Mechanical Properties of Silicon Oxycarbide Ceramic Foams

The mechanical properties of ceramic foams obtained through a novel process that uses the direct foaming and pyrolysis of preceramic polymer/polyurethane solutions were investigated. The elastic modulus, flexural strength, and compressive strengths were obtained for foams in the as-pyrolyzed condition; values up to 7.1 GPa, 13 MPa, and 11 MPa, respectively, were obtained. The strength of the foam was virtually unchanged at temperatures up to 1200°C in air; however, long-term exposure at 1200°C led to a moderate degradation in strength, which was attributed to the evolution of intrastrut porosity during the oxidation of residual free carbon, as well as devitrification of the foams struts.  

聚硅氧烷先驱体转化制备三维Cf/Si-O-C复合材料的研究

研究了含氢聚硅氧烷(PSO)与二乙烯基苯(DVB)的交联与裂解。结果表明:只有在氯铂酸的催化作用下,PSO与DVB才能完全交联。DVB/PSO质量比对陶瓷产率的影响较大,DVB/PSO＝0.5时陶瓷产率最高,达到76%。裂解产物中Si,C,O的含量分别为38.3wt%,34.3wt%,27.4wt%。以质量比为0.5的DVB/PSO体系为先驱体,采用先驱体转化法制备出三维C_f/Si-O-C复合材料。研究发现:第一次裂解时采用热压辅助可以明显提高材料的力学性能。第一次在1600℃,10MPa的条件下热压裂解5min,后续真空浸渍-常压裂解处理六个周期所制得的材料具有较高的力学性能,其弯曲强度和断裂韧性分别为502MPa,23.7MPa·m 1/2。理想的界面结合状态是其具有高性能的主要原因。  

Ceramic Microtubes from Preceramic Polymers

A novel process for the production of ceramic microtubes involving the microextrusion of preceramic polymers was studied. Microtubes with a wide range of inner and outer diameters and several centimeters long were produced from two silicone resins. A coextrusion approach was also used to extend the forming capability of the technique. The addition of carbon black resulted in electrically conductive silicon oxycarbide (SiOC) ceramic microtubes. SiOC microtubes possessed a high bending strength, ranging from ∼30–1100 MPa.  

Thermal Shock Behavior of Silicon Oxycarbide Foams

Silicon oxycarbide (SiOC) ceramic foams, obtained from the pyrolysis of a preceramic polymer, were subjected to thermal multiple cycles from 800°–1200°C to room temperature in a water bath. Flexural and compression strengths, as well as elastic modulus, were characterized before and after quenching. Excellent thermal shock and cycling resistance behavior was observed, with only moderate strength and stiffness degradation. The phase assemblage of the foam remained unchanged, and no crack formation in the foams was observed. However, microstructural characterization revealed the development of porosity in the struts and cell walls due to the oxidation of residual carbon in the amorphous SiOC material, thereby contributing to a small decrease in stiffness after quenching.  

Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy Study of Nonstoichiometric Silicon-Carbon-Oxygen Glasses

Crystallization behavior of Si-C-O glasses in the temperature range of 1000°–1400°C was investigated using transmission electron microscopy (TEM) in conjunction with electron energy-loss spectroscopy (EELS). Si-C-O glasses were prepared by pyrolysis of polysiloxane networks obtained from homogeneous mixtures of triethoxysilane, T^H, and methyldiethoxysilane, D^H. Si-C-O glass composition depended on the molar ratio of the precursors utilized. At a ratio of T^H/D^H= 1, the formation of a carbon-rich glass was observed, whereas a ratio of T^H/D^H= 9 yielded a Si-C-O glass with excess free silicon. Both materials were amorphous at 1000°C, but showed a distinct difference in crystallization behavior on annealing at high temperature. Although T^H/D^H= 1 revealed a small volume fraction of SiC precipitates in addition to a very small amount of residual free carbon at 1400°C, T^H/D^H= 9 showed, in addition to SiC crystallites, numerous larger silicon precipitates (20–50 nm), even at 1200°C. Both materials underwent a phase separation process, SiC _x O_2(1-x)→ x SiC + (1 - x )SiO₂, when annealed at temperatures exceeding 1200°C.  

热压辅助先驱体裂解制备三维编织碳纤维增强Si-O-C复合材料的研究

以聚硅氧烷为先驱体 ,采用先驱体转化法制备三维编织 Cf/ Si- O- C复合材料。研究发现 ,第一次裂解时采用热压辅助可以明显提高材料的致密度和力学性能。第一次在 1 6 0 0℃ / 1 0 MPa的条件下热压裂解 5 min,后续真空浸渍 -常压裂解处理六个周期所制得的材料具有较高的力学性能 ,其弯曲强度和断裂韧性分别为 5 0 2 MPa,2 3 .7MPa.m1 /2 。讨论了制备工艺对材料结构和性能的影响 ,理想的界面结构与较高的致密度是其具有高性能的主要原因  

以聚硅氧烷为先驱体制备Al-SiCp/Si-O-C陶瓷复合材料

以聚硅氧烷为先驱体,SiC为惰性填料,Al为活性填料,考察了活性填料Al在聚硅氧烷转化制备Si-OC复合材料中的应用.研究发现:600℃时,活性填料Al能与聚硅氧烷裂解产生的含碳小分子气体反应生成Al4C3,800℃时能与N2反应生成AlN;这2个反应同时伴有体积膨胀,能有效弥补聚硅氧烷裂解时的线收缩.活性填料Al的引入能起到增强作用;含20%Al(体积分数)的SiC/Si-O-C复合材料的弯曲强度是不含Al的1.36倍;活性填料Al的引入能显著改善SiC/S-O-C复合材料的耐高温和抗氧化性能,但不能提高其抗热震性能.  

Chemical Durability of Silicon Oxycarbide Glasses

Silicon oxycarbide (SiOC) glasses with controlled amounts of Si—C bonds and free carbon have been produced via the pyrolysis of suitable preceramic networks. Their chemical durability in alkaline and hydrofluoric solutions has been studied and related to the network structure and microstructure of the glasses. SiOC glasses, because of the character of the Si—C bonds, exhibit greater chemical durability in both environments, compared with silica glass. Microphase separation into silicon carbide (SiC), silica (SiO₂), and carbon, which usually occurs in this system at pyrolysis temperatures of >1000°–1200°C, exerts great influence on the durability of these glasses. The chemical durability decreases as the amount of phase separation increases, because the silica/silicate species (without any carbon substituents) are interconnected and can be easily leached out, in comparison with the SiOC phase, which is resistant to attack by OH⁻ or F⁻ ions.  

Synthesis and Characterization of Silicon Oxycarbide Glasses

It has been found that X-ray amorphous silica glasses containing up to 18% carbon can be synthesized using a sol/gel process. In this study, the sols were prepared using four different organometallic precursors—methyl-, ethyl-, propyl-, and phenyltrimethoxysilanes. ¹H NMR,¹³C NMR, and TGA revealed that the methoxy groups are hydrolyzed in the solutions and, therefore, are absent in the gels. But the alkyl groups are retained in the dry gels. The ²⁹Si NMR data verified that the Si—C bonds associated with these alkyl groups are intact in the dry gels. Most importantly, however, Si—C bonds are found in the glasses obtained after heat-treating the gels at high temperature in an inert atmosphere; i.e., the synthesis does, in fact, create an oxycarbide network structure. TGA showed that the dense oxycarbide glasses are stable to 1000°C in argon and in air.  

Phase Separation in an SiCO Glass Studied by Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy

SiCO glasses prepared from sol–gel precursors via pyrolysis in argon at temperatures ranging from 1000° to 1400°C were studied by transmission electron microscopy (TEM), in conjunction with electron energy-loss spectroscopy (EELS). EELS analysis showed that stoichiometric SiCO glass underwent phase separation, forming SiO₂- and SiC-based environments. This process started at ∼1200°C. However, at temperatures >1300°C, precipitation of nanometer-sized SiC particles embedded in vitreous SiO₂ was monitored by high-resolution TEM.