Fabrication of LiNi0.5 + δMn0.5 − δO2 nanofibers by electrospinning

Polycrystalline tetranary LiNi_0.5 + δMn_0.5 − δO₂ nanofibers have been successfully fabricated by a sol-gel assisted electrospinning technique. The structures and properties of fabricated nanofibers were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and thermal gravimetric analysis (TGA). After heat treatment of the electrospun fibers at a temperature of 800 °C, the LiNi_0.5 + δMn_0.5 − δO₂ phase was found without other trace phases. Multilayered nanoparticles with a grain size of 50 nm or less within a single fiber are notable from TEM. In this study, it was shown that the sol-gel assisted electrospun LiNi_0.5 + δMn_0.5 − δO₂ fibers could be formed with the α-NaFeO₂ type crystal structure at a temperature lower than that in a typical solid-state or sole sol-gel process and possess good thermal stability as high as 800 °C.     

Aging response of the Ti–Nb system biomaterials with β-stabilizing elements

Effects of aging temperature and the contents of β-stabilizing elements on the composition of martensite α′′ in two Ti–Nb alloys and the resulting mechanical properties were investigated for biomedical applications. The microstructures were examined by means of optical microscopy (OM) and X-ray diffraction (XRD). Vickers hardness, compressive elastic modulus and the yield strength have been measured. The results show that the decomposition mode of the martensite α′′ in two studied alloys depends on aging treatment and the contents of β-stabilizing elements. Various microstructures such as α, (α + β) and (β + ω) phases were observed to precipitate in the studied alloys after the aging treatments performed at 523 K, 773 K, 883 K and 1023 K for 0.5 h, respectively. Afterwards, the Ti–24Nb–6Zr–7.5Sn–2Fe alloy was aged at 773 K for 1 h. The compressive elastic modulus and mechanical properties of the two alloys are found to be sensitive to the microstructural change caused by aging temperature. For the Ti–24Nb–6Zr–7.5Sn–2Fe alloy, after aging at 773 K for 1 h, its yield strength, compressive elastic modulus and Vickers hardness reach 846 MPa, 26 GPa and 398 HV, respectively. This aged alloy exhibits proper comprehensive mechanical property and strength-to-modulus ratio for biomedical implant applications.     

Study on the chemical stability of Y-doped BaCeO3 − δ and BaZrO3 − δ films deposited by aerosol deposition

Barium cerate (BaCeO₃) has high proton conductivity but rather poor chemical stability in CO₂-containing atmospheres. Barium zirconate (BaZrO₃), in contrast, is a rather stable material, but exhibits poor sinterability. In the present work, powders of Y-doped BaCeO₃ and BaZrO₃ were synthesized via the solid solution reaction method, and dense ceramic membranes with BaCe_0.9Y_0.1O₃ and BaZr_0.85Y_0.15O₃ were prepared by the aerosol deposition method at room temperature. Aerosol deposition method is a technique that enables the fabrication of ceramic films at room temperature with a high deposition rate as well as strong adhesion to the substrate. The powders and aerosol-deposited membranes were characterized by X-ray diffraction, particle size analysis, scanning electron microscopy, and X-ray elemental mapping. The chemical stability of powders and aerosol-deposited membranes with BaCe_0.9Y_0.1O₃ and BaZr_0.85Y_0.15O₃ against water and carbon dioxide has been investigated, and it was found that BaZr_0.85Y_0.15O₃ materials showed a better chemical compatibility.     

Phase transitions in Sr1 + xCo0.8Fe0.2O3 − δ oxides

The phase transitions that take place in Sr_1 + xCo_0.8Fe_0.2O_3 − δ (− 0.2 ≤ x ≤ 0.1) oxides are reported here. Thermogravimetric analysis (TGA) showed that the oxides with − 0.2 ≤ x ≤ 0 were prone to undergo oxygen-vacancy disorder-order phase transitions, while others with x = 0.05, 0.1 had more stable crystal structures during oxygen-desorption processes in nitrogen. These results were further confirmed by high-temperature in-situ X-ray techniques. The changes in activation energies of three typical oxides, Sr_1 + xCo_0.8Fe_0.2O_3 − δ (x = − 0.2, 0, 0.1), used as oxygen-permeable membranes were investigated. The phase transitions in Sr_1 + xCo_0.8Fe_0.2O_3 − δ (x = − 0.2, 0) have also been detected in differential scanning calorimetry (DSC) profiles.     

Crossover of magnetoresistance from positive to negative in La0.5Sr0.5CoO3 − σ/Si heterostructure

The magnetoresistance (MR) properties of a heterostructure fabricated by depositing a La_0.5Sr_0.5CoO_3 − σ film on an n-type Si substrate have been studied. The heterostructure exhibits a good rectifying behavior. A negative MR at T = 210 K and a positive MR at T = 300 K are observed for all bias currents whereas; for temperatures ranging from 240 to 280 K the MR changes from being positive to negative with the increase of the bias current. The observed behavior of the MR effect is discussed in terms of current-induced ferromagnetic spin order.     

Investigation of visible light photocatalytic behavior of Bi4V2O11−δ and BIMEVOX (ME = Al, Ga) oxides

A study of photocatalytic properties of Bi₄V₂O_11−δ for the degradation of common organic dyes such as methylene blue (MB) under visible light was carried out. Other identified bismuth based visible light photocatalysts such as Bi₂GaVO₇, Bi₂YVO₈ and Bi₂AlVO₇ were reinvestigated to understand their structural, and photocatalytic properties. Our experiments involving the synthesis of Bi₂YVO₈ indicated merely a mixture of BiYO₃ and BiVO₄, instead of the reported oxide containing bismuth in +3 and +5 oxidation states (J. Luan, et al., Mater. Res. Bull. 43 (2008) 3332). We have further shown the similarity of Bi₂AlVO₇ and Bi₂GaVO₇ photocatalysts with that of the metal ions substituted Bi₄V₂O_11−δ (BIMEVOX; ME = Al, Ga) based on the results of powder X-ray diffraction, UV-vis diffuse reflectance and photocatalytic studies. In general, photocatalytic behavior of Bi₄V₂O_11−δ and Bi₄V_2−xM_xO_11−δ (M = Al, Ga; x = 0.4) were found to be moderate for the decomposition of MB under visible light irradiation.     

Properties of superconducting, polycrystalline dysprosium-doped Bi1.6Pb0.5Sr2−xDyxCa1.1Cu2.1O8+δ (0 ≤ x ≤ 0.5)

The structural and superconducting properties of dysprosium (Dy) doped (Bi,Pb)-2212 superconductor have been studied. Dy concentration is varied from x = 0.0 to 0.5 in a general stoichiometry of Bi_1.6Pb_0.5Sr_2−xDy_xCa_1.1Cu_2.1O_8+δ. It is found that the Dy atoms enter into the crystal structure by replacing Sr atoms and induce significant change in lattice parameter, microstructure, hole-concentration and normal state conductivity of the system. The critical temperature (T_C) and critical current density (J_C) at self-field of the Dy-doped samples enhance considerably at optimum doping levels. Maximum T_C of 92.3 K (for x = 0.4) and J_C of 1390 A/cm² at 64 K (for x = 0.2) are observed for doped samples as against 79.4 K and 127 A/cm², respectively, for the pure sample. The results are discussed on the basis of the change in hole-concentration due to Dy-doping at Sr-site of (Bi,Pb)-2212 superconductor.     

On the νSiO infrared absorption of polysiloxane films

The infrared absorption of polysiloxanes involves a strong band at around 1050 cm^− 1, attributed to the antisymmetric vibration of siloxane bridges. The splitting of this band into two components is generally attributed to coupling between next-neighbor siloxane groups along the polysiloxane chain. From a quantitative analysis of the spectra of these materials, we find that this splitting is larger when the material is in thin-film form, and that the relative intensity of the two components is polarization dependent. We show that these effects are fully understandable in the theoretical framework of infrared absorption by thin films, and are related to long-range dipolar interactions responsible for the longitudinal-transverse splitting effect in crystalline materials. As a consequence, the polarization dependence of the infrared absorption observed for thin films does not appear to be associated with an orientational ordering in the film.     

Effect of the doped nitrogen on the optical properties of β-Ga2O3 nanowires

In this study, optical properties of the nitrogen-doped β-Ga₂O₃ nanowires (N-doped β-Ga₂O₃ NWs) were synthesized by exposing β-Ga₂O₃ NWs under high input power nitrogen plasma (2 kW), using a microwave plasma enhanced chemical vapor deposition (MPECVD) system. The nitrogen contents in the NWs were as-prepared about 7.4, 8.9, 9.7, 13.9, 19.3, and 26.6 at.%, respectively. Low temperature (10 K) cathodoluminescence (CL) spectra exhibit significantly different optical properties for the different nitrogen contents. The CL result of the N-doped β-Ga₂O₃ NWs (210 s N₂ plasma treatment) exhibited four distinct emission peaks at 378, 516, 759, and 970 nm. The possible light emission mechanism including the effect of the nitrogen dopant was discussed.     

Effect of stacking fault probability and ε martensite on damping capacity of Fe–16%Mn alloy

The damping capacity of a Fe–16%Mn–1%Mg–2%Si (wt.%) alloy has been studied with respect to factors like stacking fault probability, ε martensite, and cold rolling. It was found that the damping capacity of 8% cold rolled specimen is much higher than 0% cold rolled specimen. In the 0% rolled specimen, the stacking faults are responsible for the damping capacity characterized by the large amplitude dependence. The improvement in damping capacity by cold rolling is attributed to the formation of ε martensite. As the temperature increases, the damping capacity improves, reaching its maximum around 1000 °C. A further increase in the temperature, however, degrades the damping capacity. The area of the γ/ε boundaries is the major factor for damping capacity. Heat treatment at 1100 °C reduces the number of ε martensite plates, leading to area reduction of γ/ε boundaries despite an increase in amount of ε martensite.     

A comparative study of Pr substitution at Y and Ba sites in YBa2Cu3O7 − δ

Aimed at identifying the factors which suppress the superconductivity in cuprate perovskites I have investigated the effect of substituting Pr ions at the Y and Ba sites in YBa₂Cu₃O_7 − δ system using structural, transport, iodometric, and photoemission studies. The rate of Tc depression in the case when Pr substitutes the Ba site is much higher than the case when it substitutes the Y. This is explained as being due to a combined effect of the factors such as depletion of itinerant holes due to depletion of the oxygen content, the Pr 4f-O 2p hybridization, shortening of c-axis causing Cooper pair-breaking, and the loss of orthorhombicity.     

Preparation and properties of La1 − xAgyMnO3 + δ thin epitaxial films

We report here the preparation and properties of La_1 − xAg_yMnO_3 + δ thin epitaxial films. The original two-step preparation procedure was developed. At first, La_1 − xMnO_3 + δ were grown epitaxially by metal-organic chemical vapor deposition on the single-crystal substrates (001) and (110) SrTiO₃, (001) LaAlO₃, (111) and (001) ZrO₂(Y₂O₃). Treatment by the vapor of the metallic silver in the oxygen atmosphere (at 1 bar and 20 bar) was the second step resulting in the selective absorption of silver by La_1 − xMnO_3 + δ phase. The value of y depended on the process conditions and revealed different kinetics of the silver absorption for (001) and (110) orientation of La_1 − xMnO_3 + δ films. The films prepared were characterized by X-ray diffraction, scanning electron microscopy with energy-dispersion X-ray analysis, high resolution transmission electron microscopy, X-ray photoelectron spectroscopy, electrical resistivity and magnetoresistance measurements in a four-probe configuration. We have found that metal-insulator transition temperature (T_p) in the series La_1 − xAg_xMnO_3 + δ possessed a maximum of 380 K at x = 0.15. Thus, T_p of La_1 − xAg_xMnO_3 + δ films was significantly higher than ever reported in the literature for the La_1 − xAg_xMnO_3 + δ ceramics. La_1 − xAg_xMnO_3 + δ films demonstrated the important role of the ferromagnetic fluctuations above Curie temperature T_c resulting in the sign change of the resistivity curve temperature slope dR / dT and a significant shift of T_p well above T_c. The maximum of the magnetoresistance on the temperature scale was close to dR / dT maximum. The intrinsic magnetoresistance values as high as 22% at 310 K and 50% at 280 K were measured in the magnetic field of 1 T in the series of La_1 − xAg_yMnO_3 + δ epitaxial films.     

Low-temperature sintered ZnNb2O6–CaTiO3 ceramics with near-zero τf

The phases, microstructure and microwave dielectric properties of ZnNb₂O₆–xCaTiO₃ ceramics with BaCu(B₂O₅) glass additions prepared by solid state reaction method were charactered by using X-ray diffraction, Scanning electron microscopy and Advantest network analyzer. The τ_f of ZnNb₂O₆ was modified to near 0 ppm °C⁻¹ by incorporating CaTiO₃ with opposite τ_f values on the basis of Lichtenecker empirical rule. The microwave dielectric properties of ZnNb₂O₆–xCaTiO₃ (x = 8.0 wt.%) samples with BaCu(B₂O₅) glass additives sintered in 900–1000 °C were investigated, and the results indicated that the behaviors of the ε_r and Q × f were associated with the sintering temperature and the amount of BaCu(B₂O₅) glass. The sintering temperature of the ceramics was reduced to 950 °C from 1175 °C. Addition of 5.0 wt.% BaCu(B₂O₅) glass in ZnNb₂O₆–xCaTiO₃ (x = 8.0 wt.%) ceramics sintered at 950 °C showed excellent dielectric properties of ε_r = 20.2, Q × f = 14,100 GHz (f = 7.3 GHz) and τ_f = 0 ppm °C⁻¹. Moreover, the material had a chemical compatibility with silver, which represented a promising candidate materials for low-temperature-co-fired ceramics applications.     

The phase transformation and crystallization kinetics of (1 − x)Li2O–xNa2O–Al2O3–4SiO2 glasses

The phase transformation and crystallization kinetics of (1 − x)Li₂O–xNa₂O–Al₂O₃–4SiO₂ glasses have been studied by using differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron diffraction (ED) analysis. The crystallization temperature at the exothermic peak increases from 1171 to 1212 K when the Na₂O content increases from 0 to 0.6 mol. The crystalline phase is composed of spodumene crystallization when the Na₂O content increases from 0 to 0.6 mol. The activation energy of spodumene crystallization decreases from 444.0 ± 22.2 to 284.0 ± 10.8 kJ mol⁻¹ when the Na₂O content increases from 0 to 0.4 mol. Moreover, the activation energy increases from 284.0 ± 10.8 to 446.0 ± 23.2 kJ mol⁻¹ when the Na₂O content increases from 0.4 to 0.6 mol. The crystallization parameters m and n approach 2, indicating that the surface nucleation and two-dimensional growth are dominant in (1 − x)Li₂O–xNa₂O–Al₂O₃–4SiO₂ glasses.     

Chemical stability and electrical properties of BaCe0.85Y0.15O3−δ–Ce0.85Y0.15O2−δ composite bulk samples for use as central membrane materials in dual PCFC–SOFC fuel cells

The goal of the presented research was to determine the physicochemical properties of composite samples obtained by mixing BaCe_0.85Y_0.15O_3−δ (BCY15) and Ce_0.85Y_0.15O_2−δ (YDC15) in different ratios, and to achieve a better understanding of how these ratios affect the electrical conductivity, chemical stability and morphology of BCY15–YDC15 composite materials. It was determined that the samples are chemically stable in H₂O-containing atmospheres at 600 °C. Furthermore, the porosity of the samples increases with the addition of YDC15 to BCY15. Both the porosity and the BCY15/YDC15 ratio affect the stability of the studied samples. The total activation energy (E_t) values of the composite samples, determined via resistance measurements conducted in air at temperatures between 200 and 800 °C, are in the range of 0.590 ± 0.017 eV (E_t of BCY15) to 1.132 ± 0.008 eV (E_t of YDC15). This indicates that the properties of activation energy for composite materials are additive; the presence of both BCY15 and YDC15 affects the activation energy values. The different morphologies of the samples also influence the conductivity within the respective samples. The electrical conductivity values of the composite samples obtained at temperatures from 200 to 500 °C are in the order of magnitude of 10⁻⁷–10⁻³ S/cm. These values are between those determined for pure BCY15 and YDC15 at the respective measuring temperatures. Consequently, the materials show promise for application as porous central membranes (CM) in dual PCFC–SOFC fuel cells operating in the temperature range 600–700 °C.     

Study of YBaCo4O7 + δ thin films grown by sputtering technique on (1012)-oriented sapphire substrates

We report the growth of thin films of the cobaltite YBaCo₄O_7 + δ by means of the dc magnetron sputtering technique at high oxygen pressure onto r (1012) sapphire substrates. The films were characterized according to their structural, morphological, electrical, magnetic, and optical properties. An analysis of the X-ray diffraction pattern indicates that the films grown on r-sapphire substrates are single phase polycrystalline. Despite the high growth temperature (850 °C), no indication of interface reaction (formation of BaAlO₄ or Y₂O₃) is detected. Measurements of resistivity as a function of temperature reveal a semiconductor-like character of the grown films. No indication of possible transitions is observed in the temperature range 50-300 K. The electronic transport mechanism seems to be dominated by Mott variable range hopping (VRH) conduction. Fitting the VRH model to the experimental data allows one to estimate the density of states of the material at the Fermi level N(E_F). The resistivity measured in magnetic fields as strong as 5 T increases notably, and positive magnetoresistance values as high as ~ 60% at 100 K are obtained. Magnetization measurements show well defined hysteresis loops at 300 K and 5 K. Nevertheless, calculated values of the magnetization have ended up being too small for the ferro- or ferrimagnetic states. Raman spectra, in turn, allow one to identify bands associated with vibrating modes of CoO₄ and YO₆ in tetrahedral and octahedral configurations, respectively. Additional bands which seem to stem from Co ions in octahedral configuration are also clearly identified. Measurements of transmittance and reflectance show two well defined energy gaps at 3.7 and 2.2 eV.     

Morphology and structure of La1.85Sr0.15CuO4 + δ thin films deposited on (100) SrTiO3 substrates by dc magnetron sputtering

La_1.85Sr_0.15CuO_4 + δ thin films were deposited by dc magnetron sputtering. Relaxing time intervals were introduced in the deposition process for improving the quality of the thin films. Atomic force microscopy and X-ray diffraction were used to examine the morphology and structure of the thin films. The study reveals that the time intervals inserted in the deposition process improve the morphology of the thin films, and shows that the thicker the film, the better the crystalline quality and the superconducting property for both deposition processes.     

Thermodynamic properties of LaFeO3−δ and LaFe12O19

The standard Gibbs energies of formation of lanthanum orthoferrite (LaFeO_3−δ) and hexaferrite (LaFe₁₂O₁₉) were determined using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the electrolyte and pure oxygen gas at ambient pressure as the reference electrode. From emf of the solid-state cell, the Gibbs energy of formation of nonstoichiometric orthoferrite (LaFeO_3−δ) is obtained. To derive values for the stoichiometric phase, variation of the oxygen nonstoichiometric parameter δ with oxygen partial pressure was measured using thermogravimetry under controlled gas mixtures. The results obtained for LaFeO₃ and LaFe₁₂O₁₉ can be summarized by the following equations, which represent the formation of ternary oxides from their component binary oxides: ½La₂O₃ + ½Fe₂O₃ → LaFeO₃; ΔG° (LaFeO₃) (±450) (J mol⁻¹) = −62920 − 2.12T (K), and ½La₂O₃ + 9/2Fe₂O₃ + Fe₃O₄ → LaFe₁₂O₁₉; ΔG° (LaFe₁₂O₁₉) (±200) (J mol⁻¹) = −103900 + 21.25T (K). These data are discussed critically in comparison with thermodynamic values reported in the literature from a variety of measurements. The values obtained in this study are consistent with calorimetric entropy and enthalpy of formation of the perovskite phase and with some of the Gibbs energy measurements reported in the literature. For the lanthanum hexaferrite (LaFe₁₂O₁₉) there are no prior thermodynamic measurements for comparison.     

Soft chemistry synthesis of MxV2O5 + ε·nH2O (MCo, Ni, Cu, Zn) nanowires

Recently a simple method was used for preparing nanowires M_xV₂O_5 + ε·nH₂O (MMg, Mn). It consists of mixing a boiling solution of vanadium oxide with the corresponding metal nitrate. In the present paper, this method was explored for preparing other nanowires layered M_xV₂O_5 + ε·nH₂O compounds (MTi, Cr, Fe, Co, Ni, Cu, and Zn). The results obtained show that If the precipitates are formed immediately after mixing the two solutions, such in case of titanium, chromium and iron, the structure and particles shape of the products are different from the layered compound M_xV₂O_5 + ε·nH₂O. However, if the precipitates start to appear only after several minutes of stirring, such in case of cobalt, nickel, copper and zinc, the phases obtained are similar to layered nanowires M_xV₂O_5 + ε·nH₂O. The amount of the metal inserted “M” was found to be lower than 25 at.% in all as-prepared samples. Nickel containing sample shows the highest inserted amount.     

Structural and dielectric properties of Li2O–ZnO–BaO–B2O3–CuO glasses

Glass samples of the system (15Li₂O–30ZnO–10BaO–(45 − x)B₂O₃–xCuO where x = 0, 5, 10 and 15 mol%) were prepared by using the melt quenching technique. A number of studies, viz. density, differential thermal analysis, FT-IR spectra, a.c. conductivity and dielectric properties (constant εφ, loss tan δ, a.c. conductivity, σ_ac, over a wide range of frequency and temperature) of these glasses were carried out as a function of copper ion concentration. The analysis of the results indicate that the density increases while molar volume decreases with increasing of copper content indicates structural changes of the glass matrix. The glass transition temperature, T _g, and crystallization temperature, T _c, increase with the variation of concentration of CuO referred to the growth in the network connectivity in this concentration range, while glass-forming ability parameter (T _c − T _g) decreases with increasing CuO content, indicates an increasing concentration of copper ions that take part in the network-modifying positions. The FT-IR spectra evidenced that the main structural units are BO₃, BO₄, and ZnO₄. The structural changes observed by varying the CuO content in these glasses and evidenced by FTIR investigation suggest that the CuO plays a network modifier role in these glasses while ZnO plays the role of network formers. The dielectric constant decreased with increase in temperature and CuO content. The variation of a.c. conductivity with the concentration of CuO passes through a maximum at 5 mol%. In the high temperature region, the a.c. conduction seems to be connected with the mixed conduction viz., electronic conduction and ionic conduction.