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At least 505 records · Page 28

Oxygen vacancy migration and impact on high voltage DC polarization in 0.8BaTiO 3 –0.2BiZn 0.5 Ti 0.5 O 3

Electrical polarization and defect transport are examined in 0.8BaTiO 3 –0.2BiZn 0.5 Ti 0.5 O 3 , an attractive capacitor material for high power electronics. Oxygen vacancies are suggested to be the majority charge carrier at or below 250°C with a grain conduction hopping activation energy of 0.97 eV and 0.92 eV for thermally stimulated depolarization current (TSDC) and impedance spectroscopy measurements, respectively. At higher temperature, thermally generated electronic conduction with an activation energy of 1.6 eV is dominant. Significant oxygen vacancy concentration is indicated (up to ~1%) due to cation vacancy formation (i.e., acceptor defects) from observed Bi (and likely Zn) volatility. Oxygen vacancy diffusivity is estimated to be 10 -12.8 cm 2 /s at 250°C. Low diffusivity and high activation energies are indicative of significant defect interactions. Dipolar oxygen vacancy defects are also indicated, with an activation energy of 0.59 eV from TSDC measurements. In conclusion, the large oxygen vacancy content leads to a short lifetime during high voltage (30 kV/cm), high temperature (250°C) direct current (DC) electrical measurements.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Mechanism of blue-light-induced plasma-membrane depolarization in etiolated cucumber hypocotyls

A large, transient depolarization of the plasma membrane precedes the rapid blue-light (BL)-induced growth suppression in etiolated seedlings of Cucumis sativus L. The mechanism of this voltage transient was investigated by applying inhibitors of ion channels and the plasma-membrane H(+)-ATPase, by manipulating extracellular ion concentrations, and by measuring cell input resistance and ATP levels. The depolarizing phase was not affected by Ca(2+)-channel blockers (verapamil, La3+) or by reducing extracellular free Ca2+ by treatment with ethylene glycol-bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA). However, these treatments did reduce the rate of repolarization, indicating an inward movement of Ca2+ is involved. No effects of the K(+)-channel blocker tetraethylammonium (TEA+) were detected. Vanadate and KCN, used to inhibit the H(+)-ATPase, reduced or completely inhibited the BL-induced depolarization. Levels of ATP increased by 11-26% after 1-2 min of BL. Input resistance of trichrome cells, measured with double-barreled microelectrodes, remained constant during the onset of the depolarization but decreased as the membrane voltage became more positive than -90 mV. The results indicate that the depolarization mechanism initially involves inactivation of the H(+)-ATPase with subsequent transient activation of one or more types of ion channels.

NASA Program Space Biology↗

Anionic Oxygen Redox in the High-Lithium Material Li 8 SnO 6

Lithiated transition metal oxide cathode materials that combine oxygen-anion redox [O 2 – /(O 2 ) n– ] with cation redox offer substantial capacities and higher voltage than cathodes without oxygen redox, but oxygen-anion redox is usually accompanied by the formation of peroxo or superoxo species that may cause oxygen release. To clarify the relationship between the oxygen release and peroxide and superoxide dimers without the complication of transition-metal redox, we performed density functional theory calculations to study the layered Li 8 SnO 6 cathode because it has only oxygen-anion redox during delithiation. Features with O–O distances of ~1.5 Å (corresponding to the formation of a peroxide) were observed at 75% lithium concentration, and further delithiation to 62.5% lithium concentration shortened the O–O bond distance to ~1.3 Å (corresponding to the formation of superoxide). The solely anionic oxygen redox stabilizes the delithiated structure of Li 8–x SnO 6 , and it does not cause structural disorder or release oxygen gas. Ab initio molecular dynamics calculations in the supercell at 300 K indicate that oxygen dimerization may occur at 75% lithium concentration. On the (0001) surface with a high lithium concentration (98%), oxygen dimerization is unfavorable. The calculations by HSE06 show that oxygen redox in Li 8 SnO 6 offers an initial voltage (vs Li/Li + ) greater than 4.2 V. The GGA+U calculations indicate that the Li + -polaron in Li 95 Sn 12 O 72 migrates with a migration barrier of only 0.43 eV. Here, this work also quantifies a solely anionic oxygen redox mechanism in Li 8 SnO 6 , and it provides a deeper understanding of anionic oxygen redox in Li-excess oxide cathode materials.

25 ENERGY STORAGE↗

Computer controlled performance mapping of thermionic converters: effect of collector, guard-ring potential imbalances on the observed collector current-density, voltage characteristics and limited range performance map of an etched-rhenium, niobium planar converter

The effect of collector, guard-ring potential imbalance on the observed collector-current-density J, collector-to-emitter voltage V characteristic was evaluated in a planar, fixed-space, guard-ringed thermionic converter. The J,V characteristic was swept in a period of 15 msec by a variable load. A computerized data acquisition system recorded test parameters. The results indicate minimal distortion of the J,V curve in the power output quadrant for the nominal guard-ring circuit configuration. Considerable distortion, along with a lowering of the ignited-mode striking voltage, was observed for the configuration with the emitter shorted to the guard ring. A limited-range performance map of an etched-rhenium, niobium, planar converter was obtained by using an improved computer program for the data acquisition system.

Manista, E. J.↗

Interfacial and Kinetic Origins of Voltage Loss in Neutral Zinc‐Air Batteries

Rechargeable zinc-air batteries are promising candidates for grid-scale energy storage; however, their practical deployment is limited by oxygen electrocatalysis inefficiencies and interfacial instabilities, particularly outside conventional alkaline electrolytes. Here, in this work, zinc-air batteries operating under neutral electrolyte conditions using ZnCl 2 soaked KC-PAA-PAM gel polymer electrolytes and electrochemically synthesized Ni/Fe layered double hydroxide electrocatalysts is investigated. Ni/Fe-LDH is intentionally employed as an OER-biased benchmark catalyst to diagnose electrolyte and interface driven limitations rather than as a bifunctional ORR/OER solution. Full cells exhibit highly stable cycling over hundreds of hours, yet operate at substantially suppressed charge and discharge voltages relative to the thermodynamic value. Electrochemical impedance analysis shows that ohmic losses contribute only minimally to this voltage suppression. Post-mortem X-ray photoelectron spectroscopy reveals metallic zinc accumulation on the air cathode and chloride-containing species on the anode, indicating parasitic interfacial processes. Synchrotron-based soft X-ray absorption spectroscopy confirms stable Ni 2+ and Fe 3+ oxidation states during cycling, consistent with OER-biased catalytic behavior, while neutral-electrolyte oxygen evolution measurements demonstrate strong electrolyte-induced suppression of oxygen kinetics. Together, these results show that electrolyte chemistry and cathode-side parasitic processes, rather than catalyst identity alone, dominate voltage losses in neutral zinc-air batteries, providing mechanistic insight into the fundamental challenges associated with neutral electrolyte operation.

Long duration energy storage↗

Unintended gas breakdowns in narrow gaps of advanced plasma sources for semiconductor fabrication industry

Occurrence of unintended gas breakdown in the narrow gaps of plasma processing chambers is one of the critical challenges in developing advanced plasma sources. Here, we present a combined experimental and theoretical study of unintended discharges in the narrow gaps of plasma processing chambers and report significant drop of the gas breakdown voltage in the presence of a background plasma facing the gap. Experimentally measured breakdown voltages decrease in subsequent breakdown events due to wall erosion caused by the discharge. Therefore, preventing and mitigating the first discharge is of paramount importance. An analysis of kinetic simulation results indicates that the charged particle influx from the background plasma in the processing chamber into the gap is responsible for the onset of early breakdown: higher charged particle density within the gap modifies the electric field profile, allowing unintended breakdowns to occur at a significantly reduced threshold voltage.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Developing Antimatter Containment Technology: Modeling Charged Particle Oscillations in a Penning-Malmberg Trap

The NASA MSFC Propulsion Research Center (PRC) is conducting a research activity examining the storage of low energy antiprotons. The High Performance Antiproton Trap (HiPAT) is an electromagnetic system (Penning-Malmberg design) consisting of a 4 Tesla superconductor, a high voltage confinement electrode system, and an ultra high vacuum test section; designed with an ultimate goal of maintaining charged particles with a half-life of 18 days. Currently, this system is being experimentally evaluated using normal matter ions which are cheap to produce and relatively easy to handle and provide a good indication of overall trap behavior, with the exception of assessing annihilation losses. Computational particle-in-cell plasma modeling using the XOOPIC code is supplementing the experiments. Differing electrode voltage configurations are employed to contain charged particles, typically using flat, modified flat and harmonic potential wells. Ion cloud oscillation frequencies are obtained experimentally by amplification of signals induced on the electrodes by the particle motions. XOOPIC simulations show that for given electrode voltage configurations, the calculated charged particle oscillation frequencies are close to experimental measurements. As a two-dimensional axisymmetric code, XOOPIC cannot model azimuthal plasma variations, such as those induced by radio-frequency (RF) modulation of the central quadrupole electrode in experiments designed to enhance ion cloud containment. However, XOOPIC can model analytically varying electric potential boundary conditions and particle velocity initial conditions. Application of these conditions produces ion cloud axial and radial oscillation frequency modes of interest in achieving the goal of optimizing HiPAT for reliable containment of antiprotons.

Chakrabarti, S.↗

High-fidelity modeling of breakdown in helium: initiation processes and secondary electron emission

Understanding the role of physical processes contributing to breakdown is critical for many applications in which breakdown is undesirable, such as capacitors, and applications in which controlled breakdown is intended, such as plasma medicine, lightning protection, and materials processing. The electron emission from the cathode is a critical source of electrons which then undergo impact ionization to produce electrical breakdown. In this study, the role of secondary electron yields due to photons (γ ph ) and ions (γ i ) in direct current breakdown is investigated using a particle-in-cell direct simulation Monte Carlo model. The plasma studied is a one-dimensional discharge in 50 Torr of pure helium with a platinum cathode, gap size of 1.15 cm, and voltages of 1.2–1.8 kV. The current traces are compared with experimental measurements. Larger values of γ ph generally result in a faster breakdown, while larger values of γ i result in a larger maximum current. The 58.4 nm photons emitted from He(2 1 P) are the primary source of electrons at the cathode before the cathode fall is developed. Of the values of γ ph and γ i investigated, those which provide the best agreement with the experimental current measurements are γ ph = 0.005 and γ i = 0.01. In this work, these values are significantly lower than those in the literature for pristine platinum or for a graphitic carbon film which we speculate may cover the platinum. This difference is in part due to the limitations of a one-dimensional model but may also indicate surface conditions and exposure to a plasma can have a significant effect on the secondary electron yields. The effects of applied voltage and the current produced by a UV diode which was used to initiate the discharge, are also discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The Role of Electron Localization in Covalency and Electrochemical Properties of Lithium-Ion Battery Cathode Materials

Following the fundamental research conducted by J. B. Goodenough, the important role of electron localization induced by elemental substitution is studied. The size and electron negativity of host and substituting ions are two important factors in tuning material properties such as local structure and transition metal (TM) oxygen covalency. However, another factor, electron localization, which is widely studied in catalyst research but largely overlooked for battery materials, deserves systematic studies. A combined investigation using synchrotronbased X-ray spectroscopy and theoretical calculations is carried out on the Li-Co-Mn-O model system in which the substituting cation Mn 4+ , with its 3d 3 electronic structure, is used as a promoter for electron localization. Results indicate that electron localization greatly influences the Co - O bond by making it less covalent, which increases the delithiation voltage. It is also found that during charge/discharge, electron localization tends to make TM K-edge X-ray absorption near edge spectroscopy (XANES) spectra show a more “rigid shift” behavior while electron delocalization makes the XANES exhibit a “shape change.” It clearly explains why the K-edge XANES data of some TM oxides show no “rigid shift” while the nominal valence states changed. This work highlights the importance of electron localization with guidance for XANES interpretation.

25 ENERGY STORAGE↗

Reversible solid oxide cells: Early performance and microstructural evolution during electrolysis and switched mode operation

Incorporating more renewables into our energy mix will require a diversity of technological solutions. Reversible solid oxide cell systems (RSOCs) operating reversibly between fuel cell and electrolysis modes with high round-trip efficiencies offer one such solution. However, questions remain about the stability of the oxygen and fuel electrodes under reversible operation. Here, in this study, single cells with the configuration Ni-YSZ|YSZ|GDC10|NNO-NDC50|NNO are operated by reversible cycling under potentiostatic conditions. Test conditions are chosen to be representative of average stack conditions that are likely to be encountered during operation of a stack constructed of such cells. The results of reversible cycling over 500 h (21 cycles) are compared with operating the cells under potentiostatic conditions in the electrolysis-only mode (i.e., without cycling). Voltage-current density (DC), AC complex impedance spectroscopy, distribution of relaxation times (DRT) analysis, and scanning electron microscopy (SEM) indicate excellent reversibility and stability of the neodymium nickelate-based oxygen electrodes in both electrolysis and reversible cycling modes. Degradation behavior is attributed to the loss and coarsening of connected Ni particles in the fuel electrode, particularly in the active layer. However, reversible operation mitigates this degradation compared to operation in the electrolysis-only (SOEC-only) mode.

25 ENERGY STORAGE↗

Switching X-Ray Tubes Remotely

Convenient switch and relay circuit reduces risk of accidents. Proposed switching circuit for x-ray inspection system enables operator to change electrical connections to x-ray tubes remotely. Operator simply flips switch on conveniently-located selector box to change x-ray heads. Indicator lights on selector box show whether 160 or 320-kV head connected. Relays in changeover box provides proper voltages and coolants. Chance of making wrong connections and damaging equipment eliminated.

Bulthuis, Ronald V.↗

Alternate cathodes for sodium-metal chloride batteries

Various metal chlorides were tested as possible cathode materials for sodium-metal batteries (in addition to Fe and Ni chlorides, which have been already developed to a stage of commercialization), using an electrochemical cell consisting of a pyrex tube, heated to 250 C, with the metal wire as working electrode, concentric Ni foil as counterelectrode, and high-purity Al as reference electrode. In particular, the aim of this study was to identify metal chlorides insoluble even in neutral melts, possible at the interface during overcharge, in order to eliminate the failure mode of the cell through a cationic exchange of the dissolved metal ions with sodium beta-double-prime alumina solid electrolyte. Results indicate that Mo and Co are likely alternatives to FeCl2 and NiCl2 cathodes in sodium batteries. The open circuit voltages of Na/CoCl(x) and Na/MoCl(x) cells at 250 C would be 2.55 V and 2.64 V, respectively.

Ratnakumar, B. V.↗

Surface-Activated Corrosion in Tin–Lead Halide Perovskite Solar Cells

Mixed tin–lead halide perovskite solar cells have promising power conversion efficiencies, but long-term stability is still a challenge. Here, we examine the stability of a 60:40 tin–lead perovskite to better understand diminished device performance upon thermal treatment, both in ambient and inert atmosphere. Operando X-ray diffraction shows a stable bulk structure of the perovskite absorber, leading to the hypothesis that surface chemistry dominates the degradation mechanism. X-ray photoelectron spectroscopy reveals two new observations post-thermal annealing that accompany previously reported Sn 4+ evolution: (i) the formation of I 3 – intermediates preceding I 2 loss at the surface and (ii) evidence of under-coordinated tin and lead surface sites (Sn δ<2+ and Pb δ<2+ , respectively) in inert and ambient conditions. These two species indicate an activated corrosion (i.e., both oxidation and reduction) process at the surface as a possible chemical pathway for degradation, which is expected to be accelerated under operando voltage and light biases.

14 SOLAR ENERGY↗

Non-contact Current-Voltage (I-V) Tracer for Photovoltaics

This report presents a non-contact approach to simultaneously obtain current-voltage (I-V) curves of photovoltaic (PV) substrings and modules in a string without the need of disconnecting the individual modules from the string. There are two types of I-V curve tracers currently available in the marketplace, capacitor-based and electronic load-based. The primary requirement of these conventional I-V tracers is the disconnection of individual modules in the string so the individual modules contacted through the connectors of the individual modules. These contact-tracers have three major limitations in the utility scale power plants: First limitation – Weather and Accuracy: The mass-produced commercial contact-tracers cannot obtain the I-V curves of both string and its modules (as high as 30 modules), almost simultaneously (within about 5 minutes) at, practically, a single irradiance level, a single module temperature, a single spectrum and a single AOI (angle of incidence). This inability of the contact-tracers forces the testing personnel to wait for an extended or multiple sunny (>800 W/m 2 ) duration(s) of a cloudy day. This is a serious limitation as waiting for the sunny conditions or days is a huge practical challenge in almost all locations, except desert locations. Also, since the I-V curves are obtained at different prevailing weather conditions, it becomes critical to translate all the measured I-V curves of 30 modules in the string to a single test condition, for example STC (standard test conditions), so the underperforming modules can be identified. The accuracy of translation equations is heavily influenced by the irradiance level and temperature, spectral and AOI ranges; Second limitation - Safety: The second limitation is related to the high voltage electrical safety of the test personnel during disconnecting and reconnecting of individual modules or cable connectors from the string under daylight conditions and damaging of the original module connectors (especially the field aged connectors) during the disconnecting and reconnecting process; Third limitation – Labor: The third limitation is related to the enormous amount of time and hardship for the test personnel under prevailing (often harsh) protracted field conditions. This project was executed by Arizona State University in collaboration with its industry partner, PV Measurements Inc. (PVM). To mitigate all the three challenges of the state-of-the-art equipment indicated above, we utilized a non-contact I-V (NCIV) tracer approach. In this approach, we utilized an electrostatic voltmeter (ESV) and voltage sensor/probe combination to obtain I-V curves. The ESV units are extensively used in the high voltage industry but not in the PV industry. To obtain the simultaneous I-V curves of the substrings and modules within a string, we utilized multiple commercial ESV-Probe sets. In this approach, we utilized a non-contact voltage sensor (called, Probe) placed on the glass surface of the module (above the last cell of the module). This probe senses the module voltage (with respect to ground) through measured capacitance which is dictated by the surface charges (which in turn is dictated by the module voltage) and transmits the sensed voltage to the voltmeter (called, ESV or NCV, non-contact voltmeter). The current is sensed by a non-contact hall sensor. In a 30-module string, the 30th probe obtains the entire string I-V along with the string I-V obtained by the electronic load. so that the I-V curves of the substrings and modules can be obtained by NCIV without the need of disconnecting the individual modules in the string. The string I-V curves obtained by the electronic load and NCIV can be compared for the accuracy determination. One can use 30 ESV units and 30 Probes to obtain 30 I-V curves of a 30-module string or use just 5 ESV units and 30 Probes in conjunction with 5 six-channel switchboxes (called, 6:1 switchboxes). To reduce the equipment cost, we utilized the 6:1 switchbox approach so the number of ESV units is reduced from 30 to 5. The approaches, achievements and challenges of this project are detailed in this report.

14 SOLAR ENERGY↗

Spacecraft Electrostatic Radiation Shielding

This project analyzed the feasibility of placing an electrostatic field around a spacecraft to provide a shield against radiation. The concept was originally proposed in the 1960s and tested on a spacecraft by the Soviet Union in the 1970s. Such tests and analyses showed that this concept is not only feasible but operational. The problem though is that most of this work was aimed at protection from 10- to 100-MeV radiation. We now appreciate that the real problem is 1- to 2-GeV radiation. So, the question is one of scaling, in both energy and size. Can electrostatic shielding be made to work at these high energy levels and can it protect an entire vehicle? After significant analysis and consideration, an electrostatic shield configuration was proposed. The selected architecture was a torus, charged to a high negative voltage, surrounding the vehicle, and a set of positively charged spheres. Van de Graaff generators were proposed as the mechanism to move charge from the vehicle to the torus to generate the fields necessary to protect the spacecraft. This design minimized complexity, residual charge, and structural forces and resolved several concerns raised during the internal critical review. But, it still is not clear if such a system is costeffective or feasible, even though several studies have indicated usefulness for radiation protection at energies lower than that of the galactic cosmic rays. Constructing such a system will require power supplies that can generate voltages 10 times that of the state of the art. Of more concern is the difficulty of maintaining the proper net charge on the entire structure and ensuring that its interaction with solar wind will not cause rapid discharge. Yet, if these concerns can be resolved, such a scheme may provide significant radiation shielding to future vehicles, without the excessive weight or complexity of other active shielding techniques.

Source record↗

Effect of Inductive Coil Geometry on the Operating Characteristics of a Pulsed Inductive Plasma Accelerator

Operational characteristics of two separate inductive thrusters with coils of different cone angles are explored through thrust stand measurements and time-integrated, un- filtered photography. Trends in impulse bit measurements indicate that, in the present experimental configuration, the thruster with the inductive coil possessing a smaller cone angle produced larger values of thrust, in apparent contradiction to results of a previous thruster acceleration model. Areas of greater light intensity in photographs of thruster operation are assumed to qualitatively represent locations of increased current density. Light intensity is generally greater in images of the thruster with the smaller cone angle when compared to those of the thruster with the larger half cone angle for the same operating conditions. The intensity generally decreases in both thrusters for decreasing mass ow rate and capacitor voltage. The location of brightest light intensity shifts upstream for decreasing mass ow rate of propellant and downstream for decreasing applied voltage. Recognizing that there typically exists an optimum ratio of applied electric field to gas pressure with respect to breakdown efficiency, this result may indicate that the optimum ratio was not achieved uniformly over the coil face, leading to non-uniform and incomplete current sheet formation in violation of the model assumption of immediate formation where all the injected propellant is contained in a magnetically-impermeable current sheet.

Hallock, Ashley K.↗

Effect of Inductive Coil Geometry on the Operating Characteristics of an Inductive Pulsed Plasma Thruster

Operational characteristics of two separate inductive thrusters with conical theta pinch coils of different cone angles are explored through thrust stand measurements and time- integrated, unfiltered photography. Trends in impulse bit measurements indicate that, in the present experimental configuration, the thruster with the inductive coil possessing a smaller cone angle produced larger values of thrust, in apparent contradiction to results of a previous thruster acceleration model. Areas of greater light intensity in photographs of thruster operation are assumed to qualitatively represent locations of increased current density. Light intensity is generally greater in images of the thruster with the smaller cone angle when compared to those of the thruster with the larger half cone angle for the same operating conditions. The intensity generally decreases in both thrusters for decreasing mass flow rate and capacitor voltage. The location of brightest light intensity shifts upstream for decreasing mass flow rate of propellant and downstream for decreasing applied voltage. Recognizing that there typically exists an optimum ratio of applied electric field to gas pressure with respect to breakdown efficiency, this result may indicate that the optimum ratio was not achieved uniformly over the coil face, leading to non-uniform and incomplete current sheet formation in violation of the model assumption of immediate formation where all the injected propellant is contained in a magnetically-impermeable current sheet.

Hallock, Ashley K.↗

Erosion and cathodic arc plasma of Nb–Al cathodes: composite versus intermetallic

Many properties of cathodic arcs from single-element cathodes show a correlation to the cohesive energy of the cathode material. For example, the burning voltage, the erosion rate, or, to a lesser extent, plasma properties like electron temperatures or average ion energy and charge states. For multi-element cathodes, various phases with different cohesive energies can initially be present in the cathode, or form due to arc exposure, complicating the evaluation of such correlations. To test the influence of morphology and phase composition of multi-element cathodes on cathodic arc properties, a Nb–Al cathode model system was used that includes: pure Nb and Al cathodes; intermetallic Nb 3 Al, Nb 2 Al and NbAl 3 cathodes; and three composite Nb–Al cathodes with atomic ratios corresponding to the stoichiometric ratios of the intermetallic phases. Pulsed cathodic arc plasmas from these cathodes were examined using a mass-per-charge and energy-per-charge analyzer, showing that charge-state-resolved ion energy distributions of plasmas from the intermetallic and corresponding composite cathodes are nearly identical. An examination of converted layers of eroded cathodes using x-ray diffraction and scanning electron microscopy indicates the formation of a surface layer with similar phase composition for intermetallic and their corresponding composite cathode types. The average arc voltages do not follow the trend of cohesive energies of Nb, Al and intermetallic Nb–Al phases, which have been calculated using density functional theory. Possible reasons for this effect are discussed based on the current knowledge of multi-element arc cathodes and their arc plasma available in literature.

36 MATERIALS SCIENCE↗