CN109554708A - A kind of ultralimit titanium alloy and preparation method thereof - Google Patents
A kind of ultralimit titanium alloy and preparation method thereof Download PDFInfo
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- CN109554708A CN109554708A CN201811645669.0A CN201811645669A CN109554708A CN 109554708 A CN109554708 A CN 109554708A CN 201811645669 A CN201811645669 A CN 201811645669A CN 109554708 A CN109554708 A CN 109554708A
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- titanium alloy
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000010410 layer Substances 0.000 claims abstract description 170
- 239000000919 ceramic Substances 0.000 claims abstract description 58
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 238000000576 coating method Methods 0.000 claims abstract description 55
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 238000000151 deposition Methods 0.000 claims abstract description 33
- 239000012790 adhesive layer Substances 0.000 claims abstract description 29
- 239000010970 precious metal Substances 0.000 claims abstract description 15
- 239000006260 foam Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 239000004615 ingredient Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 26
- 229910021389 graphene Inorganic materials 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052580 B4C Inorganic materials 0.000 claims description 7
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 3
- 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
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 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
- 239000000463 material Substances 0.000 abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010936 titanium Substances 0.000 abstract description 11
- 229910052719 titanium Inorganic materials 0.000 abstract description 11
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
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- 230000000052 comparative effect Effects 0.000 description 17
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 230000008901 benefit Effects 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- 208000016261 weight loss Diseases 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005480 shot peening Methods 0.000 description 5
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- 239000007921 spray Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 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 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
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- 229910052727 yttrium Inorganic materials 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910001021 Ferroalloy Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 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
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910001128 Sn alloy 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
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
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- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009690 centrifugal atomisation Methods 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 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
- 238000011161 development Methods 0.000 description 1
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- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
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- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
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- 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
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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
- C23C28/30—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/061—Special surface effect
- B05D5/063—Reflective effect
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
-
- 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
- C23C28/30—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
-
- 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
- C23C28/30—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
-
- 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
- B05D2202/00—Metallic substrate
- B05D2202/30—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W)
- B05D2202/35—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W) based on Ti
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention belongs to titanium materials technology fields, disclose a kind of ultralimit titanium alloy and preparation method thereof, including titanium alloy substrate, titanium alloy substrate surface has been sequentially depositing composite tie layer, composite ceramic layer, reflecting layer, catadioptric layer, insulating layer and foam carbon-coating；Composite tie layer includes the adhesive layer for being deposited on titanium alloy substrate 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.It by that can be promoted to using temperature and be higher than former titanium alloy-based 100-500 DEG C of bulk melting point, to realize use of the titanium alloy under ultralimit environment in titanium alloy substrate surface depositing multilayer coatings by the present invention.Ultralimit titanium alloy provided by the invention has splendid high-temperature mechanics and chemical stability, can use under conditions of being more than its titanium alloy-based bulk melting point, increase use scope.
Description
Technical field
The invention belongs to titanium alloy material preparation technical field, and in particular to a kind of ultralimit titanium alloy and its preparation side
Method.
Background technique
Titanium alloy has intensity height, specific gravity is small, corrosion resistance is good, heat resistance is high, hardness is high and good with the compatibility of biology
The features such as, titanium-base alloy is just widely used in the fields such as Aeronautics and Astronautics, submarine, medical treatment, first practical titanium when 20th century
Alloy is the Ti-6Al-4V alloy that the U.S. in 1954 succeeds in developing, and then becomes the trump alloy in titanium alloy industry, the alloy
Usage amount has accounted for the 75%~85% of whole titanium alloys.Other many titanium alloys can be regarded as changing for Ti-6Al-4V alloy
Type.Titanium alloy at low and ultra-low temperatures, is still able to maintain its mechanical property.Low temperature performance well, the extremely low titanium alloy of interstitial element,
Such as TA7, certain plasticity is also able to maintain at -253 DEG C.Titanium alloy is the new important knot of one kind used in aerospace industry
Structure material, such as the U.S. high-altitude SR-71 high-speed reconnaissance plane (flight Mach number 3,26212 meters of flying height), titanium accounts for aircaft configuration
The 93% of weight is known as " full titanium " aircraft.
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 the running speed of engine is gradually increased, and the surface temperature of engine blade is just caused to be gradually increased, although
Titanium alloy has numerous excellent performances, but since its current ultimate-use (limiting service) temperature only has 400~500 DEG C, with high thrust ratio
The demand of aero-engine is higher and higher, also just proposes tightened up requirement to the performance of various high-temperature component materials, in addition
Metal be more than its fusing point half at a temperature of work when, will be there is a phenomenon where softening, i.e. ring of the titanium alloy at 540 DEG C or so
When working under border, it will soften, the phenomenon that reduced performance, i.e., existing current titanium alloy cannot (be more than in ultralimit temperature
The melting temperature of titanium alloy) under use.
It is generally believed that when a kind of material cannot be under high temperature environment in use, can go to seek another fusing point higher
Material, such as people usually will be considered that the higher nickel alloy of fusing point, ferroalloy etc. can substitute titanium alloy at higher temperatures
Work, but the atomic weight of this kind of alloy is big, leads to the material of same thickness, and nickel alloy or ferroalloy can be heavier, so that this kind of conjunction
Although gold can satisfy the requirement of high temperature, it cannot achieve the effect that lightweight, and the aircraft such as aircraft will raise speed, key just exists
In the weight of aircraft, there is bottleneck in this speed-raising for allowing for the aircraft such as aircraft.If therefore not changing material
Situation raises speed to aircraft, can only just shorten the service life of aircraft.
Summary of the invention
The invention is intended to provide a kind of ultralimit titanium alloy and preparation method thereof, it is unable to satisfy with solving existing titanium alloy
The problem of being used at a temperature of ultralimit.
To achieve the above object, the present invention provides following base case:
A kind of ultralimit titanium alloy, including titanium alloy substrate, the titanium alloy substrate surface have been sequentially depositing compoiste adhering
Layer and composite ceramic layer；Composite tie layer includes being deposited on the adhesive layer on titanium alloy substrate surface and being deposited on tie layer surface
Layer of precious metal；Composite ceramic layer includes B layers of A layers of ceramics and ceramics.
The technical program the utility model has the advantages that
Inventor has developed a kind of ultralimit titanium alloy, it is (super in ultralimit temperature to meet titanium 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 titanium alloy, to meet the needs of aircraft manufacture.It is continuously attempted in inventor
Titanium alloy can be used temperature by depositing the coating centainly matched in titanium 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 titanium 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 titanium alloy, which is promoted 2-3 DEG C, thus applicant this
Research is the very big progress in the use of titanium alloy.
The technical program can be greatly improved by depositing composite tie layer and composite ceramic layer on titanium alloy substrate
The use temperature of titanium alloy, to adapt to use of titanium alloy under the conditions of ultralimit temperature.Composite tie layer is deposited, can be improved
Bond effect between each coating and titanium alloy substrate, avoids coating from falling off in use.Composite ceramic layer is deposited, it can
The conduction for reducing heat, to improve the use temperature of titanium alloy substrate.The technical program is by the cooperation of each coating, so that titanium
The use temperature of alloy has obtained greatly being promoted.
In conclusion the present invention has following technical effect that
1, ultralimit titanium alloy provided by the invention has splendid high-temperature mechanics and chemical stability, can be more than it
It is used under conditions of titanium alloy-based bulk melting point, increases use scope.
2, it by that can be promoted to using temperature and be higher than original in titanium alloy substrate surface depositing multilayer coatings by the present invention
100-500 DEG C of titanium alloy-based bulk melting point, to realize use of the titanium alloy under ultralimit environment.
3, ultralimit titanium 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, improves the use temperature of material, ultralimit titanium alloy is applied in aviation
In the preparation of the engine blade of device, and it is able to satisfy engine temperature raised use demand when aircraft raises speed, realizes boat
The speed-raising of pocket.
Further, the adhesive layer with a thickness of 20-30 μm, layer of precious metal with a thickness of 40-60 μm, composite ceramic layer
With a thickness of 100-150 μm, the reflecting layer with a thickness of 10-30 μm is also sequentially depositing on composite ceramic layer, with a thickness of 20-30 μm
Catadioptric layer, the insulating layer with a thickness of 100-200 μm and the foam carbon-coating with a thickness of 20-200 μm.
The utility model has the advantages that reflecting layer has the effect of reflecting heat source, so that the heat source of titanium alloy surface is reduced, so that improving makes
Use temperature.Catadioptric layer is deposited, refraction of the infrared ray in coating can be stopped, to reduce the temperature of titanium alloy substrate, therefore
So that the use temperature of the titanium alloy of preparation improves.The effect of depositing insulating layer is, due in superfast environment, material
Surface be easy to happen ionization, and insulating layer can completely cut off conductive ion that ionization generates or electronics enters titanium alloy substrate
In, to resist erosion of the charge to titanium alloy substrate.The carbon of foam carbon-coating vaporizes cooling when in use, and in titanium alloy substrate
Surface forms vaporization film, Heat transmission is further prevented, to improve the use temperature of titanium alloy.And pass through the thickness to each coating
The setting of degree enables to the use temperature of the ultralimit titanium alloy of preparation to improve, and goes back simultaneously in the heat insulation for guaranteeing coating
Its weight is controlled, convenient for the use of aircraft.
Further, the bonding composition of layer is the mixing of one or more of MCrAlY, NiAl, NiCr-Al, Mo alloy
Object, MCrAlY NiCrCoAlY, NiCoCrAlY, CoNiCrAlY or CoCrAlY；The ingredient of layer of precious metal be Au, Pt, Ru,
One of Rh, Pd, Ir or a variety of alloys.
The utility model has the advantages that in tri- kinds of materials of NiCrCoAlY, NiCoCrAlY, CoNiCrAlY, according to chemical formula each element content
It successively reduces, the proportion between each element is different, therefore material obtained is different.Adhesive layer has good bond effect, makes
The bond effect for obtaining subsequent coating and titanium alloy substrate is good, reduces the probability that falls off of coating；And noble metal itself has antioxygen
The characteristic of change can be prevented effectively, and under high temperature, oxygen is to adhesive layer and titanium alloy-based internal diffusion, to improve the antioxygen of coating
Change performance, 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 the ingredient that ceramic layer is most-often used in current thermal barrier coating, preparation process
Maturation is conveniently bought；And ZrO2-RETaO4Have the effect of high expansion coefficient and lower thermal conductivity, wherein lower thermal conductivity can be reduced
External heat be transmitted to it is titanium alloy-based in vivo so that titanium alloy substrate is able to maintain lower temperature under hot environment；And
For high expansion coefficient, due to being used as a whole between coating, be not it is single in action, and high expansion
Coefficient is in order to match with the thermal expansion coefficient of adhesive layer, since the thermal expansion coefficient of noble metal adhesive layer is also larger, in this way
In Thermal Cycling (during i.e. constantly heating is cooling), the thermal mismatch stress (thermal expansion coefficient of ceramic layer and adhesive layer
The stress that difference generates) it is smaller, and then improve the service life of coating.(for popular, when two thermal expansion coefficient differences are larger
Coating when being deposited together, when heating or cooling, the degrees of expansion of two coatings is seriously different, will lead to two coatings
Between stress increase, the problem of cracking, or even fall off so as to cause between two coatings.)
Further, the ingredient in the reflecting layer is REVO4、RETaO4、Y2O3One or more of mixture.
The utility model has the advantages that the reflection coefficient of REVO4, RETaO4, Y2O3 are high, therefore good to the reflecting effect of heat radiation, greatly
Reduction hot environment under, the temperature of titanium alloy substrate, to improve the use temperature of the titanium alloy of preparation.
Further, the ingredient of the catadioptric layer is the mixture of one or both of graphene or boron carbide, and stone
The spatial distribution of black alkene and boron carbide is in disorderly arranged state.
The utility model has the advantages that since the spatial distribution of graphene or boron carbide is in disorderly arranged state, although graphene or carbon
Change boron refractive index with higher, when infrared light is when being irradiated on graphene catadioptric layer, disorderly arranged graphene can be with
Enhance the refraction of light in all directions, incident light is avoided to reflect in the same direction, achievees the effect that refraction dispersion, in this way
The intensity decline for entering the infrared light in coating, to reduce the temperature of coating and titanium alloy substrate.
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 during high-speed flight, outer surface and the air of aircraft rub by taking aircraft as an example
It wipes, so that air generates ionization and forms conductive ion or electronics, and inventor uses epoxy resin, phenol by experimental verification
The organic coatings such as urea formaldehyde can effectively resist charge and enter in coating and titanium alloy substrate, thus reduce conduction electrons or
The erosion of ion pair tin alloy weld seam.
The present invention also provides another technical solution, a kind of preparation method of ultralimit titanium alloy, comprising the following steps:
Step 1: depositing adhesive layer on titanium alloy substrate surface；In tie layer surface depositing noble metal layer, so that adhesive layer
Composite tie layer is formed with layer of precious metal, the overall thickness of the composite tie layer is 60-90 μm；
Step 2: in B layers of A layers of the compoiste adhering layer surface deposition ceramics and ceramics that step 1 obtains, so that A layers of ceramics and pottery
B layers of formation composite ceramic layer of porcelain, the overall thickness of composite ceramic layer are 100-150 μm；
Step 3: in the composite ceramics layer surface deposition of reflective layer that step 2 obtains, reflecting layer with a thickness of 10-30 μm；
Step 4: the reflection layer surface obtained in step 3 deposits catadioptric layer, catadioptric layer with a thickness of 20-30 μm；
Step 5: in the catadioptric layer surface depositing insulating layer that step 4 obtains, insulating layer with a thickness of 100-200 μm；
Step 6: the surface of insulating layer obtained in step 5 deposits foam carbon-coating, foam carbon-coating with a thickness of 20-200 μm, from
And form ultralimit titanium alloy.
The technical program the utility model has the advantages that
It is controlled by the thickness to each coating being deposited on titanium alloy substrate, has both been able to achieve the ultralimit titanium of preparation
Alloy is increased to above 100-500 DEG C of former titanium alloy fusing point using temperature, and has splendid corrosion resistance.Simultaneously also
The weight that can be avoided the larger caused ultralimit titanium alloy prepared of coating layer thickness, which increases larger situation, to be occurred, so that
Ultralimit titanium alloy is able to satisfy the use of aircraft.
Further, in the step 2, forming B layers of ceramics is ZrO2-RETaO4For powder, the ZrO2-RETaO4Powder
The partial size of body is 10~70 μm, and pattern is spherical in shape.
The utility model has the advantages that using partial size for 10~70 μm, and the ZrO that pattern is spherical in shape2-RETaO4The coating of powder preparation, by
Spherical in shape in powder, the surface of such powder is smooth, so that the mobility of powder is preferable, has obtained the ceramic coating of high quality.
Further, in the step 1, before depositing adhesive layer, titanium alloy substrate surface is pre-processed, it is described pre-
Processing is including degreasing and removes impurity；After the titanium alloy substrate surface preparation, shot-peening is carried out to the surface of titanium alloy substrate
Processing, so that the surface roughness of titanium alloy substrate is 60-100 μm.
The utility model has the advantages that carrying out degreasing to titanium alloy substrate surface before depositing adhesive layer and removing impurity treatment, can keep away
Exempt from greasy dirt and impurity enters in coating, to influence the quality of coating, and then avoids what coating occurred that cracking even falls off from asking
Topic；By carrying out bead to titanium alloy substrate surface, the roughness on titanium alloy substrate surface can be improved, to improve titanium conjunction
The adhesive strength of golden matrix surface and adhesive layer reduces the probability that adhesive layer is fallen off.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of ultralimit titanium alloy of the present invention；
Fig. 2 is the embodiment of the present invention 1 and creep experiments under high temperature of the comparative example 13 under 50MPa stress, at a temperature of 1900 DEG C
Curve graph；
Fig. 3 is the salt air corrosion experimental curve 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: titanium alloy substrate 1, adhesive layer 2, layer of precious metal 3, ceramics A layer 4, pottery
Porcelain B layer 5, reflecting layer 6, catadioptric layer 7, insulating layer 8, foam carbon-coating 9.
The present invention provides a kind of ultralimit titanium alloys, as shown in Figure 1, including titanium alloy substrate 1,1 table of titanium alloy substrate
Face is sequentially depositing composite tie layer, with a thickness of 100-150 μm of composite ceramic layer, the reflecting layer 6 with a thickness of 10-30 μm, thickness
For 20-30 μm of catadioptric layer 7, with a thickness of 100-200 μm of insulating layer 8 and with a thickness of 20-200 μm of foam carbon-coating 9.It is wherein multiple
Closing adhesive layer is the adhesive layer 2 for being deposited on 1 surface of titanium alloy substrate and the layer of precious metal 3 for being deposited on 2 surface of adhesive layer, adhesive layer
2 with a thickness of 20-30 μm, layer of precious metal with a thickness of 40-60 μm, the ingredient of adhesive layer 2 is MCrAlY, NiAl, NiCr-Al,
The mixture of one or more of Mo alloy, MCrAlY NiCrCoAlY, NiCoCrAlY, CoNiCrAlY or CoCrAlY；
The ingredient of layer of precious metal 3 is one of Au, Pt, Ru, Rh, Pd, Ir or a variety of alloys；Composite ceramic layer includes being deposited on pottery
Porcelain A layer 4 and ceramics B layer 5, the ingredient of ceramic A layer 4 are YSZ or rare earth zirconate (RE2Zr2O7, RE=Y, Gd, Nd, Sm, Eu or
Dy), the ingredient of ceramic B layer 5 is ZrO2-RETaO4(RE=Y, Gd, Nd, Sm, Eu, Dy, Er, Yb, Lu)；Reflecting layer 6 is REVO4、
RETaO4、Y2O3One or more of mixture, wherein RE=Y, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu.Catadioptric layer 7
Ingredient be one or both of graphene and boron carbide mixture, and the spatial distribution of graphene and boron carbide is in nothing
Sequence ordered state；The ingredient of insulating layer 8 is the mixture of one or more of epoxy resin, phenolic resin, ABS resin.
Wherein ZrO2-RETaO4Powder is prepared using following methods, comprising the following steps:
Step (1): by ZrO2Powder, rare earth oxide (RE2O3) powder, tantalum pentoxide (Ta2O5) powder progress predry
Dry, pre-dried temperature is 600 DEG C, and the pre-dried time is 8h；According to ZrO2-RETaO4Molar ratio weigh it is dry after
ZrO2Powder, rare earth oxide (RE2O3) powder, tantalum pentoxide (Ta2O5) powder；Powder after predrying is added to ethyl alcohol
In solvent, mixed solution is obtained, so that the molar ratio of RE:Ta:Zr is 1:1:1 in mixed solution；Again using ball mill to mixing
Solution carries out ball milling 10h, and the revolving speed of ball mill is 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)2-RETaO4
Powder B, reaction temperature be 1700 DEG C, reaction time 10h；And it is sieved using the sieve of 300 mesh to powder B.
Step (3): the powder B after sieving in step (2) is mixed to get slurry with deionized water solvent, organic adhesive
C, wherein the mass percent of powder B is 25% in slurry C, and the mass percent of organic adhesive is 2%, remaining is solvent,
Organic adhesive uses polyvinyl alcohol or gum arabic,；Recycle centrifugal atomization that slurry C is dried, when dry
Temperature be 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 use the sieve of 300 mesh
It is sieved to sintered material grain D, obtains the ZrO that partial size is 10~70 μm and pattern is spherical in shape2-RETaO4Ceramic powder.
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 prepared by the above method2-RETaO4Can satisfy APS spraying technology to diameter of particle and
The requirement of pattern.
Inventor has shown that in parameter area of the invention, the ultralimit titanium alloy of preparation makes through a large number of experiments
Maximum is promoted with temperature, and the weight gain of titanium alloy is small, each coating composition and the optimal ultralimit titanium alloy of thickness, and this
30 groups therein are listed in invention 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 titanium alloy of the present invention and preparation method thereof
Show:
The ingredient and thickness of each coating in a kind of embodiment 1-10 of the ultralimit titanium alloy of table 1 and preparation method thereof
The ingredient and thickness of each coating in a kind of embodiment 11-20 of the ultralimit titanium alloy of table 2 and preparation method thereof
The ingredient and thickness of each coating in a kind of embodiment 21-30 of the ultralimit titanium alloy of table 3 and preparation method thereof
Now by taking embodiment 1 as an example, to another technical solution of the invention, a kind of preparation method progress of ultralimit titanium alloy
Explanation.
A kind of preparation method of ultralimit titanium alloy, comprising the following steps:
Step 1: the greasy dirt and impurity on titanium alloy substrate surface are removed using infusion method, titanium alloy substrate in the present embodiment
Titanium alloy substrate is impregnated 0.5~1.5h using solvent or aqueous slkali by material selection TC4 titanium alloy, and wherein solvent is main
Ingredient is ethyl alcohol and surfactant, and aqueous slkali main component is sodium hydroxide, tertiary sodium phosphate, sodium carbonate sodium metasilicate etc., alkali soluble
The pH value of liquid is 10~11, is cleaned using solvent to titanium alloy substrate surface in the present embodiment, and greasy dirt and impurity cleaning are dry
Titanium alloy substrate is taken out after net, is dried after recycling deionized water to rinse well.
Recycle compressed air shotblasting machine to titanium alloy substrate surface carry out bead, the compressed air shotblasting machine used be JCK-SS500-6A from
Dynamic conveying type compressed air shotblasting machine, the shot-peening material that when shot-peening uses is any one in iron sand, glass ball and ceramic pellet, the present embodiment
It is middle to use iron sand, and the partial size of iron sand is 0.3-0.8mm, the partial size of iron sand is 0.5mm in the present embodiment；It is titanium alloy-based after shot-peening
The surface roughness of body is 60-100 μm, and the surface roughness of titanium alloy substrate is 80 μm in the present embodiment, is convenient for coating and titanium
The bonding of alloy substrate.
Step 2: the titanium alloy substrate surface after shot-peening deposits composite tie layer, first with HVOF method (supersonic speed fire
Flame spray coating method) or Ultrasonic Arc Sprayed method titanium alloy substrate surface spraying layer of Ni CrCoAlY as adhesive layer, this reality
Example is applied using HVOF method, the technological parameter of HVOF method are as follows: powder diameter is 25-65 μm, oxygen flow 2000SCFH, kerosene stream
Amount is 18.17LPH, carrier gas 12.2SCFH, powder sending quantity 5RPM, barrel length 5in, spray distance 254mm.
EB-PVD method (electro beam physics vapour deposition method) is recycled to deposit layer of Au conduct on NiCrCoAlY adhesive layer
Layer of precious metal, to form composite tie layer.Gas pressure intensity when depositing Au is less than 0.01Pa, the technological parameter of EB-PVD method
Are as follows: pressure 0.008Pa, deposition rate 6nm/min, and the fusing point ratio of the temperature of titanium alloy substrate and titanium alloy substrate is less than
0.3.The adhesive layer of deposition with a thickness of 20 μm, layer of precious metal with a thickness of 50 μm.
Step 3: using APS (air plasma spraying), HVOF, PS-PVD or EB-PVD method on the surface of composite tie layer
It sprays one layer of YSZ and is used as A layers of ceramics, HVOF method is used in the present embodiment, HVOF method is recycled to spray one on A layers of YSZ ceramics
Layer ZrO2- YTaO4 is used as B layers of ceramics, forms composite ceramic layer；Wherein A layers of ceramics with a thickness of 70 μm, ceramic B layers of thickness
It is 80 μm.
Step 4: spraying one layer of Y in composite ceramics layer surface using HVOF method2O3Transparent ceramic material is as reflecting layer, spray
The reflecting layer of painting with a thickness of 10 μm.
Step 5: using brushing method in Y2O3One layer of graphene of reflecting layer external coating as catadioptric layer, catadioptric layer
With a thickness of 20 μm.
Due to graphene specific surface area with higher, extremely in the solution, therefore graphene needs indissoluble before overcoating
Ultrasonic disperse and separation of solid and liquid are carried out, i.e., graphene is mutually uniformly mixed with micron-sized carbon powder material first, then will
Mixed-powder imports and carries out ultrasonic activation mixing in solution, and solution is to be added to have the ethyl alcohol of 1% dispersing agent molten in the present embodiment
Liquid will be uniformly mixed later solution and be separated micron-sized carbon dust using filter paper, is finally blended with the molten of graphene
Liquid be coated on reflecting layer surface, after the titanium alloy for being coated with graphene catadioptric layer is put into drying box, at a temperature of 60 DEG C
Dry 2h.
In addition after graphene carries out ultrasonic disperse, the spatial distribution of graphene is rearranged in all directions, so that
The spatial distribution of graphene is in disorderly arranged state, such graphene although refractive index with higher, when incident light is irradiating
When on to graphene catadioptric layer, the refraction of light in all directions is can be enhanced in disorderly arranged graphene, and incident light is avoided to exist
It is reflected in same direction, achievees the effect that refraction dispersion, enter the incident intensity decline in coating in this way.
Step 6: using brushing method in graphene catadioptric layer surface one layer of epoxy resin of brushing as insulating layer, insulating layer
With a thickness of 150 μm.
Step 7: brush one layer of foam carbon-coating on epoxy resin insulating layers using brushing method, foam carbon-coating with a thickness of 20
μm。
Embodiment 2-29 is identical as the preparation process of embodiment 1, and difference is only that the ingredient of each coating as shown in Table 1
It is different from thickness；Embodiment 30 is the difference from embodiment 1 is that A layers of ceramics are different with B layers of ceramics of spraying sequence in step 3.
In addition 13 groups of comparative examples are set and embodiment 1-30 compares experiment.
Table 4 is the ingredient and thickness of each coating of comparative example 1-12:
Comparative example 1-12 is identical as the preparation method of embodiment 1, difference be only that the ingredient of each coating as shown in table 3 with
Thickness is different, and comparative example 13 is the TC4 titanium alloy substrate of non-depositing coating.
Following experiment is carried out using the titanium alloy that embodiment 1-30, comparative example 1-13 are provided:
1, creep experiments under high temperature:
It is tensile test specimen by the titanic alloy machining prepared using embodiment 1-30 and comparative example 1-13, utilizes model RMT-
The electronic type high-temerature creep permanent strength testing machine of D5 carries out creep experiments under high temperature, and maximum test load is 50KN, test load
Controlling precision is within ± 5%, and deformation measurement range is 0~10mm, and speed adjust range is 0~50mm/min-1, deformation resolution
Rate is 0.001mm, and high temperature furnace temperature control range is 200~2000 DEG C, a length of 150mm in soaking zone.
The test specimen of embodiment 1-30, comparative example 1-13 are put into electronic type high-temerature creep permanent strength testing machine, and
Make test specimen be in unstress state (under unstress state, test specimen can free wxpansion, and high-temerature creep is total in temperature and stress
It is deformed increase with time under same-action, therefore heating rate does not influence creep).By testing machine be adjusted to stress be 50MPa,
Temperature is 1300 DEG C, and records following data, and as shown in table 5, a indicates the steady creep time (min) of each test specimen in table 5；B table
Show that the time (min) of creep rupture occurs for each test specimen.
By taking embodiment 1 and comparative example 13 as an example, as shown in Fig. 2, being tested for the high-temerature creep of embodiment 1 and comparative example 13 bent
Line chart, (A) indicates the titanium alloy-based bottom material of TC4 of non-depositing coating in comparative example 13 in Fig. 2, and (B) indicates embodiment 1 in Fig. 2
The material being prepared.
From figure 2 it can be seen that there are 3 ranks for (A) and the creep of (B) testpieces at a temperature of 1900 DEG C under 50MPa stress
Section: the first stage is shorter, and creep rate is larger, is transitioned into the second stage of creep quickly, and secondary creep rate reaches
Minimum value, and this stage is longer, is substantially at steady state creep process；When the phase III, creep rate is risen rapidly, and creep becomes
Shape rapidly develops, until creep rupture occurs for material damage.It can find under 50MPa stress simultaneously, under the conditions of 1900 DEG C of temperature,
(A) test specimen is just broken in a very short period of time, illustrates that titanium alloy can hardly carry under the conditions of being higher than melting temperature
Load, and (B) test specimen can keep preferable mechanical property under conditions of 1900 DEG C and it is not broken for a long time, have excellent
High temperature resistance.
2, salt air corrosion is tested:
The titanic alloy machining that embodiment 1-30, comparative example 1-13 are provided is at 50mm × 25mm × 2mm test specimen, then carries 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 5 ± 0.5%NaCl solution continuously to test specimen sprinkling, and in table 5
After middle record certain time (8,24,48,72h), the weight-loss ratio of each test specimen.As shown in figure 3, for embodiment 1 and 13 salt of comparative example
The relation curve of mist corrosion weight loss amount and etching time, (A) indicates the TC4 titanium alloy of non-depositing coating in comparative example 13 in Fig. 3
Base material, (B) indicates the material that embodiment 1 is prepared in Fig. 3.
From figure 3, it can be seen that two kinds of titanium alloys have visibly different corrosion regularity, for (A) test specimen, (TC4 titanium is closed
Golden testpieces), with the extension of etching time, corrosion weight loss numerical value is in the trend increased.Wherein, corrode initial stage (8-24h), examination
There are oxidation films on sample surface, hinder titanium alloy substrate to contact with solution, corrosion rate is smaller.Corrode mid-term (24-48h), solution
In Cl-(chloride ion) has penetrated oxidation film, a large amount of Cl-It is adsorbed on matrix, increases point corrosion pit, original point corrosion pit adds
It is deep, hence it is evident that accelerate corrosion rate.Continuously by spraying after 48h, corrosion product is evenly distributed, and thickness increases, and almost covers sample
Whole surface, Cl-It needs to contact with titanium alloy substrate across corrosion product, reduces matrix surface absorption Cl-Quantity,
Reduce corrosion rate.It totally sees, TC4 titanium alloy corrosion weight loss amount is much higher than titanium-based surface composite material, and titanium-based surface is compound
Material corrodes since the presence of coating there is no, quality is almost without changing.
A indicates the steady creep time (min) of each test specimen in table 5；B indicates that the time of creep rupture occurs for each test specimen
(min)；
C indicates the weight-loss ratio (v/mg.cm2) that test specimen after NaCl solution 8h is continuously sprayed to test specimen；
D indicates the weight-loss ratio (v/mg.cm2) of test specimen after continuously spraying NaCl solution for 24 hours to test specimen；
E indicates the weight-loss ratio (v/mg.cm2) that test specimen after NaCl solution 48h is continuously sprayed to test specimen；
F indicates the weight-loss ratio (v/mg.cm2) that test specimen after NaCl solution 72h is continuously sprayed to test specimen.
Table 5 is the experimental result of creep experiments under high temperature and salt spray test
By table 5 it is found that the titanium alloy that the comparative example beyond parameter area of the invention obtains, high temperatures are substantially
Decline, is broken, and corrosion resistance is poor in a relatively short period of time.
In conclusion by depositing anti-oxidant composite tie layer, composite ceramic layer, reflecting layer, catadioptric on titanium alloy
Titanium alloy can be promoted to 100-500 DEG C higher than former fusing point using temperature by layer, insulating layer and foam carbon-coating, and resistance to
Corrosivity also greatly improves.The ultralimit titanium alloy of ultralimit titanium alloy preparation method preparation provided by the invention uses temperature
Degree range is big, corrosion resistance is strong, and wherein each effect of embodiment 1 is best.
What has been described above is only an embodiment of the present invention, and the common sense such as well known specific structure and characteristic are not made herein in scheme
Excessive description.It, without departing from the structure of the invention, can be with it should be pointed out that for those skilled in the art
Several modifications and improvements are made, these also should be considered as protection scope of the present invention, these all will not influence what the present invention was implemented
Effect and patent practicability.The scope of protection required by this application should be based on the content of the claims, in specification
The records such as specific embodiment can be used for explaining the content of claim.
Claims (10)
1. a kind of ultralimit titanium alloy, including titanium alloy substrate, it is characterised in that: the titanium alloy substrate surface has been sequentially depositing
Composite tie layer and composite ceramic layer；Composite tie layer includes being deposited on the adhesive layer on titanium alloy substrate surface and being deposited on bonding
The layer of precious metal of layer surface；Composite ceramic layer includes B layers of A layers of ceramics and ceramics.
2. a kind of ultralimit titanium alloy according to claim 1, it is characterised in that: the adhesive layer with a thickness of 20-30 μ
M, layer of precious metal with a thickness of 40-60 μm, composite ceramic layer with a thickness of 100-150 μm, be also sequentially depositing on composite ceramic layer
There are the reflecting layer with a thickness of 10-30 μm, the catadioptric layer with a thickness of 20-30 μm, with a thickness of 100-200 μm of insulating layer and thickness
For 20-200 μm of foam carbon-coating.
3. a kind of ultralimit titanium alloy according to claim 2, it is characterised in that: the bonding composition of layer be MCrAlY,
The mixture of one or more of NiAl, NiCr-Al, Mo alloy, MCrAlY NiCrCoAlY, NiCoCrAlY,
CoNiCrAlY or CoCrAlY；The ingredient of layer of precious metal is one of Au, Pt, Ru, Rh, Pd, Ir or a variety of alloys.
4. a kind of ultralimit titanium 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 titanium alloy according to claim 5, it is characterised in that: the ingredient in the reflecting layer is REVO4、
RETaO4、Y2O3One or more of mixture.
6. a kind of ultralimit titanium alloy according to claim 6, it is characterised in that: the ingredient of the catadioptric layer is graphite
The mixture of one or both of alkene or boron carbide, and the spatial distribution of graphene and boron carbide is in disorderly arranged state.
7. a kind of ultralimit titanium alloy according to claim 6, 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.
8. a kind of preparation method of ultralimit titanium alloy according to claim 4-7 any one, which is characterized in that including
Following steps:
Step 1: depositing adhesive layer on titanium alloy substrate surface；In tie layer surface depositing noble metal layer, so that adhesive layer and expensive
Metal layer formed composite tie layer, the adhesive layer with a thickness of 20-30 μm, the layer of precious metal with a thickness of 40-60 μm；
Step 2: in B layers of A layers of the compoiste adhering layer surface deposition ceramics and ceramics that step 1 obtains, so that A layers of ceramics and ceramics B
Layer forms composite ceramic layer, and the overall thickness of composite ceramic layer is 100-150 μm；
Step 3: in the composite ceramics layer surface deposition of reflective layer that step 2 obtains, reflecting layer with a thickness of 10-30 μm；
Step 4: the reflection layer surface obtained in step 3 deposits catadioptric layer, catadioptric layer with a thickness of 20-30 μm；
Step 5: in the catadioptric layer surface depositing insulating layer that step 4 obtains, insulating layer with a thickness of 100-200 μm；
Step 6: the surface of insulating layer obtained in step 5 deposits foam carbon-coating, foam carbon-coating with a thickness of 20-200 μm, thus shape
At ultralimit titanium alloy.
9. a kind of preparation method of ultralimit titanium alloy according to claim 8, it is characterised in that: in the step 2, shape
At ceramic B layers of ZrO2-RETaO4For powder, the ZrO2-RETaO4The partial size of powder is 10~70 μm, and pattern is spherical in shape.
10. a kind of preparation method of ultralimit titanium alloy according to claim 8, it is characterised in that: in the step 1,
Before depositing adhesive layer, titanium alloy substrate surface is pre-processed, the pretreatment is including degreasing and removes impurity；It is described
After titanium alloy substrate surface preparation, bead is carried out to the surface of titanium alloy substrate, so that the surface of titanium alloy substrate is thick
Rugosity is 60-100 μm.
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| EP19903063.6A EP3904555A4 (en) | 2018-12-29 | 2019-11-12 | Ultralimit alloy and preparation method therefor |
| US17/419,250 US11530485B2 (en) | 2018-12-29 | 2019-11-12 | Ultralimit alloy and preparation method therefor |
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| CN1077444A (en) * | 1992-02-18 | 1993-10-20 | 约翰逊马西有限公司 | Coated ceramic article |
| CN1986889A (en) * | 2005-12-21 | 2007-06-27 | 联合工艺公司 | Platinum modified nicocraly bondcoat for thermal barrier coating |
| WO2007139694A2 (en) * | 2006-05-26 | 2007-12-06 | Praxair Technology, Inc. | Blade tip coatings using high purity powders |
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| CN1077444A (en) * | 1992-02-18 | 1993-10-20 | 约翰逊马西有限公司 | Coated ceramic article |
| CN1986889A (en) * | 2005-12-21 | 2007-06-27 | 联合工艺公司 | Platinum modified nicocraly bondcoat for thermal barrier coating |
| WO2007139694A2 (en) * | 2006-05-26 | 2007-12-06 | Praxair Technology, Inc. | Blade tip coatings using high purity powders |
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| WO2020134655A1 (en) * | 2018-12-29 | 2020-07-02 | 昆明理工大学 | Ultralimit alloy and preparation method therefor |
| US11530485B2 (en) | 2018-12-29 | 2022-12-20 | Kunming University Of Science And Technology | Ultralimit alloy and preparation method therefor |
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