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At least 847 records · Page 47

Dose-Response Evaluation of Braslet-M Occlusion Cuffs

Introduction: Braslet-M is a set of special elasticized thigh cuffs used by the Russian space agency to reduce the effects of the head-ward fluid shift during early adaptation to microgravity by sequestering fluid in the lower extremities. Currently, no imaging modalities are used in the calibration of the device, and the pressure required to produce a predictable physiological response is unknown. This investigation intends to relate the pressure exerted by the cuffs to the extent of fluid redistribution and commensurate physiological effects. Materials and Methods: Ten healthy subjects with standardized fluid intake participated in the study. Data collection included femoral and internal jugular vein imaging in two orthogonal planes, pulsed Doppler of cervical and femoral vessels and middle cerebral artery, optic nerve imaging, and echocardiography. Braslet-M cuff pressure was monitored at the skin interface using pre-calibrated pressure sensors. Using 6 and 30 head-down tilt in two separate sessions, the effect of Braslet-M was assessed while incrementally tightening the cuffs. Cuffs were then simultaneously released to document the resulting hemodynamic change. Results: Preliminary analysis shows correlation between physical pressure exerted by the Braslet-M device and several parameters such as jugular and femoral vein cross-sections, resistivity of the lower extremity vascular bed, and others. A number of parameters reflect blood redistribution and will be used to determine the therapeutic range of the device and to prevent unsafe application. Conclusion: Braslet-M exerts a physical effect that can be measured and correlated with many changes in central and peripheral hemodynamics. Analysis of the full data set will be required to make definitive recommendations regarding the range of safe therapeutic application. Objective data and subjective responses suggest that a safer and equally effective use of Braslet can be achieved when compared with the current non-imaging calibration techniques.

Ebert, Douglas↗

Electroanalytical Measurement of Interphase Formation at a Li Metal–Solid Electrolyte Interface

The interphase between Li metal and solid electrolytes dictates performance in Li metal batteries. For the solid electrolyte Lipon, in this study we electroanalytically measure a capacity loss of 1.03 ± 0.16 μAh/cm 2 when Lipon first contacts Li metal. Assuming this capacity is all lost to interphase formation, this corresponds to a maximum Li consumption of 5.0 ± 0.8 nm to form an interphase ~4.7 nm thick. From dynamic electrochemical impedance spectroscopy (dEIS) during Li plating, we determine that nonlinear chaotic spectra demark this interphase formation and that this occurs immediately upon initiation of Li plating. dEIS also reveals interfacial resistance during both plating and stripping that decreases as the amount of plated Li increases.

25 ENERGY STORAGE↗

Detection of a Cobalt-Containing Interphase at the Li 6 PS 5 Cl-NMC111 Interface by In Situ μ XANES and EIS

Sulfide electrolyte all-solid-state lithium batteries (ASLBs) with uncoated Li-Ni x Mn y Co 1–x–y O 2 (NMC) cathodes suffer from a large capacity loss during initial cycling and an increase in cell impedance. Decomposition reactions are known to occur at the Li 6 PS 5 Cl-NMC111 interface due to incompatibility between the two materials. If a stabilizing coating is applied to the NMC, it delivers full capacity during initial charge. However, the loss in capacity during discharge still occurs. The interface was studied by μ XANES and through EIS analysis. A chemically-formed interphase was detected by μ XANES, evident from reduction of Co at an uncoated NMC particle surface. This interphase was produced by decomposition at rest. To study the effect of the interphase on electrochemically active surface area, piecewise in situ EIS was performed and the data was modeled using a transmission line model (TLM). The charge transfer resistance R CT was used to estimate the volume specific active surface area (a act ). The median value for a act was 296 cm –1 , a factor of 7.5 lower than the theoretical value of 2216 cm –1 . This provided evidence of a lower electrochemically active surface area in the ASLB.

36 MATERIALS SCIENCE↗

High-current, high-voltage AlN Schottky barrier diodes

AlN Schottky barrier diodes with low ideality factor (<1.2), low differential ON-resistance (<0.6 mΩ cm 2 ), high current density (>5 kA cm −2 ), and high breakdown voltage (680 V) are reported. The device structure consisted of a two-layer, quasi-vertical design with a lightly doped AlN drift layer and a highly doped Al 0.75 Ga 0.25 N ohmic contact layer grown on AlN substrates. A combination of simulation, current–voltage measurements, and impedance spectroscopy analysis revealed that the AlN/AlGaN interface introduces a parasitic electron barrier due to the conduction band offset between the two materials. This barrier was found to limit the forward current in fabricated diodes. Further, we show that introducing a compositionally-graded layer between the AlN and the AlGaN reduces the interfacial barrier and increases the forward current density of fabricated diodes by a factor of 10 4 .

Quiñones, C. E. (ORCID:0000000192703747)↗

Study program to develop and evaluate die and container materials for the growth of silicon ribbons

The development and evaluation of proprietary coatings of pure silicon carbide, silicon nitride, and aluminum nitride on less pure hot pressed substrates of the respective ceramic materials, is described. Silicon sessile drop experiments were performed on coated test specimens under controlled oxygen partial pressure. Prior to testing, X-ray diffraction and SEM characterization was performed. The reaction interfaces were characterized after testing with optical and scanning electron microscopy and Auger electron spectroscopy. Increasing the oxygen partial pressure was found to increase the molten silicon contact angle, apparently because adsorbed oxygen lowers the solid-vapor interfacial free energy. It was also found that adsorbed oxygen increased the degree of attack of molten silicon upon the chemical vapor deposited coatings. Cost projections show that reasonably priced, coated, molten silicon resistant refractory material shapes are obtainable.

Addington, L. A.↗

A basic design fault in ceramic flat packs

Recent moisture resistance tests of various multilayer top brazed ceramic flat packs and leaded and unleaded chip carriers has revealed a serious design defect. These packages, which utilize a tungsten interconnect system, in the presence of high humidity, suffer a galvanic corrosion which anodically consumes the tungsten. This process can continue until the package suffers an open circuit. The test results indicate that the lead plating system does not adequately seal off the interface area where the tungsten strips egresses from the inside of the package.

Drotman, B.↗

Buoyancy-driven instabilities and the nonlinear breakup of a sheared magnetic layer

Motivated by problems concerning the storage and subsequent escape of the solar magnetic field, a study has been made of how a magnetic layer embedded in a convectively stable atmosphere evolves due to axisymmetric instabilities driven by magnetic buoyancy. The initial equilibrium consists of a toroidal field sheared by a weaker poloidal component. The linear stability problem is investigated for both ideal and resistive MHD, and the nonlinear evolution is followed by numerical integration of the equations of motion. In all cases, the instability is greatly affected by the distribution and strength of the poloidal field. In particular, both the horizontal and vertical scales of the motions are controlled by the location of the surface on which the poloidal field vanishes: the resonant surface. In the nonlinear regime, a resonant surface close to the interface between the magnetized and field-free fluid leads to the localization of the instability, so that only a fraction of the magnetic region is disrupted by the motions. By contrast, a deeply seated resonant surface leads to the complete disruption of the layer and to the formation of large, helical magnetic fragments whose identity is preserved for the entire simulation.

Cattaneo, Fausto↗

Utilizing the unique charge extraction properties of antimony tin oxide nanoparticles for efficient and stable organic photovoltaics

Simultaneously enhancing device performance and longevity, as well as balancing the requirements on cost, scalability, and simplification of processing, is the goal of interface engineering of organic solar cells (OSCs). In our work, we strategically introduce antimony (Sb 3+ ) cations into an efficient and generic n-type SnO 2 nanoparticles (NPs) host during the scalable flame spray pyrolysis synthesis. Accordingly, a significant switch of conduction property from an n-type character to a p-type character is observed, with a corresponding shift in the work function (WF) from 4.01 ± 0.02 eV for pristine SnO 2 NPs to 5.28 ± 0.02 eV for SnO 2 NPs with 20 mol. % Sb content (ATO). Both pristine SnO 2 and ATO NPs with fine-tuned optoelectronic properties exhibit remarkable charge carrier extraction properties, excellent UV resistance and photo-stability being compatible with various state-of-the-art OSCs systems. The reliable and scalable pristine SnO 2 and ATO NPs processed by doctor-blading in air demand no complex post-treatment. Our work offers a simple but unique approach to accelerate the development of advanced interfacial materials, which could circumvent the major existing interfacial problems in solution-processed OSCs.

14 SOLAR ENERGY↗

Heterogeneous Corrosion Pathways in Pt–Ni Nanododecahedra Revealed by In Situ Liquid Cell TEM

Unraveling nanoscale corrosion pathways is essential for understanding materials degradation mechanisms and designing corrosion-resistant metal alloys. Here, in this study, we directly visualize the corrosion of Pt–Ni nanododecahedra in 0.1 M HCl using liquid cell TEM. Each nanoparticle features a Ni-rich core and a Pt-rich frame. Our observation reveals that corrosion proceeds in two distinct stages: first the Ni-rich core dissolves without forming porosity, yielding small Pt nanocrystals and transient NiCl 2 ·6H 2 O at the retreating interfaces; then the Pt-rich frame fragments into ∼5 nm Pt 3 Ni nanocrystals that subsequently dissolve uniformly, accompanied by fleeting Pt chlorides. A percolation-based theory explains the observed behaviors: The core’s ∼8% Pt lies below the Pt connectivity threshold, preventing Pt scaffold formation, whereas the frame’s 48% Ni exceeds the Ni percolation threshold and collapses. Ordered Pt 3 Ni suppresses Ni percolation, thereby enforcing uniform dissolution. These findings reveal how composition and structural ordering govern heterogeneous corrosion in Pt–Ni architectured nanoparticles.

Liquid phase TEM↗

Effect of cycling on the lithium/electrolyte interface in organic electrolytes

Nondestructive methods such as ac impedance spectroscopy and microcalorimetry are used to study the effect of cell cycling on the lithium/electrolyte interface. The reactivity of both uncycled and cycled lithium towards various electrolytes is examined by measuring the heat evolved from the cells under open-circuit conditions at 25 C by microcalorimetry. Cycled cells at the end of charge/discharge exhibited considerably higher heat output compared with the uncycled cells. After 30 d of storage, the heat output of the cycled cells is similar to that of the uncycled cells. The cell internal resistance increases with cycling, and this is attributed to the degradation of the electrolyte with cycling.

Surampudi, S.↗

Novel Nanolaminates for Aerospace Applications

Nanolaminate manufacturing (NLM) is a new way of developing materials whose properties can far exceed those of homogeneous materials. Traditional alloys, composites and bulk laminates tend to average the properties of the materials from which they were made. With nanostructured materials, the high density of interfaces between dissimilar materials results in novel material properties. For example, materials made -from alternating nanoscale layers of metals and oxides have exhibited thermal conductivities far below those of the oxides themselves. Also, metallic nanolaminates can have peak strengths 100 times lager than the bulk constituent metals. Recent work at MSFC has focused on the development of nickel/aluminum oxide (Ni/Al2O3)) nanolaminates. Ni/Al2O3 nanolaminates are expected to have better strength, creep and fatigue resistance, oxygen compatibility, and corrosion resistance than the traditional metal-matrix composites of this material, which has been used in a variety of aerospace applications. A chemical vapor deposition (CW) system has been developed and optimized for the deposition of nanolaminates. Nanolaminates with layer thicknesses between 10 and 300 nm have been successfully grown and characterization has included scanning electron microscopy (SEM) and atomic force microscopy (AFM) Nanolaminates have a large variety of potential applications. They can be tailored to have both very small and anisotropic thermal conductivities and are promising as thermal coatings for both rock$ engine components and aerobraking structures. They also have the potential to be used in aerospace applications where strength at high temperatures, corrosion resistance or resistance to hydrogen embrittlement is important. Both CVD and magnetron sputtering facilities are available for the deposition of nanolayered materials. Characterization equipment includes SEM, AFM, X-ray diffraction, transmission electron microscopy, optical profilometry, and mechanical tensile pull testing.

Volz, Martin↗

Simulating the Gradually Deteriorating Performance of an RTG

Degra (now in version 3) is a computer program that simulates the performance of a radioisotope thermoelectric generator (RTG) over its lifetime. Degra is provided with a graphical user interface that is used to edit input parameters that describe the initial state of the RTG and the time-varying loads and environment to which it will be exposed. Performance is computed by modeling the flows of heat from the radioactive source and through the thermocouples, also allowing for losses, to determine the temperature drop across the thermocouples. This temperature drop is used to determine the open-circuit voltage, electrical resistance, and thermal conductance of the thermocouples. Output power can then be computed by relating the open-circuit voltage and the electrical resistance of the thermocouples to a specified time-varying load voltage. Degra accounts for the gradual deterioration of performance attributable primarily to decay of the radioactive source and secondarily to gradual deterioration of the thermoelectric material. To provide guidance to an RTG designer, given a minimum of input, Degra computes the dimensions, masses, and thermal conductances of important internal structures as well as the overall external dimensions and total mass.

Wood, Eric G.↗

Operating Stresses and Their Effects on Degradation of LSM-Based SOFC Cathodes

The performance of solid oxides fuel cells (SOFCs) with four different Mn excess of lanthanum strontium manganite (LSM) -based cathodes were examined under different temperatures (1,000 °C, 900 °C), current densities (0, 380, and 760 mA cm -2 ), and cathode atmospheres (p O 2 )=0.1,0.15,0.21) for durations ranging from 58 to 1,008 h. Each yttria-stabilized zirconia (YSZ) electrolyte-supported “button” cell had a porous Ni/YSZ composite anode and a porous LSM/YSZ composite cathode. The cells’ output voltage versus time were recorded and electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) measurements were performed every 24 hours. The total area specific resistance (ASR) was calculated from these measurements. The values of ASR from both EIS and LSV were comparable between each other but lower than that from durability test. Distribution of relaxation times (DRT) analysis was performed to investigate the electrochemical processes and their corresponding relaxation frequencies as well as their attributions to the total ASR. The series resistance and parallel resistance that obtained from the equivalent circuit fit of the Nyquist plot were higher at low temperature and low p O 2 regardless of LSM compositions. The area of the peaks derived from DRT analysis increased with time during individual tests. The microstructures of the tested cells were examined using scanning electron microscopy and energy-dispersive x-ray spectroscopy (SEM/EDS). Manganese oxide particles were observed near the cathode-electrolyte interface after prolonged (1,008 h) testing in air of a cell with LSM of 11% manganese excess, and after a short test (58 h) under low oxygen (p O 2 = 0.10) in a cell with LSM of 5% manganese excess. However, the role of MnOx in cell degradation is still unknown.

08 HYDROGEN↗

Development of a Robust Reference Electrode in Aggressive Chemical and Radiation Environments in the Hanford Waste Tanks

The Hanford site stores more than 200 million liters of radioactive and chemically hazardous wastes from the production of weapons materials. The wastes are stored in 177 underground carbon-steel storage tanks, separated between 149 single shell tanks (SSTs) and 28 double shell tanks (DSTs). The DSTs provide critical retrieval and interim storage before the waste is vitrified in the Waste Treatment and Isolation Plant (WTP). The tanks will need to remain in-service far beyond the initial 40-year design life, and effective corrosion control practices must remain in force to extend the tanks’ lifespans. This effort includes direct measurements of corrosion rate (e.g., ultrasonic measurements and corrosion coupons) and electrochemical processes (e.g., linear polarization measurements and open circuit potential measurements). The Hanford site began monitoring the corrosion potential in select DSTs in 2008. Of the 45 reference electrodes that have been installed, 29 have failed and 6 others provided unreliable results. DOE-EM is supporting a 3-year program to develop a chemical and radiation resistant reference electrode for application in the Hanford tanks. The first year of the program focused on understanding the failure mechanism for the reference electrodes and identification of candidate construction materials that would mitigate degradation of the electrodes in the waste environment. During the second year of the program, the objectives were to: 1) test candidate materials under simulated waste conditions, 2) design components that will extend the service life of the electrode, 3) fabricate materials for prototype reference electrodes, and 4) assemble prototype reference electrodes for accelerated testing. The reference electrode is constructed of four principal parts: 1) junction, 2) casing, 3) inner chamber backfill materials, and 4) the sensing wire. Principally, improvements of the junction, casing, and inner chamber backfill materials are being pursued. The junction material at the interface between the waste and the inner chamber of the reference electrode was identified as a critical component in the failure of the reference electrodes. Nine candidate replacement junction materials were tested under simulated waste conditions to evaluate permeation rate. These materials included a variety of polymeric and ceramic materials, some of which were 3-D printed. Thus far, porous polyvinylidene fluoride materials have performed satisfactorily and are being considered for prototype development. The commercial electrode casing materials in general have performed well. Additionally, 3-D printing of chemically and mechanically stable materials is being investigated as a means for further improvement in fabrication consistency. SRNL has also investigated altering the reference electrode design to extend the service life. The new design of the interior of the reference electrode casing creates a longer, more tortuous path between the junction material and the electrode sensing wire. A finite element model was used to optimize the design without adversely impacting the circuit resistance of the electrode during the measurements, thus preserving the measurement accuracy while enhancing the service life. The inner chamber back fill materials are also critical to the performance of the reference electrode. Materials that are resistant to intruding tank waste and provide a conductive path to the sensing wire were investigated. Gel and powder materials that are interspersed with a conductive chloride bearing material were tested for their influence on diffusion and electrode resistance. All the investigated materials and components will be assembled, with collaboration from commercial vendors, to fabricate the initial prototypes. Accelerated testing of the prototypes will be initiated in Year 2 of the program and will be completed in Year 3. A recommendation on the materials of construction and the design of the new robust reference electrode will be presented to the Hanford tank farm facility.

Sykes, Kiana [Savannah River National Laboratory (↗

Tunable topological Hall effects in noncollinear antiferromagnet Mn 3 Sn/Pt bilayers

Noncollinear antiferromagnet Mn3Sn has attracted wide interest as it is a candidate for Weyl semimetal. Here, we report the observation of topological Hall like signals in Mn3Sn/Pt bilayers grown on Al 2 O 3 (0001). X-ray diffraction and scanning transmission electron microscopy results confirm the high epitaxial quality of the c-axis-oriented Mn3Sn films. The detected topological Hall resistivity shows a broad temperature range from 210 to 365 K by tuning the thickness of Mn3Sn from 3 to 15 nm. Compared with previously reported topological Hall effects in Mn3Sn at temperatures below 50 K, the observed high-temperature topological Hall signal is likely due to the stabilization of topological spin textures enabled by the strong spin–orbit coupling of the Pt overlayer and the Dzyaloshinskii–Moriya interaction at the Mn3Sn/Pt interface.

36 MATERIALS SCIENCE↗

Power electronics for low power arcjets

In anticipation of the needs of future light-weight, low-power spacecraft, arcjet power electronics in the 100 to 400 W operating range were developed. Limited spacecraft power and thermal control capacity of these small spacecraft emphasized the need for high efficiency. Power topologies similar to those in the higher 2 kW and 5 to 30 kW power range were implemented, including a four transistor bridge switching circuit, current mode pulse-width modulated control, and an output current averaging inductor with an integral pulse generation winding. Reduction of switching transients was accomplished using a low inductance power distribution network, and no passive snubber circuits were necessary for power switch protection. Phase shift control of the power bridge was accomplished using an improved pulse width modulation to phase shift converter circuit. These features, along with conservative magnetics designs allowed power conversion efficiencies of greater than 92.5 percent to be achieved into resistive loads over the entire operating range of the converter. Electromagnetic compatibility requirements were not considered in this work, and control power for the converter was derived from AC mains. Addition of input filters and control power converters would result in an efficiency of on the order of 90 percent for a flight unit. Due to the developmental nature of arcjet systems at this power level, the exact nature of the thruster/power processor interface was not quantified. Output regulation and current ripple requirements of 1 and 20 percent respectively, as well as starting techniques, were derived from the characteristics of the 2 kW system but an open circuit voltage in excess of 175 V was specified. Arcjet integration tests were performed, resulting in successful starts and stable arcjet operation at power levels as low as 240 W with simulated hydrazine propellants.

Hamley, John A.↗

In-situ and in-operando analysis of voltage losses using sense wires for proton exchange membrane water electrolyzers

Proton exchange membrane water electrolyzer development requires understanding processes at the materials and interface levels to reach the required performance and lifetime targets for increasing market penetration. To achieve the required progress, it is critical to develop advanced in-situ diagnostics that allow observation of the changes that come with the reduction of catalyst loading combined with long-term intermittent operation. This work presents an internal voltage sensing method that enables observing internal voltage drops in an operating electrolyzer cell. It allows the total cell resistance to be separated into anode, CCM, and cathode resistance. The method is demonstrated by operating cells with different anode porous transport layers (PTLs). The changing properties of the PTLs result in significant variations of the resistances. Enhancing the PTL properties with a protective coating reduces the anode resistance significantly. In addition to these observations, the method enables a real-time monitoring of resistance related values that impact performance in water electrolyzers. Long-term experiments with the method allow us to gain insights into processes that occur during operation such as conditioning or degradation. The internal voltage sensing method presented in this study is a novel technique for diagnosing, analyzing, and optimizing water electrolyzers and other energy conversion devices.

42 ENGINEERING↗