Oxygen ionic conductivity of La2NiO4+δ via interstitial oxygen defect

The ionic conduction properties of La₂NiO_4+δ were studied from oxygen permeation flux and defect-related transport properties. The effects of the applied oxygen chemical potential gradient and temperature on the oxygen permeability of La₂NiO_4+δ at various thickness are reported. The thermally activated oxygen permeation flux increased monotonically with increasing oxygen chemical potential gradient, yielding a maximum of 0.15 cc min^?1 cm^?2 under air/N₂ conditions for the 0.95 mm-thick La₂NiO_4+δ specimen at 900 °C. The oxygen ion conductivity of La₂NiO_4+δ was calculated as a function of temperature and oxygen partial pressure by differentiating the chemical diffusion equation for the oxygen permeation flux based on the dominant electronic transference number. In addition, the oxygen ion conductivity was extracted successfully by solving the Nernst–Einstein equation combining with the calculated self-diffusion coefficient of oxygen from the chemical diffusivity and thermodynamic enhancement factor from the equilibrium oxygen nonstoichoimetry of a La₂NiO_4+δ specimen, and a deviation of the OPP dependence of 1/6 power was observed.     

Collision induced absorption spectra of the fundamental band of D2 in binary mixtures D2-Kr at 298 K

The enhancement spectrum of the collision induced absorption of D₂ in its fundamental band region 2600-4000 cm⁻¹ in binary mixtures D₂-Kr was studied at 298 K for base densities of D₂ in the range 9-20 amagat and for partial densities of Kr in the range 7-120 amagat. The binary absorption coefficient of the band has been determined from the measured integrated absorption coefficient and found to be 3.9 × 10⁻³ cm⁻² amagat⁻². An analysis of the experimental spectrum was carried out by assuming appropriate line-shape functions and the half-width parameters δ₁, δ₂, δ_d and δ_c of the long range quadrupole, and of the short range overlap induced transitions have been determined. Good agreement was obtained between the recorded spectrum of the fundamental band and the synthetic profile.     

Multipole mixing ratios of transitions in Te

Gamma-gamma directional correlation measurements were made on nine transitions in ¹²⁴Te with a NaI(Tl)-Ge(Li) detector arrangement and multichannel analysis. The multipole mixing ratios obtained were δ(646) = 0.000±0.001, δ(714) = 1.5_−0.3^+0.6, δ(723) = −3.3±0.2, δ(1437) = 3.7_−2.0^+2.7, δ(1489) = −3.4_−1.5^+0.9, δ(968) = −0.03_−0.05^+0.06, δ(1368) = −0.045±0.090, δ(1045) = 0.041_−0.041^+0.047, δ(1691) = −0.02±0.01, and δ(2091) = 0.00_−0.03^+0.02. The first δ is M3/E2, the next three are E2/M1, and the last five are M2/E1. The retardation (a factor of approximately 50) of the crossover to cascade transitions from the 2039 keV, third 2⁺ level to the second and first 2⁺ levels is essentially the same for both the M1 and E2 components. In addition, spin and parity assignments of 2⁺ were made for the 2039 and 2092 keV levels.     

Investigation of electrical properties of organic 4-tricyanovinyl-N,N-diethylaniline thin film

Thin films of 4-tricyanovinyl-N,N-diethylaniline (TCVA) with different thickness were prepared using thermal evaporation technique. A relative permittivity, ?_r, of 3.04 was estimated from the dependence of capacitance on film thickness. The current density-voltage (J-V) characteristics of TCVA thin films have been investigated at different temperatures. At low-voltage region, the current conduction in the Au/TCVA/Au sandwich structures obeys Ohm's law. At the higher-voltage regions, the charge transport phenomenon appears to be space-charge-limited current (SCLC) dominated by an exponential distribution of traps with total trap concentration of 1.21 × 10²² m⁻³. In addition, various electrical parameters were determined.     

Electrical conductivity of 4-tricyanovinyl-N,N-diethylaniline

Physical characterizations of 4-tricyanovinyl-N,N-diethylaniline, TCVA, have been reported. The differential scanning calorimetry measurements of TCVA showed that this compound is stable up to 423 K. The temperature dependence of electrical conductivity, in the temperature range from 298 to 403 K, was studied on pellet samples of TCVA with evaporated ohmic Au electrodes. The electrical conductivity was found to be 7.01×10⁻⁹ Ω⁻¹ cm⁻¹ at room temperature. The temperature dependence of the electrical conductivity is typical for semiconducting compounds. The current density-voltage (J-V) characteristics of TCVA pellet samples have been investigated at different temperatures. In low-voltage region, the conduction current obeys Ohm's law while the charge transport phenomenon appears to be space-charge-limited current in the higher voltage regions.     

Critical anomaly and finite size scaling of the self-diffusion coefficient for Lennardben Jones fluids by non-equilibrium molecular dynamic simulation

We use non-equilibrium molecular dynamics simulations to calculate the self-diffusion coefficient, D, of a Lennard-Jones fluid over a wide density and temperature range. The change in self-diffusion coefficient with temperature decreases by increasing density. For density ρ^* = ρσ³ = 0.84 we observe a peak at the value of the self-diffusion coefficient and the critical temperature T^* = kT/ε = 1.25. The value of the self-diffusion coefficient strongly depends on system size. The data of the self-diffusion coefficient are fitted to a simple analytic relation based on hydrodynamic arguments. This correction scales as N^-α, where α is an adjustable parameter and N is the number of particles. It is observed that the values of α < 1 provide quite a good correction to the simulation data. The system size dependence is very strong for lower densities, but it is not as strong for higher densities. The self-diffusion coefficient calculated with non-equilibrium molecular dynamic simulations at different temperatures and densities is in good agreement with other calculations from the literature.     

Oxygen nonstoichiometry, thermo-chemical stability and lattice expansion of La0.6Sr0.4FeO3 − δ

The oxygen nonstoichiometry of La_0.6Sr_0.4FeO_3 − δ was measured at intermediate temperatures (773 to 1173 K) between 1 bar and the decomposition oxygen partial pressure by thermogravimetry and coulometric titration. The decomposition of the ABO₃ perovskite phase was found to occur at low oxygen partial pressures (below 10^− 20 bar). Using an atmosphere-controlled high-temperature XRD setup, the rhombohedral lattice parameters were obtained between 10^− 4 and 1 bar at 773 to 1173 K. A phase transition from rhombohedral to cubic might be expected to occur at high temperatures and for δ near the plateau at δ = [Sr] / 2. The lattice expansion was separated into “pure” thermal and chemically induced expansion by combining the lattice parameters with the oxygen nonstoichiometry data. The linear thermal expansion was formulated with a “pure” thermal expansion coefficient of α_th = 11.052 · 10^− 6 K^− 1 and a chemical expansion coefficient of α_chem = 1.994 · 10^− 2.The results were compared with previous data obtained for La_0.6Sr_0.4Co_1 − yFe_yO_3 − δ with y = 0.2-0.8. La_0.6Sr_0.4FeO_3 − δ was confirmed to show the highest thermo-chemical stability. While the chemical expansion of La_0.6Sr_0.4Co_1 − yFe_yO_3 − δ seems little affected by the iron content, the thermal expansion coefficient was the lowest for La_0.6Sr_0.4FeO_3 − δ.     

Computational and experimental study of the cluster size distribution in MAPLE

A combined experimental and computational study is performed to investigate the origin and characteristics of the surface features observed in SEM images of thin polymer films deposited in matrix-assisted pulsed laser evaporation (MAPLE). Analysis of high-resolution SEM images of surface morphologies of the films deposited at different fluences reveals that the mass distributions of the surface features can be well described by a power-law, Y(N) ∝ N^−t, with exponent −t ≈ −1.6. Molecular dynamic simulations of the MAPLE process predict a similar size distribution for large clusters observed in the ablation plume. A weak dependence of the cluster size distributions on fluence and target composition suggests that the power-law cluster size distribution may be a general characteristic of the ablation plume generated as a result of an explosive decomposition of a target region overheated above the limit of its thermodynamic stability. Based on the simulation results, we suggest that the ejection of large matrix-polymer clusters, followed by evaporation of the volatile matrix, is responsible for the formation of the surface features observed in the polymer films deposited in MAPLE experiments.     

The decomposition pressure,congruent melting point and electrical resistivity of cerium nitride

The melting point of CeN in nitrogen was determined at pressures between 10⁻² and 21 atmospheres. Congruent melting was observed at T = 2575 ± 20°C and P = 5 ± 1 atmospheres. With lower nitrogen pressures, the melting point was related to the applied (or decomposition) pressure by the equation log P_atmos(N₂) = 18·5 − 5·1 × 10⁴/T. The electrical resistivities of samples prepared from these melts were measured at temperatures between 150–900°K. The room temperature resistivity of congruently melted samples was 21 μΩ-cm, which may be compared with the value of 75 μΩ-cm for cerium metal at this temperature. These samples had a positive (metallic) temperature dependence of resistivity of 0·11 μΩ-cm/°C at room temperature and increased with temperature to a value of 0·22 μΩ-cm/°C at a temperature of 700°K. The noncongruently melted samples had a similar behavior, but with somewhat higher values of resistivity. The room temperature Seebeck coefficients for both types of samples were approximately + 5 μV/°C, relative to platinum.     

H and K spin-lattice relaxation, ionic motion and Raman processes in the proton conducting KHSeO4 single crystal

The spin-lattice relaxation rates of ¹H and ³⁹K nuclei in KHSeO₄ crystals were studied in the temperature range 160-400 K. The spin-lattice relaxation recovery of ¹H nucleus in this crystal can be represented with a single exponential function, and the relaxation T₁⁻¹ curve of ¹H can be represented with the Bloembergen-Purcell-Pound (BPP) function. The relaxation process of ³⁹K with dominant quadrupole relaxation can be described by a linear combination of two exponential functions. T₁⁻¹ for the ³⁹K nucleus was found to have a very strong temperature dependence, T₁⁻¹=βT⁷. Rapid variations in relaxation rates are associated with critical fluctuations in the electronic spin system. The T⁷ temperature dependence of the Raman relaxation rate is shown here to be due to phonon-magnon coupling.     

Asymptotics of unit Burger number rotating and stratified flows for small aspect ratio

Rotating and stably stratified Boussinesq flow is investigated for Burger number unity in domain aspect ratio (height/horizontal length) δ<1 and δ=1. To achieve Burger number unity, the non-dimensional rotation and stratification frequencies (Rossby and Froude numbers, respectively) are both set equal to a second small parameter ?<1. Non-dimensionalization of potential vorticity distinguishes contributions proportional to (?δ)⁻¹, δ⁻¹ and O(1). The (?δ)⁻¹ terms are the linear terms associated with the pseudo-potential vorticity of the quasi-geostrophic limit. For fixed δ=1/4 and a series of decreasing ?, numerical simulations are used to assess the importance of the δ⁻¹ contribution of potential vorticity to the potential enstrophy. The change in the energy spectral scalings is studied as ? is decreased. For intermediate values of ?, as the flow transitions to the (δ?)⁻¹ regime in potential vorticity, both the wave and vortical components of the energy spectrum undergo changes in their scaling behavior. For sufficiently small ?, the (δ?)⁻¹ contributions dominate the potential vorticity, and the vortical mode spectrum recovers k⁻³ quasi-geostrophic scaling. However, the wave mode spectrum shows scaling that is very different from the well-known k⁻¹ scaling observed for the same asymptotics at δ=1. Visualization of the wave component of the horizontal velocity at δ=1/4 reveals a tendency toward a layered structure while there is no evidence of layering in the δ=1 case. The investigation makes progress toward quantifying the effects of aspect ratio δ on the ?→0 asymptotics for the wave component of unit Burger number flows. At the lowest value of ?=0.002, it is shown that the horizontal kinetic energy spectral scalings are consistent with phenomenology that explains how linear potential vorticity constrains energy in the limit ?→0 for fixed δ.     

Interatomic potentials for the ground state X 0 and the two excited states 1, 0 of the intercombination cadmium line 326.1 nm broadened by Kr pressure

The temperature dependence of the Cd line absorption profile at 326.1 nm perturbed by Kr has been carefully studied over a spectral range extending from 800 cm⁻¹ in the blue wing to 1200 cm⁻¹ in the red wing using a high-resolution double-beam spectrometer. The atomic densities of krypton (N_Kr) and cadmium (N_Cd) were (2.015±0.07)×10¹⁹ and (3.62±0.05)×10¹⁸ cm⁻³, respectively. The temperature dependence of the studied line profile was analyzed in the framework of the quasi-static theory. The van der Waals coefficient differences between the ground ¹0⁺ state and the two excited states ³0⁺ and ³1 (ΔC₆⁰ and ΔC₆¹) were obtained from the near red wing profile using Kuhn's law. The values of ΔC₆⁰ and ΔC₆¹ are found to be equal to 37.8±2 and 58.5±3 eV Å⁶, respectively. The ground (X ¹0⁺), and the excited (³1, ³0⁺) state potentials at the internuclear separations from 3.2 to 6.3 Å were determined. The well depths with their positions for these states are respectively equal to 134±7 cm⁻¹, 3.95±0.2 Å; 72.3±4 cm⁻¹, 4.95±0.3 Å; and 471±12 cm⁻¹, 3.6 Å. The obtained well depths with their allowable errors are in good agreement with the values obtained before for the Cd-Kr system from some theoretical results and molecular beams experiments.     

Investigation on the electric properties in molten quaternary systems by MD simulation

For the pyrochemical reprocessing of spent metallic fuels in molten salt, it is of importance to estimate the enrichment degree of Cs. The molecular dynamics simulation has been carried out on molten quaternary systems (Li, Na, K, Cs)Cl at 625K and (Li, Na, K, Cs)F at 727K for the various compositions in order to investigate the electric properties, i.e., the electric conductivity, self-diffusion coefficient, self-exchange velocity and the relative differences in the internal cation mobilities of Cs in molten LiCl-NaCl-KCl eutectic mixtures and in the FLINAK melts. These results allow us to conclude that the electric conductivities, self-diffusion coefficients and self-exchange velocities of Li⁺, Na⁺, K⁺ and Cs⁺ with reference to Cl⁻ and F⁻ have almost similar tendencies for each composition. We found it possible to enrich at up to χ_Cs = 0.38 in molten LiCl-NaCl-KCl eutectic as well as LiCl-KCl system and up to χ_Cs = 0.42 in the FLINAK melts as well as in molten FLINA system. In addition, the sequence of the simulated electric conductivity in molten quaternary alkali chloride and fluoride systems was in a fair agreement with that of the current simulated self-exchange velocities and self-diffusion coefficients.     

Functional self-similarity,scaling and a renormalization group calculation of the partition function for a non-ideal chain

The hypothesis of asymptotic self-similarity for nonideal polymer chains is used to derive the functional and differential equations of a new renormalization group. These equations are used to calculate the partition functions of randomly jointed chains with hard-sphere excluded-volume interactions. Theoretical predictions are compared with Monte Carlo calculations based on the same microscopic chain model. The excess partition function converges very slowly to its true asymptotic form δQ(N→∞)∼κ^N−1. The conventional asymptotic formula, δQ(N→∞)∼κ^N−1N^γ−1, is found to be applicable for chains of moderate length and for excluded-volume interactions appropriate to the subclass of flexible self-avoiding chains.     

Novel Ba-Sc-Si-oxide and oxynitride phosphors for white LED

Alkaline earth silicates, which comprise a host material doped with rare-earth minerals, show excellent luminescence properties with various crystal structures and high stability. From results of this study, we report luminescence properties of Ba₉Sc₂Si₆O₂₄:Eu²⁺ and Ba₉Sc_2+δSi₆O_24−3δN_3δ:Eu²⁺ as a novel alkaline earth silicate and silicon oxynitride phosphors for white LEDs. Using a conventional solid-state reaction, Ba₉Sc₂Si₆O₂₄:Eu²⁺ samples were synthesized and Ba₉Sc_2+δSi₆O_24−3δN_3δ:Eu²⁺ samples were obtained by nitrization of Ba₉Sc_2+δSi₆O₂₄:Eu²⁺. The samples can be excited by blue light, exhibiting green (Ba₉Sc₂Si₆O₂₄:Eu²⁺) and yellow (Ba₉Sc_2+δSi₆O_24−3δN_3δ:Eu²⁺) efficiently, which are emissions for use in white LEDs essentially.     

Temperature behavior of the Kohlrausch exponent for a series of vinylic polymers modelled by an all-atomistic approach

The Kohlrausch-Williams-Watt (KWW) function, or stretched exponential function, is usually employed to reveal the time dependence of the polymer backbone relaxation process, the so-called α relaxation, at different temperatures. In order to gain insight into polymer dynamics at temperatures higher than the glass transition temperature T _g , the behavior of the Kohlrausch exponent, which is a component of the KWW function, is studied for a series of vinylic polymers, using an all-atomistic simulation approach. Our data show very good agreement with published experimental results and can be described by existing phenomenological models. The Kohlrausch exponent exhibits a linear dependence with temperature until it reaches a constant value of 0.44, at 1.26T _g , revealing the existence of two regimes. These results suggest that, as the temperature increases, the dynamics progressively change until it reaches a plateau. The non-exponential character then describes subdiffusive motion characteristic of polymer melts.     

The transverse spin-1 Ising model with random interactions

The phase diagrams of the transverse spin-1 Ising model with random interactions are investigated using a new technique in the effective field theory that employs a probability distribution within the framework of the single-site cluster theory based on the use of exact Ising spin identities. A model is adopted in which the nearest-neighbor exchange couplings are independent random variables distributed according to the law P(J_ij)=pδ(J_ij−J)+(1−p)δ(J_ij−αJ). General formulae, applicable to lattices with coordination number N, are given. Numerical results are presented for a simple cubic lattice. The possible reentrant phenomenon displayed by the system due to the competitive effects between exchange interactions occurs for the appropriate range of the parameter α.     

Chemomechanical properties and microstructural stability of nanocrystalline Pr-doped ceria: An in situ X-ray diffraction investigation

The chemomechanical properties and microstructural stability of nanocrystalline Pr_xCe_1 − xO_2 − δ solid solutions are studied as a function of temperature by in situ X-ray diffraction measurements under oxidizing conditions at P(O₂) ~ 200 mbar. The chemical expansion coefficient of nanocrystalline powder specimens, operative at intermediate temperatures during which Pr⁴⁺ is reduced to Pr³⁺, is found to be similar to that obtained for coarse-grained Pr_xCe_1 − xO_2 − δ. This is contrary to reports regarding variation of physical and chemical properties with crystallite size. The thermal expansion coefficient, measured under conditions for which Pr_xCe_1 − xO_2 − δ is highly oxygen deficient, was found to be greater than that measured for fully oxidized Pr_xCe_1 − xO_2 − δ, with potential sources of these changes discussed. Moreover, the microstructure of nanocrystalline Pr_xCe_1 − xO_2 − δ is observed to have excellent stability at working temperatures below 800 °C, enabled by the inherent microstrain in the structure, highlighting the potential application of this material for solid state electrochemical devices.     

Defect structure and oxide ion transport in Sr- and Cr-doped LaCoO3 − δ

The results of oxygen nonstoichiometry, δ, measured by means of coulometric technique as a function of oxygen partial pressure, p_o2, in temperature range 1223 ≤ T, K ≤ 1323 are presented for the perovskite-type doped with chromium solely LaCo_0.7Cr_0.3O_3 − δ and simultaneously doped both with strontium and chromium La_0.7Sr_0.3Co_0.7Cr_0.3O_3 − δ cobaltites. The limit stability of the latter was found to exceed that of undoped cobaltite LaCoO_3 − δ on six orders of magnitude of p_o2 at a given temperature. The modeling of the defect structure of these perovskites was carried out and its adequate model was found. Chemical and self-diffusion coefficients of oxygen vacancies and oxygen ionic conductivity and ionic transport numbers were measured for the first time for La_0.7Sr_0.3Co_0.7Cr_0.3O_3 − δ as a function of oxygen partial pressure p_o2and temperature in the ranges − 4 ≤ log(p_o2, atm) ≤ 0 and 1223 ≤ T, K ≤ 1323, respectively. The additional substitution of Sr for La in LaCo_0.7Cr_0.3O_3 − δ was shown to lead to noticeable increase of ionic conductivity and oxygen chemical diffusion coefficient at given values of oxygen partial pressure and temperature as compared to lanthanum cobaltite doped with chromium solely. Self-diffusion coefficient of oxygen vacancies and their mobility in La_0.7Sr_0.3Co_0.7Cr_0.3O_3 − δ were found to be dependent on oxygen partial pressure and nonstoichiometry unlike undoped and doped with chromium lanthanum cobaltites.     

Mean work functions effective for negative-ionic, electronic and positive-ionic emissions from polycrystalline surfaces

To elucidate the thermionic property of polycrystalline surfaces, a further study is made on the mean work functions (φ⁻, φ^e and φ⁺) effective for negative-ionic, electronic and positive-ionic emissions. Comparison between theoretical analyses and experimental data yields the conclusions as follows. (1) The equation of φ⁻ = φ^e holds always with both mono- and polycrystalline surfaces. (2) The relation of φ⁻ = φ^e < φ⁺ applies to polycrystalline surfaces because they bear the thermionic contrast (Δφ^* ≡ φ⁺ − φ^e > 0). (3) The value of Δφ^* ranges from ∼0.4 to 0.9 eV depending upon the surface species of polycrystalline metals (e.g., W, Re and Pt), whilst Δφ^* = 0 for monocrystalline surfaces. (4) When the degree of monocrystallization (δ_m) is less than ∼50%, the theoretical value of Δφ^* is virtually independent of δ_m and agrees well with experimental data, nearly the same within ±0.1 eV among the so-called “polycrystalline” surfaces of W. (5) As δ_m increases beyond ∼80 up to 100%, Δφ^* decreases rapidly down to 0 eV, showing again a good agreement between theory and experiment. (6) Our theoretical model is valid in evaluating the effective mean work functions, irrespective of the range of δ_m.