Thermodynamic Assessment of the ZrO2—CeO2 and ZrO2—CeO1.5 Binary System

An optimal set of thermodynamic parameters of the ZrO2-CeO1.5 system has been obtained using phase diagram data by modern CALPHAD (CAL culation of PHAse Diagrams) technique.The liquid and other solid solution phases were regarded as substitutional solution.The ordered ZrCe2O7 phase was treated as a stoichiometric compound.The ZrO2-CeO2 system has been re-optimized with new reference state.A comparison between the ZrO2-CeO2 system and ZrO2-CeO1.5 system has been made through calculation.With the calculation, the experimental information is well reproduced and a good agreement is obtained.     

Prediction of the Isothermal Sections in the ZrO2-YO1.5-CeO2 System

The experimental work on the ZrO2-YO1.5-CeO2 system, its limiting quasi-binaries and previous thermodynamic assessments are reviewed and evaluated. Isothermal sections of ZrO2-YO1.5-CeO2 system in the temperature region between 1450 and 1800 C are estimated according to the substitutional model using the Bonnier equation. The CSS + YSS two-phase region of the calculated isothermal section at 1700 degreesC was found to be in good agreement with the experimentally obtained ternary diagram of Longo and Podda. The phase composition in the ZrO2-rich corner however disagreed significantly.     

Stuey of Thermodynamic Properties of Nonstoichiometric Phase 〈Zr1—zCezO2—x〉 with Compound Energy Model

Using compound energy model (CEM), the thermodynamic properties of and were evaluated. The evaluation was based on the optimization of ZrO2-CeO2 and ZrO2-CeO1.5 systems, as well as the miscibility gap in CeO1.5-CeO2 system. Except the cubic fluorite structure phase assessed with compound energy model, all the other solution phases were assessed with subsitutional solution model. The model parameters were evaluated through fitting the selected experimental data by means of thermodynamic optimization. A set of parameters with thermodynamics self-consistency was obtained and satisfactorily described the complex relation between y in and the partial pressure of oxygen at different temperatures, also the interdependence among miscellaneous factors such as temperature, oxygen partial pressure, the reduction amount of CeO2 as well as the nonstoichiometry in cubic phase . The calculated results seem to be reasonable when put into the explanation of pressureless sintering of CeO2-stabilized ZrO2 powder compacts at a controlled oxygen partial pressure.     

均匀沉淀-水热法制备稳定Y-Ce-ZrO2纳米粉体

以尿素为沉淀剂,采用均匀沉淀-水热法成功地制备了2mol%Y2O3-5.5mol?O2稳定的纳米四方相ZrO2.研究了溶液的浓度、水浴时间、水热时间对ZrO2粉体的晶型和形貌的影响.结果表明在一定工艺条件下可制备平均粒径在10-20nm,粒度分布窄,分散性好的纳米稳定Y2O3-CeO2-ZrO2粉体.     

纳米掺杂Al2O3/ZrO2等离子喷涂涂层组织结构研究

利用大气等离子喷涂技术,在N80钢基体上制备纳米掺杂Al2O3/ZrO2热障涂层。利用XRD、SEM等观察分析了纳米掺杂Al2O3/ZrO2粉末及等离子喷涂涂层组织形貌及结构,结果表明,Al2O3/ZrO2等离子喷涂粉末是由纳米包覆微米级粒子及少量的纳米团聚体球团粒子构成。纳米掺杂等离子喷涂Al2O3/ZrO2涂层的微观组织形貌复杂,存在着纳米柱状晶薄壳内包裹着微米级柱状晶、未熔化的ZrO2陶瓷粒子嵌镶在晶体内部的独特晶内结构。涂层主要由α-Al2O3及亚稳四方相t,-ZrO2相构成。     

Study of Thermodynamic Properties of Nonstoichiometric Phase with Compound Energy Model

Using compound energy model (CEM), the thermodynamic properties of and were evaluated. The evaluation was based on the optimization of ZrO2-CeO2 and ZrO2-CeO1.5 systems, as well as the miscibility gap in CeO1.5-CeO2 system. Except the cubic fluorite structure phase assessed with compound energy model, all the other solution phases were assessed with subsitutional solution model. The model parameters were evaluated through fitting the selected experimental data by means of thermodynamic optimization. A set of parameters with thermodynamics self-consistency was obtained and satisfactorily described the complex relation between y in and the partial pressure of oxygen at different temperatures, also the interdependence among miscellaneous factors such as temperature, oxygen partial pressure, the reduction amount of CeO2 as well as the nonstoichiometry in cubic phase . The calculated results seem to be reasonable when put into the explanation of pressureless sint     

MnOx-CeO2-Al2O3 mixed oxides for soot oxidation: activity and thermal stability

MnO(x)-CeO(2)-Al(2)O(3) mixed oxides were prepared by impregnating manganese acetate and cerium nitrate on alumina powders using the sol-gel method. The thermal stabilities of MnO(x)-CeO(2) and Al(2)O(3)-modified mixed oxides were evaluated by treating at 800 °C in dry air flow for 20h. The introduction of Al(2)O(3) markedly increases the textural stability of the catalyst with a relatively high dispersion of MnO(x) and CeO(2), remaining a strong synergistic effect between these two oxides. The NO oxidation activity of the ternary oxides experiences a smaller loss after high-temperature calcination, and a low soot oxidation temperature is attained in the presence of NO.     

Low Temperature Synthesis of Single-crystal Alpha Alumina Platelets by Calcining Bayerite and Potassium Sulfate

Single-crystal alpha alumina (α-Al2O3) platelets were synthesized by calcining a powder mixture of bayerite (α-Al(OH)3) and potassium sulfate (K2SO4) at 900℃. The crystalline phase evolutions and morphologies of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The synthesized samples mainly consisted of single-crystal α-Al2O3 platelets with a diameter of 0.5-1.5 μm and a thickness of 50-150 nm. Moreover, with 3, 5, and 8 wt% (referred to the obtained alumina) α-Al2O3 seeds adding into the powder mixture of bayerite and potassium sulfate, the average diameter of α-Al2O3 platelets can be reduced to 450, 240, and 220 nm, respectively. It is found that the sequence of the phase transformation is the bayerite (α-Al(OH)3) → boehmite (γ-AlOOH) →γ-Al2O3 →α-Al2O3. Further analysis indicated that K2SO4 can promote the phase transformation from γ-Al2O3 to α-Al2O3 and the formation of single-crystal α-Al2O3 platelets might be attributed to the liquid phase K3Al(SO4)3.     

纳米级氧化铝及掺钡氧化铝的物相转变

采用直接沉淀法后低温煅烧获得纳米级氧化铝,采用蒸发溶剂法直接掺入Ba2+获得掺杂氧化铝,分别高温煅烧后获得煅烧样品,并对样品进行热分析、X射线衍射测试和透射电镜观察。结果表明,纳米级氧化铝及其掺杂Ba2+后随温度升高时的物相转变顺序为γ-Al2O3—δ-Al2O3—θ-Al2O3—α-Al2O3,各相转变发生时的温度范围为100~200℃;Ba2+的引入不改变转变顺序,但提高了各转变所需的温度。     

基于高温熔凝法Al_2O_3/ZrO_2/YAG共晶陶瓷显微组织演变规律

作为超高温结构材料,共晶氧化物陶瓷的力学性能和显微组织密切相关。采用高温熔凝法制备Al_2O_3/ZrO_2/YAG共晶陶瓷体,研究熔体温度和结晶种子对凝固组织影响规律,运用经典形核机制和Jackson-Hunt共晶生长模型探讨了凝固组织的演变机理。研究表明,随着熔体温度升高(1750~2000℃),凝固体物相组成从α-Al_2O_3,c-ZrO_2和YAG转变为α-Al_2O_3,c-ZrO_2和亚稳相YAP。凝固组织依次经历:非共晶Al_2O_3/ZrO_2/YAG、不规则共晶Al_2O_3/ZrO_2/YAG、纳米纤维状共晶Al_2O_3/ZrO_2/YAG和复杂粗大的亚稳复合陶瓷Al_2O_3/ZrO_2/YAP。分析表明,凝固组织的演变源于异质晶核点不断钝化导致形核过冷度和凝固路径改变,所以合理选择熔体温度和结晶种子是共晶组织调控的关键。     

纳米氧化铝的相变研究

以硫酸铝为原料,用沉淀法制取纳米氧化铝,研究了其相变过程。用XRD、SEM、AFM及IR等手段对不同温度下煅烧所得的产品进行了表征。结果表明,该方法制备的氧化铝粉体呈球形、团聚程度轻、粒度分布较均匀、γ相和δ相平均粒径20-30nm、α相平均粒径53nm,其物相变化次序为：非晶态Al2O3→γ-Al2O3→δ-A12O3→α-Al2O3。     

纳米SiC颗粒对Al2O3基体中ZrO2约束稳定的影响

采用热压的方法制备了纳米SiC颗粒复合的Al2O3-ZrO2陶瓷材料，研究了纳米SiC颗粒对样品烧结性能以及对Al2O3基体中ZrO2约束稳定的影响。结果表明，纳米SiC颗粒的加入影响样品的烧结性能。处于晶界的纳米SiC颗粒降低了基体材料对ZrO2颗粒的约束，不利于四方相ZrO2在室温下的保留。     

Calculation of the Quasiternary Systems:Si_3N_4-Y_2O_3-SiO_2,Y_2O_3-SiO_2-BeO and Y_2O_3-Al_2O_3-BeO

Based on the thermodynamic model of Kaufman for the calculation of quasibinary and quasiternary system, numerical method for the calculation of stable equilibrium is developed and thermodynamic data of undefined phases are discussed in this work for several ceramic systems.The calculated isothermal sections in Si3N4-Y2O3-SiO2 system meet well with other previous calculated phase diagrams and experimental results. The diagrams in Y2O3-SiO2-BeO and Y2O3-Al2O3-BeO systems are calculated for the approach of prediction.     

纳米氧化铝粉体的绿色合成及其物相转变控制研究

以氯化铝、碳酸钠为原料,采用直接沉淀法,并于500～1,200℃煅烧,制备纳米Al2O3粉体。然后用TiO2、BaO对纳米Al2O3粉体掺杂,控制其物相转变过程。通过X射线衍射仪、差式扫描量热仪和透射电子显微镜分析纯净和掺杂后的纳米Al2O3的物相转变过程。结果表明,直接沉淀法所得水合Al2O3,经500℃煅烧后可转变为纳米活性Al2O3,粒径约为10 nm;纯净和掺杂Al2O3样品经1,200℃煅烧2 h后均为纳米粉体,其粒径为40～50 nm;在较高温度下,掺杂氧化钡对Al2O3的物相转变具有强烈抑制作用,粉体直至1,200℃仍未转变为结晶良好的α-Al2O3物相;而氧化钛则对其物相转变有显著促进作用,在1,000℃时粉体的主要物相即为α-Al2O3,1,100℃之后粉体已完全转变为α-Al2O3。     

Transformation of Sc2O3-doped tetragonal zirconia polycrystals by aging under hydrothermal conditions

The phase transformation of less than 6 mol% Sc2O3-doped tetragonal zirconia polycrystals consisting of fine grains has been investigated. Dense bodies with homogeneous microstructures doped with 3.5 to 5 mol% Sc2O3 sintered at 1300°C for 1 h consisted mostly of a tetragonal phase. Within 20 h of aging under hydrothermal conditions at 180°C, the amount of monoclinic ZrO2 on the surface of the 4 to 5 mol% Sc2O3-doped specimens sintered at 1400°C was saturated and reached a constant value, and the increase in the amount of monoclinic ZrO2 showed a sigmoidal type of kinetic transformation. The apparent activation energy for the phase transformation in Sc2O3-doped zirconia was 84–91 kJ/mol. Based on the hydrothermal aging results, the possible existence of a larger two-phase (cubic+tetragonal) region is suggested, and the phase boundary between the cubic+tetragonal and cubic phase in the ZrO2-Sc2O3 system is proposed.     

添加Al_2O_3对SiC板粒／Y－TZP复合材料力学性能的影响

本文以ＳｉＣ板粒、ＺｒＯＣｌ２－８Ｈ２Ｏ、ＡｌＣｌ３和Ｙ（ＭＯ）３为原料，利用共沉淀和热压烧结工艺，制备ＳｉＣ板粒／Ｙ－ＴＺＰ和（含Ａｌ２Ｏ３）ＳｉＣ板粒／Ｙ－ＴＺＰ复合材料．测试了材料的室温和高温力学性能．研究了添加Ａｌ２Ｏ３对ＳｉＣ板粒／Ｙ－ＴＺＯ复合材料的影响．结果表明，ＳｉＣ板粒／Ｙ－ＴＺＰ复合材料与Ｙ－ＴＺＰ陶瓷相比，其室温强度和韧性出现明显下降，高温强度也没有改善；而在ＳｉＣ板粒与Ｙ－ＴＺＰ复合的基础上，添加Ａｌ２Ｏ３可明显提高材料的强度和断裂韧性，同时，材料的高温强度也获得显著改善．     

喷涂氧化铝粉体及其在等离子射流下的变化

用烧结法生产喷涂氧化铝。实验采用水冷非转移式等离子喷枪 ,工作气体为N2 、H2 ,其纯度 99.9%。稳定相α-Al2 O3经等离子射流熔融、淬冷后 ,转变为亚稳相γ -Al2 O3及球化低钠氧化铝 ,经试验确定 ,Al2 O3的相变历程如下 :α -Al2 O3等离子射流 熔体 淬冷 γ -Al2 O380 0℃ ε -Al2 O3110 0℃ α -Al2 O3     

Microstructure characteristics of ZrO2 coating produced by atmospheric pressure chemical vapor deposition

To settle the problem of low growth rate when prepare ZrO2 thermal barrier coating by Metalorganic CVD (MOCVD), a simple method was employed-atmospheric pressure CVD (APCVD). The paper firstly thermodynamic calculated the effect of O/Zr ratio and temperature on phase formation at various H/C ratios for ZrCl4-CO2-H2-Ar system. With temperature increment, the solid phase changes from C+ monoclinic ZrO2 to Monoclinic ZrO2 then to tetragonal ZrO2. With the increase of H/C ratio, the phase zone of C+ monoclinic ZrO2 expands. XRD and Raman spectrum were employed to measure phase structure of ZrO2 coating at different temperature. At 1300 degrees C, the coating contains a small amount tetragonal ZrO2 phase besides monoclinic phase; at 1100 degrees C, the coating is composed of monoclinic ZrO2 phase and a little C. The surface SEM images show the small grains evolve to polycrystals which have clear crystal form when raising temperature. The cross-section images show that dense ZrO2 column crystals arrange normal to the substrate.     

Microstructure and fracture behaviour of ZrO2 (2 mol% Y2O3) reinforced with SiC whiskers

The microstructure, mechanical properties, fracture behaviour and toughening mechanisms of 20 vol% SiCw–ZrO2 (2 mol% Y2O3) composite were investigated by X-ray diffraction, scanning and transmission electron microscopies, energy dispersive analysis of X-rays, high-resolution electron microscopy techniques and the three-point bending test. The results show that the ZrO2 (2 mol% Y2O3) matrix is well strengthened and toughened by 20 vol% SiCw. The SiC whiskers are directly bonded to the matrix with no interfacial reaction layer or amorphous phase. The main toughening mechanisms of the composite are crack deflection, dynamic tetragonal to monoclinic ZrO2 transformation, whisker pull-out and crack bridging. In addition, the fracture behaviour of the composite was observed using an in situ fracture technique.     

SiC-ZrO2(3Y)-Al2O3纳米复相陶瓷的力学性能和显微结构

本文介绍用非均相沉淀方法制备的纳米ＳｉＣ－ＺｒＯ２（３Ｙ）－Ａｌ２Ｏ３复合粉体经放电等离子超快速烧得到晶内型的纳米复相陶瓷,超快速烧结的升温速率为６００℃／ｍｉｎ,在烧结温度不保温,迅即在３ｍｉｎ内冷却至６００℃以下。