CN116445018A - High-temperature oxidation resistant protective coating for titanium alloy surface and preparation method thereof - Google Patents
High-temperature oxidation resistant protective coating for titanium alloy surface and preparation method thereof Download PDFInfo
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- CN116445018A CN116445018A CN202310410974.6A CN202310410974A CN116445018A CN 116445018 A CN116445018 A CN 116445018A CN 202310410974 A CN202310410974 A CN 202310410974A CN 116445018 A CN116445018 A CN 116445018A
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 63
- 230000003647 oxidation Effects 0.000 title claims abstract description 62
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 62
- 239000011253 protective coating Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 73
- 239000011248 coating agent Substances 0.000 claims abstract description 70
- 239000010410 layer Substances 0.000 claims abstract description 39
- 239000002344 surface layer Substances 0.000 claims abstract description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims abstract description 21
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 26
- 239000002694 phosphate binding agent Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 19
- 238000005507 spraying Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010790 dilution Methods 0.000 claims description 12
- 239000012895 dilution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005488 sandblasting Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- 244000137852 Petrea volubilis Species 0.000 claims description 6
- YQOPHINZLPWDTA-UHFFFAOYSA-H [Al+3].[Cr+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Al+3].[Cr+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YQOPHINZLPWDTA-UHFFFAOYSA-H 0.000 claims description 6
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- NXMRPJWKUHQMML-UHFFFAOYSA-K [Cr+3].P(=O)([O-])([O-])[O-].[Mg+2] Chemical compound [Cr+3].P(=O)([O-])([O-])[O-].[Mg+2] NXMRPJWKUHQMML-UHFFFAOYSA-K 0.000 claims description 5
- DOEVMNBDNQNWEJ-UHFFFAOYSA-K aluminum;magnesium;phosphate Chemical compound [Mg+2].[Al+3].[O-]P([O-])([O-])=O DOEVMNBDNQNWEJ-UHFFFAOYSA-K 0.000 claims description 5
- 238000001723 curing Methods 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 238000013461 design Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 238000013007 heat curing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims description 2
- 238000007788 roughening Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 10
- 230000007774 longterm Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 238000005303 weighing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 239000004033 plastic Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000007667 floating Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004372 laser cladding Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/546—No clear coat specified each layer being cured, at least partially, separately
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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
- 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
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
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- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
The invention provides a high-temperature oxidation resistant protective coating for a titanium alloy surface and a preparation method thereof, belonging to the technical field of surface protection of metal and alloy materials. The high-temperature oxidation resistant protective coating consists of a double-layer structure, wherein the bottom layer is an inorganic phosphate insulating and shielding layer filled with spherical aluminum powder and nano silicon dioxide with different sizes, and the molten expansion of the aluminum powder under the high-temperature condition and the barrier and shielding effect of a densified oxide layer formed by preferential reaction with oxygen molecules are fully utilized, so that the oxidation of the surface of a titanium alloy matrix in a long-term high-temperature environment is avoided. The surface layer is an inorganic phosphate hole sealing layer filled with a small amount of nano titanium dioxide, the high fluidity of the surface layer coating is fully utilized to further improve the compactness and the smoothness of the whole coating, and the excellent high-temperature oxidation resistance protection effect of the composite coating is realized. The coating prepared by the invention is firmly combined with the titanium alloy matrix, has simple coating process, and meets the high-temperature oxidation resistance protection requirement of large-scale complex special-shaped titanium alloy structural members.
Description
Technical Field
The invention relates to a high-temperature oxidation resistant protective coating, in particular to a long-term high-temperature oxidation resistant protective coating for a titanium alloy surface and a preparation method thereof, and belongs to the technical field of surface protection.
Background
Compared with metal materials such as high-temperature alloy and steel, the titanium alloy has the performance advantages of low density, high specific strength, fatigue resistance, corrosion resistance, wide working temperature range and the like, and has wide application in the field of aeroengines, for example, key parts such as fans, low-pressure compressors and high-pressure compressors, such as blades, discs, blisks, journals, shafts, casings and the like, and various pipelines, fasteners and the like are made of titanium alloy materials. At present, the consumption of the titanium alloy on the advanced aero-engine is about 25% -40% of the weight of the whole machine, and the massive use of the titanium alloy in the field of aviation plays a key role in reducing the structural weight of the engine, improving the thrust-weight ratio (or the power-weight ratio), reducing the fuel consumption rate and the like.
However, titanium alloys can lead to surface oxidation in long term high temperature environments, resulting in reduced performance, especially when temperatures exceeding 500 ℃, where the titanium alloy surface oxidizes to form loose, porous surfacesTiO of (C) 2 The layer has poor protective performance. Meanwhile, as the interstitial atoms such as O, N have high solid solubility in the alloy, the content of the interstitial atoms is increased after long-time exposure under high-temperature conditions, so that the titanium alloy has high-temperature oxygen embrittlement phenomenon, and the alloy is invalid. The main methods for solving the oxidation failure in the high-temperature environment of the titanium alloy are alloying, surface modification, application of high-temperature oxidation-resistant protective coating and the like, wherein the oxidation-resistant coating technology is one of the most effective and main technologies. According to the difference of the preparation process, the common preparation methods of the high-temperature protective coating on the surface of the titanium alloy at present comprise plasma spraying, laser cladding, magnetron sputtering, thermal diffusion infiltration, melt sintering, ion implantation, physical/chemical vapor deposition, bonding coating technology and the like. The bonding coating technology can carry out coating construction at lower temperature under simpler experimental environment, has simple, convenient and economic process, is suitable for coating construction and protection of complex special-shaped structural members, and is a relatively promising technical method. However, the common problem of the existing bonding type high-temperature oxidation resistant coating is that the high-temperature resistance with good bonding strength with the titanium alloy matrix is poor, and the bonding strength and the film forming property of the coating material with good high-temperature resistance are poor. In view of this, the present invention has been made.
Disclosure of Invention
The invention mainly aims to provide a high-temperature oxidation resistant protective coating on the surface of a titanium alloy and a preparation method thereof. The high-temperature oxidation resistant coating prepared by the invention is well combined with the titanium alloy matrix under the long-term high-temperature condition, and can meet the long-term high-temperature oxidation resistant protection requirement of the titanium alloy structure below 650 ℃. Meanwhile, the preparation method of the coating is simple, the coating process is convenient, and the coating is particularly suitable for long-term high-temperature oxidation resistance protection of the surface of the complex curved surface special-shaped titanium alloy structural member.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the high-temperature oxidation resistant protective coating for the surface of the titanium alloy is of a double-layer structure design, the bottom layer is an inorganic phosphate oxidation resistant protective layer filled with spherical aluminum powder with different sizes and nano silicon dioxide, and the surface layer is an inorganic phosphate hole sealing layer filled with nano titanium dioxide; the bottom layer comprises the following components in percentage by mass: 10-20% of a first inorganic phosphate binder, 40-50% of spherical aluminum powder with different sizes, 5-10% of nano silicon dioxide and the balance of deionized water; the surface layer comprises the following components in percentage by mass: 40-50% of a second type of inorganic phosphate binder, 10-20% of nano titanium dioxide and the balance of deionized water; the first inorganic phosphate is inorganic aluminum magnesium phosphate or inorganic aluminum phosphate binder, and the second inorganic phosphate is inorganic aluminum chromium phosphate or inorganic magnesium chromium phosphate binder.
The spherical aluminum powder with different sizes is a mixture of two spherical aluminum powder with different size distributions, the particle size of the first spherical aluminum powder is 1-2 mu m, the particle size of the second spherical aluminum powder is 3-4 mu m, and the ratio of the two spherical aluminum powder to the second spherical aluminum powder is 1:1-5:1. The particle size of the nano silicon dioxide is 2-9 nm, and the purity is more than 99.9%. The particle size of the nano titanium dioxide is 20-40 nm, and the purity is more than 99.5%.
The high-temperature oxidation resistant protective coating for the titanium alloy surface consists of a double-layer structure, wherein the bottom layer is a first inorganic phosphate insulating and shielding layer filled with spherical aluminum powder and nano silicon dioxide composite filler with different sizes, and oxidation of the titanium alloy substrate surface in a long-term high-temperature environment is avoided by utilizing the barrier and shielding effects of fusion expansion of aluminum powder particles under a high-temperature condition and preferential reaction of aluminum powder and partial oxygen molecules to form an oxide densification layer; the surface layer is a second type inorganic phosphate hole sealing layer filled with a small amount of nano titanium dioxide and having high fluidity, and the high fluidity of the second type inorganic phosphate paint is fully utilized to further improve the compactness and the smoothness of the whole coating. The double-layer structure design finally ensures that the composite coating has excellent high-temperature oxidation resistance protection effect. Meanwhile, the selected first-class phosphate binder and the second-class phosphate binder have good high-temperature stability and excellent bonding strength with the titanium alloy matrix, so that the first-class phosphate binder and the second-class phosphate binder still maintain good bonding strength and excellent oxidation resistance and protection under the repeated high-temperature impact environment.
The preparation method of the high-temperature oxidation resistant protective coating on the surface of the titanium alloy comprises the following steps:
(1) Preparation of the coating: adding a first type of inorganic phosphate binder into deionized water, adding spherical aluminum powder with different sizes, stirring, adding nano silicon dioxide, and stirring and uniformly mixing to obtain a primer; adding deionized water into the second inorganic phosphate binder for dilution, then continuously adding nano titanium dioxide, and stirring and uniformly mixing to obtain a surface layer coating;
(2) Titanium alloy surface pretreatment
Carrying out sand paper polishing or sand blasting roughening treatment on the surface of the titanium alloy matrix, and cleaning the surface by an organic solvent to obtain a clean titanium alloy roughened surface;
the abrasive paper with the abrasive paper roughness of 1000-1600 meshes is selected, the abrasive paper blasting pressure is preferably 4-6 MPa, the organic solvent is acetone or absolute ethyl alcohol, the ultrasonic treatment is carried out for 2 times in the cleaning treatment process, and the ultrasonic time is more than 15 minutes each time;
(3) Coating the surface of titanium alloy with primer
Uniformly coating the primer on the surface of the coarsened titanium alloy matrix by using an air spray gun or a brush coating mode, controlling the thickness of the primer through the coating times, placing the titanium alloy matrix at room temperature for surface drying, heating and thermally curing the titanium alloy matrix in a high-temperature furnace, and naturally cooling the titanium alloy matrix to the room temperature;
in order to obtain better uniformity, air spray guns are preferably selected for spraying, the pressure of the spray guns is 0.4-0.5 MPa, the thickness of a bottom layer is controlled to be 15-20 mu m, the standing time at room temperature is 3-8 h, the heating curing condition is that the temperature is kept at 110-120 ℃ for 2h, and then the temperature is raised to 330-350 ℃ for 1 h;
(4) Continuously coating surface layer paint on titanium alloy bottom layer
Coating the surface layer on the surface of the solidified bottom layer by using an air spray gun or a brush coating mode, controlling the thickness of the surface layer through the spraying times, and obtaining a high-temperature oxidation resistant protective coating after heating and heat curing in a high-temperature furnace after the surface of the coating is dried;
the thickness of the surface layer is 5-10 mu m, the heating curing condition is that the temperature is raised to 300-310 ℃ after the heat preservation is carried out for 2 hours at 110-120 ℃, and the heat preservation is carried out for 1-h.
Compared with the prior art, the invention has the following effects and benefits:
(1) The composite coating consists of a bottom layer isolation shielding layer and a double-layer structure of a surface layer high-fluidity densification layer, and can meet the long-term high-temperature oxidation resistance protection requirement of a titanium alloy substrate below 650 ℃;
(2) The bottom continuous phase binder of the composite coating is inorganic aluminum magnesium phosphate or inorganic aluminum phosphate binder, has good high-temperature stability and good bonding strength with a titanium alloy substrate, and still has good bonding strength under the conditions of repeated heat shock and long-term high temperature;
(3) The basic binder of the surface layer of the composite coating is inorganic aluminum chromium phosphate or inorganic magnesium chromium phosphate binder, has a structure similar to that of the bottom layer binder, can ensure good bonding strength between the bottom layer and the surface layer, and simultaneously, the surface layer is filled with a small amount of nano titanium dioxide, so that the compactness and surface smoothness of the whole coating can be obviously improved due to the characteristics of low viscosity and high fluidity, and the excellent high-temperature oxidation resistance and protection performance of the composite coating are endowed;
(4) The method is simple, is suitable for industrial production, has simple and convenient coating process, and is particularly suitable for high-temperature oxidation resistance protection of the surface of the complex special-shaped titanium alloy structural member.
Drawings
FIG. 1 is a cross-sectional morphology diagram of the composite coating prepared in example 1 after heat preservation at 650 ℃ of 300 h;
FIG. 2 is a cross-sectional morphology of the composite coating of comparative example 1 after thermal insulation 300 h at 650 ℃.
Detailed Description
The technical scheme of the present invention will be further described in detail with reference to several preferred examples and accompanying drawings, wherein specific conditions and test methods not explicitly described in the following examples and comparative examples are generally conventional, and materials used in the examples and comparative examples are commercially available.
Example 1
Preparation of primer: accurately weighing 15g of aluminum magnesium phosphate binder in a three-neck flask, adding 30g of deionized water for dilution, mechanically stirring at room temperature, slowly adding 30g of spherical aluminum powder with the particle size of 1-2 microns, continuously mechanically stirring at room temperature for 1 hour after 20g of spherical aluminum powder with the particle size of 3-4 microns, adding 5g of nano silicon dioxide, continuously stirring for 1 hour, and transferring to a plastic tank for later use;
surface coating is prepared from the following steps: accurately weighing 40g of chromium aluminum phosphate binder in a three-neck flask, adding 40g of deionized water for dilution, continuously adding 20g of nano titanium dioxide, mechanically stirring for 1 hour, and uniformly mixing for later use;
preparing a high-temperature oxidation resistant coating: and (3) carrying out sand blasting treatment on a TC4 titanium alloy test piece, then carrying out ultrasonic cleaning in acetone, uniformly spraying a primer on a TC4 substrate by using a compressed air spray gun with the pressure of 0.4MPa, controlling the thickness of the coating to be about 18 microns through repeated spraying, standing at room temperature for 5 hours, keeping the temperature in a muffle furnace at 120 ℃ for 2 hours, then continuously heating to 340 ℃ for 1 hour, naturally cooling to room temperature, polishing the surface by using 800-mesh sand paper, removing surface layer floating powder and coarsening, continuously spraying a surface layer coating on the primer, controlling the thickness to be about 10 microns, continuously keeping the temperature in the muffle furnace at 110 ℃ for 2 hours, heating to 310 ℃ for 1 hour, and naturally cooling to room temperature to obtain the high-temperature oxidation resistant protective coating prepared on the titanium alloy surface.
Example 2
Preparation of primer: accurately weighing 18g of aluminum phosphate binder in a three-neck flask, adding 27g of deionized water for dilution, mechanically stirring at room temperature, slowly adding 40g of spherical aluminum powder with the particle size of 1-2 microns, continuously mechanically stirring at room temperature for 1 hour after 10g of aluminum powder with the particle size of 3-4 microns, adding 5g of nano silicon dioxide, continuously stirring for 1 hour, and transferring to a plastic tank for standby;
preparing a surface layer coating: accurately weighing 40g of chromium aluminum phosphate binder in a three-neck flask, adding 40g of deionized water for dilution, continuously adding 20g of nano titanium dioxide, mechanically stirring for 1 hour, and uniformly mixing for later use;
preparing a high-temperature oxidation resistant coating: and (3) carrying out sand blasting treatment on a TC4 titanium alloy test piece, then carrying out ultrasonic cleaning in acetone, uniformly spraying a surface layer coating on a TC4 substrate by using a compressed air spray gun with the pressure of 0.4MPa, controlling the thickness of the coating to be about 18 microns through repeated spraying, standing for 5 hours at room temperature, keeping the temperature in a muffle furnace at 120 ℃ for 2 hours, then continuously heating to 340 ℃ for 1 hour, naturally cooling to room temperature, polishing the surface by using 800-mesh sand paper, removing surface layer floating powder and coarsening, continuously spraying a surface layer coating on a bottom layer, controlling the thickness to be about 10 microns, continuously keeping the temperature in the muffle furnace at 110 ℃ for 2 hours, heating to 310 ℃ for 1 hour, and naturally cooling to room temperature to obtain the high-temperature oxidation resistant protective coating prepared on the titanium alloy surface.
Example 3
Preparation of primer: accurately weighing 18g of aluminum phosphate binder in a three-neck flask, adding 27g of deionized water for dilution, mechanically stirring at room temperature, slowly adding 40g of spherical aluminum powder with the particle size of 1-2 microns, continuously mechanically stirring at room temperature for 1 hour after 10g of aluminum powder with the particle size of 3-4 microns, adding 5g of nano silicon dioxide, continuously stirring for 1 hour, and transferring to a plastic tank for standby;
preparing a surface layer coating: accurately weighing 50g of chromium-magnesium phosphate binder in a three-neck flask, adding 30g of deionized water for dilution, continuously adding 20g of nano titanium dioxide, mechanically stirring for 1 hour, and uniformly mixing for later use;
preparing a high-temperature oxidation resistant coating: and (3) carrying out sand blasting treatment on a TC4 titanium alloy test piece, then carrying out ultrasonic cleaning in acetone, uniformly spraying a surface layer coating on a TC4 substrate by using a compressed air spray gun with the pressure of 0.4MPa, controlling the thickness of the coating to be about 18 microns through repeated spraying, standing for 5 hours at room temperature, keeping the temperature in a muffle furnace at 120 ℃ for 2 hours, then continuously heating to 340 ℃ for 1 hour, naturally cooling to room temperature, polishing the surface by using 800-mesh sand paper, removing surface layer floating powder and coarsening, continuously spraying a surface layer coating on a bottom layer, controlling the thickness to be about 10 microns, continuously keeping the temperature in the muffle furnace at 110 ℃ for 2 hours, heating to 310 ℃ for 1 hour, and naturally cooling to room temperature to obtain the high-temperature oxidation resistant protective coating prepared on the titanium alloy surface.
Example 4
Preparation of primer: accurately weighing 16g of aluminum phosphate binder in a three-neck flask, adding 26g of deionized water for dilution, mechanically stirring at room temperature, slowly adding 44g of spherical aluminum powder with the particle size of 1-2 microns, continuously mechanically stirring at room temperature for 1 hour after 10g of aluminum powder with the particle size of 3-4 microns, adding 5g of nano silicon dioxide, continuously stirring for 1 hour, and transferring to a plastic tank for standby;
preparing a surface layer coating: accurately weighing 48g of chromium-magnesium phosphate binder in a three-neck flask, adding 32g of deionized water for dilution, continuously adding 18g of nano titanium dioxide, mechanically stirring for 1 hour, and uniformly mixing for later use;
preparing a high-temperature oxidation resistant coating: and (3) carrying out sand blasting treatment on a TC4 titanium alloy test piece, then carrying out ultrasonic cleaning in acetone, uniformly spraying a surface layer coating on a TC4 substrate by using a compressed air spray gun with the pressure of 0.4MPa, controlling the thickness of the coating to be about 18 microns through repeated spraying, standing for 5 hours at room temperature, keeping the temperature in a muffle furnace at 120 ℃ for 2 hours, then continuously heating to 340 ℃ for 1 hour, naturally cooling to room temperature, polishing the surface by using 800-mesh sand paper, removing surface layer floating powder and coarsening, continuously spraying a surface layer coating on a bottom layer, controlling the thickness to be about 10 microns, continuously keeping the temperature in the muffle furnace at 110 ℃ for 2 hours, heating to 310 ℃ for 1 hour, and naturally cooling to room temperature to obtain the high-temperature oxidation resistant protective coating prepared on the titanium alloy surface.
Comparative example 1
Preparation of primer: accurately weighing 15g of aluminum magnesium phosphate binder in a three-neck flask, adding 30g of deionized water for dilution, mechanically stirring at room temperature, slowly adding 30g of spherical aluminum powder with the particle size of 1-2 microns, continuously mechanically stirring at room temperature for 1 hour after 20g of aluminum powder with the particle size of 3-4 microns, adding 5g of nano silicon dioxide, continuously stirring for 1 hour, and transferring to a plastic tank for later use;
preparing a high-temperature oxidation resistant coating: and (3) carrying out sand blasting treatment on the TC4 titanium alloy test piece, then carrying out ultrasonic cleaning in acetone, uniformly spraying the primer on the TC4 base material by using a compressed air spray gun with the pressure of 0.4MPa, controlling the thickness of the coating to be about 28 microns through multiple spraying, standing for 5 hours at room temperature, then carrying out heat preservation in a muffle furnace at 120 ℃ for 2 hours, then continuously heating to 340 ℃ for 1 hour, and naturally cooling to the room temperature to obtain the protective coating of the primer coated on the titanium alloy surface.
Comparative example 2
Preparing a surface layer coating: accurately weighing 40g of chromium aluminum phosphate binder in a three-neck flask, adding 40g of deionized water for dilution, continuously adding 20g of nano titanium dioxide, mechanically stirring for 1 hour, and uniformly mixing for later use;
preparing a high-temperature oxidation resistant coating: and (3) carrying out sand blasting treatment on the TC4 titanium alloy test piece, then carrying out ultrasonic cleaning in acetone, uniformly spraying the surface layer coating on the TC4 substrate by using a compressed air spray gun with the pressure of 0.4MPa, controlling the thickness of the coating to be about 28 microns through multiple spraying, standing for 5 hours at room temperature, carrying out heat preservation in a muffle furnace for 2 hours at 110 ℃, then carrying out heat preservation for 1 hour at 310 ℃, and naturally cooling to the room temperature to obtain the high-temperature oxidation resistant protective coating of the surface layer coating on the titanium alloy surface.
After the high temperature oxidation resistant protective coating prepared on the surface of TC4 by the method described in examples 1 to 4 and comparative examples 1 to 2 was kept for 300 hours in a high temperature muffle furnace at 650 ℃, the cross section of the coating and the oxidation condition of the substrate were observed under a scanning electron microscope (see fig. 1 and 2), the oxidation degree of the titanium alloy substrate was represented by the thickness of the oxidation layer, and the thickness results of the oxidation layer after the heat treatment of examples and comparative examples are shown in table 1 below.
As can be seen from Table 1, the high temperature oxidation resistant protective coating prepared by the method of the invention has good high temperature oxidation resistance. Comparing examples 1-4 with comparative example 1, the primer alone, when used as a titanium alloy high temperature oxidation resistant coating layer, exhibited a certain oxidation resistance, but the titanium alloy substrate surface oxide layer (contaminated layer) still had a thickness exceeding 12 microns (fig. 2), exhibiting a poor high temperature oxidation resistance. Comparing examples 1 to 4 with comparative example 2, when the top coat paint alone was used as the high temperature oxidation resistant coating, the coating had substantially no high temperature oxidation resistant effect. Obviously, by the design of the double-layer structure, the composite coating shows excellent high-temperature oxidation resistance protection effect on the surface of the titanium alloy.
In addition, the inventors have conducted corresponding experiments using other process conditions listed above in place of the corresponding process conditions in examples 1-4, and the like, and the content of the verification required and the product of examples 1-4 are close. Therefore, the verification contents of each example are not described one by one, and only examples 1 to 4 are used as representative to describe the excellent points of the present invention.
It should be understood that the foregoing is only a few embodiments of the present invention, and it should be noted that other modifications and improvements can be made by those skilled in the art without departing from the inventive concept of the present invention, which fall within the scope of the present invention.
Claims (6)
1. The high-temperature oxidation resistant protective coating for the surface of the titanium alloy is characterized in that: the high-temperature oxidation resistant protective coating is of a double-layer structure design, the bottom layer is an inorganic phosphate oxidation resistant protective layer filled with spherical aluminum powder with different sizes and nano silicon dioxide, and the surface layer is an inorganic phosphate hole sealing layer filled with nano titanium dioxide; the bottom layer comprises the following components in percentage by mass: 10-20% of a first inorganic phosphate binder, 40-50% of spherical aluminum powder with different sizes, 5-10% of nano silicon dioxide and the balance of deionized water; the surface layer comprises the following components in percentage by mass: 40-50% of a second type of inorganic phosphate binder, 10-20% of nano titanium dioxide and the balance of deionized water;
the first inorganic phosphate is inorganic aluminum magnesium phosphate or inorganic aluminum phosphate binder, and the second inorganic phosphate is inorganic aluminum chromium phosphate or inorganic magnesium chromium phosphate binder.
2. The high temperature oxidation resistant protective coating for a titanium alloy surface of claim 1, wherein: the spherical aluminum powder with different sizes is a mixture of two spherical aluminum powder with different size distributions, the particle size of the first spherical aluminum powder is 1-2 mu m, the particle size of the second spherical aluminum powder is 3-4 mu m, and the ratio of the two spherical aluminum powder to the second spherical aluminum powder is 1:1-5:1.
3. The high temperature oxidation resistant protective coating for a titanium alloy surface of claim 1, wherein: the particle size of the nano silicon dioxide is 2-9 nm, and the purity is more than 99.9%.
4. The high temperature oxidation resistant protective coating for a titanium alloy surface of claim 1, wherein: the particle size of the nano titanium dioxide is 20-40 nm, and the purity is more than 99.5%.
5. The method for preparing the high-temperature oxidation resistant protective coating for the surface of the titanium alloy according to any one of claims 1 to 4, wherein: the preparation method of the high-temperature oxidation resistant protective coating comprises the following steps:
(1) Adding a first type of inorganic phosphate binder into deionized water, adding spherical aluminum powder with different sizes, stirring, adding nano silicon dioxide, and stirring and uniformly mixing to obtain a primer; adding deionized water into the second inorganic phosphate binder for dilution, then continuously adding nano titanium dioxide, and stirring and uniformly mixing to obtain a surface layer coating;
(2) Performing sand paper polishing or sand blasting roughening treatment on the titanium alloy substrate, and cleaning the titanium alloy substrate by an organic solvent to obtain a clean titanium alloy roughened surface;
(3) Uniformly coating the primer on the roughened surface of the alloy by using an air spray gun or a brush coating mode, controlling the thickness of the primer by coating times, placing the primer at room temperature, and naturally cooling to room temperature after heating and heat curing in a high-temperature furnace;
(4) And continuously coating a surface layer on the surface of the solidified bottom layer by using an air spray gun or a brush coating mode, controlling the thickness of the surface layer through the spraying times, and obtaining the high-temperature oxidation resistant protective coating after the surface of the coating is dried and heated in a high-temperature furnace.
6. The method for preparing the high-temperature oxidation resistant protective coating for the surface of the titanium alloy according to claim 5, wherein the method comprises the following steps: the heating and curing conditions of the bottom layer in the step (3) are that the temperature is kept at 110-120 ℃ for 2h, then the temperature is raised to 330-350 ℃ for 1-h; and (3) heating and curing the surface layer in the step (4) under the condition of heat preservation at 110-120 ℃ for 2 hours, and then heating to 300-310 ℃ and preserving heat for 1 h.
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