In-situ hot pressing/solid-liquid reaction synthesis of dense titanium silicon carbide bulk ceramics

 An in-situ hot pressing/solid-liquid reaction process was developed for the synthesis of dense polycrystalline Ti₃SiC₂ ceramics using Ti, Si, and graphite powders as starting materials. The present work demonstrated that this process was one of the most effective and simple methods for the preparation of dense bulk Ti₃SiC₂ materials. Lattice constants of a=3.068 and c=17.645 are calculated for Ti₃SiC₂ made through this process. The synthesis temperature influenced the phase composition, microstructure and mechanical properties of Ti₃SiC₂ prepared at different temperatures. And bulk materials with flexural strength of 480 MPa and fracture toughness of 7.88 MPa.m^1/2 were obtained at 1600°C. The high fracture toughness and strength are discussed based on microstructure analysis. Received: 31 July 1998 / Accepted: 28 August 1998     

Nanostructured SiC ceramics prepared by a new process—Crystallization of interfacial glass

Large bulk and fully dense SiC based nanoceramics with average grain size of 50 nm and 20–30 wt.% nanometer sized α-Sialon, Al_xSi_{3 − x}O₆ and α-SiO₂ interfacial phases were prepared by a new process, crystallization of interfacial glass, using LMAS glass-coated SiC powder as starting material. The process involves two major steps: densification by hot pressing, and crystallization of interfacial glass by annealing treatment. The densification was controlled by interfacial glass content, hot pressing temperature, and hot pressing pressure; density 99.8% theoretical being reached for SiC/30 wt. % glass nanoceramics hot-pressed at 1520 °C and 22 MPa for 30 min. The crystallization was complete and nearly all the interfacial glass was transformed into nanocrystalline phases after 800 °C and 900 °C for 5 h annealing treatments. Plastic flow and rearrangement of particles and interfacial glass infiltration are densification mechanisms. A large number of nanometer sized SiC powder particles serve as nucleating agents, e.g. hetero-nucleation, and are responsible for interfacial glass crystallization. A characteristic of the present process is that there is no SiC grain growth during densification and interfacial glass crystallization.     

微量SiO2添加对Pr:Lu3Al5O12陶瓷光学及闪烁性能的影响

在制备透明陶瓷时, 广泛采用烧结助剂来提升陶瓷的光学质量。但烧结助剂的添加可能会恶化陶瓷的发光性能。本研究采用真空预烧结合热等静压烧结制备了0.25at%Pr:LuAG闪烁陶瓷, 研究了微量SiO₂烧结助剂对陶瓷光学及闪烁性能的影响。结果表明, 添加少于200 ppm的微量SiO₂(1 ppm表示添加量为1×10^-6 g/g)能有效促进热等静压过程中气孔的排出, 有效提升了Pr:LuAG陶瓷的光学性能。150 ppm SiO₂添加的Pr:LuAG陶瓷在400 nm处的直线透过率约为77%。同时研究了预烧温度及时间对Pr:LuAG陶瓷光学性能的影响。在实现完全闭气孔结构时, 进一步升高预烧温度或延长保温时间会降低热等静压过程中的致密化速率, 不利于气孔的排出, 从而降低了Pr:LuAG陶瓷的光学质量。此外, 添加微量SiO₂对Pr:LuAG陶瓷闪烁性能的影响较小。添加微量SiO₂结合热等静压烧结是制备Pr掺杂石榴石闪烁陶瓷的有效途径。     

柔性陶瓷三元层状碳化物Ti3SiC2的金属特性

Ti3SiC2兼有金属和陶瓷材料的优异性能，是新一代高性能高温结构材料、电工材料、自润滑轴承的理想侯选对象。重点介绍制备Ti3SiC2的主要方法：气相沉积法、自蔓延高温合成法、热压和热等静压法、放电等离子烧结法，并论述了Ti3SiC2的未来研究方向和潜在的应用前景。     

Hot-pressed ceramic SiC–YAG materials

Dense SiC-based ceramic materials containing yttrium aluminum garnet (YAG) as an oxide sintering aid have been prepared by hot pressing in the temperature range 1750–1850°C. As a result of melting, the oxides fill spaces between the SiC particles, contributing to the densification of the material and mass transport during the hot pressing process. The present results demonstrate that relatively small amounts of the oxides (≤5 wt %) are needed to ensure a high degree of densification of the SiC–YAG materials. The best physicomechanical properties are offered by the SiC + 3 wt % YAG material sintered at a temperature of 1850°C: ρ = 3.24 ± 0.01 g/cm³, П = 1.1 ± 0.1%, σ_b = 640 ± 10 MPa; K_Ic = 6.4 ± 0.2 MPa m^1/2, Еel = 410 ± 20 GPa, and HV = 26.0 ± 0.2 GPa. This material experiences predominantly intercrystalline fracture.     

制备工艺对热压烧结SiC/SiC复合材料结构与性能的影响

采用纳米SiC和亚微米SiC粉料作为基体形成原料,通过热压烧结技术制备了SiC/SiC 复合材料.研究了粉料颗粒、烧结温度、烧结压力对复合材料显微结构和各种性能的影响.结果显示,采用纳米碳化硅粉体可有效降低烧结温度,促进复合材料的致密化过程,在1780℃、20MPa条件下可获得性能优良的复合材料.而采用亚微米SiC粉体,复合材料的致密化过程需要较高的温度,但随着密度的增加,基体与纤维之间的作用力增强,不利于性能的提高.     

铜钛硅碳石墨合金材料摩擦磨损性能研究

为研究铜钛硅碳石墨合金材料摩擦磨损性能,通过常规的粉末冶金方法制备了铜钛硅碳石墨材料。对样品硬度等性能的测试,选择出87%Cu的最优配方。再用无流磨损和载流磨损实验测试其摩擦磨损性能,进而通过扫描电镜对磨损表面进行观察,探讨摩擦磨损机理。结果表明,无流磨损过程中,磨损量呈线性增长,磨损的主要形式为梨削;载流磨损过程中,磨损量呈非线性增长,随着行程的增加,磨损率降低,磨损的主要形式有梨削和电弧烧损,磨损率降低可能是杂质Al相弥散强化铜基体所致,其微观机理是一个复杂的各种机理的组合。     

Sinter-HIP of polymer-derived Al2O3–SiC composites with high SiC contents

Submicrometer Al₂O₃ composites with more than 20 vol.% of SiC particles were produced using a multiple infiltration of porous bodies with a liquid polymer SiC precursor. The fully dense composites were successfully densified using a sinter-HIP process. Parameters of sintering and HIP steps are discussed with respect to both densification and microstructure evolution of the composites. The initial pressure during the sintering step plays an important role for the preparation of fully dense composites with a submicrometer alumina matrix at 1750 °C. Optimized densification schedule of sinter-HIP represents a novel approach of densification at relatively mild conditions compared to previously reported or common densification methods of Al₂O₃–SiC composites with high SiC content, such as pressureless sintering, hot pressing and post-HIPing. The method expands the possibilities for preparation of alumina based composites with SiC volume fraction > 20 vol.%, filling the gap in available literature data.     

PROCESSING AND PERFORMANCE OF SEVERAL SiC WHISKER-REINFORCED Al2O3 MATRIX COMPOSITES

The influence of different SiC whiskers on the processing and performance of Al₂O₃ matrix composites were investigated. Three types of commercial SiC whiskers produced in the United States were used. The composites contained 30 v/o of SiC whisker and were consolidated by both hot pressing (HP) and hot pressing followed by hot isostatic pressing (HP/HIP) techniques. The microstructure, mechanical properties, fracture behavior and toughening mechanisms of the composites were evaluated. The results show that the whisker types and processing techniques have profound effect on the densification and the properties of the composites.     

金刚石表面形成Ti3SiC2的反应机理

采用Ti、Si、TiC、金刚石磨料为原料,通过放电等离子烧结(SPS),制备了Ti3SiC2陶瓷结合剂金刚石材料.研究结果表明,Ti-Si-2TiC试样经SPS加热的过程中位移、位移率和真空度在1200℃时发生明显变化,表明试样发生了物理化学变化.XRD分析结果表明1200℃时试样发生化学反应生成了Ti3SiC2.随着温度升高,试样中Ti3SiC2含量逐渐增加.当烧结温度为1200℃、1300℃、1400℃和1500℃时,产物中Ti3SiC2含量分别为65.9%、79.97%、87.5%和90.1%.在Ti/Si/2TiC粉料中添加适量的金刚石5%和10%进行烧结,并未抑制Ti3SiC2的反应合成.SEM观察表明,金刚石与基体结合紧密,同时其表面生长着发育良好的Ti3SiC2板条状晶粒.提出了一种金刚石表面形成Ti3SiC2的机制,即金刚石表面的碳原子首先与周围的Ti反应生成TiC,然后TiC再与Ti-Si相发生化学反应,生成Ti3SiC2.     

Micro-mechanical modeling the densification behavior of titanium metal matrix composites

Vacuum hot pressing has been used for the development of Ti-MMCs using foil–fiber–foil method, and a unified micro-mechanical model has been presented to determine the densification behavior. The effects of processing conditions on the consolidation, together with microstructural evolutions of the materials have been investigated. The explicit representation of fiber array, which is coupled with deformation behavior of matrix materials, is modeled in finite element simulation to determine the effect of geometrical arrangements on densification process. The approach is then used to model the densification behavior of porous plastic materials using the parameters obtained, and comparisons are made with experimental data. As shown by the results, either increasing temperature or pressure leads to increasing densification rate but the conditions should be determined by the precisely controlled geometrical arrangements with processing conditions. Further experimental investigation of the densification behavior of SiC/Ti–6Al–4V composites using thermo-acoustic emission analysis has been performed, and the results obtained are compared with the model predictions. Good comparisons are achieved.     

三元层状碳化物Ti3SiC2的研究进展

本文综合介绍Ti3SiC2的最新研究进展.三元碳化物Ti3SiC2属于层状六方晶体结构,空间群为P63/mmC;它同时具有金属和陶瓷的优良性能,有良好的导电和导热能力,高弹性模量和低维氏显微硬度,在室温下可切削加工,在高温下能产生塑性变形,良好的高温热稳定性和优秀的抗氧化性能;应用CVD、SHS、HP/HIP等方法可制备该化合物,用HIP方法能制备高纯、致密的Ti3SiC2陶瓷;Ti3SiC2陶瓷材料自身有抵抗损伤的机理.     

原位生成TiC/Ti5Si3纳米复合材料的显微结构研究

研究了原位生成ＴｉＣ／Ｔｉ_５Ｓｉ_３纳米复合材料的显微结构．实验结果表明,以ＳｉＣ和Ｔｉ 为原料,通过反应热压工艺可以原位合成ＴｉＣ／Ｔｉ_５Ｓｉ_３复合材料,其中的大部分ＴｉＣ粒子为纳 米粒子．ＴｉＣ晶粒与Ｔｉ_５Ｓｉ_３晶粒的晶界上存在原子台阶．复合材料还含有少量Ｔｉ_３ＳｉＣ_２相．这 些Ｔｉ_３ＳｉＣ_２相主要呈棒状分布在Ｔｉ_５Ｓｉ_３基体中,另有少量Ｔｉ_３ＳｉＣ_２相位于大的ＴｉＣ晶粒内．     

Processing and properties of zirconia-toughened alumina ceramics

Al₂O₃:ZrO₂ ceramics have been prepared from physically mixed pure oxide powders. The results indicate that careful processing of the starting powders and a two-stage sintering process can avoid expensive processing methods like hot pressing/hot isostatic pressing used for achieving high densification. The mechanical properties were measured and the resultant microstructure studied to explain the toughening behaviour of this material.     

Mechanical property improvements in Nicalon SiC fibre reinforced silicon nitride ceramics by oxide coating of Si3N4 starting powders

Ceramic matrix composites are attractive as candidate materials for high-temperature applications offering some advantages compared to monolithic ceramics and high-temperature metal alloys. SiC fibre reinforced silicon nitride is one such composite system. However, the processing route is critical to the production of a reliable composite. In this study, silicon nitride matrix densification was improved and sintering temperature was lowered by coating of Si₃N₄ particles with oxides deposited from hydrolysed metal alkoxides. The solution containing oxide coated Si₃N₄ powders was used as a slurry to infiltrate Nicalon SiC fibre tows. Following previous studies, the fibres were heat-treated in carbon monoxide to improve mechanical and surface properties. Infiltrated green bodies were hot-pressed at elevated temperatures to produce dense composites. The results showed that particle coating accelerated densification kinetics, eliminated pores and reduced the required hot-pressing temperature. There was also less fibre degradation as a result of the lower temperature of densification. Bending strength and fracture toughness of the composites were measured and fractography was conducted using scanning electron microscope. Composites manufactured using coated Si₃N₄ powders showed improved properties, specifically matrix stiffening and delayed crack initiation under load.     

Ti3SiC2-64vol%SiC复相陶瓷高温氧化机理研究

采用热等静压原位合成了高致密的Ti₃SiC₂-64vol%SiC复相陶瓷. 通过热重实验研究其在1100~1450℃中空气气氛的高温氧化行为和机理. 研究显示,复相陶瓷的等温动力学曲线遵循抛物线型氧化或抛物线型直线型氧化规律. SiC (64vol%)的引入显著提高了Ti₃SiC₂-SiC材料的抗氧化能力. XRD及SEM-EDS分析显示,氧化膜由外层金红石型TiO₂和非晶态SiO₂组成,过渡层为TiO₂与SiO₂混合物. 高温下（1400℃）,非晶态SiO₂的形成改变了TiO₂膜的生长形态,形成致密TiO₂膜,有效阻碍了氧的扩散. 长时间氧化其抛物线速率常数比在1200℃下氧化低一个数量级. 材料在1400℃下的抗氧化性能明显优于在1200℃下的抗氧化性能.     

粘结剂含量对石墨材料电、热传导性能的影响

以煅后石油焦和煤沥青为基本原料，采用热压工艺制备了一系列石墨材料。考察了粘结剂含量对石墨材料电、热传导性能的影响。在实验基础上，阐明了粘结剂与骨料颗粒在热混捏与热压过程中相互作用原理。结果表明，石墨材料的传导性能不仅依赖于原料种类、粒度，而且与其质量百分配比也有关系。经过分析认为，粘结剂含量小于25W／％时，随着粘结剂含量的增加，石墨材料传导性能增强的原因可归结为石墨材料的骨料颗粒气孔率得到降低和颗粒间微裂纹减少所致；而粘结剂含量超过25W／％时，材料的传导性能随着粘结剂含量的增加而降低的原因可归结为骨料颗粒间粘结剂的γ组分以气态形式挥发使得材料气孔率增加所致。     

Hot pressing of SiC-TiC composites

Sintering behaviour during hot pressing of SiC-TiC composite ceramics has been investigated with special emphasis on the effect of various processing parameters on the density and mechanical properties of the sintered body. At hot pressing temperatures greater than 2000° C, significant densification occurred in SiC-50 wt%TiC (–0.5 wt%B-1 wt%C) composites. The room temperature flexural strength of the sintered body increased with the hot pressing temperature up to 2000° C and reached a highest value of 710 MPa in accordance to the variation of density with temperature. In sintering of composites without additives, densification was enhanced with the addition of up to 25 wt%TiC, with relative densities higher than 98% observed when hot pressing at 2150° C for 2h.     

碳化硅轻型反射镜的研究进展

反射镜材料需具有低密度、高弹性模量、高热导率和低热膨胀系数.比较了不同反射镜材料的物理性能和机械性能,与传统光学材料对比,碳化硅具有优越的物理性能和热性能,被认为是轻型反射镜材料的首选.综述了碳化硅反射镜材料常用制备方法的特点.认为反应烧结法和热等静压法适用于制备SiC反射镜基体材料,化学气相沉积法适合用于基体材料增密和制备反射层,反应烧结法结合化学气相沉积工艺是制备SiC反射镜的高效低成本工艺.     

熔盐辅助合成Dy3Si2C2包裹SiC粉体及其陶瓷的烧结行为

碳化硅陶瓷因自身优良的物理化学性能而具有广泛的应用前景。碳化硅的化学键结合特性决定了其难以烧结成型, 因此如何制备高质量碳化硅陶瓷是领域内的难点之一。本研究以三元稀土碳化物Dy₃Si₂C₂作为新型SiC陶瓷的烧结助剂, 依据Dy-Si-C体系的高温相转变原位促进碳化硅的烧结致密化。采用放电等离子烧结技术, 利用金属Dy与SiC反应生成Dy₃Si₂C₂, 对Dy₃Si₂C₂包裹的SiC粉体进行烧结。在1800 ℃、45 MPa的烧结条件下, 得到了致密度为99%、热导率为162.8 W·m ^-1·K ^-1的高纯度碳化硅陶瓷。进一步的研究表明, 高温下Dy₃Si₂C₂与SiC发生共晶反应, 在晶界处产生的液相促进了SiC陶瓷的致密化, 表明稀土层状碳化物Re₃Si₂C₂ (Re=La, Ce…)有助于SiC的烧结致密。