CN117049787A - Thermal protection metal enamel composite coating with low infrared emissivity and preparation method thereof - Google Patents
Thermal protection metal enamel composite coating with low infrared emissivity and preparation method thereof Download PDFInfo
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- CN117049787A CN117049787A CN202310998898.5A CN202310998898A CN117049787A CN 117049787 A CN117049787 A CN 117049787A CN 202310998898 A CN202310998898 A CN 202310998898A CN 117049787 A CN117049787 A CN 117049787A
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- 210000003298 dental enamel Anatomy 0.000 title claims abstract description 176
- 238000000576 coating method Methods 0.000 title claims abstract description 124
- 239000011248 coating agent Substances 0.000 title claims abstract description 120
- 239000002131 composite material Substances 0.000 title claims abstract description 101
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 94
- 239000002184 metal Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 25
- 239000000956 alloy Substances 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 13
- 238000005260 corrosion Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims description 43
- 239000000725 suspension Substances 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 34
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008213 purified water Substances 0.000 claims description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000292 calcium oxide Substances 0.000 claims description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 11
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 11
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 9
- GNLCAVBZUNZENF-UHFFFAOYSA-N platinum silver Chemical compound [Ag].[Ag].[Ag].[Pt] GNLCAVBZUNZENF-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000003746 surface roughness Effects 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 229910003460 diamond Inorganic materials 0.000 claims description 6
- 239000010432 diamond Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 244000137852 Petrea volubilis Species 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000013535 sea water Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000035939 shock Effects 0.000 abstract description 3
- 238000010288 cold spraying Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000004321 preservation Methods 0.000 description 5
- 229910000601 superalloy Inorganic materials 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000003064 anti-oxidating effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000004584 weight gain Effects 0.000 description 4
- 235000019786 weight gain Nutrition 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002320 enamel (paints) Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
- C23D5/00—Coating with enamels or vitreous layers
- C23D5/02—Coating with enamels or vitreous layers by wet methods
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the technical field of functional coatings and composite materials thereof, in particular to a thermal protection metal enamel composite coating with low infrared emissivity and a preparation method thereof. The composite coating is prepared by cold spraying and sintering a high-temperature resistant enamel layer, a platinum-doped enamel layer and a metal layer. Wherein, the thickness of the enamel layer is 5-10 mu m, the thickness of the platinum-doped enamel layer is 5-10 mu m, and the thickness of the metal layer is 10-15 mu m. The invention promotes the seamless connection of enamel and metal layer by high temperature creep during enamel sintering, and reduces the internal stress of the coating; the high chemical inertness of enamel ensures the excellent corrosion resistance, high temperature resistance and oxidation resistance of the coating, and the toughness of the enamel is improved by the doping of platinum; the metal layer has low infrared emissivity and high temperature stability. The invention makes the coating possess the characteristics of high temperature corrosion resistance, oxidation resistance, thermal shock resistance, high bonding strength and low infrared emissivity, and can be used for reducing the surface emissivity of various high temperature alloy parts and providing heat protection effect.
Description
Technical field:
the invention relates to the technical field of functional coatings and composite materials thereof, in particular to a heat protection metal enamel composite coating with low infrared emissivity and a preparation method thereof, and the coating can be used for reducing the surface emissivity of various high-temperature alloy parts and providing a heat protection effect.
The background technology is as follows:
with the rapid development of the world aerospace technology, infrared detection based on the difference between a target and background infrared radiation has become a common means for detecting enemy aircraft in modern war. During high speed flight of an aircraft, the aerodynamic heat released by the combustion of fuel and the intense friction between the aircraft surface and the atmosphere can cause certain components, such as: the nozzle, the cone of the fairing, etc. are affected by high temperature (up to 900 ℃). The infrared radiation of the thermal component in the wave bands of 3-5 μm and 8-14 μm will be significantly higher than the surrounding environment, which is of interest for infrared detectors. Therefore, reducing the infrared radiation of the thermal components is a primary task to increase the viability of the aircraft.
According to Stephen-Boltzmann's law, the intensity of infrared radiation is proportional to the infrared emissivity of the material and the surface temperature. Thus, reducing the aircraft surface temperature and infrared emissivity are two effective ways to reduce aircraft infrared radiation, while the surface temperature of the hot component is primarily contributed by the heat released by the combustion of the fuel. Thus, directly lowering the surface temperature may sacrifice the dynamics of the aircraft. It is apparent that coating the thermal member with a low infrared emissivity material is a more efficient and convenient method of reducing infrared radiation.
According to the characteristics of the infrared low-emissivity material, the infrared low-emissivity coating with middle-high temperature application potential at present is roughly divided into three categories of metal micro powder coating, metal film and inorganic low-emissivity coating. However, there are many problems with low emissivity coatings in our country: (1) The temperature resistance rating of the coating material is not high enough and a novel infrared low emissivity coating system is needed. (2) The high-temperature service life is short and the stability is poor, and the main appearance is that: the coating is easy to crack and peel under severe conditions such as high-temperature low-temperature thermal impact, high-temperature salt corrosion, gas hot corrosion and the like. (3) complex process: has high requirements on manufacturing equipment, environment and the like. (4) the overall emissivity does not reach the practical application level, etc. According to the service requirements of national defense construction and industrial development on the low-emissivity coating on the surface of the high-temperature alloy, development of a thermal protection metal enamel composite coating with low infrared emissivity is needed.
Disclosure of Invention
The invention aims to provide a thermal protection metal enamel composite coating with low infrared emissivity and a preparation method thereof, so that the coating has the characteristics of high-temperature corrosion resistance, oxidation resistance, thermal shock resistance, high bonding strength and low infrared emissivity.
The technical scheme of the invention is as follows:
the composite coating is sequentially an enamel layer, a platinum-doped enamel layer and a metal layer from inside to outside, wherein the metal layer is a pure platinum layer or a platinum-silver alloy layer, the thickness of the enamel layer is 5-10 mu m, the thickness of the platinum-doped enamel layer is 5-10 mu m, and the thickness of the metal layer is 10-15 mu m; the composition of each layer of the composition is as follows:
enamel layer: 50-65% of silicon dioxide, 6-11% of zirconium dioxide, 3-10% of aluminum oxide, 2-6% of boron trioxide, 3-7% of calcium oxide, 7-13% of strontium oxide, 2-6% of potassium oxide, and 16-22% of total content of calcium oxide, strontium oxide and potassium oxide;
platinum-doped enamel layer: 80-90% of enamel glaze and 10-20% of platinum; wherein, the enamel glaze component is the same as the enamel layer component: 50-65% of silicon dioxide, 6-11% of zirconium dioxide, 3-10% of aluminum oxide, 2-6% of boron trioxide, 3-7% of calcium oxide, 7-13% of strontium oxide, 2-6% of potassium oxide, and 16-22% of total content of calcium oxide, strontium oxide and potassium oxide;
metal layer: silver 0-50% and platinum 50-100%.
The preparation method of the thermal protection metal enamel composite coating with low infrared emissivity comprises the following steps: 1) Smelting enamel glaze; 2) Preparing enamel micropowder; 3) Preparing composite enamel suspension; 4) Spraying composite enamel suspension; 5) Preparing a platinum-doped composite enamel suspension; 6) Spraying platinum-doped composite enamel suspension; 7) Preparing a metal powder suspension; 8) Spraying a metal powder suspension; 9) The composite coating is fired and polished after cooling.
The preparation method of the thermal protection metal enamel composite coating with low infrared emissivity comprises the steps 1) to 4) of preparing an enamel layer, and specifically comprises the following steps:
step 1): ball milling and mixing various oxides according to the formula of the enamel layer, wherein the rotating speed is 300-350 r/min, the time is 20-30 hours, and the heating and smelting are carried out after the uniform mixing, and the smelting process is as follows: RT-300-600 ℃, and heating at uniform speed for 0.5-1.5 hours; heating at the average speed of 25-35 minutes at the temperature of 300-600 ℃ to 800-1100 ℃; heating at a constant speed of between 800 and 1100 ℃ and between 1300 and 1550 ℃ for 0.5 to 1.5 hours; maintaining the constant temperature of 1300-1550 ℃ for 1-2 hours, and then performing water quenching to obtain enamel glaze particles;
step 2): carrying out ball milling on enamel glaze particles obtained after water quenching to obtain enamel micro powder with the particle size less than or equal to 5 mu m;
step 3): absolute ethyl alcohol or purified water is taken as dispersing agent, 10 ml to 30ml of absolute ethyl alcohol or purified water required by 1 gram of enamel micropowder is mixed, and the enamel suspension with uniform dispersion is obtained through magnetic stirring and ultrasonic vibration for 15min to 30 min;
step 4): and uniformly spraying enamel suspension on the surface of the high-temperature alloy part by using an air compressor, wherein the spraying pressure is 0.2-0.4 MPa, and the spraying distance is 15-40 cm.
The preparation method of the thermal protection metal enamel composite coating with low infrared emissivity comprises the steps of spraying, drying for 20-30 min by a baking oven at 200-300 ℃ to obtain an initial enamel layer.
The preparation method of the thermal protection metal enamel composite coating with low infrared emissivity comprises the steps of 5) to 6) preparing a platinum-doped enamel layer, and specifically comprises the following steps:
step 5): preparing platinum-doped composite enamel powder from enamel micro powder and platinum powder, mixing 10-30 ml of absolute ethyl alcohol or purified water required by 1g of platinum-doped composite enamel powder with absolute ethyl alcohol or purified water serving as a dispersing agent, magnetically stirring and ultrasonically oscillating for 15-30 min to obtain uniformly dispersed platinum-doped composite enamel suspension;
step 6): and uniformly spraying the platinum-doped composite enamel suspension on the enamel layer on the surface of the high-temperature alloy part by using an air compressor, wherein the spraying pressure is 0.2-0.4 MPa, and the spraying distance is 15-40 cm.
The preparation method of the thermal protection metal enamel composite coating with low infrared emissivity comprises the steps of spraying, drying for 20-30 min by a baking oven at 200-300 ℃ to obtain the platinum-doped enamel layer.
The preparation method of the thermal protection metal enamel composite coating with low infrared emissivity comprises the steps 7) to 8) of preparing a metal layer, and specifically comprises the following steps:
step 7): preparing silver powder and platinum powder according to a proportion or directly taking the platinum powder as metal powder, wherein the particle size of the original powder of the silver powder and the platinum powder is less than or equal to 10 mu m, taking absolute ethyl alcohol or purified water as a dispersing agent, mixing 30-35 ml of absolute ethyl alcohol or purified water required by 1 gram of metal powder, and carrying out magnetic stirring and ultrasonic vibration for 3-5 min to obtain a uniformly dispersed metal powder suspension;
step 8): and uniformly spraying the metal powder suspension on the platinum-doped enamel layer on the surface of the high-temperature alloy part by using an air compressor, wherein the spraying pressure is 0.2-0.4 MPa, and the spraying distance is 15-40 cm.
The preparation method of the thermal protection metal enamel composite coating with low infrared emissivity comprises the steps of spraying, drying for 20-30 min by a baking oven at 200-300 ℃ to obtain a metal layer.
The preparation method of the thermal protection metal enamel composite coating with low infrared emissivity comprises the following step 9): after being sprayed and dried in sequence, the original blank of the composite coating of the enamel layer, the platinum-doped enamel layer and the metal layer is obtained, and then sintering treatment is carried out, wherein two sintering schemes are adopted: (1) Sintering the dried composite coating original blank at a high temperature of 1000-1100 ℃ for 10-20 min, taking out, and cooling in the atmosphere; after cooling, polishing by using 2000-mesh sand paper and then using 1-micrometer diamond grinding paste until the surface roughness of the coating is Ra less than or equal to 2 mu m, thus obtaining the heat protection metal enamel composite coating; (2) Firstly, preserving heat of the dried composite coating original blank for 1-3 hours at 800-950 ℃, then heating to 1000-1100 ℃ in a furnace, sintering at high temperature for 10-20 min, cooling to 600-800 ℃ in the furnace, taking out and cooling in the atmosphere; and (3) after cooling, polishing by using 2000-mesh sand paper and then using 1-micrometer diamond grinding paste until the surface roughness of the coating is Ra less than or equal to 2 mu m, thus obtaining the heat protection metal enamel composite coating.
The preparation method of the thermal protection metal enamel composite coating with low infrared emissivity comprises the following performance indexes:
thickness less than or equal to 25 μm, surface roughness: ra is less than or equal to 2 mu m, bonding strength is less than or equal to 15MPa, no crack exists when air cooling is performed 1000 times at 900 ℃, heat insulation temperature is less than or equal to 100 ℃, seawater immersion corrosion resistance life is less than or equal to 150h, salt spray corrosion resistance life is less than or equal to 1000h, and gas hot corrosion rate is less than or equal to 0.5g/m 2 h, completely resisting oxidation at 900 ℃; infrared emissivity is less than 0.15 at 50 ℃ and 900 ℃ in the wave bands of 3-5 mu m and 8-14 mu m.
The design idea of the invention is as follows:
the composite coating designed by the invention is mainly sprayed on a high-temperature alloy matrix, and is prepared by sequentially carrying out cold spraying and sintering on three layers, namely a high-temperature resistant enamel layer, a platinum-doped enamel layer and a metal layer (platinum or platinum silver alloy), from inside to outside. Based on good interfacial bonding force between enamel and high-temperature alloy and chemical inertness in the range of room temperature to 900 ℃, the coating is ensured to have excellent interfacial bonding, high-temperature oxidation resistance and corrosion resistance. In addition, the high temperature creeps during enamel sintering, thereby fully ensuring the seamless connection between the enamel and the metal layer and reducing the internal stress of the coating. The compactness and the surface smoothness of the outermost metal layer are ensured by the enamel layer and the platinum-doped enamel layer, and meanwhile, the toughness of the enamel coating doped with high-toughness heat-resistant metal platinum particles is greatly improved. The platinum or platinum-silver alloy has high-temperature oxidation resistance, so that the coating has low emissivity and high-temperature stability.
The components of the enamel glaze in the enamel layer designed by the invention are strictly required: 3-7% of calcium oxide, 7-13% of strontium oxide and 2-6% of potassium oxide, and the total content of the calcium oxide, the strontium oxide and the potassium oxide is controlled to be 16-22%, so that the chemical combination of an enamel layer and an alloy matrix is ensured, and the high-temperature structural stability and the excellent antioxidation effect are achieved; in addition, the enamel component ensures the high-temperature fluidity of the enamel and the compatibility of the enamel and platinum particles, and ensures good matching with a high-temperature alloy matrix and a surface alloy layer.
The invention has the advantages and beneficial effects that:
(1) In the enamel layer, the network forming agent component of the enamel is high in content and good in high-temperature stability; in addition, high-stability strontium oxide is used for replacing cosolvent components such as high-activity zinc oxide, sodium oxide and the like in the traditional enamel, so that the sintering temperature of the enamel coating is increased to the sintering temperature of the metal layer, and meanwhile, excessive interface reaction between the coating and the matrix alloy is inhibited, and the interface structure of the coating and the alloy is controllable.
(2) The platinum-doped enamel layer improves the toughness of the enamel, reduces the sintering stress of the enamel and improves the thermal shock spalling resistance by doping the heat-resistant metal platinum particles.
(3) The metal layer has low infrared emissivity and high temperature stability, and is well mechanically embedded with the platinum-doped enamel layer in a spraying manner, the platinum or platinum-silver alloy with smooth surface can reduce the emissivity of the whole part to below 0.15, and the high temperature stability of the platinum or platinum-silver alloy can ensure that the platinum or platinum-silver alloy can be used for a long time at 900 ℃, so that the emissivity is reduced, and meanwhile, the service life of the high-temperature part can be obviously prolonged.
(4) The thermal protection metal enamel composite coating with low infrared emissivity does not need any expensive equipment, has simple preparation process and can be sprayed on the surfaces of high-temperature alloy parts with various shapes.
Drawings
FIG. 1 is a macroscopic morphology of a low infrared emissivity thermal protection metallic enamel composite coating prepared on a superalloy GH536 substrate.
FIG. 2 is a graph showing the average values of the dynamic curves of the oxidative weight gain at 900℃of three parallel groups of heat-shielding metal enamel composite coating samples and GH536 alloy matrix samples, respectively; in the figure, the abscissa Time is Time (h), and the ordinate Weight gain is Weight gain (mg.cm) -2 ) The method comprises the steps of carrying out a first treatment on the surface of the The Bare alloy is GH536 alloy matrix sample, and Composite coating is heat protection metal enamel composite coating sample.
Fig. 3 is a microscopic morphology SEM image of a low infrared emissivity thermal protection metal enamel composite coating prepared on a superalloy GH536 substrate.
Fig. 4 is an SEM image of the profile of the tensile test section-enamel layer of the thermal protection metal enamel composite coating with low infrared emissivity after heat preservation at 900 ℃ for 500 hours.
Fig. 5 is an SEM image of the cross section of the tensile test-metal layer morphology of the thermal protection metal enamel composite coating with low infrared emissivity after heat preservation at 900 ℃ for 500 hours.
Detailed Description
The following examples are further detailed description of the present invention, it being understood that these are merely illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1:
in the embodiment, the spraying object is a GH536 high-temperature alloy sample, and the thermal protection metal enamel composite coating with low infrared emissivity is prepared by the following process:
(1) Melting enamel glaze:
the enamel comprises the following components in percentage by weight: 64% of silicon dioxide, 9% of zirconium dioxide, 3% of aluminum oxide, 6% of boron trioxide, 4% of calcium oxide, 10% of strontium oxide and 4% of potassium oxide.
Ball milling and mixing the oxides, rotating at 320 rpm for 24 hours, and heating and smelting after uniformly mixing, wherein the smelting process is as follows:
RT (room temperature) is heated to 500 ℃, and the temperature is heated at an average speed for 1 hour;
heating to 1000 ℃ at 500 ℃ and uniformly heating for 30 minutes;
heating to 1425 ℃ at 1000 ℃ and uniformly heating for 1 hour;
maintaining the constant temperature of 1425 ℃ for 1.5 hours, and then carrying out water quenching to obtain enamel granules.
(2) Enamel micropowder preparation: and (3) performing planetary ball milling (rotating speed is 320 rpm, time is 100 hours) on enamel glaze particles obtained after water quenching to prepare enamel micro powder with the particle size smaller than 5 mu m.
(3) Preparing enamel suspension: according to 1g enamel micropowder: preparing a composite enamel suspension by using 16ml of absolute alcohol, and magnetically stirring and ultrasonically oscillating for 20min to obtain the uniformly dispersed composite enamel suspension.
(4) Spraying an enamel layer: spraying the composite enamel suspension on a GH536 superalloy sample by an air compressor under the atmospheric pressure of 0.3MPa for 20cm, and drying by a 250 ℃ oven for 25min to obtain an initial enamel layer with the thickness of 6 mu m.
(5) Preparing a platinum-doped composite enamel suspension:
80% of enamel and 20% of platinum (the component of the enamel in the platinum-doped enamel layer is the same as the enamel layer).
Preparing platinum-doped composite enamel powder from enamel micro powder and platinum powder according to 1g of platinum-doped composite enamel powder: preparing a platinum-doped composite enamel suspension by using 16ml of absolute alcohol, and magnetically stirring and ultrasonically oscillating for 20min to obtain the uniformly dispersed platinum-doped composite enamel suspension.
(6) Spraying of platinum-doped composite enamel suspension: the platinum-doped composite enamel suspension is sprayed on a sample by an air compressor under the atmospheric pressure of 0.3MPa for 20cm, and the platinum-doped enamel layer with the thickness of 8 mu m is obtained after the platinum-doped composite enamel suspension is dried for 25min by a 250 ℃ oven.
(7) Preparing a metal powder suspension: according to the weight ratio of silver powder to platinum powder of 1:1 preparing metal powder, taking absolute ethyl alcohol as a dispersing agent, taking 1g of absolute ethyl alcohol required by the metal powder as 32ml, magnetically stirring and ultrasonically oscillating for 4min to obtain a uniformly dispersed metal powder suspension.
(8) Spraying of metal powder suspension: the metal powder suspension is sprayed on a sample by an air compressor under the atmospheric pressure of 0.3MPa, the spraying distance is 20cm, and the metal layer is obtained after drying for 25min by a 250 ℃ oven, wherein the thickness of the metal layer is 10 mu m.
(9) Firing the composite coating and polishing after cooling: drying the coated product at 250 ℃ for 30min after spraying the coated product to obtain an original blank of the composite coating; and (5) sintering the dried composite coating original blank at 1050 ℃ for 15min, taking out, and cooling to room temperature in the atmosphere. After cooling, the coating was polished with 2000 mesh sandpaper and then with a 1 micron diamond paste until the surface roughness of the coating was ra=2 μm.
The macro morphology of the prepared coating is shown in figure 1, and the coating is compactThe surface has no appearance defects such as bubbles, cracks and the like. The coating sample prepared in this way was oxidized at 900℃for 500 hours at an oxidation rate of 0.007g/m 2 h (less than 0.1 g/m) 2 h) Reaching the complete oxidation resistance level. The kinetics of the average oxidized weight gain at 900 ℃ for three parallel sets of composite coating samples and GH536 alloys is shown in figure 2. Measuring the coating emissivity 0.0937 (3-5 μm band) and 0.0564 (8-14 μm band) at 50 ℃; the emissivity of the coating at 950 ℃ is 0.0752 (3-5 μm band) and 0.0742 (8-14 μm band). The shrinkage is less than or equal to 1.33 percent. The tensile bond strength of the initial sample was 23.0MPa, and the tensile bond strength was 18.2MPa after 500h incubation at 900 ℃.
Comparative example 1
The difference from example 1 is that: and 7, preparing a metal powder suspension, wherein the weight ratio of silver powder to platinum powder is 17:3.
after sintering, the surface of the composite coating is vitrified and has a porous structure under the glass.
Comparative example 2
The difference from example 1 is that: steps 5 and 6 are omitted.
Polishing after sintering, and making the surface of the composite coating smooth and compact, wherein the microscopic morphology of the section of the coating is shown in figure 3. Roughness was measured: ra=1.8 μm, coating emissivity 0.0966 (3-5 μm band) and 0.0646 (8-14 μm band) at 50 ℃.
Comparative example 3
The difference from example 1 is that: step 4, after spraying the enamel layer, placing the blank at 1050 ℃ for sintering for 15min, cooling, and then spraying sand (the pressure is 0.1 MPa) on the surface of the coating and cleaning; and 6, after spraying the platinum-doped enamel layer, placing the blank at a high temperature of 1050 ℃ for sintering for 15min, cooling, and then spraying sand (the pressure is 0.1 MPa) on the surface of the coating and cleaning.
The rest follows the procedure in example 1, and the composite coating is placed at 900 ℃ for heat preservation for 500 hours, and the metal layer is cracked and falls off after air cooling.
Comparative example 4
The difference from example 1 is that: polishing to roughness in step 9: ra=7μm.
The resulting coatings had a coating emissivity of 0.1430 (3-5 μm band) and 0.0877 (8-14 μm band) at 50 ℃.
Example 2
IN this example, the spray coating object was changed to superalloy IN738, and the thermal protection metal enamel composite coating with low infrared emissivity was prepared IN the same process as IN example 1.
The prepared coating is compact, the surface has no appearance defects such as bubbles, cracks and the like, and the coating sample prepared in the way reaches a complete antioxidation level after being oxidized at the high temperature of 900 ℃ for 500 hours.
Example 3
In this example, the spray coating object was changed to high temperature alloy K444, and the thermal protection metal enamel composite coating with low infrared emissivity was prepared in the same process as in example 1.
The prepared coating is compact, the surface has no appearance defects such as bubbles, cracks and the like, and the coating sample prepared in the way reaches a complete antioxidation level after being oxidized at the high temperature of 900 ℃ for 500 hours.
Example 4
In this example, the spray coating object was changed to superalloy K438, and the thermal protective metal enamel composite coating with low infrared emissivity was prepared in the same process as in example 1.
The prepared coating is compact, the surface has no appearance defects such as bubbles, cracks and the like, and the coating sample prepared in the way reaches a complete antioxidation level after being oxidized at the high temperature of 900 ℃ for 500 hours.
Example 5
In this embodiment, step 9 in embodiment 1 is changed to: drying the coated product at 250 ℃ for 30min after spraying the coated product to obtain an original blank of the composite coating; the dried composite coating original blank is firstly subjected to heat preservation for 2 hours at 800 ℃, then is sintered for 15 minutes from 800 ℃ to 1050 ℃ within 15 minutes, finally is cooled to 600 ℃ in a furnace, is taken out and is cooled to room temperature in the atmosphere. After cooling, the coating was polished with 2000 mesh sandpaper and then with a 1 micron diamond paste until the surface roughness of the coating was ra=2 μm.
The prepared composite coating is compact, and the surface of the composite coating has no appearance defects such as bubbles, cracks and the like. The coating sample prepared in this way has tensile bonding strength of 19.4MPa after heat preservation for 500h at 900 ℃, and the microscopic morphology of the section of the sample after stretching is shown in fig. 4 and 5.
Comparative example 5
The difference from example 5 is that: the diameter of the platinum powder particles used in the process is 50-100 mu m.
The prepared composite coating is compact, the surface of the composite coating has no appearance defects such as bubbles, cracks and the like, and the platinum-silver alloy phase on the surface of the coating sample prepared by the method is unevenly distributed.
Comparative example 6
The difference from example 5 is that: strontium oxide in the enamel composition is exchanged for equal weight sodium oxide.
The prepared composite coating has uneven surface and has the defects of bubbles, cracks and the like locally.
Comparative example 7
The difference from example 5 is that: the strontium oxide in the enamel composition is replaced by zinc oxide of equal weight.
The prepared composite coating has uneven surface and has the defects of bubbles, cracks and the like locally.
The results of the examples and comparative examples show that:
(1) The invention is suitable for various high-temperature alloy matrixes;
(2) The enamel and the high-temperature alloy have good interfacial bonding force, and the chemical inertness in the range of room temperature to 900 ℃ ensures that the coating has excellent high-temperature oxidation resistance and corrosion resistance. The high temperature creeping of enamel during sintering fully ensures the seamless connection of enamel and metal layer, reduces the internal stress of the coating, and simultaneously ensures the compactness and smooth surface of the metal layer on the outermost layer.
(3) The incorporation of high toughness heat resistant metal particles in the enamel improves the toughness of the coating.
(4) The uniform distribution of the platinum or platinum silver alloy phase provides the coating with both low emissivity and high temperature stability.
The applicant states that although the detailed composition and method of preparation of the present invention have been shown and described, it will be apparent to those skilled in the art that the present invention is not limited to practice with the aid of the detailed composition and method of preparation described above. Any improvement, substitution of product raw materials, addition of auxiliary components and the like of the invention are within the protection scope and the disclosure scope of the invention.
Claims (10)
1. The heat protection metal enamel composite coating with low infrared emissivity is characterized in that the composite coating sequentially comprises an enamel layer, a platinum-doped enamel layer and a metal layer from inside to outside, wherein the metal layer is a pure platinum layer or a platinum-silver alloy layer, the thickness of the enamel layer is 5-10 mu m, the thickness of the platinum-doped enamel layer is 5-10 mu m, and the thickness of the metal layer is 10-15 mu m; the composition of each layer of the composition is as follows:
enamel layer: 50-65% of silicon dioxide, 6-11% of zirconium dioxide, 3-10% of aluminum oxide, 2-6% of boron trioxide, 3-7% of calcium oxide, 7-13% of strontium oxide, 2-6% of potassium oxide, and 16-22% of total content of calcium oxide, strontium oxide and potassium oxide;
platinum-doped enamel layer: 80-90% of enamel glaze and 10-20% of platinum; wherein, the enamel glaze component is the same as the enamel layer component: 50-65% of silicon dioxide, 6-11% of zirconium dioxide, 3-10% of aluminum oxide, 2-6% of boron trioxide, 3-7% of calcium oxide, 7-13% of strontium oxide, 2-6% of potassium oxide, and 16-22% of total content of calcium oxide, strontium oxide and potassium oxide;
metal layer: silver 0-50% and platinum 50-100%.
2. A method for preparing a thermal protective metal enamel composite coating having low infrared emissivity as claimed in claim 1, comprising the steps of: 1) Smelting enamel glaze; 2) Preparing enamel micropowder; 3) Preparing composite enamel suspension; 4) Spraying composite enamel suspension; 5) Preparing a platinum-doped composite enamel suspension; 6) Spraying platinum-doped composite enamel suspension; 7) Preparing a metal powder suspension; 8) Spraying a metal powder suspension; 9) The composite coating is fired and polished after cooling.
3. The method for producing a heat-protective metal enamel composite coating having a low infrared emissivity according to claim 2, characterized in that steps 1) to 4) produce an enamel layer, in particular:
step 1): ball milling and mixing various oxides according to the formula of the enamel layer, wherein the rotating speed is 300-350 r/min, the time is 20-30 hours, and the heating and smelting are carried out after the uniform mixing, and the smelting process is as follows: RT-300-600 ℃, and heating at uniform speed for 0.5-1.5 hours; heating at the average speed of 25-35 minutes at the temperature of 300-600 ℃ to 800-1100 ℃; heating at a constant speed of between 800 and 1100 ℃ and between 1300 and 1550 ℃ for 0.5 to 1.5 hours; maintaining the constant temperature of 1300-1550 ℃ for 1-2 hours, and then performing water quenching to obtain enamel glaze particles;
step 2): carrying out ball milling on enamel glaze particles obtained after water quenching to obtain enamel micro powder with the particle size less than or equal to 5 mu m;
step 3): absolute ethyl alcohol or purified water is taken as dispersing agent, 10 ml to 30ml of absolute ethyl alcohol or purified water required by 1 gram of enamel micropowder is mixed, and the enamel suspension with uniform dispersion is obtained through magnetic stirring and ultrasonic vibration for 15min to 30 min;
step 4): and uniformly spraying enamel suspension on the surface of the high-temperature alloy part by using an air compressor, wherein the spraying pressure is 0.2-0.4 MPa, and the spraying distance is 15-40 cm.
4. The method for preparing a thermal protection metal enamel composite coating with low infrared emissivity according to claim 3, wherein the initial enamel layer is obtained after the thermal protection metal enamel composite coating is sprayed and dried for 20-30 min by an oven with the temperature of 200-300 ℃.
5. The method for producing a heat-protective metal enamel composite coating having low infrared emissivity according to claim 2 or 4, characterized in that steps 5) to 6) produce a platinum-doped enamel layer, in particular:
step 5): preparing platinum-doped composite enamel powder from enamel micro powder and platinum powder, mixing 10-30 ml of absolute ethyl alcohol or purified water required by 1g of platinum-doped composite enamel powder with absolute ethyl alcohol or purified water serving as a dispersing agent, magnetically stirring and ultrasonically oscillating for 15-30 min to obtain uniformly dispersed platinum-doped composite enamel suspension;
step 6): and uniformly spraying the platinum-doped composite enamel suspension on the enamel layer on the surface of the high-temperature alloy part by using an air compressor, wherein the spraying pressure is 0.2-0.4 MPa, and the spraying distance is 15-40 cm.
6. The method for preparing a thermal protection metal enamel composite coating with low infrared emissivity according to claim 5, wherein the platinum-doped enamel layer is obtained after the thermal protection metal enamel composite coating is dried for 20-30 min by a baking oven at 200-300 ℃ after being sprayed.
7. The method for producing a heat-protective metal enamel composite coating having a low infrared emissivity according to claim 2 or 6, characterized in that steps 7) to 8) produce a metal layer, in particular:
step 7): preparing silver powder and platinum powder according to a proportion or directly taking the platinum powder as metal powder, wherein the particle size of the original powder of the silver powder and the platinum powder is less than or equal to 10 mu m, taking absolute ethyl alcohol or purified water as a dispersing agent, mixing 30-35 ml of absolute ethyl alcohol or purified water required by 1 gram of metal powder, and carrying out magnetic stirring and ultrasonic vibration for 3-5 min to obtain a uniformly dispersed metal powder suspension;
step 8): and uniformly spraying the metal powder suspension on the platinum-doped enamel layer on the surface of the high-temperature alloy part by using an air compressor, wherein the spraying pressure is 0.2-0.4 MPa, and the spraying distance is 15-40 cm.
8. The method for preparing a thermal protection metal enamel composite coating with low infrared emissivity according to claim 7, wherein the metal layer is obtained after the thermal protection metal enamel composite coating is sprayed and dried for 20-30 min by an oven with the temperature of 200-300 ℃.
9. The method for producing a heat-protective metal enamel composite coating having a low infrared emissivity according to claim 2 or 8, wherein step 9) comprises: after being sprayed and dried in sequence, the original blank of the composite coating of the enamel layer, the platinum-doped enamel layer and the metal layer is obtained, and then sintering treatment is carried out, wherein two sintering schemes are adopted: (1) Sintering the dried composite coating original blank at a high temperature of 1000-1100 ℃ for 10-20 min, taking out, and cooling in the atmosphere; after cooling, polishing by using 2000-mesh sand paper and then using 1-micrometer diamond grinding paste until the surface roughness of the coating is Ra less than or equal to 2 mu m, thus obtaining the heat protection metal enamel composite coating; (2) Firstly, preserving heat of the dried composite coating original blank for 1-3 hours at 800-950 ℃, then heating to 1000-1100 ℃ in a furnace, sintering at high temperature for 10-20 min, cooling to 600-800 ℃ in the furnace, taking out and cooling in the atmosphere; and (3) after cooling, polishing by using 2000-mesh sand paper and then using 1-micrometer diamond grinding paste until the surface roughness of the coating is Ra less than or equal to 2 mu m, thus obtaining the heat protection metal enamel composite coating.
10. The method for producing a heat-protective metal enamel composite coating having a low infrared emissivity according to claim 2 or 9, characterized in that the performance index of the composite coating is as follows:
thickness less than or equal to 25 μm, surface roughness: ra is less than or equal to 2 mu m, bonding strength is less than or equal to 15MPa, no crack exists when air cooling is performed 1000 times at 900 ℃, heat insulation temperature is less than or equal to 100 ℃, seawater immersion corrosion resistance life is less than or equal to 150h, salt spray corrosion resistance life is less than or equal to 1000h, and gas hot corrosion rate is less than or equal to 0.5g/m 2 h, completely resisting oxidation at 900 ℃; infrared emissivity is less than 0.15 at 50 ℃ and 900 ℃ in the wave bands of 3-5 mu m and 8-14 mu m.
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