On the origin of irreproducible behaviour of Na1−xLixNbO3 solid solutions

The irreproducibility of electrical properties of Na_0.88Li_0.12NbO₃ solid solution on thermal cycling reported by M.A.L. Nobre and S. Lanfredi is explained by gradual decomposition of the supersaturated solid solution below ca. 800 °C.     

Optical and electric properties of Nb-doped anatase TiO2 single crystal

Nb-doped anatase TiO₂ single crystal has been grown by chemical vapour transport method. Raman spectra shows that the obtained crystal with Nb of 0.08 wt% has typical anatase structure. An absorption band was observed at around 2.2 eV, which seems to be due to the d-d transition in the conduction band. The electron paramagnetic resonance and electric resistivity measurements show that the doped niobium makes quite shallow donor level whose orbital is d_xy-like centered at the titanium position of anatase.     

Two different synthetic routes involving the reaction of dodecylamine or nicotinamide with crystalline lamellar vanadylphosphate

The crystalline lamellar compound, VOPO₄·2H₂O, was employed as host to react with a long monoamine aliphatic chain, dodecylamine, and with an aromatic derivative, nicotinamide, using two distinct synthetic approaches: in the solid state and from aqueous solution. The resulting compounds were characterized by elemental analysis, infrared spectroscopy, X-ray diffractometry, thermogravimetry and SEM microscopy. From X-ray diffraction patterns, the calculated increase of the interlayer distance was 2.05 nm for the dodecylamine, containing product, which is in agreement with the intercalation process, and was observed with both reactions routes. On the contrary, the guest nicotinamide molecule was not inserted into the lamellar cavity. The reaction in the solid state caused a small modification of the phosphate microstructure, in comparison with the solution procedure. The aliphatic amine molecules are oriented in a bilayer inside the host cavity by forming an angle of 67° with the inorganic lamella. The thermal decomposition for both series of synthesized compounds did not demonstrate any difference in behavior.     

EPR investigations of oxidation effects in (V1−xMox)2−δO3

Electron paramagnetic resonance (EPR) investigations has been carried out on the new family of molybdenum doped vanadium sesquioxides (V_1−xMo_x)_2−δO₃. The oxidation effects were monitored from the rate of paramagnetic V⁴⁺ created when the sample is exposed to the air. The effects of the oxidation time, sample temperature, and annealing at 1000 °C under a diluted hydrogen atmosphere on the EPR signal features are analyzed. The V⁴⁺ concentration in the oxidized samples is determined and the relaxation effects driven by the conduction electrons are pointed out from the thermal behaviour of the EPR line features. EPR spectra of all the oxidized samples also reveal a small ferromagnetic contribution strongly correlated with the V⁴⁺ content.     

2‐connected 7‐coverings of 3‐connected graphs on surfaces

An m‐covering of a graph G is a spanning subgraph of G with maximum degree at most m. In this paper, we shall show that every 3‐connected graph on a surface with Euler genus k ≥ 2 with sufficiently large representativity has a 2‐connected 7‐covering with at most 6k ? 12 vertices of degree 7. We also construct, for every surface F² with Euler genus k ≥ 2, a 3‐connected graph G on F² with arbitrarily large representativity each of whose 2‐connected 7‐coverings contains at least 6k ? 12 vertices of degree 7. © 2003 Wiley Periodicals, Inc. J Graph Theory 43: 26–36, 2003     

Electrochemical characterization of poly(vinylidenefluoride)-zinc triflate gel polymer electrolyte and its application in solid-state zinc batteries

Gel polymer electrolyte (GPE) films comprising of poly(vinylidenefluoride), propylene carbonate, ethylene carbonate and zinc trifluoromethane sulfonate are prepared and characterized. The composition of GPE is optimized to contain minimum liquid components with a maximum specific conductivity of 3.94×10⁻³ S cm⁻¹ at (25±1) °C. A detailed investigation on the properties such as ionic conductivity, transport number, electrochemical stability window, reversibility of Zn/Zn²⁺ couple and Zn/gel electrolyte interfacial stability have been carried out. The ionic conductivity follows a VTF behaviour with an activation energy of about 0.0014 eV. Cationic transport number varies from 0.51 at 25 °C to 0.18 at 70 °C. Several cells have been assembled with GPE as the electrolyte, zinc as the anode, γ-MnO₂ as the cathode and their charge–discharge behaviour followed. Capacity values of 105, 82, 64 and 37 mAh/g of MnO₂ have been achieved at 10, 50, 100 and 200 μA/cm² discharge current densities, respectively. The discharge capacity values are almost constant for about 55 cycles for all values of current densities. Cyclic voltammetric study of MnO₂ electrode in Zn/GPE/MnO₂ cell clearly shows intercalation/deintercalation of Zn²⁺.     

Luminescence enhancement by hydrogenation of Si:Er,O

Erbium (Er)- and oxygen (O)-doped Cz–Si was additionally doped with hydrogen, using plasma enhanced chemical vapour deposition. Photoluminescence (PL) spectra show a large enhancement especially for samples treated with solid phase epitaxy before hydrogenation and annealing at 900°C later. Secondary ion mass spectroscopy measurements give evidence for an enhanced diffusion of O and Er at this temperature towards the surface. Etching shows that the PL does not stem from the heavily doped surface layer but from a deeper region with lower Er concentration. This conclusion is supported by the appearance of the so-called “cubic” centre with low solubility. Comparing the PL yield of the hydrogenated samples to that of samples with similar Er volume concentration but without hydrogenation still gives a large enhancement. We thus conclude that hydrogen can enhance the solubility of the cubic centre in Si:Er,O.     

Laplacians and the Cheeger Inequality for Directed Graphs

We consider Laplacians for directed graphs and examine their eigenvalues. We introduce a notion of a circulation in a directed graph and its connection with the Rayleigh quotient. We then define a Cheeger constant and establish the Cheeger inequality for directed graphs. These relations can be used to deal with various problems that often arise in the study of non-reversible Markov chains including bounding the rate of convergence and deriving comparison theorems.Received September 8, 2004     

Metallization of U3O8via catalytic electrochemical reduction with Li2O in LiCl molten salt

The concept of a novel electrochemical reduction process for the treatment of spent nuclear fuels in Li₂O-LiCl molten salt was proposed and fresh tests using U₃O₈ powder were carried out to elucidate the reaction mechanism and verify the feasibility of the process. Electrolysis of Li₂O and reduction of U₃O₈ powder took place simultaneously at the cathode part of the electrolysis cell via a catalytic EC mechanism and the conversion of U₃O₈ to U metal was more than 99%. This revised version was published online in June 2006 with corrections to the Cover Date.     

Investigation of the Li1+xV3O8 electrode–organic electrolyte interface by scanning photoelectron microscopy

To investigate the formation of a solid electrolyte interface (SEI) on the Li_1+xV₃O₈ electrode surface in the thermodynamic stability range of the organic electrolyte, we applied scanning photoelectron microscopy (SPEM) to a pristine electrode and to an electrode after ten cycles. The F K-edge absorption spectrum of the cycled electrode showed that LiF forms on the electrode surface during the lithium insertion–extraction process in the Li_1+xV₃O₈/Li cell. The photoelectron spectrum for the cycled electrode showed intense spectral features corresponding to Li 1s, F 2s, F 2p, and P 2p electron signals, whereas these spectral features were of negligible intensity for the pristine electrode. The above results give strong support for the formation of an SEI that consists of LiF and compounds containing phosphorus during operation of the battery. The SPEM images also revealed that the fluorine distribution on the surface of the cycled electrode was inhomogeneous.