CN113277868A - Light carbon fiber/carbon composite thermal field material and preparation method thereof - Google Patents
Light carbon fiber/carbon composite thermal field material and preparation method thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 71
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 63
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 58
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000003763 carbonization Methods 0.000 claims abstract description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005087 graphitization Methods 0.000 claims abstract description 19
- 238000006482 condensation reaction Methods 0.000 claims abstract description 14
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 claims description 48
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 32
- 239000003431 cross linking reagent Substances 0.000 claims description 22
- 238000005470 impregnation Methods 0.000 claims description 17
- -1 tripropylene glycol dipropylene ether ester Chemical class 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- NBZANZVJRKXVBH-GYDPHNCVSA-N alpha-Cryptoxanthin Natural products O[C@H]1CC(C)(C)C(/C=C/C(=C\C=C\C(=C/C=C/C=C(\C=C\C=C(/C=C/[C@H]2C(C)=CCCC2(C)C)\C)/C)\C)/C)=C(C)C1 NBZANZVJRKXVBH-GYDPHNCVSA-N 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 7
- 238000004321 preservation Methods 0.000 abstract description 3
- 238000005452 bending Methods 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 229920001568 phenolic resin Polymers 0.000 description 11
- 239000005011 phenolic resin Substances 0.000 description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010000 carbonizing Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- OTVQRGYKTKXMBM-UHFFFAOYSA-N 2-ethenylphenol formaldehyde Chemical compound C=O.C(=C)C1=C(C=CC=C1)O OTVQRGYKTKXMBM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
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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
- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C04B2235/6562—Heating rate
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Abstract
The invention provides a light carbon fiber/carbon composite thermal field material with small density, good heat preservation performance, high purity, high strength and simple and quick preparation process and a preparation method thereof, the invention creatively uses radiation to induce heat to initiate phenolic condensation reaction, uses radiation to crosslink ethylene compounds to form a vinyl crosslinking grafted carbon fiber network, then initiates phenolic condensation reaction to form a phenolic crosslinking network by the heat emitted in the radiation vinyl crosslinking reaction process, and prepares the light carbon fiber/carbon composite thermal field material by high-temperature carbonization and graphitization high-efficiency low energy consumption of multiple network cured products; the bending strength of the obtained light carbon fiber/carbon composite thermal field material is 3.0MPa, and the density is 0.14g/cm3The content of impurities can be controlled below 20 ppm.
Description
Technical Field
The invention relates to the technical field of carbon fiber/carbon composite heat insulation materials, in particular to a light carbon fiber/carbon composite thermal field material and a preparation method thereof.
Background
The light carbon fiber/carbon composite thermal field material has the characteristics of low density, good heat preservation performance, high purity, good mechanical performance, simple processing and forming and the like, so that the light carbon fiber/carbon composite thermal field material is widely applied to high-temperature thermal fields such as a polycrystalline silicon ingot furnace thermal field, a monocrystalline silicon straight-pull furnace thermal field, a semiconductor crystal growth furnace thermal field, a sapphire crystal growth furnace thermal field, an optical fiber stretching furnace thermal field and the like.
In the existing preparation method of the carbon fiber/carbon composite thermal field material, the basic preparation process comprises the following steps: the method comprises the following steps of carbon fiber soft felt surface treatment, phenolic resin impregnation, mould pressing, high-temperature carbonization and graphitization. The preparation method has the following problems: (1) in the surface treatment process, the bonding property of the carbon fiber and the phenolic resin is poor, so that the prepared carbon fiber/carbon interface bonding property is poor, and the mechanical property is poor; (2) in the impregnation process, solvents such as alcohol and the like are added to reduce the viscosity of the resin in the process of impregnating the carbon fiber soft felt with the phenolic resin, so that the carbon fiber soft felt and the phenolic resin are fully impregnated, the impregnation uniformity is improved, then the treatment is carried out in a drying mode, and the addition of the solvents can cause environmental pollution; (3) in the pressing process, the carbon fiber felt impregnated with the phenolic resin needs to be further pressed, cured and molded, the whole curing process takes more than 10 hours, the production efficiency is low, and meanwhile, a large amount of energy consumption is consumed for heating a press; (4) in the high-temperature carbonization and graphitization processes, the residual carbon content is low after conventional phenolic resin is carbonized, the mechanical property is low, the mechanical property caused by interface problems is poor, the solvent pollution problem caused by a high-viscosity solubilizer is solved, the problems of low efficiency and high energy consumption caused by long high-temperature pressing and pressing time and the problems of poor mechanical property caused by low residual carbon content are urgently needed to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the existing material and the preparation method and provide the light carbon fiber/carbon composite thermal field material which is small in density, good in heat preservation performance, high in purity and strength, simple and quick in preparation process.
The invention also aims to provide a method for preparing the light carbon fiber/carbon composite thermal field material with a novel resin structure and rapid curing and forming.
According to the invention, a vinyl crosslinking grafted carbon fiber network is formed by using an irradiation crosslinking ethylene compound, then a phenolic crosslinking network is formed by initiating a phenolic polycondensation reaction through heat released in the irradiation vinyl crosslinking reaction process, a multiple network cured product is quickly prepared into the light carbon fiber/carbon composite thermal field material through high-temperature carbonization and graphitization, and the obtained light carbon fiber/carbon composite thermal field material can reach or even exceed the index reached by a conventional preparation method.
The technical scheme adopted by the invention is as follows:
the light carbon fiber/carbon composite thermal field material comprises the following raw materials in parts by weight:
activated carbon fiber soft felt: 100 portions of
Vinyl phenol: 10-30 parts of
Formaldehyde: 4 to 12 portions of
Ammonia water: 0.4 to 1.2 portions of
Vinyl co-crosslinking agent: 1-3 parts of
The activated carbon fiber soft felt is prepared by carrying out air-laying and needle-punching felt forming on long carbon fibers treated by a vinyl silane coupling agent, wherein the ratio of Z-direction fibers to X-Y-direction fibers of the activated carbon fiber soft felt is 1: (50-150) the density is 500-700 g/cm2The thickness is 10 +/-1 mm; the length of the long carbon fiber is 10-15 cm.
The vinylphenol is preferably p-vinylphenol or o-vinylphenol.
Under the irradiation of an electron accelerator, vinyl phenol, a vinyl crosslinking agent and the activated carbon fiber soft felt are subjected to crosslinking, the distance between the vinyl phenol and the activated carbon fibers is shortened, heat is released, and then the condensation reaction of phenol and formaldehyde is further initiated.
The mass part of the vinylphenol is preferably 4 to 12 parts.
And carrying out condensation reaction on the formaldehyde and the vinylphenol to form a phenolic resin cross-linked network, so as to form the phenolic resin cross-linked network.
The mass concentration of the ammonia water is 10-100%.
The ammonia water initiates the condensation polymerization reaction of the vinylphenol and the formaldehyde under the action of irradiation crosslinking heat, and plays a role of an initiator.
The vinyl auxiliary crosslinking agent includes but is not limited to vinyl bond-containing monovinyl low molecular compound, divinyl crosslinking agent and polyvinyl crosslinking agent;
wherein, the monoethylene low molecular compound includes but is not limited to styrene, acrylate;
divinyl crosslinkers include, but are not limited to, tripropylene glycol dipropylene ether ester;
polyvinyl crosslinkers include, but are not limited to, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triallyl isocyanurate;
when the vinyl auxiliary crosslinking agent is an acrylic compound, the vinyl auxiliary crosslinking agent can play a role in promoting crosslinking, and can perform a co-crosslinking reaction with vinylphenol under the action of energy initiated by irradiation to form an irradiated vinyl crosslinking network. The irradiated vinyl crosslinked network further forms a cross network with the phenolic resin crosslinked network, so that the distance between benzene ring structures in the whole large crosslinked network is shortened, high carbon residue is formed in the high-temperature carbonization and graphitization processes, and the strength of the carbon fiber/carbon material is improved.
The invention also aims to provide a method for preparing the light carbon fiber/carbon composite thermal field material with high production efficiency, simple operation, high purity, small pollution and low energy consumption, namely high efficiency and low energy consumption.
A preparation method of a light carbon fiber/carbon composite thermal field material comprises the following steps:
(1) liquid-phase impregnation: directly spraying and impregnating the activated carbon fiber soft felt by using a resin system of vinyl phenol, a vinyl auxiliary crosslinking agent, formaldehyde and ammonia water;
(2) irradiation-initiated vinyl crosslinking: the method comprises the following steps of (1) rapidly initiating vinyl phenol and a vinyl auxiliary crosslinking agent to carry out vinyl crosslinking reaction through electron beam irradiation, and simultaneously carrying out crosslinking reaction on vinyl on part of the vinyl phenol and vinyl groups on carbon fibers to form a vinyl crosslinking network;
(3) reaction heat initiated phenolic condensation reaction: the vinyl crosslinking reaction heat promotes ammonia water to initiate phenolic aldehyde polycondensation crosslinking reaction of formaldehyde and a vinylphenol compound to form a phenolic aldehyde crosslinking network, and the vinyl crosslinking network and the phenolic aldehyde crosslinking network are crossed with each other to form a double-crosslinking cured product;
(4) carbonization and graphitization: and putting the cured product into a high-temperature furnace under the pressing of a graphite plate to directly carry out carbonization and graphitization reaction, and quickly preparing the light carbon fiber/carbon composite thermal field material.
Directly spraying liquid phase impregnation on the carbon fiber soft felt to ensure that the resin is fully contacted with the carbon fiber soft felt, and impregnating the carbon fiber by using a low-viscosity polymer precursor;
the invention does not need to add a diluting solvent, and the preparation process is more environment-friendly and pollution-free.
The whole preparation process does not need to add a metal catalyst, and the final product has high purity after carbonization.
In the electron beam irradiation process in the step (2), the irradiation voltage is 0.1-2MeV, and the current is 0.1-20 mA. The irradiation time is 1min-30 min.
The invention can rapidly crosslink vinyl groups to form a vinyl crosslinking network within five minutes, improves the efficiency, does not need high-temperature curing, reduces the energy consumption, and is one of the innovation points of the invention.
In addition, the vinyl phenol and formaldehyde with special structures are used for initiating a crosslinking reaction in a chain manner, so that the reaction efficiency is greatly improved.
The thermal initiation of the phenolic condensation reaction by irradiation is another aspect of the present invention.
In the step (4), the temperature in the carbonization process is 400-600 ℃.
Vacuumizing in the carbonization process.
In the step (4), the temperature of the graphitization process is 2000-2800 ℃. The heating rate is 50-200 ℃/h.
The material is fixed by using a mold in the phenolic condensation reaction and is formed by pressing.
The pressure in the pressing process is 5-20MPa, and the curing time is 3-6 h.
The light carbon fiber/carbon composite thermal field material (see the square plate and the circular plate of the light carbon fiber/carbon composite thermal field material in the attached figure 2 for details) has the following advantages:
(1) low density and high strength
The invention leads the vinyl phenolic resin to be subjected to double-network crosslinking and grafting actionThe cross-linking density is high, the vinyl phenolic resin is tightly combined with the carbon fiber, the intermolecular distance is small, the residual carbon is less, the finally carbonized and graphitized material has lower density and higher mechanical property, the material strength is high, and the operation and use are facilitated. The density of the material can be controlled between 0.14 and 0.20g/cm3The bending strength can reach 3.0 MPa.
(2) High purity
According to the invention, by selecting a novel resin system, combining a polymer precursor method and an irradiation crosslinking method, no metal catalyst is required to be added in the curing process of the vinyl phenol formaldehyde, the obtained material has high purity after carbonization and graphitization, and the impurity content can be controlled below 20 ppm.
(3) Environment-friendly
A small molecular compound system is used in the preparation process, so that the impregnation is easy, the problem that the conventional resin is high in viscosity and difficult to impregnate is solved, and meanwhile, the solvent pollution is avoided in the reaction process, so that the preparation method is very environment-friendly.
(4) High efficiency and low energy consumption
In the preparation process, the heat of the irradiation crosslinking polyethylene is used for initiating the phenolic condensation reaction, the heating and the curing are not needed, the energy consumption is low, in addition, the irradiation crosslinking initiation rate is high, and the vinyl crosslinking can be initiated within 5 minutes.
The light carbon fiber/carbon composite thermal field material obtained by the invention can be directly used in a high-temperature furnace protected by vacuum and inert gas, can be stably used at the temperature of 1000-2500 ℃, and is especially an essential heat insulation material for a polycrystalline silicon ingot furnace, a monocrystalline silicon straight-pull furnace thermal field, a semiconductor crystal growth furnace thermal field, a sapphire crystal growth furnace thermal field and an optical fiber stretching furnace thermal field.
Drawings
FIG. 1 is a schematic diagram showing an example of a method for preparing a lightweight carbon fiber/carbon composite thermal field material according to the present invention;
FIG. 2 is an example of a square plate and a circular plate of the lightweight carbon fiber/carbon composite thermal field material prepared by the present invention.
Detailed Description
The present invention will be described in further detail below by way of examples. However, the present invention is not limited to the following examples.
Example 1
The preparation method of the light carbon fiber/carbon composite thermal field material comprises the following steps:
(1) liquid-phase impregnation: preparing a novel resin system (10 parts of vinyl phenol, 1 part of styrene, 4 parts of formaldehyde and 0.4 part of ammonia water), and uniformly mixing and stirring for later use; and then compounding the carbon fiber soft felt with the cut carbon fiber soft felt by a spraying liquid phase impregnation method, wherein the final mass ratio of the spraying liquid to the carbon fiber is 15: 100, respectively;
(2) irradiation-initiated vinyl crosslinking: and flatly paving the soaked sample on a tray to perform irradiation to initiate vinyl crosslinking, and transmitting the irradiation back and forth, wherein the type and the working condition of the electron accelerator are GJ-2E-EB,2MeV and 10 mA. The irradiation time is 5 min.
(3) Reaction heat initiated phenolic condensation reaction: and (3) quickly putting the irradiated sample into a die for compression molding, wherein the compression pressure is 10MPa, the heating and curing are not needed for 5 hours, and the vinyl crosslinking network and the phenolic crosslinking network are crossed with each other to finally form a double-crosslinking cured product.
(4) Carbonization and graphitization: and (3) putting the cured product into a graphite mold, fixing, and then carbonizing and graphitizing at 400 ℃/3h +600 ℃/3h +800 ℃/1h +2400 ℃/2h, at a heating rate of 100 ℃/h and under a vacuum pressure of 10-8000 Pa. And (5) cooling to normal temperature by water, taking out, and weighing.
The final product has a flexural strength of 3.0MPa and a density of 0.14g/cm3The impurity content was 15 ppm.
Example 2
(1) Liquid-phase impregnation: preparing a novel resin system (20 parts of vinyl phenol, 2 parts of vinyl co-crosslinking agent tripropylene glycol dipropylene ether ester, 8 parts of formaldehyde and 0.8 part of ammonia water), and uniformly mixing and stirring for later use; and then compounding the carbon fiber soft felt with the cut carbon fiber soft felt by a spraying liquid phase impregnation method, wherein the final mass ratio of the spraying liquid to the carbon fiber is 30: 100, respectively;
(2) irradiation-initiated vinyl crosslinking: and flatly paving the soaked sample on a tray to perform irradiation to initiate vinyl crosslinking, and transmitting the irradiation back and forth, wherein the type and the working condition of the electron accelerator are GJ-2E-EB,2MeV and 10 mA. The irradiation time is 5 min.
(3) Reaction heat initiated phenolic condensation reaction: and (3) quickly putting the irradiated sample into a die for compression molding, wherein the compression pressure is 10MPa, the heating and curing are not needed for 5 hours, and the vinyl crosslinking network and the phenolic crosslinking network are crossed with each other to finally form a double-crosslinking cured product.
(4) Carbonization and graphitization: and (3) putting the cured product into a graphite mold, fixing, and then carbonizing and graphitizing, wherein the carbonization and graphitization system is 400 ℃/3h +600 ℃/3h +800 ℃/1h +2400 ℃/2h, the heating rate is 100 ℃/h, and the vacuum pressure is 10-8000 Pa. And (5) cooling to normal temperature by water, taking out, and weighing.
The final product has a flexural strength of 3.6MPa and a density of 0.16g/cm3The impurity content was 16 ppm.
Example 3
(1) Liquid-phase impregnation: preparing a novel resin system (30 parts of vinylphenol, 3 parts of vinyl auxiliary crosslinking agent triallyl isocyanurate, 12 parts of formaldehyde and 1.2 parts of ammonia water), and uniformly mixing and stirring for later use; and then compounding the carbon fiber soft felt with the cut carbon fiber soft felt by a spraying liquid phase impregnation method, wherein the final mass ratio of the spraying liquid to the carbon fiber is 45: 100, respectively;
(2) irradiation-initiated vinyl crosslinking: and flatly paving the soaked sample on a tray to perform irradiation to initiate vinyl crosslinking, and transmitting the irradiation back and forth, wherein the type and the working condition of the electron accelerator are GJ-2E-EB,2MeV and 10 mA. The irradiation time is 5 min.
(3) Reaction heat initiated phenolic condensation reaction: and (3) quickly putting the irradiated sample into a die for compression molding, wherein the compression pressure is 10MPa, the heating and curing are not needed for 5 hours, and the vinyl crosslinking network and the phenolic crosslinking network are crossed with each other to finally form a double-crosslinking cured product.
(4) Carbonization and graphitization: and (3) putting the cured product into a graphite mold, fixing, and then carbonizing and graphitizing, wherein the carbonization and graphitization system is 400 ℃/3h +600 ℃/3h +800 ℃/1h +2400 ℃/2h, the heating rate is 100 ℃/h, and the vacuum pressure is 10-8000 Pa. And (5) cooling to normal temperature by water, taking out, and weighing.
The final product has a flexural strength of 4.1MPa and a density of 0.18g/cm3The impurity content was 19 ppm.
Comparative example 1
(1) Liquid-phase impregnation: preparing a novel resin system (30 parts of vinylphenol, 3 parts of vinyl auxiliary crosslinking agent triallyl isocyanurate, 12 parts of formaldehyde and 1.2 parts of sodium hydroxide), and uniformly mixing and stirring for later use; and then compounding the carbon fiber soft felt with the cut carbon fiber soft felt by a spraying liquid phase impregnation method, wherein the final mass ratio of the spraying liquid to the carbon fiber is 45: 100, respectively;
(2) irradiation-initiated vinyl crosslinking: and flatly paving the soaked sample on a tray to perform irradiation to initiate vinyl crosslinking, and transmitting the irradiation back and forth, wherein the type and the working condition of the electron accelerator are GJ-2E-EB,2MeV and 10 mA. The irradiation time is 5 min.
(3) Reaction heat initiated phenolic condensation reaction: and (3) quickly putting the irradiated sample into a die for compression molding, wherein the compression pressure is 10MPa, the heating and curing are not needed for 5 hours, and the vinyl crosslinking network and the phenolic crosslinking network are crossed with each other to finally form a double-crosslinking cured product.
(4) Carbonization and graphitization: and (3) putting the cured product into a graphite mold, fixing, and then carbonizing and graphitizing, wherein the carbonization and graphitization system is 400 ℃/3h +600 ℃/3h +800 ℃/1h +2400 ℃/2h, the heating rate is 100 ℃/h, and the vacuum pressure is 10-8000 Pa. And (5) cooling to normal temperature by water, taking out, and weighing.
The final product has a flexural strength of 4.0MPa and a density of 0.185g/cm3The impurity content was 500 ppm. The impurity content of the finally prepared product seriously exceeds the standard.
Comparative example 2
(1) Liquid-phase impregnation: preparing a novel resin system (30 parts of phenol, 3 parts of vinyl auxiliary crosslinking agent triallyl isocyanurate, 12 parts of formaldehyde and 1.2 parts of ammonia water), and uniformly mixing and stirring for later use; and then compounding the carbon fiber soft felt with the cut carbon fiber soft felt by a spraying liquid phase impregnation method, wherein the final mass ratio of the spraying liquid to the carbon fiber is 45: 100, respectively;
(2) irradiation-initiated vinyl crosslinking: and flatly paving the soaked sample on a tray to perform irradiation to initiate vinyl crosslinking, and transmitting the irradiation back and forth, wherein the type and the working condition of the electron accelerator are GJ-2E-EB,2MeV and 10 mA. The irradiation time is 5 min.
Until now, the liquid resin system could not be crosslinked under irradiation condition, the resin could not be cured, the solid material could not be prepared, and the sample preparation failed.
Claims (10)
1. The light carbon fiber/carbon composite thermal field material is characterized in that the raw materials for preparing the material comprise the following components in parts by mass:
activated carbon fiber soft felt: 100 portions of
Vinyl phenol: 10-30 parts of
Formaldehyde: 4 to 12 portions of
Ammonia water: 0.4 to 1.2 portions of
Vinyl co-crosslinking agent: 1-3 parts.
2. The lightweight carbon fiber/carbon composite thermal field material as claimed in claim 1, wherein the soft activated carbon fiber felt is a soft carbon fiber felt treated with a vinyl silane coupling agent, the soft activated carbon fiber felt is prepared by subjecting long carbon fibers treated with a vinyl silane coupling agent to an air-laying and needle-punching felt forming process, and the ratio of Z-direction fibers to X-Y in-plane fibers of the soft activated carbon fiber felt is 1: (50-150) the density is 500-700 g/cm2The thickness is 10 +/-1 mm; the length of the long carbon fiber is 10-15 cm.
3. The lightweight carbon fiber/carbon composite thermal field material according to claim 1 or 2, wherein the vinylphenol is p-vinylphenol or o-vinylphenol.
4. The light carbon fiber/carbon composite thermal field material as claimed in claim 1, wherein under the irradiation of an electron accelerator, vinyl phenol is subjected to a crosslinking reaction with a vinyl crosslinking agent and the activated carbon fiber soft felt.
5. The lightweight carbon fiber/carbon composite thermal field material as claimed in claim 1, wherein the mass concentration of the ammonia water is 10-100%.
6. The light carbon fiber/carbon composite thermal field material according to claim 1, wherein the vinyl auxiliary crosslinking agent is a vinyl bond-containing mono-ethylene low molecular compound, a divinyl crosslinking agent, or a polyvinyl crosslinking agent; the monoethylene low molecular compound is selected from styrene and/or acrylate, the divinyl cross-linking agent is selected from tripropylene glycol dipropylene ether ester, and the polyvinyl cross-linking agent is selected from one or more of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate or triallyl isocyanurate.
7. The method of producing a lightweight carbon fiber/carbon composite thermal field material as claimed in any one of claims 1 to 6, characterized in that the method comprises the steps of:
(1) liquid-phase impregnation: directly spraying and impregnating the activated carbon fiber soft felt with vinyl phenol, a vinyl auxiliary crosslinking agent, formaldehyde and ammonia water;
(2) irradiation-initiated vinyl crosslinking: the method comprises the following steps of (1) rapidly initiating vinyl phenol and a vinyl auxiliary crosslinking agent to carry out vinyl crosslinking reaction through electron beam irradiation, and simultaneously carrying out crosslinking reaction on vinyl on part of the vinyl phenol and vinyl groups on carbon fibers to form a vinyl crosslinking network;
(3) reaction heat initiated phenolic condensation reaction: the vinyl crosslinking reaction heat promotes ammonia water to initiate phenolic aldehyde polycondensation crosslinking reaction of formaldehyde and a vinylphenol compound to form a phenolic aldehyde crosslinking network, and the vinyl crosslinking network and the phenolic aldehyde crosslinking network are crossed with each other to form a double-crosslinking cured product;
(4) carbonization and graphitization: and putting the cured product into a high-temperature furnace under the pressing of a graphite plate to directly carry out carbonization and graphitization reaction, and quickly preparing the light carbon fiber/carbon composite thermal field material.
8. The method for preparing a lightweight carbon fiber/carbon composite thermal field material as claimed in claim 7, wherein the material is fixed by using a mold in the phenolic condensation reaction and is formed by pressing.
9. The method for preparing a lightweight carbon fiber/carbon composite thermal field material according to claim 7 or 8, wherein the pressure during pressing is 5-20MPa and the curing time is 3-6 h.
10. The method for preparing a carbon fiber/carbon composite thermal field material as claimed in claim 7 or 8, wherein the temperature during the carbonization is 400-600 ℃, the vacuum is applied during the carbonization, the temperature during the graphitization is 2000-2800 ℃, and the temperature rise rate is 50-200 ℃/h.
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