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.

Effect of chemical vapor infiltration treatment on the wave-absorbing performance of carbon fiber/cement composites

Short carbon fibers were treated at high temperatures around 1100℃ through chemical vapor infiltration technology. A thinner layer ofpyrocarbon was deposited on the fiber surface. The dispersion of carbon fibers in a cement matrix and the mechanical properties of carbon fiber/cement composites were investigated by scanning electron microscopy （SEM） and other tests. The reflec- tivity of electromagnetic waves by the composites was measured in the frequency range of 8.0-18 GHz for different carbon fiber contents of 0.2wt%, 0.4wt%, 0.6wt%, and 1.0wt%. The results show that the reflectivity tends to increase with the increase of fiber content above 0.4wt%. The minimum reflectivity is -19.3 dB and the composites exhibit wave-absorbing performances. After pyrocarbon is deposited on the fiber, all the refiectivity data are far greater. They are all above -10 dB and display mainly wave-reflecting performances.

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 ℃.

Design,preparation,and structure of particle preforms for Si_3N_(4(P))/Si_3N_4 radome composites prepared using chemical vapor infiltration process

A particle preform was designed and prepared by conglomerating and cold-pressed process, which was condensed by chemical vapor infiltration （CVI） process to fabricate silicon nitride particles reinforced silicon nitride composites. The conglomerations are of almost sphericity after conglomerated. There are large pores among the conglomerations and small pores within themselves in the preform according to the design and the test of pore size distribution. The pore size of the preform is characterized by a double-peak distribution. The pore size distribution is influenced by conglomeration size. Large pores among the conglomerations still exist after infiltrated Si3N4 matrix. The conglomerations, however, are very compact. The CVI Si3N4 looks like cauliflowershaped structure. 2008 University of Science and Technology Beijing. All rights reserved.

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.

Chemical vapor infiltration of pyrocarbon from methane pyrolysis: kinetic modeling with texture formation

A complete mechanism of methane pyrolysis is proposed for chemical vapor infiltration of pyrocarbon with different textures, which contains a detailed homogeneous mechanism for gas reactions and a lumped heterogeneous mechanism for pyrocarbon deposition. This model is easily applied to simulate gas compositions and pyrocarbon deposition in a vertical hot-wall flow reactor in the temperature range of 1,323–1,398 K without any adjusting parameters and presents better results than previous mechanisms. Results have shown that the consumption of methane and the production of hydrogen are well enhanced due to pyrocarbon deposition. Pyrocarbon deposition prevents the continuously increasing of acetylene composition and leads to the reduction in the mole fraction of benzene at long residence times in the gas phase. The carbon growth with active sites on the surface is the controlling mechanism of pyrocarbon deposition. C1 species is the precursor of pyrocarbon deposition at 1,323 K,and the primary source over the whole temperature range. As temperature increases, gas phase becomes more mature and depositions from acetylene, benzene and polyaromatic hydrocarbons become more prevalent. A general pyrocarbon formation mechanism is derived with the specific precursors and illustrates that the maturation of gas compositions is beneficial to forming planar structures with hexagonal rings or pentagon-heptagon pairs, namely, high textured pyrocarbon. The results are in well agreement with experiments.

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.

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.

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.

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.

Wear behavior of SiC/PyC composite materials prepared by electromagnetic-field-assisted CVI

Silicon carbide/pyrolytic carbon (SiC/PyC) composite materials with excellent performance of self-lubrication and wear resistance were prepared on SiC substrates by electromagnetic-field-assisted chemical vapor infiltration (CVI). The composition and microstructure of the SiC/PyC materials were investigated in detail by XRD, SEM and EDS, etc. The effects of the deposition temperature on the section features and wear resistance of the SiC/PyC were studied. The results show that the PyC layers were deposited onto SiC substrates spontaneously at a lower deposition temperature. The SiC substrates deposited with PyC can significantly reduce the wear rate of the self-dual composite materials under dry sliding condition. The wear tests suggest that the SiC/PyC composite materials own a better wear resistance property when the deposition temperature is 800 °C, and the wear rate is about 64.6% of that without the deposition of PyC.

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.

Fabrication and characterization of SiO_(2(f))/Si)_3N_4 composites

A silicon dioxide fiber-reinforced silicon nitride matrix （SiOJSi3N4） composite used for radomes was prepared by chemical vapor infiltration （CVI） process using the SiCl4-NH3-H2 system. The effects of the process conditions, including infiltration temperature, infiltration time, and gas flux were investigated. The energy dispersion spectra （EDS） result showed that the main elements of this composite contained Si, N, and O. The X-ray diffraction （XRD） results indicated that phases of the composite before and after treatment at 1350℃ were all amorphous. A little fiber pull-out was observed on the cross section of the composite by scan electron microscope （SEM）. As a result, the composite exhibited good thermal stability, but an appropriate interface was necessary between the fiber and the matrix.

In-situ preparation, modulation and mechanism of refractory metal carbide gradient coating

TiC, ZrC and TaC modified layers were in-situ prepared on graphite matrix by chemical vapor infiltration method with metal salts as the activator. Taking the TiC modified layer as an example, through thermodynamic calculation and experiment, the thermal decomposition process of raw materials(Ti/K_(2)TiF_(6)) was analyzed, the formation mechanism of TiC was determined, and the distribution of TiC modified layer was modulated. The results show that activator K_(2)TiF_(6)has higher decomposition temperature than NH4Cl, which is conducive to improving the utilization rate of raw materials in the gas infiltration process. Increasing the content of Ti powder can increase the concentration of reaction gas and contribute to the formation of TiC modified layer. When the molar ratio of Ti to K_(2)TiF_(6)is 3:1, the surface thickness and infiltration depth of Ti C are 5.42 and 136.24 μm, respectively. Increasing the reaction temperature can improve the rate of in-situ reaction and the thickness of TiC surface layer. When the experimental temperature rises to 1600 °C, the TiC surface layer thickness increases to 20.27 μm.

Thermal Conductivity of Carbon/Carbon Composites with the Fiber/Matrix Interface Modified by Silicon Carbide Nanofibers

Silicon carbide nanofibers grew on the surface of carbon fibers of a unidirectional carbon preform by CCVD and then chemical vapor infiltration was used to densify the preform to get the SiCNF-C/C composite. The effects of silicon carbide nanofibers on the microstructure of the pyrolytic carbon and the thermal conductivity of the SiCNF-C/C composite were investigated. Results show that silicon carbide nanofibers on the surface of carbon fibers induce the deposition of high texture pyrolytic carbon around them. The interface bonding between carbon fibers and pyrolytic carbon is well adjusted. So the efficiency of heat transfer in the interface of the composite is well enhanced. The thermal conductivity of the SiCNF-C/C composite is greater than that of the C/C composite, especially the thermal conductivity perpendicular to the fiber axis.

Nanoinfiltration behavior of carbon nanotube based nanocomposites with enhanced mechanical and electrical properties

In this work,carbon nanotube(CNT)based nanocomposites with high mass fraction are proposed by in-situ bridging carbon matrix into CNT paper through optimized chemical vapor infiltration(CVI).Nanoinfiltration behavior of CNTs is basically investigated under the CVI process.The contact between each CNT can be strengthened and the conductive pathways can be established,resulting in the better mechanical and electrical properties.Compared with the pristine CNT paper,the CNT/C composite after pyrolysis process confirms a remarkable advance in tensile strength(up to 310±13 MPa)and Young’s modulus(up to 2.4±0.1 GPa).Besides,a notable feature of electrical conductivity also shows an improvement up to 8.5 S/cm,which can be attributed to the mass fraction of CNT(41 wt%)breaking the limits of percolation thresholds and the efficient densification of this sample to establish the conductive pathways.This study has a broad application in the development of the multi-functional electrical and engineering materials.

Mechanical Properties and Oxidation Behaviors of Self-Healing SiCf/SiC-SiBCN Composites Exposed to H_(2)O/O_(2)/Na_(2)SO_(4)Environments

The oxidation behaviors and their influence on the mechanical properties of self-healing SiCf/SiC-SiBCN composites were investigated in H_(2)O/O_(2)and H_(2)O/O_(2)/Na_(2)SO_(4)environments at 1200‒1350℃for 100 h.As the temperatures increase from 1200 to 1350℃,the oxidation rate constants increase from 0.45×10^(–7)to 1.58×10^(–7)mg^(2)/(mm^(4) h)in H_(2)O/O_(2),and from 1.02×10^(–7)to 3.42×10^(–7)mg^(2)/(mm^(4) h)in H_(2)O/O_(2)/Na_(2)SO_(4).The involvement of Na_(2)SO_(4)leads to the formation of a loose lamellar oxide layer,the breakage of the SiBCN/CVI-SiC interface and the decrease in the oxide viscosity,thus accelerating the oxidation of the composites.The composites show the maximum retention rate of strength(102%,535.71 MPa)after oxidation in H_(2)O/O_(2)at 1200℃due to the good self-healing capacity of the produced glass,while the minimum(82%,430.56 MPa)in H_(2)O/O_(2)/Na_(2)SO_(4)at 1350℃caused by the severe microstructural corrosion derived from Na_(2)SO_(4).

Enhanced mechanical property and tunable dielectric property of SiC_(f)/SiC-SiBCN composites by CVI combined with PIP

The SiBCN matrix via chemical vapor infiltration(CVI)or/and polymer infiltration pyrolysis(PIP)technologies was orderly introduced to SiC_(f)/SiC composites to optimize the mechanical property and electromagnetic(EM)shielding effectiveness simultaneously.The BN interface with the thickness of 350 nm was designed to obtain a little stronger interface bonding.The flexural strength of SiC_(f)/SiC-SiBCN composites reached 545.45±29.59 MPa thanks to the crack deflection between the CVI SiC and CVI SiBCN,as well as CVI SiBCN and PIP SiBCN matrix because of the modulus difference between them.The fracture toughness(KiC)with the value of 16.02±0.94 MPa·m^(1/2) was obtained owing to the extension of crack propagation path.The adverse effect of stronger interface bonding was eliminated by the design of matrix microstructure for SiC_(f)/SiC-SiBCN composites.The thermal conductivity in the thickness direction was 7.64 W·(m·K)^(-1) at 1200℃and the electric resistivity decreased to 1.53×10^(3) Ω·m.The tunable dielectric property was obtained with the coordination of wave-absorption CVI SiBCN matrix and impedance matching PIP SiBCN matrix,and the total shielding effectiveness(SE_(T))attained 30.01 dB.It indicates that the SiC_(f)/SiC-SiBCN composites have great potential to be applied as structural and functional materials.

Effect of nickel introduced by electroplating on pyrocarbon deposition of carbon-fiber preforms

In order to improve the deposition rate and microstructure of pyrocarbon, nickel was introduced by electroplating on carbon fibers and used as a catalyst during the deposition of pyrocarbon at 1000 C using methane as a precursor gas. The distribution of nickel catalyst and the microstructure of pyrocarbon were characterized by scanning electron microscopy（SEM）, energy dispersive spectroscopy（EDS）, X-ray diffraction（XRD）, and Raman micro-spectrometry. Results show that nano-sized nickel particles could be well distributed on carbon fibers and the pyrocarbon deposited catalytically had a smaller d002 value and a higher graphitization degree compared with that without catalyst. In addition, the deposition rate of pyrocarbon in each hour was measured.The deposition rate of pyrocarbon in the first hour was more than 10 times when carbon cloth substrates were doped with nickel catalysts as compared to the pure carbon cloths. The pyrocarbon gained by rapid deposition may include two parts, which are generation directly on the nickel catalyst and formation with the carbon nanofibers as crystal nucleus.