Study of phase transition in ZrO2 doped with Pb3O4

Electrical conductivity of ZrO₂ doped with Pb₃O₄ has been measured at different temperatures for different molar ratios (x=0, 0.01, 0.02, 0.03, 0.04, 0.05 and 0.06). The conductivity increases due to migration of vacancies, created by doping. The conductivity increases with increase in temperature till 180 °C and thereby decreases due to collapse of the fluorite framework. A second rise in conductivity at higher temperatures beyond 500-618 °C is due to phase transition of ZrO₂. DTA and X-ray powder diffraction were carried out for confirming doping effect and transition in ZrO₂.The addition of Pb₃O₄ to ZrO₂ shifted the phase transition of ZrO₂ due to the interaction between Pb₃O₄ and ZrO₂.     

Partial electronic conductivity and electrolytic domain of bilayer electrolyte Zr0.84Y0.16O1.92/Ce0.9Gd0.1O1.95

Partial electronic conductivity and total conductivity have been determined by Hebb-Wagner polarization method and a.c. impedance spectroscopy, respectively, on bilayer electrolyte Zr_0.84Y_0.16O_1.92(YSZ)/Ce_0.9Gd_0.1O_1.95(GDC) with thickness ratios 10^− 3/1 and 10^− 4/1 at 800°, 900° and 1000 °C, respectively. While their ionic conductivities remain close to that of GDC, the electronic conductivities are suppressed the more from that of GDC towards that of YSZ the higher the thickness ratio, as expected. Even when the GDC-side is exposed to reducing atmosphere, the electronic conductivity is also suppressed, but to a less extent. It is suggested that oxygen activity distribution is discontinuous across the YSZ/GDC interface under ion-blocking condition, refuting the “continuity hypothesis” that has been usually adopted in calculating the oxygen activity distribution across a multilayer of mixed conductor oxides. The electrolytic domain widths of the bilayer electrolyte are reported depending on temperature, thickness ratio and direction of oxygen activity gradient imposed.     

Room temperature lithium fast-ion conduction and phase relationship of LiI stabilized LiBH4

In the present work, we focus attention on the effect of LiI addition to newly discovered pure lithium ion conductor, LiBH₄. Solid solution of the composition LiBH₄-LiI (LiI: 6.25-33.3 mol%) was synthesized by solid state reaction. Electrical conductivity was measured from room temperature to 140 °C by ac impedance method, which revealed the fast-ion conduction phase of LiBH₄ can be stabilized to lower temperature, below the room temperature. Solid solution with LiI showed higher conductivities and lower activation energies in comparison with LiBH₄. Powder XRD measurement was carried out at 120 °C (just above the transition temperature of LiBH₄). The lattice constants of the solid solution were determined. DSC measurement showed a systematic compositional dependence on the transition temperature. The stabilization mechanism was discussed.     

Rapid microwave-assisted hydrothermal synthesis of Bi12TiO20 hierarchical architecture with enhanced visible-light photocatalytic activities

Flower-like Bi₁₂TiO₂₀ hierarchical nanostructures composed of numerous nanobelts were synthesized at 180 °C within 1 h by a microwave-assisted hydrothermal method in the presence of cetyltrimethylammonium bromide (CTAB) for the first time. The as-prepared products were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultraviolet–visible (UV–vis) absorption spectroscopy. Furthermore, the hierarchical Bi₁₂TiO₂₀ nanostructures exhibited higher photocatalytic activities in the degradation of Rhodamine B under visible-light irradiation than that of the samples prepared without CTAB. In addition, the role of CTAB cationic surfactant has been investigated thoroughly and a possible mechanism is proposed.     

Preparation and characterization of SrSnO3 nanorods

Perovskite strontium stannate (SrSnO₃) nanorods were prepared by annealing the precursor SnSr(OH)₆ nanorods at 600 °C for 3 h. The precursor nanorods were hydrothermally synthesized at 160 °C for 16 h using Sr(NO₃)₂ and SnCl₄·5H₂O as starting materials in the presence of surfactant cetyltrimethyl ammonium bromide (CTAB). As-prepared samples were characterized by X-ray diffraction (XRD), thermogravimetric-differential thermal analysis (TG-DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and infrared ray spectroscopy (IR). The results show that the as-synthesized powders are made of SrSnO₃ one-dimensional nanorods of about 0.2-1 μm length and 100-150 nm diameter. Possible formation mechanism of SrSnO₃ with nanorod structure under certain conditions was preliminarily analyzed, in which it was thought that CTAB played an important role in the formation process of the nanorod structure. Electrochemical performance of the samples versus Li metal was also evaluated for possible use in lithium-ion batteries.     

DC and AC conductivities of (As2S3)100−x(AsSe0.5Te0.5I)x chalcogenide glasses

The DC and AC conductivities of samples from the system (As₂S₃)_100−x(AsSe_0.5Te_0.5I)_x, where x=0, 5, 10, 15, 20, 25, 30, 35, 50, 70 and 90 mol%, were measured as a function of temperature. Besides, the AC conductivities of the samples with x=10 and 30 were measured as a function of frequency from room temperature to the glass transition temperature. The DC conductivity dependence on temperature is of the Arrhenius type, whereas the value of the pre-exponential factor suggests the electrical conduction by localized states in the band tails and by localized states near the Fermi level. The small values of the conduction activation energy (10⁻²-10⁻¹ eV) obtained at higher frequencies suggest that the conduction in these materials is due to hopping of charge carriers between close defect states near the Fermi level.     

CTAB assisted growth and characterization of nanocrystalline CuO films by ultrasonic spray pyrolysis technique

An aqueous solution of cupric nitrate trihydrate (Cu(NO₃)₂·3H₂O) modified with cetyltrimetylammonium bromide (CTAB) is used to deposit CuO films on glass substrate by chemical spray pyrolysis technique. The thermal analysis shows that the dried CTAB doped precursor decomposes by an exothermic reaction and suggests that minimum substrate temperature for film deposition should be greater than 270 °C. X-ray diffraction (XRD) studies indicate the formation of monoclinic CuO with preferential orientation along (0 0 2) plane for all film samples. The CTAB used as cationic surfactant in precursor results in the suppression of grain growth in films along the (1 1 0), (0 2 0) and (2 2 0) crystal planes of CuO. Surfactant modified films showed an increase in crystallite size of 14 nm at substrate temperature of 300 °C. The scanning electron micrographs (FESEM) confirm the uniform distribution of facets like grains on the entire area of substrate. CTAB modified films show a significant reduction in the particle agglomeration. Electrical studies of the CuO films deposited at substrate temperature of 300 °C with and without surfactant reveal that the CTAB doping increase the activation energy of conduction by 0.217 eV and room temperature response to ammonia by 9%. The kinetics of the ammonia gas adsorption on the film surface follows the Elovich and Diffusion models.     

Spectroscopic characterization approach to study surfactants effect on ZnO2 nanoparticles synthesis by laser ablation process

Zinc peroxide nanoparticles having grain size less than 5 nm were synthesized using pulsed laser ablation in aqueous solution in the presence of different surfactants and solid zinc target in 3% H₂O₂. The effect of surfactants on the optical and structure of ZnO₂ was studied by applying different spectroscopic techniques. Structural properties and grain size of the synthesized nanoparticles were studied using XRD method. The presence of the cubic phase of zinc peroxide in all samples was confirmed with XRD, and the grain sizes were 4.7, 3.7, 3.3 and 2.8 nm in pure H₂O₂, and H₂O₂ mixed with SDS, CTAB and OGM respectively. For optical characterization, FTIR transmittance spectra of ZnO₂ nanoparticles prepared with and without surfactants show a characteristic ZnO₂ absorption at 435-445 cm⁻¹. FTIR spectrum revealed that the adsorbed surfactants on zinc peroxide disappeared in case of CTAB and OGM while it appears in case of SDS. This could be due to high critical micelles SDS concentration comparing with others which is attributed to the adsorption anionic nature of this surfactant. Both FTIR and UV-vis spectra show a red shift in the presence of SDS and blue shift in the presence of CTAB and OGM. The blue shift in the absorption edge indicates the quantum confinement property of nanoparticles. The zinc peroxide nanoparticles prepared in additives-free media was also characterized by Raman spectra which show the characteristic peaks at 830-840 and 420-440 cm⁻¹.     

Effects of protons and acceptor substitution on the electrical conductivity of La6WO12

Transport properties and non-stoichiometry of La_1−xCa_xW_1/6O₂ and La_1−yW_1/6O₂ (x=0, 0.005, 0.05; y=0.05, 0.1) have been characterized by means of impedance spectroscopy, the EMF-technique, H⁺/D⁺ isotope exchange, and thermogravimetry in the temperature range 300-1200 °C as a function of oxygen partial pressure and water vapor partial pressure. The materials exhibit mixed ionic and electronic conductivities; n- and p-type electronic conduction predominate at high temperatures under reducing and oxidizing conditions, respectively. Protons are the major ionic charge carrier under wet conditions and predominates the conductivity below ∼750 °C. The maximum in proton conductivity is observed for LaW_1/6O₂ with values reaching 3×10⁻³ S/cm at approximately 800 °C. The high proton conductivity for the undoped material is explained by assuming interaction between water vapor and intrinsic (anti-Frenkel) oxygen vacancies.     

Preparation, structure and oxide ion conductivity in Ce6−xYxMoO15−δ (x=0.1-1.4) solid solutions

The Ce_6−xY_xMoO_15−δ solid solution with fluorite-related structure have been characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), IR, Raman, scanning electric microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) methods. The electric conductivity of samples is investigated by Ac impedance spectroscopy. An essentially pure oxide-ion conductivity of the oxygen-deficiency was observed in pure argon, oxygen and air. The highest oxygen-ion conductivity was found in Ce_5.5Y_0.5MoO_15−δ ranging from 5.9×10⁻⁵ (S cm⁻¹) at 300 °C to 1.3×10⁻² (S cm⁻¹) at 650 °C, respectively. The oxide-ion conductivities remained stable over 80 h-long test at 800 °C. These properties suggested that significant oxide-ionic conductivity exists in these materials at moderately elevated temperatures.     

Electrical properties vs. microstructure of nanocrystallized V2O5-P2O5 glasses — An extended temperature range study

An electronically conducting nanomaterial was synthesized by nanocrystallization of a 90V₂O₅·10P₂O₅ glass and its electrical properties were studied in an extended temperature range from − 170 to + 400 °C. The conductivity of the prepared nanomaterial reaches 2 ? 10^− 1 S cm^− 1 at 400 °C and 2 ? 10^− 3 S cm^− 1 at room temperature. It is higher than that of the original glass by a factor of 25 at room temperature and more than 100 below − 80 °C. A key role in the conductivity enhancement was ascribed to the material's microstructure, and in particular to the presence of the large number of small (ca. 20 nm) grains of crystalline V₂O₅. The observed conductivity dependencies are discussed in terms of the Mott's theory of the electronic hopping transport in disordered systems. Since V₂O₅ is known for its ability to intercalate lithium, the presented results might be helpful in the development of cathode materials for Li-ion batteries.     

Proton NMR relaxation study of the CsHSO4 solid acid system

At 141 °C the solid acid CsHSO₄ is known to undergo transition to a superprotonic phase that is characterized by dramatic (several-order-of-magnitude) increases in hydrogen ion conductivity. Proton NMR spin-spin relaxation time T₂ measurements reported here for CsHSO₄ also reveal substantial increases (factors of 20-30) in the vicinity of the transition temperature. In the temperature range just below the transition (70-136 °C), T₂ increases by a factor of order 10 relative to the rigid-lattice regime, suggesting motional narrowing of the NMR resonance line. In the regime of motional narrowing, the activation energy barrier to diffusion is 0.40 eV, as determined from the present T₂ results. NMR spin-lattice relaxation T₁ measurements also show behavior consistent with transition to a regime of rapid hydrogen motion. In particular, proton T₁'s decrease with temperature (from 80 to 120 °C), and then drop sharply near the transition temperature. Above the transition temperature, T₁ exhibits a minimum in which the correlation time is found to be ∼2 ns.     

Hydrothermal synthesis, characterization and Raman studies of Eu activated Gd2O3 nanorods

Eu³⁺ (8 mol%) activated gadolinium oxide nanorods have been prepared by hydrothermal method without and with surfactant, cityl trimethyl ammonium bromide (CTAB). Powder X-ray diffraction (PXRD) studies reveal that the as-formed product is in hexagonal Gd(OH)₃:Eu phase and subsequent heat treatment at 350 and 600 °C transforms the sample to monoclinic GdOOH:Eu and cubic Gd₂O₃:Eu phases, respectively. The structural data and refinement parameters for cubic Gd₂O₃:Eu nanorods were calculated by the Rietveld refinement. SEM and TEM micrographs show that as-obtained Gd(OH)₃:Eu consists of uniform nanorods in high yield with uniform diameters of about 15 nm and lengths of about 50-150 nm. The temperature dependent morphological evolution of Gd₂O₃:Eu without and with CTAB surfactant was studied. FTIR studies reveal that CTAB surfactant plays an important role in converting cubic Gd₂O₃:Eu to hexagonal Gd(OH)₃:Eu. The strong and intense Raman peak at 489 cm⁻¹ has been assigned to A_g mode, which is attributed to the hexagonal phase of Gd₂O₃. The peak at ∼360 cm⁻¹ has been assigned to the combination of F_g and E_g modes, which is mainly attributed to the cubic Gd₂O₃ phase. The shift in frequency and broadening of the Raman modes have been attributed to the decrease in crystallite dimension to the nanometer scale as a result of phonon confinement.     

A SIMS study on Mg diffusion in Zn0.94Mg0.06O/ZnO heterostructures grown by metal organic chemical vapor deposition

Zn_0.94Mg_0.06O/ZnO heterostructures have been grown on 2 in. sapphire wafer using metal organic chemical vapor deposition (MOCVD). Photoluminescence (PL) mapping demonstrates that Mg distribution on the entire wafer is very uniform (standard deviation of Mg concentration/mean Mg concentration = 1.38%) with average concentration of ∼6%. The effect of annealing on the Mg diffusion in Zn_0.94Mg_0.06O/ZnO heterostructures has been investigated in detail by using secondary ion mass spectrometry (SIMS). All the Mg SIMS depth profiles have been fitted by three Gaussian distribution functions. The Mg diffusion coefficient in the as-grown Zn_0.94Mg_0.06O layer deposited at 700 °C is two orders of magnitude lower than that of annealed samples, which clearly indicates that the deposition temperature of 700 °C is much more beneficial to grow ZnMgO/ZnO heterostructures and quantum wells.     

Fluoride glasses in the InF3-GaF3-YF3-PbF2-CaF2-ZnF2 system

New glasses have been synthesized in a multicomponent system based on indium fluoride. Samples of a few mm in thickness were obtained. They are transparent and homogeneous. Main physical properties such as density, characteristic temperatures, density, thermal expansion and refractive index have been measured. The evolution versus composition is reported for samples with the formula: (35−x) InF₃-xGaF₃-10YF₃-25PbF₂-15CaF₂-15ZnF₂. T_g lies between 260 and 296 °C while melting starts around 480 °C. Glass samples are stable at room temperature. By comparison with other standard fluoride glasses, they exhibit higher refractive index and density.     

Surfactant effect on the upconversion emission and decay time of ZrO2:Yb-Er nanocrystals

Luminescent properties of doped ZrO₂:Er³⁺ and codoped ZrO₂:Yb³⁺-Er³⁺ nanocrystals with average size ∼54 nm were analyzed as a function of non-ionic surfactant (Pluronic F-127) concentration. Surfactant and non-surfactant samples were prepared by the sol-gel micelle process with hydrothermal aging and annealed at 1000 °C for 5 h. The introduction of the surfactant reduces the presence of impurities such as OH and CO₂ on both samples, and increments the tetragonal phase for codoped nanocrystals. It induces an increment larger than 90% and 70% for doped and codoped, respectively, for an optimum molar ratio of 0.0082. The observed enlargement of fluorescence decay time is partly the result of the nanosize effect but is dominated by the reduction of impurities attached on the nanocrystalline surface.     

A stable NH4PO3-glass proton conductor for intermediate temperature fuel cells

A stable and conductive composite material based on NH₄PO₃ and amorphous oxides (SiO₂-P₂O₅) has been prepared by a wet-chemical route following with firing in ammonia. The composite showed high proton conductivity in both ambient air and humidified 5% H₂/Ar. A total conductivity of 6.0-19 mS/cm in the temperature range of 150-250 °C has been achieved. The conductivity (about 19 mS/cm) is stable in humidified 5% H₂/Ar during ageing at 175 °C for over 100 h. This material is a potential electrolyte for intermediate temperature fuel cells and other electrochemical devices.     

Structure and luminescent properties of LaNbO4 synthesized by sol-gel process

The luminescence properties of LaNbO₄ synthesized by the citric gel process were investigated. The crystallized orthorhombic and monoclinic biphasic structure forms at temperatures below 1100 °C and well-crystallized monoclinic LaNbO₄ is obtained by heat treatment at a temperature of 1200 °C for 3 h. All of LaNbO₄ phosphors derived from the citric gel method exhibit red-shifted excitation spectra as the calcining temperature increased from 700 to 1200 °C. The effect of the heat treatment conditions on the peak shape and the peak positions of the photoluminescence (PL) emission are undetectable, and the PL spectra excited at 260 nm have a blue emission band maximum at 408 nm, corresponding to the self-activated luminescence center of LaNbO₄. The sample heat treated at 1100 °C for 3 h showed the highest absorption and fluorescence intensities among the prepared samples.     

Syntheses and properties of the Fe-Co/Fe3O4 ferrites

The Fe alloy-ferrite composites Fe-Co/Fe₃O₄ are synthesized by using disproportion of Fe (II) and reduction of Co (II) by Fe⁰ in a concentrated and boiling KOH solution. The Fe alloy and ferrites are prepared in aqueous solution without any templet and surfactants at low temperature. Their structures and magnetic properties are investigated by X-ray diffractometer (XRD) and vibrating sample magnetometer (VSM). From the results of XRD, it is shown that the samples have b.c.c and f.c.c structure of Fe, and the spinel structures of the ferrite before calcinations; the samples have b.c.c and spinel structures after calcinations at 300 °C; and the samples have only f.c.c structure and the spinel structures calcined at 500 °C.