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At least 145 records · Page 8

Thin film oxygen partial pressure sensor

The development is described of a laboratory model oxygen partial pressure sensor using a sputtered zinc oxide thin film. The film is operated at about 400 C through the use of a miniature silicon bar. Because of the unique resistance versus temperature relation of the silicon bar, control of the operational temperature is achieved by controlling the resistance. A circuit for accomplishing this is described. The response of sputtered zinc oxide films of various thicknesses to oxygen, nitrogen, argon, carbon dioxide, and water vapor caused a change in the film resistance. Over a large range, film conductance varied approximately as the square root of the oxygen partial pressure. The presence of water vapor in the gas stream caused a shift in the film conductance at a given oxygen partial pressure. A theoretical model is presented to explain the characteristic features of the zinc oxide response to oxygen.

Wortman, J. J.↗

Transparent conducting thin films for spacecraft applications

Transparent conductive thin films are required for a variety of optoelectronic applications: automotive and aircraft windows, and solar cells for space applications. Transparent conductive coatings of indium-tin-oxide (ITO)-magnesium fluoride (MgF2) and aluminum doped zinc oxide (AZO) at several dopant levels are investigated for electrical resistivity (sheet resistance), carrier concentration, optical properties, and atomic oxygen durability. The sheet resistance values of ITO-MgF2 range from 10(exp 2) to 10(exp 11) ohms/square, with transmittance of 75 to 86 percent. The AZO films sheet resistances range from 10(exp 7) to 10(exp 11) ohms/square with transmittances from 84 to 91 percent. It was found that in general, with respect to the optical properties, the zinc oxide (ZnO), AZO, and the high MgF2 content ITO-MgF2 samples, were all durable to atomic oxygen plasma, while the low MgF2 content of ITO-MgF2 samples were not durable to atomic oxygen plasma exposure.

Perez-Davis, Marla E.↗

Nanoarray-Based Monolithic Adsorbers for SO 2 Removal

Nanoarray-based monolithic catalysts have been developed for various applications, including CO oxidation, hydrocarbon combustion, lean NO x trapping, and low-pressure CO 2 hydrogenation. In this work, SO 2 adsorption properties have been explored and evaluated on the cordierite honeycomb monoliths grown with zinc oxide nanoarray (ZnO), zinc oxide nanoarray washcoated by BaCO 3 nanoparticles (ZnO/BaCO 3 ), and manganese oxide nanowire array with cryptomelane structure (MnO x ) at a temperature range from 50 to 425 °C. All samples show temperature-dependent SO 2 adsorption behaviors. The adsorption results reveal the performance order: MnO x > ZnO/BaCO 3 > ZnO, with ~ 90% SO 2 adsorbed in MnO x at 425 °C. Washcoated BaCO 3 contributes to the improvement of SO 2 adsorption in ZnO nanoarray, and the best performance displayed in MnO x may be attributed to their high specific surface area. After regeneration, nanoarrays all exhibit good thermal stability during test-regeneration cycles. No additional phase is formed in regenerated ZnO nanoarrays (ZnO-R), while BaCO 3 is converted to BaSO 4 in the regenerated ZnO/BaCO 3 nanoarrays (ZnO/BaCO 3 -R), and the sulfur species (possibly MnSO 4 ) and Mn 2 O 3 are found in regenerated MnO x nanoarrays (MnO x -R). It is noted that a small amount of sulfur species (possibly MnSO 4 ) may promote the SO 2 adsorption of MnO x -R at a lower temperature, while the formed Mn 2 O 3 contributes to the deactivation of MnO x -R.

36 MATERIALS SCIENCE↗

Ferroelectricity in Atomic Layer Deposited Wurtzite Zinc Magnesium Oxide Zn 1– x Mg x O

Conformal deposition of wurtzite ferroelectrics, which is needed for their use in scaled nonvolatile memories, is challenging using current physical vapor deposition techniques. To overcome the conformality barrier, this work demonstrates ferroelectricity in wurtzite Zn 1− x Mg x O thin films prepared by plasma-enhanced atomic layer deposition, which is a non-line-of-sight deposition method. Films ranging in composition from x = 0.00 to x = 0.58 are predominantly wurtzite phase and exhibit a (0001)-texture. Increasing the magnesium content decreases the c/a ratio, increases the optical bandgap energy, increases the piezoelectric response, and enables polarization reversal. Clear polarization switching is demonstrated in 50 nm thick Zn 1− x Mg x O films by piezoresponse force microscopy in compositions containing x = 0.46 and x = 0.58.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Primary battery design and safety guidelines handbook

This handbook provides engineers and safety personnel with guidelines for the safe design or selection and use of primary batteries in spaceflight programs. Types of primary batteries described are silver oxide zinc alkaline, carbon-zinc, zinc-air alkaline, manganese dioxide-zionc alkaline, mercuric oxide-zinc alkaline, and lithium anode cells. Along with typical applications, the discussions of the individual battery types include electrochemistry, construction, capacities and configurations, and appropriate safety measures. A chapter on general battery safety covers hazard sources and controls applicable to all battery types. Guidelines are given for qualification and acceptance testing that should precede space applications. Permissible failure levels for NASA applications are discussed.

Bragg, Bobby J.↗

Corrosion of Zinc Cold Spray Coatings in a Wet Sweet and Sour Gas Environment

Internal corrosion is a problem for steel pipelines transporting natural gas or CO 2 containing water and partial pressures of H 2 S higher than 0.3 kPa (0.05 psi). This work aims to mitigate internal corrosion in steel pipelines transporting natural gas containing H 2 S using cold spray coatings. Two types of the cold spray binary metallic coatings (zinc chromium [ZnCr]. zinc niobium [ZnNb]) were studied using electrochemical techniques: potentiodynamic polarization, linear polarization resistance, and electrochemical impedance spectroscopy. The corrosion resistance of cold spray coatings (ZnCr, ZnNb) was evaluated in an environment containing 4 bar CO 2 pressure, simulating the partial pressures found in gas transmission lines over a solution of 3.5 wt% NaCl heated to 40°C. A concentration of 0.003 M Na 2 S 2 O 3 ·5H 2 O, corresponding to H 2 S partial pressures around 0.079 bar (1.146 psi), was used to simulate sour conditions. Postcorrosion surface characterization was performed using a scanning electron microscope (SEM) equipped with an energy-dispersive x-ray spectroscope (EDS) and x-ray diffraction analysis. The data showed that the presence of 0.003 M Na 2 S 2 O 3 ·5H 2 O shifted the corrosion potential to more anodic values and decreased the corrosion current density. Both coatings showed similar behavior after 1 h of exposure in the CO 2 /H 2 S environment, indicating that similar electrochemical reactions were occurring on ZnNb and ZnCr. SEM images and EDS surface analyses for specimens showed a significant change in the surface chemical composition of carbon steel coated with ZnNb and ZnCr after 24 h of immersion. In the presence of thiosulfate (under sour conditions), the formation of corrosion product layers (ZnCO 3 and ZnS) on top of ZnNb and ZnCr coatings increased their corrosion resistance, which helped to reduce their corrosion by a factor of 2. Under a sweet environment, the corrosion rates for steel coated with cold spray coatings after 14 d of exposure are lower than that for galvanized steel by a factor of 5 due to the ZnCO 3 layer formed on top of the coatings. The ZnCO 3 layer formed on the steel surface acts as a physical barrier against corrosion by blocking the diffusion of corrosive species to the surface. No localized attack was observed. ZnCr Cold spray coating with defect showed promising corrosion protection against CO 2 corrosion (sweet corrosion) after 14 d of exposure to a CO 2 environment. Here, the scratch on the coating simulated damage created in service, and it was deep enough to expose the substrate material (steel). The formation of zinc oxide (ZnO) and zinc carbonate (ZnCO 3 ) on the scratch confirmed the cathodic protection of the steel by ZnCr and ZnNb coatings.

36 MATERIALS SCIENCE↗

Microscopic Investigation of H 2 Reduced CuO x /Cu(111) and ZnO/CuO x /Cu(111) Inverse Catalysts: STM, AP-XPS, and DFT Studies

Understanding the reduction mechanism of ZnO/CuO x interfaces by hydrogen is of great importance for advancing the performance of industrial catalysts for CO 2 hydrogenation to methanol. Here, the reduction of pristine and ZnO-modified CuO x /Cu(111) by H 2 was investigated using ambient pressure scanning tunnelling microscopy (AP-STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory (DFT). The morphological changes and reaction rates seen for the reduction of CuO x /Cu(111) and ZnO/CuO x /Cu(111) are very different. On CuO x /Cu(111), perfect "44" and "29" structures displayed a very low reactivity towards H 2 at room temperature. A long induction period associated with an autocatalytic process was observed to enable the reduction by the removal of chemisorbed non-lattice oxygen initially and lattice oxygen sequentially at the CuO x -Cu interface, which led to formation of oxygen deficient "5-7" hex and honeycomb structures. In the final stages of the reduction process, regions of residual oxygen species and metallic Cu were seen. The addition of ZnO particles to CuO x /Cu(111) opened new reaction channels. On the ZnO sites, the dissociation of H 2 was fast and H adatoms easily migrated to adjacent regions of copper oxide. This hydrogen spillover substantially enhanced the rate of oxygen removal, resulting in the rapid reduction of the copper oxide located in the periphery of the zinc oxide islands with no signs for the reduction of ZnO. The deposited ZnO completely modified the dynamics for H 2 dissociation and hydrogen migration, providing an excellent source for CO 2 hydrogenation processes on the inverse oxide/metal system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Testing piezoelectric sensors in a nuclear reactor environment

Several Department of Energy Office of Nuclear Energy (DOE-NE) programs, such as the Fuel Cycle Research and Development (FCRD), Advanced Reactor Concepts (ARC), Light Water Reactor Sustainability, and Next Generation Nuclear Power Plants (NGNP), are investigating new fuels, materials, and inspection paradigms for advanced and existing reactors. A key objective of such programs is to understand the performance of these fuels and materials during irradiation. In DOE-NE’s FCRD program, ultrasonic based technology was identified as a key approach that should be pursued to obtain the high-fidelity, high-accuracy data required to characterize the behavior and performance of new candidate fuels and structural materials during irradiation testing. The radiation, high temperatures, and pressure can limit the available tools and characterization methods. In this work piezoelectric transducers capable of making these measurements are developed. Specifically, three piezoelectric sensors (Bismuth Titanate, Aluminum Nitride, and Zinc Oxide) are tested in the Massachusetts Institute of Technology Research reactor to a fast neutron fluence of 8.65x1020 nf/cm2. It is demonstrated that Bismuth Titanate is capable of transduction up to 5 x1020 nf/cm2, Zinc Oxide is capable of transduction up to at least 6.27 x1020 nf/cm2 , and Aluminum Nitride is capable of transduction up to at least 8.65x x1020 nf/cm2.

T. Reinhardt, Brian↗

Rechargeable alkaline zinc–manganese oxide batteries for grid storage: Mechanisms, challenges and developments

Rechargeable alkaline Zn–MnO 2 (RAM) batteries are a promising candidate for grid-scale energy storage owing to their high theoretical energy density rivaling lithium-ion systems (~400 Wh/L), relatively safe aqueous electrolyte, established supply chain, and projected costs below $100/kWh at scale. In practice, however, many fundamental chemical and physical processes at both electrodes make it difficult to achieve commercially competitive energy density and cycle life. In this paper, we present a detailed and timely analysis of the constituent materials, current commercial status, electrode processes, and performance-limiting factors of RAM batteries. We also examine recently reported strategies in RAM and related systems to address these issues through additives and modifications to the electrode materials and electrolyte, special ion-selective separators and/or coatings, and unconventional cycling protocols. We conclude with a critical summary of these developments and discussion of how future studies should be focused toward the goal of energy-dense, scalable, and cost-effective RAM systems.

25 ENERGY STORAGE↗

Switching kinetics in ferroelectric zinc magnesium oxide thin films

The switching kinetics of RF-magnetron reactively sputtered ~200 nm thick Zn 1-x Mg x O (ZMO) ferroelectric thin films with x = 0.41 and x = 0.27 prepared on Pt/Ti/SiO 2 /Si substrates were studied at applied fields near the coercive fields, ranging from 3.4 to 5.1 MV cm -1 , and at temperatures ranging from room temperature to 100 °C. Polarization reversal in ZMO followss the Kolmogorov-Avrami-Ishibashi kinetics model for nucleation and growth at applied fields near the coercive field, and obeys an individual column switching (ICS) model at higher applied fields required to switch most of the spontaneous polarization. Switching in the high-applied field regime can be described using either the Gaussian or inverse gamma distribution functions depending on the mole fraction of magnesium in the film. The switching current transients of the high-Mg content ZMO film (x = 0.41) are always bi-modal, whereas the low Mg composition film (x = 0.27) is described by the Gaussian distribution initially following wake-up, and becomes bimodal with continued cycling. Rayleigh-like behavior of the dielectric constant revealed a simultaneous increase of the irreversible and decrease of the reversible contributions to the dielectric constant, which was ascribed to an increase in the density of mobile domain walls with cycling and resulted in faster switching.

30 DIRECT ENERGY CONVERSION↗

Wake up and retention in zinc magnesium oxide ferroelectric films

Zn 0.64 Mg 0.36 O (ZMO) is a newly discovered ferroelectric oxide with the wurtzite structure. Epitaxial Zn 0.64 Mg 0.36 O films from 0.036 to 0.5 μm in thickness are grown on Pt/sapphire with the crystallographic c-axis out of plane. At room temperature, the remanent polarization is ~80 μC/cm 2 and the coercive field is ~3 MV/cm. The coercive field is strongly temperature dependent up to 240 °C with a pseudo-activation energy of 23 ± 0.3 meV, suggesting that polarization reversal occurs through an extrinsic process such as domain wall motion. ZMO films can be woken up in 20 electric field cycles on driving near the coercive field; they wake up in a single loop at fields in excess of 4 MV/cm. A thermally activated fluid imprint process, with a pseudo-activation energy of 67 ± 8 meV, enlarges the coercive field by several hundred kV cm –1 after switching the polarization. Additionally, ZMO films exhibit excellent retention characteristics; no reduction in the polarization is observed up to 1000 h from room temperature to 200 °C bakes. Here, this current early generation of ZMO films can survive several thousand switching cycles before dielectric breakdown occurs.

36 MATERIALS SCIENCE↗

Thickness scaling and ferroelectric switching in wurtzite structure zinc magnesium oxide thin films

This study reports the thickness scaling of sputtered ferroelectric Zn 0.61 Mg 0.39 O (ZMO) thin films down to 43 nm. Encapsulated IrO 2 /ZMO/Ir capacitors exhibited switchable polarizations exceeding 50 μC cm −2 and coercive fields that increased from 3.9 to 4.4 MV cm −1 as the thickness decreased. Switching kinetics are best described by the simultaneous non-linear nucleation and the growth model. Bimodal switching is prevalent at low thicknesses, with the fastest switching times measured to be approximately 400 ns. Device encapsulation made ZMO switching kinetics more abrupt, potentially due to changes in the concentration of atmosphere-induced defects such as hydroxides. These results demonstrate stable ferroelectricity and sub-microsecond switching in sub-50 nm wurtzite ZMO, highlighting its potential as a low-voltage ferroelectric for integrated nonvolatile memory applications.

36 MATERIALS SCIENCE↗

Study of the zinc-silver oxide battery system

Theoretical and experimental models for the evaluation of current distribution in flooded, porous electrodes are discussed. An approximation for the local current distribution function was derived for conditions of a linear overpotential, a uniform concentration, and a very conductive matrix. By considering the porous electrode to be an analog of chemical catalyst structures, a dimensionless performance parameter was derived from the approximated current distribution function. In this manner the electrode behavior was characterized in terms of an electrochemical Thiele parameter and an effectiveness factor. It was shown that the electrochemical engineering approach makes possible the organizations of theoretical descriptions and of practical experience in the form of dimensionless parameters, such as the electrochemical Thiele parameters, and hence provides useful information for the design of new electrochemical systems.

Nanis, L.↗