CN113698223A - Sandwich structure C/C ultrahigh-temperature ceramic composite material and preparation method thereof - Google Patents
Sandwich structure C/C ultrahigh-temperature ceramic composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of ceramic composite material preparation, in particular to a sandwich structure C/C ultrahigh-temperature ceramic composite material and a preparation method thereof. The preparation method specifically comprises the following steps: spreading short fibers on two sides of the carbon fiber preform, and preparing the sandwich fiber preform by adopting a needling process; placing the sandwich fiber preform in a chemical vapor deposition furnace, and depositing one or two of pyrolytic carbon or silicon carbide by adopting a chemical vapor deposition method to obtain a sandwich structure C/C porous framework; introducing the superhigh temperature ceramic phase into the sandwich structure C/C porous skeleton by adopting one or more methods of precursor impregnation-pyrolysis, chemical vapor deposition or high-temperature infiltration reaction to obtain the sandwich structure C/C superhigh temperature ceramic composite material. The innovation of the structural design and preparation of the C/C ultrahigh-temperature ceramic composite material is realized, and the ablation resistance and the thermal shock resistance of the C/C matrix can be effectively improved through the modification of the ultrahigh-temperature ceramic matrix.
Description
Technical Field
The invention relates to the technical field of ceramic composite material preparation, in particular to a sandwich structure C/C ultrahigh-temperature ceramic composite material and a preparation method thereof.
Background
The C/C composite material has the characteristics of low density, high specific strength, corrosion resistance, thermal shock resistance, good high-temperature stability and the like, and particularly, the mechanical property of the C/C composite material does not decrease or increase reversely in a high-temperature environment of not more than 2300 ℃; the unique high temperature properties of C/C composites have therefore attracted particular attention in the aerospace field. At present, the material becomes an ideal high-temperature structural material, and has great application potential in the field of aerospace. The carbon material starts to be oxidized at the temperature higher than 400 ℃ in an aerobic environment, and the oxidation rate is rapidly increased along with the temperature, so that the structure of the material is damaged, and the performance is seriously reduced. Therefore, the defect that the C/C composite material is easy to oxidize in an aerobic environment restricts the engineering application and popularization.
The modification of ultra-high temperature ceramic (UHTC) matrix is an effective method for improving the high-temperature oxidation resistance and ablation resistance of the C/C composite material. The prior ultrahigh temperature ceramic matrix modification technology comprises chemical vapor infiltration, high temperature infiltration reaction, precursor impregnation cracking, slurry impregnation modification and the like. Because the molecular weight of the precursor of refractory metals hafnium, zirconium and tantalum is relatively large, the uniform permeation of HfC, ZrC and TaC is difficult to realize in the chemical vapor permeation process, and the hole sealing phenomenon is easy to occur on the surface layer, so the application and popularization are limited to a certain extent. Although the slurry dipping modification method can introduce superfine ceramic particles into the C/C porous skeleton, the introduced ceramic particles are not uniformly distributed in a matrix, and a hole sealing phenomenon is easy to generate in the dipping process, so that the further densification of subsequent materials is hindered. Although the precursor impregnation cracking and high temperature infiltration reaction techniques are mature, they have the same disadvantages. The precursor impregnation cracking process has the defects of long period, high cost and the like, and the yield of the ceramics after the cracking of the currently developed ultrahigh-temperature ceramic precursor is low and contains a certain carbon phase, so that the actual content of the ultrahigh-temperature ceramic in the prepared material is low, and the improvement degree of the high-temperature ablation resistance of the material is limited. Although the high-temperature infiltration reaction can prepare the C/C ultrahigh-temperature ceramic composite material with high ceramic phase content, in the infiltration process, because the infiltration material and the carbon matrix do not react sufficiently, the prepared ceramic matrix often has infiltration residual simple substance phases (such as Si, Zr and the like), and the residual simple substance phases with low melting points often become weak links of ablation, thereby influencing the further improvement of the ablation resistance of the material.
Disclosure of Invention
Aiming at the technical problems, the content of the ultrahigh-temperature ceramic phase of the composite material is improved, and the high-temperature ablation resistance of the material is further improved.
In view of the above object, an embodiment of the present invention provides a preparation method of a sandwich structure C/C ultra-high temperature ceramic composite material, which specifically includes the following steps:
s1, spreading short fibers on two sides of the carbon fiber preform, and preparing the sandwich fiber preform of the short fiber layer, the common carbon fiber layer and the short fiber layer by adopting a needling process;
s2, placing the sandwich fiber preform in a chemical vapor deposition furnace, and depositing one or two of pyrolytic carbon or silicon carbide by a chemical vapor deposition method to obtain a sandwich structure C/C porous skeleton;
and S3, introducing the superhigh temperature ceramic phase into the sandwich structure C/C porous skeleton by adopting one or more methods of precursor impregnation-pyrolysis, chemical vapor deposition or high-temperature infiltration reaction to obtain the sandwich structure C/C superhigh temperature ceramic composite material.
Further, the carbon fiber preform is a carbon fiber woven or wound body, and specifically is a multi-dimensional fiber preform of a carbon cloth lamination, a needled felt, a three-dimensional piercing structure, a needling structure and a sewing structure.
Furthermore, the volume density of the short fiber layer in the sandwich fiber preform is lower than that of the common carbon fiber layer, and the volume density of the short fiber layer is less than or equal to 0.3g/cm3。
Further, the short fiber has a fiber length of 2-15 cm.
Further, the thickness of the short fiber layer is 0.2-10 mm.
Further, the step S2 of depositing the pyrolytic carbon by using a chemical vapor deposition method specifically includes: propylene is used as a carbon source gas, nitrogen is used as a carrier gas, the deposition pressure is less than or equal to 10KPa, and the deposition temperature is 850-1100 ℃.
The process of depositing silicon carbide by using the chemical vapor deposition method in the step S2 specifically includes: trichloromethylsilane is used as a precursor raw material, hydrogen is used as a carrier gas, trichloromethylsilane steam is brought into a mixing tank in a bubbling mode, Ar and hydrogen are used as diluent gases, the deposition pressure is less than or equal to 1KPa, and the deposition temperature is 1150 ℃.
Further, the ultrahigh-temperature ceramic is SiC, ZrC, HfC, TaC and ZrB2、HfB2One or more of (a).
Further, the precursor impregnation-cracking method in step S3 specifically includes: repeatedly dipping, drying and pyrolyzing the C/C porous skeleton by using an ultrahigh-temperature ceramic precursor as a impregnant; and when the crusting and hole sealing phenomena occur in the dipping-cracking process, carrying out hole opening treatment, and then carrying out the next round of dipping, drying and high-temperature cracking.
The high-temperature infiltration process in the step S3 specifically includes: one or more of zirconium, hafnium, silicon metal or alloy thereof is used as an infiltration agent, and an ultrahigh-temperature ceramic phase is formed in the C/C porous framework through infiltration reaction; vacuumizing to below 0.8kPa, heating to 1400-2300 ℃ at a heating rate of 2-15 ℃/min, preserving the temperature for more than or equal to 0.5h, and then naturally cooling to room temperature.
Based on the same inventive concept, the sandwich structure C/C ultrahigh temperature ceramic composite material is prepared by the preparation method.
Further, the composite material comprises a C/C ultrahigh-temperature ceramic inner layer and a high-content ultrahigh-temperature ceramic outer layer, and the thickness of the high-content ultrahigh-temperature ceramic outer layer is 0.2-7 mm.
Has the advantages that:
(1) according to the invention, the interlayer structure carbon fiber preform is prepared, short fibers are spread on two sides of the common carbon fiber preform to form an interlayer structure with completely different densities of the inner layer and the outer layer, and the content of the ultra-high temperature ceramic phase in the outer layer is improved through subsequent chemical vapor deposition and introduction of high temperature ceramic, so that the antioxidant ablation-resistant protection effect similar to the ultra-high temperature ceramic coating is achieved, the thickness of the outer layer of the ultra-high temperature ceramic can reach 0.2-7mm, and the coating is thicker than the common ultra-high temperature ceramic coating, the thermal shock resistance of the coating is improved, and the ablation resistance of the composite material can be obviously improved, especially the service life under the condition of dynamic gas scouring.
(2) The sandwich structure C/C ultrahigh-temperature ceramic composite material realizes the fusion of the excellent ablation resistance of the outer layer of the ultrahigh-temperature ceramic and the good high-temperature mechanical property of the inner layer of the C/C ultrahigh-temperature ceramic, and effectively solves the problem of insufficient high-temperature ablation resistance of the material while ensuring the good high-temperature mechanical property of the inner layer of the C/C ultrahigh-temperature ceramic.
(3) The outer layer of the ultrahigh-temperature ceramic in the sandwich structure C/C ultrahigh-temperature ceramic composite material is connected with the inner layer through fiber needling, and due to the reinforcing and toughening effect of the short fibers, compared with a common ultrahigh-temperature ceramic coating, the outer layer has better bonding performance and high-temperature thermal shock resistance, and the defects of thermal shock resistance and bonding performance of the conventional ultrahigh-temperature ceramic coating are overcome.
(4) The preparation method of the sandwich structure C/C ultrahigh-temperature ceramic composite material is suitable for industrial production, and has the advantages of controllable structure (adjustable inner and outer layer thicknesses), capability of preparing large-size and complex-shape special-shaped parts and the like.
Drawings
FIG. 1 is a microscopic morphology diagram of a sandwich structure C/C-ZrC-SiC composite material provided in example 1 of the present invention; wherein (a) is a microscopic topography of an outer layer and an inner layer of the sandwich structure C/C-ZrC-SiC composite superhigh temperature ceramic; (b) is a morphology chart of short fibers and ZrC-SiC ceramic phases in the outer layer of the sandwich structure C/C-ZrC-SiC composite material; (c) a ZrC-SiC ceramic phase microscopic amplifying topography picture filled around short fibers in the outer layer of the sandwich structure C/C-ZrC-SiC composite material; (d) the microscopic amplified morphology of the ZrC-SiC ceramic phase of the sandwich structure C/C-ZrC-SiC composite material near the inner layer area is shown;
FIG. 2 is a microscopic morphology diagram and a spectrum analysis result of an inner layer of the sandwich structure C/C-ZrC-SiC composite material provided in example 1 of the present invention; wherein (a) is a microscopic topography of an inner layer of the sandwich structure C/C-ZrC-SiC composite material; (b) is a spectrum analysis diagram of the ceramic phase in the inner layer material of the sandwich structure C/C-ZrC-SiC composite material;
FIG. 3 is a cross-sectional micro-topography of a sandwich structure C/C-ZrC-SiC composite material after an oxyacetylene flame is ablated for 60s according to example 1 of the present invention; wherein (a) is a sectional partition microscopic topography picture of a sandwich structure C/C-ZrC-SiC composite material subjected to oxyacetylene flame ablation for 60s, and (b) is ZrO of an outermost layer 1 region after ablation2An enlarged topography of the outer layer, and (c) SiO in the 2 region after ablation2Microcosmic enlarged topography of the enrichment layer; (d) for 3-zone ZrO after ablation2Microscopic amplified topography of the particle accumulation inner layer;
FIG. 4 is a microscopic morphology diagram of the outer layer and the inner layer of the sandwich structure C/C-ZrC-SiC composite material provided in example 2 of the present invention; wherein (a) is a microstructure diagram of the outer layer of the sandwich structure C/C-ZrC-SiC composite material; (b) is a micro-topography of the inner layer of the common needling C/C-ZrC-SiC composite material with the sandwich structure; (c) the local microscopic enlarged topography of the outer layer of the sandwich structure C/C-ZrC-SiC composite material is shown; (d) is a microscopic amplified topography of the ceramic phase in the outer layer of the sandwich structure C/C-ZrC-SiC composite material.
Description of the reference numerals
1-1, short fiber; 1-2, fiber cloth; 1-3, ZrC-SiC ceramic particles close to the inner layer of the ceramic matrix; 3-1, SiO2(ii) a 3-2, resin; 3-3, ZrO2Fine particles; 4-1, fiber cloth; 4-2, a CVISIC interface layer; 4-3, carbon fibers; 4-4 pyrolytic carbon layer; 4-5 and ZrC-SiC ceramic particles.
Detailed Description
In order to more clearly illustrate the technical content of the present invention, the detailed description is given herein with reference to specific examples and drawings, and it is obvious that the examples are only preferred embodiments of the technical solution, and other technical solutions that can be obviously derived by those skilled in the art from the technical content disclosed still belong to the protection scope of the present invention.
In the embodiment of the invention, the chemical reagents used are all analytical grade reagents, and are obtained by purchasing or preparing by an existing method.
Example 1
Taking a needled carbon fiber preform as an inner layer, spreading short fibers on the upper surface and the lower surface of the needled carbon fiber preform, and connecting the inner layer structure and the outer layer structure in a needling manner to prepare the carbon fiber preform with a sandwich structure, wherein the density of the common needled carbon fiber preform of the inner layer is 0.45g/cm3The volume density of the outer layer of the short fiber is less than or equal to 0.3g/cm3After the short fiber outer layer is connected by needling, the overall density of the prepared carbon fiber preform with the sandwich structure is 0.35g/cm3And the thickness of the short fiber outer layer is about 6 mm.
And densifying the carbon fiber preform with the sandwich structure by adopting a chemical vapor deposition process. The densification process takes propylene as a carbon source gas and nitrogen as a carrier gas, the deposition temperature is 980 ℃, and the deposition pressure is less than 3 kPa. After 120h of chemical vapor deposition, the density of the prepared material is 1.07g/cm3The sandwich structure of (1) C/C porous material.
Mixing polycarbosilane and zirconium alkoxide in a mass ratio of 1:2, dissolving in dimethylbenzene to form an organic ceramic precursor solution, and repeatedly carrying out ultrahigh-temperature ceramic densification treatment on the C/C porous body with the sandwich structure by adopting a ceramic precursor impregnation-cracking process. The specific process comprises the following steps: putting the sandwich structure C/C porous body prepared by chemical vapor deposition into an impregnation tank, vacuumizing to below 2kPa, putting an organic ceramic precursor solution into the impregnation tank to immerse the sandwich structure C/C porous body, and taking out a blank after vacuum impregnation for 0.5 h; and putting the dried C/C porous body with the sandwich structure into a graphitization furnace for pyrolysis treatment, introducing argon as protective gas, heating to 1400-1600 ℃ for pyrolysis treatment, and keeping the temperature for 60 min. In the process of densification, when the crusting and hole sealing phenomena appear on the surface of the material, the material needs to be subjected to surface machining and hole opening treatment, and then the next round of densification treatment can be carried outThe above precursor impregnation-cleavage process was repeated. After machining and repeated dipping-cracking densification, the finally prepared sandwich structure C/C-ZrC-SiC composite material has the density of 2.01g/cm3And the thickness of the outermost fiber reinforced ZrC-SiC layer reaches 4 mm.
The picture of the sandwich structure C/C-ZrC-SiC composite material object prepared in the example 1 mainly consists of an outer layer of short fiber reinforced ZrC-SiC ultra-high temperature ceramic and an inner layer of the C/C-ZrC-SiC composite material. Because the content of carbon fiber in the outer layer is lower than that of the inner layer of the C/C-ZrC-SiC composite material, a compact outer layer with higher content of the ultra-high temperature ceramic can be prepared on the surface after a subsequent ultra-high temperature ceramic matrix modification process, and the thickness of the carbon fiber reinforced ultra-high temperature ceramic outer layer reaches several millimeters magnitude.
FIG. 1 is a microstructure and morphology diagram of a sandwich structure C/C-ZrC-SiC composite material prepared in example 1. FIG. 1a is a microscopic morphology diagram of the outer layer and the inner layer of the prepared sandwich structure C/C-ZrC-SiC composite material ultrahigh-temperature ceramic, and it can be seen from the diagram that the total thickness of the short fiber reinforced ZrC-SiC outer layer is about 4mm, after the matrix modification process of repeated precursor impregnation and cracking, a large amount of ZrC-SiC ceramic phase with higher contrast is filled around the short fibers in the outer layer, and the area of the white bright phase is obviously larger than that of the gray black carbon fiber phase, which indicates that the content of the ultrahigh-temperature ceramic phase in the outer layer is higher than that in the inner layer of the common C/C-ZrC-SiC composite material. The short fibers in the outer layer of the ultra-high temperature ceramic can play a role in enhancing and toughening, and the high-temperature thermal shock resistance of the outer layer of the ultra-high temperature ceramic is improved. FIG. 1b is a morphology diagram of short fibers and ZrC-SiC ceramic phases in the outer layer, and FIG. 1c is an enlarged view of the frame selection of FIG. 1b, namely a microscopic enlarged morphology diagram of the ZrC-SiC ceramic phases filled around the short fibers in the outer layer, so that the ZrC-SiC ceramic phases are mainly filled around the short fibers in a fine particle form, and the particles are tightly bonded and have a compact structure; the results of energy spectrum analysis show that the fine ceramic particles mainly contain three elements of Zr, Si and C, and are consistent with the phase composition of the material. FIG. 1d is a microscopic magnified topography of the ZrC-SiC ceramic phase near the inner region, showing that the ZrC-SiC ceramic near the inner region has more micropore defects than the ceramic phase in the outer region. FIG. 2a is a microscopic enlarged morphology of the inner layer of the C/C-ZrC-SiC composite material, and it can be seen that a large number of continuous long fiber layers exist in the inner layer, and the content of fibers in the inner layer is significantly higher than that in the outer layer, and because the sizes and the number of micropores in the continuous long fiber layers are both lower than those in the outer layer, the content of ZrC-SiC ultrahigh-temperature ceramic filled in the continuous long fiber layers is lower, resulting in that the content of ZrC-SiC ceramic phase in the inner layer of the C/C-ZrC-SiC composite material is significantly lower than that in the outer layer. FIG. 2b shows the result of the spectrum analysis of the ceramic phase in the inner layer material, and it can be seen that the ceramic phase mainly contains three elements of Zr, Si, and C, further illustrating the formation of the ZrC-SiC ceramic phase.
In order to investigate the high-temperature ablation resistance of the C/C-ZrC-SiC composite material with the ultra-thick carbon fiber reinforced ZrC-SiC outer layer and adopting the heat flow density of 3.2MW/m2The oxyacetylene flame carries out high-temperature ablation resistance comparison test on the sandwich structure C/C-ZrC-SiC composite material with the outer layer thickness of 4mm and the common needle-punched C/C-ZrC-SiC composite material. The ablation result proves that after 60s of oxyacetylene flame ablation, the linear ablation rate and the mass ablation rate of the common needling C/C-ZrC-SiC composite material are respectively 0.011mm/s and 0.0019g/s, while the linear ablation rate and the mass ablation rate of the sandwich structure C/C-ZrC-SiC composite material with the outer layer thickness of 4mm are respectively 0.0038mm/s and 0.0013g/s, compared with the prior art, the carbon fiber reinforced ZrC-SiC outer layer can play a role in oxidative ablation protection similar to a coating, so that the linear ablation rate of the C/C-ZrC-SiC composite material with the sandwich structure is reduced by one order of magnitude, and the mass ablation rate is also reduced by 31.6%. After ablation, because a continuous compact oxide protective layer similar to a coating is not formed on the surface of the material, a certain amount of carbon fibers are partially exposed in an ablation central area, the protective effect of the oxide protective film formed on the surface is limited, and after the C/C-ZrC-SiC composite material with the interlayer structure and the outer layer thickness of 4mm is ablated, a continuous compact white oxide protective layer is formed in the ablation central area, the material is complete in whole, the good protective effect is achieved on an internal matrix, and the excellent ablation protective effect of the carbon fiber reinforced ZrC-SiC outer layer on the material matrix is further illustrated. FIG. 3 is a cross-sectional view of a sandwich structure C/C-ZrC-SiC composite material with an outer layer thickness of 4mm after ablation, and as can be seen from FIG. 3a, Zr is reinforced by 4mm carbon fibersThe C-SiC outer layer can play a protective effect similar to a coating, after ablation, the section of an ablation central area on the surface layer of the material only forms an oxide protective layer with the thickness of about 210 mu m, the oxide protective layer is tightly combined with the lower carbon fiber reinforced ZrC-SiC outer layer, and the outer layer does not fall off or lose efficacy, so that the introduction of the carbon fibers can effectively improve the high-temperature thermal shock resistance of the ultrahigh-temperature ceramic layer. In addition, it can be clearly seen that after ablation, 3 different oxide protective layers are formed from inside to outside on the oxide protective layer on the surface layer of the ablation center, and from outside to inside, the outermost region 1 is mainly ZrO2Outer layer (FIG. 3 b), region 2 is SiO2Enriched layer (FIG. 3 c), zone 3 is mainly ZrO2An inner layer of particle packing (fig. 3d, which is an enlarged view of the box in fig. 3 c); the carbon fiber reinforced ZrC-SiC layer below the oxide layer is continuous and compact in structure, and no obvious oxidation ablation sign occurs after ablation, so that the ablation protection effect similar to a coating can be achieved in the ablation process of the ultra-thick carbon fiber reinforced ZrC-SiC outer layer, and the C/C-ZrC-SiC composite material with the sandwich structure has excellent high-temperature ablation resistance and long-time ablation resistance potential.
Example 2
Taking a needled carbon fiber preform as an inner layer, spreading short fibers on the upper surface and the lower surface of the needled carbon fiber preform, and connecting the inner layer structure and the outer layer structure in a needling manner to prepare the carbon fiber preform with a sandwich structure, wherein the density of the common needled carbon fiber preform of the inner layer is 0.45g/cm3The volume density of the outer layer of the short fiber is less than or equal to 0.3g/cm3After the outer layer of the short fiber is connected by needling, the density of the prepared carbon fiber preform with the sandwich structure is 0.35g/cm3And the thickness of the short fiber outer layer is about 5 mm.
And densifying the carbon fiber preform by adopting a chemical vapor deposition process. The densification process takes propylene as a carbon source gas and nitrogen as a carrier gas, the deposition temperature is 980 ℃, and the deposition pressure is less than 3 kPa. After 100h of chemical vapor deposition, the density of the prepared material is 0.96g/cm3The sandwich structure of (1) C/C porous material. Introducing SiC matrix by chemical vapor deposition process with trichloromethylsilane (CH)3SiCl3) As a precursor raw material, taking hydrogen as a carrier gas to carry MTS steam in a bubbling wayCarried into a mixing tank with Ar and hydrogen as diluent gases. The deposition pressure is 1KPa, the deposition temperature is 1150 ℃, and the deposition time is 25 h. After SiC chemical vapor deposition, the density of the prepared C/C-SiC porous material with the sandwich structure is 1.1g/cm3。
And further densification is performed by adopting a precursor impregnation cracking process. The specific process comprises the following steps: mixing polycarbosilane and zirconium alkoxide in a mass ratio of 1:2, dissolving in dimethylbenzene to form an organic ceramic precursor solution, and repeatedly carrying out ultrahigh-temperature ceramic densification treatment on the C/C-SiC porous body with the sandwich structure by adopting a ceramic precursor impregnation-cracking process. The specific process comprises the following steps: putting the sandwich structure C/C-SiC porous material prepared by chemical vapor deposition into an impregnation tank, vacuumizing to below 2kPa, putting an organic ceramic precursor solution into the impregnation tank to immerse the sandwich structure C/C-SiC porous body, and taking out a blank after vacuum impregnation for 0.5 h; and putting the dried C/C-SiC porous body with the sandwich structure into a graphitization furnace for pyrolysis treatment, introducing argon as protective gas, heating to 1400-1600 ℃ for pyrolysis treatment, and keeping the temperature for 60 min. In the process of densification, when the surface of the material has a crusting hole sealing phenomenon, the surface of the material needs to be subjected to machining and hole opening treatment, and then the next round of densification can be performed. Repeating the precursor impregnation-cracking process, machining and repeatedly impregnating, cracking and densifying to finally obtain the sandwich structure C/C-ZrC-SiC composite material with the density of 2.02g/cm3The thickness of the outermost fiber reinforced ZrC-SiC layer reaches 3 mm; the thickness of the outermost fiber reinforced ZrC-SiC layer reaches 3mm, and the density reaches 2.04g/cm3While the density of the common C/C-ZrC-SiC composite material of the inner layer is only 1.95g/cm3。
FIG. 4 is a diagram of a sandwich structure C/C-ZrC-SiC composite material object obtained in example 2. As can be seen from FIG. 4a, the outer layer of the prepared sandwich structure C/C-ZrC-SiC composite material mainly consists of the short fiber reinforced ZrC-SiC superhigh temperature ceramic outer layer, and the thickness of the composite material is obviously more than 1mm (the actual thickness is 3 mm). FIG. 4b is a microscopic morphology of the inner layer of a common needle-punched C/C-ZrC-SiC composite material with a sandwich structure, and it can be seen that an obvious fiber cloth layer exists in the inner layer, and the fiber content is obviously higher than that in the outer layer. Fig. 4c is an enlarged local topography of the outer layer, and it can be seen that a relatively significant CVISiC interface layer is formed between the black carbon fiber and pyrolytic carbon region and the white ZrC-SiC ceramic region, and the SiC interface layer is tightly wrapped around the outer surface of the pyrolytic carbon. FIG. 4d is a microscopic enlarged morphology of the ceramic phase in the outer layer, and it can be seen that the carbon fiber surface is sequentially wrapped with black pyrolytic carbon and gray SiC interface layer, and the pores between the fibers are filled with a large amount of ZrC-SiC ceramic particles. The microstructure characterization result of fig. 4 further confirms that the formation of the ultra-thick carbon fiber reinforced ZrC-SiC ultra-high temperature ceramic outer layer, and the content of carbon fibers in the outer layer of the sandwich structure is obviously lower than that of the inner layer of the common needling C/C-ZrC-SiC composite material. As the thickness of the outer layer of the ultra-high temperature ceramic reaches millimeter magnitude, compared with the common ultra-high temperature ceramic coating (less than or equal to 0.3 mm), the ultra-high temperature ceramic coating has the potential of long-time ablation resistance and protection in the ablation process.
Example 3
Taking a puncture carbon fiber preform as an inner layer, spreading short fibers on the upper surface and the lower surface of the puncture carbon fiber preform, and connecting the inner layer structure and the outer layer structure by adopting a needling mode to prepare the carbon fiber preform with the sandwich structure, wherein the density of the puncture carbon fiber preform is 0.75g/cm3The volume density of the outer layer of the short fiber is less than or equal to 0.3g/cm3After the outer layer of the short fiber is connected by needling, the density of the prepared carbon fiber preform with the sandwich structure is 0.65g/cm3The outer layer of staple fibers is about 5mm thick. Firstly, a carbon fiber preform is densified by adopting a chemical vapor deposition process. The densification process takes propylene as a carbon source gas and nitrogen as a carrier gas, the deposition temperature is 980 ℃, and the deposition pressure is less than 3 kPa. After 240h of chemical vapor deposition, the density of the prepared material is 1.35g/cm3The sandwich structure of (1) C/C porous material. Dissolving hafnium alkoxide in xylene to form an organic ceramic precursor solution, and repeatedly carrying out ultrahigh-temperature ceramic densification treatment on the C/C porous body with the sandwich structure by adopting a ceramic precursor dipping-cracking process. The specific process comprises the following steps: putting the sandwich structure C/C porous body prepared by chemical vapor deposition into an impregnation tank, vacuumizing to below 2kPa, putting an organic ceramic precursor solution into the impregnation tank to immerse the sandwich structure C/C porous body, and taking out a blank after vacuum impregnation for 0.5 h; putting the dried C/C porous body with the sandwich structure into a graphitization furnace for pyrolysisAnd (3) treating, introducing argon as protective gas, heating to 1500-1600 ℃ for cracking treatment, and keeping the temperature for 60 min. Repeating the precursor impregnation-cracking process for 6 times to obtain the low-density sandwich structure C/C-HfC composite material with the density of 1.6g/cm3. And machining and cutting the low-density sandwich structure C/C-HfC composite material into blocks, and further densifying by taking Zr-Si metal powder as an infiltration agent through infiltration reaction. The specific process comprises the following steps: embedding the low-density sandwich structure C/C-HfC composite material in Zr-Si metal powder, putting the Zr-Si metal powder and the Zr-Si metal powder into a graphite crucible together, and then putting the graphite crucible into a high-temperature graphitization furnace. Vacuumizing to below 0.8kPa, heating to 1700-2100 ℃ at the heating rate of 2-15 ℃/min, preserving the temperature for more than or equal to 0.5h, and then naturally cooling to room temperature. After high-temperature infiltration reaction, the final density of the prepared sandwich structure C/C-HfC-ZrC-SiC composite material is 2.3g/cm3The thickness of the most ceramic outer layer is 3 mm.
The above-mentioned embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications of the technical solutions and concepts of the present invention should be covered by the scope of the present invention.
Claims (8)
1. The preparation method of the sandwich structure C/C ultrahigh-temperature ceramic composite material is characterized by comprising the following steps of:
s1, spreading short fibers on two sides of the carbon fiber preform, and preparing the sandwich fiber preform of the short fiber layer, the common carbon fiber layer and the short fiber layer by adopting a needling process; the volume density of the short fiber layer in the sandwich fiber preform is lower than that of the common carbon fiber layer, and the volume density of the short fiber layer is less than or equal to 0.3g/cm3(ii) a The length of the short fiber is 2-15 cm; the thickness of the short fiber layer is 0.2-10 mm;
s2, placing the sandwich fiber preform in a chemical vapor deposition furnace, and depositing one or two of pyrolytic carbon or silicon carbide by a chemical vapor deposition method to obtain a sandwich structure C/C porous skeleton;
and S3, introducing the superhigh temperature ceramic phase into the sandwich structure C/C porous skeleton by adopting one or more methods of precursor impregnation-pyrolysis, chemical vapor deposition or high-temperature infiltration reaction to obtain the sandwich structure C/C superhigh temperature ceramic composite material.
2. The method for preparing a sandwich structure C/C ultra-high temperature ceramic composite material according to claim 1, wherein the carbon fiber preform is a carbon fiber woven or wound body, in particular a carbon cloth laminate, a needle felt, a multi-dimensional fiber preform of a three-dimensional, needle punched and stitched structure.
3. The method for preparing a sandwich structured C/C ultra high temperature ceramic composite according to claim 1, wherein the short fibers have a fiber length of 2-15 cm.
4. The method for preparing the sandwich structure C/C ultrahigh-temperature ceramic composite material according to claim 1, wherein the step S2 of depositing pyrolytic carbon by chemical vapor deposition specifically comprises the following steps: taking propylene as a carbon source gas and nitrogen as a carrier gas, wherein the deposition pressure is less than or equal to 10KPa, and the deposition temperature is 850-1100 ℃;
the process of depositing silicon carbide by using the chemical vapor deposition method in the step S2 specifically includes: trichloromethylsilane is used as a precursor raw material, hydrogen is used as a carrier gas, trichloromethylsilane steam is brought into a mixing tank in a bubbling mode, Ar and hydrogen are used as diluent gases, the deposition pressure is less than or equal to 1KPa, and the deposition temperature is 1150 ℃.
5. The method for preparing sandwich structure C/C ultra-high temperature ceramic composite material according to claim 1, wherein the ultra-high temperature ceramic is SiC, ZrC, HfC, TaC, ZrB2、HfB2One or more of (a).
6. The method for preparing the sandwich structure C/C ultra-high temperature ceramic composite material according to claim 1, wherein the precursor impregnation-cracking method in the step S3 is specifically as follows: repeatedly dipping, drying and pyrolyzing the C/C porous skeleton by using an ultrahigh-temperature ceramic precursor as a impregnant; when the crusting and hole sealing phenomena occur in the dipping-cracking process, carrying out hole opening treatment, and then carrying out next round of dipping, drying and high-temperature cracking;
the high-temperature infiltration process in the step S3 specifically includes: one or more of zirconium, hafnium, silicon metal or alloy thereof is used as an infiltration agent, and an ultrahigh-temperature ceramic phase is formed in the C/C porous framework through infiltration reaction; vacuumizing to below 0.8kPa, heating to 1400-2300 ℃ at a heating rate of 2-15 ℃/min, preserving the temperature for more than or equal to 0.5h, and then naturally cooling to room temperature.
7. A sandwich structured C/C ultra high temperature ceramic composite material, characterized in that it is obtained by the preparation method according to any of claims 1 to 6.
8. The sandwich structured C/C ultra high temperature ceramic composite according to claim 7, wherein the composite comprises an inner layer of C/C ultra high temperature ceramic and an outer layer of high content ultra high temperature ceramic, the outer layer of high content ultra high temperature ceramic having a thickness of 0.2-7 mm.
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