SiC结合刚玉材料的抗高炉渣侵蚀性

采用电熔刚玉、Si粉和SiC粉为原料,用酚醛树脂做结合剂,混练成型后于1 450℃埋炭烧成,采用静态坩埚抗渣试验研究了烧后试样对碱度为1.1的高炉渣在1 500℃的抗渣侵蚀性。结果表明:Si与C、CO在高温下原位反应生成纤维状SiC,形成原位SiC结合刚玉材料,该材料具有良好的抗侵蚀性能,渣蚀厚度都在2.6mm以下,其中,加入8%(w)Si粉和5%(w)SiC粉的试样抗渣侵蚀性最好。通过对抗侵蚀后试样的侵蚀层、渗透层和未变层的相组成和显微结构的分析认为:(1)这种复合材料抗渣侵蚀性能良好的主要原因是熔渣难润湿的SiC自身抗渣侵蚀性较好,且原位生成的纤维状SiC穿插在刚玉骨架结构的空隙中,阻挡了熔渣的侵蚀和渗透;(2)熔渣侵蚀材料的过程是SiC先被氧化,然后其氧化产物SiO2与熔渣中的CaO和SiO2以及材料基质中的A l2O3反应生成钙长石低熔相。     

加入SiC、SiAlON对刚玉-SiC-SiAlON材料组成、结构和力学性能的影响

以刚玉和8%Si粉为原料,1500℃埋碳烧后得刚玉-SiC-SiAlON复合材料.本文研究在加入8%Si粉基础上,另加入0～10%SiC或SiAlON粉对刚玉-SiC-SiAlON复合材料组成、结构和力学性能的影响.结果表明:加入SiC或SiAlON首先可促进Si反应完全,生成更多非氧化物使试样微膨胀量增加,重量增加;同时使试样的显气孔率提高,常温抗折强度降低;加入SiC使试样的结构疏松,高温力学性能下降;但由于生成较多O-SiAlON以及气孔率提高使试样的抗热震性明显提高;加入SiAlON,试样中生成较多的SiC,并有粒状的β-SiAlON存在,可明显提高试样的高温力学性能.     

干熄炉用碳化硅耐火材料抗CO侵蚀性研究

研究了SiAlON(主要为Si_4Al_2O_2N_6)结合SiC、复相氮化物(Si_2N_2O/Si_3N_4)结合Si C和β-SiC结合Si C材料在1 000℃、CO气氛(C+CO_2=2CO)中分别侵蚀100、200、300和400 h后其质量、显气孔率、常温耐压强度以及物相组成和显微结构的变化。结果表明:1)复相氮化物结合Si C材料抗CO侵蚀性最好,CO侵蚀后其常温耐压强度大幅度增大,达到363 MPa; SiAlON结合SiC的次之,为200 MPa;β-SiC结合SiC的最差,为136MPa。2)复相氮化物结合SiC材料被CO侵蚀后,其致密度增大较多; SiAlON结合SiC材料被CO侵蚀后,SiAlON发生Al2O_3脱溶,有新生针状产物;β-SiC结合SiC材料被CO侵蚀后,生成了少量方石英或石英。     

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.     

矾土基β-SiAlON结合刚玉-碳化硅复合材料的制备及性能

采用电熔刚玉(≤0.088mm、≤1mm和3～1mm三种粒度)、碳化硅颗粒(3～1mm)、Al2O3微粉、高铝矾土粉、Al粉和Si粉为原料,通过1500℃5h氮化反应制备了矾土基βSiAlON(z设计值为2)结合刚玉-碳化硅复合材料,研究了碳化硅颗粒加入量(分别为0、10%、20%、30%、40%)、Al2O3微粉加入量(分别为0、1%、3%、5%、7%)和βSiAlON理论生成量(分别为15%、20%和25%)对复合材料密度、显气孔率和常温强度的影响,以及不同βSiAlON理论生成量试样的热态抗折强度与温度(400～1400℃)的关系,并借助于XRD、SEM和EDS对复合材料进行了相组成和显微结构分析。结果表明:(1)随碳化硅颗粒加入量的增加,复合材料的体积密度下降,显气孔率和常温强度增加,加入30%碳化硅颗粒时,材料的综合性能较好。(2)随Al2O3微粉加入量的增加,复合材料的体积密度增加,显气孔率下降,其加入量以3%为宜。(3)复合材料的热态抗折强度随温度升高而增加,在1000℃时达到最高值;1000℃以后,强度下降,但在1400℃,βSiAlON理论生成量为20%和25%的矾土基βSiAlON结合刚玉-碳化硅复合材料的强度仍高于其常温时的强度。其原因是互相交错的柱状βSiAlON结合相填充在刚玉和SiC骨架的空隙中,起到了增强、增韧的作用。     

原位反应生成Sialon结合Al2O3-C材料的抗渣侵蚀机理

以电熔白刚玉、单质硅粉和石墨为主要原料,在氮气气氛下1450℃保温4h原位生成Sialon结合Al2O3-C材料,采用静态坩埚法对烧后的Sialon结合Al2O3-C材料在1600℃下进行抗渣实验.采用XRD分析氮化后Al2O3-C材料的物相组成,用SEM和EDS分别对渣蚀后材料的显微结构和成分进行分析.结果表明:Al2O3-C材料高温氮化后能够生成较多β-Sialon相和少量的SiC相;热力学分析表明,Sialon和SiC本身氧化产生的SiO2和Al2O3,溶解到渣中,降低渣的侵蚀和渗透;SEM结果表明,渣的渗透主要是沿刚玉颗粒边缘进行的,随着渗透的深入,CaO含量不断下降.     

Al粉、Si粉对低碳Al2O3-C滑板显微结构和高温力学性能的影响

为了改善低碳Al2O3-C滑板的高温力学性能,在质量分数65%的电熔白刚玉颗粒、25%的白刚玉细粉、6%活性α-Al2O3粉、4%的石墨+炭黑、外加4%酚醛树脂的滑板配料中,分别以3%(w)的Al粉或Si粉或3%(w)Al粉+3%(w)Si粉等量替代白刚玉细粉,混匀后在150 MPa下压制成140 mm×25 mm×25 mm的试样,经200℃24 h干燥,1 400℃埋焦炭处理3 h后,检测其高温抗折强度和抗热震性,并分析物相组成及显微结构。结果表明:单加Al粉的试样高温抗折强度高于单加Si粉的,但前者热震后残余抗折强度比后者低;与单加Al粉或Si粉的试样相比,同时加Al粉和Si粉的试样具有更高的高温抗折强度和更优的抗热震性。力学性能的变化与试样中原位生成的非氧化物相密切相关:在单加Al粉或Si粉的试样中分别有棒状AlN晶须或纤维状SiC晶须生成;而同时加Al粉和Si粉的试样中除了有AlN晶须和SiC晶须生成外,还原位生成了六角板状的SiAlON相,并相互交织在一起。     

矾土基β-SiAlON结合刚玉复合材料抗氧化性能研究

研究了1250~1350℃间矾土基βSiAlON结合刚玉复合材料的氧化行为,并与氧化铝基βSiAlON结合刚玉复合材料的氧化行为进行了对比。结果表明, 1250℃以上,矾土基βSiAlON结合刚玉复合材料的抗氧化性能优于氧化铝基βSiAlON结合刚玉复合材料的,材料的氧化属保护型,氧化后表面组成为莫来石和SiO2。建立了该材料氧化前期、中期、后期的动力学模型,表征了其氧化过程,与试验结果基本相符。     

金属复合Al2O3基耐火材料的研究进展

介绍了金属复合Al2O3基耐火材料的研究进展,重点介绍了金属加入物对Al2O3基耐火材料性能的影响。加入金属可提高材料的常温和高温强度、断裂韧性、抗热震性和抗侵蚀性等,从而提高了材料的使用寿命。材料性能优化的原因是加入的金属反应生成了碳化物、氮化物和SiAlON(或AlON),以及少量金属熔融后的助烧结作用。     

浇注成型SiAlON结合刚玉质透气砖的研制

以板状刚玉为骨料,Al2O3微粉、Si粉为主要基 质成分,采用振动浇注成型方式生产SiAlON结合刚玉 质材料。研究了不同结合体系以及Si粉和烧结助剂加 入量对材料性能的影响。选择水化结合体系,Si粉加入 量9.5%,烧结助剂0.5%的配方进行抗渣性研究,探讨 材料的抗渣机理。在实验室工作基础上于工业氮化炉 内于1450℃左右氮化烧成,生产出强度高,热震稳定性 和抗渣性能良好的SiAlON结合刚玉质透气砖。     

SiC/SiC复合材料及其应用

日本开发的Nicalon和Tyranno两种品牌的SiC纤维占有世界上绝对性的市场份额。SiC/SiC复合材料典型的界面层是500 nm厚的单层热解碳(PyC)涂层或多层(PyC-SiC)n涂层,在湿度燃烧环境及中高温条件下界面层的稳定性是应用研究的重点。SiC/SiC复合材料,包括CVI-SiC基体和日本开发的Tyranno hex和NITE-SiC基体等,具有耐高温、耐氧化性和耐辐射性的特点,在航空涡轮发动机部件、航天热结构部件及核聚变反应堆炉第一壁材料等方面正开展工程研制应用。     

Microstructure and tensile behavior of (BN/SiC)n coated SiC fibers and SiC/SiC minicomposites

Interphase plays an important role in the mechanical behavior of SiC/SiC ceramic-matrix composites (CMCs). In this paper, the microstructure and tensile behavior of multilayered (BN/SiC)_n coated SiC fiber and SiC/SiC minicomposites were investigated. The surface roughness of the original SiC fiber and SiC fiber deposited with multilayered (BN/SiC), (BN/SiC)₂, and (BN/SiC)₄ (BN/SiC)₈ interphase was analyzed through the scanning electronic microscope (SEM) and atomic force microscope (AFM) and X-ray diffraction (XRD) analysis. Monotonic tensile experiments were conducted for original SiC fiber, SiC fiber with different multilayered (BN/SiC)_n interfaces, and SiC/SiC minicomposites. Considering multiple damage mechanisms, e.g., matrix cracking, interface debonding, and fibers failure, a damage-based micromechanical constitutive model was developed to predict the tensile stress-strain response curves. Multiple damage parameters (e.g., matrix cracking stress, saturation matrix crack stress, tensile strength and failure strain, and composite’s tangent modulus) were used to characterize the tensile damage behavior in SiC/SiC minicomposites. Effects of multilayered interphase on the interface shear stress, fiber characteristic strength, tensile damage and fracture behavior, and strength distribution in SiC/SiC minicomposites were analyzed. The deposited multilayered (BN/SiC)_n interphase protected the SiC fiber and increased the interface shear stress, fiber characteristic strength, leading to the higher matrix cracking stress, saturation matrix cracking stress, tensile strength and fracture strain.     

Growing SiC Nanowires on Tyranno-SA SiC Fibers

A new in situ process for growing SiC nanowires on Tyranno-SA SiC fibers (2-D, plain-woven) was developed using the thermal decomposition of methyltrichlorosilane in hydrogen. The process was performed using a chemical vapor infiltration system. β-SiC nanowires ∼100-nm thick and several tens of micrometers long were successfully synthesized on the fibers. The growing of the SiC nanowires suggests a conditions-dependent process.     

基于核应用下碳化硅陶瓷及其复合材料的连接研究进展

SiC陶瓷及其复合材料凭借其自身固有的核辐射下的稳定性而有望成为新一代核裂变以及未来核聚变反应堆中重要的结构材料.能否满足核应用环境下各种苛刻条件而实现完美连接是其能够得到最终应用的关键.本文综述了目前国际上基于核应用上SiC陶瓷及其复合材料的几种连接工艺的发展情况.     

Densification and enhancement of SiC particulate-reinforced fine-grain SiC ceramic

Dense sintering of SiC nanopowder under low temperature and pressure remains a big challenge, because of the great resistance caused by the severe agglomeration of nanopowder. A novel sintering strategy is proposed to prepare SiC composite ceramics by sintering the mixture of SiC nanopowder and SiC micron powder at low temperature and pressure. The SiC micron powder was in the size of 100 µm with little sintering activity, which was designed as a pressure conductor to promote the densification of SiC nanopowder. Experimental results showed that the SiC micron powder had a significant effect on increasing of the sintering density of nanopowder and improving the mechanical properties of SiC ceramics. An SiC composite ceramic with a relative density of 98%, a Vickers hardness of 22.6 GPa, and a fracture toughness of 5.43 MPa m^1/2 could be sintered by spark plasma sintering under 1700°C and 30 MPa by adding 30 wt.% 100 µm SiC micron powder as reinforcements.     

TEM structure of (PyC/SiC)n multilayered interphases in SiC/SiC composites

Two generations of multilayered interphases, composed of carbon and silicon carbide, have been developed to act as a mechanical fuse in SiC/SiC composites with improved oxidation resistance. Pyrocarbon is an ideal interfacial material, from the mechanical point of view, whereas SiC has a good oxidation resistance. In the multilayered interphase, the carbon mechanical fuse is split into thin sublayers, each being protected against oxidation by the neighbouring SiC-based glass former layers. A first generation of multilayers as synthesised by means of isobaric-CVI with sublayers with micrometric thickness. Then, in order to push forward the concept, pressure pulsed-CVI was involved to deposit nanometric scale sublayers. In this work, transmission electron microscopy was developed to characterise the two generations of materials. The microstructure of the layers and the influence of the fibrous preforms on the structure of the layers were studied. Examinations were then performed on the loaded samples and damaging mode characterised at nanometric scale.     

SiC/SiC minicomposites with structure-graded BN interphases

BN interphases in SiC/SiC minicomposites were produced by infiltration of fibre tows from BF₃–NH₃–H₂ gaseous system. During interphase one-step processing, the tow travels through a reactor containing a succession of different hot areas. By TEM characterization, the BN interphases were found to be made of a structural gradient: from isotropic to highly anisotropic. The very first coating is poorly organised and allows to protect the fibre from a further chemical attack by the reactant mixture. The minicomposites were tensile tested at room temperature with unloading-reloading cycles. The BN interphases act as mechanical fuses; the fibre/matrix bonding intensity ranges from weak to rather strong depending on the tow travelling rate during interphase infiltration. The specimen lifetimes at 700°C under a constant tensile loading were measured in dry and moist air. Compared to a pyrocarbon reference interphase, the BN interphases significantly improve the oxidation resistance of the SiC/SiC minicomposites.     

Polymer-derived SiC ceramic aerogels with in-situ growth of SiC nanowires

Herein, the SiC ceramic aerogels with in-situ growth of SiC nanowires (SiC_w/SiC CAs) have been synthesized by polymer‐derived ceramics (PDCs) method. The morphology, microstructure, and phase composition of the as-prepared samples were systematically investigated through SEM, XRD, TEM, Raman spectrum, FT-IR spectrum, and XPS spectrum techniques. The results showed that the as-obtained SiC_w has a diameter of about 80 nm and a length of 1–3.5 μm. In addition, the formation mechanism and evolution process of growth SiC_w were systematically studied using a VLS growth mechanisms. The way in this work could be expanded to synthesize other Si-based porous ceramic aerogel nanostructed with nanowires.     

Effect of BN nanoparticle content in SiC matrix on microstructure and mechanical properties of SiC/SiC composites

BN-nanoparticle-containing SiC-matrix-based composites comprising SiC fibers and lacking a fiber/matrix interface (SiC/BN + SiC composites) were fabricated by spark plasma sintering (SPS) at 1800°C for 10 min under 50 MPa in Ar. The content of added BN nanoparticles was varied from 0 to 50 vol.%. The mechanical properties of the SiC/BN + SiC composites were investigated thoroughly. The SiC/BN + SiC composites with a BN nanoparticle content of 50 vol.%, which had a bulk density of 2.73 g/cm³ and an open porosity of 5.8%, exhibited quasiductile fracture behavior, as indicated by a short nonlinear region and significantly shorter fiber pullouts owing to the relatively high modulus. The composites also exhibited high strength as well as bending, proportional limit stress, and ultimate tensile strength values of 496 ± 13, 251 ± 30, and 301 MPa ± 56 MPa, respectively, under ambient conditions. The SiC fibers with contents of BN nanoparticles above 30 vol.% were not severely damaged during SPS and adhered to the matrix to form a relatively weak fiber/matrix interface.     

Synthesis of V-doped SiC powder for growth of semi-insulating SiC crystals

V-doped semi-insulating (VDSI) SiC crystal is a promising substrate for high-frequency electronic devices achieved using GaN epitaxial films. However, V doping in a SiC crystal is difficult to control owing to the different sublimation temperatures of VC and SiC. The amount of V changes depending on the growth sequence, which has been a significant concern in VDSI SiC substrates in terms of wafer reliability.In this study, therefore, we aimed to synthesize a single source by vaporizing Si, C, and V under the same conditions to improve the doping issue in VDSI SiC. We synthesized V-doped SiC powder as the starting material for VDSI SiC substrate based on thermodynamic modeling, and the synthesized powder was used to grow a VDSI SiC crystal via physical vapor transport.Finally, considering the homogeneous V concentration in the grown crystal, the synthesized V-doped SiC was observed to be effective to grow VDSI SiC independent of the growth sequence.