Hole distribution in La2−xSrxCu1−yZn(Ni)yO4 (x ⩽ 1/8)

Simulation with interacting-potentials has been performed to investigate hole distribution in La_2−xSr_xCu_1−yZn(Ni)_yO₄ (y = 1/32 and x ⩽ 1/8). It is found that the orderly distributed hole configurations are more energetically favorable than the randomly distributed hole configurations. Moreover, the doped Zn²⁺ and Ni²⁺ ions can both act as stabilizing centers to localize the holes in their vicinity leading to an atomic-scale inhomogeneous distribution of holes. This atomic-scale inhomogeneities of holes obtained from our simulation is similar to that predicted by the “Swiss Cheese” model.     

Crystal structure and thermal expansion of LaCr1−xMgxO3, 0 < x ≤ 0.25

Solid solution LaCr_1?xMg_xO₃, 0 < х ≤ 0.25 was prepared by heating stoichiometric amounts of appropriate oxides in air at 1400 °C, 48 h. At room temperature it crystallizes in orthorhombically distorted GdFeO₃-type structure (a ≈ √2 × a_per; b ≈ √2 × a_pe; c ≈ 2 × a_per, where a_per – perovskite subcell parameter). High-temperature X-ray powder diffraction (HT XRPD) and dilatometry revealed first order phase transition to rhombohedral perovskite phase (R-3c, a ≈ √2 × a_per, c ≈ 2√3 × a_per) at 260–311 °C (OR phase transition). Crystal structures of room-temperature orthorhombic and high-temperature rhombohedral phases for LaCr_0.75Mg_0.25O₃ were refined using HT XRPD data. Temperature of OR phase transition increases gradually with increasing of magnesium content. Low-temperature orthorhombic phase exhibits TEC lower in comparison with high-temperature rhombohedral one (e.g. for LaCr_0.85Mg_0.15O₃ TEC(O) = 8.8 ppm K^?1; TEC(R) = 11.6 ppm K^?1). TEC for rhombohedral phase increases with increasing magnesium content from 10.4 ppm K^?1 for LaCr_0.95Mg_0.05O₃ to 12.1 ppm K^?1 for LaCr_0.75Mg_0.25O₃.     

Thermoelectric properties of Re6GaxSeyTe15−y (0 ≤ x ≤ 2; 0 ≤ y ≤ 7.5)

Thermoelectric properties of Re₆Ga_xSe_yTe_15?y (0 ≤ x ≤ 2; 0 ≤ y ≤ 7.5) were studied in the temperature range 90–320 K. The measurements revealed p-type semi-conductivity in all samples. Relatively high values of the Seebeck coefficients, α, were obtained in all samples. The electrical resistivities and room temperature Seebeck coefficients increased as selenium concentrations increased, for each value of x. The room temperature Seebeck coefficients and resistivities decreased as gallium content increased, for each value of y. Low carrier concentrations were found at room temperatures, in agreement with large Seebeck coefficient values. Measurements suggested hopping conduction between 150 K and 280 K for all samples. Temperature dependences of the Seebeck coefficient below 150 K were accounted for by phonon drag effect. The power factors for the samples were calculated. Theoretical discussions of dependences of the measured quantities on temperature and composition are given. Usefulness of these materials as thermoelectrics is also discussed.     

Synthesis and characterization of flower-like CuIn1−xGaxS2 (x = 0.3) microspheres

We report the formation and characterization of the flower-like CuIn_1?xGa_xS₂ (x = 0.3) microspheres using CuCl₂·2H₂O, GaCl₃, InCl₃ and l-cystine in the mixed solvent of ethylene glycol and distilled water (1:2, v/v) at 200 °C for 24 h. XRD results indicated that the CuIn_0.7Ga_0.3S₂ nanostructures have a (1 1 2) preferred orientation. The EDS and XPS analyses of the sample revealed that Cu, In, Ga and S were present in an atomic ratio of approximately 1:0.7:0.3:2. FESEM and TEM images showed that the product was microspheres, consisting of nanoplates with the thickness of about 20 nm. The optical properties were investigated by ultraviolet–visible (UV–vis) absorption spectroscopy and Raman spectroscopy. UV–vis absorption spectrum indicated that the band gap of as-synthesized flower-like CuIn_0.7Ga_0.3S₂ microspheres was about 2.427 eV. Raman spectrum of the obtained CuIn_0.7Ga_0.3S₂ exhibited a high-intensity peak at 302 cm^?1 could be assigned as A1-mode.     

Structural and electrical properties of high-quality 0.41 μm-thick InSb films grown on GaAs (1 0 0) substrate with InxAl1−xSb continuously graded buffer

High-quality InSb was grown on a GaAs (1 0 0) substrate with an InAlSb continuously graded buffer (CGB). The temperatures of In, Al K-cells and substrate were modified during the growth of InAlSb CGB. The cross-section TEM image reveals that the defects due to lattice-mismatch disappear near lateral structures in CGB. The measured electron mobility of 0.41 μm-thick InSb was 46,300 cm²/Vs at 300 K. These data surpass the electron mobility of state-of-the-art InSb grown by other methods with similar thickness of InSb.     

Atomic diffusion in the Fe [0 0 1] ∑ = 5 (3 1 0) and (2 1 0) symmetric tilt grain boundary

Both the formation and diffusion activation energies of single vacancy migrating intra-layer and inter-layer near the Fe [0 0 1] Σ = 5 (3 1 0) and (2 1 0) symmetric tilt grain boundaries have been calculated by using the MAEAM and a MD method. From energy minimization, the vacancy concentration in the second layer is higher than the one in the other layers for both (3 1 0) and (2 1 0) STGBs. By the diffusion activation energies of the vacancies migrating intra-layer and inter-layer, the vacancies located from the first to the eighth layers of (3 1 0) STGB as well as the ones located from the first to the tenth layers of (2 1 0) STGB are favorably migrated to the second layer. Thus there is a vacancy aggregation tendency to the second layer near the grain boundary. For the vacancy migrating intra-layer and inter-layer, the influences of the grain boundary are respectively as far as to the fifth and eighth layers for (3 1 0) STGB as well as to the sixth and tenth layers for (2 1 0) STGB.     

Synthesis and electrical conductivity of La0.6Sr0.4Ru1−xMgxO3−δ (x = 0–0.6) perovskite solid solution

Sr and Mg were doped at La- and Ru-sites of perovskite oxide LaRuO₃, respectively, to enhance electrical conductivity and catalytic property as a cathode material for a low temperature solid oxide fuel cell. Crystal structure and particle morphology of La_0.6Sr_0.4Ru_1?xMg_xO_3?δ powders (shorten as LSRM) and electrical conductivity of sintered LSRM were studied. LSRM powders (x = 0–0.6) were prepared by co-precipitation method using metal nitrate solutions and ammonium carbonate solution. The freeze-dried powders were heated at 1273 K in air to form LSRM solid solution of orthorhombic structure. The true densities and particle sizes of LSRM solid solution, where valence of Ru was estimated to be 3+, decreased with increasing Mg content. The electrical conductivity of LSRM at x = 0–0.3 was almost independent of temperature and was in a range of 19–360 S cm^?1 at 1073 K. Hole conduction contributed to the high electrical conductivities. LSRM at x = 0.4 and 0.5 was a mixed conductor of oxide ions and holes, and showed a conductivity of 11 S cm^?1 at 1073 K in air. This conductivity decreased at a lower oxygen pressure and reached a constant value below 10 Pa of oxygen pressure.     

Thermo-optical properties of LaMg1 − xNixAl11O19 (0 ≤ x ≤ 1) hexaaluminates for metallic thermal protection system

LaMg_1 ? xNi_xAl₁₁O₁₉ (x = 0, 0.25, 0.5, 0.75, 1) ceramics are fabricated by pressureless-sintering method at 1700 °C for 10 h in air. The microstructure and thermo-optical properties of LaMg_1 ? xNi_xAl₁₁O₁₉ ceramics are investigated by the X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy measurements. The influence of NiO doping on structure and thermo-optical properties of LaMg_1 ? xNi_xAl₁₁O₁₉ ceramics is investigated. The partial substitution of Ni²⁺ for Mg²⁺ results in a significant increase in emissivity at low wavelengths as compared with unmodified LaMgAl₁₁O₁₉. When the Ni²⁺ content increases to x = 0.75 or above, LaMg_1 ? xNi_xAl₁₁O₁₉ ceramics have a high emissivity value above 0.70 at low wavelengths at 500 °C. The measured emissivity of all LaMg_1 ? xNi_xAl₁₁O₁₉ ceramics shows a similar trend in the wavelength range of 6 to 14 μm.     

Two-photon absorption of Tl1−xIn1−xSnxSe2 (x = 0, 0.1, 0.2, 0.25) single crystalline alloys and their nanocrystallites

Two-photon absorption (TPA) of Tl_1−xIn_1−xSn_xSe₂ (x = 0, 0.1, 0.2, 0.25) was studied at CO₂ laser wavelength 9.4 μm with pulse duration 1 μs. The studies were performed at different temperatures and for the nanocrystallite sizes varying within the 7–200 nm. The nanocrystals were fabricated by mechanical milling with simultaneous acoustical field treatment and porous filter size separation. The studies have shown that the TPA may be enhanced during the decrease of the nanocrystallite sizes below 50–60 nm. There exists also some critical x value at which the TPA value begin substantially to increase. The comparison with other chalcogenide crystals is performed. The studied nanocrystallites are relatively stable to the infrared laser treatment and are not hygroscopic which allow to use them in different IR optoelectronic devices.     

Electronic structure of Cu100−xZrx (x = 40, 50, 60) metallic glasses

The electronic structure of Cu_100−xZr_x (x = 40, 50, 60) metallic glasses was investigated by ultraviolet photoelectron spectroscopy and X-ray photoemission spectroscopy, the valence band spectra of these alloys were analyzed by a large shift of the Cu d-band peaks to higher binding energies upon increasing Cu content. Photoemission experiments and first-principles calculations prove that the values of density of states at Fermi level of Cu_100−xZr_x metallic glasses are mainly dominated by Zr rather than Cu. This work will enlighten further research on understanding the inheritance of metallic glasses and designing new metallic glasses with unique properties.     

Microwave-assisted synthesis and characterization of Ti1 − xVxO2 (x = 0.0–0.10) nanopowders

Ti_1 ? xV_xO₂ (x = 0.0–0.10) nanopowders were successfully synthesized by a microwave-assisted sol–gel technique and their crystal structure and electronic structure were investigated. The products were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman and UV–Vis spectroscopy. The results revealed that TiO₂ powders maintained the anatase phase for calcination temperature below 600 °C, but gradually changed to the rutile phase above 800 °C. The formation of the rutile phase was completed at 1000 °C. For Ti_1 ? xV_xO₂ (x = 0.05) powders, the phase transformation appeared at 600 °C. The absorption edge of Ti_1 ? xV_xO₂ (x > 0) powders broadened to the visible region with increasing V concentration and a strong visible light absorption was obtained with 10% V doping. V doping and subsequent coexistence of both anatase and rutile phases in our Ti_1 ? xV_xO₂ nanoparticles are considered to be responsible for the enhanced absorption of visible light up to 800 nm.     

Structure,nonstoichiometry, sintering and oxygen permeability of perovskite SrCo1−2x(Fe,Nb)xO3−δ (x = 0.05, 0.10) oxides

The novel Fe/Nb co-substituted SrCo_1?2x(Fe,Nb)_xO_3?δ (x = 0.05, 0.10) oxides have been synthesized and characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetry (TG), and scanning electron microscopy (SEM). The XRD and DSC results demonstrate that the structural stability of the Fe/Nb co-substituted samples x = 0.05, 0.10 is improved greatly compared to the sample x = 0.00. The Fe/Nb co-doping in the SrCoO_3?δ oxide results in the improved structural stability of the SrCo_1?2x(Fe,Nb)_xO_3?δ (x = 0.05, 0.10) oxides. The nonstoichiometric and sintering properties were investigated by TG and SEM, and the oxygen permeation fluxes were measured at 800–950 °C for the sample x = 0.10. The improved oxygen permeability of the ceramic SrCo_1?2x(Fe,Nb)_xO_3?δ (x = 0.10) membrane compared to the (Ba_0.5Sr_0.5)(Co_0.8Fe_0.2)O_3?δ and SrCo_0.8Fe_0.2O_3–δ membranes, was observed under an air/He oxygen partial pressure gradient at 800–950 °C.     

XPS and Mössbauer studies on BaSn1−xNbxO3 (x ≤ 0.100)

A few compositions of perovskite oxide BaSn_1?xNb_xO₃ (with x ≤ 0.10) system, prepared by solid state ceramic method, have been studied employing XPS and Mössbauer spectroscopy techniques. Mössbauer spectra of these compositions in the temperature range of 78–300 K reveal that the oxidation state of Sn is +4. In XPS measurements, compositions with x ≤ 0.010 show no evidence of Nb⁵⁺ signal whereas the compositions with x ≥ 0.050 show clear evidence of Nb⁵⁺ signals indicating some unreacted Nb₂O₅ component in the system. This confirms the earlier report where presence of small amount of unreacted Nb₂O₅ was predicted.     

Electrical properties of nanostructures (CoFeZr)x + (Al2O3)1−x with use of alternating current

CoFeZr–Al₂O₃ nanocomposite films of 3–5 μm thickness, containing metallic alloy nanoparticles embedded into the dielectric alumina matrix, have been deposited on a glass ceramic substrate using magnetron sputtering of composite target in Ar gas ambient. Measurements of AC conductance and lagging have been performed within the frequency range of 50 Hz–1 MHz at the temperatures from 79 K to 373 K in the initial (as-deposited) samples as well as directly after their isochronous (15 min) annealings within the temperature range from 398 K to 648 K with 25 K step.The observed variations of real part AC electrical conductivity with temperature and frequency σ_real(T, f) in the as-deposited films display transition from dielectric to metallic behaviour when crossing the percolation threshold x_C in the studied nanocomposites. After annealing of the samples below the x_C the σ_real(T, f) progress follows the hopping law of electron conductivity with sigmoidal frequency dependence. The samples being far beyond the percolation threshold revealed transition from metallic to activational σ_real(T) law after high-temperature annealing attributed to the internal oxidation of metallic nanoparticle by excess of oxygen presented in the as-deposited samples.     

In vitro biocompatibility and antimicrobial activity of wet chemically prepared Ca10−xAgx(PO4)6(OH)2 (0.0 ≤ x ≤ 0.5) hydroxyapatites

Herein, we report the effect of silver ions on the physical, antimicrobial and cytocompatibility properties of wet chemically synthesized silver doped Ca_10?xAg_x(PO₄)₆(OH)₂ (0.0 ≤ x ≤ 0.5) hydroxyapatites (HAp). Silver ions containing HAp exhibit the comparable density, hardness and enhanced antimicrobial properties, in comparison to parent HAp. The optical absorption measurements confirm the presence of silver ions in the doped compositions, which are responsible for as increased antimicrobial property of doped HAp materials for x > 0.3. The cytotoxicity behavior of the doped HAp was evaluated using mouse fibroblast (L929) cell line. The important result has been that doped HAp (x > 0.3) exhibit statistically (significant) lower cell viability in comparison to undoped HAp. However, no difference in cellular functionality on doped HAp surfaces, in terms of cell adhesion and proliferation could be qualitatively observed in reference to undoped HAp. In order to explain the observed antimicrobial and cell viability properties, the in vitro release of Ag⁺ ions has been quantified using Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) and solubility was measured by weight loss in acetate buffer solution.     

Electrical conductivity of Ca1−xSrxTi0.65Fe0.35O3−δ, x = 0, 0.5 and 1, polycrystalline compounds in the 300–500 K range

Bulk and grain boundary electrical conductivity of oxygen deficient Ca_xSr_1?xTi_0.65Fe_0.35O_3?δ, x = 0, 0.5 and 1.0, polycrystalline specimens were evaluated by impedance spectroscopy measurements in the 5 Hz–13 MHz frequency range from 300 to 500 K. The ceramic powders were synthesized by solid state reaction and by a chemical route, the polymeric precursor technique. The X-ray diffraction of the samples at room temperature shows the following perovskite crystalline structures: cubic for x = 0 and orthorhombic for x = 0.5 and 1.0. The impedance plots are composed of two semicircles ascribed to grains (bulk) and interfaces (grain boundaries) contributions. The impedance data show that sintered pellets using powders prepared by solid state synthesis present higher intergranular and intragranular resistivity values than pellets prepared by the chemical route. Observations of scanning probe microscopy topographic images of the surfaces of the sintered pellets show evident differences between the grain morphology of the pellets prepared with powders synthesized by the two routes.     

Magnetic and structural properties of nanostructured (Fe65Co35)100−xCrx (x = 0, 10) powders prepared by mechanical alloying process

This work focuses on the preparation of nanostructured (Fe₆₅Co₃₅)_100−xCr_x (x = 0, 10) powders by mechanical alloying. The powders are milled for different milling times (up to 90 h). Characterizations of the milled powders were carried out by X-ray diffraction (XRD), scanning electron microscopy (SEM) and vibratory sample magnetometer (VSM). It was observed that the formation of bcc-FeCo and bcc-FeCoCr phases were completely accomplished after 60 and 90 h of milling, respectively. The grain size decreases and the microstrain increases with increasing the milling time. In the initial stages of milling (up to 15 h) for the (Fe₆₅Co₃₅)₉₀Cr₁₀ powders, the saturation magnetization (M_s) decreased but further milling (up to 90 h) increased the M_s. However, the trend for coercivity was different and three stages were observed. An initial increasing stage (up to 15 h of milling), followed by a reducing middle stage (up to 60 h of milling) and then again an increasing final stage (up to 90 h milling). Besides, for the same milling time of 90 h, the addition of 10 at.% of Cr to Fe₆₅Co₃₅ powders leads to higher coercivity and lower saturation magnetization.     

Novel SrCo1 − 2x(Fe,Nb)xO3 − δ (x = 0.05, 0.10) oxides targeting CO2 capture and O2 enrichment: Structural stability and oxygen sorption properties

The novel Fe/Nb co-doped SrCo_1 ? 2x(Fe,Nb)_xO_3 ? δ (x = 0.05, 0.10) perovskite oxides were synthesized by the solid-state method. Structural and chemical stability of the SrCo_1 ? 2x(Fe,Nb)_xO_3 ? δ (x = 0.05, 0.10) oxides were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and X-ray diffraction (XRD). The results demonstrated that the structural and chemical stability of the Fe/Nb co-doped SrCo_1 ? 2x(Fe,Nb)_xO_3 ? δ (x = 0.05, 0.10) is improved significantly. The oxygen sorption properties of the SrCo_1 ? 2x(Fe,Nb)_xO_3 ? δ (x = 0.05, 0.10) oxides were investigated between 300–900 °C in air, and the high oxygen sorption capacity of 11.5 and 10.3 mL O₂ (STP)/g oxide, respectively, are obtained.