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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]{sup +}[F(HF){sub 2.3}]{sup −} Ionic Liquid

A new methodology for gas-phase uranium ion formation is described in which UO{sub 2} is dissolved in neat N-ethyl,N′-methylimidazolium fluorohydrogenate ionic liquid [EMIm{sup +}][F(HF){sub 2.3}{sup −}], yielding a blue-green solution. The solution was diluted with acetonitrile and then analyzed by electrospray ionization mass spectrometry. UF{sub 6}{sup −} (a U(V) species) was observed at m/z = 352, and other than cluster ions derived from the ionic liquid, nothing else was observed. When the sample was analyzed using infusion desorption chemical ionization, UF{sub 6}{sup −} was the base peak, and it was accompanied by a less intense UF{sub 5}{sup −} that most likely was formed by elimination of a fluorine radical from UF{sub 6}{sup −}. Formation of UF{sub 6}{sup −} required dissolution of UO{sub 2} followed by or concurrent with oxidation of uranium from the + 4 to the + 5 state and finally formation of the fluorouranate. Dissolution of UO{sub 3} produced a bright yellow solution indicative of a U(VI) species; however, electrospray ionization did not produce abundant U-containing ions. The abundant UF{sub 6}{sup −} provides a vehicle for accurate measurement of uranium isotopic abundances free from interference from minor isotopes of other elements and a convenient ion synthesis route that is needed gas-phase structure and reactivity studies like infrared multiphoton dissociation and ion-molecule dissociation and condensation reactions. The reactive fluorohydrogenate ionic liquid may also enable conversion of uranium in oxidic matrices into uranium fluorides that slowly oxidize to uranyl fluoride under ambient conditions, liberating the metal for facile measurement of isotope ratios without extensive chemical separations. .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Smoothed particle hydrodynamics modeling and analysis of oxide reduction process for uranium oxides

A common kinetic feature for oxide reduction chemical/electrochemical processes is oxygen transport via a porous metallic layer, which has been considered as a rate-determining step for reducing uranium oxides to metallic uranium. Accounting this kinetic behavior must involve the resolution of the moving reactive interface between shrinking oxide and expanding metal phases. This study presents a numerical model using smoothed particles hydrodynamics (SPH) to effectively deal with the evolution of the shrinking core reaction interface and oxygen transport via mass transfer of lithium oxide (Li 2 O) species in multiple mass transfer domains. We successfully validated the proposed model against a theoretical derivation for the oxide reduction process handling a shrinking oxide core with molten salt and metal ash medium on a simple planar geometry. Armed with successful validation results, the model examined a realistic reactant geometry to extend the arguments beyond the one-dimensional analyses, allowing the proposed model to apply to general application scenarios with multi-dimensional geometry. Here, this study demonstrated that the proposed model could simulate and evaluate an arbitrary reaction basket design without iterative experimental trials, which is prohibitive for a scaled high-temperature molten salt study in an inert environment. The construct potentially provides not only deep insights on multiphysics behaviors governing the process dynamics but also a robust framework for evaluating and screening candidate basket designs in the most cost-effective manner.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2018

Interfacial design and strengthening mechanisms of AZ91 alloy reinforced with in-situ reduced graphene oxide

Highlights: • An in-situ process was developed to synthesize magnesium alloy composite reinforced by graphene. • Microstructure and phase composition of oxide films were investigated by OM, SEM, EDS and XRD analysis. • The interfacial structure of Mg composites reinforced with reduced graphene oxide was characterized. • The interfacial reaction mechanisms between GO (graphene oxide) and the Mg metal was studied. - Abstract: This work highlights to develop an in-situ process to disperse uniformly graphene possessing good interfacial bonds with the matrix of Mg alloy. A homogeneous distribution of graphene in the matrix has been successfully obtained through in-situ reduction of graphene oxide (RGO) by sintering process after the graphene oxide (GO) was uniformly dispersed in AZ91 powders. The interface product nano-sized MgO can significantly improve the interfacial bonding strength between RGO and α-Mg with analysis by transmission electron microscopy. The orientation relationships of ( 2-bar 00){sub MgO}//( 1-bar 10 2-bar ){sub α‐Mg} and [011]{sub MgO}//[2 4-bar 2 3-bar ]{sub α‐Mg} with the semi-coherent interface characteristics were clarified for the first time at the interface of MgO/α-Mg, suggesting a good lattice space matching. By employing such process, a composite containing 0.5 wt% of GO shows an 85.7% and 61.4% increase in yield strength and elongation, respectively, over unreinforced AZ91 alloy. The underlying strengthening mechanisms of in-situ reduced graphene oxide are discussed in detail.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Role of Manganese in Accelerating the Oxidation of Pb(II) Carbonate Solids to Pb(IV) Oxide at Drinking Water Conditions

Pb(II) carbonate solids are corrosion products that form on the inner surfaces of lead service lines (LSLs) and can be oxidized by free chlorine to form Pb(IV) oxide (PbO 2 ). The formation of PbO 2 can maintain low dissolved lead concentrations in drinking water, but PbO 2 can dissolve if a free chlorine residual is not maintained. Experiments demonstrated that the oxidation of Pb(II) carbonate by free chlorine was faster with manganese (Mn). Without Mn(II), the oxidation of Pb(II) carbonate was an autocatalytic process. With Mn(II), the overall oxidation rate was 2 orders of magnitude faster than without Mn(II). X-ray diffraction and free chlorine consumption profiles indicated that δ-MnO 2 was formed within several minutes of the reaction of Mn(II) with free chlorine, and δ-MnO 2 catalyzed the oxidation of Pb(II) carbonate by free chlorine. Free chlorine consumption profiles for Pb(II) carbonate with and without Mn(II) were interpreted based on the kinetics and stoichiometry of the underlying chemical reactions. These findings highlight the importance of Mn in accelerating the formation of PbO 2 in water with Pb(II) carbonate solids and free chlorine, and it may help explain why PbO 2 is observed on LSLs of some but not all water systems that use free chlorine.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Chasing the Achilles’ Heel in Hybrid Systems of Diruthenium Water Oxidation Catalysts Anchored on Indium Tin Oxide: The Stability of the Anchor

The development of hybrid devices for photo-driven water oxidation with dinuclear molecular ruthenium catalysts on solid supports aims both at high efficiencies of the catalyst and at high stability of the linking to the surface. We herein report a systematic study regarding the stability of catalysts anchored on an indium tin oxide (ITO) support via different acid functional groups at the ligand backbone: viz., a single carboxylate anchor, two carboxylate anchors, and a phosphonate anchor. The integrity of the hybrid electrodes ITO|mesoITO|catalyst was evaluated under acidic aqueous conditions as a function of the applied electric potential below and above the onset of the oxygen evolution reaction (OER). Rotating ring disk electrode (RRDE) experiments allowed us to distinguish between the water oxidation and the desorption processes. X-ray photoemission (XPS) and X-ray absorption spectroscopy (XAS) after electrochemical treatment showed high chemical stability of the catalyst core structure but pronounced dependence of the hybrid stability on the oxidation state of the ruthenium center. A combination of these different spectroscopic techniques shed light on the mechanisms underlying catalyst desorption. Specifically, catalysts equipped with carboxylate anchors are found to continuously desorb already at low applied potentials below the OER onset, while for the more rugged phosphonate-based hybrid oxidative P–C(aryl) bond cleavage is proposed to occur, but only after reaching the high-valent Ru V Ru IV state. These findings reveal specific challenges for anchoring strategies in molecular water oxidation catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Selective Oxidation of Acetaldehyde to Acetic Acid on Pd–Au Bimetallic Model Catalysts

Acetic acid is a widely employed reactant in the chemical industry, and it is also used as a food ingredient. Here, we report a catalytic reaction pathway for the gas-phase selective oxidation of acetaldehyde to acetic acid on a Pd–Au(111) heterogeneous model catalyst. On an oxygen precovered Pd–Au surface, acetaldehyde is selectively oxidized to acetic acid from 250 to 340 K. Using FT-IR, the formation of acetate species is detected from 160 to 260 K on this surface, which is a widely known adsorbate derived from acetic acid on metal surfaces. With higher Pd coverages, the acetaldehyde is less selectively oxidized to acetic acid, and near 375 K, CO 2 , H 2 O, CH 4 , and H 2 are evolved, evidence for the decarboxylation of acetate. Finally, in our density functional theory calculations, we confirm that the relative energy difference between the acetate state and the decarboxylated state decreases as Pd ensemble size increases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Simultaneous Activation of CH4 and CO2 for Concerted C-C Coupling at the Oxide-Oxide Interfaces

Catalytic conversion of CO2 and CH4 to value-added platform chemicals via the direct C-C coupling provides one of the most effective routes that not only address global climate change but also alleviate the dependency on traditional fossil fuels. Herein, three oxide-on-oxide catalysts that can realize direct C-C coupling on the basis of simultaneous activation of CH4 and CO2 were investigated using density functional theory (DFT) calculations. With the formation of oxide-on-oxide interfacial sites between the substrate (In2O3) and dispersed oxides ((ZnO)3, (ZrO2)3, or Ga2O3), it is found that CO2 can be activated at the defective site of In2O3 while the C-H bond of CH4 can be simultaneously activated at the M-O pair of the supported metal oxide. In contrast to the Eley-Rideal mechanism that C-C coupling of CO2 and CH3 stabilized on Zn-doped ceria follows, the formation of a Zn-C-C-O transition state at the active centers originates from a Langmuir-Hinshelwood mechanism where the activated CO2 also enhances the dissociative adsorption of CH4. There is a linear relationship between the C-C coupling reaction energy/activation barrier and CH4 dissociation energy. The results indicate that dissociative adsorption of CH4 plays a dominant role in the direct C-C coupling, whereas the adsorption/activation of CO2 is less significant. DFT calculation results of CH4 and CO2 to acetic acid on the (ZnO)3/In2O3 catalyst surface indicates that the C-C coupling step is the kinetically most relevant step. Compared with Ga2O3/In2O3 and (ZrO2)3/In2O3 catalyst surfaces, (ZnO)3/In2O3(110) is more active for the acetic acid formation. The present work provides new mechanistic insights into the direct C-C coupling of CH4 and CO2, which would be useful to design more efficient catalyst.

CH4 activation, C-C coupling, supported oxides, In↗
DOE OSTI2020

Void formation during cyclic oxidation of oxide dispersion strengthened FeCrAl alloys

Here, oxide dispersion strengthened FeCrAl alloys are considered for various high-temperature applications due to their excellent mechanical properties and oxidation resistance, but void formation is a concern for component durability. Cyclic oxidation testing was conducted on alloy MA956 and PM2000 at 1100–1200ºC for durations of up to 10,000 h and the void content was determined from optical cross-sections by image analysis. At 1100ºC, 100 h cycle, the low void concentrations measured were consistent with two competing mechanisms proposed in the literature: coalescence of process-induced nano-voids and alloy sintering. At 1200ºC using 1 h cycles, the void concentration was much higher, reaching ~3% to 6% for specimens tested to breakaway oxidation. The void growth was attributed to the high oxidation rates and the annihilation of oxidation-induced vacancies at the surface of the process-induced voids.

36 MATERIALS SCIENCE↗
NASA NTRS1987

Phase equilibria in the iron oxide-cobalt oxide-phosphorus oxide system

Two novel ternary compounds are noted in the present study of 1000 C solid-state equilibria in the Fe-Co-P-O system's Fe2O3-FePO4-Co3(Po4)2-CoO region: CoFe(PO4)O, which undergoes incongruent melting at 1130 C, and Co3Fe4(PO4)6, whose incongruent melting occurs at 1080 C. The liquidus behavior-related consequences of rapidly solidified cobalt ferrite formation from cobalt ferrite-phosphate melts are discussed with a view to spinel formation. It is suggested that quenching from within the spinel-plus-liquid region may furnish an alternative to quenching a homogeneous melt.

De Guire, Mark R.↗