Chemical stability of hydroxysulphate green rust synthetised in the presence of foreign anions: carbonate, phosphate and silicate

Hydroxysulphate green rust species were precipitated in the presence of various anions. is stable at ∼pH 7 and is transformed into a mixture of magnetite and ferrous hydroxide when the pH raised at ∼12. In the presence of carbonate species, is partially transformed into a mixture of magnetite and siderite at ∼pH 8.5. This transformation is stopped when silicate anions are present in the solution. As already observed for phosphate anions, the adsorption of silicate anions on the lateral faces of the crystals may explain this stabilization effect. Sulphate anions are easily exchanged by carbonate species at ∼pH 10.5. In contrast, anionic exchange between sulphate and phosphate anions was not observed.     

Laboratory Intercomparison on the Determination of the Fe(II)/Fe(III) Ratio in Glass Using Mössbauer Spectroscopy

A Perturbed Angular Correlation (PAC) study was performed on the system that presents a rich variety of structural and magnetic phase transitions as a function of the oxygen content (δ) or as a function of temperature (T). The PAC signal at room temperature allowed the determination of the Electrical Field Gradient (EFG) parameters and to correlate them with the lattice average symmetry namely the orthorhombic (O′ or O*) Pbnm and rhombohedral (R) phases measured by X-ray diffraction.     

Diffusion of proton in alumina-rich nonstoichiometric magnesium aluminate spinel

The phenomenon of the diffusion of proton and deuteron in a single crystal of magnesium aluminate spinel was studied by infrared absorption. The chemical diffusion coefficient of proton was determined by the relaxation time of the absorption intensity upon the substitution of deuteron with proton. The temperature dependence of the chemical diffusion coefficient of proton for was expressed as . The chemical diffusion coefficient of proton was found to be independent of the composition of spinel and of the atmosphere. Paper presented at the 11th Euro Conference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15 2007.     

Critical behavior of La0.67−y (Sr, Ba, Ca)0.33+y Mn1−x Sn x O3 (x = 0.01, 0.02, y = 0, 0.07) perovskites

The magnetic critical behavior of the manganese perovskite series $ {\text{La}}_{{0.67 - y}} {\left( {{\text{Sr,}}\,\,{\text{Ba,}}\,\,{\text{Ca}}} \right)}_{{0.33 + y}} {\text{Mn}}_{{1 - x}} {\text{Sn}}_{x} {\text{O}}_{3} The magnetic critical behavior of the manganese perovskite series (x = 0.01, 0.02, y = 0, 0.07) is studied by means of dc magnetic measurements and ¹¹⁹Sn M?ssbauer spectroscopy. The structure can be described by a rhombohedral unit cell (space group R–3C) for the samples where the A-site is occupied by La and Sr or La and Ba ions and orthorhombic unit cell (space group Pnma) for the samples where the A-site is occupied by La and Ca ions. Arrott and scaling plots show that the samples, where the A-site is occupied by La and Sr or La and Ba ions, follow the behavior of a conventional second-order ferromagnetic transition. In contrast, the samples that contain La and Ca ions in the A-site show anomalous behavior around Curie point. M?ssbauer measurements show two magnetic phases below T _c. One of them exhibits stronger exchange interactions with more rapid electron transfer between Mn³⁺/Mn⁴⁺, compared to the other.     

Energy dependence of the charge exchange reaction from muonic hydrogen to oxygen

The charge exchange reaction of negative muons from the atom to oxygen has been measured in gaseous mixtures of H₂ + O₂. The measurements were performed at three different relative oxygen concentrations ranging from 0.2% to 0.8% and total pressures 3.5–15 bar. A mean transfer rate of , describing the transfer from the ground state of thermalized atoms to oxygen, was determined. In order to investigate the energy dependence of the transfer rate, Monte Carlo simulations of the thermalization and the muon transfer were carried out. The comparison of measured and simulated time spectra yielded an epithermal transfer rate =3.9 10¹¹ s^-1 in the energy interval 0.12–0.22 eV. The analysis with the model of Two components shows that all measured time spectra can be reproduced with the same set of parameters.     

Selectivity of anion exchange membrane modified with polyethyleneimine

Previous works have been made on the improvement of selectivity of ion exchange membranes using adsorption of polyelectrolyte on the surface of the materials. The modification of the surface material in the case of an anion exchange membrane concerns the hydrophilic/hydrophobic balance properties and its relationship with the hydration state. Starting from this goal, the AMX membrane has been modified, in this work, by adsorption of polyethyleneimine on its surface. Many conditions of modification of the AMX membrane surface were studied. A factorial experimental design was used for determining the influent parameters on the AMX membrane modification. The results obtained have shown that the initial concentration of polyethyleneimine and the pH of solution were the main influent parameters on the adsorption of polyethyleneimine on the membrane surface. Competitive ion exchange reactions were studied for the modified and the unmodified membrane involving $ {\text{C}}{{\text{l}}^{ - }} $ , $ {\text{NO}}_3^{ - } $ and $ {\text{SO}}_4^{{2 - }} $ ions. All experiments were carried out at constant concentration of 0.3?mol?L^?1 and at 25?°C. Ion exchange isotherms for the binary systems $ \left( {{\text{C}}{{\text{l}}^{ - }}/{\text{NO}}_3^{ - }} \right) $ , $ \left( {{\text{C}}{{\text{l}}^{ - }}/{\text{SO}}_4^{{2 - }}} \right) $ and $ \left( {{\text{NO}}_3^{ - }/{\text{SO}}_4^{{2 - }}} \right) $ were studied. The obtained results show that chloride was the most sorbed and the selectivity order both for the modified membrane and the unmodified one is: $ {\text{Cl}} > {\text{NO}}_3^{ - } > {\text{SO}}_4^{{2 - }} $ , under the experimental conditions. Selectivity coefficients $ {\text{K}}_{{{\text{C}}{{\text{l}}^{ - }}}}^{{{\text{NO}}_3^{ - }}} $ , $ {\text{K}}_{{2{\text{C}}{{\text{l}}^{ - }}}}^{{{\text{SO}}_4^{{2 - }}}} $ and $ {\text{K}}_{{2{\text{NO}}_3^{ - }}}^{{{\text{SO}}_4^{{2 - }}}} $ for the three binary systems and for the two membranes were determined. It was also observed that for the modified membrane the selectivity towards sulfate ion decrease and the modified membrane became more selective towards monovalent anions.     

Ion exchange equilibrium between cation exchange membranes and aqueous solutions of K+/Na+, K+/Ca2+, and Na+/Ca2+

Equilibrium between synthetic ion exchangers and solutions of cations has been the subject of this investigation. Competitive ion exchange reactions were studied for two cation exchange membranes (CMX and CRP) involving K⁺, Na⁺, and Ca²⁺ ions. The ionic strength of the equilibrating solutions was maintained constant, but the molar fraction varied; all experiments were conduced with nitrate as nonexchanging anions at 25 °C. Adsorption isotherm for the three binaries systems: K⁺/Na⁺, K⁺/Ca²⁺, and Na⁺/Ca²⁺ were studied. The obtained results show that potassium was the most strongly sorbed and the selectivity order for CMX and CRP membranes is K⁺>Ca²⁺>Na⁺ at 0.1 M, under the experimental conditions. Selectivity coefficients , , and for the three binaries and for the two membranes were determined at an ionic strength of 0.1 M and at a constant temperature of 25 °C. We remark that all the selectivity coefficient values are quite different from the unit. Ternary equilibrium was taken for the Ca²⁺/K⁺/Na⁺ system. It was found that binary selectivity data could be successfully used to predict the ternary ion exchange equilibrium.     

NMR Studies on the Internal Structure of High-T c Superconductors and Other Anorganic Compounds

Spatially-resolved NMR is used to probe internal structures in highly correlated superconductors of optimally-doped (T _c = 85 K) and a heavy fermion superconductor CeCoIn₅ (T _c = 2.3 K). The characteristic change of the properties of ²⁰⁵Tl-NMR in the vortex state provides a clear evidence of the antiferromagnetic order in the vortex cores below 20 K in . We also obtain anomalous ¹¹⁵In-NMR spectra of CeCoIn₅, which provides a microscopic evidence for the occurrence of a spatially-modulated superconducting order parameter expected in a Fulde–Ferrel–Larkin–Ovchinnkov (FFLO) state.     

Study of the ion exchange equilibrium of Cl−, NO_3^{ - } , and SO_4^{{2 - }} ions on the AMX membrane

Equilibrium between the ion exchange membrane and solutions of anions at various valences has been the subject of this investigation. Competitive ion exchange reactions were studied on a strong base anion exchange membrane AMX manufactured by Tokuyama, commercialized by Eurodia, involving Cl^?, $ {\text NO}_3^{ - } $ and $ {\text SO}_4^{{2 - }} $ ions. Solution concentrations studied were 0.05 and 0.1 M for all the systems reported. Experiments were performed with sodium as the counter ion, and the temperature was kept constant (T?=?298 K). Ionic exchange isotherms for the binary systems— $ {{\text Cl}^{ - }}/{\text NO}_3^{ - } $ , $ {{\text Cl}^{ - }}/{\text SO}_4^{{2 - }} $ , and $ {\text NO}_3^{ - }/{\text SO}_4^{{2 - }} $ —were established. The obtained results show that the sulfate was the most strongly sorbed, and the selectivity order is $ {\text SO}_4^{{2 - }} > {\text NO}_3^{ - } > {{\text Cl}^{ - }} $ at 0.05 M and $ {\text NO}_3^{ - } > {\text SO}_4^{{2 - }} > {{\text Cl}^{ - }} $ at 0.1 M under the experimental conditions. Selectivity coefficients $ K_{{{{{\text Cl} }^{ - }}}}^{{{\text NO}_3^{ - }}} $ , $ K_{{2{{{\text Cl} }^{ - }}}}^{{{\text SO}_4^{{2 - }}}} $ , and $ K_{{2{\text NO}_3^{ - }}}^{{{\text SO}_4^{{2 - }}}} $ for the three binary systems were determined. All the results given by this membrane were compared with those obtained, in the same conditions, with the RPA membrane (produced by RHONE POULENC). Ternary equilibrium data were taken for $ {{\text Cl}^{ - }}/{\text NO}_3^{ - }/{\text SO}_4^{{2 - }} $ . The prediction of the ternary system based only on the binary data was consistent with the experimental data obtained for this system. The good agreement between the experimental and the predicted data showed that the proposed framework can be considered as an effective method to predict many ternary systems from binary systems.     

Laser-diode-excited Blue Upconversion in Tm3+/Yb3+-codoped TeO2-Ga2O3-R2O (R=Li, Na, K) Glasses

This paper reports on intense blue upconversion in Tm³⁺/Yb³⁺ codoped TeO₂-Ga₂O₃-R₂O(R=Li, Na, K) glasses upon excitation with commercial available laser diode (LD). Effects of alkali ions on the Raman spectra, thermal stability and spectroscopic properties of the tellurite-gallium glasses have also been investigated. Energy transfer and the involved upconversion mechanisms have been discussed. Intense blue upconversion emission centered at 476 nm along with a weak red emission at 650 nm has been observed upon excitation of 977 nm LD, assigned to the transitions of , and and/or of Tm³⁺, respectively. The blue upconversion intensity has a cubelike dependence on incident pump laser power, indicating a three-photon process. However, a quadratic dependence of the 476 nm upconversion intensity on the incident pump laser power has been observed when samples under excitation of 808 nm LD due to a two-photon absorption process. Enhanced upconversion luminescence have been observed with replacing K⁺ for Na⁺ and Li⁺.     

Determination of heavy quark non-perturbative parametersfrom spectral moments in semileptonic B decays

Moments of the hadronic invariant mass and of the lepton energy spectra in semileptonic B decays have been determined with the data recorded by the DELPHI detector at LEP. From measurements of the inclusive b-hadron semileptonic decays, and imposing constraints from other measurements on b- and c-quark masses, the first three moments of the lepton energy distribution and of the hadronic mass distribution, have been used to determine parameters which enter into the extraction of |V_cb| from the measurement of the inclusive b-hadron semileptonic decay width. The values obtained in the kinetic scheme are: and include corrections at order 1/m_b³. Using these results, and present measurements of the inclusive semileptonic decay partial width of b-hadrons at LEP, an accurate determination of |V_cb| is obtained: Received: 26 April 2005, Revised: 16 September 2005, Published online: 16 November 2005     

The electrochemical reactivity of the NiP<Subscript>3</Subscript> skutterudite-type phase with lithium

We report the electrochemical Li reactivity of the cubic NiP₃ phase, a candidate for anode applications for Li-ion batteries. NiP₃ reacts with nine lithium per formula unit leading to a first cycle reversible capacity of 1,475 mAh/g at an average potential of 0.9 V vs. Li+/Li°. Electrochemical measurements and complementary X-ray diffraction showed that NiP₃ presents a conversion process competing with an insertion process. A good cycleability may only be obtained on a limited potential window, excluding the low-potential region. This paper was presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Search for new oxide-ion conducting materials in the ceria family of oxides

We have adopted a modified combustion route, namely, a mixed fuel process (MFP) to prepare a novel series of nano-crystalline single- and multiple-doped ceria compositions with controlled powder characteristics, large surface area, finer particle size, high sinterability, and high oxide ion conductivity at intermediate temperatures (500–700 °C). Using the mixed fuel process, we have prepared nano-particles of single- and multiple-doped ceria powders with dopants such as Ca, Gd, and Sm and a suitable combination of the same. In the pursuit for identifying new oxide-ion-conducting materials in this family of oxides, we have pursued the idea of co-doping effect on the single doped compositions with proper introduction of a second dopant. Effect of these dopants on the thermal decomposition and physico–chemical characteristics of the precursor and the powders prepared thereby were studied in detail. Finally, the effects of multiple co-doping on the microstructural and electrical properties were compared to understand the origin of the effect of dopant characteristics on the oxide ion conductivity of Ce_1−x M _x O₂ solid solutions. Our experimental results established unequivocally that co-doping is very effective in identifying new materials with remarkably high ionic conductivity with substantial reduction in the cost for technological applications. Among the studied compositions, the maximum conductivity with minimum activation energy was observed for the triply co-doped CCGS composition (; E _a = 0.56 eV), which is much higher compared to the conductivity exhibited by most of the reported co-doped ceria compositions. In conclusion, an effective way to improve the oxide ion conductivity of ceria-based oxides by proper choice of dopants and co-doping is achieved.     

Mössbauer Study of Microstructure and Magnetic Properties (Co,Ni)–Zr Substituted Ba Ferrite Particles

The β-NMR of short-lived β-emitter in a rutile TiO₂ single crystal has been measured as functions of temperature and external magnetic field. Atomic motion induced spin lattice relaxation was observed for two known sites, O substitutional and interstitial sites. The data were analyzed in terms of the thermal atomic jump, which suggests that the motion of defects around the substitutional ¹²N atom for O, and of the interstitial ¹²N atom are attributed to the spin lattice relaxation. The electric field gradients have shown temperature dependence for both sites, which is probably due to the thermal expansion of rutile.     

Direct ammonia proton-conducting solid oxide fuel cells prepared by a modified suspension spray

A dense (BCSO) membrane was fabricated by a modified suspension spraying on porous NiO–BCSO anode support. In the process, the suspension was directly prepared by ball-milling the BaCO₃, CeO₂, and Sm₂O₃ powders in ethanol. A dense and uniform electrolyte layer in the thickness of 10 μm was successfully prepared on porous anode support by suspension spray process after co-sintering at 1,400 °C for 5 h. With (NSMO) cathode, a single cell was assembled and tested with hydrogen and ammonia as fuels, respectively. The hydrogen-fueled cell exhibits 1.01 V for open circuit voltage (OCV) and 560 mW/cm² for peak power density at 700 °C. In comparison, the cell in ammonia displays a similar performance (1.02 V for OCV and 530 mW/cm² for output), which indicates the liquid ammonia is a promising substitute for hydrogen. Moreover, the fuel cell displays good interface contacts. To sum up, ammonia-fueled solid oxide fuel cells prepared by this simple suspension spray is an alternative way to promote the commercialization.     

A-site deficient lanthanum-calcium chromite-titanates doped with 3d transition metals: synthesis,oxygen nonstoichiometry,electrical conductivity,and catalytic activity

Six (M = Cr, Mn, Fe, Co, Ni, Cu) and two (M = Ni, Cu) single-phase compositions were prepared by conventional solid-state reactions. Oxygen nonstoichiometry, electrical conductivity, phase transformations under reduction-reoxidation at high temperatures and catalytic activity for hydrocarbons oxidation of these compositions were investigated in a wide temperature and oxygen partial pressure range. The Cu-, Ni-, Co-, and Fe-containing compositions are decomposed in reducing Ar/H₂O/H₂ atmosphere with pH₂O / pH₂ = 0.3 at 1,000 °C, while the Cr- and Mn-containing ceramics remain stable at the same conditions. The metallic particles of the added 3d elements formed after decomposition were registered by X-ray diffraction method in case of Cu- and Ni-containing compositions. These formed composites can be completely reoxidized with formation of initial compositions by treatment in air at 1,000 °C. The electrical conductivity of the ceramics investigated in air and Ar/H₂O/H₂ gas flow increases with rising M content. The highest catalytic activity for oxidation of CH₄ and C₃H₆, which was comparable with the activity of the composite, shows the Cu-containing powders. Dedicated to Prof. Dr. Werner Weppner     

Weber potential from finite velocity of action?

The Weber potential energy U for charges q and q' separated by the distance R is U = (qq'/R)[1 – (dR/dt)²/2c²]. If this potential arises from a finite velocity c of energy transfer Q', where the retarded rate of transfer from q' to q is dQ(t-R/c)/dt = Q'[1 – (dR/dt)/c] and where the advanced rate from q to q' is dQ(t+R/c)/dt = Q'[1 + (dR/dt)/c], then the resultant time-average root-mean-square action is given by . Identifying Q' with the Coulomb potential energy qq'/R, the Weber potential is obtained. Using the same argument, Newtonian gravitation yields a corresponding Weber potential energy, qq'/R being replaced by ( - Gmm'/R).     

Experimental test of special relativity by laser spectroscopy

The Doppler-free laser-spectroscopic frequency measurement of Doppler-shifted optical lines in forward and backward direction of a fast ion beam permits a sensitive test of the relativistic Doppler-formula and, hence, the relativistic time dilation factor . An experiment on metastable ⁷Li⁺, stored at a velocity of v = 0.064c in the Heidelberg heavy-ion storage ring TSR, has confirmed time dilation with unprecedented accuracy. Latest tests at two different ion-velocities (v = 0.03c and v = 0.064c) will enhance these measurements. An improved version of this experiment will be carried out at the experimental storage ring (ESR) at the Gesellschaft für Schwerionenforschung (GSI) in Darmstadt. The ESR permits ⁷Li⁺ to be stored at v = 0.33c which promises an improvement of the sensitivity to deviations from γ _SR by an order of magnitude. A first test at the ESR has shown the feasibility for this kind of experiment.     

Al,F-doped new perovskite lithium fast ion conductor Li3x La2/3−x□1/3−2x Ti1−y Al y O3−y F y (x=0.11)

Al, F-doped new perovskite lithium ion conductors (x=0.11) have been prepared by solid state reaction. It is found that a pure perovskite-structured phase with space group of P4mm(99) exits in the composition range of 0<y≤0.10. The sample with y=0.02 possesses the highest ionic conductivity of 1.06×10⁻³ S/cm at room temperature, and its decomposing voltage is 2.3 V. The factors affecting the conductivity of this system are discussed.     

Laplace Sequences of Surfaces in Projective Space and Two-Dimensional Toda Equations

We find that the Laplace sequences of surfaces of period n in projective space P _n–1 have two types, while type II occurs only for even n. The integrability condition of the fundamental equations of these two types have the same form