CN116803953A - High-temperature-resistant long-life ablation-resistant ceramic modified carbon/carbon composite material and preparation method and application thereof - Google Patents
High-temperature-resistant long-life ablation-resistant ceramic modified carbon/carbon composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 102
- 238000002679 ablation Methods 0.000 title claims abstract description 73
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- 239000000919 ceramic Substances 0.000 title claims abstract description 31
- 150000001721 carbon Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 20
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 37
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- 238000000151 deposition Methods 0.000 claims description 17
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Abstract
The invention discloses a high-temperature-resistant and long-life ablation-resistant ceramic modified carbon/carbon composite material and a preparation method and application thereof, and belongs to the technical field of preparation of anti-oxidation and ablation-resistant carbon/carbon composite materials. According to the invention, the HfC ultra-high temperature ceramic is introduced into the porous C/C composite material through PIP, so that the uniform distribution of the HfC ultra-high temperature ceramic in the carbon matrix is realized. ZrC is generated by virtue of the reaction of Zr-Cu powder and a carbon matrix, so that the rapid densification of the matrix at low temperature is realized, and the ceramic modified C/C composite material which can be applied for a long time in a high-flow strong-scouring ablation environment is prepared. The heat flux density of the HfC-ZrC-Cu synergistically modified C/C composite material prepared by the invention is 4.18MW/m 2 Oxyacetylene flame of (a)The sample is still complete after 600s of lower cycle ablation, and the mass ablation rate and the line ablation rate are respectively 0.544mg/s and 0.107 mu m/s, so that the sample has excellent cycle ablation resistance.
Description
Technical Field
The invention belongs to the technical field of preparation of anti-oxidation anti-ablation carbon/carbon composite materials, and particularly relates to a high-temperature-resistant long-service-life anti-ablation ceramic modified carbon/carbon composite material, and a preparation method and application thereof.
Background
Typical working environment characteristics such as high temperature, long time, aerobic, complex heat/force load and the like enable hypersonic aircrafts to provide urgent demands and serious challenges for heat protection and heat structural materials, and development of novel high temperature-resistant, long-life anti-oxidation and anti-ablation composite materials is urgently needed to meet the demands of development in the fields of aerospace industry and national defense science and technology. The C/C composite material is considered as one of the most promising new materials because of its low density, high specific strength, high modulus of orientation, low coefficient of thermal expansion, and especially the ability to maintain high strength at ultra-high temperatures, however its susceptibility to oxidation under high temperature aerobic environments severely limits its application.
It has been proposed to introduce ultra-high temperature ceramics into the matrix of the C/C composite to increase its oxidation resistance and reduce the ablation rate so that it can withstand higher gas temperatures or longer operating times. Precursor impregnation cracking (PIP), reaction infiltration (RMI), chemical Vapor Infiltration (CVI), gas phase siliconizing (GSI), slurry Impregnation (SI) and other methods developed by scholars at home and abroad successfully introduce various oxidation-resistant ablative ceramics into the C/C composite material.
The GSI can prepare a uniform and compact C/C-SiC composite material, effectively prevents oxygen permeation, and has a thermal expansion coefficient which is relatively matched with that of the C/C composite material, so that the composite material is not easy to crack at high temperature. However, si is easy to remain in the matrix in the gas phase siliconizing process, and the Si is quickly volatilized in a high-temperature environment due to lower melting point and vapor pressure, so that the stability of service performance is not facilitated. The SI technology is simple and has lower cost, but particles are easy to agglomerate on the surface of the material, so that the surface layer is sealed, and more pores are reserved in the surface layer; PIP can introduce various ceramics at the same time in the C/C composite material, but precursor ceramics have low yield, compact modified C/C composite material can be prepared only by repeated dipping-drying-cracking cycles, so that the production period is long, the volume shrinkage of the precursor after cracking is large, and cracks and air holes are easy to generate; the CVI method can be prepared at a lower temperature, the residual stress in the material is small, the carbon fiber is hardly damaged, and the component design on the microscopic scale can be realized. However, the requirements on equipment are high, the preparation period is long, the production cost is high, and the phenomenon of surface crusting is easy to form in the preparation process, so that the further densification is influenced; RMI has the advantages of short period, low cost, low residual porosity and near net forming, but because of the higher reaction temperature in the RMI method, unavoidable severe reaction exists between the fiber and the melt, and certain damage is easily caused to the carbon fiber in the C/C matrix, so that the mechanical property of the composite material is poor. Therefore, if the RMI method can be organically combined with other preparation processes, the damage of melt to fiber in the infiltration preparation process can be avoided, and the performance of the composite material can be effectively improved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a high-temperature-resistant and long-service-life ablation-resistant ceramic modified carbon/carbon composite material, and a preparation method and application thereof, which can effectively avoid the technical problem that the fiber is damaged by melt in the preparation process, so that the carbon/carbon composite material has poor cyclic ablation resistance.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of a high-temperature-resistant and long-service-life ablation-resistant ceramic modified carbon/carbon composite material, which comprises the following steps:
1) Uniformly mixing a hafnium carbide (HfC) ceramic precursor with xylene to prepare an HfC ceramic precursor solution;
2) Adopting thermal gradient chemical vapor deposition method to prepare the material with the density of 1.0-1.3g/cm 3 C/C composite material of (2), drying for later use;
3) Placing the C/C composite material prepared in the step 2) into HfC ceramic precursor solution for vacuum infiltration treatment, and then drying;
4) Carrying out ultrasonic vibration treatment on the C/C composite material treated in the step 3), and drying for later use;
5) Carrying out high-temperature heat treatment on the C/C composite material obtained by the treatment in the step 4) under the protection of argon;
6) Repeating the steps 3) to 5) until the density of the sample is increased to 1.5-1.8g/cm 3 ；
7) Fully embedding the sample obtained in the step 6) by adopting Zr-Cu powder, then heating to 1100-1300 ℃ from room temperature under vacuum condition, carrying out heat preservation treatment for 2-4 h, cooling to 800 ℃, and then cooling to room temperature to obtain the high-temperature-resistant and long-service-life ablation-resistant ceramic modified carbon/carbon composite material.
Preferably, in step 1), xylene and HfC ceramic precursor mixture is used because of the better dispersibility of the HfC ceramic precursor in xylene.
Preferably, in step 1), the HfC ceramic precursor solution comprises 40% -50% of the total mass of the HfC ceramic precursor solution and 50% -60% of the xylene.
Preferably, in step 2), the specific operations include:
the 2.5D needled carbon felt preform is deposited for 15 to 25 hours under the conditions that the pressure is 6 to 12kPa and the temperature is 900 to 1200 ℃, the flow of natural gas in the deposition process is controlled to be 2 to 5L/min, and the deposition is cooled to room temperature to obtain the carbon felt preform with the density of 1.0 to 1.3g/cm 3 C/C composite of (C).
Further preferably, in step 2), the method further comprises the step of preparing a material having a density of 1.0-1.3g/cm 3 The C/C composite material of (2) is processed into a wafer sample for performing an ablation test, and the reason for processing the wafer sample is to facilitate the ablation test.
In the step 2), the C/C composite material is placed in absolute ethyl alcohol for ultrasonic cleaning for 10-30min, and then is placed in an oven for drying at 60-90 ℃ for 1-3h for standby.
Preferably, in step 3), a density of 1.0-1.3g/cm is used 3 Placing the C/C composite material in the HfC ceramic precursor solution prepared in the step 1), performing vacuum infiltration treatment under the vacuum degree of 0.05-0.1MPa for 30-60min, and then taking out the C/C composite material and drying at 60-100 ℃ for 24-48h. The vacuum impregnation treatment is to make the HfC ceramic precursor more easily impregnate the inside of the C/C composite.
Preferably, in the step 4), the C/C composite material treated in the step 3) is placed in dimethylbenzene, subjected to ultrasonic oscillation for 1-3min, subjected to ultrasonic power of 50-100W, and dried at 60-90 ℃ for 1-3h for later use. This step will remove the poorly bound precursor.
In the step 5), the C/C composite material treated in the step 4) is treated for 1-2 hours at 1600-1850 ℃ under the protection of argon.
Preferably, in step 7), a vacuum is applied to 1.0X10 -2 MPa; heating to 1100-1300 ℃ at a heating rate of 5 ℃/min; cooling to 800 ℃ at a cooling rate of 5 ℃/min, and cooling to room temperature along with a furnace to obtain the high-temperature-resistant and long-service-life ablation-resistant ceramic modified carbon/carbon composite material, namely the compact HfC-ZrC-Cu modified C/C composite material.
The invention also discloses the high-temperature-resistant long-life ablation-resistant ceramic modified carbon/carbon composite material prepared by the preparation method.
The invention also discloses application of the high-temperature-resistant long-life ablation-resistant ceramic modified carbon/carbon composite material in preparation of hypersonic aircrafts.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the high-temperature-resistant long-life ablation-resistant ceramic modified carbon/carbon composite material, an innovative thought of preparing the HfC-ZrC-Cu synergistically modified C/C composite material by combining a PIP process and a low-temperature RMI process is provided for the first time, on one hand, the HfC ultra-high-temperature ceramic is introduced into the porous C/C composite material through PIP, so that the even distribution of the HfC ultra-high-temperature ceramic in a carbon matrix is realized, on the other hand, the low-temperature RMI process is adopted, zrC is generated by virtue of the reaction of Zr-Cu powder and the carbon matrix, the rapid densification of the matrix at low temperature is realized, and the ceramic modified C/C composite material capable of being applied for a long time under a high-flow strong-erosion ablation environment is prepared. The low-temperature RMI process not only reduces the damage to the fiber caused by the reaction infiltration process, but also can slow down the Zr-C reaction rate, thereby improving the compactness of the material.
Experimental results show that the heat flux density of the HfC-ZrC-Cu synergistically modified C/C composite material prepared by the invention is 4.18MW/m 2 Is ablated by oxygen acetylene flameAfter 600s, the sample is still complete, and the mass ablation rate and the line ablation rate are respectively 0.544mg/s and 0.107 mu m/s, so that the sample has excellent anti-cycle ablation performance.
Drawings
FIG. 1 is an XRD pattern of a HfC-ZrC-Cu co-modified C/C composite;
FIG. 2 is an SEM photograph and EDS energy spectrum of a HfC-ZrC-Cu synergistically modified C/C composite; wherein, (a) is a high magnification photograph; (b) and (c) are low magnification photographs; (d), (e) and (f) are EDS spectra;
FIG. 3 is a photograph of macroscopic morphology of the HfC-ZrC-Cu synergistically modified C/C composite material before and after ablation: (a) prior to ablation; (b) after 120s of ablation; (c) after 240s ablation; (d) after 360s ablation; (e) after 480s of ablation; (f) after 600s of ablation;
FIG. 4 is a photomicrograph of the microscopic morphology and EDS pattern of the center and edge regions of the HfC-ZrC-Cu co-modified C/C composite material after 600s cycle ablation: (a) and (b) being central regions; (c) an EDS profile;
FIG. 5 is a SEM photograph and EDS energy spectrum of a cross section of a HfC-ZrC-Cu co-modified C/C composite material after 600s cycle ablation: wherein, (a) a low magnification photograph; (b) high magnification photographs; (c) The (d), (e) and (f) are C, O, zr and Hf element surface energy spectrums respectively.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the attached drawing figures:
hafnium carbide ceramic precursors (HfC ceramic precursors) used in the following examples of the present invention were purchased from the institute of Process engineering, national academy of sciences.
Example 1
1) Weighing a certain proportion of HfC ceramic precursor, mixing with dimethylbenzene, wherein the mass fraction of the organohafnium polymer is 40wt%, and the mass fraction of the dimethylbenzene is 60wt%, and carrying out ultrasonic treatment and magnetic stirring to obtain HfC ceramic precursor solution;
2) And cleaning and drying the 2.5D needled carbon felt preform, putting the cleaned and dried carbon felt preform into a thermal gradient furnace, pumping the pressure in the deposition furnace to 8kPa by using a vacuum pump, performing deposition for 20 hours at 1000 ℃, controlling the flow of natural gas to be 3.5L/min in the deposition process, powering off and cooling after the deposition is completed, and cooling to room temperature to obtain the low-density C/C composite material.
3) The density of the catalyst is 1.0g/cm 3 Processing the low-density C/C into a wafer with the size of phi 30mm multiplied by 5mm, placing the wafer into absolute ethyl alcohol for ultrasonic cleaning for 10min, and placing the wafer into an oven for drying at 60 ℃ for 3h for later use;
4) And (3) placing the sample obtained in the step (3) into the HfC ceramic precursor solution obtained in the step (1) for infiltration, and controlling the vacuum degree to be 0.1MPa for infiltration for 30min. The sample was then removed and dried in an oven at 70 ℃ for 40 hours;
5) Placing the sample obtained in the step 4) into dimethylbenzene for ultrasonic oscillation for 1min, and taking out the sample, placing the sample into an oven for drying at 90 ℃ for 1h for later use, wherein the ultrasonic power is 100W;
6) Placing the sample obtained in the step 5) into a high-temperature heat treatment furnace, and treating for 1.5 hours at 1650 ℃ under the protection of argon;
7) Repeating the steps 4) to 6) until the density of the sample is increased to 1.5-1.8g/cm 3 ；
8) Spreading a layer of Zr-Cu powder with the thickness of 8mm at the bottom of a graphite crucible, placing the sample obtained in the step 7) on the Zr-Cu powder, adding the Zr-Cu powder, fully embedding the sample, sealing the graphite crucible, placing the graphite crucible into a vacuum hot-pressing furnace, and vacuumizing to 1.0x10 in the whole process -2 MPa; heating to 1100 ℃ at a heating rate of 5 ℃/min, and cooling to 800 ℃ after heat preservation for 4 hours, wherein the cooling rate is 5 ℃/min; and then cooling along with the furnace after power failure, thus preparing the HfC-ZrC-Cu modified C/C composite material.
Referring to FIG. 1, the XRD pattern of the HfC-ZrC-Cu co-modified C/C composite is shown. As can be seen from fig. 1, hfC, zrC, cu and C were detected on the surface of the prepared superhigh temperature ceramic modified sample. Because of the close diffraction angles of the HfC and ZrC characteristic peaks, their peaks in the XRD pattern are overlapping. Wherein HfC is led into the C/C composite material by a PIP process, zrC and Cu are generated by the reaction of Zr-Cu alloy powder and a carbon matrix, which shows that the PIP combined low-temperature RMI process can successfully realize the multi-element ceramic co-modified C/C composite material.
Example 2
1) Weighing a certain proportion of HfC ceramic precursor, mixing with dimethylbenzene, wherein the mass fraction of the organohafnium polymer is 45wt%, and the mass fraction of the dimethylbenzene is 55wt%, and carrying out ultrasonic treatment and magnetic stirring to obtain HfC ceramic precursor solution;
2) Cleaning and drying a 2.5D needled carbon felt preform, putting the cleaned and dried carbon felt preform into a thermal gradient furnace, pumping the pressure in the deposition furnace to 10kPa by using a vacuum pump, performing deposition for 20 hours at 950 ℃, controlling the flow of natural gas to be 4L/min in the deposition process, powering off and cooling after the deposition is completed, and cooling to room temperature to obtain a low-density C/C composite material;
3) The density of the catalyst is 1.15g/cm 3 Processing the low-density C/C of (2) into a wafer with the size phi of 30mm multiplied by 5mm, placing the wafer into absolute ethyl alcohol for ultrasonic cleaning for 15min, and then placing the wafer into an oven for drying at 70 ℃ for 2.5h for later use;
4) And (3) placing the sample obtained in the step (3) into the HfC ceramic precursor solution obtained in the step (1) for infiltration, and controlling the vacuum degree to be 0.08MPa for 45min. The sample was then removed and dried in an oven at 60 ℃ for 48 hours;
5) Placing the sample obtained in the step 4) into dimethylbenzene for ultrasonic oscillation for 3min at the ultrasonic power of 50W, taking out, and placing into an oven for drying at 90 ℃ for 1h for later use;
6) Placing the sample obtained in the step 5) into a high-temperature heat treatment furnace, and treating for 2 hours at 1600 ℃ under the protection of argon;
7) Repeating the steps 4) to 6) until the density of the sample is increased to 1.5-1.8g/cm 3 ；
8) Spreading a layer of Zr-Cu powder with the thickness of 12mm at the bottom of a graphite crucible, placing the sample obtained in the step 7) on the Zr-Cu powder, adding the Zr-Cu powder, fully embedding the sample, sealing the graphite crucible, placing the graphite crucible into a vacuum hot-pressing furnace, and vacuumizing to 1.0x10 in the whole process -2 MPa; heating to 1250 ℃ at a heating rate of 5 ℃/min, and cooling to 800 ℃ after heat preservation for 2 hours, wherein the cooling rate is 5 ℃/min; and then cooling along with the furnace after power failure, thus preparing the HfC-ZrC-Cu modified C/C composite material.
Referring to fig. 2, it can be seen that after the PIP combined low temperature RMI process, a large number of HfC particles and Zr melt infiltrate into the C/C composite with the carbides uniformly distributed in the matrix. The section of the composite material consists of black, gray and white phases and dispersed tissues inside the black, gray and white phases. There were very few holes in the composite, but no significant cracks. From EDS spectra (fig. 2 (d), (e), and (f)), black phase particles mainly consist of C element, gray phase particles mainly consist of Zr element, C element, and Cu element, and white phase particles mainly consist of Hf element, C element, and Cu element; as is clear from XRD analysis, the black phase is C, the gray phase is ZrC, the white phase is HfC, and the substances dispersed in the off-white phase are residual metal Cu (fig. 2 (C)).
Example 3
1) Weighing a certain proportion of HfC ceramic precursor, mixing with dimethylbenzene, wherein the mass fraction of the organohafnium polymer is 50wt%, and carrying out ultrasonic treatment and magnetic stirring to obtain HfC ceramic precursor solution;
2) Cleaning and drying a 2.5D needled carbon felt preform, putting the cleaned and dried carbon felt preform into a thermal gradient furnace, pumping the pressure in the deposition furnace to 12kPa by using a vacuum pump, performing deposition at 900 ℃ for 25 hours, controlling the flow of natural gas to be 5L/min in the deposition process, powering off and cooling after the deposition is completed, and cooling to room temperature to obtain a low-density C/C composite material;
3) The density of the catalyst is 1.2g/cm 3 Processing the low-density C/C of (2) into a wafer with the size phi of 30mm multiplied by 5mm, placing the wafer into absolute ethyl alcohol for ultrasonic cleaning for 20min, and then placing the wafer into an oven for drying at 80 ℃ for 1.5h for later use;
4) And (3) placing the sample obtained in the step (3) into the HfC ceramic precursor solution obtained in the step (1) for infiltration, and controlling the vacuum degree to be 0.05MPa for infiltration for 60min. The sample was then removed and dried in an oven at 80 ℃ for 36h;
5) Placing the sample obtained in the step 4) into dimethylbenzene for ultrasonic oscillation for 2min, and placing the sample into an oven for drying at 60 ℃ for 3h for standby after taking out the sample and placing the sample into an ultrasonic power of 80W;
6) Placing the sample obtained in the step 5) into a high-temperature heat treatment furnace, and treating for 1h at 1850 ℃ under the protection of argon;
7) Repeating the steps 4) to 6) until the density of the sample is increased to 1.5-1.8g/cm 3 ；
8) Spreading a layer of Zr-Cu powder with the thickness of 10mm at the bottom of a graphite crucible, placing the sample obtained in the step 7) on the Zr-Cu powder, adding the Zr-Cu powder, fully embedding the sample, sealing the graphite crucible, placing the graphite crucible into a vacuum hot-pressing furnace, and vacuumizing to 1.0x10 in the whole process -2 MPa; heating to 1200 ℃ at a heating rate of 5 ℃/min, and cooling to 800 ℃ after heat preservation for 3 hours, wherein the cooling rate is 5 ℃/min; and then cooling along with the furnace after power failure, thus preparing the HfC-ZrC-Cu modified C/C composite material.
Referring to fig. 3, fig. 3 is a photograph of macroscopic morphology of the HfC-ZrC-Cu synergistically modified C/C composite material prepared in this example before and after ablation. As can be seen in fig. 3, a white solid coating appears on the ablated surface of the sample. As can be seen from fig. 3 (b) and (C), after ablating for 120s and 240s, the white area portion of the surface of the HfC-ZrC-Cu synergistically modified C/C composite is substantially complete, and no black carbon matrix is exposed. After 360s ablation (shown in fig. 3 (d)), the white areas of the ablation center of the HfC-ZrC-Cu synergistically modified C/C composite became incomplete. After 480s of ablation (shown in (e) of fig. 3), the central oxide film ablated by the HfC-ZrC-Cu synergistically modified C/C composite material has the signs of sintering and melting, the edge oxide film has slight bulges, and the overall fluctuation is smaller. After 600s ablation, the oxide film on the surface of the HfC-ZrC-Cu synergistically modified C/C composite material has no obvious change (shown in (f) of fig. 3), and the oxide film in the central area almost covers the internal material in the whole area, so that the composite material has excellent high-temperature resistance, long service life and ablation resistance.
Example 4
1) Weighing a certain proportion of HfC ceramic precursor, mixing the HfC ceramic precursor with dimethylbenzene, wherein the mass fraction of the organohafnium polymer is 42wt%, the mass fraction of the dimethylbenzene is 58wt%, and carrying out ultrasonic treatment and magnetic stirring to obtain HfC ceramic precursor solution;
2) Cleaning and drying a 2.5D needled carbon felt preform, putting the cleaned and dried carbon felt preform into a thermal gradient furnace, pumping the pressure in the deposition furnace to 6kPa by using a vacuum pump, performing deposition for 15 hours at 1200 ℃, controlling the flow of natural gas to be 2L/min in the deposition process, powering off and cooling after the deposition is completed, and cooling to room temperature to obtain the low-density C/C composite material;
3) The density of the catalyst is 1.25g/cm by thermal gradient chemical vapor deposition 3 Processing the low-density C/C of (2) into a wafer with the size phi of 30mm multiplied by 5mm, placing the wafer into absolute ethyl alcohol for ultrasonic cleaning for 25min, and then placing the wafer into an oven for drying at 80 ℃ for 2h for later use;
4) And (3) placing the sample obtained in the step (3) into the HfC ceramic precursor solution obtained in the step (1) for infiltration, and controlling the vacuum degree to be 0.06MPa for infiltration for 50min. The sample was then removed and dried in an oven at 90 ℃ for 30 hours;
5) Placing the sample obtained in the step 4) into dimethylbenzene for ultrasonic oscillation for 2min, and taking out the sample and placing the sample into an oven for drying at 80 ℃ for 1.5 hours for later use, wherein the ultrasonic power is 70W;
6) Placing the sample obtained in the step 5) into a high-temperature heat treatment furnace, and treating for 1.5 hours at 1700 ℃ under the protection of argon;
7) Repeating the steps 4) to 6) until the density of the sample is increased to 1.5-1.8g/cm 3 ；
8) Spreading a layer of Zr-Cu powder with the thickness of 15mm at the bottom of the graphite crucible, placing the sample obtained in the step 7) on the Zr-Cu powder, adding the Zr-Cu powder, fully embedding the sample, sealing the graphite crucible, placing the graphite crucible into a vacuum hot-pressing furnace, and vacuumizing to 1.0x10 in the whole process -2 MPa; heating to 1300 ℃ at a heating rate of 5 ℃/min, and cooling to 800 ℃ after heat preservation for 2 hours, wherein the cooling rate is 5 ℃/min; and then cooling along with the furnace after power failure, thus preparing the HfC-ZrC-Cu modified C/C composite material.
FIG. 4 is an SEM photograph and an EDS map of a center region and an edge region of the HfC-ZrC-Cu collaborative modified C/C composite material prepared in the present example after cyclic ablation. As can be seen from FIG. 4 (a), the heat flux density was 4.18MW/m 2 After 600s of circulation in oxyacetylene ablation environment, a dense oxide layer is formed on the surface of the sample. As can be seen from fig. 4 (a), the sample remains intact after cyclic ablation, and no significant oxidative ablation occurs. From EDS spectroscopy (fig. 4 (c)) analysis, this region is composed mainly of Zr element, hf element, and O element. The glass layer material generated by ablating the central region of the sample (FIG. 4 (a)) was ZrO 2 And HfO 2 The solution of the material is generated by high-temperature melting, and the melt spreads on the surface of an ablated sample under the action of strong air flow to form a barrier layer, so that the oxidizing atmosphere is prevented from entering the material, and the material plays a key role in improving the ablation resistance of the material. It can also be seen from fig. 4 (b) that some micropores exist in the center surface. During the ablation process, cu vapor, CO and CO 2 The massive escape of the gases to the outside of the material can result in an ablated surface HfO 2 -ZrO 2 The protection layer forms a hole. Cu volatilizes and can play a role in sweating, so that the ablation temperature of the surface of the sample is reduced, and the long-time anti-ablation performance of the sample is improved.
Example 5
1) Weighing a certain proportion of HfC ceramic precursor, mixing with xylene, wherein the mass fraction of the organohafnium polymer is 48wt%, and the mass fraction of the xylene is 52wt%, and performing ultrasonic treatment and magnetic stirring to obtain HfC ceramic precursor solution;
2) Cleaning and drying a 2.5D needled carbon felt preform, putting the cleaned and dried carbon felt preform into a thermal gradient furnace, pumping the pressure in the deposition furnace to 9kPa by using a vacuum pump, performing deposition for 18 hours at 1100 ℃, controlling the flow of natural gas to be 3L/min in the deposition process, powering off and cooling after the deposition is completed, and cooling to room temperature to obtain a low-density C/C composite material;
3) The density of the catalyst is 1.3g/cm 3 Processing the low-density C/C of (2) into a wafer with the size phi of 30mm multiplied by 5mm, placing the wafer into absolute ethyl alcohol for ultrasonic cleaning for 30min, and placing the wafer into an oven for drying at 90 ℃ for 1h for later use;
4) And (3) placing the sample obtained in the step (3) into the HfC ceramic precursor solution obtained in the step (1) for infiltration, and controlling the vacuum degree to be 0.09MPa for infiltration for 40min. The sample was then removed and dried in an oven at 100 ℃ for 24 hours;
5) Placing the sample obtained in the step 4) into dimethylbenzene for ultrasonic oscillation for 1min, and taking out the sample, placing the sample into an oven for drying at 70 ℃ for 2h for later use, wherein the ultrasonic power is 90W;
6) Placing the sample obtained in the step 5) into a high-temperature heat treatment furnace, and treating for 1h at 1800 ℃ under the protection of argon;
7) Repeating the steps 4) to 6) until the density of the sample is increased to 1.5-1.8g/cm 3 ；
8) Spreading a layer of Zr-Cu powder with the thickness of 9mm at the bottom of the graphite crucible, placing the sample obtained in the step 7) on the Zr-Cu powder, adding the Zr-Cu powder, fully embedding the sample, sealing the graphite crucible, placing the graphite crucible into a vacuum hot-pressing furnace, and vacuumizing to 1.0x10 in the whole process -2 MPa; heating to 1150 ℃ at a heating rate of 5 ℃/min, and cooling to 800 ℃ after heat preservation for 4 hours, wherein the cooling rate is 5 ℃/min; and then cooling along with the furnace after power failure, thus preparing the HfC-ZrC-Cu modified C/C composite material.
Referring to FIG. 5, a cross-sectional SEM photograph and an EDS map of a central region of the HfC-ZrC-Cu collaborative modified C/C composite material prepared in the present example after cyclic ablation are shown. As can be seen from FIGS. 5 (a) and (b), the heat flux density was 4.18MW/m 2 After 600s of cyclic ablation in oxyacetylene ablation environment, the section of the sample has no ablation dent and oxide layerThe compactness is good. As can be seen from the surface energy spectra (FIGS. 5 (c), (d), (e) and (f)) thereof, the oxide layer contains a large amount of Zr element and Hf element, illustrating HfO 2 With ZrO 2 Has good solid solution effect. The complete and dense oxide layer is beneficial to preventing the oxyacetylene flame from further corroding the internal matrix, and further shows excellent anti-ablation performance.
In addition, the ablation performance test of the HfC-ZrC-Cu collaborative modified C/C composite materials prepared in the above examples 1 to 5 of the present invention shows that the thermal flux density of the composite material is 4.18MW/m 2 The sample is still complete after 600s of cyclic ablation under oxyacetylene flame, and the comprehensive average data shows that the mass ablation rate and the linear ablation rate are respectively 0.544mg/s and 0.107 mu m/s, and the excellent cyclic ablation resistance is shown. The mass ablation rate and the line ablation rate for specific examples are shown in table 1:
TABLE 1 ablative Properties of materials prepared in different examples
In summary, the invention prepares the HfC-ZrC-Cu synergistically modified C/C composite material by adopting the PIP combined low-temperature RMI process. In one aspect, the PIP process introduces HfC into the porous C/C composite, achieving a uniform distribution of HfC ceramic in the carbon matrix. On the other hand, the rapid densification treatment of the C/C-HfC composite material obtained by PIP is realized by adopting low-temperature reaction infiltration Zr-Cu alloy, and the low-temperature RMI technology not only reduces the damage to fibers in the reaction infiltration process, but also can slow down the Zr-C reaction rate, thereby improving the compactness of the material.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The preparation method of the high-temperature-resistant and long-service-life ablation-resistant ceramic modified carbon/carbon composite material is characterized by comprising the following steps of:
1) Uniformly mixing a hafnium carbide ceramic precursor with xylene to prepare a hafnium carbide ceramic precursor solution;
2) The density is 1.0-1.3g/cm by adopting a thermal gradient chemical vapor deposition method 3 C/C composite material of (2), drying for later use;
3) Placing the C/C composite material into a hafnium carbide ceramic precursor solution for vacuum infiltration treatment, and then drying;
4) Carrying out ultrasonic vibration treatment on the C/C composite material treated in the step 3), and drying for later use;
5) Carrying out high-temperature heat treatment on the C/C composite material obtained by the treatment in the step 4) under the protection of argon;
6) Repeating the steps 3) to 5) until the density of the C/C composite material is increased to 1.5 to 1.8g/cm 3 ；
7) Increasing the density to 1.5-1.8g/cm 3 The C/C composite material is fully embedded by adopting Zr-Cu powder, then the temperature is raised to 1100-1300 ℃ from room temperature under vacuum condition, the heat preservation treatment is carried out for 2-4 hours, the temperature is reduced to 800 ℃, and then the temperature is cooled to room temperature, so that the high-temperature-resistant and long-life anti-ablation ceramic modified carbon/carbon composite material is prepared.
2. The method for preparing the high-temperature-resistant long-life ablation-resistant ceramic modified carbon/carbon composite material according to claim 1, wherein in the step 1), the hafnium carbide ceramic precursor accounts for 40% -50% of the total mass of the hafnium carbide ceramic precursor solution, and the xylene accounts for 50% -60%.
3. The method for preparing the high-temperature-resistant long-life ablation-resistant ceramic modified carbon/carbon composite material according to claim 1, wherein in the step 2), the specific operations comprise: the 2.5D needled carbon felt preform is deposited for 15 to 25 hours under the conditions that the pressure is 6 to 12kPa and the temperature is 900 to 1200 ℃, the flow of natural gas in the deposition process is controlled to be 2 to 5L/min, and the deposition is cooled to room temperature to obtain the carbon felt preform with the density of 1.0 to 1.3g/cm 3 C/C composite of (C).
4. The method for preparing the high-temperature-resistant long-life ablation-resistant ceramic modified carbon/carbon composite material according to claim 3, wherein in the step 2), the prepared density is 1.0-1.3g/cm 3 Placing the C/C composite material in absolute ethyl alcohol, ultrasonically cleaning for 10-30min, placing in an oven, drying at 60-90 ℃ for 1-3h for standby.
5. The method for preparing the high-temperature-resistant long-life ablation-resistant ceramic modified carbon/carbon composite material according to claim 1, wherein in the step 3), the C/C composite material is placed in an HfC ceramic precursor solution, infiltration treatment is carried out under the condition that the vacuum degree is controlled to be 0.05-0.1MPa, the infiltration time is 30-60min, and then a wafer sample is taken out at 60-100 ℃ and dried for 24-48h.
6. The method for preparing the high-temperature-resistant long-life ablation-resistant ceramic modified carbon/carbon composite material according to claim 1, wherein in the step 4), the C/C composite material treated in the step 3) is placed in dimethylbenzene, subjected to ultrasonic vibration for 1-3min, subjected to ultrasonic power of 50-100W, and dried at 60-90 ℃ for 1-3h after being taken out for later use.
7. The method for preparing the high temperature resistant, long life and ablation resistant ceramic modified carbon/carbon composite material according to claim 1, wherein in step 5), the treatment is performed for 1-2 hours at 1600-1850 ℃ under the protection of argon.
8. The method for preparing the high temperature resistant, long life and ablation resistant ceramic modified carbon/carbon composite material according to claim 1, wherein in step 7), the vacuum is applied to 1.0x10 -2 MPa; heating to 1100-1300 ℃ at a heating rate of 5 ℃/min; cooling to 800 ℃ at a cooling rate of 5 ℃/min, and cooling to room temperature along with a furnace to obtain the high-temperature-resistant and long-service-life ablation-resistant ceramic modified carbon/carbon composite material, namely the compact HfC-ZrC-Cu modified C/C composite material.
9. A high temperature resistant long life ablation resistant ceramic modified carbon/carbon composite material made by the method of any one of claims 1 to 8.
10. The use of the high temperature resistant long life ablation resistant ceramic modified carbon/carbon composite material of claim 9 in the preparation of hypersonic aircraft.
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