Kinetics of pyrolytic carbon infiltration for the preparation of ceramic/carbon and carbon/carbon composites

Carbon/carbon and zeolite/carbon composites have been prepared by pyrolytic carbon infiltration of organic and inorganic substrates with different porous structures. The chemical vapour infiltration kinetics of these substrates has been studied in a thermogravimetric system at atmospheric pressure, using benzene as pyrolytic carbon precursor. The rate of pyrolytic carbon infiltration seems to depend on the porosity of the substrate available to the pyrolytic carbon precursor, irrespective of the nature of the substrate studied. Activation energy values of about 180 kJ/mol were found for the different substrates used in the temperature range of 700-800 °C, where the cracking reaction of benzene takes place, predominantly, in a heterogeneous form. At higher temperatures homogeneous reactions compete with heterogeneous ones and higher values of activation energies (280-380 kJ/mol) were obtained. The oxidation of the pyrolytic carbon deposited on the different substrates studied takes place in the same range of temperature, which suggests the presence of a similar pyrolytic carbon structure on substrates of different nature or a similar accessibility to the deposited layer.     

Effect of carrier gas on bulk density and microstructure distribution of carbon/carbon composites fabricated by thermal gradient chemical vapor infiltration

The effect of the type of carrier gas on the bulk density and microstructure distribution of carbon/carbon (C/C) composites fabricated by thermal gradient chemical vapor infiltration from propylene was investigated. The results show that the type of carrier gas has an appreciable influence on the radial distribution of density and microstructure of the C/C composites. When N₂ is used as carrier gas, the average bulk density of the carbon disk is 1.54 g/cm³ after 400-h infiltration, and the radial density difference of the disk is 0.24 g/cm³. Furthermore, smooth laminar pyrolytic carbon forms at the outer wall of the disks. When H₂ is used as carrier gas, an entirely rough laminar pyrolytic carbon matrix and C/C disks with average bulk density of 1.67 g/cm³ are obtained in the same time, and the radial density difference of the disk is only 0.11 g/cm³. No matter which of these two carrier gases is used, the lower density zone is found to be at or near the middle of the disks.     

Mechanical properties and ablation resistance of HfC nanowire modified carbon/carbon composites

Hafnium carbide nanowires (HfCnws) were in-situ grown in carbon/carbon (C/C) composites, and subsquently the preforms were densified by isothermal chemical vapor infiltration to obtain HfCnws modified carbon/carbon (HfCnws-C/C) composites. Morphology and microstructure of HfCnws were examined, and the effect of HfCnws on the mechanical property and ablation resistance of C/C composites were also investigated. Results show that introducing HfCnws refined the grain size of pyrolytic carbon (PyC). The out-of-plane compression, interlaminar shear and flexual strength of HfCnws-C/C composites increased by 120.80%, 45.60% and 94.65%, respectively compared with pure C/C, and the HfCnws-C/C shows good ablation resistance under oxy-acetylene flame ablation.     

Influence of graphitization temperature on microstructure and mechanical property of C/C-SiC composites with highly textured pyrolytic carbon

C/C-SiC composites with highly textured pyrolytic carbon (HT PyC) were prepared by a combining chemical vapor infiltration and liquid silicon infiltration. The effect of HT PyC graphitization before and after 2327 and 2723 K on C/C-SiC composites was investigated. The mechanical properties decreased with increasing graphitization temperature, but graphitization treatment changed the fracture behavior from brittle like to pseudo-ductile. The decrease in bending strength from 306.21 to 243.69 MPa resulted from the weak interfacial bonding between HT PyC and fiber, and the good orientation of graphite layers. The crack at border of fiber bundle and longitudinal crack in HT PyC shortened the path of crack propagation, resulting in fracture toughness decrease from 21.11 to 14.72 MPa·m^1/2. A more pseudo-ductile behavior was due to the longer pull-out of fibers, the better orientation of graphite layers, the sliding of sublayers, and the deflection and propagation caused by the transverse cracks.     

Friction behaviors of carbon/carbon composites with different pyrolytic carbon textures

Friction and wear properties of carbon/carbon (C/C) composites with a smooth laminar (SL), a medium textured rough laminar (RL) and a high textured RL pyrolytic carbon texture were investigated with a home-made laboratory scale dynamometer to simulate airplane normal landing (NL), over landing (OL) and rejected take-off (RTO) conditions. The morphology of worn surfaces at different braking levels was observed with scanning electron microscopy. The results show that C/C composites with RL have nearly constant friction coefficients, stable friction curves and proper wear loss at different braking levels, while friction coefficients of C/C composites with SL pyrolytic carbon decrease intensely and their oxidation losses increase greatly under OL and RTO conditions. Therefore, C/C composites with a high and medium textured RL pyrolytic carbon may satisfy the requirements of aircraft brakes. The good friction and wear properties of C/C composites with RL are due to the properties of RL, which leads to a uniform friction film forming on the friction surface.     

高性能C/C复合材料制备工艺研究

对制备C/C复合材料的化学气相渗透工艺进行了系统的实验研究,着重分析了热解碳的沉积过程。研究表明,在化学气相渗透的初始阶段,热解碳主要在碳纤维表面沉积,并与碳纤维之间形成了界面结合;随后,热解碳的沉积继续填充碳纤维预制体内部的气孔。这一过程有助于缓解纤维与陶瓷基体之间的界面应力。研究表明,通过调节热解碳的沉积时间可以得到具有一定密度梯度的C/C复合材料。     

Microstructure and interlaminar shear property of carbon fiber-SiC nanowire/pyrolytic carbon composites with SiC nanowires growing at different positions

In order to improve the interlaminar shearing strength of carbon fiber/pyrolytic carbon (Cf/PyC) composites, SiC nanowires (SiCNWs) growing at different positions were introduced into carbon fiber/pyrolytic carbon composites to generate carbon fiber-SiC nanowire/pyrolytic carbon (Cf-SiCNWs/PyC) composites. Cf-SiCNWs/PyC composites were prepared by sol-gel and isothermal chemical vapor infiltration (ICVI) method. The morphology, microstructure and compositions of composites were investigated by SEM, TEM, XRD and XPS. The interlaminar shearing strength was tested and the effect of SiCNWs growth positions on the interlaminar shearing strength was investigated. The results showed that SiCNWs were consisted of perfect single crystalline structure of β-SiC with diameter of 160–200 nm. The SiCNWs could grow at four kinds of positions to combine with carbon fibers to form multi-scaled reinforcements (micro-scaled carbon fibers and nanoscaled SiCNWs). The interlaminar shear strength of Cf-SiCNWs/PyC composites were increased by 78% compared with Cf/PyC composites without SiCNWs. The improvement of interlaminar shear strength was attributed to bridging and pull-out of multi-scaled reinforcements composed of carbon fibers and SiCNWs as well as the enhancement of fiber/matrix interface bonding generated by SiCNWs growing at different positions.     

Densification of a 2D carbon fiber preform by isothermal, isobaric CVI: Kinetics and carbon microstructure

Chemical vapor infiltration of a 2D carbon fiber preform with a 0/0/90/90° fiber architecture and a fiber volume fraction of 22.5% was investigated as a function of methane pressure at various temperatures as well as a function of infiltration time at constant pressure. Inside-outside densification was obtained at the most attractive temperature of 1095 °C up to 29 kPa resulting in a maximum bulk density of 1.84 g cm⁻³ and a matrix density of 2.17 g cm⁻³, which corresponds to high-textured carbon. Texture formation can be perfectly explained with the earlier proposed particle-filler model. Studies at increasing infiltration times suggest a recrystallization of carbon deposited in the early stages of the infiltration.     

Electrically induced liquid infiltration for the synthesis of carbon/carbon–silicon carbide composite

The electrically induced liquid infiltration (EILI) method for the synthesis of carbon/carbon–silicon carbide (C/C–SiC) materials was developed. The method involves Joule preheating of a porous carbon/carbon preform surrounded by silicon media, followed by silicon infiltration into the pore structure, and its reaction with carbon to form pore-free C/C–SiC composite. This technique is characterized by high heating rates (10²–10³ K/s) and short processing times (5–20 s), which distinguish it from conventional approaches. The influence of maximum treatment temperature, as well as preheating rate on the depth of infiltration, reaction kinetics, and the material microstructure was investigated. C/C–SiC composite with a compressive strength which was twice that of the initial C/C material was synthesized.     

The chemical vapor deposition of carbon on carbon fibers

The relations between chemical vapor deposition (CVD) parameters and the resultant pyrolytic carbon microstructures have been examined for matrix deposition in fibrous carbon substrates. The parameters considered are temperature (1200–1450°C), pressure (20–630 Torr), C/H ratio ($\text{1}\text{4}\text{–}\text{1}\text{14}$), total flow rate (2–16) 1/min), and carbon felt density (0·12–0·23 g/cm³). Most of the data obtained are in agreement with a CVD model for carbon; where agreement is not obtained, it is surmised that the assumptions of the model may not be satisfied.     

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).     

A new strategy for high-value reutilization of recycled carbon fiber: Preparation and friction performance of recycled carbon fiber felt-based C/C-SiC brake pads

To achieve the high-value reutilization of recycled carbon fiber (rCF), a new strategy of preparing rCF-based C/C-SiC brake pads is proposed in this work. The results show that the rCF possesses crystal structure and tensile strength comparable with those of virgin CF (vCF) exception of pyrolytic char adhering to the surface of rCF after pyrolysis. The rCF was converted into C/C composites through impregnation-pyrolysis. Pyrolytic char was found to have no evident negative effect on the densification rates of the rCF C/C composites. By reactive melt infiltration, the rCF C/C-SiC composites were fabricated based upon the rCF C/C composites. The achieved rCF C/C-SiC composites do not differ markedly from the vCF group control in terms of microstructure and bending strength. Furthermore, the thermal diffusion coefficients of the rCF C/C-SiC composites are very close to those of vCF C/C-SiC composites in the temperature range 25°C-300 °C. The coefficient of friction values of the rCF C/C-SiC composites are as stable as those of vCF control group, both being maintained at approximately 0.4 during friction test, whether at 25 °C or 300 °C. The wear rate of the rCF C/C-SiC composites is 3.8 μm·min⁻¹, nearly indistinguishable from that of the vCF C/C-SiC composites, i.e., 4.5 μm·min⁻¹, further suggesting that the two materials resemble each other closely. The rCF C/C-SiC composites exhibit great potential for use as alternative brake pads to serve auto braking systems. This work opens up a new path for high-value reuse of rCF.     

Hydrogen diffusion and solubility in pyrolytic carbon

Tritium diffusion coefficients and deuterium solubilities have been measured for laminar pyrolytic carbon in the temperature range 900–1500°C. The tritium diffusion coefficients were much lower than those for metals at equivalent temperatures, but the activation energy for the diffusion was much higher (～-100 kcal/mole). Tritium diffusion coefficients measured for silicon-doped pyrolytic carbon were over an order of magnitude higher than the values for the undoped laminar pyrolytic carbon. The solubility of deuterium in laminar pyrolytic carbon was found to decrease with increasing temperature and exhibited a pressure dependence of $\text{p.}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$     

Reaction Mechanism and Microstructure Development of Zr–Si Alloyed Melt‐Infiltrated ZrC‐Modified C/C Composite

ZrC ceramic modified‐C/C composite is prepared by a quick and low‐cost reactive melt infiltration process with a Zr‐Si8.8 alloy. Reaction kinetics and mechanism of pyrolytic carbon with the infiltrated Zr‐Si8.8 alloy are investigated. A continuous ZrC layer is found to be formed around pyrolytic carbon due to the in situ reaction and its thickness parabolically increases with an increase in reaction time period. Zr concentration in the alloyed melts decreases due to the reaction between Zr and pyrolytic carbon and Zr₂Si phase precipitates from the residual alloyed melts. A model for the growth of ZrC layer is established to describe the reaction kinetics of pyrolytic carbon with Zr‐Si8.8 alloy. The calculated thickness of the reaction‐formed ZrC layer is in good agreement with the experimental data. Based on the Arrhenius equation, the activation energy of the reaction between carbon and Zr‐Si8.8 alloy is 313.2 KJ/mol, smaller than that of the reaction between carbon and pure zirconium. The microstructure of the reactive melt‐infiltrated ZrC‐modified C/C composite is characterized by optical microscope, SEM, EDS, XRD, and TEM. The mechanism of the reaction between pyrolytic carbon and Zr‐Si8.8 alloy is discussed on the basis of the characterization results and phase diagram. A schematic is proposed to understand the reaction mechanism between pyrolytic carbon and Zr‐Si8.8 alloy and microstructure development of the ZrC‐modified C/C composite.     

Superhydrophilicity on nano-rough carbon surfaces achieved by hyperthermal oxygen-atom beam exposure

In order to investigate a method to increase hydrophilicity on nano-rough carbon surfaces, a nano-rough surface of C₆₀ film and an atomically flat surface of highly oriented pyrolytic graphite (HOPG) were oxidized by hyperthermal oxygen-atom beam exposure and the hydrophilicities of the surfaces were investigated. Superhydrophilicity were achieved on these exposed carbon surfaces, which had low O/C ratio of approximately 28% and surface roughness (Ra) of approximately 3 nm. The direct oxidations on sp² bonded carbon atoms (basal plane) of these two carbon materials by the exposure of hyperthermal O-atom beam would contribute the superhydrophilicity.     

Mechanical enhancement of C/C composites via the formation of a machinable carbon nanofiber interphase

C/C composites with improved mechanical strength were synthesized using a filler constituted by a carbon felt covered with catalytically grown carbon nanofibers (CNFs) and a carbonaceous matrix generated by the pyrolysis of a phenolic resin. First, the synthesis method of the filler allows the homogeneous deposition and anchorage of CNFs on the host microfilaments at a rapid densification rate. Carbon nanofibers grown this way lead to the formation of numerous micro- and nanobridges between the microfilaments, conferring a significant improvement of the mechanical resistance of the CNF/C system allowing one to tailor its dimensions and shape. Thus, further fabrication of C/C composites can be achieved: the CNF/microfilament structure was infiltrated with a phenolic resin and carbonized at 650 °C to generate a carbonaceous matrix by thermal decomposition. Similar experiments on the microfilaments carried out at the same synthesis time, without catalyst and at higher reaction temperatures led to the deposition of a pyrolytic carbon sheath and to poor mechanical enhancements. This clearly indicates the advantage of using CNF growth as an efficient densification process before infiltration. Such C/C composites exhibit high-quality bonding between the two carbon phases, the matrix and the CNF/microfilament filler, via the formation of a considerable amount of CNF interphase.     

Oxidation behavior of carbon/carbon-boron nitride composites fabricated by additives and chemical vapor infiltration

Carbon/carbon-boron nitride (C/C-BN) composites were manufactured by adding hexagonal boron nitride (h-BN) powders into carbon fiber preform and a subsequent chemical vapor infiltration (CVI) process for deposition of pyrolytic carbon (PyC). Microstructure and oxidation behavior of carbon/carbon composites with 9?vol% h-BN (C/C-BN9) were studied in comparison to carbon/carbon (C/C) composites. Results showed that with the addition of h-BN powders, a regenerative laminar (ReL) PyC with higher texture was achieved. Note that the introduction of h-BN powder make great contributes to graphitization degree of PyC, leading to larger oxidation activation energy. Moreover, under an air atmosphere, h-BN started to oxidize above 800?°C, and generated molten boron oxide (B₂O₃) which prohibited oxygen diffusion by filling in pores, cracks and other defects. As these reasons mentioned above, after oxidation tests under an air atmosphere, mass losses of C/C-BN9 composites were lower than that of C/C composites at all test temperatures (600–900?°C), indicating that the oxidation resistance of C/C-BN9 composites is better than that of C/C composites.     

Pyrolytic carbon layers—an electron spin resonance analysis

Chemical vapour infiltration is simulated by deposition of pyrolytic carbon on planar boron nitride substrates and carbon fibers in a hot-wall tubular reactor at about 1100 °C for varied pressure and flow-velocity of methane. The degree of orientation of the deposited graphite-like domains can be monitored via orientation and temperature dependence of the electron spin resonance parameters (g-tensor, linewidth). The electronic structure of the localized defects and conduction electrons is accessible by a quantitative modelling of these parameters. The interaction of the built-in hydrogen atoms with the unpaired electron spins is analysed by electron-proton spin double resonance technique (Overhauser shift)     

Effect of preform and carbon matrix on bending strength of Cf/Cu/C composites

Aiming to obtain composites with appropriate mechanical properties for pantograph sliders, copper mesh modified carbon/carbon (C_f/Cu/C) composites were prepared by chemical vapor infiltration (CVI) in C₃H₆ +?N₂ atmosphere and impregnation-carbonization (I-C) with furan resin. In this paper, C_f/Cu/C composites with two kinds of preforms and carbon matrixes were obtained. The effect of preforms and carbon matrixes on bending strength was investigated. The results indicated that the bending strength of carbon fiber/copper mesh reinforced pyrolytic carbon matrix composites was about 181.39–195.43?MPa, while that reinforced resin carbon matrix composites had the worst bending strength around 54.45–57.04?MPa, in terms of the same preform. The bending strength of C_f/Cu/C composites in the parallel orientation and vertical orientation were also similar. As for C_f/Cu/C composites with the same carbon matrix, the bending strength of C_f/Cu/C composites with non-woven fiber/fiber web/copper mesh type preform was higher than that with fiber web/copper mesh type preform. However, the bending strength of carbon fiber/copper mesh reinforced resin carbon matrix composites showed the opposite trend, and its reasons were analyzed and discussed taking advantage of the fracture mechanisms.     

Reaction of glassy carbon with oxygen

A glassy carbon, GC-30, from Tokai Electrode Manufacturing Co., Ltd. has been reacted in O₂ between 750 and 850°C. At low carbon burn-offs the reaction has an activation energy of 63 ± 3 kcal/mole. Changes in dimensions of samples as a function of burn-off at 900°C were studied. Dimensional changes are compared with those resulting from the oxidation of highly oriented pyrolytic graphite. For comparable sample shapes, glassy carbon is more reactive than highly oriented pyrolytic graphite.