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Addition of oxygen to and distribution of oxides in tantalum alloy T-111 at low concentrations

Oxygen was added at 820 and 990 C at an oxygen pressure of about .0003 torr. The technique permitted predetermined and reproducible oxygen doping of the tantalum alloy (T-111). Based on the temperature dependency of the doping reaction, it was concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the tantalum and tungsten oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and oxygen from other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C but not at 820 C. The vaporization of WO3 has no apparent effect on the doping reaction.

Stecura, S.↗

Dissolution kinetics of small amounts of oxygen in tantalum alloy T-111 and internal oxide displacement reactions during annealing

Oxygen was added to T-111 (Ta-8W-2Hf, wt. %) at 820 and 990 C at an oxygen pressure of about 0.0003 torr. The technique employed permitted predetermined and reproducible doping of T-111 up to 3.0 at. % oxygen. Based on the temperature dependence of the doping reaction, it is concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the latter oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and of other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high-temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C. The vaporization of WO3 has no apparent affect on the doping reaction.

Stecura, S.↗

Garnet melt viscosity, surface tension and drainage

Good surface morphology and layer uniformity of LPE-grown Bi YIG films are favored by fast melt removal after growth. Three flux modifying oxides: MoO3, V2O3, and WO3 are compared with respect to their effect on viscosity, surface tension and melt drainage. All three oxides increased the viscosities of Bi-garnet melts, but the viscosities and drainage times of V2O3 and MoO3 modified melts were smaller than those of WO3 modified melts. The liquid-gas surface tension was found to be temperature independent. The drainage process was strongly temperature dependent, 40 to 60 kcal/mol, whereas the viscosities of melts had activation energies of 11 to 16 kcal/mol. Contact angles of 16 + or - 2 deg were measured on frozen melt drops.

Luther, L. C.↗

Solid-state reprogrammable analog resistive devices for electronic neural networks

The fabrication and performance of WO3-based, solid-state, three-terminal device configurations as programmable analog memory elements are reported. These transistorlike device structures exhibit good resistance progammability with a remarkable resolution of a few percent of the resistive strength over a four orders of magnitude dynamic range. The most critical component of these devices is an insulating layer between the active WO3 and the cation donor layer. The progamming characteristics and operation mechanisms of the device are described, and probable reaction mechanisms critical to the device stability are discussed.

Ramesham, R.↗

Work Functions for Models of Scandate Surfaces

The electronic structure, surface dipole properties, and work functions of scandate surfaces have been investigated using the fully relativistic scattered-wave cluster approach. Three different types of model surfaces are considered: (1) a monolayer of Ba-Sc-O on W(100), (2) Ba or BaO adsorbed on Sc2O3 + W, and (3) BaO on SC2O3 + WO3. Changes in the work function due to Ba or BaO adsorption on the different surfaces are calculated by employing the depolarization model of interacting surface dipoles. The largest work function change and the lowest work function of 1.54 eV are obtained for Ba adsorbed on the Sc-O monolayer on W(100). The adsorption of Ba on Sc2O3 + W does not lead to a low work function, but the adsorption of BaO results in a work function of about 1.6-1.9 eV. BaO adsorbed on Sc2O3 + WO3, or scandium tungstates, may also lead to low work functions.

Mueller, Wolfgang↗

Preparation and evaluation of thin-film sodium tungsten bronzes

Thin films of sodium tungsten bronze (NaxWO3) were investigated as reversible sodium ion electrodes for solid electrolytes. The films were made by electron beam evaporation of the three phases, W metal, Na2WO4, and WO3, followed by sintering. The substrates were sodium beta alumina disks and glass slides. X-ray diffraction analyses of the films showed that sintering in dry nitrogen with prior exposure to air lead to mixed phases. Sintering in vacuum with no air exposure produced tetragonal I bronze with a nominal composition of Na0.31WO3, single phase within the limits of X-ray diffraction detectability. The films were uniform and adherent on sodium beta alumina substrates. The ac and dc conductivities of the beta alumina were measured with the sodium tungsten bronze films as electrodes. These experiments indicated that the tetragonal I bronze electrodes were not completely reversible. This may have resulted from sodium ion blocking within the bronze film or at the bronze beta alumina interface. Methods for attempting to make more completely reversible electrodes are suggested.

Kautz, H. E.↗

Photovoltage response to temperature change at oxide semiconductor electrodes

A study has been carried out on single crystal electrodes of TiO2, SrTiO3, and alpha-Fe2O3 and polycrystalline WO3 to investigate the effect of cell temperature on the onset potential of n-type oxide semiconductor electrodes. It is found that the change of the onset potential with temperature is due to the potential change across the Helmholtz layer. The amount of this change depends on the point of zero zeta potential (pzzp) of the semiconductor electrode. The possibility of increasing the solar-to-chemical energy conversion efficiency of a photochemical cell by increasing the cell temperature is discussed.

Reichman, B.↗

Programmable Analog Memory Resistors For Electronic Neural Networks

Electrical resistance of new solid-state device altered repeatedly by suitable control signals, yet remains at steady value when control signal removed. Resistance set at low value ("on" state), high value ("off" state), or at any convenient intermediate value and left there until new value desired. Circuits of this type particularly useful in nonvolatile, associative electronic memories based on models of neural networks. Such programmable analog memory resistors ideally suited as synaptic interconnects in "self-learning" neural nets. Operation of device depends on electrochromic property of WO3, which when pure is insulator. Potential uses include nonvolatile, erasable, electronically programmable read-only memories.

Ramesham, Rajeshuni↗

Solid-state thin-film memistor for electronic neural networks

This paper reports on a tungsten-oxide-based, nonvolatile, electrically reprogrammable, variable resistance device as an analog synaptic memory connection for electronic neural networks. A voltage controlled, reversible injection of H(+) ions in electrochromic thin films of WO3 is utilized to modulate its resistance. A hygroscopic thin film of Cr2O3 is the source of H(+) ions. The resistance of the device can be tailored and stabilized over a wide dynamic range (about 4 orders of magnitude), and the programming speed is modulated by the control voltage. The suitability of such a device in terms of its response speed, reversibility, stability, and cyclability for its use in electronic neural networks is discussed.

Thakoor, S.↗

Epitaxial heterojunctions of oxide semiconductors and metals on high temperature superconductors

Epitaxial heterojunctions formed between high temperature superconductors and metallic or semiconducting oxide barrier layers are provided. Metallic perovskites such as LaTiO3, CaVO3, and SrVO3 are grown on electron-type high temperature superconductors such as Nd(1.85)Ce(0.15)CuO(4-x). Alternatively, transition metal bronzes of the form A(x)MO(3) are epitaxially grown on electron-type high temperature superconductors. Also, semiconducting oxides of perovskite-related crystal structures such as WO3 are grown on either hole-type or electron-type high temperature superconductors.

Vasquez, Richard P.↗

Thermal Control using Electrochromism

The applicability of a charge balanced electrochromic device to modulate the frequencies in the thermal infrared region is examined in this study. The device consisted of a transparent conductor, WO3 anode, PMMA/LiClO4 electrolyte, V2O5 cathode and transparent conductor. The supporting structure in the device is SnO2 coated glass and the edges are sealed with epoxy to reduce moisture absorption. The performance evaluation comprised of cyclic voltammetric measurements and determination of transmittance at various wavelengths. The device was subjected to anodic and cathodic polarization by sweeping the potential at a rate of 10 mV/sec from -0.8V to 1.8V. The current versus voltage profile indicated no reaction between -0.5 and +0.5 V. The device is colored green at 1.8V with a transmittance of 5% at a wavelength, lambda=900 nm and colorless at -0.8V with a transmittance of 74% at lambda=500 nm. The optical modulation is limited to 400-1500 nm and there is no activity in the thermal infrared. The switching time is 75 seconds for transmittance to decrease from 74% to 50%. The device yielded reproducible values for transmittance when cycled between colored and bleached states by application of 1.8V and -0.8V, respectively.

Vaidyanathan, Hari↗

Thermal Control Using Electrochromism

The applicability of a charge balanced electrochromic device to modulate the frequencies in the thermal infra red region is examined in this study. The device consisted of a transparent conductor, WO3 anode, PMMA/LiClO4, electrolyte, V2O5, cathode and transparent conductor. The supporting structure in the device is SnO2 coated glass and the edges are sealed with epoxy to reduce moisture absorption. The performance evaluation comprised of cyclic voltammetric measurements and determination of transmittance at various wavelengths. The device was subjected to anodic and cathodic polarization by sweeping the potential at a rate of 10 mV/sec from -0.8 V to 1.8 V. The current versus voltage profile indicated no reaction between -0.5 and +0.5 V. The device is colored green at 1.8 V with a transmittance of 5% at a wavelength, lambda = 900 nm and colorless at -0.8 V with a transmittance of 74% at X = 500 nm. The optical modulation is limited to 400-1500 nm and there is no activity in the thermal infrared. The switching time is 75 seconds for transmittance to decrease from 74% to 50%. The device yielded reproducible values for transmittance when cycled between colored and bleached states by application of 1.8 V and -0.8 V, respectively.

Vaidyanathan, Hari↗

Correlation of Predicted and Observed Optical Properties of Multilayer Thermal Control Coatings

Thermal control coatings on spacecraft will be increasingly important, as spacecraft grow smaller and more compact. New thermal control coatings will be needed to meet the demanding requirements of next generation spacecraft. Computer programs are now available to design optical coatings and one such program was used to design several thermal control coatings consisting of alternating layers of WO3 and SiO2. The coatings were subsequently manufactured with electron beam evaporation and characterized with both optical and thermal techniques. Optical data were collected in both the visible region of the spectrum and the infrared. Predictions of solar absorptance and infrared emittance were successfully correlated to the observed thermal control properties. Functional performance of the coatings was verified in a bench top thermal vacuum chamber.

Jaworske, Donald A.↗

Thermal Control Using Electrochromism

The applicability of a charge balanced electrochromic device to modulate the frequencies in the thermal infrared region is examined in this study. The device consisted of a transparent conductor, WO3, anode, PMMA/LiClO4 electrolyte, V2O5 cathode and transparent conductor. The supporting structure in the device is SnO2 coated glass and the edges are sealed with epoxy to reduce moisture absorption. The performance evaluation comprised of cyclic voltammetric measurements and determination of transmittance at various wavelengths. The device was subjected to anodic and cathodic polarization by sweeping the potential at a rate of 10 mV/sec from -0.8V to 1.8V. The current versus voltage profile indicated no reaction between -0.5 and +0.5 V. The device is colored green at 1.8 V with a transmittance of 5% at a wavelength, lambda = 900 nm and colorless at -0.8 V with a transmittance of 74% at lambda = 500 nm. The optical modulation is limited to 400-1500 nm and there is no activity in the thermal infrared. The switching time is a function of temperature and time for coloring reaction was slower than the bleaching reaction. The device yielded reproducible values for transmittance when cycled between colored and bleached states by application of 1.8V and -0.8V, respectively.

Vaidyanathan, Hari↗

Micro- and Nanostructured Metal Oxide Chemical Sensors for Volatile Organic Compounds

Aeronautic and space applications warrant the development of chemical sensors which operate in a variety of environments. This technical memorandum incorporates various kinds of chemical sensors and ways to improve their performance. The results of exploratory investigation of the binary composite polycrystalline thick-films such as SnO2-WO3, SnO2-In2O3, SnO2-ZnO for the detection of volatile organic compound (isopropanol) are reported. A short review of the present status of the new types of nanostructured sensors such as nanobelts, nanorods, nanotube, etc. based on metal oxides is presented.

Alim, M. A.↗

Palmer Station, Antarctica: A Ground-Based Spaceflight Analog Suitable for Validation of Biomedical Countermeasures for Deep Space Missions

Astronauts are known to exhibit a variety of immunological alterations during spaceflight including changes in leukocyte distribution and plasma cytokine concentrations, a reduction in T-cell function, and subclinical reactivation of latent herpesviruses. These alterations are most likely due to mission-associated stressors including circadian misalignment, microgravity, isolation, altered nutrition, and increased exposure to cosmic radiation. Some of these stressors may also occur in terrestrial situations. This study sought to determine if crewmembers performing overwinter deployment at Palmer Station, Antarctica displayed similar immune alterations. The larger goal was to validate a ground analog suitable for the evaluation of countermeasures designed to protect astronauts during future deep space missions. For this pilot study, plasma, saliva, hair, and health surveys were collected from Palmer Station, Antarctica winterover participants at baseline, and at five overwinter timepoints. Twenty-six subjects consented to participate over the course of two seasons. Initial sample processing was performed at Palmer, and eventually stabilized samples were returned to the Johnson Space Center for analysis. A white blood cell differential was performed (real time) using a fingerstick blood sample to determine alterations in basic leukocyte subsets throughout the winterover. Plasma and saliva samples were analyzed for 30 and 13 cytokines, respectively. Saliva was analyzed for cortisol concentration and three latent herpesviruses (DNA by qPCR), EBV, HSV1, and VZV. Hair samples were analyzed for several hormones, as a measure of stress over prolonged periods of time. Voluntary surveys related to general health and adverse clinical events were distributed to participants. It is noteworthy that due to logistical constraints due to COVID-19, the baseline samples for each season were collected in Punta Arenas, Chile, after long international travel and during isolation. Therefore, the palmer pre mission samples may not reflect a true normal ‘baseline’. Minimal alterations were observed in leukocyte distribution during overwinter. The mean percentage of monocyte concentration elevated at one timepoint. Plasma G-CSF, IL1RA, MCP-1, MIP-1β, TNFα and VEGF were decreased during at least one overwinter timepoint, whereas RANTES was significantly increased. No statistically significant changes were observed in mean saliva cytokine concentrations. Salivary cortisol was substantially elevated throughout the entire winterover compared to baseline. Compared to shedding levels observed in healthy controls (23%), the percentage of participants who shed EBV was higher throughout all winterover timepoints (52-60%). Five subjects shed HSV1 during at least one timepoint throughout the season compared to no subjects shedding during pre-deployment. Finally, VZV reactivation, common in astronauts but exceptionally rare in ground-based stress analogs, was observed in one subject during pre-deployment and a different subject at WO2 and WO3. These pilot data, somewhat influenced by the COVID-19 situation, do suggest that participants at Palmer Station do undergo immunological alterations similar to, but likely in reduced magnitude, as those observed in astronauts. We suggest that overwinter at Palmer Station may be suitable test analog for spaceflight biomedical countermeasures designed to mitigate clinical risks for deep space missions.

Space↗