CN117776750A - C/SiC composite material, preparation method thereof, heat conduction member and heating furnace - Google Patents
C/SiC composite material, preparation method thereof, heat conduction member and heating furnace Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 19
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- 239000005011 phenolic resin Substances 0.000 claims abstract description 73
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 72
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Abstract
The invention provides a C/SiC composite material and a preparation method thereof, a heat conduction member and a heating furnace, and the preparation method comprises the following preparation steps: mixing the nano silicon powder with high carbon residue thermosetting phenolic resin to obtain first mixed slurry; impregnating carbon fibers into the first mixed slurry to obtain a prepreg; and (3) carbonizing and calcining the prepreg sequentially. According to the method, the nano silicon powder and the thermosetting phenolic resin are mixed first, so that more in-situ reaction points exist between the resin and the silicon powder, the full reaction between silicon and carbon in the calcining treatment process is promoted to form C/SiC, the generation of free silicon can be reduced, the in-situ reaction temperature of Si and C can be reduced, and the production cost is reduced; in addition, carbon fibers are immersed in the mixture, and thermosetting phenolic resin and silicon powder can better infiltrate into gaps of the carbon fibers, so that a carbon fiber/SiC composite material with higher density is obtained, and the mechanical property of the C/SiC composite material is improved.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a C/SiC composite material, a preparation method thereof, a heat conduction member and a heating furnace.
Background
The C/SiC composite material has high specific strength, high specific modulus, high heat conductivity, high friction coefficient, low thermal expansion coefficient, excellent corrosion resistance and oxidation resistance, can normally work in extremely severe service environments such as high overload, high heat flow, strong scouring and ablation, and the like, has long service life and strong environmental applicability, so that the application fields are very wide, and the aerospace field and the friction braking field are two main application fields.
At present, the siliconizing method is an important preparation method which is favored because the preparation period is shorter, and the net molding of large complex components is easy to realize. The siliconizing method can be classified into two types of liquid phase siliconizing (Liquid Silicon Infiltration, LSI) and vapor phase siliconizing (Gaseous Silicon Infiltration, GSI) according to the silicon source morphology. In LSI preparation, the sample is not separated from the silicon particles by the graphite rod, and the silicon particles are heated to a molten state, and then react with the sample in a liquid state, so that the sample is easier to permeate under the condition that two phases are completely wetted in the permeation process, and free Si particles are easy to remain in the incompletely wetted two phases, thereby reducing the strength of the composite material. After the GSI is heated to a molten state during preparation, the GSI reaches a boiling evaporation state through means such as vacuumizing and the like, and Si contacts and enters a sample in a gaseous state and reacts; although the gaseous silicon molecules are smaller and easier to permeate, sufficient silicon sources are needed to achieve a more sufficient reaction, and in doing so, a higher heat treatment temperature is needed to change the Si particles into a gaseous state, which is a high requirement on equipment and a high manufacturing cost.
Disclosure of Invention
Based on the above, it is necessary to provide a C/SiC composite material having good mechanical properties, a method for preparing the same, a heat conductive member, and a heating furnace.
The first aspect of the invention provides a preparation method of a C/SiC composite material, which comprises the following preparation steps:
mixing the nano silicon powder with high carbon residue thermosetting phenolic resin to obtain first mixed slurry;
impregnating carbon fibers into the first mixed slurry to obtain a prepreg;
and (3) carbonizing and calcining the prepreg sequentially.
According to the preparation method, the nano silicon powder and the thermosetting phenolic resin serving as a carbon source are firstly mixed, so that more in-situ reaction points can be formed between the thermosetting phenolic resin and the silicon powder after the thermosetting phenolic resin is carbonized, the silicon and the carbon can be promoted to fully react to form C/SiC in the calcining treatment process, the generation of free silicon can be further reduced, the in-situ reaction temperature of Si and C can be reduced, gaseous Si is not needed in the preparation process, and the preparation cost is reduced; in addition, carbon fibers are immersed in the mixture, and thermosetting phenolic resin and silicon powder can better infiltrate into gaps of the carbon fibers, so that a carbon fiber/SiC composite material with higher density, namely a C/SiC composite material, is obtained, and the mechanical property of the C/SiC composite material is improved.
In some embodiments of the present application, the method of preparation meets at least one of the following conditions:
(1) The carbon residue rate of the thermosetting phenolic resin is more than or equal to 55%;
(2) The thermosetting phenolic resin is in a liquid state at normal temperature and normal pressure;
(3) The viscosity of the thermosetting phenolic resin at 25 ℃ is 100 mpa.s-1000 mpa.s;
(4) The viscosity of the first mixed slurry is 120 mpa.s-400 mpa.s at 25-80 ℃.
In some embodiments of the present application, the thermosetting phenolic resin is selected from at least one of a boron phenolic resin, a barium phenolic resin, and an ammonia phenolic resin; and/or the average grain diameter of the nano silicon powder is 30nm-100nm.
In some embodiments of the present application, in the first mixed slurry, a molar ratio of the C element in the thermosetting phenolic resin to the Si element in the nano silicon powder is (2-4): 1.
in some embodiments of the present application, the carbon fiber is selected from at least one of T300, T600, T700, T800, and T1000.
In some embodiments of the present application, the carbon fiber prepreg has a liquid carrying rate of 1% to 5%.
In some embodiments of the present application, the method of preparation meets at least one of the following conditions:
(1) The carbonization temperature of the carbonization treatment is 750-900 ℃;
(2) The carbonization treatment time is 10-15 h;
(3) The calcination temperature of the calcination treatment is 1300-1500 ℃;
(4) The calcination treatment time is 2-5 h.
The invention also provides the C/SiC composite material obtained by the preparation method.
In a third aspect of the present invention, there is provided a heat conductive member comprising the above-described C/SiC composite material.
In a fourth aspect of the present invention, there is provided a heating furnace comprising the above heat conductive member.
Detailed Description
The present invention is described more fully below in order to facilitate an understanding of the present invention. And provides a preferred embodiment of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It should be understood that these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present invention may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present invention are scaled up or down within the scope of the disclosure of the embodiments of the present invention. Specifically, the weight described in the specification of the embodiment of the present invention may be mass units known in the chemical industry field such as μ g, mg, g, kg.
Carbon residue refers to the mass of solid residue left by the resin material during combustion or thermal decomposition at a high temperature of 800 c as a percentage of the initial resin mass.
In one embodiment of the invention, a preparation method of a C/SiC composite material is provided, which comprises the following preparation steps S10-S30:
s10, mixing nano silicon powder with thermosetting phenolic resin to obtain first mixed slurry;
s20, immersing carbon fibers in the first mixed slurry to obtain carbon fiber prepreg;
and S30, carbonizing and calcining the carbon fiber prepreg sequentially.
According to the preparation method, the nano silicon powder and the thermosetting phenolic resin serving as a carbon source are firstly mixed, so that more in-situ reaction points can be formed between the thermosetting phenolic resin and the silicon powder after the thermosetting phenolic resin is carbonized, the silicon and the carbon can be promoted to fully react to form C/SiC in the carbonization treatment process, the generation of free silicon can be further reduced, the in-situ reaction temperature of Si and C can be reduced, gaseous Si is not needed in the preparation process, and the preparation cost is reduced; in addition, carbon fibers are immersed in the mixture, and thermosetting phenolic resin and silicon powder can better infiltrate into gaps of the carbon fibers, so that a carbon fiber/SiC composite material with higher density, namely a C/SiC composite material, is obtained, and the mechanical property of the C/SiC composite material is improved.
In some embodiments, the nano-silicon powder has an average particle size of 30nm to 100nm. It is understood that the average particle size of the nano silicon powder may be 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 100nm. Further, the average particle diameter of the nano silicon powder may be a range of values formed by any two of the above-mentioned point values. Preferably, the average particle size of the nano silicon powder is 30nm-60nm. Compared with micron-sized silicon powder, the nano silicon powder has smaller particle size and larger specific surface area and higher reactivity. The particle size of the nano silicon powder is further controlled, so that the nano silicon powder can be better dispersed in the resin, and the effective reactive point is further improved. The effective reactive point refers to the reactive point of the nano silicon powder which reacts with the thermosetting phenolic resin.
In some embodiments, the char yield of the thermosetting phenolic resin is greater than or equal to 55%. Further, the carbon residue rate of the thermosetting phenolic resin is 60-70%. The carbon residue rate of the thermosetting phenolic resin can be controlled to further control the in-situ reaction point of carbon and silicon, and the generation amount of SiC is controlled, so that the mechanical property and the heat conducting property of the C/SiC composite material are better controlled.
In some embodiments, the thermosetting phenolic resin is in a liquid state at ambient temperature and pressure. The liquid resin is easier to be uniformly mixed with the silicon powder, and is beneficial to the more sufficient contact between the nano silicon powder and carbon active sites in the resin.
In some embodiments, the thermosetting phenolic resin has a viscosity of 100 mpa-s to 1000 mpa-s at 25 ℃. It will be appreciated that the thermosetting phenolic resin may have a viscosity of 100 mpa.s, 200 mpa.s, 300 mpa.s, 500 mpa.s, 800 mpa.s or 1000 mpa.s at 25 ℃. Further, the viscosity of the thermosetting phenol resin at 25 ℃ may be a range of values consisting of any two of the above-mentioned point values. Preferably, the thermosetting phenolic resin has a viscosity of 100 mpa.s to 300 mpa.s at 25 ℃.
In some embodiments, the thermosetting phenolic resin is selected from at least one of a boron phenolic resin, a barium phenolic resin, and an ammonia phenolic resin. Preferably, the thermosetting phenolic resin is a borophenolic resin.
In some embodiments, in the first mixed slurry, the molar ratio of the C element in the thermosetting phenolic resin to the Si element in the nano silicon powder is (2-4): 1. preferably, the molar ratio of the C element in the thermosetting phenolic resin to the Si element in the nano silicon powder is 3:1. the molar ratio of the C element in the thermosetting phenolic resin to the Si element in the nanometer silicon powder is controlled, so that enough SiC is generated to ensure the performance of the C/SiC composite material, and excessive free silicon is not generated.
In some embodiments, the first mixed slurry has a viscosity of 120 mpa-s to 400 mpa-s at 25 ℃ to 80 ℃.
In some embodiments, the carbon fibers are impregnated in the first mixed slurry at a temperature of 25 ℃ to 80 ℃. The viscosity of the first mixed slurry may vary with temperature based on the characteristics of the thermosetting resin. By controlling the temperature of the first mixed slurry at the time of impregnation, the viscosity of the first mixed slurry can be adjusted. Further, when the carbon fiber is immersed in the first mixed slurry, the temperature of the first mixed slurry is adjusted within the temperature range of 25-80 ℃ to enable the viscosity of the first mixed slurry to reach 120 mpa.s-300 mpa.s. The viscosity of the first mixed slurry in the impregnation process is controlled within a lower range, so that better impregnation performance can be provided, the slurry can more easily permeate into fiber gaps, and the mechanical property of the composite material is improved. Meanwhile, the viscosity of the first mixed slurry is controlled, so that the loss and volatilization of the resin can be further reduced, and the process difficulty is reduced.
In some embodiments, the carbon fibers are added to the first mix in the form of a carbon fiber web.
In some embodiments, the carbon fiber is selected from at least one of T300, T600, T700, T800, and T1000.
In some embodiments, the carbon fiber prepreg has a liquid carrying rate of 1% -5%. The liquid carrying rate of the carbon fiber prepreg refers to the percentage of the weight gain variation before and after the carbon fiber impregnation to the mass of the carbon fiber. Namely, the calculation formula of the liquid carrying rate of the carbon fiber prepreg is as follows: the liquid carrying rate of the carbon fiber prepreg= (mass of the carbon fiber prepreg-mass of the carbon fiber)/mass of the carbon fiber x 100%.
Further, the liquid carrying rate of the carbon fiber prepreg may be 1%, 2%, 3%, 4% or 5%. Further, the liquid carrying rate of the carbon fiber prepreg may be a range of values constituted by the above-mentioned arbitrary point values. Preferably, the liquid carrying rate of the carbon fiber prepreg is 5%. The control of the liquid carrying rate of the carbon fiber prepregs is beneficial to lamination and adhesion among the carbon fiber prepregs, so that the interlayer bonding effect of the carbon fiber prepregs is improved, and the finally prepared C/SiC composite material is not easy to deform and crack.
In some embodiments, the carbon fibers are immersed in the first mixed slurry for a period of time ranging from 4 hours to 6 hours.
In some embodiments, the carbonization temperature of the carbonization treatment is 700 ℃ to 900 ℃. It is understood that the temperature of the carbonization treatment may be 700 ℃, 750 ℃, 800 ℃, 850 ℃, or 900 ℃. Further, the carbonization treatment temperature may be a range of values constituted by the above arbitrary point values. Preferably, the temperature of the carbonization treatment is 750 ℃ 900 ℃. The carbonization temperature is controlled, so that the nano silicon powder and active site carbon in the thermosetting phenolic resin can react to form the SiC material.
In some embodiments, the carbonization treatment is for a period of time ranging from 10 hours to 15 hours. It is understood that the carbonization treatment is performed for 10h, 11h, 12h, 13h, 14h or 15h. Further, the time of the carbonization treatment may be a range value constituted by the above arbitrary point values. Preferably, the carbonization treatment is carried out for a period of time ranging from 12h to 36h. By controlling the carbonization time, enough reaction between the nano silicon powder and the resin can be carried out to generate more SiC.
In some embodiments, the steps of impregnating the carbon fibers with the first mixture and carbonizing may be repeated a plurality of times in sequence. Further, it may be sequentially repeated 2 to 3 times.
In some embodiments, the calcination temperature of the calcination process is 1300 ℃ to 1500 ℃. It is understood that the calcination temperature is 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, or 1500 ℃. Further, the calcination temperature of the calcination treatment is 1450-1500 ℃.
In some embodiments, the calcination treatment is for a period of time ranging from 2 hours to 5 hours.
In some embodiments, the calcination treatment is performed under inert gas atmosphere conditions.
Further, the inert gas may be nitrogen, argon or helium.
In some embodiments, the step of shaping the carbon fiber prepreg further comprises prior to carbonizing the carbon fiber prepreg. The carbon fiber prepreg can be manufactured into rough blanks with various shapes and appearances through molding treatment, and then the C/SiC composite material with the required shape is obtained.
In some embodiments, the molding process may be performed by way of molding or autoclave.
In some embodiments, compression molding is performed by a molding press.
In some embodiments, the pressure of the molding press is 10MPa to 50MPa.
In some embodiments, the temperature of the molding press is 150 ℃ to 200 ℃.
In some embodiments, the molding time of the molding press is 1h-2h.
In some embodiments, in step S10, when the nano silicon powder is mixed with the thermosetting phenolic resin, a dispersing agent may be further added to obtain a mixed slurry.
In some embodiments, the dispersant is selected from at least one of polyvinyl alcohol, sulfonate, cetyltrimethylammonium bromide.
In some embodiments, the mass ratio of dispersant to nano silicon powder is 1: (14-16).
In one embodiment of the present invention, there is provided a C/SiC composite material obtained by the above-described preparation method.
In one embodiment of the present invention, there is provided a heat conductive member comprising the above-described C/SiC composite material.
In some embodiments, the heat conducting member may be applied to brake pads, thermal field structural members of heating furnaces, and aerospace plane pipe fittings.
In one embodiment of the present invention, there is provided a heating furnace including the above heat conductive member.
Further, heating furnaces include, but are not limited to, single crystal furnaces, vacuum furnaces, flame heating furnaces, induction heating furnaces, and atmosphere control furnaces.
In order to make the objects, technical solutions and advantages of the present invention more concise, the present invention will be described in the following specific examples, but the present invention is by no means limited to these examples. The following examples are only preferred embodiments of the present invention, which can be used to describe the present invention, and should not be construed as limiting the scope of the invention. It should be noted that any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
In order to better illustrate the present invention, the following description of the present invention will be given with reference to examples. The following are specific examples.
Example 1
(1) According to C: si=3: 1, weighing 50nm nano silicon powder and thermosetting barium phenolic resin (model: holy spring barium phenolic resin TA-02, viscosity: 300 mpa.s at 25 ℃ and carbon residue rate: 60%), adding the nano silicon powder into the thermosetting barium phenolic resin, and stirring and mixing to obtain a first mixed slurry.
(2) And (3) weighing the carbon fibers of the T300, wherein the weight of the carbon fibers is 40% of the total mass of the first mixed slurry, and weaving the carbon fibers into carbon fiber mesh cloth.
(3) Heating the first mixture obtained in the step (1) to 80 ℃ to obtain mixed slurry with the viscosity of 120 mPa.s; and (3) immersing the carbon fiber mesh cloth in the step (2) in the mixed slurry with the viscosity of 120 mPa.s for 4-6 hours to obtain the carbon fiber prepreg with the liquid carrying rate of 4%.
(4) Preparing 300mm 20mm coarse blanks from the carbon fiber prepreg obtained in the step (3) through a molding press, wherein the parameters of the molding press include: the pressure is 30MPa, the temperature is 180 ℃, and the compression molding time is 1h.
(5) Carbonizing the rough blank obtained in the step (4) in a carbonizing furnace at 750 ℃ for 12 hours.
(6) Sintering the carbonized preform obtained in the step (5) for 2 hours in nitrogen atmosphere at 1350 ℃, and cooling along with a furnace to obtain the C/SiC composite material.
Example 2
The preparation method of this example is substantially identical to the preparation method of example 1, except that the first mixed slurry of this example includes thermosetting barium phenolic resin and nano silicon powder C: si=4: 1, a step of; other preparation conditions and process parameters were identical to those of example 1.
Example 3
The preparation method of this example is substantially identical to the preparation method of example 1, except that the first mixed slurry of this example includes thermosetting barium phenolic resin and nano silicon powder C: si=2: 1, a step of; other preparation conditions and process parameters were identical to those of example 1.
Example 4
The preparation method of this example is identical to that of example 1, except that the thermosetting barium phenolic resin in step (1) is replaced with thermosetting ammonia phenolic resin (model: holy spring PF9601, viscosity at 25 ℃ C. Is 150 mpa.s, carbon residue ratio is 55%), C: si=3: 1, other preparation conditions and process parameters were identical to those of example 1.
Example 5
The preparation method of this example is identical to that of example 1, except that the thermosetting barium phenolic resin of step (1) is replaced with boron phenolic resin (model: holy spring PF9506, viscosity at 25 ℃ C.: 170 mpa.s, carbon residue ratio: 68%), C: si=3: 1, other preparation conditions and process parameters were identical to those of example 1.
Example 6
The preparation method of this example is basically identical to that of example 1, except that the nano silicon powder used in step (1) of this example has a particle size of 100nm, and other preparation conditions and process parameters are identical to those of example 1.
Example 7
The preparation method of this example was identical to that of example 1, except that the nano silicon powder in step (1) of this example had a particle diameter of 60nm, and other preparation conditions and process parameters were identical to those of example 1.
Example 8
The preparation method of this example was identical to that of example 1, except that the particle size of the nano silicon powder in step (1) of this example was 30nm, and other preparation conditions and process parameters were identical to those of example 1.
Example 9
The production method of this example was identical to example 1 except that the liquid carrying rate of the carbon fiber prepreg obtained in step (2) of this example was 1%, and other production conditions and process parameters were identical to example 1.
Example 10
The production method of this example was identical to example 1, except that the liquid carrying rate of the carbon fiber prepreg obtained in step (2) of this example was 5%, and other production conditions and process parameters were identical to example 1.
Example 11
The preparation method of this example was identical to that of example 1, except that the carbonized preform obtained in step (6) of this example was sintered at 1500℃and the other preparation conditions and process parameters were identical to those of example 1.
Example 12
(1) According to C: si=4: 1, weighing 80nm nano silicon powder and thermosetting barium phenolic resin, adding the nano silicon powder into the thermosetting barium phenolic resin, and stirring and mixing to obtain first mixed slurry.
(2) And (3) weighing the carbon fibers of the T800, wherein the weight of the carbon fibers is 40% of the total mass of the first mixed slurry, and weaving the carbon fibers into carbon fiber mesh cloth.
(3) Heating the first mixture obtained in the step (1) to 40 ℃ to obtain mixed slurry with the viscosity of 300 mPas, and immersing the carbon fiber mesh cloth in the step (2) in the mixed slurry with the viscosity of 300 mPas for 4-6 hours to obtain the carbon fiber prepreg with the liquid carrying rate of 5%.
(4) Preparing 300mm 20mm coarse blanks from the carbonized fiber prepreg obtained in the step (3) through a molding press, wherein the parameters of the molding press include: the pressure was 40MPa, the temperature was 200℃and the compression molding time was 1.5h.
(5) Carbonizing the rough blank obtained in the step (4) in a carbonization furnace at 800 ℃ for 10 hours.
(6) Repeating the steps (3) - (5) for 1 time to obtain a carbonization treatment preform.
(7) Sintering the carbonized preform obtained in the step (6) for 2 hours in nitrogen atmosphere at 1450 ℃, and cooling along with a furnace to obtain the C/SiC composite material.
Example 13
(1) According to C: si=2: 1, weighing 30nm of nano silicon powder and thermosetting barium phenolic resin, adding the nano silicon powder into the thermosetting barium phenolic resin, and stirring and mixing to obtain first mixed slurry. (2) And (3) weighing the carbon fiber of the T1000, wherein the weight of the carbon fiber is 30% of the total mass of the first mixed slurry, and weaving the carbon fiber.
(3) Heating the first mixture obtained in the step (1) to 80 ℃ to obtain mixed slurry with the viscosity of 150 mPa.s; and (3) immersing the carbon fiber mesh cloth in the step (2) in the mixed slurry with the viscosity of 150 mPa.s for 4-6 hours to obtain the carbon fiber prepreg with the liquid carrying rate of 3%.
(4) Preparing 300mm 20mm coarse blanks from the carbonized fiber prepreg obtained in the step (3) through a molding press; the molding press parameters include: the pressure is 15MPa, the temperature is 150 ℃, and the compression molding time is 1.8h.
(5) Carbonizing the rough blank obtained in the step (3) in a carbonization furnace at 900 ℃ for 14h.
(6) Repeating the steps (3) - (5) for 2 times to obtain a carbonization treatment preform.
(7) Sintering the carbonized preform obtained in the step (6) for 2 hours in nitrogen atmosphere at 1500 ℃, and cooling along with a furnace to obtain the C/SiC composite material.
Example 14
(1) According to C: si=3: 1, weighing 50nm of nano silicon powder and thermosetting boron phenolic resin, and adding the nano silicon powder into the thermosetting boron phenolic resin to obtain first mixed slurry. Polyethylene, 3% of the total mass of the mixed slurry, was added thereto as a dispersant, and stirred and mixed.
(2) And (3) weighing the carbon fibers of the T700, wherein the weight of the carbon fibers is 30% of the total mass of the first mixed slurry, and weaving the carbon fibers into carbon fiber mesh cloth.
(3) Heating the first mixture obtained in the step (1) to 80 ℃ to obtain mixed slurry with the viscosity of 120 mPa.s; and (3) immersing the carbon fiber mesh cloth in the step (2) in mixed slurry with the viscosity of 120 mPa.s for 4-6 hours to obtain the carbon fiber prepreg with the liquid carrying rate of 5%.
(4) Preparing 300mm 20mm coarse blanks from the carbonized fiber prepreg obtained in the step (3) through a molding press; the molding press parameters include: the pressure was 16MPa, the temperature was 110℃and the press molding time was 2.0 hours.
(5) Carbonizing the rough blank obtained in the step (3) in a carbonization furnace at 900 ℃ for 16 hours.
(6) Repeating the steps (3) - (5) for 2 times to obtain a carbonization treatment preform.
(7) Sintering the carbonized preform obtained in the step (6) for 2 hours in nitrogen atmosphere at 1500 ℃, and cooling along with a furnace to obtain the C/SiC composite material.
Comparative example 1
(1) According to C: si=3: 1, weighing 50nm nano silicon powder and thermosetting barium phenolic resin.
(2) And (3) weighing the carbon fiber of T300, wherein the weight of the carbon fiber is 40% of the total mass of the nano silicon powder and the thermosetting barium phenolic resin in the step (1), and weaving the carbon fiber into carbon fiber mesh cloth.
(3) The method comprises the steps of respectively placing nano silicon powder, thermosetting barium phenolic resin and carbon fiber in a chemical vapor siliconizing furnace of FSJ-800 x 1000, and preparing the C/SiC composite material by a vapor siliconizing method without contact of the nano silicon powder, the thermosetting barium phenolic resin and the carbon fiber.
Temperature control program of chemical vapor siliconizing furnace: raising the temperature from room temperature to 800 ℃ at the speed of 8 ℃/min, raising the temperature to 1500 ℃ at the speed of 6 ℃/min, and preserving the heat for 5 hours to ensure the liquefaction of the silicon particles. And then raising the temperature to 1700 ℃ at 7 ℃/min, simultaneously starting a vacuumizing device to ensure that the vacuum degree in the furnace reaches 1.6MPa, and cooling along with the furnace after heat preservation and pressure maintaining reaction for 2 hours to obtain the C/SiC composite material.
Comparative example 2
(1) According to C: si=3: 1, weighing 50nm nano silicon powder and thermosetting barium phenolic resin.
(2) T300 is selected as the carbon fiber, and three-dimensional needling is adopted to weave the carbon fiber into a prefabricated member; and mixing the carbon fiber prefabricated member, the nano silicon powder and the thermosetting barium phenolic resin, and placing the mixture in a siliconizing furnace, and preparing the C/SiC composite material by a liquid phase siliconizing method.
The liquid phase siliconizing method temperature control program is as follows: and (3) heating to 1500 ℃ from room temperature at 8 ℃/min to melt silicon particles, vacuumizing to negative pressure of 0.6MPa, reacting for 2 hours, and cooling with a furnace to obtain the C/SiC composite material.
Comparative example 3
This comparative example is substantially identical to the preparation method of example 1, except that in step (1), the nano silicon powder of 50nm is replaced with silicon powder of 2 μm, and C: si=3: 1, other steps and process conditions were identical to those of example 1.
Comparative example 4
This comparative example was substantially identical to the preparation method of example 1, except that the thermosetting barium phenolic resin in step (1) was replaced with a thermoplastic epoxy resin (model E51, viscosity at 25 ℃ C.: 250 mpa.s, char residue: 40%), and C: si=3: 1, other steps and process conditions were identical to those of example 1.
Performance testing
Density, tensile strength and flexural strength: the test was carried out according to the method specified in GB/T19076-2022.
Thermal conductivity coefficient: the test was carried out according to the method specified in GB/T3651-2008.
The performance test data for each example and comparative example are shown in table 1:
TABLE 1
As can be seen from Table 1, comparative example 1, which was a C/SiC composite material prepared by a vapor phase siliconizing method, had a tensile strength of 109MPa, a flexural strength of 116MPa, and a thermal conductivity of 10 W.m -1 ·K -1 . In the embodiment 1, the tensile strength of the prepared C/SiC composite material reaches 150MPa, the bending strength reaches 190MPa, and the heat conductivity coefficient also reaches 16. Although, the density of examples 1-14 was lower than that of the C/SiC composite material prepared in comparative example 1; however, examples 1 to 14 are excellent in mechanical properties as compared with comparative example 1. In combination, the C/SiC composite materials of examples 1-14 have good compactness, mechanical strength and heat conduction performance.
Comparative example 2 the mechanical properties and thermal conductivity of the resulting C/SiC composite material were also inferior to example 1 by using a liquid phase siliconizing method, mixing carbon fibers, nano silicon powder and barium phenolic resin together, and then directly calcining at high temperature without carbonization. Probably because comparative example 2 was not carbonized, the carbon in the raw resin did not have sufficient time and temperature conditions to generate sufficient resin-based carbon, and further resulted in lower SiC content in the subsequent high-temperature calcination process, and thus the mechanical properties and thermal conductivity of the prepared C/SiC composite material were reduced.
Comparative examples 3, 4 the nano-silica fume and the thermosetting barium phenolic resin of example 1 were replaced with micro-silica fume and thermoplastic resin, respectively. As can be seen from Table 2, the C/SiC composites prepared in comparative example 3 and comparative example 4 have lower areal density, mechanical properties and thermal conductivity than those of example 1. The specific nano silicon powder and thermosetting resin are selected to have important influence on improving the compactness, mechanical strength and heat conducting property of the C/SiC composite material.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is, therefore, indicated by the appended claims, and the description may be intended to interpret the contents of the claims.
Claims (10)
1. The preparation method of the C/SiC composite material is characterized by comprising the following preparation steps:
mixing nano silicon powder with thermosetting phenolic resin to obtain first mixed slurry;
impregnating carbon fibers into the first mixed slurry to obtain carbon fiber prepreg;
and (3) carbonizing and calcining the carbon fiber prepreg sequentially.
2. The method of preparation of claim 1, wherein the method of preparation meets at least one of the following conditions:
(1) The carbon residue rate of the thermosetting phenolic resin is more than or equal to 55%;
(2) The thermosetting phenolic resin is in a liquid state at normal temperature and normal pressure;
(3) The viscosity of the thermosetting phenolic resin at 25 ℃ is 100 mpa.s-1000 mpa.s;
(4) The viscosity of the mixture is 120 mpa.s-400 mpa.s at 25-80 ℃.
3. The method of preparing according to claim 2, wherein the thermosetting phenolic resin is selected from at least one of a boron phenolic resin, a barium phenolic resin and an ammonia phenolic resin; and/or the number of the groups of groups,
the average grain diameter of the nanometer silicon powder is 30nm-100nm.
4. A method according to any one of claims 1 to 3, wherein in the first mixed slurry, the molar ratio of the C element in the thermosetting phenolic resin to the Si element in the nano silicon powder is (2 to 4): 1.
5. a method according to any one of claims 1 to 3, wherein the carbon fibres are selected from at least one of T300, T600, T700, T800 and T1000.
6. A method of preparation as claimed in any one of claims 1 to 3 wherein the carbon fibre prepreg has a liquid carrying rate of 1% to 5%.
7. A method of preparation according to any one of claims 1 to 3, wherein the method of preparation meets at least one of the following conditions:
(1) The carbonization temperature of the carbonization treatment is 750-900 ℃;
(2) The carbonization treatment time is 10-15 h;
(3) The calcination temperature of the calcination treatment is 1300-1500 ℃;
(4) The calcination treatment time is 2-5 h.
8. A C/SiC composite material produced by the production method according to any one of claims 1 to 7.
9. A heat conductive member, characterized in that the heat conductive member comprises the C/SiC composite material of claim 8.
10. A heating furnace, characterized in that the heating furnace comprises the heat conductive member according to claim 9.
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