CN109609952A - A kind of ultralimit magnesium alloy and preparation method thereof - Google Patents
A kind of ultralimit magnesium alloy and preparation method thereof Download PDFInfo
- Publication number
- CN109609952A CN109609952A CN201811640744.4A CN201811640744A CN109609952A CN 109609952 A CN109609952 A CN 109609952A CN 201811640744 A CN201811640744 A CN 201811640744A CN 109609952 A CN109609952 A CN 109609952A
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- CN
- China
- Prior art keywords
- layer
- magnesium alloy
- ultralimit
- ceramics
- layers
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 138
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010410 layer Substances 0.000 claims abstract description 172
- 239000000919 ceramic Substances 0.000 claims abstract description 64
- 239000002131 composite material Substances 0.000 claims abstract description 43
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000012790 adhesive layer Substances 0.000 claims abstract description 25
- 238000000151 deposition Methods 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 235000006708 antioxidants Nutrition 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000006260 foam Substances 0.000 claims abstract description 14
- 239000010970 precious metal Substances 0.000 claims abstract description 10
- 239000004615 ingredient Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 229910052580 B4C Inorganic materials 0.000 claims description 8
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000001680 brushing effect Effects 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 230000003746 surface roughness Effects 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229910000943 NiAl Inorganic materials 0.000 claims description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 239000007769 metal material Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 37
- 238000005260 corrosion Methods 0.000 description 20
- 230000007797 corrosion Effects 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 230000008901 benefit Effects 0.000 description 10
- 238000005507 spraying Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000007749 high velocity oxygen fuel spraying Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 208000016261 weight loss Diseases 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000005480 shot peening Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- 229910001021 Ferroalloy Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000002742 anti-folding effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 240000006409 Acacia auriculiformis Species 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009690 centrifugal atomisation Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000012720 thermal barrier coating Substances 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
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- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
- C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX layer
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- 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
- C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
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- 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
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
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- 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
- C23C4/129—Flame spraying
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- 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
- C23C4/131—Wire arc spraying
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- 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
Abstract
The invention belongs to a kind of magnesium alloy technical field of metal material, disclose a kind of ultralimit magnesium alloy and preparation method thereof, including magnesium alloy substrate, magnesium alloy matrix surface has been sequentially depositing anti-oxidant composite tie layer, composite ceramic layer, reflecting layer, antireflection layer, insulating layer, foam carbon-coating；Anti-oxidant composite tie layer includes the adhesive layer for being deposited on magnesium alloy matrix surface and the layer of precious metal for being deposited on tie layer surface；Composite ceramic layer includes B layers of A layers of ceramics and ceramics.When preparation, anti-oxidant composite tie layer, composite ceramic layer, reflecting layer, antireflection layer, insulating layer, foam carbon-coating are successively deposited on Mg alloy surface, just form ultralimit magnesium alloy.The use temperature of ultralimit magnesium alloy provided by the invention is increased to above former 100-500 DEG C of magnesium alloy fusing point, is able to achieve and uses at a temperature of ultralimit.
Description
Technical field
The invention belongs to a kind of magnesium alloy metal material fields, and in particular to a kind of ultralimit magnesium alloy and its preparation side
Method.
Background technique
Magnesium alloy has the small (1.8g/cm of density as a kind of current important metal material3Left and right), intensity is high, elasticity
Modulus is big, good heat dissipation, absorb shock resistance are good, the excellent spy such as better than the corrosive nature of big, resistance to organic matter and alkali that absorbs impact load-carrying ability
Property, it is mainly used for the industrial departments such as Aeronautics and Astronautics, transport, chemical industry, rocket.Magnesium alloy is aircraft, spacecraft and rocket-powered missile
Most light metal structure material used in process industry, mainly for the manufacture of the part of low load.
It is also higher and higher to the rate request of aircraft with the development of technology with the actual demand of society, aircraft
Speed-raising means that engine running speed is promoted, and the running temperature of engine is also promoted therewith, so that engine
The temperature such as gear casing, oil pump and oil pipe are also promoted.And magnesium alloy is very stable in gasoline, kerosene and lubricating oil, therefore usually
Engine gear casing, oil pump and oil pipe are prepared by magnesium alloy.The magnesium alloy fusing point of magnesium alloy is used at 650 DEG C or so
Even more 70% or so of its fusing point, and at high temperature, magnesium alloy easily aoxidizes temperature, therefore when aircraft speed-raising, magnesium alloy
It is not able to satisfy and is used under the conditions of each part temperatures of engine are raised, therefore meet and use (super at a temperature of ultralimit
Limit temperature is the melting temperature for being more than magnesium alloy).
And in the research process for promoting vehicle flight speeds, in order to adapt to the promotion of its engine temperature, it will usually
Using the higher melting-point alloy such as ferroalloy as the primary structural material of production aircraft, but the weight of ferroalloy is larger,
Using ferroalloy as the raw material of manufacture aircraft engine, the weight that will lead to aircraft engine significantly increases,
The flying speed that will lead to aircraft instead slows down, and is not able to satisfy actual demand.If right and the case where not changing material
Aircraft raises speed, and can only just shorten the service life of aircraft.
Summary of the invention
The invention is intended to provide a kind of ultralimit magnesium alloy and preparation method thereof, it is unable to satisfy with solving magnesium alloy in super
The problem of being used at a temperature of limit.
To achieve the above object, the present invention provides following base case, a kind of ultralimit magnesium alloy, including magnesium alloy base
Body, magnesium alloy matrix surface have been sequentially depositing anti-oxidant composite tie layer and composite ceramic layer；Anti-oxidant composite tie layer includes
It is deposited on the adhesive layer of magnesium alloy matrix surface and is deposited on the layer of precious metal of tie layer surface；Composite ceramic layer includes ceramics A
B layers of layer and ceramics.
The technical program the utility model has the advantages that
Inventor has developed a kind of ultralimit magnesium alloy, it is (super in ultralimit temperature to meet magnesium alloy by largely studying
Cross its melting temperature) under use.In R&D process, it is generally believed that when environment temperature be higher than alloy use temperature it
Afterwards, it will think that the alloy cannot be carried out at such a temperature using and then other dystectic alloys being needed to carry out using and sending out
Bright people goes around, and trial improves magnesium alloy, to meet the needs of aircraft manufacture.It is continuously attempted in inventor
Magnesium alloy can be used temperature by depositing the coating centainly matched in Mg alloy surface by very pleasantly surprised discovery in the process
It is increased to above 100-500 DEG C of former fusing point, the use temperature of magnesium alloy will be greatly improved, to meet the need of manufacture aircraft
It asks；And under high temperature environment, it is all very difficult that the use temperature of magnesium alloy, which is promoted 2-3 DEG C, thus applicant this
Research is the very big progress in the use of magnesium alloy.
The technical program, can be significantly by depositing anti-oxidant composite tie layer and composite ceramic layer on magnesium alloy substrate
Raising magnesium alloy use temperature, to adapt to magnesium alloy in the use of ultralimit temperature.Deposit anti-oxidant composite tie layer, energy
The bond effect between each coating and magnesium alloy substrate is enough improved, coating is avoided to fall off in use.Deposit composite ceramics
Layer, can reduce the conduction of heat, to improve the use temperature of magnesium alloy substrate.
In conclusion the present invention has following technical effect that
1, ultralimit magnesium alloy provided by the invention has splendid high-temperature mechanics and chemical stability, can be more than it
It is used under conditions of magnesium alloy substrate fusing point, enhances use scope.
2, it by that can be promoted to using temperature and be higher than original in magnesium alloy matrix surface depositing multilayer coatings by the present invention
100-500 DEG C of magnesium alloy substrate fusing point, to realize use of the magnesium alloy under ultralimit environment.
3, ultralimit magnesium alloy provided by the invention has splendid corrosion resistance, thus under acid or alkaline conditions
Greatly increased using the time, thus can be reduced material corrosion and caused by waste, save the cost.
4, the present invention broken when environment temperature be higher than material using temperature just can only more conversion materials traditional thought
Confine, by depositing coating on the surface of the material, improve the use temperature of material, ultralimit magnesium alloy is enabled to be suitable for speed-raising
In aircraft preparation afterwards, and the service life of aircraft will not be shortened.
Further, the anti-oxidant composite tie layer with a thickness of 100-200 μm, composite ceramic layer with a thickness of 150-
500 μm, composite ceramic layer is also sequentially depositing the reflecting layer of 10-30 μ m-thick, the antireflection layer of 10-30 μ m-thick, 10-200 μm outside
The foam carbon-coating of thick insulating layer and 20-200 μ m-thick.
The utility model has the advantages that deposition of reflective layer has the effect of reflecting heat source, so that the heat source of Mg alloy surface is reduced, to mention
Operation at high temperature.Antireflection layer is deposited, refraction of the infrared ray in coating can be stopped, so that the temperature of magnesium alloy substrate is reduced,
So that the use temperature of the magnesium alloy of preparation improves.Insulating layer can completely cut off the generation of magnesium alloy matrix surface ionization, support
Erosion of the anti-charge to basis material.The carbon of foam carbon-coating vaporizes cooling when in use, and forms vapour in magnesium alloy matrix surface
Change film, Heat transmission is further prevented, to improve the use temperature of magnesium alloy.The technical program is made by the cooperation of each coating
The use temperature for obtaining magnesium alloy has obtained greatly being promoted.And by the setting of the thickness to each coating, enable to prepare
The use temperature of ultralimit magnesium alloy improve, and its weight increases less, the characteristic with lightweight, makes convenient for production aircraft
With.
Further, the ingredient of the adhesive layer is the mixing of one or more of MCrAlY, NiAl, NiCr-Al, Mo
Object, MCrAlY NiCrCoAlY, NiCoCrAlY, CoNiCrAlY or CoCrAlY；The ingredient of adhesive layer be Au, Pt, Ru, Rh,
The alloy of one or more of Pd, Ir.
The utility model has the advantages that the proportion in tri- kinds of materials of NiCrCoAlY, NiCoCrAlY, CoNiCrAlY between each element is different,
Therefore material obtained is different.Adhesive layer has good bond effect, so that the bonding of subsequent coating and magnesium alloy body
Effect is good, reduces the probability that falls off of coating；And noble metal itself has oxidation resistant characteristic, can effectively prevent, and under high temperature, oxygen
It is spread into adhesive layer and magnesium alloy substrate, to improve the antioxygenic property of coating, improves the service life of coating.
Further, the ingredient of A layers of the ceramics is YSZ or rare earth zirconate (RE2Zr2O7)；Ceramic B layers of ingredient is
ZrO2-RETaO4。
The utility model has the advantages that YSZ or rare earth zirconate, are a kind of substances generally used as thermal barrier coating, are easily obtained.
ZrO2-RETaO4Characteristic with low heat conductivity, high expansion, low heat conductivity can reduce the conduction of heat, so that in hot environment
Under, magnesium alloy substrate keeps low temperature, to improve the use temperature of the magnesium alloy of preparation；And high expansion coefficient be in order to bonding
The thermal expansion coefficient of layer matches, since the thermal expansion coefficient of noble metal adhesive layer is also larger, in this way in Thermal Cycling (i.e.
Constantly heating it is cooling during), the thermal mismatch stress (stress that thermal expansion coefficient difference generates) of ceramic layer and adhesive layer compared with
It is small, and then improve the service life of coating.It (for popular, is deposited together when two thermal expansion coefficients differ biggish coating
When, when heating up or cooling down, the degrees of expansion of two coatings is seriously different, and the stress that will lead between two coatings increases,
The problem of cracking, or even falling off so as to cause between two coatings.)
Further, the ZrO2-RETaO4It is spherical in shape, and partial size is 10-70 μm.
The utility model has the advantages that spraying effect is good when enabling to deposit B layers ceramic, and make ceramic B layers of bond effect good.
Further, the ingredient in the reflecting layer is REVO4、RETaO4、Y2O3One or more of mixture.
The utility model has the advantages that REVO4、RETaO4, the reflection coefficient of Y2O3 it is high, therefore heat source can be reflected, reduce heat radiation, drop
Low magnesium alloy substrate temperature, to improve the use temperature of the magnesium alloy of preparation.
Further, the ingredient of the antireflection layer is the mixture of one or both of graphene or boron carbide, and stone
The crystal structure of black alkene and boron carbide is in disorderly arranged state.
The utility model has the advantages that graphene and boron carbide although refractive index with higher, when incident light is being irradiated to antireflection layer
When upper, the refraction of light in all directions is can be enhanced in disorderly arranged graphene and boron carbide, avoids incident light in same direction
It is upper to reflect, achieve the effect that refraction dispersion, enters the incident intensity decline in coating in this way.
Further, the ingredient of the insulating layer is the mixed of one or more of epoxy resin, phenolic resin, ABS resin
Close object.
The utility model has the advantages that aircraft is in use, when shell and air occur friction and ionize, epoxy resin, phenolic resin,
Conduction electrons can be isolated in ABS resin, resist erosion of the charge to magnesium alloy substrate.
The present invention also provides another base case, a kind of preparation method of ultralimit magnesium alloy, comprising the following steps:
Step 1:
Adhesive layer is deposited in magnesium alloy matrix surface first, then in tie layer surface depositing noble metal layer, so that adhesive layer
Anti-oxidant composite tie layer is formed with layer of precious metal, the overall thickness of anti-oxidant composite tie layer is 100-200 μm；
Step 2:
B layers of A layers of deposition ceramics and ceramics on layer of precious metal surface, so that A layers of ceramics and B layers of formation composite ceramics of ceramics
Layer, the overall thickness of composite ceramic layer are 150-500 μm；
Step 3:
In composite ceramics layer surface deposition of reflective layer, reflecting layer with a thickness of 10-30 μm；
Step 4:
In reflecting layer external coating antireflection layer, antireflection layer with a thickness of 10-30 μm；
Step 5:
In antireflection layer surface brushing insulating layer, insulating layer with a thickness of 10-200 μm；
Step 6:
Surface of insulating layer brushing foam carbon-coating, foam carbon-coating with a thickness of 20-200 μm, to form ultralimit magnesium alloy.
The technical program has the beneficial effect that
It is controlled by the thickness to each coating being deposited on magnesium alloy substrate, has both been able to achieve the ultralimit magnesium of preparation
Alloy is increased to above 100-500 DEG C of former magnesium alloy fusing point using temperature, and has splendid corrosion resistance.Simultaneously also
The weight that can be avoided the larger caused ultralimit magnesium alloy prepared of coating layer thickness, which increases larger situation, to be occurred, so that
Ultralimit magnesium alloy is able to maintain the characteristic of lightweight, but can ultralimit at a temperature of use, mentioned to meet existing aircraft
The requirement of speed.
Further, in the step 1, before depositing adhesive layer, the greasy dirt of magnesium alloy matrix surface is removed；And to magnesium
The surface of alloy substrate carries out bead, so that the surface roughness of magnesium alloy substrate is 60-100 μm.
The utility model has the advantages that can be increased by the greasy dirt of removal magnesium alloy matrix surface viscous between magnesium alloy substrate and coating
Tie effect.And biggish internal stress can be generated during curing of coatings, utilizes the magnesium alloy base after compressed air shotblasting machine bead
The roughness in body surface face can effectively eliminate the problems in stress collection, therefore can prevent coating cracking.And surface roughness
In the presence of the quality that can support a part of coating, be conducive to eliminate sagging phenomenon.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of ultralimit magnesium alloy of the present invention；
Fig. 2 is the curve graph of the creep test of the embodiment of the present invention 1 and comparative example 13 at 50MPa, 900 DEG C；
Fig. 3 is the salt air corrosion experimental result schematic diagram of the embodiment of the present invention 1 and comparative example 13.
Specific embodiment
It is further described below by specific embodiment:
Appended drawing reference in Figure of description includes: magnesium alloy substrate 1, anti-oxidant composite tie layer 2, adhesive layer 21, expensive
Metal layer 22, composite ceramic layer 3, ceramics A layer 31, ceramics B layer 32, reflecting layer 4, antireflection layer 5, insulating layer 6, foam carbon-coating 7.
The present invention provides a kind of ultralimit magnesium alloys, as shown in Figure 1, including magnesium alloy substrate 1,1 table of magnesium alloy substrate
Face be sequentially depositing the anti-oxidant composite tie layer 2 of 100-200 μ m-thick, 150-500 μm of composite ceramic layer 3,10-30 μ m-thick it is anti-
Penetrate the foam carbon-coating 7 of layer 4, the antireflection layer 5 of 10-30 μ m-thick, the insulating layer 6 of 10-200 μ m-thick and 20-200 μ m-thick.Wherein resist
Aoxidizing composite tie layer 2 is the adhesive layer 21 for being deposited on 1 surface of magnesium alloy substrate and the noble metal for being deposited on 21 surface of adhesive layer
Layer 22, the ingredient of adhesive layer 21 are the alloy of one or more of MCrAlY, NiAl, NiCr-Al, Mo, and MCrAlY is
NiCrCoAlY, NiCoCrAlY, CoNiCrAlY or CoCrAlY, the ingredient of layer of precious metal 22 are in Au, Pt, Ru, Rh, Pd, Ir
One or more of alloys；Composite ceramic layer 3 includes being deposited on ceramic A layer 31 and ceramics B layer 32, and ceramic A layer 31 is close to expensive
Close to layer of precious metal 22, the ingredient of ceramic A layer 31 is YSZ or rare earth zirconate (RE for metal layer 22 or ceramics B layer 322Zr2O7, RE
=Y, Nd, Eu, Gd, Dy, Sm), the ingredient of ceramic B layer 32 is ZrO2-RETaO4, ZrO2-RETaO4It is spherical in shape, and partial size is 10-
70 μm, chemical general formula RE1-x(Ta/Nb)1-x(Zr/Ce/Ti)2xO4, RE=Y, Nd, Eu, Gd, Dy, Er, Yb, Lu, Sm；Instead
The ingredient for penetrating layer 4 is REVO4、RETaO4、Y2O3One or more of mixture, RE=Y, Nd, Eu, Gd, Dy, Er, Yb,
Lu,Sm.The ingredient of antireflection layer 5 is the mixture of one or both of graphene and boron carbide, and graphene and boron carbide
Crystal structure be in disorderly arranged state；The ingredient of insulating layer 6 be one of epoxy resin, phenolic resin, ABS resin or
Several mixtures.
The present invention utilizes ZrO2-RETaO4As B layers ceramic, have the effect of lower thermal conductivity, high expansion rate, be able to achieve drop
Conduction low in calories；And the ZrO being prepared by the following method2-RETaO4It can satisfy the requirement of APS spraying technology.
ZrO2-RETaO4It is prepared using following methods, comprising the following steps:
Step (1):
By zirconium oxide (ZrO2) powder, RE oxide powder (RE2O3), tantalum pentoxide (Ta2O5) powder progress predry
Dry, pre-dried temperature is 600 DEG C, and the pre-dried time is 8h；And according to molar ratio be 2x:(1-x): (1-x) weighs oxidation
Zirconium (ZrO2) powder, RE oxide powder RE2O3, oxidation two tantalum (Ta2O5) powder is added in alcohol solvent, obtains mixing molten
Liquid, so that the molar ratio of RE:Ta:Zr is (1-x): (1-x): 2x in mixed solution；Mixed solution is carried out using ball mill again
Ball milling 10h, the revolving speed of ball mill are 300r/min.
The slurry obtained after ball milling is dried using Rotary Evaporators (model: N-1200B), drying temperature 60
DEG C, the dry time is 2h, and the powder after drying is used to the sieve of 300 mesh, obtains powders A.
Step (2):
Use high-temperature solid phase reaction method that ingredient is made as ZrO powders A obtained in step (1)2Adulterate RETaO4Powder
B, reaction temperature are 1700 DEG C, reaction time 10h；And it is sieved using the sieve of 300 mesh to powder B.
Step (3):
Powder B after sieving in step (2) is mixed to get slurry C with deionized water solvent, organic adhesive, wherein starching
The mass percent for expecting powder B in C is 25%, and the mass percent of organic adhesive is 2%, remaining is solvent, organic bonding
Agent uses polyvinyl alcohol or gum arabic；Recycle centrifugal atomization that slurry C is dried, temperature when dry is
600 DEG C, centrifugal speed 8500r/min, obtain dry material grain D；
Step (4):
By material grain D that step (3) obtains 1200 DEG C at a temperature of be sintered 8h, then using 300 mesh sieve to sintering after
Material grain D sieving, obtaining partial size is 10~70nm and pattern ZrO spherical in shape2-RETaO4Ceramic powder.
Inventor has shown that in parameter area of the invention, the ultralimit magnesium alloy of preparation makes through a large number of experiments
Maximum is promoted with temperature, and the weight gain of magnesium alloy is small, each optimal ultralimit magnesium alloy of parameter area, and in the present invention
30 groups therein are listed to be illustrated.
Each parameter such as table 1, table 2,3 institute of table of the embodiment 1-30 of a kind of ultralimit magnesium alloy of the present invention and preparation method thereof
Show: (thickness unit: μm)
Table 1
Table 2
Table 3
Now by taking embodiment 1 as an example, to another technical solution of the invention, a kind of preparation method progress of ultralimit magnesium alloy
Explanation.
A kind of preparation method of ultralimit magnesium alloy, comprising the following steps:
Step 1:
It selects AM50A magnesium alloy as magnesium alloy substrate in the present embodiment, removes magnesium alloy matrix surface using infusion method
Greasy dirt and impurity, first by magnesium alloy substrate be immersed in emulsification detergent remover or aqueous slkali in, wherein emulsification detergent remover it is main
Ingredient is ethyl alcohol and surfactant, and aqueous slkali main component is sodium hydroxide, tertiary sodium phosphate, sodium carbonate sodium metasilicate, this implementation
Example uses aqueous slkali soaking magnesium alloy substrate.It is impregnated by between the pH value adjustment of aqueous slkali to 10~11, then by magnesium alloy substrate
It in aqueous slkali, is taken out after impregnating 0.5-1.5h, soaking time is 1h in the present embodiment, and clear water is recycled to rinse well and dry
It is dry.Compressed air shotblasting machine is recycled to carry out bead to magnesium alloy matrix surface, the compressed air shotblasting machine used is that JCK-SS500-6A is passed automatically
Defeated formula compressed air shotblasting machine, for any one in iron sand, glass ball and ceramic pellet, the present embodiment uses the shot-peening material that when shot-peening uses
Iron sand, and the partial size of iron sand can be 0.3-0.8mm, the partial size of iron sand is 0.5mm in the present embodiment；Magnesium alloy substrate after shot-peening
Surface roughness be 60-100 μm, the surface roughness of magnesium alloy substrate is 80 μm in the present embodiment, is closed convenient for coating and magnesium
The bonding of auri body.
Step 2:
The surface of AM50A magnesium alloy after shot-peening deposits anti-oxidant composite tie layer, first with HVOF or Supersonic
For fast electric arc spraying in the surface of magnesium alloy substrate spraying layer of Ni CrCoAlY as adhesive layer, the present embodiment uses HVOF method,
Powder diameter when spraying is 25-65 μm, oxygen flow 2000SCFH, kerosene oil flow 18.17LPH, carrier gas are
12.2SCFH, powder sending quantity 5RPM, barrel length 5in, spray distance 254mm.
EB-PVD method is recycled to deposit layer of Au on NiCrCoAlY as layer of precious metal, to be formed anti-oxidant compound
Adhesive layer.Gas pressure intensity when depositing Au is less than 0.01Pa, and pressure used in the present embodiment is 0.008Pa, and magnesium alloy base
The temperature of body and the fusing point ratio of magnesium alloy substrate are less than 0.3.The adhesive layer of deposition with a thickness of 50 μm, the thickness of layer of precious metal
It is 50 μm.
Step 3:
One layer of YSZ is sprayed as A layers of ceramics, originally on the surface of adhesive layer using APS, HVOF, PS-PVD or EB-PVD method
Embodiment uses APS method, and APS method is recycled to spray one layer of YTaO on ceramic A4As B layers ceramic, formation composite ceramic layer；
Wherein A layers of ceramics with a thickness of 70 μm, ceramic B layers with a thickness of 80 μm.
Step 4:
One layer of Y is sprayed in ceramic B layer surface using HVOF, PS-PVD or EB-PVD method2O3Transparent ceramic material is as reflection
Layer, the present embodiment use HVOF method, the reflecting layer of spraying with a thickness of 10 μm.
Step 5:
Graphene is mutually uniformly mixed with micron-sized carbon powder material, then mixed-powder is imported in solution and is surpassed
Acoustic vibration mixes, and solution is that the ethanol solution for having 1% dispersing agent is added in the present embodiment, will be uniformly mixed later solution benefit
Micron-sized carbon dust is separated with filter paper.The solution for being blended with graphene again is painted on the surface in reflecting layer as anti-folding
Layer is penetrated, then the magnesium alloy for being coated with graphene antireflection layer is put into drying box, dry 2h, the anti-folding of brushing at a temperature of 60 DEG C
Penetrate layer with a thickness of 10 μm.
Step 6:
In one layer of epoxy resin of antireflection layer surface brushing as insulating layer, thickness of insulating layer is 10 μm.
Step 7:
On the insulating layer brush one layer of foam carbon-coating, foam carbon-coating with a thickness of 20 μm, obtain ultralimit magnesium alloy.
Embodiment 2-29 is only that parameter as shown in Table 1 is different from the difference of embodiment 1；Embodiment 30 and embodiment 1
Difference be A layers of ceramics in step 3 it is different with B layers of ceramics of spraying sequence.
Experiment:
13 groups of comparative examples are set and embodiment 1-30 compares experiment, each parameter of comparative example 1-12 is as shown in table 4:
Table 4
Comparative example 1-12 is only that each parameter as shown in table 3 is different from the difference of embodiment 1, and comparative example 13 is AM50A
Magnesium alloy.
Following experiment is carried out using the magnesium alloy that embodiment 1-30, comparative example 1-13 are provided:
Creep experiments under high temperature:
The magnesium alloy provided using embodiment 1-30 and comparative example 1-13 is processed as to the column of long 187mm, diameter 16mm
Test specimen, utilize model RMT-D5 electronic type high-temerature creep permanent strength testing machine carry out creep experiments under high temperature.
The test specimen of embodiment 1-30, comparative example 1-13 are put into electronic type high-temerature creep permanent strength testing machine, and opened
Dynamic test machine, so that testing machine heats up, in temperature-rise period, test specimen is in unstress state, and (under unstress state, test specimen can
Free wxpansion, and high-temerature creep is to deform increase with time at temperature and stress collective effect, therefore heating rate is to creep
It does not influence).When the temperature of testing machine reaches 900 DEG C, it is 50MPa that testing machine, which is adjusted to stress, and it is real to carry out high-temerature creep
It tests, by taking embodiment 1 and comparative example 13 as an example, ((A) indicates comparative example 13 to experimental result in Fig. 2, and (B) indicates to implement as shown in Figure 2
Example 1), the results are shown in Table 5 for the specific experiment of embodiment 1-30 and comparative example 1-13.
As can be drawn from Figure 2, there are 3 stages in (A), the creep of (B) test specimen, but more than AM50A magnesium alloy fusing point
At a temperature of later, (A) test specimen just has occurred creep rupture in a very short period of time, therefore it can be concluded that, it is being higher than AM50A magnesium
At a temperature of alloy melting point, AM50A magnesium alloy can hardly load.And (B) test specimen is obtained compared to (A) test specimen creep-resistant property
Apparent raising, the steady state creep time of (B) test specimen is longer, it can be observed that creep curve passes through longer steady state creep rank
It has entered the tertiary creep stage after section and creep rupture occurs.Therefore it can be concluded that, more than AM50A magnesium alloy fusing point temperature
Under degree, ultralimit magnesium alloy provided by the invention maintains preferable power compared to original AM50A magnesium alloy, ultralimit magnesium alloy
Learn performance and it is not broken, have excellent high temperature resistance.
Salt air corrosion experiment:
Embodiment 1-30, comparative example the 1-13 magnesium alloy provided are processed into 50mm × 25mm × 2mm test specimen, then carried out
Oil removing, processing of rust removing, and clean, dry.Use YWX/Q-250B salt air corrosion case as experimental facilities, and simulates GB/
The atmospheric corrosion environment of T2967.3-2008.
Embodiment 1-30, comparative example the 1-13 test specimen provided are suspended in experimental facilities, and experimental facilities is adjusted to
Temperature is 50 ± 1 DEG C, PH 3.0-3.1, and recycling concentration is that 5 ± 0.5%NaCl solution is continuously sprayed to test specimen.With embodiment
1 and comparative example 13 for, continuously to test specimen spray concentration be 5 ± 0.5%NaCl solution 8h, for 24 hours, after 48h, 72h, the mistake of test specimen
Rate is ((A) indicates comparative example 13 in Fig. 3, and (B) indicates embodiment 1) as shown in Figure 3 again, the tool of embodiment 1-30 and comparative example 1-13
Body experimental result is as shown in table 5.
In conjunction with Fig. 3, it can be concluded that, (A), (B) test specimen have visibly different corrosion regularity, for (A) test specimen, with corruption
The extension of time is lost, corrosion weight loss numerical value is in the trend increased.Wherein, corrode initial stage (8-24h), specimen surface has oxidation
Film hinders magnesium alloy substrate to contact with solution, and corrosion rate is smaller.Corrode mid-term (24-48h), the Cl in solution-It has penetrated
Oxidation film, a large amount of Cl-It is adsorbed on matrix, increases point corrosion pit, original point corrosion pit is deepened, hence it is evident that accelerates corrosion rate.
Continuously by spraying after 48h, corrosion product is evenly distributed, and thickness increases, and almost covers sample whole surface, Cl-It needs across corruption
Erosion product could be contacted with magnesium alloy substrate, reduce matrix surface absorption Cl-Quantity, reduce corrosion rate.Totally see,
(A) test specimen corrosion weight loss amount is much higher than (B) test specimen, and (B) test specimen corrodes since the presence of coating there is no, quality
Almost without changing, therefore ultralimit magnesium alloy provided by the present application has preferable corrosion resistance.
Experimental result is as shown in table 5: (A, 50MPa, at 900 DEG C each test specimen the steady creep time (min)；B,50MPa,
The time (min) of creep rupture occurs for each test specimen at 900 DEG C；B, the weight-loss ratio of test specimen after NaCl solution 8h is continuously sprayed to test specimen
(v/mg.cm2)；B, the weight-loss ratio (v/mg.cm of test specimen after continuously spraying NaCl solution for 24 hours to test specimen2)；E, it is continuously sprayed to test specimen
Spill the weight-loss ratio (v/mg.cm of test specimen after NaCl solution 48h2)；F, the weightlessness of test specimen after NaCl solution 72h is continuously sprayed to test specimen
Rate (v/mg.cm2))
Table 5
It can be seen that by depositing anti-oxidant composite tie layer, composite ceramic layer, reflecting layer, antireflection on magnesium alloy
The use temperature of magnesium alloy can be promoted to and be higher than former 100-500 DEG C of fusing point by layer, insulating layer and foam carbon-coating, and corrosion resistant
Corrosion also greatly improves.And by the way that the thickness control of each coating in range provided by the invention, is enabled to prepare
Ultralimit magnesium alloy each effect it is best.And the maximum operation (service) temperature of the magnesium alloy beyond parameter area provided in this embodiment
It is much lower compared to ultralimit magnesium alloy provided by the invention, and its corrosion resistance is also poor.
For those skilled in the art, under the premise of not departing from technical solution of the present invention design, can also make
Several modifications and improvements out, these also should be considered as protection scope of the present invention, these all will not influence the effect of this patent implementation
Fruit and patent practicability.
Claims (10)
1. a kind of ultralimit magnesium alloy, including magnesium alloy substrate, it is characterised in that: magnesium alloy matrix surface has been sequentially depositing antioxygen
Change composite tie layer and composite ceramic layer；Anti-oxidant composite tie layer includes being deposited on the adhesive layer of magnesium alloy matrix surface and sinking
Layer of precious metal of the product in tie layer surface；Composite ceramic layer includes B layers of A layers of ceramics and ceramics.
2. a kind of ultralimit magnesium alloy according to claim 1, it is characterised in that: the thickness of the anti-oxidant composite tie layer
Degree is 100-200 μm, composite ceramic layer with a thickness of 150-500 μm, 10-30 μ m-thick is also sequentially depositing outside composite ceramic layer
Reflecting layer, the antireflection layer of 10-30 μ m-thick, the insulating layer of 10-200 μ m-thick and 20-200 μ m-thick foam carbon-coating.
3. a kind of ultralimit magnesium alloy according to claim 2, it is characterised in that: the ingredient of the adhesive layer is
The mixture of one or more of MCrAlY, NiAl, NiCr-Al, Mo, MCrAlY NiCrCoAlY, NiCoCrAlY,
CoNiCrAlY or CoCrAlY；The ingredient of adhesive layer is the alloy of one or more of Au, Pt, Ru, Rh, Pd, Ir.
4. a kind of ultralimit magnesium alloy according to claim 2, it is characterised in that: the ingredient of A layers of the ceramics be YSZ or
Rare earth zirconate (RE2Zr2O7)；Ceramic B layers of ingredient is ZrO2-RETaO4。
5. a kind of ultralimit magnesium alloy according to claim 4, it is characterised in that: the ZrO2-RETaO4It is spherical in shape, and
Partial size is 10-70 μm.
6. a kind of ultralimit magnesium alloy according to claim 2, it is characterised in that: the ingredient in the reflecting layer is REVO4、
RETaO4、Y2O3One or more of mixture.
7. a kind of ultralimit magnesium alloy according to claim 2, it is characterised in that: the ingredient of the antireflection layer is graphite
The mixture of one or both of alkene or boron carbide, and the crystal structure of graphene and boron carbide is in disorderly arranged state.
8. a kind of ultralimit magnesium alloy according to claim 2, it is characterised in that: the ingredient of the insulating layer is asphalt mixtures modified by epoxy resin
The mixture of one or more of rouge, phenolic resin, ABS resin.
9. a kind of preparation method of ultralimit magnesium alloy according to claim 2-8 any one, which is characterized in that including
Following steps:
Step 1:
Adhesive layer is deposited in magnesium alloy matrix surface first, then in tie layer surface depositing noble metal layer, so that adhesive layer and expensive
Metal layer forms anti-oxidant composite tie layer, and the overall thickness of anti-oxidant composite tie layer is 100-200 μm；
Step 2:
B layers of A layers of deposition ceramics and ceramics on layer of precious metal surface, so that A layers of ceramics and B layers of formation composite ceramic layer of ceramics, multiple
The overall thickness for closing ceramic layer is 150-500 μm；
Step 3:
In composite ceramics layer surface deposition of reflective layer, reflecting layer with a thickness of 10-30 μm；
Step 4:
In reflecting layer external coating antireflection layer, antireflection layer with a thickness of 10-30 μm；
Step 5:
In antireflection layer surface brushing insulating layer, insulating layer with a thickness of 10-200 μm；
Step 6:
Surface of insulating layer brushing foam carbon-coating, foam carbon-coating with a thickness of 20-200 μm, to form ultralimit magnesium alloy.
10. a kind of preparation method of ultralimit magnesium alloy according to claim 9, it is characterised in that: in the step 1,
Before depositing adhesive layer, the greasy dirt of magnesium alloy matrix surface is removed；And bead is carried out to the surface of magnesium alloy substrate, make
The surface roughness for obtaining magnesium alloy substrate is 60-100 μm.
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| CN201811640744.4A CN109609952B (en) | 2018-12-29 | 2018-12-29 | Ultra-limit magnesium alloy and preparation method thereof |
| EP19903063.6A EP3904555A4 (en) | 2018-12-29 | 2019-11-12 | Ultralimit alloy and preparation method therefor |
| PCT/CN2019/117283 WO2020134655A1 (en) | 2018-12-29 | 2019-11-12 | Ultralimit alloy and preparation method therefor |
| JP2021538453A JP7242867B2 (en) | 2018-12-29 | 2019-11-12 | Superalloy and its manufacturing method |
| US17/419,250 US11530485B2 (en) | 2018-12-29 | 2019-11-12 | Ultralimit alloy and preparation method therefor |
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| WO2020134655A1 (en) * | 2018-12-29 | 2020-07-02 | 昆明理工大学 | Ultralimit alloy and preparation method therefor |
| CN113173787A (en) * | 2021-03-08 | 2021-07-27 | 江苏大学 | Gadolinium zirconate/gadolinium tantalate composite ceramic and preparation method thereof |
| CN113981381A (en) * | 2021-10-29 | 2022-01-28 | 昆明理工大学 | Light material surface coating for fuselage of low-altitude flight rescue unmanned aerial vehicle for fire disaster and preparation method thereof |
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