation of Si sheet samples for various special studies, including solar cell fabrication; (5) evaluation of the properties of the Si sheet material produced by the CVD process; and (6) fabrication and evaluation of experimental solar cell structures, using impurity diffusion and other standard and near-standard processing techniques supplemented late in the program by the in situ CVD growth of n(+)/p/p(+) sheet structures subsequently processed into experimental cells.

Ruth, R. P.↗

Combinatorial Synthesis of Oxysulfides in the Lanthanum–Bismuth-Copper System

Establishing synthesis approaches for a target material constitutes a grand challenge in materials research, which is compounded with use-inspired specifications on the format of the material. Solar photochemistry using thin film materials is a promising technology for which many complex materials are being proposed, and the present work describes application of combinatorial methods to explore the synthesis of predicted La–Bi–Cu oxysulfide photocathodes, in particular alloys of LaCuOS and BiCuOS. The variation in concentration of three cations and two anions in thin film materials, and crystallization thereof, is achieved by a combination of reactive sputtering and thermal processes including reactive annealing and rapid thermal processing. Composition and structural characterization establish composition-processing-structure relationships that highlight the breadth of processing conditions required for synthesis of LaCuOS and BiCuOS. The relative irreducibility of La oxides and limited diffusion indicate the need for high temperature processing, which conflicts with the temperature limits for mitigating evaporation of Bi and S. Collectively the findings indicate that alloys of these phases will require reactive annealing protocols that are uniquely tailored to each composition, motivating advancement of dynamic processing capabilities to further automate discovery of synthesis routes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Study of Oxygen Diffusion in Reduced LiNbO{sub 3} Crystals

Using the method of impedance spectroscopy and optical density measurements, the diffusion of oxygen in single crystals of lithium niobate of the congruent composition after the reductive thermochemical processing is studied. The parameters describing the diffusion of oxygen in the temperature range 493–693 K are established.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Encapsulated diffusion of sulphur into InP

This talk outlines a simple process for the fabrication of n(+)-p solar cells in indium phosphide. Large area cells (greater than 0.25 sq cm) have been made by this process, with a photovoltaic conversion efficiency of 15.21 percent under AM0 conditions of illumination. An ideality factor of 1.1 and a saturation current density of 8 x 10 to the minus 15th power A/sq cm have been observed for these cells. The technique for cell fabrication involves the diffusion of sulfur into InP by an open tube process, and gives highly reproducible results from run to run. A vacuum-deposited layer of gallium sulphide (Ga2S3) was used as the source for sulfur diffusion, with a chemically vapor deposited SiO2 cap layer to prevent decomposition of the InP surface during heat treatment. Diffusions were carried out in a flowing nitrogen ambient at 585 to 708 C, and characterized by their surface carrier concentration and the diffusion constant. The diffusion profile for sulfur in InP is estimated to be of the complementary error function type. The activation energy of the diffusion was estimated to be 1.94 eV. The technique described here is ideally suited for the fabrication of shallow n(+)-p junctions in InP, and has been used for space-borne solar cells.

Parat, K. K.↗

Laminar Premixed and Diffusion Flames (Ground-Based Study)

Ground-based studies of soot processes in laminar flames proceeded in two phases, considering laminar premixed flames and laminar diffusion flames, in turn. The test arrangement for laminar premixed flames involved round flat flame burners directed vertically upward at atmospheric pressure. The test arrangement for laminar jet diffusion flames involved a round fuel port directed vertically upward with various hydrocarbon fuels burning at atmospheric pressure in air. In both cases, coflow was used to prevent flame oscillations and measurements were limited to the flame axes. The measurements were sufficient to resolve soot nucleation, growth and oxidation rates, as well as the properties of the environment needed to evaluate mechanisms of these processes. The experimental methods used were also designed to maintain capabilities for experimental methods used in corresponding space-based experiments. This section of the report will be limited to consideration of flame structure for both premixed and diffusion flames.

Dai, Z.↗

Flat-plate solar array project process development area: Process research of non-CZ silicon material

Several different techniques to simultaneously diffuse the front and back junctions in dendritic web silicon were investigated. A successful simultaneous diffusion reduces the cost of the solar cell by reducing the number of processing steps, the amount of capital equipment, and the labor cost. The three techniques studied were: (1) simultaneous diffusion at standard temperatures and times using a tube type diffusion furnace or a belt furnace; (2) diffusion using excimer laser drive-in; and (3) simultaneous diffusion at high temperature and short times using a pulse of high intensity light as the heat source. The use of an excimer laser and high temperature short time diffusion experiment were both more successful than the diffusion at standard temperature and times. The three techniques are described in detail and a cost analysis of the more successful techniques is provided.

Campbell, R. B.↗

Continuous Flow Photoelectrochemical Reactor with Gas Permeable Photocathode: Enhanced Photocurrent and Partial Current Density for CO 2 Reduction

Photoelectrochemical (PEC) CO 2 reduction using a photocathode is an attractive method for making valuable chemical products due to its simplicity and lower overpotential requirements. However, previous PEC processes have often been diffusion-limited leading to low production rates of the CO 2 reduction reaction, due to inefficient gas diffusion through the liquid electrolyte to the catalyst surface, particularly at high current densities. In this study, a gas-permeable photocathode in a continuous flow PEC reactor is incorporated, which facilitates the direct supply of CO 2 gas to the photocathode-electrolyte interface, unlike dark reaction-based flow reactors. This concept is demonstrated using Ag-TiO 2 on carbon paper, illuminated through a quartz window and flowing liquid electrolyte. CO 2 supply is managed via pressure and flow control on the non-illuminated side of the carbon paper. The photocurrent density is significantly influenced by the flow rates and pressure of CO 2 gas, and the electrolyte flow rates. Compared to the traditional H-cell, the continuous PEC flow reactor achieves ≈10-fold increase in CO faradaic efficiency, 30-fold increase in production rate and 16-fold increase in stability without catalyst modifications. This work provides essential insights into the design and application of continuous gas-liquid flow PEC reactor systems, highlighting their potential for other PEC reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electroless Formation of Hybrid Lithium Anodes for Fast Interfacial Ion Transport

Abstract Rechargeable batteries based on metallic anodes are of interest for fundamental and application‐focused studies of chemical and physical kinetics of liquids at solid interfaces. Approaches that allow facile creation of uniform coatings on these metals to prevent physical contact with liquid electrolytes, while enabling fast ion transport, are essential to address chemical instability of the anodes. Here, we report a simple electroless ion‐exchange chemistry for creating coatings of indium on lithium. By means of joint density functional theory and interfacial characterization experiments, we show that In coatings stabilize Li by multiple processes, including exceptionally fast surface diffusion of lithium ions and high chemical resistance to liquid electrolytes. Indium coatings also undergo reversible alloying reactions with lithium ions, facilitating design of high‐capacity hybrid In‐Li anodes that use both alloying and plating approaches for charge storage. By means of direct visualization, we further show that the coatings enable remarkably compact and uniform electrodeposition. The resultant In‐Li anodes are shown to exhibit minimal capacity fade in extended galvanostatic cycling when paired with commercial‐grade cathodes.

Choudhury, Snehashis↗

Electroless Formation of Hybrid Lithium Anodes for Fast Interfacial Ion Transport

Abstract Rechargeable batteries based on metallic anodes are of interest for fundamental and application‐focused studies of chemical and physical kinetics of liquids at solid interfaces. Approaches that allow facile creation of uniform coatings on these metals to prevent physical contact with liquid electrolytes, while enabling fast ion transport, are essential to address chemical instability of the anodes. Here, we report a simple electroless ion‐exchange chemistry for creating coatings of indium on lithium. By means of joint density functional theory and interfacial characterization experiments, we show that In coatings stabilize Li by multiple processes, including exceptionally fast surface diffusion of lithium ions and high chemical resistance to liquid electrolytes. Indium coatings also undergo reversible alloying reactions with lithium ions, facilitating design of high‐capacity hybrid In‐Li anodes that use both alloying and plating approaches for charge storage. By means of direct visualization, we further show that the coatings enable remarkably compact and uniform electrodeposition. The resultant In‐Li anodes are shown to exhibit minimal capacity fade in extended galvanostatic cycling when paired with commercial‐grade cathodes.

Choudhury, Snehashis↗

Processing and microstructure of ZrB 2 –SiC composite prepared by reactive spark plasma sintering

In-situ formation of ZrB 2 –SiC composites was investigated by reactive spark plasma sintering of precursor powders according to the reaction B4C + 2ZrC + 3Si → 3SiC + 2ZrB 2 . The reaction and process presented here involves a diffusion reaction between B4C and ZrC which facilitates the formation of ZrB 2 , while liquid phase sintering of silicon facilitates atomic diffusion and combines with free C from the B4C and ZrC reaction to form SiC within minutes of heating and there were some residual unreacted precursor materials. An interpenetrating matrix of ZrB 2 –SiC was formed that shows increased fracture toughness (6.03 ± 0.45 MPa m 1/2 ) despite relatively low density (95 %).

36 MATERIALS SCIENCE↗

Tuning Electrogenerated Chemiluminescence Intensity Enhancement Using Hexagonal Lattice Arrays of Gold Nanodisks

Electrogenerated chemiluminescence (ECL) microscopy shows promise as a technique for mapping chemical reactions on single nanoparticles. The technique’s spatial resolution is limited by the quantum yield of the emission and the diffusive nature of the ECL process. To improve signal intensity, ECL dyes have been coupled with plasmonic nanoparticles, which act as nanoantennas. Here, we characterize the optical properties of hexagonal arrays of gold nanodisks and how they impact the enhancement of ECL from the coreaction of tris(2,2'-bipyridyl)dichlororuthenium(II) hexahydrate and tripropylamine. Here, we find that varying the lattice spacing results in a 23-fold enhancement of ECL intensity because of increased dye-array near-field coupling as modeled using finite element method simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗