硅粉对刚玉-氮化硅复合材料表面氧化膜的影响

将T-60氧化铝粉、氮化硅粉和硅粉分别按50%、37.5%和12.5%的质量分数配料混合,经压制成型后,在空气中于1600℃保温2h烧成制得刚玉-氮化硅复合材料试样,借助于XRD、SEM、EDS等研究了加入硅粉对刚玉-氮化硅复合材料表面氧化膜组成和结构的影响。结果表明:在空气中烧成的刚玉-氮化硅复合材料表面氧化膜主要由富硅玻璃相、刚玉和莫来石组成;在刚玉-氮化硅复合材料中引入硅粉能减小氧化膜厚度,并能提高氧化膜的致密程度。     

矾土基β-SiAlON结合刚玉-碳化硅复合材料抗氧化性能的研究

研究了矾土基β-SiAlON(质量分数分别为15%、20%和25%)结合刚玉-碳化硅复合材料在1100～1300℃间的氧化行为。结果表明:复合材料具有较好的抗氧化性能,其氧化属保护型氧化,原因在于氧化后试样的表面存在着非晶质薄层,在非晶质薄层下又有一氧化致密层,阻止、减缓了O2向复合材料内部的进一步扩散;氧化层中的物相主要为β-SiAlON、碳化硅氧化后生成的莫来石和方石英;在氧化后期,复合材料的表观氧化活化能基本随着β-SiAlON含量的增加而增大,β-SiAlON含量为25%的复合材料的表观氧化活化能高达9586kJ.mol-1。     

空气气氛中烧成刚玉-氮化硅复合材料的研究

对刚玉-氮化硅复合材料在氮气中埋炭、空气中埋炭和空气 3种气氛中加热时可能发生的、对烧结有影响的重要反应进行了热力学分析,然后按m(Al2O3 ) : m(Si3N4 ) =62. 5: 37. 5的配比制成试样,在上述 3种气氛中于 1600℃保温 2h烧成,并对烧成后试样的性能、相组成以及空气气氛中烧成后试样的显微结构进行了分析。结果表明:在氮气中埋炭或空气中埋炭烧成时,材料的烧结情况没有在空气气氛中的好;在氮气中埋炭和空气中埋炭烧成后试样中分别生成了少量的β SiAlON或SiC,而在空气气氛中烧成后试样中出现了莫来石、石英和X相,残留了较多的β Si3N4;在空气气氛中烧成后,试样断面明显分为氧化层和非氧化层,其间有一沉积致密层。     

反应烧结氮化硅-碳化硅复合材料的氮化机理

为分析反应烧结氮化硅结合碳化硅(Si3N4-SiC)材料中微观结构和氮化硅分布不均匀的原因,对在隔焰燃气氮化梭式窑中应用反应烧结氮化方法制备的氮化硅结合碳化硅复合材料进行结构研究和热力学分析。结果表明:材料中的氮化硅以纤维状和柱状两种形状存在。Si的氮化机理为:Si首先被氧化成气态SiO,降低了体系的氧分压,当氧分压足够低时,Si与N2直接反应形成柱状Si3N4,气态SiO亦可与N2反应生成氮化硅,这是一个气-气反应,故生成的Si3N4为纤维状。氮化反应前SiO主要分布于材料孔隙和表面,因而生成的氮化硅分布不均匀,导致了反应烧结Si3N4-SiC材料结构的不均匀。     

氮化硅-莫来石复合材料的制备

以莫来石、氮化硅为主要原料,铝酸钙水泥、硅微粉为结合系统,制备了氮化硅-莫来石复合材料,并与莫来石材料进行了对比。试样自然干燥24h脱模后,再经110℃烘干24h,分别在空气气氛下于1000℃、1300℃和1500℃热处理3h。检测各温度热处理后试样的体积密度(B.D)、常温抗折强度(M.O.R)、常温耐压强度(C.C.S)以及试样的热膨胀系数、耐磨性能和抗热震性能。结果表明,经过1000℃、1300℃和1500℃热处理后,氮化硅-莫来石复合材料的常温抗折强度和常温耐压强度均大于莫来石材料的常温抗折强度和常温耐压强度。在本实验条件下,在莫来石基材料中添加氮化硅并不能提高材料的耐磨性能。在1250℃～1400℃温度之间,氮化硅-莫来石复合材料的热膨胀系数小于莫来石材料的热膨胀系数。氮化硅-莫来石复合材料试样热震后的耐压强度大于莫来石材料试样热震后的耐压强度,但耐压强度保持率小于莫来石材料。     

Si粉对矾土-氮化硅复合材料"自阻碍氧化"能力的影响

以高铝矾土和氮化硅为主原料,二氧化硅微粉、高铝水泥、α-Al2O3微粉等为辅助原料,Si粉为添加剂,外加定量的水和分散剂配制成70%(质量分数,下同)高铝矾土和10%氮化硅的矾土-氮化硅浇注料,并利用回转抗渣试验研究了不添加与外加2%和4%的Si粉对矾土-氮化硅浇注料抗高炉渣(碱度为1.3)侵蚀性能的影响。结果表明,添加Si粉明显改善其抗侵蚀性能,而且随添加量的增加,侵蚀指数显著降低。分析认为:1)矾土-氮化硅材料中非氧化物材料在表层的氧化和相继形成的SiO(g)在表层的沉积,使表面形成致密层,使材料具有"自阻碍氧化"能力;2)Si3N4氧化时,不论是生成SiO2还是SiO气体,均伴随着N2的生成和逸出,不利于材料表层致密度的提高;3)Si的存在不仅增加SiO的生成量,而且消除了N2的生成和排出,大大提高了表层的致密度,显著改善了复合材料的"自阻碍氧化"能力和抗渣铁侵蚀性能。     

不同气氛下合成的SiAlON结合刚玉或碳化硅材料的研究

以刚玉细粉、碳化硅细粉、氮化硅细粉、α-Al2O3,微粉和金属Al粉为主要原料,聚乙烯醇为结合剂,经球磨、混练、困料和成型后,分别在空气裸烧(氧化气氛)、埋石墨粉(还原气氛)、埋石墨+碳化硅混合粉(还原气氛)3种气氛下进行1 600℃6 h热处理制备了SiAlON结合刚玉或碳化硅复合耐火材料,并研究了刚玉或碳化硅粉加入量(7.5%～90%,质量分数)和烧成气氛对SiAlON相的生成量、晶体形貌以及耐火制品的相组成、显微结构和性能的影响.结果表明:(1)随着刚玉粉含量的增加,3种气氛下烧后的SiAlON结合刚玉材料的致密度均增大,烧结性能增强;但氧化气氛下烧结性能好于还原气氛下的.(2)2种还原气氛下烧成的Si A10N结合刚玉试样的相组成均为刚玉、SiAlON和SiC;而在氧化气氛下烧成的试样出现了分层现象,其非氧化层主要为SiAlON、刚玉和少量的莫来石.(3)不同气氛下烧成的SiAlON结合刚玉材料中均有柱状或纤维状的SiAlON生成,但氧化气氛下的SiAlON柱状物比还原气氛下的要粗壮、完整得多,且成群生长.(4)随着SiC粉含量的增加,SiAlON结合碳化硅材料在2种还原气氛下烧后的致密度降低,烧结性能下降;而在氧化气氛下烧后严重氧化,形成了较厚的釉层.     

添加Si粉和Si3N4粉对Al2O3-SiC材料抗侵蚀性的影响

以40%～46%(质量分数,下同)的烧结刚玉(8～1 mm)和30%的碳化硅(0.5～0.074 mm)为主要原料,SiO2微粉(d50=2 μm)、高铝水泥、α-Al2O3微粉(d50=4 μm)等为辅助原料,Si粉(≤0.074 mm)和Si3N4粉(≤0.074 mm)为添加剂,外加定量的水和分散剂而制成Al2O3-SiC复合材料.利用回转侵蚀试验研究了分别添加3%和6%的Si粉或Si3N4粉对Al2O3-SiC复合材料抗高炉渣(碱度为1.3)侵蚀性能及表面致密层状况的影响.试验结果表明:添加Si粉有利于试样表面致密层的形成,明显改善其抗侵蚀性能,且随着Si粉添加量增加,致密层厚度增加;而添加Si3N4粉对表面致密层的形成和改善抗渣性能并没有明显贡献.     

硅莫砖的技术性能及其在水泥回转窑的应用

碳化硅与高铝矾土熟料生产碳化硅莫来石符合耐火制品的工艺技术发展,由于碳化硅氧化产生二氧化硅,与三氧化二铝反应形成莫来石(3Al2O3.2SiO2),能提高制品致密度和强度,在制品表面形成保护膜,可防止碳化硅进一步氧化,使碳化硅在高铝碳化硅砖中保持一定含量,提高制品的热震稳定性、耐磨性、抗侵蚀性。高强致密硅莫砖在水泥回转窑筒体上除烧成带以外的各个段带的使用寿命比高铝砖提高3～4倍。     

不同种类莫来石对碳化硅质浇注料性能的影响

采用不同种类烧结莫来石、碳化硅、SiO2微粉、Secar71水泥和p-Al2O3为主要原料,制备了不同种类莫来石-碳化硅浇注料,研究了浇注料的常温物理性能、高温抗折强度、抗热震性能、耐磨性能和抗碱性能,并借助SEM和EDS进行了显微结构和微区能谱分析.结果表明:富SiO2玻璃相促进试样的烧结,使得加入M45试样的显气孔率最小,强度最大,加入M60试样的显气孔率最大,强度较小;加入M45试样的高温抗折强度、抗热震性能最差,加入M60试样的高温抗折强度、抗热震性能最好;随着莫来石中Al2O3含量的增加,试样的常温耐磨性能逐渐变好,抗碱性能逐渐变差.     

Anisotropy of Silicon Nitride with Aligned Silicon Nitride Whiskers

A model based on anisotropic sintering shrinkage of silicon nitride with aligned silicon nitride whisker seeds was built in order to provide an easy way to obtain information on how the large elongated grains were aligned. The method requires a simple measuring device for the information. XRD analysis showed a good correlation with predictions of the model. Both predictions of the model and experimental results indicated that the fraction of aligned large elongated grains increased as the whisker content increased.     

Coating of Fine-Grained Silicon Nitride Whiskers on Fiber-like Silicon Nitride

Fine-grained silicon nitride (Si3N4) whiskers were coated on Si3N4 fibers through a vapor-liquid-solid mechanism under the following process. After the oxide glass of a Si-Al-Y-O system was coated on seed Si3N4 fibers, the coated fibers were heated at 1490°C and 700° in the vapor of the Si-N system which was generated by decomposition of amorphous Si3N4. The resulting specimens looked just like rose twigs. The Si3N4 whiskers were precipitated by nucleation in a liquid phase generated by melting of the oxide glass layers on the Si3N4 fibers.     

Silicon Nitride Joining

Hot-pressed Si₃N₄ was joined using an Mgo-A1₂O₃-SiO₂ glass composition chosen to approximate the oxide portion of the grain-boundary phase in the ceramic. After it has been heated at 1550° to 1650°, the interface of the joined ceramic is an interlocking mixture of Si₂N₂O, β-Si₃N₄, and a residual oxy-nitride glass. The kinetics of reactions between Si₃N₄ and the molten joining composition were studied by X-ray diffraction analysis of the phases present in Si₃N4 powder-glass mixtures quenched after varied heat treatments. Analytical transmission electron microscopy of the composition and micro-structure of the reaction zone in joined specimens, together with the X-ray diffraction results, suggests that the driving force for joining is the lowering of the Si₃N₄ interfacial energy when it is wet by the molten silicate, augmented by the negative Gibbs energy for the reaction SiO₂( l ) + Si₃N₄= 2Si₂N₂O.     

Si3N4及其复合材料强韧化研究进展

简述了氮化硅陶瓷的结构、性能和制备工艺，并分别通过自增韧补强、纤维／晶须强韧化、层状结构强韧化、相变强韧化以及颗粒弥散强韧化等方法对氮化硅陶瓷的强韧化研究进行了分类叙述。     

Texture in Silicon Nitride Seeded with Silicon Nitride Whiskers of Different Sizes

Silicon nitride ceramics seeded with 3 wt%β-Si₃N₄ whiskers of two different sizes were prepared by a modified tape casting and gas pressure sintering. The fine whiskers had a higher aspect ratio than the coarse whiskers. Quantitative texture analysis including calculation of the orientation distribution function (ODF) was used for obtaining the degrees of preferred orientation of sintered samples. The maximum multiples of random distribution (mrd) values of samples seeded with the fine and coarse whiskers were large, greater than 15 and 9, respectively. Meanwhile, the mrd value of a sample seeded with fine whiskers was only 9 when it was prepared by conventional tape casting. The microstructures and the XRD data revealed that the well-aligned whiskers grew significantly after sintering and dominated the texture. Differences among the degrees of preferred orientation of the samples were explained using Jeffrey's model on rotation of elliptical particles carried by a viscous fluid.     

Machinability of Silicon Nitride/Boron Nitride Nanocomposites

The machinability and deformation mechanism of Si₃N₄/BN nanocomposites were investigated in the present work. The fracture strength of Si₃N₄/BN microcomposites remarkably decreased with increased hexagonal graphitic boron nitride ( h -BN) content, although machinability was somewhat improved. However, the nanocomposites fabricated using the chemical method simultaneously had high fracture strength and good machinability. Hertzian contact tests were performed to clarify the deformation behavior by mechanical shock. As a result of this test, the damage of the monolithic Si₃N₄ and Si₃N₄/BN microcomposites indicated a classical Hertzian cone fracture and many large cracks, whereas the damage observed in the nanocomposites appeared to be quasi-plastic deformation.     

Studies on Abrasive Wear of Monolithic Silicon Nitride and a Silicon Carbide Whisker-Reinforced Silicon Nitride Composite

Results presented in this paper demonstrate the roles of the most important parameters that govern abrasive wear of experimental ceramics. SEM studies of the abraded surfaces evidenced two main kinds of failures: microdropping of grain(s) and powder-type wear track(s) resulting from the brittle microfracturing of parts of grain(s). There were whiskers in the surface, and whisker pullouts occurring during wear processes are believed to be the reasons for the lower wear rates of SiCw/Si₃N₄ composite ceramics under experimental conditions.     

Chemical-Vapor-Infiltrated Silicon Nitride, Boron Nitride, and Silicon Carbide Matrix Composites

Composites of carbon/chemical-vapor-deposited (CVD) Si₃N₄, carbon/CVD BN, mullite/CVD SiC, and SiC yarn/CVD SiC were prepared to determine if there were inherent toughness in these systems. The matrices were deposited at high enough temperatures to ensure that they were crystalline, which should make them more stable at high temperatures. The fiber-matrix bonding in the C/Si₃N₄ composite appeared to be too strong; the layers of BN in the matrix of the C/BN were too weakly bonded; and the mullite/SiC composite was not as tough as the SiC/SiC composites. Only the SiC yarn/CVD SiC composite exhibited both strength and toughness.     

Reactivity of Aluminum Nitride Powder in Aqueous Silicon Nitride and Silicon Carbide Slurries

The reactivity of AlN powder with water in supernatants obtained from centrifuged Si₃N₄ and SiC slurries was studied by monitoring the pH versus time. Various Si₃N₄ and SiC powders were used, which were fabricated by different production routes and had surfaces oxidized to different degrees. The reactivity of the AlN powder in the supernatants was found to depend strongly on the concentration of dissolved silica in these slurries relative to the surface area of the AlN powder in the slurry. The hydrolysis of AlN did not occur if the concentration of dissolved silica, with respect to the AlN powder surface, was high enough (1 mg SiO₂/(m² AlN powder)) to form a layer of aluminosilicates on the AlN powder surface. This assumption was verified by measuring the pH of more concentrated (31 vol%) Si₃N₄ and SiC suspensions also including 5 wt% of AlN powder (with respect to the solids).     

Nonaqueous Processing of Silicon for Reaction-Bonded Silicon Nitride

Ethanolic silicon suspensions, with and without a polyethoxylated amine of low molecular weight, were studied by rheological, adsorption, electrophoretic, and sedimentation methods. Pellets were pressure-cast and nitrided to form reaction-bonded silicon nitride. Density and binding strength in the green state relate well to rheological behavior and other collodial aspects of the suspensions used, particularly the additive's role and distribution. Density and degree of nitridation in the final state are not importantly affected by the additive's use. Its greatest benefit is to modify the binding strength in the green state. The mode by which this small molecule affects the processing of silicon consists of adsorption, combined with an increased electrostatic interparticle repulsion which increases the suspension viscosity and that of undried pellets. Although the improved binding strength is accompanied by decreased green and nitrided densities, high degrees of conversion to silicon nitride are still achieved.