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At least 415 records · Page 23

Mechanism of incipient oxidation of bulk chemical vapor deposited Si3N4

X-ray photoelectron spectroscopy was employed, in conjunction with ion bombardment, to analyze the chemical composition profile across thin (less than 50 nm) oxide films on chemically vapor deposited Si3N4. The thermal oxides were grown in dry oxygen at 1100 C on samples with or without native oxide film (formed in room air). The results show that the thermal oxidation product was silicon oxynitride of graded N:O ratio, and that the presence of a native oxide film promotes the formation of a SiO2 crust over the oxynitride. It is proposed that the fundamental mechanism of Si3N4 oxidation is progressive O-for-N substitution in the silicon oxynitride unit tetrahedron, which is best designated SiN(2-x)O(2+x), where x is also an index of depth. The corresponding equation for nonstoichiometric oxidation of Si3N4 describes a bulk (rather than an interface) reaction process, with significant implications for O2 and N2 fluxes and diffusivities.

Ogbuji, L. U. T.↗

Cationic vinyl pyridine copolymers and products thereof

Quaternized, cross-linked, insoluble copolymers of unsubstituted and substituted vinyl pyridines and a dihalo organic compound are spontaneously formed at ambient temperature on mixing the two monomers in bulk, in solution or in suspension. The amount of cross-linking may be varied according to the composition and reaction conditions. The polymer product exhibits ion exchange capacity and undergoes a reversible color change from black at a pH above 7 to yellow at a pH below 7. The polymer may be formed in the presence of preformed polymers, substrates such as porous or impervious particles or films to deposit an ion exchange film in situ or on the surface of the substrate. The coated or resin impregnated substrate may be utilized for separation of anionic species from aqueous solution.

Rembaum, Alan↗

Design Evolution and Verification of the A-3 Chemical Steam Generator

Following is an overview of the Chemical Steam Generator system selected to provide vacuum conditions for a new altitude test facility, the A-3 Test Stand at Stennis Space Center (SSC) in Bay St. Louis, MS. A-3 will serve as NASA s primary facility for altitude testing of the J-2X rocket engine, to be used as the primary propulsion device for the upper stages of the Ares launch vehicles. The Chemical Steam Generators (CSGs) will produce vacuum conditions in the test cell through the production and subsequent supersonic ejection of steam into a diffuser downstream of the J-2X engine nozzle exit. The Chemical Steam Generators chosen have a rich heritage of operation at rocket engine altitude test facilities since the days of the Apollo program and are still in use at NASA White Sands Test Facility (WSTF) in New Mexico. The generators at WSTF have been modified to a degree, but are still very close to the heritage design. The intent for the A-3 implementation is to maintain this heritage design as much as possible, making minimal updates only where necessary to substitute for obsolete parts and to increase reliability. Reliability improvements are especially desired because the proposed system will require 27 generators, which is nine times the largest system installed in the 1960s. Improvements were suggested by the original design firm, Reaction Motors, by NASA SSC and NASA WSTF engineers, and by the A-3 test stand design contractor, Jacobs Technology, Inc. (JTI). This paper describes the range of improvements made to the design to date, starting with the heritage generator and the minor modifications made over time at WSTF, to the modernized configuration which will be used at A-3. The paper will discuss NASA s investment in modifications to SSC s E-2 test facility fire a full-scale Chemical Steam Generator in advance of the larger steam system installation at A-3. Risk mitigation testing will be performed in early 2009 at this test facility to verify that the CSGs operate as expected. The generator which will undergo this testing is of the most recent A-3 configuration, and will be instrumented far in excess of what is normally required for operation. The extra data will allow for easier troubleshooting and more complete knowledge of expected generator performance. In addition, the early testing will give SSC personnel experience in operating the CSG systems, which will expedite the process of installation and activation at A-3. Each Chemical Steam Generator is supported by a complement of valves, instruments, and flow control devices, with the entire assembly called a "module." The generators will be installed in groups of three, historically called "units". A module is so called because of its modular ability to be replaced or serviced without disturbing the other two modules installed on the same unit. A module is pictured in Figure 1, shown with its generator secured by white bands in its shipping (vs. installed) configuration. The heritage system at WSTF is composed of a single unit (three generator modules), pictured in Figure 2 as it was installed in 1965. In contrast, A-3 will have nine units operating in parallel to achieve vacuum conditions appropriate for testing the J-2X engine. Each of the combustors operates in two modes and achieves the so-called "full-steam" mode after all three of its stages ignite. Ignition of the first stage is achieved by exciting a spark plug; the second stage and main stage are lit by the flame front of the previous stage. The main stage burns approximately 97% of the total propellant flow and uses the heat energy to vaporize water into superheated steam. While the main stage remains unlit, the combustor is in so-called "idle" mode. In the WSTF system, this idle mode is not optimized for water usage, and does not need to be, as the water is pumped from a large reservoir. The water supply at A-3 will be contained in tanks with finite volume, so water optimization is preferred for the modnized configuration. Multiple solutions for this issue have been proposed, with the leading concept being a change to the operational definition of "idle mode," with the generator running in a lower heat flux condition.

Kirchner, Casey K.↗

B‐MWW Zeolite: The Case Against Single‐Site Catalysis

Abstract Boron‐containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously been demonstrated by several spectroscopic characterization techniques that the surface of these boron‐containing ODH catalysts oxidize and hydrolyze under reaction conditions, forming an amorphous B 2 (OH) x O (3− x /2) ( x= 0–6) layer. Yet, the precise nature of the active site(s) remains elusive. In this Communication, we provide a detailed characterization of zeolite MCM‐22 isomorphously substituted with boron (B‐MWW). Using 11 B solid‐state NMR spectroscopy, we show that the majority of boron species in B‐MWW exist as isolated BO 3 units, fully incorporated into the zeolite framework. However, this material shows no catalytic activity for ODH of propane to propene. The catalytic inactivity of B‐MWW for ODH of propane falsifies the hypothesis that site‐isolated BO 3 units are the active site in boron‐based catalysts. This observation is at odds with other traditionally studied catalysts like vanadium‐based catalysts and provides an important piece of the mechanistic puzzle.

Altvater, Natalie R.↗

On the Effects of Aliovalent Substitutions in Thermoelectric Zintl Pnictides. Varied Polyanionic Dimensionality and Complex Structural Transformations–The Case of Sr 3 ZnP 3 vs Sr 3 Al x Zn 1– x P 3

The structures and the transport properties of a novel family of Zintl phosphides and arsenides with the formula AE 3 ZnPn 3 and the solid solutions AE 3 Al x Zn 1–x Pn 3 , AE 3 ZnAs y P 1–y (AE = Sr, Eu; Pn = P, As) are reported. Crystals of nine new phases have been obtained via Pb-flux reactions and used for structural work by means of single-crystal X-ray diffraction methods. The derived orthorhombic structure is without a direct analog, and features unusual structural units, where the Zn atoms are in both distorted tetrahedral and trigonal-planar coordination of pnictogens. Electronic structure calculations reveal moderately wide bandgaps for Sr 3 ZnP 3 and Sr 3 ZnAs 3 , on the order of 0.70 and 0.63 eV, respectively. Electrical transport measurements above room temperature indicate relatively high resistivity values above 500 K (ρ ≈ 4.8 Ω cm and above), but some of the samples exhibit very high Seebeck coefficients, as large as 300 μV/K at 560 K for Sr 3 ZnAs 3 . Aliovalent substitutions in AE 3 ZnPn 3 , achieved by the partial replacement of Zn 2+ with Al 3+ cations promote occupational and positional disorder, which causes structural transformation towards the disordered variant of the Sr 5 Al 2 Sb 6 structure type. Such substitutions also change the dimensionality of the polyanionic sub-lattice in the resulting quaternary AE 3 Al x Zn 1–x Pn 3 phases. Furthermore, preliminary transport property data on the latter reveal nine times lower electrical resistivity (ρ 500 ≈ 0.5 Ω cm) together with a significantly enhanced Seebeck coefficient, αmax ≈ 430 μV/K at 560 K.

36 MATERIALS SCIENCE↗

Integrating density functional theory into reductive dechlorination research

Abstract Chlorinated organics have been frequently detected in groundwaters, threatening the quality of drinking water supplies worldwide. A promising method for groundwater remediation involves reductive dechlorination (RD), in which chlorine atoms are sequentially removed and substituted by hydrogen, producing less harmful byproducts. In this paper, for the first time, RD research is reviewed in light of the growing incorporation of density functional theory (DFT) as a research tool. DFT has been used to uncover a variety of reaction properties for a range of relevant groundwater pollutants, including 1,2,3‐trichloropropane, hexachlorobenzene, and various dioxins. DFT models have revealed the role of surface interactions in driving the kinetics of catalytically driven RD. Mechanisms involved with biologically mediated RD have also been elucidated with insights gleaned from DFT. Issues and challenges for future research are also discussed.

Das Schober, Jaya↗

f-Element complexes with benzyl and cyclohexyl substituted trihydroborates

Actinide complexes containing the simplest borohydrides (BH 4 ) 1- and (MeBH 3 ) 1- can exhibit remarkably highly volatility, which creates unique hazards and handling challenges, especially when making measurements on solid samples under vacuum. Here we describe efforts to prepare new actinide borohydride complexes with attenuated volatility by adding bulkier benzyl (Bn) and cyclohexyl (Cy) substituents to boron. Reactions of ThCl 4 , UI 3 (thf) 4 , and NdI 3 with the mixed alkali metal salt Li/K(BnBH 3 )(thf) n yielded Th(BnBH 3 ) 4 (thf) 2 , U(BnBH 3 ) 4 (thf) 2 , and K[Nd(BnBH 3 ) 4 ], respectively. Notable amongst these, the reaction with UI 3 (thf) 4 proceeds via oxidation of U(III) to U(IV) despite the presence of reducing borohydride ligands. Similarly, reactions of the same metal halides with four equivalents of Li(CyBH 3 )(Et 2 O) n yielded Th(CyBH 3 ) 4 , U(CyBH 3 ) 4 (thf) 2 , and [Li(Et 2 O) 3 ][Nd(CyBH 3 ) 4 ]. Single crystal X-ray diffraction studies of the M(BnBH 3 ) 4 (thf) 2 complexes with M = Th and U confirmed their formulations. Furthermore, the complexes have approximate D 2d point group symmetry and adopt bicapped hexagonal antiprismatic coordination geometries with axial thf ligands and κ 3 -BnBH 3 ligands bound in the equatorial plane. K[Nd(BnBH 3 ) 4 ] and [Li(Et 2 O) 3 ][Nd(CyBH 3 ) 4 ], which were prepared for comparison to U(III) complexes that were unsuccessfully targeted, were also structurally characterized to reveal complex anions with tetrahedral arrangements of trihydroborate ligands bound to Nd(III). Crystals obtained for Th(CyBH 3 ) 4 and U(CyBH 3 ) 4 (thf) 2 were not suitable for XRD studies, but 1 H and 11 B NMR spectra were consistent with their formulations. Collectively, these complexes represent rare examples of structurally characterized f-element trihydroborate complexes with carbon substituents other than methyl.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating the hydrolysis of cryogenically layered molybdenum hexafluoride through a disordered hydrogen-bonded network

Molybdenum hexafluoride (MoF6) is used as a non-radioactive substitute for uranium to study the hydrolysis of metal hexafluorides. Molybdenum hexafluoride gas and water vapor, from the air, were sequentially layered onto a diamond substrate kept at liquid nitrogen temperature using a custom designed cryogenic cell with a copper cold finger. Reaction progress was monitored by transmission Fourier Transform Infrared Spectroscopy (FTIR) through the layers and diamond substrate over several hours while allowing the substrate to warm. Changes in the modes in the 500–1000 cm -1 region are tracked as the reaction progresses in order to identify intermediate species. Strong absorption features are also observed in the 1000–3000 cm -1 range, suggesting the presence of ionic dissociation intermediates trapped in a disordered H-bonded network of cryogenic hydrofluoric acid. Here, a possible reaction pathway is proposed and the final hydrolysis product is characterized by FTIR, UV-vis, and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Uptake and binding of La 3+ and Cr 3+ ions by alkali metal substituted alpha-zirconium phosphate

The conversion of alpha-zirconium phosphate, Zr(HPO 4 ) 2 ·H 2 O, to the K-, Rb-, and Cs-phases and the subsequent ion exchange behavior of these alkali metal phases, A-ZrP, with La 3+ and Cr 3+ have been investigated. The conversion to the A-ZrP phases was achieved by reaction with metal chloride, metal hydroxide solution, and confirmed through various techniques, including X-ray powder diffraction, thermogravimetry analysis, IR spectroscopy, scanning and transmission electron microscopy, and X-ray photoelectron spectroscopy. The effect of material hydration, which increased the interlayer distance, was also examined. The ion exchange behavior of the A-ZrP showed strong affinity for both La 3+ , a representative for trivalent lanthanide metals, and Cr 3+ , a representative for the trivalent transition metals, with a rapid, near quantitative removal of the M 3+ ions at a pH of 3 when the ion concentration was ≤25% of the ion exchange capacity of the materials. Additionally, the ion affinity was shown to be pH and concentration-dependent, decreasing with a decrease in pH or an increase in ion concentration. Lastly, the binding strength of La- and Cr-loaded ZrP materials was examined through a series of leaching experiments in a carbonate buffer, phosphate buffer, HEPES buffer, and a series of EDTA solutions at various concentrations. No observable leaching occurred in the carbonate buffer, phosphate buffer, HEPES buffer, or when the EDTA concentration was below 0.1 mM. These results highlight the potential for the A-ZrP materials to provide a platform for trivalent transition metal and trivalent lanthanide radionuclide capture for various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic reforming of methane with H 2 S via dynamically stabilized sulfur on transition metal oxides and sulfides

Reforming of methane with H 2 S is a promising path to directly utilize sour natural gas reserves, although some aspects of the mechanism and structure–function relations remain elusive. In this report we show that metal oxides of group 4–6 elements, which are inert for steam and dry methane reforming reactions, are active and stable (pre)catalysts for the H 2 S reforming of methane. The key active sites are sulfur species (S*) that are dynamically bound to metal cations during catalysis. Similar H/D isotope exchange patterns and universal rate inhibition by H 2 on representative catalysts indicate that H 2 S decomposition and recombination of surface hydrogen atoms are quasi-equilibrated, whereas CH 4 dissociation steps are reversible, yet not quasi-equilibrated. An in-depth analysis of the kinetic data and isotopic substitution effects identifies S*-mediated C–H bond cleavage as the most plausible rate-limiting step common for all catalysts, with subtle yet essential differences between 3d and 4d/5d catalysts in the thermodynamic stability of S*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sulfur Conversion to Donor‐Acceptor Ladder Polymer Networks through Mechanochemical Nucleophilic Aromatic Substitution for Efficient CO 2 Photoreduction

The development of synthetic methods capable of converting elemental sulfur into conjugated porous sulfur‐rich polymers remains a great challenge, although direct utilization of this readily available feedstock can significantly enrich its uses and circumvent environmental problems during sulfur storage. Here, we report herein mechanochemical (MC) nucleophilic aromatic substitution (S N Ar) that enables sulfur conversion into thianthrene‐bridged porous ladder polymer networks with dense donor‐acceptor (D−A) molecular junctions. We demonstrate that the key lies in the generation of bent thianthrene units through a solid‐state ball‐milling condensation reaction between 1,2‐dihaloarenes and elemental sulfur. We also show that the assembling of D−A structural motifs into porous networks affords efficient visible‐light‐driven photocatalytic reduction of carbon dioxide (CO 2 ) with water (H 2 O) vapor, in the absence of any additional photosensitizer, sacrificial agents or cocatalysts. Exceptional photoinduced charge separation along with boosted exciton dissociation results in a high‐performance of carbon monoxide (CO) production rate of 306.1 μmol g −1 h −1 with near 100 % CO selectivity, which is accompanied by H 2 O oxidation to O 2 , as confirmed by both experimental and theoretical results. We anticipate this novel MC S N Ar approach will advance processing techniques for direct sulfur utilization and facilitate new possibilities for the synthesis of D−A ladder polymer networks with promising potential in photocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Examining experimental nitrogen-based emissions trends from ammonia/diesel and ammonia/hydrogen/diesel combustion

Ammonia has garnered interest as an alternative fuel for power sectors with heavy payload and distance requirements, such as shipping. In this study, ammonia was used in a dual-fuel compression-ignition combustion strategy to overcome some of its technical barriers, using a diesel pilot to ignite a premixed mixture of ammonia and air. Mixtures of premixed ammonia and hydrogen were also explored to evaluate whether the inclusion of hydrogen improves nitrogen-based emissions from the combustion process. A single-cylinder version of a Cummins ISB 6.7 L engine platform was used to experimentally study these effects at various global air/fuel ratios and hydrogen energy fractions. Hydrogen inclusion produced pronounced NOx and N2O emissions, while inclusion of trapped residuals increased N2O but reduced NOx. The two most recent and relevant mechanisms available in the literature—those from Xu and Zhang-Ren-Kokjohn—were used in a chemical kinetics analysis to examine the observed differences in the NOx trends from two dual-fuel ammonia/diesel datasets: (1) in which a portion of the premixed ammonia was substituted with hydrogen and (2) in which the effect of hot trapped residuals was evaluated with only ammonia/air premixed mixtures. The analysis with both mechanisms showed agreement with experimental trends; however, contributions from thermal vs. fuel-borne NOx pathways showed disagreement. A reaction pathway analysis showed that the HNO to NO pathway was the key to NO formation in the mixture.

Tyrewala, Daanish [ORNL] (ORCID:0000000208599324)↗

Nucleophilic Displacement Reactions of Silver-Based Metal–Organic Chalcogenolates

Here, we report nucleophilic displacement reactions that can increase the dimensionality or coordination number of silver-based metal–organic chalcogenolates (MOChas). MOChas are crystalline ensembles containing one-dimensional (1D) or two-dimensional (2D) inorganic topologies with structures and properties defined by the choice of metal, chalcogen, and ligand. MOChas can be readily prepared from a variety of small-molecule ligands and metals or metal ions. Although MOChas offer ligand diversity, most reported examples use relatively small ligands, typically involving short alkyl chains, aryl rings, or molecular cages. This is because larger, more complex molecules often yield poor product morphologies with indeterminate structures. In this study, we overcame this limitation by employing a ligand exchange strategy whereby a 1D MOCha, silver(I) methyl 2-mercaptobenzoate (2MMB), is used as a silver source for preparing 2D examples. The reaction proceeds generally toward products composed of the stronger nucleophile. We show that the reaction prefers displacing 1D topologies to yield 2D ones and replacing thiolates with selenolates. We performed a study to characterize the mechanism by which organic chalcogenols and dichalcogenides exchange with MOChas. The collected data and product analysis support a proposed mechanism of nucleophilic substitution, explaining how both organic chalcogenols and dichalcogenides can displace ligands in MOChas. This work provides a new synthetic route that will enable the preparation of more elaborate MOChas and heterostructures thereof. This approach enabled the preparation of previously inaccessible oligophenyl MOChas, which were successfully solved via small-molecule serial femtosecond crystallography (smSFX) at the SPring-8 Ångström Compact Free Electron LAser (SACLA) facility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Centaur D-1T propulsion and propellant systems

A description is presented of the propulsion and propellant systems of the Centaur D-1T, an improved version of the Centaur high energy upper state. The primary change to the propulsion system to provide three-burn capability was the addition of radiation shielding to the propellant duct. The redundant valves and feed paths were added to the H202 supply and reaction control system to increase system tolerance to the most probable causes of failure. Other changes were made to enhance mission capability of the Centaur, and represent an increase in inherent reliability of the vehicle through reduction of single failure points and by substitution of more reliable components.

Goette, W. E.↗

Laboratory degradation of Kapton in a low energy oxygen ion beam

An atomic oxygen ion beam, accelerated from a tunable microwave resonant cavity, was used at Lewis Research Center to bombard samples of the widely used polyimide Kapton. The Kapton experienced degradation and mass loss at high rates, which may be comparable to those found in Space Shuttle operations if the activation energy supplied by the beam enabled surface reactions with the ambient oxygen. The simulation reproduced the directionality (ram-wake dependence) of the degradation, the change in optical properties of the degraded materials, and the structure seen in scanning electron micrographs of samples returned on the Shuttle Trails with a substituted argon ion beam produced no rapid degradation. Energy Dispersive X-ray Analysis (EDAX) showed significant surface composition changes in all bombarded samples. Mass loss rates and surface composition changes are discussed in terms of the possible oxidation chemistry of the interaction. Finally, the question of how the harmful degradation of materials in low Earth orbit can be minimized is addressed.

Ferguson, D. C.↗

Laboratory degradation of Kapton in a low energy oxygen ion beam

An atomic oxygen ion beam, accelerated from a tunable microwave resonant cavity, was used at Lewis Research Center to bombard samples of the widely used polyimide Kapton. The Kapton experienced degradation and mass loss at high rates, which may be comparable to those found in Space Shuttle operations if the activation energy supplied by the beam enabled surface reactions with the ambient oxygen. The simulation reproduced the directionality (ram-wake dependence) of the degradiation, the change in optical properties of the degraded materials, and the structure seen in scanning electron micrographs of samples returned on the Shuttle Trails with a substituted argon ion beam produced no rapid degradation. Energy Dispersive X-ray Analysis (EDAX) showed significant surface composition changes in all bombarded samples. Mass loss rates and surface composition changes are discussed in terms of the possible oxidation chemistry of the interaction. Finally, the question of how the harmful degradation of materials in low earth orbit can be minimized is addressed.

Ferguson, D. C.↗

On Soot Inception in Nonpremixed Flames and the Effects of Flame Structure

A simplified three-step model of soot inception has been employed with high activation energy asymptotics to study soot inception in nonpremixed counterflow systems with emphasis on understanding the effects of hydrodynamics and transport. The resulting scheme yields three zones: (1) a fuel oxidation zone wherein the fuel and oxidizer react to form product as well as a radical R, (e.g., H), (2) a soot/precursor formation zone where the radical R reacts with fuel to form "soot/precursor" S, and (3) a soot/precursor consumption zone where S reacts with the oxidizer to form product. The kinetic scheme, although greatly simplified, allows the coupling between soot inception and flame structure to be assessed. The results yield flame temperature, flame location, and a soot/precursor index S(sub I) as functions of Damkohler number for S formation. The soot/precursor index indicates the amount of S at the boundary of the formation region. The flame temperature indirectly indicates the total amount of S integrated over the formation region because as S is formed less heat release is available. The results show that unlike oxidation reactions, an extinction turning-point behavior does not exist for soot. Instead, the total amount of S slowly decreases with decreasing Damkohler number (increasing strain rate), which is consistent with counterflow flame experiments. When the Lewis number of the radical is decreased from unity, the total S reduces due to reduced residence time for the radical in the soot formation region. Similarly, when the Lewis number of the soot/precursor is increased from unity the amount of S increases for all Damkohler numbers. In addition to studying fuel-air (low stoichiometric mixture fraction) flames, the air-side nitrogen was substituted into the fuel, yielding diluted fuel-oxygen (high stoichiometric mixture fraction) flames with the same flame temperature as the fuel - air flames. The relative flame locations were different however, and, consistent with counterflow flame experiments, this difference was found to dramatically reduce the total amount of S generated because the change in stoichiometric mixture fraction affects residence times, temperatures and concentrations in the soot/precursor formation and consumption zones. Furthermore, while the soot/precursor consumption reaction had a negligible effect on the soot process for fuel-air flames it was very important to diluted fuel - oxygen flames.

Chao, B. H.↗