TiH2在裂解聚碳硅烷制备复合材料中的应用

研究ＴｉＨ２粉在以聚碳硅烷为先驱体裂解制备ＳｉＣ陶瓷材料中的应用,结果表明,ＴｉＨ２粉能缓和聚碳硅烷的裂解反应,增加先驱体的陶瓷产率,提高陶瓷材料性能,然而,先驱体在裂解过程中的线性收缩率和气孔率却随着ＴｉＨ２粉的加和气孔率却随着ＴｉＨ２粉的加入而增加。     

铬粉在裂解聚碳硅烷制备陶瓷材料中的应用

研究了Cr粉在以聚碳硅烷（PCS）为先驱体裂解制备SiC陶瓷材料中的应用。结果表明,Cr在较低的温度下减慢PCS的裂解反应,在较高的温度下则加剧PCS的裂解,且能增加先驱体的陶瓷产率,降低先驱体在裂解 的线性收缩率和气孔率,提高陶瓷材料性能。     

活性填料在先驱体转化制备陶瓷材料中的应用

综述了用先驱体法制备陶瓷材料的特点,针对先驱体法气孔率高及收缩率大的不足,提出了三个解决办法,其中着重讨论了活性填料的选择原则及其在先驱体裂解制备陶瓷中的特点、应用及国内外研究现状．     

活性填料在先驱体转化陶瓷基复合材料及其构件中有应用

有机聚合物先驱体由于其分子可设计性好、成型方便、低温裂解转化为陶瓷的特点,在陶瓷纤维和纤维增韧陶瓷基复合材料的制备中表现出极大的优势。针对先驱体转化法体积收缩大、孔隙率高的不足,在先驱体中引入适当的活性填料是解决其不足的有效方法。以聚碳硅烷(PCS)为 SiC 陶瓷的先驱体,以金属(Al、Cr、Mo、Ta、Ti、W、Zr)、非金属(B、Si)及其化合物(CrSi_2、TiH_2、TiB_2)微粉为活性填料,对活性填料控制的 PCS 裂解陶瓷的陶瓷产率、线收缩率、密度、力学性能、产物结构等进行了系统的研究。对活性填料控制的 PCS 先驱体裂解陶瓷的尺寸变化进行了模型分析。从理论上揭示了活性填料的临界体积分数与活性填料反应的产率、反应前后的密度比之间的相关性。通过对 PCS/Al/SiC/N_2裂解体系反应热力学参数的计算,从理论上预测可能发生的反应与不可能发生反应。将热分析反应动力学方法应用到活性填料 Al 控制的 PCS 先驱体的裂解中。分别研究了 N_2中纯 PCS、纯 Al、Al/SiC、PCS/Al/SiC 体系各阶段的表观活化能及其裂解-反应机理函数以 X 射线衍射,电子显微镜元素线扫描等方法对 PCS/Al/SiCN_2体系的裂解-反应机理进行研究。在含活性填料的先驱体转化法制备纤维复合材料的致密化-密度增长模型中,引入体积收缩率的参数,对先驱体转化法纤维复合材料的密度增长模型进行了修正。将活性填料 Al 应用到单向 M40JB 纤维和吉林碳纤维增强 SiC 陶瓷基复合材料及反坦克导弹陶瓷喷管的制备工艺中,并对裂解产物进行了表征,获得很好的效果。这一结果对促进先驱体转化法陶瓷构件在武器装备中的应用具有重要意义。     

活性填料在制备陶瓷基复合材料中的应用

研究了Ｔｉ,ＴｉＨ２等活性填料在聚碳硅烷先驱体裂解制备ＳｉＣ陶瓷材料中的应用,Ｔｉ、ＴｉＨ２等可增加聚碳硅烷的裂解陶瓷产率,可与Ｎ２气氛反应生成氮化物,导致体积膨胀而降低陶瓷的气孔率,提高材料性能。     

先驱体转化陶瓷涂层的裂解方法研究进展

随着金属零部件服役工况条件的日益苛刻,针对金属零部件不同的服役条件和失效特点,选择不同的陶瓷材料体系,采用适当工艺技术在金属零部件表面制备高性能的陶瓷涂层防护涂层并赋予其特殊功能,已成为解决金属零部件在苛刻工况下可靠服役的有效途径.先驱体转化陶瓷法作为一种原位制备陶瓷涂层的新型方法,利用先驱体聚合物良好的流动性、成型性、分子结构可设计性等特点,将先驱体涂层通过裂解转化为陶瓷涂层,在材料表面形成致密的防护涂层.裂解是先驱体从有机物转化为陶瓷涂层的重要途径,传统加热炉裂解利用程序化升温可在金属、多孔材料、纤维或纤维增强复合材料表面实现陶瓷涂层的连续化、批量化制备,设备简单,易于控制,但加热炉裂解对基体的热影响大,无法在熔点较低或结构复杂的基体上制备陶瓷涂层.激光裂解可选择性地控制热量的输入,裂解迅速、加热均匀,对基体热影响小,可制备出具有特殊成分的陶瓷涂层,但先驱体要能够吸收激光,激光裂解效率较低.离子辐照是无热裂解方式,裂解迅速,但效率低、成本较高.本文总结了先驱体转化陶瓷涂层裂解方法的研究进展,分析了加热炉裂解、激光裂解和离子辐照裂解的优缺点.未来将探索新的可控制备陶瓷涂层的方法与技术,揭示先驱体转化陶瓷微观结构的演变规律,实现陶瓷涂层致密化和裂纹缺陷的精确控制是今后需要重点发展的方向.     

微波烧结工艺制备陶瓷材料的研究现状

微波烧结作为一种陶瓷制备工艺,因其与传统烧结工艺相比体现出快速高效、节能环保等一系列优点而备受关注.主要介绍了采用微波烧结工艺制备陶瓷材料及陶瓷基复合材料的特点；在先驱体裂解、粉末烧结制备陶瓷材料方面对微波烧结工艺与传统烧结工艺进行比较,表明微波烧结工艺是一种极具潜力的技术；最后提出微波烧结工艺在未来发展过程中亟待解决的若干问题.     

由有机硅油和铝粉制备Si-Al-O-N-C陶瓷粉末

用高含氢硅油HPSO与二乙烯三胺反应交联制备了稳定的Si-O-N-C溶胶,然后加入活性组分Al粉制备了Si-Al-O-N-C先驱体凝胶,并在N2气中裂解,制备了Si-Al-O-N-C陶瓷粉末.用FT-IR、TG/DTA、XRD和TEM研究了先驱体的热分解转化过程.研究表明:得到的Si-Al-O-N-C陶瓷粉末中含有非晶相和Si、AlN、SiC、Al3O3N微晶,粉体颗粒呈球形,其粒径在50～150 nm左右.     

活性填料铬在取碳硅烷裂解陶瓷中的应用

研究了活性填料铬（Ｃｒ）在聚碳硅烷（ＰＣＳ）先驱体裂解陶瓷中的应用。研究表明,活性填料Ｃｒ能有效降低陶瓷素坯的气孔率。Ｃｒ可与ＰＣＳ气态裂解产物和Ｎ２气氛反应生成新的化合物,可明显提高ＰＣＳ的陶瓷产率。当Ｃｒ／ＰＣＳ为３５％ｖｏｌ时,坯体的陶瓷产率为１００％。在先驱体中引入Ｃｒ能有效地抑制坯体在裂解过程中的收缩。Ｃｒ含量越高,素坯裂解后的收缩越小。当Ｃｒ／ＰＣＳ为４６％ｖｏｌ时,素坯在裂解前后线收     

先驱体陶瓷

综述了用先驱体法制备陶瓷纤维、陶瓷基复合材料等的特点及其研究进展,针对制备陶瓷基复合材料基体的有机聚合物先驱体,提出了先驱体必须满足的理化特性和结构特征,同时还针对先驱体法高气孔率及高收缩率的不足,提出了３个解决办法,并着重讨论了活性填料在先驱体裂解制备陶瓷基复合材料中的特点与应用。     

活性填料铬在聚碳硅烷裂解陶瓷中的应用

研究了活性填料铬 (Cr)在聚碳硅烷 (PCS)先驱体裂解陶瓷中的应用。研究表明 ,活性填料 Cr能有效降低陶瓷素坯的气孔率。 Cr可与 PCS气态裂解产物和 N2 气氛反应生成新的化合物 ,可明显提高 PCS的陶瓷产率。当 Cr/ PCS为 3 5% vol时 ,坯体的陶瓷产率为 1 0 0 %。在先驱体中引入 Cr能有效地抑制坯体在裂解过程中的收缩。Cr含量越高 ,素坯裂解后的收缩越小。当 Cr/PCS为 4 6% vol时 ,素坯在裂解前后线收缩率为 0 ;由于生成产物的体积效应较大 ,以及与 Si C热膨胀系数的不匹配性 ,导致陶瓷烧成体强度有所下降。用 X-衍射法 (XRD)分析了烧成产物的物相组成 ,扫描电子显微镜 (SEM)观察了陶瓷烧成体的断口形貌。     

活性填料钼在聚碳硅熔转化陶瓷中的应用

研究了活性填料钼（Mo）在聚碳硅烷（PCS）先驱体转化陶瓷中的应用。研究表明,活性填料Mo能有效降低陶瓷素坯的气孔率。Mo可与PCS气态裂解碳氢产物、游离碳和N2气氛反应生成新的化合物,可明显提高PCS的陶瓷产率。当Mo/PCS为25％（vol)时,坯体的陶瓷产率为100％。Mo还有能效地提高烧成体的强度。     

Synthesis and properties of ceramic fibers from polycarbosilane/polymethylphenylsiloxane polymer blends

We synthesized ceramic fibers based on silicon carbide (SiC) from polymer blends of polycarbosilane (PCS) and polymethylphenylsiloxane (PMPhS) by melt-spinning and radiation curing. PMPhS was compatible with PCS up to 30 mass%, and formed a transparent melt at temperatures higher than 513 K. The softening point was also lowered by adding PMPhS and 15 mass% of PMPhS to PCS was the most suitable condition for obtaining thin fibers with an average diameter of 14.4 μm. Due to the lowered softening point of the PCS–PMPhS fibers, γ-ray curing in air was adopted. The ceramic yield of the cured fiber was 85.5% after pyrolysis at 1273 K. In spite of the small diameter, the resulting tensile strength at 1273 K was rather limited at 0.78 GPa. Blooming of the PMPhS component during pyrolysis may have caused surface defects. After high-temperature pyrolysis at 1673–1773 K, a porous nanocrystalline SiC fiber with a unique microstructure was obtained with surface area of 70–150 m²/g. When the fiber was pyrolyzed at the same temperature under a highly reductive atmosphere, wire bundle-shaped fibers were obtained by gas evolution and reactions.     

3D Cf/SiC抗高温氧化复合材料的制备及其构件的工程试验

采用低分子量聚碳硅烷(PCS)通过先驱体浸渍裂解(PIP)工艺、化学气相沉积(CVD)和粉末烧结技术相结合制备了3D C_f/SiC抗高温氧化复合材料。运用FTIR、¹H-NMR、凝胶渗透色谱法(GPC)、热失重-差热(TGA-DTA)、X射线衍射仪(XRD)和透射电子显微镜(TEM)等手段研究了低分子量PCS的结构及其无机化过程。结果表明: PCS的主要结构为[—Si(CH₃,H)—CH₂—]n,数均分子量为420,陶瓷化产率为70％左右,在1 200 ℃时基本转化为微晶态的β-SiC;3D C_f/SiC复合材料及其构件具有较好的耐高温氧化性能。     

Electron spin resonance studies of amorphous and crystallized residues derived from pyrolysis of pre-ceramic polymers

ESR spectra are presented for pyrolysis residues derived from 5 pre-ceramic polymers: polycarbosilane (PCS), hydridomethylcyclosilazane (HMCS), hydridomethylcyclopolysilazane (HMCPS), polydiphenylsilazane (PDPS) and polymethylsilylethylenediamine (PMSED). The amorphous black and white residues derived from 1100°C pyrolysis in N2 and NH3, respectively, exhibit symmetric peaks with g values of 2.003. This is compatible with values obtained for unpaired spins existing in carbon impurities that remain in the ceramic residues after pyrolysis of the organosilicon precursor polymers. The spin concentrations of black residues obtained from pyrolysis of pre-ceramic polymers at 1100°C in N2 are invariably higher in magnitude than those measured for white-grey residues generated by initial 1100°C-NH3 pyrolysis of pre-ceramic polymers showing that the NH3 pyrolysis removes polymer-associated carbon more efficiently from ceramic residues than 1100°C-N2 pyrolysis. The Si2N2O/Si3N4 powders produced are purer and have lower ESR activity than commercial Si3N4. When the black residues are crystallized at 1550°C under Ar, carbon is removed and the ESR activity reduced. The ESR signal becomes asymmetric and exhibits some partially resolved structure. Crystallization of white-grey residues is accompanied by an overall increase in ESR activity caused in part by the uptake of carbon from the graphite resistance furnace. For the PCS- and PDPS-derived white-grey residues, additional ESR activity probably arises from the creation of defects in the crystalline Si2N2O formed as a result of the 1550°C firing. In general, ESR properties of the pyrolytic residues correlate well with the relative conducting properties of the corresponding ceramic coatings.     

低分子量聚碳硅烷制备3D-Cf/SiC复合材料

研究了低分子量聚碳硅烷 (PCS) 通过先驱体浸渍裂解 (PIP) 工艺制备C_f/SiC复合材料。分析表明:PCS的数均分子量为400,活性较强,陶瓷化产率为70％左右,在1200℃基本转化为微晶态的β-SiC。分别通过3种不同升温速率制备了3D-C_f/SiC复合材料试样,其弯曲强度分别为745.2MPa、686.7MPa和762.5MPa,明显高于文献报道3D-C_f/SiC复合材料弯曲强度300~500MPa的水平。试样断口的SEM照片均显示长的纤维拔出,有良好的增韧效果,低分子量PCS裂解得到的基体比较致密。实验结果说明,低分子量PCS适合于制备3D-C_f/SiC复合材料,并且提高升温裂解速率对材料性能影响很小。      

Synthesis of SiC ceramic fibers from nuclear reactor irradiated polycarbosilane ceramic precursor fibers

Polycarbosilane (PCS) ceramic precursor fibers are irradiated in a nuclear reactor and pyrolyzed under inert atmosphere. Bridge structure of Si–CH₂–Si is formed in the irradiated products by the rupture of Si–H bonds and succeeding cross-linking. When irradiated at the neutron fluence of 2.2 × 10¹⁷ cm⁻² under N₂ atmosphere, the gel content and ceramic yield at 1,273 K of PCS fibers are up to 80% and 94.3%, respectively, and their pyrolysis products are still fibrous, which illuminates that the infusibility of PCS fibers has been achieved. FT-IR spectra indicate that the chemical structure of pyrolysis products is very similar to that of pure SiC, while X-ray diffraction curves suggest that β-SiC microcrystals are formed in the fibers, and their mean grain size is about 7.5 nm. The oxygen content (1.69–3.77 wt%) is much lower than that of conventional SiC fibers by oxidation curing method (about 15 wt%). Tensile strength of the SiC fibers is up to 2.72 GPa, which demonstrates that their mechanical properties are excellent. After heat-treated at 1,673 K in air for an hour or at 1,873 K under Ar gas atmosphere for 0.5 h, their external appearance is still undamaged and dense, and their tensile strength decreases to a small extent, which verifies that heat resistance of the SiC fibers is eximious.