TiO2/Nd2Zr2O7复合物的合成及催化性能

通过溶胶-凝胶法成功合成了TiO2/Nd2Zr2O7复合氧化物.采用X射线衍射、透射电子显微镜、扫描电子显微镜对材料进行了表征,并对其比表面积进行了测试.结果表明:TiO2均匀地包覆在了Nd2Zr2O7颗粒的表面,其包覆量为50.36％(质量分数);TiO2/Nd2Zr2O7复合物的BET比表面积为25.62 m2/g,比Nd2Zr2O7纳米晶的表面积3.48 m2/g大得多.通过降解甲基橙评价产物的光催化活性,证实TiO2/Nd2Zr2O7复合物具有好的光催化活性.通过Nd2Zr2O7,TiO2和TiO2/Nd2Zr2O7在20 min内降解甲基橙的降解量分别为20.1％,70.7％和88.2％.     

Large third-order optical nonlinearity of ZnO–Bi2O3–B2O3 glass–ceramic containing Bi2ZnB2O7 nanocrystals

Homogeneous transparent optical glass–ceramics precipitated with unique nonlinear crystals are promising materials for photonic applications. We have utilized heat treatment method to prepare transparent ZnO–Bi₂O₃–B₂O₃ glass–ceramic containing Bi₂ZnB₂O₇ nonlinear nanocrystals. A large third-order nonlinear susceptibility χ⁽³⁾ of glass–ceramic is measured by Z-scan technique, which mainly attributed to unique [BiO₆] and [B₂O₅] units in Bi₂ZnB₂O₇ crystal structure and the quantum size effect of nanoparticles. The discovery is of great potential in the application of nonlinear optical integrated devices.     

固态无机电解质Li7La3Zr2O12的改性研究进展

作为一种固态无机电解质材料,石榴石型立方相Li₇La₃Zr₂O₁₂具有较高的室温锂离子电导率、较宽的电化学窗口和优良的热稳定性等特点,是高安全性、高能量密度固态锂离子电池实现商业化应用的关键。阐述了Li₇La₃Zr₂O₁₂的晶体结构与锂传导机理,综述了元素掺杂、聚合物电解质复合、烧结助剂引入、表面包覆或修饰等方式对Li₇La₃Zr₂O₁₂的物相结构稳定性、界面阻抗与相容性、烧结活性、离子电导率等进行改性的最新研究进展。最后,针对Li₇La₃Zr₂O₁₂在产业化应用中所面临的障碍与挑战,提出了制备新工艺的开发、离子电导率的多重改性以及柔性复合电解质膜的结构设计与优化等应对策略,为推动高性能固态锂离子电池的发展提供依据。     

Plasma-sprayed La2Ce2O7 thermal barrier coatings against calcium–magnesium–alumina–silicate penetration

As one of promising thermal barrier coating (TBC) candidates, La₂Ce₂O₇ (LC) has attracted increasing attention because of its low thermal conductivity and potential capability to be operated above 1250 °C. In this paper, the microstructure evolution and mechanical properties of the plasma-sprayed LC TBC with calcium–magnesium–alumina–silicate (CMAS) glassy deposits at 1250 °C were investigated. Due to chemical reaction between the CMAS deposits and LC coating, a dense sealing layer, mainly composed of Ca₂(La_xCe_1−x)₈(SiO₄)₆O_6−4x and CeO₂, was formed on the coating after heat-treatment at 1250 °C and effectively prevented CMAS from further penetration. The interaction layer had the micro-hardness of ∼10–12 GPa, relatively harder than the LC coating.     

Hot corrosion behavior of (Gd0.9Sc0.1)2Zr2O7 in V2O5 molten salt at 700–1000 °C

Hot corrosion behavior of (Gd_0.9Sc_0.1)₂Zr₂O₇ ceramic exposed to V₂O₅ molten salt at 700–1000 °C was investigated, providing better understanding of its corrosion resistance as a promising thermal barrier coating. Obvious corrosion reaction occurred between (Gd_0.9Sc_0.1)₂Zr₂O₇ and V₂O₅ molten salt after 4 h heat treatment, corrosion products being temperature dependent. At 700 °C, large amount of Sc₂O₃ doped ZrV₂O₇ and GdVO₄, together with a minor amount of Sc₂O₃-stabilized tetragonal ZrO₂ (t-ZrO₂), formed on the sample surfaces. With the increase of the test temperature, Sc₂O₃ doped ZrV₂O₇ turned to decompose, leading to the formation of more t-ZrO₂. At 900 °C and 1000 °C, the corrosion products were composed of GdVO₄ and t-ZrO₂. The mechanism by which the corrosion reaction occurs is proposed based on phase diagrams and Lewis acid-base rule.     

表面活性剂对Sm2Zr2O7纳米热障涂层材料烧结性能的影响

采用水热合成法制备Sm2Zr2O,纳米晶体,研究了聚乙二醇(PEG)、十六烷基三甲基溴化铵(CTAB)、十二烷基苯磺酸钠(SDBS)三种不同类型的表面活性剂对材料相结构、分散性能以及烧结性能的影响.实验结果表明:材料的物化性能与表面活性剂的类型密切相关,阳离子表面活性剂的添加抑制了材料由萤石结构向烧绿石结构的转变,样品比表面积为174.67 m2·g-1,经过高温烧结后块材的体积收缩和相对密度分别为24.5％和81.2％.相比之下,阳离子表面活性剂CTAB对于提高材料的抗烧结性能方面要明显好于非离子表面活性剂PEG和阴离子表面活性剂SDBS.     

湿化学法制备石榴石型固态电解质Li7La3Zr2O12

锂电池因能量密度高、循环寿命长、绿色清洁等特点被广泛应用,但其液态电解质易泄漏、挥发,且隔膜易被锂枝晶刺穿造成短路,引发危险。固态电解质大多是不具燃烧性的无机材料,室温下离子电导率较高、电化学窗口宽且适用温度范围广。因此,采用固态电解质替代液态电解质具有十分重要的意义。相对于其他类型固态电解质,石榴石型氧化物Li₇La₃Zr₂O₁₂（LLZO）具有离子电导率高、电化学窗口宽（>5V vs. Li/Li⁺）、对锂稳定性好和热稳定性高等特点,是非常具有发展潜力的无机固态电解质。本文采用溶胶-凝胶法和低温燃烧法两种湿化学法合成LLZO粉末,对应的电解质片在40℃时的离子电导率分别为1.22×10^-5S/cm和3.87×10^-6S/cm,活化能分别为0.34eV和0.32eV。从实验结果综合比较,溶胶-凝胶法为最佳制备方法。     

Phase evolution and microstructural studies in CaZrTi2O7 (zirconolite)–Sm2Ti2O7 (pyrochlore) system

From the characterization of a series compositions with general stoichiometry as Ca_1−xZr_1−xSm_2xTi₂O₇ (0.00 ≤ x ≤ 1.00), the phase evolution between zirconolite (CaZrTi₂O₇) and pyrochlore type Sm₂Ti₂O₇ has been elucidated. All the compositions were prepared by high temperature solid state reaction and characterized by powder X-ray diffraction (XRD) and electron probe for microanalyses (EPMA). Three major phase fields, namely two layer (2-M) or four layer (4-M) monoclinic zirconolite and cubic pyrochlore structure types were observed in this system. In addition, a feeble amount of perovskite type phase is found to coexist with zirconolite phase. 4-M zirconolite phase is observed as single phase field at the composition with x = 0.30 and 0.35, while cubic pyrochlore phase is observed as single phase at the compositions with x ≥ 0.60. Further, the composition and microstructure of coexisting phases are verified by back scattered electron image and EPMA studies.     

Stability in the system CaO–Al2O3–H2O

The solubility of AH₃, CAH₁₀, C₂AH_7.5, and C₃AH₆ was determined experimentally at 7 to 40 °C and up to 570 days. During the reaction of CA, at 20 °C and above initially C₂AH_7.5 formed which was unstable in the long-term. The solubility products calculated indicate that the solubilities of CAH₁₀, C₂AH_7.5 and C₄AH₁₉ increase with temperature while the solubility of C₃AH₆ decreases. Thus at temperatures above 20 °C, C₃AH₆ is stable, while at lower temperature also CAH₁₀ and C₄AH₁₉ are stable, depending on the C/A ratio.At early hydration times, CAH₁₀ can be stable initially at 30 °C and above, as the formation of amorphous AH₃ stabilises CAH₁₀ with respect to C₃AH₆ + 2AH₃. With time, as the solubility AH₃ decreases due to the formation of microcrystalline AH₃, CAH₁₀ becomes unstable at 20 °C and above.     

Chemical Stability of ZnO–Na2O–SO3–P2O5 Glasses

We report on chemical stability and corrosion behavior of highly depolymerized sulfophosphate glasses from the system ZnO–Na₂O–SO₃–P₂O₅ in aqueous solution, providing data on weight loss, ion release rates, and modifications of surface topology as a function of time, temperature and pH value. Observations seem consistent with the previously developed structural model of chemical heterogeneity, where cations Na⁺ and Zn²⁺ cluster selectively in the vicinity of sulfate and phosphate anions, respectively.     

石榴石型固态电解质Li7La3Zr2O12的改性研究现状

固态电解质是高安全性、高能量密度的全固态锂电池的核心部件,其典型代表Li₇La₃Zr₂O₁₂(LLZO)具有高离子电导率、高机械强度、高电化学稳定性、低界面阻抗以及对锂金属负极良好的稳定性等优势,是科研人员重点关注的对象之一,但与液态电解质相比,目前LLZO仍存在低离子电导率和与电极固-固界面接触等问题。本文主要简介了LLZO的晶体结构、改性方式等对其离子电导率及界面阻抗的影响,同时对LLZO现存的问题进行了总结,对LLZO的未来发展方向进行了展望,为探索全固态锂电池的实际生产应用提供理论指导。     

Surface and bulk crystallization in Nd2O3–Al2O3–SiO2–TiO2 glasses

Neodymium aluminosilicate (Nd₂O₃–Al₂O₃–SiO₂; NdAS) glasses have been investigated for the effect of concentration of TiO₂ on the crystallization mechanism and for the effect of surface condition on crystal growth. NdAS glasses with 0–10 wt.% TiO₂ were heat-treated for nucleation and crystal growth and were examined for phase separation and morphology of surface crystals as well as for crystal growth rate. All the glasses exhibit surface crystallization, however, the glass having 8 wt.% TiO₂ also exhibits internal crystallization after a two-stage heat treatment. Surface crystallization was dependent on the condition of the glass surface and the amount of TiO₂. The crystal growth on the cut surface was faster than on the fractured surface and the growth rate in surface increased with increasing TiO₂. The phase separation found in NdAS glasses containing above 8 wt.% TiO₂, was confirmed to be an important factor controlling the internal crystallization process in Nd₂O₃–Al₂O₃–SiO₂–TiO₂ glasses.     

Fabrication and characterization of La2Zr2O7 films on different buffer architectures for YBa2Cu3O7?δ coated conductors by RF magnetron sputtering

La₂Zr₂O₇ (LZO) films were grown on different buffer architectures by radio frequency magnetron sputtering for the large-scale application of YBa₂Cu₃O_7−x (YBCO)-coated conductors. The three different buffer architectures were cerium oxide (CeO₂), yttria-stabilized zirconia (YSZ)/CeO₂, and CeO₂/YSZ/CeO₂. The microstructure and surface morphology of the LZO film were studied by X-ray diffraction, optical microscopy, field emission scanning electron microscopy, and atomic force microscopy. The LZO films prepared on the CeO₂, YSZ/CeO₂, and CeO₂/YSZ/CeO₂ buffer architectures were preferentially c-axis-oriented and highly textured. The in-plane texture of LZO film on CeO₂ single-buffer architecture was ∆ φ = 5.5° and the out-of-plane texture was ∆ ω = 3.4°. All the LZO films had very smooth surfaces, but LZO films grown on YSZ/CeO₂ and CeO₂/YSZ/CeO₂ buffer architectures had cracks. The highly textured LZO film grown on CeO₂-seed buffered NiW tape was suitable for the epitaxial growth of YBCO film with high currents.     

Dielectric Characteristics of Ceramics in BaO–Nd2O3–TiO2–Ta2O5 System

Dielectric ceramics in the BaO–Nd₂O₃–TiO₂–Ta₂O₅ system were prepared and characterized. The ceramics with tungsten–bronze structure based on the compositions Ba₂NdTi₂Ta₃O₁₅ and Ba₅NdTi₃Ta₇O₃₀ had a high dielectric constant (>100) with a lower frequency-dependency when complete densification was achieved; a low dielectric loss was obtained in the former.     

Dielectric Relaxation in CaO–Bi2O3–B2O3 Glasses

Glasses in the system CaO–Bi₂O₃–B₂O₃ (in molar ratio) have been prepared using melt-quenching route. Ion transport characteristics were investigated for this glass using electric modulus, ac conductivity and impedance measurements. The ac conductivity was rationalized using Almond–West power law. Dielectric relaxation has been analyzed based on the behavior of electric modulus behavior. The activation energy associated with the electrical relaxation determined from the electric modulus spectra was found to be 1.76 eV, close to that the activation energy for dc conductivity (1.71 eV) indicating that the same species took part in both the processes. The stretched exponent β (0.5–0.6) is invariant with temperature for the present glasses.     

Crystallization of Glasses in the K2O–Nb2O5–SiO2System

The changes in the structure and phase composition of glasses in the K₂O–Nb₂O₅–SiO₂system upon their heat treatment in the temperature range 700–800°C are studied by the small-angle X-ray scattering (SAXS) technique and X-ray powder diffraction. It is demonstrated that the crystallization is the primary process giving rise to microinhomogeneities in glasses due to heat treatment. Nanocrystals of an unidentified niobium-containing phase precipitate in glasses with the formation of regions with a decreased content of potassium and niobium oxides. An increase in the duration of heat treatment at the studied temperatures results in an increase in the size of nanocrystals without change in their phase composition. This is accompanied by the disappearance of diffusion zones, which leads to a decrease in the SAXS intensity in the range of small scattering angles and, correspondingly, to a decrease in the light scattering intensity.     

MgB4O7-K2B4O7-Na2B4O7-H2O 四元体系288 K介稳相平衡研究

中国青藏高原的盐湖资源丰富,以富含硼酸盐资源而闻名,且钾、镁储量较大,所以深入开展含硼多组分介稳相平衡的研究,对开发中国盐湖中硼、镁等资源有着重要意义.采用等温蒸发法进行了MgB4O7-K2B4O7-Na2B4O7-H2O四元体系288 K时的介稳相平衡研究,测定了该体系介稳相平衡的溶解度和液相密度.研究发现该四元体系为简单共饱和型,无复盐形成;根据溶解度数据绘制了相图,相图中有一个四元共饱点E和3条单变度曲线E1-E,E2-E,E3-E;平衡固相分别为MgB4O7·9H2O,Na2B4O7·10H2O和K2B4O7·4H2O;由相图可知K2B4O7对Na2B4O7具有盐溶作用.     

Bioactivity investigation of glass and glass ceramics in Li2O–SiO2–CaO–P2O5–CaF2 system

Abstract

Glass samples in Li₂O–SiO₂–CaO–P₂O₅–CaF₂ system with different contents of P₂O₅, CaO and CaF₂ in relative ratios responded to fluoroapatite (FA) composition (referred to P₂O₅ addition) have been prepared and heat treated at 550 and 750°C to obtain glass ceramics. Bioactivity of all samples has been proved in vitro by the presence of new layer of apatite-like phases formed after soaking in simulated body fluid (SBF). The development and the apatitic character of created layers have been demonstrated by Fourier transform infrared analysis. Scanning electron microscopy and electron probe microanalysis have demonstrated that the density and the thickness of new layer depend on P₂O₅ content, crystallisation temperature and immersion time. The bioactivity has been enhanced by P₂O₅ addition as well in the case of the base glasses as in the case of glass ceramics. The additional heat treatment appeared to inhibit the bioactive behaviour, though the longer SBF acting leads to the additional formation of apatite-like layer. The mechanical properties, expressed as Vicker hardness, have been found higher and increasing with P₂O₅ in glass ceramics treated at 750°C comparatively with base glass samples and the highest value of 7˙37 GPa has been achieved by 14 wt-%P₂O₅ addition. The same content of P₂O₅ in glass ceramics heat treated at 550°C resulted in a decrease in hardness to a minimum value from all samples. The increase and decrease in hardness responded to development and suppression of crystallisation respectively. The inhibition of crystallisation has been affected by the presence of 'amorphous' FA according to X-ray diffraction and differential thermal analysis results.     

Antibacterial and photocatalytic active transparent TiO2 crystallized CaO–BaO–B2O3–Al2O3–TiO2–ZnO glass nanocomposites

Transparent TiO₂ crystallized 5CaO–10BaO–65B₂O₃–Al₂O₃–20TiO₂–10ZnO (CBBATZ) glass nanocomposites were fabricated using melt-quenching technique followed by specific heat treatments. As-quenched glass samples were provided three different heat treatments at 630°C for 3, 5, and 10 hours in order to obtain different amounts of TiO₂ nanocrystals in the glass. The presence of rutile phase of TiO₂ nanocrystals in glass was confirmed by X-ray diffraction. The glass nanocomposite heat treated for 10 hours showed a hydrophobic nature with contact angle of 90.90°. Contact angle decreased from 90.90 to 22.20°, when irradiated under ultraviolet (UV) radiation for 45 minutes. This photoinduced hydrophilicity showed a photocatalytic and self-cleaning properties of glass nanocomposite. During photocatalytic ink test, the maximum change in color of Resurin (Rz) ink and 60% degradation in absorbance of ink within 150 minutes under UV radiation were found for glass nanocomposite heat treated at 10 hours. Also, 78% degradation in absorbance of methylene blue dye (pollutant) within 180 minutes under UV irradiation was found for glass naocomposite heat-treated at 10 hours. Antibacterial performance of transparent glass nanocomposite against Escherichia coli was evaluated as well. More than 95% of the bacterial cells were degraded with glass nanocomposite heat-treated at 10 hours. CBBATZ glass nanocomposite found to impart the antibacterial effect through generation of reactive oxygen species (ROS) in aqueous medium. ROS species which was confirmed in the bacterial cell through intracellular ROS generation kit. During evaluation of mechanical properties using nanoindentation technique, the values of hardness and reduced modulus increased by ~26% and 10%, respectively, for glass nanocomposite heat-treated at 10 hours as compared to as-quenched glass.