CN106116626A - A kind of preparation method of oxidation resistant carbon carbon composite heat-insulated material - Google Patents
A kind of preparation method of oxidation resistant carbon carbon composite heat-insulated material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 125
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 47
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 32
- 239000004917 carbon fiber Substances 0.000 claims abstract description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000009413 insulation Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000005011 phenolic resin Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 230000005855 radiation Effects 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 229920000548 poly(silane) polymer Polymers 0.000 claims abstract description 9
- 230000003026 anti-oxygenic effect Effects 0.000 claims abstract description 7
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- 238000005087 graphitization Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 24
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 17
- -1 polyethylene Polymers 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920003257 polycarbosilane Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000002349 favourable effect Effects 0.000 claims 1
- 230000008595 infiltration Effects 0.000 claims 1
- 238000001764 infiltration Methods 0.000 claims 1
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 2
- 230000003078 antioxidant effect Effects 0.000 abstract description 2
- 238000010894 electron beam technology Methods 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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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- C04B35/806—
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
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- C—CHEMISTRY; METALLURGY
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
- C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/616—Liquid infiltration of green bodies or pre-forms
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
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- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
- C04B2235/9684—Oxidation resistance
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Abstract
The present invention relates to the preparation method of a kind of oxidation resistant carbon carbon composite heat-insulated material, oxidation resistant carbon carbon composite heat-insulated material is to prepare through steps such as dipping polysilane presoma, cross-linking radiation, impregnated phenolic resin, high temperature sinterings using carbon fiber heat insulation felt material as idiosome, idiosome.The polysilane cross-linked by electron beam irradiation during high temperature sintering will be converted into carbofrax material and be coated on carbon fiber surface, play antioxidative effect, high temperature graphitization can improve the antioxygenic property of material with carbon element simultaneously, above anti-oxidation method can be greatly improved the antioxygenic property of material, and the service life of material can bring up to more than 2 years from 1 year.
Description
Technical field
The invention belongs to carbon carbon composite heat-insulated material technical field, be specifically related to a kind of oxidation resistant carbon carbon composite heat-insulated material
Preparation method, be to be used directly in the high temperature furnace of vacuum and inert gas shielding, can stablize at a temperature of 1000-2500 DEG C
Use, especially polycrystalline silicon ingot or purifying furnace and the requisite heat-barrier material of monocrystal silicon straight pull furnace thermal field.The invention belongs to high temperature joint
Can field.
Background technology
Carbon carbon composite heat-insulated material has the features such as high temperature resistant, good rigidly, processability are good, is widely used in aviation boat
My god, communication optical fiber, new forms of energy, high-performance ceramic manufacture, field of crystal growth, and along with the development of new forms of energy photovoltaic industry, when
Front polycrystalline ingot furnace and the heat-barrier material of thermal field of single crystal furnace, the most concerned become a focus.
The field that carbon carbon composite heat-insulated material present stage Application comparison is many is polycrystalline-silicon furnace field and monocrystaline silicon stove field.
High temperature furnace during using in order to improve its application efficiency, often 400 DEG C of temperature blow-ons the most higher, empty after blow-on
Gas enters, and is very easy to cause the oxidation of carbon carbon composite heat-insulated material, and the service life ultimately resulting in insulation material reduces, sometimes
Half a year will be changed once, and add cost also can affect production efficiency simultaneously.Therefore the antioxidation of carbon carbon composite heat-insulated material
Performance just becomes very important performance indications of carbon carbon composite heat-insulated material.
By being relatively effective method in carbon one layer of fire-resistant oxidation resistant coating of carbon composite heat-insulated material surface-coated, but
The research being present stage this respect is the most fewer；And it is not that each high-temperaure coating is suitable in crystal silicon stove using,
Because high-temperaure coating sometimes can overflow in silicon wafer material, and then affect the generating efficiency of silicon wafer material.Present stage exists
Carbon one layer of carbofrax material of carbon composite heat-insulated material surface-coated is the very effective method improving its antioxygenic property, but
This method does not ensures that each carbon fiber can be carbonized silicon materials and be coated with, and therefore preparing one can be coated with completely
The coat of silicon carbide of carbon fibre material becomes a very important research field.
Because of proportion and the high sublimation temperature (about 2700 DEG C) of carborundum 3.2, carborundum is well suited as the former of high temperature furnace
Material.Under any pressure that can reach, it is all without fusing, and has at a fairly low chemism.Therefore carborundum powder is used
Carry out the most difficult realization of method of carbon coated fiber.The method using silicon carbide precursor herein prepares coat of silicon carbide, thus
The preparation method of a kind of oxidation resistant carbon carbon composite heat-insulated material is provided.
Summary of the invention
Present invention aim at providing a kind of can the coat of silicon carbide of carbon coated carbon composite heat-insulated material completely, improve carbon
The antioxygenic property of carbon composite heat-insulated material.The preparation method of a kind of oxidation resistant carbon carbon composite heat-insulated material is i.e. provided.
A kind of oxidation resistant carbon carbon composite heat-insulated material is using carbon fiber heat insulation felt material as idiosome, and idiosome is poly-through dipping
The oxidation resistant carbon carbon composite heat-insulated material that the steps such as silane precursor, cross-linking radiation, impregnated phenolic resin, high temperature sintering prepare.
A kind of preparation method of oxidation resistant carbon carbon composite heat-insulated material, the preparation of its oxidation resistant carbon carbon composite heat-insulated material
Journey is as follows:
(1) carbon fiber heat insulation felt material is selected: the present invention is using a kind of high-temperature resistant carbon fiber heat insulation felt as blank of material, and it is fine
Dimension orientation anisotropy X-Y plane is 50-250:1 with Z-direction fiber portion rate, and its grammes per square metre is 500 g/m2-900 g/m2, thickness
It is 1 cm；
(2) preparation of silicon carbide precursor material solution: utilize Polycarbosilane prepared by Wurtz coupled method as preparation carbonization
The persursor material of silicon, is dissolved in xylene solvent, and its concentration is 10%, and wherein the structure of polysilane is-((R1)Si
(R2))m-((R3) Si(R4))n-, wherein R1-R4For-H ,-CH2,-CH=CH2Or C6H5；
(3) silicon carbide precursor impregnation of carbon fibers heat insulation felt material: before heat insulation felt material is put into the above-mentioned carborundum prepared
Driving and take out after impregnating 30 minutes in body material solution, be vacuum dried 1 hour in vacuum drying oven, baking temperature is 100 DEG C；Heat insulation
Felt material is 1:1 with the mass ratio of silicon carbide precursor material solution；
(4) cross-linking radiation processes: by material prepared in (3) with after polyethylene plastic bag plastic packaging, in electron accelerator underdrive
Irradiation 50 kGy-100 kGy, electron accelerator energy be 2MeV, 10mA；
(5) impregnated phenolic resin material: carbon fiber felt radiation treatment in (4) crossed uses phenol resin solution to soak
Stain, wherein novolac solution is phenolic aldehyde ethanol solution, and the solid content of phenolic aldehyde is 30-40%；Carbon fiber felt and the mass ratio of phenolic resin
For 1:1-1.5；The liquid impregnation agent that dipping calculates passing ratio at normal temperatures sprays in blank of material, and spraying must
Uniformly；
(6) it is dried: the fiber felt impregnated in (5) is placed in vacuum equipment by the way of negative pressure, returns after ethanol is absorbed
Receive, control ethanol content below 5%；Dried sample is hung on iron wire net rack stand-by, and storage temperature is less than 30 DEG C；
(7) die-filling press curing: post release paper in a mold, then loading mould neat for the blank of material impregnated in (6)
In tool, after mould be put in 30T swaging machine carry out disposal molding compacting；Pressure is 0.625kgf/cm2；Carry cured, Gu
Change temperature room temperature to 175 DEG C, 3-6 hour hardening time；Recommend to be raised to 175 DEG C to heat up per hour 50 DEG C from room temperature, the coldest
But to less than 50 DEG C, take out from press；
(8) high temperature sintering: the intermediate products that step (7) is cured load high temperature sintering furnace, and every piece of intermediate products utilize high density
Carbon carbon material carries out spacing control, under 10-8000Pa pressure, is warmed up to 400 DEG C with 75 DEG C/h, and then 25 DEG C/h is warmed up to
500 DEG C, 500 DEG C are incubated 2 hours, then reach 2400 DEG C with the heating rate of 25-100 DEG C per hour, at high temperature carry out clean
Change processes, and makes metals content impurity carbon carbon composite heat-insulated material within 200ppm；Described heating rate suggestion: 25
DEG C/h is warmed up to 600 DEG C from 500 DEG C, 30 DEG C/h to 750 DEG C, 750 DEG C of constant temperature 2 hours, then 40 DEG C/h was warmed up to 950 DEG C,
50 DEG C/h is warmed up to 1200 DEG C, and 55 DEG C/h is warmed up to 1500 DEG C, and 60 DEG C/h is warmed up to 1800 DEG C, and 70 DEG C/h is warmed up to 2000 DEG C,
75 DEG C/h is warmed up to 2200 DEG C, and 80 DEG C/h is warmed up to 2400 DEG C, 2400 DEG C insulation 1 hour after stop heating, Temperature fall is to room
Come out of the stove after temperature.
Persursor material in above-mentioned steps (2) must choose, and selects the functional group containing carbon-carbon double bond as far as possible, with
It is beneficial to the formation of cross-linking radiation structure.
Irradiation sample in above-mentioned steps (4) must be placed in polyethylene plastic packaging bag, prevents oxygen in irradiation process
Penetrating into, transmission irradiation ensures heat radiation in time simultaneously, and irradiation dose also to be controlled well, controls crosslinking degree.
In above-mentioned steps (7), 30T press is the multi-daylight press of the transformation of the way.Pressing process is disposably to be pressed into required thickness
Degree (if 50mm thickness carbon carbon composite heat-insulated material is that after being disposably pressed into 53mm, sintering shrinkage forms).Once can suppress 3 pieces
The cured article of above 2000mm*2000mm*53mm.
Intermediate products in above-mentioned steps (7) must be controlled with high density carbon carbon limited block, controls the equal of product
Even property, the most beneficially the being heated evenly property of material.
The high-temperature process of above-mentioned steps (8) can carry out carbonization and graphitization to phenolic resin.Rising phenolic aldehyde along with temperature
Progressively being carbonized, by the coarse structure of carbon fiber surface, the phenolic aldehyde material with carbon element after carbonization can well be carried out with carbon fiber
Coupling, finally at 2400 DEG C graphitization and make a kind of high-strength light carbon carbon composite heat-insulated material.
The polysilane cross-linked by electron beam irradiation during high temperature sintering will be converted into carbofrax material cladding
At carbon fiber surface, playing antioxidative effect, high temperature graphitization can improve the antioxygenic property of material with carbon element simultaneously, more than anti-
Method for oxidation can be greatly improved the antioxygenic property of material, and the service life of material can bring up to more than 2 years from 1 year.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail.But the present invention is not limited only to the following example.
Embodiment 1
The preparation method of a kind of oxidation resistant carbon carbon composite heat-insulated material, the preparation process of its oxidation resistant carbon carbon composite heat-insulated material is such as
Under:
(1) carbon fiber heat insulation felt material is selected: the present invention is using a kind of high-temperature resistant carbon fiber heat insulation felt as blank of material, and it is fine
Dimension orientation anisotropy X-Y plane is 50-250:1 with Z-direction fiber portion rate, and its grammes per square metre is 600 g/m2, thickness is 10mm；
(2) preparation of silicon carbide precursor material solution: utilize Polycarbosilane prepared by Wurtz coupled method as preparation carbonization
The persursor material of silicon, is dissolved in xylene solvent, and its concentration is 10%；Wherein the structure of polysilane is-((R1)Si
(R2))m-((R3) Si(R4))n-, wherein R1-R4For-H ,-CH2,-CH=CH2Or C6H5；
(3) silicon carbide precursor impregnation of carbon fibers heat insulation felt material: before heat insulation felt material is put into the above-mentioned carborundum prepared
Driving and take out after impregnating 30 minutes in body material solution, be vacuum dried 1 hour in vacuum drying oven, baking temperature is 100 DEG C；Heat insulation
Felt material is 1:1 with the mass ratio of silicon carbide precursor material solution；
(4) cross-linking radiation processes: by material prepared in (3) with after polyethylene plastic bag plastic packaging, in electron accelerator underdrive
Irradiation 50 kGy, electron accelerator energy be 2MeV, 10mA；
(5) impregnated phenolic resin material: carbon fiber felt radiation treatment in (4) crossed uses phenol resin solution to soak
Stain, wherein novolac solution is phenolic aldehyde ethanol solution, and the solid content of phenolic aldehyde is 30%；Carbon fiber felt with the mass ratio of phenolic resin is
1:1；The liquid impregnation agent that dipping calculates passing ratio at normal temperatures sprays in blank of material, and spraying must be uniform；
(6) it is dried: the fiber felt impregnated in (5) is placed in vacuum equipment by the way of negative pressure, returns after ethanol is absorbed
Receive, control ethanol content below 5%；Dried sample is hung on iron wire net rack stand-by, and storage temperature is less than 30 DEG C；
(7) die-filling press curing: post release paper in a mold, then loading mould neat for the blank of material impregnated in (6)
In tool, after mould be put in 30T swaging machine carry out disposal molding compacting.Pressure is 0.625kgf/cm2；Carry cured, Gu
Change temperature room temperature to 175 DEG C, 3 hours hardening times；Recommend to be raised to 175 DEG C to heat up per hour 50 DEG C from room temperature, then cool down
To less than 50 DEG C, take out from press；
(8) high temperature sintering: the intermediate products that step (7) is cured load high temperature sintering furnace, and every piece of intermediate products utilize high density
Carbon carbon material carries out spacing control, under 10-8000Pa pressure, is warmed up to 400 DEG C with 75 DEG C/h, and then 25 DEG C/h is warmed up to
500 DEG C, 500 DEG C are incubated 2 hours, are warmed up to 600 DEG C with 25 DEG C/h from 500 DEG C, and 30 DEG C/h is warmed up to 750 DEG C, at 750 DEG C of constant temperature
2 hours, then 40 DEG C/h was warmed up to 950 DEG C, and 50 DEG C/h is warmed up to 1200 DEG C, and 55 DEG C/h is warmed up to 1500 DEG C, and 60 DEG C/h heats up
To 1800 DEG C, 70 DEG C/h is warmed up to 2000 DEG C, and 75 DEG C/h is warmed up to 2200 DEG C, and 80 DEG C/h is warmed up to 2400 DEG C, 2400 DEG C of insulations 1
Stop heating after hour, come out of the stove after Temperature fall to room temperature.
Embodiment 2
The preparation method of a kind of oxidation resistant carbon carbon composite heat-insulated material, the preparation process of its oxidation resistant carbon carbon composite heat-insulated material is such as
Under:
(1) carbon fiber heat insulation felt material is selected: the present invention is using a kind of high-temperature resistant carbon fiber heat insulation felt as blank of material, and it is fine
Dimension orientation anisotropy X-Y plane is 50-250:1 with Z-direction fiber portion rate, and its grammes per square metre is 800 g/m2, thickness is 10 mm；
(2) preparation of silicon carbide precursor material solution: utilize Polycarbosilane prepared by Wurtz coupled method as preparation carbonization
The persursor material of silicon, is dissolved in xylene solvent, and its concentration is 10%；Wherein the structure of polysilane is-((R1)Si
(R2))m-((R3) Si(R4))n-, wherein R1-R4For-H ,-CH2,-CH=CH2Or C6H5；
(3) silicon carbide precursor impregnation of carbon fibers heat insulation felt material: before heat insulation felt material is put into the above-mentioned carborundum prepared
Driving and take out after impregnating 30 minutes in body material solution, be vacuum dried 1 hour in vacuum drying oven, baking temperature is 100 DEG C；Heat insulation
Felt material is 1:1 with the mass ratio of silicon carbide precursor material solution；
(4) cross-linking radiation processes: by material prepared in (3) with after polyethylene plastic bag plastic packaging, in electron accelerator underdrive
Irradiation 60kGy, electron accelerator energy be 2MeV, 10mA；
(5) impregnated phenolic resin material: carbon fiber felt radiation treatment in (4) crossed uses phenol resin solution to soak
Stain, wherein novolac solution is phenolic aldehyde ethanol solution, and the solid content of phenolic aldehyde is 40%；Carbon fiber felt with the mass ratio of phenolic resin is
1:1.5；The liquid impregnation agent that dipping calculates passing ratio at normal temperatures sprays in blank of material, and spraying must be equal
Even；
(6) it is dried: the fiber felt impregnated in (5) is placed in vacuum equipment by the way of negative pressure, returns after ethanol is absorbed
Receive, control ethanol content below 5%；Dried sample is hung on iron wire net rack stand-by, and storage temperature is less than 30 DEG C；
(7) die-filling press curing: post release paper in a mold, then loading mould neat for the blank of material impregnated in (6)
In tool, after mould be put in 30T swaging machine carry out disposal molding compacting；Pressure is 0.625kgf/cm2；Carry cured, Gu
Change temperature room temperature to 175 DEG C, 3 hours hardening times；Recommend to be raised to 175 DEG C to heat up per hour 50 DEG C from room temperature, then cool down
To less than 50 DEG C, take out from press；
(8) high temperature sintering: the intermediate products that step (7) is cured load high temperature sintering furnace, and every piece of intermediate products utilize high density
Carbon carbon material carries out spacing control, under 10-8000Pa pressure, is warmed up to 400 DEG C with 75 DEG C/h, and then 25 DEG C/h is warmed up to
500 DEG C, 500 DEG C are incubated 2 hours, are warmed up to 750 DEG C with 40 DEG C/h from 500 DEG C, at 750 DEG C of constant temperature 2 hours, then 40 DEG C/h liter
Temperature is to 950 DEG C, and 50 DEG C/h is warmed up to 1200 DEG C, and 60 DEG C/h is warmed up to 1800 DEG C, and 70 DEG C/h is warmed up to 2200 DEG C, 80 DEG C/h liter
Temperature to 2400 DEG C, 2400 DEG C insulation 1 hour after stop heating, come out of the stove after Temperature fall to room temperature.
Claims (9)
1. an oxidation resistant carbon carbon composite heat-insulated material, is characterized in that it being using carbon fiber heat insulation felt material as idiosome, idiosome warp
Cross oxidation resistant carbon carbon that the dipping step such as polysilane presoma, cross-linking radiation, impregnated phenolic resin, high temperature sintering prepares compound every
Hot material.
2. oxidation resistant carbon carbon composite heat-insulated material as claimed in claim 1 a kind of, the high-temperature resistance carbon fiber described in its feature every
Fiber orientation anisotropy X-Y plane in hot felt blank of material and Z-direction fiber portion rate are 50-250:1, and its grammes per square metre is 500
g/m2-900 g/m2, thickness is 10mm.
3. oxidation resistant carbon carbon composite heat-insulated material as claimed in claim 1 a kind of, the high-temperature resistance carbon fiber described in its feature every
Hot felt needs to carry out impregnating by polysilane persursor material, cross-links, produce coat of silicon carbide after pyroreaction thus improve system
The antioxygenic property of standby carbon carbon composite heat-insulated material.
4. a preparation method for oxidation resistant carbon carbon composite heat-insulated material, the preparation process of its oxidation resistant carbon carbon composite heat-insulated material
As follows:
(1) carbon fiber heat insulation felt material is selected: the present invention is using a kind of high-temperature resistant carbon fiber heat insulation felt as blank of material, and it is fine
Dimension orientation anisotropy X-Y plane is 50-250:1 with Z-direction fiber portion rate, and its grammes per square metre is 500 g/m2-900 g/m2, thickness
For 10mm；
(2) preparation of silicon carbide precursor material solution: utilize Polycarbosilane prepared by Wurtz coupled method as preparation carbonization
The persursor material of silicon, is dissolved in xylene solvent, and its concentration is 10%；Wherein the structure of polysilane is-((R1)Si
(R2))m-((R3) Si(R4))n-, wherein R1-R4For-H ,-CH2,-CH=CH2Or C6H5；
(3) silicon carbide precursor impregnation of carbon fibers heat insulation felt material: before heat insulation felt material is put into the above-mentioned carborundum prepared
Driving and take out after impregnating 30 minutes in body material solution, be vacuum dried 1 hour in vacuum drying oven, baking temperature is 100 DEG C；Heat insulation
Felt material is 1:1 with the mass ratio of silicon carbide precursor material solution；
(4) cross-linking radiation processes: by material prepared in (3) with after polyethylene plastic bag plastic packaging, in electron accelerator underdrive
Irradiation 50 kGy-100 kGy, electron accelerator energy be 2MeV, 10mA；
(5) impregnated phenolic resin material: carbon fiber felt radiation treatment in (4) crossed uses phenol resin solution to soak
Stain, wherein novolac solution is phenolic aldehyde ethanol solution, and the solid content of phenolic aldehyde is 30-40%；Carbon fiber felt and the mass ratio of phenolic resin
For 1:1-1.5；The liquid impregnation agent that dipping calculates passing ratio at normal temperatures sprays in blank of material, and spraying must
Uniformly；
(6) it is dried: the fiber felt impregnated in (5) is placed in vacuum equipment by the way of negative pressure, returns after ethanol is absorbed
Receive, control ethanol content below 5%；Dried sample is hung on iron wire net rack stand-by, and storage temperature is less than 30 DEG C；
(7) die-filling press curing: post release paper in a mold, then loading mould neat for the blank of material impregnated in (6)
In tool, after mould be put in 30T swaging machine carry out disposal molding compacting；Pressure is 0.625kgf/cm2；Carry cured, Gu
Change temperature room temperature to 175 DEG C, 3-6 hour hardening time；Recommend to be raised to 175 DEG C to heat up per hour 50 DEG C from room temperature, the coldest
But to less than 50 DEG C, take out from press；
(8) high temperature sintering: the intermediate products that step (7) is cured load high temperature sintering furnace, and every piece of intermediate products utilize high density
Carbon carbon material carries out spacing control, under 10-8000Pa pressure, is warmed up to 400 DEG C with 75 DEG C/h, and then 25 DEG C/h is warmed up to
500 DEG C, 500 DEG C are incubated 2 hours, then reach 2400 DEG C with the heating rate of 25-100 DEG C per hour, at high temperature carry out clean
Change processes, and makes metals content impurity carbon carbon composite heat-insulated material within 200ppm；Described heating rate suggestion: 25
DEG C/h is warmed up to 600 DEG C from 500 DEG C, 30 DEG C/h to 750 DEG C, 750 DEG C of constant temperature 2 hours, then 40 DEG C/h was warmed up to 950 DEG C,
50 DEG C/h is warmed up to 1200 DEG C, and 55 DEG C/h is warmed up to 1500 DEG C, and 60 DEG C/h is warmed up to 1800 DEG C, and 70 DEG C/h is warmed up to 2000 DEG C,
75 DEG C/h is warmed up to 2200 DEG C, and 80 DEG C/h is warmed up to 2400 DEG C, 2400 DEG C insulation 1 hour after stop heating, Temperature fall is to room
Come out of the stove after temperature.
The preparation method of a kind of high-strength light carbon carbon composite heat-insulated material the most as claimed in claim 4, the step described in its feature
Rapid 4(2) in persursor material must choose, select the functional group containing carbon-carbon double bond as far as possible, be beneficial to cross-linking radiation
The formation of structure.
The preparation method of a kind of high-strength light carbon carbon composite heat-insulated material the most as claimed in claim 4, the step described in its feature
Rapid 4(4) in irradiation sample must be placed in polyethylene plastic packaging bag, prevent the infiltration of oxygen, simultaneously transmission in irradiation process
Irradiation ensures heat radiation in time, and irradiation dose also to be controlled well, controls crosslinking degree.
The preparation method of a kind of high-strength light carbon carbon composite heat-insulated material the most as claimed in claim 4, the step described in its feature
Rapid 4(7) in 30T press be the multi-daylight press of the transformation of the way；Pressing process is disposably to be pressed into required thickness (such as 50mm thickness carbon
Carbon composite heat-insulated material is that after being disposably pressed into 53mm, sintering shrinkage forms)；Once can suppress the 2000mm* of more than 3 pieces
The cured article of 2000mm*53mm.
The preparation method of a kind of high-strength light carbon carbon composite heat-insulated material the most as claimed in claim 4, the step described in its feature
Rapid 4(7) in intermediate products must be controlled with high density carbon carbon limited block, control the uniformity of product, the most favourable
Being heated evenly property in material.
The preparation method of a kind of high-strength light carbon carbon composite heat-insulated material the most as claimed in claim 4, the step described in its feature
Rapid 4(8) high-temperature process phenolic resin can be carried out carbonization and graphitization；Along with the rising phenolic aldehyde of temperature is progressively carbonized, logical
Crossing the coarse structure of carbon fiber surface, the phenolic aldehyde material with carbon element after carbonization can well couple with carbon fiber, finally exists
Graphitization at 2400 DEG C and make a kind of high-strength light carbon carbon composite heat-insulated material.
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| CN108690322A (en) * | 2018-06-14 | 2018-10-23 | 西北工业大学 | A kind of preparation method at carbon fiber interface |
| TWI701215B (en) * | 2019-05-21 | 2020-08-11 | 日商杰富意化學股份有限公司 | Method for manufacturing negative-electrode material for li-ion secondary cell |
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| CN113121242A (en) * | 2021-03-05 | 2021-07-16 | 中国科学院上海硅酸盐研究所 | Short carbon fiber toughened silicon carbide composite material and preparation method thereof |
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