Y_2O_3添加方式对Al_2O_3陶瓷烧结过程中的物相变化影响

采用非均匀沉淀法和机械球磨法2种方法添加Y2O3获得Al2O3陶瓷,通过研究烧结过程中Al2O3陶瓷的物相变化,对比了2种添加方法的优劣。结果表明:对于非均匀沉淀法制备的Al2O3复合粉体来说,烧结过程中开始生成钇铝石榴石(YAG)相的温度约为1 400℃,低于机械球磨法添加Y2O3烧结过程中YAG的生成温度;YAG的生成量大于机械球磨法;加入较少量的Y2O3(0.05%,质量分数)即可检测到Y3+在Al2O3晶格中的固溶态。扫描电子显微镜照片和面扫结果显示烧结过程中生成的YAG位于Al2O3晶界处。     

Y_2O_3-Al_2O_3粉体固相反应制备Y-Al-O体系陶瓷的对比研究

研究了摩尔比n(Y2O3):n(Al2O3)分别为2:1、1:1和3:5的粉体在不同温度发生的相变及其高温烧结的陶瓷。Y2O3-Al2O3粉体经球磨后在1750℃真空烧结制备陶瓷。用差热-热重、X射线衍射及扫描电子显微镜表征制备的Y2O3-Al2O3材料。结果表明:在低于800℃时,Y2O3-Al2O3之间未发生反应;在1000℃煅烧后,出现Y4Al2O9(YAM)相;1200℃煅烧后,出现YAlO3(YAP)相和钇铝石榴石(yttrium aluminumgarnet,YAG)相。n(Y2O3):n(Al2O3)=3:5粉体在1400℃煅烧后生成YAG纯相。n(Y2O3):n(Al2O3)=2:1、3:5粉体烧结的陶瓷的物相分别为YAM相和YAG相,其相对体积密度分别为97.8%和99.95%,n(Y2O3):n(Al2O3)=1:1粉体烧结陶瓷的物相为多相共存,3种配比制备陶瓷断口的形貌差别较大。     

复相陶瓷涂层Al-TiO2-B2O3体系热力学与动力学分析

采用Al-TiO2-B2O3反应体系并利用机械合金化(MA)原位合成Al2O3-TiB2复合相,对Al-TiO2-B2O3反应体系标准反应吉布斯自由能(ΔGT)进行计算,并应用Starink法计算其反应活化能 ,计算结果表明:Al2O3和TiB2的生成可能性较大,XRD分析的结果也证实了这一点;利用差示扫描量热分析(DSC)对反应体系进行了研究,分析了Al2O3-TiB2复合相的生成过程;MA 5 h后粉体的Ea为361.35 kJ·mol-1,MA 20 h后粉体的Ea为188.35 kJ·mol-1.     

醇-水法制备Al2O3-ZrO2复合粉体及其表征

以Al(OH)3和ZrOCl2·8H2O为起始原料,以NH4HCO3为沉淀剂,在醇-水混合溶液中获得前驱体,将前驱体在空气中煅烧,制备了Al2O3-ZrO2复合粉体.探讨了不同煅烧温度对Al2O3-ZrO2复合粉体的物相组成和显微形貌的影响.采用综合热分析仪、X-射线衍射仪、扫描电镜等手段对粉体进行表征.结果表明:前驱体中含锆化合物主要以无定形的形式存在,当煅烧温度为600℃时,粉体中出现较强的t-ZrO2衍射峰,Al(OH)3的衍射峰肖失.当煅烧温度增加到1200℃时,粉体中主要存在α-Al2O3和t-ZrO2主晶相衍射峰.前驱体经600℃热处理后所制备的Al2O3-ZrO2复合粉体粒度分布均匀且大多数颗粒在50 ～ 100 nm之间;随着煅烧温度的升高,Al2O3-ZrO2复合粉体颗粒出现长大,且其显微形貌由球状颗粒为主逐渐向球状、片状以及短棒状等多样化结构过渡.     

液相沉淀法制备ZrO2/Al2O3纳米复合粉体

以NH4Al(SO4)2·12H2O,ZrOCl2·8H2O,Y(NO)3为原材料,用NH4HCO3作沉淀剂,控制滴定速度小于5 mL/min,采用液相沉淀法制备了超细3Y-ZrO2/Al2O3前驱体.前驱体为分散的碱式碳酸盐,在1 200℃煅烧得到了分散性良好,平均粒径为20 nm的t-ZrO2和α-Al2O3两相分布均匀的纳米复合粉体.X射线衍射分析显示前驱体在煅烧过程中无中间相γ-Al2O3,θ-Al2O3生成.所制备的粉体具有高的烧结活性.在1 450℃烧结后烧结体相对致密度可达97.4%.     

高分子网络凝胶法制备纳米YAG-Y2O3复合粉体

采用高分子网络凝胶法制备纳米YAG-Y2O3复合粉体,对网络凝胶机理和胶体的煅烧过程进行了研究.研究表明1100℃煅烧时,由于Y3+在初始溶液中浓度较高,产物完全为Al2Y4O9,AlYO3和Y3Al2(AlO4)3等过渡相;其最佳煅烧温度为1200℃,与其它制备方法相比温度降低50～100℃.当单体和网络剂的摩尔比为5:1时,所制备的纳米YAG-Y2O3复合粉体的颗粒尺寸不大于50nm,粒径范围窄,且无团聚产生;当单体和网络剂比例偏于5:1时,颗粒尺寸长大比较严重.     

溶胶-凝胶法引入烧结助剂制备SiC-Y3Al5O12复相陶瓷

以碳化硅、六水硝酸钇、九水硝酸铝和六次甲基四胺为主要原料,通过溶胶-凝胶法引入Al2O3和Y2O3复合烧结助剂,液相烧结制备得到SiC-Y3Al5O12(Y3Al5O12简称YAG)复相陶瓷.采用DTA、TEM、XRD等分析测试技术研究了溶胶-凝胶法引入复合烧结助剂过程及复合烧结助剂对SiC-YAG陶瓷的烧结性能、力学性能、物相组成与显微结构的影响.结果表明干凝胶在920℃左右已完全转变成YAG相,最终获得的YAG粒径小,并均匀分散在SiC表面的SiC-YAG复合粉体;复合粉体先干压、再等静压成型后,在1860℃下烧结45 min,所制得复相陶瓷的相对密度达到了96.5%,抗弯强度达到486 MPa,断裂韧性达到5.7 MPa·m1/2.     

改进的沉淀包裹法制备ZrO2-Al2O3复合粉体

以工业Al2O3和ZrOCl2·8H2O为主要原料,采用改进的沉淀包裹法制备了n(3Y)ZrO2-Al2O3复合粉体,通过实验确定了主要工艺参数,所得粉体主晶相为t-ZrO2和α-Al2O3,分散性良好.     

FeTiO3-Al-C系统的反应热力学及Al2O3-TiC/Fe 复合材料的制备

充分利用天然矿物钛铁矿（FeTiO3）中的铁和钛,采用反应烧结技术,成功制备了Al2O3-TiC/Fe陶瓷复合材料.在真空热压炉中实现了合成与烧结一体化,为陶瓷复合材料的低成本制备进行了有益的探索研究.对钛铁矿-Al-C系统的热力学过程进行了详细的理论分析.研究表明：系统主要发生铝热还原反应,中间产物为多种钛的氧化物,系统反应后热力学上最为稳定的物质为Al2O3,TiC和Fe;系统反应最高温度低于Al2O3的熔化温度.通过实验研究,分析了产物的物相、结构和性能.反应烧结的最终产物主要为TiC,Al2O3和Fe.此外,还有少量Fe-Al相,大部分为Al2O3.TiC晶体颗粒尺寸约为3～5 μm,分布较为均匀,Fe分布于Al2O3,TiC晶粒之间.Y2O3和Cr2O3添加剂可以提高复合材料的抗弯强度.     

高介电材料Y2O3 薄膜的微结构及界面特性的研究

采用射频反应磁控溅射金属钇耙的方法,在硅衬底成功制备了高介电Y2O3薄膜.并深入研究了Y2O3薄膜的微结构和Y2O3/Si 体系的界面结构在高温退火过程中的变化规律.研究结果表明:在400～500 ℃之间,Y2O3 薄膜有一个从单斜相向立方相的物相结构转变过程.在高温退火过程中,Y2O3/Si有界面层SiO2生成,并且随着退火温度增加,界面层SiO2 的厚度也在逐渐增加.     

钕-铝系稀土色料的研制

通过钕-铝系列色料合成实验,分析不同配比及不同矿化剂等对色料呈色效果的影响,确定最佳工艺方法。对实验结果进行XRD及色度分析,确定其主晶相为钕酸铝,试样的明度均在70以上,色彩鲜艳亮丽。     

Polycrystalline In2O3 and In2O3/Y2O3 photoanodes

Single crystal In₂O₃ shows promise as a photoanode for the decomposition of water. Because of various difficulties in the preparation of the single crystal material, two simple techniques were developed for the preparation of polycrystalline In₂O₃ anodes. One method involves the thermal decomposition of the nitrate while the other utilizes the chemical vapour deposition technique. Voltammograms and photoresponse spectra of these anodes are compared to the single crystal material. Among other observations, it is noted that the quantum efficiencies of the thermally decomposed films are comparable to the single crystal material. It is also shown that the on-set potential can be shifted to more negative values by forming the mixed oxide In₂O₃/Y₂O₃.     

Phase equilibrium in binary La2O3-Dy2O3 and ternary CeO2-La2O3-Dy2O3 systems

Cerium oxide doped with oxides of rare earth elements is a multifunctional material, a wide range of uses which is associated with its unique physicochemical properties. Phase diagrams of multicomponent systems are the physicochemical basis for the creation of new materials with improved characteristics.In this work, phase equilibria in ternary CeO₂–La₂O₃–Dy₂O₃ and binary La₂O₃–Dy₂O₃ systems in the whole concentration range were studied. No new phases have been identified in these systems. An isothermal section of the phase diagram of the CeO₂–La₂O₃–Dy₂O₃ system at a temperature of 1500 °С is constructed. No new phases have been detected in the system. It was found that in the studied ternary system solid solutions are formed on the basis of (F) modification of CeO₂ with structure of fluorite type, monoclinic (B), cubic (C) and hexagonal (A) modifications of Ln₂O₃.In the La₂O₃–Dy₂O₃ binary system (1500–1100 °С) three types of solid solutions are formed: based on hexagonal modification A-La₂O₃, monoclinic modification B-Dy₂O₃ and cubic modification C-Dy₂O₃ separated by two-phase fields (A+B) and (B+C), respectively. The boundaries of the regions of homogeneity of solid solutions based on A-La₂O₃ are determined by compositions containing 35–40, 20–25, 15–20 mol% Dy₂O₃ at 1500, 1250, 1100 °C, respectively. From the obtained data it follows that the solubility of Dy₂O₃ in the hexagonal modification of lanthanum oxide is 39 mol% at 1500 °C, 23 mol. % at 1250 °C and 16 mol% at 1100 °C. The limits of existence of solid solutions based on monoclinic B-modification are determined by compositions containing 30–35, 65–60 (1250 °С), 35–40, 55–60 (1100 °С) 40–45, 70–75 (1500 °C) mol% Dy₂O₃.In the studied system, with a decrease in temperature from 1500° to 1100°C, there is a decrease in the solubility of La₂O₃ in the crystal lattice of cubic solid solutions of C-type from 16 to 10 mol%.     

Na2O-Al2O3-Fe2O3系烧结过程中铝、铁的反应行为

以Al2O3, Fe2O3和Na2CO3为原料,对Na2O-Al2O3-Fe2O3系烧结过程中的反应行为进行了详细研究. 基于溶出率与时间、温度的关系,证明Na2O×Al2O3和Na2O×Fe2O3的生成反应动力学都服从Zhuralev-Lesokin-Tempelman模型,表观活化能分别为186.59和80.92 kJ/mol,表明Na2O×Fe2O3比Na2O×Al2O3在动力学上更易形成;Al2O3易与Na2O×Fe2O3反应形成Na2O×Al2O3和Fe2O3,在1273 K烧结30 min,所得熟料Al2O3溶出率达98.51%;Fe2O3对Na2O×Al2O3的形成有双重作用,在1273 K下可加速Na2O×Al2O3的形成,超过1323 K,促使Na2O×Al2O3分解成Na2O和b-Al2O3,且随着温度升高或时间延长,分解程度增高,从而导致熟料中Al2O3溶出率显著降低.     

Fe2O3-MnO-Cr2O3-La2O3系统紫色颜料的制备及表征

采用溶胶均匀共沉淀法于低温下合成了含少量稀土氧化物La2O3的紫色颜料，并采用颜色测定、SEM、XRD等手段对颜料的颜色、检度及结晶构造等进行了表征。     

Separation of Phases by Spinodal Decomposition in the Systems Al2O3−Cr2O3 and Al2O3−Cr2O3−Fe2O3

Separation of phases was investigated in the hexagonal (rhombohedral) systems Al₂O₃−Cr₂O₃ and Al₂O₃−Cr₂O₃−Fe₂O₃. The binary system shows a miscibility gap with a T_c of 950°C; the miscibility gap for the ternary system was determined for a constant Cr₂O₃ content of 16.6 mol%. Dark field transmission electron microscopy of solid solutions annealed within the miscibility gap showed dark and light lamellas ∼50 to 200 Å thick. X-ray diffraction results for the solid solutions in the ternary system indicated that, in the early stages of annealing, broadening occurred only on (hkl) reflections where l≠0. There was no major change in the X-ray diffraction patterns of the annealed solid solutions in the binary system. Electron diffraction results indicated, however, that phase separation in both systems proceeded in the [001] direction. Solid solutions in the binary system separated very slowly; the separation could be enhanced hydrothermally. The mechanism of the separation of phases in both systems is spinodal and proceeds as follows: solid solution→intermediate modulated phase→equilibrium phases.     

ß-Al2O3 synthesis from m-Al2O3

-Al₂O₃ formation fromm-Al₂O₃ was found by a new convenient technique. By thermal decomposition of a complex compound, trioxalatoaluminate Na _x (NH₄)_3–x [Al(C₂O₄)₃]yH₂O(0.091 x 0.333;y= 3), a very fine powder ofm-Al₂O₃ was formed. The decomposition process was examined by thermal analysis and X-ray diffraction and the phase relation of the system Na₂O-Al₂O₃ in the midtemperature region between 600 and 1200° C is discussed briefly. The tablet ofm-Al₂O₃ was fired at 1600° C for 30 min to prepare dense-Al₂O₃ ceramics, the apparent density of which was greater than 95% of the theoretical value. The sintered tablet was examined from the structural point of view and the electrical conductivity was measured by an a.c. method to verify that the procedure of the complex decomposition is a suitable technique for-Al₂O₃ synthesis.     

Oxide/oxide composites in the system Cr2O3-Y2O3-Al2O3

Ceramic compacts in the systems Al₂O₃–Y₂O₃, Cr₂O₃–Y₂O₃ and Y₃(Cr_yAl_1-y)₅O₁₂ (Cr-doped YAG) were prepared by solid state reaction in calcined co-precipitated powder mixtures of appropriate compositions. Various solid-solution phases were formed, e.g. Y₃(Al_1-xCr_x)₅O₁₂, YAl_yCr_1-yO₃ and Al_2-xCr_xO₃. Composite materials in the pseudo-binary or ternary systems Al₂O₃–Y₃Al₅O₁₂, Cr₂O₃–Y₂O₃ and Y₃(Al_1–xCr_x)₅O₁₂–YAl_yCr_1–yO₃–(Al_zCr_1−z)₂O₃ were obtained by hot-pressing appropriate powder precursors at 1600–1650°C for 1 h. The microstructure of the prepared materials was studied in a scanning electron microscope with element analysis facilities. X-ray diffraction was used to reveal the phases present and their lattice parameters. The chemical compatibility of these phases was investigated. The results are discussed with a special emphasis on the solubility of Cr in the YAG structure, and on the compatibility relationship between Cr-doped YAG and its neighbouring phases. A gel-coating process for preparing Al₂O₃–YAG composites with tailored microstructures is also described.     

Bactericidal Effectiveness of O3, O3/H2O2 and O3/TiO2 on Clostridium perfringens

The purpose of this research is to evaluate the bactericidal capacity of different Advanced Oxidation Treatments (AOTs) based on ozone: ozone, ozone/hydrogen peroxide and ozone/titanium dioxide on a wild strain of Clostridium perfringens, a fecal bacterial indicator in drinking water. The dose of ozone consumed ranges from 0.6 mg L^?1 min^?1 to 5.13 mg L^?1 min^?1 depending on the process and on the sample. In the treatments combined with O₃, H₂O₂ dose utilized is 0.04 mM and TiO₂ dose, 1 g L^?1. In order to evaluate the influence of natural organic matter and suspension solids over the disinfection rate, treatments are performed with two types of water – natural water from Ebro River (Zaragoza, Spain) and NaCl solution 0.9%. To achieve 4 log units of inactivation, 3.6 mg O₃ L^?1 is necessary in O₃ treatment, 4.25 mg O₃ L^?1 in O₃/TiO₂ system and 2.7 mg O₃ L^?1 in O₃/H₂O₂ after processing the natural water. In NaCl solution, to get the same inactivation, 0.42 mg O₃ L^?1 is necessary in O₃ treatment, 1.15 mg O₃ L^?1 in O₃/TiO₂ system and 0.06 mg O₃ L^?1 in O₃/H₂O₂ process. Even though the three treatments studied have a high bactericidal activity due to the number of surviving bacteria decreases to non-detectable levels, O₃/H₂O₂ is the most effective system for eliminating C. perfringens cells in a lower contact time, followed by O₃ and finally O₃/TiO₂ system.