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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

High-performance all-solid-state Li–S batteries enabled by an all-electrochem-active prelithiated Si anode

The development of all-solid-state Li–S batteries has been greatly impeded by dendrite growth and dendrite penetration, which are both related to the Li metal anode. As a compromised alternative, we report lithium silicide (Li x Si) as a dendrite-free and high-capacity anode with Li source. Here, the as-synthesized Li x Si is relatively soft, highly electronically conductive, and with a high Li diffusivity. These distinctive properties make Li x Si anode viable as an “all-electrochem-active” electrode (consisted of 100 wt.% Li x Si). Compared with the typical composite electrode, the all-electrochem-active electrode not merely maximizes the electrode-level energy density but also minimizes the electrolyte-related interfacial degradation. Li x Si symmetric cell demonstrates a reversible cycling at 4 mA cm –2 for over 320 h. Stress change and morphological evolution of the Li x Si electrode are investigated upon dealloying/alloying. When paired with a S cathode (active mass loading of 3 mg cm –2 ), Li x Si–S full cell shows a good cycling behavior over 500 cycles and rate performance (69% capacity retained at 1.2C) even at 25 °C.

25 ENERGY STORAGE↗
DOE OSTI2021

Multiphysics and Multiscale Modeling of Coupled Transport of Chloride Ions in Concrete

Chloride ions (Cl−)-induced corrosion is one of the main degradation mechanisms in reinforced concrete (RC) structures. In most situations, the degradation initiates with the transport of Cl− from the surface of the concrete towards the reinforcing steel. The accumulation of Cl− at the steel-concrete interface could initiate reinforcement corrosion once a threshold Cl− concentration is achieved. An accurate numerical model of the Cl− transport in concrete is required to predict the corrosion initiation in RC structures. However, existing numerical models lack a representation of the heterogenous concrete microstructure resulting from the varying environmental conditions and the indirect effect of time dependent temperature and relative humidity (RH) on the water adsorption and Cl− binding isotherms. In this study, a numerical model is developed to study the coupled transport of Cl− with heat, RH and oxygen (O2) into the concrete. The modeling of the concrete microstructure is performed using the Virtual Cement and Concrete Testing Laboratory (VCCTL) code developed by the U.S. National Institute of Standards and Technology (NIST). The concept of equivalent maturation time is utilized to eliminate the limitation of simulating concrete microstructure using VCCTL in specific environmental conditions such as adiabatic. Thus, a time-dependent concrete microstructure, which depends on the hydration reactions coupled with the temperature and RH of the environment, is achieved to study the Cl− transport. Additionally, Cl− binding isotherms, which are a function of the pH of the concrete pore solution, Cl− concentration, and weight fraction of mono-sulfate aluminate (AFm) and calcium-silicate-hydrate (C-S-H), obtained from an experimental study by the same authors are utilized to account for the Cl− binding of cement hydration products. The temperature dependent RH diffusion was considered to account for the transport of Cl− with moisture transport. The temperature and RH diffusion in the concrete domain, composite theory, and Cl− binding and water adsorption isotherms are used in combination, to estimate the ensuing Cl− diffusion field within the concrete. The coupled transport process of heat, RH, Cl−, and O2 is implemented in the Multiphysics Object-Oriented Simulation Environment (MOOSE) developed by the U.S. Idaho National Laboratory (INL). The model was verified and validated using data from multiple experimental studies with different concrete mixture proportions, curing durations, and environmental conditions. Additionally, a sensitivity analysis was performed to identify that the water-to-cement (w/c) ratio, the exposure duration, the boundary conditions: temperature, RH, surface Cl− concentration, Cl− diffusion coefficient in the capillary water, and the critical RH are the important parameters that govern the Cl− transport in RC structures. In a case study, the capabilities of the developed numerical model are demonstrated by studying the complex 2D diffusion of Cl− in a RC beam located in two different climatic regions: warm and humid weather in Galveston, Texas, and cold and dry weather in North Minnesota, Minnesota, subjected to time varying temperature, RH, and surface Cl− concentrations.

composite theory↗
NASA NTRS2001

Growth and Morphology of Supercritical Fluids, a Fluid Physics Experiment Conducted on Mir, Complete

The Growth and Morphology of Supercritical Fluids (GMSF) is an international experiment facilitated by the NASA Glenn Research Center and under the guidance of U.S. principal investor Professor Hegseth of the University of New Orleans and three French coinvestigators: Daniel Beysens, Yves Garrabos, and Carole Chabot. The GMSF experiments were concluded in early 1999 on the Russian space station Mir. The experiments spanned the three science themes of near-critical phase separation rates, interface dynamics in near-critical boiling, and measurement of the spectrum of density fluctuation length scales very close to the critical point. The fluids used were pure CO2 or SF6. Three of the five thermostats used could adjust the sample volume with the scheduled crew time. Such a volume adjustment enabled variable sample densities around the critical density as well as pressure steps (as distinct from the usual temperature steps) applied to the sample. The French-built ALICE II facility was used for these experiments. It allows tightly thermostated (left photograph) samples (right photograph) to be controlled and viewed/measured. Its diagnostics include interferometry, shadowgraph, high-speed pressure measurements, and microscopy. Data were logged on DAT tapes, and PCMCIA cards and were returned to Earth only after the mission was over. The ground-breaking near critical boiling experiment has yielded the most results with a paper published in Physical Review Letters (ref. 1). The boiling work also received press in Science Magazine (ref. 2). This work showed that, in very compressible near-critical two-phase pure fluids, a vapor bubble was induced to temporarily overheat during a rapid heating of the sample wall. The temperature rise in the vapor was 23-percent higher than the rise in the driving container wall. The effect is due to adiabatic compression of the vapor bubble by the rapid expansion of fluid near the boundary during heatup. Thermal diffusivity is low near the critical point, so getting heat out of the compressed bubble is observably slow. This gives the appearance of a backward heat flow, or heat flow from a cold surface to a warm fluid.

Wilkinson, R. Allen↗
NASA NTRS2002

Development of a New Membrane Casting Apparatus for Studying Macrovoid Defects in Low-G

A new membrane-casting apparatus is developed for studying macrovoid defects in polymeric membranes made by the wet- and dry-casting process in low-gravity. Macrovoids are large (10-50 micron), open cavities interspersed among the smaller pores in the substructure under the gelled skin surface layer of the cast membrane. Although their occurrence is considered endemic to the wet- and dry-casting process since they can lead to compaction or skin rupture in the membrane process, recent studies suggest several useful applications such as transdermal and osmotic drug delivery systems, miniature bioreactors, etc. However, lack of knowledge about the macrovoid formation mechanism is an obstacle to further development of applications using them. An on-going debate is the role of the surface-tension-driven solutocapillary convection during macrovoid formation. The rapid growth of macrovoids within 1-5 seconds and the high polymer concentration in and near macrovoids make it difficult to explain the mechanism of macrovoid growth by diffusion alone, which is the widely accepted hypothesis proposed by Reuvers et al. The hypothesis advanced by our research group can explain this rapid growth via a mechanism that involves diffusion from the casting solution in the meta-stable region to the macrovoid enhanced by solutocapillary convection induced by the steep nonsolvent concentration gradient in the vicinity of the macrovoid. Since macrovoid growth is hypothesized to be the interplay of a solutocapillary-induced driving force counteracted by viscous drag and buoyancy, eliminate the latter provides a means for testing this hypothesis. Moreover, free convection mass transfer in the nonsolvent immersion bath used to cause phase-separation in membrane casting complicates developing a model for both the wet-casting process and macrovoid growth. The low-g environment minimizes gravitationally induced free convection thereby permitting a tractable solution to the ternary diffusion equations that characterize membrane formation. NASA's Parabolic Flight Research Aircraft provides a small window of low-g (approximately 25 s) that can be used to study macrovoid development in both wet- and dry-cast membranes if an appropriate casting apparatus is used. This casting apparatus should be able to cast the membrane in both low- and high-g in a manner so that essential one-dimensional mass transfer conditions are achieved to insure lateral uniformity in the membrane. The apparatus used in previous research on membrane casting in low-gravity was operated with the plunger driven mechanism. The spring-loaded plunger pushes the bottom block containing the polymer casting solution well directly under the absorbent chamber located in the upper stationary block. However, membranes made via this casting apparatus often displayed lateral nonuniformities that precluded obtaining quantitative information on the macrovoid growth process. Thus, it was necessary to determine the reason for these structural irregularities observed in the low-g casting apparatus. Both experimental as well as computer simulation studies of the low-g casting apparatus established that the impulsive action of the plunger caused the undesired structural nonuniformities. The simulation results showed that the width-to-depth aspect ratio of the shallow well that contains the casting solution in this apparatus was not an important factor in minimizing this problem. Even for a 40:1 (width : depth) aspect ratio, any convection induced by the horizontal motion of the interface of the casting solution will be damped out within 6.25x10(exp 4) seconds. However, the experimental studies revealed that the impulsive motion of the plunger caused a 'sloshing' of the casting solution that had to be eliminated. Therefore, the plungerdriven mechanism was changed to a cam-driven mechanism that did not cause any impulsive motion of the casting solution. Other refinements to this new membrane-casting apparatus include provision for removing the membranes from the casting wells in a less destructive manner. This was accomplished by using a slit geometry for the casting well that permitted disassembly for removal of the cast membrane. The materials used in the construction of this casting apparatus were chosen to insure wetting at the side walls and to maintain precise control of the thickness of the polymer solution in the casting well. An additional provision in this new casting apparatus is the ability to carry out both wet- as well as dry-casting. As such, this apparatus permitted the first studies of the wet-casting of polymeric membranes in low-g. Both wet- and dry-casting experiments on NASA's KC-135 research aircraft employing this new membrane-casting apparatus are scheduled in July 2002. The morphology of the resulting membranes will be characterized using an environmental scanning electron microscope (ESEM). The results of these low-g studies will be reported later.

Lee, Hanyong↗
DOE OSTI2023

Chromium Tolerant, Highly Active and Stable Electrocatalytic Internal Surface Coating for Cathode of Commercial SOFCs (Final Report)

This project is aimed to develop a chromium (Cr) tolerant, highly active, and stable coating layer on the internal surfaces of the porous composite cathode from commercially available SOFCs. Such coating layer was developed using the additive manufacturing process of Atomic Layer Deposition (ALD) and has been applied on the cathode consisting of either an electronic conductor of LaxSr 1-x MnyO 3-δ (LSM) or mixed ionic and electronic conducting La x Sr 1-x Co y Fe 1-y O 3-δ (LSCF). PI's work has demonstrated that the internal surface of cathode from the commercial cells, can be further tailored using ALD coating to dramatically enhance the cell performance. For instance, ALD layer consisting heterostructured nano composite of nano-Pt and nano-(Mn 0.8 Co 0.2 ) 3 O 4 oxide on the internal surface of porous LSM/YSZ cathode from SOFCs, has resulted in the large reduction of the cell polarizations resistance by up to 53%, and enormous increase of power density over 370%. For the cells with LSCF/Sm 2 O 3 doped CeO 2 (SDC) cathode, the conformal layer of nano-composite consisting of superjacent CoOx and subjacent minimum amount of Pt nano-grains has resulted in the power density enhancement by 126% for the large scale industry tubular cells at 750°C, and both the performance enhancement and nanostructure of the ALD layer are stable over ~ 2000 h continuous operation performed at industry test station. In the meanwhile, those ALD coating layer developed by PI's work is also inherently Cr-tolerant, and could act as physical barrier for preventing Cr diffusion into the cathode backbone, so as to mitigate the Cr poisoning effect on the cathode. In this project, the impact of Cr on the performance of those ALD coated commercial cells has been evaluated. Based on evolution of the cell performance, the ALD coating layer chemistry and ALD coating layer thickness has been optimized to maximize the overall Cr tolerance, cell power density and cell longevity. Different ALD coating has been applied onto the internal surface of LSM/YSZ and LSCF/SDC backbone respectively. The architecture/scaffold structures on the internal surface of different cathode, designed by this project, was catalogued and analyzed using High Resolution Transmission Electron Microscopy (HRTEM), and cell power/durability performance are assured via comprehensive electrochemical performance testing in the industry operation relevant conditions. The impact of the electrochemical operation current density, the water humidity, the cell operation temperature, and cell operation duration on the Cr tolerance of ALD coated cells has been systematically investigated. There is completely different nanostructure degradation mechanisms between LSM and LSCF cells induced by Cr contamination. For the LSCF/SDC baseline cell, With the Cr source, there is no apparent Sr surface segregation phase even for the baseline cell operated for 3000 h at 750 °C. With the Cr source, there is significant amorphous (SrCr)Ox phase accumulated in the original pore region. For the commercial baseline cells, Cr contaminants on the LSM electrode severely impacted the entire cell's electrochemical performance and nanostructure degradation. Those degradations include (1). Peak power density loss of 64 % after 109 h of operation. The dramatic increase in Rp (2). They are cracking at LSM/SSZ interface, LSM grains. SSZ remains intact but with (CrMn)Ox. By contrast, ALD coating (MnCo)Ox/Pt dramatically improves the Cr resistance, as follows (1). ALD-coated cell with a power density is 280-380 % of the baseline cell, depending on the ALD layer thickness. (2). For a cell with a 20 nm thick ALD layer, there is a large performance enhancement (> 200 % power density) induced by ALD coating of Cr-tolerant Mn 0.8 Co 0.2 Ox. (3). For a cell with a 20 nm thick ALD layer, after 168 h at 750 °C power density of the ALD-coated cell is ~ 600% of that baseline cell upon operation with Cr contamination for 109 h. The ALD coating on the internal surface of cathode developed by this project integrated multi-functions. Those multi-functions include (1). Dramatically improving the cell power density for the commercial cells; (2). Dramatically improving contamination resistance of the cathode, for being an excellent protection coating layer sealing off Cr contamination. (3). Dramatically increasing the cell longevity by potentially preventing the microstructure evolution and grain coarsening of the cathode. Overall, this project will provide a simple solution to simultaneously enhance power density and increase the reliability, robustness, and endurance of commercial SOFCs, over the entire operating temperature range of 650-800 °C. For the inherently functional SOFC, the ALD coating of LSM based cathode mitigate the Cr-contamination. Power density of ALD-coated cell is ~ 600% of that baseline cell upon operation with Cr contamination. In addition to SOFCs, the novel on-demand design approach and creation of multifunctional heterogeneous architecture on the electrode surface presented in this work opens further research for their application in other types of fuel cells, batteries, and sensors for which electrochemical reactions on the surface are similarly critical.

36 MATERIALS SCIENCE↗
NASA NTRS1993

Immiscible phase incorporation during directional solidification of hypermonotectics

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

Andrews, J. Barry↗
NASA NTRS1999

Microgravity Transport Phenomena Experiment (MTPE) Overview

The Microgravity Transport Phenomena Experiment (MTPE) is a fluids experiment supported by the Fundamentals in Biotechnology program in association with the Human Exploration and Development of Space (BEDS) initiative. The MTP Experiment will investigate fluid transport phenomena both in ground based experiments and in the microgravity environment. Many fluid transport processes are affected by gravity. Osmotic flux kinetics in planar membrane systems have been shown to be influenced by gravimetric orientation, either through convective mixing caused by unstably stratified fluid layers, or through a stable fluid boundary layer structure that forms in association with the membrane. Coupled transport phenomena also show gravity related effects. Coefficients associated with coupled transport processes are defined in terms of a steady state condition. Buoyancy (gravity) driven convection interferes with the attainment of steady state, and the measurement of coupled processes. The MTP Experiment measures the kinetics of molecular migration that occurs in fluids, in response to the application of various driving potentials. Three separate driving potentials may be applied to the MTP Experiment fluids, either singly or in combination. The driving potentials include chemical potential, thermal potential, and electrical potential. Two separate fluid arrangements are used to study membrane mediated and bulk fluid transport phenomena. Transport processes of interest in membrane mediated systems include diffusion, osmosis, and streaming potential. Bulk fluid processes of interest include coupled phenomena such as the Soret Effect, Dufour Effect, Donnan Effect, and thermal diffusion potential. MTP Experiments are performed in the Microgravity Transport Apparatus (MTA), an instrument that has been developed specifically for precision measurement of transport processes. Experiment fluids are contained within the MTA fluid cells, designed to create a one dimensional flow geometry of constant cross sectional area, and to facilitate fluid filling and draining operations in microgravity. The fluid cells may be used singly for bulk solutions, or in a Stokes diaphragm configuration to investigate membrane mediated phenomena. Thermal and electrical driving potentials are applied to the experiment fluids through boundary plates located at the ends of the fluid cells. In the ground based instrument, two constant temperature baths circulate through reservoirs adjacent to the boundary plates, and establish the thermal environment within the fluid cells. The boundary plates also serve as electrodes for measurement and application of electrical potentials. The Fluid Manipulation System associated with the MTA is a computer controlled system that enables storage and transfer of experiment fluids during on orbit operations. The system is used to automatically initiate experiments and manipulate fluids by orchestrating pump and valve operations through scripted sequences. Unique technologies are incorporated in the MTA for measurement of fluid properties. Volumetric Flow Sensors have been developed for precision measurement of total fluid volume contained within the fluid cells over time. This data is most useful for measuring the kinetics of osmosis, where fluid is transported from one fluid cell to another through a semipermeable membrane. The MicroSensor Array has been designed to perform in situ measurement of several important fluid parameters, providing simultaneous measurement of solution composition at multiple locations within the experiment fluids. Micromachined sensors and interface electronics have been developed to measure temperature, electrical conductivity, pH, cation activity, and anion activity. The Profile Refractometer uses a laser optical system to directly image the fluid Index of Refraction profile that exists along the MTA fluid cell axis. A video system acquires images of the RI profile over time, and records the transport kinetics that occur upon application of chemical, thermal, or electrical driving potentials. Image processing algorithms have been developed to analyze the refractometer images on a pixel by pixel basis, calibrating and scaling the measured Index of Refraction profile to correlated solution properties of interest such as density, concentration, and temperature. Additional software has been developed to compile the processed images into a three dimensional matrix that contains fluid composition data as a function of experiment time and position in the fluid cell. These data are combined with data from the other sensor systems, and analyzed in the context of transport coefficients associated with the various transport phenomena. Analysis protocols have been developed to measure the transient kinetics, and steady state distribution of fluid components that occur in response to the applied driving potentials. The results are expressed in terms of effective transport coefficients. Experiments have been performed using a variety of solutes, and results generated are that are in agreement with published transport coefficient values.

Mason, Larry W.↗
DOE OSTI2025

The role of sample–window coupling in shock temperature experiments

Radiometric studies of opaque materials under shock compression probe a sample–window interface that may be very different than the bulk state. Subtle experimental details, particularly an initial sample–window gap vs an adhesively bonded stack, have tremendous influence on measured temperature. This work experimentally tests gapped vs bonded targets and theoretically investigates observed differences in the measured temperature. The results indicate that perturbations created by a thin adhesive are smaller than those suggested by a previous work, whereas sample–window gaps alter the measured state more significantly than that previously realized.

Adhesives↗
DOE OSTI2023

Rapid Simulation of Unconventional Reservoirs by Multidomain Multiresolution Modeling Based on the Diffusive Time of Flight

Summary The fast marching method (FMM)-based rapid flow simulation has been shown to accelerate simulation efficiency by orders of magnitude by transforming 3D simulation to equivalent 1D simulation using the concept of the “diffusive time of flight” (DTOF). However, the 1D transformation does not directly apply to multiwell problems. In this paper, we propose a novel DTOF-based multidomain multiresolution discretization scheme to accelerate multiwell simulation of unconventional reservoirs. Our method formulates multiwell simulation problems based on the DTOF which displays the pressure front propagation in unconventional reservoirs. The DTOF contours are used to partition the reservoir into local and shared domains. A local domain is where the flow is dominated by a single well, and the shared domain is where the fluid flow is influenced by multiple wells. The DTOF contours expand independently in local domains and interfere in the shared domain. After the partitioning, each domain is discretized using a multiresolution scheme whereby the original 3D fine mesh is preserved near the wells to account for detailed physics including gravity, and the rest of the domain is discretized into 1D mesh based on the DTOF contours to alleviate the simulation workload. The power and efficacy of our approach are demonstrated using synthetic and field-scale simulation models with different degrees of geologic and well-completion complexity. The simulation results, number of active cells, and computation time for the proposed discretization scheme are compared with the original high-fidelity 3D model for each case. The results show that the proposed method is suitable for multiwell simulation problems in unconventional reservoirs and can accelerate flow simulations by orders of magnitude with minimal loss of accuracy. The novelty of this work is the creation of DTOF-derived multiresolution discretization with local and shared domains to simplify and accelerate the calculation of subsurface flow problems, especially in unconventional reservoirs. Our workflow can be easily interfaced with commercial simulators, making it suitable for large-scale field applications.

Engineering↗
DOE OSTI2022

Smoothed particle hydrodynamics modeling and analysis of oxide reduction process for uranium oxides

A common kinetic feature for oxide reduction chemical/electrochemical processes is oxygen transport via a porous metallic layer, which has been considered as a rate-determining step for reducing uranium oxides to metallic uranium. Accounting this kinetic behavior must involve the resolution of the moving reactive interface between shrinking oxide and expanding metal phases. This study presents a numerical model using smoothed particles hydrodynamics (SPH) to effectively deal with the evolution of the shrinking core reaction interface and oxygen transport via mass transfer of lithium oxide (Li 2 O) species in multiple mass transfer domains. We successfully validated the proposed model against a theoretical derivation for the oxide reduction process handling a shrinking oxide core with molten salt and metal ash medium on a simple planar geometry. Armed with successful validation results, the model examined a realistic reactant geometry to extend the arguments beyond the one-dimensional analyses, allowing the proposed model to apply to general application scenarios with multi-dimensional geometry. Here, this study demonstrated that the proposed model could simulate and evaluate an arbitrary reaction basket design without iterative experimental trials, which is prohibitive for a scaled high-temperature molten salt study in an inert environment. The construct potentially provides not only deep insights on multiphysics behaviors governing the process dynamics but also a robust framework for evaluating and screening candidate basket designs in the most cost-effective manner.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Coupling between interfacial charge and mechanical deformation at high temperatures in ceramics. Final report

Basic research, under this project, has led to new fundamental discoveries in the effect of electric field (and temperature) on diffusion kinetics, electroluminescence and electronic conductivity in ceramic materials. For example, yttria stabilized zirconia sinters in just seconds well below 1000°C, while, at the same time, exhibiting a highly non-linear rise in conductivity, and intense electroluminescence. The phenomenon has been shown to occur in nearly all ceramics whether they are ionic or electronic conductors, or insulators. The rise in conductivity leads to Joule heating but in-situ measurements with a platinum standard at APS and Brookhaven (NSLS-II) have shown that the temperatures are much below what would have been needed to sinter in a few seconds. We have explored the hypothesis that huge concentrations of Frenkel pairs of vacancies and interstitials are produced. While these point defects accelerate sintering (by the interstitials being transported to the pores and the vacancies to the grain boundaries), they may also produce electron-hole pairs which can impart high electrical conductivity or recombine to emit photons. Many measurements, including in-situ measurements of lattice expansion are consistent with this hypothesis. However, the energy barrier for generating Frenkels in zirconia for example is much larger than can be expected at temperature and electrical fields in these experiments. Most recent work suggests that short wavelength phonons play a critical role in the genesis of the “flash” phenomenon. For example, the Debye temperature has been shown to be the lower bound for initiating flash. Molecular dynamics simulations have shown that large concentrations of Frenkel pairs can form under the proliferation of “optical” phonons at the edge of the Brillouin zone, that is with a wavelength at or below the lattice parameter. This project has led to the development of new experimental techniques as well as a software hardware interface for process and control and data analysis in real time, with a time scale of less than one second. This approach spells a new paradigm in materials science research. It potential impact on high rate manufacturing is self evident.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Through‐Plane Conductive Hydrophobic Electrodes for CO 2 Electrolysis to Ethylene

Copper catalyst gas diffusion electrodes (GDEs) have demonstrated unique electrochemical selectivity converting CO 2 to C 2 -hydrocarbons such as ethylene and ethanol but have been challenged by their hydrophobic chemical stability and internal electrical resistance leading to low energy efficiency. Carbon-supported GDEs have low electrical resistance but lack sufficient stability at industrially relevant current densities. While polymer-supported GDEs have improved hydrophobicity, they also display high in-plane electrical resistance, particularly at industrial scales. Here, in this work, we demonstrate a composite gas diffusion layer that combines hydrophobic porous polymers with an electrically conductive backbone addressing these core gas diffusion electrode (GDE) scaling challenges. We investigate the material properties of standalone porous perfluoropolyether (PFPE) polymers, including porosity and surface morphology, under varying processing conditions and then incorporate these polymers into a porous copper foam. This composite enhances the mechanical rigidity necessary for cell assembly and provides a through-plane electrical conduction path to reduce electrical resistive losses. This enhanced PFPE composite GDE displays efficient CO 2 reduction, achieving 15% ethylene energy efficiency at 100 cm 2 . These findings contribute to the development of advanced catalyst materials and electrode architectures and promote scalable strategies for electrochemical conversion of CO 2 into high-value carbon products.

Chemistry↗
NASA NTRS1995

First spectral observations of the diffuse background with the Extreme Ultraviolet Explorer

We present the first results from the analysis of the spectroscopic observations of diffuse extreme ultraviolet (EUV) emission taken with the Extreme Ultraviolet Explorer (EUVE) spectrometers in the wavelength range 160-740 A. Although not designed or optimized for diffuse observation, the EUVE spectrometers are the most sensitive diffuse EUV spectrometer in orbit. The spectral resolution for diffuse emission of the medium and long-wavelength spectrometers are 17 and 34 A FWHM, respectively. During the period from 1992 July 25 to 1992 August 19, the spectrometers surveyed a 2 x 20 deg field scanned from (l, b) = (24 deg, -28 deg) to (44 deg, -74 deg) with a total effective exposure time of 575,232 s. The only emission lines detected were those of He I and He II (584, 537, 304 A) with intensities consistent with local geocoronal and/or interplanetary scattering of solar radiation (584 A = 1.30 rayleighs; 537 A = 0.040 R; and 304 A = 0.029 R). Models of the soft X-ray background, which results from a 10(exp 6) K plasma (Local Bubble) surrounding the neutral gas near the Sun (Local Cloud), predict that most of the flux from the hot plasma appears as emission lines in the EUV. We have compared these spectral predictions with our observations to place limits on the emission measure versus temperature of the proposed hot plasma. Using the same plasma model, we derived emissions measures for our data and the C and B soft X-ray bands of the Wisconsin rocket survey. We find that our limits for the plasma emission measure are a factor of 5-10 below the C- and B-band emission measures over the temperature range from 10(exp 5.7) to 10(exp 6.4) K. We explore possible scenarios that could reconcile our results with the X-ray surveys and conclude that depletion or a nonequilibrium plasma state rather than absorption are the more likely explanations of the discrepancy. We also show that our spectrum is inconsistent with the spectrum from the approximately 10(exp 5) K gas at the conductive interface between the hot Local Bubble and the cooler Local Cloud given by Slavin (1989). In addition, we place new limits on the helium ionization parameter in the Sun's vicinity caused by the 10(exp 6) K plasma in the Local Bubble.

Jelinksy, P.↗
NASA NTRS1998

Profile Evolution Simulation in Etching Systems Using Level Set Methods

Semiconductor device profiles are determined by the characteristics of both etching and deposition processes. In particular, a highly anisotropic etch is required to achieve vertical sidewalls. However, etching is comprised of both anisotropic and isotropic components, due to ion and neutral fluxes, respectively. In Ar/Cl2 plasmas, for example, neutral chlorine reacts with the Si surfaces to form silicon chlorides. These compounds are then removed by the impinging ion fluxes. Hence the directionality of the ions (and thus the ion angular distribution function, or IAD), as well as the relative fluxes of neutrals and ions determines the amount of undercutting. One method of modeling device profile evolution is to simulate the moving solid-gas interface between the semiconductor and the plasma as a string of nodes. The velocity of each node is calculated and then the nodes are advanced accordingly. Although this technique appears to be relatively straightforward, extensive looping schemes are required at the profile corners. An alternate method is to use level set theory, which involves embedding the location of the interface in a field variable. The normal speed is calculated at each mesh point, and the field variable is updated. The profile comers are more accurately modeled as the need for looping algorithms is eliminated. The model we have developed is a 2-D Level Set Profile Evolution Simulation (LSPES). The LSPES calculates etch rates of a substrate in low pressure plasmas due to the incident ion and neutral fluxes. For a Si substrate in an Ar/C12 gas mixture, for example, the predictions of the LSPES are identical to those from a string evolution model for high neutral fluxes and two different ion angular distributions.(2) In the figure shown, the relative neutral to ion flux in the bulk plasma is 100 to 1. For a moderately isotropic ion angular distribution function as shown in the cases in the left hand column, both the LSPES (top row) and rude's string method (bottom row) predict tapered profiles. The LSPES uses an AD with a FWHM = 13.5 degrees, and rude's model uses a ratio of sheath voltage to ion temperature of 50. The more anisotropic IADs produce profiles with more vertical sidewalls and a wider bottom surface, as shown in the right hand column. Here, the LSPES has an AD with a FWHM = 2 degrees, and rude's model uses a ratio of 500 of sheath voltage to ion temperature. The agreement between the LSPES and rude's model is excellent in both cases. We will present etching profiles generated by the LSPES, including calculations of the re-emitted fluxes of both neutrals and ions off of the profile walls. In addition, we will show the effect of geometric structures (overhangs, etc.) on the etching profiles. Other physical aspects, such as surface diffusion, will also be included in the model.

Hwang, Helen H.↗
DOE OSTI2020

Role of the Terrestrial Biosphere in Atmospheric Chemistry and Climate

The terrestrial biosphere–atmosphere interface provides a key chemical, biological, and physical lower boundary for the atmosphere. The presence of vegetation itself modifies the physical boundary, or the biogeophysical aspects of the system, by controlling important climate drivers such as soil moisture, light environment, and temperature. The leaf surface area of the terrestrial biosphere provides additional surface area for emissions, and it can be up to 55% of the total Earth’s surface area during the boreal summer. Vegetation also influences the biogeochemical aspects of the system by emitting a broad suite of reactive trace gases such as biogenic volatile organic compound (BVOC) emissions and climate-relevant primary biological aerosol particles (PBAP). Many of these emissions are a function of meteorological and climatological conditions at the surface, including temperature, light environment, soil moisture, and winds. Once emitted, they can be processed in the troposphere through a suite of chemical reactions. BVOC can contribute to the formation of ozone and secondary organic aerosols (SOA), and PBAP can rupture to form smaller particles with climatic relevance. These emissions and subsequent aerosol products can influence atmospheric processes that affect the surface climate, such as the attenuation of radiation, the formation of greenhouse gases such as ozone that can feedback to surface air temperature, and the alteration of clouds and subsequent precipitation. These atmospheric changes can then feedback to the land surface and emissions themselves, creating positive or negative feedback loops that can dampen or amplify the emission response. For the dominant BVOC isoprene, the feedback response to temperature can be positive or negative depending on ambient temperatures that drive isoprene emissions. The feedback response to soil moisture and precipitation can be positive, negative, or uncoupled depending on the moisture content of the soil and the total atmospheric aerosol loading. For light, the isoprene response can be positive or negative depending on the role of diffuse light. Overall, these feedbacks highlight the dynamical response of the biosphere to changing atmospheric conditions across a range of time scales, from minutes for trace gases and aerosols, to months for phenological changes, to years for land cover and land use change. Here, the dynamic aspect of this system requires us to understand, simulate, and predict the complex feedbacks between the biosphere and atmosphere and understand their role in the simulation and understanding of climate and global change. From the observational perspective, these feedbacks are challenging to identify in observations, and predictive modeling tools provide a crucial link for understanding how these feedbacks will change under warming climate scenarios.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Multi-technique characterization of spray coated and roll-to-roll coated gas diffusion fuel cell electrodes

Here this work reports the characterization of catalyst layer (CL) structure and composition for a set of gas-diffusion electrodes (GDEs) fabricated by different coating methods with the goal of developing a better understanding of CL processing-structure-property-performance relationships. The CL coating techniques used in this study were ultrasonic spray coating, and two roll-to-roll (R2R) methods - gravure and slot die. Scanning transmission electron microscopy (STEM) coupled with X-ray energy dispersive spectroscopy (EDS) analysis of GDE cross-sections provided bulk information, while scanning electron microscopy (SEM) with EDS and X-ray photoelectron spectroscopy (XPS) were used to investigate the near surface and surface composition of the CLs that will be in direct contact with the membrane once the membrane electrode assembly (MEA) is constructed. This study demonstrates that common quantification parameters, namely the F:Pt ratio extracted from cross-sectional STEM-EDS maps and top-down CL measurements with SEM and XPS, along with roughness parameters quantified from SEM micrographs are useful parameters in explaining and potentially predicting performance trends. Additionally, it highlights the importance of understanding key CL surface properties for advancing the manufacturability of high-performance components for polymer electrolyte membrane (PEM) technologies.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

A quantitative model of charge injection by ruthenium chromophores connecting femtosecond to continuous irradiance conditions

A kinetic framework for the ultrafast photophysics of tris(2,2-bipyridine)ruthenium(II) phosphonated and methyl-phosphonated derivatives is used as a basis for modeling charge injection by ruthenium dyes into a semiconductor substrate. By including the effects of light scattering, dye diffusion, and adsorption kinetics during sample preparation and the optical response of oxidized dyes, quantitative agreement with multiple transient absorption datasets is achieved on timescales spanning femtoseconds to nanoseconds. In particular, quantitative agreement with important spectroscopic handles—the decay of an excited state absorption signal component associated with charge injection in the UV region of the spectrum and the dynamical redshift of a ~500 nm isosbestic point—validates our kinetic model. Pseudo-first-order rate coefficients for charge injection are estimated in this work, with an order of magnitude ranging from 10 11 to 10 12 s –1 . The model makes the minimalist assumption that all excited states of a particular dye have the same charge injection coefficient, an assumption that would benefit from additional theoretical and experimental exploration. Here, we have adapted this kinetic model to predict charge injection under continuous solar irradiation and find that as many as 68 electron transfer events per dye per second take place, significantly more than prior estimates in the literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2000

Over-Expression, Purification and Crystallization of Human Dihydrolipoamide Dehydrogenase

Dehydrolipoamide dehydrogenase (E3; dihydrolipoan-tide:NAD+ oxidoreductase, EC 1.8.1.4) is a common catalytic component found in pyruvate dehydrogenase complex, alpha-ketoglutarate dehydrogenase complex, and branched-chain cc-keto acid dehydrogenase complex. E3 is also a component (referred to as L protein) of the glycine cleavage system in bacterial metabolism (2). Active E3 forms a homodimer with four distinctive subdomain structures (FAD binding, NAD+ binding, central and interface domains) with non-covalently but tightly bound FAD in the holoenzyme. Deduced amino acids from cloned full-length human E3 gene showed a total of 509 amino acids with a leader sequence (N-terminal 35 amino acids) that is excised (mature form) during transportation of expressed E3 into mitochondria membrane. So far, three-dimensional structure of human E3 has not been reported. Our effort to achieve the elucidation of the X-ray crystal structure of human E3 will be presented. Recombinant pPROEX-1 expression vector (from GIBCO BRL Life Technologies) having the human E3 gene without leader sequence was constructed by Polymerase Chain Reaction (PCR) and subsequent ligation, and cloned in E.coli XL1-Blue by transformation. Since pPROEX-1 vector has an internal His-tag (six histidine peptide) located at the upstream region of a multicloning site, one-step affinity purification of E3 using nickelnitriloacetic acid (Ni-NTA) agarose resin, which has a strong affinity to His-tag, was feasible. Also a seven-amino-acid spacer peptide and a recombinant tobacco etch virus protease recognition site (seven amino acids peptide) found between His-tag and first amino acid of expressed E3 facilitated the cleavage of His-tag from E3 after the affinity purification. By IPTG induction, ca. 15 mg of human E3 (mature form) was obtained from 1L LB culture with overnight incubation at 25C. Over 98% of purity of E3 from one-step Ni-NTA agarose affinity purification was confirmed by SDS-PAGE analysis. For crystallization, E3 samples were prepared with and without His-tag. To minimize the aggregation of E3, apo- and holo- forms of E3s were tested, as well as a mutated E3. Dynamic light scattering measurements revealed that the E3 preparations without His-tag and substrate are highly monodispersive with regard to homodimers. Consequent crystallization trials of this E3 preparation led to single crystals of E3 grown by the vapor diffusion method. Crystals were obtained within a few days from solution containing poly (ethylene glycol) monomethyl ether 5000 as a precipitant. Autoindexing and integration of the X-ray diffraction data showed that E3 crystals belong to an orthorhombic system with unit cell parameters a-- 123. 1, b= 165.3 and c=214.3A. Further optimization of protein preparation and crystallization experiments for the structural determination will be discussed.

Hong, Y. S.↗