CN109665855A - A kind of preparation method of carbon/carbon-to-nitrogen boron Antifriction Composites - Google Patents
A kind of preparation method of carbon/carbon-to-nitrogen boron Antifriction Composites Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 80
- 239000002002 slurry Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000012545 processing Methods 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005087 graphitization Methods 0.000 claims abstract description 26
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 19
- 239000004917 carbon fiber Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 230000020477 pH reduction Effects 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 28
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- 238000001764 infiltration Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 15
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- 238000000498 ball milling Methods 0.000 claims description 11
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000002296 pyrolytic carbon Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 229910052582 BN Inorganic materials 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 11
- 238000010792 warming Methods 0.000 description 11
- 125000000524 functional group Chemical group 0.000 description 10
- 230000006399 behavior Effects 0.000 description 8
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- 239000013078 crystal Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229940068984 polyvinyl alcohol Drugs 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000003026 anti-oxygenic effect Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
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- 229910000077 silane Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
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- 238000004108 freeze drying Methods 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 229910015844 BCl3 Inorganic materials 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 235000006708 antioxidants Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- 238000003701 mechanical milling Methods 0.000 description 1
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- 238000005498 polishing Methods 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
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- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 230000002829 reductive effect Effects 0.000 description 1
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
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- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/583—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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Abstract
The invention discloses a kind of carbon/carbon-to-nitrogen boron Antifriction Composites preparation methods, by the C/C green body acidification through graphitization processing, washing to neutrality obtains pretreatment C/C green body, then it is soaked in the solution containing modifying agent, reaction obtains functionalized C/C green body, then functionalized C/C green body is impregnated in h-BN slurry again, C/C-BN precast body obtained by drying, C/C-BN precast body is again through carbon source carbonization density, graphitization processing up to C/C-BN Antifriction Composites；The modifying agent is selected from silane coupling agent or polyvinyl alcohol (PVA).The method using impregnating slurry that the present invention initiates obtains BN matrix, after being functionalized processing to C/C green body, BN powder effectively can be introduced C/C green body during dipping sizing agent.The method can effectively avoid the damage of carbon fiber, guarantee that C/C-BN composite material has excellent structural strength.Gained C/C-BN composite material has excellent friction and wear behavior.
Description
Technical field
The present invention relates to a kind of carbon/carbon-to-nitrogen boron Antifriction Composites preparation methods, belong to new material technology field.
Background technique
C/C composite material has low-density, high intensity, excellent thermal conductivity, suitable coefficient of friction and small volume mill
It the advantages that damage, good workability, has been widely used in brake material, while being also many autoclaves, chemical industry equipment and height
Friction material first in the mechanical structure of speed rotation.And C/C composite material is applied as the sealing such as aero-engine between centers
It is required that low coefficient of friction and small abrasion also become the focus studied both at home and abroad.
However C/C friction material starts to aoxidize for 400 DEG C or so in air, oxidation significantly reduces the braking ability of material
And service life, and when being used for sealing material, coefficient of friction and wear rate are all excessive, the average friction of C/C friction material
Coefficient is up to 0.35, so how further to improve the coefficient of friction and wear rate of the C/C friction material applied to sealing material,
It will be the key points and difficulties that future studies need to pay close attention to.
There are three types of crystal structure, hexagonal boron nitride (h-BN), close-packed hexagonal boron nitride and cubic boron nitrides for boron nitride.Its
In, hexagonal boron nitride (h-BN) is that the excellent high temperature solid lubricant of one kind not only has excellent heat compared with carbon material
Physical property also has more superior antioxygenic property and friction and wear behavior.Its inoxidizability of hexagonal boron nitride is obvious
Better than carbon/carbon composite, the obvious initial oxidation temperature of h-BN is at 850 DEG C, and carbon/carbon composite starts oxygen at 450 DEG C
Change.And there are many similitudes, including density, thermal coefficient, thermal capacitance and crystal structure between BN and C.It is taken using the part h-BN
For carbon matrix in carbon/carbon composite, it can get antioxygenic property and the good fibre reinforced charcoal of frictional behaviour and six side's nitrogen
Change boron (C/C-BN) friction material.The coefficient of friction and wear rate of C/C-BN friction material are insensitive to the variation that can be carried, with pottery
When porcelain ball antithesis, coefficient of friction is low, and BN, which aoxidizes the B2O3 film to be formed, can be improved the antioxygenic property of material, and to material
Friction and wear behavior influences smaller.
At present about domestic and international, the research of C/C-BN friction material is relatively fewer, and the technique for preparing BN matrix mainly has elder generation
Drive body infiltration pyrolysis method (Precursor Infiltration and Pyrolysis, PIP) and chemical vapor infiltration
(Chemical Vapor Infiltration,CVI)。
Document [" High density carbon fiber/boron nitride matrix composites:
Fabrication of composites with exceptional wear resistance.Seghi Steven, Lee,
James Economy, James.Carbon, 43 (2005) 2035-2043 "] disclose it is a kind of using infiltration pyrolysis method preparation
C/C-BN friction material.This C/C-BN friction material compared with C/C composite material, wear rate be only the latter 50% even
It is lower.They think, the introducing of h-BN improve material it is different can carry under friction film stability, reduce oxidative wear and
The generation of graininess abrasive dust to reduce abrasion, and reduces and can carry and the influence of temperature.But it is split by precursor dipping
The BN of solution preparation, level spacing d (002) is bigger, and precursor is also easy to produce crackle, hole during Pintsch process.
Document " Microstructure and tribological behaviors of C/C-BN composites
fabricated by chemical vapor infiltration.Fan,Xiaomeng,Yin,Xiaowei,Cheng,Yu,
Zhang, Litong, Cheng, Laifei.Ceramics International, 38 (2012) 6137-6144 " are using chemical gas
It mutually permeates, with BCl3-NH3-Ar-H2For gas source, h-BN is deposited in carbon fiber surface, after 1600 DEG C of heat treatment, finds gas
The interplanar distance for mutually depositing obtained BN isLower than the interplanar distance of the BN obtained under low-temperature treatment, lesser crystal face
Spacing improves the anti-moisture absorption capacity of BN matrix, but due to BCl3For toxic gas, so actual production is restricted.
In addition the BN of chemical vapor infiltration preparation is mostly undefined structure, and stability is poor, and chemical vapor deposition process governing factor is more
And it is complicated, BN is difficult to control accurately at division aspect.
Domestic patent (CN101875562B) disclose it is a kind of first using layer spread method dusting, it is two-sided in monolayer carbon web tire
Uniform adhesion BN powder, net tire carry out needle thorn to the net tire of superposition after being layering, the fiber preform of burgy containing BN material are made, then
Pyrolysis carbon matrix is obtained using CVI method, carbon fiber reinforced carbon and boron nitride double-matrix (C/C-BN) friction material is made.However it should
On the one hand method can increase the difficulty of needle thorn, in addition BN powder is easy to damage carbon fiber, so that mechanical properties decrease.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of with uniform institutional framework, anti-oxidant
The carbon of performance and friction and wear behavior/carbon-to-nitrogen boron (C/C-BN) Antifriction Composites preparation method, the preparation method
It is simple and easy to control, at low cost, the period is short.
To achieve the goals above, the invention provides the following technical scheme:
A kind of preparation method of carbon/carbon-to-nitrogen boron Antifriction Composites of the present invention: by the C/C green body through graphitization processing
Acidification, washing to neutrality obtain pretreatment C/C green body, are then soaked in the solution containing modifying agent, and reaction obtains function
The C/C green body of change, then functionalized C/C green body is impregnated in BN slurry, it is drying to obtain C/C-BN precast body, C/C-BN is prefabricated
Body is through carbon source carbonization density, graphitization processing up to C/C-BN composite friction material；The modifying agent be selected from silane coupling agent or
Polyvinyl alcohol (PVA).
The method using impregnating slurry that the present invention initiates obtains BN matrix, by being functionalized processing to C/C green body
Afterwards, BN powder effectively can be introduced into C/C green body during dipping sizing agent, at the same in this process without vacuum condition and
Pressurized conditions only can be introduced BN slurry (slurry of the powder containing BN) inside precast body by the capillary force of itself,
Simultaneously introduced BN powder can inside precast body interlayer it is evenly dispersed, without there is a phenomenon where reunite.The method can
The damage of carbon fiber is effectively avoided, guarantees that C/C-BN composite friction material has excellent mechanical property.
Preferred scheme, the preparation method of the C/C green body through graphitization processing: by carbon fiber precast body in 2100-
It removes photoresist at 2300 DEG C processing, then using propylene as gas source, pyrolytic carbon layer is obtained by chemical vapor infiltration (CVI method), using
2100-2300 DEG C of graphitization processing.
As a further preference, the carbon fiber precast body is selected from 2.5D needle and pierces whole felt, and the 2.5D needle thorn is whole
The density of felt is 0.55-0.65g/cm3。
As a further preference, the density of the C/C green body is 0.7-0.8g/cm3。
Preferred scheme, the C/C green body through graphitization processing are immersed in nitric acid solution in 50-60 DEG C of acidification 1-
2h, the mass fraction of nitric acid is 50-65% in the nitric acid solution.
Preferred scheme, when modifying agent is silane coupling agent, the solution containing modifying agent, solvent is ethyl alcohol and water
The mass ratio of mixed solvent, the ethyl alcohol and water is 9-12:1.
Preferred scheme, when modifying agent is silane coupling agent, in the solution containing modifying agent, the quality point of modifying agent
Number is 4-10%.
As a further preference, when modifying agent is silane coupling agent, in the solution containing modifying agent, modifying agent
Mass fraction is 4-6%.
Preferred scheme, when modifying agent is polyvinyl alcohol, in the solution containing modifying agent, solvent is water, modifying agent
Mass fraction be 25-35%.
Preferred scheme, pretreatment C/C green body are soaked in the solution containing modifying agent, adjust pH to 4-5, ultrasonic hydrolysis is anti-
2-3h is answered, then at 70-85 DEG C of dry 2-2.5h, obtains functionalized C/C green body.
Preferred scheme, the silane coupling agent are sweet selected from γ-aminopropyl triethoxysilane (KH-550), γ-shrink
In oily ether oxygen propyl trimethoxy silicane (KH-560), γ-methacryloxypropyl trimethoxy silane (KH-570)
It is at least one.
Preferred scheme, in the BN slurry, the solid content (volume fraction) of BN powder is 10-33vol%.
Preferred scheme, the pH value of the BN slurry are 6-8.In the present invention, stream of the pH value of BN slurry for slurry
Dynamic performance can have a certain impact.
In the present invention, according to the difference of BN slurry solid concentration, it is 0.9g/cm that density, which can be obtained,3-1.2g/cm3C/
C-BN precast body.
Preferred scheme, first through surface preparation, the mode of the surface preparation is the BN powder in the BN slurry
Using the following two kinds scheme,
Scheme one: BN powder is placed in air atmosphere and is heat-treated 55-65min at 850-870 DEG C；
Or
Scheme two: BN powder, deionized water, tetramethyl ammonium hydroxide solution are mixed according to mass ratio 8-10:3-6:1,
Then ball milling 10-15h, drying, is heat-treated 5-7h at 550-650 DEG C under air atmosphere；The tetramethylammonium hydroxide
In solution, the mass fraction of tetramethylammonium hydroxide is 5-10%；
The temperature of the drying is 120-150 DEG C.
Inventors have found that making BN powder that there is hydrophilic group by carrying out surface preparation to BN powder, can making
BN powder is evenly dispersed in the slurry, so that the good fluidity of slurry, in addition during carrying out surface preparation, treatment conditions
It is also required to effectively control, the BN powder surface of low-level oxidation for the moment, is such as being formed using scheme, by control time and temperature, is being made
Oxidation weight gain hereinafter, can obtain the optimal BN slurry of mobile performance at this time, while will not bring the excessive damage of BN in 0.3g
Consumption.And scheme two is no for the oxidizing condition of BN so harsh, but the time is longer, suitable for being prepared on a large scale process.
To be further preferred, the BN powder is hexagonal AlN powder, and partial size is 0.8-1 μm, purity >=98%.
Preferred scheme, matching for the BN slurry take process are as follows: disperse the BN powder through surface preparation in containing dispersion
In the aqueous solution of agent, then for ball milling up to BN slurry, the dispersing agent is polyethyleneimine and/or ammonium polyacrylate；It is described to contain
The pH value of the aqueous solution of dispersing agent is 6-8.
BN slurry viscosity of the invention that take of matching is low, good flowing properties.
As a further preference, the revolving speed of the ball milling be 160-190r/min, time 1-1.5h, ratio of grinding media to material 5:
1-7:1。
As a further preference, the additional amount of the dispersing agent is the 3.8-4.5% of BN powder quality.
Preferred scheme, the dip time are 5-15min.
In the present invention, when carrying out pretreatment to C/C green body and the good slurry of reasonable disposition is good, only C/C will need to be pre-processed
Green body, which is soaked in slurry, stands 5-15min, and dipping can be completed, it can be seen that is equivalent to dipping in the prior art, this hair
It is bright i.e. simple and quick, but dipping can be brought uniformly, and do not damage the effect of fiber.
Preferred scheme, the temperature of the drying are 80-85 DEG C, and the dry time is 1.5-2h.
In the present invention, the step of the drying can be equal using the drying of the equipment such as the baking oven of freeze-drying or routine
Can, thus generally for save the cost, conventional baking oven drying can be used, need at this time by above-mentioned temperature and when
Between, it control effectively to drying, otherwise drying time is too long, be easy to cause powder in the aggregation on surface, forms the shell of enamel-like.
And if being the phenomenon that being not in surface crust when using freeze-drying.
Preferred scheme, mode of the C/C-BN precast body through carbon source carbonization density is phase carbon source resin impregnation carbonization
Density or gas phase carbon source CVI density, preferably gas phase carbon source CVI density.
When as a further preference, using phase carbon source resin impregnation carbonization density, using furane resins as liquid phase
Carbon source.
In the present invention, when using the density of phase carbon source impregnation carbonization, using existing conventional techniques.
As a further preference, the phase carbon source resin impregnation carbonization thickening technology are as follows: soak C/C-BN precast body
Stain is in 60-65 DEG C of furane resins, dipping >=1h under vacuum, and phosphoric acid is then added in furane resins, continues Vaccum Permeating
Stain 30-50min, then impregnating by pressure 1.5-2.5h is carried out, after the completion of dipping, then solidification is carbonized；
The pressure when impregnating by pressure is 1.4-1.6MPa,
The cured temperature program is to be warming up to 60-120 DEG C, keeps the temperature 4-5h, then proceedes to be warming up to 120-180 DEG C,
5-7h is kept the temperature, is finally warming up to 190-200 DEG C, keeps the temperature 1.5-3h.
The temperature of the carbonization is to be warming up to 900-1000 DEG C, and the time of carbonization is 1-2h, heating rate is 1-5 DEG C/
min。
When as a further preference, using gas phase carbon source CVI density, with methane, one of propylene or natural gas
As carbon-source gas, using hydrogen as diluent gas, the volume ratio of the carbon-source gas and diluent gas is 1:1-3, and gas phase is heavy
The product time is 80-150 hours, and depositing temperature is 800-1100 DEG C.
Preferred scheme, the temperature of graphitization processing are 1800-2100 DEG C, and the temperature-time of graphitization processing is 8-15h.
Preferred scheme, the density of the C/C-BN composite friction material are 1.5-1.75g/cm3。
The method using impregnating slurry that the present invention initiates obtains BN matrix, by being functionalized processing to C/C green body
Afterwards, BN powder effectively can be introduced into C/C green body during dipping sizing agent, at the same in this process without vacuum condition and
Pressurized conditions only can be introduced BN slurry (slurry of the powder containing BN) inside precast body by the capillary force of itself,
BN powder introduced simultaneously can uniformly disperse inside precast body, without there is a phenomenon where reunite.After dipping drying
It can be obtained C/C-BN precast body, pyrocarbon matrix then prepared simultaneously while fixed and package BN powder by CVI vapor deposition,
Last graphitization processing obtains C/C-BN Antifriction Composites, and preparation method of the invention can effectively avoid the damage of carbon fiber,
Guarantee that C/C-BN composite friction material has excellent mechanical property and friction and wear behavior.
Introduced BN matrix especially of the invention will not only damage fiber, but also be evenly distributed, in friction process
The formation of friction film is fast, broad covered area, and it is not in wavy rank that friction film covers smooth in the region of fiber and matrix
The rupture of terraced structure and friction film, and carbon fiber lacking of being rubbed, such carbon fiber can support surface well friction film,
Synergistic effect is lower so that coefficient of friction and wear rate are effectively reduced.
Compared with prior art, advantage and good effect are embodied in:
(1) present invention prepares C/C- in the technique that the pioneering method using impregnating slurry is combined with chemical vapor infiltration
BN friction material, material structure is uniform, and simple production process is easily-controllable, and preparation cost is low.
(2) it by the solid concentration of control BN slurry and the sedimentation time of chemical vapor infiltration, can control in material
The content of BN matrix and pyrolytic carbon, to realize the control to material microstructure and performance.
(3) with the net tire by certain density, with layer spread method dusting, lamination needle thorn is compound again and passes through chemical vapor infiltration
Saturating method is comparatively, the performance of carbon fiber is retained in composite material prepared by the present invention, with needle injection h-BN slurry
The method of material is compared, and method of the invention will not damage carbon fiber, and the effect of fibre reinforced is saved, short preparation period.
This is because h-BN is introduced into green body by capillary force, and it is not damaged to carbon fiber, enable laminated cloth layer good
Play the role of enhancing, and is not necessarily to external auxiliary vacuum equipment.
(4) C/C-BN friction material prepared by the present invention has excellent friction and wear behavior, and coefficient of friction is low and stablizes,
It is wear-resistant, while also there are high intensity, high temperature resistant, the series of advantages such as corrosion-resistant.
In conclusion simple production process of the present invention is easily-controllable, preparation cost is low, is suitable for industrialized production.Institute of the present invention
The C/C-BN composite friction material microstructure and properties of preparation are controllable, even tissue, and intensity is high, and high temperature resistant is corrosion-resistant, friction
Polishing machine is excellent, has broad application prospects.
Detailed description of the invention
TEM figure in Fig. 1 embodiment 1 after h-BN Powder Oxidation.
The lamellar structure TEM figure of h-BN powder in Fig. 2 embodiment 1.
TEM figure in Fig. 3 embodiment 2 after h-BN powder hydrolysis+oxidation.
TEM figure in Fig. 4 embodiment 2 after h-BN powder hydrolysis+oxidation.
The distributed areas SEM of particle schemes after C/C porous body dipping BN slurry in Fig. 5 embodiment 3.
The distributed areas SEM of particle schemes after C/C porous body dipping BN slurry in Fig. 6 embodiment 3.
The grinding defect morphology SEM figure of gained C/C-BN composite material in Fig. 7 embodiment 1.
The grinding defect morphology SEM figure of gained C/C-BN composite material in Fig. 8 embodiment 1.
Specific embodiment
Below with reference to example, the present invention will be further described.
In the examples below, the C/C-BN friction material and comparative sample C/ prepared using the test of Archimedes's drainage
The density and percent opening of C composite carry out friction and wear behavior test, examination on HT-1000 ball disk friction wear testing machine
Sample having a size ofMating plate use diameter forSilicon nitride ball, experiment condition are as follows: speed: 0.5m/s
Pressure: 5N, 25 DEG C of temperature, 450 DEG C
Embodiment 1
(1) density is 0.55g/cm3D refraction statics carbon felt, using T-700 without latitude carbon cloth and net tire lamination, adjacent nothing
Latitude carbon cloth machine direction is vertical, punctures technique with relay and prepares carbon felt.
(2) vacuum heat treatment: using D refraction statics carbon felt as prefabricated component, with heating rate (10 appropriate in vacuum atmosphere
DEG C/min) it is warming up to 2100 DEG C of progress vacuum heat treatments, soaking time 1h.
(3) chemical vapor infiltration: propylene is carbon-source gas, pierces whole felt precast body to needle and deposits, sedimentation time is
30-40h, obtaining density is about 0.7g/cm3C/C precast body.C/C precast body is protected in 2100 DEG C of progress graphitization processings again
Warm time 1h.
(4) functional group's grafting of low-density green body
The resulting low-density green body of step (1) is immersed in acidification 2h in dust technology (concentration), filtration washing is into
Property, then be immersed in silane resin acceptor kh-550, silane coupling agent: ethyl alcohol: in water=1:17.1:1.9 mixed solution,
PH to 4-5 is adjusted with acetic acid, ultrasonic hydrolysis reacts 2h, and 85 DEG C of dry 2h obtain grafting functionalized C/C green body through functional group.
(5) the BN slurry of the low viscosity of different solid concentrations is prepared
It uses polyethyleneimine (PEI) as dispersing agent, is added to the water, obtain the aqueous solution containing dispersing agent, and adjust to contain and divide
The pH value of water solution of powder is that 7, BN powder is handled by high temperature low-level oxidation, and the temperature of the high temperature low-level oxidation processing is 870 DEG C,
Time is 55min, and gained low-level oxidation BN powder is as shown in Figs. 1-2, after h-BN Powder Oxidation, does not destroy its original lamella
Structure only has the oxide layer of 4-7nm at the edge of crystal grain, it can be seen that the crystal form of h-BN particle is complete, and interlayer spacing isThen BN powder is added in the aqueous solution containing dispersing agent, and in a planetary ball mill, ball milling 1h, prepares solid phase
Content is the BN aqueous-based ceramic slurry of 30v%, and the additional amount of the dispersing agent is the 4.2% of BN powder quality, the BN powder
For hexagonal AlN powder, the average grain diameter of BN powder is 800nm.
(6) C/C green body functionalized in step (5) is immersed in 10min in the BN aqueous-based ceramic slurry in step (4),
Obtain C/C-BN precast body.
(7) it dries: removing the moisture in the D refraction statics entirety felt in step (6) after dipping, drying temperature 80
DEG C, time 1.5h.
(8) chemical vapor infiltration: the needle of step (7) resulting powder containing BN is pierced into whole felt and is placed in chemical vapor deposition stove
In, the Pyrolytic Carbon Matrix Carbon of whole felt surface depositional packages hexagonal AlN powder is pierced in the needle of powder containing hexagonal boron nitride using chemical vapor infiltration
Body, is made fibre reinforced charcoal and boron nitride double-matrix (C/C-BN) composite material, when CVI density, using propylene as carbon-source gas,
Using hydrogen as diluent gas, the volume ratio of the carbon-source gas and diluent gas is 1:1, and vapor deposition times are that 150h is small
When, depositing temperature is 950 DEG C.Then by C/C-BN composite material, graphitization processing 10h is compound to get C/C-BN at 2100 DEG C
Friction material.The density of gained C/C-BN composite material is 1.58g/cm3。
After tested, C/C-BN composite material its bending strength 180.76MPa obtained by the present embodiment, compressive strength are
147.9MPa, coefficient of friction 0.09, wear rate are 5.4 × 10-5mm3N-1m-1。
For C/C-BN composite material obtained by the present embodiment in friction process, it is (flat that coefficient of friction is always held at 0.15 or less
Be 0.09) friction jumping phenomenon it is unobvious, the formation by Fig. 7,8 observation, friction film is fast, and broad covered area, friction film exists
The region of fiber and matrix all covers smooth, the rupture of wavy hierarchic structure and friction film, and carbon fiber does not occur
What is rubbed lacks, the friction film of so good support surface of carbon fiber energy, so that coefficient of friction and wear rate reduce.
Embodiment 2
(1) density is 0.55g/cm3D refraction statics carbon felt, using T-700 without latitude carbon cloth and net tire lamination, adjacent nothing
Latitude carbon cloth machine direction is vertical, punctures technique with relay and prepares carbon felt.
(2) vacuum heat treatment: using D refraction statics carbon felt as prefabricated component, with heating rate (10 appropriate in vacuum atmosphere
DEG C/min) it is warming up to 2100 DEG C of progress vacuum heat treatments, soaking time 1h.
(3) chemical vapor infiltration: propylene is carbon source gas, pierces whole felt precast body to needle and deposits, sedimentation time 30-
40h, obtaining density is about 0.7g/cm3C/C precast body.Again by C/C precast body in 2100 DEG C of progress graphitization processings, heat preservation
Time 1h.
(4) functional group's grafting of low-density green body
The resulting low-density green body of step (1) is immersed in acidification 2h in dust technology (concentration), filtration washing is into
Property, then be immersed in silane coupling agent KH-560, silane coupling agent: ethyl alcohol: in water=1:17.1:1.9 mixed solution,
PH to 4-5 is adjusted with acetic acid, ultrasonic hydrolysis reacts 2h, and 85 DEG C of dry 2h obtain grafting functionalized C/C green body through functional group.
(5) the BN slurry of the low viscosity of different solid concentrations is prepared
It uses polyethyleneimine (PEI) as dispersing agent, is added to the water, obtain the aqueous solution containing dispersing agent, and adjust to contain and divide
The pH value of water solution of powder is 7, h-BN powder and deionized water and 10% tetramethyl ammonium hydroxide solution according to 100g:
The ratio of 60ml:10ml mixes, ball milling 48h, and hydrolysis occurs under strongly alkaline conditions for the particle surface of h-BN anti-in mechanical milling process
It answers.Powder after surface hydrolysis 150 DEG C at a temperature of be dried for standby.600 DEG C in air atmosphere of powder, at 6h thermal oxide
Reason, the pretreated BN powder of gained as shown in figures 3 and 4, effect with 850 DEG C pre-oxidize and as effect, all only in h-BN
Lamella edge generates the oxide layer of 4-8nm, keeps its complete lamellar structure.Then BN powder is added containing the water-soluble of dispersing agent
In liquid, and in a planetary ball mill, ball milling 1h prepares the BN aqueous-based ceramic slurry that solid concentration is 20v%, the dispersing agent
Additional amount be the 4.2% of BN powder quality, the BN powder is hexagonal AlN powder, and the average grain diameter of BN powder is 800nm.
(6) C/C green body functionalized in step (5) is immersed in 10min in the BN aqueous-based ceramic slurry in step (4),
Obtain C/C-BN precast body.
(7) it dries: removing the moisture in the D refraction statics entirety felt in step (6) after dipping, drying temperature 85
DEG C, time 1.5h.
(8) chemical vapor infiltration: the needle of step (7) resulting powder containing BN is pierced into whole felt and is placed in chemical vapor deposition stove
In, the Pyrolytic Carbon Matrix Carbon of whole felt surface depositional packages hexagonal AlN powder is pierced in the needle of powder containing hexagonal boron nitride using chemical vapor infiltration
Body, is made fibre reinforced charcoal and boron nitride double-matrix (C/C-BN) composite material, when CVI density, using natural gas as carbon source gas
Body, using hydrogen as diluent gas, the volume ratio of the carbon-source gas and diluent gas is 1:3, vapor deposition times 150h
Hour, depositing temperature is 950 DEG C.Then by C/C-BN composite material, graphitization processing 10h answers at 2100 DEG C to get C/C-BN
Close friction material.The density of gained C/C-BN composite material is 1.68g/cm3。
After tested, C/C-BN composite material its bending strength 138.59MPa obtained by the present embodiment, compressive strength are
147.9MPa, 0.15 wear rate of coefficient of friction are 3.9 × 10-5mm3N-1m-1。
Embodiment 3:
(1) density is 0.55g/cm3D refraction statics carbon felt, using T-700 without latitude carbon cloth and net tire lamination, adjacent nothing
Latitude carbon cloth machine direction is vertical, punctures technique with relay and prepares carbon felt.
(2) vacuum heat treatment: using D refraction statics carbon felt as prefabricated component, with heating rate (10 appropriate in vacuum atmosphere
DEG C/min) it is warming up to 2100 DEG C of progress vacuum heat treatments, soaking time 1h.
(3) chemical vapor infiltration: propylene is carbon source gas, pierces whole felt precast body to needle and deposits, sedimentation time 30-
40h, obtaining density is about 0.7g/cm3C/C precast body.Again by C/C precast body in 2100 DEG C of progress graphitization processings, heat preservation
Time 1h.
(4) functional group's grafting of low-density green body
The resulting low-density green body of step (1) is immersed in acidification 2h in dust technology (concentration), filtration washing is into
Property, then be immersed in the poly-vinyl alcohol solution that mass fraction is 30%, ultrasonic immersing 2h, 85 DEG C of dry 2h are obtained through official
It can the functionalized C/C green body of group's grafting.
(5) the BN slurry of the low viscosity of different solid concentrations is prepared
It uses polyethyleneimine (PEI) as dispersing agent, is added to the water, obtain the aqueous solution containing dispersing agent, and adjust to contain and divide
The pH value of water solution of powder is that 7, BN powder is handled by high temperature low-level oxidation, and the temperature of the high temperature low-level oxidation processing is 860 DEG C,
Time is 55min, then BN powder is added in the aqueous solution containing dispersing agent, and in a planetary ball mill, ball milling 1h, preparation
Solid concentration is the BN aqueous-based ceramic slurry of 10v%, and the additional amount of the dispersing agent is the 4.2% of BN powder quality, the BN
Powder is hexagonal AlN powder, and the average grain diameter of BN powder is 800nm.
(6) C/C green body functionalized in step (5) is immersed in 10min in the BN aqueous-based ceramic slurry in step (4),
Obtain C/C-BN precast body.
(7) it dries: removing the moisture in the D refraction statics entirety felt in step (6) after dipping, drying temperature 80
DEG C, time 1.5h.
From, as can be seen that BN slurry is filled primarily in the chopped fibers of net plies, BN particle is due to function in Fig. 5,6
The effect of group is tightly adsorbed on the surface of carbon fiber outer layer pyrolysis carbon protective layer, and the lamellar structure of particle is obvious, in fibrous termination
It can see that the shelly-shaped pattern that particle is constituted, particle are formed in fiber surface in such a way that rubble is piled up and coated, due to drying
Moisture evaporation and the bridging of BN lamellar structure in the process acts on, and can make between particle that there are holes, between particles rear
When continuous densification, resin filling forms the similar mosaic texture in cobblestone floor between particles, so that particle is by resin
Carbon fixation.Particle can wrap up fiber and can also be uniformly distributed in carbon base body in this way.
(8) C/C-BN precast body: being put into step (7) is resulting in impregnating autoclave by resin impregnation carbonization, vacuumizes and adds
For hot submersion tank to 60-65 DEG C, heat preservation is no less than 1h.The phosphoric acid of resin quality 6-8% is added in resin storage tank, keeps the temperature 30-
50min.Stopping vacuumizes, and inflated with nitrogen is forced into 1.4-1.6MPa, 60-65 DEG C of impregnating autoclave constant temperature, constant pressure 1.4-1.6MPa, leaching
Stain 2h.Solidification temperature: 60-120 DEG C of 4-5h 120-190 DEG C 5-7h, 190 DEG C of 2h.Carbonization heating rate is 1 DEG C/min, is warming up to
900 DEG C, keep the temperature 1h.Finally by C/C-BN composite material at 2100 DEG C graphitization processing 10h to get C/C-BN composite material.
The density of gained C/C-BN composite material is 1.75g/cm3。
After tested, C/C-BN composite material its bending strength 153.60MPa obtained by the present embodiment, compressive strength are
137.33MPa, 0.15 wear rate of coefficient of friction are 4.5 × 10-5mm3N-1m-1。
Comparative example 1
(1) density is 0.55g/cm3D refraction statics carbon felt, using T-700 without latitude carbon cloth and net tire lamination, adjacent nothing
Latitude carbon cloth machine direction is vertical, punctures technique with relay and prepares carbon felt.
(2) vacuum heat treatment: using D refraction statics carbon felt as prefabricated component, with heating rate (10 appropriate in vacuum atmosphere
DEG C/min) it is warming up to 2100 DEG C of progress vacuum heat treatments, soaking time 1h.
(3) chemical vapor infiltration: propylene is carbon source gas, pierces whole felt precast body to needle and deposits, sedimentation time 30-
40h, obtaining density is about 0.7g/cm3C/C precast body.Again by C/C precast body in 2100 DEG C of progress graphitization processings, heat preservation
Time 1h.
(4) functional group's grafting of low-density green body
The resulting low-density green body of step (1) is immersed in acidification 2h in dust technology (concentration), filtration washing is into
Property, then be immersed in polyglycol solution, water and temperature 60 C, ultrasonic 2h, 85 DEG C of dry 2h, obtain pretreated C/C
Green body.
(5) the BN slurry of the low viscosity of different solid concentrations is prepared
It uses polyethyleneimine (PEI) as dispersing agent, is added to the water, obtain the aqueous solution containing dispersing agent, and adjust to contain and divide
The pH value of water solution of powder is that 7, BN powder is handled by high temperature low-level oxidation, and the temperature of the high temperature low-level oxidation processing is 870 DEG C,
Time is 55min, then BN powder is added in the aqueous solution of the aqueous solution containing dispersing agent, and in a planetary ball mill, ball
1h is ground, the BN aqueous-based ceramic slurry that solid concentration is 30v% is prepared, the additional amount of the dispersing agent is BN powder quality
4.2%, the BN powder is hexagonal AlN powder, and the average grain diameter of BN powder is 800nm.
The slurry prepared in this comparative example 1 cannot permeate C/C green body well, so that powder is in surface crust, and cause
The very big concentration gradient of surfaces externally and internally, so that powder infusion is uneven.
Comparative example 2
(1) density is 0.55g/cm3D refraction statics carbon felt, using T-700 without latitude carbon cloth and net tire lamination, adjacent nothing
Latitude carbon cloth machine direction is vertical, punctures technique with relay and prepares carbon felt.
(2) vacuum heat treatment: using D refraction statics carbon felt as prefabricated component, with heating rate (10 appropriate in vacuum atmosphere
DEG C/min) it is warming up to 2100 DEG C of progress vacuum heat treatments, soaking time 1h.
(3) chemical vapor infiltration: propylene is carbon source gas, pierces whole felt precast body to needle and deposits, sedimentation time 30-
40h, obtaining density is about 0.7g/cm3C/C precast body.Again by C/C precast body in 2100 DEG C of progress graphitization processings, heat preservation
Time 1h.
(4) functional group's grafting of low-density green body
The resulting low-density green body of step (1) is immersed in acidification 2h in dust technology (concentration), filtration washing is into
Property, then be immersed in silane resin acceptor kh-550, silane coupling agent: ethyl alcohol: in water=1:17.1:1.9 mixed solution,
PH to 4-5 is adjusted with acetic acid, ultrasonic hydrolysis reacts 2h, and 85 DEG C of dry 2h obtain grafting functionalized C/C green body through functional group.
(5) the BN slurry of the low viscosity of different solid concentrations is prepared
It uses polyethyleneimine (PEI) as dispersing agent, is added to the water, obtain the aqueous solution containing dispersing agent, and adjust to contain and divide
The pH value of water solution of powder is that 7, BN powder does not pass through the processing of high temperature low-level oxidation, also without carrying out 10% tetramethylammonium hydroxide
Solution hydrolyzes the operating procedure of reheating oxidation processes, directly BN powder is added in the aqueous solution containing dispersing agent, and planetary
In ball mill, ball milling 1h can not prepare the slurry of good fluidity, lead to powder agglomates or sticky, and the BN powder is six sides
BN powder, the average grain diameter of BN powder are 800nm.
Comparative example 3
(1) density is 0.55g/cm3D refraction statics carbon felt, using T-700 without latitude carbon cloth and net tire lamination, adjacent nothing
Latitude carbon cloth machine direction is vertical, punctures technique with relay and prepares carbon felt.
(2) vacuum heat treatment: using D refraction statics carbon felt as prefabricated component, with heating rate (10 appropriate in vacuum atmosphere
DEG C/min) it is warming up to 2100 DEG C of progress vacuum heat treatments, soaking time 1h.
(3) chemical vapor infiltration: propylene is carbon source gas, pierces whole felt precast body to needle and deposits, sedimentation time 30-
40h, obtaining density is about 0.7g/cm3C/C precast body.Again by C/C precast body in 2100 DEG C of progress graphitization processings, heat preservation
Time 1h.
(4) functional group's grafting of low-density green body
The resulting low-density green body of step (1) is immersed in acidification 2h in dust technology (concentration), filtration washing is into
Property, then be immersed in silane resin acceptor kh-550, silane coupling agent: ethyl alcohol: in water=4:17.1:1.9 mixed solution,
PH to 4-5 is adjusted with acetic acid, room temperature or 30 DEG C or less ultrasonic hydrolysis react 2h, and 85 DEG C of dry 2h obtain grafting through functional group
Functionalized C/C green body.It can be seen that having the sediment of white on the surface of green body, cause inside green body without grafting upper function
Group, prevent BN slurry from penetrating into green body well.
Claims (10)
1. a kind of carbon/carbon-to-nitrogen boron Antifriction Composites preparation method, it is characterised in that: by the C/C base through graphitization processing
Body acidification, washing to neutrality obtain pretreatment C/C green body, are then soaked in the solution containing modifying agent, react acquisition official
The C/C green body of energyization, then functionalized C/C green body is impregnated in BN slurry, it is drying to obtain C/C-BN precast body, C/C-BN is pre-
Body processed is through carbon source carbonization density, graphitization processing up to C/C-BN Antifriction Composites；The modifying agent is selected from silane coupling agent
Or PVA.
2. a kind of carbon according to claim 1/carbon-to-nitrogen boron Antifriction Composites preparation method, which is characterized in that institute
It states the preparation method of the C/C green body through graphitization processing: carbon fiber precast body is removed photoresist activation processing at 2100-2300 DEG C,
Again using propylene as carbon source, pyrolytic carbon layer is obtained by chemical vapor infiltration, using 2100-2300 DEG C of graphitization processing；Institute
It states carbon fiber precast body and is selected from the whole felt of 2.5D needle thorn, the density that the 2.5D needle pierces whole felt is 0.55-0.65g/cm3；Institute
The density for stating C/C green body is 0.7-0.85g/cm3。
3. a kind of carbon according to claim 1/carbon-to-nitrogen boron Antifriction Composites preparation method, which is characterized in that warp
The C/C green body of graphitization processing is immersed in nitric acid solution the nitric acid in 50-60 DEG C of acidification 1-2h, the nitric acid solution
Mass fraction is 50-65%.
4. a kind of carbon according to claim 1/carbon-to-nitrogen boron Antifriction Composites preparation method, it is characterised in that: pre-
Processing C/C green body is soaked in the solution containing modifying agent, adjusts pH to 4-5, and ultrasonic hydrolysis reacts 2-3h, dry, obtains function
The C/C green body of change；
When modifying agent is silane coupling agent, the solution containing modifying agent, solvent is the mixed solvent of ethyl alcohol and water, the second
The mass ratio of alcohol and water is 9-12:1；The mass fraction of modifying agent is 4-10%；
When modifying agent is polyvinyl alcohol, in the solution containing modifying agent, solvent is water, and the mass fraction of modifying agent is 25-
35%.
5. a kind of carbon according to claim 1 or 4/carbon-to-nitrogen boron Antifriction Composites preparation method, feature exist
In: the silane coupling agent is selected from least one of KH-550, KH-560, KH-570.
6. a kind of carbon according to claim 1/carbon-to-nitrogen boron Antifriction Composites preparation method, it is characterised in that:
In the BN slurry, the solid content of BN powder is 10-33vol%；
The pH value of the BN slurry is 6-8；
The BN powder is hexagonal AlN powder, and partial size is 0.8-1 μm, purity >=98%.
7. a kind of carbon according to claim 1 or 6/carbon-to-nitrogen boron Antifriction Composites preparation method, feature exist
In:
For BN powder in the BN slurry first through surface preparation, the mode of the surface preparation is using the following two kinds side
Case,
Scheme one: BN powder is placed in air atmosphere and is heat-treated 55-65min at 850-870 DEG C；
Or
Scheme two: BN powder, deionized water, tetramethyl ammonium hydroxide solution are mixed according to mass ratio 8-10:3-6:1, then
Ball milling 10-15h, drying, is heat-treated 5-7h at 550-650 DEG C under air atmosphere；
In the tetramethyl ammonium hydroxide solution, the mass fraction of tetramethylammonium hydroxide is 5-10%.
8. a kind of carbon according to claim 7/carbon-to-nitrogen boron Antifriction Composites preparation method, it is characterised in that:
Matching for the BN slurry takes process are as follows: disperses the BN powder through surface preparation in the aqueous solution containing dispersing agent, so
For ball milling up to BN slurry, the dispersing agent is polyethyleneimine and/or ammonium polyacrylate afterwards；The aqueous solution containing dispersing agent
PH value is 6-8.
9. a kind of carbon according to claim 8/carbon-to-nitrogen boron Antifriction Composites preparation method, it is characterised in that:
The revolving speed of the ball milling is 160-190r/min, time 1-1.5h, ratio of grinding media to material 5:1-7:1；The dispersing agent adds
Enter the 3.8-4.5% that amount is BN powder quality.
10. a kind of carbon according to claim 1/carbon-to-nitrogen boron Antifriction Composites preparation method, it is characterised in that:
Mode of the C/C-BN precast body through carbon source carbonization density is the density of phase carbon source resin impregnation carbonization or gas phase carbon source
CVI density, preferably gas phase carbon source CVI density；
When using gas phase carbon source CVI density, using any one in methane, propylene, natural gas as carbon-source gas, made with hydrogen
For diluent gas, the volume ratio of the carbon-source gas and diluent gas is 1:1-3, and vapor deposition times are 80-150 hours, is sunk
Accumulated temperature degree is 800-1100 DEG C,
The temperature of the graphitization processing is 1800-2100 DEG C, and the temperature-time of graphitization processing is 8-15h；
The density of the C/C-BN Antifriction Composites is 1.5-1.75g/cm3。
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