Effects of infiltration conditions on the densification behavior of carbon/carbon composites prepared by a directional-flow thermal gradient CVI process

Multiple quasi three-dimensioned carbon fibre preforms with disk-like shape were simultaneously densified by a directional flow thermal gradient CVI process. The effects of infiltration conditions, including temperature (ranging from 850 to 1050 °C), temperature gradient (5 and 10 °C/mm), pressure (2.5, 5.0, 7.5 and 9.5 kPa) and the type of carrier gas (N₂ or H₂), on the densification behavior of the resultant carbon/carbon composites were investigated. The results showed that lower temperatures (below 900 °C), a larger temperature gradient and higher pressure are favorable for higher average bulk density and homogeneous infiltration. Carbon/carbon composites disks with an average bulk density of 1.78 g/cm³ were achieved in one CVI cycle at a total pressure of 9.5 kPa. It was also found that adding N₂ carrier gas has no pronounced influence on the densification of the preforms. As compared to N₂, H₂ had positive effects on the densification of the preforms for temperatures above 900 °C, but it had negative effects on the densification when the control temperature was as low as 850 °C.     

Friction performance of C/C composites prepared using rapid directional diffused chemical vapor infiltration processes

A technology used to prepare C/C composites using a rapid directional diffused (RDD) chemical vapor infiltration process has been investigated. General RDD technologies were explored, and optimal parameters were determined. The friction and wear properties of this material were researched. The results showed that in the RDD process, propylene and nitrogen were rapidly and directionally diffused into the carbon preforms enabling carbon deposition to occur from the inside of the preform to the outside. This method prevents the formation of an outer crust on the surface of preforms and facilitates uniformity of densification. With the RDD process no surface machining was required between chemical vapor infiltration (CVI) cycles thereby enabling continuous densification and reducing the CVI cycle times. The optimum processing conditions for RDD CVI were as follows; furnace temperature 950 °C; and furnace pressure 6.7 kPa. The C/C composites produced using RDD CVI processing exhibited good friction performance. Their curves of the brake moment with the velocity are stable under dry conditions, and their wet brake moment is greatly reduced. The average thickness wear is decreased to 9.5×10⁻⁴ mm/surface/stop.     

Fabrication of carbon/carbon composites by an electrified preform heating CVI method

Carbon/carbon composites are manufactured using the electrified preform producing directly heat CVI process. The preforms are prepared by laminating the carbon fiber felts with crossply reinforcement, and infiltrated with carbon using natural gas or propylene as a reactant, with nitrogen as diluent at atmospheric pressure. The relations between the resistivity of samples and infiltration time are determined under the operating conditions. The results indicate that the preforms have gained a high infiltration rate by this technology, and the samples have higher densities using natural gas rather than propylene. Their highest average bulk densities are up to 1.71 g/cm³ after the preforms of 1100×500×35 mm size have been densified for 80 h using natural gas. The carbon fibres in the preforms have not been damaged by this technology as yet, and the composites prepared have sufficiently high flexural properties. As the brake angular velocity is increased with the constant brake moment inertia and specific pressure, the average coefficient of friction for the composites prepared using natural gas is linearly and greatly decreased, but the variations of the brake moment inertia have a slight influence on the average coefficient of the friction when the brake angular velocity and specific pressure are kept constant. Their average thickness wear is 13×10⁻⁴ mm/surface per stop.     

Sharp indentation behavior of carbon/carbon composites and varieties of carbon

Sharp indentation tests on carbon fiber and carbon matrix composites (C/C composite) were carried out over a wide load range from 0 to 2 N on three different cross sections: normal, parallel and inclined to the fiber axis. For comparison purposes, a variety of carbons including HOPG, glassy C, and pyrocarbon films was also examined. Both the fibers and the matrices displayed first a purely elastic response and second crack-induced damage. A purely elastic behavior was also observed with most of the varieties of carbon considered. Young’s modulus was extracted from the indentation curves either at maximum or at various forces, using the Sneddon equation of elastic response on loading (elastic indentation) or a classical equation based on elastic recovery on unloading (elastoplastic indentation). Results are discussed with respect to features of structure and heterogeneity of material in the stressed volume.     

Oxidation behavior of SiC/glaze-precursor coating on carbon/carbon composites

In order to improve the oxidation behavior of carbon/carbon composites in a wide range of temperature, a new SiC/glaze-precursor coating was developed.The SiC layer was produced by slurry and sintering, while the glaze precursor layer was prepared by slurry and drying. The microstructures and phase compositions of the coating were analyzed by SEM and XRD, respectively. The oxidation resistance of the coated composites was investigated using both isothermal and temperature-programmed thermogravimetric analysis in the temperature range from room temperature to 1600 °C. The results showed that the oxidation behavior of the coating was mainly controlled by the diffusion of oxygen during the test.The coating showed excellent oxidation resistance and self-healing ability in a wide range of temperature.     

The influence of thermal gradient on pyrocarbon deposition in carbon/carbon composites during the CVI process

A thermal gradient CVI process was investigated. A graphite heater in the center of a carbon felt disk preform was heated by Joule heating to a temperature of 900 °C, the carbon felt had a low thermal conductivity, and the rapid natural gas flow cooled the exterior surface of the preform. The rate constant of the chemical vapor deposition reaction increased exponentially with increasing temperatures with pyrocarbon being formed only in the designated deposition zone. Plugging of surface pores in the preforms, which often occurs in the isothermal CVI technology was unusual in this thermal gradient CVI process. As the deposition process went on, the deposited zone moved progressively towards the outside surface of the preform. The electrical resistance between two electrodes decreased gradually while the power of the thermal gradient CVI furnace increased non-linearly with the progressive densification. The temperature distribution in the thermal gradient furnace changed non-linearly with time and position. The relationship between temperature and position in the deposition zone followed the classical Fourier law. The microstructure of pyrocarbon at different positions was discussed.     

Mullite-Al2O3-SiC oxidation protective coating for carbon/carbon composites

In order to exploit the unique high temperature mechanical properties of carbon/carbon (C/C) composites, a new type of oxidation protective coating has been produced by a two-step pack cementation technique in an argon atmosphere. XRD analysis showed that the internal coating obtained from the first step was a gradient SiC layer that acts as a buffer layer, and the multi-layer coating formed in the second step was an Al₂O₃-mullite layer. It was found that the as-received coating characterized by excellent thermal shock resistance on the surface of C/C composites during exposure to an oxidizing atmosphere at 1873 K, could effectively protect the C/C composites from oxidation for 45 h. The failure of the coating is due to the formation of bubble holes on the coating surface.     

Oxidation protective multilayer coatings for carbon-carbon composites

An oxidation protective double layered coating was deposited on a carbon-carbon composite (C/C) using a simple and low cost method. A surface modification of the C/C was obtained by direct reaction of liquid silicon with the C/C, promoting the formation of a 5-10 μm β-SiC layer on the composite surface. The inner layer, in contact with the C/C, is a composite made with a barium borosilicate glass matrix (SABB) and boron carbide particles; the outer layer is another composite layer formed by a SABB glass matrix and yttrium oxide particles. The layers are deposited by a slurry technique. Oxidation tests were carried out in a furnace in air, in order to verify the coating stability and its effectiveness. No mass loss of the C/C composite was observed after 100 h at 1200°C, while after 150 h at 1300°C the C/C mass loss did not exceed 1%.     

Oxidation and defect control of CVD SiC coating on three-dimensional C/SiC composites

Two kinds of multi-layer CVD SiC coatings were prepared on a three-dimensional C/SiC composite. Oxidation behavior of the coating and the composite were studied and the effect of defects in the coating on its oxidation protection property were investigated. Above 1200 °C, thickness of the oxide film formed on the coating was related to oxidation time by the Fick’s first law X(t)²=Bt, the diffusion rate constant increased with oxidation temperature according to the Arrhenius’ relation ln B=−32?483/T+1.4048. Morphology of the interface between the CVD SiC and its oxide film was different after oxidation at temperatures from 1200 to 1500 °C. It was interpreted by consideration of the interfacial stress produced by thermal expansion mismatch and the CO gas pressure produced by interfacial reaction.     

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.     

Hierarchical material modeling of carbon/carbon composites

Unidirectional, long fiber carbon/carbon composites fabricated by chemical vapor infiltration (CVI) consisting of carbon fibers in a pyrolytic carbon matrix are anisotropic materials. It is practically impossible to identify experimentally the elastic properties (modules) of this anisotropic material. The aim of this investigation is to predict the elastic properties of this composite theoretically. The study of this material with the help of microscopy gives information about the very complicated anisotropic structure of this composite at each length scale. That is the reason that a hierarchical model for this material is developed, which consists of four length levels. A methodology for identification of the elastic properties for such composites is proposed. The problem is solved with the help of a homogenization procedure for each level.     

Effects of needle-punched felt structure on the mechanical properties of carbon/carbon composites

The effects of needle-punched felt structure, including mass ratio of non-woven cloth to short-cut fiber web, PAN-based carbon fiber types of non-woven cloth and thickness of unit (one layer of non-woven cloth and short-cut web was named as a unit), on the flexural properties of C/C composites from pressure gradient CVI are discussed. Results show that flexural strength and modulus increase when mass ratio of non-woven cloth to short-cut fiber web changes from 7:3 to 6:4 and that PAN-based carbon fiber types of non-woven cloth strongly influence the flexural properties. The strength of C/C composites is not linear with the strength of non-woven cloth carbon fiber because of the important interface between carbon fiber and matrix carbon. It is suitable to choose T300 or T700 as reinforcing carbon fiber for C/C composites in the present study. An optimum unit number per cm of the needle-punched felts for higher flexural properties exists.     

A reduced reaction model for carbon CVD/CVI processes

Carbon-carbon composites are produced by chemical vapor deposition/chemical vapor infiltration (CVD/CVI) processes. Models of carbon-carbon composite production processes will help reduce production costs. Reliable process models must, however, include details of the gas phase kinetics in order to identify optimal conditions. We have combined detailed gas phase kinetics, surface kinetics, and a pore closure model to predict pore geometry changes with respect to time. To determine the dominant gas phase kinetics, we reduced a large set of reactions to a minimal set using a sensitivity, rate, and dimensional analysis approach. These robust and relatively fast techniques can be used under a variety of conditions, including those within the pores of the composite. The process model shows that the deposition profile depends on the kinetic model chosen. Using the more realistic reaction model, conditions for uniform, or inside-out, densification can be suggested.     

Chemical vapor deposition and infiltration processes of carbon materials

The chemical vapor deposition (CVD) and the chemical vapor infiltration (CVI) processes of carbon materials are reviewed starting from the historical aspects and including the latest developments in the preparation of C/C composites. Our presentation is based on an analysis of the different types of reactors, of the composite materials with different types of pyrocarbon as matrices and a comparison between the different processes. In particular, the classical isothermal-isobaric technique and temperature or pressure gradient reactors, which lead to a higher deposition efficiency, are compared. A complementary aspect is the structural and physical analysis of the deposited pyrocarbons: they are considered as reproducible metastable phases which are obtained under non-equilibrium thermodynamic conditions. The final relevant point concerns the relationship between the process parameters and the type of pyrocarbon. In particular, the so-called rough laminar microstructure, useful for most composite applications, is described.     

Oxidation behavior of three dimensional C/SiC composites in air and combustion gas environments

A three dimensional C/SiC composite was prepared and flexural strengths during combustion atmosphere and weight changes in air were investigated. When oxidized in air, the C/SiC composite gained weight above the cracking temperature, and lost weight below the cracking temperature. The weight loss reached its maxumum value at about 700°C. When oxidized during combustion atmosphere, the composite always lost weight due to the large temperature gradient along the specimen. The strengths were lowest at the area close to the nozzle wall where the flame temperature was about 700°C. There were four oxidation zones along the specimens. There was an unoxidized zone (I) at the surporting end. Close to this was the cracking-oxidation zone (II). At the high-temperature end was the coating-oxidation zone (IV). Between the coating-oxidation and cracking-oxidation zones was the transition zone (III). Uniform, non-uniform and superficial oxidation regimes were observed which were considered to be responsible for the weight changes in air and strength changes during combustion atmosphere.     

Design of a C/SiC functionally graded coating for the oxidation protection of C/C composites

To reduce the residual thermal stress between the carbon fiber-reinforced carbon (C/C) composites and the SiC coating layer, functionally graded materials (FGM) consisting of a C/SiC compositionally graded layer (C/SiC interlayer) were adopted. After designing the compositional distribution of the C/SiC interlayer which can relieve the thermal stress effectively, the deposition conditions of the entire compositional range of the C/SiC composites were determined using a thermodynamic calculation. According to the design and calculation the C/SiC interlayer and the SiC outer layer were deposited on the C/C composites by a low pressure chemical vapor deposition (LPCVD) method at deposition temperatures of 1100 and 1300 °C. The stress calculation and the experimental results suggested that the SiC-rich compositional profile in the FGM layer is the most effective for relieving the thermal stress and increasing the oxidation resistance.     

Effect of additives on mechanical properties of oxidation-resistant carbon/carbon composite fabricated by rapid CVD method

The optimum composition of additives was obtained by the orthogonal design test method for oxidation-resistant carbon/carbon composites (C/C) fabricated by the rapid CVD method. The effect of additives on mechanical properties was examined. The additives used in this test included silicon carbide, silicon nitride, and metal borides. Additives doped into the matrix of C/C increase not only the initial oxidation temperature from 400 to 657°C (64%), but also its flexural strength from 121 to 254 MPa (110%), and flexural modulus from 25 to 45 GPa (96%). The increase of mechanical properties is considered to be due to the formation of a metallic carbon–boron compound in the microstructure.