Bi2O3对K2O–B2O3–SrO–Al2O3–Nb2O5–SiO2玻璃陶瓷介电储能性能的影响

随着电力电子系统的不断发展,高功率脉冲电容器的需求增多。电介质电容器因具有放电功率大、充放电速度快及性能稳定等优点,在电力系统、电子器件、脉冲电源等方面发挥着重要作用,广泛应用于民用领域及军事领域。通过熔融压延制备玻璃基体,采用可控结晶工艺研究了不同含量的Bi₂O₃ (x=0.0%、1.0%、2.0%、4.0%,摩尔分数)对K₂O–B₂O₃–Sr O–Al₂O₃–Nb₂O₅–SiO₂玻璃陶瓷物相演化、微观结构、介电和储能性能的影响。在该玻璃陶瓷中,KSr₂Nb₅O₁₅为主要析出晶相,当Bi₂O₃的加入量为x=2.0%(摩尔分数)时,热处理温度为950℃时,玻璃陶瓷样品的储能密度最大可达到1.27 J/cm³,室温下介电常数可达342,是热处...     

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.     

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.     

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%.     

钛合金熔炼用Y2O3–Al2O3–MgO–CaO系耐火材料的设计与制备

坩埚耐火材料对钛合金熔炼的质量非常重要,为开发高性能新型坩埚材料,以工业Y₂O₃和Al₂O₃–MgO–CaO系粉末(AMC)为原料,制备出Y₂O₃–Al₂O₃–MgO–CaO系复合耐火材料,研究了烧结温度(1 500℃、1 600℃)和AMC含量(0、25%、50%、75%和100%,质量分数)对所制备耐火材料的物相组成、烧结性能(线收缩率、体积收缩率、显气孔率、体积密度)、常温耐压强度、抗热震性能和显微结构的影响。结果表明：相对于Y₂O₃和AMC材料,复合材料的性能均有所提高;提高烧结温度,其性能更佳;且随着AMC含量的提高,复合材料的线收缩率、体积收缩率、体积密度和常温耐压强度随之增大,显气孔率降低;当AMC的质量含量为75%时,1 500℃烧结3 h制得复合材料的综合性能最优,其显气孔率为4.37%,常温耐压强度为274.99 MPa,3次水冷热震后残余强度为16...     

Emission analysis of CdO–Bi2O3–B2O3 glasses doped with Eu and Tb

This article reports on the emission properties of cadmium bismuth borate (CdBiB) glasses as a function of doping concentrations of Eu³⁺ and Tb³⁺ ions. The functional groups present in the glasses have been identified by analyzing FT-IR spectra. The emission spectra of Eu³⁺ and Tb³⁺:CdBiB glasses have shown reddish green emissions at 616 nm (⁵D₀→⁷F₂) under the excitation at 465 nm and at 547 nm (⁵D₄→⁷F₅) under the excitation at 485 nm, respectively. The Judd–Ofelt (J–O) theory was applied to evaluate the J–O intensity parameters from the absorption and the emission spectra; by using the J–O intensity (Ω_λ) parameters, spontaneous emission transition probability (A), total radiative transition rate (A_T), radiative lifetime (τ_R) and branching ratios (β) of the various emission transitions have been computed for both Eu³⁺ and Tb³⁺:CdBiB glasses. The quenching behavior in the emission intensity with increased concentration of Eu³⁺ and Tb³⁺ was observed, which could be useful for optimizing the compositions toward practical applications.     

多组元BaO–SrO–CaO–MgO–Al2O3–2SiO2环境障涂层的制备与抗CaO–MgO–Al2O3–SiO2腐蚀性能

采用固相法制备不同摩尔 Ba、Sr、Ca、Mg 配比的 Ba O–Sr O–Ca O–Mg O–Al₂O₃–SiO₂ （BSCMAS）陶瓷材料,研究多组元陶瓷的制备工艺、显微结构及其抗 CMAS 腐蚀性能。结果表明：通过调控 MgO 的含量,在 1 400 ℃条件下制备了Ba_0.3Sr_0.3Ca_0.35Mg_0.05Al₂Si₂O₈ (B_0.3S_0.3C_0.35M_0.05AS)单相多组元陶瓷材料。在 1 250、1 300 ℃和 1 350 ℃对 B_0.3S_0.3C_0.35M_0.05AS 进行 CMAS 腐蚀实验,相比于 Ba_0.5Sr_0.5Al     

Low temperature sintering and microwave dielectric properties of Li2ZnTi3O8 ceramics doped with ZnO–La2O3–B2O3 glass

Li₂ZnTi₃O₈ ceramics doped with ZnO–La₂O₃–B₂O₃ glass were prepared by the conventional solid-state ceramic route. The effects of the ZnO–La₂O₃–B₂O₃ glass on the sintering temperature, phase composition, microstructure and microwave dielectric properties of Li₂ZnTi₃O₈ ceramics were investigated. The addition of ZLB glass can reduce the sintering temperature of Li₂ZnTi₃O₈ ceramic from 1075 °C to 925 °C without obvious degradation of the microwave dielectric properties. Only a single phase Li₂ZnTi₃O₈ with cubic spinel structure is formed in Li₂ZnTi₃O₈ ceramic with ZLB addition sintered at 925 °C. Typically, 1.0 wt% ZLB-doped Li₂ZnTi₃O₈ ceramic sintered at 925 °C can reach a maximum relative density of 95.8% and exhibits good microwave dielectric properties of ε_r=24.34, Q×f=41,360 GHz and τ_f=−13.4 ppm/°C. Moreover, this material is compatible with Ag electrode, which makes it a promising candidate for LTCC application.     

Fe2O3/Ni2O3/Al2O3催化剂制备及其催化氧化靛蓝废水研究

以三氧化二铝为载体,采用浸渍沉淀法制备系列Fe2O3/Ni2O3/Al2O3催化剂。采用TG-DTA,XRD及ESEM等技术对催化剂进行表征,确定催化剂的最佳焙烧温度为460℃。以次氯酸钠为氧化剂,同时考察m(三氧化二镍)/m(三氧化二铝)、m(三氧化二铁)/m(三氧化二镍)、m(次氯酸钠)∶m(靛蓝废水)、pH对印染靛蓝废水处理的影响。结果表明:m(三氧化二镍)/m(三氧化二铝)=0.3,m(三氧化二铁)/m(三氧化二镍)=0.04,m(次氯酸钠)∶m(靛蓝废水)=1∶11,pH=7,反应温度为20℃,常压反应时间为2 h时,COD的去除率为95.3%。     

Eutectic crystallization in the UO2–Al2O3–HfO2 ceramic phase diagram

In the frame of the Generation IV Sodium Fast Reactor (SFR) safety studies, a core catcher with a sacrificial material could be placed at the bottom of the nuclear reactor. Its role is to dilute the (U, Pu)O₂ molten fuel in case of a hypothetical core meltdown accident. A Al₂O₃–HfO₂ ceramic is a candidate for the sacrificial material. To understand how the molten fuel would mix with this sacrificial material, the UO₂–Al₂O₃–HfO₂ system was investigated at CEA Cadarache PLINIUS corium platform. The eutectic position of the UO₂–Al₂O₃–HfO₂ was determined: the eutectic temperature is 1728±22 °C (2001±22 K) and the eutectic composition is 30 wt% UO₂–35 wt% Al₂O₃–35 wt% HfO₂. Then, the pseudo-binary UO₂–(50 wt% Al₂O₃–50 wt% HfO₂) phase diagram has been proposed.     

Pressureless sintered Al2O3–SiC nanocomposites

Al₂O₃ + 5 vol% SiC composite ceramics were prepared via a conventional powder processing route followed by pressureless sintering. Commercially available Al₂O₃ and SiC powders were milled together in an aqueous suspension. The slurry was freeze granulated, and green bodies were obtained by cold isostatic pressing of the granules. Pressureless sintering was carried out in a nitrogen atmosphere at 1750 and 1780 °C. Near full density (>99%) was achieved at 1780 °C. Densification at the lower sintering temperature was promoted by smaller additions of MgO. Vickers hardness and indentation fracture toughness varied around 18 GPa and 2.3 MPa m^1/2 after sintering at 1780 °C. Transmission electron microscopy revealed that the SiC particles were located predominantly to the interior of the matrix grains and well distributed throughout the composite microstructures. The intragranular particles had sizes in the range 50–200 nm while the intergranular particles were larger, typically 200–500 nm in diameter.     

CMAS (CaO–MgO–Al2O3–SiO2) resistance of Y2O3-stabilized ZrO2 thermal barrier coatings with Pt layers

Calcium–magnesium–alumina–silicate (CMAS) corrosion significantly affects the durability of thermal barrier coatings (TBCs). In this study, Y₂O₃ partially stabilized ZrO₂ (YSZ) TBCs are produced by electron beam-physical vapor deposition, followed by deposition of a Pt layer on the coating surfaces to improve the CMAS resistance. After exposure to 1250 °C for 2 h, the YSZ TBCs were severely attacked by molten CMAS, whereas the Pt-covered coatings exhibited improved CMAS resistance. However, the Pt layers seemed to be easily destroyed by the molten CMAS. With increased heat duration, the Pt layers became thinner. After CMAS attack at 1250 °C for 8 h, only a small amount of Pt remained on the coating surfaces, leading to accelerated degradation of the coatings. To fully exploit the protectiveness of the Pt layers against CMAS attack, it is necessary to improve the thermal compatibility between the Pt layers and molten CMAS.     

Al2O3/Fe2O3吸附剂脱除硫化氢的性能

采用共沉淀法制备了氧化铝改性的氧化铁吸附剂,并采用比表面积(BET)、X射线衍射(XRD)技术对吸附剂进行了表征。在固定吸附床上,考察了制备条件及吸附条件对吸附剂脱除硫化氢性能的影响。结果表明,引入氧化铝能显著提高氧化铁对硫化氢的吸附净化能力。氧化铁与氧化铝质量比为1∶0.5,造孔剂十六烷基三甲基溴化铵(CTAB)质量分数为2%,焙烧温度500℃时,采用共沉淀法的负载氧化铝吸附剂的吸附效果最好。在气速20 mL/min,吸附温度80℃时,脱硫率和穿透硫容可分别达到99.3%和105 mg/g,其穿透硫容比未经改性的活性氧化铁提高了49.8 mg/g。     

V2O5、NiO、Fe2O3和钒渣对Al2O3/MgAl2O4的腐蚀机理

研究了V2O5、NiO、Fe2O3和钒渣对Al2O3和MgAl2O4尖晶石的腐蚀。把Al2O3和MgAl2O4试样分别同上述氧化物一起从室温加热到1 400℃、1 450℃和1 500℃,加热速率为10℃.min-1。用XRD和SEM对每个系统的腐蚀机理进行了分析。结果显示,所研究的氧化物对Al2O3的影响弱于对MgAl2O4的影响。氧化铝被NiO侵蚀形成NiAl2O4尖晶石,MgAl2O4尖晶石被V2O5侵蚀形成MgV2O6。本文还观察到钒渣中的成分Fe2O3、Mg、Ni、V和Fe分散到了Al2O3结构中。另一方面,Fe2O3、Ca、S、Si、Na、Mg、V和Fe分散到了MgAl2O4结构中。最后,把得到的结果与FactSage软件的预测结果进行了对比。     

Mechanosynthesis of nanocomposites in TiO2–B2O3–Mg–Al quaternary system

The mechanochemical behavior of TiO₂–B₂O₃–Mg–Al quaternary system to synthesize various composite nanopowders was studied. A mixture of boron oxide and titanium dioxide powders along with different amounts of magnesium and aluminum was milled using a high-energy planetary ball mill to persuade necessary conditions for the occurrence of a mechanically induced self-sustaining reaction (MSR). Results showed that the formation of composite nanopowders was influenced strongly by the reducing agents content. In the absence of Al (100 wt% Mg), TiB₂ nanopowder was formed after 34 min of milling. In the presence of x wt% Mg–y wt% Al (x=40 and 70; y=100−x), mechanical activation was completed after 37–40 min which caused the formation of TiB₂–MgFe_0.6Al_1.4O₄ composite nanopowders. In the case of 10 wt% Mg–90 wt% Al, a ternary nanocomposite (TiB₂–MgAl₂O₄–Al₂O₃) was produced after 43 min of milling. Besides, Al₂O₃–TiB₂ nanocomposite was formed after 90 min of milling in the absence of Mg (100 wt% Al). From the SEM images, mechanochemical process reached a steady state after short milling times where the particles have become homogenized in size and shape. The reaction mechanism steps were proposed to clarify the reactions occurring during mechanochemical process.     

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.     

基于Fe2O3的片状α-Al2O3包覆研究

首先以片状α-Al₂O₃为基质,以Fe Cl₃为铁源,采用液相沉积法制备了Fe₂O₃/α-Al₂O₃珠光颜料,并借助SEM、EDS、XRD等手段对制备的珠光颜料进行性能表征,考察了反应p H值、反应温度、铁盐浓度、添加剂用量等因素对片状α-Al₂O₃包覆率的影响,得到了制备铁系包覆片状α-Al₂O₃的最佳制备工艺参数,同时了解了各参数影响包覆率的主次顺序,并在此基础上着重探讨了六偏磷酸钠对包覆率产生影响的机理。结果表明：影响包覆率的主次顺序依次为反应p H值、反应温度、添加剂用量、铁盐浓度;在最优的工艺参数下制备出来Fe₂O₃/α-Al₂O₃的包覆率为20.93%;样品的表面形貌光滑平整且包覆完整。     

电熔镁砂在CaO–Al2O3–SiO2熔渣中的溶解行为

作为镁质耐火材料的重要原料，电熔镁砂在低密度高强钢精炼用CaO–Al₂O₃–SiO₂系熔渣中的溶解是影响炉衬使用寿命及钢质量的重要因素。本工作采用高温激光共聚焦显微观测系统研究了1 600℃下镁砂在该熔渣中的溶解行为，探究了镁砂颗粒的形状、质量及熔渣CaO和SiO₂质量分数比(即C/S)对其溶解行为的影响。结果表明：镁砂主要形状对其溶解速率影响较小；溶解速率随质量增大呈近线性下降，随C/S的增加而先降低后增加；镁砂颗粒的溶解曲线受质量影响更大，其溶解模型n值分别对应1/2、2/3、3/5，这为深入理解镁质耐火材料的渣蚀行为和提质优化提供指导。     

Al2O3-3Al2O3·2SiO2-ZrO2耐火材料的相组成

Al2O3-SiO2-ZrO2系耐火材料应用范围广,特别被用作陶瓷辊,具有力学强度高、抗热震性能优良、耐碱类化合物侵蚀和高温蠕变率低的特性。Al2O3-SiO2-ZrO2系耐火材料性能很大程度上取决于其结晶相和玻璃相的总量和化学成分,采用定量XRPD和XRF研究了原料中Al2O3/SiO2比和氧化铝颗粒尺寸分布对结晶相和玻璃相的总量及其化学成分的影响。耐火材料由莫来石、刚玉、ZrO2的多晶体和总量各异的玻璃相组成。莫来石含量及其晶胞参数和成分随烧成温度改变,但主要受原料中Al2O3/SiO2比的影响。