CN114195541A - Preparation method and application of carbon/carbon composite material impregnation slurry containing polyimide - Google Patents

Preparation method and application of carbon/carbon composite material impregnation slurry containing polyimide Download PDF

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CN114195541A
CN114195541A CN202111667798.1A CN202111667798A CN114195541A CN 114195541 A CN114195541 A CN 114195541A CN 202111667798 A CN202111667798 A CN 202111667798A CN 114195541 A CN114195541 A CN 114195541A
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carbon
polyimide
composite material
carbon composite
slurry
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郭逸
陈胜绪
李开明
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Fuyoute Shandong New Material Technology Co ltd
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Abstract

The invention discloses a preparation method and application of polyimide-containing carbon/carbon composite material impregnation slurry, and belongs to the technical field of carbon/carbon composite materials. The preparation method comprises the following steps: mixing polyimide and absolute ethyl alcohol, performing ball milling treatment, drying and sieving to obtain polyimide powder; and mixing the polyimide powder and graphite powder, adding water, carrying out ball milling treatment for 8-12 h, adding a thickening agent, a surfactant and a dispersing agent, and continuing ball milling treatment for 8-12 h to obtain the carbon/carbon composite material impregnation slurry containing polyimide. The slurry is used for preparing the carbon/carbon composite material, so that the matrix carbon residue of single impregnation cracking in a liquid phase impregnation method can be effectively increased, and the production period of the liquid phase impregnation cracking method is shortened. Meanwhile, the strength of the carbide can be increased, the rheological property is better, the purpose of full flow densification is further realized, and the performance of the prepared carbon/carbon composite material product is more excellent and perfect.

Description

Preparation method and application of carbon/carbon composite material impregnation slurry containing polyimide
Technical Field
The invention belongs to the technical field of carbon/carbon composite materials, and particularly relates to a preparation method and application of polyimide-containing carbon/carbon composite material impregnation slurry.
Background
Carbon/carbon composites are carbon matrix composites reinforced with carbon fibers and fabrics thereof. The material has the advantages of low density, high strength, high specific modulus, high thermal conductivity, low expansion coefficient, good friction performance, good thermal shock resistance, high dimensional stability and the like, is a few of candidate materials applied at the temperature of more than 1650 ℃ at present, and has the highest theoretical temperature of 2600 ℃ higher, so the material is considered to be one of high-temperature materials with the greatest development prospect. The chemical vapor deposition (CVI) method has the advantages of accurate control of the preparation process and excellent product performance, and is the earliest and most widely applied method in the preparation of carbon/carbon composite materials in laboratories and industrial production. But the method has low preparation efficiency, long period and high cost. Therefore, in the last two decades, researchers of carbon/carbon composite materials have continuously developed new preparation technologies, such as a liquid-phase impregnation cracking method (also called a liquid-phase impregnation-carbonization method).
The liquid-phase impregnation cracking process is mainly characterized in that the bonding impregnant which is converted into the liquid phase is extruded and impregnated into the carbon fiber preform by applying pressure from the outside, and the bonding impregnant is converted into a matrix through the pyrolysis process at high temperature so as to prepare the carbon/carbon composite material with high compactness. The liquid-phase impregnation cracking process has low requirements on sintering furnaces and pressure equipment and lower cost, and the high-performance carbon/carbon composite material with regular size can be obtained only by applying certain pressure in the sintering and impregnation process, so that the liquid-phase impregnation cracking process is widely used at present and plays a vital role in scientific research. In addition, the liquid phase impregnation cracking process can also adopt the traditional high-pressure impregnation and pressure equipment, has the advantages of simple process, good compactness degree of the prepared composite material, high dimensional stability, excellent and average mechanical property and the like, and can be used in a large scale in the industrial production process. Compared with the CVI technology, the liquid-phase impregnation cracking technology has the advantages of high carbon matrix hardness, corrosion resistance, low cost, short period and suitability for preparing large sample pieces.
Most of liquid phase precursors used in the liquid phase impregnation cracking process are resin and asphalt, particularly, phenolic resin is applied more frequently, but a large amount of carbon-containing gas molecules need to be released in the cracking process of the phenolic resin, so that the residual carbon rate in a matrix is low, the volume shrinkage is large, repeated impregnation is needed, the production period and the process complexity are greatly increased, and the problems of high cost and long preparation period exist. Therefore, it is necessary to develop a new carbon/carbon composite material impregnation slurry, improve the matrix carbon residue of single impregnation cracking in the liquid phase impregnation method, and shorten the production period of the liquid phase impregnation cracking method.
Disclosure of Invention
The invention aims to provide the carbon/carbon composite material impregnation slurry, which improves the matrix carbon residue of single impregnation cracking in a liquid phase impregnation method and shortens the production period of the liquid phase impregnation cracking method.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes of the invention is a preparation method of carbon/carbon composite material dipping slurry containing polyimide, which comprises the following steps: mixing polyimide powder and graphite powder, adding water, and performing ball milling treatment to obtain the carbon/carbon composite material impregnation slurry containing polyimide.
Further, the polyimide powder is prepared by pretreating blocky polyimide, wherein the pretreatment comprises the following specific operations: mixing the blocky polyimide with absolute ethyl alcohol, carrying out ball milling treatment, drying and sieving to obtain polyimide powder; the graphite powder is natural crystalline flake graphite powder.
Further, the mass volume ratio of the blocky polyimide to the absolute ethyl alcohol is 1g:2ml, the ball-material ratio of ball-milling treatment is 2:1, the ball-milling treatment time is 8-12 hours, and the sieving is 120-mesh sieving.
Further, mixing polyimide powder and graphite powder, adding water, adding a thickening agent, a surfactant and a dispersing agent after ball milling treatment, and continuing ball milling treatment, wherein the specific operation is as follows: mixing polyimide powder and graphite powder, adding water, carrying out ball milling treatment for 8-12 h, then adding a thickening agent, a surfactant and a dispersing agent, and carrying out ball milling treatment for 8-12 h to obtain the carbon/carbon composite material impregnation slurry containing polyimide, wherein the polyimide powder comprises the following components in percentage by mass: graphite powder: water is 0.5-1.25: 1: 10.
further, after polyimide powder and graphite powder are mixed, firstly adding a sphere, then adding water, wherein the sphere comprises the following components in percentage by mass: (polyimide powder + graphite powder) ═ 2: 1.
Further, the mass percentage of the thickening agent is 1.5-3 wt% of the carbon/carbon composite material dipping slurry containing the polyimide, the surfactant is 1-2 wt% of the carbon/carbon composite material dipping slurry containing the polyimide, and the dispersing agent is 0.5-1 wt% of the carbon/carbon composite material dipping slurry containing the polyimide.
Further, the thickening agent is methyl cellulose, the surfactant is triton, and the dispersing agent is polyethylene glycol.
In the second technical scheme of the invention, the carbon/carbon composite material dipping slurry containing polyimide is prepared according to the preparation method of the carbon/carbon composite material dipping slurry containing polyimide.
In the third technical scheme of the invention, the application of the carbon/carbon composite material impregnating slurry containing polyimide in the preparation of the carbon/carbon composite material is provided.
In the fourth technical scheme of the invention, the carbon/carbon composite material is prepared by taking carbon fibers as a prefabricated body and taking the carbon/carbon composite material impregnation slurry containing polyimide as impregnation slurry through a liquid-phase impregnation pyrolysis method, wherein the carbon fibers are shaped carbon fiber fabrics.
According to the fifth technical scheme, the carbon/carbon composite material containing polyimide is soaked in the slurry and coated on the surface of the shaped carbon fiber fabric to obtain a slurry-containing prefabricated body, the slurry-containing prefabricated body is cured and molded to obtain a carbon/carbon composite material blank, and the carbon/carbon composite material blank is subjected to carbonization and high-temperature sintering to obtain the carbon/carbon composite material.
Further, the step of coating the carbon/carbon composite material impregnation slurry containing polyimide on the surface of the shaped carbon fiber fabric is to coat the carbon/carbon composite material impregnation slurry containing polyimide on the surface of the shaped carbon fiber fabric through a winding process or a dipping process.
Further, the carbon/carbon composite material dipping slurry containing polyimide is coated on the surface of the shaped carbon fiber fabric, and the process of curing and molding the slurry-containing prefabricated body can be carried out once or repeatedly for many times until the volume fraction of the carbon fibers in the obtained carbon/carbon composite material blank is 35-45%.
The method for calculating the volume fraction of the carbon fibers in the carbon/carbon composite material blank comprises the following steps: taking a sample in unit volume, removing slurry in the sample, weighing the weight of the fiber in the obtained sample, and obtaining the volume of the fiber in the sample in unit volume by using the density of the carbon fiber, wherein the proportion of the fiber volume in the total volume is volume fraction.
Further, the impregnation treatment is atmospheric pressure impregnation treatment or pressure impregnation treatment.
Further, the temperature of the curing molding is 400-600 ℃, and the time is 24-48 h.
Further, the temperature of the carbonization treatment is 800-1000 ℃, the time of the carbonization treatment is 2-4 h, the temperature of the high-temperature sintering treatment is 1500-2000 ℃, and the time of the high-temperature sintering treatment is 2-4 h.
The preparation process flow of the carbon/carbon composite material impregnation slurry containing polyimide and the preparation process flow of the carbon/carbon composite material by using the carbon/carbon composite material impregnation slurry as the impregnation slurry are shown in fig. 1.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, polyimide is used as a liquid phase precursor, and is mixed with absolute ethyl alcohol for ball milling to obtain polyimide powder, and then the polyimide powder is mixed with graphite powder, water, a thickening agent, a surfactant and a dispersing agent for ball milling to obtain carbon/carbon composite material impregnation slurry containing polyimide. Compared with the existing impregnation slurry taking thermosetting resin as a liquid phase precursor, the impregnation slurry containing the polyimide-containing carbon/carbon composite material prepared by the invention has the advantages that the thermosetting resin can volatilize various non-carbon components in the pyrolysis process, so that the impregnation-carbonization sintering cycle needs to be carried out for many times in the densification process, and meanwhile, most of the pyrolysis carbon is hard carbon, the high-temperature graphitization difficulty is higher, so that the prepared carbon/carbon composite material has poorer mechanical property. On the contrary, the thermoplastic polyimide used in the invention begins to soften gradually with the rise of the temperature, the wetting angle of the thermoplastic polyimide on the carbon fiber preform is also reduced gradually, and the wetting angle is about 30 degrees when the temperature reaches the impregnation temperature (slightly higher than the softening point temperature of the polyimide), so that the impregnant polyimide can spontaneously permeate into the pores of the porous preform, thereby completing the full densification of the composite material, effectively increasing the residual carbon content of the matrix subjected to single impregnation cracking in the liquid phase impregnation method, and shortening the production period of the liquid phase impregnation cracking method. Meanwhile, the carbon residue rate of the polyimide is higher, and the polyimide is easier to graphitize, so that the carbonization yield is higher, and the performance of the material is better. By using the polyimide as a liquid phase precursor, the carbon residue can be further improved, the strength of the carbide is increased, the rheological property is better, the purpose of full flow densification is further realized, and the performance of the prepared carbon/carbon composite material product is more excellent and perfect.
(2) The polyimide powder and the natural crystalline flake graphite powder are used as main raw materials, and the solid content of the matrix can be improved by the natural crystalline flake graphite powder. In addition, the mass ratio of the polyimide powder to the graphite powder also affects the performance of the impregnation slurry, and further affects the performance of the prepared carbon/carbon composite material, when the mass ratio of the polyimide powder to the graphite powder is too large (more than 1.25:1), the content of the polyimide is too much, so that excessive pores are generated during cracking, and the density of a final product is too low; when the mass ratio of the polyimide powder to the graphite powder is too small (less than 0.5:1), the content of the imide is too small, and the polyimide plays a role in bonding during curing, so that the bonding effect of the polyimide is limited during curing, and the strength of a final product is lower than 100 MPa; according to the invention, the mass ratio of the polyimide powder to the graphite powder is limited to 0.5-1.25: 1, so that the excellent mechanical property of the obtained carbon/carbon composite material can be ensured.
(3) The performance of the carbon/carbon composite material is in relation to the impregnation slurry and the specific process operation of the liquid phase impregnation-carbonization process, the polyimide is used as an impregnation precursor, the natural crystalline flake graphite is used as a matrix, the molded carbon fiber is used as a reinforcement, and the prefabricated body is sintered through curing molding, carbonization hot-pressing sintering and high-temperature sintering, so that the carbon/carbon composite material with excellent mechanical property, relatively high compactness and good dimensional stability is prepared. Compared with the traditional process, the process has the advantages of short process flows of curing molding, carbonization, high-temperature sintering and the like, low requirement on production equipment, high production efficiency, convenience for batch production and the like, thereby achieving the purposes of shortening the preparation period and reducing the cost and having important industrial application value.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is an overall process flow diagram of a preparation process flow of a carbon/carbon composite material impregnation slurry containing polyimide and a preparation process flow of a carbon/carbon composite material by using the impregnation slurry as the impregnation slurry.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
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. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
(1) Pretreatment of polyimide: weighing 100g of blocky polyimide, placing the blocky polyimide into a ball milling tank, adding 200g of spheres into the ball milling tank to ensure that the ball-to-material ratio is 2:1, finally adding 200ml of absolute ethyl alcohol into the ball milling tank, carrying out ball milling treatment for 8 hours (the rotation speed of the ball milling treatment is 280r/min), standing and drying the obtained solution after ball milling, and sieving the solution with a 120-mesh sieve to obtain polyimide powder with small and uniform particle size.
(2) Preparation of impregnation slurry: adding 100g of polyimide powder prepared in the step (1) and 200g of natural flake graphite powder (the mass ratio of the polyimide powder to the natural flake graphite powder is 0.5:1) into a ball milling tank in sequence, adding 600g of spheres, ensuring that the ball-material ratio is 2:1, finally adding 2000g of distilled water (the mass of the distilled water is 10 times of that of the natural crystalline flake graphite powder), carrying out ball milling treatment (the rotating speed of the ball milling treatment is 280r/min), carrying out ball milling treatment for 8 hours, adding 36g of thickening agent methylcellulose (accounting for 1.5 percent of the weight of the whole slurry), 24g of surfactant triton (accounting for 1 percent of the weight of the whole slurry) and 12g of dispersant polyethylene glycol (accounting for 0.5 percent of the weight of the whole slurry), continuing ball milling treatment (the rotating speed of the ball milling treatment is 280r/min), and obtaining the carbon-carbon composite material dipping slurry containing polyimide after 8h of ball milling treatment.
Example 2
(1) Pretreatment of polyimide: weighing 100g of blocky polyimide, placing the blocky polyimide into a ball milling tank, adding 200g of spheres into the ball milling tank to ensure that the ball-to-material ratio is 2:1, finally adding 200ml of absolute ethyl alcohol into the ball milling tank, carrying out ball milling treatment for 8 hours (the rotation speed of the ball milling treatment is 280r/min), standing and drying the obtained solution after ball milling, and sieving the solution with a 120-mesh sieve to obtain polyimide powder with small and uniform particle size.
(2) Preparation of impregnation slurry: adding 75g of polyimide powder prepared in the step (1) and 100g of natural flake graphite powder into a ball milling tank in sequence (the mass ratio of the polyimide powder to the natural flake graphite powder is 0.75:1), adding 350g of spheres, ensuring that the ball-material ratio is 2:1, finally adding 1000g of distilled water (the mass of the distilled water is 10 times of that of the natural crystalline flake graphite powder), carrying out ball milling treatment (the rotating speed of the ball milling treatment is 280r/min), carrying out ball milling treatment for 12h, adding 25g of thickening agent methylcellulose (accounting for 2% of the weight of the whole slurry), 18g of surfactant triton (accounting for 1.5% of the weight of the whole slurry) and 9g of dispersant polyethylene glycol (accounting for 0.75% of the weight of the whole slurry), continuing ball milling treatment (the rotating speed of the ball milling treatment is 280r/min), and obtaining the carbon-carbon composite material dipping slurry containing polyimide after 12h of ball milling treatment.
Example 3
(1) Pretreatment of polyimide: weighing 100g of blocky polyimide, placing the blocky polyimide into a ball milling tank, adding 200g of spheres into the ball milling tank to ensure that the ball-to-material ratio is 2:1, finally adding 200ml of absolute ethyl alcohol into the ball milling tank, carrying out ball milling treatment for 8 hours (the rotation speed of the ball milling treatment is 280r/min), standing and drying the obtained solution after ball milling, and sieving the solution with a 120-mesh sieve to obtain polyimide powder with small and uniform particle size.
(2) Preparation of impregnation slurry: adding 100g of polyimide powder prepared in the step (1) and 100g of natural flake graphite powder (the mass ratio of the polyimide powder to the natural flake graphite powder is 1:1) into a ball milling tank in sequence, adding 400g of spheres, ensuring that the ball-material ratio is 2:1, finally adding 1000g of distilled water (the mass of the distilled water is 10 times of that of the natural crystalline flake graphite powder), carrying out ball milling treatment (the rotating speed of the ball milling treatment is 280r/min), carrying out ball milling treatment for 8 hours, adding 38g of thickening agent methylcellulose (accounting for 3% of the weight of the whole slurry), 26g of surfactant triton (accounting for 2% of the weight of the whole slurry) and 13g of dispersant polyethylene glycol (accounting for 1% of the weight of the whole slurry), continuing ball milling treatment (the rotating speed of the ball milling treatment is 280r/min), and obtaining the carbon-carbon composite material dipping slurry containing polyimide after 8h of ball milling treatment.
Example 4
(1) Pretreatment of polyimide: weighing 100g of blocky polyimide, placing the blocky polyimide into a ball milling tank, adding 200g of spheres into the ball milling tank to ensure that the ball-to-material ratio is 2:1, finally adding 200ml of absolute ethyl alcohol into the ball milling tank, carrying out ball milling treatment for 8 hours (the rotation speed of the ball milling treatment is 280r/min), standing and drying the obtained solution after ball milling, and sieving the solution with a 120-mesh sieve to obtain polyimide powder with small and uniform particle size.
(2) Preparation of impregnation slurry: adding 100g of polyimide powder prepared in the step (1) and 80g of natural flake graphite powder into a ball milling tank in sequence (the mass ratio of the polyimide powder to the natural flake graphite powder is 1.25:1), adding 360g of spheres, ensuring that the ball-material ratio is 2:1, finally adding 800g of distilled water (the mass of the distilled water is 10 times of that of the natural crystalline flake graphite powder), carrying out ball milling treatment (the rotating speed of the ball milling treatment is 280r/min), carrying out ball milling treatment for 8 hours, adding 31g of thickening agent methylcellulose (accounting for 3% of the weight of the whole slurry), 21g of surfactant triton (accounting for 2% of the weight of the whole slurry) and 10g of dispersant polyethylene glycol (accounting for 1% of the weight of the whole slurry), continuing ball milling treatment (the rotating speed of the ball milling treatment is 280r/min), and obtaining the carbon-carbon composite material dipping slurry containing polyimide after 8h of ball milling treatment.
Application example (preparation of carbon/carbon composite Material)
The overall preparation cycle in the following application examples refers to the time from the start of the pretreatment of the weighed block of polyimide to the time of the whole process of obtaining the final carbon/carbon composite material after high-temperature sintering.
Application example 1
(1) 12K carbon fiber tows are used as a preform material and are placed into the carbon/carbon composite material impregnation slurry containing polyimide prepared in example 1 to be impregnated at normal pressure for 6 hours. And after the impregnation is finished, taking out the carbon fiber fabric, removing the redundant slurry on the surface (on the counter extrusion roller, removing the redundant slurry on the surface by controlling the clearance of the counter extrusion roller), and then heating, pressurizing and curing at the curing temperature of 350 ℃, at the curing pressure of 5MPa and for 48h to obtain the shaped carbon fiber fabric.
(2) The shaped carbon fiber fabric prepared in the step (1) is immersed in the carbon/carbon composite material impregnation slurry containing polyimide prepared in the embodiment 1, then pressurized to 1MPa for pressurized liquid phase impregnation, the impregnation time is 6h, the shaped carbon fiber fabric is taken out, the surface excess slurry is removed (on a counter extrusion roller, the surface excess slurry is removed by controlling the clearance of the counter extrusion roller), a slurry-containing preform is obtained, then the slurry-containing preform is heated and cured, the curing temperature is 300 ℃, the curing time is 24h, and the cured impregnated fabric, namely a carbon/carbon composite material green body (the volume fraction of carbon fibers is 35%) is obtained after the curing is finished.
(3) Carbonizing the carbon/carbon composite material blank prepared in the step (2) at 900 ℃ for 2h, and then sintering at 1500 ℃ for 2h to obtain the carbon/carbon composite material blank with the density of 1.75g/cm3The preparation period of the carbon/carbon composite material is 7.5 days (the ball milling and mixing time in the process of preparing the dipping slurry is 24 hours; 54 hours are needed for dipping and curing a 12K carbon fiber tow in the dipping slurry to obtain the shaped carbon fiber, 30 hours are needed for dipping and curing the shaped carbon fiber fabric in the dipping slurry to obtain a carbon/carbon composite material blank, 72 hours are needed for carbonizing and high-temperature sintering of the carbon/carbon composite material blank in combination with subsequent cooling, 7.5 days are needed for the whole preparation period), and the preparation cost is 800-1000 yuan/kg.
Application example 2
The same as in application example 1 except that the polyimide-containing carbon/carbon composite impregnating slurry prepared in example 1 was replaced with the polyimide-containing carbon/carbon composite impregnating slurry prepared in example 2. The volume fraction of carbon fibers in the carbon/carbon composite material blank obtained in the step (2) is 40%, the whole preparation period is 7.8 days (the ball milling and mixing time in the process of preparing the impregnating slurry is 32 hours; 54 hours is needed for soaking and curing a 12K carbon fiber tow in the impregnating slurry to obtain a shaped carbon fiber, 30 hours is needed for soaking and curing a shaped carbon fiber fabric in the impregnating slurry to obtain a carbon/carbon composite material blank, 72 hours is needed for carbonizing and high-temperature sintering of the carbon/carbon composite material blank in combination with subsequent cooling, and 7.8 days is needed for the whole preparation period).
Application example 3
The same as in application example 1 except that the polyimide-containing carbon/carbon composite impregnating slurry prepared in example 1 was replaced with the polyimide-containing carbon/carbon composite impregnating slurry prepared in example 3. And (3) the volume fraction of the carbon fibers in the carbon/carbon composite material blank obtained in the step (2) is 43%. The whole preparation period is 7.5 days (the ball milling and mixing time in the process of preparing the dipping slurry is 24 hours; 54 hours are needed for dipping and curing the 12K carbon fiber tows in the dipping slurry to obtain the shaped carbon fibers; 30 hours are needed for dipping and curing the shaped carbon fiber fabrics in the dipping slurry to obtain the carbon/carbon composite material blank, 72 hours are needed for carbonizing and sintering the carbon/carbon composite material blank at high temperature in combination with subsequent cooling, and 7.5 days are needed for the whole preparation period).
Application example 4
The same as in application example 1 except that the polyimide-containing carbon/carbon composite impregnating slurry prepared in example 1 was replaced with the polyimide-containing carbon/carbon composite impregnating slurry prepared in example 4. And (3) the volume fraction of the carbon fibers in the carbon/carbon composite material blank obtained in the step (2) is 45%. The whole preparation period is 7.5 days (the ball milling and mixing time in the process of preparing the dipping slurry is 24 hours; 54 hours are needed for dipping and curing the 12K carbon fiber tows in the dipping slurry to obtain the shaped carbon fibers; 30 hours are needed for dipping and curing the shaped carbon fiber fabrics in the dipping slurry to obtain the carbon/carbon composite material blank, 72 hours are needed for carbonizing and sintering the carbon/carbon composite material blank at high temperature in combination with subsequent cooling, and 7.5 days are needed for the whole preparation period).
Comparative example 1
The slurry is impregnated with a carbon/carbon composite containing a phenolic resin to prepare a carbon/carbon composite. The carbon/carbon composite material impregnating slurry containing the phenolic resin is prepared from liquid phenolic resin and absolute ethyl alcohol, wherein the liquid phenolic resin is purchased from Jinan Shengquan group GmbH. The model is PF-7215, and the content of phenolic resin is 75 wt%.
The specific preparation process comprises the following steps:
(1) 12K carbon fiber tows are used as a preform material and are placed into the carbon/carbon composite material impregnation slurry containing polyimide prepared in example 1 to be impregnated at normal pressure for 6 hours. And after the impregnation is finished, taking out the carbon fiber fabric, removing the redundant slurry on the surface (on the counter extrusion roller, removing the redundant slurry on the surface by controlling the clearance of the counter extrusion roller), and then heating, pressurizing and curing at the curing temperature of 350 ℃, at the curing pressure of 5MPa and for 48h to obtain the shaped carbon fiber fabric.
(2) Dissolving liquid phenolic resin by using absolute ethyl alcohol to obtain impregnating slurry containing phenolic resin (the concentration of the phenolic resin is 50 wt%), pouring the prepared impregnating slurry containing the phenolic resin into an impregnating kettle, putting the shaped carbon fiber fabric into the impregnating slurry in the impregnating kettle, vacuumizing for 2 hours, pressurizing the impregnating kettle to 5MPa by using nitrogen, keeping for 6 hours to fully impregnate the sample, releasing pressure and taking the sample out of the kettle. And (2) treating the impregnated sample in a baking oven at 200 ℃ for 10h to complete the curing and post-curing processes of the resin, finally placing the sample in a carbonization furnace, performing temperature programming carbonization (heating from room temperature to 300 ℃ for 1h, heating to 400 ℃ for 1h, heating to 600 ℃ for 1h, heating to 800 ℃ for 1h, heating to 1000 ℃ for 1h, heating to 1300 ℃ for 1h, heating to 1600 ℃ for 1h, heating to 1800 ℃ for 1h, heating to 2000 ℃ for 1h, wherein the heating rate is about 100 ℃/h), and transferring to a graphitization furnace for graphitization at 2400 ℃ for 1h to obtain the carbon/carbon composite material sample. And repeating the impregnation, curing, carbonization and graphitization, and circulating for 7-8 times to prepare the carbon/carbon composite material with a certain density.
The density of the prepared carbon/carbon composite material is 1.73g/cm3The preparation period of the whole is30 days (54 hours are needed for dipping and curing the 12K carbon fiber tows in the dipping slurry to obtain the shaped carbon fibers, the period of dipping-curing-carbonizing-graphitizing (including the temperature rise process and the cooling process) is about 4 days, seven cycles are about 28 days, the whole preparation period is about 30 days), and the preparation cost is 1200 yuan/kg.
The carbon residue rate of the polyimide is more than 70 percent through testing, and the carbon residue rate of the common phenolic resin impregnant is about 53 percent. Therefore, the carbon/carbon composite material is prepared by adopting the carbon/carbon composite material dipping slurry containing polyimide as the dipping slurry, so that the carbon residue of the matrix subjected to single dipping and cracking in the liquid phase dipping method can be increased, and the dipping times can be further reduced.
Effect verification
The carbon/carbon composite materials prepared in application examples 1 to 4 and comparative example 1 were subjected to density and mechanical property tests.
The density test method comprises the following steps: the density of the carbon/carbon composite was measured in this experiment using archimedes drainage methods (archimedes's).
The mechanical property test method comprises the following steps: in this experiment, the flexural strength of the material was determined by the three-point short beam bending method, according to the standard GB-6569-1986, and was tested using an universal tester (Instron-1186). The size of a carbon/carbon composite material sample is 40mm multiplied by 4mm multiplied by 3mm (length multiplied by width multiplied by thickness), the surface of the sample needs to be ground flat after being cut into specified size by an inner diameter slicer, and chamfer processing needs to be carried out on the edge angle of the sample, so as to avoid measurement error caused by stress concentration. The test span of the experiment is 30mm, and the pressure head loading speed is 0.5 mm/min. Since the dispersion of the bending strength is taken into consideration, the average value of 6 test pieces per test specimen is taken as the bending strength of the material.
The test results are shown in table 1:
TABLE 1
Density/g.cm-3 Flexural strength/MPa
Application example 1 1.74 263.5
Application example 2 1.72 238.5
Application example 3 1.76 272.7
Application example 4 1.78 270.3
Comparative example 1 1.73 195.1
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A preparation method of carbon/carbon composite material impregnation slurry containing polyimide is characterized by comprising the following steps: mixing polyimide powder and graphite powder, adding water, and performing ball milling treatment to obtain the carbon/carbon composite material impregnation slurry containing polyimide.
2. The method for preparing the carbon/carbon composite material impregnation slurry containing the polyimide according to claim 1, wherein the polyimide powder is prepared by pretreating bulk polyimide, and the pretreatment comprises the following specific operations: mixing the blocky polyimide with absolute ethyl alcohol, carrying out ball milling treatment, drying and sieving to obtain polyimide powder; the graphite powder is natural crystalline flake graphite powder.
3. The preparation method of the carbon/carbon composite material impregnation slurry containing polyimide according to claim 2, wherein the mass volume ratio of the blocky polyimide to the absolute ethyl alcohol is 1g:2ml, the ball-to-material ratio of ball-milling treatment is 2:1, the ball-milling treatment time is 8-12 h, and the sieving is 120-mesh sieving.
4. The preparation method of the carbon/carbon composite material impregnation slurry containing polyimide according to claim 1, wherein the polyimide powder and graphite powder are mixed, water is added, and after ball milling treatment, a thickening agent, a surfactant and a dispersing agent are further added to continue ball milling treatment, and the specific operations are as follows: mixing polyimide powder and graphite powder, adding water, carrying out ball milling treatment for 8-12 h, then adding a thickening agent, a surfactant and a dispersing agent, and carrying out ball milling treatment for 8-12 h to obtain the carbon/carbon composite material impregnation slurry containing polyimide, wherein the polyimide powder comprises the following components in percentage by mass: graphite powder: water is 0.5-1.25: 1: 10.
5. the method for preparing the carbon/carbon composite impregnation slurry containing polyimide according to claim 4, wherein the thickener is 1.5 to 3 wt% of the carbon/carbon composite impregnation slurry containing polyimide, the surfactant is 1 to 2 wt% of the carbon/carbon composite impregnation slurry containing polyimide, and the dispersant is 0.5 to 1 wt% of the carbon/carbon composite impregnation slurry containing polyimide, in terms of mass%.
6. A polyimide-containing carbon/carbon composite impregnating slurry prepared by the method for preparing a polyimide-containing carbon/carbon composite impregnating slurry according to any one of claims 1 to 5.
7. Use of the polyimide-containing carbon/carbon composite impregnating slurry according to claim 6 for the preparation of carbon/carbon composites.
8. A carbon/carbon composite material characterized by being produced by a liquid phase impregnation pyrolysis method using carbon fibers as a preform and the polyimide-containing carbon/carbon composite material impregnation slurry of claim 7 as an impregnation slurry, the carbon fibers being a shaped carbon fiber fabric.
9. The method for preparing the carbon/carbon composite material according to claim 8, wherein the carbon/carbon composite material impregnated slurry containing polyimide is coated on the surface of the shaped carbon fiber fabric to obtain a slurry-containing preform, the slurry-containing preform is cured and molded to obtain a carbon/carbon composite material green body, and the carbon/carbon composite material green body is subjected to carbonization and high-temperature sintering to obtain the carbon/carbon composite material.
10. The method for producing a carbon/carbon composite material according to claim 9, wherein the temperature of the carbonization treatment is 800 to 1000 ℃, the time of the carbonization treatment is 2 to 4 hours, the temperature of the high-temperature sintering treatment is 1500 to 2000 ℃, and the time of the high-temperature sintering treatment is 2 to 4 hours.
CN202111667798.1A 2021-12-31 2021-12-31 Preparation method and application of carbon/carbon composite material impregnation slurry containing polyimide Pending CN114195541A (en)

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