CN116535971A - Ultra-temperature-resistant high-temperature-resistant protective coating, preparation method thereof and ultra-temperature-resistant high-temperature-resistant protective coating - Google Patents
Ultra-temperature-resistant high-temperature-resistant protective coating, preparation method thereof and ultra-temperature-resistant high-temperature-resistant protective coating Download PDFInfo
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- 239000011253 protective coating Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 40
- 239000004005 microsphere Substances 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000919 ceramic Substances 0.000 claims abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 7
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 7
- 239000011215 ultra-high-temperature ceramic Substances 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 5
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 5
- -1 polysiloxane Polymers 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 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 claims description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 11
- 238000002679 ablation Methods 0.000 description 7
- 238000005488 sandblasting Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000009991 scouring Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000002468 ceramisation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
- C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses an ultra-temperature-resistant high-temperature-resistant protective coating, a preparation method thereof and an ultra-temperature-resistant high-temperature-resistant protective coating, wherein the coating comprises the following components in parts by weight: 10-20 parts of sodium lithium silicate composite liquid; 10-20 parts of crosslinkable silicon-based resin; 40-60 parts of ultra-high temperature ceramic hollow microspheres; 10-20 parts of short ceramic fibers; 0.5-5 parts of coupling agent; 0.5-2 parts of carboxymethyl cellulose. The coating prepared by the coating has excellent heat resistance, the components of tantalum oxide/hafnium oxide/zirconium oxide contained in the coating are oxide systems with highest melting points, the hollow microsphere also has lower heat conductivity, and the coating has heat resistance in chemical composition and heat insulation in physical structure, so that excellent heat resistance can be obtained. And inorganic silicate and cross-linkable curing resin are used as the adhesive of ceramic powder and ceramic fiber, so that the evenness of the film forming of the coating is improved, the simplified preparation of the coating is realized, and the advantage of process molding is obvious.
Description
Technical Field
The invention relates to the technical field of inorganic coating materials, in particular to an ultra-temperature-resistant high-temperature-resistant protective coating, a preparation method thereof and an ultra-temperature-resistant high-temperature-resistant protective coating.
Background
With the rapid development of the aerospace technology, a space launching pad faces more severe high-temperature high-speed airflow impact in the task execution process, the launching pad body material is mostly made of common steel or alloy steel, and in order to avoid the thermal structure damage of the body material, a silicon rubber resin coating is mostly adopted for coating protection. Chinese patent No. 201210514151.X discloses a thermal protective coating material with epoxy resin, curing agent polyamide and liquid rubber as organic bottom layers, water glass, curing agent sodium fluorosilicate, sand, cement and refractory aggregate as inorganic surface layers. The thickness of the coating material is large (10-35 mm), the heat resistance is limited to be within 1800 ℃, and the ablation oxidation scouring in the environment exceeding 2000 ℃ cannot be satisfied.
Ultra-high temperature resistant ceramics (UHTC), especially carbides and borides of refractory metals Zr, hf, ta (e.g. ZrC, hfC, taC, zrB) 2 、HfB 2 、TaB 2 ) Has a high melting point of more than 3000 ℃, and the oxide can cover the surface of the material to inhibit the material from further oxidation, so the material is one of the most ideal heat protection materials in the ultra-high temperature field in the future. However, the preparation of such thermal protective coatings requires severe process requirements, and the coating is often carried out by a plasma spraying process.
To sum up, in order to meet the development requirement of the heat-proof function of the structural member of the launching pad in the high-temperature service environment, new high-temperature heat-proof material and manufacturing method must be developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an ultra-temperature-resistant heat-protective coating with excellent heat resistance, and also correspondingly provides a preparation method for preparing the heat-protective coating and a coating prepared from the heat-protective coating.
In order to solve the technical problems, the invention adopts the following technical scheme:
the ultra-temperature-resistant high-temperature heat protective coating comprises the following components in parts by weight: 10-20 parts of sodium lithium silicate composite liquid; 10-20 parts of crosslinkable silicon-based resin; 40-60 parts of ultra-high temperature ceramic hollow microspheres; 10-20 parts of short ceramic fibers; 0.5-5 parts of coupling agent; 0.5-2 parts of carboxymethyl cellulose.
Preferably, the lithium sodium silicate composite liquid is prepared by the following method: and (3) putting sodium silicate and lithium silicate into a reaction kettle according to a mass ratio of 1.5-2.5:1, heating to 750-850 ℃ and preserving heat for 1.5-2.5 hours, continuously heating to 1100-1300 ℃ and preserving heat for 1.5-2.5 hours, and gradually cooling to normal temperature to obtain the sodium lithium silicate composite solution.
Preferably, the crosslinkable silicone-based resin is a liquid polysiloxane or a liquid vinylpolycarbosilane.
Preferably, the ultra-high temperature ceramic hollow microsphere is one or more of tantalum oxide hollow microsphere, hafnium oxide hollow microsphere, zirconium oxide hollow microsphere and zirconium silicon composite hollow microsphere.
Preferably, the ultra-high temperature ceramic hollow microspheres comprise zirconium-silicon composite hollow microspheres and further comprise one or more of tantalum oxide hollow microspheres, hafnium oxide hollow microspheres and zirconium oxide hollow microspheres.
Preferably, the zirconium-silicon composite hollow microsphere is prepared by the following method: carrying out solvothermal treatment on a precursor solution containing zirconium-silicon solution and phenolic resin to obtain precursor microspheres; and calcining the precursor microsphere in a segmented manner to obtain the zirconium-silicon composite hollow microsphere.
The melting point of the zirconia is as high as 2700 ℃, so that the coating prepared by adding the zirconia hollow microsphere coating is extremely excellent in theory of heat protection performance, but the zirconia ceramic phase transition is found in the high-temperature service process near the phase transition temperature of the zirconia, and the microsphere rupture easily occurs in the high-temperature thermal shock environment. The zirconium-silicon composite hollow microsphere prepared by the invention can solve the problems, and the principle is as follows: the silicon oxide softened near the phase transition temperature becomes a buffer medium for volume shrinkage and expansion in the temperature change process, and guarantees the integrity of the complex-phase hollow microspheres.
Preferably, the zirconium silicon solution is a mixture of metal inorganic salt and alcohol solution, and the metal inorganic salt comprises Zr 4+ Inorganic salts of (C) and Si-containing compounds 4+ The alcohol solution is a mixed solution of a chelating agent and alcohol.
In the metal inorganic salt, zr 4+ And Si (Si) 4+ The molar ratio is 1:1-4.
In the precursor solution, zr 4+ And Si (Si) 4+ The molar ratio of the sum of the moles of (C) to the mole of the phenolic resin is 2-6:1.
Preferably, the temperature of the solvothermal treatment is 150-250 ℃, and the time of the solvothermal treatment is 5-24 hours.
Preferably, the specific process of the staged calcination is as follows: heating to 600-800 ℃ at a heating rate of 1-5 ℃/min, preserving heat for 1-5 h under vacuum or inert atmosphere, and then cooling along with a furnace; then heating to 1000-1500 ℃ at a heating rate of 10-20 ℃/min, preserving heat for 1-5 h in an air atmosphere, and finally cooling along with the furnace.
Preferably, the Zr-containing material 4+ The inorganic salt of (C) is ZrCl 4 、ZrOCl 2 ·8H 2 O or Zr (NO) 3 ) 4 ·5H 2 O, said Si-containing 4+ The inorganic salt of (C) is SiCl 4 。
Preferably, the alcohol solution is a mixture of a chelating agent and an alcohol.
Preferably, the chelating agent is acetylacetone or a polyhydroxy compound, and the alcohol is one or more of methanol, ethanol and propanol.
Preferably, the molar ratio of the metal inorganic salt, the chelating agent and the alcohol is 1:2-3:16-36.
Preferably, the short ceramic fibers are one or more of alumina fibers, mullite fibers, basalt fibers and zirconia fibers.
The invention also provides a preparation method of the high temperature heat resistant protective coating, which comprises the following steps:
the lithium sodium silicate composite liquid and the crosslinkable silicon-based resin are stirred uniformly, then ceramic hollow microspheres, short ceramic fibers, a coupling agent and carboxymethyl cellulose are added and stirred for 1-2 hours, and after uniform stirring, a PH regulator is added until the PH value is 8-10, so that the ultra-high temperature heat resistant protective coating is obtained.
Preferably, the pH regulator is formed by mixing 5% ammonia water and 3% sulfuric acid solution.
The invention also provides an ultra-temperature heat resistant protective coating which is prepared by coating the ultra-temperature heat resistant protective coating or the ultra-temperature heat resistant protective coating prepared by the method on the surface of a substrate and curing at normal temperature.
Preferably, the substrate is made of a metal material.
Preferably, the surface of the substrate is subjected to a surface treatment prior to coating, the surface treatment comprising surface blasting, the process parameters of the surface blasting being: the air pressure is 0.1-0.4MPa, the sand blasting distance is 100-150mm, and the sand particle size is 40-120 meshes.
Compared with the prior art, the invention has the advantages that:
1. the coating prepared by the ultra-high temperature heat resistant protective coating has excellent heat resistance, the components of tantalum oxide/hafnium oxide/zirconium oxide contained in the coating are oxide systems with highest melting points, the hollow microsphere structure also endows the coating with lower heat conductivity, and the coating has heat resistance in chemical composition and heat insulation in physical structure, so that excellent heat resistance can be obtained.
2. According to the ultra-temperature-resistant high-temperature heat protection coating, the inorganic silicate and the cross-linkable curing resin are used as the adhesive of the ceramic powder and the ceramic fiber, so that the evenness of film forming of the coating is improved, the simplified preparation of the coating is realized, and the advantage of process molding is obvious.
Drawings
FIG. 1 is a macroscopic photograph of the ultra-high temperature resistant protective coating prepared by the invention;
FIG. 2 is a macroscopic photograph of the ultra-high temperature resistant thermal protective coating made according to the present invention;
FIG. 3 is a high temperature examination chart of the ultra-high temperature resistant thermal protective coating prepared in example 2; wherein (a) is an ablation process map; (b) drawing is a drawing of the macro topography of the sample after ablation; (c) drawing is a sample surface micro topography after ablation; and (d) drawing is a microscopic profile of the cross section of the sample after ablation.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
Example 1:
the preparation method of the ultra-high temperature resistant thermal protective coating comprises the following steps:
firstly, uniformly stirring 10 parts of lithium sodium silicate composite liquid and 20 parts of crosslinkable liquid polysiloxane resin, then adding 50 parts of hafnium oxide ceramic hollow microspheres, 15 parts of zirconia short ceramic fibers, 4 parts of coupling agent and 1 part of carboxymethyl cellulose, stirring for 2 hours, uniformly stirring to obtain a coating, and finally adding a PH regulator to adjust the PH value of the coating to 8, wherein the macroscopic photograph of the coating is shown in figure 1.
The coating is coated on a stainless steel substrate to prepare the ultra-high temperature heat resistant protective coating:
firstly, carrying out surface sand blasting treatment on a stainless steel substrate, controlling the sand blasting air pressure to be 0.1MPa, controlling the sand blasting distance to be 100mm, and controlling the sand particle size to be 40 meshes. The coating obtained in the embodiment is coated on the surface of a substrate, and the coating is cured for 7 days at normal temperature to obtain the ultra-high temperature resistant thermal protection coating, and the macroscopic photograph of the coating is shown in figure 2.
The heat conductivity coefficient of the ultra-high temperature resistant protective coating obtained by the embodiment is only 0.05W/m.K at 25 ℃, and the resin is subjected to in-situ ceramization after being checked for 180s by a 1800 ℃ high-temperature gas scouring oxidation ablation experiment, so that the coating has good integrity, plays a role in heat protection, and has a good application prospect.
Example 2:
the preparation method of the ultra-high temperature resistant thermal protective coating comprises the following steps:
firstly, uniformly stirring 10 parts of lithium sodium silicate composite liquid and 10 parts of crosslinkable liquid polysiloxane resin, then adding 60 parts of hafnium oxide ceramic hollow microspheres, 15 parts of zirconia short ceramic fibers, 3 parts of coupling agent and 2 parts of carboxymethyl cellulose, stirring for 2 hours, uniformly stirring to obtain a coating, and finally adding a PH regulator to regulate the PH value of the coating to 9.
The coating is coated on a stainless steel substrate to prepare the ultra-high temperature heat resistant protective coating:
firstly, carrying out surface sand blasting treatment on a stainless steel substrate, controlling the sand blasting air pressure to be 0.3MPa, controlling the sand blasting distance to be 120mm, and controlling the sand particle size to be 80 meshes. The coating obtained in the embodiment is coated on the surface of a substrate, and the ultra-temperature-resistant high-temperature heat protection coating can be obtained after curing for 7 days at normal temperature.
The heat conductivity coefficient of the ultra-high temperature resistant protective coating obtained by the embodiment is only 0.03W/m.K at 25 ℃, and the thermal conductivity coefficient is checked for 120s through a 2300 ℃ high-temperature gas scouring oxidation ablation experiment, as shown in figure 3, the contained resin is ceramic in situ, the coating integrity is good, the heat protection effect is achieved, and the application prospect is good.
The foregoing description is not intended to limit the invention in any way, but is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The ultra-high temperature resistant heat protective coating is characterized by comprising the following components in parts by weight: 10-20 parts of sodium lithium silicate composite liquid; 10-20 parts of crosslinkable silicon-based resin; 40-60 parts of ultra-high temperature ceramic hollow microspheres; 10-20 parts of short ceramic fibers; 0.5-5 parts of coupling agent; 0.5-2 parts of carboxymethyl cellulose.
2. The ultra-high temperature resistant thermal protective coating according to claim 1, wherein the sodium lithium silicate composite liquid is prepared by the following method: and (3) putting sodium silicate and lithium silicate into a reaction kettle according to a mass ratio of 1.5-2.5:1, heating to 750-850 ℃ and preserving heat for 1.5-2.5 hours, continuously heating to 1100-1300 ℃ and preserving heat for 1.5-2.5 hours, and gradually cooling to normal temperature to obtain the sodium lithium silicate composite solution.
3. The ultra-high temperature resistant thermal protective coating according to claim 1, wherein the crosslinkable silicone-based resin is a liquid polysiloxane or a liquid vinylpolycarbosilane.
4. The ultra-high temperature resistant thermal protective coating according to claim 1, wherein the ultra-high temperature ceramic hollow microspheres are one or more of tantalum oxide hollow microspheres, hafnium oxide hollow microspheres, zirconium silicon composite hollow microspheres.
5. The ultra-high temperature resistant thermal protective coating according to claim 4, wherein the zirconium-silicon composite hollow microspheres are prepared by the following method: carrying out solvothermal treatment on a precursor solution containing zirconium-silicon solution and phenolic resin to obtain precursor microspheres; and calcining the precursor microsphere in a segmented manner to obtain the zirconium-silicon composite hollow microsphere.
6. The ultra-high temperature resistant thermal protective coating according to claim 5, wherein the zirconium silicate solution is a mixture of a metal inorganic salt and an alcohol solution, the metal inorganic salt comprising Zr-containing 4+ Inorganic salts of (C) and Si-containing compounds 4+ The alcohol solution is a mixed solution of a chelating agent and alcohol.
7. The ultra-high temperature resistant thermal protective coating according to claim 5, wherein the specific process of the staged calcination is as follows: heating to 600-800 ℃ at a heating rate of 1-5 ℃/min, preserving heat for 1-5 h under vacuum or inert atmosphere, and then cooling along with a furnace; then heating to 1000-1500 ℃ at a heating rate of 10-20 ℃/min, preserving heat for 1-5 h in an air atmosphere, and finally cooling along with the furnace.
8. The ultra-high temperature resistant thermal protective coating according to claim 1, wherein the short ceramic fibers are one or more of alumina fibers, mullite fibers, basalt fibers, zirconia fibers.
9. A method of preparing the ultra-high temperature resistant thermal protective coating of any one of claims 1-8, comprising the steps of:
the lithium sodium silicate composite liquid and the crosslinkable silicon-based resin are stirred uniformly, then ceramic hollow microspheres, short ceramic fibers, a coupling agent and carboxymethyl cellulose are added and stirred for 1-2 hours, and after uniform stirring, a PH regulator is added until the PH value is 8-10, so that the ultra-high temperature heat resistant protective coating is obtained.
10. An ultra-temperature-resistant protective coating, which is obtained by coating the ultra-temperature-resistant protective coating prepared by the method of any one of claims 1 to 8 or the ultra-temperature-resistant protective coating prepared by the method of claim 9 on the surface of a substrate and curing at normal temperature.
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