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At least 109 records · Page 6

Synthesis, Structure, and Transport Properties of YbSb2Te4 and YbSb4Te7 for Thermoelectric Applications

Very little work has been done in the Yb-Sb-Te system of compounds. Exploratory synthesis of various compounds in the system has been performed in the search for new thermoelectric materials. The compounds in the system were examined due to the fact that the system is known to act as a concentrated Kondo system, a heavy fermion. Heavy fermions are known to possess high densities of state which are useful in thermoelectric applications. TWO compounds in the system, YbSb2Te4 and YbSb4Te7, have been successfully synthesized in bulk by two methods: low temperature mechanical alloying and high temperature direct synthesis. The Hall mobility, Seebeck coefficient, electrical resistivity, and thermal conductivity were measured on both the unannealed and annealed compounds up to 550 C to determine the dimensionless thermoelectric figure of merit, ZT. The results indicate that both compounds make promising candidates for use in thermoelectric devices.

Guloy, Amado S.↗

Porosity in Sr 1-x Ca x FeO 3-δ oxygen carriers: The role of surface area and pretreatment on storage activity

Perovskite oxides have generated interest as robust, low-temperature oxygen carrier materials for a variety of clean energy applications, including chemical looping gasification and air separations. Methods to improve O 2 desorption kinetics are vital to allow these carriers to compete economically with traditional metal oxide carriers or cryogenic separations. In this report we investigated the cumulative roles that surface area, pretreatment, and elemental composition have on the oxygen storage properties of a state-of-the-art carrier system, Sr 1-x Ca x FeO 3-δ (x = 0.20, 0.25, 0.30) synthesized using multiple methods. Porous materials synthesized by the Pechini, or citrate, method had their surface area controlled using the synthesis temperature. The high surface area of the Sr 0.7 Ca 0.3 FeO 3-δ materials is most beneficial at low operating temperatures, such as 350 and 400 °C, as their reduction rates are twice as fast as those obtained with their bulk counterparts. These effects are observed at higher operating temperatures and within a single composition, but temperature tunability using variable Ca 2+ substitution in the Sr 1-x Ca x FeO 3-δ overshadows the improvements gained from higher surface areas. Additionally, we establish that pretreatment in N2 at an elevated temperature is necessary to enhance kinetics further. For maximum efficiency, pretreatment at the synthesis temperature is suggested for the Pechini method-synthesized systems, whereas 800 °C is adequate for bulk materials.

36 MATERIALS SCIENCE↗

3D simulations of spinlike flames in Co/Al multilayers with enhanced conduction losses

Reactive Co/Al multilayers are uniformly structured materials that may be ignited to produce rapid and localized heating. Prior studies varying the bilayer thickness (i.e., sum of two individual layers of Co and Al) have revealed different types of flame morphologies, including: (a) steady/planar, (b) wavy/periodic, and (c) transverse bands, originating in the flame front. These instabilities resemble the “spin waves” first observed in the early studies of solid combustion (i.e., Ti cylinder in a N 2 atmosphere), and are likewise thought to be due to the balance of heat released by reaction and heat conduction forward into the unreacted multilayer. However, the multilayer geometry and three-dimensional (3D) edge effects are relatively unexplored. In this work, a new diffusion-limited reaction model for Co/Al multilayers was implemented in large, novel 3D finite element analysis (FEA) simulations, in order to study the origins of these spinlike flames. This reaction model builds upon previous work by introducing three new phase-dependent property models for: (1) the diffusion coefficient, (2) anisotropic thermal conductivity tensor, and (3) bulk heat capacity, as well as one additional model for the bilayer-dependent heat of reaction. These novel 3D simulations are the first to predict both steady and unsteady flames in Co/Al multilayers. Moreover, two unsteady modes of flame propagation are identified, which depend on the enhanced conduction losses with slower flames, as well as flame propagation around notched edges. Finally, future work will consider the generality of the current modeling approach and also seek to define a more generalized set of stability criteria for additional multilayer systems.

42 ENGINEERING↗

Quantifying the effects of artificial aging on the ignition and self-propagating reactions of Ni(V)/Al multilayers

Bimetallic, reactive multilayers are uniformly structured materials composed of alternating nanoscale layers that may be ignited to produce self-propagating intermetallic-formation reactions. When reactive multilayers age, there is a change in local composition and loss of stored chemical energy due to mass transport and rearrangement at the interfaces. Here, to quantify the long-term reliability of commercial Ni(V)/Al multilayers, the effects of accelerated aging on both ignition sensitivity and self-propagating reactions have been examined. Thermally aged samples were characterized using transmission electron microscopy, differential scanning calorimetry, and laser ignition combined with high-speed videography. The analytically quantifiable nature of both continuous wave laser ignition and reactive wave propagation enabled calculations of Arrhenius rate constants for as-received and various heat-treated multilayers. With heat treatment, there is a change in the intermixed thickness and interfacial chemistry that decreases the activation energy for point ignition but increases it for self-propagating reactions. This finding implies that with increased thermal aging, the reaction becomes easier to facilitate in the solid state but harder in the liquid phase.

Energetic material↗

Research on radiation detectors, boiling transients, and organic lubricants

The accomplishments of a space projects research facility are presented. The subjects discussed are: (1) a study of radiation resistant semiconductor devices, (2) synthesis of high temperature organic lubricants, (3) departure from phase equilibrium during boiling transients, (4) effects of neutron irradiation on defect state in tungsten, and (5) determination of photon response function of NE-213 liquid scintillation detectors.

Source record↗

Chemical Evolution and the Origin of Life: Bibliography 1975

This bibliography is the sixth annual supplement to the comprehensive bibliography on the same subject which was published in Space Life Sci.We would like to draw attention to a recently published cumulative bibliography on this same subject: Biochemical Origin of Life: Chemistry and Life. Soil and Water and Its Relationship to Origin of Life. MR - Studies of Prebiotic Polypeptides. Energy, Matter, and Life. Prospects for the Future Orientation of Scientific Research. Photochemical Formation of Self Sustaining Coacervates. Photochemical Formation of Self-Sustaining Coacervates. Comparative Study of Abiogenesis of Cysteine and Other Amino Acids Catalyzed by Various Metal Ions. Protein Structure and the Molecular Evolution of Biological Energy Conversion. Origin of Life. Clues from Relations Between Chemical Compositions of Living Organisms and Natural Environments. Shock Synthesis of Amino Acids II.', Origins of Life 6(1-2). Dynamics of the Chemical Evolution of Earth's Primitive Atmosphere. The Mechanisms of Amino Acids Synthesis by High Temperature Shock-Waves. Theory of Chemical Evolution. Physical Foundations of Probability of Biogenesis.

West, Martha W.↗

High-Temperature Fe-Based Fischer–Tropsch Synthesis: Experimentally Validated Kinetic Models Implemented at Pellet and Reactor Scales

Pellet- and reactor-scale models for Fischer–Tropsch synthesis (FTS) with a Fe–K/silica catalyst were developed to investigate the sensitivity of the hydrocarbon products and carbon dioxide selectivity to process conditions and feed composition at high temperature (350–400 °C), moderate pressure (1–10 bar), and a range of H 2 /CO ratios (3–1). The major objective of this paper is to develop, validate, and evaluate a high-temperature FTS model that is then used to assess the feasibility of process integration with syngas production. Since there is limited kinetic data available, in literature at these conditions, bench-scale reactor tests were conducted to obtain operational data for parameter fitting of kinetic expressions used in the model. This resulting kinetic model demonstrated agreement with the experimental data with an R 2 of 0.97 to the testing data set and, thus, was feasible to apply at pellet and reactor scales. Here, multiple pellet sizes were modeled to detail the role of transport limitations as the sphere’s diameter approached and exceeded 1 mm. Application of the reactor model indicated that hydrocarbon selectivity depended strongly on temperature, whereas the ratio of olefin to paraffin products decreased with increasing temperature, pressure, and H 2 /CO ratio. Product selectivity was not sensitive to the conversion of carbon monoxide. Furthermore, the roles of the pressure and H 2 /CO ratio were closely coupled. At a H 2 /CO ratio of 3, only slight variations in selectivity occurred over a pressure range of 1–20 bar, whereas at a ratio of 1, selectivity could vary by as much as 30% over the same pressure range. At pressures below 5 bar and temperatures above 350 °C, minimal selectivity to heavy hydrocarbons (C 12+ ) is obtained, and selectivity to midrange products (C 5–11 ) rapidly declined as pressure dropped below 5 bar, which indicated that an operational pressure of at least 5 bar is needed to achieve reasonable yields in this temperature range. These results, while tentative, provide guidelines for further experimentation and evaluation of integrated FTS processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Economizing on Precious Metals in Three-Way Catalysts: Thermally Stable and Highly Active Single-Atom Rhodium on Cera for NO Abatement under Dry and Industrially Relevant Conditions

We show for the first time that atomically dispersed Rh cations on ceria, prepared via high-temperature atom trapping synthesis, are the active species for (CO+NO) reaction. This provides a direct link with the organometallic homogeneous Rh(I) complexes capable of catalyzing dry (CO+NO) reaction but without the stability concern. In particular, thermally stable Rh cations in 0.1wt% Rh1/CeO2 achieve full NO conversion with a TOF of ~ 330 hr-1 per Rh atom at 120 °C. Under dry conditions, the main product above 100 °C is N2 with N2O being the minor product. The presence of water promotes low-temperature activity of 0.1wt% Rh1/CeO2 starting at 50 °C with full NO conversion at ~120 °C. In the case with the wet stream, however, ammonia and nitrogen are the main products with only minor N2O amounts. NH3 formation at such low temperatures is attractive because of the potential to use this as a passive SCR system. Because of the uniformity of Rh ions on the support, we are able to observe the intermediates of (CO+NO) reaction via infrared measurements on Rh cations on zeolite and ceria. Furthermore, we show that ammonia formation correlates with the WGS activity of the material and thus, rhodium hydride Rh-H species are involved in this reaction: we detect Rh(CO)Hx species on ceria using isotopic IR measurements. These findings provide new mechanistic understanding for the catalytically active species in TWC catalysis and open up a new avenue for the synthesis of novel emissions control catalysts with 100% atom economy of ultra-expensive precious metals such as Rh.

Khivantsev, Konstantin↗

Isothermal solidification for high-entropy alloy synthesis

Kinetically trapping the high-temperature states through rapid cooling solidification is widely used for the synthesis of high-entropy alloys (HEAs), especially those with intrinsically immiscible elemental combinations. However, strategies need to be developed to overcome the fundamental limitations of rapid cooling solidification in controlling the crystallinity, structure and morphology of HEAs. Here, in this study, we introduce an isothermal solidification strategy for the synthesis of HEAs by rapidly altering the metal alloy composition through liquid–liquid interface reactions at low temperatures, for example, from 25 °C to 80 °C. We use gallium (Ga)-based metal as the sacrificial reagent and mixing medium. By directing the reactions to the interfaces between the Ga-based liquid metal and an aqueous metal ion solution, the foreign metal ions can be reduced at the interfaces and incorporated into the liquid metal quickly. HEAs with various crystallinity (single crystal, mesocrystal, polycrystal and amorphous), morphology (zero, two and three dimensions) and compositions can be achieved through the isothermal solidification. Ga can be completely consumed, resulting in Ga-free HEAs. If desired, Ga can be one of the metal elements in the final products. In situ liquid phase transmission electron microscopy (TEM) studies and theoretical analysis show the isothermal solidification mechanisms. Our direct observations show the enhanced mixing of liquid metal elements and the solidification process with fluctuating nucleation dynamics. The isothermal solidification marks a powerful strategy for HEA synthesis through an unexplored pathway of kinetically trapping the high-entropy states.

Zhang, Qiubo [Lawrence Berkeley National Laborator↗

Low-temperature access to active iron and iron/nickel nitrides as potential electrocatalysts for the oxygen evolution reaction

Low-temperature, scalable routes to transition metal nitride (TMN) nanoparticles are desirable for a wide range of applications, yet their synthesis typically requires high temperatures (>350 °C) and reactive gas environments (e.g., NH 3 or H 2 /N 2 ). Here, we report a colloidal synthesis of mono- and bimetallic TMN nanoparticles using preformed metal carbonyl clusters as precursors and urea or diethylenetriamine (DETA) as nitrogen sources. This strategy enables access to size-controlled, phase-pure ε-Fe 3 N x and Fe y Ni 3−y N nanoparticles at temperatures below 300 °C, without the need for flowing reactive gas atmospheres. By systematically varying nitrogen precursor, reaction temperature, and cluster identity, we achieve tunable nitrogen stoichiometry (x) and phase selectivity between N-rich and N-poor TMNs. Structural and magnetic characterization confirms clean decomposition of the precursors and phase formation consistent with controlled nitridation at the nanoscale. Preliminary electrochemical measurements in alkaline media demonstrate that these materials exhibit oxygen evolution reaction (OER) overpotentials comparable to RuO 2 , highlighting their viability for future electrocatalytic applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

Socki, Richard A.↗

Synthesis and development of low cost, high temperature N-arylene polybenzimidazole foam material

Polymer (and foam) studies followed two basic routes: (1) formation of high molecular weight uncyclized polyamide followed by subsequent fusion and cyclodehydration to yield NABI (foam) and (2) polymer and foam formation by reaction of diphenyl esters (or anhydrides) with the tetramine. The latter route was found much more attractive since considerable versatility in both basic polymer structure and crosslinkability is achievable. Preliminary studies on BAB, phthalic anhydride (PA), and 3, 3 (prime), 4, 4(prime) benzo pheno netetracarboxylic acid dianhydride (BTDA) as crosslinked polymer precursors were conducted. Nonmelting rigid char forming foams with densities as low as 2.7 lb/cubic ft. were achieved. The program was successful in the preparation of a potentially low cost, low density, high char yield, high temperature foam material.

Harrison, E. S.↗

Glass precursor approach to high-temperature superconductors

The available studies on the synthesis of high T sub c superconductors (HTS) via the glass precursor approach were reviewed. Melts of the Bi-Sr-Ca-Cu-O system as well as those doped with oxides of some other elements (Pb, Al, V, Te, Nb, etc.) could be quenched into glasses which, on further heat treatments under appropriate conditions, crystallized into the superconducting phase(s). The nature of the HTS phase(s) formed depends on the annealing temperature, time, atmosphere, and the cooling rate and also on the glass composition. Long term annealing was needed to obtain a large fraction of the 110 K phase. The high T sub c phase did not crystallize out directly from the glass matrix, but was preceded by the precipitation of other phases. The 110 K HTS was produced at high temperatures by reaction between the phases formed at lower temperatures resulting in multiphase material. The presence of a glass former such as B2O3 was necessary for the Y-Ba-Cu-O melt to form a glass on fast cooling. A discontinuous YBa2Cu3O(7-delta) HTS phase crystallized out on heat treatment of this glass. Attempts to prepare Tl-Ba-Ca-Cu-O system in the glassy state were not successful.

Bansal, Narottam P.↗