Study of AC electrical properties of V2O5–P2O5–B2O3–Dy2O3 glasses

The AC conductivity of glass samples of composition 60V₂O₅–5P₂O₅–(35−x)B₂O₃–xDy₂O₃, 0.4≤x≤1.2 has been analyzed. The samples were prepared by the usual melt-quench technique. The prepared compounds were analyzed by X-ray diffraction (XRD) and thermo gravimetric–differential thermal analysis (TG/DTA). The activation energies were evaluated using glass transition temperature (T_g) and peak temperature of crystallization (T_c) from TG/DTA. The dependence of activation energy on composition was discussed. The electrical conductance and capacitance were measured over a frequency range of 20 Hz to 1 MHz and a temperature range of 303–473 K; these reveal semiconducting features based predominantly on an ionic mechanism. The dielectric and complex-impedance response of the sample is discussed. The relaxation time was found to increase with increasing temperature. Jonscher's universal power law is applied to discuss the conductivity. The electrode polarization was found to be negligible and confirmed from electrical modulus.     

Effects of liquid phases on densification of TiO2-doped Al2O3–ZrO2 composite ceramics

This study investigated the densification behaviors and microstructural evolution of Al₂O₃–ZrO₂ (3Y) composite ceramics doped with four different amounts of TiO₂ (0, 1, 4, and 8 wt%; denoted as 0T, 1T, 4T, and 8T, respectively) to clarify the effect of TiO₂ dopants on densification. The shrinkage rate during densification increased with the increase in the amount of TiO₂. The development of grain boundary feature was also examined. The undoped ceramic showed clean grain boundaries. Thin liquid grain boundary phases were observed in 1T, whereas large liquid phases were found on the grain boundary and at the junction pockets in 4T and 8T. The results were discussed in terms of the relationship between densification and grain boundary feature.     

Investigation of the effect of ZrO2 and ZrO2/Al2O3 additions on the hot-pressing and properties of equimolecular mixtures of α- and β-Si3N4

In this work, hot-pressing of equimolecular mixtures of α- and β-Si₃N₄ was performed with addition of different amounts of sintering additives selected in the ZrO₂–Al₂O₃ system. Phase composition and microstructure of the hot-pressed samples was investigated. Densification behavior, mechanical and thermal properties were studied and explained based on the microstructure and phase composition. The optimum mixture from the ZrO₂–Al₂O₃ system for hot-pressing of silicon nitride to give high density materials was determined. Near fully dense silicon nitride materials were obtained only with the additions of zirconia and alumina. The liquid phase formed in the zirconia and alumina mixtures is important for effective hot-pressing. Based on these results, we conclude that pure zirconia is not an effective sintering additive. Selected mechanical and thermal properties of these materials are also presented. Hot-pressed Si₃N₄ ceramics, using mixtures from of ZrO₂/Al₂O₃ as additives, gave fracture toughness, K_IC, in the range of 3.7–6.2 MPa m^1/2 and Vicker hardness values in the range of 6–12 GPa. These properties compare well with currently available high performance silicon nitride ceramics. We also report on interesting thermal expansion behavior of these materials including negative thermal expansion coefficients for a few compositions.     

Dehydrogenation of propane in the presence of N2O over In2O3―Al2O3 mixed oxide catalysts

Dehydrogenation of propane coupled with N₂O over a series of binary In₂O₃―Al₂O₃ mixed oxides was investigated. In contrast to the poor performance for sole N₂O decomposition, a remarkable synergy was identified between N₂O decomposition and propane dehydrogenation. Among the catalysts tested, the In₂O₃―Al₂O₃ sample containing a 20 mol% In₂O₃ showed the highest activity for propane dehydrogenation in the presence of N₂O. Moreover, stability far superior to those of the conventional iron-based materials was observed, attributable to the moderate surface acidity of the In―Al―O composite. The essential role of N₂O is suggested to generate active oxygen species facilitating propane dehydrogenation.     

Synthesis and characterization of MgAl2O4–ZrO2 composites

Different types of dense 5–97% ZrO₂–MgAl₂O₄ composites have been prepared using a MgAl₂O₄ spinel obtained by calcining a stoichiometric mixture of aluminium tri-hydroxide and caustic MgO at 1300 °C for 1 h, and a commercial yttria partially stabilized zirconia (YPSZ) powder as starting raw materials by sintering at various temperatures ranging from 1500 to 1650 °C for 2 h. The characteristics of the MgAl₂O₄ spinel, the YPSZ powder and the various sintered products were determined by X-ray diffraction (XRD), scanning electron microscopy (SEM), BET surface area, particle size analysis, Archimedes principle, and Vickers indentation method. Characterization results revealed that the YPSZ addition increases the sintering ability, fracture toughness and hardness of MgAl₂O₄ spinel, whereas, the MgAl₂O₄ spinel hampered the sintering ability of YPSZ when sintered at elevated temperatures. A 20-wt.% YPSZ was found to be sufficient to increase the hardness and fracture toughness of MgAl₂O₄ spinel from 406 to 1314 Hv and 2.5 to 3.45 MPa m^1/2, respectively, when sintered at 1600 °C for 2 h.     

The influence of In2O3 on electrical characteristics of iron mixed Li2O–PbO–B2O3–SiO2–Bi2O3 multi-component glass system

Glasses of the composition 19Li₂O–20PbO–20B₂O₃–30SiO₂–(10−x) Bi₂O₃–1Fe₂O₃: xIn₂O₃ with six values of x (0 to 5.0) were synthesized. Dielectric properties viz., dielectric constant, ε′(ω), loss, tan δ, ac conductivity, σ_ac, electric modulus, M(ω) over wide ranges of frequency and temperature and also dielectric break down strength have been studied as a function of In₂O₃ concentration. The temperature dispersion of real part of dielectric constant, ε′(ω) has been analyzed using space charge polarization model. The dielectric loss (and also the electric moduli) variation with frequency and temperature exhibited relaxation effects and these effects were attributed to the divalent iron ion complexes. The ac conductivity exhibited maximal effect, whereas the activation energy for the conductivity demonstrated minimal magnitude at about 1.0 mol% of In₂O₃. The conductivity mechanism is understood due to the polaronic transfer between Fe²⁺ and Fe³⁺ ions. The low temperature ac conductivity mechanism is explained following the quantum mechanical tunneling model. Spectroscopic studies viz., optical absorption and ESR spectra have revealed that the redox ratio (Fe²⁺/Fe³⁺) is maximal when the concentration of In₂O₃ is ~1.0 mol%. The higher values of dielectric parameters observed at 1.0 mol% of In₂O₃ are attributed to the presence of iron ions largely in divalent state and act as modifiers. The analysis of these results together with spectroscopic studies has indicated that when In₂O₃ is present in the glass matrix in higher concentrations (more than 1.0 mol%) iron ions predominantly exist in trivalent state, occupy substitutional positions and make the glass more rigid. Such enhanced rigidity of the network is causing the decrease of dielectric parameters with the concentration of In₂O₃. Finally it is concluded that In₂O₃ mostly participate in the glass network in octahedral positions and make act as reducing agent (for iron ions) in the studied glass matrix when its concentration is ≤1.0 mol%.     

Microwave dielectric characteristics of Nb2O5-added 0.9Al2O3–0.1TiO2 ceramics

The sintering characteristics, phase composition, and microwave dielectric properties of Nb₂O₅-added 0.9Al₂O₃–0.1TiO₂ ceramics sintered at 1300–1500 °C have been investigated. Results show that Nb⁵⁺ and Al³⁺ can co-substitute for Ti⁴⁺ and form Ti_0.8Al_0.1Nb_0.1O₂, which can lower effectively the sintering temperature, and improve the quality factor of 0.9Al₂O₃–0.1TiO₂ ceramics.     

Fe2+催化H2O2、S2O82-、S2O82--H2O2降解橙黄G

以偶氮染料橙黄G(OG)为目标污染物,研究Fe2+分别催化H2O2、S2O82-、H2O2-S2O82-降解0.1 mmol/LOG Fe2+/H2O2体系,[Fe2+]=1 mmol/L,pH=3,[H2O2]0=10 mmol/L,降解30 min OG脱色率为96%,随着pH值增大和[H2O2]0>10 mmol/L,OG脱色率减小,呈线性变化。Fe2+/S2O82-体系,随着S2O82-初始浓度增加OG脱色率增大,随着pH值增大OG脱色率减小,呈非线性变化。Fe2+/H2O2-S2O82-体系,pH=3,[H2O2]0=2 mmol/L,[S2O82-]0>10 mmol/L时OG脱色率持续增大。Fe2+/H2O2-S2O82-体系矿化率最高。利用乙醇和硝基苯作为分子探针,采用分子探针竞争实验鉴定该体系中产生的SO4.和OH.。     

PbBr2-PbCl2-PbF2-PbO-P2O5系统 玻璃性能研究

研究了PbBr     

Influences of La and Er on structure and properties of Bi2O3–B2O3 glass

Bi₂O₃·2B₂O₃ glasses doped with La₂O₃ and Er₂O₃ were prepared by the melting-quenching method with AR-grade oxides. IR analysis was used to investigate the glass network structure. The characteristic temperatures including the glass transition temperature (T_g), crystallization temperature (T_p), and melting temperature (T_m) were estimated by DSC. The coefficient of thermal expansion (α), mass density (D), and Vickers hardness (H_v) were also measured. The results show that the basic network structure of Bi₂O₃·2B₂O₃ glasses doped with rare-earth oxides consists of chains composed of [BO₃], [BO₄], and [BiO₆] units. La₂O₃ and Er₂O₃ act as network modifiers. As the doping concentrations of the rare-earth oxides were increased, T_g increased and α decreased, indicating that a more rigid glass was obtained. Er₂O₃ reduces the melting temperature and prevents glass crystallization. La₂O₃ contributes to the improvement of the microhardness of Bi₂O₃·2B₂O₃ glass.     

Physical properties of pseudo quaternary Na2B4O7 – SiO2 – MoO3 – Dy2O3 glasses

Pseudo quaternary Na₂B₄O₇–SiO₂–MoO₃–Dy₂O₃ glasses with various concentrations of Dy₂O₃ were synthesized and characterized by ultrasound, DTA and X-ray diffraction (XRD). It was found that, the density, the molar volume and the elastic moduli increased while the ultrasonic velocities and the packing density decreased with increasing of Dy₂O₃ concentration. The lower values of the radii and the bond length of B₂O₃, compared to those of Dy₂O₃, decreased the interatomic forces between the reactant glass forming cations and oxygens inside the glassy network. Accordingly, this will increase the molar volume and in the same time will decrease the average cross-link density, the ultrasonic velocities, the glass transition temperature and the thermal stability. Also, this may result in a high density glass sample which will increase the elastic moduli. Based on Lasocka's model, a good correlation between the temperature of both glass transition ($T_{\mathit{gl}}$) and crystallization peak ($T_{\mathit{pc}})$was observed.     

Crystallographic characterization of silicon nitride ceramics sintered with Y2O3–Al2O3 or E2O3–Al2O3 additions

Silicon nitride ceramics were sintered using Y₂O₃–Al₂O₃ or E₂O₃–Al₂O₃ (E₂O₃ denotes a mixed oxide of Y₂O₃ and rare-earth oxides) as sintering additives. The intergranular phases formed after sintering was investigated using high-resolution X-ray diffraction (HRXRD). The use of synchrotron radiation enabled high angular resolution and a high signal to background ratio. Besides the appearance of β-Si₃N₄ phase the intergranular phases Y₃Al₅O₁₂ (YAG) and Y₂SiO₅ were identified in both samples. The refinement of the structural parameters by the Rietveld method indicated similar crystalline structure of β-Si₃N₄ for both systems used as sintering additive. On the other hand, the intergranular phases Y₃Al₅O₁₂ and Y₂SiO₅ shown a decrease of the lattice parameters, when E₂O₃ was used as additive, indicating the formation of solid solutions of E₃Al₅O₁₂ and E₂SiO₅, respectively.     

Effect of Fe2O3 on properties and densification of Ce0.8Gd0.2O2−δ by PCAS

Dense Ce_0.8Gd_0.2O_2−δ was sintered by pulsed current activated sintering (PCAS) within 6 min from Ce_0.8Gd_0.2O_2−δ nanopowder prepared by co-precipitation method. Sintering was accomplished under the combined effects of a pulsed current and mechanical pressure. Highly dense Ce_0.8Gd_0.2O_2−δ with relative density of up to 96.3% was produced under simultaneous application of an 80-MPa pressure and the pulsed current. The effects of Fe₂O₃ additions on the sintering behavior, ionic conductivities, and mechanical properties of the Ce_0.8Gd_0.2O_2−δ were investigated.     

Crystallization behavior and properties of K2O–CaO–Al2O3–SiO2 glass-ceramics

In order to obtain high-strength anorthite glass-ceramics, K₂O–CaO–Al₂O₃–SiO₂ quaternary glass and relevant glass-ceramics were prepared and investigated. The results show that anorthite along with kalsilite or leucite was precipitated from the parent glass. Kalsilite crystals were formed firstly and then converted into leucite through reacting with SiO₂ in the glass phase. The morphology of the crystals was dependent on the heat-treatment temperature. Column crystals were transformed into fine granular grains when the sintering temperature changed from 900 °C to 1100 °C. The activation energy (E_α) and avrami constant (n) were also calculated as 463.81 KJ/mol and 3.74 respectively, indicating that bulk nucleation and three-dimensional crystal growth were the dominating mechanisms in the temperature range 1000–1100 °C. The maximum value of the flexural strength for the glass-ceramics containing leucite was 248 MPa and the coefficient of thermal expansion (CTE) was in the range 5.69~11.94×10⁻⁶ K⁻¹. The leucite is the main reason for the high CTEs and high flexural strength of glass-ceramics.     

Piezocatalytic performance of Fe2O3−Bi2MoO6 catalyst for dye degradation

A Fe₂O₃−Bi₂MoO₆ heterojunction was synthesized via a hydrothermal method. Scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray, powder X-ray diffraction, Fourier transform infrared spectroscopy and ultra-violet−visible near-infrared spectrometry were performed to measure the structures, morphologies and optical properties of the as-prepared samples. The various factors that affected the piezocatalytic property of composite catalyst were studied. The highest rhodamine B degradation rate of 96.6% was attained on the 3% Fe₂O₃−Bi₂MoO₆ composite catalyst under 60 min of ultrasonic vibration. The good piezocatalytic activity was ascribed to the formation of a hierarchical flower-shaped microsphere structure and the heterostructure between Fe₂O₃ and Bi₂MoO₆, which effectively separated the ultrasound-induced electron–hole pairs and suppressed their recombination. Furthermore, a potential piezoelectric catalytic dye degradation mechanism of the Fe₂O₃−Bi₂MoO₆ catalyst was proposed based on the band potential and quenching effect of radical scavengers. The results demonstrated the potential of using Fe₂O₃−Bi₂MoO₆ nanocomposites in piezocatalytic applications.     

Synthesis of γ-Ga2O3-Al2O3 solid solutions by spray pyrolysis method

Synthesis of the γ-Ga₂O₃-Al₂O₃ solid solutions by spray pyrolysis was examined. Spherical particles were obtained using an aqueous solution of Al(NO₃)₃ and Ga(NO₃)₃ with HNO₃. For Ga-rich composition, γ-phase solid solutions were directly crystallized by the spray pyrolysis. For Al-rich composition, spray pyrolysis gave amorphous products unless a sufficient thermal energy was supplied during the spray pyrolysis. Subsequent calcination of the amorphous products gave γ-Ga₂O₃-Al₂O₃ solid solutions. However, physical properties of the solid solutions were affected by the spray pyrolysis conditions.     

Phase equilibria and liquidus surface of CaO-SiO2–5 wt%MgO-Al2O3-TiO2 slag system

The lack of phase equilibria relations and liquidus surface thermodynamic information for CaO-SiO₂–5?wt%MgO-Al₂O₃-TiO₂ system has seriously restricted the comprehensive utilization of the titanium resources. In present study, the phase equilibrium relationships were investigated for CaO-SiO₂–5?wt%MgO-Al₂O₃-TiO₂ phase diagram system at 1300?°C and 1400?°C using the high temperature equilibrium technique followed by X-Ray Fluoroscopy (XRF), X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM) and Energy Dispersive X-ray spectroscope (EDX) analysis. In the composition range studied, the liquid phase, melilite solid solution phase and CaO·TiO₂ phase were found. The two-phase equilibrium of liquid coexisting with CaO·TiO₂ phase was intensively dicussed, and the spatial liquidus surfaces at 1300?°C, 1400?°C and 1450?°C (data from literatures only) for liquid coexisting with CaO·TiO₂ phase were first constructed in CaO-SiO₂–5?wt%MgO-Al₂O₃-TiO₂ tetrahedral phase diagram, which can realize a visual understanding of the phase relation change trendency in 3-dimensional space.     

Determination of the eutectic solubility lines of the ternary system NaHCO3–Na2CO3–H2O

A crystallizer was built and a procedure developed to accurately measure the eutectic solubility lines where ice and salt coexist in equilibrium with the solution, for potential application of Eutectic Freeze Crystallization. The eutectic solubility lines of the ternary system NaHCO₃–Na₂CO₃–H₂O were determined experimentally and calculated with the extended UNIQUAC model. The extended UNIQUAC model describes the experimental data quite well. Anhydrous NaHCO₃ and Na₂CO₃·10H₂O were the only two types of crystals present in equilibrium with ice crystals in the ternary system. At the quadruple point NaHCO₃ and Na₂CO₃·10H₂O are in equilibrium with a solution of about 4.34 wt% of Na₂CO₃ and 4.77 wt% of NaHCO₃ at −3.32 °C. The anhydrous NaHCO₃ crystals were needle shaped with lengths between 5 and 10 μm, that were agglomerated into particles of about 100–300 μm, while the Na₂CO₃·10H₂O crystals were hexagonally shaped with sizes between 100 and 500 μm.     

Structural and magnetic properties of Li2O–Fe2O3 ceramic nanostructures

xLi₂O–(1−x)α-Fe₂O₃ (x=0.1, 0.3, 0.5, and 0.7) nanoparticle systems were successfully synthesized by mechanochemical activation of Li₂O and α-Fe₂O₃ mixtures for 0–12 h of ball milling time. The study aims at exploring the formation of magnetic oxide semiconductors at the nanoscale, which is of crucial importance for catalysis, sensing and electrochemical applications. X-ray powder diffraction (XRD), Mössbauer spectroscopy and magnetic measurements were used to study the phase evolution of xLi₂O–(1−x)α-Fe₂O₃ nanoparticle systems under the mechanochemical activation process. Rietveld refinement of the XRD patterns yielded the values of the particle size as function of composition and milling times and indicated the presence of Li-substituted hematite and tetra lithium iron oxide LiFeO₂, along with the formation of multiple phases for large x values and long milling times. The Mössbauer studies showed that the spectrum of the mechanochemically activated composites evolved from a sextet for hematite to sextets and a doublet upon duration of the milling process with lithium oxide. Magnetic measurements recorded at 5 K to room temperature (RT) in an applied magnetic field of 50,000 Oe showed that the magnetization of the milled samples is larger at low temperatures than at RT and increases with decreasing particle size. Zero field cooling measurements made possible the determination of the blocking temperatures of the specimens as function of ball milling time and evidenced the occurrence of superparamagnetism in the studied samples. This result correlates well with the observed presence of a quadrupole-split doublet in the Mössbauer spectra.     

Effectiveness factor of fast (Fe3+/Fe2+), moderate (Cl2/Cl?) and slow (O2/H2O) redox couples using IrO2-based electrodes of different loading

The effectiveness factor, E _f, (fraction of the electrode surface that participates effectively in the investigated reaction) of fast (Fe³⁺/Fe²⁺), moderate (Cl₂/Cl⁻) and slow (O₂/H₂O) redox couples has been estimated using IrO₂-based electrodes with different loading. The method of choice was linear sweep voltammetry (measurement of the anodic peak current) for the Fe³⁺/Fe²⁺ redox couple and steady-state polarization (determination of the exchange current) for the O₂ and Cl₂ evolution reactions. The results have shown that the effectiveness factor depends strongly on the kinetics of the investigated redox reaction. For the Fe³⁺/Fe²⁺ redox couple, effectiveness factors close to zero (max 4%) have been obtained contrary to the O₂ evolution reaction where effectiveness factors close to 100% can be achieved, all being independent of IrO₂ loading. For the Cl₂ evolution reaction, intermediate values of the effectiveness factor have been found and they decrease strongly, from 100% down to about 60%, with increasing loading.