Processing,properties and microstructure of SiC foam derived from epoxy-modified polycarbosilane

SiC foams having controlled porosity were fabricated using epoxy modified polycarbosilane (EMPCS). The EMPCS was synthesized by refluxing adequate amount of epoxy and polycarbosilane (PCS) in THF solution at 150 °C. The EMPCS having epoxy content of 0%, 10% and 20% by weight were termed as PCS, 10EMPCS and 20EMPCS respectively. Thermal foaming of the EMPCS was carried out at 1000 °C under inert atmosphere followed by ceramization at 1200, 1400 and 1600 °C under vacuum. The cell size of the ceramized SiC foam was found to be varying between 100 and 700 µm. The ceramized SiC foams were characterized for their density, porosity and compressive strength. Total porosity was found to be 81.8 ± 3.9, 87 ± 4.1 and 90.6 ± 4.6% for the PCS, 10EMPCS and 20EMPCS based SiC foams while their bulk densities were found to be 0.6 ± 0.03, 0.4 ± 0.02 and 0.3 ± 0.01 g/cc respectively. Compressive strength was found to be the highest for the SiC foams ceramized at 1600 °C for all the types of EMPCS. The compressive strength of the 10EMPCS is found to be 2.2 ± 0.2 MPa, 2.5 ± 0.2 MPa and 3.8 ± 0.3 MPa for the foams pyrolyzed at 1200 °C, 1400 °C and 1600 °C respectively while the strength was 1.9 ± 0.1 MPa, 2.1 ± 0.2 MPa and 2.9 ± 0.2 MPa for the 20EMPCS based SiC. The 20EMPCS based SiC foam of thickness 10 mm was exposed to oxy-acetylene flame for 120 s, back face temperature was found to be around 300 °C. Microstructure and phase analysis was carried out to understand the effect of epoxy content and ceramization temperature on physical, mechanical and thermal properties of different types of the SiC foams.     

Porous SiC using polycarbosilane/camphene solutions: Roles of freeze casting parameters

In order to control the pore characteristics and macroscopical performance of porous ceramics, roles of the freeze casting parameters are the key points. Herein, aligned dendritic porous SiC was fabricated by freeze casting of PCS-camphene solutions with different solid loading, freeze front velocity, temperature gradient, and freezing temperature. Influence of these parameters on the microstructure and compressive strength of porous SiC was investigated. With increasing the PCS content, freeze temperature, freeze front velocity or temperature gradient, degree of undercooling of the camphene was increased, resulting in the formation of smaller pore size, decreased porosity and increased compressive strength. Compared to variables of freeze temperature and temperature gradient, increased freeze front velocity was more efficiency in improving the compressive strength of porous SiC, owing to the formation of smaller pore size and longer secondary dendritic crystals. Promising micron-sized porous SiC with high porosity (79.93 vol%) and satisfactory strength (15.84 MPa) was achieved for 10% PCS-camphene solution under optimized freezing conditions.     

Porous SiC ceramics with dendritic pore structures by freeze casting from chemical cross-linked polycarbosilane

In this study, a commercial polycarbosilane (PCS) and divinylbenzene (DVB) were used as the preceramic polymer precursor and crosslinking agent, respectively to form porous silicon carbide (SiC) ceramics by freeze casting DVB/camphene/PCS solutions. Porous silicon carbide (SiC) with a dendritic pore structure and connecting bridges was obtained after pyrolysis at 1200 °C. The effects of DVB and PCS content on the rheological properties of the solution and the morphological characteristics and the compressive strengths of SiC ceramics were investigated. The use of DVB and the resulting chemical cross-linking yielded modified pore characteristics and much lower oxygen content in pyrolyzed SiC compared to the conventional thermal curing method. A compressive strength of 18.7 MPa was obtained for pyrolyzed SiC prepared with 20 wt% PCS and a 0.2 DVB/PCS mass ratio.     

Protecting nuclear graphite from liquid fluoride salt and oxidation by SiC coating derived from polycarbosilane

Modification process has been conducted on commercial nuclear graphite IG-110 (Toyo Tanso Co., Ltd., Japan) by impregnation and pyrolysis of polycarbosilane (PCS) solution for getting the modified IG-110 (M-IG-110) coated by dense SiC coating for molten salt reactor. The microstructure and properties of graphite were systematically investigated and compared before and after the modification process. Results indicated that the M-IG-110 possessed of more excellent integrated properties including molten salt barrier property and oxidation resistance than bare IG-110 due to the filling effect of SiC particles in the pores of M-IG-110 and dense SiC coating adhering to the surface of M-IG-110. The fluoride salt infiltration amount of M-IG-110 under 5 atm was only 1.1 wt%, which was much less than 14.9 wt% for bare IG-110. The SiC coating derived from PCS exhibited remarkable compatibility with graphite substrate under high temperature and gave rise to excellent oxidation resistance of M-IG-110.     

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.     

Modification of polycarbosilane as a precursor with high ceramic yield for oxygen-free SiC fibers

Polycarbosilane (PCS) was modified by addition of 1 wt% polyborazine and subsequent heat treatment at 70-400 °C. The modified PCS exhibited highly improved ceramic yield from original 63% to 78% by heating at 70 °C for 10 h. The molecular weight of the PCS modified at higher temperatures markedly increased, then was rendered infusible but soluble PCS in organic solvent on heating at 300 °C. H-NMR indicated that original PCS was enhanced by dehydrocoupling reaction between Si-H groups. Solution of the modified PCS was hand-drawn to fibers, followed by direct pyrolysis up to 1,400 °C without air-curing step to convert into oxygen-free SiC fibers. The morphology and crystalline phase were determined by SEM and XRD analysis, respectively. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8-10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University. Mr. Cao worked at CNU under co-advisor system.     

Microstructures,dielectric response and microwave absorption properties of polycarbosilane derived SiC powders

Carbon-rich SiC powders with high dielectric loss were prepared via pyrolysis of polycarbosilane (PCS). The effects of pyrolysis temperature on microstructures, dielectric response and microwave absorption properties in X-band (8.2–12.4 GHz) of PCS-derived SiC powders were investigated. The PCS-derived SiC powders are mainly composed of SiC nanocrystal, turbostratic carbon and amorphous phase (SiC and/or C). The size of SiC nanocrystals and the graphitization degree of carbon both increase with the elevation of pyrolysis temperature. Furthermore, the residual carbon is transformed from amorphous into turbostratic structure with a phenomenon of regional enrichment. Moreover, the relative complex permittivity increases notably with the higher pyrolysis temperature. Meanwhile, the dielectric loss tangent increases from 0.19 to 0.57, while the microwave impedance decreases from 73.20 to 53.58. The optimal reflection loss of ?35 dB for PCS-derived SiC powders is obtained when the pyrolysis temperature is 1500 °C, which exhibits a great application prospect in microwave absorbing materials.     

Improved dielectric and electromagnetic interference shielding properties of ferrocene-modified polycarbosilane derived SiC/C composite ceramics

In order to enhance the dielectric and electromagnetic interference shielding (EMI) properties, the SiC/C composite ceramics were fabricated by pyrolysis of ferrocene-modified polycarbosilane. The microstructure evolutions, dielectric properties, EMI and microwave absorption properties of SiC/C composite ceramics were investigated. The increases of both ferrocene contents and annealing temperatures led to the increases of crystallizations of SiC and carbons. Crystallized carbons including carbon nanowires, turbostratic carbons, onion-like carbons and graphene-like carbons were obtained in the materials. The carbon nanowires were longest when the 5 wt.% ferrocene-modified polycarbosilane was annealed at 1250 °C. These carbons played a more important role than SiC in the increases of dielectric and EMI properties. The average real and imaginary permittivities of materials increased from 4.4 and 0.7 to 38.9 and 39.6, respectively. The materials exhibited high total shielding effectiveness, high absorption shielding effectiveness and low reflection shielding effectiveness, which were 36.6, 30.1 and 6.5 dB, respectively.     

Thermostatic pyrolysis process of cured polycarbosilane fiber

As precursor fiber of advanced SiC fiber, cured polycarbosilane (PCS) fiber is prepared, and thermostatic pyrolysis of this fiber is studied in detail. Since the weight change is the most important characteristic of the pyrolysis degree of cured PCS fiber, a precise balance is applied on-line to follow the weight change of the cured PCS fiber, which was carried out in a standing style furnace. In thermostatic pyrolysis, the degree of pyrolysis, which is characterized by the weight loss of the fiber, and the properties of the final SiC fibers were found to be strongly dependent on the process conditions such as N² flow and the amount of fibers. From much evidence, it is the offgas evacuated in the process that plays an important role by accelerating pyrolysis and increasing pyrolysis degree.     

Pressure‐less joining of C/SiC and SiC/SiC by a MoSi2/Si composite

A MoSi₂/Si composite obtained in situ by reaction of silicon and molybdenum at 1450°C in Ar flow is proposed as pressure‐less joining material for C/SiC and SiC/SiC composites. A new “Mo‐wrap” technique was developed to form the joining material and to control silicon infiltration in porous composites. MoSi₂/Si composite joining material infiltration inside coated and uncoated C/SiC and SiC/SiC composites, as well as its microstructure and interfacial reactions were studied. Preliminary mechanical strength of joints was tested at room temperature and after aging at service temperatures, resulting in interlaminar failure of the composites in most cases.     

Effect of in situ grown SiC nanowires on microstructure and mechanical properties of C/SiC composites

Hexagonal-shaped SiC nanowires were in situ formed in C/SiC composites with ferrocene as catalyst in the densification process of polymer impregnation and pyrolysis. The effect of SiC nanowires on microstructure and properties of the composites were studied. The results show that the in situ formed SiC nanowires were hexagonal, mostly with diamer of about 250 nm, and grew by the vapor–liquid–solid (VLS) mechanism. The C/SiC composite with nanowires shows higher bulk density and flexural strength than the one with no SiC nanowires, and the high temperature flexural strength behavior of C/SiC composites with SiC nanowires was evaluated.     

Joining of SiCf/SiC using polycarbosilane and polysilazane preceramic mixtures

Polycarbosilane (PCS)/polysilazane (PSZ) preceramic mixtures with weight ratios of 100/0, 75/25, 50/50, 25/75, and 0/100 were used as a filler for the joining of SiC_f/SiC to obtain high purity SiC at the joining region. SiC_f/SiC was fabricated by the electrophoretic infiltration of a SiC-based matrix phase into Tyranno SA3 SiC fabrics followed by hot-pressing at 1750?°C under 20?MPa for 2?h in an Ar atmosphere. Microstructural analysis confirmed a sound join without cracks after joining at 1750?°C for 2?h under a pressure of 10?MPa. SiC was the only phase remaining at the joint when PCS was used, while a small amount of Si₃N₄ along with the main SiC were observed in the join using PSZ. The flexural strengths of the butt-joint SiC_f/SiC were 120 and 137?MPa for the samples joined using a pure PCS and PSZ at 1750?°C, respectively, whereas those joined using the mixture fillers showed relatively lower strength.     

High-temperature microstructural evolution of SiCN fibers derived from polycarbosilane with different C/N ratios

Research into the high-temperature microstructural evolution of SiCN ceramic fibers is important for the aerospace application of advanced ceramic matrix composites in harsh environments. In this work, we studied the microstructural evolution of SiCN fibers with different C/N ratios that derived from polycarbosilane fibers at the annealing temperature range of 1400∼1600 °C. These results showed that the phase separation of SiC_xN_y phase and the two-dimension grain growth process of free carbon nanoclusters could be processed at the researched temperature range. As the annealing temperature increased to 1600 °C, the crystallization of amorphous SiC and Si₃N₄ could be detected. SEM and Raman analysis showed that the decomposition and carbothermal reduction of the Si₃N₄ phase at high temperatures played primary roles in contributing to the fiber strength degradation. Thus, a higher C/N ratio, which is beneficial for inhibiting the decomposition of amorphous Si₃N₄, helps SiCN fibers retain high tensile strength at high temperatures.     

SiC颗粒增强不饱和聚酯树脂复合材料的力学性能

采用万能试验机和硬度计测试研究了SiC颗粒含量和粒径对不饱和聚酯树脂基复合材料力学性能的影响,通过扫描电子显微镜观察了拉伸试样的端口形貌。结果表明,填充的SiC质量分数为10%时,其不饱和聚酯树脂复合材料拉伸强度达到最大,8000目、1000目SiC填充体系拉伸强度分别为53.2MPa,44.8MPa,较纯树脂体系提高68.1%,41.5%。当SiC质量分数为30%时,SiC填充体系的弹性模量较纯树脂体系提高25.8%以上,硬度提高2.3%以上,SiC颗粒尺寸对复合材料的弹性模量和硬度影响不大。SiC/不饱和聚酯树脂复合材料的断裂属脆性断裂。     

空间望远镜用C/SiC镜面研制综述

综述了空间望远镜的主镜用高强度、高表面精度、低热膨胀系数的低温（约4K）用镜面的制备和检测过程.日本将Φ710mm的高强度反应烧结SiC材料已用于红外望远镜镜面.在短切炭纤维增强C/C复合材料毛坯的基础上进行液相硅渗透（LSI）而制备的C/SiC复合材料在光学镜面方面具有更大的优势.通过提高C/C复合材料毛坯中沥青基炭纤维体积分数及控制硅化速度,可有效地提高LSI-C/SiC复合材料的机械性能和表面光学精度;通过不同规格的炭纤维的混杂化,可使C/SiC复合材料热膨胀系数的各向异性降低至小于4％的差异.SiC、Si-SiC浆料涂层处理可有效地提高表面精度至2 nm rms的极高要求.     

Modeling the pyrolysis of preceramic polymers: A kinetic study of the polycarbosilane SMP-10

A material model was developed to predict changes in mass, density and thus volume of cured preceramic polymers for CMC matrices as they pyrolyze into ceramics. Because part warpage and delaminations are most likely to occur when matrix strain rates and strain rate gradients are the highest, the ability to accurately predict changes in a matrix material’s volume is essential to determining the processing conditions that will efficiently minimize composite scrap rates. Experimental and model analysis of the SiC forming polycarbosilane, SMP-10, revealed that volume shrinkage is initially driven by mass loss, is quickly dominated by density’s contribution, and has both temperature and time at temperature dependencies, where density is not a simple function of mass yield. While material density is rarely reported in the open literature, the ability to predict changes in density is essential to accurately predicting the volume yield of preceramic polymers used in ceramic matrix composites.     

锆石/SiC复合物的抗热震性

测试锆石/碳化硅(30%)复合试样的抗热震性需要在高于1 000℃的温度下进行,并与气孔率值几乎相同的纯锆石试样相比较.结果证实了淬火试样的断裂应力未受到合成SiC微粒对淬火温度升高的影响.另一方面,发现重要的温差△T在复合物中要高于纯锆石试样,低于它时材料保持其初始强度.X-射线衍射分析显示了复合试样表面层的锆石分解并生成了由内核和外壳组成的试样.     

环氧树脂/改性SiC复合材料的制备及性能

采用硅烷偶联剂KH-560和丙烯酰胺对SiC进行表面改性,将其添加到环氧树脂中制备环氧树脂/改性SiC复合材料.采用傅里叶变换红外光谱仪、X射线衍射仪以及接触角测试仪探究改性SiC的性能,并对复合材料的性能进行测试.结果表明:SiC表面带有憎水基团,与环氧树脂相容性提高;SiC用量为环氧树脂质量的20％时,拉伸强度和弯...     

碳化硅/环氧树脂导热复合材料的制备与性能

采用浇铸成型法制备碳化硅/环氧树脂(SiC/EP)导热复合材料,研究了SiC种类、粒径、用量和表面改性方法对SiC/EP复合材料的导热性能、力学性能和热性能等影响。结果表明:SiC/EP复合材料的导热系数随纳米级SiC用量增加而增大,当φ(纳米级SiC)=17.80%时,导热系数为0.954 6 W/(m.K);SiC/EP复合材料的弯曲强度和冲击强度随纳米级SiC用量增加均呈先升后降态势,当φ(纳米级SiC)=3.50%时,两者均达到最大值。SiC经表面改性后可有效提高复合材料的导热性能和力学性能,并且改性SiC的加入可有效降低EP的玻璃化转变温度。     

The effect of high temperature heat treatment on the tribological property of a carbon fiber/pyrolytic carbon/silicon carbide composite using polycarbosilane

The carbon fiber/pyrolytic carbon/silicon carbide (C_f/SiC) composite was prepared by precursor infiltration and pyrolysis (PIP), and the link between antifriction effect and microstructure evolution of the composite by increasing heat treatment temperature was studied by a reciprocating pin-on-disk configuration under dry sliding condition. The results indicate that the changing structure of fiber-matrix interface and SiC matrix of the composite by increasing heat treated temperature could influence the carbon content of friction surface, resulting an obvious difference in tribological property. The friction coefficient is reduced 24.3%, 26.8%, 33.9% at different test frequencies after 1800 °C heat treatment without aggravating wear. The finding paves us an effective way to modify the tribological property of C_f/SiC composite (PIP).