Organometallic polymer-derived interfacial coatings on carbon and SiC fibers

Organosilicon and organogermanium polymers containing unsaturated carbon–carbon bonds were used as precursors for the SiC-based interfacial coatings on commercially available carbon and silicon carbide fibers and fabrics. The approach based on usage of the organometallic polymer solutions allowed to obtain uniform, adherent, crack-free and non-bridging SiC-based interfacial coatings on carbon and SiC fibers. The coated fibers retain their tensile strength. The morphology, composition, structure of coated fibers were evaluated by various analytical techniques. The drop-like germanium-containing phase was detected in the organogermanium polymer-derived coating on carbon and SiC fibers.     

Effect of the fabrication process on the microstructural evolution of carbon fibers and flexural property on C/SiC composites by the NITE method

Nano-infiltration and transient eutectic phase (NITE) SiC matrix composites are designed for application in aerospace propulsion systems, particularly in fasteners and thrusters. A variety of carbon fibers with different properties have been selected as reinforcements for SiC matrix composites. Carbon fibers are known to be stable at high temperatures; however, the effects of high applied pressure at high temperatures on the fiber microstructure evolution and mechanical properties are not well-known. As a scoping study for fabricating NITE C/SiC composites, the behaviors of various carbon fibers in SiC composites. Pitch-based fibers, namely, GRANOX XN-05 and YS-90A, and a polyacrylonitrile-based fiber, namely, TORAYCA T-300B, were selected for matrix reinforcement. The 3-point bending test results indicated pseudo-ductile behaviors in the cases of YS-90A and T-300B fiber reinforcements. Fracture resistance evaluation based on the single-notch bending test indicated that the YS-90A fiber reinforced composite afforded the highest fracture resistance among the three C/SiC composites. The microstructure evolution on YS-90A and T-300B fibers was limited to near the fiber surface. Therefore, YS-90A and T-300B carbon fibers are potential candidates for reinforcement in NITE C/SiC composites.     

Si－C－O－N系统相稳定性及制备C－SiC纤维和SiC涂层的研究

根据Ｓｉ－Ｃ－Ｏ－Ｎ系统的相稳定性计算，绘制了于平衡状态下相稳定性与Ｎ＿２分压和Ｏ＿２分压以及相稳定性与Ｎ＿２分压和ＳｉＯ分压的关系图，发展了以气态ＳｉＯ与碳纤维反应将碳纤维转变为ＳｉＣ纤维，以及气态ＳｉＯ与ＣＯ反应于碳纤维上形成ＳｉＣ涂层的新方法。本文介绍这两种方法的工艺原理和主要实验结果。     

Structural evolution and mechanical properties of Cansas-III SiC fibers after thermal treatment up to 1700 °C

The effects of thermal treatment on the Cansas-Ⅲ SiC fibers were investigated via heating at temperatures from 900 to 1700 ℃ for 1–5 h in argon atmosphere. The composition and morphology of the SiC fibers were characterized and the tensile strength of the SiC fiber bundles was analyzed via two-parameter Weibull distribution analysis. The results showed that the thermal treatment has negligible influence on the microstructure of the SiC fibers at temperatures ≤ 1100 ℃. At temperatures ≥ 1300 ℃, the surface of the fibers became rough with some visible particles. Particularly, at 1700 °C, numbers of holes appeared. With the increasing of heating temperature and holding time, the average tensile strength of the SiC fibers decreased gradually from 1.81 to 1.01 GPa. The decreasing of tensile strength can be attributed to the increase of critical defect sizes, grain growth and phase transformation (β→α) of SiC.     

Synthesis of a silicon carbide coating on carbon fibers by deposition of a layer of pyrolytic carbon and reacting it with silicon monoxide

A method for preparing a SiC coating on carbon fibers is presented. The SiC coating was generated from the reaction of silicon monoxide (SiO) with a pyrolytic carbon (PyC) layer deposited on the fibers. The influence of holding time on the microstructure of the SiC layer was discussed. The oxidation behaviors of the uncoated and SiC coated carbon fibers were compared. The formation mechanism of the SiC coating was evaluated. With increased reaction time, the SiC coating becomes thicker and its surface becomes rough. The oxidation resistance of the carbon fiber was improved by the SiC coating. The initial oxidation temperature of the SiC coated carbon fiber is about 200 °C higher than that of the uncoated carbon fiber. The growth of the SiC coating is mainly attributed to the indirect reactions of SiO with PyC in the SiO/SiC/C system, in which silicon is considered a critical intermediate product.     

In Situ Gas–Solid Reaction and Oxidation Resistance of Silicon Carbide Coating on Carbon Fibers

Silicon carbide (SiC) coating on carbon fibers was realized based on in situ low‐temperature gas–solid reaction processing in which carbon reacted with Si vapor at the temperature of 1200°C–1300°C. X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), and energy‐dispersive spectroscopy (EDS) analysis showed that the SiC coating was uniform and crystallized by beta‐SiC. The oxidation resistant properties of the SiC‐coated carbon fibers were significantly improved according to isothermal oxidation measurement. The initial oxidation temperature of the SiC‐coated carbon fibers was about 200°C higher than that of the raw carbon fibers. The SiC‐coating carbon fibers treated at 1250°C possessed higher antioxidant property than the one treated at 1300°C.     

Flexible ultrafine nearly stoichiometric polycrystalline SiC fibers with excellent oxidation resistance and superior thermal stability up to 1900 °C

Flexible ultrafine SiC fibers with superior high-temperature stability and excellent oxidation resistance are regarded as one of the most promising materials for high-temperature applications. However, excess oxygen and carbon in the ultrafine SiC fibers limit their thermal stability due to decomposition of the SiC_xO_y phase. In the present work, flexible ultrafine nearly stoichiometric polycrystalline SiC fibers were fabricated by combining the electrospinning technique and polymer-derived ceramic method. The ultrafine SiC fibers exhibited superior high-temperature stability and oxidation resistance. The retention rates of tensile strength were 90.0 %, 94.2 % and 86.4 % after heat treatment in argon at 1800 °C, 1900 °C and 2000 °C, respectively. TG results of the fibers showed little weight loss of only 1.52 % at 1900 °C in Ar and the weight gain of only 4.1 % up to 1500 °C in air. Such improved thermal stability was achieved through sintering at high temperature for elimination of excess oxygen and carbon with Al doped as the sintering aid to restrain the grain coarsening. The ultrafine SiC fibers still exhibited excellent flexibility without obvious damage when they were heated by the butane blowtorch flame of about 1100 °C in air. Furthermore, the infrared thermography illustrated that the ultrafine SiC fiber membrane also had good thermal insulation performance. The outstanding mechanical properties and thermal stability of ultrafine SiC fibers suggest their potential applications at the high temperature and harsh environment.     

Morphology and microstructure of 2.5 dimension C/SiC composites ablated by oxyacetylene torch

SiC ceramic matrix composites reinforced by 2.5 dimension carbon fibers were prepared by low-pressure chemical vapor infiltration. The ablation performance of the composites was characterized by an oxyacetylene torch. The morphology and microstructure of the as-ablated composite were examined by scanning electron microscopy. The composition of the new phase was confirmed by energy dispersive spectroscopy and X-ray diffraction. Three clear annular regions appeared on the surface of the as-ablated sample and each region had different ablation mechanism. Sublimation was the main ablation behavior in the centre region. Oxidation was the main ablation behavior in the middle region. Silica particles mainly resulted from the oxidation and deposition of Si and SiO gas from the centre to the outer region. The ablation mechanism of the C/SiC composites under oxyacetylene flame was a combined effect of thermo-physicals attack and thermo-chemicals ablation.     

Si－C－O－N系统相稳定性和相稳定性图

对Ｓｉ－Ｃ－Ｏ－Ｎ系统进行了平衡状态下的相稳定性计算，绘制了在１４７３Ｋ和１５７３Ｋ下的Ｓｉ３Ｎ４、ＳｉＣ、Ｓｉ２Ｎ２Ｏ和ＳｉＯ２相稳定性与Ｎ２分压和Ｏ２分压的关系图以及Ｎ２分压和ＳｉＯ分区的关系图，Ｓｉ３Ｎ４／Ｓｉ２Ｎ２Ｏ／ＳｉＣ、ＳｉＯ２／Ｓｉ２Ｎ２Ｏ／ＳｉＣ两个三固相平衡点与Ｎ２分压、Ｏ２分压和ＳｉＯ分压以及温度的函数关系日。并以此确定Ｃ纤维－ＳｉＣ纤维转变和Ｃ纤维上涂层ＳｉＣ过程中，为获得稳定ＳｉＣ相的气体分压。     

Additive manufacturing of high mechanical strength continuous Cf/SiC composites using a 3D extrusion technique and polycarbosilane-coated carbon fibers

A novel additive manufacturing approach is herein reported for manufacturing high mechanical strength continuous carbon fiber-reinforced silicon carbide (C_f/SiC) composite materials. Continuous carbon fibers were coated with polycarbosilane (PCS) using a colloidal evaporative deposition process and then coextruded with high solid content SiC ink. The zeta potential of the SiC ink was adjusted to optimize the printing ability of the suspension. During sintering, small SiC grains and whiskers were generated in the gaps in and around the PCS-coated carbon fibers, which led to the improved flexural strength and density of the composites. Meanwhile, the PCS coating on the surface of the carbon fibers prevented the carbon fibers from reacting with SiO gas generated by reactions between the SiC matrix and SiO₂ and sintering additives (Al₂O₃ and Y₂O₃), effectively preserving the structural integrity of the carbon fibers. Compared to the SiC specimens containing uncoated carbon fibers, the density of the specimens fabricated with coated carbon fibers was increased from 2.51 to 2.85 g/cm³, and the strength was increased from 190 to 232 MPa.     

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。     

Microstructural,strength, and creep characterization of Sylramic™, Sylramic™-iBN and super Sylramic™-iBN SiC fibers

The chemical composition, microstructure, strength, and thermal stability of polymer-derived Sylramic? SiC fibers fabricated by Dow Corning and COI Ceramics, Inc., and nitrogen-treated Sylramic? SiC fibers, referred to as Sylramic?-iBN and Super Sylramic?-iBN SiC fibers, were investigated and compared. The baseline Sylramic? SiC fibers fabricated by both vendors as well as the nitrogen-treated Sylramic? SiC fibers are composed mostly of β-SiC (～97 wt%) with small amounts of TiB₂ (～2 wt%), amorphous carbon (～1 wt%) and trace amounts of B₄C. Most of the amorphous carbon is segregated at the core/interior of the fibers. Both baseline and nitrogen-treated Sylramic? SiC fibers have similar grain size and pore size distribution, except for a thin layer of in-situ grown crystalline BN (30–70 nm) on the surface of Sylramic?-iBN and Super Sylramic?-iBN fibers. Wide variation in strength within a batch as well as between batches is observed in both baseline and nitrogen-treated Sylramic? SiC fibers but both types of fibers are microstructurally stable at temperatures to 1800 °C in argon and nitrogen environments compared to Nicalon?-S and Tyranno®-SA SiC fibers. Under the same creep condition, Super Sylramic?-iBN fibers show better creep resistance compared to Sylramic?, Sylramic?-iBN, Hi-Nicalon?-S, and Tyranno®-SA fibers. Possible reasons for strength variability and the mechanism of in-situ BN formation on Sylramic? SiC fibers are discussed.     

Microstructure control of highly oriented short carbon fibres in SiC matrix composites fabricated by direct ink writing

A novel method is proposed for fabricating highly oriented carbon fibre reinforced SiC ceramic composites (C_f/SiC) by direct ink writing (DIW). For the first time, the control of carbon fibers’ orientation in DIW was studied by numerical simulation. An interfacial layer was prepared by chemical vapor infiltration (CVI). The microstructure and phase composition of C_f/SiC were studied by scanning electron microscopy and X-ray diffraction, respectively. The results showed that fibers of different interfacial thicknesses could be obtained effectively by varying the CVI time. The breakage of short fibres remarkably improved the fracture toughness of the parts. The specimens showed excellent mechanical properties with bending strength of 274 ± 13 MPa and fracture toughness of 5.82 ± 0.25 MPa m^1/2. This method could be extended to the preparation of other resin and ceramic composites.     

Relationship between microstructure and electromagnetic properties of SiC fibers

The microstructure and electromagnetic (EM) properties of four kinds of SiC fibers have been studied. These fibers are composed of amorphous SiC_xO_y, SiC nanocrystallines, free carbon, and nanopores, whose volume fractions are analyzed quantitatively. The content of free carbon notably affects the fiber's conductivity: the logarithm of conductivity increases linearly with the increase in the free carbon content when the volume fraction sum of free carbon and SiC exceed the percolation threshold. The EM loss mechanism is mainly composed of the conduction loss caused by free carbon and the polarization loss caused by SiC nanocrystallines. The content of free carbon is the decisive factor for the type of EM loss mechanism: the proportion of conduction loss increases linearly with the increase in free carbon content. Conduction loss is necessary for good EM absorption property, and polarization loss favors broadband absorption. For SiC fibers dominated by polarization loss, excellent absorption properties can be obtained in composites with higher fiber volume fraction (>20 vol%), which is crucial for structural absorbing materials.     

Fracture Toughness of 2-D Woven SiC/SiC CVI-Composites with Multilayered Interphases

Relations between fracture toughness and fiber/matrix interphases were examined on various SiC/SiC composites made by chemical vapor infiltration (CVI) and reinforced with woven fiber bundles. Strong and weak fiber/matrix bondings were obtained using multilayered interphases consisting of various combinations of carbon and SiC layers of different thickness and using fibers which had been previously treated. Fracture toughness was estimated using the J - integral and using strain energy release rate computed with a model taking into account the presence of a process zone of matrix microcracks. Both approaches evidenced similar trends. It appeared that higher toughness was obtained with those composites possessing strong interphases and subject to dense matrix microcracking.     

SiC/C纤维热力学生长机理研究

使用乙二醇作为稀释剂将硅溶胶稀释,得到不同浓度的硅溶胶溶液,用作涂覆商用碳纤维的原料。碳纤维表面改性后涂覆硅溶胶溶液,取出后在Ar气氛中于1 600 ℃保温30 min,硅溶胶涂层与碳纤维发生碳热还原反应形成SiC覆盖层。对制得的产物进行形貌和结构表征,并根据热力学数据对SiC包覆层的生长动力学和高温扩散机制进行研究。计算结果表明,反应过程为扩散控制。SiC/C纤维比碳纤维有更优异的耐高温氧化性能,为低成本制备新型陶瓷纤维提供可借鉴的思路和热力学依据。     

Hole exit quality and machined surface integrity of 2D Cf/SiC composites drilled by PCD tools

The brittle matrix and the anisotropic reinforcing phase of C_f/SiC composites bring great challenges to the machining process. Polycrystalline diamond (PCD) tool was used to drill 2D C_f/SiC composites. The influence of thrust force on hole exit defects was analyzed, and the transformation rule of material removal mechanism and surface generation of hole were studied. With the increase of feed rate, the thrust force increased and the hole exit defects increased. Specific drilling energy was used as an index to quantitatively describe the energy consumption of material removal. With the increase of feed rate and the decrease of cutting speed, the brittle fracture mode of carbon fibers changed from micro-brittle fracture inside carbon fiber to macro-brittle fracture. Although the machined surface of carbon fibers produced by micro-brittle fracture was composed of many micro-fracture, the hole surface was flat overall. Therefore, the hole surface roughness was small.     

Synthesis of C/SiC core-shell fibers through siliconization of carbon fibers with SiO gas in semi-closed reactor

Novel C/SiC core-shell fibers have been synthesized through incomplete conversion of carbon fibers by their siliconization with SiO gas. The synthesis was performed in the laboratory-made semi-closed batch-type reactor at 1380 °C for 3 h using a 9:1 M ratio mixture of Si and SiO₂ powders as a solid source of SiO gas. The conversion rate of carbon into SiC was 34.0%. All synthesized fibers had a distinct C/SiC core-shell composite structure. The fiber product was of fairly good uniformity in respect of the shell thickness which varied approximately from 0.6 μm to 0.8 μm depending on the location of fibers inside the reactor. It was revealed that the formation of the shell was the result of inward growth of the SiC product layer. The effectiveness of the proposed semi-closed reactor for the synthesis of C/SiC core-shell fibers has been demonstrated.     

Effect of short carbon fiber content on the mechanical properties of TiB2-based composites prepared by spark plasma sintering

In this study, TiB₂-30 vol% SiC composites containing 0, 5, 10, and 15 vol% short carbon fibers (C_f) were produced by spark plasma sintering (SPS). The effect of carbon fiber content on microstructure, density, and mechanical properties (micro-hardness and flexural strength) of the fabricated composites was studied. Scanning electron microscopy (SEM) results indicated that the fibers were uniformly dispersed in the TiB₂–SiC matrix using wet ball milling before SPS process. Fully dense TiB₂–SiC–C_f composites were achieved by SPS process at 1900°C for 10 min under 30 MPa. With the addition of fibers, the relative density of the composites did not change considerably. Mechanical tests revealed that microhardness was reduced about 19% by the incorporation of carbon fibers, whereas the flexural strength improved significantly. However, the flexural strength diminished by adding carbon fibers above to critical value (5 vol%) due to residual thermal stresses, nonhomogeneous structure and graphitization of carbon fibers. It was found that the composite with 5 vol% C_f had the highest flexural strength (482 MPa), which was enhanced by 20% compared with the TiB₂–SiC composite.     

Carbothermal Synthesis of Boron Nitride Coatings on Silicon Carbide

Pure BN coatings have been synthesized on the surface of SiC powders and fibers by a novel carbothermal nitridation method. Three stages are involved in the process: first, formation of a carbon layer on the SiC by the extraction of Si with chlorine; second, infiltration of the resulting nanoporous carbide-derived carbon (CDC) coating by a saturated boric acid solution; and finally, nitridation in ammonia at atmospheric pressure to produce the pure BN coating. X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and electron energy loss spectroscopy (EELS) were used to characterize the phase, elemental composition, and surface morphology of the coatings. The intermediate carbon layer acts as a template for BN growth, facilitates the formation of BN, and prevents the degradation of SiC fibers during nitridation. The whole process is simple, cost-effective, and less toxic due to the use of H₃BO₃ and NH₃ as precursors at atmospheric pressure compared with most commonly used chemical vapor deposition (CVD) methods. Uniform BN coatings obtained by this method prevent the bridging of fibers in the tow. The coating of powders is possible, which cannot be achieved by conventional CVD methods.