Extensive research and process development has been conducted on the electrolytic reduction of actinide oxides in molten LiCl-Li 2 O. It is now accepted that the reduction of these metal oxides occurs via two separate reduction mechanisms: direct electro-chemical reduction and mediated chemical reduction by metallic lithium. The deposition of metallic lithium at the cathode (mediated chemical reduction mechanism) during the process is known to be essential in order to achieve high process throughputs and reduction yields, and yet a knowledge gap exists regarding the nature of metallic lithium in this system. This review summarizes the formation of lithium during the process and its dispersion into the molten salt electrolyte. Previously reported aspects of the physical chemistry of the LiCl-Li 2 O-Li system are presented with a specific focus on the dispersion of Li in the solution. Finally, issues regarding the effect of the presence of lithium on the electrolytic reduction process are discussed. Evidence shows that electrochemically generated metallic lithium is likely a significant source of experimental uncertainty, low current efficiency and Li 2 O consumption in the oxide reduction process. The reduction of uranium, plutonium and minor actinide oxides to a metallic form is an important nuclear fuel cycle process.2-9 The ability of metallic lithium to reduce various uranium oxides, importantly UO 2 and U 3 O 8 , has been known for many years.10 A molten salt metalothermic reduction process employing metallic lithium (Li) as a reductant dissolved in molten LiCl was first developed by Argonne National Laboratory (ANL) to consolidate a variety of forms of actinide oxides for integration into a single electrometallurgical reprocessing system. 11-13 An electrolytic process, often referred to as electro-deoxidation or simply oxide reduction, was subsequently developed as a more controllable method of reducing metal oxides. A feasibility study conducted by Poa et al. demonstrated that oxides of uranium and plutonium could be reduced electrochemically in molten salts as long as the reduction potential of the metal oxide in question was more noble than the cation of the electrolyte.14,15 This approach was further developed by Gourishankar et al. to better understand processes chemistry and develop the electrolytic cell technology. 13,[16][17][18][19][20] Independent research conducted by Fray, Farthing, and Chen (FFC) applied the principles of electrochemical reduction in molten salt electrolytes to a variety of metal oxide reduction processes. 21,22 The FFC process has been the subject of several literature reviews.23-25 While these review articles address the processes associated with the reduction of nuclear fuel in LiCl, they focus on the electro-deoxidation phenomena and the CaCl 2 -CaO system. Additionally, the process engineering of the electrolytic reduction of nuclear fuel, and experience in incorporating oxide fuel into pyroprocessing, has been the focus of a recent review article. 26 The current review wi...
This study reports the synthesis of Zn x Cd 1Àx Se quantum dot-sensitized titania nanotube array photoelectrodes using a successive ionic layer adsorption and reaction technique and evaluates the photoelectrochemical performance as anodes. The effect of altering the number of sensitization cycles and annealing temperature on optical and photoelectrochemical properties of prepared photoanodes was studied. Surface morphology of the sensitized tubes was analyzed by scanning electron microscopy, while the phase composition was determined using X-ray diffraction and X-ray photoelectron spectroscopy techniques. Spectral response measurements indicated that TiO 2 nanotube arrays coupled with Zn x Cd 1Àx Se quantum dots synthesized in 7 cycles of deposition and annealed at 300 C for 1 h under N 2 exhibited excellent photoelectrochemical properties. The notably high photovoltaic characteristics demonstrate the potential of the Zn x Cd 1Àx Se/TiO 2 heterostructure as an efficient photoanode.
Molten mixtures of lithium chloride and metallic lithium are of significant interest in various metal oxide reduction processes. These solutions have been reported to exhibit seemingly anomalous physical characteristics that lack a comprehensive explanation. In the current work, the physical chemistry of molten solutions of lithium chloride and metallic lithium, with and without lithium oxide, was investigated using in situ Raman spectroscopy. The Raman spectra obtained from these solutions were in agreement with the previously reported spectrum of the lithium cluster, Li8. This observation is indicative of a nanofluid type colloidal suspension of Li8 in a molten salt matrix. It is suggested that the formation and suspension of lithium clusters in lithium chloride is the cause of various phenomena exhibited by these solutions that were previously unexplainable.
Corrosion behavior of Inconel 625 and 718 in subcritical, supercritical and ultrasupercritical water was studied as a function of temperature and time. The change in the chemistry of the as-received surface film on Inconel 625 and 718 after exposure to subcritical water at 325°C and supercritical water at 425°C and 527.5°C for 2 hours was studied. After exposure to 325°C subcritical water, the CrO4 2based film formed; however minor quantities of NiFexCr2-xO4 spinel compounds were observed. The oxide film formed on both alloys when exposed to supercritical water at 425°C consisted of NiFexCr2-xO4 spinel. The surface films on both alloys were identified as NiFe2O4 when exposed to supercritical water at 527.5°C. To characterize the fully developed oxide layer, studies were conducted at test solution temperatures of 527.5 and 600°C. Samples were exposed to these temperatures for 24, 96, and 200 hours. Surface chemistry was analyzed using Xray diffraction, as well as Raman and X-ray photoelectron spectroscopies. Inconel 718 exhibited greater mass gain than Inconel 625 for all temperatures and exposure times. The differences in corrosion behavior of the two alloys are attributed to the lower content of chromium and increased iron content of Inconel 718 as compared to Inconel 625.
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