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At least 739 records · Page 41

High-Temperature Oxidation Behavior of FeCoCrNi+(Cu/Al)-Based High-Entropy Alloys in Humid Air

Previous studies showed some transition metal high-entropy alloy (HEA) compositions can have good oxidation resistance in air up to 800 °C. Four equiatomic HEAs have been developed based on FeCoCrNi with additions of Mn, Cu, Al or Al+Cu. The oxidation behavior of these HEAs was compared in humid (10 vol.% H2O) air at 800 °C for 100–500 h to investigate the influence of water vapor on the oxidation mechanisms. The Cu- and Al-containing alloys exhibited improved oxidation resistance over the Mn composition. For the Cu-containing alloy, a local attack of the Cu-rich phase was observed, which formed an Fe/Ni/Co/Cr spinel that was surrounded by Cr2O3. This oxide was thicker for the humid air atmosphere when compared to dry air, and the transition of the Cu oxide to the spinel was accelerated. The Al-containing HEA formed a thin Al2O3 scale with humidity suppressing AlN formation and forming a smoother oxide layer. The Al+Cu composition had the highest overall oxidation resistance (minimal local attack, no nitridation) and also showed a smooth oxide scale topography under humid air oxidation as opposed to a plate-like, rougher scale under dry air.

Crystallography↗

Perspectives on Dye Sensitization of Nanocrystalline Mesoporous Thin Films

Recent advances in our mechanistic understanding of dye-sensitized electron transfer reactions occurring at metal oxide interfaces are described. These advances were enabled by the advent of mesoporous thin films, comprised of anatase TiO 2 nanocrystallites, that are amenable to spectroscopic and electrochemical characterization in unprecedented molecular-level detail. The metal-to-ligand charge transfer (MLCT) excited states of Ru polypyridyl compounds serve as the dye sensitizers. Excited-state injection often occurs on ultrafast time scales with yields that can be tuned from unity to near zero through modification of the sensitizer or the electrolyte composition. Transport of the injected electron and the oxidized sensitizer (hole hopping) are both operative in the composite mechanism for charge recombination between the injected electron and the oxidized sensitizer. Sensitizers that contain a pendant electron donor, as well as core/shell SnO 2 /TiO 2 nanostructures, often prolong the lifetime of the injected electron and provide fundamental insights into adiabatic and nonadiabatic electron transfer mechanisms. Regeneration of the oxidized sensitizer by iodide is enhanced through halogen bonding, orbital pathways, and ion pairing. A substantial ~10 MV cm –1 electric field is created by electron injection into TiO 2 nanocrystallites that induces ion migration, reports on the sensitizer dipole orientation, and (in some cases) reorients or flips the sensitizer. Dye-sensitized conductive oxides also promote long-lived charge separation with bias dependent kinetics that provide insights into the reorganization energies associated with electron and proton-coupled electron transfer in the electric double layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Glass breaking strength: The role of surface flaws and treatments

Although the intrinsic strength of silicon dioxide glass is of the order of 10 to the 6th power lb/sq in, the practical strength is roughly two orders of magnitude below this theoretical limit, and depends almost entirely on the surface condition of the glass, that is, the number and size of flaws and the residual surface compression (temper) in the glass. Glass parts always fail in tension when these flaws grow under sustained loading to some critical size. Research associated with glass encapsulated crystalline-Si photovoltaic (PV) modules has greatly expanded our knowledge of glass breaking strength and developed sizeable data base for commercially available glass types. A detailed design algorithm is developed for thickness sizing of rectangular glass plates subject to pressure loads. Additional studies examine the strength of glass under impact loading conditions such as that caused by hail. Although the fundamentals of glass breakage are directly applicable to thin film modules, the fracture strength of typical numerical glass must be replaced with data that reflect the high temperature tin oxide processing, laser scribing, and edge processing peculiar to thin film modules. The fundamentals of glass breakage applicable to thin film modules and preliminary fracture strength data for a variety of 1 ft square glass specimens representing preprocessed and post processed sheets from current amorphous-Si module manufacturers are presented.

Moore, D.↗

Kinetic Study on Alloying Element Transfer During an Electroslag Remelting Process

Experimental and theoretical studies have been carried out to investigate the effects of slag on the alloying elements in ingots during the electroslag remelting (ESR) process with a focus on developing a mass-transfer model to understand the mechanism of slag-metal reaction. Stainless steel 1Cr21Ni5Ti was used as the electrode and remelted with two different kinds of slags using a 50-kg ESR furnace. The contents of sulfur, aluminum, titanium and silicon along the axial direction of the produced ingots were analyzed. On the basis of the penetration and film theories, the theoretical model developed in this work elucidates the kinetics of the slag-metal reaction revealing the mechanism of alloying element transfer during the ESR process. The calculation results obtained from the model agree well with the experimental results. The model indicates that the resultant [O] coming from the desulfurization reaction of (O{sup 2−}) + [S] = (S{sup 2−}) + [O] causes the oxidation of alloying elements in steel by [M] + [O] = (MO). The distribution ratio of sulfur L{sub S} decreases with the increase of slag temperature in the first slag-temperature-rising period, and the concentration of sulfur in the ingot at the beginning of the ESR process is lower than in the rest of the process because of the combination of the large distribution ratio of sulfur L{sub S} and excellent kinetic conditions. The concentration of aluminum along the height of the ingot has an increasing trend in the first slag-temperature-rising period, while it has a decreasing trend in the rest of the process. Two methods can solve this problem: one is starting up the ESR furnace by high temperature molten slag technology and the other is continually adding extra titania into the molten slag in the first slag-temperature-rising period.

36 MATERIALS SCIENCE↗

Preventing Fires in Cryogenic Oxidizer Lines

Friction and compression induced ignition prevented by heat-dissipation layer. Thin layer of copper placed inside surfaces of pipes and other parts in contact with flowing liquid oxygen, fluorine, or other oxidizers. Copper layer of only 0.001 to 0.005 inch (0.0254 to 0.127 mm) ensures heat away from hotspots thereby discouraging ignition. Copper layer increases oxygen ignition threshold of pipe by 5 to 20 times.

Wagner, W. R.↗

Transparent, Conductive Coatings Developed for Arc-Proof Solar Arrays

Transparent, conductive thin-film coatings have many potential applications where a surface must be able to dissipate electrical charges without sacrificing its optical properties. Such applications include automotive and aircraft windows, heat mirrors, optoelectronic devices, gas sensors, and solar cell array surfaces for space applications. Many spacecraft missions require that solar cell array surfaces dissipate charges in order to avoid damage such as electronic upsets, formation of pinholes in the protective coatings on solar array blankets, and contamination due to deposition of sputtered products. In tests at the NASA Lewis Research Center, mixed thin-films of sputter-deposited indium tin oxide (ITO) and magnesium fluoride (MgF2) that could be tailored to the desired sheet resistivity, showed transmittance values of greater than 90 percent. The samples evaluated were composed of mixed, thin-film ITO/MgF2 coatings, with a nominal thickness of 650 angstroms, deposited onto glass substrates. Preliminary results indicated that these coatings were durable to vacuum ultraviolet radiation and atomic oxygen. These coatings show promise for use on solar array surfaces in polar low-Earth-orbit environments, where a sheet resistivity of less than 10(exp 8)/square is required, and in geosynchronous orbit environments, where a resistivity of less than 10(exp 9)/square is required.

Source record↗

In situ Study on the Evolution of Atomic and Electronic Structure of LaTiO 3 /SrTiO 3 System

As with other transition-metal oxide interfaces, LaTiO 3 /SrTiO 3 interfaces exhibit interesting electronic properties, such as a two-dimensional electron gas. While the available Mott states and multiple pathways to metallicity in LaTiO 3 can lead to a variety of applications in oxide electronics, the origin of the different properties remains uncertain. Herein, utilizing real-time, in situ x-ray diffraction at the synchrotron, robust but thin LaTiO 3 /SrTiO 3 heterostructures were fabricated using oxide molecular beam epitaxy. A thickness of six unit cells was determined to be critical, at which point the LaTiO 3 /SrTiO 3 heterostructures begin to sustain sharp, well-defined interfaces. The layers of LaTiO 3 and SrTiO 3 were sufficiently thin to benefit from the finite escape length of electrons at resonant soft x-ray photoemission, and the heterostructures were transferred in vacuo after growth to another chamber for synchrotron-based x-ray photoemission spectroscopy studies. With the x-ray energy tuned to the Ti-2p resonance, the LaTiO 3 /SrTiO 3 interfaces could be probed with enough penetration depth and selectivity. It is shown that all of the heterointerfaces exhibit the two-dimensional electron gas.

36 MATERIALS SCIENCE↗

Nonlinear electrical transport near the metal–insulator transition in V 4 O 7 thin films

Nonlinear electrical transport associated with correlated electronic states has been widely investigated in transition-metal oxides near metal–insulator transitions. Here, in this study, we investigate nonlinear transport and threshold switching in sputter-deposited V 4 O 7 thin films grown on fused silica substrates. Temperature-dependent transport measurements show a metal–insulator transition near 240 K with negligible thermal hysteresis, defining the temperature scale that governs the nonlinear electrical response. Current–voltage measurements reveal reproducible bipolar threshold switching over a broad temperature range, with the threshold voltage decreasing systematically as the transition temperature is approached. Electrothermal finite-element simulations reproduce the measured switching characteristics and show that switching occurs when localized Joule heating drives a confined region of the device toward the transition temperature. The simulated peak local temperature at threshold lies close to the intrinsic metal–insulator transition temperature of V 4 O 7 , establishing that the nonlinear electrical response originates from electrothermal feedback acting on the strongly temperature-dependent conductivity near the transition. These results identify V 4 O 7 thin films as a model correlated-oxide system in which volatile threshold switching emerges from proximity to an extended metal–insulator transition.

25 ENERGY STORAGE↗

Observation of interacting polaronic gas behavior in Ta-doped TiO 2 thin films via terahertz time-domain spectroscopy

Transparent conductive oxides (TCOs)—materials that have the twin desirable features of high optical transmission and electrical conductivity—play an increasingly significant role in the fields of photovoltaics and information technology. As an excellent TCO, Ta-doped anatase TiO 2 shows great promise for a wide range of applications. Here, terahertz time-domain spectroscopy is used to study the complex optical conductivity $\tilde{σ}$ (ω) of the TCO—heavily Ta-doped TiO 2 thin films with different Ta-doping concentrations, in the frequency range of 0.3–2.7 THz and the temperature range of 10–300 K. Fitting the complex optical conductivity to a Drude-like behavior allows us to extract the temperature dependence of the effective mass, which suggests the existence of many-body large polarons. Moreover, the carrier scattering rate of Ta-doped TiO 2 with different carrier concentrations agrees with the interacting polaron gas theory. Our results suggest that with increasing electron density in TiO 2 , the interaction between polarons is larger and electron–phonon coupling is smaller, which is beneficial for achieving high mobility and conductivity in TiO 2 .

36 MATERIALS SCIENCE↗

Theoretical Prediction and Experimental Verification of IrO x Supported on Titanium Nitride for Acidic Oxygen Evolution Reaction

Reducing iridium (Ir) catalyst loading for acidic oxygen evolution reaction (OER) is a critical strategy for large-scale hydrogen production via proton exchange membrane (PEM) water electrolysis. However, simultaneously achieving high activity, long-term stability, and reduced material cost remains challenging. To address this challenge, we develop a frame-work by combining density functional theory (DFT) prediction using model surfaces and proof-of-concept experimental ver-ification using thin films and nanoparticles. DFT results predict that oxidized Ir monolayers over titanium nitride (IrO x /TiN) should display higher OER activity than IrO x while reducing Ir loading. Further, this prediction is verified by depositing Ir monolayers over TiN thin films via physical vapor deposition. The promising thin film results are then extended to commercially viable powder IrO x /TiN catalysts, which demonstrate a lower overpotential and higher mass activity than commercial IrO 2 , and a long-term stability of 250 hours to maintain a current density of 10 mA cm -2 . The superior OER performance of IrO x /TiN is further confirmed using proton exchange membrane water electrolyzer (PEMWE), which shows a lower cell voltage than commercial IrO 2 to achieve a current density of 1 A cm -2 . Both DFT and in situ X-ray absorption spectroscopy reveal that the high OER performance of IrO x /TiN strongly depends on the IrO x - TiN interaction via direct Ir-Ti bonding. This study highlights the importance of close interaction between theoretical prediction based on mechanistic understanding and experimental verification based on thin film model catalysts to facilitate the development of more practical powder IrO x /TiN catalysts with high activity and stability for acidic OER.

08 HYDROGEN↗

Thin film temperature sensor

Thin film surface temperature sensors were developed. The sensors were made of platinum-platinum/10 percent rhodium thermocouples with associated thin film-to-lead wire connections and sputtered on aluminum oxide coated simulated turbine blades for testing. Tests included exposure to vibration, low velocity hydrocarbon hot gas flow to 1250 K, and furnace calibrations. Thermal electromotive force was typically two percent below standard type S thermocouples. Mean time to failure was 42 hours at a hot gas flow temperature of 1250 K and an average of 15 cycles to room temperature. Failures were mainly due to separation of the platinum thin film from the aluminum oxide surface. Several techniques to improve the adhesion of the platinum are discussed.

Grant, H. P.↗

Effect of simulated Earth reentry exposure on mechanical properties of several oxide dispersion strengthened and superalloy sheet materials

The effects of simulated multiple reentry into the earth's atmosphere on the mechanical properties of several high temperature metallic sheet materials were evaluated. The materials included five tin-gage (nominally 0.025- or 0.037-cm) oxide dispersion strengthened (ODS) alloys and two thin-gage (nominally 0.037-cm) superalloys. Multiple reentry conditions were simulated through cyclic Plasma Arc Tunnel (PAT) exposure. PAT exposure generally consisted of 100 cycles of 600 second duration at 1255, 1366, or 1477 K in a Mach 4.6 airstream with an impact pressure of nominally 800 N/m2. PAT exposure generally produced a uniform oxide scale, oxide pits or intergranular oxidation, Kirkendall porosity, and alloy depletion zones except for the aluminum-containing ODS alloys. Only a uniform oxide scale was formed on the aluminum-containing ODS alloys. PAT exposure did not significantly affect the mechanical properties of the thin-gage (nominally 0.025- or 0.037-cm) alloys evaluated. Thus it appears that the microstructural changes produced by Plasma Arc Tunnel exposure has little influence on mechanical properties.

Whittenberger, J. D.↗

Manipulating the metal-to-insulator transition and magnetic properties in manganite thin films via epitaxial strain

Strain engineering of epitaxial transition metal oxide heterostructures offers an intriguing opportunity to control electronic structures by modifying the interplay between spin, charge, orbital, and lattice degrees of freedom. Here, we demonstrate that the electronic structure, magnetic and transport properties of La 0.9 Ba 0.1 MnO 3 thin films can be effectively controlled by epitaxial strain. Spectroscopic studies and first-principles calculations reveal that the orbital occupancy in Mn eg orbitals can be switched from the d 3z 2 -r 2 orbital to the d x 2 -y 2 orbital by varying the strain from compressive to tensile. Further, the change of orbital occupancy associated with Mn 3d-O 2p hybridization leads to dramatic modulation of the magnetic and electronic properties of strained La 0.9 Ba 0.1 MnO 3 thin films. Under moderate tensile strain, an emergent ferromagnetic insulating state with an enhanced ferromagnetic Curie temperature of 215 K is achieved. These findings not only deepen our understanding of electronic structures, magnetic and transport properties in the La 0.9 Ba 0.1 MnO 3 system, but also demonstrate the use of epitaxial strain as an effective knob to tune the electronic structures and related physical properties for potential spintronic device applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ultrasmooth Epitaxial Pt Thin Films Grown by Pulsed Laser Deposition

Platinum (Pt) thin films are useful in applications requiring high-conductivity electrodes with excellent thermal and chemical stability. Ultrasmooth and epitaxial Pt thin films with single-crystalline domains have the added benefit of providing ideal templates for the subsequent growth of heteroepitaxial structures. Here, we grow epitaxial Pt (111) electrodes (ca. 30 nm thick) on sapphire (α-Al 2 O 3 (0001)) substrates with pulsed laser deposition. This versatile technique allows control of the growth process and fabrication of films with carefully tailored parameters. X-ray scattering, atomic-force microscopy, and electron microscopy provide structural characterization of the films. Various gaseous atmospheres and temperatures were explored to achieve epitaxial growth of films with low roughness. A two-step (500 °C/300 °C) growth process was developed, yielding films with improved epitaxy without compromising roughness. The resulting films possess ultrasmooth interfaces (<3 Å) and high electrical conductivity (6.9 × 10 6 S/m). Finally, Pt films were used as current collectors and templates to grow lithium manganese oxide (LiMn 2 O 4 (111)) epitaxial thin films, a cathode material used in Li-ion batteries. In conclusion, using a solid-state ionogel electrolyte, the films were highly stable when electrochemically cycled in the 3.5-4.3 V vs Li/Li + range.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Volume Ice Radiolysis in the Outer Solar System

The primary energy flux of charged particle components of the heliospheric and magnetospheric environments of the solar system is primarily carried by highly penetrating energetic particles. Although laboratory experiments on production of organics and oxidants typically only address effects on very thin surface layers, energy deposition occurs on surfaces of icy bodies of the outer solar system to meters in depth. Time scales for significant radiolytic deposition vary from thousands of years at millimeter depths on Europa to billions of years in the meters-deep regolith of Kuiper Belt Objects. Radioisotope decay (e.g., K-40) also contributes to volume radiolysis as the only energy source at much greater depths. Radiolytic oxygen is a potential resource for life within Europa and a partial source of oxygen for Saturn's magnetosphere and Titan's upper atmosphere. Interactions of very high energy cosmic rays with ices at Titan's surface may provide one of the few sources of oxidants in that highly reducing environment. The red colors of low-inclination classical Kuiper Belt Objects at 40-50 AU, and Centaur objects originating from this same population, may arise from volume radiolysis of deep ice layers below more refractory radiation crusts eroded away by surface sputtering and micrometeoroid impacts. A variety of techniques are potentially available to measure volume radiolysis products and have been proposed for study as part of the new Space Physics of Life initiative at NASA Goddard Space Flight Center. The technique of Electron Paramagnetic Resonance (EPR) has been used in medical studies to measure oxidant production in irradiated human tissue for cancer treatment. Other potential techniques include optical absorption spectroscopy and standard wet chemical analysis. These and other potential techniques are briefly reviewed for applicability to problems in solar system ice radiolysis and astrobiology.

Cooper, John F.↗

Evaluation of oxide-coated iridium-rhenium chambers

Iridium-coated rhenium (Ir-Re) provides long life operation of radiation-cooled rockets at temperatures up to 2200 C. Ceramic oxide coatings could be used to increase Ir-Re rocket lifetimes and allow operation in highly oxidizing environments. Ceramic oxide coatings promise to serve as both thermal and diffusion barriers for the iridium layer. Seven ceramic oxide-coated Ir-Re, 22-N rocket chambers were tested with gaseous hydrogen/gaseous oxygen (GHz/G02) propellants. Five chambers had thick (over 10 mils), monolithic coatings of either hafnia (HfO2) or zirconia (ZrO2). Two chambers had coatings with thicknesses less than 5 mils. One of these chambers had a thin-walled coating of ZrO2 infiltrated with sol gel HfO2. The other chamber had a coating composed of an Ir-oxide composite. The purpose of this test program was to assess the ability of the oxide coatings to withstand the thermal shock of combustion initiation, adhere under repeated thermal cycling, and operate in aggressively oxidizing environments. All of the coatings survived the thermal shock of combustion and demonstrated operation at mixture ratios up to 11. Testing the Ir-oxide composite-coated chamber included over 29 min at mixture ratio 16. The thicker walled coatings provided the larger temperature drops across the oxide layer (up to 570 C), but were susceptible to macrocracking and eventual chipping at a stress concentrator. The cracks apparently resealed during firing, under compression of the oxide layer. The thinner walled coatings did not experience the macrocracking and chipping of the chambers that was seen with the thick, monolithic coatings. However, burn-throughs in the throat region did occur in both of the thin-walled chambers at mixture ratios well above stoichiometric. The burn-throughs were probably the result of oxygen diffusion through the oxide coating that allowed the underlying Ir and Re layers to be oxidized. The results of this test program indicated that the thin-walled oxide coatings are better suited for repeated thermal cycling than the thick-walled coating, while thicker coatings may be required for operation in aggressively oxidizing environments.

Reed, Brian D.↗

High-Pressure Lightweight Thrusters

Returning samples of Martian soil and rock to Earth is of great interest to scientists. There were numerous studies to evaluate Mars Sample Return (MSR) mission architectures, technology needs, development plans, and requirements. The largest propulsion risk element of the MSR mission is the Mars Ascent Vehicle (MAV). Along with the baseline solid-propellant vehicle, liquid propellants have been considered. Similar requirements apply to other lander ascent engines and reaction control systems. The performance of current state-ofthe- art liquid propellant engines can be significantly improved by increasing both combustion temperature and pressure. Pump-fed propulsion is suggested for a single-stage bipropellant MAV. Achieving a 90-percent stage propellant fraction is thought to be possible on a 100-kg scale, including sufficient thrust for lifting off Mars. To increase the performance of storable bipropellant rocket engines, a high-pressure, lightweight combustion chamber was designed. Iridium liner electrodeposition was investigated on complex-shaped thrust chamber mandrels. Dense, uniform iridium liners were produced on chamber and cylindrical mandrels. Carbon/carbon composite (C/C) structures were braided over iridium-lined mandrels and densified by chemical vapor infiltration. Niobium deposition was evaluated for forming a metallic attachment flange on the carbon/ carbon structure. The new thrust chamber was designed to exceed state-of-the-art performance, and was manufactured with an 83-percent weight savings. High-performance C/Cs possess a unique set of properties that make them desirable materials for high-temperature structures used in rocket propulsion components, hypersonic vehicles, and aircraft brakes. In particular, more attention is focused on 3D braided C/Cs due to their mesh-work structure. Research on the properties of C/Cs has shown that the strength of composites is strongly affected by the fiber-matrix interfacial bonding, and that weakening interface realizes pseudo-plastic behavior with significant increase in the tensile strength. The investigation of high-temperature strength of C/Cs under high-rate heating (critical for thrust chambers) shows that tensile and compression strength increases from 70 MPa at room temperature to 110 MPa at 1,773 K, and up to 125 MPa at 2,473 K. Despite these unique properties, the use of C/Cs is limited by its high oxidation rate at elevated temperatures. Lining carbon/carbon chambers with a thin layer of iridium or iridium and rhenium is an innovative way to use proven refractory metals and provide the oxidation barrier necessary to enable the use of carbon/ carbon composites. Due to the lower density of C/Cs as compared to SiC/SiC composites, an iridium liner can be added to the C/C structure and still be below the overall thruster weight. Weight calculations show that C/C, C/C with 50 microns of Ir, and C/C with 100 microns of Ir are of less weight than alternative materials for the same construction.

Holmes, Richard↗

Surface stability of SrNbO 3+δ grown by hybrid molecular beam epitaxy

4d transition metal oxides have emerged as promising materials for numerous applications including high mobility electronics. SrNbO 3 is one such candidate material, serving as a good donor material in interfacial oxide systems and exhibiting high electron mobility in ultrathin films. However, its synthesis is challenging due to the metastable nature of the d 1 Nb 4+ cation and the limitations in the delivery of refractory Nb. To date, films have been grown primarily by pulsed laser deposition (PLD), but development of a means to grow and stabilize the material via molecular beam epitaxy (MBE) would enable studies of interfacial phenomena and multilayer structures that may be challenging by PLD. To that end, SrNbO 3 thin films were grown using hybrid MBE for the first time using a tris(diethylamido)(tert-butylimido) niobium precursor for Nb and an elemental Sr source on GdScO 3 substrates. Varying thicknesses of insulating SrHfO 3 capping layers were deposited using a hafnium tert-butoxide precursor for Hf on top of SrNbO 3 films to preserve the metastable surface. Grown films were transferred in vacuo for x-ray photoelectron spectroscopy to quantify elemental composition, density of states at the Fermi energy, and Nb oxidation state. Ex situ studies by x-ray absorption near edge spectroscopy and scanning transmission electron microscopy illustrate that the SrHfO 3 capping plays an important role in preserving the crystalline quality of the material and the Nb 4d 1 metastable charge state under atmospheric conditions.

36 MATERIALS SCIENCE↗