CN106946582B - Large-size special-shaped carbon-based composite material component and preparation method thereof - Google Patents
Large-size special-shaped carbon-based composite material component and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a large-size special-shaped carbon-based composite material component and a preparation method thereof. The component comprises the following components in percentage by mass: 20-35% of carbon fiber, 35-75% of pyrolytic carbon and 5-15% of SiC. The preparation method comprises the following steps: according to the required part shape, firstly needling the continuous carbon fiber to obtain the carbon fiber with the density of 0.4-0.55 g/cm3The preform of (a); fixing the inner and outer surfaces of the prefabricated blank by using a graphite mold; and then sequentially carrying out high-temperature heat treatment, first carbon deposition, mould unloading, rough machining, second carbon deposition, graphite treatment, silicon steam bath and finish machining to obtain a finished product. The invention solves the problems that large-size special-shaped carbon-based composite material components are easy to deform after standing for a long time and in the preparation process, and the obtained product has the advantages of good mechanical property, low thermal expansion coefficient, high thermal conductivity, good chemical stability and the like, is convenient for industrial production, and can be applied to the fields of aerospace, transportation, biomedical use and the like.
Description
Technical Field
The invention relates to the technical field of composite materials; in particular to a large-size special-shaped carbon-based composite material component and a preparation method thereof.
Background
The carbon-based composite material is a composite material consisting of a carbon fiber framework and a matrix (carbon base, ceramic base and the like), is a structural and functional integrated engineering material with excellent high-temperature performance, and has the advantages of low density, high strength, high modulus, high temperature resistance, ablation resistance, space high-energy particle irradiation resistance and the like, so that the carbon-based composite material is greatly developed and is applied to the fields of aerospace, military industry, civil materials (such as nuclear reactors, high-temperature bearings, carbon crucibles, thermal sealing rings and the like) and the like.
Taking the thermal protection system of an aerospace vehicle as an example, the thermal protection system of the aerospace vehicle is more and more favored to be used for ceramic thermal protection mainly based on nonmetal. In the 2 nd 1 st 2003, when the American Columbia space shuttle returns to the earth, high-temperature airflow enters the inside of the aircraft body due to the falling of the heat insulation tile, and finally the aircraft is destroyed and death occurs, thus resulting in tragic events in the history of space flight. The root causes of the accident are: the fuselage surface of the Columbia space shuttle has 2 ten thousand heat insulation tiles and 2300 heat insulation gaskets, the number is large, the heat insulation tiles are arranged on the fuselage surface in an adhesion mode, the reliability is poor, and the damage is easy. If a large-size heat-proof panel is adopted, the heat-proof panel can be integrally formed at one time, the number of parts and connecting pieces is reduced, the weight of the machine body can be obviously reduced, the manufacturing and assembling time is reduced, more importantly, potential safety hazards caused by the multiple connection of the heat-proof panel are reduced, and the safety and reliability are greatly improved.
However, the molding preparation technology of the large-size special-shaped carbon-based composite material member is a difficulty. At present, large-size special-shaped composite material members are mainly obtained through continuously developed connecting technologies, and a plurality of connecting methods are applied, such as bonding, welding and mechanical connection, wherein bolt connection has the advantages of capability of bearing larger load, convenience in disassembly and maintenance, safety and reliability, easiness in inspection of connection quality, mature technology and the like, and is one of the most common connecting methods in the current composite material mechanical connection. However, the composite material bolt is generally used in a very harsh environment, and various factors in the environment, such as temperature, humidity, vibration, loading conditions and the like, can cause the failure of the bolt structure, thereby causing accidents; in addition, the screw hole matched with the bolt structure is prepared from the carbon-based composite material, so that the defects of long period, high cost, low yield and the like exist.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a large-size special-shaped carbon-based composite material component and a preparation method thereof, the method solves the problems that a carbon fiber prefabricated part is easy to deform, a thin-wall carbon-based composite component is easy to stand for a long time, and the carbon-based composite material prepared by the method is easy to deform in the preparation process, and has the advantages of good mechanical property, small thermal expansion coefficient, high thermal conductivity, good chemical stability and the like.
The invention relates to a large-size special-shaped carbon-based composite material component; the material comprises the following components in percentage by mass:
20-35% of carbon fiber;
35 to 75 percent of pyrolytic carbon
SiC 5-15％。
The invention relates to a large-size special-shaped carbon-based composite material component; the large-size profiled carbon-based composite member comprises a thin-walled carbon-based composite member.
The invention relates to a large-size special-shaped carbon-based composite material component; the density of the surface layer is higher than that of the core part.
The invention relates to a preparation method of a large-size special-shaped carbon-based composite material member, which comprises the following steps:
step one
According to the required part shape, firstly needling continuous carbon fiber into a prefabricated blank; the density of the prefabricated blank is 0.4-0.55 g/cm3(ii) a Fixing the inner and outer surfaces of the prefabricated blank by using a graphite mold; obtaining a spare blank;
step two
Carrying out high-temperature heat treatment on the spare blank obtained in the step one under the protective atmosphere; obtaining a spare blank after heat treatment; the temperature of the high-temperature heat treatment is more than or equal to 600 ℃;
step three
Placing the spare blank subjected to the heat treatment in the step two into a deposition furnace; preparing pyrolytic carbon by a thermal gradient chemical vapor infiltration method; the obtained density is 0.8-1.0 g/cm3The low-density carbon fiber reinforced matrix carbon composite blank of (a); when the pyrolytic carbon is deposited by a chemical vapor deposition method, controlling the temperature to be more than or equal to 1000 ℃ and the time to be more than or equal to 50 hours;
step four
Removing the graphite mold, performing rough machining on the low-density carbon fiber reinforced matrix carbon composite blank obtained in the step three, removing burrs and adhesive substances on the surface of the blank, and finding a reference to correct the deformation amount; obtaining a rough-processed low-density carbon fiber reinforced matrix carbon composite blank;
step five
Placing the rough-processed low-density carbon fiber reinforced matrix carbon composite blank in a deposition furnace, and depositing pyrolytic carbon by adopting an isothermal chemical vapor deposition method until the density is 1.3-1.5 g/cm3The carbon fiber reinforced matrix carbon composite blank of (1); when preparing pyrolytic carbon by adopting a chemical vapor deposition method, controlling the time to be more than or equal to 200 hours and the temperature to be more than or equal to 1100 ℃;
step six
Under the protective atmosphere, the density obtained in the fifth step is 1.3-1.5 g/cm3The carbon fiber reinforced matrix carbon composite blank is subjected to graphitization treatment, the graphitization degree is improved, and the carbon fiber reinforced matrix carbon composite blank after graphitization treatment is obtained; during graphitization treatment, controlling the pressure in the furnace to be 0.1-0.2MPa, the temperature to be 2000-2500 ℃ and the time to be 4-8 hours;
step seven
Placing the carbon fiber reinforced matrix carbon composite blank obtained in the step six after the graphitization treatment on silicon powder, vacuumizing, heating to 1500-1800 ℃ for steam bath until the density is 1.4-1.6 g/cm3The composite blank of (a); when in steam bath, the pressure in the furnace is controlled to be 0.1-0.2 MPa;
step eight
The density obtained in the step seven is 1.4-1.6 g/cm3The composite blank of (a); performing finish machining according to a design drawing; and obtaining a finished product.
In the present invention, the finishing does not include reshaping the profile; but includes finishing the existing profile.
The invention relates to a preparation method of a large-size special-shaped carbon-based composite material component, which comprises the following steps of firstly needling continuous carbon fibers into a prefabricated blank according to the required part appearance; the scheme of needling out the prefabricated blank is as follows: adopting carbon fiber laid cloth or twill cloth and a tire net to alternately overlay and lay, and then adopting lower barb to continuously needle the overlaid laid cloth or twill cloth and the net tire to form an integral structure fabric; the layering mode of the weftless fabric or the twill fabric is 0 degree/45 degree/90 degrees, and the needling density is 35-45 needles/cm3The needling depth is 18-25mm, and when the needle is needled, the barb needling takes a small part of fibers in the parallel direction of the prefabricated body to the vertical direction.
As a preferred scheme, according to the preparation method of the large-size special-shaped carbon-based composite material member, 14-18 layers of materials are paved according to the thickness per centimeter, and carbon fiber non-woven cloth or twill cloth and tire net are alternately stacked and layered. The material comprises carbon fiber laid cloth, twill cloth and a tire net.
According to the preparation method of the large-size special-shaped carbon-based composite material member, in the first step, the inner surface and the outer surface of the carbon fiber preform are punched, limited and fixed by a graphite mold, the limiting cushion blocks are 3-8 mm, the bottom of the carbon fiber preform is bound with graphite by carbon fibers, and the distance between the bottom of the carbon fiber preform and the graphite is 12-18 mm.
The invention relates to a preparation method of a large-size special-shaped carbon-based composite material member, and in the second step, the temperature of high-temperature heat treatment is 600-800 ℃ and the time is 0.5-2 hours. And during high-temperature heat treatment, controlling the pressure in the furnace to be micro-positive pressure (namely slightly exceeding 0 scale of a vacuum pressure gauge). The protective gas is preferably an inert gas.
And (4) through the high-temperature heat treatment in the second step, not only can the stress generated by the carbon fiber preform in the needling process be relieved, but also organic glue and other impurities coated on the surface of the carbon fiber in a bundle form can be removed. Meanwhile, the heat treatment at the temperature can also solve the problems that the high-modulus carbon fiber is easy to break and agglomerate and the like.
The invention relates to a preparation method of a large-size special-shaped carbon-based composite material component, which comprises the following steps of placing a spare blank obtained in the step two after heat treatment in a deposition furnace; isotropic pyrolytic carbon densification is carried out on the carbon fiber by adopting a thermal gradient chemical vapor infiltration method; when the thermal gradient chemical vapor infiltration is carried out, the carbon source gas is hydrocarbon or natural gas with the carbon atom number less than or equal to 3; preferably, the carbon-containing gas is a hydrocarbon gas such as methane, propylene, propane, natural gas, etc., the diluent gas is nitrogen, hydrogen or a mixed gas thereof, the ratio of the carbon-containing gas to the diluent gas is 1: 1-3, the time is 50-150 hours, and the temperature is 1000-1200 ℃. As a preferable condition, the flow rate of the carbon source gas is 10-30L/min at the time of deposition. The gas pressure in the furnace is less than or equal to 1.2 KPa.
The invention relates to a preparation method of a large-size special-shaped carbon-based composite material member, wherein one of the main functions in the third step is molding.
According to the preparation method of the large-size special-shaped carbon-based composite material member, pyrolytic carbon is inevitably generated at the contact part of the graphite mold and the carbon fiber preform when pyrolytic carbon is deposited in the third step; in the fourth step, when the graphite mold is removed, damage to the preform deposited with pyrolytic carbon is inevitably caused. However, even if the damage is caused at this time, the damage can be compensated by the fifth step.
The invention relates to a preparation method of a large-size special-shaped carbon-based composite material member, and in the fifth step, when pyrolytic carbon is deposited by adopting an isothermal chemical vapor deposition method, the carbon source is hydrocarbon or natural gas with the carbon atom number less than or equal to 3; preferably, hydrocarbon gas such as methane, propylene, propane, natural gas and the like is selected as diluent gas, nitrogen, hydrogen or mixed gas thereof is selected as diluent gas, the ratio of the carbon source gas to the diluent gas is 1: 1-3, the deposition time is 200-300 hours, and the deposition temperature is 1100-1300 ℃. As a preferable condition, the flow rate of the carbon source gas is 28-50L/min at the time of deposition. Preferably, the pressure of the gas in the furnace is 1.5KPa or less. As a further preferred condition, the deposition temperature in step five is greater than the infiltration temperature in step three. The flow rate of the carbon source gas in the fifth step is larger than that of the carbon source gas in the third step.
In the fifth step, the deposition temperature cannot be too low, and the deposition time cannot be too short, because the damage to the preform deposited with the pyrolytic carbon caused by the graphite mold removed in the fourth step is compensated in the fifth step.
In the sixth step, when the large-size special-shaped carbon-based composite material member is a thin-wall member, the graphitization time is not too long.
The invention relates to a preparation method of a large-size special-shaped carbon-based composite material member, and in the seventh step, the heat preservation time of the steam bath reaction is 10-30 min. The time of the silicon steam bath is strictly controlled, and one of the functions of the silicon steam bath is to ensure the proper thickness of the SiC coating on the surface of the large-size special-shaped carbon-based composite material.
The invention relates to a preparation method of a large-size special-shaped carbon-based composite material member. And (4) sealing and filling the carbon-based composite material obtained in the step six by adopting silicon vapor, and reacting with carbon on the surface layer to generate the SiC coating. Preferably, the carrier container for the silicon powder is a graphite container.
The invention relates to a preparation method of a large-size special-shaped carbon-based composite material component.
Has the advantages that:
the invention strictly controls the composition and the needling mode of the carbon fiber preform, and can achieve the effect of large size and special shape. After obtaining the prefabricated body in a specific needling mode, fixing the prefabricated body by using a graphite mold, and then carrying out high-temperature treatment, so that the prefabricated body is not easy to deform during the high-temperature treatment; in the molding process of the carbon fiber prefabricated part, the graphite mold is limited, so that the prefabricated part is not easy to deform in the thermal gradient chemical vapor infiltration process, and simultaneously, a certain amount of pyrolytic carbon is formed between the surface and the inner gap of the prefabricated part after the thermal gradient chemical vapor infiltration treatment, so that the test piece can hardly deform when the subsequent isothermal chemical vapor deposition treatment is carried out, and the probability of deformation of the test piece is reduced to the utmost extent through the three measures. This provides a prerequisite for the production of large-size profiled carbon-based composite members, in particular large-size profiled carbon-based composite members in which thin walls are present.
According to the invention, the inner and outer surfaces of the carbon fiber preform are punched, limited and fixed by the graphite mold, so that the carbon fiber preform with a larger porosity can be obtained, necessary conditions are provided for solving the problem that the preform is easy to deform, and the rapid densification is favorably realized during thermal gradient chemical vapor infiltration. Rapid densification may reduce the standing time, which is also advantageous for solving the problem of easy deformation.
The rough machining of the carbon fiber prefabricated part is carried out after the carbon fiber prefabricated part is molded, the fact that the density of the test piece is not high in the stage is considered, and if the size of some positions of the test piece does not meet the requirement of a product, the rough machining can be carried out through machining or filling in the stage. Meanwhile, the mold is removed after the thermal gradient chemical vapor infiltration treatment, and although damage to the preform may be caused at the moment, the damage can be compensated by the subsequent isothermal chemical vapor deposition, which is one of the reasons why the parameters in the step five are strictly controlled.
The invention strictly controls the technological parameters of thermal gradient chemical vapor infiltration and isothermal chemical vapor deposition, and can obtain the isotropic pyrolytic carbon. The isotropic pyrolytic carbon has compact structure, small grain size and uniform performance, has the common advantages of high temperature resistance, wear resistance and the like of common carbon materials, and also has the characteristics of high strength, excellent sealing property and the like. The thermal gradient chemical vapor infiltration is mainly to densify the pores of the core of the preform and to mold the preform; isothermal chemical vapor deposition is primarily directed to densifying the pores of the surface layer of the preform. Thus, the carbon-based composite member has a higher density of the skin than the core, and a lighter weight member material can be obtained.
In a word, the preparation process is reasonable, and the components and the density distribution design of the materials used by the component are also very reasonable. Under the synergistic effect of the steps of the preparation process, the problem that the large-size special-shaped carbon-based composite material is easy to deform in the preparation process is solved, and a finished product with excellent performance is obtained. With the increase of the size of the special-shaped component, the surface connection is greatly reduced, the workload of installation and maintenance is reduced, and the safety and reliability of the equipment are greatly improved.
Drawings
Fig. 1 is a schematic view of a space imaging lens barrel developed by using the large-size special-shaped carbon-based composite material prepared in example 1.
Fig. 2 is a view of a diaphragm of a satellite main mirror made of a large-size special-shaped carbon-based composite material prepared in example 2.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
(1) PAN-based T700(12K) laid fabric produced by Nippon Dongli corporation and a net tire are alternately superposed and then are knitted into a fabric with the volume density of 0.45 +/-0.02 g/cm3A carbon fiber preform having an outer diameter of 211mm, a height of 280mm and a wall thickness of 4.5 mm. The layering mode of the non-woven cloth is 0 degree/45 degree/90 degree. When needling, the needling density is 45 needles/cm3The depth of the needle insertion is 18 mm. When laying, 18 layers of carbon fiber are laid on the 1cm thick layer (namely 16 layers of the total layer number of the laid non-woven cloth and the net tire on the 1cm thick layer)。
(2) And (3) carrying out high-temperature heat treatment on the carbon fiber preform in a high-temperature treatment furnace, and keeping the temperature for 30min at 800 ℃ in a nitrogen atmosphere.
(3) And (3) placing the carbon fiber preform in a CVI furnace, and performing thermal gradient chemical vapor infiltration by using propylene as a main carbon source gas and nitrogen as a carrier gas. The deposition temperature is 1200 ℃, the propylene flow is 15L/min, the nitrogen flow is 20L/min, the bore pressure is 1.0KPa, and the time is 150 hours. Obtaining a density of 1.0g/cm3The low-density carbon fiber reinforced matrix carbon composite material.
(4) And (3) unloading the graphite mold, roughly processing the low-density carbon fiber reinforced matrix carbon composite material, turning burrs and adhesive substances on the surface of the blank, and finding a reference to correct the deformation.
(5) And (3) placing the carbon fiber preform in a CVI furnace, and carrying out isothermal chemical vapor deposition by using propylene as a main carbon source gas and nitrogen as a carrier gas. The deposition temperature is 1300 ℃, the propylene flow rate is 30L/min, the nitrogen flow rate is 60L/min, the bore pressure is 1.0KPa, and the deposition time is 250 hours. Obtaining a density of 1.5g/cm3The carbon fiber reinforced matrix carbon composite of (1).
(6) Graphitizing the carbon-based composite material under the pressure of 0.1MPa and under the protection of argon gas at the temperature of 2500 ℃ for 4 hours;
(7) in a high-temperature vacuum furnace, silicon powder is placed in a graphite crucible, a carbon-based composite material member is placed on the silicon powder, and then steaming bath is carried out to obtain the carbon-based composite material member with the density of 1.6g/cm3A large-size special-shaped carbon-based composite material. The steam bath reaction is carried out for 30min at the pressure of 0.2MPa and the temperature of 1800 ℃. In the large-size special-shaped carbon-based composite material, 28.1 wt% of carbon fiber, 65.6 wt% of pyrolytic carbon and 6.3 wt% of SiC are contained;
(8) the large-size special-shaped carbon-based composite material is machined according to the drawing of a corresponding component, the special-shaped carbon-based composite material space imaging lens barrel with the outer diameter phi of 210mm, the height of 260mm and the wall thickness of 3.5mm is prepared, and the schematic diagram of the assembled camera lens barrel is shown in figure 1.
Irradiation tests and sine vibration tests with the acceleration of 17.6G are carried out in the Chinese space technology research institute, and the large-size special-shaped carbon-based composite material lens barrel is proved to have excellent strength and size stability.
Example 2:
(1) the PAN-based T700(12K) twill cloth produced by Nippon Dongli company and the net tire are alternately overlaid and layered, the layering mode of the non-woven cloth is 0 degree/45 degrees/90 degrees, and the volume density of the non-woven cloth is 0.50g/cm through needle punching3The carbon fiber preform for a satellite diaphragm of (1). When needling, the needling density is 35 needles/cm3The depth of the needle insertion is 25 mm. When laying, 14 layers of carbon fibers are laid on the layer with the thickness of 1 cm.
(2) And (3) carrying out high-temperature heat treatment on the carbon fiber preform in a high-temperature treatment furnace, and keeping the temperature for 2h at 800 ℃ in a nitrogen atmosphere.
(3) And (3) placing the carbon fiber preform in a CVI furnace, and performing thermal gradient chemical vapor infiltration by using propylene as a main carbon source gas and nitrogen as a carrier gas. The deposition temperature is 1200 ℃, the propylene flow rate is 20L/min, the nitrogen flow rate is 60L/min, the bore pressure is 1.0KPa, and the time is 50 hours. The density obtained was 0.8g/cm3The low-density carbon fiber reinforced matrix carbon composite material.
(4) And (3) unloading the graphite mold, roughly processing the low-density carbon fiber reinforced matrix carbon composite material, turning burrs and adhesive on the surface of the blank, and finding a reference to correct the deformation.
(5) And (3) placing the carbon fiber preform in a CVI furnace, and carrying out isothermal chemical vapor deposition by using propylene as a main carbon source gas and nitrogen as a carrier gas. The deposition temperature is 1300 ℃, the propylene flow rate is 40L/min, the nitrogen flow rate is 60L/min, the bore pressure is 1.0KPa, and the deposition time is 300 hours. Obtaining a density of 1.3g/cm3The carbon fiber reinforced matrix carbon composite of (1).
(6) Carrying out catalytic graphitization treatment on the carbon-based composite material under the protection of argon gas at a micro-positive pressure for 8 hours at a temperature of 2300 ℃;
(7) in a high-temperature vacuum furnace, silicon powder is placed in a graphite crucible, a carbon-based composite material member is placed on the silicon powder, and then steaming bath is carried out to obtain the carbon-based composite material member with the density of 1.5g/cm3A large-size special-shaped carbon-based composite material. The steam bath reaction heat preservation time is 1h, the pressure is 0.2MPa, and the temperature is 1700 ℃. In the large-size special-shaped carbon-based composite material, 33.3 wt% of carbon fiber, 53.4 wt% of pyrolytic carbon and 13.3 wt% of SiCwt％；
(8) The large-size special-shaped carbon-based composite material main mirror diaphragm prepared is machined according to the drawing of a corresponding component, and a real object diagram after the weather satellite diaphragm is assembled is shown in figure 2. The integral processing needs to meet the integral assembly requirement.
Vibration tests of 1/4 magnitude were carried out on a large-size profiled carbon-based composite diaphragm on a vibration table of model V8-440 of LDS, Inc. in UK. The experimental results show that: the first-order frequency of the X-direction diaphragm is 94Hz, and the magnification is 1.2; the first-order frequency of the diaphragm in the Y direction is 95Hz, and the magnification is 1.3; the first order frequency of the diaphragm in the Z direction is 96Hz, and the magnification is 1.7. The test result shows that the large-size special-shaped carbon-based composite diaphragm has higher first-order frequency and smaller amplification factor, can pass a full-scale vibration test, has margin in rigidity and can continuously reduce the weight. The early-stage sample of the product is already applied to a wind cloud fourth satellite successfully launched by a Changchang third carrier rocket at the West Chang satellite launching center No. 11 in 2016 years in China.
Example 3:
(1) the PAN-based T700(12K) laid fabric produced by Nippon Dongli company and the net tire are alternately overlaid and layered, the layering mode of the laid fabric is 0 degree/45 degrees/90 degrees, and the volume density of the knitted fabric is 0.45g/cm3The carbon fiber preform of (1). When needling, the needling density is 35 needles/cm3The depth of the needle insertion is 18 mm. When laying, 14 layers of carbon fibers are laid on the layer with the thickness of 1 cm.
(2) And (3) carrying out high-temperature heat treatment on the carbon fiber preform in a high-temperature treatment furnace, and keeping the temperature for 2 hours at 600 ℃ in a nitrogen atmosphere.
(3) And (3) placing the carbon fiber preform in a CVI furnace, and performing thermal gradient chemical vapor infiltration by using propylene as a main carbon source gas and nitrogen as a carrier gas. The deposition temperature is 1000 ℃, the natural gas flow rate is 30L/min, the nitrogen flow rate is 60L/min, the bore pressure is 1.0KPa, and the time is 50 hours. The density obtained was 0.8g/cm3The low-density carbon fiber reinforced matrix carbon composite material.
(4) And (3) unloading the graphite mold, roughly processing the low-density carbon fiber reinforced matrix carbon composite material, turning burrs and adhesive on the surface of the blank, and finding a reference to correct the deformation.
(5) And placing the carbon fiber preform in a CVI furnace, and carrying out isothermal chemical vapor deposition by using natural gas as a main carbon source gas and nitrogen as a carrier gas. The deposition temperature is 1100 ℃, the propylene flow rate is 50L/min, the nitrogen flow rate is 70L/min, the bore pressure is 1.5KPa, and the deposition time is 200 hours. Obtaining a density of 1.3g/cm3The carbon fiber reinforced matrix carbon composite of (1).
(6) Carrying out catalytic graphitization treatment on the carbon-based composite material under the protection of argon gas at a micro-positive pressure for 8 hours at a temperature of 2000 ℃;
(7) in a high-temperature vacuum furnace, silicon powder is placed in a graphite crucible, a carbon-based composite material member is placed on the silicon powder, and then steaming bath is carried out to obtain the large-size special-shaped carbon-based composite material with the density of 1.45g/cm 3. The steam bath reaction is carried out for 0.5h at the pressure of 0.2MPa and the temperature of 1750 ℃. In the large-size special-shaped carbon-based composite material, 31.0 wt% of carbon fiber, 58.6 wt% of pyrolytic carbon and 10.4 wt% of SiC are used;
(8) and machining the prepared large-size special-shaped carbon-based composite material according to the drawing of the corresponding component, wherein the integral machining needs to meet the integral assembly requirement.
Claims (5)
1. A large-size special-shaped carbon-based composite material component; the method is characterized in that: the material comprises the following components in percentage by mass:
20-35% of carbon fiber;
35 to 75 percent of pyrolytic carbon
SiC 5-15％；
The surface layer density of the large-size special-shaped carbon-based composite material member is higher than the core density;
the large-size special-shaped carbon-based composite material member is prepared by the following steps:
step one
According to the required part shape, firstly needling continuous carbon fiber into a prefabricated blank; the density of the prefabricated blank is 0.4-0.55 g/cm3(ii) a Fixing the inner and outer surfaces of the prefabricated blank by using a graphite mold; obtaining a spare blank;
step two
Carrying out high-temperature heat treatment on the spare blank obtained in the step one under the protective atmosphere; obtaining a spare blank after heat treatment; the temperature of the high-temperature heat treatment is 600-800 ℃, and the time is 0.5-2 hours;
step three
Placing the spare blank subjected to the heat treatment in the step two into a deposition furnace; isotropic pyrolytic carbon densification is carried out on the carbon fiber by adopting a thermal gradient chemical vapor infiltration method; when the thermal gradient chemical vapor infiltration is carried out, the carbon source gas is hydrocarbon or natural gas with the carbon atom number less than or equal to 3; the diluent gas is nitrogen, hydrogen or a mixed gas thereof, the ratio of the carbon source gas to the diluent gas is 1: 1-3, the flow rate of the carbon source gas is 10-30L/min, the time is 50-150 hours, and the temperature is 1000-1200 ℃; the obtained density is 0.8-1.0 g/cm3The low-density carbon fiber reinforced matrix carbon composite blank of (a);
step four
Removing the graphite mold, performing rough machining on the low-density carbon fiber reinforced matrix carbon composite blank obtained in the step three, removing burrs and adhesive substances on the surface of the blank, and finding a reference to correct the deformation amount; obtaining a rough-processed low-density carbon fiber reinforced matrix carbon composite blank;
step five
Placing the rough-processed low-density carbon fiber reinforced matrix carbon composite blank in a deposition furnace, and depositing pyrolytic carbon by adopting an isothermal chemical vapor deposition method until the density is 1.3-1.5 g/cm3The carbon fiber reinforced matrix carbon composite blank of (1);
when the isothermal chemical vapor deposition method is adopted to deposit pyrolytic carbon, the carbon source is hydrocarbon or natural gas with the carbon atom number less than or equal to 3; the diluent gas is nitrogen, hydrogen or a mixed gas thereof, the ratio of the carbon source gas to the diluent gas is 1: 1-3, the flow rate of the carbon source gas is 28-50L/min, the deposition time is 200-300 hours, and the deposition temperature is 1100-1300 ℃;
step six
Under the protective atmosphere, the density obtained in the fifth step is 1.3-1.5 g/cm3The carbon fiber reinforced matrix carbon composite blank is subjected to graphitization treatment, the graphitization degree is improved, and the carbon fiber reinforced matrix carbon composite blank subjected to graphitization treatment is obtained(ii) a During graphitization treatment, controlling the pressure in the furnace to be 0.1-0.2MPa, the temperature to be 2000-2500 ℃ and the time to be 4-8 hours;
step seven
Placing the carbon fiber reinforced matrix carbon composite blank obtained in the step six after the graphitization treatment on silicon powder, vacuumizing, heating to 1500-1800 ℃ for steam bath until the density is 1.4-1.6 g/cm3The composite blank of (a); when in steam bath, the pressure in the furnace is controlled to be 0.1-0.2 MPa;
step eight
The density obtained in the step seven is 1.4-1.6 g/cm3The composite blank of (a); performing finish machining according to a design drawing; and obtaining a finished product.
2. A large size profiled carbon-based composite member according to claim 1, wherein: firstly, needling continuous carbon fibers into a prefabricated blank according to the required part shape; the scheme of needling out the prefabricated blank is as follows: adopting carbon fiber laid cloth or twill cloth and a tire net to alternately overlay and lay, and then adopting lower barb to continuously needle the overlaid laid cloth or twill cloth and the net tire to form an integral structure fabric; the layering mode of the weftless fabric or the twill fabric is 0 degree/45 degree/90 degrees, and the needling density is 35-45 needles/cm3The needling depth is 18-25mm, and when the needle is needled, the barb needling takes a small part of fibers in the parallel direction of the prefabricated body to the vertical direction.
3. A large size profiled carbon-based composite member according to claim 1, wherein: in the first step, according to the thickness of each centimeter, a mode of laying 14-18 layers of materials is adopted, and carbon fiber non-woven cloth or twill cloth and tire net are alternately stacked and layered.
4. A large size profiled carbon-based composite member according to claim 1, wherein: in the first step, the inner surface and the outer surface of the carbon fiber preform are punched, limited and fixed by a graphite mold, the limiting cushion blocks are 3-8 mm, the bottom of the carbon fiber preform is bound with graphite by carbon fibers, and the distance is 12-18 mm.
5. A large size profiled carbon-based composite member according to claim 1, wherein: and in the seventh step, the heat preservation time of the steam bath reaction is 10-30 min.
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