CN115849958B - Thermal protection coating of ceramic matrix composite material and preparation method and application thereof - Google Patents
Thermal protection coating of ceramic matrix composite material and preparation method and application thereof Download PDFInfo
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- 239000011153 ceramic matrix composite Substances 0.000 title claims abstract description 85
- 238000000576 coating method Methods 0.000 title claims abstract description 71
- 239000011248 coating agent Substances 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 230000003647 oxidation Effects 0.000 claims abstract description 59
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 59
- 239000010703 silicon Substances 0.000 claims abstract description 58
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 58
- 238000007789 sealing Methods 0.000 claims abstract description 57
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 155
- 239000000843 powder Substances 0.000 claims description 98
- 238000005507 spraying Methods 0.000 claims description 97
- 238000000034 method Methods 0.000 claims description 38
- 239000012790 adhesive layer Substances 0.000 claims description 26
- 239000011253 protective coating Substances 0.000 claims description 25
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 25
- 229910052726 zirconium Inorganic materials 0.000 claims description 24
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 21
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 15
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 11
- 239000004917 carbon fiber Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910010293 ceramic material Inorganic materials 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011226 reinforced ceramic Substances 0.000 claims description 10
- 230000003064 anti-oxidating effect Effects 0.000 claims description 9
- 229910026551 ZrC Inorganic materials 0.000 claims description 7
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims description 7
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- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
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- XTDAIYZKROTZLD-UHFFFAOYSA-N boranylidynetantalum Chemical compound [Ta]#B XTDAIYZKROTZLD-UHFFFAOYSA-N 0.000 claims description 3
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- 239000003973 paint Substances 0.000 claims 3
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 29
- 239000000292 calcium oxide Substances 0.000 description 28
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 28
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 229910000449 hafnium oxide Inorganic materials 0.000 description 17
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 13
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 description 13
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- 238000012360 testing method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- 239000010937 tungsten Substances 0.000 description 5
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910000676 Si alloy Inorganic materials 0.000 description 3
- 229910000946 Y alloy Inorganic materials 0.000 description 3
- CEPICIBPGDWCRU-UHFFFAOYSA-N [Si].[Hf] Chemical compound [Si].[Hf] CEPICIBPGDWCRU-UHFFFAOYSA-N 0.000 description 3
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- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001093 Zr alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
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- 238000005580 one pot reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- XHFLMVUWWQVXGR-UHFFFAOYSA-N tungsten yttrium Chemical compound [Y]=[W] XHFLMVUWWQVXGR-UHFFFAOYSA-N 0.000 description 1
- OJYBUGUSFDKJEX-UHFFFAOYSA-N tungsten zirconium Chemical compound [Zr].[W].[W] OJYBUGUSFDKJEX-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Coating By Spraying Or Casting (AREA)
Abstract
The invention provides a thermal protection coating of a ceramic matrix composite material, a preparation method and application thereof, wherein the thermal protection coating comprises a hole sealing layer, a silicon-based oxidation-resistant bonding layer and a heat insulation burn-resistant layer which are sequentially arranged on the surface of the ceramic matrix composite material; the hole sealing layer contains W, si, Y and Hf; the silicon-based oxidation-resistant bonding layer contains a metal component, wherein the metal component comprises Zr element and/or Y element; the heat-insulating and burning-resistant layer is Yb 2 O 3 HfO co-doped with CaO 2 A material layer; according to the invention, the pore sealing, oxidation resistance, heat insulation and ablation resistance coatings with different functions are combined together, the advantages of the pore sealing, oxidation resistance, heat insulation and ablation resistance coatings are brought into play, a three-layer composite coating system is formed, and the temperature resistance effect of the ceramic matrix composite is improved.
Description
Technical Field
The invention relates to the technical field of preparation of high-temperature thermal protection coatings, in particular to a thermal protection coating of a ceramic matrix composite material, and a preparation method and application thereof.
Background
At present, ceramic matrix composite materials are widely applied to high-temperature components such as combustion chambers, regulating plates, wing front edges and the like of aviation and aerospace aircrafts, and the long-time working temperature is increased to 2200 ℃ or even higher. Since ceramic matrix composites without protective coatings will severely degrade in high temperature and water oxygen environments, ultra-high temperature thermal protective coatings are necessary for ultra-high temperature applications of ceramic matrix composites.
CN111718208A discloses a method for preparing a high-temperature resistant coating for ceramic matrix composite, which uses tetraethoxysilane and N, N-dimethylformamide as an anti-gelling agent and a dispersing agent respectively, and adopts a dipping-mould pressing low-temperature gelation-high-temperature pyrolysis process to obtain the coating on the surface of the ceramic matrix composite. The coating is only suitable for thermal protection of the surface of a composite material with a flat plate or regular structure, and cannot be applied to a sample with a complex structure. The main component of the coating is silicon carbide, and the effective use temperature is not more than 2200 ℃.
CN109987971a discloses a high-temperature long-time antioxidation coating on the surface of a carbon fiber reinforced silicon carbide ceramic matrix composite material, and a silicon carbide inner layer is deposited on the surface of the silicon carbide ceramic matrix composite material by adopting a chemical vapor deposition process; boron oxide, zirconium boride, silicon carbide, silicon dioxide and aluminum oxide are used as coating raw materials, silica sol is used as an adhesive, and ZrB is prepared on the silicon carbide inner layer by adopting a brushing-sintering process 2 -a SiC-based intermediate layer; then preparing an SiC outer layer on the surface of the intermediate layer by using a chemical vapor deposition process to finally obtain SiC/ZrB 2 -SiC/SiC composite oxidation resistant coating. The coating is mainly applied to antioxidation of composite materials, and mainly comprises silicon carbide, wherein the effective use temperature is not more than 2200 ℃.
CN114773075A discloses an ultra-high temperature ceramic matrix composite material with La/Y doped ZrC-SiC coating, embedding powders with different components are arranged in a gradient way by adopting a gradient embedding method, and the reaction of a silicon-zirconium alloy melt and a carbon matrix and the reaction of the silicon-zirconium alloy melt and lanthanum oxide/yttrium oxide (La 2 O 3 /Y 2 O 3 ) And carbon powder mixture, preparing the C/ZrC-SiC ultrahigh-temperature ceramic matrix composite material with the La/Y doped ZrC-SiC coating by one-step reaction, wherein the obtained material matrix has various ultrahigh-temperature ceramic components, and the surface of the material is subjected to in-situ reaction to generate an ablation-resistant coating. The main component of the coating is silicon carbide, the effective use temperature is not more than 2500 ℃, the coating is thinner, and the coating is not resistant to high-temperature scouring.
In summary, the surface of the ceramic matrix composite is provided with BSAS (BaO-SrO-Al) 2 O 3 -SiO 2 ) Coating, rare earth silicate coating, etc., the working temperature is not higher than 2500 ℃, and the working life is very short.
Disclosure of Invention
In view of the problems existing in the prior art, the invention provides a thermal protection coating of a ceramic matrix composite material, a preparation method and application thereof, which combines hole sealing, antioxidation, heat insulation and burning resistance layers with different functions, and develops respective advantages to form a composite coating system with a three-layer structure.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a thermal protection coating of a ceramic matrix composite, which comprises a hole sealing layer, a silicon-based oxidation-resistant bonding layer and a heat-insulating and burning-resistant layer which are sequentially arranged on the surface of the ceramic matrix composite;
the hole sealing layer contains W, si, Y and Hf;
the silicon-based oxidation-resistant bonding layer contains a metal component, wherein the metal component comprises Zr element and/or Y element;
the heat-insulating and burning-resistant layer is Yb 2 O 3 HfO co-doped with CaO 2 A material layer.
The thermal protection coating provided by the invention comprises a hole sealing layer, wherein the ceramic matrix composite material generally comprises a porous structure, and the hole sealing layer of W-Si-Y-Hf after high-temperature heat treatment can greatly reduce the open porosity of the surface of the ceramic matrix composite material and solve the problem of the general through hole defect of the closed cavity structure of the ceramic matrix composite material; the silicon-based oxidation-resistant bonding layer comprising Zr element and/or Y element can improve the interface matching between the ceramic matrix and the subsequent heat insulation and sintering resistance, improve the bonding strength of the coating and the matrix, and simultaneously have the functions of preventing diffusion and invasion of oxygen atoms and preventing the matrix element from escaping at high temperature; rare earth yttrium oxide (Yb) 2 O 3 ) And calcium oxide (CaO) co-doped hafnium oxide (HfO) 2 ) The heat-insulating and burning-resistant layer reduces the surface temperature of the ceramic matrix composite material by selecting Yb 2 O 3 HfO co-doped with CaO 2 A material layer capable of preventing HfO 2 The phase change occurs at high temperature to cause volume change, and the condition of poor pulverization and spraying effect in the spraying process can be prevented, the heat insulation and burning resistance layer can prevent the performance degradation of the ceramic matrix composite material at high temperature, and the reduction ofThe erosion loss of the coating in the high-speed air flow can prevent the diffusion and permeation of oxygen elements into the coating system.
Preferably, the mass ratio of W to Si to Y to Hf in the hole sealing layer is 1:1.5-2.5:0.9-1.1:0.9-1.1, for example, 1:1.5:0.9:0.9, 1:2.5:0.9, 1:1.8:0.9, 1:1.5:1:0.9, 1:1.5:0.9:1.0, 1:1.8:1.0:0.9, 1:1.7:0.9, or 1:1.5:1.1:0.9, etc.
The invention further preferably selects the mass ratio of W to Si to Y to Hf in the hole sealing layer in the range, which is more beneficial to the material of the hole sealing layer to be introduced into the pores of the ceramic matrix material; on the other hand, it is more compatible with silicon-based oxidation-resistant adhesive layers.
Preferably, the mass fraction of the metal component in the silicon-based oxidation-resistant adhesive layer is 40-55%, for example, 40%, 42%, 43%, 45%, 47%, 48%, 50%, 51%, 52% or 55%.
Preferably, the molar ratio of zirconium to yttrium in the silicon-based oxidation-resistant adhesive layer is 0.8-0.9:1, for example, 0.8:1, 0.82:1, 0.83:1, 0.84:1, 0.85:1, 0.86:1, 0.87:1, 0.88:1, or 0.9:1, etc.
The molar ratio of zirconium to yttrium in the silicon-based oxidation-resistant adhesive layer is 0.8-0.9:1, and the proportion of the zirconium to yttrium is strictly controlled, so that the silicon-based oxidation-resistant adhesive layer can be better compatible with the hole sealing layer and the heat-insulating and flame-resistant layer, and the heat resistance of the coating is improved.
Preferably, yb in the heat-insulating and burning-resistant layer 2 O 3 The mole fraction of (2) is 8 to 10%, for example, 8%, 8.3%, 8.5%, 8.7%, 8.9%, 9.2%, 9.4%, 9.6%, 9.8% or 10%, etc., but the present invention is not limited to the recited values, and other values not recited in the range are equally applicable.
The CaO molar fraction in the heat insulating and flame resistant layer is preferably 3 to 5%, and may be, for example, 3%, 3.3%, 3.5%, 3.7%, 3.9%, 4.2%, 4.4%, 4.6%, 4.8%, or 5%, but is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, yb in the heat-insulating and burning-resistant layer 2 O 3 And CaO molar ratioFor example, 1.9 to 2.5:1, 2.0:1, 2.1:1, 2.2:1, 2.4:1, or 2.5:1, etc., but are not limited to the recited values, and other values not recited in the range are equally applicable.
The Yb in the heat-insulating and burning-resistant layer is further preferable 2 O 3 And the mole fraction of CaO in the above range and preferably the mole ratio of the two is 1.9-2.5:1, has better heat-resistant and heat-insulating effects. With HfO 2 Is mainly heat-insulating and fire-resistant material, but HfO 2 The crystal phase transformation easily occurs at high temperature, and the transformation of the crystal phase easily causes the volume change, thereby causing the conditions of cracking and the like of the heat insulation and burning resistant layer, and Yb 2 O 3 The compound of CaO and the catalyst is used as a stabilizer, and the preferable molar ratio is 1.9-2.5:1, which is more beneficial to stabilizing HfO under the ultra-high temperature condition 2 Finally, the heat-resistant temperature of the heat-insulating and burning-resistant layer is improved, and Yb needs to be selected in consideration of the compatibility with the silicon-based oxidation-resistant bonding layer 2 O 3 The synergistic effect of the composite material and CaO serving as a stabilizer is better.
Preferably, hfO in the heat-insulating and burning-resistant layer 2 The molar fraction of (a) is 85 to 89%, for example, 85%, 85.5%, 85.9%, 86.4%, 86.8%, 87.3%, 87.7%, 88.2%, 88.6% or 89%, etc., but the present invention is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the composition of the ceramic matrix composite comprises a carbon fiber reinforced ceramic material.
The present invention is not particularly limited in the manner of reinforcing the carbon fibers of the carbon fiber-reinforced ceramic material, and the like, and carbon fiber-reinforced ceramic materials known to those skilled in the art may be used, and concretely, references Dewei NI, yuan CHENG, jiaping ZHANG, ji-Xuan LIU, ji ZOU, bowen CHEN, haoyang WU, hejun LI, shaoming DONG, jiecai HAN, xinchong ZHANG, qiangang FU, guo-Jun ZHANG. Advanced in ultra-high temperature ceramics, composites, and coatings [ J ]. Advanced ceramics (english), 2022,11 (1): 1-56, for example, T300-reinforced ceramic materials, T700-reinforced ceramic materials, T800-reinforced ceramic materials, or the like, or carbon fiber-reinforced ceramic materials described in CN 111454073A or CN113526972A may be used.
Preferably, the ceramic material comprises any one or a combination of at least two of silicon carbide, zirconium carbide, hafnium carbide, tantalum boride, zirconium boride or hafnium boride, wherein typical but non-limiting combinations are combinations of silicon carbide and zirconium carbide, combinations of hafnium carbide and zirconium carbide, combinations of silicon carbide and hafnium carbide, combinations of tantalum carbide and zirconium carbide, and combinations of tantalum boride and hafnium boride.
The coating is more preferably suitable for ceramic matrix composite materials of carbon fiber reinforced ceramics, and a silicon-based antioxidation bonding layer formed by the ceramic matrix composite materials and the carbon fiber reinforced ceramics are more compatible.
The thickness of the sealing layer is preferably 0.1 to 0.2mm, and may be, for example, 0.1mm, 0.12mm, 0.13mm, 0.14mm, 0.15mm, 0.16mm, 0.17mm, 0.18mm, 0.19mm, or 0.2mm, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
The thickness of the silicon-based oxidation-resistant adhesive layer is preferably 0.1 to 0.2mm, and may be, for example, 0.1mm, 0.12mm, 0.13mm, 0.14mm, 0.15mm, 0.16mm, 0.17mm, 0.18mm, 0.19mm, or 0.2mm, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
The thickness of the heat-insulating and flame-resistant layer is preferably 0.2 to 0.5mm, and may be, for example, 0.2mm, 0.24mm, 0.27mm, 0.3mm, 0.34mm, 0.37mm, 0.4mm, 0.44mm, 0.47mm, or 0.5mm, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
In a second aspect, the present invention provides a method for preparing a thermal protective coating of a ceramic matrix composite according to the first aspect, the method comprising the steps of:
(1) Spraying a hole sealing layer on the surface of the ceramic matrix composite material for the first time and performing heat treatment;
(2) A silicon-based antioxidation bonding layer is sprayed on the surface of the hole sealing layer for the second time;
(3) And thirdly spraying a heat-insulating and burning-resistant layer on the surface of the silicon-based oxidation-resistant bonding layer.
The preparation method provided by the second aspect of the invention can prepare the thermal protection coating by spraying, and has simple preparation process and short flow; and the fire resistance of the ceramic matrix composite is remarkably improved by sequentially spraying the hole sealing layer, the silicon-based oxidation-resistant adhesive layer and the heat-insulating and fire-resistant layer.
Preferably, the first spraying in the step (1) includes atmospheric plasma spraying.
The particle size of the powder used for the first spraying is preferably 40 to 150. Mu.m, for example, 40 μm, 53 μm, 65 μm, 77 μm, 89 μm, 102 μm, 114 μm, 126 μm, 138 μm or 150 μm, etc., but the powder is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
The power of the first spraying is preferably 25 to 35kW, and may be, for example, 25kW, 27kW, 28kW, 29kW, 30kW, 31kW, 32kW, 33kW, 34kW, 35kW, or the like, but not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the powder feeding rate of the first spraying is 35-45 g/min, for example, 35g/min, 37g/min, 38g/min, 39g/min, 40g/min, 41g/min, 42g/min, 43g/min, 44g/min or 45g/min, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the distance of the first spraying is 80 to 120mm, for example, 80mm, 85mm, 89mm, 94mm, 98mm, 103mm, 107mm, 112mm, 116mm or 120mm, etc., but the first spraying is not limited to the recited values, and other non-recited values within the range are equally applicable.
The temperature of the heat treatment is preferably 1000 to 1500 ℃, and may be 1000 ℃, 1050 ℃, 1110 ℃, 1160 ℃, 1220, 1270 ℃, 1330 ℃, 1380 ℃, 1440 ℃, 1500 ℃ or the like, for example, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the second spraying in the step (2) includes atmospheric plasma spraying.
The particle size of the powder used for the second spraying is preferably 40 to 150. Mu.m, for example, 40 μm, 53 μm, 65 μm, 77 μm, 89 μm, 102 μm, 114 μm, 126 μm, 138 μm or 150 μm, etc., but the powder is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
Preferably, the volume fraction of the silicon powder of the metal component in the second spraying is 40-60%, for example, 40%, 43%, 45%, 47%, 49%, 52%, 54%, 56%, 58% or 60%, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
The invention further preferably selects the volume fraction of the silicon powder of other metal elements except tungsten in the range, has the effects of improving the high-temperature viscosity of the bonding layer after oxidation and reducing the stress generated by the mismatch of the thermal expansion of the bonding layer and the heat insulation burn-resistant layer, has the phenomena of non-oxidation resistance, mismatch of the thermal expansion coefficient and the like of the bonding layer when the content of Zr element or Y element is too high, has the problem of local generation of holes caused by low high-temperature viscosity of oxidation products of the bonding layer when the content of Zr element or Y element is too low, and can be partially failed due to overlarge thermal stress.
Preferably, the in-spray powder in step (2) comprises silicon tungsten powder and silicon powder of other metals.
Preferably, the silicon powder of the other metal comprises a silicon zirconium powder and/or a silicon yttrium powder.
The invention preferably adopts silicon tungsten powder and silicon powder of other metals for spraying, and compared with the silicon tungsten powder and metal simple substance powder for spraying, the invention has the advantages that the substrate is tungsten element, the other main elements are silicon element, zirconium or yttrium is doped in tungsten silicon substrate, and the powder feeding and spraying are carried out through the silicon substrate powder, so that the silicon substrate has better compatibility with ceramic substrate materials.
The power of the second spraying is preferably 25 to 30kW, and may be, for example, 25kW, 27kW, 28kW, 29kW, 30kW, 31kW, 32kW, 33kW, 34kW, 35kW, or the like, but not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the powder feeding rate of the second spraying is 30-40 g/min, for example, 30g/min, 32g/min, 33g/min, 34g/min, 35g/min, 36g/min, 37g/min, 38g/min, 39g/min or 40g/min, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the distance of the second spraying is 80 to 120mm, for example, 80mm, 85mm, 89mm, 94mm, 98mm, 103mm, 107mm, 112mm, 116mm or 120mm, etc., but the second spraying is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the third spraying method in the step (3) comprises atmospheric plasma spraying.
The particle size of the powder used for the third spraying is preferably 40 to 150. Mu.m, for example, 40 μm, 53 μm, 65 μm, 77 μm, 89 μm, 102 μm, 114 μm, 126 μm, 138 μm or 150 μm, etc., but the powder is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
The power of the third spraying is preferably 35 to 40kW, and may be, for example, 35kW, 36kW, 37kW, 38kW, 39kW, 40kW, or the like, but not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the powder feeding rate of the third spraying is 35-45 g/min, for example, 35g/min, 37g/min, 38g/min, 39g/min, 40g/min, 41g/min, 42g/min, 43g/min, 44g/min or 45g/min, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
The third spraying distance is preferably 80 to 100mm, and may be, for example, 80mm, 83mm, 85mm, 87mm, 89mm, 92mm, 94mm, 96mm, 98mm, or 100mm, etc., but is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the powder in the powder feeding in the step (3) comprises Yb 2 O 3 Powder, caO powder and HfO 2 And (3) powder.
Preferably, the preparation method further comprises: the sprayed surface of the ceramic matrix composite is pretreated before the surface of the ceramic matrix composite is sprayed.
Preferably, the pretreatment includes cleaning the sprayed surface with compressed air and then performing sandblasting.
The pressure of the compressed air is preferably 0.15 to 0.25MPa, and may be, for example, 0.15MPa, 0.16MPa, 0.17MPa, 0.18MPa, 0.19MPa, 0.2MPa, 0.21MPa, 0.22MPa, 0.23MPa, 0.25MPa, or the like.
Preferably, the blasting treatment employs-80 mesh to +325 mesh carborundum.
Preferably, the blasting angle between the blasting gun and the test piece is 50 ° to 60 °, for example, 50 °, 51 °, 52 °, 53 °, 54 °, 55 °, 57 °, 58 °, 60 °, or the like.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) The method comprises the steps of firstly spraying a hole sealing layer on the surface of a ceramic matrix composite material, wherein the spraying power is 25-35 kW, the powder feeding rate is 35-45 g/min, the spraying distance is 80-120 mm, and the ceramic matrix composite material is subjected to heat treatment at 1000-1500 ℃;
(2) A silicon-based antioxidation bonding layer is sprayed on the surface of the hole sealing layer, the spraying power is 25-30 kW, the powder feeding speed is 30-40 g/min, and the spraying distance is 80-120 mm;
(3) And a third heat-insulating and burning-resistant layer is sprayed on the surface of the silicon-based oxidation-resistant adhesive layer, wherein the spraying power is 35-40 kW, the powder feeding rate is 35-45 g/min, and the spraying distance is 80-100 mm.
In a third aspect, the present invention provides the use of a thermal protective coating of a ceramic matrix composite according to the first aspect in the field of aerospace, aircraft, regulating blade or wing leading edge.
The heat protection coating provided by the invention can resist high temperature of 2700 ℃, so that the heat protection coating can play a role in heat insulation and burn resistance in the application.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The thermal protection coating of the ceramic matrix composite material provided by the invention combines pore sealing, oxidation resistance, heat insulation and ablation resistance coatings with different functions, exerts respective advantages, forms a composite coating system with a three-layer structure, can still keep good matrix and coating structure integrity after being placed for 300 seconds at 2700 ℃ under the preferable condition, and has good temperature resistance effect;
(2) The preparation method of the thermal protection coating of the ceramic matrix composite material provided by the invention has the advantages of short flow, simple preparation process and suitability for large-scale production;
(3) The thermal protection coating of the ceramic matrix composite material provided by the invention can be applied to thermal protection of ceramic matrix composite material superhigh temperature parts, and is suitable for being applied to the fields of aerospace, aircrafts, regulating plates or wing front edges.
Drawings
Fig. 1 is a schematic structural view of a thermal protective coating according to embodiment 1 of the present invention.
FIG. 2 is a surface view of the thermal protective coating of example 1 of the present invention after being ablated at 2700 ℃.
In the figure: 1-ceramic matrix composite; 2-a hole sealing layer; a 3-silicon-based oxidation-resistant adhesive layer; 4-a heat-insulating and burning-resistant layer.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
It should be noted that, in the description of the present invention, unless explicitly specified and limited otherwise, the terms "disposed," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art in a specific case.
As a specific embodiment of the present invention, a thermal protection coating of a ceramic matrix composite is provided, where the thermal protection coating includes a hole sealing layer, a silicon-based oxidation-resistant adhesive layer and a heat insulation burn-resistant layer sequentially disposed on the surface of the ceramic matrix composite; the hole sealingThe layer contains W, si, Y and Hf; the silicon-based oxidation-resistant bonding layer contains a metal component, wherein the metal component comprises Zr element and/or Y element; the heat-insulating and burning-resistant layer is Yb 2 O 3 HfO co-doped with CaO 2 A material layer.
The mass ratio of W to Si to Y to Hf in the hole sealing layer is 1:1.5-2.5:0.9-1.1:0.9-1.1. Yb in the heat-insulating and burning-resistant layer 2 O 3 The mole fraction of (2) is 8-10%, the mole fraction of CaO is 3-5%, hfO 2 The mole fraction of (2) is 85-89%.
The ceramic matrix composite comprises carbon fiber reinforced silicon carbide or carbon fiber reinforced zirconium carbide.
The thickness of the hole sealing layer is 0.1-0.2 mm; the thickness of the silicon-based oxidation-resistant adhesive layer is 0.1-0.2 mm; the thickness of the heat-insulating and burning-resistant layer is 0.2-0.5 mm.
As another embodiment of the present invention, there is provided a method for preparing a thermal protective coating of a ceramic matrix composite, the method comprising the steps of:
(1) The method comprises the steps of firstly spraying a hole sealing layer on the surface of a ceramic matrix composite material, wherein the spraying power is 25-35 kW, the powder feeding rate is 35-45 g/min, the spraying distance is 80-120 mm, and the ceramic matrix composite material is subjected to heat treatment at 1000-1500 ℃;
(2) A silicon-based antioxidation bonding layer is sprayed on the surface of the hole sealing layer, the spraying power is 25-30 kW, the powder feeding speed is 30-40 g/min, and the spraying distance is 80-120 mm;
(3) And a third heat-insulating and burning-resistant layer is sprayed on the surface of the silicon-based oxidation-resistant adhesive layer, wherein the spraying power is 35-40 kW, the powder feeding rate is 35-45 g/min, and the spraying distance is 80-100 mm.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Example 1
The embodiment provides a thermal protection coating of ceramic matrix composite, as shown in FIG. 1, which comprises a ceramic matrix composite layer sequentially arrangedThe ceramic matrix composite material comprises a hole sealing layer 2, a silicon-based oxidation-resistant bonding layer 3 and a heat-insulating and burning-resistant layer 4 which are arranged on the surface of a ceramic matrix composite material 1; the hole sealing layer contains W, si, Y and Hf; the silicon-based oxidation-resistant bonding layer contains a metal component, wherein the metal component comprises Zr element and/or Y element; the heat-insulating and burning-resistant layer is Yb 2 O 3 HfO co-doped with CaO 2 A material layer.
The mass ratio of W to Si to Y to Hf in the hole sealing layer is 1:2.0:1.0:1.0. Yb in the heat-insulating and burning-resistant layer 2 O 3 Is 9% by mole, 4% by mole of CaO, hfO 2 The molar fraction of (2) was 87%.
The ceramic matrix composite comprises a carbon fiber reinforced zirconium carbide boride composite (see in particular Sun Q, zhang H F, huang C B, zhang W G. Fabrication of C/C-SiC-ZrB) 2 ultra-high temperature composites through liquid–solid chemical reaction[J].Crystals,2021,11(11):1352.)。
The thickness of the hole sealing layer is 0.15mm; the thickness of the silicon-based oxidation-resistant bonding layer is 0.15mm; the thickness of the heat-insulating and burning-resistant layer is 0.3mm.
The embodiment also provides a preparation method of the thermal protection coating of the ceramic matrix composite, which comprises the following steps:
(1) Cleaning the surface of the ceramic matrix composite material by using dry and clean compressed air, carrying out sand blasting pretreatment on the material spraying surface by using a suction type dry sand blasting machine, using-80-100-mesh silicon carbide, wherein the sand blasting angle between a spray gun and a test piece is 55 degrees, and the pressure of an air compressor is 0.16MPa;
spraying a hole sealing layer on the surface of the ceramic matrix composite material for the first time, spraying tungsten-silicon alloy powder (tungsten content of 54 wt%), silicon-yttrium alloy powder (yttrium content of 45 wt%) and silicon-hafnium alloy powder (hafnium content of 52 wt%) in the hole sealing layer, wherein the particle size of the powder is 40-120 mu m, the spraying power is 28kW, the powder feeding rate is 38g/min, the spraying distance is 100mm, and carrying out heat treatment at 1200 ℃;
(2) A silicon-based oxidation-resistant bonding layer is sprayed on the surface of the hole sealing layer, wherein the base powder is silicon tungsten powder, silicon zirconium powder (the zirconium content is 42 wt%) and silicon yttrium powder (the yttrium content is 45 wt%) (the molar ratio of zirconium to yttrium is 0.85:1), the volume ratio of the silicon zirconium powder to the silicon yttrium powder is 55%, the particle size of the powder is 70-150 mu m, the spraying power is 28kW, the powder feeding rate is 30g/min, and the spraying distance is 100mm;
(3) A third spraying heat insulation and burning resistance layer is sprayed on the surface of the silicon-based oxidation resistance bonding layer, and the powder is 9% Yb 2 O 3 4% CaO, the balance being HfO 2 The particle size of the powder is 40-100 mu m, the spraying power is 35kW, the powder feeding speed is 35g/min, and the spraying distance is 100mm.
As shown in FIG. 2, after being subjected to plasma ablation at 2700 ℃ and 300 seconds, the hafnium oxide melt on the surface of the coating is spread, and after being cooled by air, longitudinal cracks are generated, but the whole coating remains intact and does not fall off.
Example 2
The embodiment provides a thermal protection coating of a ceramic matrix composite, which comprises a hole sealing layer, a silicon-based oxidation-resistant bonding layer and a heat-insulating and burning-resistant layer which are sequentially arranged on the surface of the ceramic matrix composite; the hole sealing layer contains W, si, Y and Hf; the silicon-based oxidation-resistant bonding layer contains a metal component, wherein the metal component comprises Zr element and/or Y element; the heat-insulating and burning-resistant layer is Yb 2 O 3 HfO co-doped with CaO 2 A material layer.
The mass ratio of W to Si to Y to Hf in the hole sealing layer is 1:2.5:1.1:1.1. Yb in the heat-insulating and burning-resistant layer 2 O 3 Is 8% by mole, 4% by mole of CaO, hfO 2 The molar fraction of (2) was 88%.
The composition of the ceramic matrix composite comprises a carbon fiber reinforced zirconium boride silicon carbide composite (specific references Wu H T, xie C M, zhang J H, zhang W G.Fabry and Properties of 2D C/C-ZrB) 2 -ZrC-SiC Composites by Hybrid Precursor Infiltration and Pyrolysis.Adv.Appl.Ceram.,2013,112:366-373)。
The thickness of the hole sealing layer is 0.1mm; the thickness of the silicon-based oxidation-resistant bonding layer is 0.2mm; the thickness of the heat-insulating and burning-resistant layer is 0.2mm.
The embodiment also provides a preparation method of the thermal protection coating of the ceramic matrix composite, which comprises the following steps:
(1) Cleaning the surface of the ceramic matrix composite material by using dry and clean compressed air, carrying out sand blasting pretreatment on the material spraying surface by using a suction type dry sand blasting machine, using-80 mesh to +325 mesh silicon carbide, enabling the sand blasting angle between a spray gun and a test piece to be 50 degrees, and enabling the pressure of an air compressor to be 0.20MPa;
spraying a hole sealing layer on the surface of the ceramic matrix composite material for the first time, spraying tungsten-silicon alloy powder (tungsten content is 52 wt%), silicon-yttrium alloy powder (yttrium content is 44 wt%) and silicon-hafnium alloy powder (hafnium content is 50 wt%), wherein the particle size of the powder is 50-150 mu m, the spraying power is 35kW, the powder feeding rate is 35g/min, the spraying distance is 120mm, and carrying out heat treatment at 1500 ℃;
(2) A silicon-based oxidation-resistant bonding layer is sprayed on the surface of the hole sealing layer, wherein the base powder is silicon tungsten powder, silicon zirconium powder (the zirconium content is 40 wt%) and silicon yttrium powder (the yttrium content is 44 wt%) (the molar ratio of zirconium to yttrium is 0.9:1), the volume ratio of the silicon zirconium powder to the silicon yttrium powder is 60%, the particle size of the powder is 40-120 mu m, the spraying power is 25kW, the powder feeding rate is 40g/min, and the spraying distance is 120mm;
(3) A third spraying heat insulation and burning resistance layer is sprayed on the surface of the silicon-based oxidation resistance bonding layer, and the powder is 8% Yb 2 O 3 4% CaO, the balance being HfO 2 The particle size of the powder is 40-150 mu m, the spraying power is 35kW, the powder feeding speed is 45g/min, and the spraying distance is 90mm.
Example 3
The embodiment provides a thermal protection coating of a ceramic matrix composite, which comprises a hole sealing layer, a silicon-based oxidation-resistant bonding layer and a heat-insulating and burning-resistant layer which are sequentially arranged on the surface of the ceramic matrix composite; the hole sealing layer contains W, si, Y and Hf; the silicon-based oxidation-resistant bonding layer contains a metal component, wherein the metal component comprises Zr element and/or Y element; the heat-insulating and burning-resistant layer is Yb 2 O 3 HfO co-doped with CaO 2 A material layer.
The mass ratio of W to Si to Y to Hf in the hole sealing layer is 1:1.5:0.9:0.9. Yb in the heat-insulating and burning-resistant layer 2 O 3 Is 10% by mole, 4.5% by mole of CaO, hfO 2 The molar fraction of (2) was 85.5%.
The composition of the ceramic matrix composite comprises a carbon fiber reinforced silicon carbide hafnium carbide composite (specifically referred to as Jiexen Li, xi Wei, min Ge, weigang Zhang. Preparation and microstructure characterizations of novel C/C-Zr (Hf) B 2 -Zr(Hf)C-SiC composites.Materials Science Forum,2014,788:593-597.)。
The thickness of the hole sealing layer is 0.2mm; the thickness of the silicon-based oxidation-resistant bonding layer is 0.1mm; the thickness of the heat-insulating and burning-resistant layer is 0.5mm.
The embodiment also provides a preparation method of the thermal protection coating of the ceramic matrix composite, which comprises the following steps:
(1) Cleaning the surface of the ceramic matrix composite material by using dry and clean compressed air, carrying out sand blasting pretreatment on the material spraying surface by using a suction type dry sand blasting machine, using-80 mesh to +325 mesh silicon carbide, enabling a sand blasting angle between a spray gun and a test piece to be 60 degrees, and enabling the pressure of an air compressor to be 0.25MPa;
spraying a hole sealing layer on the surface of the ceramic matrix composite material for the first time, spraying tungsten-silicon alloy powder (tungsten content is 52 wt%), silicon-yttrium alloy powder (yttrium content is 40 wt%) and silicon-hafnium alloy powder (hafnium content is 48 wt%) in the hole sealing layer, wherein the particle size of the powder is 50-120 mu m, the spraying power is 25kW, the powder feeding rate is 45g/min, the spraying distance is 80mm, and carrying out heat treatment at 1000 ℃;
(2) A silicon-based oxidation-resistant bonding layer is sprayed on the surface of the hole sealing layer, wherein the base powder is silicon tungsten powder, silicon zirconium powder (the zirconium content is 40 wt%) and silicon yttrium powder (the yttrium content is 40 wt%) (the molar ratio of zirconium to yttrium is 0.85:1), the volume ratio of the silicon zirconium powder to the silicon yttrium powder is 50%, the particle size of the powder is 40-150 mu m, the spraying power is 30kW, the powder feeding rate is 30g/min, and the spraying distance is 80mm;
(3) A third spraying heat insulation and burning resistance layer is sprayed on the surface of the silicon-based oxidation resistance bonding layer, and the powder is 10 percent of Yb 2 O 3 5% CaO, the balance being HfO 2 Is mixed with the powder mixture of (2)The particle size of the powder is 50-150 mu m, the spraying power is 40kW, the powder feeding speed is 40g/min, and the spraying distance is 85mm.
Example 4
This example provides a thermal protective coating for ceramic matrix composites, which replaces the silicon yttrium powder with the silicon zirconium powder except that the silicon zirconium powder is only incorporated in the silicon-based oxidation-resistant adhesive layer, and the remainder is the same as example 1.
Example 5
This example provides a thermal protective coating for a ceramic matrix composite, which is the same as example 1 except that the molar ratio of zirconium to yttrium is 1.2:1.
Example 6
This example provides a thermal protective coating for a ceramic matrix composite that is the same as example 1 except that the molar ratio of zirconium to yttrium is 0.5:1.
Example 7
This example provides a ceramic matrix composite thermal protective coating having a mole fraction of 3% CaO removed resulting in Yb 2 O 3 The procedure of example 1 was followed except that the molar ratio to CaO was 3:1.
Example 8
This example provides a ceramic matrix composite thermal protective coating having a mole fraction of 5% CaO removed resulting in Yb 2 O 3 The procedure of example 1 was followed except that the molar ratio to CaO was 1.8:1.
Example 9
The embodiment provides a thermal protection coating of a ceramic matrix composite, which is prepared by the same method as that of embodiment 1 except that zirconium powder, yttrium powder and tungsten powder are doped, and the element proportion and the element content are kept unchanged.
Comparative example 1
The comparative example provides a thermal protective coating of a ceramic matrix composite material, which has no CaO added to the thermal insulation and burn-resistant layer, and the content of CaO is replaced by Yb 2 O 3 Except for this, the procedure was the same as in example 1.
Comparative example 2
This comparative example provides a thermal protective coating of a ceramic matrix composite that is free of Yb addition to the heat insulating and burn resistant layer 2 O 3 The content was the same as in example 1 except that CaO was used instead.
Comparative example 3
This comparative example provides a thermal protective coating for a ceramic matrix composite, the tungsten-silicon based oxidation resistant adhesive layer being the same as example 1 except that no Zr and Y are added.
Comparative example 4
The comparative example provides a thermal protective coating of a ceramic matrix composite, wherein Zr and Y in the tungsten-silicon based oxidation resistant adhesive layer are all replaced by manganese, and the rest is the same as in example 1.
Comparative example 5
The comparative example provides a thermal protective coating of a ceramic matrix composite, wherein Zr and Y in the tungsten-silicon based oxidation resistant adhesive layer are all replaced by cobalt, and the rest is the same as in example 1.
Comparative example 6
This comparative example provides a thermal protective coating of a ceramic matrix composite, the remainder being the same as example 1 except that no hole sealing layer is provided.
The testing method comprises the following steps: the material prepared above was left at 2700℃for 300 seconds, and the ablated surface was observed.
The test results of the above examples and comparative examples are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) The comprehensive examples 1-3 show that the thermal protection coating of the ceramic matrix composite provided by the invention can still keep the surface intact without falling off after ablation after being placed for 300 seconds at the temperature of 2700 ℃, and has good tolerance;
(2) It can be seen from the combination of example 1 and example 4 that in example 1, silicon zirconium powder and silicon yttrium powder are doped in the silicon-based oxidation-resistant adhesive layer at the same time, compared with the silicon zirconium powder in example 4, the surface morphology after ablation in example 1 is only slightly melted and the coating is still complete without falling off, but in example 4, the situation that the ablation center part falls off is difficult to resist the high temperature of 2700 ℃, so that the invention preferably simultaneously doped with zirconium and yttrium, thereby further improving the heat insulation and burning resistance of the coating;
(3) As can be seen from the combination of examples 1 and examples 5 to 6, the molar ratio of zirconium to yttrium in example 1 is 0.85:1, and compared with the molar ratios of 1.2:1 and 0.5:1 in examples 5 to 6, the surface morphology of the thermal protection coating after being ablated at 2700 ℃ in example 1 is obviously better than that of examples 5 to 6, so that the invention is shown that the molar ratio of zirconium to yttrium is preferably controlled in a specific range, the compatibility of the silicon-based oxidation-resistant adhesive layer, the hole sealing layer and the heat insulation and burning-resistant layer is better improved, and the heat insulation and burning resistance of the whole thermal protection coating is further improved;
(4) As can be seen from a combination of example 1 and examples 7 to 8, yb in the heat-insulating and flame-resistant layer 2 O 3 The mol ratio of CaO to CaO has obvious influence on the ablation resistance of the coating, and the invention preferably controls Yb 2 O 3 The molar ratio of CaO to the coating can avoid the situation that the coating is seriously ablated to form holes at the temperature of 2700 ℃, and the performance of the thermal protection coating is optimized;
(5) It can be seen from the combination of examples 1 and 9 that in example 1, compared with the spraying of zirconium powder, yttrium powder and tungsten powder in the same proportion in example 9, the coating in example 1 is complete and has no shedding phenomenon after ablation, while the coating in example 9 is totally shed and does not resist the high temperature of 2700 ℃, thus indicating that besides the proportion of each layer, a silicon-based oxidation-resistant adhesive layer which is more uniformly distributed and has good compatibility of each component can be obtained by adopting tungsten-zirconium powder and tungsten-yttrium powder in the spraying silicon-based oxidation-resistant adhesive layer, and the final thermal protection coating is ensured not to shed;
(6) As can be seen from the combination of example 1 and comparative examples 1 to 2, caO and Yb were doped simultaneously in the heat-insulating and flame-resistant layer 2 O 3 Can resist the high temperature of 2700 ℃; as can be seen from the same comprehensive examples 1 and comparative examples 3 to 5, the silicon-based oxidation-resistant adhesive layer is free from adding Zr and Y or is replaced by other elements, and the coating directly falls off, so that the invention improves the heat-resistant effect of the heat-protective coating by optimizing the compositions of the heat-insulating and flame-resistant layer and the silicon-based oxidation-resistant adhesive layer;
(7) As can be seen from the combination of example 1 and comparative example 6, the absence of the sealing layer in comparative example 6 results in the difficulty in good contact of the silicon-based oxidation-resistant adhesive layer with the porous ceramic composite material, and the coating falling off phenomenon occurs after ablation at 2700 ℃.
The applicant states that the detailed process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, i.e. it does not mean that the present invention must be implemented depending on the above detailed process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (26)
1. The thermal protection coating of the ceramic matrix composite is characterized by comprising a hole sealing layer, a silicon-based oxidation-resistant bonding layer and a heat-insulating and burning-resistant layer which are sequentially arranged on the surface of the ceramic matrix composite;
the hole sealing layer contains W, si, Y and Hf;
the silicon-based oxidation-resistant bonding layer contains a metal component, wherein the metal component comprises Zr element and/or Y element;
the heat-insulating and burning-resistant layer is Yb 2 O 3 HfO co-doped with CaO 2 A material layer;
the mass ratio of W to Si to Y to Hf in the hole sealing layer is 1:1.5-2.5:0.9-1.1:0.9-1.1;
the mass fraction of the metal components in the silicon-based oxidation-resistant adhesive layer is 40-55%;
yb in the heat-insulating and burning-resistant layer 2 O 3 The mole fraction of (2) is 8-10%;
the mol fraction of CaO in the heat-insulating and burning-resistant layer is 3-5%;
HfO in the heat-insulating and burning-resistant layer 2 The mole fraction of (2) is 85-89%.
2. The thermal protective coating of claim 1, wherein the composition of the ceramic matrix composite comprises a carbon fiber reinforced ceramic material.
3. The thermal protective coating of claim 2, wherein the ceramic material comprises any one or a combination of at least two of silicon carbide, zirconium carbide, hafnium carbide, tantalum boride, zirconium boride or hafnium boride.
4. The thermal protection coating of claim 1, wherein the pore sealing layer has a thickness of 0.1-0.2 mm.
5. The thermal protective coating of claim 1, wherein the silicon-based oxidation-resistant adhesive layer has a thickness of 0.1-0.2 mm.
6. The thermal protective coating of claim 1, wherein the thickness of the heat insulating and fire resistant layer is 0.2-0.5 mm.
7. A method for preparing a thermal protective coating of a ceramic matrix composite according to any one of claims 1 to 6, comprising the steps of:
(1) Spraying a hole sealing layer on the surface of the ceramic matrix composite material for the first time and performing heat treatment;
(2) A silicon-based antioxidation bonding layer is sprayed on the surface of the hole sealing layer for the second time;
(3) And thirdly spraying a heat-insulating and burning-resistant layer on the surface of the silicon-based oxidation-resistant bonding layer.
8. The method of claim 7, wherein the first spraying in step (1) comprises atmospheric plasma spraying.
9. The method according to claim 7, wherein the particle size of the powder used for the first spraying is 40 to 150 μm.
10. The method of claim 7, wherein the first spraying power is 25-35 kw.
11. The method for preparing the powder according to claim 7, wherein the powder feeding rate of the first spraying is 35-45 g/min.
12. The method for preparing the paint according to claim 7, wherein the distance of the first spraying is 80-120 mm.
13. The method according to claim 7, wherein the temperature of the heat treatment is 1000 to 1500 ℃.
14. The method of claim 7, wherein the second spraying in step (2) comprises atmospheric plasma spraying.
15. The method according to claim 7, wherein the particle size of the powder used for the second spraying is 40 to 150 μm.
16. The method of claim 7, wherein the volume fraction of the silicon powder of the metal component in the second spraying is 40-60%.
17. The method of claim 7, wherein the second spraying power is 25-30 kw.
18. The method according to claim 7, wherein the second spraying is performed at a powder feeding rate of 30-40 g/min.
19. The method for preparing the paint according to claim 7, wherein the distance of the second spraying is 80-120 mm.
20. The method of claim 7, wherein the third spraying in step (3) comprises atmospheric plasma spraying.
21. The method according to claim 7, wherein the particle size of the powder used for the third spraying is 40 to 150 μm.
22. The method according to claim 7, wherein the power of the third spraying is 35-40 kw.
23. The method for preparing the powder according to claim 7, wherein the powder feeding rate of the third spraying is 35-45 g/min.
24. The method for preparing the paint according to claim 7, wherein the third spraying distance is 80-100 mm.
25. The preparation method according to claim 7 or 8, characterized in that the preparation method comprises the steps of:
(1) A hole sealing layer is sprayed on the surface of the ceramic matrix composite material, the spraying power is 25-35 kW, the powder feeding speed is 35-45 g/min, the spraying distance is 80-120 mm, and the ceramic matrix composite material is subjected to heat treatment at 1000-1500 ℃;
(2) A silicon-based antioxidation bonding layer is sprayed on the surface of the hole sealing layer, the spraying power is 25-30 kW, the powder feeding speed is 30-40 g/min, and the spraying distance is 80-120 mm;
(3) And a third heat-insulating and burning-resistant layer is sprayed on the surface of the silicon-based oxidation-resistant adhesive layer, the spraying power is 35-40 kW, the powder feeding rate is 35-45 g/min, and the spraying distance is 80-100 mm.
26. Use of a thermal protective coating of a ceramic matrix composite according to any one of claims 1 to 6 in the field of aerospace, regulating sheets or wing leading edges.
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