Er2O3掺杂Gd2(Zr0.8Ti0.2)2O7陶瓷的物理性能

用固相反应法制备(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇(摩尔分数x=0,0.2,0.4)陶瓷并测试其晶体结构、显微形貌和物理性能,研究了Er₂O₃掺杂的影响。结果表明,(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇陶瓷具有立方烧绿石结构,显微结构致密,在室温至1200℃高温相的稳定性良好;Er³⁺掺杂降低了陶瓷材料的热导率和平均热膨胀系数,当x=0.2时,其1000℃的热导率最低(为1.26 W·m^-1·k^-1)。同时,Er³⁺掺杂还提高了这种材料的硬度和断裂韧性。     

片状Al2O3对Al2O3/FEP复合材料热导率的影响

通过混炼工艺制备了片状Al₂O₃填充聚全氟乙丙烯(FEP)复合材料,以颗粒状Al₂O₃为对比样品,研究了片状Al₂O₃形状和尺寸对 FEP基复合材料热导率的影响,利用SEM观察了FEP基复合材料的微观形貌。结果表明：在低填充量下,Al₂O₃颗粒在FEP基体中呈“海岛”状分布,没有形成连续的导热网链,但其热导率明显提高;复合材料拉伸强度与断裂伸长率随Al₂O₃含量的增加而减小;低填充量时复合材料热导率的提高主要来自Al₂O₃的微细片状结构,这种微细片状结构一方面提高了有效导热路径,另一方面增加了颗粒与基体之间接触面积,因此有利于热导率的提高。     

大气等离子体喷涂Sm2Zr2O7涂层的结构和性能

稀土锆酸盐材料具有比Y2O3部分稳定ZrO2陶瓷低的热导率,是新型热障涂层的潜在候选材料之一.利用大气等离子体喷涂技术以喷雾造粒的Sm2Zr2O7粉体制备涂层,并在相同条件下沉积8wt%Y2O3稳定ZrO2涂层.对比评价了两种涂层的结构、热物理性能和力学性能.X射线衍射结果表明,制备态Sm2Zr2O7涂层为缺陷萤石结构.扫描电镜分析显示,Sm2Zr2O7和8wt%Y2O3稳定ZrO2涂层为典型的层状结构,内部有很多气孔、裂纹等缺陷.800℃测得的Sm2Zr2O7涂层的热导率为0.44 W/(m.K),比相同条件下测得的8wt%Y2O3稳定ZrO2涂层的热导率低~40%,两者的热膨胀系数相似.力学测试结果显示,Sm2Zr2O7涂层的抗折强度、硬度和弹性模量均低于8wt%Y2O3稳定ZrO2涂层.     

热处理对Bi2O3-B2O3-SiO2凝胶玻璃粉体结构与性能的影响

采用溶胶-凝胶法制备了一种Bi₂O₃-B₂O₃-SiO₂系玻璃粉体,在200 ℃、400 ℃、600 ℃和800 ℃温度下分别对凝胶玻璃粉体进行热处理,借助SEM、TEM、XRD、FT-IR、Raman、XPS、DSC、热膨胀仪及“纽扣”烧结实验分别测定了经不同温度热处理后玻璃粉体的结构与性能,分析了其结构变化对玻璃粉体转变温度T_g和烧结特性的影响。结果显示,在实验温度范围内,随热处理温度升高,Bi³⁺逐渐进入玻璃网络中,[BiO₆]八面体和[BiO₃]三角体、[BO₄]四面体和[BO₃]三角体分别与[SiO₄]四面体以顶角相连的方式构建玻璃网络结构。O1s和Bi4f的电子结合能逐渐增大,B1s的电子结合能减小,玻璃网络结构稳定性增强,导致玻璃转变温度T_g及玻璃膨胀软化点温度T_d升高、 润湿性降低且热膨胀系数略有降低。经600 ℃热处理后,玻璃粉体具有较优的烧结性能,T_g、T_d分别约为485 ℃及542 ℃,热膨胀系数α约为7.067×10-6/℃。     

Y2O3添加量对Al2O3/ZrO2共晶陶瓷显微组织及力学性能的影响

为探索第三组元Y₂O₃添加对Al₂O₃/ZrO₂共晶陶瓷显微组织与机械性能的影响,本文利用低温度梯度的高温熔凝法制备了直径为20 mm的Al₂O₃/ZrO₂(Y₂O₃)共晶陶瓷块体,采用SEM、EDS及XRD技术对共晶陶瓷进行微结构分析,并利用维氏压痕法对其硬度和断裂韧性进行测试。SEM结果表明,凝固组织由群集的共晶团结构组成,随着Y₂O₃添加量的增加,共晶团形态由胞状转变为枝晶状,内部相间距在1~2 μm范围内变化。力学测试表明,Y₂O₃摩尔分数小于1.1%时,由于组织内部存在低硬度m-ZrO₂及微裂纹缺陷,故陶瓷硬度较低,约为(9.53±0.22 )GPa;当Y₂O₃摩尔分数为1.1%时,陶瓷硬度最大,约为(18.05±0.27)GPa;当Y₂O₃的摩尔分数大于1.1%时,由于共晶团边界区内气孔缺陷及粗大组织增多,引起陶瓷硬度值略有下降。低Y₂O₃摩尔分数添加时,陶瓷断裂韧性相对较高,约为(6.30±0.16)MPa·m^1/2,这与其内部存在大量微裂纹缺陷有关;随着Y₂O₃添加量的增加,陶瓷的微裂纹数量减少、边界区内缺陷增多,断裂韧性降低。     

超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

纳米-Al2O3/SiO2加入量对MgO-Al2O3-SiO2复相陶瓷烧结机理的影响

为了探究纳米-Al₂O₃/SiO₂加入量对MgO-Al₂O₃-SiO₂复相陶瓷烧结行为的作用机理。以微米级MgO、纳米级Al₂O₃和SiO₂为主要原料制备陶瓷基复合材料。通过XRD和 SEM等检测手段对烧后试样的物相组成和微观结构进行测试与表征,重点研究Al₂O₃/SiO₂的加入对复相陶瓷物相组成、微观结构及烧结性能的影响。结果表明:随着Al₂O₃/SiO₂加入量的增大,试样烧后相对密度和烧后线变化率呈先增大后减小再增大的趋势,加入15%Al₂O₃/SiO₂(质量分数)的试样经1 500 ℃烧结后,其相对密度可以达到94%。引入的Al₂O₃/SiO₂与基体中的MgO生成镁铝尖晶石与镁橄榄石相,原位反应伴随的体积膨胀,抵消部分烧结过程中的体积收缩。Al₂O₃/SiO₂加入量为75%(质量分数)的试样经1 400 ℃烧结后,基体中有大量堇青石相生成,随着煅烧温度提高到1 500 ℃,堇青石分解所产生的高温液相促进了试样的烧结收缩。     

Al2O3基陶瓷材料增韧的研究进展

Al_2O_3基陶瓷材料具有高的化学稳定性,有较好的应用前景,但其脆性限制了它的推广应用,对氧化铝陶瓷进行增韧是解决其脆性问题的一条重要途径。简要介绍了目前氧化铝陶瓷的增韧方法和增韧机理,综述了氧化铝陶瓷增韧的研究现状,分析了氧化铝陶瓷增韧研究中存在的主要问题,展望了氧化铝陶瓷增韧的发展方向,提出了原位生长及复合增韧是高性能Al_2O_3基陶瓷材料的研究重点。     

超重力下燃烧合成ZrO2(4Y)/Al2O3的成分、显微组织与力学性能

采用超重力下燃烧合成技术,通过调整ZrO₂体积分数,制备出不同成分与显微组织形态的ZrO₂(4Y)/Al₂O₃复合陶瓷,研究了材料成分、显微组织与力学性能之间的关系。XRD、SEM和EDS结果表明：当ZrO₂体积分数低于37%,陶瓷熔体生成为生长取向各异且以ZrO₂四方相亚微米纤维镶嵌于α-Al₂O₃上的棒状共晶团为基体的复合陶瓷;当ZrO₂体积分数高于40%,复合陶瓷基体则生长为略呈球形的ZrO₂四方相微米晶粒。性能测试结果显示,随着ZrO₂体积分数增加 , 陶瓷相对密度逐渐降低,陶瓷硬度与断裂韧性均在ZrO₂体积分数为33%时出现最高值,而陶瓷弯曲强度则在ZrO₂体积分数为29%达到最大值。     

Ti掺杂β-Ga2O3电子结构和光学性质的第一性原理计算

采用基于密度泛函理论框架下的第一性原理计算方法,研究了Ti 掺杂β-Ga₂O₃系统的电子结构和光学性质。计算结果表明,Ti 替代八面体的Ga(2)时系统形成能最低,容易在实验上合成;Ti掺杂在导带底附近引入了浅施主能级,极大地提高了β-Ga₂O₃系统的导电性。Ti 掺杂时稳定体系倾向于自旋极化态,且费米面处自旋极化率接近100%。光学性质的计算结果显示,Ti 掺杂β-Ga₂O₃是极具潜力的n型紫外透明的半导体。     

Electrical conductivity of 5 mol.% Yb2O3 and 5 mol.% Gd2O3 co-doped Sm2Zr2O7

Sm₂Zr₂O₇ co-doped with and without 5 mol.% Yb₂O₃ and 5 mol.% Gd₂O₃ were prepared by a pressureless-sintering method at 1973 K for 10 h in air. The relative density, structure and electrical conductivity were investigated by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance spectra measurements. Both Sm₂Zr₂O₇ and (Sm_0.9Gd_0.05Yb_0.05)₂Zr₂O₇ ceramics exhibit a single phase of pyrochlore-type structure. The grain conductivity, grain-boundary conductivity and total conductivity obey the Arrhenius relation, respectively, and gradually increase with increasing temperature from 723 to 1173 K. (Sm_0.9Gd_0.05Yb_0.05)₂Zr₂O₇ ceramic is the oxide-ion conductor in an oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The grain conductivity, grain-boundary conductivity and total conductivity of (Sm_0.9Gd_0.05Yb_0.05)₂Zr₂O₇ with dual Yb³⁺ + Gd³⁺ doping are higher than those of undoped Sm₂Zr₂O₇ at identical temperature levels.     

无机固体电解质Li7La3Zr2O12的制备及掺杂改性研究进展

无机固体电解质由于其安全性能高、能量密度大等特点备受研究者的青睐。其中Garnet型锂离子无机固体电解质Li_7La_3Zr_2O_(12)具有较高的离子导电率,较低的界面电阻,优良的稳定性能和电化学性能,在未来的全固态锂离子电池、锂空气电池等领域有着广阔的应用前景。主要从Li_7La_3Zr_2O_(12)的晶体结构、制备工艺和掺杂改性等方面详细阐述无机固态电解质Li_7La_3Zr_2O_(12)的研究进展。     

Microstructural study of YBa2Cu3O7/SrTiO3/YBa2Cu3O7 heteroepitaxial trilayer films grown on (100) SrTiO3 substrates

Detailed transmission electron microscopic study has been carried out on heteroepitaxial YBa₂Cu₃O₇/SrTiO₃/YBa₂Cu₃O₇ trilayer thin films grown on (100)SrTiO₃ substrates prepared by DC and RF magnetron sputtering. The microstructural results showed the existence of somea-axis-oriented YBCO grains 20–90 nm wide in thec-axis-oriented YBCO matrix. Some of thea-axis grains in the lower YBCO thin film layer have protruded into the above SrTiO₃ layer, which may cause short circuit between the two YBCO superconducting layers. This is unsuitable for the application of trilayer thin films for microelectronic devices. The defects on the surface of the substrates would also influence the growth quality of the YBCO thin films.     

Raman scattering studies of ultrathin-layer YBa2Cu3O7/PrBa2Cu3O7 superlattices

We present Raman scattering studies ofc-oriented ultrathin-layer superconducting (YBa₂Cu₃O₇) _m /(PrBa₂Cu₃O₇) _n superlattices. For the superlattice with (m=2,n=1) sequence, Raman spectra reveal a new line in the spectral region around 320 cm^–1. It is interpreted as a mode representing a combination of IR optical phonons of the Y-sublayers with an admixture of aB _1g type Raman active vibration in the Pr sublayers. This new line, which is similar to those from the interior of the Brillouin zone of the original lattice, does not exhibit superconductivity-induced self-energy effects, although its counterpart in the pure substance does. No additional line is found in the (m=1,n=2) superlattice in the same region, supporting our interpretation for the (m=2,n=1) sample.     

Structure and thermal conductivity of Gd2(TixZr1 − x)2O7 ceramics

The Gd₂(Ti_xZr_1 − x)₂O₇ (x = 0, 0.25, 0.50, 0.75, 1.00) ceramics were synthesized by solid state reaction at 1650 °C for 10 h in air. The relative density and structure of Gd₂(Ti_xZr_1 − x)₂O₇ were analyzed by the Archimedes method and X-ray diffraction. The thermal diffusivity of Gd₂(Ti_xZr_1 − x)₂O₇ from room temperature to 1400 °C was measured by a laser-flash method. The Gd₂Zr₂O₇ has a defect fluorite-type structure; however, Gd₂(Ti_xZr_1 − x)₂O₇ (0.25 ≤ x ≤ 1.00) compositions exhibit an ordered pyrochlore-type structure. Gd₂Zr₂O₇ and Gd₂Ti₂O₇ are infinitely soluable. The thermal conductivity of Gd₂(Ti_xZr_1 − x)₂O₇ increases with increasing Ti content under identical temperature conditions. The thermal conductivity of Gd₂(Ti_xZr_1 − x)₂O₇ first decreases gradually with the increase of temperature below 1000 °C and then increases slightly above 1000 °C. The thermal conductivity of Gd₂(Ti_xZr_1 − x)₂O₇ is within the range of 1.33 to 2.86 W m^− 1 K^− 1 from room temperature to 1400 °C.     

微波和真空烧结制备La2O3掺杂Al2O3透明陶瓷

通过共沉淀法制备La2O3掺杂Al_2O_3纳米粉,粉体经压制后分别采用微波和真空烧结制备Al_2O_3透明陶瓷。结果表明:Al_2O_3粉末颗粒大小均匀,近似球形,为40~60nm;两种烧结方式制备的试样XRD图中均为α-Al_2O_3,未检测到其它相。La2O3掺杂量为1%时,随烧结温度升高,两种烧结方法得到的Al_2O_3陶瓷的相对密度和抗弯强度均呈上升趋势,且微波烧结陶瓷的相对密度和抗弯强度明显高于真空烧结。1500℃烧结时,随La2O3掺杂量的增加,Al_2O_3陶瓷的相对密度均先增大后减小,当La2O3掺杂量为1%时,Al_2O_3陶瓷的相对密度和抗弯强度均最大。微波烧结陶瓷的透光率明显高于真空烧结,且其断口晶粒比真空烧结明显细少。     

La2O3、Nd2O3、Y2O3对高岭石高温相变动力学的影响

利用综合热分析技术、X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)和扫描电镜(SEM)研究了La_2O_3、Nd_2O_3、Y_2O_3对高岭石高温条件下转变成莫来石过程的作用,并采用Kissinger方程、Ozawa方程以及JMA修正方程(Ⅰ)和(Ⅱ)分析了La_2O_3、Nd_2O_3、Y_2O_3对高岭石高温相变动力学的影响。结果表明:3种稀土氧化物的掺入对高岭石的相变动力学参数产生了影响,相变活化能和频率因子与未掺入稀土氧化物的高岭石相比有所降低,析晶方式则未发生变化,均属于体积晶化。对比掺入3种稀土氧化物的高岭石相变活化能和频率因子可以看出,Y_2O_3对于高岭石高温条件下相变的促进作用最为明显,相变活化能最低。稀土氧化物对于高岭石高温相变产物影响不大,主晶相为莫来石相,次晶相为方石英相,但稀土氧化物的掺入使得方石英相的结晶度明显提高。     

Comparative analysis of crystal field effects and optical spectroscopy of six-coordinated Mn ion in the Y2Ti2O7 and Y2Sn2O7 pyrochlores

The electronic energy levels of the six-coordinated Mn⁴⁺ ion in the pyrochlores Y₂B₂O₇ (B = Sn⁴⁺, Ti⁴⁺) have been computed using the exchange charge model of crystal field theory. The calculated Mn⁴⁺ energy levels and their trigonal splitting are in good agreement with the experimental spectra. The calculated crystal field parameters show that the higher crystal field strength in Y₂Sn₂O₇ arises from an increased orbital overlap effect between the Mn⁴⁺ ion and the nearest oxygen ions, which are located at the 48f crystallographic position of the pyrochlore lattice. This increased overlap in Y₂Sn₂O₇ occurs despite the fact that the Mn⁴⁺-O²⁻ bond distance in Y₂Sn₂O₇ is longer than in Y₂Ti₂O₇ and is attributed to a lack of hybridization (covalent bonding) between the filled 2p orbital of oxygen ion occupying the 48f site of the pyrochlore lattice and the filled Sn⁴⁺ 4d¹⁰ orbital. The low temperature emission spectrum of Mn⁴⁺ activated Y₂Sn₂O₇ is analyzed in terms of a weak zero phonon line (R-line) with accompanying vibrational side bands.     

纳米Al2O3/聚醚砜-环氧树脂复合材料的介电性能及热稳定性能

本实验制备了纳米Al_2O_3/聚醚砜-环氧树脂复合材料,考察了不同纳米氧化铝和聚醚砜的用量对复合体系力学和介电性能的影响,并对其热稳定性能进行了研究。结果表明:当添加1phr纳米氧化铝(Nano-Al_2O_3)和5phr聚醚砜(PES)时,三元复合材料EP/5PES/1Al_2O_3的拉伸强度提高到58 MPa,断裂伸长率达到13%,冲击强度达到16.2kJ/m~2,相比纯环氧树脂分别提高了61.1%、20.3%和8.0%。而且在100Hz的室温测试条件下,EP/5PES/1Al_2O_3材料的介电常数和介电损耗分别达到7.6和0.016,较纯环氧树脂均有一定幅度的增加。热重分析(TG)结果表明,EP/5PES/1Al_2O_3复合材料的初始分解温度为358℃,比纯环氧树脂提高了14℃,说明热稳定性有较大幅度的提高。