CN116444299B - Gradient heat-proof and insulation integrated material and preparation method thereof - Google Patents
Gradient heat-proof and insulation integrated material and preparation method thereof Download PDFInfo
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- CN116444299B CN116444299B CN202310731402.8A CN202310731402A CN116444299B CN 116444299 B CN116444299 B CN 116444299B CN 202310731402 A CN202310731402 A CN 202310731402A CN 116444299 B CN116444299 B CN 116444299B
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- heat
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- phenolic resin
- proof
- pica
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- 239000000463 material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000009413 insulation Methods 0.000 title description 23
- 239000002131 composite material Substances 0.000 claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- 230000004888 barrier function Effects 0.000 claims abstract description 29
- 230000007704 transition Effects 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims description 98
- 239000010410 layer Substances 0.000 claims description 87
- 229920001568 phenolic resin Polymers 0.000 claims description 72
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 71
- 239000005011 phenolic resin Substances 0.000 claims description 71
- 239000000243 solution Substances 0.000 claims description 67
- 239000002002 slurry Substances 0.000 claims description 60
- 229920001169 thermoplastic Polymers 0.000 claims description 60
- 239000004416 thermosoftening plastic Substances 0.000 claims description 60
- 238000005245 sintering Methods 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 34
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- 238000000498 ball milling Methods 0.000 claims description 25
- ADHFMENDOUEJRK-UHFFFAOYSA-N 9-[(4-fluorophenyl)methyl]-n-hydroxypyrido[3,4-b]indole-3-carboxamide Chemical compound C1=NC(C(=O)NO)=CC(C2=CC=CC=C22)=C1N2CC1=CC=C(F)C=C1 ADHFMENDOUEJRK-UHFFFAOYSA-N 0.000 claims description 24
- 241001482237 Pica Species 0.000 claims description 24
- 239000011863 silicon-based powder Substances 0.000 claims description 22
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
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- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
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- 229910016006 MoSi Inorganic materials 0.000 claims description 4
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 3
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- 239000007791 liquid phase Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
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- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910006501 ZrSiO Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005524 ceramic coating Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 230000002051 biphasic effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
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- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 230000035882 stress Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- 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
- C04B35/524—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 obtained from polymer precursors, e.g. glass-like carbon material
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- Ceramic Products (AREA)
Abstract
The invention discloses a gradient heat-proof and heat-insulating integrated material and a preparation method thereof, wherein a porous C-PICA composite material is used as a heat-insulating layer structural material matrix, and a nano porous structure can effectively limit gaseous and solid heat transfer to achieve a heat-insulating effect; the carbon barrier layer plays a role in protecting the matrix material from being corroded by liquid melt and reducing fiber damage; the SiC transition layer can reduce the thermal stress between the substrate and the coating and improve the problem of interface compatibility; the ZrC-SiC heat-resistant layer prevents further erosion of heat flow, improves the application temperature of the material, and can exert the synergistic effect of all the components. The heat-proof and heat-insulating integrated material has the characteristics of high temperature resistance, light weight, excellent heat insulating capability and the like, is low in cost, simple in preparation process, has good artificial controllability and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of preparation of heat-proof and heat-proof integrated materials, and particularly relates to a gradient heat-proof and heat-proof integrated material and a preparation method thereof.
Background
In recent years, with the development of aerospace industry, the flying speed of a high-speed aerospace vehicle in the atmosphere is continuously increased, the flying time is continuously prolonged, the pneumatic heat transfer on the surface of a fuselage is rapidly increased, the external temperature of the vehicle is increased, the heat is continuously transferred to an internal area with lower temperature, and the damage to precise instruments in a cabin is easily caused. Under such conditions, the choice of thermal protection material is particularly important in order to ensure proper operation of the electronic components within the aircraft.
Low density ablative thermal protective materials are of interest because of their light weight, low thermal conductivity, heat protection and thermal insulation. PICA composite material is typical representative of the material, PICA is a low-density carbon/phenolic heat-proof and insulating functional material formed by impregnating and filling carbon fiber preform with porous phenolic resin, the porous resin in the ablation environment weakens solid and gaseous heat conduction to keep the material low in heat conductivity, and simultaneously, the resin is carbonized to absorb heat to form a carbonized layer, so that further erosion and ablation of heat flow are prevented. However, PICA composite materials are easily oxidized in high-temperature and long-time aerobic environments, so that the heat protection efficiency of the materials is reduced, and the application of the PICA composite materials is greatly limited.
The coating technology can effectively realize the isolation of the matrix from the external aerobic environment, is a mature and simple technology, and can protect the matrix for a long time in the high-temperature aerobic environment. In various superhigh temperature ceramic coating systems, zrC has melting point as high as 3540 ℃ and oxidation product ZrO 2 Has a low oxygen diffusion coefficient and low thermal conductivity at high temperatures; siC with lower thermal expansion coefficient is introduced as a second phase, and a glass phase SiO is formed at high temperature 2 Can be combined with ZrO 2 Forming a composite oxide film, zrO 2 Forming a framework structure to realize the stability of the oxide layer structure in a high-temperature environment, and SiO 2 Then distributed in ZrO 2 The skeleton plays a role in healing hole cracks, so that the penetration of oxygen is effectively limited, and gas scouring is resisted.
At present, the methods for preparing the ceramic coating at home and abroad mainly comprise a chemical vapor deposition method, a plasma spraying method, an embedding method, a slurry method and the like. Document one "X YANG, Q-Z HUANG, X CHANG, et al Preparation of ZrC-SiC Multi-coating on Graphite with ZrSiO 4 Powder via Pack Cementation [J]JOURNAL OF INORGANIC MATERIALS, 2009, 25:41-46' zircon sand (ZrSiO) 4 ) The ZrC-SiC composite coating is prepared on the surface of the graphite by an embedding method, and the composite coating mainly comprises an SiC enriched inner layer and a ZrC outer layer, and the coating is tightly combined with a matrix. However, the carbon fiber in the PICA composite material is not protected by an interface layer, so that the carbon fiber is easy to react with a metal melt to cause fiber damage, and the liquid melt has large penetration depth due to the capillary force of the nano holes, even penetrates through the whole material, so that the formed ceramic layer is cracked. Document two, "T FENG, M TONG, S YAO, et al A New Assistant Method for Characterizing Ablation Resistance of ZrC-SiC Dispersive Biphasic Coating on C/C Composites [J]Coatings, 2019, 9:735, "ZrCl employed 4 -CH 4 -Si-H 2 The ZrC-SiC dual-phase coating is prepared by the Ar system on the surface of the C/C composite material by a one-step chemical vapor deposition method, and ZrC and SiC phases are uniformly dispersed. However, the mesoporous pore diameter of the PICA composite material is easy to block the diffusion of large-diameter molecules of the gas reactant, and the coating cracks due to larger residual thermal stress. The plasma spraying method has high equipment requirements and high price, and can not obtain uniform coating on the surface of a large-sized special-shaped piece. In contrast, the slurry brushing and infiltration method has the advantages of simple process, simple and convenient operation, low equipment requirement and the like, and the thickness of the coating has better artificial controllability, and is simultaneously suitable for industrial production of the surface coating of the large-scale complex component.
Disclosure of Invention
Aiming at the problems that the traditional thermal protection material in the prior art has low thermal protection and insulation efficiency, high density and high cost and is difficult to service in an ultra-high temperature and ultra-high speed pneumatic environment, the first aim of the invention is to provide a preparation method of a high temperature resistant gradient thermal protection and insulation integrated material.
The second aim of the invention is to provide the gradient heat-proof and heat-insulating integrated material prepared by the preparation method.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention relates to a preparation method of a gradient heat-proof and heat-insulating integrated material, which comprises the steps of brushing slurry A containing thermoplastic phenolic resin and graphite powder on the surface of a porous C-PICA composite material, carrying out primary sintering treatment, forming a carbon barrier layer on the surface of the porous C-PICA composite material, brushing slurry B containing thermoplastic phenolic resin, si powder and SiC fine powder on the surface of the porous C-PICA composite material, carrying out secondary sintering treatment, forming a SiC transition layer on the surface of the porous C-PICA composite material, and finally, carrying out secondary sintering treatment on the slurry B containing thermoplastic phenolic resin and ZrSi powder 2 And (3) brushing slurry C of the powder on the surface of the porous C-PICA composite material, performing third sintering treatment, and forming a ZrC-SiC heat-proof layer on the surface of the porous C-PICA composite material to obtain the gradient heat-proof and heat-proof integrated material.
According to the preparation method provided by the invention, the porous C-PICA composite material is used as the heat insulation layer structure material, the slurry A containing the thermoplastic phenolic resin and the graphite powder is firstly adopted to brush on the surface of the porous C-PICA composite material, and the carbon barrier layer is formed on the surface of the porous C-PICA composite material through the first sintering; the carbon barrier layer can solve the problem of liquid phase depth penetration caused by matrix capillary force in the subsequent coating preparation process, avoid the reduction of pores, and simultaneously prevent the damage to carbon fibers without interface layer protection, thereby playing a role of barrier. Then on the basis of the carbon barrier layer, the SiC transition layer is manufactured, the ZrC-SiC heat-proof layers are tightly combined, no obvious interface exists, and the gradient heat-proof and heat-proof integrated material finally has excellent ablation resistance and heat-proof performance.
In the invention, the thermoplastic phenolic resin is obtained by acid catalysis of phenol-formaldehyde, and a certain amount of curing agent and catalyst are added into the thermoplastic phenolic resin, so that the thermoplastic phenolic resin has the characteristics of porosity, high specific surface area, excellent thermal stability and the like, and the density is as low as 0.1-0.3 g/cm 3 The thermal conductivity is as low as 0.03W/(m.K).
In a preferred scheme, the preparation method of the porous C-PICA composite material comprises the following steps: injecting the thermoplastic phenolic resin solution D into a mold filled with a carbon fiber needled felt, performing a curing reaction to obtain a PICA composite material, and carbonizing the PICA composite material in a non-oxidizing atmosphere to obtain the porous C-PICA composite material.
Further preferably, in the thermoplastic phenolic resin solution D, the mass fraction of the thermoplastic phenolic resin is 30-80%.
In the present invention, the thermoplastic phenolic resin solution is obtained by dissolving a thermoplastic phenolic resin in at least one of absolute ethyl alcohol, isopropyl alcohol and xylene.
Further preferably, a combination ofThe apparent density of the carbon fiber needled felt is 0.15-0.65 g/cm 3 。
Further preferably, the temperature of the curing reaction is 100-300 ℃, and the time of the curing reaction is 12-48 h.
In the actual operation process, after the curing reaction is finished, the PICA composite material is put into an oven at 80 ℃ to be dried for 24-48 hours under normal pressure, and the PICA composite material is obtained.
Further preferably, the non-oxidizing atmosphere is a vacuum atmosphere or an argon atmosphere.
Further preferably, the carbonization treatment comprises the following steps: firstly, heating to 300-600 ℃ at a heating rate of 1-2 ℃/min, preserving heat for 0.5-2 h, and then heating to 800-1400 ℃ at a heating rate of 2-6 ℃/min, preserving heat for 1-3 h.
In the carbonization treatment process, the temperature is slowly raised to 300-600 ℃ for heat preservation, and the inventor discovers that in the temperature section, the benzene ring structure of the phenolic resin is broken to a certain extent, small molecular gas products such as hydrogen, carbon dioxide and the like are formed through dehydration condensation of the benzene ring, and the samples have larger phenomena of weightlessness and volume shrinkage. If the temperature rise rate is too high, a large amount of gas cannot be discharged in a short time, and air pressure is easily formed in the sample, so that many holes and cracks are generated.
In the actual operation process, after the carbonization treatment and heat preservation are completed, cooling to room temperature, taking out, ultrasonically cleaning for 0.5-2 h, and placing in a baking oven at 120 ℃ for drying for 2h to obtain the porous C-PICA composite material.
Preferably, the density of the porous C-PICA composite is 0.45g/cm 3 ~0.9 g/cm 3 The porosity is 50% -65%.
In the preferred scheme, slurry A containing thermoplastic phenolic resin and graphite powder is brushed on the surface of a porous C-PICA composite material, dried at 80-120 ℃, brushed and dried for 2-6 times repeatedly, and subjected to primary sintering treatment.
In the preferred scheme, in the slurry A, the mass fraction of the graphite powder is 5-20wt%. The mass fraction of the graphite powder in the slurry A is controlled within the range, the performance of the finally obtained gradient heat-proof and heat-insulating integrated material is optimal, and if the addition amount of the graphite powder is excessive, the overall chemical reaction activity of the carbon barrier layer is reduced, so that the formation of good chemical reaction at the subsequent coating interface is not facilitated; the addition amount of graphite powder is too small, and cracks and holes generated by partial volume shrinkage of the resin cannot be filled, so that the density of the carbon barrier layer is reduced, and the barrier effect is reduced.
In the preferred scheme, in the slurry A, the particle size of graphite powder is 1-5 mu m, and the purity is more than or equal to 99.5%.
In the invention, the particle size of the graphite powder is controlled in the range, and finally, the performance of all materials is optimal, if the particle size of the graphite powder is too small, the phenomena of agglomeration and uneven distribution of powder easily occur in a coating part area, and the graphite powder even enters a deeper position in a matrix to cause the blockage of original pores in the matrix; the graphite powder particles have overlarge diameters, cannot enter the pores of the surface layer of the material, and the pinning effect between the coating and the matrix is weakened.
In a preferred scheme, the preparation process of the slurry A comprises the following steps: and dissolving the thermoplastic phenolic resin in an organic solvent, adding graphite powder, and stirring for 2-4 hours to obtain the phenolic resin.
Further preferably, the organic solvent is at least one selected from the group consisting of absolute ethanol, isopropyl alcohol, and xylene.
Further preferably, in the slurry a, the mass ratio of the thermoplastic phenolic resin to the organic solvent is 1 to 6:1.
in a preferred scheme, the first sintering treatment is performed in a non-oxidizing atmosphere, and the first sintering treatment is performed by heating to 900-1200 ℃ at a heating rate of 3-5 ℃/min and preserving heat for 1-3 hours.
In a preferred embodiment, the thickness of the carbon barrier layer is 80-300 μm. Through controlling the number of times of brushing, the thickness of the carbon barrier layer is in the range of 80-300 mu m, and finally, the performance of all materials is optimal, if the thickness of the carbon barrier layer is too thin, the effect of complete barrier cannot be achieved, fibers are easy to directly contact with follow-up powder materials, fiber corrosion is caused, the mechanical properties of the materials are affected to a certain extent, if the thickness of the carbon barrier layer is too thick, the interfacial shear stress is increased, and meanwhile, the carbon barrier layer is easy to crack or fall due to the discharge of a large number of small molecular substances in the coating.
Preferred embodiments, provided thatThe slurry B comprises the following components in parts by weight: 10-40 parts of SiC fine powder, 20-60 parts of Si powder, 5-15 parts of thermoplastic phenolic resin solution E, 3-10 parts of C powder and SiO 2 4-20 parts of powder, al 2 O 3 4-20 parts of powder, wherein the mass ratio of Si powder to SiC fine powder is 1.5-3.5: 1, in the thermoplastic phenolic resin solution E, the mass fraction of the thermoplastic phenolic resin is 15-65%.
According to the slurry B, siC powder and Si powder are used as main components of the slurry B, and the mass ratio of the Si powder to the SiC powder is controlled to be 1.5-3.5: 1, thereby forming more SiC nanowires in the sintering process, obviously toughening the subsequently prepared ultra-high temperature coating, and in addition, siO is doped in the slurry B 2 、Al 2 O 3 Can reduce the sintering temperature of SiC, promote the densification of the coating, and in addition, part of SiO 2 Can be combined with Al 2 O 3 Mullite (3 Al) 2 O 3 2SiO 2 ) Mullite has a similar coefficient of thermal expansion as SiC, and also enhances the mechanical strength and thermal shock resistance of SiC.
If the mass ratio of the Si powder to the SiC fine powder is less than 1.5, more SiC nanowires cannot be generated in the coating, and the coating has no obvious toughening effect on the subsequently prepared ultra-high temperature coating; if the mass ratio of Si powder to SiC fine powder is more than 3.5, a large amount of residues generated by the volume expansion of the reaction of the carbon and the ceramic exist on the surface of the coating due to the special structure of the porous carbon.
Further preferably, the purity of the SiC fine powder is more than or equal to 99%, and the particle size is 0.1-1 mu m; the Si powder, the C powder and the SiO 2 Powder, al 2 O 3 The purity of the powder is more than or equal to 99.5%, the granularity of Si powder and C powder is less than or equal to 325 meshes, and SiO 2 Powder, al 2 O 3 The granularity of the powder is less than or equal to 1200 meshes.
Further preferably, the SiC fine powder is surface-modified with a silane coupling agent. The inventor finds that the SiC fine powder surface-modified by the silane coupling agent can further improve the dispersibility of the slurry B, increase the solid content, avoid the generation of larger agglomerates and improve the sintering activity of the slurry B.
Further preferably, the method for obtaining the slurry B comprises the following steps: according to the design proportion, firstly preparing SiC fine powder, si powder, thermoplastic phenolic resin solution E, C powder and SiO 2 Powder, al 2 O 3 Placing SiC fine powder into a solution containing a silane coupling agent, performing ultrasonic vibration at 60-80 ℃ for 10-60 min, performing ball milling and mixing for 12-24 h to obtain a modified SiC fine powder solution, and then adding Si powder, thermoplastic phenolic resin solution E, C powder and SiO 2 Powder, al 2 O 3 And adding the powder into the modified SiC fine powder solution, ball milling to obtain ball milling slurry, and uniformly mixing the ball milling slurry and PVB solution for 12-24 hours to obtain slurry B.
Still more preferably, in the solution containing the silane coupling agent, the mass fraction of the silane coupling agent is 2% -4%.
Still more preferably, in the solution containing the silane coupling agent, the silane coupling agent is KH-550 (gamma-aminopropyl triethoxysilane)
Still more preferably, in the solution containing the silane coupling agent, the solvent is composed of absolute ethyl alcohol and deionized water, wherein the mass ratio of the absolute ethyl alcohol to the deionized water is 75-90:10-25. The inventors found that KH-550 can be sufficiently dissolved by using an aqueous ethanol solution.
The SiC fine powder is modified by adopting the silane coupling agent, the alkoxy groups can fully react with-OH groups on the surface of the SiC powder to be coated on the SiC powder, and the action energy among the particles is greatly weakened by combining ultrasonic vibration, so that agglomeration among the particles can be effectively prevented, and the dispersibility of the SiC powder is improved.
Still further preferably, the powder-liquid mass ratio of the SiC fine powder to the solution containing the silane coupling agent is 1: 1-4.
Still more preferably, the mass ratio of the ball milling slurry to the PVB solution is 1-4: 1, wherein in the PVB solution, the mass ratio of PVB to solvent is 1: 30-45, wherein the solvent is absolute ethyl alcohol.
In the actual operation process, after the PVB powder is added into absolute ethyl alcohol, the PVB powder is heated to 40 ℃ by a constant-temperature magnetic stirrer and stirred for 4-8 hours, and then PVB solution is obtained.
In the preferred scheme, slurry B containing thermoplastic phenolic resin, si powder and SiC fine powder is brushed on the surface of the porous C-PICA composite material, dried, brushed and dried for 2-4 times repeatedly, and then the second sintering treatment is carried out.
Preferably, the second sintering treatment comprises the following steps: heating to 300-400 ℃ at a heating rate of 2-3 ℃/min under vacuum conditions, preserving heat for 0.5-1.5 h, then introducing protective atmosphere to normal pressure, heating to 1400-1800 ℃ at a heating rate of 4-8 ℃/min, and sintering to 1-5 h.
By sintering the procedures, the finally obtained coating is the most compact and flat.
In a preferred scheme, the thickness of the SiC transition layer is 100-400 mu m.
In a preferred scheme, the preparation process of the slurry C comprises the following steps: zrSi is made of 2 Powder, thermoplastic phenolic resin F and C powder according to the mass ratio of 15-40: 3-10: 1, mixing to obtain a mixed solution, adding a permeation assisting agent, a sintering assisting agent and a defoaming agent into the mixed solution, and performing ball milling and mixing for 12-24 hours to obtain the thermoplastic phenolic resin F, wherein the mass fraction of the thermoplastic phenolic resin F is 20-60%.
Further preferably, the ZrSi 2 The purity of the powder is more than or equal to 99 percent, and the granularity is less than or equal to 300 meshes. The purity of the C powder is more than or equal to 99.5 percent, and the granularity is less than or equal to 1500 meshes.
Further preferably, the permeation assisting agent is selected from one or more of Ti, B, siC, zrC powder, and the adding amount of the permeation assisting agent is 3-5% of the mass of the mixed solution.
Further preferably, the burn aid is selected from Al 2 O 3 、Y 2 O 3 、MoSi 2 、TaSi 2 One or more of the powders, wherein the addition amount of the permeation assisting agent is 5-10% of the mass of the mixed solution.
Further preferably, the defoaming agent is one or more of n-octanol, polyurethane and silicone oil, and the adding amount of the defoaming agent is 0.1-1% of the mass of the mixed solution.
Slurry C in the invention is ZrSi 2 ZrSi as a raw material for ZrC coating 2 The melting point of the alloy is 1620 ℃ which is lower than the melting point 1850 ℃ of pure metal Zr, the ZrC coating can be prepared at relatively reduced temperature,during sintering, the coating powder material is prepared from Al 2 O 3 、Y 2 O 3 、MoSi 2 、TaSi 2 More liquid phases can be generated to promote sintering under the action of the sintering aid, and a relatively compact coating is finally obtained through particle rearrangement and material transmission; part of coating powder material permeates into the SiC coating and the carbon coating under the action of the permeation promoter and reacts with residual carbon sources in the coating to form a ceramic phase, so that the bonding strength of the coating is greatly improved; by utilizing the defoaming and foam inhibiting capabilities of the defoaming agent, the generation of bubbles in the slurry mixing process can be limited under low concentration, and the defect of insufficient compactness of the coating prepared by brushing the traditional slurry is overcome.
Preferably, the thermoplastic phenolic resin and ZrSi are contained 2 And (3) brushing the slurry C of the powder on the surface of the porous C-PICA composite material, drying, and repeating brushing and drying for 4-8 times, and performing third sintering treatment.
In a preferred scheme, the third sintering treatment is performed under a protective atmosphere, wherein the third sintering treatment is performed by heating to 1600-2000 ℃ at a heating rate of 7-15 ℃/min, preserving heat for 1-2 hours, cooling to 1000-1200 ℃ at a temperature of 5-8 ℃/min, and cooling with a furnace. After the third sintering is finished, the temperature is reduced to 1000-1200 ℃ at a slower cooling speed, so that the thermal stress accumulated in the coating is fully and properly applied, the cracking and falling of the coating are avoided, and a complete and compact coating can be obtained.
In a preferred scheme, the thickness of the ZrC-SiC heat-resistant layer is 50-200 mu m.
In the preferred scheme, the composite material obtained after the ZrC-SiC heat-proof layer is formed on the surface of the porous C-PICA composite material is placed in impregnating solution, the gradient heat-proof and heat-proof integrated composite material is obtained through impregnating and curing reaction, and the impregnating solution consists of thermoplastic phenolic resin solution G and curing agent. The inventor finds that the heat insulation performance of the gradient heat insulation integrated composite material is seriously reduced due to the change of the crystallite size and the contact area between particles of the matrix after coating, and therefore, the integral heat insulation performance of the composite material can be further improved by dipping the thermoplastic phenolic resin solution again to fill cracks and holes generated by carbonization in the matrix.
In the invention, the coating is arranged on a single surface of the porous C-PICA composite material, impregnating liquid is easier to enter cracks and holes of the material in the impregnation process, the influence on the coating surface is not very large, and the coating surface is not required to be impregnated.
Further preferably, in the thermoplastic phenolic resin solution G, the mass fraction of the thermoplastic phenolic resin is 30 to 80%.
Further preferably, the curing agent is HMTA (hexamethylenetetramine), and the adding amount of the curing agent is 1-5% of the mass of the thermoplastic phenolic resin solution G.
Further preferably, the impregnation is pressure impregnation, the pressure of the pressure impregnation is 2.5-5.5 MPa, and the time of the pressure impregnation is 0.5-2 h. The adoption of pressurized impregnation can enable the impregnating solution to be immersed into the material to fill the defects more quickly, thereby being beneficial to improving the preparation efficiency.
Further preferably, the temperature of the curing reaction is 150-250 ℃, and the time of the curing reaction is 18-36 h.
The invention also provides the gradient heat-proof and heat-insulating integrated material prepared by the preparation method.
The gradient heat-proof and heat-proof integrated material is composed of a heat-proof layer structure material and a composite coating layer arranged on the heat-proof layer structure material, wherein the heat-proof layer structure material is a porous C-PICA composite material, and the composite coating layer is composed of a carbon barrier layer, a SiC transition layer and a ZrC-SiC heat-proof layer.
Principle and advantages
According to the preparation method provided by the invention, the porous C-PICA composite material is used as the heat insulation layer structure material, the slurry A containing the thermoplastic phenolic resin and the graphite powder is firstly brushed on the surface of the porous C-PICA composite material, and the carbon barrier layer is formed on the surface of the porous C-PICA composite material through first sintering, the graphite powder in the carbon barrier layer can fill defects generated by shrinkage of the resin, and the filling of the slurry only exists on the surface of the porous matrix, so that the original pore structure of the heat insulation layer is not influenced, the carbon barrier layer can protect the matrix material from corrosion, and the original mechanical property of the material is maintained. In the preparation of the SiC transition layer, modified powder and SiO 2 、Al 2 O 3 The introduction of the SiC coating can improve the compactness of the SiC coating, improve the performance of the SiC coating, fully exert the function of a transition layer of the SiC coating and reduce the thermal stress between the coatings. ZrSi in ZrC-SiC heat protection layer 2 The melting point is low, and the finally prepared coating is relatively smooth by combining the sintering aid, the permeation aid and the defoaming agent, so that the ZrC-SiC heat-resistant layer prevents heat flow from further erosion, and the application temperature of the material is increased. Finally, the phenolic resin solution is soaked under pressure, so that the heat insulation performance of the heat insulation integrated material, which is lost due to the too high carbonization temperature, is compensated.
The gradient heat-proof and heat-insulating integrated material adopts the porous C-PICA composite material as a heat-insulating layer structure material matrix, and the nano porous structure can effectively limit gaseous and solid heat transfer, so that the heat-insulating effect is achieved; the carbon barrier layer plays a role in protecting the matrix material from being corroded by liquid melt and reducing fiber damage; the SiC transition layer can reduce the thermal stress between the substrate and the coating and improve the problem of interface compatibility; the ZrC-SiC heat-resistant layer prevents further erosion of heat flow and improves the application temperature of the material.
Compared with the prior art, the invention has the advantages and positive effects that:
(1) The invention provides a high-temperature-gradient heat-proof and insulation integrated material. The nano porous structure of the thermal insulation layer PICA-based composite material can limit gas heat transfer, and has excellent thermal insulation performance; the carbon barrier layer, the SiC transition layer and the ZrC-SiC heat-proof layer can play a synergistic effect of all the components, and the heat-proof efficiency of the PICA-based composite material is remarkably improved. The application temperature of the high-temperature-resistant gradient heat-proof integrated material can reach more than 1800 ℃, and the material has wide application prospect in key areas such as a manned aircraft return cabin, a strategic missile warhead, a propulsion system of an ultra-high speed aircraft and the like.
(2) The carbon coating slurry can be greatly infiltrated into the carbonized porous PICA composite material, so that the effective filling of the surface of a porous substrate is realized, and the interface bonding strength between a substrate and a coating is greatly improved; the carbon coating can solve the problem of liquid phase depth penetration caused by matrix capillary force in the subsequent coating preparation process, prevents damage to carbon fibers without interface layer protection, and plays a role in blocking.
(3) The SiC transition layer can reduce the thermal stress between the substrate and the coating, and improve the compatibility problem between the ZrC-SiC coating and the substrate; the modified SiC powder in the SiC slurry does not generate obvious agglomerates in the subsequent high-temperature sintering, and meanwhile, the Si powder and the carbon coating on the surface of the matrix react more sufficiently, so that the prepared SiC coating is more compact and smoother and has more excellent oxidation resistance.
(4) The ZrC-SiC heat-resistant layer can provide long-time high-temperature oxidation protection for the PICA-based composite material, the coating powder material permeates into the direction of the matrix under the action of the permeation assisting agent in the sintering process, reacts with a carbon source between the transition layer and the carbon layer and fills the pores of the original coating, so that the bonding strength between the coating is greatly improved, meanwhile, the sintering assisting agent and the defoaming agent further promote densification of the coating, the bonding between the layers is tight, no obvious interface exists, and the problems of chemical and mechanical compatibility are effectively solved.
(5) The slurry brushing and infiltration method adopted by the invention has the advantages of simple process, convenient operation and applicability to the surface of large-size special-shaped components. By regulating and controlling parameters such as carbonization and brushing processes, sintering temperature, heat preservation time and the like, the thickness and the components of the coating can be flexibly controlled. In addition, the invention can prepare the coating on one or more surfaces of the PICA-based composite material, so that the material can further impregnate the phenolic resin solution to improve the overall density, fill the defect of the material and further improve the heat insulation performance of the material.
Drawings
FIG. 1 is a gradient heat-proof and heat-proof integrated material structure, wherein 1 is a PICA-based heat-proof layer, 2 is a carbon barrier layer, 3 is a SiC transition layer, and 4 is a ZrC-SiC heat-proof layer.
Fig. 2 is a picture of the PICA composite prepared in example 1, wherein fig. 2 (a) is a picture of XY back-scattered electrons and fig. 2 (b) is a picture of Z back-scattered electrons.
FIG. 3 is a high-magnification back-scattered electron image of the porous carbon matrix of the C-PICA thermal barrier of example 1.
FIG. 4 is an X-ray diffraction pattern of a coating in the integrated gradient heat shielding material prepared in example 1.
FIG. 5 is a schematic diagram showing the back scattering of the coating cross section in the integrated gradient heat shielding material prepared in example 1.
FIG. 6 is a cross-sectional low-power back-scattered electron image of the integrated gradient heat shielding material prepared in comparative example 2.
Detailed Description
Example 1
With an apparent density of 0.33g/cm 3 Injecting 55wt% of thermoplastic phenolic resin solution into a mould provided with the fiber needled felt under the pressure of 0.1Mpa, preserving heat for 24 hours at 200 ℃ for solidification, and drying at 80 ℃ for 24 hours at normal pressure to obtain the carbon fiber needled felt with the apparent density of 0.74g/cm 3 PICA composite of (C). The PICA composite material is placed in a vacuum tube furnace, the temperature is raised to 300 ℃ at 2 ℃/min under vacuum condition, the heat is preserved for 0.5h, then the temperature is raised to 900 ℃ at 5 ℃/min under argon condition, the heat is preserved for 3h, and the apparent density is obtained after ultrasonic cleaning and drying, wherein the apparent density is 0.67 g/cm 3 Porous C-PICA composite with 62% porosity.
Mixing thermoplastic phenolic resin and isopropanol according to a mass ratio of 1:3, adding 10wt% of graphite powder, stirring for 2 hours, brushing on the surface of the C-PICA composite material, repeating for 3 times, solidifying and drying at 120 ℃, placing the sample in a vacuum tube furnace, and performing heat treatment according to the same heating procedure to obtain a carbon coating with the thickness of about 100 mu m on the surface of the C-PICA composite material.
The mass ratio is as follows: siC:40wt% phenolic resin solution: c: si: siO (SiO) 2 ：Al 2 O 3 =20: 11:6:45:8:8 preparing powder, placing SiC in a solution containing 2.5wt% of a silane coupling agent (solvent absolute ethyl alcohol: deionized water=90:10), and preparing solid-liquid mass ratio of 1:3, ultrasonically vibrating the solution at 60 ℃ for 30min, putting the solution and other prepared powder into a ball milling tank, ball milling and mixing for 24h to obtain ball milling slurry, and mixing the ball milling slurry and PVB solution according to the mass ratio of 1:1, stirring for 3 hours to obtain a mixed slurry, brushing the mixed slurry on the surface of a sample with a carbon-containing coating, repeatedly brushing for 4 times and drying, placing the sample in a heat treatment furnace, heating to 350 ℃ under vacuum condition, preserving heat for 0.5 hours, and then adding at 5 ℃/min under argon conditionAnd sintering for 2 hours at 1500 ℃ to obtain the SiC transition layer with the thickness of about 300 mu m.
ZrSi is made of 2 Powder, 30wt% phenolic resin solution and C powder according to the mass ratio of 25:4:1, adding 7wt% of mixed powder of ZrC and Ti as permeation promoter and 10wt% of sintering promoter Al 2 O 3 Placing the powder and 0.8wt% of n-octanol into a ball milling tank, stirring for 24 hours to obtain ball milling slurry, brushing on the surface of a sample, repeating for 5 times, drying, heating to 1900 ℃ at 7 ℃/min, preserving heat for 1 hour, cooling to 1100 ℃ at 8 ℃/min, and cooling with a furnace to obtain the ZrC-SiC heat-resistant layer with the thickness of about 150 mu m.
The PICA composite material prepared in example 1 was observed by scanning electron microscopy, and the phenolic resin matrix filled the macropores between fibers (fig. 2 (a)), and the fiber surface exhibited good interfacial bonding with the phenolic resin (fig. 2 (b)). With the increase of carbonization temperature, a large amount of micromolecular gas escapes, after the phenolic resin is pyrolyzed into carbon, the nano porous network structure is more remarkable (figure 3), the average pore diameter of the nano porous network structure is smaller than the free path (70 nm) of gas molecules, the collision probability among the gas molecules can be effectively reduced, the gas conduction is inhibited, and a good heat insulation effect can be achieved. From the sample XRD patterns (FIG. 4), it is seen that the coating phase mainly consists of ZrC and SiC, and the peaks of ZrC and SiC are high and sharp, which means that the ceramic phase content is high and the crystallinity is good, and at the same time, part of free carbon exists. The cross section of the coating is observed to be complete in structure, the layers are tightly combined, no larger holes and obvious penetrability cracks are found, the white ZrC phase and the gray SiC phase in the coating are uniformly distributed, and the overall thickness of the coating is about 550 mu m.
After the prepared gradient heat-proof and insulation integrated material is ablated for 300 seconds by 2073K oxyacetylene, the mass ablation rate is 1.5710 -5 g/s, line ablation rate of-1.110 -3 The temperature of the back surface is 487 ℃ at most in mm/s.
Then adding 1.5wt% HMTA into 55wt% thermoplastic phenolic resin solution to obtain impregnating solution, carrying out pressurized impregnation on the gradient heat-insulating integrated composite material obtained in the step in the embodiment 1, wherein the impregnating pressure is 3MPa, the pressurizing time is 2h, and curing reaction is carried out for 24h at 180 ℃ after the impregnation. The temperature of the back surface of the integrated heat insulation and protection device is further reduced by 96 ℃ through testing the gradient.
Example 2
With an apparent density of 0.5g/cm 3 Injecting 30wt% of thermoplastic phenolic resin solution into a mould provided with the fiber needled felt under the pressure of 0.15Mpa, preserving heat for 24 hours at 200 ℃ for solidification, and drying at 80 ℃ for 24 hours under normal pressure to obtain the carbon fiber needled felt with the apparent density of 0.63g/cm 3 PICA composite of (C). The PICA composite material is placed in a vacuum tube furnace, the temperature is raised to 350 ℃ at 2 ℃/min under vacuum condition, the temperature is kept for 0.5h, then the temperature is raised to 1050 ℃ at 5 ℃/min under argon condition, the temperature is kept for 1h, and the apparent density is obtained after ultrasonic cleaning and drying 3 Porous C-PICA composite with 67% porosity.
Mixing thermoplastic phenolic resin and absolute ethyl alcohol according to the mass ratio of 1:2, adding 15wt% of graphite powder, stirring for 2 hours, brushing on the surface of the C-PICA composite material, repeating for 4 times, solidifying and drying at 120 ℃, placing the sample in a vacuum tube furnace, and performing heat treatment according to the same heating procedure to obtain the carbon coating with the thickness of about 150 mu m on the surface of the C-PICA composite material.
The mass ratio is as follows: siC:35wt% phenolic resin solution: c: siO (SiO) 2 ：Si：Al 2 O 3 =15: 15;8:10:42:10 preparing powder, placing SiC in a solution containing 2wt% of a silane coupling agent (solvent absolute ethanol: deionized water=85:15), and preparing solid-liquid mass ratio 1:3, ultrasonically vibrating the solution at 60 ℃ for 30min, putting the solution and other prepared powder into a ball milling tank, ball milling and mixing for 24h to obtain ball milling slurry, and mixing the ball milling slurry and PVB solution according to the mass ratio of 1:2, mixing, stirring for 2 hours to obtain mixed slurry, brushing the mixed slurry on the surface of a carbon-containing coating sample, repeating brushing for 4 times, drying, placing the sample in a heat treatment furnace, heating to 350 ℃ under vacuum condition, preserving heat for 0.5 hours, heating to 1500 ℃ under argon condition at 5 ℃/min, and sintering for 2 hours to obtain the SiC transition layer with the thickness of about 250 mu m.
ZrSi is made of 2 Powder, 30wt% of phenolic aldehydeResin solution and C powder according to the mass ratio of 30:7:1, adding 5wt% of mixed powder of permeation assisting agent B and Ti, 7wt% of sintering assisting agent Al 2 O 3 And MoSi 2 Powder, 0.5wt% polyurethane, placing the powder into a ball milling tank, stirring for 24 hours to obtain ball milling slurry, brushing the ball milling slurry on the surface of a sample, repeating the process for 4 times, heating to 1900 ℃ at 10 ℃/min after drying, preserving heat for 1 hour, cooling to 1100 ℃ at 7 ℃/min, cooling with a furnace to obtain a ZrC-SiC heat-proof layer with the thickness of about 100 mu m to obtain a gradient heat-proof and heat-proof integrated material, and ablating the gradient heat-proof and heat-proof integrated material with 2073K oxyacetylene for 210 seconds to obtain a mass ablation rate of 1.1510 - 5 g/s, line ablation rate of-0.8310 -3 The temperature of the back surface is 287 ℃ at most.
Then adding 1wt% HMTA into 55wt% thermoplastic phenolic resin solution to obtain impregnating solution, carrying out pressurized impregnation on the gradient heat-insulating integrated composite material obtained in the same example 2 through the steps, wherein the impregnating pressure is 3MPa, the pressurizing time is 2h, and curing reaction is carried out for 24h at 180 ℃ after the impregnation. The temperature of the back surface of the integrated heat insulation layer is further reduced by 65 ℃ through testing the gradient heat insulation.
Comparative example 1
The same preparation conditions as in example 1 were used, except that: in the preparation process of the ZrC-SiC heat-resistant layer, no permeation aid, no sintering aid and no defoaming agent are added. The result shows that after high-temperature sintering treatment, more holes and cracks appear on the ZrC-SiC heat-resistant layer, and the heat-resistant layer falls off after long-time ablation.
Comparative example 2
The same preparation conditions as in example 1 were used, except that: and (3) removing the carbon barrier layer to prepare the carbon barrier layer. The result shows that obvious cracks exist between the SiC transition layer and the matrix, and the combination between the coating and the matrix is poor; and meanwhile, under the action of capillary force of a matrix, silicon vapor generated in the sample penetrates through the whole sample to pollute the sample, and carbon fibers without interface layers are subjected to siliconizing corrosion.
Comparative example 3
The same preparation conditions as in example 2 were used, except that: the particle size of graphite powder adopted in the slurry A is less than 600nm. The results show that: the carbon barrier layer in the prepared gradient heat-proof and insulation integrated composite material is only 20 mu m, a large amount of slurry A enters the inside of a matrix, the phenomenon of powder agglomeration occurs in part of the region, the original pore structure of the material is also influenced, and under the same condition, the back temperature is 45 ℃ higher than that of the embodiment 2.
Comparative example 4
The same preparation conditions as in example 2 were used, except that: mass ratio of Si powder to SiC fine powder=1. The results show that: the SiC nanowire content at the interface of the SiC coating and the rest coating is obviously reduced, and the coating is cracked between layers after the composite material is ablated for a long time.
Claims (10)
1. A preparation method of a gradient heat-proof and heat-insulating integrated material is characterized by comprising the following steps of: brushing slurry A containing thermoplastic phenolic resin and graphite powder on the surface of a porous C-PICA composite material, performing a first sintering treatment to form a carbon barrier layer on the surface of the porous C-PICA composite material, brushing slurry B containing thermoplastic phenolic resin, si powder and SiC fine powder on the surface of the porous C-PICA composite material, performing a second sintering treatment to form a SiC transition layer on the surface of the porous C-PICA composite material, and finally, brushing the slurry B containing thermoplastic phenolic resin and ZrSi on the surface of the porous C-PICA composite material 2 Brushing slurry C of the powder on the surface of the porous C-PICA composite material, performing sintering treatment for the third time, and forming a ZrC-SiC heat-proof layer on the surface of the porous C-PICA composite material to obtain the gradient heat-proof and heat-proof integrated material; the preparation method of the porous C-PICA composite material comprises the following steps: injecting the thermoplastic phenolic resin solution D into a mold filled with a carbon fiber needled felt, performing a curing reaction to obtain a PICA composite material, and carbonizing the PICA composite material in a non-oxidizing atmosphere to obtain the porous C-PICA composite material.
2. The method for preparing the gradient heat-proof and heat-insulating integrated material according to claim 1, which is characterized in that: in the thermoplastic phenolic resin solution D, the mass fraction of the thermoplastic phenolic resin is 30-80%;
the apparent density of the carbon fiber needled felt is 0.15-0.65 g/cm 3 ；
The temperature of the curing reaction is 100-300 ℃, and the time of the curing reaction is 12-48 h;
the carbonization treatment comprises the following steps: firstly, heating to 300-600 ℃ at a heating rate of 1-2 ℃/min, preserving heat for 0.5-2 h, and then heating to 800-1400 ℃ at a heating rate of 2-6 ℃/min, preserving heat for 1-3 h;
the density of the porous C-PICA composite material is 0.45g/cm 3 ~0.9g/cm 3 The porosity is 50% -65%.
3. The method for preparing the gradient heat-proof and heat-insulating integrated material according to claim 1, which is characterized in that: brushing slurry A containing thermoplastic phenolic resin and graphite powder on the surface of a porous C-PICA composite material, drying at 80-120 ℃, and then repeatedly brushing and drying for 2-6 times, and performing primary sintering treatment;
in the slurry A, the mass fraction of graphite powder is 5-20wt%;
in the slurry A, the particle size of graphite powder is 1-5 mu m, and the purity is more than or equal to 99.5%;
the preparation process of the slurry A comprises the following steps: dissolving thermoplastic phenolic resin in an organic solvent, adding graphite powder, and stirring for 2-4 hours to obtain the epoxy resin;
the organic solvent is at least one selected from absolute ethyl alcohol, isopropyl alcohol and dimethylbenzene;
in the slurry A, the mass ratio of the thermoplastic phenolic resin to the organic solvent is 1-6: 1, a step of;
the first sintering treatment is carried out in a non-oxidizing atmosphere, wherein the first sintering treatment comprises the steps of heating to 900-1200 ℃ at a heating rate of 3-5 ℃/min and preserving heat for 1-3 hours;
the thickness of the carbon barrier layer is 80-300 mu m.
4. The method for preparing the gradient heat-proof and heat-insulating integrated material according to claim 1, which is characterized in that: the slurry B comprises the following components in parts by weight: 10-40 parts of SiC fine powder20-60 parts of Si powder, 5-15 parts of thermoplastic phenolic resin solution E, 3-10 parts of C powder and SiO 2 4-20 parts of powder, al 2 O 3 4-20 parts of powder, wherein the mass ratio of Si powder to SiC fine powder is 1.5-3.5: 1, in the thermoplastic phenolic resin solution E, the mass fraction of the thermoplastic phenolic resin is 15-65%;
the purity of the SiC fine powder is more than or equal to 99 percent, and the particle size is 0.1-1 mu m; the Si powder, the C powder and the SiO 2 Powder, al 2 O 3 The purity of the powder is more than or equal to 99.5%, the granularity of Si powder and C powder is less than or equal to 325 meshes, and SiO 2 Powder, al 2 O 3 The granularity of the powder is less than or equal to 1200 meshes.
5. The method for preparing the gradient heat-proof and heat-insulating integrated material according to claim 4, which is characterized in that: the SiC fine powder is subjected to surface modification by a silane coupling agent;
the method for obtaining the slurry B comprises the following steps: according to the design proportion, firstly preparing SiC fine powder, si powder, thermoplastic phenolic resin solution E, C powder and SiO 2 Powder, al 2 O 3 Placing SiC fine powder into a solution containing a silane coupling agent, performing ultrasonic vibration at 60-80 ℃ for 10-60 min, performing ball milling and mixing for 12-24 h to obtain a modified SiC fine powder solution, and then adding Si powder, thermoplastic phenolic resin solution E, C powder and SiO 2 Powder, al 2 O 3 Adding the powder into the modified SiC fine powder solution, performing ball milling to obtain ball milling slurry, and uniformly mixing the ball milling slurry and PVB solution for 12-24 hours to obtain slurry B;
in the solution containing the silane coupling agent, the mass fraction of the silane coupling agent is 2% -4%;
in the solution containing the silane coupling agent, the silane coupling agent is KH-550;
in the solution containing the silane coupling agent, the solvent consists of absolute ethyl alcohol and deionized water, wherein the mass ratio of the absolute ethyl alcohol to the deionized water is 75-90:10-25;
the mass ratio of the SiC fine powder to the solution containing the silane coupling agent is 1: 1-4;
the mass ratio of the ball milling slurry to the PVB solution is 1-4: 1, wherein in the PVB solution, the mass ratio of PVB to solvent is 1: 30-45, wherein the solvent is absolute ethyl alcohol.
6. The method for preparing the gradient heat-proof and heat-insulating integrated material according to claim 1 or 4, which is characterized in that: brushing slurry B containing thermoplastic phenolic resin, si powder and SiC fine powder on the surface of the porous C-PICA composite material, drying, and then repeatedly brushing and drying for 2-4 times, and performing secondary sintering treatment;
the second sintering treatment comprises the following steps: heating to 300-400 ℃ at a heating rate of 2-3 ℃/min under vacuum condition, preserving heat for 0.5-1.5 h, then introducing protective atmosphere to normal pressure, heating to 1400-1800 ℃ at a heating rate of 4-8 ℃/min, and sintering to 1-5 h;
the thickness of the SiC transition layer is 100-400 mu m.
7. The method for preparing the gradient heat-proof and heat-insulating integrated material according to claim 1, which is characterized in that: the preparation process of the slurry C comprises the following steps: zrSi is made of 2 Powder, thermoplastic phenolic resin F and C powder according to the mass ratio of 15-40: 3-10: 1, mixing to obtain a mixed solution, adding a permeation assisting agent, a sintering assisting agent and a defoaming agent into the mixed solution, and performing ball milling and mixing for 12-24 hours to obtain the thermoplastic phenolic resin F, wherein the mass fraction of the thermoplastic phenolic resin F is 20-60%;
the ZrSi 2 The purity of the powder is more than or equal to 99 percent, and the granularity is less than or equal to 300 meshes; the purity of the C powder is more than or equal to 99.5%, and the granularity is less than or equal to 1500 meshes;
the permeation assisting agent is one or more selected from Ti, B, siC, zrC powder, and the adding amount of the permeation assisting agent is 3-5% of the mass of the mixed solution;
the sintering aid is selected from Al 2 O 3 、Y 2 O 3 、MoSi 2 、TaSi 2 One or more of the powders, wherein the addition amount of the permeation assisting agent is 5-10% of the mass of the mixed solution;
the defoaming agent is one or more of n-octanol, polyurethane and silicone oil, and the adding amount of the defoaming agent is 0.1-1% of the mass of the mixed solution.
8. According to claim 1 or 7The preparation method of the gradient heat-proof and heat-insulating integrated material is characterized by comprising the following steps of: to be thermoplastic phenolic resin and ZrSi 2 Brushing the slurry C of the powder on the surface of the porous C-PICA composite material, drying, and then repeatedly brushing and drying for 4-8 times, and performing third sintering treatment;
the third sintering treatment is carried out under a protective atmosphere, wherein the third sintering treatment is carried out by heating to 1600-2000 ℃ at a heating rate of 7-15 ℃/min, preserving heat for 1-2 h, cooling to 1000-1200 ℃ at a cooling rate of 5-8 ℃/min, and cooling with a furnace;
the thickness of the ZrC-SiC heat-resistant layer is 50-200 mu m.
9. The method for preparing the gradient heat-proof and heat-insulating integrated material according to claim 1, which is characterized in that: placing the composite material obtained after the ZrC-SiC heat-proof layer is formed on the surface of the porous C-PICA composite material into impregnating solution, and carrying out impregnation and curing reaction to obtain the gradient heat-proof and heat-proof integrated composite material, wherein the impregnating solution consists of thermoplastic phenolic resin solution G and curing agent;
in the thermoplastic phenolic resin solution G, the mass fraction of the thermoplastic phenolic resin is 30-80%;
the curing agent is HMTA, and the addition amount of the curing agent is 1-5% of the mass of the thermoplastic phenolic resin solution G;
the impregnation is pressurized impregnation, the pressure of the pressurized impregnation is 2.5-5.5 MPa, the temperature of the curing reaction is 150-250 ℃, and the time of the curing reaction is 18-36 h.
10. The gradient heat-insulating integrated material prepared by the preparation method of any one of claims 1 to 9, which is characterized in that: the gradient heat-proof and heat-insulating integrated material consists of a heat-insulating layer structure material and a composite coating layer arranged on the heat-insulating layer structure material, wherein the heat-insulating layer structure material is a porous C-PICA composite material, and the composite coating layer consists of a carbon barrier layer, a SiC transition layer and a ZrC-SiC heat-proof layer from bottom to top.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10126865A1 (en) * | 2001-06-01 | 2002-12-12 | Neue Materialien Wuerzburg Gmb | Porous carbon element for use in thermal insulation, anti-adhesive or anti-reflection coatings or as electrically-conductive material has a ceramic-like oxidation-protection coating |
| CA2939288A1 (en) * | 2015-08-28 | 2017-02-28 | Rolls-Royce High Temperature Composites, Inc. | Ceramic matrix composite including silicon carbide fibers in a ceramic matrix comprising a max phase compound |
| CN106496927A (en) * | 2016-11-03 | 2017-03-15 | 华东理工大学 | A kind of low-density ablation heat insulation type composite and preparation method thereof |
| WO2017107735A1 (en) * | 2015-12-25 | 2017-06-29 | 深圳市勒马制动科技有限公司 | Method for preparing carbon-ceramic brake material and method for preparing carbon-ceramic brake disc |
| CN108585947A (en) * | 2018-06-28 | 2018-09-28 | 航天材料及工艺研究所 | A kind of lightening fire resistant thermally protective materials and preparation method thereof |
| CN109968757A (en) * | 2019-04-22 | 2019-07-05 | 中国人民解放军国防科技大学 | Ablation-resistant light heat-proof heat-insulation integrated composite material and preparation method thereof |
| CN112174684A (en) * | 2020-09-30 | 2021-01-05 | 中南大学 | SiC composite coating for porous heat-insulating carbon material and preparation method thereof |
| WO2022174624A1 (en) * | 2021-11-02 | 2022-08-25 | 航天材料及工艺研究所 | High-temperature-resistant and oxidation-resistant light-weight heat-insulation foam material and preparation method therefor |
| CN114956848A (en) * | 2022-04-29 | 2022-08-30 | 吉林联科特种石墨材料有限公司 | Preparation method of integrated cylindrical heat-insulating material with graphite efficient barrier layer |
-
2023
- 2023-06-20 CN CN202310731402.8A patent/CN116444299B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10126865A1 (en) * | 2001-06-01 | 2002-12-12 | Neue Materialien Wuerzburg Gmb | Porous carbon element for use in thermal insulation, anti-adhesive or anti-reflection coatings or as electrically-conductive material has a ceramic-like oxidation-protection coating |
| CA2939288A1 (en) * | 2015-08-28 | 2017-02-28 | Rolls-Royce High Temperature Composites, Inc. | Ceramic matrix composite including silicon carbide fibers in a ceramic matrix comprising a max phase compound |
| WO2017107735A1 (en) * | 2015-12-25 | 2017-06-29 | 深圳市勒马制动科技有限公司 | Method for preparing carbon-ceramic brake material and method for preparing carbon-ceramic brake disc |
| CN106496927A (en) * | 2016-11-03 | 2017-03-15 | 华东理工大学 | A kind of low-density ablation heat insulation type composite and preparation method thereof |
| CN108585947A (en) * | 2018-06-28 | 2018-09-28 | 航天材料及工艺研究所 | A kind of lightening fire resistant thermally protective materials and preparation method thereof |
| CN109968757A (en) * | 2019-04-22 | 2019-07-05 | 中国人民解放军国防科技大学 | Ablation-resistant light heat-proof heat-insulation integrated composite material and preparation method thereof |
| CN112174684A (en) * | 2020-09-30 | 2021-01-05 | 中南大学 | SiC composite coating for porous heat-insulating carbon material and preparation method thereof |
| WO2022174624A1 (en) * | 2021-11-02 | 2022-08-25 | 航天材料及工艺研究所 | High-temperature-resistant and oxidation-resistant light-weight heat-insulation foam material and preparation method therefor |
| CN114956848A (en) * | 2022-04-29 | 2022-08-30 | 吉林联科特种石墨材料有限公司 | Preparation method of integrated cylindrical heat-insulating material with graphite efficient barrier layer |
Non-Patent Citations (1)
| Title |
|---|
| 酚醛浸渍碳烧蚀体(PICA)的制备、结构及性能;贾献峰;刘旭华;乔文明;凌立成;龙东辉;;宇航材料工艺(01);第81-84+94页 * |
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