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

Full-size image

, 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.     

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.     

Bi2O3助熔剂对CaO-B2O3-SiO2/Al2O3玻璃陶瓷复合材料性能的影响

以CaO-B₂O₃-SiO₂(CBS)玻璃粉体和Al₂O₃陶瓷粉体为原料,通过在CBS与Al₂O₃的质量比固定为50:50的玻璃-陶瓷复合材料中添加适量的Bi₂O₃作为烧结助熔剂,探讨了Bi₂O₃助熔剂对CBS/Al₂O₃复合材料的烧结性能、介电性能、抗弯强度和热膨胀系数的影响规律.研究表明:Bi₂O₃助熔剂能通过降低CBS玻璃的转变温度和黏度促进CBS/Al₂O₃复合材料的致密化进程,于880 ℃下烧结即能获得结构较致密、气孔较少的CBS/Al₂O₃复合材料.然而,过量添加Bi₂O₃将使玻璃的黏度过低,从而恶化CBS/Al₂O₃复合材料的烧结性能、介电性能及抗弯强度.当Bi₂O₃的添加量为CBS/Al₂O₃复合材料的1.5wt%时,于880 ℃下烧结即能获得最为致密的CBS/Al₂O₃复合材料,密度为2.82 g·cm^-3,这一材料具有良好的介电性能(介电常数为7.21,介电损耗为1.06×10^-3),抗弯强度为190.34 MPa,0~300 ℃的热膨胀系数为3.52×10^-6 K^-1.     

Synthesis, phase transformation and dielectric properties of sol–gel derived Bi2Ti2O7 ceramics

Sol–gel derived Bi₂Ti₂O₇ ceramic powders have been prepared from methoxyethoxides of bismuth and titanium (molar ratio of Ti/Bi = 1.23 and water/alkoxides = 1.31). The Bi₂Ti₂O₇ phase was stable at a low temperature (700 °C), but it then transformed into mixed phases of Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁ at 850–1150 °C. The single phase of Bi₂Ti₂O₇ reoccurred at 1200 °C. Dielectric properties and ferroelectric behavior of samples sintered at 1150 and 1200 °C were examined. Under frequency of 1 MHz, samples sintered at 1150 and 1200 °C had a dielectric constant of 101.3 and 104.2, and a loss tangent of 0.0193 and 0.0145, respectively. Only the sample sintered at 1150 °C showed ferroelectric behavior, where remanent polarization is 3.77 μC cm⁻² and coercive field is 24 kV cm⁻¹. Thus, the Bi₂Ti₂O₇ did not exhibit ferroelectricity, but the mixed phase of Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁ did.     

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.     

Bi2O3薄膜的制备及其电阻开关特性的研究

电阻式存储器由于具有众多的优点有望成为最有前景的下一代高速非挥发性存储器的选择之一.实验利用射频磁控溅射法在重掺硅上沉积了Bi2O3薄膜,并对该薄膜的结晶状态和Au/Bi2O3/n+Si/Al结构的电阻开关特性进行了研究.XRD分析结果表明,射频磁控溅射法沉积所得的Bi2O3薄膜结晶性能好,(201)取向明显.I-V曲线测试结果表明,Au/Bi2O3/n+Si/Al结构具有单极性电阻开关特性.通过对不同厚度Bi2O3薄膜的Au/Bi2O3/n+Si/Al结构I-V特性比较发现,随着薄膜厚度的增加,电阻开关的Forming、Set和Reset阈值电压均随之增加.对于Bi2O3薄膜厚度为31.2 nm的Au/Bi2O3/n+Si/Al结构,其Forming、Set和Reset阈值电压均低于4 V,符合存储器低电压工作的要求.     

AuAg/Bi2O3复合材料的光催化降解和还原性能

先用聚丙烯酰胺凝胶法制备出Bi₂O₃颗粒,然后用光还原法将粒径为6~18 nm的AuAg合金纳米颗粒修饰在Bi₂O₃颗粒表面,制备出AuAg/Bi₂O₃复合光催化剂。AuAg合金纳米颗粒的等离子体共振吸收效应(SPR)使AuAg/Bi₂O₃复合物能吸收波长为~577 nm的可见光,拓展了Bi₂O₃的光响应范围,还促进了Bi₂O₃中光生电荷的分离。以甲基橙(MO)、罗丹明(RhB)和铬离子(Cr(VI))作为目标反应物,在模拟太阳光和可见光照射下考察了AuAg/Bi₂O₃的光催化降解和还原活性,发现AuAg合金纳米颗粒修饰提高了Bi₂O₃的光催化性能。用模拟太阳光照射2 h后,RhB和MO的降解率以及Cr(VI)的还原效率分别提高了~34.2%,~38.0%和~56.7%。同时,AuAg/Bi₂O₃还具有良好的光催化和结构稳定性。基于以上结果,提出了AuAg合金纳米颗粒对Bi₂O₃光催化性能的改性机理。     

Pyroelectric properties of BST/PLT composite thick films with addition of xPbO–(1 − x)B2O3 glass

The Ba_xSr_1−xTiO₃ (BST)/Pb_1−xLa_xTiO₃ (PLT) composite thick films (20 μm) with 12 mol% amount of xPbO–(1 − x)B₂O₃ glass additives (x = 0.2, 0.35, 0.5, 0.65 and 0.8) have been prepared by screen-printing the paste onto the alumina substrates with silver bottom electrode. X-ray diffraction (XRD), scanning electron microscope (SEM) and an impedance analyzer and an electrometer were used to analyze the phase structures, morphologies and dielectric and pyroelectric properties of the composite thick films, respectively. The wetting and infiltration of the liquid phase on the particles results in the densification of the composite thick films sintered at 750 °C. Nice porous structure formed in the composite thick films with xPbO–(1 − x)B₂O₃ glass as the PbO content (x) is 0.5 ≥ x ≥ 0.35, while dense structure formed in these thick films as the PbO content (x) is 0.8 ≥ x ≥ 0.65. The volatilization of the PbO in PLT and the interdiffusion between the PLT and the glass lead to the reduction of the c-axis of the PLT phase. The operating temperature range of our composite thick films is 0–200 °C. At room temperature (20 °C), the BST/PLT composite thick films with 0.35PbO–0.65B₂O₃ glass additives provided low heat capacity and good pyroelectric figure-of-merit because of their porous structure. The pyroelectric coefficient and figure-of-merit F_D are 364 μC/(m² K) and 14.3 μPa^−1/2, respectively. These good pyroelectric properties as well as being able to produce low-cost devices make this kind of thick films a promising candidate for high-performance pyroelectric applications.     

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%.     

氮掺杂Bi2O3光催化剂的制备及其可见光催化性能

以硝酸铋和六次甲基四胺为原料,采用沉淀法合成了不同氮掺杂量的Bi2O3(N-Bi2O3)粉体,并采用XRD、FT-IR、XPS、UV-Vis、PL手段对其晶相结构和光谱特征等进行了表征.研究结果表明,未掺杂Bi2O3为单斜相α-Bi2O3,氮掺杂Bi2O3则为四方相β-Bi2O3和Bi5O7NO3组成的混晶,氮原子替代了Bi2O3晶格中部分氧原子,形成了Bi N键而稳定存在.氮掺杂能促进β-Bi2O3的生成.与未掺杂Bi2O3粉体相比,氮掺杂样品的吸收带边发生了明显红移,荧光强度明显减弱.甲基橙在可见光下的降解实验表明,氮掺杂Bi2O3具有良好的可见光催化活性.     

Precipitation of ZnO in Al2O3-doped zinc borate glass ceramics

Crystallization behavior of the oxide semiconductor ZnO in zinc borate glass was investigated. The precipitated crystalline phase of glass ceramics containing a small amount of Al₂O₃ was α-Zn₃B₂O₆ whereas that of the glass ceramics containing a large amount of Al₂O₃ was ZnO. It was found that the c-oriented precipitation of ZnO in a glass ceramic was brought about by the in-plane crystal growth of needle-like ZnO crystallites along the a-axis. Amount of Al₂O₃ that can make glass network affected the coordination state of B₂O₃ in the glass, and a three-coordinated BO₃ unit was preferentially formed in the glass containing a higher amount of Al₂O₃. The present results suggest that crystallization of ZnO from multi-component glass is dominated by the local coordination state of the mother glass.     

Fluorescence line narrowing study of Cr ions in cordierite glass nucleating MgAl2O4 nanocrystals

The luminescence of Cr³⁺ ions in cordierite glass nucleating MgAl₂O₄ nanocrystallites has been investigated. The time resolved fluorescence line narrowing measurements and the temperature dependence of the homogeneous line width show that most Cr³⁺ ions are inside the nanocrystallites. Cr³⁺ ions occupy non-equivalent crystal sites, due to the Mg²⁺–Al³⁺ inversion effect. The values of the homogeneous line width compare well with those of previous studies in crystals. No surface effect has been observed due to the large size of the crystals.     

Preparation and optical properties of sol–gel derived Er-doped Al2O3–Ta2O5 films

Thin films of the system xAl₂O₃–(100 − x)Ta₂O₅–1Er₂O₃ were prepared by a sol–gel method and a dip-coating technique. The influences of the composition and the crystallization of the films on Er³⁺ optical properties were investigated. Results of X-ray diffraction indicated that the crystallization temperature of Ta₂O₅ increased from 800 to 1000 °C with increased values of x. In crystallized films, the intensities of the visible fluorescence and upconversion fluorescence tend to decrease with an increase in x values, due to the high phonon energy of Al₂O₃; the strongest fluorescence is observed in a crystallized film for x = 4 heat treated at 1000 °C. In amorphous films obtained by heat treatment at relatively low temperatures the Er³⁺ fluorescence could not be observed because strong fluorescence from organic residues remaining in the films thoroughly covered the Er³⁺ fluorescence. On the other hand, the Er³⁺ upconversion fluorescence in the amorphous films was observed to be stronger than that in the crystallized films. The strongest upconversion fluorescence is observed in an amorphous film for x = 75 heat treated at 800 °C.     

Effects of growth conditions on the domain structure and dielectric properties of (1 − x)Pb(Sc1/2Nb1/2)O3–xPbTiO3 single crystals

The studies of the (1 − x)Pb(Sc_1/2Nb_1/2)O₃–xPbTiO₃ (PSN–PT) single crystals reveal that the chemical and physical properties of the materials are affected by the growth conditions. By the measurements of the dielectric constant as a function of temperature upon cooling, it is found that crystals grown from the same charged stoichiometric composition (x = 0.425), but under different flux environments (i.e. the composition of flux and the flux to PSN–PT ratios are varied), show anomalies (i.e. phase transitions) at different temperatures. This phenomenon is attributed to the complex local chemical structure of the PSN–PT solid solution single crystals with B-site random occupancy of three different cations (Sc³⁺, Nb⁵⁺ and Ti⁴⁺). The dielectric and domain structure of the PSN–PT crystals with composition near the morphotropic phase boundary (MPB) are investigated, showing much more complex situations compared with Pb(Sc_1/2Nb_1/2)O₃.     

热处理温度对Bi2O3/ATO复合功能填料红外-可见光兼容隐身性能的影响

采用固相法制备了Bi2O3/ATO复合功能填料,借助于XRD、SEM、分光光度计和辐射率仪研究了热处理温度分别对复合功能填料的物相组成、微观形貌、可见光及红外隐身性能的影响。结果表明,随着热处理温度的升高,复合功能填料的红外辐射率先下降后升高,当热处理温度为800℃时,复合功能填料的红外辐射率最低,达到了0.67。填料的最高反射峰出现在黄橙光范围内,但是,样品在可见光区的反射峰面积和平均反射率均随着热处理温度的升高逐渐增大。因此,复合功能填料的颜色亮度可以根据煅烧温度进行调节,适于制备多色红外迷彩涂料。     

Bi2O3纳米晶玻璃三阶非线性光吸收性质的研究

利用溶胶凝胶法结合气氛控制方式合成了含Bi2O3纳米晶钠硼硅玻璃.利用X射线粉末衍射仪(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、X射线能量色散谱(EDX)、扫描模式透射电子显微镜(STEM)、高分辨透射电子显微镜(HRTEM)以及选区电子衍射(SAED)对掺杂在钠硼硅玻璃中Bi2O3纳米晶的形貌和微结构进行了表征,同时,利用飞秒开孔Z-scan技术详细地研究了Bi2O3纳米晶玻璃在800 nm处不同激发光强度下的三阶非线性光吸收性质.结果表明,在钠硼硅玻璃中形成了尺寸小于10 nm的Bi2O3单斜晶系纳米晶.随着激发光强度的增强,该玻璃的三阶非线性光吸收性质产生由饱和吸收向反饱和吸收的转变.进一步,计算得到的该玻璃三阶非线性极化率χ(3)的数量级范围在10-19~10-18m2/V2之间.这一结果说明该玻璃具有良好的非线性光学性能,并且在光限幅器等非线性光学领域具有潜在的应用价值.     

多层陶瓷结构Al2O3-Fe2O3/3Y-TZP梯度复合陶瓷的制备及性能

为更好地实现口腔修复体的美学修复效果,采用掺杂不同含量Fe₂O₃（0.01wt%~0.09wt%）和Al₂O₃（0.1wt%）的3 mol% Y₂O₃稳定的ZrO₂（3Y-TZP）粉体为原料,经过铺粉、压制、烧结等工艺制得色度渐变的多层陶瓷结构Al₂O₃-Fe₂O₃/3Y-TZP梯度复合陶瓷。对该梯度复合陶瓷的色度分布、烧结性能和力学性能进行检测,同时研究了Fe₂O₃和Al₂O₃的掺杂对3Y-TZP陶瓷组织和性能的影响。结果表明,制得的Al₂O₃-Fe₂O₃/3Y-TZP梯度复合陶瓷色度由红黄向白色沿成分变化方向呈梯度变化,与天然牙齿色度分布规律一致;力学性能呈梯度变化并从无色端到有色端逐渐降低,但仍满足牙科使用需求（≥ 800 MPa）;在无色瓷层中掺杂微量Al₂O₃（0.1wt%）可以改善Al₂O₃-Fe₂O₃/3Y-TZP梯度复合陶瓷的烧结性能,避免在预烧结过程中发生开裂。微量Fe₂O₃和Al₂O₃的掺杂会促进其在烧结过程中的致密化及晶粒长大;微量Fe₂O₃（0.01wt%）和Al₂O₃（0.1wt%）的掺杂有助于提高3Y-TZP陶瓷的挠曲强度,然而随着Fe₂O₃掺杂量的继续增多（≤ 0.09wt%）挠曲强度降低。      

Sensitivity enhancement for H2 gas detection using a SnO2–Ag2O–PdOx nanocrystalline system

Thick film H₂ sensors were fabricated using SnO₂ loaded with Ag₂O and PdO_x. The composition that gave highest sensitivity for H₂ was in the wt.% ratio of SnO₂:Ag₂O:PdO_x as 93:5:2. The nano-crystalline powders of SnO₂–Ag₂O–PdO_x composites synthesized by sol–gel method were screen printed on alumina substrates. Fabricated sensors were tested against gases like H₂, CH₄, C₃H₈, C₂H₅OH and SO₂. The composite material was found sensitive against H₂ at the working temperature 125 °C, with minor interference of other gases. H₂ gas as low as 100 ppm can be detected by the present fabricated sensors. It was found that the sensors based on SnO₂–Ag₂O–PdO_x nanocrystalline system exhibited high performance, high selectivity and very short response time to H₂ at ppm level. These characteristics make the sensor to be a promising candidate for detecting low concentrations of H₂.     

Infrared optical properties of Bi2Ti2O7 thin films by spectroscopic ellipsometry

Bi₂Ti₂O₇ thin films have been grown directly on n-type GaAs (1 0 0) by the chemical solution decomposition technique. X-ray diffraction analysis shows that the Bi₂Ti₂O₇ thin films are polycrystalline. The optical properties of the thin films are investigated using infrared spectroscopic ellipsometry (3.0–12.5 μm). By fitting the measured ellipsometric parameter (Ψ and Δ) data with a three-phase model (air/Bi₂Ti₂O₇/GaAs), and Lorentz–Drude dispersion relation, the optical constants and thickness of the thin films have been obtained simultaneously. The refractive index and extinction coefficient increase with increasing wavelength. The fitted plasma frequency ω_p is 1.64×10¹⁴ Hz, and the electron collision frequency γ is 1.05×10¹⁴ Hz, and it states that the electron average scattering time is 0.95×10⁻¹⁴ s. The absorption coefficient variation with respect to increasing wavelength has been obtained.     

Sintering Behavior and Microwave Dielectric Properties of MgTiO3 Ceramics Doped with B2O3 by Sol-Gel Method

The B2O3-doped MgTiO3 powders and ceramics have been prepared by sol-gel method using Mg(NO3)2·6H2O, Ti(C4H9O)4 and H3BO3 as the starting materials. The sintering behavior and microwave dielectric properties of ceramics prepared from powders with different particle sizes were investigated. The gels were calcined at 650, 700, 750, 800, 850 and 900 C and the derived particle sizes of powders were 20-30 nm, 30-40 nm, 40-60 nm, 60-90 nm, 90-120 nm and 120-150 nm, respectively. The nanoparticles with the size of 30-60 nm benefited the sintering process with high surface energy whereas nanoparticles with the size of 20-30 nm damaged the microwave dielectric properties due to the pores in the ceramics. The addition of B2O3 used as a liquid sintering aid reduced the sintering temperature of MgTiO3 ceramic, which was supposed to enter the MgTiO3 lattice and resulted in the formation of (MgTi)2(BO3)O phase. The B2O3-doped MgTiO3 ceramic sintered at 1100 C and prepared from the nanoparticles of 40-60 nm had compact structure and exhibited good microwave dielectric properties: εr=17.63, Q × f=33,768 GHz and τ f= 48×10 6 C 1.