CN109665855B - Preparation method of carbon/carbon-boron nitride antifriction composite material - Google Patents
Preparation method of carbon/carbon-boron nitride antifriction composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon/carbon-boron nitride antifriction composite material, which comprises the steps of acidizing a graphitized C/C blank, washing to be neutral to obtain a pretreated C/C blank, then soaking the pretreated C/C blank in a solution containing a modifier to react to obtain a functionalized C/C blank, then soaking the functionalized C/C blank in h-BN slurry, drying to obtain a C/C-BN preform, and carbonizing, densifying and graphitizing the C/C-BN preform by a carbon source to obtain the C/C-BN antifriction composite material; the modifier is selected from silane coupling agent or polyvinyl alcohol (PVA). The BN matrix is obtained by adopting a slurry dipping method for the first time, and BN powder can be effectively introduced into the C/C blank body in the slurry dipping process after the C/C blank body is functionalized. The method can effectively avoid the damage of the carbon fiber and ensure that the C/C-BN composite material has excellent structural strength. The obtained C/C-BN composite material has excellent frictional wear performance.
Description
Technical Field
The invention relates to a preparation method of a carbon/carbon-boron nitride antifriction composite material, belonging to the technical field of new materials.
Background
The C/C composite material has the advantages of low density, high strength, excellent thermal conductivity, proper friction coefficient, small volume abrasion, good processability and the like, is commonly applied to brake materials, and is also a friction first material in a plurality of autoclaves, chemical equipment and high-speed rotating mechanical structures. The C/C composite material is applied to sealing of aeroengine shafts and the like, and low friction coefficient and small abrasion are also the focus of domestic and foreign research.
However, the C/C friction material starts to oxidize at about 400 ℃ in air, the oxidation significantly reduces the braking performance and the service life of the material, and when the material is used for sealing materials, the friction coefficient and the wear rate are both too large, and the average friction coefficient of the C/C friction material is as high as 0.35, so how to further improve the friction coefficient and the wear rate of the C/C friction material applied to the sealing materials still remains a key point and a difficulty point to be paid attention to in future research.
Boron nitride has three crystal structures, hexagonal boron nitride (h-BN), hexagonal close-packed boron nitride and cubic boron nitride. Among them, hexagonal boron nitride (h-BN) is an excellent high-temperature solid lubricant, which has not only excellent thermophysical properties but also more superior oxidation resistance and frictional wear properties as compared with carbon materials. The oxidation resistance of the hexagonal boron nitride is obviously superior to that of the carbon/carbon composite material, the h-BN obviously starts to oxidize at 850 ℃, and the carbon/carbon composite material starts to oxidize at 450 ℃. And there are many similarities between BN and C, including density, thermal conductivity, heat capacity and crystal structure. The h-BN is adopted to partially replace a carbon matrix in the carbon/carbon composite material, so that carbon fiber reinforced carbon and hexagonal boron nitride (C/C-BN) friction materials with good oxidation resistance and friction performance can be obtained. The friction coefficient and the wear rate of the C/C-BN friction material are insensitive to the change of load, when the C/C-BN friction material is coupled with a ceramic ball, the friction coefficient is low, a B2O3 film formed by BN oxidation can improve the oxidation resistance of the material, and the influence on the friction and wear performance of the material is small.
At present, research on C/C-BN friction materials at home and abroad is relatively less, and processes for preparing a BN matrix mainly comprise a Precursor impregnation cracking method (PIP) and a Chemical Vapor Infiltration method (CVI).
The document "High density carbon fiber/boron nitride matrix composites: preparation of composites with an explicit fibrous resistance. seghi Steven, Lee, James economi, James carbon,43(2005) 2035-. Compared with the C/C composite material, the wear rate of the C/C-BN friction material is only 50 percent or even lower than that of the C/C composite material. They believe that the introduction of h-BN improves the stability of the tribofilm of the material under different energy loads, reduces the oxidative wear and the generation of particulate abrasive dust, thereby reducing the wear and reducing the influence of energy loads and temperature. However, the BN prepared by a precursor impregnation cracking method has a relatively large layer spacing d (002), and the precursor is easy to generate cracks and holes in the high-temperature cracking process.
Article of literature "Microstructural and cubic bearings of C/C-BN compositions characterized by chemical vapor infiltration, Fan, Xiameng, Yin, Xiaoweii, Cheng, Yu, Zhang, Litong, Cheng, Laifei, ceramics International,38(2012)6137-3-NH3-Ar-H2h-BN is deposited on the surface of the carbon fiber as a gas source, and after the heat treatment at 1600 ℃, the interplanar spacing of BN obtained by vapor deposition is found to be
The smaller interplanar spacing leads to an improved moisture absorption resistance of the BN matrix, but due to the BCl, the BN matrix has a lower interplanar spacing than BN obtained under low-temperature treatment3Is a toxic gas, so the practical production is limited. In addition, most of BN prepared by the chemical vapor infiltration method has an amorphous structure, the stability is poor, the chemical vapor deposition process has a plurality of and complicated control factors, and the form of the BN component is difficult to accurately control.
Domestic patent (CN101875562B) discloses that powder is scattered by adopting a layer-by-layer method, BN powder is uniformly adhered to two surfaces of a single-layer carbon fiber net blank, the net blank is laminated layer by layer and then the laminated net blank is needled to prepare a carbon fiber preform material containing the BN powder, and then a pyrolytic carbon matrix is obtained by utilizing a CVI method to prepare a carbon fiber reinforced carbon and boron nitride double-matrix (C/C-BN) friction material. However, the method increases the difficulty of needling, and besides, the BN powder easily damages the carbon fibers, so that the mechanical property is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a carbon/carbon-boron nitride (C/C-BN) antifriction composite material with uniform tissue structure, oxidation resistance and frictional wear performance, and the preparation method is simple and easy to control, low in cost and short in period.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention relates to a preparation method of a carbon/carbon-boron nitride antifriction composite material, which comprises the following steps: acidifying the graphitized C/C blank, washing to be neutral to obtain a pretreated C/C blank, then soaking in a solution containing a modifier to react to obtain a functionalized C/C blank, soaking the functionalized C/C blank in BN slurry, drying to obtain a C/C-BN preform, and carbonizing, densifying and graphitizing the C/C-BN preform by a carbon source to obtain a C/C-BN composite friction material; the modifier is selected from silane coupling agent or polyvinyl alcohol (PVA).
The BN matrix is obtained by adopting the slurry dipping method for the first time, after the C/C blank is functionalized, BN powder can be effectively introduced into the C/C blank in the slurry dipping process, meanwhile, vacuum conditions and pressurization conditions are not needed in the process, the BN slurry (slurry containing the BN powder) can be introduced into the interior of the preform only through the capillary force of the BN slurry, and meanwhile, the introduced BN powder can be uniformly dispersed among the inner layers of the preform without agglomeration. The method can effectively avoid the damage of the carbon fiber and ensure that the C/C-BN composite friction material has excellent mechanical property.
In a preferred embodiment, the preparation method of the graphitized C/C body comprises the following steps: the carbon fiber preform is degummed at 2100-graded temperature of 2300 ℃, then the propylene is used as an air source, a pyrolytic carbon layer is obtained by a chemical vapor infiltration method (CVI method), and then the graphitization treatment at 2100-graded temperature of 2300 ℃ is carried out.
As a further preference, the carbon fiber preform is selected from 2.5D needled bulk felts, the 2.5D needled bulk felt having a density of 0.55-0.65g/cm3。
Further preferably, the density of the C/C body is 0.7-0.8g/cm3。
Preferably, the graphitized C/C green body is soaked in a nitric acid solution for acidification treatment for 1-2h at 50-60 ℃, and the mass fraction of nitric acid in the nitric acid solution is 50-65%.
Preferably, when the modifier is a silane coupling agent, the solvent of the solution containing the modifier is a mixed solvent of ethanol and water, and the mass ratio of the ethanol to the water is 9-12: 1.
Preferably, when the modifier is a silane coupling agent, the mass fraction of the modifier in the solution containing the modifier is 4-10%.
Further preferably, when the modifier is a silane coupling agent, the mass fraction of the modifier in the modifier-containing solution is 4 to 6%.
Preferably, when the modifier is polyvinyl alcohol, the solvent in the modifier-containing solution is water, and the mass fraction of the modifier is 25-35%.
Preferably, the pretreated C/C body is soaked in a solution containing a modifier, the pH value is adjusted to 4-5, ultrasonic hydrolysis reaction is carried out for 2-3h, and then drying is carried out for 2-2.5h at 70-85 ℃ to obtain the functionalized C/C body.
Preferably, the silane coupling agent is at least one selected from the group consisting of gamma-aminopropyltriethoxysilane (KH-550), gamma-glycidoxypropyltrimethoxysilane (KH-560), and gamma-methacryloxypropyltrimethoxysilane (KH-570).
In a preferred embodiment, the solid content (volume fraction) of the BN powder in the BN slurry is 10 to 33 vol%.
In a preferred embodiment, the pH value of the BN slurry is 6-8. In the present invention, the pH of the BN slurry has some effect on the flow properties of the slurry.
In the present invention, a density of 0.9g/cm can be obtained depending on the solid content of the BN slurry3-1.2g/cm3The C/C-BN preform of (1).
In a preferable scheme, the BN powder in the BN slurry is subjected to surface pretreatment firstly, and the surface pretreatment adopts the following two schemes,
the first scheme is as follows: placing the BN powder in an air atmosphere to carry out heat treatment at 850-870 ℃ for 55-65 min;
or
Scheme II: mixing BN powder, deionized water and a tetramethylammonium hydroxide solution according to a mass ratio of 8-10:3-6:1, then ball-milling for 10-15h, drying, and then carrying out heat treatment for 5-7h at the temperature of 550-650 ℃ in an air atmosphere; in the tetramethylammonium hydroxide solution, the mass fraction of the tetramethylammonium hydroxide is 5-10%;
the drying temperature is 120-150 ℃.
The inventor finds that by performing surface pretreatment on BN powder to enable the BN powder to have hydrophilic groups, the BN powder can be uniformly dispersed in slurry, so that the slurry has good fluidity, and in addition, in the surface pretreatment process, the treatment conditions also need to be effectively controlled, for example, when the scheme is adopted, a micro-oxidized BN powder surface is formed, and the time and the temperature are controlled to enable the oxidation weight to be increased to be below 0.3g, the BN slurry with the best fluidity can be obtained, and meanwhile, excessive loss of BN can not be brought. And the second scheme is not so harsh on the oxidation condition of BN, but has longer time, and is suitable for a large-scale preparation process.
For further optimization, the BN powder is hexagonal BN powder, the particle size is 0.8-1 mu m, and the purity is more than or equal to 98%.
In a preferred scheme, the preparation process of the BN slurry comprises the following steps: dispersing the surface-pretreated BN powder into an aqueous solution containing a dispersing agent, and then carrying out ball milling to obtain BN slurry, wherein the dispersing agent is polyethyleneimine and/or ammonium polyacrylate; the pH value of the aqueous solution containing the dispersing agent is 6-8.
The BN slurry prepared by the invention has low viscosity and good flow property.
Preferably, the rotation speed of the ball mill is 160-190r/min, the time is 1-1.5h, and the ball-to-material ratio is 5:1-7: 1.
More preferably, the addition amount of the dispersant is 3.8 to 4.5% by mass of the BN powder.
Preferably, the dipping time is 5-15 min.
In the invention, when the pretreatment is carried out on the C/C green body and the slurry is reasonably prepared, the impregnation can be finished only by soaking the pretreated C/C green body in the slurry and standing for 5-15min, and the method is equivalent to the impregnation in the prior art, so that the method is simple and quick, but can bring the effect of uniform impregnation without damaging fibers.
Preferably, the drying temperature is 80-85 ℃, and the drying time is 1.5-2 h.
In the invention, the drying step can be performed by freeze drying or drying in a conventional oven or other equipment, so that the conventional oven can be used for drying in order to save cost, and at the moment, the drying is effectively controlled according to the temperature and time, otherwise, the drying time is too long, so that the powder is easily aggregated on the surface to form a glaze-shaped shell. And if freeze drying is adopted, the phenomenon of surface incrustation can not occur.
In a preferred scheme, the mode of carbonizing and densifying the C/C-BN preform by a carbon source is liquid-phase carbon source resin impregnation carbonization and densification or gas-phase carbon source CVI densification, and the preferred mode is gas-phase carbon source CVI densification.
More preferably, in the case of impregnating, carbonizing and densifying with a liquid-phase carbon source resin, a furan resin is used as the liquid-phase carbon source.
In the invention, when the liquid-phase carbon source is adopted for impregnation, carbonization and densification, the conventional technology can be adopted.
Preferably, the liquid-phase carbon source resin impregnation, carbonization and densification process comprises the following steps: soaking the C/C-BN preform in furan resin at 60-65 ℃ for more than or equal to 1 hour in vacuum, then adding phosphoric acid into the furan resin, continuing vacuum impregnation for 30-50min, then carrying out pressurized impregnation for 1.5-2.5 hours, curing after the impregnation is finished, and then carbonizing;
the pressure during the pressure impregnation is 1.4-1.6MPa,
the temperature rise procedure of the solidification is to raise the temperature to 60-120 ℃, keep the temperature for 4-5h, then continue to raise the temperature to 120-180 ℃, keep the temperature for 5-7h, finally raise the temperature to 190-200 ℃ and keep the temperature for 1.5-3 h.
The carbonization temperature is increased to 900-.
More preferably, when the vapor phase carbon source CVI is used for densification, one of methane, propylene or natural gas is used as a carbon source gas, hydrogen is used as a diluent gas, the volume ratio of the carbon source gas to the diluent gas is 1:1-3, the vapor deposition time is 80-150 hours, and the deposition temperature is 800-.
In the preferable scheme, the temperature of the graphitization treatment is 1800-2100 ℃, and the time of the graphitization treatment is 8-15 h.
In a preferred embodiment, the density of the C/C-BN composite friction material is 1.5-1.75g/cm3。
The BN matrix is obtained by adopting the slurry dipping method for the first time, after the C/C blank is functionalized, BN powder can be effectively introduced into the C/C blank in the slurry dipping process, meanwhile, vacuum conditions and pressurization conditions are not needed in the process, the BN slurry (slurry containing the BN powder) can be introduced into the interior of the prefabricated body only through the capillary force of the BN slurry, and meanwhile, the introduced BN powder can be uniformly dispersed in the interior of the prefabricated body without agglomeration. The preparation method can effectively avoid the damage of the carbon fiber and ensure that the C/C-BN composite friction material has excellent mechanical property and frictional wear property.
Particularly, the BN matrix introduced by the invention does not damage fibers, is uniformly distributed, is quickly formed in the friction process, has wide coverage, is smoothly covered in the fiber and matrix areas, does not have a wavy step structure and the friction membrane is broken, and has less carbon fiber abraded, so that the carbon fiber can well support the friction membrane on the surface, and the friction coefficient and the wear rate are effectively reduced under the synergistic action.
Compared with the prior art, the advantages and positive effects are as follows:
(1) the C/C-BN friction material is prepared by the original process of combining the slurry impregnation method and the chemical vapor infiltration, the material tissue is uniform, the production process is simple and easy to control, and the preparation cost is low.
(2) By controlling the solid content of the BN slurry and the deposition time of chemical vapor infiltration, the contents of a BN matrix and pyrolytic carbon in the material can be controlled, thereby realizing the control of the microstructure and the performance of the material.
(3) Compared with the method of spraying powder by a layer-laying method, laminating and needling the powder by a layer-laying method and performing chemical vapor infiltration, the performance of the carbon fiber in the composite material prepared by the invention is kept, and compared with the method of injecting h-BN slurry by a needle, the method of the invention does not damage the carbon fiber, the effect of reinforcing the carbon fiber is preserved, and the preparation period is short. The reason is that the h-BN is introduced into the blank body through the capillary force, so that the carbon fiber is not damaged, the weftless fabric layer can well play a reinforcing role, and external auxiliary vacuum equipment is not needed.
(4) The C/C-BN friction material prepared by the invention has excellent friction and wear properties, low and stable friction coefficient, wear resistance, high strength, high temperature resistance, corrosion resistance and a series of advantages.
In conclusion, the production process is simple and easy to control, the preparation cost is low, and the method is suitable for industrial production. The C/C-BN composite friction material prepared by the invention has controllable microstructure and performance, uniform structure, high strength, high temperature resistance, corrosion resistance, excellent friction and wear performance and wide application prospect.
Drawings
FIG. 1 TEM image of the oxidized h-BN powder in example 1.
FIG. 2 TEM image of the lamellar structure of the h-BN powder from example 1.
FIG. 3 TEM image of h-BN powder after hydrolysis + oxidation in example 2.
FIG. 4 TEM image of h-BN powder after hydrolysis + oxidation in example 2.
FIG. 5 SEM image of the distribution area of particles after impregnating the C/C porous body with BN slurry in example 3.
FIG. 6 SEM image of the distribution area of particles after impregnating the C/C porous body with BN slurry in example 3.
FIG. 7 SEM image of the grinding crack morphology of the C/C-BN composite material obtained in example 1.
FIG. 8 SEM image of the grinding crack morphology of the C/C-BN composite material obtained in example 1.
Detailed Description
The present invention is further illustrated by the following examples.
In the following examples, the density and the open porosity of the prepared C/C-BN friction material and the C/C composite material as a control were measured by the Archimedes drainage method, and the frictional wear performance was measured on a HT-1000 ball-pan frictional wear tester with a sample size of
The mating part adopts a diameter of
The experimental conditions of the silicon nitride ball are as follows: speed: pressure 0.5 m/s: 5N at 25 deg.C and 450 deg.C
Example 1
(1) The density was 0.55g/cm3The three-dimensional needled carbon felt is prepared by laminating T-700 laid carbon cloth and a net tire, wherein the fiber direction of the adjacent laid carbon cloth is vertical, and a relay piercing process is adopted.
(2) Vacuum heat treatment: taking the three-dimensional needled carbon felt as a prefabricated part, heating to 2100 ℃ at a proper heating rate (10 ℃/min) in a vacuum atmosphere, and carrying out vacuum heat treatment for 1 h.
(3) Chemical vapor infiltration: depositing the needled whole felt preform by using propylene as a carbon source gas for 30-40h to obtain a density of about 0.7g/cm3The C/C preform of (1). And graphitizing the C/C preform at 2100 ℃ for 1 h.
(4) Functional group grafting of low-density blank
Soaking the low-density green body obtained in the step (1) in dilute nitric acid (concentration) for acidification treatment for 2h, filtering and washing to be neutral, and soaking the green body in a silane coupling agent KH-550, wherein the silane coupling agent: ethanol: adjusting the pH value to 4-5 with acetic acid in a mixed solution of water 1:17.1:1.9, carrying out ultrasonic hydrolysis reaction for 2h, and drying at 85 ℃ for 2h to obtain a C/C blank functionalized by grafting a functional group.
(5) Preparing low-viscosity BN slurry with different solid phase contents
Using Polyethyleneimine (PEI) as a dispersing agent, adding the PEI into water to obtain an aqueous solution containing the dispersing agent, adjusting the pH value of the aqueous solution containing the dispersing agent to be 7, carrying out high-temperature micro-oxidation treatment on BN powder at 870 ℃ for 55min, wherein the obtained micro-oxidation BN powder is shown in a figure 1-2, and after the h-BN powder is oxidized, the original lamellar structure of the h-BN powder is not damaged, only an oxide layer with the thickness of 4-7nm is arranged at the edge of a crystal grain, so that the h-BN particle can be seen to have complete crystal form, and interlamination is realizedA distance of
And then adding BN powder into an aqueous solution containing a dispersing agent, and carrying out ball milling for 1h in a planetary ball mill to prepare the BN water-based ceramic slurry with the solid content of 30 v%, wherein the adding amount of the dispersing agent is 4.2% of the mass of the BN powder, the BN powder is hexagonal BN powder, and the average particle size of the BN powder is 800 nm.
(6) And (3) dipping the C/C green body functionalized in the step (5) in the BN water-based ceramic slurry in the step (4) for 10min to obtain a C/C-BN prefabricated body.
(7) Drying: and (4) removing the water in the three-dimensional needled whole felt soaked in the step (6), wherein the drying temperature is 80 ℃, and the time is 1.5 h.
(8) Chemical vapor infiltration: and (3) placing the needled whole felt containing the BN powder obtained in the step (7) into a chemical vapor deposition furnace, and depositing a pyrolytic carbon matrix wrapping the hexagonal BN powder on the surface of the needled whole felt containing the hexagonal boron nitride powder by adopting a chemical vapor infiltration method to prepare the carbon fiber reinforced carbon and boron nitride dual-matrix (C/C-BN) composite material, wherein when CVI is densified, propylene is used as a carbon source gas, hydrogen is used as a diluent gas, the volume ratio of the carbon source gas to the diluent gas is 1:1, the vapor deposition time is 150 hours, and the deposition temperature is 950 ℃. And graphitizing the C/C-BN composite material at 2100 ℃ for 10h to obtain the C/C-BN composite friction material. The density of the obtained C/C-BN composite material is 1.58g/cm3。
Tests prove that the C/C-BN composite material obtained in the embodiment has the bending strength of 180.76MPa, the compression strength of 147.9MPa, the friction coefficient of 0.09 and the wear rate of 5.4 multiplied by 10-5mm3N-1m-1。
In the friction process of the C/C-BN composite material obtained in the embodiment, the friction coefficient is always kept below 0.15 (average is 0.09), the friction mutation phenomenon is not obvious, through the observation of figures 7 and 8, the friction film is fast to form and wide in coverage, the friction film is flat in the areas of fibers and a base body, a wavy step structure and the breakage of the friction film are avoided, and the carbon fibers are less abraded, so that the carbon fibers can well support the friction film on the surface, and the friction coefficient and the abrasion rate are reduced.
Example 2
(1) The density was 0.55g/cm3The three-dimensional needled carbon felt is prepared by laminating T-700 laid carbon cloth and a net tire, wherein the fiber direction of the adjacent laid carbon cloth is vertical, and a relay piercing process is adopted.
(2) Vacuum heat treatment: taking the three-dimensional needled carbon felt as a prefabricated part, heating to 2100 ℃ at a proper heating rate (10 ℃/min) in a vacuum atmosphere, and carrying out vacuum heat treatment for 1 h.
(3) Chemical vapor infiltration: propylene is used as carbon source gas to deposit the needled whole felt preform for 30-40h to obtain the density of about 0.7g/cm3The C/C preform of (1). And graphitizing the C/C preform at 2100 ℃ for 1 h.
(4) Functional group grafting of low-density blank
Soaking the low-density blank obtained in the step (1) in dilute nitric acid (concentration) for acidification treatment for 2h, filtering and washing to be neutral, and soaking the blank in a silane coupling agent KH-560, wherein the silane coupling agent: ethanol: adjusting the pH value to 4-5 with acetic acid in a mixed solution of water 1:17.1:1.9, carrying out ultrasonic hydrolysis reaction for 2h, and drying at 85 ℃ for 2h to obtain a C/C blank functionalized by grafting a functional group.
(5) Preparing low-viscosity BN slurry with different solid phase contents
And (2) adding Polyethyleneimine (PEI) serving as a dispersing agent into water to obtain an aqueous solution containing the dispersing agent, adjusting the pH value of the aqueous solution containing the dispersing agent to be 7, mixing the h-BN powder, deionized water and 10% tetramethylammonium hydroxide solution according to the proportion of 100g to 60ml to 10ml, and carrying out ball milling for 48h, wherein the surfaces of h-BN particles are subjected to hydrolysis reaction under a strong alkaline condition in the ball milling process. Drying the powder with hydrolyzed surface at 150 deg.c for further use. The powder is subjected to thermal oxidation treatment at 600 ℃ for 6h in the air atmosphere, the obtained pre-treated BN powder has the same effect as that of pre-oxidation at 850 ℃ as shown in figures 3 and 4, and only an oxide layer with the thickness of 4-8nm is generated at the edge of a lamella of h-BN, so that the complete lamella structure of the BN is maintained. And then adding BN powder into an aqueous solution containing a dispersing agent, and carrying out ball milling for 1h in a planetary ball mill to prepare the BN water-based ceramic slurry with the solid content of 20 v%, wherein the adding amount of the dispersing agent is 4.2% of the mass of the BN powder, the BN powder is hexagonal BN powder, and the average particle size of the BN powder is 800 nm.
(6) And (3) dipping the C/C green body functionalized in the step (5) in the BN water-based ceramic slurry in the step (4) for 10min to obtain a C/C-BN prefabricated body.
(7) Drying: and (4) removing the water in the three-dimensional needled whole felt soaked in the step (6), wherein the drying temperature is 85 ℃, and the time is 1.5 h.
(8) Chemical vapor infiltration: and (3) placing the needled whole felt containing the BN powder obtained in the step (7) into a chemical vapor deposition furnace, and depositing a pyrolytic carbon matrix wrapping the hexagonal BN powder on the surface of the needled whole felt containing the hexagonal boron nitride powder by adopting a chemical vapor infiltration method to prepare the carbon fiber reinforced carbon and boron nitride dual-matrix (C/C-BN) composite material, wherein when CVI is densified, natural gas is used as a carbon source gas, hydrogen is used as a diluent gas, the volume ratio of the carbon source gas to the diluent gas is 1:3, the vapor deposition time is 150 hours, and the deposition temperature is 950 ℃. And graphitizing the C/C-BN composite material at 2100 ℃ for 10h to obtain the C/C-BN composite friction material. The density of the obtained C/C-BN composite material is 1.68g/cm3。
Tests prove that the C/C-BN composite material obtained in the embodiment has the bending strength of 138.59MPa, the compression strength of 147.9MPa and the friction coefficient of 0.15 and the wear rate of 3.9 multiplied by 10-5mm3N-1m-1。
Example 3:
(1) the density was 0.55g/cm3The three-dimensional needled carbon felt is prepared by laminating T-700 laid carbon cloth and a net tire, wherein the fiber direction of the adjacent laid carbon cloth is vertical, and a relay piercing process is adopted.
(2) Vacuum heat treatment: taking the three-dimensional needled carbon felt as a prefabricated part, heating to 2100 ℃ at a proper heating rate (10 ℃/min) in a vacuum atmosphere, and carrying out vacuum heat treatment for 1 h.
(3) Chemical vapor infiltration: propylene is used as carbon source gas to deposit the needled whole felt preform for 30-40h to obtain the density of about 0.7g/cm3The C/C preform of (1).And graphitizing the C/C preform at 2100 ℃ for 1 h.
(4) Functional group grafting of low-density blank
And (2) soaking the low-density blank obtained in the step (1) in dilute nitric acid (concentration) for acidification treatment for 2h, filtering and washing to be neutral, soaking the blank in a polyvinyl alcohol solution with the mass fraction of 30%, ultrasonically soaking for 2h, and drying at 85 ℃ for 2h to obtain the C/C blank functionalized by grafting functional groups.
(5) Preparing low-viscosity BN slurry with different solid phase contents
Adding Polyethyleneimine (PEI) serving as a dispersing agent into water to obtain a dispersing agent-containing aqueous solution, adjusting the pH value of the dispersing agent-containing aqueous solution to 7, subjecting BN powder to high-temperature micro-oxidation treatment at 860 ℃ for 55min, adding the BN powder into the dispersing agent-containing aqueous solution, and performing ball milling for 1h in a planetary ball mill to prepare BN water-based ceramic slurry with the solid content of 10 v%, wherein the adding amount of the dispersing agent is 4.2% of the mass of the BN powder, the BN powder is hexagonal BN powder, and the average particle size of the BN powder is 800 nm.
(6) And (3) dipping the C/C green body functionalized in the step (5) in the BN water-based ceramic slurry in the step (4) for 10min to obtain a C/C-BN prefabricated body.
(7) Drying: and (4) removing the water in the three-dimensional needled whole felt soaked in the step (6), wherein the drying temperature is 80 ℃, and the time is 1.5 h.
As can be seen from fig. 5 and 6, the BN slurry is mainly filled in the chopped fiber layer of the mesh layer, BN particles are tightly adsorbed on the surface of the pyrolytic carbon protective layer of the carbon fiber outer layer due to the function of functional groups, the lamellar structure of the particles is obvious, the shell-like morphology formed by the particles can be seen at the ends of the fibers, the particles form a coating on the surface of the fibers in a manner of tiling and gravel stacking, pores exist among the particles due to the evaporation of moisture during the drying process and the bridging effect of the BN lamellar structure, and when the particles are subsequently densified, the resin is filled among the particles to form a cobblestone floor-like mosaic structure, so that the particles are fixed by the resin carbon. So that the particles can both encapsulate the fibers and be uniformly distributed in the carbon matrix.
(8) Resin impregnation and carbonization: and (4) putting the C/C-BN prefabricated body obtained in the step (7) into an impregnation tank, vacuumizing and heating the impregnation tank to 60-65 ℃, and preserving heat for not less than 1 hour. Adding phosphoric acid with the mass of 6-8% of the resin into the resin storage tank, and preserving the heat for 30-50 min. The vacuum was stopped and nitrogen was charged to 1.4 to 1.6MPa, keeping the temperature of the dipping tank constant at 60 to 65 ℃ and keeping the pressure constant at 1.4 to 1.6MPa, and dipping for 2 hours. Curing temperature: 60-120 ℃, 4-5h 120-190 ℃, 5-7h, 190 ℃ 2 h. The carbonization heating rate is 1 ℃/min, the temperature is increased to 900 ℃, and the temperature is kept for 1 h. Finally, graphitizing the C/C-BN composite material at 2100 ℃ for 10h to obtain the C/C-BN composite material. The density of the obtained C/C-BN composite material is 1.75g/cm3。
Tests prove that the C/C-BN composite material obtained in the embodiment has the bending strength of 153.60MPa, the compression strength of 137.33MPa and the friction coefficient of 0.15 and the wear rate of 4.5 multiplied by 10-5mm3N-1m-1。
Comparative example 1
(1) The density was 0.55g/cm3The three-dimensional needled carbon felt is prepared by laminating T-700 laid carbon cloth and a net tire, wherein the fiber direction of the adjacent laid carbon cloth is vertical, and a relay piercing process is adopted.
(2) Vacuum heat treatment: taking the three-dimensional needled carbon felt as a prefabricated part, heating to 2100 ℃ at a proper heating rate (10 ℃/min) in a vacuum atmosphere, and carrying out vacuum heat treatment for 1 h.
(3) Chemical vapor infiltration: propylene is used as carbon source gas to deposit the needled whole felt preform for 30-40h to obtain the density of about 0.7g/cm3The C/C preform of (1). And graphitizing the C/C preform at 2100 ℃ for 1 h.
(4) Functional group grafting of low-density blank
And (2) soaking the low-density blank obtained in the step (1) in dilute nitric acid (concentration) for acidification treatment for 2h, filtering and washing to be neutral, soaking the blank in polyethylene glycol solution, performing ultrasonic treatment for 2h at the temperature of 60 ℃ with water, and drying for 2h at the temperature of 85 ℃ to obtain a pretreated C/C blank.
(5) Preparing low-viscosity BN slurry with different solid phase contents
Adding Polyethyleneimine (PEI) serving as a dispersing agent into water to obtain a dispersing agent-containing aqueous solution, adjusting the pH value of the dispersing agent-containing aqueous solution to be 7, subjecting BN powder to high-temperature micro-oxidation treatment at 870 ℃ for 55min, adding the BN powder into the dispersing agent-containing aqueous solution, and performing ball milling for 1h in a planetary ball mill to prepare a BN water-based ceramic slurry with the solid content of 30 v%, wherein the adding amount of the dispersing agent is 4.2% of the mass of the BN powder, the BN powder is hexagonal BN powder, and the average particle size of the BN powder is 800 nm.
The slurry prepared in comparative example 1 cannot well penetrate the C/C green body, so that the powder is crusted on the surface, and the large concentration gradient of the inner and outer surfaces is caused, so that the powder is not uniformly impregnated.
Comparative example 2
(1) The density was 0.55g/cm3The three-dimensional needled carbon felt is prepared by laminating T-700 laid carbon cloth and a net tire, wherein the fiber direction of the adjacent laid carbon cloth is vertical, and a relay piercing process is adopted.
(2) Vacuum heat treatment: taking the three-dimensional needled carbon felt as a prefabricated part, heating to 2100 ℃ at a proper heating rate (10 ℃/min) in a vacuum atmosphere, and carrying out vacuum heat treatment for 1 h.
(3) Chemical vapor infiltration: propylene is used as carbon source gas to deposit the needled whole felt preform for 30-40h to obtain the density of about 0.7g/cm3The C/C preform of (1). And graphitizing the C/C preform at 2100 ℃ for 1 h.
(4) Functional group grafting of low-density blank
Soaking the low-density green body obtained in the step (1) in dilute nitric acid (concentration) for acidification treatment for 2h, filtering and washing to be neutral, and soaking the green body in a silane coupling agent KH-550, wherein the silane coupling agent: ethanol: adjusting the pH value to 4-5 with acetic acid in a mixed solution of water 1:17.1:1.9, carrying out ultrasonic hydrolysis reaction for 2h, and drying at 85 ℃ for 2h to obtain a C/C blank functionalized by grafting a functional group.
(5) Preparing low-viscosity BN slurry with different solid phase contents
Adding Polyethyleneimine (PEI) serving as a dispersing agent into water to obtain a dispersing agent-containing aqueous solution, adjusting the pH value of the dispersing agent-containing aqueous solution to be 7, directly adding BN powder into the dispersing agent-containing aqueous solution without high-temperature micro-oxidation treatment or the operation step of hydrolysis and thermal oxidation treatment of 10% tetramethylammonium hydroxide solution, and performing ball milling for 1h in a planetary ball mill to prepare slurry with good flowability, so that the powder is agglomerated or sticky, wherein the BN powder is hexagonal BN powder, and the average particle size of the BN powder is 800 nm.
Comparative example 3
(1) The density was 0.55g/cm3The three-dimensional needled carbon felt is prepared by laminating T-700 laid carbon cloth and a net tire, wherein the fiber direction of the adjacent laid carbon cloth is vertical, and a relay piercing process is adopted.
(2) Vacuum heat treatment: taking the three-dimensional needled carbon felt as a prefabricated part, heating to 2100 ℃ at a proper heating rate (10 ℃/min) in a vacuum atmosphere, and carrying out vacuum heat treatment for 1 h.
(3) Chemical vapor infiltration: propylene is used as carbon source gas to deposit the needled whole felt preform for 30-40h to obtain the density of about 0.7g/cm3The C/C preform of (1). And graphitizing the C/C preform at 2100 ℃ for 1 h.
(4) Functional group grafting of low-density blank
Soaking the low-density green body obtained in the step (1) in dilute nitric acid (concentration) for acidification treatment for 2h, filtering and washing to be neutral, and soaking the green body in a silane coupling agent KH-550, wherein the silane coupling agent: ethanol: adjusting the pH value to 4-5 with acetic acid in a mixed solution of water-4: 17.1:1.9, carrying out ultrasonic hydrolysis reaction at room temperature or below 30 ℃ for 2h, and drying at 85 ℃ for 2h to obtain a C/C blank functionalized by grafting functional groups. It can be seen that there is a white precipitate on the surface of the green body, resulting in no grafting of functional groups inside the green body, so that the BN slurry does not well penetrate into the green body.
Claims (9)
1. A preparation method of a carbon/carbon-boron nitride antifriction composite material is characterized by comprising the following steps: soaking the graphitized C/C blank in a nitric acid solution, acidizing for 1-2h at 50-60 ℃, wherein the mass fraction of nitric acid in the nitric acid solution is 50-65%, washing to be neutral to obtain a pretreated C/C blank, then soaking in a solution containing a modifier, reacting to obtain a functionalized C/C blank, soaking the functionalized C/C blank in BN slurry, drying to obtain a C/C-BN preform, and carbonizing, densifying and graphitizing the C/C-BN preform by using a carbon source to obtain the C/C-BN antifriction composite material; the modifier is selected from silane coupling agent or PVA.
2. The method for preparing the carbon/carbon-boron nitride antifriction composite material according to claim 1, characterized in that the method for preparing the graphitized C/C body is as follows: degumming and activating the carbon fiber preform at 2100-graded temperature of 2300 ℃, obtaining a pyrolytic carbon layer by using propylene as a carbon source through a chemical vapor infiltration method, and performing graphitization treatment at 2100-graded temperature of 2300 ℃; the carbon fiber preform is selected from a 2.5D needled whole felt, and the density of the 2.5D needled whole felt is 0.55-0.65g/cm3(ii) a The density of the C/C blank is 0.7-0.85g/cm3。
3. The preparation method of the carbon/carbon-boron nitride antifriction composite material according to claim 1, characterized in that: soaking the pretreated C/C blank body in a solution containing a modifier, adjusting the pH value to 4-5, performing ultrasonic hydrolysis reaction for 2-3h, and drying to obtain a functionalized C/C blank body;
when the modifier is a silane coupling agent, the solvent of the solution containing the modifier is a mixed solvent of ethanol and water, and the mass ratio of the ethanol to the water is 9-12: 1; the mass fraction of the modifier is 4-10%;
when the modifier is polyvinyl alcohol, the solvent in the modifier-containing solution is water, and the mass fraction of the modifier is 25-35%.
4. A method of preparing a carbon/carbon-boron nitride antifriction composite material in accordance with claim 1 or 3, characterized in that: the silane coupling agent is at least one selected from KH-550, KH-560 and KH-570.
5. The preparation method of the carbon/carbon-boron nitride antifriction composite material according to claim 1, characterized in that:
in the BN slurry, the solid content of BN powder is 10-33 vol%;
the pH value of the BN slurry is 6-8;
the BN powder is hexagonal BN powder, the particle size is 0.8-1 mu m, and the purity is more than or equal to 98%.
6. A method of preparing a carbon/carbon-boron nitride antifriction composite material in accordance with claim 1 or 5, characterized in that:
the BN powder in the BN slurry is subjected to surface pretreatment in a mode of adopting the following two schemes,
the first scheme is as follows: placing the BN powder in an air atmosphere to carry out heat treatment at 850-870 ℃ for 55-65 min;
or
Scheme II: mixing BN powder, deionized water and a tetramethylammonium hydroxide solution according to a mass ratio of 8-10:3-6:1, then ball-milling for 10-15h, drying, and then carrying out heat treatment for 5-7h at the temperature of 550-650 ℃ in an air atmosphere;
in the tetramethylammonium hydroxide solution, the mass fraction of the tetramethylammonium hydroxide is 5-10%.
7. The method for preparing the carbon/carbon-boron nitride antifriction composite material according to claim 6, characterized in that:
the preparation process of the BN slurry comprises the following steps: dispersing the surface-pretreated BN powder into an aqueous solution containing a dispersing agent, and then carrying out ball milling to obtain BN slurry, wherein the dispersing agent is polyethyleneimine and/or ammonium polyacrylate; the pH value of the aqueous solution containing the dispersing agent is 6-8.
8. The method for preparing the carbon/carbon-boron nitride antifriction composite material according to claim 7, characterized in that:
the rotation speed of the ball milling is 160-190r/min, the time is 1-1.5h, and the ball-material ratio is 5:1-7: 1; the addition amount of the dispersing agent is 3.8-4.5% of the mass of the BN powder.
9. The preparation method of the carbon/carbon-boron nitride antifriction composite material according to claim 1, characterized in that:
the C/C-BN prefabricated body is subjected to carbon source carbonization and densification in a mode of liquid-phase carbon source resin impregnation carbonization and densification or gas-phase carbon source CVI densification;
when a gas-phase carbon source CVI is adopted for densification, any one of methane, propylene and natural gas is taken as a carbon source gas, hydrogen is taken as a diluent gas, the volume ratio of the carbon source gas to the diluent gas is 1:1-3, the vapor deposition time is 80-150 hours, the deposition temperature is 800-,
the temperature of the graphitization treatment is 1800-2100 ℃, and the time of the graphitization treatment is 8-15 h;
the density of the C/C-BN antifriction composite material is 1.5-1.75g/cm3。
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| CN110713386B (en) * | 2019-11-28 | 2022-04-05 | 湖南博云新材料股份有限公司 | Preparation method of C/SiC friction material |
| CN110981518B (en) * | 2019-12-17 | 2021-01-01 | 湖南金博碳素股份有限公司 | Carbon-ceramic composite material brake disc and preparation method thereof |
| CN112341229B (en) * | 2020-11-09 | 2022-09-20 | 航天特种材料及工艺技术研究所 | Gradient C/ZrC-SiC superhigh temperature ceramic matrix composite and preparation method thereof |
| CN112662449B (en) * | 2020-12-23 | 2022-11-18 | 陕西科技大学 | High-dispersion amorphous carbon coated hexagonal boron nitride nanosheet and preparation method thereof |
| CN116178036B (en) * | 2023-02-24 | 2024-04-05 | 陕西美兰德新材料股份有限公司 | Carbon-carbon composite material supporting rod and preparation method thereof |
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| CN101875562B (en) * | 2010-01-21 | 2012-05-23 | 中南大学 | Method for preparing carbon fiber reinforced carbon and hexagonal boron nitride double-matrix friction material |
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