CN112110748A - Preparation method of two-dimensional high-thermal-conductivity C/C-ZrC-SiC composite material - Google Patents
Preparation method of two-dimensional high-thermal-conductivity C/C-ZrC-SiC composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a two-dimensional high-thermal-conductivity C/C-ZrC-SiC composite material. Firstly, weaving mesophase pitch-based carbon fibers into carbon cloth after two-stage carbonization; then spraying intermediate phase asphalt powder and Si-Zr alloy powder and then carrying out vacuum hot pressing. And (3) performing carbonization treatment after hot-pressing and demolding, and performing graphitization and ceramic treatment after carbonization. Finally, the graphitized composite material is continuously densified to 2.11g/cm by a precursor liquid impregnation pyrolysis method3The C/C-ZrC-SiC composite material with better oxidation resistance and ablation resistance has a thermal conductivity coefficient of 150-250W/(mK) in the X or Y direction.
Description
Technical Field
The invention belongs to the technical field of structural function integrated composite materials, and particularly relates to a preparation method of a two-dimensional high-thermal-conductivity C/C-ZrC-SiC composite material.
Background
The ultrahigh-temperature ceramic modified C/C composite material inherits the characteristics of the C/C composite material and the ultrahigh-temperature ceramic, has the excellent characteristics of light weight, high strength, corrosion resistance, oxidation resistance, thermal shock resistance, ablation resistance, good high-temperature mechanical property and the like, is an ideal candidate material serving in a future ultrahigh-temperature environment, and is a typical ultrahigh-temperature ceramic modified C/C composite material. However, if the high thermal conductivity C/C-ZrC-SiC composite material adopts the mesophase pitch-based carbon fiber as a reinforcement and a carrier for heat conduction, the mechanical property and the thermal conductivity of the final composite material are obviously reduced due to the high modulus and poor weaving process property of the high thermal conductivity mesophase pitch-based carbon fiber, and the fiber damage is easy to occur during weaving. And how to improve the heat-conducting property of the C/C-ZrC-SiC, namely, the reliability of the material component of the composite material is improved by reducing the surface temperature of the composite material in service is also a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method of a two-dimensional high-thermal-conductivity C/C-ZrC-SiC composite material which is light in weight, high in strength, corrosion-resistant, oxidation-resistant, thermal shock-resistant, ablation-resistant and good in high-temperature mechanical property.
The invention provides a preparation method of a C/C-ZrC-SiC composite material, which comprises the following steps:
(1) carrying out primary carbonization on the mesophase pitch carbon fibers to obtain carbon fibers I, then carrying out secondary carbonization on the carbon fibers I to obtain carbon fibers II, weaving the carbon fibers II into carbon cloth I, spraying a suspension of mesophase pitch powder onto the surface of the carbon cloth I, and drying to obtain the carbon cloth II; then spraying Si-Zr alloy powder on the surface of the carbon cloth II to obtain carbon cloth III;
(2) after the carbon cloth III is subjected to vacuum hot pressing and three-stage carbonization, carrying out graphite and ceramic treatment to obtain a porous C/C-ZrC-SiC composite material skeleton;
(3) and (3) carrying out dipping pyrolysis densification on the porous C/C-ZrC-SiC composite material skeleton by adopting precursor liquid comprising an organic zirconium source and an organic silicon source to obtain the two-dimensional C/C-ZrC-SiC composite material.
The temperature of the primary carbonization is 500-700 ℃.
The strength of the carbon fiber I is 0.30-0.45 GPa.
The modulus of the carbon fiber I is 8-50 GPa.
The temperature of the secondary carbonization is 1000-1800 ℃.
The strength of the carbon fiber II is 100-300 GPa.
The modulus of the carbon fiber II is 1-2 GPa.
The carbon cloth I is plain, twill or satin carbon cloth.
The spraying is two-sided spraying.
The step (1) further comprises the step of performing rubber mold rolling on the carbon cloth II.
The pressure of the vacuum hot pressing is 1-5 Mpa.
The air pressure of the vacuum hot pressing is less than 9 kPa.
The heating rate of the vacuum hot pressing is 0.1-2 ℃/min.
The temperature of the vacuum hot pressing is 450-550 ℃.
The atmosphere of the tertiary carbonization comprises nitrogen.
The temperature rise rate of the third-stage carbonization is 0.5-5 ℃/min.
The temperature of the tertiary carbonization is 1000 ℃.
And the heat preservation time of the third-stage carbonization is 10-60 min.
The pressure of the graphite and the ceramic is 0.1-1 Mpa.
The heating rate of the graphite and the ceramic is 1-10 ℃/min
The temperature of the graphite and the ceramic is 2900-3100 ℃.
The heat preservation time of the graphite and the ceramic is 10-60 min.
The dissolution ratio of the suspension of the mesophase pitch powder is 12-17 g/100 ml.
The liquid phase of the suspension of mesophase pitch powder comprises isopropanol.
The weight of the mesophase pitch powder is 60-70 wt% of the weight of the carbon fiber II.
The particle size of the Si-Zr alloy powder is 0.1-10 mu m.
The atomic ratio of Si to Zr in the Si-Zr alloy powder is 4: 1.
The spraying amount of the Si-Zr alloy powder is 65-75 wt% of the mass of the carbon cloth II
The organic silicon source comprises polycarbosilane.
The organozirconium source comprises an organozirconium compound.
The solvent adopted by the precursor liquid comprises xylene.
The weight ratio of the organic silicon source to the organic zirconium source is 12: (4-6).
The dissolution ratio of the precursor solution is 80-90 g/100 ml.
And the impregnation pyrolysis densification is to impregnate the porous C/C-ZrC-SiC composite material skeleton into the precursor liquid, and then to carry out curing and pyrolysis.
The curing temperature is 80-120 ℃.
The curing time is 1-4 h.
The curing atmosphere comprises nitrogen or argon.
The pyrolysis temperature is 1400-1600 ℃.
The method comprises the steps of firstly carrying out low-temperature primary carbonization on mesophase pitch carbon fibers obtained after pitch spinning oxidation to obtain low-temperature carbon fibers I, and then carrying out high-temperature secondary carbonization on the low-temperature carbon fibers I to obtain high-temperature carbon fibers II. The two-stage carbonization of the mesophase pitch carbon fiber can adjust the carbon fiber, the modulus and the strength, so that the mesophase pitch carbon fiber is not easy to damage during weaving, simultaneously, broken filaments during carbon cloth molding and the volume shrinkage of subsequent heat treatment are reduced, and finally, the phenomenon of thermal mismatch in the composite material is reduced. And then spraying the solution of the intermediate phase asphalt powder and the Si-Zr alloy powder on the upper surface and the lower surface of the carbon cloth II, carrying out vacuum hot pressing on the carbon cloth II to ensure that the intermediate phase asphalt powder and the Si-Zr alloy powder are uniformly attached to the surface of the carbon fiber, then carbonizing the carbon cloth II, carrying out graphite and ceramic treatment on the carbon cloth II, and quickly introducing the ZrC-SiC complex phase ceramic into the carbon fiber to obtain the carbon cloth uniformly attached with ZrC and SiC, thereby introducing a high heat conduction channel into the composite material. And finally, the residual pores and cracks in the composite material skeleton are further sealed and filled by utilizing the immersion pyrolysis of the precursor solution, and finally the C/C-ZrC-SiC composite material with good heat conductivity, good thermal protection performance and good mechanical performance can be prepared at low cost.
In some embodiments of the invention, the temperature for primary carbonization of the mesophase pitch carbon fiber is 500-700 ℃; the strength of the carbon fiber I obtained after the first-stage carbonization is 0.30-0.45 GPa; the modulus is 8-50 GPa. The modulus and strength of the carbon fibers increase with increasing temperature and time of the heat treatment. The primary low-temperature carbonization can endow the carbon fiber with certain strength so as to prevent the carbon fiber from being directly broken when the high-temperature carbonization is used for drafting the carbon fiber.
In some embodiments of the invention, the temperature for secondary carbonization of the carbon fiber I is 1000-1800 ℃; the strength of the obtained carbon fiber II is 100-300 GPa, and the modulus is 1-2 GPa. The secondary high-temperature carbonization can eliminate the buckling defect of the carbon fiber and endow the carbon fiber with higher strength. If the carbonization temperature is too low, the strength is low although the modulus of the carbon fiber is low, and the carbon fiber is easy to damage in the subsequent weaving process; if the carbonization temperature is too high, although the strength is improved, the modulus is increased more, the flexibility of the yarn is drastically reduced, and the knitting performance is also reduced.
In certain embodiments of the present invention, the carbon cloth I woven from the carbon fibers II is a plain, twill or satin carbon cloth. Carbon cloth woven with carbon fibers into other textures can also implement the invention.
In some embodiments of the present invention, the spraying method used when spraying the powder on the surfaces of the carbon cloth I and the carbon cloth II is two-sided spraying. The invention can also be realized by adopting other spraying modes.
In some embodiments of the invention, the carbon cloth II is also subjected to a glue-die roll after the powder is sprayed. The rubber mold rolling can improve the uniformity and the evenness of the carbon cloth. The invention can be realized without using the rubber mold rolling.
In some embodiments of the invention, the pressure for vacuum hot pressing the carbon cloth III is 1-5 MPa. The pressure of the vacuum hot pressing is less than 9 kPa. The heating rate of the vacuum hot pressing is 0.1-2 ℃/min. The temperature of the vacuum hot pressing is 450-550 ℃. Preferably, the temperature system of the vacuum hot pressing garden is RT-260 ℃, and the heating rate is 1-2 ℃/min; 260-500 ℃, and the heating rate is 0.1-0.5 ℃/min. The adopted temperature is too high, the carbon fiber can be directly carbonized, the temperature is too low, and the coking reaction of the carbon fiber is incomplete.
In certain embodiments of the present invention, the atmosphere for the tertiary carbonization of the carbon cloth III is preferably nitrogen. The temperature rise rate during the third-stage carbonization is 0.5-5 ℃/min. The temperature for three-stage carbonization is 1000 ℃, and the heat preservation time is 10-60 min. The preferable temperature rising system of the third-stage carbonization is as follows: the temperature rising rate of RT-500 ℃ is 5 ℃/min; the temperature rise rate is 0.5-1 ℃/min at 500-1000 ℃; and heating to 1000 ℃, preserving the heat for 10-60min, and naturally cooling to room temperature.
In some embodiments of the present invention, the temperature for the graphite and ceramic treatment of the carbon cloth III is 2900-3100 ℃. The atmosphere for the graphite and ceramization treatment is preferably argon. The preferable temperature rising system is as follows: RT-1600 ℃, and the heating rate is 5-10 ℃/min; the temperature rise rate is 1-3 ℃/min at 1600-2200 ℃, and the pressure of 0.1-1 MPa is applied to the sample; the temperature rise rate of 2200 to 3000 ℃ is 3 to 5 ℃/min, and after the final temperature is kept for 10 to 60min, the mixture is naturally cooled to the room temperature. The invention does not need to respectively perform graphitization treatment and ceramic treatment on the carbon cloth III, and can directly combine the graphitization treatment and the ceramic treatment into a heat treatment process. The heat conduction of the mesophase pitch-based carbon fiber can be initiated only when the graphitization temperature is higher than 2800 ℃, and in the process, when the heat treatment temperature reaches 1800-2200 ℃, the Si-Zr alloy can be introduced into the mesophase pitch-based carbon fiber and generates a carbonization reaction to become ZrC and SiC. Therefore, the carbon cloth III simultaneously completes the ceramic process of the Si-Zr alloy in the graphitization process, and the porous C/C-ZrC-SiC composite material framework is obtained.
In certain embodiments of the invention, the mesophase pitch powder is dispersed in an alcohol to form a suspension. The suspension of the mesophase pitch powder can also be prepared by adopting other organic solvents such as ether, phenol and the like. Preferably, the alcohol may be selected from isopropanol. The invention can also be carried out with other types of alcohols.
In certain embodiments of the present invention, the suspension dissolution ratio of the mesophase pitch powder is 12 to 17g/100 ml. If the dissolution ratio is too large, the layering and the uneven dispersion of the suspension can be caused; too small a dissolution ratio may result in reduced spraying efficiency.
In certain embodiments of the present invention, in the carbon cloth I, the mass of the mesophase pitch powder is 60 to 70 wt% of the mass of the carbon fiber. If the mass fraction of the carbon fibers is too low, the thermal conductivity and the strength of the prepared composite material are not high; when the mass fraction of the carbon fibers is too high, it is difficult to form a composite material having a uniform composition.
In some embodiments of the present invention, the vacuum hot pressing is performed at a pressure of 1 to 5MPa and a pressure of less than 9 kPa. The temperature adopted by the vacuum hot pressing is 900-1000 ℃. The adopted temperature is too high, the carbon fiber can be directly carbonized, the temperature is too low, and the coking reaction of the carbon fiber is incomplete.
In certain embodiments of the present invention, the Si-Zr powder has a particle size of 0.1 to 10 μm. The dispersion uniformity is difficult to control due to the overlarge grain size of the Si-Zr powder, and the component segregation is easy to generate during the heat treatment reaction; and if the particle size is too small, the powder is easy to agglomerate. The atomic ratio of Si to Zr in the Si-Zr powder is 4: 1. The spraying amount of the Si-Zr powder is 65-75 wt% of the mass of the carbon fiber.
In certain embodiments of the present invention, the organic silicon source employed is polycarbosilane; the organic zirconium source used is an organic zirconium compound. The invention can also be realized by adopting other organic silicon sources. Preferably, the organozirconium compound may be zirconium acetylacetonate. The invention can also be practiced with other organozirconium compounds.
In some embodiments of the present invention, in the precursor solution of the organic zirconium source and the organic silicon source, the weight ratio of the organic silicon source to the organic zirconium source is 12: (4-6). The weight ratio of the organosilicon source to the organozirconium source affects the SiC content. If the SiC content is too high or too low, the ablation resistance effect of the ZrC-SiC complex phase ceramic is not good. In the ZrC-SiC complex phase ceramic, SiC can form self-healing SiO2The oxygen barrier layer improves the oxidation resistance of the composite material; and ZrC can be oxidized to form ZrO during the use of the composite material2；ZrO2Is a high temperature alloy which can improve the scouring resistance of the composite material.
In some embodiments of the present invention, the dissolution ratio of the precursor solution of the organozirconium source and the organosilicon source is 80 to 90g/100 ml.
In certain embodiments of the present invention, the impregnation pyrolysis method employed is specifically: and (3) dipping the carbon cloth in the precursor solution comprising the organic zirconium source and the organic silicon source, and then curing and pyrolyzing the precursor solution.
In some embodiments of the invention, the curing temperature is 80-120 ℃; the curing time is 1-4 h; the pyrolysis temperature is 1400-1600 ℃.
In certain embodiments of the present invention, the solvent that dissolves the organozirconium source and the organosilicon source is xylene. Other organic solvents may also be selected. The invention can also be realized by adopting other organic solvents which can dissolve the organic zirconium source and the organic silicon source.
In some embodiments of the present invention, the curing temperature is 80-120 ℃.
In certain embodiments of the present invention, the curing atmosphere is nitrogen or argon. The invention can also be practiced with other inert atmospheres.
Compared with the prior art, the invention further optimizes the modulus and strength of the carbon fiber by adopting a two-stage carbonization method, improves the weaving manufacturability of the mesophase pitch-based carbon fiber, reduces broken filaments and volume shrinkage of subsequent heat treatment during weaving and forming of the mesophase pitch-based carbon fiber, and finally reduces the phenomenon of thermal mismatch in the composite material.
When the traditional metal infiltration method is introduced into a hot channel, the damage to fibers is overlarge, the ceramic phase distribution is uneven, and the cycle of introducing the precursor liquid impregnation pyrolysis method into the hot channel is long, and the cost is high. Compared with the prior art, the precursor liquid immersion pyrolysis method introduces a high-thermal-conductivity channel into the composite material, quickly introduces uniform ZrC-SiC complex phase ceramic by using a hot pressing method, and further seals and fills pores and cracks in the graphitized-ceramized composite material by using precursor liquid immersion pyrolysis, so that the C/C-ZrC-SiC composite material with high thermal conductivity is obtained. The C/C-ZrC-SiC composite material prepared by the preparation method disclosed by the invention has the advantages of better thermal protection performance and thermal conductivity, small mechanical property loss and lower cost, and is an engineering preparation method of a high-thermal-conductivity carbon fiber ceramic matrix composite material with potential. The C/C-ZrC-SiC composite material prepared by the method in some specific technical schemes has the thermal conductivity coefficient of 150-250W/(m.K) in the X or Y direction.
In conclusion, the invention has the following beneficial effects:
1. according to the invention, the two-stage carbonization temperature is reasonably designed to adjust the mode by the strength and the modulus of the mesophase pitch-based carbon fiber, and then the low-mode mesophase pitch-based carbon fiber is woven into a two-dimensional fabric, so that the volume shrinkage of broken filaments and subsequent heat treatment during the weaving of the carbon fiber is reduced, and the mismatch of the shrinkage of the carbon fiber and the mesophase pitch in the subsequent heat treatment process is avoided.
2. The invention forms the high heat conduction channel in the composite material by spraying the mesophase pitch on the surface of the mesophase pitch-based carbon fiber carbon cloth and combining with the subsequent carbonization and graphitization. The SiC-ZrC complex phase ceramic is quickly introduced by spraying Si-Zr alloy powder on the mesophase pitch, and the reactivity and uniformity of the SiC-ZrC are ensured by controlling the components of the Si-Zr alloy powder.
3. The invention ensures that the Si-Zr alloy powder and the pitch carbon fully react through reasonable heat treatment temperature, and does not damage carbon fiber; the graphitization and the ceramic treatment of the composite material are carried out together, the preparation process is simplified, and the pores and cracks caused by the graphitization and the ceramic treatment are filled with the SiC-ZrC complex phase ceramic generated by the subsequent immersion and pyrolysis of a few precursor liquids, so that the thermal protection performance of the composite material is optimized.
Detailed Description
The invention is further described below with reference to specific embodiments.
In a specific embodiment of the invention, the mesophase pitch-based carbon fiber is prepared by obtaining continuous filaments through melt spinning, non-melting and heat treatment processes, and pre-oxidizing and carbonizing the continuous filaments.
Example 1
Firstly, the mesophase pitch carbon fiber is subjected to primary carbonization at 500 ℃ to obtain carbon fiber I with the modulus of 8GPa and the strength of 0.30 GPa. And (3) performing secondary carbonization treatment on the carbon fiber I at 1000 ℃, and adjusting the modulus of the carbon fiber to be 105GPa and the strength to be 1.02GPa to obtain the carbon fiber II. Weaving the carbon fiber II into plain woven carbon cloth I. And then preparing an intermediate phase asphalt powder suspension with a dissolution ratio of 15g/100ml by using isopropanol, uniformly spraying two surfaces of the intermediate phase asphalt powder suspension to the plain carbon cloth I, and drying until the mass of the intermediate phase asphalt powder is 60 wt% of that of the carbon fiber to obtain the carbon cloth II. Continuously spraying Si-Zr alloy powder with the powder granularity of 0.1 mu m and the atomic ratio of Si to Zr of 4: 1 on two sides of the carbon cloth II; the spraying amount of the metal powder is 65 wt% of the mass of the carbon fiber, and the carbon cloth III is obtained. And (3) carrying out glue film rolling on the carbon fiber cloth III.
And then, placing the carbon cloth III in a steel die for laminating and vacuum hot pressing. The pressure of the sample during vacuum hot pressing is 1MPa, and the vacuumizing pressure is 8.5 kPa. The temperature rising system of the vacuum hot pressing is RT-260 ℃, and the temperature rising rate is 2 ℃/min; the temperature is 260-500 ℃, and the heating rate is 0.5 ℃/min. After hot-pressing and demoulding, carbonizing the carbon cloth III at 1000 ℃, wherein the carbonizing atmosphere is nitrogen, the temperature rising system is that the temperature rising rate is 5 ℃/min at RT-500 ℃ and the air pressure is 1kPa (1 atmosphere is 0 kPa); the temperature rise rate is 1 ℃/min at 500-1000 ℃; heating to 1000 deg.C, keeping the temperature for 60min, and naturally cooling to room temperature. After carbonization, graphitizing and ceramic treatment are carried out at 3000 ℃ to obtain the porous C/C-ZrC-SiC composite material skeleton. The atmosphere for graphitization and ceramic treatment is argon. The temperature rising system of the graphitization and the ceramic treatment is RT-1600 ℃, and the temperature rising rate is 10 ℃/min; the temperature rise rate is 3 ℃/min at 1600-2200 ℃, and the pressure of 0.2MPa is applied to the sample; the temperature rise rate of 2200-3000 ℃ is 5 ℃/min, the final temperature is kept for 60min, and then the product is naturally cooled to the room temperature.
And finally, dissolving 60g of polycarbosilane and 25g of zirconium acetylacetonate in 100ml of dimethylbenzene together to obtain the ZrC-SiC liquid-phase precursor solution. ZrC-SiC liquid-phase precursor liquid is adopted to treat the porous C-After being impregnated by the C-ZrC-SiC composite material framework solution and cured for 4h at 80 ℃, the temperature is raised to 1400 ℃ at the temperature rise rate of 5 ℃/min in the argon atmosphere so as to be ceramized. A density of 2.11g/cm was obtained3The C/C-ZrC-SiC composite material. The heat conductivity coefficient of the C/C-ZrC-SiC composite material in the X or Y direction is 152W/(m.K), the linear ablation rate of plasma ablation at 2400 ℃ is 0.82 mu m/s, and the oxidative oxidation weight loss of static air at 1500 ℃ is 5.73mg/cm2。
Example 2
First, mesophase pitch carbon fibers were subjected to primary carbonization at 600 ℃ to obtain carbon fibers I having a modulus of 36GPa and a strength of 0.37 GPa. And (3) performing secondary carbonization treatment on the carbon fiber I at 1600 ℃, and adjusting the modulus of the carbon fiber to be 220GPa and the strength to be 1.6GPa to obtain the carbon fiber II. Weaving the carbon fiber II into eight satin carbon cloths I. And then preparing an intermediate phase asphalt powder suspension with a dissolution ratio of 15g/100ml by using isopropanol, uniformly spraying two surfaces of the intermediate phase asphalt powder suspension to the plain carbon cloth I, and drying until the mass of the intermediate phase asphalt powder is 65 wt% of that of the carbon fiber to obtain the carbon cloth II. Continuously spraying Si-Zr alloy powder with the powder granularity of 5 mu m and the atomic ratio of Si to Zr of 4: 1 on two sides of the carbon cloth II; the spraying amount of the metal powder is 70 wt% of the mass of the carbon fiber, and the carbon cloth III is obtained. And (3) carrying out glue film rolling on the carbon fiber cloth III.
And then, placing the carbon cloth III in a steel die for laminating and vacuum hot pressing. The pressure of the sample is 3MPa during vacuum hot pressing, and the vacuumizing pressure is 8 kPa. The temperature rising system of the vacuum hot pressing is RT-260 ℃, and the temperature rising rate is 1 ℃/min; the temperature is 260-500 ℃, and the heating rate is 0.1 ℃/min. After hot-pressing and demoulding, carbonizing the carbon cloth III at 1000 ℃, wherein the carbonizing atmosphere is nitrogen, the temperature rising system is that the temperature rising rate is 5 ℃/min at RT-500 ℃ and the air pressure is 3kPa (1 atmosphere is 0 kPa); the temperature is 500-1000 ℃, and the heating rate is 0.5 ℃/min; heating to 1000 deg.C, keeping the temperature for 10min, and naturally cooling to room temperature. After carbonization, graphitizing and ceramic treatment are carried out at 3000 ℃ to obtain the porous C/C-ZrC-SiC composite material skeleton. The atmosphere for graphitization and ceramic treatment is argon. The temperature rising system of the graphitization and the ceramic treatment is RT-1600 ℃, and the temperature rising rate is 5 ℃/min; the temperature rise rate is 1 ℃/min at 1600-2200 ℃, and the pressure of 1MPa is applied to the sample; the temperature rise rate of 2200-3000 ℃ is 3 ℃/min, the final temperature is kept for 10min, and then the product is naturally cooled to the room temperature.
And finally, dissolving 60g of polycarbosilane and 25g of zirconium acetylacetonate in 100ml of dimethylbenzene together to obtain the ZrC-SiC liquid-phase precursor solution. Impregnating the porous C/C-ZrC-SiC composite material framework solution by adopting a ZrC-SiC liquid-phase precursor solution, curing for 2h at the temperature of 100 ℃, and heating to 1500 ℃ at the temperature rise rate of 5 ℃/min in an argon atmosphere to ceramize the porous C/C-ZrC-SiC composite material framework solution. The C/C-ZrC-SiC composite material with the density of 2.18g/cm3 was obtained. The thermal conductivity coefficient of the C/C-ZrC-SiC composite material in the X or Y direction is 246W/(m.K), the linear ablation rate of plasma ablation at 2400 ℃ is 0.71 mu m/s, and the oxidative oxidation weight loss of static air at 1500 ℃ is 4.28mg/cm2。
Example 3
Firstly, the mesophase pitch carbon fiber is subjected to primary carbonization at 700 ℃ to obtain carbon fiber I with the modulus of 48GPa and the strength of 0.45 GPa. And (3) performing secondary carbonization treatment on the carbon fiber I at 1800 ℃, and adjusting the modulus of the carbon fiber to 290GPa and the strength to 2GPa to obtain the carbon fiber II. Weaving the carbon fiber II into twill carbon cloth I. And then preparing an intermediate phase asphalt powder suspension with a dissolution ratio of 15g/100ml by using isopropanol, uniformly spraying two surfaces of the intermediate phase asphalt powder suspension to the plain carbon cloth I, and drying until the mass of the intermediate phase asphalt powder is 70 wt% of that of the carbon fiber to obtain the carbon cloth II. And continuously spraying powder with the granularity of 10 mu m on two sides of the carbon cloth II, wherein the atomic ratio of Si to Zr is 4: 1 of Si — Zr alloy powder; the spraying amount of the metal powder is 75 wt% of the mass of the carbon fiber, and the carbon cloth III is obtained. And (3) carrying out glue film rolling on the carbon fiber cloth III.
And then, placing the carbon cloth III in a steel die for laminating and vacuum hot pressing. The pressure of the sample is 5MPa during vacuum hot pressing, and the vacuumizing pressure is 5 kPa. The temperature rising system of the vacuum hot pressing is RT-260 ℃, and the temperature rising rate is 1.5 ℃/min; the temperature is 260-500 ℃, and the heating rate is 0.3 ℃/min. After hot-pressing and demoulding, carbonizing the carbon cloth III at 1000 ℃, wherein the carbonizing atmosphere is nitrogen, the temperature rising system is 5kPa (1 atmosphere is 0kPa), and the temperature rising rate is 5 ℃/min from RT to 500 ℃; the temperature rise rate is 0.8 ℃/min at 500-1000 ℃; heating to 1000 deg.C, keeping the temperature for 30min, and naturally cooling to room temperature. After carbonization, graphitizing and ceramic treatment are carried out at 3000 ℃ to obtain the porous C/C-ZrC-SiC composite material skeleton. The atmosphere for graphitization and ceramic treatment is argon. The temperature rising system of the graphitization and the ceramic treatment is RT-1600 ℃, and the temperature rising rate is 8 ℃/min; the temperature rise rate is 2 ℃/min at 1600-2200 ℃, and the pressure of 0.5MPa is applied to the sample; the temperature rise rate of 2200-3000 ℃ is 4 ℃/min, and after the final temperature is kept for 30min, the product is naturally cooled to the room temperature.
And finally, dissolving 60g of polycarbosilane and 25g of zirconium acetylacetonate in 100ml of dimethylbenzene together to obtain the ZrC-SiC liquid-phase precursor solution. Impregnating the porous C/C-ZrC-SiC composite material framework solution by adopting a ZrC-SiC liquid-phase precursor solution, curing for 1h at 120 ℃, and heating to 1600 ℃ at a heating rate of 8 ℃/min in an argon atmosphere to ceramize the porous C/C-ZrC-SiC composite material framework solution. A density of 2.13g/cm was obtained3The C/C-ZrC-SiC composite material. The thermal conductivity coefficient of the C/C-ZrC-SiC composite material in the X direction or the Y direction is 208W/(m.K), the linear ablation rate of plasma ablation at 2400 ℃ is 0.94 mu m/s, and the static air oxidation weight loss at 1500 ℃ is 8.65mg/cm 2.
Claims (10)
1. A preparation method of a two-dimensional high-thermal-conductivity C/C-ZrC-SiC composite material is characterized by comprising the following steps:
the method comprises the following steps:
(1) carrying out primary carbonization on the mesophase pitch carbon fibers to obtain carbon fibers I, then carrying out secondary carbonization on the carbon fibers I to obtain carbon fibers II, weaving the carbon fibers II into carbon cloth I, spraying a suspension of mesophase pitch powder onto the surface of the carbon cloth I, and drying to obtain the carbon cloth II; then spraying Si-Zr alloy powder on the surface of the carbon cloth II to obtain carbon cloth III;
(2) after the carbon cloth III is subjected to vacuum hot pressing and three-stage carbonization, carrying out graphite and ceramic treatment to obtain a porous C/C-ZrC-SiC composite material skeleton;
(3) and (3) carrying out dipping pyrolysis densification on the porous C/C-ZrC-SiC composite material skeleton by adopting precursor liquid comprising an organic zirconium source and an organic silicon source to obtain the two-dimensional C/C-ZrC-SiC composite material.
2. The method of preparing a two-dimensional C/C-ZrC-SiC composite material according to claim 1, wherein:
the temperature of the primary carbonization is 500-700 ℃;
the strength of the carbon fiber I is 0.30-0.45 GPa;
the modulus of the carbon fiber I is 8-50 GPa.
3. The method of preparing a two-dimensional C/C-ZrC-SiC composite material according to claim 1, wherein:
the temperature of the secondary carbonization is 1000-1800 ℃;
the strength of the carbon fiber II is 100-300 GPa;
the modulus of the carbon fiber II is 1-2 GPa.
4. The method of preparing a two-dimensional C/C-ZrC-SiC composite material according to claim 1, wherein:
the carbon cloth I is plain, twill or satin carbon cloth;
the spraying is two-sided spraying;
the step (1) further comprises the step of performing rubber mold rolling on the carbon cloth II.
5. The method of preparing a two-dimensional C/C-ZrC-SiC composite material according to claim 1, wherein:
the pressure of the vacuum hot pressing is 1-5 Mpa;
the air pressure of the vacuum hot pressing is less than 9 kPa;
the heating rate of the vacuum hot pressing is 0.1-2 ℃/min;
the temperature of the vacuum hot pressing is 450-550 ℃;
the atmosphere of the tertiary carbonization comprises nitrogen;
the temperature rise rate of the third-stage carbonization is 0.5-5 ℃/min;
the temperature of the third-stage carbonization is 1000 ℃;
the heat preservation time of the three-stage carbonization is 10-60 min;
the pressure of the graphite and the ceramic is 0.1-1 Mpa;
the heating rate of the graphite and the ceramic is 1-10 ℃/min
The temperature of the graphite and the ceramic is 3000 ℃;
the heat preservation time of the graphite and the ceramic is 10-60 min.
6. The method of preparing a two-dimensional C/C-ZrC-SiC composite material according to claim 1, wherein:
the dissolution ratio of the suspension of the mesophase pitch powder is 12-17 g/100 ml;
the liquid phase of the suspension of mesophase pitch powder comprises isopropanol;
the weight of the mesophase pitch powder is 60-70 wt% of the weight of the carbon fiber II.
7. The method of preparing a two-dimensional C/C-ZrC-SiC composite material according to claim 1, wherein:
the granularity of the Si-Zr alloy powder is 0.1-10 mu m;
the atomic ratio of Si to Zr in the Si-Zr alloy powder is 4: 1;
the spraying amount of the Si-Zr alloy powder is 65-75 wt% of the mass of the carbon cloth II.
8. The method of preparing a two-dimensional C/C-ZrC-SiC composite material according to claim 1, wherein:
the organic silicon source comprises polycarbosilane;
the organozirconium source comprises an organozirconium compound;
the solvent adopted by the precursor liquid comprises xylene.
9. The method of preparing a two-dimensional C/C-ZrC-SiC composite material according to claim 1, wherein:
the weight ratio of the organic silicon source to the organic zirconium source is 12: 4-6;
the dissolution ratio of the precursor solution is 80-90 g/100 ml.
10. The method of preparing a two-dimensional C/C-ZrC-SiC composite material according to claim 1, wherein:
the impregnation pyrolysis densification is to impregnate a porous C/C-ZrC-SiC composite material skeleton into the precursor liquid, and then to carry out curing and pyrolysis;
the curing temperature is 80-120 ℃;
the curing time is 1-4 h;
the curing atmosphere comprises nitrogen or argon;
the pyrolysis temperature is 1400-1600 ℃.
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