Comparison of the electrochemical behavior of CeO2–SnO2 and CeO2–TiO2 electrodes produced by the Pechini method

CeO₂–SnO₂ and CeO₂–TiO₂ thin films were prepared by the Pechini method and their characteristics were compared, using a fractional factorial design to quantify the effect of five preparation variables. It was observed that CeO₂–SnO₂ electrodes show a greater electrochemical response than the CeO₂–TiO₂ films. The best intercalation charge densities were 18.11 and 9.91 mC/cm² for CeO₂–SnO₂ and CeO₂–TiO₂, respectively. Both films were optically inactive with transparencies, in most cases, higher than 90%.     

Effect of preparation conditions on properties of atomic layer deposited TiO2 films in Mo–TiO2–Al stacks

TiO₂ films were grown by atomic layer deposition on Mo electrodes in order to elucidate the dominating conductance mechanism and its dependence on the growth chemistry. TiCl₄ and Ti(OC₂H₅)₄ served as titanium precursors, and H₂O or H₂O₂ as oxygen precursors. The films grown at lower temperatures were amorphous. With increasing growth temperatures the crystallization first started in the TiCl₄–H₂O process. The films grown in this process were clearly leakier compared to the films grown from Ti(OC₂H₅)₄ and H₂O and from Ti(OC₂H₅)₄ and H₂O₂. In the Ti(OC₂H₅)₄-based processes, the application of H₂O₂ instead of H₂O resulted in the films with considerably lowered conductivity, although structural differences in these films were insignificant. Space–charge-limited currents were prevailing in all our amorphous Mo–TiO₂–Al packages. Measurements at different temperatures suggested quite high trap densities likely due to the presence of impurities and structural disorder, while the strong differences in conductivity seemed to be due to different densities of gap states.     

Preparation of B-doped a-Si1−xCx:H films and heterojunction p–i–n solar cells by the Cat-CVD method

B-doped a-Si_1−xC_x:H films for a window layer of Si thin film solar cells have been prepared by the Cat-CVD method. It is found that C is effectively incorporated into the films by using C₂H₂ as a C source gas, where an only little C incorporation is observed from CH₄ and C₂H₆ under similar deposition conditions. Using a-Si_1−xC_x:H films grown from C₂H₂, heterojunction p–i–n solar cells have been prepared by the Cat-CVD method. The cell structure is (SnO₂ Asahi-U)/ZnO/a-Si_1−xC_x:H(p)/a-Si:H(i)/μc-Si:H(n)/Al. The obtained conversion efficiency was 5.4%.     

The preparation and gas sensitivity study of polythiophene/SnO2 composites

Nanocomposites of SnO₂ and polythiophene (PTP) were synthesized by the in situ chemical oxidative polymerization method. These nanocomposites were characterized by FTIR, transmission electron microscope (TEM), X-ray diffraction (XRD) and thermogravimetric and differential thermal analysis (TG–DTA) techniques, which proved the polymerization of thiophene monomer and the strong interaction between polythiophene and SnO₂. The composites were used for gas sensing to methanol (MeOH), ethanol (EtOH), acetone, and NO_x at different working temperature. It was found that PTP/SnO₂ materials with different PTP mass percent (1%, 5%, 10%, 20% and 30%) could detect NO_x with very higher selectivity and sensitivity at much lower working temperature than the reported SnO₂. The PTP/SnO₂ nanocomposites responded to NO_x at concentration as low as 10 ppm. PTP/SnO₂ composite containing 5 mass% PTP showed the highest sensitivity at room temperature. The sensing mechanism of PTP/SnO₂ nanocomposites to NO_x was presumed to be the effects of p–n heterojunction between PTP and SnO₂.     

电解液组分对TiCP/Ti6Al4V复合材料微弧氧化膜耐蚀性及耐磨性影响

采用微弧氧化技术在 TiC_P/Ti6Al4V 复合材料表面制备陶瓷膜。在NaAlO₂和NaH₂PO₂两种溶液体系中通过添加不同添加剂 NaOH、C₁₀H₁₂CaNa₂N₂O₈·4H₂O和Na₂SiO₃, 研究电解液组分对陶瓷膜组织、耐蚀性和耐磨性的影响。结果表明: 在NaH₂PO₂电解液体系中生成的膜层由金红石型和锐钛矿型TiO₂相组成, 而在NaAlO₂体系中除了生成TiO₂外, 还生成了Al₂TiO₅和γ-Al₂O₃。添加NaOH可以加快微弧氧化反应速率, 添加NaAlO₂和Na₂SiO₃有利于提高膜层的硬度, NaH₂PO₂溶液体系中形成的膜层厚度是NaAlO₂溶液体系的2~3倍。 在NaAlO₂和NaH₂PO₂电解液体系中生成的膜层, 其耐腐蚀性能排序均为: Na₂SiO₃>C₁₀H₁₂CaNa₂N₂O₈·4H₂O>NaOH。在NaAlO₂电解液体系中生成的膜层的耐磨性能排序为: Na₂SiO₃>NaOH>C₁₀H₁₂CaNa₂N₂O₈·4H₂O, 而在NaH₂PO₂电解液体系中生成的膜层的耐磨性能排序为: Na₂SiO₃>C₁₀H₁₂CaNa₂N₂O₈·4H₂O>NaOH。TiC_P/Ti6Al4V复合材料经过微弧氧化处理后, 耐磨性和耐蚀性均优于基体, 在NaH₂PO₂+Na₂SiO₃电解液中生成的微弧氧化膜的耐蚀性最好, 耐磨性也较好, 其腐蚀电流密度较钛基复合材料基体降低约2个数量级, 因此综合性能最好。     

Corrosion of magnesia–chrome brick in molten MgO–Al2O3–SiO2–CaO–FetO slag

The corrosion of magnesia–chrome (MgO–Cr₂O₃) brick in molten MgO–Al₂O₃–SiO₂–CaO–Fe_tO slag has been characterized using a dynamic rotary slag corrosion testing for various test cycles at 1650 °C. The open porosity decreases from 15.3 to 4.0% for three cycles, then it gradually increases from 4.0 to 4.8% when the test is extended to nine cycles, in which the permeating depth of the slag maintains at about 20 mm. The XRD pattern of the permeated layer shows the presence of the MgO, MgCr₂O₄ and CaMgSiO₄ phases. In the interior of the permeating layer cracks are formed and corrosion starts at the pores and cracks of MgO and decreases gradually. However, at 20–40 mm beneath the permeated layer edge, different shapes of MgO particles are found.     

Crystal structure, thermal analysis and IR spectroscopic investigation of (C6H9N2)H2XO4 (X = As, P)

Crystals of 2-amino-4-methylpyridinium dihydrogenmonoarsenate (C₆H₉N₂)H₂AsO₄ and 2-amino-4-methylpyridinium dihydrogenmonophosphate (C₆H₉N₂)H₂PO₄ have been prepared and grown at room temperature. These materials are isotypic with the following unit cell dimensions (C₆H₉N₂)H₂AsO₄: a = 12.4415(5) Å, b = 6.8224(3) Å, c = 11.3524(5) Å, Z = 4, V = 963.60(6) Å³; (C₆H₉N₂)H₂PO₄: a = 12.4410(9) Å, b = 6.7165(3) Å, c = 11.3417(5) Å, Z = 4, V = 925.09(10) Å³. The common space group is Pnma. The structure of these compounds has been determined by X-ray data collection on single crystals of (C₆H₉N₂)H₂AsO₄ and (C₆H₉N₂)H₂PO₄. Due to the strong hydrogen-bond network connecting the H₂XO₄ groups, the anionic arrangement must be described as a linear organization. The chains composed by the macroanion spread along the b-direction, approximately centered by x = 0 and 1/2. All atoms of the structure, except one oxygen atom, are located in the mirror planes situated at y = 1/4 and 3/4, imparting an internal mirror symmetry to the anionic and the cationic entities. The linear macroanions are crossed by organic cations lying in mirrors perpendicular to the b-direction; this atomic arrangement is then described by a three-dimensional network of hydrogen bonds, built up by two types, O–HO bonds inside the chains and N–HO bonds linking adjacent chains. The thermal properties of both compounds are investigated as well as the IR properties supported by group theoretical analyses.     

Investigation on the cross sensitivity of NO2 sensors based on In2O3 thin films prepared by sol-gel and vacuum thermal evaporation

In₂O₃ thin films have been prepared from commercially available pure In₂O₃ powders by high vacuum thermal evaporation (HVTE) and from indium iso-propoxide solutions by sol-gel techniques (SG). The films have been deposited on sapphire substrates provided with platinum interdigital sputtered electrodes. The as-deposited HVTE and SG films have been annealed at 500°C for 24 and 1 h, respectively. The film morphology, crystalline phase and chemical composition have been characterised by SEM, glancing angle XRD and XPS techniques. After annealing at 500°C the films’ microstructure turns from amorphous to crystalline with the development of highly crystalline cubic In₂O_3−x (JCPDS card 6-0416). XPS characterisation has revealed the formation of stoichiometric In₂O₃ (HVTE) and nearly stoichiometric In₂O_3−x (SG) after annealing. SEM characterisation has highlighted substantial morphological differences between the SG (highly porous microstructure) and HVTE (denser) films. All the films show the highest sensitivity to NO₂ gas (0.7–7 ppm concentration range), at 250°C working temperature. At this temperature and 0.7 ppm NO₂ the calculated sensitivities (S=R_g/R_a) yield S=10 and S=7 for SG and HVTE, respectively. No cross sensitivity have been found by exposing the In₂O₃ films to CO and CH₄. Negligible H₂O cross has resulted in the 40–80% relative humidity range, as well as to 1 ppm Cl₂ and 10 ppm NO. Only 1000 ppm C₂H₅OH has resulted to have a significant cross to the NO₂ response.     

Systematic search for energetically favored isomers of large fullerenes C122–C130 and C162–C180

Based on the methodology by Cioslowski et al. [J. Cioslowski, N. Rao, D. Moncrieff, J. Am. Chem. Soc. 122 (2000) 8265–8270], two empirical fit equations to predict the standard enthalpy of formation are obtained over large number of calculation results at B3LYP/6-31G* theory level for fullerene isomers, which can be used as a preliminary and second-level screening tool, respectively, for large fullerenes. By applying these equations in screening the whole isolated pentagon rule (IPR) isomers, the energetically favored isomers of large fullerenes C₁₂₂–C₁₃₀ and C₁₆₂–C₁₈₀ were predicted at the B3LYP/6-31G* density functional theory level for the first time. Our results show that the lowest energy isomers of C₁₇₄ (2473259: C_3v) and C₁₈₀ (4071832: I_h) possess much lower relative energy and larger HOMO–LUMO gaps. Moreover, the ionization energy and electron affinity of the lowest energy isomers were also investigated.     

Effect of SnO2 on the photocatalytical properties of TiO2 films

TiO₂/SnO₂ thin films with different tin atomic percentages were successfully prepared on glass substrates by the spray pyrolysis method from an alcoholic solution of TiO[C₅H₇O₂]₂ with different concentrations of SnCl₄. The TiO₂/SnO₂ thin films prepared at 450 °C presented the anatase phase in polycrystalline configuration from %Sn = 0 in the starting solution up to %Sn = 20, at higher tin content the films present an amorphous configuration. The resulting thin films have a homogeneous surface structure with some porosity. The photocatalytical properties of the films were evaluated with the degradation of methylene blue. The products of the degradation reaction were identified by ¹H nuclear magnetic resonance and the film properties were studied by atomic force microscopy, scanning electron microscopy, UV–Vis spectroscopy, and X-ray diffraction.     

Electrical properties of glasses in the Na2O–MoO3–P2O5 system

A range of coloured electronic or mixed ionic–electronic glasses has been evidenced in the Na₂O–MoO₃–P₂O₅ system. The properties of these glasses have been studied along different composition lines corresponding either to a fixed Na₂O content or a constant Mo/P ratio. An EPR spectroscopy investigation of these glasses has allowed to determine the Mo⁵⁺ ion percentages in these materials. The electrical properties of these glasses have been studied by impedance spectroscopy, and the electronic and ionic contributions have been evaluated. The properties of these sodium glasses have been compared with those of lithium glasses with the same compositions.     

Microstructures, densification and mechanical properties of TiC–Al2O3–Al composite by field-activated combustion synthesis

Dense TiC–Al₂O₃–Al composite was prepared with Al, C and TiO₂ powders by means of electric field-activated combustion synthesis and infiltration of the molten metal (here Al) into the synthesized TiC–Al₂O₃ ceramic. An external electric field can effectively improve the adiabatic combustion temperature of the reactive system and overcome the thermodynamic limitation of reaction with x < 10 mol. Thereby, it can induce a self-sustaining combustion synthesis process. During the formation of Al₂O₃–TiC–Al composite, Al is molten first, and reacted with TiO₂ to form Al₂O₃, followed by the formation of TiC through the reaction between the displaced Ti and C. Highly dense TiC–Al₂O₃–Al with relative density of up to 92.5% was directly fabricated with the application of a 14 mol excess Al content and a 25 V cm⁻¹ field strength, in which TiC and Al₂O₃ particles possess fine-structured sizes of 0.2–1.0 μm, with uniform distribution in metal Al. The hardness, bending strength and fracture toughness of the synthesized TiC–Al₂O₃–Al composite are 56.5 GPa, 531 MPa and 10.96 MPa m^1/2, respectively.     

Preparation of nanocrystalline SnO2 thin film coated Al2O3 ultrafine particles by fluidized chemical vapor deposition

Fluidized chemical vapor deposition (FCVD) technology was developed for coating SnO₂ thin film on Al₂O₃ ultrafine particles. TEM and HREM analysis found that SnO₂ films with different structures were deposited by controlling the coating temperature, reactant concentration, etc. Nanocrystalline SnO₂ film was coated at 573.15 K by gas phase reaction of SnCl₄ with H₂O. EPMA and EDS studies indicated that the distribution of SnO₂ inner and outer of the agglomerates was uniform. Nucleation and film deposition were coexisted mechanism during the FCVD coating process. The fraction of SnO₂ in the composite particles increased with increasing coating temperature, SnCl₄ concentration, and coating time. The mass fraction of SnO₂ in the composite particles increased strongly with the ratio of P_H2O and P_SnCl4 at low mole ratio of H₂O with SnCl₄, but increased little under the conditions of excess H₂O with respect to SnCl₄.     

Visualization and model development of Marangoni convection in NH3–H2O systemVisualization et développement d'un modèle de convection de Marangoni dans un système à NH3–H2O

The objectives of this paper are to obtain experimental data of surface tension and interfacial tension, and to develop a new model of Marangoni convection for the best selection of heat transfer additive in ammonia–water absorption systems. The basic mechanism of Marangoni convection in absorption systems was reviewed from the viewpoints of the surface tension and the interfacial tension gradients. Marangoni convection was successfully visualized using a shadow graphic method. The solubility limits of the additives in ammonia–water solution ranged from 500 to 3000 ppm depending on the heat transfer additives. These values are much higher than those in LiBr–H₂O solution in which the solubility ranged from 70 to 400 ppm. The temperature gradient of the surface tension should not be a criterion for Marangoni convection inducement in NH₃–H₂O system. The concentration and temperature gradients of the interfacial tension should not be a criterion for Marangoni convection inducement in NH₃–H₂O system. The magnitude of the interfacial tension did not affect the occurrence of Marangoni convection either. It was found that addition of the heat transfer additive beyond the solubility limit assisted Marangoni convection occurrence, but should not be a criterion for Marangoni convection inducement. It was proposed that the radical-out model should be a criterion for Marangoni convection inducement within the solubility limit in NH₃–H₂O system.     

Thermoluminescence of Tb doped Gd2O2S phosphor

Thermoluminescence (TL) of gadolinium oxysulfide activated with terbium (Gd₂O₂S:Tb) is investigated. The glow curves of Gd₂O₂S:Tb phosphor recorded in the temperature range of 93–500 K with a heating rate of 0.52 K s⁻¹ shows five prominent glow peaks. Comparison of the glow curves exhibited by different samples prepared with varying firing conditions reveals some interesting results. In this phosphor capture centers are mainly formed due to variable valency activators, trace impurities and point defects, which create defects in the sub-lattice. The observed TL spectra suggest a multiplicity of electron and hole traps. The main peak that observed at 150 K is attributed to point defects arising out of sulfur vacancies. These vacancies give rise to electron traps, which are found to be associated with terbium centers. This is confirmed by the monochromatic glow curves observed at wavelengths corresponding to the characteristic terbium emission (⁵D₃–⁷F_n, ⁵D₄–⁷F_n). Removal of this glow peak under H₂S firing indicates the localized character of the concerned centers.     

Conduction analysis of Li2O doped 0.2[Pb(Mg1/3Nb2/3)]–0.8[PbTiO3–PbZrO3] ceramics fabricated by columbite precursor method

We have fabricated 0.2Pb(Mg_1/3Nb_2/3)O₃–0.8Pb(Zr_0.475Ti_0.525)O₃ [PMN–PZT] ceramics doped with various amounts of Li₂O (0, 0.05, 0.1, 0.2, 0.3 wt.%) using the columbite precursor method. The effects of Li-doping on the conduction behavior of PMN–PZT ceramics are discussed in relation to the low frequency dielectric dispersion and frequency domain measurement. The Li-doped PMN–PZT ceramics sintered at 950 °C showed a sufficient densification with large dielectric constant and low dielectric loss. The incorporation of Li⁺ ion in PMN–PZT ceramics led to an appreciable reduction in electrical conductivity and further enhanced the ferroelectric and piezoelectric properties. The activation energies of PMN–PZT + xLi₂O (x = 0, 0.05, 0.1, 0.2, 0.3 wt.%) ceramics calculated from ac conductivity measurement using the Arrhenius relation were 1.05, 1.25, 1.27, 1.38 and 1.41 eV, respectively. The conduction behavior is examined in the low frequency and high temperature region and the results are discussed in detail through crystal defect mechanism.     

Doping and electrical characteristics of in-situ heavily B-doped Si1−x−yGexCy films epitaxially grown using ultraclean LPCVD

Doping and electrical characteristics of in-situ heavily B-doped Si_1−x−yGe_xC_y (0.22<x<0.6, 0<y<0.02) films epitaxially grown on Si(100) were investigated. The epitaxial growth was carried out at 550°C in a SiH₄–GeH₄–CH₃SiH₃–B₂H₆–H₂ gas mixture using an ultraclean hot-wall low-pressure chemical vapor deposition (LPCVD) system. It was found that the deposition rate increased with increasing GeH₄ partial pressure, and only at high GeH₄ partial pressure did it decrease with increasing B₂H₆ as well as CH₃SiH₃ partial pressures. With the B₂H₆ addition, the Ge and C fractions scarcely changed and the B concentration (C_B) increased proportionally. The C fraction increased proportionally with increasing CH₃SiH₃ partial pressures. These results can be explained by the modified Langmuir-type adsorption and reaction scheme. In B-doped Si_1−x−yGe_xC_y with y=0.0054 or below, the carrier concentration was nearly equal to C_B up to approximately 2×10²⁰ cm⁻³ and was saturated at approximately 5×10²⁰ cm⁻³, regardless of the Ge fraction. The B-doped Si_1−x−yGe_xC_y with high Ge and C fractions contained some electrically inactive B even at the lower C_B region. Resistivity measurements show that the existence of C in the film enhances alloy scattering. The discrepancy between the observed lattice constant and the calculated value at the higher Ge and C fraction suggests that the B and C atoms exist at the interstitial site more preferentially.     

Determining crystallization kinetic parameters of Li2O–Al2O3–SiO2 glass from derivative differential thermal analysis curves

The kinetic parameters such as crystallization activation energy, E, and the frequency factor, ν, of Li₂O–Al₂O₃–SiO₂ glass were determined by a new non-isothermal method. The method is described by the equation

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, where β is the heating rate and T_f is the inflection-point temperature of differential thermal analysis (DTA). The value of T_f is determined as the maximum peak temperature on derivative differential thermal analysis (DDTA) curves. Values of E and ν of Li₂O–Al₂O₃–SiO₂ glass were also determined by two existing non-isothermal methods, namely the Kissinger plot and the Ozawa plot, and compared with those determined by isothermal method. Values of E and ν determined by the proposed equation were 332 kJ/mol and 1.4×10¹³ s⁻¹, respectively. They are excellent agreement with the isothermal analysis results, 336 kJ/mol and 1.8×10¹³ s⁻¹, respectively. In contrast, both the Kissinger equation and the Ozawa equation give much higher values of E and ν.     

Structural, electrical and optical characteristics of SnO2:Sb thin films by ultrasonic spray pyrolysis

Antimony-doped tin oxide (SnO₂:Sb) thin films were fabricated by an ultrasonic spray pyrolysis method. The effect of antimony doping on the structural, electrical and optical properties of tin oxide thin films were investigated. Tin(II) chloride dehydrate (SnCl₂·2H₂O) and antimony(III) chloride (SbCl₃) were used as a host and a dopant precursor. X-ray diffraction analysis showed that the non-doped SnO₂ thin film had a preferred (211) orientation, but as the Sb-doping concentration increased, a preferred (200) orientation was observed. Scanning electron microscopy studies indicated that the polyhedron-like grains observed for the non-doped SnO₂ thin films became rounder and decreased in size with the Sb-doping concentration. The lowest resistivity (about 8.4 × 10^− 4 Ω·cm) was obtained for the 3 at.% Sb-doped films. Antimony-doping led to an increase in the carrier concentration and a decrease in Hall mobility. The transmittance level in the near infrared region was lowered with the Sb-doping concentration.     

Structural characterization of CxByNz (x=0.1 to x=0.2) layers obtained by laser-driven synthesis

C_xB_yN_z layers have been prepared by laser-assisted chemical vapour deposition (CVD) in a gas atmosphere containing C₂H₄, B₂H₆ and NH₃ where the starting composition ratio could vary in a large range. The characterization of these C–B–N materials was made by XRD, EPMA, XPS, optical and scanning electron microscopy. The chemical composition of C–B–N layers tended to a composition C₁B₆N₃ on the line BN–‘B₃C’. The turbostratic structure of C–B–N layers could be influenced and modified as a function of composition. XPS investigations confirmed the single-phase nature and the existence of bonding between all the elements. Some planar structures, containing especially CB₂N groups, were suggested for the ‘unit cell’ of these C–B–N solid solutions, in agreement with EPMA and XPS analysis.