超重力下燃烧合成大体积凝固态Al2O3/ZrO2（4Y）研究

通过在铝热剂中引入ZrO2(4Y)混合粉末,以超重力下燃烧合成方式,制备出Al2O3/ZrO2(4Y)自生复合陶瓷板材,并研究了复合陶瓷微观结构、生长机理与力学性能.XRD、SEM与EDS结果显示,Al2O3/32%ZrO2(4Y)复合陶瓷基体为亚微米t-ZrO2纤维成三角对称分布其上、取向各异的棒状共晶团,而Al2O3/37%ZrO2(4Y)复合陶瓷则以分布均匀的微米级t-ZrO2球晶为基体.Al2O3/32%ZrO2(4Y)复合陶瓷的强化归因于小尺寸共晶团边界及残余压应力增韧、相变增韧机制引发的高断裂韧性所致;同时,细小t-ZrO2球晶所具有的小尺寸缺陷及相变增韧与微裂纹增韧机制所引发的高断裂韧性也使Al2O3/37%ZrO2(4Y)复合陶瓷得以强化.     

SiO2对Al2O3凝胶纤维相变的影响

以尿素催化硅酸乙酯水解制得SiO2溶胶。采用29Si NMR、27 Al NMR、FT-IR、TEM、DTA、XRD和SEM等对SiO2溶胶、Al2O3凝胶纤维化学结构和微观结构研究结果表明,该SiO2溶胶稳定性好,含有大量的单硅酸Si(OH)4,能和Al2O3表面的Al—OH反应生成Al—O—Si键而有效地将其包裹,从而阻止了过渡态Al2O3微晶的相互接触,抑制了α-Al2O3的成核和生长。     

Al2O3/ZrO2/ZrSiO4复合材料的研究

在Al2O3颗粒补强锆英石陶瓷的研究基础上,探讨了Al2O3与ZrO2共同对锆英石陶瓷的协同补强增韧行为.制备的锆英石基复合材料的室温抗弯强度和断裂韧性分别可达383.31MPa、4.39 MPa·m12.采用XRD分析了复合材料的相组成,采用SEM观察复合材料的断面形貌.结果显示:ZrSiO4为主要晶相,另外还有少量Al2O3和ZrO2存在;第二种增强体ZrO2的最佳引入量为20％(质量分数);确定复合材料的强韧化是由Al2O3和ZrO2颗粒引起的裂纹偏转、微裂纹增韧与ZrO2颗粒引起的相变增韧共同作用而实现的,断裂方式主要为穿晶断裂.     

Al2O3掺杂对Ba4Sm9.33Ti18O54陶瓷显微结构和介电性能的影响

采用固相反应法制备了Ba4Sm9.33Ti18O54(简称BST)xwt%Al2O3(x=0~1.5)微波介质陶瓷.研究了掺杂Al2O3对BST陶瓷的显微结构和介电性能的影响.扫描电镜和能谱分析结果显示:未掺杂的BST陶瓷中有少量Sm2Ti2O7相,随着增加Al2O3掺入量,Sm2Ti2O7相消失,BST陶瓷中先后产生了BaTi4O9(x≥0.6)和BaAl2Ti5O14(x≥1.0)两种新相.介电性能测试结果表明Sm2Ti2O7相的消失以及少量BaTi4O9相的形成,能显著提高BST陶瓷的Qf值,但会降低陶瓷的介电常数.当Al2O3的掺入量从0.6wt%增加到1.0wt%时,BaTi4O9相的量逐渐增加,引起BST陶瓷的Qf值略微下降.BaAl2Ti5O14相的产生会同时降低BST陶瓷的介电常数和Qf值.掺入0.6wt%Al2O3的BST陶瓷在1340℃烧结3 h后具有最佳的介电性能:εr=74.7,Qf=10980 GHz,τf=–11.8×10-6/℃.     

SHS纳米组织Al2O3-ZrO2共晶复相陶瓷断裂力学研究

通过对纳米组织Al2O3-ZrO2共晶复相陶瓷的Vickers压痕测试、SEM观察与XRD分析,发现诱发该复相陶瓷中位裂纹扩展的压痕压制载荷临界值为30kg,复相陶瓷的裂纹扩展主要受晶内型纳米相微观结构所控制,分布于纳米组织Al2O3-ZrO2共晶复相陶瓷中的ZrO2纳米相的结构、含量与分布及ZrO2纳米相与基体相之间的残余应力场决定着该复相陶瓷的断裂力学.     

激光双面区熔Al2O3/Y3Al5O12共晶自生复合陶瓷的制备与表征

采用激光区熔凝固技术制备大尺寸Al2O3/Y3Al5O12(YAG)共晶自生复合陶瓷,考察双面区熔条件下大尺寸氧化物共晶陶瓷的熔化及凝固成形规律,采用扫描电镜、能谱和X射线衍射对其凝固组织特征进行了表征和分析.研究结果表明:在优化的凝固工艺下,激光双面区熔增加了熔凝层的厚度,获得了熔凝层厚度8.2 mm,长度65.0 mm,致密度达98.5%±1%的Al2O3/YAG共晶陶瓷;共晶熔凝层厚度随激光扫描速率的减小而增加,随激光功率的增大而增大,并且致密度随着激光功率的增大呈现先增大后减小的趋势;双面区熔后的Al2O3/YAG共晶陶瓷微观组织由均一分布、相互交织的Al2O3和YAG共晶相组成,共晶层片间距较小(1.0~3.5μm),且与凝固速度满足Jackson-Hunt公式;共晶间距随扫描速率的增大逐渐减小;双面区熔界面处共晶组织生长具有连续性,界面结合良好;共晶陶瓷的Vickers硬度为(18.6±1.0)GPa.     

Al2O3含量对PVDF/PVC/Al2O3共混中空纤维膜的影响

以聚偏氯乙烯(PVDF)、聚氯乙烯(PVC)和纳米氧化铝(Al2O3)三元共混,制备中空纤维膜,探讨Al2O3含量对膜性能的影响。结果表明,由于适量Al2O3的加入,中空纤维膜膜孔结构明显改善,大孔减少,微孔增多;亲水性明显提高。Al2O3为最佳含量3%时,水通量和截留率分别达到了289L/(h·m2)和77.2%。     

离心-凝胶注模成型制备梯度多孔Al2O3陶瓷

以造孔剂PMMA、纳米Al2O3颗粒为主要原料,利用离心-凝胶注模成型工艺制备梯度多孔Al2O3陶瓷,研究了pH值对Al2O3浆料粘度的影响,观察了Al2O3浆料的凝胶固化过程,分析了离心转速和离心时间对生坯密度梯度的影响,观察了烧结产物的显微组织并对其压缩强度进行测试。研究结果表明引发剂的含量对Al2O3浆料的凝胶固化过程影响不大。随着催化剂含量的增加,Al2O3浆料的起始凝胶固化时间缩短,整个凝胶固化反应过程缩短。随着离心转速的增加和离心时间的延长,试样顶部和底部的生坯密度加大,梯度分离现象变得明显。当离心转速为1000r/min,离心5min后,制备的梯度多孔Al2O3陶瓷顶部的孔隙度为52.1%,中间为38.4%,底部为15.7%,孔隙呈现连续的梯度变化,烧结产物的抗压强度为67.2MPa。     

固相反应法制备MgAl2O4纳米粉体及其烧结行为研究

在800℃下煅烧Al(OH)3和MgSO4混合粉末,冷却后经过水洗得到了结晶良好的MgAl2O4纳米粉体.采用DSC/TG、XRD、TEM和SEM等分析手段研究了混合粉末中Mg/Al原子比对颗粒尺寸及团聚状况的影响,以及MgAl2O4纳米粉体的烧结性能.所制备的MgAl2O4纳米粉体平均颗粒尺寸为12 nm,尺寸分布窄,团聚少.MgAl2O4的生成归因于γ-Al2O3和MgSO4的固相反应.MgAl2O4纳米粉体显示了良好的烧结活性,在1450℃烧结1 h即能获得相对密度为95%的MgAl2O4陶瓷.     

微弧等离子喷涂碳纳米管/纳米Al2O3-TiO2复合涂层高温性能研究

采用等离子喷涂技术制备了5wt%CNTs/Al2O3-TiO2复合涂层,借助SEM、热红联仪和RAM反射率测试系统对CNTs/Al2O3-TiO2复合涂层的组织结构、高温氧化性能、电磁特性进行了分析.结果表明:CNTs/Al2O3-TiO2复合涂层的组织结构致密、孔隙率低,CNTs分散均匀,碳纳米管与Al2O3-TiO2陶瓷粘结剂之间具有良好的界面相容性.在20～700℃高温氧化过程中,CNTs起始失重温度为471.29℃,CNTs/Al2O3-TiO2复合涂层的高温氧化性能有一定提高,起始失重温度从471.29℃提高到507.8℃,而碳纳米管的失重率从100%下降到33.68%.CNTs/Al2O3-TiO2复合涂层具有较好的高温吸波性能,25℃时复合涂层的反射率峰值为-7.86dB.随温度的升高,CNTs/Al2O3-TiO2复合涂层的反射率峰值不断减小,谐振频率向低频移动,300℃时复合涂层的反射率峰值为-12.88dB,小于-5dB频带宽为4.48GHz.     

Effect of doping with Co2O3, TiO2, Fe2O3, and Mn2O3 on the properties of Ce0.8Gd0.2O2?δ

The effects of Co, Fe, Mn, and Ti oxide additions on the sinterability and crystal-chemical, thermal, and electrical properties of Ce_0.8Gd_0.2O_2−δ have been studied. The results indicate that these oxides enhance the sinterability of the mixed oxide, regardless of whether they were introduced before or after synthesis. The most effective sintering aid is Co₂O₃. The lattice parameters of Ce_0.8Gd_0.2O_2−δ samples containing different metal oxide additions (1 mol %) are refined in space group Fm3m. The temperature-dependent thermal expansion data are used to determine the linear thermal expansion coefficients of the samples. Manganese oxide additions reduce the electrical conductivity of Ce_0.8Gd_0.2O_2−δ, whereas the other dopants increase it in the order Ti < Fe < Co. The activation energy for conduction increases in the order Co < Ti < Fe < Mn. Original Russian Text ? E.Yu. Pikalova, A.N. Demina, A.K. Demin, A.A. Murashkina, V.E. Sopemikov, N.O. Esina, 2007, published in Neorganicheskie Material, 2007, Vol. 43, No. 7, pp. 830–837.     

The vibrational spectra of the intermediate compounds in the system Y2O3P2O5 and Gd2O3P2O5

The Infrared- and Raman-spectra of the intermediate compounds were studied for clues to their structural behavior as related to luminescence response. It was found that the degree of polymerization of PO₄ polyhedra increases in the phosphate-rich region and perhaps in the RE-oxide-rich region as well which was evident from the shift of stretching bands towards the higher energy side. Except in orthophosphates, the PO₄ polyhedra occupy more than one non-equivalent lattice site in all the phosphates.     

High-pressure modifications of CaAl2O4 and CaGa2O4

The modifications of CaAl₂O₄ and CaGa₂O₄ with the stuffed tridymite structure were examined under high temperatures (600 ～ 1500 °C) and high pressures (10 ～ 40 kb). Calcium monoaluminate CaAl₂O₄ was found to transform to three kinds of high-pressure modifications. The original CaAl₂O₄ (CA-I) changed to the phase CA-II which had m-CaGa₂O₄ type structure with a different array of tetrahedra in the six-membered rings of tetrahedron. The phase CA-II transformed either to the phase CA-IV with CaFe₂O₄ type structure or to an unknown phase (CA-III) under high pressures. The phase CA-IV was obtained under the pressures above 30 kb and at the temperatures above 1000 °C. Calcium monogallate CaGa₂O₄ transformed to the CaFe₂O₄ type structure above 30kb and 700 °C. No phases such as CA-II and CA-III were found. The structural relations among these modifications were discussed.     

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.     

Les phases SrLa2Al2O7 et SrGd2Al2O7

SrLa₂Al₂O₇ and SrGd₂Al₂O₇ belong to the structural type Sr₃Ti₂O₇. In SrGd₂Al₂O₇ strontium and gadolinium occupy respectively the 12 and 9 coordinated sites, whereas in SrLa₂Al₂O₇ the homologous cations are statistically distributed. The fluorescence spectra of both phases activated by Eu³⁺ ions show that the only possible position of Eu³⁺ is the 9 coordinated site.     

Nanocrystallization of SrBi2Nb2O9 from glasses in the system Li2B4O7---SrO---Bi2O3---Nb2O5

Transparent glasses in the system (100−x)Li₂B₄O₇–x(SrO---Bi₂O₃---Nb₂O₅) (10≤x≤60) (in molar ratio) were fabricated by a conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via X-ray powder diffraction (XRD) and differential thermal analyses (DTA) respectively. Glass–ceramics embedded with strontium bismuth niobate, SrBi₂Nb₂O₉ (SBN) nanocrystals were produced by heat-treating the as-quenched glasses at temperatures higher than 500 °C. Perovskite SBN phase formation through an intermediate fluorite phase in the glass matrix was confirmed by XRD and transmission electron microscopy (TEM). Infrared and Raman spectroscopic studies corroborate the observation of fluorite phase formation. The dielectric constant (_r) and the loss factor (D) for the lithium borate, Li₂B₄O₇ (LBO) glass comprising randomly oriented SBN nanocrystals were determined and compared with those predicted based on the various dielectric mixture rule formalism. The dielectric constant was found to increase with increasing SBN content in LBO glass matrix.     

Phase relations in the CaAl2O4|CaGa2O4 system

The solid state reactions and the phase relations in the CaAl₂O₄|CaGa₂O₄ system, of which both end-members have the stuffed tridymite structure, were examined by using three kinds of starting materials; A (CaCO₃ + (Al,Ga)₂O₃), B (CaAl₂O₄ + CaGa₂O₄) and C (CaCO₃ + Al₂O₃ + Ga₂O₃). In the starting material B, a very low rate of solid state reaction between CaAl₂O₄ and CaGa₂O₄ was found, which seemed to be due to very slow interchange of Al³⁺ and Ga³⁺ located in tetrahedra of this structure. In order to obtain the probable equilibrium phase relations, it was necessary to use the starting material A. In the present system, a new phase was found in a wide range of composition as a stable phase, which was supposed to have the same structure as so-called metastable phase of CaGa₂O₄ and different array of tetrahedra from either CaAl₂O₄ or CaGa₂O₄|I.     

Glasses and glass-ceramics in the SrO–TiO2–Al2O3–SiO2–B2O3 system and the effect of P2O5 additions

The glass formation abilities of various compositions in SrO–TiO₂–Al₂O₃–SiO₂, SrO–TiO₂–B₂O₃–SiO₂, SrO–TiO₂–Al₂O₃–B₂O₃, and SrO–TiO₂–Al₂O₃–SiO₂–B₂O₃ systems were studied. Many new compositions were found to be suitable for the casting of crack-free, optically clear glasses of different color and with glass transition temperatures ranging from 595 to 775 °C. The crystallization behavior, structure, and thermal expansion behavior of selected glasses were analyzed by DTA, XRD, dilatometry, and heat treatment. The effect of P₂O₅ on the glass structure and crystallization behavior was also studied. P₂O₅ played a dual role depending on composition. In some glasses it acted as a nucleating agent while in others it suppressed crystallization. Heat treatment of borate and borosilicate glasses transformed them into glass-ceramics while comparable SrO–TiO₂–Al₂O₃–SiO₂ glasses showed a lower tendency to crystallize and form glass-ceramics under the same conditions.     

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。     

Synthesis, structure and exchange bias in Cr2O3/CrO2/Cr2O5 particles

We report on the synthesis, structure and magnetic properties of a novel exchange bias system with Cr₂O₃/CrO₂/Cr₂O₅ interfaces. Chromium oxide particles with mixed chromium valences were prepared by sintering CrO₃ in air. X-ray diffraction patterns show that CrO₃ lost its oxygen gradually with increasing temperature and time through Cr₃O₈, Cr₂O₅, CrO₂, and finally Cr₂O₃ at temperatures above 760 K. X-ray photoelectron spectra indicate a low CrO₂ content and a binding energy of 579.3 eV for Cr 2p_3/2 photoelectrons in Cr₂O₅. Chromium dioxide was found to stably coexist with Cr₂O₃ and Cr₂O₅ in the particles. Magnetic measurements show hysteresis loop shifts in the sample, indicating an exchange bias induced by antiferromagnetic Cr₂O₃/Cr₂O₅ in ferromagnetic CrO₂. An exchange bias of 9 mT at 5 K and a coercivity of 26.3 mT were observed in the chromium oxide particles containing CrO₂.