A Numerical Study of Densification Behavior of Silicon Carbide Matrix Composites in Isothermal Chemical Vapor Infiltration

We studied the characteristics of two-scale pore structure of preform in the deposition process and the mass transfer of reactant gas in dual-scale pores, and observed the physiochemical phenomenon associated with the reaction. Thereby, we established mathematical models on two scales, respectively, preform and reactor. These models were used for the numerical simulation of the process of ceramic matrix composites densified by isothermal chemical vapor infiltration(ICVI). The models were used to carry out a systematic study on the influence of process conditions and the preform structure on the densification behaviors. The most important findings of our study are that the processing time could be reduced by about 50% without compromising the quality of the material, if the processing temperature is 950-1 000 ℃ for the first 70 hours and then raised to 1 100 ℃.

Ablation properties of C/C composites with various needled preforms prepared by isothermal chemical vapor infiltration

The ablation properties of C/C composites with four different needled preforms prepared by isothermal chemical vapor infiltration （ICVI）, which are super-thin mat lay-up, 0°/90° weftless fabric lay-up, 0°/45° weftless fabric lay-up and 0°/45° twill fabric lay-up, were quantitatively evaluated by performing the ablation tests with an engine torch. And their ablation discrepancies were analyzed according to the surface characteristic, porosity and thermal diffusivity. The results show that the 0°/45° weftless composite has a fiat eroded surface with no obvious macroscopic pits. Its thickness and mass erosion rates are decreased by about 46.8% and 34.8%, 25.0% and 27.5%, and 17.5% and 19.4% compared with those of the mat, the 0°/90° weftless and the 0°/45° twill composites, respectively. The ablation properties are mainly controlled by the thermo-chemical effect （oxidation）, and a little by the thermo-mechanical effect （mechanical denudation）. The needling fiber bundles play an important role in accelerating the ablation process and resulting in the heterogeneous ablation.

Effects of carrier gas on densification of porous carbon-carbon composites during chemical vapor infiltration

The densification rate of C/C composites fabricated by directional flow thermal gradient chemical vapor infiltration process from C 3H 6, C 3H 6 N 2 and C 3H 6 H 2 was investigated respectively. The mechanism on the role of carrier gas in chemical vapor infiltration was also discussed. The results shows that whether or not adding N 2 as carrier gas has little influences on the densification behavior of C/C composites with the controlled temperature, the partial pressure of hydrocarbon and the effective residence time of the gas phase remain constant. When the controlled temperature is not less than 1 173 K,using N 2 or H 2 as carrier gas makes pronounced differences in densifying of C/C composites. The average bulk density of C/C composites from C 3H 6 H 2 is eight to ten percent higher than that from C 3H 6 N 2. However, when the controlled temperature is not higher than 1 123 K,the densification rate of C/C composites from C 3H 6 H 2 is much lower than that from C 3H 6 N 2, which implies that effects of carrier gas on densification of C/C composites are closely related to the type of carrier gas and infiltration temperature. At higher temperature, using H 2 as carrier gas is favorable to the densification of C/C composites, while at lower temperature, hydrogen, acting as reactive gas, can inhibit the formation of pyrolytic carbon.

Densification mechanism of chemical vapor infiltration technology for carbon/carbon composites

Carbon/carbon composites were fabricated using pressure-gradient chemical vapor infiltration(CVI) technology with propane (C3H6) as the carbon precursor gas and nitrogen (N2) as the carrier gas. The chemical process of deposition of pyrolytic carbon was deduced by analyzing the component of molecules in gas phase and observing the microstructure of deposition carbon. The results show that the process of deposition starts from the breakdown of C—C single bond of propene (C3H6), and forms two kinds of active groups in the heterogeneous gas phase reaction. Afterwards, these active groups form many stable bigger molecules and deposit on carbon fiber surface. At the same time, hydrogen atoms of the bigger molecules absorbed on carbon fiber surface are eliminated and the solid pyrolytic carbon matrix is formed in the heterogeneous reaction process.

Rapid chemical vapor infiltration of C/C composites

With liquid petrol gas(LPG)as carbon source,carbon felt as porous perform and hydrogen as diluent,C/C composites were fast fabricated by using a multi-physics field chemical vapor infiltration(MFCVI)process in a self-made furnace.A set of orthogonal experiments were carried out to optimize parameters in terms of indices of density and graphitization degree.The results show the optimal indices can be achieved under the conditions of temperature 650℃,LPGconcentration 80%,gas flux 60 mL/s, total pressure 20 kPa,infiltration time 15 h.The verification experiment proves the effectiveness of the orthogonal experiments. Under the optimal conditions,the graphitization degree of 75%and bulk density of 1.69 g/cm are achieved with a uniform density distribution.At the same time,a new structure is obtained.

Oxidation mechanisms of C-SiC-TaC-C composites prepared by chemical vapor infiltration

To improve the oxidation-resistance properties,SiC and TaC species were introduced in C/C composites by chemical vapor infiltration(CVI) methods. The oxidation-resistance properties of C-SiC-TaC-C composites were studied by X-Ray diffractometry(XRD),JEOL-6360LV scanning electronic microscopy(SEM) and AdventurerTM electronic balance with precision of 0.1 mg. The results show that,1) the oxidation rate of the composites increases continuously with time at all experimental temperatures;2) The oxidation rate increases with temperature within 700-1 100 ℃,slowly in 700-800 ℃,acutely in 800-1 100 ℃;it reaches a maximum value at 1 100 ℃,then decreases within 1 100-1 400 ℃;3) The relationship curve of oxidation rate with temperature can be divided into three regions. The oxidation rate is controlled by reactivity in region Ⅰ,the mixed effects of reactivity and gas diffusion in region Ⅱ,gas phase diffusion in region Ⅲ;4) The composites exhibit a higher oxidation onset temperature in low temperature region and a lower oxidation rate at high temperature due to the oxidation of TaC to(Ta,O) and the formation of the dense SiO2-Ta2O5 oxide layer respectively. With the addition of SiC/TaC species,the oxidation-resistant properties of C/C composites can be improved effectively.

Comparative modeling of gas transport in isothermal chemical vapor infiltration process of C/SiC composites

Two comparative models taking into account of momentum, energy and mass transport coupled with chemical reaction kinetics were proposed to simulate gas transport in isothermal CVI reactor for fabrication of C/SiC composites. Convection in preform was neglected in one model where momentum transport in preform is neglected and mass transport in preform is dominated by diffusion. Whereas convection in preform was taken into account in the other model where momentum transport in preform is represented by BRINKMAN equations and mass transport in preform includes both diffusion and convection. The integrated models were solved by finite element method. The calculation results show that convection in preform have negligible effect on both velocity distribution and concentration distribution. The difference between MTS molarities in preform of the two models is less than 5×10-5, which indicates that ignorance of convection in preform is reasonable and acceptable for numerical simulation of ICVI process of C/SiC composites.

FINITE DIFFERENCE MODEL FOR SIMULATION OF DENSIFYING CARBON-CARBON COMPOSITES BY CHEMICAL VAPOR INFILTRATIONP ROCESSES

A finite difference (FD) model is proposed to simulate the chemical vapor infiltration (CVI) processes for fabrication of carbon carbon composites. With iterative operation of many discrete values, the FD based model can be used to describe and analyze the real, continuous densification processing quantitatively. Many densification characteristics of carbon carbon composites can be predicated by modeling. The prediction results can be compared with experiment value directly, which shows its good ability for practical application. Special verification experiments are designed with Iso thermal CVI processing and slender cylindroid unidirectional C/C composites are prepared to verify the accuracy of the model. The modeling curve of density versus infiltration time is in good agreement with experiment values. According to modeling analysis, the effects of infiltration temperature and fiber volume fraction on densification are also discussed preliminarily. The conclusion obtained also accords with experiment or results in other literature, further approving the accuracy of the FD based model.

GROWTH CHARACTERSAND MODEL OF PYROLYTIC CARBON IN CHEMICAL VAPOR INFILTRATION PROCESS

Chemical Vapor Infiltration (CVI) processes are the essential techniques for fabrication of high performance carbon carbon composites. Based on the polarized light and scanning electron analysis, the authors study the micro morphology and texture characteristics of pyrolytic carbon deposited in CVI process, as well as the growth behavior of pyrolytic carbon. The research shows that Rough Laminar (RL) texture has the hierarchical and self similar structural features, which reflects the stage growth and self similar behavior during the growth course of pyrolytic carbon. According to the two growth features, a laminated growth model of pyrolytic carbon is proposed with the concept of Cone Growth Units (CGU). The laminated growth model can provide a fine description for the growth course of RL pyrolytic carbon. The model indicates that formation, developing and combination of local high order structures (such as CGU structures) are the essential factors for the growth of RL texture. Smooth Laminar (SL) texture and ISO carbon come into being with long range orderliness and isotropy structure respectively, which no local high orderliness intermediate involves in.

Effect of C/SiC Volume Ratios on Mechanical and Oxidation Behaviors of C_(f)/C-SiC Composites Fabricated by Chemical Vapor Infiltration Technique

C/SiC volume ratios in carbon fiber-reinforced carbon-silicon carbide(C_(f)/C-SiC)composites may influence greatly mechanical and oxidation properties of the composites,but have not been well investigated yet.Herein,C_(f)/C-SiC composites with different C/SiC volume ratios were fabricated by chemical vapor infiltration(CVI)technique through alternating the thickness of a pyrocarbon(PyC)interlayer.The composites with C/SiC volume ratios of 0.37 and 0.84 exhibited the better comprehensive mechanical properties.The CS0.37 showed the highest flexural strength of 340.6 MPa,and CS0.84 had the maximum tensile strength of 139.1 MPa.The excellent mechanical properties were closely related to the relatively low C/SiC volume ratios and porosities,optimum interfacial bonding and reduced matrix micro-cracks.The composite with a low C/SiC volume ratio of 0.10 showed the best anti-oxidation performance due to its high SiC content.The oxidation mechanisms at 1100℃and 1400℃were discussed by considering the effect of the C/SiC volume ratios,pores and matrix micro-cracks,oxidation of carbon phase and SiC.

Numerical simulation of isothermal chemical vapor infiltration process in fabrication of carbon-carbon composites by finite element method

The chemical vapor infiltration process in fabrication of carbon-carbon composites is highly inefficient and requires long processing time. These limitations add considerably to the cost of fabrication and restrict the application of this material. Efforts have been made to study the CVI process in fabrication of carbon-carbon composites by computer simulation and predict the process parameters, density, porosity, etc. According to the characteristics of CVI process, the basis principle of FEM and mass transport, the finite element model has been established. Incremental finite element equations and the elemental stiffness matrices have been derived for the first time. The finite element program developed by the authors has been used to simulate the ICVI process in fabrication of carbon-carbon composites. Computer color display of simulated results can express the densification and distributions of density and porosity in preform clearly. The influence of process parameters on the densification of preform has been analyzed. The numerically simulated and experimental results give a good agreement.

Mechanical and dielectric properties of porous and wave-transparent Si3N4–Si3N4 composite ceramics fabricated by 3D printing combined with chemical vapor infiltration

Porous Si3N4–Si3N4 composite ceramics were fabricated by 3D printing combined with low-pressure chemical vapor infiltration(CVI).This technique could effectively improve the designability of porous Si3N4 ceramics and optimize the mechanical and dielectric properties.The effects of process parameters including the deposition time and heat treatment on the microstructure and properties of porous Si3N4–Si3N4 composite ceramics were studied.The study highlights following:When CVI processing time was increased from 0 to 12 h,the porosity decreased from68.65%to 26.07%and the density increased from 0.99 to 2.02 g/cm3.At the same time,the dielectric constant gradually increased from 1.72 to 3.60;however,the dielectric loss always remained less than0.01,indicating the excellent electromagnetic(EM)wave-transparent performance of porous Si3N4–Si3N4 composite ceramics.The maximum flexural strength of 47±2 MPa was achieved when the deposition time attained 6 h.After heat treatment,the porosity increased from 26.07%to 36.02%and the dielectric constant got a slight increase from 3.60 to 3.70 with the dielectric loss still maintaining lower than 0.01.It has been demonstrated that the porous Si3N4–Si3N4 composite ceramics are a promising structural and EM wave-transparent material suitable for high temperature service.

Microstructure of carbon fiber preform and distribution of pyrolytic carbon by chemical vapor infiltration

The carbon/carbon composites were made by chemical vapor infiltration(CVI) with needled felt preform. The distribution of the pyrolytic carbon in the carbon fib er preform was studied by polarized light microscope(PLM) and scanning electroni c microscope(SEM). The experimental results indicate that the amount of pyrolyti c carbon deposited on the surface of chopped carbon fiber is more than that on t he surface of long carbon fiber. The reason is the different porosity between th e layer of chopped carbon fiber and long carbon fiber. The carbon precursor gas which passes through the part of chopped carbon fibers decomposes and deposits o n the surface of chopped carbon fiber. The pyrolytic carbon on the surface of lo ng carbon fibers is produced by the carbon precursor gas diffusing from the chop ped fiber and the Z-d fiber. Uniform pore distribution and porosity in preform are necessary for producing C/C composites with high properties.

Modeling of gas phase diffusion transport during chemical vapor infiltration process

In order to improve the uniformity of both the concentration of gaseous reagent and the deposition of matrix within micro pores during the chemical vapor infiltration (CVI) process, a calculation modeling of gas phase diffusion transport within micro pores was established. Taken CH 3SiCl 3 as precursor for depositing SiC as example, the diffusion coefficient, decomposing reaction rate, concentration within the reactor, and concentration distributing profiling of MTS within micro pore were accounted, respectively. The results indicate that, increasing the ratio of diffusion coefficient to decomposition rate constant of precursor MTS is propitious to decrease the densification gradient of parts, and decreasing the aspect ratio (L/D) of micro pore is favorable to make the concentration uniform within pores.

The Infiltration Process and Texture Transition of 2D C/C Composites

2D needle-punched fiber felt was infiltrated by a kind of rapid isothermal chemical vapor infiltration technique. The infiltration process and texture transition of the infiltrated C/C composites were investigated. The porosity and the variations of the cumulative pore volume were determined by mercury porosimetry. The texture of matrix carbon was studied under a polarized light microscope. The results show that the relative mass gain of the sample increases directly as the infiltration time at the initial stage until 20 h, and subsequently the increasing rate of the relative mass gain decreases gradually with the prolonging of infiltration time. Three layers of pyrocarbon were formed around fibers. Low-textured pyrocarbon was obtained at the initial stage. With the densification going on, high-textured pyrocarbon was formed on the surface of low-textured pyrocarbon. Then, low-textured pyrocarbon was produced again during the final stage of densification. The texture transition is ascribed to the variation of the ratio of cumulative inner surface area to volume of pores and the gas partial pressure in pores.

Processing and properties of 2D SiC/SiC composites by precursor infiltration and pyrolysis

Two-dimensional plain-weave silicon carbide fiber fabric reinforced silicon carbide(2D-SiC/SiC)composites were molded by stacking method and densified through precursor infiltration and pyrolysis(PIP)process.SiC coating was deposited as the fiber/matrix interphase layer by chemical vapor deposition(CVD)technique.Fiber/matrix debonding and relatively long fiber pullouts were observed on the fracture surfaces.Additionally,the flexural strength and elastic modulus of the composites with and without fiber/matrix interphase layer were investigated using three-point bending test and single-edge notched beam test.The results show that the fiber fraction and the porosity of 2D-SiC/SiC composites with and without coating are 27.2%(volume fraction)and 11.1%,and 40.7%(volume fraction)and 7.5%,respectively.And the flexural strength and elastic modulus of 2D-SiC/SiC composites with and without coating are 363.3 MPa and 127.8 GPa,and 180.2 MPa and 97.2 GPa,respectively.With a proper thickness,the coating can effectively adjust the fiber/matrix interface,thus causing a dramatic increase in the mechanical properties of the composites.

Preparation and mechanical properties of carbon/carbon composites with high textured pyrolytic carbon matrix

Short carbon fiber felts with an initial porosity of 89.5% were deposited by isobaric, isothermal chemical vapor infiltration using natural gas as carbon source. The bulk density of the deposited carbon/carbon （C/C） composites was 1.89 g/cm3 after depositing for 150 h. The microstructure and mechanical properties of the C/C composites were studied by polarized light microscopy, X-ray diffraction, scanning electron microscopy and three-point bending test. The results reveal that high textured pyrolytic carbon is deposited as the matrix of the composites, whose crystalline thickness and graphitization degree highly increase after heat treatment. A distinct decrease of the flexural strength and modulus accompanied by the increase of the toughness of the C/C composites is found to be correlated with the structural changes in the composites during the heat treatment process.

Bending properties and fracture mechanism of C/C composites with high density preform

C/C composites with banded structure pyrocarbon were fabricated by fast chemical vapor infiltration（CVI）,with C3H6 as carbon source,N2 as carrier gas,and three-dimensional（3D） 12K PAN-based carbon fabric with high density of 0.94 g/cm3 as preform.Experimental results indicated that the fracture characteristics of C/C composites were closely related to the frequency of high-temperature treatment（HTT） at the break of CVI process.According to the load？displacement curves,C/C composites showed a pseudoplastic fracture after twice of HTT.After three times of HTT,load？displacement curves tended to be stable with a decreasing bending strength at 177.5 MPa.Delamination failure and intrastratal fiber fracture were observed at the cross-section of C/C composites by scanning electronic microscope.Because the content of pyrocarbon and fibers has a different distribution in layers,the C/C composites show different fracture characteristics at various regions,which leads to good toughness and bending strength.

Oxidation behavior of CVI,MSI and CVI+MSI C/SiC composites

The oxidation behavior of chemical vapor infiltration(CVI),molten silicon infiltration(MSI)and CVI+MSI C/SiC composites at 500-1 400℃was studied.The oxidation below 900℃increased successively for CVI,CVI+MSI and MSI composites.However,the oxidation of CVI composite above 1 000 ℃was much faster thanthat of MSI and CVI+MSI composites. As active carbon atoms produced by siliconization of fibers during MSI process were oxidized first and decreased initial oxidation temperature.The initial oxidation temperature of MSI,MSI+CVI and CVI composites was 526,552 and 710℃,respectively.New active carbon atoms were generated due to the breaking of 2D molecular chains during oxidation,so the activation energy of three C/SiC composites was decreased gradually at 500-800℃with oxidation process,exhibiting a self-catalytic characteristic.

Direct deposition of graphene nanowalls on ceramic powders for the fabrication of a ceramic matrix composite

Uniform mixing of ceramic powder and graphene is of great importance for producing ceramic matrix composite. In this study, graphene nanowalls(GNWs) are directly deposited on the surface of Al2 O3 and Si3 N4 powders using chemical vapor deposition system to realize the uniform mixing. The morphology and the initial stage of the growth process are investigated. It is found that the graphitic base layer is initially formed parallel to the powder surface and is followed by the growth of graphene nanowalls perpendicular to the surface. Moreover, the lateral length of the graphene sheet could be well controlled by tuning the growth temperature. GNWs/Al2 O3 powder is consolidated by using sparking plasma sintering method and several physical properties are measured. Owing to the addition of GNWs, the electrical conductivity of the bulk alumina is significantly increased.