A new class of high-entropy fluorite oxides with tunable expansion coefficients,low thermal conductivity and exceptional sintering resistance

High-temperature thermal barrier coating (TBC) materials are desired for the development of high-efficient gas turbines and diesel engines. Herein, to meet up with this requirement, a new class of high-entropy fluorite-type oxides (HEFOs) has been synthesized via a solid-state reaction method. Comparing to La₂Ce₂O₇, a promising TBC material, the HEFOs exhibit similar high thermal expansion coefficients (TECs) of 11.92×10⁻⁶∼12.11×10⁻⁶ K^-1 at temperatures above 673 K but a better TEC matching performance at the temperature range of 473–673 K. It is also found that through tuning the average A-site cation radius, the TEC of the HEFOs could be tailored efficiently. The HEFOs also possess low thermal conductivities of 1.52-1.55 W∙m^-1∙K^-1 at room temperature, which is much lower than that of La₂Ce₂O₇ and comparable to pyrochlores as Gd₂Zr₂O₇. Moreover, the HEFOs display good sintering resistance and phase stability even at temperatures as high as 1873 K. The combination of these fascinating properties makes the HEFOs good candidates for thermal barrier coating and thermal insulating materials.     

稀土矿浮选中Ce3+对含钙脉石活化作用机理研究

通过单矿物浮选试验、红外光谱分析和Zeta电位测试等方法,研究了以辛基异羟肟酸为捕收剂浮选稀土时矿浆中Ce³⁺对含钙脉石矿物萤石及方解石的活化作用机理。浮选结果表明,当辛基异羟肟酸浓度为2.0×10^-4 mol/L、矿浆中Ce³⁺浓度小于1×10^-4 mol/L时,pH值在 6~10之间时,Ce³⁺对含钙矿物萤石及方解石有活化作用。机理分析结果表明,Ce³⁺吸附在含钙矿物萤石及方解石表面形成了活性位点,可与羟肟酸根离子产生络合吸附,生成稳定的五元环络合物,增大了羟肟酸在矿物表面的吸附能力,从而活化矿物。     

离子色谱法测定萤石中氟化钙的含量

应用离子色谱法(ICS)测定萤石中氟化钙的含量。试样经氢氧化钾熔解,定容进行测定。同时进行了熔解试剂时测定结果的影响试验,并进行了一系列仪器测定精度及方法回收率试验。经过试验发现离子色谱法测定萤石中的氟化钙含量具有分析速度快、无干扰、灵敏度高、准确度高等优点,适合于大批量样品的检测,可以大大地提高工作效率。     

固体氧化物燃料电池电解质材料的研究进展

综述了现有的固体氧化物燃料电池电解质材料,包括立方萤石型、钙钛矿型、磷灰石型及几类新型的电解质材料,主要从各类材料的结构、性能、研究进展、应用情况、各类材料的优缺点及未来发展方向等方面进行了介绍。     

New class of high-entropy defect fluorite oxides RE2(Ce0.2Zr0.2Hf0.2Sn0.2Ti0.2)2O7 (RE = Y,Ho, Er,or Yb) as promising thermal barrier coatings

High-entropy ceramics exhibit great application potential as thermal barrier coating (TBC) materials. Herein, a series of novel high-entropy ceramics with RE₂(Ce_0.2Zr_0.2Hf_0.2Sn_0.2Ti_0.2)₂O₇ (RE₂HE₂O₇, RE = Y, Ho, Er, or Yb) compositions were fabricated via a solid-state reaction. X-ray diffraction (XRD) and energy dispersive spectrometry (EDS) mapping analyses confirmed that RE₂HE₂O₇ formed a single defect fluorite structure with uniform elemental distribution. The thermophysical properties of the RE₂HE₂O₇ ceramics were investigated systematically. The results show that RE₂HE₂O₇ ceramics have excellent high-temperature phase stability, high thermal expansion coefficients (10.3–11.7 × 10^?6 K^-1, 1200 ℃), and low thermal conductivities (1.10-1.37 W m^-1 K^-1, 25 ℃). In addition, RE₂HE₂O₇ ceramics have a high Vickers hardness (13.7–15.0 GPa) and relatively low fracture toughness (1.14-1.27 MPa m^0.5). The outstanding properties of the RE₂HE₂O₇ ceramics indicate that they could be candidates for the next generation of TBC materials.     

Potential thermal barrier coating materials: RE3NbO7 (RE=La, Nd,Sm, Eu,Gd, Dy) ceramics

In this work, RE₃NbO₇ ceramics are synthesized via solid‐state reaction and the phase structure is characterized by X‐ray diffraction and Raman spectroscopy. The relationship between crystal structure and thermophysical properties is determined. Except Sm₃NbO₇, each RE₃NbO₇ exhibits excellent high‐temperature phase stability. The thermal expansion coefficients increase with the decreasing RE³⁺ ionic radius, which depends on the decreasing crystal lattice energy and the maximum value reaches 11.0 × 10^?6 K^?1 at 1200°C. The minimum thermal conductivity of RE₃NbO₇ reaches 1.0 W m^?1 K^?1 and the glass‐like thermal conductivity of Dy₃NbO₇ is dominant by the high concentration of oxygen vacancy and the local structural order. The outstanding thermophysical properties pronounce that RE₃NbO₇ ceramics are potential thermal barrier coating materials.     

广西珊瑚钨锡矿田萤石的标型特征

对广西珊瑚钨锡矿田的主要脉石矿物萤石进行形态、结构和物性特征等方面研究后认为:矿田内三种不同类型矿床的成矿温度从高温向低温递减,而成矿热液性质由酸性→中性→碱性演化;萤石中锶和稀土元素含量随温度下降而变贫;萤石的晶胞参数(a_0)除受温度影响外,还与其Sr和REE含量有关;萤石的物性变化是由于锶和稀土元素含量不同而引起的。     

离子注入诱发YSZ相变和Pyrochlore纳米晶的电子显微研究

通过剖面电子显微技术研究了离子注入在单晶YSZ中诱发生成Pyrochlore纳米晶(约10nm),并使萤石结构的YSZ局部相变为焦绿石结构。在YSZ单晶中注入180keVTi+离子,注入温度为常温,Ti+注量为1×1017ions/cm2,随后在1100℃的氩气中退火2h。电子显微研究表明,Y(钇)稳定的立方ZrO2转变成为点阵常数a≈(1.024±0.005)nm的焦绿石结构A2B2O7(Y2(TixZr1-x)2O7)。生成的Y2(TixZr1-x)2O7与母相保持共格,有[110]YSZ∥[110]P和(11-1)YSZ∥(11-1)P的取向关系。阳离子有序和化学成分的重新分布被认为是这种相变发生的机理。     

萤石浮选技术的新进展

概括了我们１５年在或石浮试验与生产实践中针对药剂制度和流程结构进行改进所取得的主要成果。由于“Ｈ系列改性玻璃复合调整剂”的研制成功和中矿“双回路”在流程中的合理运用,有效地解决了萤石与含硅矿物（微细石英、片状云母等）,萤石与含硫矿物（重晶石、黄铁矿等）,萤石与其它含钙矿物（方解石、白钨矿等）的浮选分离以及萤石浮选地温度及水质的适应性,使我国萤石浮选技术取得了突破性进展。     

碱熔-离子选择性电极法测定萤石中氟化钙

氟化钙含量是评定萤石质量等级的重要指标。先采用氢氧化钠、过氧化钠于700 ℃熔融分解样品,再用盐酸(1+4)进行溶解配制成溶液,以柠檬酸钠和硝酸钾为总离子强度调节剂,以茜红素S为指示剂,建立了以离子选择性电极法测定氟离子含量来推算萤石中氟化钙含量的方法。用高温、氢氧化钠熔融样品、氢氧化钠-过氧化钠熔融样品3种分解方法对萤石样品进行处理,并对处理后的样品分别进行扫描电子显微镜(SEM)、X射线能谱(EDS)和X射线衍射(XRD)表征,结果表明高温碱熔条件下氢氧化钠能使氟化钙完全分解从而促进样品被分解完全,过氧化钠将萤石中的硫元素完全氧化成硫酸根以消除硫对测定的影响。按照实验方法测定萤石标准样品和生产样品,结果的标准偏差为0.26%~0.40%,相对标准偏差为(RSD)0.28%~0.74%,标准样品和实际样品中氟化钙的含量与认定值或参考值相符。