55 Search Results

The electrolytic reduction of TiO2 in LiCl–Li2O (1 wt.%) at 650 °C was investigated under a series of cathodic reduction potentials and applied charges to provide a mechanistic understanding of the electrochemical characteristics of the system. The optimal cathodic reduction potential was determined as being −0.3 V vs. Li/Li+. Li2TiO3 and LiTiO2 were structurally identified as intermediate and partial reduction products of the TiO2 electrolytic reduction. The reduction of LiTiO2 was extremely slow and reversible due to its high stability and the detrimental effect of Li2O accumulation within the solid particles. The most reduced product obtained in this study was LiTiO2, which was achieved when using 150% of the theoretical charge under the optimal reduction potential. The highest reduction extent obtained in this study was 25%. Based on theoretical DFT modeling, a detailed multistep reduction mechanism and scheme were proposed for TiO2 electrolytic reduction in LiCl–Li2O (1 wt.%) at 650 °C.

Prior work identified dissolution of used nuclear oxide fuel constituents from a uranium oxide matrix into molten LiCl-KCl-UCl₃ at 500°C, prompting a subsequent series of three progressive studies (including an initial scoping study, an electrolytic dissolution study, and a chemical-seeded dissolution study) to further investigate associated parameters and mechanisms. Thermodynamic calculations were performed to identify possible reaction mechanisms and their propensities in used oxide fuel constituent dissolution. Used nuclear oxide fuels with varying preconditions from fast and thermal test reactors were separately immersed in the subject salt system to assess fuel constituent migration from the bulk fuel matrix to the salt phase in an initial scoping study. Dissolution of expected fuel constituents, including alkali, alkaline earth, lanthanide, and transuranium oxides, into the chloride salt phase varied widely, ranging from 12% to 99% in the initial study. Uranium isotope blending between the salt phase and bulk fuel matrix was also observed, which was attributed to reducing conditions in the fuel matrix. Electrolytic and chemical-seeded dissolution studies were subsequently performed to effect reducing conditions in the fuel. Other parameters, including temperature (at 500°C, 650°C, 725°C, and 800°C) and uranium trichloride concentrations (at 6, 9, and 19 wt% uranium), were investigated in the latter two studies, resulting in fuel constituent dissolution above 90%. Extents of dissolution were based on initial and final fuel constituent concentrations in the oxide fuels following operations in the salt and subsequent removal of the salt via distillation. Finally, in this series of progressive studies, oxide fuel preconditioning and in situ reducing conditions, along with elevated temperature and uranium trichloride concentrations, were the primary parameters promoting used nuclear oxide fuel constituent dissolution in accordance with identified reaction mechanisms.

In this work, experiments with surrogate materials were performed at bench scale to demonstrate a halogenation technique applicable to treatment of used aluminum matrix test reactor fuel. The technique involves dissolution and separation of aluminum from used aluminum matrix test reactor fuel in molten-halide salt systems prior to treatment and disposition of the fuel’s uranium and fission products. Demonstration of the halogenation technique was performed with neodymium metal as a non-radiological surrogate for uranium metal. Experiments involved blending forms of aluminum and neodymium metal with ammonium and lithium chloride or ammonium and lithium bromide, which upon heating decomposed into ammonia gas and the respective hydrogen chloride or bromide gas. The latter reacted with the metals to form the respective aluminum and neodymium halides. At elevated temperatures, aluminum halides gasified away from the respective neodymium halides, which fused with their respective lithium halides. Samples of fused and distillate salts were collected and analyzed, yielding extents of aluminum removal that ranged from 94.5–98.2% for chlorination runs and 91.4–97.8% for bromination runs. No neodymium was detected in the distillate fractions. Some experiments were repeated with excess reactants, and a portion of aluminum chloride distillate was processed into a consolidated waste form.

Recalcitrance of lignocellulosic feedstocks to depolymerization is a significant barrier for bioenergy production approaches that require conversion of monomeric carbohydrates to renewable energy sources. This study assesses how low-cost modifications in the feedstock supply chain can be transformed into targeted pretreatments in the context of the entire bioenergy supply chain. The aim of this research is to overcome the physiochemical barriers in corn stover that necessitate increased severity in conversion in terms of chemical loading, temperature, and residence time. Corn stover samples were inoculated with a selective (Ceriporiopsis subvermispora) and non-selective (Phaenarochaete chrysosporium) lignin degrading filamentous fungal strains, then stored aerobically to determine the working envelope for fungal pretreatment to achieve lignin degradation. Dry matter loss and gross chemical makeup of corn stover varied by the length of treatment (2 and 4 weeks) and by the moisture content of the treated corn stover samples (40 and 60%, wet basis). Dry matter loss in P. chrysosporium inoculated biomass was elevated compared to the C. subvermispora inoculated biomass; however, treatment also induced additional chemical composition changes suggestive of depolymerization. Scanning electron microscope images reveal hyphae attached within cell lumen and suggest structural changes within P. chrysosporium treated corn stover after 60% moisture storage. These results highlight that fungal treatment approaches must balance loss of convertible material with the potential for reduction in recalcitrance. Techno-economic assessment (TEA) of fungal pretreatment in a short-term queuing system indicated the viability of this approach compared to conventional queuing operations. The total queuing system cost was estimated at $$\$$$$1.65/tonne of biomass stored. After applying the credit of $$\$$$$1.48/tonne from energy savings in the conversion phase using fungal pretreated biomass, the total system cost was $0.80 lower than traditional biomass queueing approach. While the TEA results suggested that treating biomass with C. subvermispora is the most economically viable storage method in the designed fungal-assisted queuing system, future research should focus on additional fungal depolymerization such as those observed in the P. chrysosporium inoculated biomass.

A series of three bench-scale experiments was performed to investigate the conversion of sodium metal to sodium chloride via reactions with non-metal and metal chlorides. Specifically, batches of molten sodium metal were separately contacted with ammonium chloride and ferrous chloride to form sodium chloride in both cases along with iron in the latter case. Additional ferrous chloride was added to two of the three batches to form low melting point consolidated mixtures of sodium chloride and ferrous chloride, whereas consolidation of a sodium-chloride product was performed in a separate batch. Samples of the products were characterized via X-ray diffraction to identify attendant compounds. The reaction of sodium metal with metered ammonium chloride particulate feeds proceeded without reaction excursions and produced pure colorless sodium chloride. The reaction of sodium metal with ferrous chloride yielded occasional reaction excursions as evidenced by temperature spikes and fuming ferrous chloride, producing a dark salt-metal mixture. This investigation into a method for controlled conversion of sodium metal to sodium chloride is particularly applicable to sodium containing elevated levels of radioactivity—including bond sodium from nuclear fuels—in remote-handled inert-atmosphere environments.

Unravelling the complex, competing pathways that can govern reactions in multicomponent systems is an experimental and technical challenge. We outline and apply a novel analytical toolkit that fully leverages the synchronicity of multimodal experiments to deconvolute causal from correlative relationships and resolve structural and chemical changes in complex materials. Here, simultaneous multimodal measurements combined diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and angular dispersive X-ray scattering suitable for pair distribution function (PDF), X-ray diffraction (XRD) and small angle X-ray scattering (SAXS) analyses. The multimodal experimental data was interpreted via multi-level analysis; conventional analyses of each data series were integrated through meta-analysis involving non-negative matrix factorization (NMF) as a dimensional reduction algorithm and correlation analysis. We apply this toolkit to build a cohesive mechanistic picture of the pathways governing silver nanoparticle formation in zeolite A (LTA), which is key to designing catalytic and separations-based applications. For this Ag-LTA system, the mechanisms of zeolite dehydration, framework flexing, ion reduction, and cluster and nanoparticle formation and transport through the zeolite are elucidated. We note that the advanced analytical approach outline here can be applied generally to multimodal experiments, to take full advantage of the efficiencies and self-consistencies in understanding complex materials and go beyond what can be achieved by conventional approaches to data analysis.

Long-term storage is a necessary unit operation in the biomass feedstock logistics supply chain, enabling biorefineries to run year-round despite daily, monthly, and seasonal variations in feedstock availability. At a minimum, effective storage approaches must preserve biomass. Uncontrolled loss of biomass due to microbial degradation is common when storage conditions are not optimized. This can lead to physical and mechanical challenges with biomass handling, size reduction, preprocessing, and ultimately conversion. This review summarizes the unit operations of dry and wet storage and how they may contribute to preserving or even improving feedstock value for biorefineries.

Corrosion tests were conducted in a high-temperature high-pressure (HTHP) autoclave to simulate the conditions of CO{sub 2} auxiliary steam drive in gas injection wells. Weight loss tests were performed with the sheets of N80 and 9Cr steels under the testing conditions. The morphology and composition of corrosion products were explored by SEM, EDS, XRD and XPS. The corrosion resistance of 9Cr steel was better than that of N80 steel under the testing conditions. The corrosion rates of N80 and 9Cr met the application requirements in CO{sub 2} auxiliary steam drive. The results broke the constraint in ISO-15156 standards. The corrosion process of N80 steel was mainly affected by the flow velocity. However, the corrosion process of 9Cr steel was mainly affected by temperature. The corrosion resistance of 9Cr steel depended on the FeCO{sub 3} content of Cr-rich layer, which was closely related to temperature. The low flow velocity influenced the diffusion process of N80 steel corrosive ions, whereas the high flow velocity influenced the integrity of corrosion scales. Considering the influence of flow velocity on the corrosion of tubing and casing, in the gas injection well, 9Cr steel and N80 steel were, respectively, selected as the materials of tubing and casing.

Highlights: • Cu- and Zn-doped Fe{sub 2}O{sub 3} nanoparticles were successfully obtained by a simple solvothermal method. • The sizes and morphologies of the doped Fe{sub 2}O{sub 3} nanoparticles could be regulated by doping with divalent cations. • The doped Fe{sub 2}O{sub 3} nanoparticles showed enhanced remanent magnetization and coercivity. • The doped Fe{sub 2}O{sub 3} nanoparticles showed excellent catalytic activity toward thermal decomposition of ammonium perchlorate. • The enhanced catalytic activity could be attributed to the defect structure induced by doping with divalent cations. - Abstract: To assess the relationship between metal ion-mediated microstructures and the macro-performance, Cu- and Zn-doped α-Fe{sub 2}O{sub 3} nanoparticles were prepared via a solvothermal method. The morphologies of the as-synthesized nanoparticles were investigated by scanning electron microscopy and transmission electron microscopy. The results revealed that the sizes and morphologies could be regulated by doping with divalent cations. The structures of the as-synthesized nanoparticles were characterized by X-ray diffraction and Raman spectroscopy, indicating that Cu{sup 2+} and Zn{sup 2+} ions had diffused into the lattice of α-Fe{sub 2}O{sub 3} matrix. The magnetization behaviors of these nanoparticles were measured to analyze the effect of doping on α-Fe{sub 2}O{sub 3}. Furthermore, the catalytic activities of Cu- and Zn-doped α-Fe{sub 2}O{sub 3} nanoparticles demonstrated that the high-temperature decomposition temperature of ammonium perchlorate could be lowered by 115 °C and 107 °C, respectively, compared to that of ammonium perchlorate without catalyst. The enhanced catalytic activity could be attributed to the defect structure induced by doping with divalent cations.

The sophisticated tail structures of DNA bacteriophages play essential roles in life cycles. Podoviruses P22 and Sf6 have short tails consisting of multiple proteins, among which is a tail adaptor protein that connects the portal protein to the other tail proteins. Assembly of the tail has been shown to occur in a sequential manner to ensure proper molecular interactions, but the underlying mechanism remains to be understood. Here, we report the high-resolution structure of the tail adaptor protein gp7 from phage Sf6. The structure exhibits distinct distribution of opposite charges on two sides of the molecule. A gp7 dodecameric ring model shows an entirely negatively charged surface, suggesting that the assembly of the dodecamer occurs through head-to-tail interactions of the bipolar monomers. The N-terminal helix-loop structure undergoes rearrangement compared with that of the P22 homolog complexed with the portal, which is achieved by repositioning of two consecutive repeats of a conserved octad sequence motif. We propose that the conformation of the N-terminal helix-loop observed in the Sf6-gp7 and P22 portal:gp4 complex represents the pre- and postassembly state, respectively. Such motif repositioning may serve as a conformational switch that creates the docking site for the tail nozzle only after the assembly of adaptor protein to the portal. In addition, the C-terminal portion of gp7 shows conformational flexibility, indicating an induced fit on binding to the portal. Furthermore, these results provide insight into the mechanistic role of the adaptor protein in mediating the sequential assembly of the phage tail.