一种新型可加工陶瓷材料: CeZrO2/CePO4

对可加工Ce-ZrO2／CePO4陶瓷材料的设计制备和性能进行了研究。结果表明：在载荷作用下弱界面处易形成微裂纹，并发生裂纹联接，使材料在加工过程中以晶粒去除形式为主，实现了该材料的金属刀具加工，且加工损伤变小。弱界面处微裂纹的形成、偏转和桥联等形式，耗散了主裂纹扩展的能量，增加了材料的断裂功，可在一定程度上改善材料的强度等力学性能。随着CePO4加入量的增加，弱界面增多，Ce-ZrO2／CePO4陶瓷材料的可加工性变好但力学性能却变差。烧成温度等工艺因素对Ce-ZrO2／25％CePO4(质量分数)陶瓷的强度等力学性能影响较大，在1550℃下加热2h，颗粒尺寸与发生裂纹桥联等形式相适应，可充分发挥弱界面的作用。     

CePO4的煅烧温度对Ce-ZrO2/CePO4材料的结构与性能影响

实验对Ce-ZrO2/CePO4材料中的CePO4进行不同温度煅烧,发现1000℃煅烧的CePO4粉末颗粒明显长大且成柱状,与Ce-ZrO2混合烧结后长成尺寸较大的层片状,增加了与Ce-ZrO2的弱结合界面尺寸,应力应变曲线更为弯曲,裂纹的不连续扩展更加曲折,表明材料的"塑性化"程度提高.基于挤压开裂的断口分析,认为Ce-ZrO2/CePO4陶瓷的"塑性化"可能源于外力作用下弱界面处的微开裂以及层片状CePO4的解理开裂、蔓延,并为适应外力进行的重排、调整.且此时材料的弯曲强度和断裂韧性达最大值421MPa和4.5MPa·m1/2.     

ZrO2/CePO4可加工陶瓷材料钻削加工的试验研究

分别用高速钢刀具和硬质合金刀具对ZrO2/CePO4可加工陶瓷材料进行钻削加工试验.通过比较ZrO2/CePO4陶瓷和低碳钢材料的加工过程,分析了ZrO2/CePO4陶瓷的加工特性、材料钻削规律及其影响因素.实验结果表明:刀具的磨损是ZrO2/CePO4钻削加工的主要特征之一.钻削ZrO2/CePO4陶瓷材料的去除过程可分为高效率和高磨损2个阶段,刀具材料影响ZrO2/CepO4可加工陶瓷材料的加工效率.可加工陶瓷的加工过程中,应选择合理的刀具参数和加工工艺参数,以获得良好的加工质量.     

氧化物/BN可加工复相陶瓷的高温氧化行为及表面裂纹修复

研究了2种可加工复相陶瓷Al2O3／BN和Y-ZrO2／BN在不同温度下的氧化行为及其热处理损伤修复。结果表明：高温时Al2O3／BN表面氧化生成致密的硼酸铝(Al18B2O33)氧扩散障碍层,并且与基体形成强结合的梯度抗氧化涂层,阻止了氧气向材料内部的快速扩散,因而具有良好的自愈合抗氧化性。而Y-ZrO2／BN复相陶瓷由于不能形成有效的氧化屏蔽,抗氧化性较差。2种复相陶瓷在900℃热处理后,表面形成的液态B2O3膜使压痕裂纹均得到愈合,压痕强度从热处理前的162MPa(Al2O3／BN)和336MPa(Y-ZrO2／BN)分别增加到热处理后的406MPa和585MPa。但在1100℃热处理2h后,由于过度的氧化会使Y-ZrO2／BN失去裂纹愈合的效果,压痕强度迅速下降。     

"塑性"CePO4陶瓷的微观结构与性能

针对应力应变曲线呈现明显非线形的"塑性"CePO4陶瓷,对其微观结构和性能进行了研究。化学法制备的CePO4颗粒随煅烧温度的升高逐渐长大。坯体在1500℃,2h烧结后的弯曲强度和断裂韧性分别为184MPa和4.8MPa·m1/2。实验发现:CePO4晶粒呈阶梯或层片状断裂形式,烧结体可用传统金属加工刀具方便地进行切削、车削和钻孔,并在车削表面发现连续的微观加工碎屑。材料的应力应变曲线呈现明显的非线性。同时,微观结构显示:受挤压表面沿挤压方向破坏前产生大量垂直于应力方向开裂的微裂纹。结果表明:CePO4陶瓷具有"塑性"或"延性"特征。基于挤压开裂的断口分析,初步认为CePO4陶瓷的"塑性"源于外力作用下自身层片结构的解理开裂、蔓延,并为适应外力进行的晶粒重排与调整。     

氧化锆基陶瓷的坯体连接及其界面研究

以含粘结剂的料浆为连接材料,在坯体状态下连接Ce-ZrO2陶瓷本身或者连接Ce—ZrO2陶瓷和25％(体积分数)CePo4-Ce-ZrO2复合陶瓷。坯体连接样品经1 450℃烧结,样品连接良好。微观结构分析表明:Ce—ZrO2陶瓷本身连接和烧结后连接区和本体材料的结构几乎无法区分,其平均抗弯强度接近母材的强度;25％CePO4-Ce-ZrO2与Ce-ZrO2连接时形成结构均匀的扩散连接区域,其微观结构与母体材料的结构相似,连接区的平均抗弯强度为319 MPa。     

可加工陶瓷的弱界面结构与性能优化研究进展

综合介绍了国内外云母玻璃陶瓷、多孔陶瓷、复相陶瓷和M_(n 1)AX_n化合物等可加工陶瓷的研究现状。重点分析了弱界面结构对可加工陶瓷在加工过程中裂纹的产生和扩展的影响,从而解释了其加工机理。探讨了弱界面结构在基体中的大小、分布与数量对可加工陶瓷性能的影响,提出了利用弱界面的显微结构设计进行性能优化的思路。展望了可加工陶瓷的重点研究方向,包括:加工机理的深入分析、表面硬化与强化技术的研究以及可加工性能的表征与评价等。     

多孔Si3N4–SiO2复相陶瓷及其性能

采用近净尺寸成型制备工艺–氧化烧结结合溶胶浸渍再烧结法,制备了多孔Si3N4–SiO2复相陶瓷。讨论了制备工艺对材料的成分、微结构和性能的影响规律。研究表明：随着硅溶胶浸渍量的增加,材料的抗弯强度、硬度、断裂韧性、密度和介电常数均增大。分别采用压痕法和单边切口梁法对材料的断裂韧性进行了测定和比较。结果表明：采用压痕法测定断裂韧性时,多孔Si3N4–SiO2复相陶瓷的增韧机理有裂纹偏转、裂纹分叉、裂纹桥接以及孔的钝化。采用单边切口梁法测定断裂韧性时,多孔Si3N4–SiO2复相陶瓷的增韧机理只有裂纹偏转。     

多孔Si3N4-SiO2复相陶瓷及其性能

采用近净尺寸成型制备工艺-氧化烧结结合溶胶浸渍再烧结法,制备了多孔Si3N4-SiO2复相陶瓷.讨论了制各工艺对材料的成分、微结构和性能的影响规律.研究表明:随着硅溶胶浸渍量的增加,材料的抗弯强度、硬度、断裂韧性、密度和介电常数均增大.分别采用压痕法和单边切口梁法对材料的断裂韧性进行了测定和比较.结果表明:采用压痕法测定断裂韧性时,多孔Si3N4-SiO2复相陶瓷的增韧机理有裂纹偏转、裂纹分叉、裂纹桥接以及孔的钝化.采用单边切口梁法测定断裂韧性时,多孔Si3N4-SiO2复相陶瓷的增韧机理只有裂纹偏转.     

可加工陶瓷的弱界面结构特征及其研究进展

评述了具有弱界面结构的可加工陶瓷的研究进展.弱界面通过层状结构相或两相间的弱结合引入材料中,在材料加工过程赋予材料一定的“塑性”,或使裂纹产生偏转、分支和桥联,改变陶瓷的断裂行为和加工去除形式.分析了陶瓷可加工性与弱界面结构设计的关系,指出了显微结构优化设计与制备高性能可加工陶瓷的途径.     

Nucleation sequence on the cation exchange process between Y0.95Eu0.05PO4 and CePO4 nanorods

Nanorods of Y0.95Eu0.05PO4@CePO4 (Y0.95Eu0.05PO4 phase was nucleated first and then a CePO4 phase was nucleated) and CePO4@Y0.95Eu0.05PO4 (CePO4 phase was nucleated first and then Y0.95Eu0.05PO4 phase was nucleated) were prepared at a relatively low temperature of 140 °C in ethylene glycol medium. Based on XRD, TEM and Raman studies it has been inferred that Y0.95Eu0.05PO4@CePO4 sample consists of a mixture of bigger (length around 800-1000 nm and width around of 80-100 nm) and smaller (length around 70-100 nm and width around 10-20 nm) nanorods, having monoclinic CePO4 and tetragonal YPO4 structure, whereas CePO4@Y0.95Eu0.05PO4 sample consists of mainly small nanorods having a single phase CePO4 structure. From the detailed luminescence studies it has been established that there exists significant incorporation of Y3+/Eu3+ ions in the CePO4 phase in CePO4@Y0.95Eu0.5PO4 sample. This has been attributed to the cation exchange taking place between Ce3+ ions in CePO4 host and Eu3+ and Y3+ ions in solution during the synthesis stage. Unlike this, such an exchange is not possible for Y0.95Eu0.05PO4@CePO4 sample synthesized under identical conditions due to the higher solubility product (Ksp) value of YPO4 compared to CePO4. Incorporation of Eu3+ in the CePO4 lattice of CePO4@Y0.95Eu0.5PO4 sample is confirmed by the significant reduction in the lifetime of 5D0 level of Eu3+ and the luminescence intensity from Eu3+, arising due to the electron transfer between the Ce3+/Ce4+ and Eu3+/Eu2+ species. These results are further supported by the non-radiative decay rates and quantum yields calculated from the emission spectrum.     

Rh2O3/monoclinic CePO4 composite catalysts for N2O decomposition and CO oxidation

CePO_4(in particular,monoclinic CePO_4)has been rarely used to make supported catalysts.Herein,monoclinic CePO_4 nanoparticles were prepared by calcining hexagonal CePO_4 nanorods(prepared by precipitation)in air at 900℃.Monoclinic CePO_4 nanowires were prepared by calcining hexagonal CePO_4 nanowires(prepared by hydrothermal synthesis at 150℃)in air at 900℃.Both monoclinic CePO_4 materials were used to support Rh_2O_3 by impregnation using Rh(NO_3)_3 as a precursor(followed by calcination).The catalytic performance of Rh_2O_3/monoclinic CePO_4 composite materials in N_2O decomposition and CO oxidation was investigated.It was found that Rh_2O_3 supported on monoclinic CePO_4 nanowires was much more active than Rh_2O_3 supported on monoclinic CePO_4 nanoparticles.The stability of catalysts as a function of reaction time on stream was studied in both reactions.The influence of co-fed CO_2,O_2,and H_2O on the catalytic activity in N_2O decomposition was also studied.These catalysts were characterized by employing N_2 adsorption–desorption,ICP-OES,XRD,TEM,XPS,H_2-TPR,O_2-TPD,and CO_2-TPD.The correlation between physicochemical properties and catalytic properties was discussed.     

热应力下陶瓷材料中裂纹扩展的声发射研究

用声发射技术监测了刚玉－莫来石质陶瓷材料在缓慢加热、冷却和骤冷时微裂纹的形成、扩展过程，发现其在冷却过程中声发射计数率的峰值约为加热过程的４００倍。材料在热应力下微裂纹的形成、生长主要发生在冷却过程中。当晶粒尺寸减小时，材料的微裂纹扩展、蔓延逐渐被抑制在较小的范围内。骤冷时，由热应力引起的微裂纹稳态扩展和失稳扩展的声发射特性与材料残余强度的变化趋势是一致的。     

Developments on the mechanical properties of MgO-MgAl2O4 composite refractories by ZrSiO4-3 mol% Y2O3 addition

Improvements and the effects of additions of ZrSiO₄-3 mol% Y₂O₃ into MgO-MgAl₂O₄ composite refractories on mechanical properties and thermal stress resistance parameters were investigated. Significant improvements were achieved on mechanical properties and R-R_st parameters up to ∼2 and ∼3-fold ratios. The major parameters improving mechanical properties and thermal behaviour of refractories were determined as follows: (i) the increase in resistance to crack initiation and propagation due to formation of Mg₂SiO₄ phase after decomposition of zircon; (ii) propagation of the microcracks formed in the structure for a short distance by interlinking each other; (iii) arresting or deviation of microcracks when reaching pores or ZrO₂ grains released after dissociation of zircon, located together with Y₂O₃ particles, and furthermore; (iv) co-presence of both intergranular and transgranular types of cracks, and with incorporation of zircon-Y₂O₃; (v) increase in density; and (vi) a significant reduction in MgO grain size.     

Microstructure and mechanical properties of ZrO2-2 mol% Y2O3 ceramics

The microstructure and mechanical properties of ZrO₂-2 mol% Y₂O₃ ceramics were studied on samples prepared by cold isostatic pressing and pressureless sintering. It was shown that the density of the alloy increases with increasing sintering temperature. The Vickers hardness decreases with the appearance of the monoclinic phase and increasing its content. Compared with the single tetragonal phase, the (t + m) dual-phase structure with microcracks has a much higher fracture toughness (16·5 MPa√m) because of a complex mechanism of toughening (transformation, microcracks and residual stresses).     

Fracture mechanism of alumina-spinel castables containing ZrO2 by wedge splitting test and digital image correlation technique

To clarify the fracture mechanism of alumina-spinel castables, two kinds of alumina-spinel castables with or without fused zirconia-alumina (FZA) were prepared. The full-field strains and crack propagation process in the region of interest (ROI) of alumina-spinel castables were investigated by wedge splitting test (WST) and digital image correlation (DIC) technique. Fractographic methods were used to analyze the crack propagation path of the castables after the WST. The results indicated that the load-displacement curve of alumina-spinel castables containing FZA exhibits a non-linear fracture, demonstrated typical ductile fracture; while that of alumina-spinel castables without FZA is linear, showed typical brittle fracture. The characteristic length reaches to 258.9 mm in FZA containing castables, more than 4 times that of the castables without FZA. In contrast, castables containing FZA has longer and more tortuous crack propagation path, larger damage zone length, which results in the increase of the dissipated energy. Crack branching can be observed around the main crack in castables containing FZA, meaning that microcracks toughening is the main mechanism for flexibility improvement of the alumina-spinel castables containing FZA, formation of micro-cracks can be attributed to the martensitic transformation of zirconia.     

Atomistic investigation of machinability of monocrystalline 3C–SiC in elliptical vibration-assisted diamond cutting

Deformation-induced characteristics of surface layer strongly rely on loading condition-related operating deformation modes. In the current study we reveal the mechanisms governing machined surface formation of hard brittle monocrystalline 3C–SiC in ultrasonic elliptical vibration-assisted diamond cutting by molecular dynamics simulations. Simulation results show different deformation modes including phase transformation, dislocation activity, and crack nucleation and propagation, as well as their correlations with surface integrity in terms of machined surface morphology and subsurface damage. In particular, molecular dynamics simulations of ordinary cutting are also carried out, which demonstrate the effectiveness of applying ultrasonic vibration of cutting tool in decreasing machining force and suppressing crack events, i.e., promoting ductile-mode cutting for achieving high surface integrity. The physical mechanism governing the machining differences between the two machining processes are also revealed. Furthermore, the effect of cutting depth on machined surface integrity under vibration-assisted cutting and ordinary cutting is addressed.     

Effect of Microstructure on Material-Removal Mechanisms and Damage Tolerance in Abrasive Machining of Silicon Carbide

Effects of microstructural heterogeneity on material-removal mechanisms and damage-formation processes in the abrasive machining of silicon carbide are investigated. It is shown that the process of material removal in a conventional silicon carbide material with equiaxed-grain micro-structure and strong grain boundaries consists of the formation and propagation of transgranular cracks which results in macroscopic chipping. However, in a silicon carbide material, containing 20 vol% yttrium aluminum garnet (YAG) second phase, with elongated-grain micro-structure and weak grain boundaries, intergranular micro-cracks are formed at the interphase boundaries, leading to dislodgment of individual grains. These different mechanisms of material-removal affect the nature of machining-induced damage. While in the conventional silicon carbide material the machining damage consists of transgranular median/radial cracks, in the heterogeneous silicon carbide material, abrasive machining produces interfacial micro-cracks distributed within a thin surface layer. These two distinct types of machining damage result in a different strength response in the two forms of silicon carbide materials. In the case of the conventional silicon carbide, grinding damage results in a dramatic decrease in strength relative to the as-polished specimens. In contrast, the ground heterogeneous silicon carbide specimens show no strength loss at all.     

煤矸石碳热还原氮化制备Sialon的研究

采用河北开滦地区的煤矸石为原料,加入一定量的碳和TiO2作为添加剂,通过碳热还原氮化法制备出了β-Sialon材料,并且β-Sialon为主晶相。实验结果经X射线衍射分析测定了反应生成物的物相组成,分析研究了C含量和Al2O3/SiO2的比例对产物组分的影响。研究结果表明,过量加入C,不利于β-Sialon相的生成或导致其有分解的趋势;适当过量加入Al2O3,有助于β-Sialon相的形成。对β-Sialon形成过程的分析表明,在实际生产工艺中可以通过控制CO的含量来控制β-Sialon生成反应进行的速度。     

先驱体法合成三元系Pb（Sc1／2Ta1／2）O3—PbZrO3—PbTiO3钙钛矿铁电陶瓷粉末

本文研究了采用不用先驱体ＳｃＴａＯ４＋Ｚｒ０．５３Ｔｉ０．４７Ｏ３（ＳＴ＋ＺＴ）和（Ｓｃ１２Ｔａ１２）０．２０Ｚｒ０．３８５Ｔｉ０．４１５Ｏ２（ＳＴＺＴ）以及采用ＳＴ＋ＺｒＯ２＋ＴｉＯ２与ＰｂＯ进行固相反应合成三元系Ｐｂ（Ｓｃ１２Ｔａ１２）０．２０－Ｚｒ０．３８５Ｔｉ０．４１５Ｏ３钙钛矿陶瓷粉末的合成机理。实验表明，两种先驱体均能与ＰｂＯ反应制得单相钙钛矿材料，合成过程中未发现焦绿石相。实验中发现，以ＳＴ＋ＺＴ为先驱体比ＳＴＺＴ先驱体更容易得到单相钙钛矿材料，其原因是ＺＴ先驱体对材料钙钛矿形成具有一定的促进作用。实验过程中发现试样随合成温度的变化有程度不同的膨胀现象，这种膨胀是采用先驱体法合成的钙钛矿粉末具有超细晶粒尺寸的主要原因。