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At least 991 records · Page 55

Preparation of Nonprecious Metal Electrocatalysts for the Reduction of Oxygen Using a Low-Temperature Sacrificial Metal

Non-platinum group metal (non-PGM) electrocatalysts for the oxygen reduction reaction (ORR) are generally composed of iron, nitrogen, and carbon synthesized through high-temperature pyrolysis. Among the various types of precursors, metal-organic frameworks (MOFs), zeolitic imidazolate framework (ZIF)-8 in particular, have often been used in the synthesis. The pyrolysis of ZIF-8 precursor relies on the use of Zn as a sacrificial metal (SM), and the optimal processing temperatures often exceed 1000 degrees C to generate active non-PGM catalysts. The high pyrolysis temperature tends to result in heterogeneous active moieties ranging from Fe single atoms to nanoparticles. In this study, we present the synthesis of non-PGM catalysts using Cd as the sacrificial metal instead of Zn. By using Cd, we were able to generate active non-PGM electrocatalysts from the MOF precursors at a low pyrolysis temperature of 750 degrees C, which helps preserve the single atomic iron active sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solder joint fatigue analysis under low temperature Martian conditions

Electronics, without requiring heater power or enclosure in a centralized 'warm electronics box,' will need to survive mean surface temperatures of -120 degrees Celsius to +20 degrees Celsius for an extended Martian mission and an operational temperature up to 85 degrees Celsisus. Since these electronics will need to survive extended cycles under these conditions, fatigue is a significant concern. The solder joint reliability of connectors on a printed wiring board was investigated.

low temperature↗

Fermi surface origin of the low-temperature magnetoresistance anomaly

Magnetoresistance (MR) at a fixed field can demonstrate a non-monotonic temperature dependence—an anomaly—in many systems, including low-dimensional chalcogenides, spin- and charge-density-wave metals, and topological semimetals. These systems are often low-carrier-density compensated metals, and the physics are expected to be quasi-classical. Nevertheless, the MR anomaly also exists in the highly conductive metals Cr, Mo, and W for both linear and quadratic field dependence, with their non-saturation attributed to either open orbit or electron-hole compensation. We argue that quantum transport across sharp Fermi surface arcs, but not necessarily the full cyclotron orbit, governs this MR anomaly, thereby accounting for the profound effects of disorder. In Cr, an overlay exists between three temperature dependences: MR at a constant high field, linear MR at a low field, and Shubnikov-de Haas (SdH) oscillations of the smallest orbit. In Mo, the MR anomaly extends beyond the temperature of its SdH oscillations but disappears before Kohler’s scaling reemerges.

Feng, Yejun [Okinawa Institute of Science and Tech↗

Reaction Pathways and Energy Consumption in NH 3 Decomposition for H 2 Production by Low Temperature, Atmospheric Pressure Plasma

Pathways for NH 3 decomposition to N 2 and N 2 H 4 by atmospheric pressure nonthermal plasma are analyzed using a combination of molecular beam mass spectrometry measurements and zero-dimensional kinetic modeling. Experimental measurements show that NH 3 conversion and selectivity towards N 2 formation scale monotonically with the specific energy input into the plasma with ~ 100% selectivity to N 2 formation achieved at specific energy inputs above 0.12 J cm −3 (3.1 eV (molecule NH 3 ) −1 ). The kinetic model recovers these trends, although it underpredicts N 2 selectivity at low specific energy input. These discrepancies can be explained by the underestimation of reaction rate coefficients for reactions that consume N 2 H x species in collisions with H radicals and/or radial nonuniformities in power deposition, gas temperature, and species concentrations that are not represented by the plug flow approximation used in the model. The kinetic model shows that N 2 formation proceeds through N 2 H x decomposition pathways rather than NH x decomposition pathways in low temperature, atmospheric pressure plasma. Higher selectivity toward N 2 production can be achieved by operating at higher NH 3 conversion and with a higher gas temperature. Furthermore, the high energy cost of NH 3 decomposition by atmospheric pressure nonthermal plasma found in this work (25–50 eV (molecule NH 3 converted) −1 ; 17–33 eV (molecule H 2 formed) −1 ) is a result of the energy requirement for electron-impact dissociation of NH 3 and the significant re-formation of NH 3 by three-body recombination reactions between NH 2 and H.

Nonthermal plasma↗

Cycling and Low Temperature Performance of Li Ion Cells

Lithium-ion cells, of DD and D size, are being developed under a contract with the USAF for NASA's Mars Rover Missions. The cells contain spirally wound electrodes of LiNi02 positive electrode material and graphite anode in cylindrical stainless steel hardware.

Li-Ion↗

High power, gel polymer lithium-ion cells with improved low temperature performance for NASA and DoD applications

Both NASA and the U.S. Army have interest in developing secondary energy storage devices that are capable of meeting the demanding performance requirements of aerospace and man-portable applications. In order to meet these demanding requirements, gel-polymer electrolyte-based lithium-ion cells are being actively considered, due to their promise of providing high specific energy and enhanced safety aspects.

high power li-ion batteries↗

Effect of chromium on low-temperature deformation of high-purity iron

A series of very low interstitial Fe-Cr alloys containing 0, 1, 3, 5, and 10 wt% Cr were prepared by vacuum melting and fabricated under argon to 1.83 mm diam wires exposed in an alumina system to wet hydrogen for 200 h at 1423 K followed by 1000 h in ZrH2-purified hydrogen at 1573 K. The wires were then transverse-rolled into thin sheet and cut into tensile specimens subjected to electropolishing and strained to fracture in a series of cryogenic baths ranging from 4.2 K to room temperature. It is shown that small Cr additions lower the twinning stress so that yielding occurs by twinning rather than by slip. Cr in amounts up to 10 wt% has little effect on the yield strength of high-purity Fe between 147 and 300 K, and ductility is not greatly affected at any test temperature. Higher solute contents provide appreciable strengthening only at temperatures of 112 K and below.

Kelley, M. J.↗

Critical roles of Cu(OH)2 in low-temperature moisture-induced degradation of Cu-SAPO-34 SCR catalyst: Correlating reversible and irreversible deactivation

Cu-SAPO-34 selective catalytic reduction (SCR) catalyst deactivates upon exposure to water vapor at temperatures lower than 100 °C, which deteriorates its application prospects. The deactivation under cycled aging-regeneration conditions can be categorized into two stages, namely reversible and irreversible deactivation. Based on SCR reaction tests, and characterizations with diffuse reflection infrared Fourier transform spectroscopy (DRIFTS), NH3 temperature-programmed desorption (NH3-TPD) and H2 temperature-programmed reduction (H2-TPR), it is concluded that the transformation of SCR active isolated Cu(II) ions to Cu(OH)2 is critical to both types of deactivation. Within the frame of reversible deactivation, Cu(OH)2 is converted back to SCR active Cu(II) ions by interacting with Brønsted acid sites during high-temperature regeneration. However, interactions between Cu(OH)2 and hydrolyzed framework Al lead to the formation of CuAl2O4-like species, causing permanent loss of active Cu(II) ions and thus, irreversible deactivation. The authors from Tsinghua University would like to acknowledge the financial support from projects of China Science and Technology Exchange Centre (No. 2016YFE0126600) and the National Key R&D Program of China (No. 2017YFC0211102). YM also acknowledges Tsinghua Scholarship for Overseas Graduate Studies for a visit to the Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the US Department of Energy (DOE) under contract DE-AC05-76RL01830. FG is supported by DOE, Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office.

Cu-SAPO-34, low-temperature deactivation, reversib↗

Nano-Ceramic Cathodes via Co-sputtering of Gd–Ce Alloy and Lanthanum Strontium Cobaltite for Low-Temperature Thin-Film Solid Oxide Fuel Cells

We report the electrochemical performance and structural characteristics of porous nanostructured ceramic cathodes for thin-film solid oxide fuel cells (TF-SOFCs) based on yttria-stabilized zirconia (YSZ) electrolytes. The nanostructured cathode is obtained through magnetron co-sputtering of gadolinium–cerium (Gd–Ce) alloy and lanthanum strontium cobaltite perovskite targets. The resultant nanostructure and composition of the ceramic cathode are controlled by adjusting the co-sputtering conditions. The peak power densities in our fabricated TF-SOFCs are the highest reported values for YSZ-based electrolyte SOFCs, showing 0.14, 0.48, 1.21, 2.56, and 3.01 W/cm2 at 450, 500, 550, 600, and 650 °C, respectively, operating under air and pure hydrogen fuel. The results show that the porosity and composition of the cathode greatly affect the resulting peak power densities. This work illustrates the capability of sputtering to produce stable, scalable, nano-ceramic cathodes with superb peak power densities when integrated in TF-SOFCs.

25 ENERGY STORAGE↗

Low temperature water-gas shift: Optimization of K loading on Pt/m-ZrO 2 for enhancing CO conversion

Previous work showed that alkali doping of Pt/ZrO 2 significantly improved the LT-WGS rate. This improvement was caused by an acceleration in the rate of formate decomposition, the rate limiting step of an associative mechanism, through electronically weakening the CH bond. In this study, the effects that potassium loading on Pt/ZrO 2 have on the rate of LT-WGS and the strength of the CH bond in intermediate formate species are explored. Catalysts were investigated using in-situ DRIFTS, TPR-MS, TPD, EXAFS, and catalyst testing. Here, loadings of 1.7 wt.% potassium or higher shifted the formate ν(CH) band to significantly lower wavenumbers, indicating weakening of the bond. For the optimal loading, 2.6 wt.% K, the formate CH bond was significantly weakened, and the surface of Pt nanoparticles remained largely uncovered. However, loadings of 3.4 wt. % and above blocked the surface of the platinum nanoparticles. This, in addition to an increasing average Pt0 cluster size, hindered platinum from assisting in dehydrogenation of formate during steam promoted formate decomposition occurring in LT-WGS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low temperature catalytic conversion of CH 4 , CO 2 , and C 2 H 4 to value-added C 3 oxygenates and olefins via C 1 -C 2 coupling on Pd-Au/CeO 2

The catalytic conversion of CH 4 and CO 2 in the presence of more reactive co-reactants C 2 H 4 and O 2 on Pd-Au/CeO 2 is achieved at 200 °C and elevated pressures. Propene and acetone were produced from the catalyzed reaction of CH 4 +C 2 H 4 +O 2 ; addition of CO 2 to the reactant stream produced methyl acetate (MAc) but it significantly reduced the C-selectivities of propene and acetone. DRIFTS experiments confirmed the formation of methoxy species from CH 4 +CO 2 at 200 °C, which is an intermediate in the formation of MAc. Here, control experiments with blanks, and with CeO 2 did not show any propene, acetone, or MAc products. The complete oxidation of C 2 H 4 was avoided; the catalyst is stable, and reactant conversions and product yields were sustained for the observed 1200 min time-on-stream, indicating that there is little or no carbon deposition and sintering. This direct coupling of CH 4 and C 2 H 4 intermediates to higher carbon-number products at 200 °C is significant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radiolytic evaluation of select sulfur chlorides (S 2 Cl 2 and SOCl 2 ) for advanced low temperature chlorination of zirconium-based used nuclear fuel cladding

New sulfur chloride compounds—sulfur monochloride (S 2 Cl 2 ) and thionyl chloride (SOCl 2 )—have been proposed as alternative chlorinating agents for the chemical decladding of zirconium-based used nuclear fuel cladding materials. However, the radiation stability of these compounds has not been thoroughly evaluated, despite envisioned process conditions involving intense, multi-component radiation fields. Knowledge of the radiation chemistry of these sulfur chlorides is essential for the development and optimization of alternative chlorination technologies. To this end, we present preliminary findings on the gamma radiolysis of neat S 2 Cl 2 and SOCl 2 at ambient temperature up to ~ 34 MGy. In this study, Raman spectroscopy and density functional theory calculations were used to identify the Raman-active degradation products from S 2 Cl 2 and SOCl 2 radiolysis. Both sulfur chloride compounds exhibited significant radiation resistance, with respect to changes in the Raman signatures of the parent compounds and the ingrowth of Raman-active degradation products. For S 2 Cl 2 , molecular chlorine (Cl 2 ) was directly identified as the predominant degradation product, which was completely consumed at higher absorbed doses (> 9 MGy). Similarly, the main degradation product from SOCl 2 radiolysis was also Cl 2 , although in this system it continued to grow in with dose over the entire dose range. Further, an “S=O” containing degradation product(s) was also identified as a compliment to Cl 2 . Overall, the perceived radiation resistance of these sulfur chloride compounds makes them suitable for inclusion in a used nuclear fuel chemical decladding process, especially as radiolytically formed Cl 2 can be used to reform the parent compounds, thereby increasing the longevity of the solvents used.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Extreme High and Low Temperature Operation of the Silicon-On-Insulator Type CHT-OPA Operational Amplifier

A new operational amplifier chip based on silicon-on-insulator technology was evaluated for potential use in extreme temperature environments. The CHT-OPA device is a low power, precision operational amplifier with rail-to-rail output swing capability, and it is rated for operation between -55 C and +225 C. A unity gain inverting circuit was constructed utilizing the CHT-OPA chip and a few passive components. The circuit was evaluated in the temperature range from -190 C to +200 C in terms of signal gain and phase shift, and supply current. The investigations were carried out to determine suitability of this device for use in space exploration missions and aeronautic applications under wide temperature incursion. Re-restart capability at extreme temperatures, i.e. power switched on while the device was soaked at extreme temperatures, was also investigated. In addition, the effects of thermal cycling under a wide temperature range on the operation of this high performance amplifier were determined. The results from this work indicate that this silicon-on-insulator amplifier chip maintained very good operation between +200 C and -190 C. The limited thermal cycling had no effect on the performance of the amplifier, and it was able to re-start at both -190 C and +200 C. In addition, no physical degradation or packaging damage was introduced due to either extreme temperature exposure or thermal cycling. The good performance demonstrated by this silicon-on-insulator operational amplifier renders it a potential candidate for use in space exploration missions or other environments under extreme temperatures. Additional and more comprehensive characterization is, however, required to establish the reliability and suitability of such devices for long term use in extreme temperature applications.

Patterson, Richard↗

Keeping Floodlight Temperature Low

Safety in explosive atmospheres enhanced. Retainer for floodlight designed to undergo relatively small temperature rise. Reaches no more than 350 degrees F (177 degrees C) with lamp operating at about 4,700 degrees F (2,600 degrees C). Satisfies 352 degrees F (188 degrees C) requirement for operation in some explosive atmospheres. Made of thermally conductive metal with coating of material having low thermal absorptivity/emissivity ratio so it conducts heat away from lamp and radiates to surroundings efficiently.

Kiss, John↗