Ion conduction in proton- and related defect (super) ionic conductors: Mechanical,electronic and structure parameters

We find the relationships among optical dielectric constant ε_∞, activation energy E_ac, averaged atomic mass per a formula unit, ∑_jm_j / N, volume V and transition temperature T_c for various type ion conductors with forms of E_ac = α / (ε_∞ ? β), E_ac = A₀ + δ / [(∑_jm_j / N) ? d], E_ac = A_v / V^2/3, and ln(T_c) = g ? hln(∑_jm_j), where α, β, δ, A₀, d, A_v, g and h are constants depending on the kinds of conduction elements. We derive those proportional forms from a simple equation of motion under the assumption of ion hopping assisted by enhanced vibration displacement of host lattice. The enhancement is induced from the large fourth-order term of the host lattice potential originating from the electronic shielding effect of Coulomb force, heavy atomic mass of constituent ion, and volume expansion under the long-range periodicity of crystal structure. This mechanism is ascertained from characteristic phenomena of various kinds of conduction elements. For impurity-type H⁺-ion or defect conductor, the proportional form is shifted from that of superionic conductor because of weakened effect of host lattice vibration mode on H⁺-ion or O-ion defect. Photo-induced spectra of mobile ion in AgCl are understood, and a small quantum effect of H⁺ -ion is suggested.     

Interaction of dioxouranium(VI) ion with EDTA at different ionic strengths

The formation of complex species of dioxouranium(VI) ion with EDTA was studied in the pH range of 1–3.5 and at 25 °C using a combination of potentiometric and spectrophotometric techniques. Results showed evidence for formation of the following species: [UO₂H₄EDTA]²⁺, [UO₂H₃EDTA]⁺, and [UO₂H₂EDTA]. Investigations were performed in sodium perchlorate as background electrolyte at 0.1, 0.3, 0.5, 0.7, and 1.0 mol dm^? 3. The parameters based on the formation constants were calculated, and the dependences of protonation and the stability constants on ionic strength are described. The dependence on ionic strength of the formation constants was analyzed using the specific ion interaction theory (SIT) model. The stability constant values at infinite dilution, obtained using SIT model, are log β°₁₄₁ = 6.77, log β°₁₃₁ = 5.99 and log β°₁₂₁ = 9.29, where indexes for the overall stability constant, β_pqr, refer to the equilibrium pUO₂²⁺ + qH⁺ + rL^4? ? M_pH_qL_r^{(2p + q ? 4r)}. The specific interaction coefficients are also reported.     

The experimental study of Ba 6pjnk |M| = 0, 1 autoionizing series

The spectra of the Ba 6pnk autoionizing Stark states with |M| = 0, 1, converging to the 6p_1/2⁺ and 6p_3/2⁺ ionization thresholds, are measured as a function of the electric field strength F. Several 6p_jnk Stark manifolds with n = 13–15 have been systematically studied in order to explore their characteristics of configuration interaction. Experimental results are analyzed by fitting them to the Lorentzian profile, from which the positions and widths are determined. Different spectroscopic properties between the Ba 6p_1/2nk and 6p_3/2nk autoionizing Stark states are investigated. Comparison between the Ba 6p_jnk autoionizing Stark states with |M| = 0 and those with |M| = 1 are made.     

Diffusion-promoted-desorption mechanism for D2 desorption from Si(100) surfaces

Temperature-programmed-desorption (TPD) spectra and isothermal desorption rates of D₂ molecules from a Si(100) surface have been calculated to reproduce experimental β_1, A-TPD spectra and isothermal desorption rate curves. In the diffusion-promoted-desorption (DPD) mechanism, hydrogen desorption from the Si(100) (2 × 1) surfaces takes place via D atom diffusion from doubly-occupied Si dimers (DODs) to their adjacent unoccupied Si dimers (UODs). Taking a clustering interaction among DODs into consideration, coverages θ_DU of desorption sites consisting of a pair of a DOD and UOD are evaluated by a Monte Carlo (MC) method. The TPD spectra for the β_1, A peak are obtained by numerically integrating the desorption rate equation R = ν_A exp(? E_d, A / k_BT)θ_DU, where ν_A is the pre-exponential factor and E_d, A is the desorption barrier. The TPD spectra calculated for E_d, A = 1. 6 eV and ν_A = 2.7 × 10⁹ /s are found to be in good agreement with the experimental TPD data for a wide coverage range from 0.01 to 0.74 ML. Namely, the deviation from first-order kinetics observed in the coverage dependent TPD spectra as well as in the isothermal desorption rate curves can be reproduced by the model simulations. This success in reproducing both the experimental TPD data and the very low desorption barrier validates the proposed DPD mechanism.     

Effect of Li-substitution on piezoelectric and ferroelectric properties of (Bi0.92Na0.92−xLix)0.5Ba0.06Sr0.02TiO3 lead-free ceramics

New lead-free ceramics (Bi_0.92Na_0.92−xLi_x)_0.5Ba_0.06Sr_0.02TiO₃ have been fabricated by a conventional ceramic technique and their electrical properties have been studied. X-ray diffraction studies reveal that Li⁺, Ba²⁺ and Sr²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure. The partial substitution of Li⁺ for Na⁺ increases the remanent polarization P_r of the ceramics. Because of the large P_r and low coercive field E_c, the ceramics with x = 0.075–0.125 exhibit excellent piezoelectric properties: d₃₃ = 189–235 pC/N, k_p = 33.6–36.3% and k_t = 51.6–54.3%. The ceramics exhibit relaxor behaviors after the substitution of Li⁺ for Na⁺. Our results also suggest that polar and non-polar phases may coexist in the ceramics at temperatures above the depolarization temperature T_d.     

Fabrication of type-II InAs/GaSb superlattice long-wavelength infrared focal plane arrays

In this paper, we present an InAs/GaSb type-II superlattice (SL) with the M-structure for the fabrication of a long-wavelength (10 μm range) infrared (LWIR) focal plane arrays (FPA), which are grown by molecular beam epitaxy (MBE). The M-structure is named for the shape of the band alignment while the AlSb layer is inserted into the GaSb layer of InAs/GaSb SL. A 320 × 256 LWIR FPA has been fabricated with low surface leakage and high R₀A product of FPA pixels by using anodic sulfide and SiO₂ physical passivation. Experiment results show that the devices passivated with anodic sulfide obviously have higher R₀A than the un-sulphurized one. The 50% cutoff wavelength of the LWIR FPA is 9.1 μm, and the R₀A is 224 Ω cm² with the average detectivity of 2.3 × 10¹⁰ cm Hz^1/2 W⁻¹.     

A new method for estimating the critical current density of a superconductor from its hysteresis loop

The critical current density J_c of some of the superconducting samples, calculated on the basis of the Bean’s model, shows negative curvature for low magnetic field with a downward bending near H = 0. To avoid this problem Kim’s expression of the critical current density, J_c = k/(H₀ + H), where J_c has positive curvature for all H, has been employed by connecting the positive constants k and H₀ with the features of the hysteresis loop of a superconductor. A relation between the full penetration field H_p and the magnetic field H_min, at which the magnetization is minimum, is obtained from the Kim’s theory. Taking the value of J_c at H = H_p according to the actual loop width, as in the Bean’s theory, and at H = 0 according to an enhanced loop width due to the local internal field, values of k and H₀ are obtained in terms of the magnetization values M⁺(?H_min), M^?(H_min), M⁺(H_p) and M^?(H_p). The resulting method of estimating J_c from the hysteresis loop turns out to be as simple as the Bean’s method.     

Low-temperature investigations of the open-framework material HfMgMo3O12

The A₂Mo₃O₁₂ family, where A³⁺ is a large trivalent cation, can show interesting thermal properties such as negative thermal expansion. One member of this family, HfMgMo₃O₁₂, where the two A³⁺ cations have been replaced by Hf⁴⁺ and Mg²⁺, has been shown to have a low positive coefficient of thermal expansion above room temperature. This property makes HfMgMo₃O₁₂ an attractive candidate as a component for solid solutions with near-zero thermal expansion. However, its properties below room temperature were unexplored. In this work we report the phase transition from orthorhombic Pnma to monoclinic P2₁/a at T～175 K with an enthalpy change of 0.27 kJ mol^?1. Relaxation calorimetry, from 5 K to 300 K, show only the small anomaly associated with this transition. The thermal conductivity, determined from 2 K to 300 K, was low, but not as low as some other materials exhibiting negative thermal expansion. Analysis of the low-temperature heat capacity indicates the presence of low-energy phonon modes in HfMgMo₃O₁₂, consistent with the low thermal conductivity. The upper bound of the Young's modulus, estimated from the effective Debye temperature derived from the low-temperature heat capacity, is 20 GPa, a relatively low value due to the flexibility of the framework structure.     

Investigation of carrier scattering mechanisms in n-Cd1−xMgxSe single crystals using Fourier Transform Infrared Spectroscopy

This paper presents results of investigations of carrier scattering mechanisms in n-Cd_1−xMg_xSe mixed crystals with magnesium content varying from x = 0 to x = 0.33. Experimental results obtained by means of the Fourier Transform Infrared Spectroscopy (FT-IR) and Hall measurements are discussed in the frame of the Drude and the quantum theories. The character of the wavelength dependence of the optical absorption coefficient in investigated crystals was found to be of the type ∼λ^p, where 2 < p < 3.5. The p = 2 is expected from the Drude theory and the relaxation time approximation. The obtained experimental values of p parameter suggest that the optical phonon and impurity scattering mechanisms are dominating scattering mechanisms in these crystals. The calculated carrier concentration from optical absorption spectrum for a n-CdSe crystal is in a good agreement with this obtained from Hall measurement.     

Structural,ferroelectric, optical properties of A-site-modified Bi0.5(Na0.78K0.22)0.5Ti0.97Zr0.03O3 lead-free piezoceramics

We reported the role of A-site modification on the structural, ferroelectric, optical and electrical field-induced strain properties of Bi_0.5(Na_0.78K_0.22)_0.5Ti_0.97Zr_0.03O₃ lead-free piezoceramics. The Li⁺ ions with concentration from 0 to 5 mol% were used to substitute at A-site. There was no phase transition when Li⁺ ions was added up to 5 mol%. The electric field-induced strain (S_max/E_max) values increased from 600 to 643 pm/V for 2 mol% Li⁺-added which results from distortion both rhombohedral and tetragonal phase structures. The band gap reduced from 2.88 to 2.68 eV and the saturation polarization decreased from 46.2 to 26.1 μC/cm² when Li⁺ ions concentration increased from 0 to 5 mol% respectively. We expect that this work could be helpful for further understanding the role of A-site dopants in comparison with B-site modification in lead-free Bi_0.5(Na,K)_0.5TiO₃-based ceramics.     

Photoionization studies of the atmospherically important species N and OH at the Elettra synchrotron radiation source

In this paper angularly resolved photoelectron spectra (PES) and constant-ionic-state (CIS) spectra are presented for the atmospherically important species N and OH.The natural width Γ, line shape parameters q and ρ² and discrete oscillator strengths f have been measured for the members of the N*[2s2p³(⁵S), np] (⁴P) ← N(⁴S) autoionizing resonances for n = 5–10. The n = 5 parameters calculated in this work are in good agreement with the values obtained previously whereas for the resonances with n = 6–10 the values of these parameters are reported for the first time. The asymmetry parameter (β) for the first band of N atoms, the N⁺(³P) ← N(⁴S) ionization, has also been measured in the photon energy range of the above autoionizing resonances.For OH, CIS spectra have been recorded for the first photoelectron band corresponding to the ionization OH⁺(X³Σ⁻, v⁺ = 0) ← OH(X²Π, v″ = 0). In these spectra, rotationally partially resolved bands associated with OH*(a¹Δ3d, v′ = 0) ← OH(X²Π, v″ = 0) resonances have been observed. Suggestions for their assignment are made on the basis of their positions and band simulations which use rotational line strength calculations.     

High resolution emission spectroscopy of the E2Π–X2Σ+ transition of SrH and SrD

Emission spectra of SrH and SrD have been studied at high resolution using a Fourier transform spectrometer. The molecules have been produced in a high temperature furnace from the reaction of strontium metal vapor with H₂/D₂ in the presence of a slow flow of Ar gas. The spectra observed in the 18 000–19 500 cm^?1 region consist of the 0–0 and 1–1 bands of the E²Π–X²Σ⁺ transition of the two isotopologues. A rotational analysis of these bands has been obtained by combining the present measurements with previously available pure rotation and vibration–rotation measurements for the ground state, and improved spectroscopic constants have been obtained for the E²Π state. The present analysis provides spectroscopic constants for the E²Π state as ΔG(½) = 1166.1011(15) cm^?1, B_e = 3.805503(32) cm^?1, α_e = 0.098880(47) cm^?1, r_e = 2.1083727(89) Å for SrH, and ΔG(½) = 839.1283(23) cm^?1, B_e = 1.918564(15) cm^?1, α_e = 0.034719(23) cm^?1, r_e = 2.1121943(83) Å for SrD.     

(p, ρ, T) and (ps, ρs,Ts) properties,and apparent molar volumes Vϕ of LiI (aq) at T = 298.15 to 398.15 K and at pressures up to p = 60 MPa

(p, ρ, T) and (p_s, ρ_s, T_s) properties, and apparent molar volumes V_ϕ of LiI (aq) at T = 298.15 to 398.15 K, at pressures up to p = 60 MPa were reported, and apparent molar volumes at infinite dilution V_ϕ⁰ have been evaluated. An empirical correlation for density of lithium iodide (aq) with pressure, temperature and molality was derived. The experiments were carried out at molalities m = 0.11053, 0.32532, 0.70013, 1.40459, 2.95059, and 4.88147 mol kg^− 1 of lithium iodide.     

Preparation and characteristics of Pr1.6Sr0.4NiO4+YSZ as composite cathode of solid oxide fuel cells

Composite cathodes of (1?x wt%)Pr_1.6Sr_0.4NiO₄+(x wt%)Y₂O₃-stabilized ZrO₂ (YSZ; x=0, 10, 20, 30, 40) abbreviated as Pr_1.6Sr_0.4NiO₄+xYSZ, were prepared. The composite cathodes with x>0 matched with electrolyte YSZ in thermal expansion coefficient (TEC) better than the cathode Pr_1.6Sr_0.4NiO₄ did. Pr_1.6Sr_0.4NiO₄+20YSZ exhibited the best performance on cathode overpotential and impedance. When the cathode overpotential was 0.1 V, the polarization current density of Pr_1.6Sr_0.4NiO₄+20YSZ was 0.28 A cm^?2, which is about 5.6 times higher than that of Pr_1.6Sr_0.4NiO₄, 0.05 A cm^?2. The area-specific resistance (ASR) for Pr_1.6Sr_0.4NiO₄+20YSZ was about 17.7% of that for Pr_1.6Sr_0.4NiO₄ at 750 °C.     

Dual frequency cavitation event sensor with iodide dosimeter

The inertial cavitation activity depends on the sonication parameters. The purpose of this work is development of dual frequency inertial cavitation meter for therapeutic applications of ultrasound waves. In this study, the chemical effects of sonication parameters in dual frequency sonication (40 kHz and 1 MHz) were investigated in the progressive wave mode using iodide dosimetry. For this purpose, efficacy of different exposure parameters such as intensity, sonication duration, sonication mode, duty factor and net ultrasound energy on the inertial cavitation activity have been studied. To quantify cavitational effects, the KI dosimeter solution was sonicated and its absorbance at a wavelength of 350 nm was measured. The absorbance values in continuous sonication mode was significantly higher than the absorbance corresponding to the pulsed mode having duty factors of 20–80% (p < 0.05). Among different combination modes (1 MHz_100% + 40 kHz_100%, 1 MHz_100% + 40 kHz_80%, 1 MHz_80% + 40 kHz_100%, 1 MHz_80% + 40 kHz_80%), the continuous mode for dual frequency sonication is more effective than other combinations (p < 0.05). The absorbance for this combined dual frequency mode was about 1.8 times higher than that obtained from the algebraic summation of single frequency sonications. It is believed that the optimization of dual frequency sonication parameters at low-level intensity (<3 W/cm²) by optically assisted cavitation event sensor can be useful for ultrasonic treatments.     

A.c. conductivity and relaxation in LiCoVO4 ceramics

The LiCoVO₄ compound is synthesized by solution-based chemical method. X-ray diffraction analysis exhibits a single phase nature of the compound with cubic structure. The dielectric constant (ε_r), tangent loss (tanδ) and a.c. conductivity (σ_ac) have been studied as a function of frequency and temperature using complex impedance spectroscopy (CIS) technique. The variation of (ε_r and tanδ) with frequency at studied temperatures shows a dispersive behavior at low frequencies. Frequency dependence of σ_ac at different temperatures obeys Jonscher’s universal power law governed by the relation: σ_ac = σ_dc + Aωⁿ, where n is the frequency exponent in the range of 0 ⩽ n ⩽ 1 and A is a constant that depends upon temperature.     

Synthesis and visible light photocatalysis water splitting property of chromium-doped Bi4Ti3O12

Photocatalysts Bi₄Ti_3 ? xCr_xO₁₂(x = 0.00, 0.06, 0.15, 0.30, 0.40, and 0.50) with perovskite structure were synthesized by sol–gel method and their electronic structures and photocatalytic activities were investigated. The Bi₄Ti_2.6Cr_0.4O₁₂ photocatalyst exhibited the highest performance of H₂ evolution in methanol aqueous solution (58.1 μmol h^? 1 g^? 1) under visible light irradiation (λ > 400 nm) without a co-catalyst, whereas no H₂ evolution is observed for Bi₄Ti₃O₁₂ under the same conditions. The UV–vis spectra indicated that the Bi₄Ti_2.6Cr_0.4O₁₂ had strong photoabsorption in the visible light region. The results of density functional theory (DFT) calculation illuminate that the conduction bands of Bi₄Ti₃O₁₂ are mainly attributable to the Ti 3d + Bi 6p orbitals, and the valence bands are composed of O 2p + Bi 6s hybrid orbitals, while the conduction bands of chromium-doped Bi₄Ti₃O₁₂ are mainly attributable to the Ti 3d + Bi 2p + Cr 3d orbitals, and the O 2p + Cr 3d hybrid obitals are the main contribution to the valence band.     

Densities and volumetric properties of 2-chloroethanol with N,N-dimethylformamide and water at different temperatures

Densities of binary mixtures of 2-chloroethanol with N,N-dimethylformamide (DMF) and water have been measured over the full range of compositions at various temperatures. From these results, excess molar volumes, V^E and excess partial molar volumes at infinite dilution, V¯_i^E,0 have been calculated. V^E for (DMF + 2-chloroethanol) mixture are positive over the whole mole fraction range and negative values are obtained for (water + 2-chloroethanol) mixture.     

Phase stability and oxygen non-stoichiometry of SrCo0.8Fe0.2O3−δ measured by in situ neutron diffraction

The phase stability, oxygen stoichiometry and expansion properties of SrCo_0.8Fe_0.2O_3−δ (SCF) were determined by in situ neutron diffraction between 873 and 1173 K and oxygen partial pressures of 5 × 10^− 4 to 1 atm. At a pO₂ of 1 atm, SCF adopts a cubic perovskite structure, space group Pm3¯m, across the whole temperature range investigated. At a pO₂ of 10^− 1 atm, a two-phase region exists below 922 K, where the cubic perovskite phase coexists with a vacancy ordered brownmillerite phase, Sr₂Co_1.6Fe_0.4O₅, space group Icmm. A pure brownmillerite phase is present at pO₂ of 10^− 2 and 5 × 10^− 4 atm below 1020 K. Above 1020 K, the brownmillerite phase transforms to cubic perovskite through a two-phase region with no brownmillerite structure observed above 1064 K. Large distortion of the BO₆ (B = Co, Fe) octahedra is present in the brownmillerite structure with apical bond lengths of 2.2974(4) Å and equatorial bond lengths of 1.9737(3) Å at 1021 K and a pO₂ of 10^− 2 atm. SCF is highly oxygen deficient with a maximum oxygen stoichiometry, 3 − δ, measured in this study of 2.58(2) at 873 K and a pO₂ of 1 atm and a minimum of 2.33(2) at 1173 K and a pO₂ of 5 × 10^− 4 atm. Significant differences in lattice volume and expansion behavior between the brownmillerite and cubic perovskite phases suggest potential difficulties in thermal cycling of SrCo_0.8Fe_0.2O_3−δ membranes.     

Mechanisms of karyotype differentiation in Cassidinae sensu lato (Coleoptera,Polyphaga, Chrysomelidae) based on seven species of the Brazilian fauna and an overview of the cytogenetic data

Among the subfamilies of Chrysomelidae, Cassidinae sensu lato (s.l.) includes 6000 species distributed in 43 tribes. Approximately 100 of these species were cytogenetically analyzed and most of them presented 2n = 18 = 16 + Xy_p, which was smaller than 2n = 20 = 18 + Xy_p considered basal for Polyphaga. However, some groups of species presented maintenance of the basal diploid number and others showed increase in this number. Certain species of the latter group also exhibited variation in the type of sex chromosome system (SCS). Considering the recent taxonomic revision accomplished for the Cassidinae s.l. species, the existence of phylogenetic relationship for some species of this subfamily, the high diversity of species of this group in the Neotropical region, and the low number of Cassidinae s.l. species karyotyped so far, the aim of the present work was to establish the main mechanisms involved in the karyotype evolution of this subfamily through the study of seven species of the Brazilian fauna and overview of the cytogenetic data. The individuals were collected in southeast and south of Brazil. The chromosomal preparations obtained from embryo and testes of adult males were stained with Giemsa solution. The species Agroiconota inedita (2n = 42 = 40 + Xy_p), Charidotella (s.str.) immaculata (2n = 22 = 20 + Xy_p), Charidotella (s.str.) sexpunctata (2n = 22 = 20 + Xy_p), and Stolas chalybaea (2n = 24 = 22 + Xy_p) revealed diploid number higher than that established as basal for Polyphaga and biarmed chromosomes. The karyotype of Cteisella confusa, Deloyala cruciata, and Metriona elatior showed the chromosomal formulae 2n = 18 = 16 + Xy_p considered modal for Cassidinae s.l. and biarmed chromosomes. The seven species exhibited easily identified sex chromosomes due to their size and/or morphology. The analysis of meiotic cells of all the species showed pachytenes with a positively heteropycnotic block probably corresponding to the sex chromosomes; diplotenes with a high number of bivalents with two chiasmata and sex chromosomes in a parachute configuration, and metaphases II that confirmed the chromosomal morphology, the type of SCS, and the regular segregation of all chromosomes. The data regarding to the number and morphology of the chromosomes, their behaviour during meiosis, and type of SCS were inedit for the majority of these species. In relation to the all Cassidinae s.l. species that presented SCS of the Xy_p type, A. inedita was that with the highest diploid number. Furthermore, this work reported for the first time the cytogenetic information of representatives of the genera Cteisella and Metriona. Taking into account the phylogenetic and cytogenetic data of Cassidinae s.l. species, the karyotype differentiation of this group seems to have occurred from the basal karyotype of Polyphaga by decrease in the chromosome number and subsequent increase in this number. Pericentric inversion, centric fusion and fission seem to have been the main mechanisms that promoted the evolution of the autosomes. However, in the sex chromosome evolution, the mechanisms involved were centric fission and/or chromosomal translocation.