CN114085092A - Closed-cell ceramic microsphere filled gradient ceramic coating and preparation method thereof - Google Patents
Closed-cell ceramic microsphere filled gradient ceramic coating and preparation method thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 122
- 239000000919 ceramic Substances 0.000 title claims abstract description 107
- 238000005524 ceramic coating Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000012700 ceramic precursor Substances 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims description 46
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- 238000007750 plasma spraying Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005121 nitriding Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229920002050 silicone resin Polymers 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 19
- 238000000576 coating method Methods 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 13
- 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 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009413 insulation Methods 0.000 abstract description 5
- 229910052863 mullite Inorganic materials 0.000 abstract description 5
- 238000005507 spraying Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 8
- 229910001069 Ti alloy Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002470 thermal conductor Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/067—Macromolecular compounds
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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Abstract
The invention discloses a preparation method of a closed-cell ceramic microsphere filled gradient ceramic coating, which comprises the steps of taking an organic resin microsphere as a core, attaching a ceramic precursor on the surface of the organic resin microsphere to obtain a solid microsphere, calcining at high temperature to obtain a hollow ceramic microsphere, mixing the hollow ceramic microsphere with a ceramic aggregate, and forming the ceramic coating on the surface of a matrix. In the invention, mullite (3 Al) is used2O3·2SiO2) The ceramic microspheres with crystal phase construct closed pore channels in the coating, and in the spraying process, ceramic aggregates with small particle size are filled in gaps among the hollow microspheres, so that the compactness of the coating is effectively improved, and intercommunicating pores are avoidedThe formation of the channels can lead the ceramic coating to have lower thermal conductivity and provide better heat insulation effect.
Description
Technical Field
The invention relates to the technical field of ceramic coatings, in particular to a closed-pore ceramic microsphere filling gradient ceramic coating and a preparation method thereof.
Background
With the development of science and technology, many industrial devices require the metal matrix to be in service in severe environments for a long time, such as high temperature, humidity, high pressure, acid and alkali, and the like, so that the service life of the metal material is greatly shortened, and the actual production requirements cannot be met. The ceramic coating has the advantages of good high temperature resistance, oxidation resistance, wear resistance, corrosion resistance and the like, and is also widely concerned by more and more scientific researchers and enterprises.
At a certain coating thickness, the heat insulation effect of the ceramic coating is closely related to the material characteristics and the structure of the ceramic layer. For structural ceramics, the static air is a poor thermal conductor, which can further reduce the thermal conductivity of the ceramics, and the interconnected pore structures can form a convection phenomenon in the heat conduction process, which cannot hinder the conduction of heat flow, thereby reducing the thermal conductivity. Therefore, the closed pore structure introduced into the ceramic coating can reduce the thermal conductivity of the ceramic coating and improve the heat insulation effect.
In order to introduce pores into the ceramic, a document entitled "a porous ceramic and a method for preparing the same" is given in patent No. 201410311168.4, which uses a self-foaming ceramic slurry, formed by room-temperature foaming and sintering at high temperature. The chemical foaming agent can generate hydrogen or carbon dioxide, and the hydrogen or carbon dioxide is discharged to form air holes. The formed pores are large, and the average pore diameter is 150-600 mu m. The gradual change porous material utilizes the gradual transfer of heat, heat one end or part of the porous organic polymer matrix of solidification moulding, the other end does not heat or keep cooling, the effect of thermal treatment is gradually passed to the other end from one end, produce the porous ceramic that heats one end for complete conversion promptly, the other end is the porous material that does not have the conversion at all, realize one end porous ceramic, the other end does not have the complete conversion, there is the obturator material that the bubble does not escape in the middle of, the inside pore pressure that this method closed the hole is great, after being heated again, form open pore structure very easily. Therefore, the closed pores of the porous ceramics with the structure are unstable and are easy to be mutually communicated to form a communicated pore structure.
Disclosure of Invention
In view of the above problems in the background art, an object of the present invention is to provide a method for preparing a closed-cell ceramic microsphere-filled gradient ceramic coating, wherein organic resin microspheres are used as cores, ceramic precursors are attached to the surfaces of the organic resin microspheres to obtain solid microspheres, the solid microspheres are calcined at a high temperature to obtain hollow ceramic microspheres, and the hollow ceramic microspheres are mixed with ceramic aggregates to form a ceramic coating on the surface of a substrate.
The technical scheme of the invention is as follows:
a preparation method of a closed-cell ceramic microsphere filled gradient ceramic coating comprises the following specific steps:
s1 preparation of solid microspheres
Taking aluminum salt as a precursor, adding a solvent, and preparing alumina sol by heating and hydrolyzing; adding silica sol, mixing uniformly, and treating for 2-5 h at the temperature of 35-60 ℃ to obtain silicon-aluminum composite sol with the viscosity of 16.8-45.0 mPa & s;
b, dipping organic resin microspheres with the particle size of 10-30 microns in the composite sol for 10-30 min, taking out, insulating in an oven at 100-120 ℃ for 12-24 h, dipping the microspheres in the composite sol, insulating, drying, and repeatedly operating for 2-5 times according to the thickness of the microspheres to obtain solid microspheres with the particle size of 40-80 microns;
s2 preparation of hollow ceramic microspheres
Sintering the obtained solid microspheres in a tube furnace, performing primary sintering at 500-600 ℃, performing secondary sintering at 900-1000 ℃ and performing tertiary sintering at 1150-1350 ℃, and cooling to obtain hollow ceramic microspheres;
s3 preparation of ceramic coating
Mixing the prepared hollow ceramic microspheres and ceramic aggregate according to the weight ratio of (0.5-1.5): 1, and depositing the ceramic microspheres and the ceramic aggregate on the surface of the alloy matrix under plasma spraying to form a ceramic coating.
Further, the ceramic aggregate comprises 30-50% of alumina, 20-35% of silicon oxide, 12-18% of silicon nitride, 8-16% of silicon carbide and 6-12% of zirconia.
Furthermore, more than 80% of the powder in the ceramic aggregate has a particle size of 20-60 μm.
Further, the organic resin microspheres are one of polystyrene microspheres, polyurethane microspheres and organic silicon resin microspheres.
Further, in step S1, the mass ratio of the alumina sol to the silica sol is (2-5): 1.
Further, in the step S2, in the primary sintering process, the heating rate is 1-5 ℃, and the sintering time is 1-2 h; in the secondary sintering process, the heating rate is 5-10 ℃/min, and the sintering time is 1-2 h; in the third sintering process, the heating rate is 5-10 ℃/min, and the sintering time is 1-2 h.
And further, a nitriding process is included, after the ceramic air microspheres are sintered in the step S2, vacuumizing is performed, nitrogen is introduced, the temperature is kept at 600-900 ℃ for 1-2 hours, then the temperature is cooled to room temperature, and the microspheres are taken out.
The invention also aims to provide the closed-cell ceramic microsphere filling gradient ceramic coating prepared by the preparation method, wherein the thickness of the ceramic coating is 0.2-1.5 mm.
The invention has the beneficial effects that:
(1) in the invention, organic resin microspheres are taken as a core, silicon-aluminum composite sol is attached to the surface of the organic resin microspheres to obtain solid microspheres, and then the solid microspheres are dried and subjected to gradient sintering to obtain hollow ceramic microspheres, wherein in the gradient sintering process, SiO is formed2With Al2O3Reacting to generate aluminosilicate, and generating mullite nanocrystal from the aluminosilicate in the high-temperature sintering process, thereby obtaining mullite (3 Al) as the main crystal phase2O3·2SiO2) The ceramic microspheres have the advantages that the excellent high-temperature chemical stability, corrosion resistance, low heat conductivity coefficient and the like of mullite are utilized, the corrosion resistance of the coating is improved, and meanwhile, the design of the hollow microspheres is beneficial to improving the wear resistance of the coating.
(2) According to the invention, the closed pore structure in the coating is formed by depending on the hollow structure in the ceramic hollow microsphere rather than forming pores by using an organic pore-forming agent, so that the uniformly distributed closed pore structure is formed in the coating, the thermal conductivity of the coating is reduced, and the hollow structure in the microsphere is not damaged in the coating preparation process.
(3) In the invention, the ceramic hollow microspheres and ceramic aggregate (containing Al) with small grain diameter are mixed2O3) Mixed, mullite (3 Al)2O3·2SiO2) The ceramic microspheres with the crystalline phase and the ceramic aggregate have high bonding strength, and in the spraying process, the ceramic aggregate with small particle size is filled in the gaps between the hollow microspheres, so that the compactness of the coating is effectively improved, the formation of a communicating pore channel is avoided, the ceramic coating has lower heat conductivity, and a better heat insulation effect is provided.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
The invention designs a preparation method of a closed-pore ceramic microsphere filled gradient ceramic coating, which comprises the following specific steps:
s1 preparation of solid microspheres
Taking aluminum salt as a precursor, adding a solvent, and preparing alumina sol by heating and hydrolyzing; the mass ratio of the alumina sol to the silica sol is (2-5): 1, the silica sol is added and mixed uniformly, and the mixture is treated for 2-5 hours at the temperature of 35-60 ℃ to obtain the silicon-aluminum composite sol with the viscosity of 16.8-45.0 mPa & s;
b, dipping organic resin microspheres with the particle size of 10-30 microns in the composite sol for 10-30 min, taking out, insulating in an oven at 100-120 ℃ for 12-24 h, dipping the microspheres in the composite sol, insulating, drying, and repeatedly operating for 2-5 times according to the thickness of the microspheres to obtain solid microspheres with the particle size of 40-80 microns;
s2 preparation of hollow ceramic microspheres
Sintering the obtained solid microspheres in a tubular furnace, wherein in the primary sintering process, the heating rate is 1-5 ℃, and the sintering is carried out for 1-2 h at 500-600 ℃; in the secondary sintering process, the temperature rise rate is 5-10 ℃/min, and sintering is carried out for 1-2 h at 900-1000 ℃; in the third sintering process, the temperature rise rate is 5-10 ℃/min, and sintering is carried out for 1-2 h at 1150-1350 ℃;
after sintering, vacuumizing, introducing nitrogen, preserving heat for 1-2 hours at the temperature of 600-900 ℃, and cooling to obtain hollow ceramic microspheres;
s3 preparation of ceramic coating
Taking more than 80% of ceramic aggregate with the powder particle size of 20-60 mu m, wherein the ceramic aggregate comprises 30-50% of alumina, 20-35% of silicon oxide, 12-18% of silicon nitride, 8-16% of silicon carbide and 6-12% of zirconia;
mixing the prepared hollow ceramic microspheres and ceramic aggregate according to the weight ratio of (0.5-1.5): 1, and depositing the ceramic microspheres and the ceramic aggregate on the surface of the alloy matrix under plasma spraying to form a ceramic coating.
Further, the organic resin microspheres are one of polystyrene microspheres, polyurethane microspheres and organic silicon resin microspheres.
Example 1
S1 preparation of solid microspheres
A, adding a proper amount of aluminum isopropoxide into a three-necked bottle, adding distilled water with the molar ratio of 110: 1 to the aluminum isopropoxide, magnetically stirring, refluxing at constant temperature of 85 ℃ for 4h, slowly dropwise adding nitric acid, controlling the pH value of the solution to be 3.5-5.5, and refluxing at constant temperature for 24h to obtain alumina sol;
adding the silica sol according to the mass ratio of the alumina sol to the silica sol of 3:1, uniformly mixing, and treating at 55 ℃ for 3 hours to obtain a silicon-aluminum composite sol with the viscosity of 28.0-33.0 mPa & s;
b, soaking the polystyrene microspheres with the particle size of 20 microns in the composite sol for 30min, taking out the polystyrene microspheres in a drying oven at 105 ℃, preserving heat for 12h, soaking the microspheres in the composite sol, preserving heat, drying, and repeatedly operating for 3 times to obtain solid microspheres with the particle size of 50 microns;
s2 preparation of hollow ceramic microspheres
Sintering the obtained solid microspheres in a tubular furnace at a heating rate of 3 ℃ for 2h at 580 ℃ in a primary sintering process; in the secondary sintering process, the heating rate is 8 ℃/min, and sintering is carried out for 2h at 1000 ℃; in the third sintering process, the heating rate is 6 ℃/min, and sintering is carried out for 2h at 1250 ℃;
nitrogen leaching treatment: after sintering, vacuumizing, introducing nitrogen, preserving heat for 2 hours at 800 ℃, and cooling to obtain hollow ceramic microspheres;
s3 preparation of ceramic coating
Taking more than 80% of ceramic aggregate with the powder particle size of 20 mu m, wherein the ceramic aggregate comprises 40% of alumina, 30% of silicon oxide, 15% of silicon nitride, 12% of silicon carbide and 8% of zirconia;
mixing the prepared hollow ceramic microspheres and ceramic aggregate according to the weight ratio of 0.8: 1, and depositing the ceramic microspheres and the ceramic aggregate on the surface of a titanium alloy TC11 matrix under plasma spraying to form a ceramic coating.
Example 2
S1 preparation of solid microspheres
A, adding a proper amount of aluminum isopropoxide into a three-necked bottle, adding distilled water with the molar ratio of 110: 1 to the aluminum isopropoxide, magnetically stirring, refluxing at a constant temperature of 85 ℃ for 4 hours, slowly dropwise adding nitric acid, controlling the pH value of the solution to be 3.5-5.5, and refluxing at the constant temperature for 24 hours to obtain alumina sol;
adding silica sol according to the mass ratio of the alumina sol to the silica sol of 3:1, uniformly mixing, and treating at 55 ℃ for 3 hours to obtain a silicon-aluminum composite sol with the viscosity of 28.0-33.0 mPa & s;
b, dipping the organic silicon resin microspheres with the particle size of 20 microns in the composite sol for 30min, taking out the organic silicon resin microspheres from a drying oven at 105 ℃, preserving heat for 12h, dipping the microspheres in the composite sol, preserving heat and drying, and repeatedly operating for 4 times to obtain solid microspheres with the particle size of 60 microns;
s2 preparation of hollow ceramic microspheres
Sintering the obtained solid microspheres in a tubular furnace at a heating rate of 3 ℃ for 2h at 580 ℃ in a primary sintering process; in the secondary sintering process, the heating rate is 8 ℃/min, and sintering is carried out for 2h at 1000 ℃; in the third sintering process, the heating rate is 6 ℃/min, and sintering is carried out for 2h at 1250 ℃;
nitrogen leaching treatment: after sintering, vacuumizing, introducing nitrogen, preserving heat for 2 hours at 800 ℃, and cooling to obtain hollow ceramic microspheres;
s3 preparation of ceramic coating
Taking more than 80% of ceramic aggregate with the powder grain diameter of 40 mu m, wherein the ceramic aggregate comprises 40% of alumina, 30% of silicon oxide, 15% of silicon nitride, 12% of silicon carbide and 8% of zirconia;
mixing the prepared hollow ceramic microspheres and ceramic aggregate according to the weight ratio of 0.8: 1, and depositing the ceramic microspheres and the ceramic aggregate on the surface of a titanium alloy TC11 matrix under plasma spraying to form a ceramic coating.
Example 3
The hollow ceramic microspheres were prepared in the same manner as in example 1 to obtain hollow ceramic microspheres having a particle size of about 50 μm.
Preparing a ceramic coating: taking more than 80% of ceramic aggregate with the powder grain diameter of 30 mu m, wherein the ceramic aggregate comprises 35% of alumina, 20% of silicon oxide, 20% of silicon nitride, 15% of silicon carbide and 10% of zirconia;
mixing the prepared hollow ceramic microspheres and ceramic aggregate according to the weight ratio of 0.8: 1, and depositing the ceramic microspheres and the ceramic aggregate on the surface of a titanium alloy TC11 matrix under plasma spraying to form a ceramic coating.
Example 4
The hollow ceramic microspheres were prepared in the same manner as in example 2 to obtain hollow ceramic microspheres having a particle size of about 60 μm.
Preparing a ceramic coating: taking more than 80% of ceramic aggregate with the powder grain diameter of 30 mu m, wherein the ceramic aggregate comprises 35% of alumina, 20% of silicon oxide, 20% of silicon nitride, 15% of silicon carbide and 10% of zirconia;
mixing the prepared hollow ceramic microspheres and ceramic aggregate according to the weight ratio of 0.8: 1, and depositing the ceramic microspheres and the ceramic aggregate on the surface of a titanium alloy TC11 matrix under plasma spraying to form a ceramic coating.
Comparative example 1
Preparing a ceramic coating: taking more than 80% of ceramic aggregate with the powder particle size of 30 mu m, wherein the ceramic aggregate comprises 55% of alumina, 30% of silicon oxide, 8% of silicon nitride, 4% of silicon carbide and 3% of zirconia;
and depositing the ceramic aggregate on the surface of the titanium alloy TC11 matrix under plasma spraying to form the ceramic coating.
And (3) testing: performance testing
And (3) testing thermal shock property: carrying out thermal shock test on the ceramic coatings in the examples 1-4 and the comparative example 1 for 10 times at the temperature of 1400 ℃, and observing the falling condition of the coatings and the improvement rate of the oxidation resistance;
oxidation weight gain test: coating the ceramic coatings in the embodiments 1-4 and the comparative example 1 on the surface of metal, measuring the weight, placing the metal in the environment of 1100 ℃ and 1150 ℃, measuring the weight, and finally obtaining the weight gain;
and (3) testing thermal conductivity: and detecting by using a thermal conductivity tester. The test results are shown in Table 1.
TABLE 1 measurement results of ceramic coating Properties
According to the data, the composite ceramic coating prepared by the invention has no crack and no drop after thermal shock test, and has good oxidation resistance, and compared with the coating obtained by direct spraying, the thermal conductivity of the composite ceramic coating is obviously lower than that of the coating obtained by direct spraying, and the composite ceramic coating has obvious difference between the two and good heat insulation performance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A preparation method of a closed-cell ceramic microsphere filling gradient ceramic coating is characterized in that organic resin microspheres are used as a core, a ceramic precursor is attached to the surface of the organic resin microspheres to obtain solid microspheres, the solid microspheres are calcined at high temperature to obtain hollow ceramic microspheres, and the hollow ceramic microspheres are mixed with ceramic aggregate to form a ceramic coating on the surface of a matrix; the method comprises the following specific steps:
s1 preparation of solid microspheres
Taking aluminum salt as a precursor, adding a solvent, and preparing alumina sol by heating and hydrolyzing; adding silica sol, mixing uniformly, and treating for 2-5 h at the temperature of 35-60 ℃ to obtain silicon-aluminum composite sol with the viscosity of 16.8-45.0 mPa & s;
b, dipping organic resin microspheres with the particle size of 10-30 microns in the composite sol for 10-30 min, taking out, insulating in an oven at 100-120 ℃ for 12-24 h, dipping the microspheres in the composite sol, insulating, drying, and repeatedly operating for 2-5 times according to the thickness of the microspheres to obtain solid microspheres with the particle size of 40-80 microns;
s2 preparation of hollow ceramic microspheres
Sintering the obtained solid microspheres in a tube furnace, performing primary sintering at 500-600 ℃, performing secondary sintering at 900-1000 ℃ and performing tertiary sintering at 1150-1350 ℃, and cooling to obtain hollow ceramic microspheres;
s3 preparation of ceramic coating
Mixing the prepared hollow ceramic microspheres and ceramic aggregate according to the weight ratio of (0.5-1.5): 1, and depositing the ceramic microspheres and the ceramic aggregate on the surface of the alloy matrix under plasma spraying to form a ceramic coating.
2. The method for preparing the closed-cell ceramic microsphere filled gradient ceramic coating according to claim 1, wherein the ceramic aggregate comprises 30-50% of alumina, 20-35% of silicon oxide, 12-18% of silicon nitride, 8-16% of silicon carbide and 6-12% of zirconium oxide.
3. The method for preparing the closed-cell ceramic microsphere filled gradient ceramic coating according to claim 2, wherein the particle size of more than 80% of powder in the ceramic aggregate is 20-60 μm.
4. The method of claim 1, wherein the organic resin microspheres are one of polystyrene microspheres, polyurethane microspheres, and silicone resin microspheres.
5. The method for preparing the closed-cell ceramic microsphere filled gradient ceramic coating according to claim 1, wherein the mass ratio of the alumina sol to the silica sol in step S1 is (2-5): 1.
6. The method for preparing the closed-cell ceramic microsphere filled gradient ceramic coating according to claim 1, wherein in the step S2, in the primary sintering process, the temperature rise rate is 1-5 ℃, and the sintering time is 1-2 h; in the secondary sintering process, the heating rate is 5-10 ℃/min, and the sintering time is 1-2 h; in the third sintering process, the heating rate is 5-10 ℃/min, and the sintering time is 1-2 h.
7. The method for preparing the closed-cell ceramic microsphere filled gradient ceramic coating according to claim 1, further comprising a nitriding process, wherein after the ceramic air microsphere is sintered in the step S2, the ceramic air microsphere is vacuumized and introduced with nitrogen, the ceramic air microsphere is insulated for 1-2 hours at the temperature of 600-900 ℃, and then the ceramic air microsphere is cooled to room temperature and taken out.
8. A closed-cell ceramic microsphere filled ceramic coating obtained by the preparation method according to any one of claims 1 to 7, wherein the thickness of the ceramic coating is 0.2 to 1.5 mm.
Taking a proper amount of aluminum isopropoxide, adding the aluminum isopropoxide into a three-necked bottle, adding distilled water with the molar ratio of 110: 1 to the aluminum isopropoxide, magnetically stirring, refluxing for 4 hours at a constant temperature of 85 ℃, slowly dropwise adding nitric acid, controlling the pH value of the solution to be 3.5-5.5, and refluxing for 24 hours at the constant temperature to obtain the alumina sol.
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