The influence of potential on the anodic dissolution of SIMFUEL (UO2)

The influence of potential on the anodic dissolution of SIMFUEL (doped uranium dioxide) has been characterized over the range 0-500 mV (versus SCE). Cathodic stripping voltammetry was used to determine the changes in surface reactivity of UO₂ in neutral solutions after different anodic oxidation timescales. Scanning electron microscopy (SEM) was used to view the damage to the SIMFUEL electrode surface which was minimal at E < 200 mV but present as local pits and eroded grains after oxidation at higher potentials. Long-term anodic oxidation at potentials below 200 mV suggests that local acidification can develop within surface asperities in the fuel and pores in corrosion product deposits accumulated on the electrode surface.     

Surface electrochemistry of UO2 in dilute alkaline hydrogen peroxide solutions

The reaction of H₂O₂ on SIMFUEL electrodes has been studied electrochemically and under open circuit conditions in 0.1 mol l⁻¹ NaCl (pH 9.8). The composition of the oxidized UO₂ surface was determined by X-ray photoelectron spectroscopy (XPS). Peroxide reduction was found to be catalyzed by the formation of a mixed U^IV/U^V (UO_2+x) surface layer, but to be blocked by the formation of U^VI (UO₂²⁺) species on the electrode surface. The formation of this U^VI layer blocks both H₂O₂ reduction and oxidation, thereby inhibiting the potentially rapid H₂O₂ decomposition process to H₂O and O₂. Decomposition is found to proceed at a rate controlled by desorption or reduction of the adsorbed O₂ species. Reduction of O₂ is coupled to the slow oxidative dissolution of UO₂ and formation of a corrosion product deposit of UO₃·yH₂O.     

Surface electrochemistry of UO2 in dilute alkaline hydrogen peroxide solutions: Part II. Effects of carbonate ions

The electrochemical reduction of hydrogen peroxide has been studied on uranium dioxide electrodes. The reduction kinetics are found to be influenced by dissolved carbonate/bicarbonate ions. The formation of hydrated U^VI species on the electrode surface is avoided in carbonate solutions, allowing H₂O₂ reduction to proceed at less cathodic potentials than in carbonate-free solutions. At more cathodic potentials, the adsorption of carbonate ions on the active reduction sites inhibits the H₂O₂ reduction reaction. Over a narrow potential region, the reduction of peroxide is catalyzed by coadsoption of H₂O₂ and HCO₃⁻/CO₃²⁻. The pH dependence of the H₂O₂ reduction reaction appears to be stronger in carbonate solutions than in solutions that do not contain carbonate. This can be attributed to the displacement of inhibiting CO₃²⁻/HCO₃⁻ adsorbed ions by OH⁻.     

H2S adsorption on polycrystalline UO2

We report results on the adsorption and desorption of H₂S on polycrystalline UO₂ at 100 and 300 K, using ultrahigh vacuum X-ray photoelectron spectroscopy (XPS), low energy ion scattering (LEIS), and temperature programmed desorption (TPD). Our work is motivated by the potential for using the large stockpiles of depleted uranium in industrial applications, e.g., in catalytic processes, such as hydrodesulfurization (HDS) of petroleum. H₂S is found to adsorb molecularly at 100 K on the polycrystalline surface, and desorption of molecular H₂S occurs at a peak temperature of 140 K in TPD. Adsorption rates of sulfur as a function of H₂S exposure are measured using XPS at 100 K; the S 2p intensity and lineshapes demonstrate that the saturation coverage of S-containing species is 1 monolayer (ML) at 100 K, and is 0.3–0.4 ML of dissociation fragments at 300 K. LEIS measurements of adsorption rates agree with XPS measurements. Atomic S is found to be stable to >500 K on the oxide surface, and desorbs at 580 K. Evidence for a recombination reaction of dissociative S species is also observed. We suggest that O-vacancies, defects, and surface termination atoms in the oxide surface are of importance in the adsorption and decomposition of S-containing molecules.     

The influence of temperature on the anodic oxidation/dissolution of uranium dioxide

The anodic dissolution of U^IVO₂ has been studied at 60 °C in 0.1 mol dm⁻³ KCl using a range of electrochemical methods and X-ray photoelectron spectroscopy (XPS). The results were compared to previous results obtained at 22 °C. This comparison shows that the threshold for the onset of anodic dissolution (−400 mV versus SCE) is not noticeably changed by this increase in temperature. However, both the oxidation of the surface (to U^IV/VO_2+x) and the rate of anodic dissolution (as U^VIO₂²⁺) leading to the formation of a U^VIO₃·yH₂O deposit are accelerated at the higher temperature. The XPS analysis shows that the conversion of U^V-U^VI occurs at lower potentials at 60 °C. Consequently, once the surface becomes blocked by the presence of a U^VIO₃·yH₂O deposit, rapid dissolution coupled to uranyl ion hydrolysis causes the development of locally acidified sites within the fuel surface at lower potentials at the higher temperature.     

Electrodissolution of cobalt in carbonate/bicarbonate media

The electrodissolution of cobalt in carbonate/bicarbonate solutions was studied at room temperature by steady state polarisation, interfacial pH measurements and Raman spectroscopy. The active dissolution of cobalt leads to an initial CoO film formation. The metal passivation occurs by a slow transformation of the CoO into a Co₃O₄ oxide. The influence of HCO₃⁻ and CO₃²⁻ anions was investigated. Two different parallel electrochemical processes were proposed to account for the anion role on the electrochemical steady state behaviour of cobalt in the studied solutions.     

Partial oxidation of methane to CO and H2 over nickel and/or cobalt containing ZrO2, ThO2, UO2, TiO2 and SiO2 catalysts

The influence of different metal oxide supports (i.e. ZrO₂, ThO₂, UO₂, TiO₂ and SiO₂) on the performance of Ni- and/or Co-containing catalysts [Ni and/or Co/MO₂ mole ratio (where M=Zr, Th, U, Ti or Si)=1.0] in the oxidative methane-to-syngas conversion at very low contact time (GHSV=5.2×10⁵ cm³ g⁻¹ h⁻¹ at STP) was investigated. The nickel-containing ZrO₂, ThO₂ and UO₂ catalysts (with or without pre-reduction by hydrogen at 500°C) showed good performance in the process; the order of their performance is NiO–ThO₂>NiO–UO₂>NiO–ZrO₂. The NiO–TiO₂ showed appreciable catalytic activity only after its reduction at 800°C. However, this catalyst and the NiO–SiO₂ catalyst showed poor performance in the process. These two catalysts are also deactivated very fast, mostly because of sintering of Ni and/or formation of catalytically inactive binary metal oxide phases by solid–solid reaction at the high catalyst calcination and/or catalytic reaction temperature. Although the Ni-containing ThO₂, UO₂ and ZrO₂ catalysts showed good performance, carbon deposition on them during the process is fast. However, because of the addition of cobalt to these catalysts (with Co/Ni=1.0), the rate of carbon deposition on them in the process is drastically reduced. This Co addition however resulted in a significant decrease in both the conversion and selectivity; the decrease in the selectivity was small.     

The importance of the amount/thickness of die wall lubricant for UO2 pellets pressing

External lubrication is often used to complete compaction process of powder materials. The main goal of this method is generally to reduce the amount of admixed internal lubricant (Zinc stearate powder) within the raw material. The application of external lubricants enhances the density uniformity and the mechanical strength of the resulting compacts. This study investigates the effects of the external lubricant amount for UO₂ powder compaction and the properties of the corresponding green pellets (corresponding to the compacts before sintering) without any admixed lubricant in the raw powder in order to evaluate the feasibility of this route in the case of nuclear powder. Results show that there is a quantity or number of layers from which the external lubricant applied on the die wall becomes detrimental to the friction index and the ejection force measured during the pressing cycle. The quality (surface defects, mechanical strength) of the green pellets can also be affected by the amount of lubricant. Thus the quantity and the thickness of the die wall lubricant must be optimized in order to assure an efficient mixed lubrication mode corresponding to the better lubrication mode in our study case.     

Hybrid inorganic-organic polymer electrolytes: synthesis, FT-Raman studies and conductivity of {Zr[(CH2CH2O)8.7]ρ/(LiClO4)z}n network complexes

This paper describes the synthesis and characterization of three-dimensional hybrid inorganic-organic networks prepared by a polycondensation reaction between Zr(O(CH₂)₃CH₃)₄ and polyethylene glycol 400 (PEG400). Eleven hybrid networks doped with varying concentrations of LiClO₄ salt were prepared. On the basis of analytical data and FT-Raman studies it was concluded that these polymer electrolytes consist of inorganic-organic networks with zirconium atoms bonded together by PEG400 bridges. These polymers are transparent with a solid rubber consistency and are very stable under inert atmosphere. Scanning electron microscopy revealed a smooth glassy surface. X-ray fluorescence microanalysis with energy dispersive spectroscopy demonstrated that all the constituent elements are homogeneously distributed in the materials. Thermogravimetric measurements revealed that these materials are thermally stable up to 262 °C. Differential Scanning Calorimetry measurements indicated that the glass transition temperature T_g of these inorganic-organic hybrids varies from −43 to −15 °C with increasing LiClO₄ concentration. FT-Raman investigations revealed the TGT (T=trans, G=gauche) conformation of polyether chains and allowed characterization of the types of ion-ion and ion-polymer host interactions in the bulk materials. The conductivity of the materials at different temperatures was determined by impedance spectroscopy over the 20 Hz-1 MHz frequency range. Results indicated that the materials conduct ionically and that their ionic conductivity is strongly influenced by the segmental motion of the polymer network and the type of ionic species distributed in the bulk material. Finally, it is to be highlighted that the hybrid network with a n_Li/n_O molar ratio of 0.0223 shows a conductivity of ca. 1×10⁻⁵ S cm⁻¹ at 40 °C.     

Effect of Mn-doping on the structure and electrical properties of (Pb0.325Sr0.675)TiO3 ceramics

Pb_0.325Sr_0.675Ti_1-xMn_xO₃ ceramics (x?=?0, 0.001, 0.005, 0.01, and 0.05) were successfully prepared by traditional solid-state reaction method. It was found that the lattice constant calculated through Rietveld refinement initially increased and then decreased with increasing Mn content, which was attributed to the variation in valence state of Mn and Ti ions. The microstructure gradually varied from the coexistence of large grains and fine grains for x?=?0 to the uniform grain for x?=?0.05 by increasing the doping Mn ions. With increasing Mn content from x?=?0 to x?=?0.05, the Curie temperature (Tc) dramatically decreased from 25?°C to ??40?°C and dielectric maximum decreased from 27,100 to 13,200. Pb_0.325Sr_0.675Ti_1-xMn_xO₃ ceramics with x?=?0.001 showed the lowest dielectric loss of 0.006 with a relatively high dielectric peak value of ~ 21,000. The grain boundaries resistance obtained from the complex impedance decreased with the increase of Mn content. The decrease in resistance was ascribed to oxygen vacancies and electronics produced by the change of ionic valence state. X-ray photoemission spectroscopy revealed that Ti ions were Ti⁴⁺ and the valences of Mn ions were deduced to be mainly in the form of Mn²⁺ and/or Mn³⁺ for ceramics with low content of Mn, while the Ti ions were in the form of Ti³⁺ and Ti⁴⁺ and Mn ions were diverse valence states with the coexistence of Mn²⁺, Mn³⁺, and Mn⁴⁺ for ceramics with x?=?0.01 and 0.05.     

Disappearance and recovery of colossal permittivity in (Nb+Mn) co-doped TiO2

We investigate the effects of doping and annealing on the dielectric properties of metal ions doped TiO₂ ceramics. Colossal permittivity (CP) above 10⁴ was observed in single Nb ion doped TiO₂, which was dominated by electron transport related interfacial polarization. Moreover, the CP can be dropped to 120 when simultaneously introducing Mn ion into the sample. The disappearance of CP behaviors maybe due to the multivalence of Mn which would inhibit the reduction of Ti⁴⁺ to Ti³⁺, and thus reduce delocalized electrons. Interestingly, the CP was recovered for the (Nb+Mn) co-doped TiO₂ after post-sintering heat treatment in N₂ atmosphere. The recovery of CP in the sample after annealing can be ascribed to the semiconducting grain and the insulating grain boundary, according to impedance spectroscopy. We therefore believe that this work can help us understand the mechanism of CP from a new perspective.     

The anodic evolution of oxygen on Co3O4 film electrodes in alkaline solutions

The Co₃O₄ film anodes for oxygen evolution were prepared by a thermal decomposition method and their anodic polarization characteristics were investigated in alkaline solutions. As a result, the polarization characteristics were found to be greatly affected by the kind of metal substrates used. Especially when Fe was used as a substrate, some Fe species were proved to be doped in the Co₃O₄ layer during the electrode preparation and the resulting electrodes showed the attractive character for oxygen evolution.     

Ionic conduction and dielectric properties of yttrium doped LiZr2(PO4)3 obtained by a Pechini-type polymerizable complex route

We report on the ion transport properties of Li_1+xZr_2-xY_x(PO₄)₃ (0.05?≤ x?≤?0.2) NASICON type nanocrystalline compounds prepared through a Pechini-type polymerizable complex method. Structural properties were characterized by means of powder X-ray diffraction, Raman spectroscopy and electron microscopy with selected area electron diffraction. Impedance spectroscopy was utilised to investigate the lithium ion transport properties. Y³⁺ doped LiZr₂(PO₄)₃ compounds showed stabilized rhombohedral structure with enhanced total ionic conductivity at 30?°C from 2.87?×?10^?7 S?cm^?1 to 0.65?×?10^?5 S?cm^?1 for x=0.05 to 0.20 respectively. The activation energies of Li_1+xZr_2-xY_x(PO₄)₃ show a decreasing trend from 0.45?eV to 0.35?eV with increasing x from 0.05 to 0.20. The total conductivity of these compounds is thermally activated, with activation energies and pre-exponential factors following the Meyer-Neldel rule. The tanδ peak position shifts to the high-frequency side with increasing yttrium content. Scaling in AC conductivity spectra shows that the electrical relaxation mechanisms are independent of temperature.     

Effect of CO2, HCO3 and CO3 on oxygen reduction in anion exchange membrane fuel cells

The effect of carbonate and bicarbonate anions on the oxygen reduction reaction was investigated in four alkaline solutions (pH ∼ 14) on a Pt disk type electrode with varying concentrations of carbonate and bicarbonate. The addition of carbonate and bicarbonate had two primary effects on the observed voltammetric behavior: i) The Tafel slope shifts positive with increasing carbonate/bicarbonate concentration, indicating that the carbonate anions may compete for surface adsorption sites; and ii) The dissolved oxygen concentration and diffusion coefficient are depressed with increasing anion concentration. Finally, adding CO₂ to the cathode stream of an anion exchange membrane fuel cell caused an improvement in the device performance under fully hydrated conditions, suggesting that the fuel cell was operating at least partially under the carbonate cycle.     

Carbonate-catalyzed chemiluminescence decomposition of peroxynitrite via (CO2)2 intermediate

Peroxynitrous acid (ONOOH) was formed by the on-line rapid reaction of acidified hydrogen peroxide with nitrite in a simple flow system. A weak chemiluminescent (CL) signal was observed due to the production of singlet oxygen (¹O₂) when ONOOH reacted with NaOH, whereas the replacement of NaOH by Na₂CO₃ markedly enhanced the CL intensity. The predominant CL-enhanced pathway was achieved by the carbonate-catalyzed decomposition of peroxynitrite (ONOO⁻). Carbonate species was regenerated in the process, that is, carbonate acts as a catalyst. Based on the studies of CL and fluorescence spectra, a possible CL mechanism from the reaction of carbonate with ONOOH was proposed. In brief, ONOOH was an unstable compound in acidic solution and could be quenched into ONOO⁻ in basic media. It was suggested that ONOO⁻ reaction with excess HCO₃⁻ proceeded via one-electron transfer to yield bicarbonate ion radicals (HCO₃√). The recombination of HCO₃√ may directly generate excited triplet dimers of two CO₂ molecules [(CO₂)₂^*]. With the decomposition of this unstable intermediate to CO₂, the energy was released by CL emission. The addition of uranine into carbonate solution caused enhancement of the CL signal, which was due to a part of excited triplet dimers of two CO₂ molecules energy to transfer to uranine, resulting in two CL peaks.     

Potentiometric measurements and impedance characteristics of Li0.30La0.57TiO3 membrane in lithium anhydrous solutions

The potentiometric response of the Li⁺ ion-selective electrode based on the fast ion conductor Li_3xLa_2/3−xTiO₃ (x = 0.10) membrane (named LLTO) as well as the impedance of the LLTO membrane/Li⁺ solution in either anhydrous or hydrated PC solvent have been carried out. A four-electrode configuration has been used for the investigation of the interfacial phenomenon. It has been shown that the LLTO membrane can be used to detect the Li⁺ activity in anhydrous solutions through a Li⁺ ion exchange mechanism. The potentiometric response shows a Nernstian behavior with a Li⁺ sensitivity of −72 mV/decade at 25 °C. This high sensitivity can be correlated to a localised hydroxylation of the oxide surface with the residual water present in the solution in combination to the Li⁺ exchange reaction. An apparent standard current density of 12 μA/cm² and a charge-transfer coefficient of 0.29 have been determined. However, as water content in the electrolyte increases, the activity domain of the detection decreases to lead to the disappearance of the Li⁺ ion exchange mechanism in Li⁺ aqueous solution. This annihilation of the exchange process may be due to the predominant catalytic reaction of [Ti-O]⁻ with H₂O and/or to the formation of a water layer on the oxide surface.     

The influence of pentavalent Nb substitution for Zr on electrical property of oxide-ion conductor Gd2Zr2O7

Gd₂(Zr_1−xNb_x)₂O_7+x (0 ≤ x ≤ 0.2) ceramics are prepared via the solid state reaction process at 1973 K for 10 h in air. Gd₂(Zr_1−xNb_x)₂O_7+x (x = 0.1, 0.2) ceramics exhibit an ordered pyrochlore-type structure, whereas Gd₂Zr₂O₇ has a defective fluorite-type structure. The electrical property of Gd₂(Zr_1−xNb_x)₂O_7+x ceramics is investigated by electrochemical impedance spectroscopy over a frequency range of 10 Hz to 8 MHz from 623 to 923 K. The electrical conductivity obeys the Arrhenius equation. The grain conductivity of Gd₂(Zr_1−xNb_x)₂O_7+x ceramics varies with doping different Nb contents, and exhibits a maximum at the Nb content of x = 0.1 in the temperature range of 623-923 K. The conductivity in hydrogen atmosphere is a little bit higher than in air in the temperature range of 723-923 K, which indicates that the doping of Zr⁴⁺ by Nb⁵⁺ can increase the proton-type conduction and reduce the oxide-ionic conduction. The conduction of Gd₂(Zr_1−xNb_x)₂O_7+x is not a pure oxide-ionic conductor.     

Structural,electrical and ferroelectric characteristics of Bi(Fe0.9La 0.1)O3

Nowadays, much attention is paid for the development of lead-free complex or mixed metal oxides, which can be utilized for multi-functional devices. This communication provides the information on synthesis (by mixed oxide route) and physical properties (structural, electrical and ferroelectric) of the polycrystalline sample of Bi(Fe_0.9La_0.1)O₃ Analysis of the phase formation and basic crystal data of the material using X-ray diffraction (XRD) technique shows an orthorhombic symmetry with well-defined cell parameters. It has been shown that a small amount (10%) of La substitution at the Fe site of BiFeO₃ suppresses the impurity phase usually observed during phase formation of BiFeO₃. The average crystallite size, calculated through applying Scherrer's technique, was found to be 68?nm. For the study of surface morphology (grain size and distribution) of the compound, the scanning electron microscope (SEM) was used. The grains of different dimension were found homogeneously distributed at the entire surface of the sample. The La substitution strongly affects the capacitive (dielectric) and resistive (electrical) characteristics of bismuth ferrite in a wide range of frequency and temperature. The contributions of grains and grain boundaries in the capacitive as well as in the resistive properties of the material at different temperatures and frequencies were studied by means of the impedance spectroscopy technique. This study has provided numerous useful and interesting data which may find potential industrial applications.     

Promotion of CO2 mass transfer in carbonate solutions

A general, physico-chemical analysis of mass transfer rate promotion in the system CO₂-potassium carbonate-water-promoter is presented. Different possible mechanisms of promoter action including homogeneous catalysis, “shuttle” mechanism and surface reactions are discussed and classified. A unified picture of promoter chemistry is presented, showing that differences between inorganic and organic promoters are predominently quantitative, not qualitative.The “shuttle” mechanism is analyzed for absorption. The analysis leads to the prediction that the CO₂ mass transfer rate may be influenced by the liquid hold up. This is related to the fact that, although the reaction in the interface region may be fast enough to enhance the mass transfer rate, the different reaction in the bulk may not be fast enough to maintain chemical equlibrium. This complex type of chemical absorption process has not been considered previously in the literature.     

Pitting corrosion of lead in sodium carbonate solutions containing NO3 ions

Pitting corrosion of Pb in Na₂CO₃ solutions (pH=10.8) containing NaNO₃ as a pitting corrosion agent has been studied using potentiodynamic anodic polarization, cyclic voltammetry and chronoamperometry techniques, complemented with scanning electron microscopy (SEM) examinations of the electrode surface. In the absence of NO₃⁻, the anodic voltammetric response exhibits three anodic peaks prior to oxygen evolution. The first anodic peak A₁ corresponds to the formation of PbCO₃ layer and soluble Pb²⁺ species in solution. The second anodic peak A₂ is due to the formation of PbO beneath the carbonate layer. Peak A₂ is followed by a wide passive region which extends up to the appearance of the third anodic peak A₃. The later is related to the formation of PbO₂. Addition of NO₃⁻ to the carbonate solution stimulates the anodic dissolution through peaks A₁ and A₂ and breaks down the dual passive layer prior to peak A₃. The breakdown potential decreases with an increase in nitrate concentration, temperature and electrode rotation rate, but increases with an increase in carbonate concentration and potential scan rate. Successive cycling leads to a progressive increase in breakdown potential. The current/time transients show that the incubation time for passivity breakdown decreases with increasing the applied anodic potential, nitrate concentration and temperature.