CN116770301B - Zirconium-based amorphous alloy-aluminum alloy composite material coating and preparation method thereof - Google Patents
Zirconium-based amorphous alloy-aluminum alloy composite material coating and preparation method thereof Download PDFInfo
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- CN116770301B CN116770301B CN202311064247.5A CN202311064247A CN116770301B CN 116770301 B CN116770301 B CN 116770301B CN 202311064247 A CN202311064247 A CN 202311064247A CN 116770301 B CN116770301 B CN 116770301B
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- aluminum alloy
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- amorphous alloy
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 184
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 112
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 238000000576 coating method Methods 0.000 title claims abstract description 71
- 239000011248 coating agent Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 233
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims abstract description 136
- 238000000034 method Methods 0.000 claims abstract description 89
- 239000000758 substrate Substances 0.000 claims abstract description 88
- 238000005507 spraying Methods 0.000 claims abstract description 71
- 230000008569 process Effects 0.000 claims abstract description 68
- 238000007750 plasma spraying Methods 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 238000004372 laser cladding Methods 0.000 claims abstract description 28
- 239000007921 spray Substances 0.000 claims description 75
- 238000002156 mixing Methods 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 44
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 36
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 238000000498 ball milling Methods 0.000 claims description 28
- 230000010355 oscillation Effects 0.000 claims description 28
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000011159 matrix material Substances 0.000 claims description 20
- 239000011268 mixed slurry Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 239000001307 helium Substances 0.000 claims description 14
- 229910052734 helium Inorganic materials 0.000 claims description 14
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 238000005253 cladding Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003945 anionic surfactant Substances 0.000 claims description 10
- 239000003093 cationic surfactant Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011863 silicon-based powder Substances 0.000 claims description 10
- 239000011258 core-shell material Substances 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 6
- -1 hydroxypropyl methyl Chemical group 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
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- 239000000126 substance Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 32
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- 239000000155 melt Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 230000009471 action Effects 0.000 description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 10
- 230000007547 defect Effects 0.000 description 8
- 229910000765 intermetallic Inorganic materials 0.000 description 8
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
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- 230000008023 solidification Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 230000005684 electric field Effects 0.000 description 2
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- 230000007246 mechanism Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
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- 238000001764 infiltration Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
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- 230000008646 thermal stress Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/026—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one amorphous metallic material layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/08—Metallic powder characterised by particles having an amorphous microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
-
- 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
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/027—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal matrix material comprising a mixture of at least two metals or metal phases or metal matrix composites, e.g. metal matrix with embedded inorganic hard particles, CERMET, MMC.
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention provides a zirconium-based amorphous alloy-aluminum alloy composite coating and a preparation method thereof, wherein the preparation method comprises the following steps: taking aluminum alloy powder as a raw material, and forming an aluminum alloy layer on the surface of a substrate by adopting a laser cladding process; the method comprises the steps of taking zirconium-based amorphous alloy powder as a raw material, and forming a zirconium-based amorphous alloy layer on the surface of an aluminum alloy layer by adopting a plasma spraying process. According to the invention, the aluminum alloy layer is prepared on the surface of the substrate by adopting a laser cladding process, and the zirconium-based amorphous alloy powder shows good wettability in spraying by utilizing a plasma spraying process, so that the zirconium-based amorphous alloy powder fully permeates and spreads on the surface of the aluminum alloy layer, the interface bonding strength between the zirconium-based amorphous alloy powder and the aluminum alloy layer is improved, and the prepared composite coating combines the corrosion resistance of the aluminum alloy and the mechanical advantage of the zirconium-based amorphous alloy, and has high corrosion resistance, high hardness and high wear resistance.
Description
Technical Field
The invention belongs to the field of manufacturing of corrosion-resistant coating materials, and relates to a zirconium-based amorphous alloy-aluminum alloy composite material coating and a preparation method thereof.
Background
With the development of modern science and technology, the requirements of industrial production on material performance are increasingly high, and as working conditions of engineering machinery and the like are increasingly harsh, the materials are required to have corrosion resistance, wear resistance and the like, so that the requirements of pure metal materials are difficult to meet. Among them, the corrosive wear behavior is a widely existing problem in the application process of materials, and causes great harm to the economic development of society. Solving and delaying equipment damage caused by corrosion and abrasion, researching the corrosion and abrasion mechanism of the material, and improving the wear resistance and the corrosion resistance of the material is the difficulty and the key point of the research in the field of the material at the present stage.
Because of the unique microstructure, the bulk amorphous alloy has excellent mechanical properties which are incomparable with those of crystalline alloys, and has wide application in the industries of aviation, aerospace, IT electronics, machinery, chemical industry and the like. In an amorphous alloy system, the zirconium-based amorphous alloy has high amorphous forming capability and a wide supercooled liquid phase region, the requirement on forming equipment is relatively low, and the formed zirconium-based bulk amorphous alloy has high strength, high elasticity, high toughness and excellent wear resistance and corrosion resistance, so that the zirconium-based bulk amorphous alloy is a preferred material for the current corrosion-resistant coating.
However, due to the limitation of the composition of the zirconium-based amorphous alloy and the influence of the oxygen and nitrogen content in the preparation process, the corrosion resistance of the zirconium-based amorphous alloy in the prior art is generally difficult to pass the limit test in the conventional salt spray test, so that the zirconium-based amorphous alloy cannot be applied to the field of outdoor tools, such as the field of metal materials with very high requirements on corrosion resistance in the automobile industry. Therefore, there is a need to adjust and improve the structure and the preparation process of the zirconium-based amorphous alloy corrosion-resistant coating, and improve the corrosion resistance of the zirconium-based amorphous alloy while ensuring the strength of the coating.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the zirconium-based amorphous alloy-aluminum alloy composite coating and the preparation method thereof.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a zirconium-based amorphous alloy-aluminum alloy composite coating, the method comprising:
taking aluminum alloy powder as a raw material, and forming an aluminum alloy layer on the surface of a substrate by adopting a laser cladding process; the surface of the aluminum alloy powder is coated with a silicon carbide layer with a thickness of 150-200nm, for example, 150nm, 155nm, 160nm, 165nm, 170nm, 175nm, 180nm, 185nm, 190nm, 195nm or 200nm, but the aluminum alloy powder is not limited to the listed values, and other non-listed values in the range of the values are equally applicable;
forming a zirconium-based amorphous alloy layer on the surface of the aluminum alloy layer by using composite amorphous alloy powder as a raw material and adopting a plasma spraying process; the composite amorphous alloy powder is of a core-shell structure and comprises an inner core and an outer shell wrapping the inner core, wherein the inner core is zirconium-based amorphous alloy powder, and the outer shell is a transition metal oxide layer.
According to the invention, the aluminum alloy layer is prepared on the surface of the substrate by adopting the laser cladding process, the aluminum alloy powder and the surface of the substrate are rapidly heated and melted under the action of the laser beam, the aluminum alloy layer which is metallurgically bonded with the surface of the substrate is formed by self-excitation cooling after the laser beam is removed, the bonding between the aluminum alloy layer and the substrate can be more compact by adopting the laser cladding process, and the phenomenon of coating falling off can not occur in the friction process, so that the characteristics of wear resistance, corrosion resistance, heat resistance, oxidation resistance and the like of the surface of the substrate are obviously improved. The zirconium-based amorphous alloy layer is formed on the basis of the aluminum alloy layer through plasma spraying, the composite coating is formed by the aluminum alloy layer and the zirconium-based amorphous alloy layer, and the aluminum alloy layer is used as a transition connecting layer, so that the substrate and the zirconium-based amorphous alloy layer are effectively combined, and the problem of galvanic corrosion caused by overlarge potential difference of interface electrodes generated by direct contact of the zirconium-based amorphous alloy layer and the substrate is solved. In addition, the invention combines the corrosion resistance of the aluminum alloy and the mechanical advantage of the zirconium-based amorphous alloy, so that the prepared composite coating has high corrosion resistance, high hardness and high wear resistance.
The invention utilizes the plasma spraying process to ensure that the zirconium-based amorphous alloy powder shows good wettability when being sprayed, so as to fully permeate and spread on the surface of the aluminum alloy layer, and the interface bonding strength between the zirconium-based amorphous alloy powder and the aluminum alloy layer is improved. In addition, in the spraying process, the mutual diffusion of atoms of the zirconium-based amorphous alloy material and the aluminum alloy material at the interface is initiated, the chemical reaction of the zirconium-based amorphous alloy material and the aluminum alloy material at the interface is promoted by means of good wettability to obtain a continuous solid solution composed of intermetallic compounds, so that a composite coating of an aluminum alloy layer-intermetallic compound layer-zirconium-based amorphous alloy layer is formed on the surface of a substrate, and material layers with different mechanical properties are functionally superposed. The intermetallic compound layer between the aluminum alloy layer and the zirconium-based amorphous alloy layer can inhibit cracks from occurring on the aluminum alloy layer, and under the action of large deformation and high impact load, the composite coating prepared by the invention still cannot generate interlayer fracture failure, and also has excellent bending deformation resistance and impact resistance on the basis of meeting the corrosion resistance requirement.
As a preferred technical solution of the present invention, the coating process of the silicon carbide layer includes:
Putting raw material powder of a silicon carbide layer and a binder into a ball mill for mixing and ball milling in a first stage to obtain a coated material, wherein the raw material powder comprises aluminum powder, silicon powder and carbon powder; then, adding aluminum alloy powder into the ball mill for mixing and ball milling in the second stage, so that the coating material coats the surface of the aluminum alloy powder to obtain a mixed material;
and (II) placing the mixed material in vacuum or protective atmosphere, adopting a gradient sintering process to enable the cladding material to be melted and then cladding the cladding material on the surface of the aluminum alloy powder, and cooling to obtain the aluminum alloy powder clad with the silicon carbide layer.
According to the invention, silicon carbide is coated on the surface of the aluminum alloy powder, so that the heat conductivity of the aluminum alloy powder can be improved, the formation of an aluminum carbide phase at an interface is inhibited, and the service stability of the zirconium-based amorphous alloy-aluminum alloy composite coating in a humid environment is improved.
In the step (I), the mass ratio of the aluminum powder, the silicon powder and the carbon powder is (0.3-0.5): (1.2-1.5): 1, for example, may be 0.3:1.2:1, 0.4:1.3:1, 0.5:1.4:1, 0.3:1.5:1, 0.4:1.3:1 or 0.5:1.3:1, but not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
The binder may be 5 to 10wt% of the total mass of the raw material powder, for example, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt% or 10wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The binder comprises any one or a combination of at least two of polyvinyl alcohol, ammonium polyacrylate or hydroxypropyl methyl fiber.
The mass ratio of the aluminum alloy powder to the raw material powder is 1 (0.01-0.05), and may be, for example, 1:0.01, 1:0.02, 1:0.03, 1:0.04, or 1:0.05, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable
The mixing ball milling time of the first stage is 50-60min, for example, 50min, 51min, 52min, 53min, 54min, 55min, 56min, 57min, 58min, 59min or 60min; the rotation speed of the ball mill is 100-150r/min, for example, 100r/min, 105r/min, 110r/min, 115r/min, 120r/min, 125r/min, 130r/min, 135r/min, 140r/min, 145r/min or 150r/min, but the method is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
The aluminum alloy powder is AlNiY alloy powder and comprises the following components in percentage by mass: al accounts for 60-70wt%, and may be 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, 66wt%, 67wt%, 68wt%, 69wt% or 70wt%, for example; ni comprises 18-20wt%, such as 18wt%, 18.2wt%, 18.4wt%, 18.6wt%, 18.8wt%, 19wt%, 19.2wt%, 19.4wt%, 19.6wt%, 19.8wt%, or 20wt%; y may be 10-20wt%, for example, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt% or 20wt%, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The particle size of the aluminum alloy powder is 30-40 μm, for example, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm, 38 μm, 39 μm or 40 μm; the powder feeding speed of the aluminum alloy powder is 20-30g/min, for example, 20g/min, 21g/min, 22g/min, 23g/min, 24g/min, 25g/min, 26g/min, 27g/min, 28g/min, 29g/min or 30g/min, but the powder feeding speed is not limited to the recited values, and other non-recited values in the numerical range are applicable.
The mixing ball milling time in the second stage is 20-30min, for example, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min or 30min, the rotation speed of the ball mill is 180-200r/min, for example, 180r/min, 182r/min, 184r/min, 186r/min, 188r/min, 190r/min, 192r/min, 194r/min, 196r/min, 198r/min or 200r/min, but not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
In the step (II), the operation process of the gradient sintering process comprises the following steps:
the temperature of the mixed material is raised to 300-400 ℃ at a temperature rising rate of 5-10 ℃/min, wherein the temperature rising rate can be 5.0 ℃/min, 5.5 ℃/min, 6.0 ℃/min, 6.5 ℃/min, 7.0 ℃/min, 7.5 ℃/min, 8.0 ℃/min, 8.5 ℃/min, 9.0 ℃/min, 9.5 ℃/min or 10.0 ℃/min, the temperature can be raised to 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃ or 400 ℃, and the temperature is kept for 1-2h, for example, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2.0h.
Subsequently, the mixture is heated to 700-800 ℃ at a heating rate of 15-30 ℃/min, wherein the heating rate may be 15 ℃/min, 16 ℃/min, 17 ℃/min, 18 ℃/min, 19 ℃/min, 20 ℃/min, 21 ℃/min, 22 ℃/min, 23 ℃/min, 24 ℃/min, 25 ℃/min, 26 ℃/min, 27 ℃/min, 28 ℃/min, 29 ℃/min or 30 ℃/min, and the temperature may be raised to 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃ or 800 ℃, and the temperature may be kept at 1-2 hours, for example, 1.0 hour, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours or 2.0 hours, but the present invention is not limited to the values recited, and other values not recited in the range of values are equally applicable.
The chemical reaction process of the gradient sintering process provided by the invention is as follows: aluminum powder and carbon powder react chemically at 300-400 ℃ to generate aluminum carbide, then the temperature is continuously raised to 700-800 ℃, and at the temperature, aluminum carbide and silicon powder react in a displacement way to generate silicon carbide, and a continuous silicon carbide layer can be formed on the surface of aluminum alloy powder by controlling the mass ratio of the aluminum powder, the silicon powder and the carbon powder.
As a preferable technical scheme of the invention, the laser cladding process is carried out in laser cladding equipment, the laser cladding equipment comprises a powder feeding device and a vacuum chamber, a laser emitter and an ultrasonic oscillation platform are arranged in the vacuum chamber, and the operation process of the laser cladding process comprises the following steps:
placing the substrate on the ultrasonic oscillation platform, and carrying out ultrasonic excitation on the substrate through the ultrasonic oscillation platform; simultaneously, the laser beam emitted by the laser emitter irradiates and scans the surface of the matrix to form a molten pool on the surface of the matrix;
and synchronously feeding the aluminum alloy powder coated with the silicon carbide layer into a molten pool through the powder feeding device along the moving path of the laser beam, and cooling to form the aluminum alloy layer.
In a preferred embodiment of the present invention, the powder feeding speed of the aluminum alloy powder is 20-30g/min, for example, 20g/min, 21g/min, 22g/min, 23g/min, 24g/min, 25g/min, 26g/min, 27g/min, 28g/min, 29g/min or 30g/min, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The scanning speed of the laser beam is 80-150m/min, for example, 80m/min, 90m/min, 100m/min, 110m/min, 120m/min, 130m/min, 140m/min or 150m/min; the emission power of the laser beam is 1-2kW, and may be, for example, 1.0kW, 1.1kW, 1.2kW, 1.3kW, 1.4kW, 1.5kW, 1.6kW, 1.7kW, 1.8kW, 1.9kW or 2.0kW; the spot diameter of the laser beam is 1 to 3mm, and may be, for example, 1.0mm, 1.2mm, 1.4mm, 1.6mm, 1.8mm, 2.0mm, 2.2mm, 2.4mm, 2.6mm, 2.8mm or 3.0mm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The aluminum alloy powder is fused on the surface of the matrix to form the aluminum alloy layer which has extremely low dilution degree with the matrix and is combined with the matrix to form the alloy, so that the performances of wear resistance, corrosion resistance, oxidation resistance and the like of the surface of the matrix can be effectively improved. However, the aluminum alloy layer prepared by the laser cladding process is easy to generate defects such as cracks, air holes and the like, and the main reason is that residual stress exists in a molten pool when aluminum alloy powder is solidified, and the difference of thermal expansion coefficients between the aluminum alloy powder and a matrix exists. Therefore, the laser cladding process adopted by the invention is particularly limited in that the scanning speed of the laser beam is 80-150m/min, the emission power of the laser beam is 1-2kW, the spot diameter is 1-3mm, and the probability of cracking and air holes of the aluminum alloy layer can be effectively reduced by controlling the laser cladding parameters, specifically:
Firstly, strictly regulating and controlling the energy density of a heat source by controlling the laser cladding parameters, the energy density E of the heat source in a molten pool,wherein P is the emission power, V is the scanning speed, and D is the spot diameter. As E increases, the aluminum alloy layer will progressively fewer cracked pores and a reduced propensity for cracking. Therefore, in order to avoid the defects of the aluminum alloy layer, the energy density of a heat source of a molten pool is controlled by adjusting laser cladding process parameters such as laser cladding power, light spot size, scanning speed and the like, so that the defects such as crack and air holes cannot occur in the aluminum alloy layer formed by cladding. In addition, under the parameter condition, the substrate is less affected by laser heat input, the internal residual stress is lower, and the thermal deformation basically cannot occur, so that a large-area aluminum alloy layer can be prepared on the surface of the substrate;
secondly, by controlling the laser cladding parameters, atomic permeation diffusion with controllable depth can be formed at the joint interface of the matrix and the aluminum alloy layer, so that an intermetallic compound layer with a certain thickness is formed at the joint interface, and the transition effect of connecting the aluminum alloy layer and the matrix is achieved;
thirdly, the aluminum alloy grains can be thinned by controlling the emission power of laser cladding, and the higher the emission power is, the higher the temperature of a molten pool is, the finer the grain growth is, and the higher the hardness is. The surface of the matrix is greatly influenced by laser heat input, and the surface temperature is higher, so that a molten pool on the surface of the matrix can be solidified to form a fine grain structure, the hardness of the joint of the matrix and the aluminum alloy layer is higher, and the effect of enhancing the interface bonding strength between the aluminum alloy layer and the matrix is achieved.
In the laser cladding process, the substrate is kept to rotate along the axis, the laser emitter moves along the radial direction of the substrate, so that a plurality of spiral molten pools are formed on the surface of the substrate, and when the substrate rotates for one circle, the focal point of the laser beam moves along the radial direction of the substrate once, so that an overlapping area exists between two adjacent molten pools formed by melting. The laser cladding method provided by the invention can better control the scanning rate, laser energy and laser path of the laser beam, and is convenient for regulating and controlling the heat input quantity and the thickness of the intermetallic compound layer at the interface of the aluminum alloy layer and the matrix.
The ultrasonic power emitted by the ultrasonic oscillation platform is 800-900W, for example, 800W, 810W, 820W, 830W, 840W, 850W, 860W, 870W, 880W, 890W or 900W, the vibration frequency of the substrate is 100-120kHz, for example, 100kHz, 102kHz, 104kHz, 106kHz, 108kHz, 110kHz, 112kHz, 114kHz, 116kHz, 118kHz or 120kHz, but the ultrasonic power is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
According to the invention, ultrasonic oscillation is carried out on the matrix in the laser cladding process, and the defects of cracks, pores and the like in the aluminum alloy layer can be further reduced by matching with the specially limited ultrasonic cladding process parameters. The action mechanism is as follows:
(1) In the laser cladding process, when aluminum alloy powder is rapidly cooled after being melted, the molten pool can not be supplemented when cooling and solidification are continued due to staggered sealing of dendrites, larger tensile stress can be generated, and when the tensile stress exceeds a certain value, cracks extending along the dendrite direction can be generated. Applying ultrasonic waves to the substrate in the cladding process, repeatedly extruding and stretching the melt in the molten pool by high-frequency vibration caused by the ultrasonic waves, and tearing the melt in the molten pool to form cavitation bubbles with low internal pressure and high temperature in the stretching process; in the extrusion process, the cavitation bubbles shrink rapidly to generate water hammer phenomenon so as to increase internal pressure, and simultaneously, instantaneous high temperature and high pressure are generated to break up growing dendrites under the action of the high temperature and the high pressure to form a plurality of fine crystal nuclei, and the fine crystal nuclei can be uniformly dispersed into a molten pool in the ultrasonic vibration process, so that the influence of tensile stress in an aluminum alloy layer is eliminated, and the possibility of cracking of the aluminum alloy layer is reduced;
(2) The aluminum alloy adopted by the invention is an AlNiY alloy, wherein Ni and Y elements contained in the alloy can form compound hard phases with disordered distribution in the cladding process, after cooling, the hardness and brittleness of the aluminum alloy layer are increased, the toughness is reduced, and the bearing capacity to tensile stress is reduced, so that cracks are easy to generate. The stirring effect of the melt in the molten pool is realized after ultrasonic oscillation is applied in the cladding process, so that the dispersed disordered hard phase can be uniformly dispersed to all parts of the molten pool, and the mechanical property of the aluminum alloy layer is improved;
(3) In the laser cladding process, the temperature of the melt at each part of the molten pool is not uniform, so that the crystallization direction is complex, and the probability of generating cracks is increased; the invention utilizes cavitation and ultrasonic stirring action of ultrasonic wave in the molten pool to enable the temperature of the melt at each part of the molten pool to be consistent, and can ensure synchronous solidification of the melt at each part of the molten pool during cooling, thereby reducing the generation of cracks;
(4) According to the invention, an impact oscillation effect is formed in a melt by utilizing an ultrasonic pulse technology, so that the growth of aluminum alloy grains, namely the kinetics of a new phase precipitation process, is improved, cluster grains are dispersed to form new crystal nuclei, and the clusters and growth of particle phases in the melt are restrained, so that the grain size is controlled to be in a nano scale and is uniformly dispersed in the melt, and along with the gradual refinement of the aluminum alloy grains, the corrosion resistance is gradually enhanced, and mainly due to the fact that the plastic deformation of an aluminum alloy layer is increased, the grain orientation of the material is more disordered, the grain disorder is improved, the number of active atoms of aluminum alloy powder is increased, the generation of passivation films on the surface of the aluminum alloy layer is promoted, and the passivation performance of the aluminum alloy layer is improved;
(5) In the process of solidification and crystallization of the aluminum alloy powder melt, a small part of air in the environment can be dissolved into the melt, so that a certain number of air hole defects are distributed in the solidified aluminum alloy layer. The small bubbles in the melt are accumulated to form large bubbles through ultrasonic oscillation, and the large bubbles float up in the molten pool and escape from the melt, so that the number of air holes in the aluminum alloy layer is reduced.
As a preferable technical scheme of the invention, the chemical general formula of the zirconium-based amorphous alloy powder is Zr a Cu b Ni c Al d Ti e Wherein 60.ltoreq.a.ltoreq.70, 10.ltoreq.b.ltoreq.15, 10.ltoreq.c.ltoreq.15, 4.ltoreq.d.ltoreq.8, 1.ltoreq.e.ltoreq.5, a may be 60, 61, 62, 63, 64, 65, 66, 67, 68, 69 or 70, b may be 10, 11, 12, 13, 14 or 15, c may be 10, 11, 12, 13, 14 or 15, d may be 4, 5, 6, 7 or 8,e and 1, 2, 3, 4 or 5, but not limited to the values recited, other non-recited values within the range of values are equally applicable, and a, b, c, d, e satisfies: a+b+c+d+e=100.
The particle diameter of the core may be 50 to 100. Mu.m, for example, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm or 100. Mu.m, but is not limited to the values recited, and other values not recited in the range are equally applicable,
the thickness of the shell is 100-120nm, for example, 100nm, 102nm, 104nm, 106nm, 108nm, 110nm, 112nm, 114nm, 116nm, 118nm or 120nm, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
The zirconium-based amorphous alloy layer prepared by the plasma spraying process provided by the invention inevitably has pores, so that water gas enters the zirconium-based amorphous alloy layer along the pores and penetrates through the zirconium-based amorphous alloy layer to enter the matrix, and the surface of the matrix is corroded. In order to avoid the problem, the surface of the zirconium-based amorphous alloy powder is coated with the transition metal oxide layer, the transition metal oxide layer generates a compact oxide film after high-temperature plasma spraying treatment and covers the surface of the Yu Gaoji amorphous alloy layer, and meanwhile, the filling effect on pores in the zirconium-based amorphous alloy layer can be achieved, so that the porosity of the zirconium-based amorphous alloy layer is reduced, and water vapor is effectively prevented from penetrating into a substrate. In addition, the addition of the transition metal oxide can play roles in purifying the melt and improving the structure, so that the zirconium-based amorphous alloy shows lower self-corrosion potential, the transition metal element has active chemical property, almost can form chemical-property stable compounds with all nonmetallic elements so as to form a stable passivation film, and the corrosion resistance of the amorphous alloy is improved.
The kind of transition metal in the transition metal oxide is not particularly limited and may be, for example, any of cerium oxide, yttrium oxide, and lanthanum oxide.
As a preferred embodiment of the present invention, the coating process of the transition metal oxide layer includes:
(1) Mixing zirconium-based amorphous alloy powder, an anionic surfactant and water to obtain a first solution; mixing transition metal oxide powder, a cationic surfactant and water to obtain a second solution;
(2) Mixing the first solution and the second solution to obtain mixed slurry, and applying pulse current to the mixed slurry in the mixing process;
(3) And after the mixing is finished, carrying out spray granulation on the mixed slurry to obtain the composite amorphous alloy powder with the core-shell structure.
The method comprises the steps of mixing an anionic surfactant with zirconium-based amorphous alloy powder, so that the anionic surfactant coats the surface of the zirconium-based amorphous alloy powder, and forming zirconium-based amorphous alloy powder with negative charges on the surface in a first solution; the cationic surfactant is mixed with the transition metal oxide powder so that the cationic surfactant coats the surface of the transition metal oxide powder, and the transition metal oxide powder with positive charges on the surface is formed in the second solution. And after the first solution and the second solution are mixed, pulse current is applied, the pulse current forms an alternating electric field, and under the action of the electric field, zirconium-based amorphous alloy powder with negative charges on the surface and transition metal oxide powder with positive charges on the surface are attracted to each other under the action of coulomb force and continuously move. Because the grain size of the zirconium-based amorphous alloy powder is far larger than that of the transition metal oxide powder, under the action of electric charge attraction, the composite amorphous alloy powder with the zirconium-based amorphous alloy powder as an inner core and the transition metal oxide powder as an outer shell and a core-shell structure can be formed. In addition, the transition metal oxide powder has the same charge, and the transition metal oxide powder attracted by the surface of the zirconium-based amorphous alloy powder can not mutually agglomerate in the coating process because the same charge is mutually repelled, so that a uniform and compact thin-layer shell can be formed on the surface of the zirconium-based amorphous alloy powder.
As a preferred embodiment of the present invention, in the step (1), the mass fraction of the zirconium based amorphous alloy powder is 45-50wt%, for example, 45wt%, 46wt%, 47wt%, 48wt%, 49wt% or 50wt%, based on 100wt% of the mass fraction of the first solution; the mass fraction of the anionic surfactant is 0.1 to 0.3wt%, for example, 0.1wt%, 0.12wt%, 0.14wt%, 0.16wt%, 0.18wt%, 0.2wt%, 0.22wt%, 0.24wt%, 0.26wt%, 0.28wt% or 0.3wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable. The anionic surfactant is an anionic surfactant.
The transition metal oxide powder is 45-50wt%, for example, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, or 50wt%, based on 100wt% of the second solution; the mass fraction of the cationic surfactant is 0.1 to 0.3wt%, for example, 0.1wt%, 0.12wt%, 0.14wt%, 0.16wt%, 0.18wt%, 0.2wt%, 0.22wt%, 0.24wt%, 0.26wt%, 0.28wt% or 0.3wt%, but is not limited to the recited values, and other non-recited values within this range are equally applicable. The cationic surfactant is a cationic surfactant.
In a preferred embodiment of the present invention, in the step (2), the first solution and the second solution are mixed according to a mass ratio of 1 (0.1-0.5), for example, 1:0.1, 1:0.2, 1:0.3, 1:0.4 or 1:0.5, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The frequency of the pulse current is 50-100Hz, and may be, for example, 50Hz, 55Hz, 60Hz, 65Hz, 70Hz, 75Hz, 80Hz, 85Hz, 90Hz, 95Hz or 100Hz, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The peak density of the pulse current is 0.1-10A/cm 2 For example, it may be 0.1A/cm 2 、1A/cm 2 、2A/cm 2 、3A/cm 2 、4A/cm 2 、5A/cm 2 、6A/cm 2 、7A/cm 2 、8A/cm 2 、9A/cm 2 Or 10A/cm 2 But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
In a preferred embodiment of the present invention, the spray granulation is performed in a centrifugal spray granulator having an inlet temperature of 300 to 350 ℃, for example, 300 ℃, 305 ℃, 310 ℃, 315 ℃, 320 ℃, 325 ℃, 330 ℃, 335 ℃, 340 ℃, 345 ℃ or 350 ℃, but the present invention is not limited to the above-mentioned values, and other non-mentioned values within the above-mentioned range are equally applicable.
The outlet temperature of the centrifugal spray granulator may be, for example, 100℃to 150℃and may be, for example, 105℃110℃115℃120℃125℃130℃135℃140℃145℃150℃but is not limited to the values listed, and other values not listed in the range are equally applicable.
The spray pressure of the centrifugal spray granulator is 0.5 to 1.5MPa, and may be, for example, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa or 1.5MPa, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The rotational speed of the centrifugal spray granulator is 10000-15000r/min, for example 10000r/min, 10500/min, 11000/min, 11500/min, 12000/min, 12500/min, 13000/min, 13500/min, 14000/min, 14500/min or 15000/min, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The feed rate of the mixed slurry is 1 to 10kg/h, and may be, for example, 1kg/h, 2kg/h, 3kg/h, 4kg/h, 5kg/h, 6kg/h, 7kg/h, 8kg/h, 9kg/h or 10kg/h, but is not limited to the values recited, and other values not recited in the range are equally applicable.
As a preferred technical scheme of the present invention, the plasma spraying process is performed in a plasma spraying device, the plasma spraying device comprises a plasma spraying cavity, a plasma spray gun and a powder feeding device, and the operation process of the plasma spraying process comprises:
placing a substrate with an aluminum alloy layer formed as a spraying substrate into the plasma spraying cavity, conveying the composite amorphous alloy powder to a nozzle of a plasma spraying gun through the powder conveying device, atomizing the composite amorphous alloy powder into molten liquid drops by plasma high-temperature flame emitted by the plasma spraying gun, spraying the surface of the spraying substrate for at least three times, wherein each spraying is carried out for a period of time, and cooling the spraying substrate during the spraying interval; and cooling along with the furnace after the spraying is finished, so as to form the zirconium-based amorphous alloy layer on the surface of the aluminum alloy layer.
According to the invention, through multiple intermittent spraying and multiple intermittent cooling, the precipitation and dispersion distribution of the nanocrystals of the zirconium-based amorphous alloy at the interface can be promoted, so that the fracture toughness of the zirconium-based amorphous alloy layer is remarkably improved; and cracks at the interface of the composite coating caused by overlarge thermal stress at the interface can be effectively prevented, so that the binding force of the composite coating and the quality of the composite coating are obviously improved.
As a preferable technical scheme of the invention, the powder feeding rate of the composite amorphous alloy powder is 40-50g/min, for example, 40g/min, 41g/min, 42g/min, 43g/min, 44g/min, 45g/min, 46g/min, 47g/min, 48g/min, 49g/min or 50g/min, but the powder feeding rate is not limited to the recited values, and other non-recited values in the numerical range are applicable.
The output power of the plasma spray gun is 10-15kW, and can be 10kW, 10.5kW, 11kW, 11.5kW, 12kW, 12.5kW, 13kW, 13.5kW, 14kW, 14.5kW or 15kW, for example; the output current is 300-400A, and may be 300A, 310A, 320A, 330A, 340A, 350A, 360A, 370A, 380A, 390A or 400A, for example, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The gas source adopted by the plasma spray gun is a mixed gas composed of argon and helium, wherein the flow of the argon is 50-80L/min, for example, 50L/min, 55L/min, 60L/min, 65L/min, 70L/min, 75L/min or 80L/min; the flow rate of helium gas is 15-20L/min, for example, 15L/min, 16L/min, 17L/min, 18L/min, 19L/min or 20L/min, but the flow rate is not limited to the recited values, and other values not recited in the range of values are equally applicable.
According to the invention, the output power and the output current of the plasma spray gun are controlled within a limited range, so that argon and helium can obtain higher activation energy, so that the argon and helium react with air and impurities adsorbed on the surface of the aluminum alloy layer and are resolved into gas phases which are separated from the surface of the aluminum alloy layer, and the plasma cleaning effect on the surface of the aluminum alloy layer is realized; and meanwhile, the atomic activity of the surface of the aluminum alloy layer can be effectively enhanced, and the interfacial bonding strength of the composite coating is improved.
The moving speed of the plasma spray gun is 800-900mm/s, for example, 800mm/s, 810mm/s, 820mm/s, 830mm/s, 840mm/s, 850mm/s, 860mm/s, 870mm/s, 880mm/s, 890mm/s or 900mm/s; the spray distance between the nozzle of the plasma spray gun and the surface of the spray substrate is 90-100mm, and may be, for example, 90mm, 91mm, 92mm, 93mm, 94mm, 95mm, 96mm, 97mm, 98mm, 99mm or 100mm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The invention particularly limits the process parameters of plasma spraying such as the output power, the output current, the moving speed, the spraying interval and the like of the plasma spraying gun, and aims to control the heat input quantity of the plasma spraying gun so as to improve the interface wettability between the zirconium-based amorphous alloy layer and the aluminum alloy layer. When the heat input amount of the plasma spray gun is too low, the composite amorphous alloy powder cannot be sufficiently melted, the composite amorphous alloy powder is still in a semi-melted state, mechanical impact can be generated when the composite amorphous alloy powder is sprayed on the surface of the aluminum alloy, and the semi-melted composite amorphous alloy powder is in an elastic deformation state, so that the atomic diffusion bonding of the composite amorphous alloy powder and the aluminum alloy powder at an interface is blocked, and therefore, the interface bonding strength between the zirconium-based amorphous alloy layer and the aluminum alloy layer cannot be improved. On the contrary, when the heat input amount of the plasma spray gun is too high, the spraying temperature at the interface is higher than the crystallization transition temperature of the zirconium-based amorphous alloy, and the temperature of the composite amorphous alloy powder at the interface cannot be conducted and diffused in time, so that the cooling speed at the interface is lower than the critical cooling speed of the zirconium-based amorphous alloy, and therefore, the crystallization phenomenon of the zirconium-based amorphous alloy can occur at the interface of the zirconium-based amorphous alloy layer and the aluminum alloy layer.
The invention can obtain reasonable heat input by adjusting the operation parameters of the plasma spraying process, such as output power, output current, moving speed of a plasma spray gun, spraying interval and the like, and mainly shows impact friction between the composite amorphous alloy powder and an aluminum alloy layer in the initial stage of plasma spraying, along with the continuous increase of the heat input, the interface temperature is increased, the viscosity of the molten composite amorphous alloy powder is reduced, the maximum value of the heat input is between the glass transition temperature and crystallization transition temperature of the composite amorphous alloy powder through the combination of different operation parameters, and at the moment, the molten zirconium-based amorphous alloy powder mainly deforms plastically, can fully infiltrate and spread on the surface of the aluminum alloy layer, and can promote the atomic diffusion at the interface. In addition, under the process conditions defined by the invention, the composite amorphous alloy powder can show superplasticity of high strain rate, so that the composite amorphous alloy powder generates superplastic deformation at the interface under the action of spraying static pressure, meanwhile, the aluminum alloy layer is heated to reduce the deformation resistance in the plasma spraying process, certain plasticity is shown, at the moment, plastic flow can be generated between the composite amorphous alloy powder and the aluminum alloy powder at the interface, so that the atomic diffusion movement rate at the interface is improved, boundary sliding is generated between the zirconium-based amorphous alloy layer and the aluminum alloy layer, and full contact, infiltration and penetration of atomic layers are realized.
The interval between two adjacent spraying is 5-10min, for example, 5.0min, 5.5min, 6.0min, 6.5min, 7.0min, 7.5min, 8.0min, 8.5min, 9.0min, 9.5min or 10.0min; the spray substrate is cooled down to 400-500 c during the intervals of spraying, for example, 400 c, 410 c, 420 c, 430 c, 440 c, 450 c, 460 c, 470 c, 480 c, 490 c or 500 c, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
In a second aspect, the invention provides a zirconium-based amorphous alloy-aluminum alloy composite coating, which is prepared by the preparation method in the first aspect.
The invention provides a preparation method of a zirconium-based amorphous alloy-aluminum alloy composite coating, which comprises the following steps of:
(1) Preparing aluminum alloy powder coated with a silicon carbide layer:
(1.1) putting raw material powder of a silicon carbide layer and a binder into a ball mill for mixing and ball milling in a first stage to obtain a coating material; wherein the raw material powder comprises aluminum powder, silicon powder and carbon powder with the mass ratio of (0.3-0.5) to (1.2-1.5) to (1), and the binder is 5-10wt% of the total mass of the raw material powder; the mixing ball milling time of the first stage is 50-60min, and the rotating speed of the ball mill is 100-150r/min;
(1.2) then, adding AlNiY aluminum alloy powder (60-70 wt% of Al, 18-20wt% of Ni and 10-20wt% of Y) with the particle size of 30-40 mu m into a ball mill, and carrying out mixed ball milling in a second stage, wherein the mass ratio of the aluminum alloy powder to the raw material powder is 1 (0.01-0.05), the mixed ball milling time in the second stage is 20-30min, and the rotating speed of the ball mill is 180-200r/min; coating the surface of the aluminum alloy powder with the coating material after the second-stage mixing ball milling to obtain a mixed material;
(1.3) placing the mixed material in vacuum or protective atmosphere, heating the mixed material, heating to 300-400 ℃ at a heating rate of 5-10 ℃/min, and preserving heat for 1-2h; then, heating to 700-800 ℃ at a heating rate of 15-30 ℃/min, and preserving heat for 1-2h; finally, cooling along with the furnace to obtain the aluminum alloy powder coated with the silicon carbide layer on the surface, wherein the coating thickness of the silicon carbide layer is 150-200nm.
(2) Preparing an aluminum alloy layer:
(2.1) placing the substrate on an ultrasonic oscillation platform, carrying out ultrasonic excitation on the substrate through the ultrasonic oscillation platform, wherein the ultrasonic power emitted by the ultrasonic oscillation platform is 800-900W, and the vibration frequency of the substrate is 100-120kHz;
(2.2) irradiating and scanning the surface of the substrate by the laser beam emitted by the laser emitter while carrying out ultrasonic oscillation on the substrate so as to form a molten pool on the surface of the substrate; the setting parameters of the laser beam include: the scanning speed of the laser beam is 80-150m/min, the emission power of the laser beam is 1-2kW, and the spot diameter of the laser beam is 1-3mm;
And (2.3) synchronously feeding the aluminum alloy powder coated with the silicon carbide layer prepared in the step (1) into a molten pool at a powder feeding speed of 20-30g/min through a powder feeding device along the moving path of the laser beam, and cooling to form the aluminum alloy layer.
(3) Preparing composite amorphous alloy powder with a core-shell structure:
(3.1) zirconium-based amorphous alloy powder (Zr) a Cu b Ni c Al d Ti e ) Mixing an anionic surfactant and water to obtain a first solution; wherein the mass fraction of the zirconium-based amorphous alloy powder is 45-50wt%, and the mass fraction of the anionic surfactant is 0.1-0.3wt%; the zirconium based amorphous alloy powder comprises a first core having a particle size in the range of 10-20 μm, a second core having a particle size in the range of 50-60 μm, and a third core having a particle size in the range of 100-120 μm;
(3.2) mixing transition metal oxide powder, a cationic surfactant and water to obtain a second solution, wherein the mass fraction of the transition metal oxide powder is 45-50wt%, and the mass fraction of the cationic surfactant is 0.1-0.3wt%;
(3.3) mixing the first solution and the second solution according to the mass ratio of 1 (0.1-0.5) to obtain mixed slurry; in the mixing process, pulse current with frequency of 50-100Hz and peak density of 0.1-10A/cm is applied to the mixed slurry 2 ；
(3.4) after the mixing is finished, introducing the mixed slurry into a centrifugal spray granulator at a feeding speed of 1-10kg/h for spray granulation, wherein the inlet temperature of the centrifugal spray granulator is 300-350 ℃, the outlet temperature of the centrifugal spray granulator is 100-150 ℃, the spray pressure is 0.5-1.5MPa, and the rotating speed is 10000-15000r/min; and carrying out spray granulation to obtain first powder, second powder and third powder, wherein the first powder comprises a first inner core and a transition metal oxide layer wrapping the first inner core, the second powder comprises a second inner core and a transition metal oxide layer wrapping the second inner core, the third powder comprises a third inner core and a transition metal oxide layer wrapping the third inner core, and the thicknesses of the transition metal oxide layers are 100-120nm.
(4) Preparing a zirconium-based amorphous alloy layer:
(4.1) placing the aluminum alloy layer formed in the step (2) into a plasma spraying cavity as a spraying substrate, and conveying the first powder, the second powder and the third powder prepared in the step (3) to a nozzle of a plasma spray gun through a powder conveying device, wherein the first powder, the second powder and the third powder are conveyed according to a mass ratio of 1 (1.5-2): 0.1-0.5, and the powder conveying speed is 40-50g/min;
(4.2) atomizing the first powder, the second powder and the third powder into molten liquid drops by a plasma spray gun, and then spraying the molten liquid drops on the surface of a spraying substrate, wherein the output power of the plasma spray gun is 10-15kW, and the output current of the plasma spray gun is 300-400A; the gas source adopted by the plasma spray gun is a mixed gas composed of argon and helium, wherein the flow rate of the argon is 50-80L/min, and the flow rate of the helium is 15-20L/min; the moving speed of the plasma spray gun is 800-900mm/s, and the spraying distance between the nozzle of the plasma spray gun and the surface of the spraying substrate is 90-100mm;
(4.3) spraying the surface of the spraying substrate for at least three times, wherein the interval between two adjacent spraying is 5-10min, and cooling the spraying substrate to 400-500 ℃ during the interval of spraying; and cooling along with the furnace after the spraying is finished so as to form a zirconium-based amorphous alloy layer on the surface of the aluminum alloy layer.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the aluminum alloy layer is prepared on the surface of the substrate by adopting the laser cladding process, the aluminum alloy powder and the surface of the substrate are rapidly heated and melted under the action of the laser beam, the aluminum alloy layer which is metallurgically bonded with the surface of the substrate is formed by self-excitation cooling after the laser beam is removed, the bonding between the aluminum alloy layer and the substrate can be more compact by adopting the laser cladding process, and the phenomenon of coating falling off can not occur in the friction process, so that the characteristics of wear resistance, corrosion resistance, heat resistance, oxidation resistance and the like of the surface of the substrate are obviously improved. The zirconium-based amorphous alloy layer is formed on the basis of the aluminum alloy layer through plasma spraying, and the composite coating is formed by the aluminum alloy layer and the zirconium-based amorphous alloy layer, so that the corrosion resistance of the aluminum alloy and the mechanical advantage of the zirconium-based amorphous alloy are combined, and the prepared composite coating has high corrosion resistance, high hardness and high wear resistance.
The invention utilizes the plasma spraying process to ensure that the zirconium-based amorphous alloy powder shows good wettability when being sprayed, so as to fully permeate and spread on the surface of the aluminum alloy layer, and the interface bonding strength between the zirconium-based amorphous alloy powder and the aluminum alloy layer is improved. In addition, in the spraying process, the mutual diffusion of atoms of the zirconium-based amorphous alloy material and the aluminum alloy material at the interface is initiated, the chemical reaction of the zirconium-based amorphous alloy material and the aluminum alloy material at the interface is promoted by means of good wettability to obtain a continuous solid solution composed of intermetallic compounds, so that a composite coating of an aluminum alloy layer-intermetallic compound layer-zirconium-based amorphous alloy layer is formed on the surface of a substrate, and material layers with different mechanical properties are functionally superposed. The intermetallic compound layer between the aluminum alloy layer and the zirconium-based amorphous alloy layer can inhibit cracks from occurring on the aluminum alloy layer, and under the action of large deformation and high impact load, the composite coating prepared by the invention still cannot generate interlayer fracture failure, and also has excellent bending deformation resistance and impact resistance on the basis of meeting the corrosion resistance requirement.
Drawings
FIG. 1 is a scanning electron microscope photograph of a composite coating prepared in example 2 of the present invention;
FIG. 2 is a scanning electron micrograph of the composite coating prepared in example 6 of the present application.
Detailed Description
The technical scheme of the application is described in detail below with reference to specific embodiments. The examples described herein are specific embodiments of the present application for illustrating the concept of the present application; the description is intended to be illustrative and exemplary in nature and should not be construed as limiting the scope of the application in its aspects. In addition to the embodiments described herein, those skilled in the art can adopt other obvious solutions based on the disclosure of the claims and the specification thereof, including those adopting any obvious substitutions and modifications to the embodiments described herein.
Example 1
The embodiment provides a preparation method of a zirconium-based amorphous alloy-aluminum alloy composite coating, which comprises the following steps:
(1) Preparing aluminum alloy powder coated with a silicon carbide layer:
(1.1) putting raw material powder of a silicon carbide layer and polyvinyl alcohol into a ball mill for mixing and ball milling in a first stage to obtain a coating material; wherein the raw material powder comprises aluminum powder, silicon powder and carbon powder with the mass ratio of 0.3:1.2:1, and polyvinyl alcohol is 5wt% of the total mass of the raw material powder; the mixing ball milling time in the first stage is 50min, and the rotating speed of the ball mill is 150r/min;
(1.2) then, charging AlNiY aluminum alloy powder (60 wt% of Al, 20wt% of Ni and 20wt% of Y) with the particle size of 30 mu m into a ball mill, and carrying out mixed ball milling in a second stage, wherein the mass ratio of the aluminum alloy powder to the raw material powder is 1:0.01, the mixed ball milling time in the second stage is 20min, and the rotating speed of the ball mill is 200r/min; coating the surface of the aluminum alloy powder with the coating material after the second-stage mixing ball milling to obtain a mixed material;
(1.3) placing the mixed material in a vacuum environment, heating the mixed material, heating to 300 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2 hours; then, heating to 700 ℃ at a heating rate of 15 ℃/min, and preserving heat for 2 hours; finally, cooling along with the furnace to obtain the aluminum alloy powder coated with the silicon carbide layer on the surface, wherein the coating thickness of the silicon carbide layer is 150nm.
(2) Preparing an aluminum alloy layer:
(2.1) placing the substrate on an ultrasonic oscillation platform, carrying out ultrasonic excitation on the substrate through the ultrasonic oscillation platform, wherein the ultrasonic power emitted by the ultrasonic oscillation platform is 800W, and the vibration frequency of the substrate is 100kHz;
(2.2) irradiating and scanning the surface of the substrate by the laser beam emitted by the laser emitter while carrying out ultrasonic oscillation on the substrate so as to form a molten pool on the surface of the substrate; the setting parameters of the laser beam include: the scanning speed of the laser beam is 80m/min, the emission power of the laser beam is 1kW, and the spot diameter of the laser beam is 1mm;
And (2.3) synchronously feeding the aluminum alloy powder coated with the silicon carbide layer prepared in the step (1) into a molten pool at a powder feeding speed of 20g/min through a powder feeding device along the moving path of the laser beam, and cooling to form the aluminum alloy layer.
(3) Preparing composite amorphous alloy powder with a core-shell structure:
(3.1) zirconium-based amorphous alloy powder having a particle diameter of 50 μm (Zr) 60 Cu 15 Ni 12 Al 8 Ti 5 ) Mixing alpha-sodium alkenyl sulfonate and water to obtain a first solution; wherein the mass fraction of the zirconium-based amorphous alloy powder is 45wt%, and the mass fraction of the alpha-sodium alkenyl sulfonate is 0.1wt%;
(3.2) mixing yttrium oxide powder, polyethyleneimine and water to obtain a second solution, wherein the mass fraction of the yttrium oxide powder is 45wt%, and the mass fraction of the polyethyleneimine is 0.1wt%;
(3.3) mixing the first solution and the second solution according to the mass ratio of 1:0.1 to obtain mixed slurry; during the mixing process, a pulsed current is applied to the mixed slurry,the frequency of the pulse current was 50Hz, and the peak density of the pulse current was 0.1A/cm 2 ；
(3.4) after the mixing is finished, introducing the mixed slurry into a centrifugal spray granulator at a feeding speed of 1kg/h for spray granulation, wherein the inlet temperature of the centrifugal spray granulator is 300 ℃, the outlet temperature of the centrifugal spray granulator is 100 ℃, the spray pressure is 0.5MPa, and the rotating speed is 10000r/min; and (3) spraying and granulating to obtain the composite amorphous alloy powder coated with the yttrium oxide layer, wherein the thickness of the yttrium oxide layer is 100nm.
(4) Preparing a zirconium-based amorphous alloy layer:
(4.1) placing the aluminum alloy layer formed in the step (2) into a plasma spraying cavity by taking the aluminum alloy layer as a spraying substrate, and feeding the composite amorphous alloy powder prepared in the step (3) into the plasma spraying cavity at a powder feeding speed of 40g/min by a powder feeding device;
(4.2) atomizing the composite amorphous alloy powder into molten liquid drops by a plasma spray gun, and then spraying the molten liquid drops on the surface of a spraying substrate, wherein the output power of the plasma spray gun is 10kW, and the output current of the plasma spray gun is 300A; the gas source adopted by the plasma spray gun is a mixed gas composed of argon and helium, wherein the flow rate of the argon is 50L/min, and the flow rate of the helium is 15L/min; the moving speed of the plasma spray gun is 800mm/s, and the spraying distance between the nozzle of the plasma spray gun and the surface of the spraying substrate is 90mm;
(4.3) spraying the surface of the sprayed substrate at least three times, wherein the interval between two adjacent spraying is 5min, and cooling the sprayed substrate to 400 ℃ during the interval of spraying; and cooling along with the furnace after the spraying is finished so as to form a zirconium-based amorphous alloy layer on the surface of the aluminum alloy layer.
Example 2
The embodiment provides a preparation method of a zirconium-based amorphous alloy-aluminum alloy composite coating, which comprises the following steps:
(1) Preparing aluminum alloy powder coated with a silicon carbide layer:
(1.1) putting raw material powder of a silicon carbide layer and ammonium polyacrylate into a ball mill for mixing and ball milling in a first stage to obtain a coating material; wherein the raw material powder comprises aluminum powder, silicon powder and carbon powder with the mass ratio of 0.4:1.3:1, and ammonium polyacrylate is 8wt% of the total mass of the raw material powder; the mixing ball milling time in the first stage is 55min, and the rotating speed of the ball mill is 120r/min;
(1.2) then, charging AlNiY aluminum alloy powder (65 wt% of Al, 19wt% of Ni and 16wt% of Y) with the particle size of 35 mu m into a ball mill, and carrying out mixed ball milling in a second stage, wherein the mass ratio of the aluminum alloy powder to the raw material powder is 1:0.03, the mixed ball milling time in the second stage is 25min, and the rotating speed of the ball mill is 190r/min; coating the surface of the aluminum alloy powder with the coating material after the second-stage mixing ball milling to obtain a mixed material;
(1.3) placing the mixed material in an argon atmosphere, heating the mixed material, heating to 350 ℃ at a heating rate of 8 ℃/min, and preserving heat for 1.5h; then, heating to 750 ℃ at a heating rate of 20 ℃/min, and preserving heat for 1.5h; finally, cooling along with the furnace to obtain the aluminum alloy powder coated with the silicon carbide layer on the surface, wherein the coating thickness of the silicon carbide layer is 180nm.
(2) Preparing an aluminum alloy layer:
(2.1) placing the substrate on an ultrasonic oscillation platform, carrying out ultrasonic excitation on the substrate through the ultrasonic oscillation platform, wherein the ultrasonic power emitted by the ultrasonic oscillation platform is 850W, and the vibration frequency of the substrate is 110kHz;
(2.2) irradiating and scanning the surface of the substrate by the laser beam emitted by the laser emitter while carrying out ultrasonic oscillation on the substrate so as to form a molten pool on the surface of the substrate; the setting parameters of the laser beam include: the scanning speed of the laser beam is 100m/min, the emission power of the laser beam is 1.5kW, and the spot diameter of the laser beam is 2mm;
and (2.3) synchronously feeding the aluminum alloy powder coated with the silicon carbide layer prepared in the step (1) into a molten pool at a powder feeding speed of 25g/min through a powder feeding device along the moving path of the laser beam, and cooling to form the aluminum alloy layer.
(3) Preparing composite amorphous alloy powder with a core-shell structure:
(3.1) zirconium-based amorphous alloy powder having a particle diameter of 80 μm (Zr) 74 Cu 11 Ni 10 Al 4 Ti 1 ) Mixing sodium dodecyl sulfate and water to obtain a first solution; wherein the mass fraction of the zirconium-based amorphous alloy powder is 48wt%, and the mass fraction of the sodium dodecyl sulfate is 0.2wt%;
(3.2) mixing cerium oxide powder, cetyltrimethylammonium bromide and water to obtain a second solution, wherein the mass fraction of the cerium oxide powder is 48wt%, and the mass fraction of the cetyltrimethylammonium bromide is 0.2wt%;
(3.3) mixing the first solution and the second solution according to the mass ratio of 1:0.3 to obtain mixed slurry; in the mixing process, pulse current with the frequency of 80Hz and the peak density of 5A/cm is applied to the mixed slurry 2 ；
(3.4) after the mixing is finished, introducing the mixed slurry into a centrifugal spray granulator at a feeding speed of 5kg/h for spray granulation, wherein the inlet temperature of the centrifugal spray granulator is 320 ℃, the outlet temperature of the centrifugal spray granulator is 120 ℃, the spray pressure is 1MPa, and the rotating speed is 13000r/min; and (3) spraying and granulating to obtain the composite amorphous alloy powder coated with the cerium oxide layer, wherein the thickness of the cerium oxide layer is 110nm.
(4) Preparing a zirconium-based amorphous alloy layer:
(4.1) placing the aluminum alloy layer formed in the step (2) into a plasma spraying cavity as a spraying substrate, and feeding the composite amorphous alloy powder prepared in the step (3) into the plasma spraying cavity at a powder feeding speed of 45g/min through a powder feeding device;
(4.2) atomizing the composite amorphous alloy powder into molten liquid drops by a plasma spray gun, and then spraying the molten liquid drops on the surface of a spraying substrate, wherein the output power of the plasma spray gun is 12kW, and the output current is 350A; the gas source adopted by the plasma spray gun is a mixed gas composed of argon and helium, wherein the flow rate of the argon is 70L/min, and the flow rate of the helium is 18L/min; the moving speed of the plasma spray gun is 850mm/s, and the spraying distance between the nozzle of the plasma spray gun and the surface of the spraying substrate is 95mm;
(4.3) spraying the surface of the sprayed substrate at least three times, wherein the interval between two adjacent spraying is 8min, and cooling the sprayed substrate to 450 ℃ during the interval of spraying; and cooling along with the furnace after the spraying is finished so as to form a zirconium-based amorphous alloy layer on the surface of the aluminum alloy layer.
Example 3
The embodiment provides a preparation method of a zirconium-based amorphous alloy-aluminum alloy composite coating, which comprises the following steps:
(1) Preparing aluminum alloy powder coated with a silicon carbide layer:
(1.1) putting raw material powder of a silicon carbide layer and hydroxypropyl methyl fibers into a ball mill for mixing and ball milling in a first stage to obtain a coating material; wherein the raw material powder comprises aluminum powder, silicon powder and carbon powder with the mass ratio of 0.5:1.5:1, and hydroxypropyl methyl fiber is 10wt% of the total mass of the raw material powder; the mixing ball milling time in the first stage is 60min, and the rotating speed of the ball mill is 100r/min;
(1.2) then, charging AlNiY aluminum alloy powder (70 wt% of Al, 18wt% of Ni and 12wt% of Y) with the particle size of 40 mu m into a ball mill, and carrying out mixed ball milling in a second stage, wherein the mass ratio of the aluminum alloy powder to the raw material powder is 1:0.05, the mixed ball milling time in the second stage is 30min, and the rotating speed of the ball mill is 180r/min; coating the surface of the aluminum alloy powder with the coating material after the second-stage mixing ball milling to obtain a mixed material;
(1.3) placing the mixed material in a vacuum environment, heating the mixed material, heating to 400 ℃ at a heating rate of 10 ℃/min, and preserving heat for 1h; then, heating to 800 ℃ at a heating rate of 30 ℃/min, and preserving heat for 1h; finally, cooling along with the furnace to obtain the aluminum alloy powder coated with the silicon carbide layer on the surface, wherein the coating thickness of the silicon carbide layer is 200nm.
(2) Preparing an aluminum alloy layer:
(2.1) placing the substrate on an ultrasonic oscillation platform, carrying out ultrasonic excitation on the substrate through the ultrasonic oscillation platform, wherein the ultrasonic power emitted by the ultrasonic oscillation platform is 900W, and the vibration frequency of the substrate is 120kHz;
(2.2) irradiating and scanning the surface of the substrate by the laser beam emitted by the laser emitter while carrying out ultrasonic oscillation on the substrate so as to form a molten pool on the surface of the substrate; the setting parameters of the laser beam include: the scanning speed of the laser beam is 150m/min, the emission power of the laser beam is 2kW, and the spot diameter of the laser beam is 3mm;
and (2.3) synchronously feeding the aluminum alloy powder coated with the silicon carbide layer prepared in the step (1) into a molten pool at a powder feeding speed of 30g/min through a powder feeding device along the moving path of the laser beam, and cooling to form the aluminum alloy layer.
(3) Preparing composite amorphous alloy powder with a core-shell structure:
(3.1) zirconium-based amorphous alloy powder (Zr) having a grain size of 100 μm 70 Cu 10 Ni 15 Al 4 Ti 1 ) Mixing fatty alcohol polyoxyethylene ether sodium sulfate and water to obtain a first solution; wherein the mass fraction of the zirconium-based amorphous alloy powder is 50wt%, and the mass fraction of the fatty alcohol polyoxyethylene ether sodium sulfate is 0.3wt%;
(3.2) mixing lanthanum oxide powder, stearyl trimethyl ammonium chloride and water to obtain a second solution, wherein the weight percent of the lanthanum oxide powder is 50wt%, and the weight percent of the stearyl trimethyl ammonium chloride is 0.3wt%;
(3.3) mixing the first solution and the second solution according to the mass ratio of 1:0.5 to obtain mixed slurry; in the mixing process, pulse current with the frequency of 100Hz and the peak density of 10A/cm is applied to the mixed slurry 2 ；
(3.4) after the mixing is finished, introducing the mixed slurry into a centrifugal spray granulator at a feeding speed of 10kg/h for spray granulation, wherein the inlet temperature of the centrifugal spray granulator is 350 ℃, the outlet temperature of the centrifugal spray granulator is 150 ℃, the spray pressure is 1.5MPa, and the rotating speed is 15000r/min; and (3) spraying and granulating to obtain the composite amorphous alloy powder coated with the lanthanum oxide layer, wherein the thickness of the lanthanum oxide layer is 120nm.
(4) Preparing a zirconium-based amorphous alloy layer:
(4.1) placing the aluminum alloy layer formed in the step (2) into a plasma spraying cavity as a spraying substrate, and feeding the composite amorphous alloy powder prepared in the step (3) into the plasma spraying cavity at a powder feeding speed of 50g/min through a powder feeding device;
(4.2) atomizing the composite amorphous alloy powder into molten liquid drops by a plasma spray gun, and then spraying the molten liquid drops on the surface of a spraying substrate, wherein the output power of the plasma spray gun is 15kW, and the output current of the plasma spray gun is 400A; the gas source adopted by the plasma spray gun is a mixed gas composed of argon and helium, wherein the flow rate of the argon is 80L/min, and the flow rate of the helium is 20L/min; the moving speed of the plasma spray gun is 900mm/s, and the spraying distance between the nozzle of the plasma spray gun and the surface of the spraying substrate is 100mm;
(4.3) spraying the surface of the sprayed substrate at least three times, wherein the interval between two adjacent spraying is 10min, and cooling the sprayed substrate to 500 ℃ during the interval of spraying; and cooling along with the furnace after the spraying is finished so as to form a zirconium-based amorphous alloy layer on the surface of the aluminum alloy layer.
Example 4
The present embodiment provides a method for preparing a zirconium-based amorphous alloy-aluminum alloy composite coating, which is different from embodiment 2 in that step (1) is omitted, an aluminum alloy layer is prepared by using aluminum alloy powder without a silicon carbide layer as a raw material, and other process parameters and operation steps are identical to those of embodiment 2.
Example 5
The present embodiment provides a method for preparing a zirconium-based amorphous alloy-aluminum alloy composite coating, which is different from embodiment 2 in that step (3) is omitted, the zirconium-based amorphous alloy powder without the cerium oxide layer is used as a raw material to prepare a zirconium-based amorphous alloy layer, and other process parameters and operation steps are identical to those of embodiment 2.
Example 6
The present embodiment provides a method for preparing a zirconium-based amorphous alloy-aluminum alloy composite coating, which is different from embodiment 2 in that steps (1) and (3) are omitted, an aluminum alloy layer is prepared by using aluminum alloy powder without a coated silicon carbide layer as a raw material, a zirconium-based amorphous alloy layer is prepared by using zirconium-based amorphous alloy powder without a coated cerium oxide layer as a raw material, and other process parameters and operation steps are exactly the same as embodiment 2.
The composite coatings prepared in examples 1 to 6 were tested for hardness, tensile strength and corrosion rate using the following test criteria and test methods:
hardness testing: the composite coatings prepared in examples 1 to 6 were subjected to hardness testing using a vickers hardness tester according to the method for vickers hardness test of GB/T7997-2014 cemented carbide, and the test results are shown in Table 1.
Tensile strength test: the tensile strength of the composite coatings prepared in examples 1-6 was tested according to GB/T17720-1999 Standard for porosity test of metallic cover layers, and the test results are shown in Table 1.
Corrosion resistance test: the composite coating prepared in examples 1-6 was cut into test samples of 10cm×10cm×0.8cm, immersed in 1mol/L aqueous hydrochloric acid, and subjected to electrochemical corrosion testing using a three-electrode electrochemical cell system, with the test samples, platinum electrode and saturated calomel electrode corresponding to the working electrode, counter electrode and reference electrode, respectively. After reaching a stable open circuit potential, at 10 -2 -10 5 The test was carried out in the frequency range of Hz and the potential disturbance was 10mV. The scanning was performed at a potential of 1mV/s in the voltage range of-1 to 3V. The corrosion potential and the corrosion current compounded during the corrosion process were detected and recorded, and the detection results are shown in table 1.
TABLE 1
As can be seen from the data in table 1, in examples 1 to 3 of the present invention, the composite coating layer composed of the aluminum alloy layer and the zirconium-based amorphous alloy layer was prepared using the aluminum alloy powder coated with silicon carbide and the zirconium-based amorphous alloy powder coated with the transition metal oxide as raw materials, and compared with examples 4, 5 and 6, the composite coating layer prepared by the preparation method provided by the present invention has excellent mechanical properties and corrosion resistance properties.
Scanning electron microscopy is carried out on the surfaces of the composite coatings prepared in the examples 2 and 6 to obtain electron micrographs shown in the figures 1 and 2, wherein figure 1 is the surface of the composite coating prepared in the example 2, and as can be seen from figure 1, the composite coating prepared in the example 2 has fine grains and compact surface and has no defects such as pores and cracks. Fig. 2 shows the surface of the composite coating prepared in example 6, and as can be seen from fig. 2, the surface of the composite coating prepared in example 6 has coarse grains, rough surface and obvious surface defects such as pores and cracks.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (12)
1. A method for preparing a zirconium-based amorphous alloy-aluminum alloy composite coating, which is characterized by comprising the following steps:
taking aluminum alloy powder as a raw material, and forming an aluminum alloy layer on the surface of a substrate by adopting a laser cladding process; wherein the surface of the aluminum alloy powder is coated with a silicon carbide layer with the thickness of 150-200 nm;
Forming a zirconium-based amorphous alloy layer on the surface of the aluminum alloy layer by taking composite amorphous alloy powder as a raw material and adopting a plasma spraying process; the composite amorphous alloy powder is of a core-shell structure and comprises an inner core and an outer shell wrapping the inner core, wherein the inner core is zirconium-based amorphous alloy powder, and the outer shell is a transition metal oxide layer.
2. The method of claim 1, wherein the coating process of the silicon carbide layer comprises:
putting raw material powder of a silicon carbide layer and a binder into a ball mill for mixing and ball milling in a first stage to obtain a coated material, wherein the raw material powder comprises aluminum powder, silicon powder and carbon powder; then, adding aluminum alloy powder into the ball mill for mixing and ball milling in the second stage, so that the coating material coats the surface of the aluminum alloy powder to obtain a mixed material;
(II) placing the mixed material in vacuum or protective atmosphere, adopting a gradient sintering process to enable the cladding material to be melted and then cladding the cladding material on the surface of the aluminum alloy powder, and cooling to obtain aluminum alloy powder coated with a silicon carbide layer;
in the step (I), the mass ratio of the aluminum powder to the silicon powder to the carbon powder is (0.3-0.5): 1.2-1.5): 1;
The binder accounts for 5-10wt% of the total mass of the raw material powder;
the binder comprises any one or a combination of at least two of polyvinyl alcohol, ammonium polyacrylate or hydroxypropyl methyl fiber;
the mass ratio of the aluminum alloy powder to the raw material powder is 1 (0.01-0.05);
the mixing ball milling time of the first stage is 50-60min, and the rotating speed of the ball mill is 100-150r/min;
the aluminum alloy powder is AlNiY alloy powder and comprises the following components in percentage by mass: 60-70wt% of Al, 18-20wt% of Ni and 10-20wt% of Y;
the grain diameter of the aluminum alloy powder is 30-40 mu m;
the mixing ball milling time of the second stage is 20-30min, and the rotating speed of the ball mill is 180-200r/min;
in the step (II), the operation process of the gradient sintering process comprises the following steps:
the temperature of the mixture is raised to 300-400 ℃ at the temperature rising rate of 5-10 ℃/min, and the temperature is kept for 1-2h; and then, heating the mixture to 700-800 ℃ at a heating rate of 15-30 ℃/min, and preserving heat for 1-2h.
3. The method according to claim 1 or 2, wherein the laser cladding process is performed in a laser cladding apparatus comprising a powder feeding device and a vacuum chamber, wherein a laser emitter and an ultrasonic oscillation platform are arranged in the vacuum chamber, and the operation process of the laser cladding process comprises:
Placing the substrate on the ultrasonic oscillation platform, and carrying out ultrasonic excitation on the substrate through the ultrasonic oscillation platform; simultaneously, the laser beam emitted by the laser emitter irradiates and scans the surface of the matrix to form a molten pool on the surface of the matrix;
and synchronously feeding the aluminum alloy powder coated with the silicon carbide layer into a molten pool through the powder feeding device along the moving path of the laser beam, and cooling to form the aluminum alloy layer.
4. The method according to claim 3, wherein the powder feeding speed of the aluminum alloy powder is 20-30g/min;
the scanning speed of the laser beam is 80-150m/min, the emission power of the laser beam is 1-2kW, and the spot diameter of the laser beam is 1-3mm;
the ultrasonic power emitted by the ultrasonic oscillation platform is 800-900W, and the vibration frequency of the matrix is 100-120kHz.
5. The method according to claim 1 or 2, wherein the zirconium based amorphous alloy powder has a chemical formula of Zr a Cu b Ni c Al d Ti e Wherein, a is more than or equal to 60 and less than or equal to 70, b is more than or equal to 10 and less than or equal to 15, c is more than or equal to 10 and less than or equal to 15, d is more than or equal to 4 and less than or equal to 8, e is more than or equal to 1 and less than or equal to 5, and a, b, c, d, e meets the following conditions: a+b+c+d+e=100;
the particle size of the inner core is 50-100 mu m;
the thickness of the shell is 100-120nm.
6. The method of claim 5, wherein the coating process of the transition metal oxide layer comprises:
(1) Mixing zirconium-based amorphous alloy powder, an anionic surfactant and water to obtain a first solution; mixing transition metal oxide powder, a cationic surfactant and water to obtain a second solution;
(2) Mixing the first solution and the second solution to obtain mixed slurry, and applying pulse current to the mixed slurry in the mixing process;
(3) And after the mixing is finished, carrying out spray granulation on the mixed slurry to obtain the composite amorphous alloy powder with the core-shell structure.
7. The method according to claim 6, wherein in the step (1), the mass fraction of the zirconium based amorphous alloy powder is 45 to 50 percent by weight based on 100 percent by weight of the mass fraction of the first solution; the mass fraction of the anionic surfactant is 0.1-0.3wt%;
the mass fraction of the transition metal oxide powder is 45-50wt% and the mass fraction of the cationic surfactant is 0.1-0.3wt% based on 100wt% of the second solution.
8. The method according to claim 6, wherein in the step (2), the first solution and the second solution are mixed at a mass ratio of 1 (0.1 to 0.5);
the frequency of the pulse current is 50-100Hz, and the peak density of the pulse current is 0.1-10A/cm 2 。
9. The method according to claim 6, wherein in the step (3), the spray granulation operation is performed in a centrifugal spray granulator having an inlet temperature of 300 to 350 ℃ and an outlet temperature of 100 to 150 ℃;
the spraying pressure of the centrifugal spray granulator is 0.5-1.5MPa, and the rotating speed of the centrifugal spray granulator is 10000-15000r/min;
the feed rate of the mixed slurry is 1-10kg/h.
10. The method of claim 5, wherein the plasma spraying process is performed in a plasma spraying apparatus comprising a plasma spraying chamber, a plasma spray gun, and a powder feeder, the plasma spraying process comprising the steps of:
placing a substrate with an aluminum alloy layer formed as a spraying substrate into the plasma spraying cavity, conveying the composite amorphous alloy powder to a nozzle of a plasma spraying gun through the powder conveying device, atomizing the composite amorphous alloy powder into molten liquid drops by plasma high-temperature flame emitted by the plasma spraying gun, spraying the surface of the spraying substrate for at least three times, wherein each spraying is carried out for a period of time, and cooling the spraying substrate during the spraying interval; and cooling along with the furnace after the spraying is finished, so as to form the zirconium-based amorphous alloy layer on the surface of the aluminum alloy layer.
11. The method of claim 10, wherein the composite amorphous alloy powder has a powder feed rate of 40-50g/min;
the output power of the plasma spray gun is 10-15kW, and the output current is 300-400A;
the gas source adopted by the plasma spray gun is a mixed gas composed of argon and helium, wherein the flow of the argon is 50-80L/min, and the flow of the helium is 15-20L/min;
the moving speed of the plasma spray gun is 800-900mm/s, and the spraying distance between the nozzle of the plasma spray gun and the surface of the spraying substrate is 90-100mm;
and the interval between two adjacent spraying is 5-10min, and the spraying substrate is cooled to 400-500 ℃ during the interval of spraying.
12. A zirconium-based amorphous alloy-aluminum alloy composite coating, characterized in that the zirconium-based amorphous alloy-aluminum alloy composite coating is prepared by the preparation method of any one of claims 1 to 11.
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