先驱体法制备含异质元素SiC陶瓷纤维的现状与进展

先驱体聚碳硅烷进行物理与化学改性，可以制备出各种含Ti,Zr,Al,B等异质元素的耐温型和吸波型SiC陶瓷纤维。含异质元素的SiC陶瓷纤维，已成为当今SiC陶瓷纤维的发展主流，着承介绍了Si-C、O，Si-Ti、C-O，Si-B-Ti-C，Si-Zr-C-O,Si-Al-C纤维的先驱体的制备及其纤维的性能。介绍了我国含异质元素SiC纤维的现状与进展，指出国内SiC纤维的发展要立足于创新的基础上开发各种高性能SiC纤维，力争做到高起点、高瞻远瞩地发展新型SiC纤维，建立拥有自主知识产权的制备工艺。     

聚铝碳硅烷的制备及应用进展

介绍了碳化硅（SiC）陶瓷纤维、含铝SiC陶瓷纤维的特点,综述了用聚碳硅烷、聚硅碳硅烷、聚二甲基硅烷与乙酰丙酮铝反应制备聚铝碳硅烷先驱体的合成方法,聚铝碳硅烷的化学结构及在制备耐超高温陶瓷纤维和发光陶瓷薄膜中的应用,评述了各种制备工艺的优缺点,提出了当前工作中需要解决的问题,并展望了今后的发展趋势。     

新型耐高温氮化物陶瓷纤维研究进展

介绍了耐高温氮化物陶瓷纤维的种类及制备方法即有机聚合物先驱体转化法;综述了Si3N4,BN,SiBN,SiBN(C)陶瓷纤维的研究进展;重点介绍了SiBN(C)陶瓷纤维的研究现状,并与SiC纤维进行性能对比.指出具有耐高温、透波性等功能结构一体化的SiBN(C)陶瓷纤维是陶瓷纤维的重要发展方向,简化先驱体的合成过程及降...     

先驱体聚碳硅烷的合成研究进展

介绍了近年来先驱体聚碳硅烷(PCS)的制备、性能和应用的研究现状和进展。着重介绍了合成先驱体PCS的主要方法：常压循环热裂解法、高压法、常压催化法和常压高温裂解法。比较了这几种合成方法的优缺点：从用PCS制备陶瓷纤维的用途来说，高压法是一种较成熟的方法，所制备的陶瓷SiC纤维的性能也较好，但装置复杂、成本较高、安全性较差；常压高温裂解法合成装置简单、成本较小、安全性也好，但使用该法制得的陶瓷SiC纤维的性能较差。     

用聚碳硅烷制备柔性疏水型碳化硅纤维毡(英文)

以聚合物先驱体转化法用陶瓷工艺与静电纺丝技术相结合制备了碳化硅(SiC)陶瓷纤维毡。以聚碳硅烷为先驱体,利用静电纺丝技术制备先驱体原纤维毡。原纤维毡经过低温交联和1 000℃以上热解,得到SiC纤维毡。当温度达到1 200℃时,纤维毡为多晶态,保持典型的三维网络结构,纤维直径约为1.1mm。电子探针分析表明,纤维毡化学组成为Si、C、以及少量O元素。SiC纤维毡具有良好的疏水性,疏水角大于130°。1 000℃热解制备的SiC纤维毡的拉伸强度为0.6MPa,断裂伸长率为45%,可应用于高温极端环境。     

先驱体制备SiC纤维的发展历程与研究进展

碳化硅(SiC)纤维具有高强度、高模量、耐高温、抗蠕变、抗氧化等优异性能,是增强耐高温陶瓷基复合材料的关键材料。介绍了先驱体法制备3代SiC纤维的发展历程:从第1代高氧碳含量SiC纤维发展到第2代低氧高碳含量SiC纤维,再到第3代近化学计量比SiC纤维,SiC纤维的微结构从非晶到微晶显著变化,纤维的耐热性能也显著提高。重点比较了第3代近化学计量比SiC纤维(Hi-Nicalon Type S纤维、Tyranno SA和Sylramic纤维等)的性质,结果表明:SiC纤维的热稳定性由近化学计量比SiC微晶的致密度和微结构决定,Sylramic和Tyranno SA纤维的组成和微结构可通过控制Si-C-O纤维的碳热还原反应来实现,烧结助剂的采用及陶瓷烧结工艺的有效应用可提高纤维的致密度。Hi-Nicalon Type S纤维的组成和微结构取决于聚碳硅烷分解过程中特定的气氛和温度。简介了SiC纤维的研究进展并讨论了其发展趋势。     

SiC(Nb)陶瓷纤维先驱体聚铌碳硅烷的合成与表征

为了提高SiC陶瓷纤维的综合性能,利用聚二甲基硅烷热解制得的产物液态聚硅烷(liquid polysilane,LPS)与五氯化铌(NbCl5)反应,制各了含铌SiC陶瓷纤维的先驱体聚铌碳硅烷(polyniobiumcarbosilane,PNCS).研究表明:反应过程中存在LPS裂解重排反应,Si-H键在反应中显示出很高的活性,FNCS分子量的增加是LPS形成的Si-H键与NbCl5发生交联反应的结果,用LPS与NbCl5为原料不但能使铌元素成功地引入到先驱体中并且分布均匀,而且由于其成本比其他原料相对低廉便于大批量合成.利用PNCS制备的Si-Nb-C-O陶瓷纤维平均强度为1.8GPa,平均直径为12 μm,耐高温性能优异.     

γ射线辐照聚碳硅烷先驱丝协同热交联制备高强度碳化硅纤维

采用γ射线在空气中辐照聚碳硅烷(polycarbosilane,PCS)先驱丝,将吸收剂量低于凝胶点剂量的PCS先驱丝在选定条件下作特殊的热交联处理,然后在惰性气氛保护下热解转化为SiC陶瓷纤维.通过红外光谱、热重分析、拉伸强度和氧含量测试研究了聚碳硅烷先驱丝的化学结构、热分解特性的变化以及烧成SiC纤维的结构与性能.结果表明:经热处理PCS的先驱丝形成了三维网络不熔不溶结构,其陶瓷产率高于未经热处理的先驱丝的陶瓷产率;经热交联处理的先驱丝所烧成的SiC纤维抗拉强度达2.3 GPa,较未经热交联处理的先驱丝所制得的SiC纤维的拉伸强度大幅提高;辐照协同热交联法制备的SiC纤维的氧含量低于直接辐照不熔化法制备的SiC纤维的氧含量.     

模压压力对SiC/SiC复合材料力学性能及力学行为的影响

采用热模压辅助聚合物先驱体浸渍裂解工艺制备了国产近化学计量比SiC纤维增强SiC陶瓷基复合材料,通过阿基米德排水法和SEM技术对SiC/SiC复合材料致密化过程进行表征,采用弯曲强度、拉伸强度和断裂韧性对SiC/SiC复合材料力学性能和力学行为进行评价。研究表明,热模压压力是影响材料结构和性能的重要因素,热模压在提升材料致密度的同时,亦造成纤维的损伤。随着热模压压力的增加,SiC/SiC复合材料力学性能先增加后降低。热模压压力适中时,致密度增加因素占优,材料力学性能较为优异;热模压压力较大时候,热模压操作对纤维性能的损伤因素逐渐凸显,基体致密化和纤维损伤两种作用机制相当。     

合成陶瓷纤维材料的制备工艺及发展趋势

作为先进复合材料的增强剂，高性能陶瓷纤维日益引起材料研究人员的广泛关注，并导致了纤维制备方法的不断发展。与其他制备方法相比，先驱体转化法更适用于制备细径、组成结构可调的陶瓷纤维，其中溶胶-凝胶法在制备陶瓷纤维方面已经显示出其优越性，并取得了巨大进展。论述了中国合成陶瓷纤维的起源、种类、性能以及应用，着重介绍了陶瓷纤维的制备方法，并指出了陶瓷纤维的发展趋势。     

Microstructure and Microchemistry of Polymer-Derived Crystalline SiC Fibers

Stoichiometric and near-stoichiometric silicon carbide fibers, derived from the polymer polycarbosilane, have been characterized by scanning Auger and transmission electron microscope techniques. Excess carbon usually appeared in the fibers, but it could be eliminated by controlling processing conditions. The fibers consisted mainly of submicrometer-sized SiC microcrystals, with a considerably twinned and stacking-faulted β-SiC structure. Free carbon, which appeared in the form of graphite, was the only detectable intergranular phase in the nonstoichioinetric SiC fibers, while the stoichiometric SiC fibers contained no detectable second phase whatsoever.     

Preparation and characterization of SiC fibers with diverse electrical resistivity through pyrolysis under reactive atmospheres

Due to their fantastic mechanical and high-temperature resistant properties, SiC fibers with electrical resistivity of different orders of magnitude are of great interest for the fabrication of advanced composites with electromagnetic wave absorbent performance as both structural and functional materials. On the basis of well-developed route to prepare SiC fibers, in this work, we demonstrated a facile strategy to fabricate SiC fibers with electrical resistivity of 10⁻¹–10⁶ Ω cm by simply employing hydrogen and ammonia as the reactive atmospheres. The SiC fibers with different electrical resistivity had favorable morphologies, with uniform elemental distribution and stable C/Si ratio towards the fiber interior. Moreover, these fibers exhibited excellent mechanical strength and high temperature performance. Due to the innovative strategy, convenient operation and scalable preparation, the method in this work can be further extended to prepare SiC base fibers with adjustable electrical resistivity from other precursors.     

Pressureless fabrication of dense monolithic SiC ceramics from a polycarbosilane

This paper presents the pressureless preparation of dense and crack-free near stoichiometric SiC monoliths via cross-linking and pyrolysis of a polycarbosilane, followed by polymer-infiltration-pyrolysis cycles. The composition and the porosity of the samples strongly depend on the processing temperature. Thus, at 1050–1100 °C, the SiC monoliths are X-ray amorphous and exhibit low amounts of oxygen and excess carbon; their porosity was rather high (>10%). Higher processing temperatures induced the crystallization of β-SiC. The removal of oxygen and excess carbon due to CO release allowed for obtaining near-stoichiometric compositions at 1700 °C. However, the residual porosity of the samples increased. The use of the PIP technique led already after six cycles to dense monoliths (residual porosity ca. 0.5%).The present study emphasizes the potential of the polymer processing technique for the fabrication of near stoichiometric and dense SiC monoliths, which might be used for structural applications in harsh conditions.     

Revealing the formation mechanism of the skin-core structure in nearly stoichiometric polycrystalline SiC fibers

The polymer-derived SiC fibers have broad application prospects in the fields of aerospace, nuclear industry and high-tech weapon. Oxygen plays an essential role in adjusting the composition, structure and tensile strength of SiC fibers. Our studies have found that introducing too much oxygen during air curing process will form the skin-core structure in nearly stoichiometric polycrystalline SiC fibers. In order to reveal the formation mechanism of the skin-core structure, gradient oxygen was introduced into the fibers. The morphologies, phase distributions and defects of the fibers were well characterized. By strictly controlling the introduction of oxygen, the polycrystalline product fiber exhibits intragranular fracture behavior and excellent high-temperature resistance. The retention rate of its tensile strength can reach up to 91% and 61% after exposure at 1800 °C for 1 h and 10 h, respectively. The present results give valuable insights into the structural optimization of the nearly stoichiometric polycrystalline SiC fibers.     

碳化硅纤维制备技术研究进展

综述了工业化制备碳化硅 (Si C)纤维技术的研究进展 ,并对化学气相沉积 (CV D)法、先驱体转化法和活性炭纤维 (A CF )转化法这三种碳化硅纤维制备方法的原理、生产工艺路线和各自的优缺点作了系统的评述。认为 CV D法已被淘汰 ,先驱体转化法是目前 Si C纤维制备研究的方向 ,A CF法是实现Si C纤维的应用最佳方法     

Fabrication of nearly stoichiometric polycrystalline SiC fibers with excellent high‐temperature stability up to 1900°C

Due to the extensive applications of SiC fiber‐reinforced composite materials in the fields of aviation, aerospace, and nuclear power, there are increasing demands for SiC fibers with both excellent mechanical performance and high‐temperature stability. In this work, nearly stoichiometric polycrystalline SiC fibers were fabricated using amorphous Si–C–Al–O fibers with excess carbon and oxygen (C/Si = 1.34, O content: 7.74 wt%). The nearly stoichiometric composition (C/Si = 1.05) of the product fibers was achieved by thermal decomposition of the starting fibers. The fibers were well‐crystallized with grain sizes of ~200 nm due to sintering at a high temperature of 1900°C. The fibers exhibited a high tensile strength and a high elastic modulus and were composed of SiC grains with twins and stacking‐faults, exhibiting intragranular fracture behavior. Furthermore, the fibers maintained their original tensile strength after being maintained at 1800°C for 5 hour or at 1900°C for 1 hour under an inert atmosphere, and they exhibited a high strength retention (97%) after exposure at 1300°C for 1 hour under air. The high‐temperature stability and creep resistance of the fibers were comparable to that of commercial Hi‐Nicalon S and Tyranno SA fibers.     

Surface charges and optical characteristic of colloidal cubic SiC nanocrystals

Colloidal cubic silicon carbide (SiC) nanocrystals with an average diameter of 4.4 nm have been fabricated by anisotropic wet chemical etching of microsized cubic SiC powder. Fourier transform infrared spectra show that these cubic SiC nanocrystals contain carboxylic acid, SiH, CH, and CH_x groups. UV/Vis absorption and photoluminescence (PL) spectroscopy clearly indicate that water and ethanol colloidal suspensions of the as-fabricated colloidal samples exhibit strong and above band gap blue and blue-green emissions. The cubic SiC nanocrystals show different surface charges in water and ethanol solutions due to the interaction of water molecules with polar Si-terminated surfaces of cubic SiC nanocrystals. The results explain the distinctive optical characteristics of colloidal cubic SiC nanocrystals in water and ethanol, and reveal that quantum confinement and surface charges play a great role in determining the optical characteristics of colloidal cubic SiC nanocrystals.     

Novel SiC synthesis method applicable to SiC solid phase sintering

Most of the present production processes of SiC sintered bodies require some powder mixing using a mechanical milling process (ball milling, and so on). In this case, relatively long hours are required, and there is the problem of contamination during the preparation process. To avoid these problems, we developed a new process for obtaining a self-sinterable, stoichiometric SiC powder, whose precursor material is water-soluble; the precursor material was synthesized from aqueous silica and citric acid containing a small amount of aluminum compound. In order to obtain the stoichiometric SiC composition, the above aqueous precursor material was adequately cured in air (200°C-400°C); subsequently carbonization reaction (~800°C) in nitrogen atmosphere, carbothermal reduction (~1600°C) in argon atmosphere, and pressureless sintering (~1900°C) were performed. Among these processes, the curing process (cross-linking process) is very important for obtaining the equivalent composition (silica and carbon) for the subsequent carbothermal reduction. In this study, the adequate curing temperature and suitable preparation condition for the carbothermal reduction were investigated for the production of stoichiometric self-sinterable SiC powder. The pressureless sintered body achieved using the obtained SiC powder demonstrated a desirable trans-crystalline fracture behavior.     

Oxide ceramic fibers via dry spinning process—From lab to fab

Oxide fibers preparation and manufacturing capabilities at Fraunhofer-Center HTL are introduced, showing the development and preparation of oxide ceramic fibers from lab scale to pilot scale up to near production scale. As a specific example, the development of an aluminosilicate fiber with mullite composition is discussed in more detail. Fiber development started from nonaqueous sol-gel precursors in the early lab scale. With increasing fiber spinning volume, precursors were switched to water-soluble systems. Transformation from green fiber to ceramic fiber was monitored by thermogravimetric and differential thermal analysis, X-ray diffraction, and scanning electron microscopy. The evolution of ceramic phases, microstructure formation, and the effects on tensile strength and Young's modulus were investigated. Weibull statistics and fracture analysis helped to understand the results. Next step will be the transition from large lab scale to pilot scale, demonstrating manufacturing capability.