Pipe-sphere model for enhancement of ionic conductivity in composite solid electrolytes

It is well-known that the ionic conductivity of a superionic conductor when dispersed with an insulator shows a remarkable enhancement. In this work we suggest that the contribution coming from grain-boundaries and dislocations is primarily responsible for this phenomenon in a number of cases. We propose a simple theoretical model for such composites and with the aid of the Effective Medium Theory (EMT) under self-consistent scheme we estimate the effective conductivity as a function of insulator volume fraction and particle size for four composites, namely CaF₂-Al₂O₃, CuCl-Al₂O₃, Sr(NO₃)₂-Al₂O₃ and SrCl₂-Al₂O₃. This model is applicable to composites where enhancement is observed for a very low insulator volume fraction and other prevalent models are inadequate. The results exhibit a good qualitative fit to the experimental data and all characterisitic experimental observations.     

Spinel lithium titanate (Li4Ti5O12) as novel anode material for room-temperature sodium-ion battery

This is the first time that a novel anode material, spinel Li₄Ti₅O₁₂ which is well known as a “zero-strain” anode material for lithium storage, has been introduced for sodium-ion battery. The Li₄Ti₅O₁₂ shows an average Na storage voltage of about 1.0 V and a reversible capacity of about 145 mAh/g, thereby making it a promising anode for sodium-ion battery. E_x-situ X-ray diffraction (XRD) is used to investigate the structure change in the Na insertion/deinsertion process. Based on this, a possible Na storage mechanism is proposed.     

Bestimmung der 15N-Häufigkeit von N2O und N2 mittels emissionsspektrometrischer continuous-flow-Messung

Abstract

Tests were made for a quantitative decomposition of N₂O to N₂ and for the setting of a statistical equilibrium in mixtures with gaseous nitrogen of nonrandom distribution by emission spectrometric continuous-flow-measurements. Under high-frequency-discharge conditions a residence time of 0.5 seconds is enough for a quantitative decomposition. In this time the statistical balance in the mixture of N₂O and N₂ is reached. The determination of the relative ¹⁵N abundance in pure N₂O or N₂ gases or in mixtures of N₂O and N₂ in a continuous-flow-emissionspectrometer can directly be achieved.     

Magnetodielectric coupling in Ca3Co2O6 triangular Ising lattice

Geometric frustration in magnetic systems is a key ingredient for magnetodielectric coupling. Ca₃Co₂O₆ system is a model of triangular Ising lattice and presenting exotic magnetic properties. With a partially disordered antiferromagnetic ground state and two steps in magnetisation to a ferrimagnetic state and to a ferromagnetic state, this oxide is a good system for studying the effect of frustration in magnetodielectric coupling. Dielectric constant measurements of single crystals of Ca₃Co₂O₆ have been done showing the sensitivity of this technique to frustration.     

Spin-lattice relaxation in multiple-pulse experiments as contrast parameter in NMR imaging of solids

The molecular motion contrast parameter for NMR imaging of solids and quasi-solids based on the spin-lattice relaxation (T _leff) in multiple-pulse experiments is discussed. For Ostroff-Waugh multiple-pulse sequence theT _leff contrast parameter is evaluated in slow and fast molecular motion regime and compared with spin-lattice relaxation in the rotating frame contrast parameter. It is shown thatT _leff is offering a good molecular motion contrast in NMR imaging of polymer systems. The radio-frequency pulse scheme forT _leff-imaging using magic-echo phase-encoding procedure for recording spatial distribution in solids is introduced. A method forT _leff-weighted imaging using gradient spin-echo valid for weak dipolar solids is also discussed. The one-dimensional protonT _leff image using Ostroff-Waugh pulse sequence in combination with frequency-encoding imaging procedure is presented for a phantom of poly(ethyleneoxide) and poly(methylmethacrylate). The distribution of mechanical stresses in a acrylate film on glass is investigated by protonT _leff-imaging. A proton spin-density image weighted byT _leff, for a mixture of two elastomers with different crosslink density is also shown.     

A New Laser Photochemical Process for Isotope Enrichment

Selective laser excitation of a specific isotopic species to its lowest electronic singlet (S₁) and triplet (T₁) states respectively, then followed by a chemical reaction for isotope separation is examined theoretically. It is found that the direct excitation to T₁ state from ground state (S₀) is an unique excitation channel for obtaining a controllable chemical reaction and for achieving a high isotope separation factor. This is due to the following important facts: 1) Resonant energy transfer from a selectively excited triplet isotopic species to an unexcited species of the other isotope present in the mixture is missing (or is very small); 2) The lifetime of the T₁ state is normally longer than that of the S₁ state; 3) There is no intersystem crossing channel that exists for the deactivation of excited isotopic species from T₁ state.

Numerical calculation is performed for the chlorine isotope separation in a mixture of thiophosgene (0.5 torr) and diethoxyethylene (1.5 torr). The result indicates that the isotopic enrichment factor is at least 2.5 × 10³ times larger for selective T₁ excitation than that for S₁ excitation.     

The kinetics of donor-acceptor pair transitions with strong phonon coupling in GaP

Donor-acceptor pair luminescence in GaP was studied by time-resolved spectroscopy, by measuring and analysing the integral band decay over many decades of intensity and time and by measuring and analysing the temperature dependence of the luminescence intensity. We report here the results obtained with some or all of these techniques for pairs involving deep as well as shallow centres. Those with a deep centre are: S_P-Si_P and Si_Ga-Si_P, in which the acceptor is the deep centre, and O_P-C_P and O_P-Zn_Ga, in which the donor is the deep centre. These pairs all have a broad, phonon-dominated luminescence band. The pairs involving shallow centres include Si_Ga-C_P, S_P-C_P and Te_P-C_P. Due to the different way of momentum conservation in these pairs, those involving a donor on a Ga-site have strong phonon co-operation and weak zero-phonon (ZP) transitions, whereas those with a donor on a P-site have strong ZP transitions.With time-resolved spectroscopy, well-resolved structure, due to a ZP pair band and its phonon replicas, is obtained for nearly all pairs. A comparison is made with the structure obtained by measuring in the stationary state at very low excitation densities. Some trends in the strength of phonon co-operation are noted. In the case of Si_Ga-C_P pairs, sharp replicas of ZP pair lines with a momentum-conserving phonon are also resolved.Using the integral band decay technique and results from time-resolved spectroscopy we have determined the transition probabilities for the total luminescence band as well as for the ZP band for nearly all pairs mentioned. The influence of incomplete saturation of the pairs during excitation with a focussed beam of an argon-ion laser is discussed and approximately corrected for. Extrapolated to zero pair separation, the total transition probability ranges from ∽ 10⁵s^-1 for Si_Ga-C_P pairs to ∽ 15 × 10⁵s^-1 for O_P-C_P and O_P-Zn_Ga pairs. The ZP probability ranges from ∽ 4 × 10³s^-1 for Si_Ga-C_P and Si_Ga-Si_P pairs to ∽ 4 × 10⁵s^-1 for S_P-C_P pairs. The transition probability for pairs in GaP is discussed in relation to the site occupied by the donor and the depth of the centres involved. The relatively high dope concentrations used in some cases, ∽ 1 to 2 × 10¹⁸cm^-3, are discussed briefly in relation to “concentration quenching”.The temperature dependence of the luminescence intensity of S_P-Si_P pairs is satisfactorily analysed with a simple linear model. The same model is applied to similar literature data on the S_P-C_P pair luminescence. Using in addition data on the average pair transition probability, trapping rate constants for hole capture by the Si_P and C_P acceptors were calculated to be ∽ 10^-9 cm³s^-1. Evidence is presented that the trapping rate constant for holes by the Zn_Ga-O_P complex is about 2 × 10^-9 cm³s^-1.     

Inelastic magnetic X-ray scattering from highly correlated electron systems: La1.2Sr1.8Mn2O7, La0.7Sr0.3MnO3 and Fe3O4

Magnetic Compton profiles have been measured for the colossal magnetoresistance manganites La_1.2Sr_1.8Mn₂O₇ and La_0.7Sr_0.3MnO₃, and for magnetite Fe₃O₄, along various crystallographic directions, over a wide range of temperatures and magnetic fields. The experimental results are interpreted via first-principles computations for the double layer manganite, La_1.2Sr_1.8Mn₂O₇, and by using a simple model involving atomic d-orbitals and free electrons for the other two compounds. For all three materials a preference for the occupation of e_g orbitals is found, particularly, for orbitals of dx²−y² symmetry. An itinerant electron contribution is adduced at all temperatures in magnetite; such a contribution also appears in La_1.2Sr_1.8Mn₂O₇, but it is present only at low temperatures in La_0.7Sr_0.3MnO₃.     

Magnetic field effects on synthesis process of high-Tc superconductors

Materials synthesis processes in high magnetic fields are investigated for high-T_c superconductors at the High Field Laboratory for Superconducting Materials, Institute for Materials Research, Tohoku University. On a melt growth process of YBa₂Cu₃O₇ bulk in magnetic fields, it was found that the crystallinity is improved. These results are due to not only the magnetic field orientation but also the decrease of the crystal growth rate by the magnetic field, which is suggested from a differential temperature analysis measurement in magnetic fields. On a chemical vapor deposition process of YBa₂Cu₃O₇ films deposited on the polycrystalline Ag substrates in high magnetic fields, the microstructure changes drastically from the rectangular large grains with 10 μm in size to the small complex shaped grains. The spiral growth mode is observed for the samples prepared at 0 T but it changes into the island growth mode for that prepared in the presence of a magnetic filed. On a partial-melt process of Bi₂Sr₂CaCu₂O₈ tapes in magnetic fields, the homogeneous texture is obtained and it results in the increase of the critical current density.     

Effect of CO2 laser irradiation on the transport properties of La0.67Ba0.33MnO3 thin film

The effect of CO₂ laser irradiation on La_0.67Ba_0.33MnO₃ epitaxial thin film was investigated. Epitaxial thin films grown by pulsed laser deposition were irradiated by a CO₂ laser in air for 10-60 s. It is shown that after CO₂ laser irradiation treatment, the crystallinity of the film is strongly enhanced. It is found that a dramatic decrease in the resistivity of the CO₂-laser-irradiated film is accompanied by a remarkable increase in its insulator-metal transition temperature and the temperature coefficient of resistance. This significant improvement of its structure and properties is achieved in several dozens of seconds and surpasses that observed in films annealed in an oxygen atmosphere at 900 ^°C for 12 h, suggesting that CO₂ laser irradiation is a new and effective tool to optimize CMR manganites for bolometric applications.     

Reactive scattering of alkali dimers K2 + I2, CH2I2, CHI3, CBr4

Angular distribution measurements of KX reactive scattering of a potassium dimer K₂ beam by I₂ and by a series of halomethane molecules are reported. The K₂ + I₂ reactive scattering is similar to that previously observed for K₂ + Br₂. The predominant reaction path yields K + KI + I with the K and KI product recoiling in the forward direction. However, the forward peak of the KI differential cross section is lower than that for K from K₂ + I₂ and is broader than that observed for KBr from K₂ + Br₂. This is attributed to slow dissociation of the I ₂ ^- ion formed in the electron jump mechanism previously proposed for K₂ + Br₂. In the halomethane reactions, both alkali atoms of the K₂ dimer become bound alkali halide molecules in all reactive collisions, despite the direct dynamics of the corresponding supersonic K atom reactions. Thus, these reactions provide compelling evidence for a second electron jump mechanism, previously proposed for the reactions of K₂ dimers with polyhalide molecules. The differential cross sections for the K₂ dimer plus halomethane reactions indicate an osculating collision complex with a lifetime at least comparable to its rotational period, perhaps much longer. This reaction complex is identified with the doubly ionic state formed by the second electron jump transition.     

Optical study of a pulsed molecular beam

By using absorption spectra in a pulsed molecular beam, the rotational temperature and the flow density of the jet are deduced. By using this technique, a comparison between a pulsed and a continuous beam is also reported for NH₃, CF₂Cl₂, and C₂H₃Cl molecular beams. Moreover, the behaviour of the temperature and density inside the pulsed beam is analyzed as a function of time for pure Ammonia. From these measurements, we deduce that a small improvement is obtained for absorption spectroscopy in the jet by using a pulsed molecular beam.     

Prediction of Γ-L and L-X crossovers in Ga<Subscript>x</Subscript>Al<Subscript>1-x</Subscript>Sb alloys by empirical pseudopotential method

Using empirical pseudopotential method Γ-L crossover is found for the Ga_0.74Al_0.26Sb. The conduction band minimum is observed to switch at the (0.87, 0, 0) point for Ga_0.51Al_0.49Sb which shifts to the X point for Ga_0.21Al_0.79Sb and remains at X leading finally to indirect band gap in AlSb. Band structure calculations for a large number of alloys are performed and bowing parameters b_X and b_L are proposed for the E_X and E_L respectively. Our findings may serve as directive to select the materials in a range of composition to examine the bowing parameters and thereby effective mass experimentally for the Ga_xAl_1-xSb alloys.     

Carbon dioxide concentration and temperature in flames by raman spectroscopy

The interpretation and prediction of high temperature Raman spectra for CO₂ in flames requires a more detailed treatment of the upper vibrational states than is required for room-temperature spectra. A method for calculating these upper state contributions is presented and is used to evaluate the results of a series of experiments. Laser Raman CO₂ spectra have been obtained for CH₄-air, CO₂ seeded CH₄-air, and CO-air flames. The results indicate that both the high and low temperature CO₂ spectra agree with the theoretical predictions. Comparison of the CO₂ temperature to the N₂ temperature, both measured at the same position in the flames, indicates a better prediction of temperature from the N₂ spectrum than from the CO₂ spectrum. Accurate values for the CO₂ concentrations, however, can be determined from a comparison of the CO₂ spectrum with the N₂ spectrum.     

Comparative study of linear entropy and negativity in molecular vibrations

The dynamical comparison of entanglement, measured by linear entropy and negativity, is carried out for initial pure separable states in vibrations of H₂O and SO₂. It is shown that both measures of an initial state with local-mode character have the same period for H₂O, while those of an initial state with normal-mode character are no longer identical in period. When the total quantum number of the initial state is one, both measures rise and lower together with the period for H₂O being larger than that for SO₂. For a suitable state in H₂O, both measures exhibit a beat phenomenon with a long period.     

Effects of oblique-incidence evaporation on magnetic properties of Fe20Ni80/Fe70Co30 bilayer film

Evaporative deposition at oblique incidence is shown to enhance the magnetic anisotropy of an Fe₂₀Ni₈₀ magnetic film and induce magnetic anisotropy in an overlying, strongly isotropic Fe₇₀Co₃₀ film. This deposition method for the formation of an underlayer of several lattice parameters in thickness and semi-hard overlayer of a few thousands Angstroms in thickness achieves a significant change in the magnetization process and strong suppression of the coercive forces of Fe₇₀Co₃₀ in the hard magnetization direction. Soft magnetization of the Fe₇₀Co₃₀ overlayer is not achieved when one of the layers is deposited at oblique incidence. It is anticipated that shape magnetic anisotropy is responsible in part for the magnetic anisotropy induced in both in Fe₂₀Ni₈₀ under- and Fe₇₀Co₃₀ overlayer by oblique incidence evaporation.     

Hydrostatic pressure effect on the metal-insulator transition in LaO0.7Ca0.3Mn1−x(Fe/Ge)xO3 perovskites

Abstract

The temperature dependences of the resistivity of La_0.7Ca_0.3Mn_1?xFe_xO₃ and La_0.7Ca_0.3Mn_1?xFe_xO₃ (0 < × < 0.04) mixed crystals were studied under hydrostatic pressures up to 15kbar. The substitution of Fe for Mn results in an increase of the resistivity and a continuous decrease of the metal-insulator transition temperature T_mi while the substitution of Ge for Mn leads to a more complicated T_mi(x)-curve. In all cases T_mi shifts under pressure with a rate between 1.6 and 2.9K/kbar and a correlation between T_mi and its pressure derivative dT_mi/dP is observed which is in accordance with the general trend of dT_mi/dP versus T_mi as derived for other manganites and is discussed in terns of a competition between superexchange and double exchange.     

Crystal face specificity of nitrogen adsorption on a platium field emission tip

The adsorption of nitrogen on platinum is studied with a field emission microscope equipped with a probe-hole assembly to enable quantitative emission measurements on individual crystal faces. The results are implemented by photoelectric measurements on platinum films. Adsorption at 80 K is found to result in a large and face-specific decrease in the work function. On crystal planes containing B₅ and B₆ sites this decrease is larger than on those exposing B₃ and B₄ sites only. No significant crystal face specificity is found, however, for the rate of temperature programmed desorption of nitrogen. It follows that the heat of nitrogen adsorption is essentially equal for faces with B₃, B₄, B₅ and B₆ sites. This result is at variance with certain postulates in the literature.     

Composition-dependent melting behaviour of NaxK55–x core–shell nanoalloys

Molecular dynamics simulations at constant temperature are performed to investigate melting-like transition in Na₁₃K₄₂, Na₁₉K₃₆ and Na₂₆K₂₉ nanoalloys using a second-moment-approximation tight-binding analytic potential to calculate the forces on the constituent atoms. A weighted histogram analysis method is employed to remove non-ergodicity issues due to the complex potential energy surface of these nanoalloys. The heat capacity shows three distinctive steps in melting for Na₁₃K₄₂, while Na₂₆K₂₉ and Na₁₉K₃₆ have two-step and one-step melting transition, respectively. The steepest descent method is used to quench the configurations in a given interval during the simulation and also study the isomerisation processes occurring at different temperatures. Analysing the configuration energies of quenched structures for the entire nanoalloy and the core atoms separately gives more details about the melting mechanism. The Lindemann parameter is also calculated at several temperatures during the simulation which shows a gradual increase for Na₁₃K₄₂ and Na₂₆K₂₉ while a sharp change is observed for Na₁₉K₃₆. These findings are in agreement with the multi-step nature of the phase transition in Na₁₃K₄₂ and Na₂₆K₂₉ and one-step melting of the Na₁₉K₃₆ magic composition.     

On the theory of superconductivity in Kondo lattice systems

An attempt is made to explain the occurrence of superconductivity in Kondo lattice systems with special reference to CeCu₂Si₂. Starting point is the Fermi liquid approach. It is generalized from a Kondo impurity to the Kondo lattice by means of the Korringa-Kohn-Rostocker method. From it a hybridization model is derived and discussed in detail. Two electron-phonon mechanisms are investigated which appear in Kondo lattices. One results from the additional phase shifts caused by the Kondo ions while the other is responsible for the so-called Kondo volume collapse. It is shown that the latter is sufficiently strong in order to explain why CeCu₂Si₂ is a superconductor while LaCu₂Si₂ is not. An estimate for the superconducting transition temperatureT _c produces the right order of magnitude.