Structure and kinetic studies of U(VI)-benzamidoxime complex in non-aqueous solutions by H- and C-NMR

The structural and kinetic studies of U(VI) complex with benzamidoxime(Hba) as ligand in CD₃COCD₃ have been studied by means of ¹H and ¹³C NMR. The Hba molecule was found to coordinate to UO₂²⁺ in the form of anionic benzamidoximate (ba), and the number of ba coordinated to UO₂²⁺ was determined to be 3 by analyzing the chemical shift of ¹³C NMR signal for Hba in the presence of UO₂²⁺. The exchange rate constants(k_ex) of ba in [UO₂(ba)₃] were determined by the NMR line-broadening method. The kinetic parameters were obtained as follows: k_ex(25°C) = 3.1 × 10³s⁻¹, ΔH^≠ = 35.8 ± 3.5 KJ mol⁻¹, and ΔS^≠ = −65 ± 13.7 J K⁻¹ mol⁻¹. The UV-visible absorption spectra of solutions containing UO₂²⁺ and Hba were also measured. The molar extinction coefficient of the complex was found to be extremely large compared with those of UO₂(L)₅²⁺ (L = unidentate oxygen donor ligands) complexes. This is due to the strong electron withdrawing of UO₂²⁺ from Hba and suggests that an interaction between UO₂²⁺ and Hba is very strong. Such a high affinity of monomeric amidoxime to UO₂²⁺ reasonably explains the high adsorptibility of amidoxime resin to U(VI) species, and is considered to result in the high recovery of U(VI) species from sea water using amidoxime resin.     

Performance of FCCI barrier foils for U-Zr-X metallic fuel

Diffusion couple tests of U-Zr or U-Zr-Ce alloys vs. ferritic martensitic steels such as HT9 or T91 were carried out in order to evaluate the performance of the diffusion barrier candidates. Elemental metal foils of Zr, Nb, Ti, Mo, Ta, V and Cr were very effective in inhibiting interdiffusion between these fuels and steels. Eutectic melting between the fuels and steels was not observed in any of the diffusion couples using these diffusion barrier foils at annealing temperatures up to 800 °C. Among the metallic foils evaluated in this study, V and Cr exhibited the most promising performances as a diffusion barrier material for eliminating the fuel cladding chemical interaction problem. However, Zr, Nb and Ti showed an active interaction with the fuel mainly due to the large U solubility.     

Model evaluation of two-group interfacial area transport equation for confined upward flow

The bubble interaction mechanisms have been analytically modeled in the first paper of this series to provide mechanistic constitutive relations for the two-group interfacial area transport equation (IATE), which was proposed to dynamically solve the interfacial area concentration in the two-fluid model. This paper presents the evaluation approach and results of the two-group IATE based on available experimental data obtained in confined upward flow, namely, 11 data sets in or near bubbly flow and 13 sets in cap-turbulent and churn-turbulent flows. The two-group IATE is evaluated in steady-state, one-dimensional (1D) form. To account for the inter-group bubble transport, the void fraction transport equation for Group-2 bubbles is also used to predict the void fraction for Group-2 bubbles. Agreement between the data and the model predictions is reasonably good and the average relative difference for the total interfacial area concentration between the 24 data sets and predictions is within 7%. The model evaluation demonstrates the capability of the two-group IATE focused on the current confined flow to predict the interfacial area concentration over a wide range of flow regimes.     

Numerical and experimental study on silica generating counterflow diffusion flames

Temperatures and concentrations of OH radicals in silica generating counterflow oxy-hydrogen diffusion flames are measured using a broadband coherent anti-Stokes Raman spectroscopy (CARS) and a planar laser induced fluorescence (PLIF) techniques to study thermo-chemical effects of SiCl₄ addition to flames. Numerical analysis considering detailed chemical reactions including silica generating reactions is also conducted. The experimental results demonstrate that temperatures decrease in preheated zone due to the increase in specific heat of the gas mixture while the decrease is mitigated in particle formation zone due to the heat release through hydrolysis and oxidation reactions of SiCl₄. Also, OH concentrations significantly decrease in silica formation flame, which can be attributed to the consumption of oxidative radicals during the silica generating reactions of SiCl₄ and depletion of OH by HCl. The numerical simulation agrees well for flames having relatively low flame temperatures of 1750 K but underestimates the decrease in OH concentration for high temperature flame over 2700 K. The disagreement for the high temperature flames would imply possible OH consumption via direct reactions between OH radicals and silicon chlorides, which is expected to be highly sensitive to temperature.     

Integrated carbon composite bipolar plate for polymer–electrolyte membrane fuel cells

The electrical resistance of bipolar plates for polymer–electrolyte membrane fuel cells (PEMFCs) should be very low to conduct the electricity generated with minimum electrical loss. The resistance of a bipolar plate consists of the bulk material resistance and the interfacial contact resistance when two such plates are contacted to provide channels for fuel and air (oxygen) supplies.     

Enhanced heat transfer performance of alumina sponge-like nano-porous structures through surface wettability control in nucleate pool boiling

For several decades, a porous surface has been recognized as an efficient medium to increase boiling performance in a nucleate boiling regime. Most feasible porous surfaces have been studied in millimeter and micron-sized domains. It has been believed that a higher wall superheat is required to commence incipient nucleate boiling under a submicron regime. In this study, we demonstrate that a significantly enhanced pool boiling heat transfer is observed in a submicron regime through three dimensionally interconnected hybrid pores: the Alumina sponge-like nano-porous structure (ASNPS). The structural uniqueness of the ASNPS leads to an enlarged surface area, increases the potential number of the active nucleation site density, and improves the vapor–liquid menisci through the reentrant pore. Simultaneously, by changing the surface wettability with a hydrophobic self-assembled monolayer (SAM) coating, the number of active nucleation site density is improved. Eventually, the combination of the ASNPS and hydrophobic SAM coating can achieve substantial heat transfer coefficient (HTC) enhancement in the nucleate boiling. Also, the thickness of the ASNPS is a critical issue to adequately augment the HTC in pool boiling. The thickness of the ASNPS is optimized by examining the boiling performance of the ASNPS fabricated in different amounts of anodizing times. A classical mechanistic model from literature was modified and compared with the experimentally obtained data. The modified mechanistic model – with the combination of forced-convection and thin liquid film evaporation – showed reasonable predictions.     

Sn self-doped α-Fe2O3 nanobranch arrays supported on a transparent,conductive SnO2 trunk to improve photoelectrochemical water oxidation

We produced hierarchically branched Fe₂O₃ nanorods on a Sb:SnO₂ transparent conducting oxide (TCO) nanobelt structure as photoanodes for photoelectrochemical water splitting. Single-crystalline SnO₂ nanobelts (NBs) surrounded by Fe₂O₃ nanorods (NRs) were synthesized by thermal evaporation, then underwent chemical bath deposition and annealing. When Fe₂O₃ was crystallized by annealing, Sn was diffused from SnO₂ NBs and incorporated to Fe₂O₃ NRs, which was confirmed through Energy dispersive spectroscopy. Unlike previous high temperature sintering (∼800 °C), Sn doped hematite NRs were obtained at a low temperature (∼650 °C). This occurred since SnO₂ NBs directly connected to Fe₂O₃ NRs are an abundant source of Sn dopant. The 3D hematite NRs on SnO₂ NBs annealed at 650 °C produce a photocurrent density of 0.88 mA/cm² at 1.23 V vs. RHE, which is 3 times higher than that of hematite NRs on a fluorine doped tin oxide (FTO) glass substrate annealed at the same temperature. The enhanced photocurrent is attributed to the improved electrical conductivity of Fe₂O₃ NRs by Sn doping, the efficient electron transport pathway by TCO nanowire and the increased surface area by hierarchically branched structure.     

Convective instabilities and transport properties in horizontal fluid layers

This paper concerns the analysis of convective instabilities and fully developed transport properties in Bénard convection. The onset of convective instabilities driven by surface-tension variations and buoyancy forces is analyzed theoretically by using the propagation theory we have developed. Based on these stability criteria, the subsequent transport correlations of fully developed buoyancy-driven convection in horizontal fluid layers are suggested. It is found that the present predictions are compared favorably with existing experimental results.