Effect of MgO on structural,thermal and conducting properties of V2-xMgxO5-δ (x = 0.05–0.30) systems

MgO containing vanadate glasses of composition V_2-xMg_xO_5-δ (x?=?0.05, 0.10, 0.15, 0.20, 0.25 and 0.30) have been prepared successfully by melt-quench technique. The structural properties of the as-quenched samples are explored with the help of X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. Thermal properties and conductivity of the samples are investigated using differential thermal analysis (DTA) and impedance spectroscopy, respectively. Density, inter-ionic distance, and fragility index are found to decrease with the addition of MgO content. Higher content of MgO improves the glass formation tendency and reduces the thermal stability of the samples. The conductivity of the V_2-xMg_xO_5-δ samples decreases as the MgO concentration increases due to hindrance in the polaronic conduction of vanadium ions. The conductivity of the samples decreases to ? 10^?4 S?m^?1 for x?=?0.30 at 300?°C, while activation energy increases to 0.38?eV. These samples may find application in solid state batteries and fuel cells due to their higher conductivity.     

Influence of fluorine source and TiO2 on glass ceramics based on red clay and magnesite

Abstract

Within the Fe₂O₃–BaO–Al₂O₃–SiO₂ glass system, the influence of different fluorine source and TiO₂ on the crystallisation behaviour and thermal expansion characteristics has been investigated. These aluminosilicate glasses, with different nucleation catalysts (TiO₂, AlF₃ and NH₄F), were successfully prepared from Saudi Arabia raw materials (red clay and magnesite). Thermal behaviour, crystalline phases, microstructures, and thermal expansion coefficient were studied by DTA, XRD, SEM techniques, as well as a dilatometer. Spinel, hexacelsian, monocelsian, kinoshitalite, and Ba-osumilite were developed in glass ceramic samples. Spinel was the early phase formed in all glasses; however, with increasing temperature, hexacelsian and kinoshitalite were developed in fluorine free glasses and fluorine containing glasses respectively. Ba-osumilite was developed and hexacelsian was converted into monocelsian during lengthy heat treatment at 1150°C. A bulk crystalline microstructure was obtained; however, a microscale structure was observed in fluorine free samples and a homogeneous nanoscale microstructure was developed in fluorine containing samples. The coefficient of thermal expansion (CTE) varied according to the phases and the heat treatment parameters. Development of spinel, hexacelsian and kinoshitalite in glass ceramic samples gave CTE values between 86·44 × 10^?7 and 52·53 × 10^?7°C^?1, whereas crystallisation of Ba-osumilite and monocelsian gave CTE values between 51·29 × 10^?7 and ?7·35 × 10^?7°C^?1.     

Synthesis and characterization of low CTE value La2O3-B2O3-CaO-P2O5 glass/cordierite composites for LTCC application

Low-softening-point La₂O₃-B₂O₃-CaO-P₂O₅ (LBCP) glass-ceramic/cordierite composite systems have been prepared in this work. Influence of the ratio of La₂O₃ to B₂O₃ and the content of cordierite on the sintering behavior, microstructure, sintering quality, thermal properties and dielectric properties of composites are studied. The results show that high La₂O₃/B₂O₃ ratio improves the crystalline quality of LBCP glass-ceramic, but also narrows its process window. The increase of cordierite content reduces the coefficient of thermal expansion (CTE) value of composites obviously. However, excess cordierite is detrimental to the densification of the composite microstructure, and too low cordierite content causes serious foaming. Sample containing 30?wt% LBCP1 glass-ceramic and 70?wt% cordierite sintered at 850?°C shows excellent properties: relative density of 95.26%, CTE value of 4.12?ppm/°C, dielectric constant of 4.78 (1?MHz)/4.52 (12.8?GHz), dielectric loss of 2.3?×?10^?3 (1?MHz)/2.5?×?10^?3 (12.8?GHz) and the ability to co-fire with silver, which suggests that LBCP glass/cordierite composite system has potential to meet the requirements of LTCC substrate material.     

Glass Formation and Characterization Studies in the TeO2–WO3–Na2O System

Glass formation behavior of the TeO₂–WO₃–Na₂O system was studied by using conventional melt‐quenching technique. A wide glass formation range was determined for the first time in the literature and thermal, physical, and structural characterization of sodium‐tungsten‐tellurite glasses were realized using differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy techniques. Glass transition (T_g) and crystallization (T_c/T_p) temperatures, glass stability (?T), density (ρ), molar volume (V_M), oxygen molar volume (V_O), and oxygen packing density (OPD) values and structural transformations in the glass network were investigated according to the equimolar substitution of TeO₂ by Na₂O+WO₃ and changing Na₂O or WO₃ at constant TeO₂.     

Concentration dependence of electric conductivity for fluorine-containing sodium borate glasses

The influence of sodium fluoride additives on the physicochemical properties of glasses in the Na₂O-B₂O₃ systems is investigated. The introduction of sodium fluoride into the Na₂O · 2B₂O₃ and Na₂O · 3B₂O₃ glasses leads to an increase in the electric conductivity. The temperature-concentration dependence of the electric conductivity has been investigated. It is shown that, in glasses of the NaF-Na₂O · 2B₂O₃ system, an increase in the volume concentration of sodium ions from 2.4 × 10⁻² to ∼3 × 10⁻² mol/cm³ is accompanied by an insignificant decrease in the activation energy E_σ from 1.44 to 1.38 eV and a sharp (by a factor of ∼30) increase in the electric conductivity. In glasses of the NaF-Na₂O · 3B₂O₃ system, an increase in the concentration of sodium ions from 1.8 × 10⁻² to ∼2.3 × 10⁻² mol/cm³ brings about an increase in the electric conductivity by a factor of approximately 100 and an increase in E_σ from 1.6 to 1.83 eV. A further increase in the concentration of sodium ions (up to 2.5 × 10⁻² mol/cm³) virtually does not affect the electric conductivity and E_σ. At the same concentration of sodium ions (∼2.46 × 10⁻² mol/cm³) in the 9.8NaF · 90.2[Na₂O · 2B₂O₃] and 57.1NaF · 42.9[Na₂O · 3B₂O₃] glasses, the electric conductivity and the activation energy are considerably higher in the glass with a larger fluorine content. The regularities revealed are interpreted in the framework of the microinhomogeneous glass structure.     

Effect of the crystalline layer on the electrical behaviour of 17.7Li2O·5.2ZrO2·68.1SiO2·9.0Al2O3 glass ceramic monoliths

Li₂O–ZrO₂–SiO₂–Al₂O₃ (LZSA) glass ceramic systems are usually obtained from powder technology to obtain materials with a low thermal expansion coefficient (CTE). However, in these cases, there is a high residual porosity. An alternative to reduce the porosity involves the production of monoliths. Nevertheless, there is still a lack of crystallisation kinetics and the final properties of glass ceramic monoliths are affected such as electrical properties. This study aims to evaluate the electrical behaviour as function of the crystalline layer thickness formed on the monolith surface of a 17.7Li₂O·5.2ZrO₂·68.1SiO₂·9.0Al₂O₃ (molar basis) glass ceramic LZSA composition. Monoliths thermally treated at 750, 800, and 850 °C were chosen to evaluate based on the range of the crystalline layer growth. Electrochemical impedance spectroscopy was used for the electrical characterisation of LZSA glass and the glass ceramics. The resistivity increased with increasing thermal treatment temperature due to the formation of lithium-based crystalline phases. The electrical conductivity at 25 °C of the glass ceramic thermally treated at 850 °C decreased to 1.4 × 10^?13 S cm^?1 from 8.7 × 10^?11 S cm^?1 for LZSA glass. Based on the electrical behaviour, monoliths thermally treated at 850 °C can be considered potential for dielectric industrial applications.     

Concentration dependence of electric conductivity for fluorine-containing sodium borate glasses

The influence of sodium fluoride additives on the physicochemical properties of glasses in the Na₂O-B₂O₃ systems is investigated. The introduction of sodium fluoride into the Na₂O · 2B₂O₃ and Na₂O · 3B₂O₃ glasses leads to an increase in the electric conductivity. The temperature-concentration dependence of the electric conductivity has been investigated. It is shown that, in glasses of the NaF-Na₂O · 2B₂O₃ system, an increase in the volume concentration of sodium ions from 2.4 × 10⁻² to ∼3 × 10⁻² mol/cm³ is accompanied by an insignificant decrease in the activation energy E_σ from 1.44 to 1.38 eV and a sharp (by a factor of ∼30) increase in the electric conductivity. In glasses of the NaF-Na₂O · 3B₂O₃ system, an increase in the concentration of sodium ions from 1.8 × 10⁻² to ∼2.3 × 10⁻² mol/cm³ brings about an increase in the electric conductivity by a factor of approximately 100 and an increase in E_σ from 1.6 to 1.83 eV. A further increase in the concentration of sodium ions (up to 2.5 × 10⁻² mol/cm³) virtually does not affect the electric conductivity and E_σ. At the same concentration of sodium ions (∼2.46 × 10⁻² mol/cm³) in the 9.8NaF · 90.2[Na₂O · 2B₂O₃] and 57.1NaF · 42.9[Na₂O · 3B₂O₃] glasses, the electric conductivity and the activation energy are considerably higher in the glass with a larger fluorine content. The regularities revealed are interpreted in the framework of the microinhomogeneous glass structure.     

Crystallization behaviour and properties of BaO-CaO-B2O3-SiO2 glasses and glass-ceramics for LTCC applications

The influence of BaO content (up to 15?mol%) on the crystallization behaviour, structure, thermal properties and microwave dielectric properties of the BaO-CaO-B₂O₃-SiO₂ glasses and glass-ceramics system was investigated. The glasses were produced by melting at 1400?°C and quenching into water, and the glass-ceramics were produced via heat treatment at temperatures between 750 and 800?°C. The results of X-ray diffraction analysis showed that increasing the BaO content raised the resistance of the glass against crystallization and favoured the transformation of β-CaSiO₃ and α-CaSiO₃ phases, which crystallized in the Ba-free and in low BaO content compositions, into SiO₂ and Ba₄Si₆O₁₆, which crystallized in compositions with higher concentrations of BaO. The BaO content had little influence on the glass transition temperature (T_g) and the linear coefficient of thermal expansion (CTE), but strongly reduced the softening point (T_s). Even the addition of BaO as minor additives resulted in a dramatic reduction of the T_s; for example, the T_s decreased from 902?°C for the Ba-free composition to 682?°C for the BaO-containing one (5%). Low values of the dielectric constant (5.9?≤?ε_r ≤?6.63) and dielectric loss (1.12?×?10^?3 ≤?tanδ?≤?3.15?×?10^?3) were measured.     

Effect of TiO2, LiF and Cr2O3 in the Crystallization of Cristobalite and Tridymite in Sintered Glass-Ceramics

Based on the poudretteite (K Na₂ B₃ Si₁₂ O₃₀) glass composition, six transparent glass frits were prepared. TiO₂, LiF and Cr₂O₃ were experimented on the base glass composition as nucleation catalysts. Only cristobalite and tridymite were developed through the sintering process of the glasses between 900 and 1100?°C. LiF enhances mainly tridymite with traces of cristobalite and in the opposite side the parent and both TiO₂ and Cr₂O₃ containing glasses catalyzed mainly cristobalite with traces of tridymite. The microstructure of the glass samples heat-treated at 1000?°C showed backbone-like, small rods, quadrant-, hexagonal crystals referred to the cristobalite and tridymite. The EDS microanalysis shows the presence of both alkalis, i.e. Na^?+? and K^?+?, in the cristobalite crystal structure while the residual glass contains K^?+?. The infrared spectroscopy indicates the band patterns of cristobalite and tridymite.     

Hot corrosion resistance of air plasma sprayed ceramic Sm2SrAl2O7 (SSA) thermal barrier coatings in simulated gas turbine environments

Samarium strontium aluminate (Sm₂SrAl₂O₇-SSA) and Yttria-stabilized zirconia (YSZ) thermal barrier coatings (TBCs) were developed on NiCrAlY bond coated Inconel 718 superalloy substrate using air plasma spray process. The hot corrosion study was conducted in simulated gas turbine environments (molten mixtures of 50?wt% Na₂SO₄ + 50?wt% V₂O₅ and 90?wt% Na₂SO₄ + 5?wt% V₂O₅ + 5?wt% NaCl) for two different temperatures of 700 and 900?°C. A developed SSA TBCs showed about 8% and 22% lower lifetime at 700 and 900?°C, respectively than YSZ TBCs in 50?wt% Na₂SO₄ +?50?wt% V₂O₅ (vanadate). The hot corrosion life of SSA TBCs being found about 13% and 39% lower than YSZ TBCs in 90?wt% Na₂SO₄ +?5?wt% V₂O₅ +?5?wt% NaCl (chloride) at 700 and 900?°C, respectively. X-ray diffraction results showed the formation of SmVO₄, SrV₂O₆, and SrSO₄ as a major hot corrosion product in 50?wt% Na₂SO₄ +?50?wt% V₂O₅ and 90?wt% Na₂SO₄ +?5?wt% V₂O₅ +?5?wt% NaCl environments respectively for SSA TBCs. Similarly, YSZ TBCs also showed YVO₄ as hot corrosion product in vanadate and chloride environments. Both the TBCs suffer a more severe hot corrosion attack in chloride environment at 900?°C. The leaching of Sr²⁺ and Y³⁺ ions from SSA and YSZ respectively play a vital role in the destabilization of coating in vanadate and chloride environments at 700 and 900?°C. In both SSA and YSZ TBCs, the leaching of ion has significantly low influence as compared to attack by chloride ions at the bond coat-top coat interface in the presence of chloride environment. The hot corrosion resistance of SSA TBCs was improved three times higher in the presence of MgO and NiO inhibitor in vanadate environment at 900?°C mainly due to the formation of a stable Ni₃V₂O₈ phase at the surface.     

Potential of integrating Na2SO4 · 10H2O pellets in solar drying system

In the current study, evolution of thermophysical properties of red chilli dried in a mixed mode solar dryer that integrates sodium sulfate decahydrate (Na₂SO₄?·?10H₂O) and sodium chloride (NaCl) as thermal storage were presented. Solar drying with Na₂SO₄?·?10H₂O reduced the drying time by 26.7 and 39%, compared to the drying time with or without NaCl. Dimensional shrinkage was gradual with a nonlinear exponential shape for the whole drying conditions. The evolution of the bulk and particle densities decreased while the porosity of the seed increased with time. The coefficient of heat and mass transfer varied from 0.0036???0.035?W/m²?K to 6.09?×?10^?9???6.2?×?10^?8?m/s, respectively. The thermal conductivity, specific heat capacity, and thermal diffusivity ranged from 0.0568 to 0.1093?W/m?K, 1,072 to 2218.7?J/kg?K, and 4.7?×?10^?5 to 5.13?×?10^?5?m²/s, respectively.     

Influence of Bi2O3/WO3 substitution on the optical,mechanical, chemical durability and gamma ray shielding properties of lithium-borate glasses

Six different lithium bismuth boro-tungstate glasses with chemical composition 20Li₂O-(20-x)Bi₂O₃-xWO₃-60B₂O₃ (x = 0, 1, 2, 3, 4 and 5 mol%) were produced by the quenching method. Then, the glasses were investigated by means of their optical, mechanical, chemical durability and gamma ray shielding properties. Measured values of density and ultrasonic velocities were used to determine the elastic properties of the glasses. The optical band gap determined using the absorbance spectrum fitting (ASF) model was found to decrease under Bi₂O₃/WO₃ substitution. The presence of BO₃, BO₄, BiO₆, and WO₄ structural groups in the glasses was confirmed by Fourier transform infrared spectroscopy (FTIR). The dissolution rate in the glass 20Li₂O–15Bi₂O₃–5WO₃–60B₂O₃ (LBWB5) was found to be 10 times lower than 20Li₂O-20Bi₂O₃– 60B₂O₃. Mass attenuation coefficients (MAC) values of the produced glasses were determined using the MCNPX Monte Carlo code and Phy-X/PSD program. The photon attenuation parameters such as half value layer (HVL), mean free path (MFP), effective atomic number (Z_eff), exposure buildup factor (EBF) and energy absorption buildup factor (EABF) were also studied. The obtained results showed that Bi₂O₃/WO₃ substitution has a direct impact on the photon attenuation abilities of produced glasses. More specifically, HVL values increased from 0.252 × 10^?2 cm for LBWB0 glass to 0.275 × 10^?2 cm for LBWB5 glass. However, different trends were observed for the photon buildup factors for the produced glasses. It can be concluded that the produced glasses have promising structural, optical, and photon attenuation properties to be used for gamma shielding applications.     

Tailoring the efficient laser-absorption-melting behavior of Bi2O3-B2O3-ZnO-Nd2O3 glass for the OLED encapsulation

The efficient 810 nm laser energy conversion of glass frit had been proven to be the key to the long-term hermetic encapsulation of Organic Light Emitting Display (OLED). A direct laser energy conversion laser-assisted Bi₂O₃-B₂O₃-ZnO-Nd₂O₃ sealing glass material without extra laser absorbent such as carbon black, was designed and systematically investigated. The addition of Nd₂O₃, as glass modifiers with higher cationic field strength, could be conducive to enhancing the polymerization of glass network structure, manifesting that the glass-transition temperature Tg, onset-crystallization temperature Tc and thermal stability ΔT (ΔT = Tc-Tg) increased, while thermal expansion coefficient CTE dropped to 9.72×10⁻⁶/°C and advantageously matched with the glass substrate (8±1×10⁻⁶/°C). More importantly, the absorption rate of BBZ-Nd glass was more than 50 % between 800∼810 nm owing to the 4f-4f electron transition of Nd³⁺ ions, and yet the reflectivity and transmittance of the wavelength at 800–810 nm were lower. As optimal compositions, the addition of 3.0 wt% Nd₂O₃ in Bi₂O₃-B₂O₃-ZnO-Nd₂O₃ glass frit with higher absorption coefficients (80 %) led to instantaneous bonding encapsulation between glass substrates without interfacial cracks or pores with the 808 nm wavelength of the laser at 20 W and 2.4 mm/s.     

Y3Ce7Ta2O23.5 and Yb3Ce7Ta2O23.5—Two kinds of novel ceramics for thermal barrier coatings

For the development of ceramic candidates for thermal barrier coatings, two kinds of new ceramics, Y₃Ce₇Ta₂O_23.5 and Yb₃Ce₇Ta₂O_23.5, were synthesized by sintering at 1873?K for 10?h. The obtained samples were composed of a single fluorite-type phase, and their relative densities are greater than 90%. Because of phonon scattering caused by the complex lattice, the large number of oxygen vacancies, and substituted atoms, the thermal conductivity is lower than that of 8YSZ. The coefficients of thermal expansion (CTEs) of these two products are located in the range of 10.22–12.57?×?10^?6/K and 9.62–12.66?×?10^?6/K, respectively, from 323?K to 1473?K, and they also exhibit excellent phase stability up to 1473?K. However, their thermal conductivities and CTEs are lower than those of RE₂Ce₂O₇ (RE?=?La, Nd, or Sm).     

Synthesis,crystal structure,and characterization of Na2SrV4O12: A low-firing dielectric vanadate

In this work, cyclotetravanadate Na₂SrV₄O₁₂ was synthesized at a relatively low sintering temperature of ∼500°C using a solid-state reaction method. X-ray diffraction and a transmission electron microscope characterization featured a tetragonal structure that was built by a 3D frame of isolated tetracyclic (V₄O₁₂)⁴⁻. Dielectric measurements demonstrated strong dependence on frequency and temperature. A low relative permittivity of ε_r ∼ 8 ± 0.2 and a dielectric (loss tanδ) ∼ 0.4 ± 0.01 was achieved at a frequency of 10 kHz and room temperature. ac impedance and conductivity analysis revealed a thermally activated migration behavior of charge carriers with a short-range hopping feature. XPS analysis validated the existence of oxygen vacancy and reduction in vanadium (from V⁵⁺ to V⁴⁺), which gave rise to charged lattice defects. The migration or hopping of such charged defects was responsible for the observed electrical behaviors. Owing to the simple composition, inexpensive raw materials and low density (2.99 g/cm³) make Na₂SrV₄O₁₂ ceramic a potential candidate for lightweight devices and in photocatalytic degradation and all-solid-state ion batteries.     

THE EFFECT OF BORIC OXIDE ON THE DEVITRIFICATION OF THE SODA-LIME-SILICA GLASSES. THE QUATERNARY SYSTEM,Na2O-CaO-B2O3-SiO21

Commercial glasses of the soda-lime-silica types do not consist solely of these three oxides, but in addition contain significant amounts of other constituents which arc introduced incidentally as impurities or deliberately for some beneficial influence. Such minor additions may have either a favorable or unfavorable influence on the tendency of the glass to devitrify, and an investigation into the effect of such minor components is desirable. Previous results with MgO and with A1₂O₃ have shown that a systematic study of a four-component system is necessary to the understanding of its devitrification relations, and that arbitrary and fragmentary excursions into such a system give little insight into the general effect of the minor constituent and may be misinterpreted to erroneous conclusions as to the effect of this constituent on glasses of slightly different composition. Accordingly, in taking up the study of the effect of B₂O₃ on the devitrification of the soda-lime-silica glasses, it was added to 21 glasses in and near the field of devitrite, Na₂O·3CaO·6SiO₂, in the ternary system, Na₂O–CaO-SiO₂, in amounts up to about 5%. In all cases the liquidus temperature was lowered, and the tendency toward devitrification reduced. Both of these effects are desirable and add to the thermal stability of the glass. With glasses containing 10% CaO, initially in the field of tridymite or so near to it that a small addition of B203 brings the resulting glass into the tridymite field, this initial lowering is replaced by an increase in the liquidus temperature which passed through a maximum at from 4 to 6% B₂O₃. With all other glasses the lowering continues, and the rate of decrease is greatest with glasses originally in the field of Na₂O·2CaO·3SiO₂. An exploration of the quaternary system showed that no new compounds are formed in any mixture that can be obtained by adding B203 in amounts up to 50% to any mixture in or near the devitrite field. It also indicated the probability that a narrow band of immiscible liquids is formed, extending across the ternary system, CaO-B₂O₃–SiO₂, and including the mineral danburite, CaO·B₂O·2SiO₂, but probably not extending far into the quaternary system. The fields of wollastonite and of Na₂O·2CaO·3SiO₂ were found to sweep out regions in the quaternary system extending over the square, Na₂O·SiO₂-Na₂O·B₂O₃-CaO-B₂O₃-CaOSO₂, and the field of Na₂O·CaO·SiO₂ was found to extend over the middle of this square, and is probably adjacent to the fields of wollastonite and of Na₂O· 2CaO·3SiO₂. A compound is formed between Na₂O·B₂O₃ and CaO·B₂O₃. There is included a general survey of the literature relative to the effect of B203 on the properties of glass.     

Reduction of crystallization ability of sodium zinc phosphate glass under X-ray radiation

The effect of X-ray radiation on the crystallization ability of maximally homogenized sodium zinc phosphate glass with a minimal light scattering value of V _v = 4 × 10^?6 cm^?1 has been investigated. The crystallization kinetics of the sodium zinc phosphate glass of the 33.9P₂O₅ · 56.6ZnO · 9.5Na₂O (mol % from analysis) composition under the conditions of homogeneous nucleation and X-ray radiation have been studied. It has been demonstrated that the crystallization properties of phosphate glasses are more sensitive to the synthesis method than those of silicate glasses. It has been established that sodium zinc phosphate glass crystals represent the main crystalline phase precipitated in the glass of the above composition. The main parameters of nucleation have been determined in glass without preliminary radiation, including stationary nucleation rate I _st, nonstationary nucleation time ??, and nucleation activation energy E _??. It have been found that the effect of the CuK _?? X-ray radiation leads to the slowing down or even cessation of the nucleation of crystals in glass (the result depends on the change in the radiation intensity along the sample depth) in the case when radiation takes place immediately during the nucleation thermal treatment of the sample in a high-temperature chamber of the X-ray device. The kinetics of sodium zinc phosphate crystallization in the samples upon their pretreatment by CuK _?? X-ray irradiation has been investigated. It has been shown that the rate of crystal nucleation in glasses exposed to X-ray radiation is lower than that in glasses without preliminary irradiation.     

PREPARATION AND THERMAL EXPANSION OF FE2-xYxW3O12 POWDER BY CITRATE SOL-GEL PROCESS

Fe_2-xY_xW₃O₁₂ powder has been synthesized by the citrate sol-gel process. A model was proposed to calculate the concentration of species in a citric solution. The calculated results could provide valuable information for determining the optimal molar ratio of cation to citric acid and pH value of solution for Fe_2-xY_xW₃O₁₂ preparation. The predicted parameters derived from this model are in good agreement with the experimental results. The prepared gel and the Fe_2-xY_xW₃O₁₂ powder were characterized by X-ray diffraction (XRD) and differential thermal analysis-thermogravimetry (DTA-TG). The results show that it is very difficult to obtain pure Fe₂W₃O₁₂ powder by the citrate sol-gel process in the temperature range 500°–1000°C, however, Y₂W₃O₁₂ can easily be prepared even at 500°C. Y₂W₃O₁₂ annealed at 1000°C for 10 h is favorable for absorbing moisture in air to form Y₂W₃O₁₂·3.3H₂O. The thermal expansion coefficients of Y₂W₃O₁₂·3.3H₂O are: α_a = ? 8.01 × 10^?6°C^?1, α_b = ? 2.51 × 10^?7°C^?1, and α_c = ? 5.55 × 10^?6°C^?1 in 473–1173 K.     

Oxygen permeability and structural stability of a novel tantalum‐doped perovskite BaCo0.7Fe0.2Ta0.1O3−δ

Dense BaCo_0.7Fe_0.2Ta_0.1O_3?δ (BCFT) perovskite membranes were successfully synthesized by a simple solid state reaction. In situ high‐temperature X‐ray diffraction indicated the good structure stability and phase reversibility of BCFT at high temperatures. The thermal expansion coefficient (TEC) of BCFT was determined to amount 1.02 × 10^?5 K^?1, which is smaller than those of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) (1.15 × 10^?5 K^?1), SrCo_0.8Fe_0.2O_3?δ (SCF) (1.79 × 10^?5 K^?1), and BaCo_0.4Fe_0.4Zr_0.2O_3?δ (BCFZ) (1.03 × 10^?5 K^?1). It can be seen that the introduction of Ta ions into the perovskite framework could effectively lower the TEC. Thickness dependence studies of oxygen permeation through the BCFT membrane indicated that the oxygen permeation process was controlled by bulk diffusion. A membrane reactor made from BCFT was successfully operated for the partial oxidation of methane to syngas at 900°C for 400 h without failure and with the relatively high, stable oxygen permeation flux of about 16.8 ml/min cm². © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Effects of Nd Content on Structure and Chemical Durability of Zirconolite–Barium Borosilicate Glass‐Ceramics

The effects of Nd₂O₃ content (0–12 wt %) on crystalline phases, microstructure, and chemical durability of barium borosilicate glass‐ceramics belonging to SiO₂–B₂O₃–Na₂O–BaO–CaO–TiO₂–ZrO₂–Nd₂O₃ system were studied. The results show that the glass‐ceramics with 2–6 wt% of Nd₂O₃ possess mainly zirconolite and titanite phases along with a small amount baddeleyite phase in the bulk. Calcium titanate appears when the Nd₂O₃ content increases to 8 wt%, and the amount of quadrate calcium titanate crystals increases with further increasing content of Nd₂O₃. For the glass‐ceramics with 6 wt% Nd₂O₃ (Nd‐6), Nd elements homogeneously distribute in zirconolite, titanite, and residual glass phases. There is a strong enrichment of Nd in calcium titanate crystals for the sample with 10 wt% Nd₂O₃. The viscosity of Nd‐6 glass is about 49 dPa·s at 1150°C. Moreover, Nd‐6 glass‐ceramics show the lower normalized leaching rates of B (LR_B), Ca (LR_Ca), and Nd (LR_Nd) when compared to that of the sample with 8 wt% Nd₂O₃. After 42 days, LR_B, LR_Ca, and LR_Nd of the Nd‐6 glass‐ceramics are about 6.8 × 10^?3, 1.6 × 10^?3, and 4.4 × 10^?6 g·m^?2·d^?1, respectively.