氮化硅陶瓷的熔盐腐蚀研究进展

氮化硅陶瓷具有优良的高温性能,广泛应用于各种高温部件中,但由于在高温时氮化硅在热力学上不稳定,易和环境介质反应产生腐蚀失效,因此氮化硅陶瓷抗腐蚀性能研究近年越来越得到重视。本文简述了氮化硅陶瓷熔盐腐蚀的背景及腐蚀性能测试方法,对氮化硅陶瓷在多种钠盐中的熔盐腐蚀机理、动力学研究等进行归纳总结,并对今后提高氮化硅陶瓷抗腐蚀性能研究提出了建议。     

碳化硅陶瓷的冲蚀磨损机理

采用自主研发的冲蚀磨损试验机,以碳素钢为参照,对碳化硅陶瓷进行冲蚀磨损实验.通过控制冲蚀角度、冲蚀时间和粒子冲蚀速度,测定碳化硅陶瓷的冲蚀磨损量,并借助于SEM对冲蚀磨损后试样的显微结构进行观察.实验结果表明:碳化硅陶瓷体积冲蚀率随角度增大而增大,在90°下达到最大;碳化硅陶瓷的冲蚀磨损机理为:在小角度下主要以切削磨损为主,在大角度下主要以脆性断裂为主.     

Ion-Exchange Parameters of Glass/Molten Salt Systems

In a systematic study of the parameters characterizing the ion-exchange process in borosilicate glass/binary molten nitrate systems, values of the thermodynamic equilibrium constant ( K ) and the nonideality constant ( n ) were determined over an extensive temperature range. The value of n decreases with an increase in temperature; in some systems, the glass is characterized by a value of n <1. The parameter n is expected to be more important than K , and its value should have a direct bearing on transport and conductance properties of the glass.     

Relationship Between Interfacial Water Layer Adhesion Loss of Silicon/Glass Fiber-Epoxy Systems: A Quantitative Study

Water at the polymer/substrate interface is often the major cause of adhesion loss in coatings, adhesives, and fiber-reinforced polymer composites. This study critically assesses the relationship between the interfacial water layer and the adhesion loss in epoxy/siliceous substrate systems. Both untreated and silane-treated Si substrates and untreated and silane-treated E-glass fibers were used. Thickness of the interfacial water layer was measured on epoxy/Si systems by Fourier transform infrared-multiple total internal reflection (FTIR-MTIR) spectroscopy. Adhesion loss of epoxy/Si systems and epoxy/E-glass fiber composites was measured by peel adhesion and short-beam shear tests, respectively. Little water accumulation at the epoxy/Si substrate interface was observed for silane-treated Si substrates, but about 10 monolayers of water accumulated at the interface between the epoxy and the untreated Si substrate following 100 h of exposure at 24 °C. More than 70% of the initial epoxy/untreated Si system peel strength was lost within 75 h of exposure, compared with 20% loss after 600 h for the silane-treated Si samples. Shear strength loss in composites made with untreated E-glass fiber was nearly twice that of composites fabricated with silane-treated fiber after 6 months of immersion in 60 °C water. Further, the silane-treated composites remained transparent, but the untreated fiber composites became opaque after water exposure. Evidence from FTIR-MTIR spectroscopy, adhesion loss, and visual observation strongly indicated that a water layer at the polymer/substrate interface is mostly responsible for the adhesion loss of epoxy/untreated siliceous substrate systems and epoxy/untreated glass fiber composites and that FTIR-MTIR is a viable technique to reliably and conveniently assess the adhesion loss attributable to water sorption at the interface.     

The Interaction of Molten Silicon with Silicon Aluminum Oxynitrides

Silicon aluminum oxynitride solid solutions (sialons) based on β-Si₃N₄ and Si₂N₂O behave differently in contact with molten sih'con. The Si₂N₂O-based sialons convert to almost pure Si₃N₄, apparently through a two-step decomposition and solution-precipitation reaction, whereas the β-Si₃N₄ sialons are preferentially attacked at the grain boundaries. The composition of the grain-boundary phase appears to control the rate of reaction.     

碳化硅陶瓷的研究进展

碳化硅陶瓷以优异的高温力学性能以及优良的耐化学腐蚀性能得到了越来越广泛的应用,本文重点介绍了碳化硅陶瓷的烧结工艺以及性能特点等。     

纳米碳颗粒/碳化硅陶瓷基复合材料的氧化行为

以微米硅(Si)和纳米碳黑(Cp)粉体为主要原料,采用经机械化学法合成的碳化硅(SiC)和15%和25%的纳米碳颗粒与碳化硅(Cp-SiC)的复合粉体,并经无压烧结得到了Cp/SiC陶瓷基复合材料,分析了在不同温度条件下Cp/SiC烧结体的氧化行为。结果表明:当温度小于700℃时,Cp/SiC复合陶瓷在空气中的氧化受C—O2反应控制,致使其为均匀氧化;700℃时,氧化后的复合材料显气孔率最大,弯曲强度达极小值;大于700℃,氧化过程受O2的气相扩散控制,呈非均匀氧化;700~900℃之间,O2通过微裂纹的扩散控制着Cp/SiC的氧化过程;900~1 100℃之间,O2通过SiC缺陷的扩散控制着Cp/SiC的氧化过程,并在1 000℃时的最初的2 h内,复合材料弯曲强度增大,且达到了极大值。同时表明,纳米碳含量是影响复合材料强度及氧化行为的关键因素,添加纳米碳质量分数为15%的Cp/SiC复合陶瓷可以作为一种抗氧化性能优良的玻璃夹具材料。     

Fracture Behavior of Multilayer Silicon Nitride/Boron Nitride Ceramics

The fracture behavior of multilayer Si₃N₄/BN ceramics in bending has been studied. The materials were prepared by a process of tape casting, coating, laminating, and hot pressing. The Si₃N₄ layers were separated by thin, weak BN interlayers. Crack patterns in bending bars were examined with a scanning electron microscope. The weak layers deflected cracks in bending and thus prevented catastrophic failure. In one well-aligned multilayer ceramic A, a main crack propagated through the specimen although along a zigzag path. A second multilayer ceramic B was made to simulate a wood grain structure. Its failure was dominated by shear cracking along the weak BN layers. Besides crack deflection, interlock bridging between toothlike layers in the wake of the main crack appeared also to contribute to toughening.     

Sintering Silicon Nitride Ceramics in Air

Silicon nitride (Si₃N₄) ceramics, prepared with Y₂O₃ and Al₂O₃ sintering additives, have been densified in air at temperatures of up to 1750°C using a conventional MoSi₂ element furnace. At the highest sintering temperatures, densities in excess of 98% of theoretical have been achieved for materials prepared with a combined sintering addition of 12 wt% Y₂O₃ and 3 wt% Al₂O₃. Densification is accompanied by a small weight gain (typically <1–2 wt%), because of limited passive oxidation of the sample. Complete α- to β-Si₃N₄ transformation can be achieved at temperatures above 1650°C, although a low volume fraction of Si₂N₂O is also observed to form below 1750°C. Partial crystallization of the residual grain-boundary glassy phase was also apparent, with β-Y₂Si₂O₇ being noted in the majority of samples. The microstructures of the sintered materials exhibited typical β-Si₃N₄ elongated grain morphologies, indicating potential for low-cost processing of in situ toughened Si₃N₄-based ceramics.     

Dissolution Rate of Silicon Nitride Ceramics into Molten CaO–Al2O3–SiO2 Slags

The dissolution rates of silicon nitride (Si₃N₄) ceramics into CaOAl₂O₃SiO₂ slags were investigated by using a rotating specimen method in the temperature range of 1773–1873 K. Dissolution rates in the present study increased as the revolution speed and temperature increased and decreased as the SiO₂ content of the slags increased. The nitrogen content of the slags increased after the Si₃N₄ ceramics had been immersed into them. The slags contained two types of nitrogen ions—N³⁻ and CN^-—because a graphite crucible was used for the experiment. N³⁻ ions were confirmed in all the slags that were used in the present work; the CN^- content was much lower than that of the N³⁻ ions, except in the slag without SiO₂. Based on those results, Ficks law of diffusion was used to analyze the dissolution rates. The dissolution mechanism of the Si₃N₄ ceramics into CaO–Al₂O₃SiO₂ slags has been discussed in this paper.     

Preparation of Silicon Carbide/Aluminum Nitride Ceramics Using Organometallic Precursors

Solid solutions of 2H -SiC/AlN can be prepared at temperatures less than 1600°C by rapid pyrolysis ("hot drop") of mixtures of [(Me₃Si)_0.80((CH₂=CH)MeSi)_1.0(MeHSi)_0.35] _n (VPS) or [MeHSiCH₂] _n (MPCS) with [R₂AlNH₂]₃, where R=Et, i -Bu or simply by slow pyrolysis of the precursor mixture in the case of [Et₂AlNH₂]₃. In contrast, slow pyrolysis of mixtures of VPS or MPCS with [ i -Bu₂AlNH₂]₃ yields a composite of 2 H -AlN and 3 C -SiC at 1600°C, which transforms into a single 2 H -SiC/AlN solid solution on heating to 2000°C. The influences of the nature of the precursor and processing conditions on the structure, composition, and purity of the SiC/AlN materials are discussed.     

碳化硅陶瓷的液相烧结及其研究进展

本文对碳化硅液相烧结添加系统及其烧结机理作了论述。有氧化物参与的碳化硅的液相烧结可以降低碳化硅的烧结温度,促进碳化硅的致密化,提高碳化硅陶瓷的性能。沿晶断裂和穿晶断裂混合断裂机理是液相烧结碳化硅陶瓷强度和韧性提高的原因,表面强化和韧化可以进一步提高碳化硅陶瓷材料的性能。     

Seamless Joining of Silicon Nitride Ceramics

High-strength joining of Si₃N₄ ceramics has been achieved by developing a process that effectively eliminates the seam, and may allow for fabrication of large or complex silicon nitride bodies. This approach to joining is based on the concept that when sintering aids are effective in bonding individual grains, they could be equally effective in joining bulk pieces of Si₃N₄. Optimization of the process led to Si₃N₄/Si₃N₄ joints with room-temperature bend strengths as high as 950 MPa, corresponding to more than 90% of the bulk strength of the Si₃N₄. At elevated temperatures of 1000° and 1200°C joint strengths of 666 and 330 MPa, respectively, were obtained, which are the highest values reported to date for these temperatures. These bend strengths are also more that 90% of the strength of bulk Si₃N₄ measured at these temperatures.     

Liquid-Phase Bonding of Silicon Nitride Ceramics

Mg-Si-O-N glasses were used to bond dense Si₃N₄ ceramic pieces by a liquid-phase diffusion bonding mechanism. In this case, it was difficult to achieve defect-free bonding because, at low nitrogen content in the glass, a large mismatch in thermal expansion coefficient produced cracks perpendicular to the bonding glass layer. With an increase in nitrogen content, the glass layer became frothy and contained "bubbles." However, when a small amount of elemental silicon was added to the glass, volatile reaction was suppressed and intimate bonding was achieved without thermal cracks.     

Electrical Joining of Silicon Nitride Ceramics

The electrical joining of sintered Si₃N₄ ceramics by Joule heating was studied. A mixture of CaF₂/kaolinite (70/30 wt%) with excellent electroheating characteristics and reactivity with Si₃N₄ ceramics was selected as a joining agent. The optimum conditions for electrical joining were determined using this joining agent. Analysis of the joint obtained under optimum conditions revealed that joining was accomplished by the formation of reaction zones and a joining layer through the mutual diffusion of the components in the joining agent and the sintering aids in the Si₃N₄. The joint layer was composed of a glassy substance consisting of Ca─Al─Si─Y─O─(F)─(N) and contained a few particles of β─Si₃N₄. Four-point bend tests indicated that joined bodies could be obtained which maintained a strength of about 300 MPa up to 800°C. Finally, a comparative study was made with a joint obtained using furnace heating. These results indicated that the joints obtained using electrical joining were superior to those produced in the furnace.     

碳化硅/堇青石复相多孔陶瓷的制备及性能研究

采用碳化硅、烧高岭土、氢氧化铝、滑石为主要原料,石墨为造孔剂制备了碳化硅/堇青石复相多孔陶瓷.研究了烧结温度和烧结助剂二氧化铈对碳化硅/堇青石复相多孔陶瓷气孔率和强度的影响,并分别用XRD和SEM分析晶相组成和断面显微结构表明:制备出的SiC多孔陶瓷的主相是SiC,结合相是堇青石与方石英,多孔陶瓷具有相互连通的开孔结构;在1350℃烧结,并保温3h,当造孔剂含量为15％时,碳化硅/堇青石复合多孔陶瓷性能最佳,其气孔率31.80％,相应的弯曲强度为63.74 MPa.在1200℃下,添加不同含量的CeO2,对烧结样品的相组成有影响,能够降低生成堇青石的温度,在CeO2含量为3％的样品中,堇青石的峰最明显,但是过量的氧化铈会抑制了堇青石的生成;随着CeO2加入量的增加,其气孔率和弯曲强度也会随之变化,1200℃下,在CeO2加入量为4％时其弯曲强度最优.但随着CeO2的含量的增加,其气孔率逐渐下降.     

Crack Deflection and Propagation in Layered Silicon Nitride/Boron Nitride Ceramics

Crack deflection and the subsequent growth of delamination cracks can be a potent source of energy dissipation during the fracture of layered ceramics. In this study, multilayered ceramics that consist of silicon nitride (Si₃N₄) layers separated by boron nitride/silicon nitride (BN/Si₃N₄) interphases have been manufactured and tested. Flexural tests reveal that the crack path is dependent on the composition of the interphase between the Si₃N₄ layers. Experimental measurements of interfacial fracture resistance and frictional sliding resistance show that both quantities increase as the Si₃N₄ content in the interphase increases. However, contrary to existing theories, high energy-absorption capacity has not been realized in materials that exhibit crack deflection but also have moderately high interfacial fracture resistance. Significant energy absorption has been measured only in materials with very low interfacial fracture resistance values. A method of predicting the critical value of the interfacial fracture resistance necessary to ensure a high energy-absorption capacity is presented.     

Stress-Enhanced Oxidation of Silicon Nitride Ceramics

Silicon nitride ceramics show an accelerated oxidation rate under load in air. This phenomenon was observed for porous and dense ceramics with and without additives in a wide temperature range (700°–1450°C) and can be interpreted as stress corrosion in oxygen-containing environments. Stresses cause an alteration of the amount and composition of oxidation products, formation of pits and cracks on stressed parts of specimens, and changes of the surface coloration and oxide scale morphology. Both tensile and compressive stresses can affect the oxidation process. An exponential dependence of mass gain on stress was found. On the other hand, oxidation of silicon nitride-based ceramics can affect the material response to mechanical stresses as, for example, deformation, cavitation and cracking. Stress-assisted chemical reaction at lower temperatures and stress-affected diffusion at higher temperatures seem to be the main reasons for the susceptibility of Si₃N₄ ceramics to stress corrosion. The effect of stress corrosion on mechanical properties is discussed.