CN107287556B - Superconducting graphene coating material and preparation method thereof - Google Patents
Superconducting graphene coating material and preparation method thereof Download PDFInfo
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- CN107287556B CN107287556B CN201710451319.XA CN201710451319A CN107287556B CN 107287556 B CN107287556 B CN 107287556B CN 201710451319 A CN201710451319 A CN 201710451319A CN 107287556 B CN107287556 B CN 107287556B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000011248 coating agent Substances 0.000 title claims abstract description 42
- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000005260 corrosion Methods 0.000 claims abstract description 51
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 47
- 229910001080 W alloy Inorganic materials 0.000 claims abstract description 39
- 230000007704 transition Effects 0.000 claims abstract description 34
- 230000007797 corrosion Effects 0.000 claims abstract description 19
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000012545 processing Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- 239000007789 gas Substances 0.000 claims description 42
- 239000010936 titanium Substances 0.000 claims description 39
- 239000013077 target material Substances 0.000 claims description 37
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 36
- 229910052719 titanium Inorganic materials 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 28
- 229910052804 chromium Inorganic materials 0.000 claims description 28
- 239000011651 chromium Substances 0.000 claims description 28
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052721 tungsten Inorganic materials 0.000 claims description 25
- 239000010937 tungsten Substances 0.000 claims description 25
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 21
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 21
- 229910052720 vanadium Inorganic materials 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 13
- 239000010955 niobium Substances 0.000 claims description 13
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 230000006378 damage Effects 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000007733 ion plating Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 24
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000000956 alloy Substances 0.000 description 13
- 239000004615 ingredient Substances 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- -1 5wt% Tungsten Chemical compound 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000756 V alloy Inorganic materials 0.000 description 1
- CRBDXVOOZKQRFW-UHFFFAOYSA-N [Ru].[Ir]=O Chemical compound [Ru].[Ir]=O CRBDXVOOZKQRFW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C14/0605—Carbon
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- 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
-
- 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
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to the technical field of graphene coating production, in particular to a superconducting graphene coating material and a preparation method thereof. A superconducting graphene coating material comprises a corrosion-resistant transition layer and a superconducting layer, wherein the corrosion-resistant transition layer is composed of a titanium alloy and a tungsten alloy, and the superconducting layer comprises graphene and graphite. The superconducting graphene coating material adopts a non-noble metal coating mode to improve the surface conductive corrosion resistance, and meanwhile, the coating has the capability of self-filling of pinholes in the use process, so that a repeatedly-circulating multilayer structure for avoiding the pinholes does not need to be designed, and meanwhile, the coating hasWith the component design of graphene, the contact resistance and the corrosion current density (the contact resistance can reach 1.1m omega cm) which are lower than those of the prior art can be achieved on the premise of not adding noble metal2The corrosion current density can reach 5 × 10‑8A/cm2) Therefore, the purposes of reducing the processing cost of the transmission part, prolonging the service life of the transmission part and improving the service performance are achieved.
Description
Technical field
The present invention relates to graphene coating material production technical field, especially a kind of superconduction graphene coating material and its system
Preparation Method.
Background technique
Electrical transmission component（Such as water electrolysis electrode, connector, connector）To the conduction of the material for making the component
Performance generally has higher requirement, thus could the more efficiently thermal losses for reducing current transmission.Simultaneously as application neck
The difference in domain, surrounding enviroment may have etching characteristic, so that electrical transmission parts surface occurs electrochemical reaction and changes
Its primary characteristic, especially water electrolysis electrode, decomposition voltage is very high to the corrosion resistance requirement of electrode generally in 2V or so,
And it surface is usually used at present coats the titanium of ruthenium-oxide iridium and increase electrode life as electrode material, but due to ruthenium, iridium
It is noble metal, cost of manufacture is high.Simultaneously as the characteristic of coating way limits, cause to bring during coating
The pin hole or defect of penetrability, and the method for generally solving problems is use increasing coating layer thickness or hidden with multilayered structure
Cover pin hole.
Summary of the invention
In order to overcome deficiency existing for existing coating, the present invention provides a kind of superconduction graphene coating material and its
Preparation method.
The technical solution adopted by the present invention to solve the technical problems is：A kind of superconduction graphene coating material, the painting
Layer material includes anti-corrosion transition zone and superconduction electric layer, and anti-corrosion transition zone is made of titanium alloy and tungsten alloy, and superconduction electric layer includes stone
Black alkene and graphite.
It according to another embodiment of the invention, further comprise that the graphene content in superconduction electric layer is 2%-10%.
According to another embodiment of the invention, further comprise, in anti-corrosion transition zone titanium alloy include titanium and vanadium, tantalum,
One of nickel, chromium, zirconium are a variety of, and wherein Ti content is 30wt%-80wt%；Tungsten alloy include tungsten and titanium, vanadium, niobium, chromium, in zirconium
It is one or more, wherein W content be 5wt%-80wt%.
According to another embodiment of the invention, further comprise, anti-corrosion transition zone with a thickness of 30nm-500nm, it is anti-corrosion
Transition zone can automatically form filler at pin hole or mechanical injuries in use, at pin hole or mechanical injuries due to
It is exposed to outer and is easy to react with oxygen, automatically form oxidation filler, be formed by oxidation product with preferable anti-corrosion
Performance and preferable conductive capability, to prevent the further occurrence of corrosion reaction.
It according to another embodiment of the invention, further comprise that superconduction electric layer is under 0.6MPa pressure test, with carbon paper
Contact resistance 1m Ω cm2-3m Ω cm2.
A kind of preparation method of superconduction graphene coating material, the anti-corrosion transition zone of coating material and superconducts and is layer by layer
Completion, filming equipment target point are disposably deposited in the Magnetic filter arc ion plating apparatus for being equipped with heated filament assisting ion source
It is not distributed in vacuum furnace body two sides, and same level possesses at least three target rigging position, wherein installation titanium alloy in side is mixed
Miscellaneous target or tungsten alloy adulterate target, and other side graphite target comprises the technical steps that：
Step 1：Workpiece pre-treatment：It puts the workpiece in ultrasonic cleaning device and successively carries out ultrasonic oil removing cleaning, pure water surpasses
Sound cleaning, pure water rinsing, water removal, hydrocarbon solvent vacuum ultrasonic cleaning, vacuum and heating drying, hydrocarbon solvent vacuum ultrasonic cleaning mistake
It is 200Pa-500Pa that vacuum degree is cleaned in journey, and it is 90 that vacuum degree, which is 100Pa-200Pa heating temperature, during vacuum and heating drying
℃；It puts the workpiece in the thermostatic container equipped with depassivation coating solution and impregnates after the completion of cleaning, temperature is maintained at 80 DEG C, continues 30
Minute；Then it puts the workpiece in clear water and is rinsed, then removed water, is then charged on specific fixture etc. to be coated；
Step 2：Plated film pre-treatment：Fixture equipped with workpiece is fitted into vacuum chamber, vacuum chamber both sides sealing door is closed,
It is then turned on vacuum pump group, vacuum system is extracted into 5 × 10 by atmospheric condition-3Pa, starting heating device make the temperature in vacuum furnace
200 DEG C -350 DEG C are heated to, argon gas is then charged with, partial pressure of ar gas 0.4Pa-1.0Pa opens heated filament heating power supply, heated filament electricity
Stream is gradually promoted to 30A-60A by 10A, is then turned on heated filament grid bias power supply, voltage is set as -30V--60V, is then turned on plating
Film machine workpiece bias, bias sets are -200V--800V, and duty ratio is set as 60%-80%, carry out substrate surface ion sputtering and
Etching activation, continues 10min-120min；Workpiece bias, heated filament bias, heated filament heating power supply are successively closed after then, reduce argon
Gas partial pressure is 0.2Pa-0.8Pa, is then turned on workpiece bias power supply, and bias sets are -600V--1000V, and duty ratio is set as
10%-80% is then turned on titanium alloy target and tungsten alloy target material, and titanium alloy target target arc stream is set as 50A-120A, and tungsten closes
Gold target material target arc stream is set as 50A-120A, carries out metal ion and bombards process, strengthens bombardment etching and activation effect, continues
5min-30min；
Step 3：Anti-corrosion transition zone deposition：Then argon gas is kept continually and steadily to input afterwards, partial pressure of ar gas maintains 0.2Pa-
0.8Pa keeps workpiece bias power supply in the open state, is -30V--800V, duty ratio 10%-80% by bias sets, keeps
Titanium alloy target is in the open state with tungsten alloy target material, and titanium alloy target arc stream is set as 50A-120A, tungsten alloy target material arc
Stream is set as 50A-120A, continues 1min-30min, completes anti-corrosion transition zone deposition；
Step 4：Superconduction electric layer deposition：Then afterwards keep workpiece bias power supply it is in the open state, by bias sets be-
30V--800V, duty ratio 10%-80% close nitrogen, keep argon gas to be continually fed into, while adjusting accordingly to partial pressure of ar gas,
So that total pressure maintains 0.2Pa-0.8Pa in vacuum chamber, tungsten alloy target material, titanium alloy target are closed, opens graphite target, target
Material arc stream is set as 50A-120A, carries out superconduction electric layer deposition, continues 1min-30min.
Beneficial effects of the present invention, this superconduction graphene coating material are promoted by the way of base metal coating
Surface conductance corrosion resisting property, while coating possesses the ability that pin hole is filled certainly in use, there is no need to design to evade needle
The multilayered structure of the iterative cycles in hole, while there is coating the ingredient of graphene to design, it can be without adding noble metal
Under the premise of reach contact resistance more lower than the prior art and corrosion electric current density（Contact resistance can reach 1.1m Ω cm2, rotten
Current density is lost up to 5 × 10-8A/cm2）, so that reaching reduces transmission part processing cost, extend transmission part service life,
Promote the purpose of service performance.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is structural schematic diagram of the invention；
1, matrix in figure, 2, anti-corrosion transition zone, 3, superconduction electric layer, at 4, pin hole or mechanical injuries, 5, filler.
Specific embodiment
If Fig. 1 is structural schematic diagram of the invention, a kind of superconduction graphene coating material, the coating material includes anti-corrosion
Transition zone 2 and superconduction electric layer 3, anti-corrosion transition zone 2 are made of titanium alloy and tungsten alloy, and superconduction electric layer 3 includes graphene and graphite.
It according to another embodiment of the invention, further comprise that the graphene content in superconduction electric layer 3 is 2%-10%.
According to another embodiment of the invention, further comprise, in anti-corrosion transition zone 2 titanium alloy include titanium and vanadium, tantalum,
One of nickel, chromium, zirconium are a variety of, and wherein Ti content is 30wt%-80wt%；Tungsten alloy include tungsten and titanium, vanadium, niobium, chromium, in zirconium
It is one or more, wherein W content be 5wt%-80wt%.
According to another embodiment of the invention, further comprise, anti-corrosion transition zone 2 with a thickness of 30nm-500nm, it is resistance to
Erosion transition zone 24 can automatically form filler 5, pin hole or mechanical injuries at pin hole or mechanical injuries in use
Place 4 is easy to react with oxygen due to being exposed to outer, automatically forms oxidation filler 5, be formed by oxidation product have compared with
Good corrosion resisting property and preferable conductive capability, to prevent the further occurrence of corrosion reaction.
It according to another embodiment of the invention, further comprise that superconduction electric layer 3 is under 0.6MPa pressure test, with carbon
The contact resistance 1m Ω cm2-3m Ω cm2 of paper.
A kind of preparation method of superconduction graphene coating material, the anti-corrosion transition zone 2 of coating material and superconducts layer by layer 3
It is that disposably deposition is completed in the Magnetic filter arc ion plating apparatus for being equipped with heated filament assisting ion source, filming equipment target
Vacuum furnace body two sides are respectively distributed to, and same level possesses at least three target rigging position, wherein titanium alloy is installed in side
It adulterates target or tungsten alloy adulterates target, other side graphite target comprises the technical steps that：
Step 1：Workpiece pre-treatment：It puts the workpiece in ultrasonic cleaning device and successively carries out ultrasonic oil removing cleaning, pure water surpasses
Sound cleaning, pure water rinsing, water removal, hydrocarbon solvent vacuum ultrasonic cleaning, vacuum and heating drying, hydrocarbon solvent vacuum ultrasonic cleaning mistake
It is 200Pa-500Pa that vacuum degree is cleaned in journey, and it is 90 that vacuum degree, which is 100Pa-200Pa heating temperature, during vacuum and heating drying
℃；It puts the workpiece in the thermostatic container equipped with depassivation coating solution and impregnates after the completion of cleaning, temperature is maintained at 80 DEG C, continues 30
Minute；Then it puts the workpiece in clear water and is rinsed, then removed water, is then charged on specific fixture etc. to be coated；
Step 2：Plated film pre-treatment：Fixture equipped with workpiece is fitted into vacuum chamber, vacuum chamber both sides sealing door is closed,
It is then turned on vacuum pump group, vacuum system is extracted into 5 × 10 by atmospheric condition-3Pa, starting heating device make the temperature in vacuum furnace
200 DEG C -350 DEG C are heated to, argon gas is then charged with, partial pressure of ar gas 0.4Pa-1.0Pa opens heated filament heating power supply, heated filament electricity
Stream is gradually promoted to 30A-60A by 10A, is then turned on heated filament grid bias power supply, voltage is set as -30V--60V, is then turned on plating
Film machine workpiece bias, bias sets are -200V--800V, and duty ratio is set as 60%-80%, carry out substrate surface ion sputtering and
Etching activation, continues 10min-120min；Workpiece bias, heated filament bias, heated filament heating power supply are successively closed after then, reduce argon
Gas partial pressure is 0.2Pa-0.8Pa, is then turned on workpiece bias power supply, and bias sets are -600V--1000V, and duty ratio is set as
10%-80% is then turned on titanium alloy target and tungsten alloy target material, and titanium alloy target target arc stream is set as 50A-120A, and tungsten closes
Gold target material target arc stream is set as 50A-120A, carries out metal ion and bombards process, strengthens bombardment etching and activation effect, continues
5min-30min；
Step 3：Anti-corrosion transition zone deposition：Then argon gas is kept continually and steadily to input afterwards, partial pressure of ar gas maintains 0.2Pa-
0.8Pa keeps workpiece bias power supply in the open state, is -30V--800V, duty ratio 10%-80% by bias sets, keeps
Titanium alloy target is in the open state with tungsten alloy target material, and titanium alloy target arc stream is set as 50A-120A, tungsten alloy target material arc
Stream is set as 50A-120A, continues 1min-30min, completes anti-corrosion transition zone deposition；
Step 4：Superconduction electric layer deposition：Then afterwards keep workpiece bias power supply it is in the open state, by bias sets be-
30V--800V, duty ratio 10%-80% close nitrogen, keep argon gas to be continually fed into, while adjusting accordingly to partial pressure of ar gas,
So that total pressure maintains 0.2Pa-0.8Pa in vacuum chamber, tungsten alloy target material, titanium alloy target are closed, opens graphite target, target
Material arc stream is set as 50A-120A, carries out superconduction electric layer deposition, continues 1min-30min.
The embodiment of the present invention one：
In the present embodiment, the titanium alloy group for forming anti-corrosion transition zone is divided into the titanium alloy containing titanium 30wt%, and wherein titanium is
β phase, other adding ingredients can be one of vanadium, tantalum, nickel, chromium, zirconium or a variety of, such as titanium and vanadium, titanium and tantalum, titanium and chromium, titanium
With binary composed by chromium and nickel, ternary even multicomponent alloy, the alloy as composed by 30wt% titanium, 20wt% vanadium, 20wt% chromium,
And being formed by alloy is BCC structure, forms another alloy of self-healing layer, component includes 5wt% tungsten, other adding ingredients
It can be one of titanium, vanadium, niobium, chromium, zirconium or a variety of, such as tungsten and vanadium, tungsten and titanium, tungsten and zirconium, tungsten and niobium and chromium, such as 5wt%
Tungsten, 80wt% niobium, alloy composed by 15wt% chromium.
It puts the workpiece in ultrasonic cleaning device and successively carries out ultrasonic oil removing cleaning, pure water ultrasonic cleaning, pure water rinsing, removes
Water, hydrocarbon solvent vacuum ultrasonic cleaning, vacuum and heating drying, hydrocarbon solvent vacuum ultrasonic cleaning Cleaning Process vacuum degree are
200Pa, it is 90 DEG C that vacuum degree, which is 100Pa heating temperature, during vacuum and heating drying；It puts the workpiece in and is equipped with after the completion of cleaning
It is impregnated in the thermostatic container of depassivation coating solution, temperature is maintained at 80 DEG C, continues 30 minutes；Then put the workpiece in clear water into
Row rinsing, is then removed water, and is then charged on specific fixture etc. to be coated；
Fixture equipped with workpiece is fitted into vacuum chamber, vacuum chamber both sides sealing door is closed, is then turned on vacuum pump group, it will
Vacuum system is extracted into 5 × 10-3Pa by atmospheric condition, and starting heating device makes the temperature in vacuum furnace be heated to 200 DEG C, then fills
Enter argon gas, partial pressure of ar gas 0.5Pa opens heated filament heating power supply, and heater current is gradually promoted to 30A by 10A, is then turned on heat
Silk grid bias power supply, voltage are set as -30V, are then turned on film plating machine workpiece bias, and bias sets are -200V, and duty ratio is set as
60%, substrate surface ion sputtering and etching activation are carried out, 20min is continued；Successively closed after then workpiece bias, heated filament bias,
Heated filament heating power supply, reduction partial pressure of ar gas are 0.5Pa, are then turned on workpiece bias power supply, and bias sets are -600V, duty ratio
It is set as 10%, is then turned on titanium alloy target and tungsten alloy target material, titanium alloy target target arc stream is set as 50A, tungsten alloy target
Material target arc stream is set as 50A, carries out metal ion and bombards process, strengthens bombardment etching and activation effect, continues 5min；
Then argon gas is kept continually and steadily to input afterwards, partial pressure of ar gas maintains 0.5Pa, keeps workpiece bias power supply to be in and opens
State is opened, is -30V by bias sets, duty ratio 10% keeps titanium alloy target and tungsten alloy target material in the open state, and titanium closes
Gold target material arc stream is set as 50A, and tungsten alloy target material arc stream is set as 50A, continues 1min, completes anti-corrosion transition zone deposition；
It then keeps workpiece bias power supply in the open state afterwards, is -30V by bias sets, duty ratio 10% closes nitrogen
Gas keeps argon gas to be continually fed into, while adjusting accordingly to partial pressure of ar gas, so that total pressure maintains 0.5Pa in vacuum chamber,
Tungsten alloy target material, titanium alloy target are closed, graphite target is opened, target arc stream is set as 50A, carries out superconduction electric layer deposition, holds
Continuous 5min.
The coating according to prepared by above-described embodiment is under 0.6MPa pressure test, contact resistance 4m Ω cm2, graphene
Content is 2%, and corrosion electric current density is 9 × 10-6A/cm2 under simulation application corrosion working conditions.
The embodiment of the present invention two：
The titanium alloy group for forming anti-corrosion transition zone is divided into the titanium alloy containing titanium 60wt%, and wherein titanium is β phase, other additions
Ingredient can be one of vanadium, tantalum, nickel, chromium, zirconium or a variety of, such as titanium and vanadium, titanium and tantalum, titanium and chromium, titanium and chromium and nickel institute group
At binary, ternary even multicomponent alloy, the alloy as composed by 60wt% titanium, 20wt% vanadium, 20wt% chromium, and be formed by conjunction
Gold be BCC structure, form self-healing layer another alloy, component include 60wt% tungsten, other adding ingredients can be titanium, vanadium,
One of niobium, chromium, zirconium are a variety of, such as tungsten and vanadium, tungsten and titanium, tungsten and zirconium, tungsten and niobium and chromium, as 60wt% tungsten, 10wt% niobium,
Alloy composed by 30wt% chromium.
It puts the workpiece in ultrasonic cleaning device and successively carries out ultrasonic oil removing cleaning, pure water ultrasonic cleaning, pure water rinsing, removes
Water, hydrocarbon solvent vacuum ultrasonic cleaning, vacuum and heating drying, hydrocarbon solvent vacuum ultrasonic cleaning Cleaning Process vacuum degree are
200Pa, it is 90 DEG C that vacuum degree, which is 100Pa heating temperature, during vacuum and heating drying；It puts the workpiece in and is equipped with after the completion of cleaning
It is impregnated in the thermostatic container of depassivation coating solution, temperature is maintained at 80 DEG C, continues 30 minutes；Then put the workpiece in clear water into
Row rinsing, is then removed water, and is then charged on specific fixture etc. to be coated；
Fixture equipped with workpiece is fitted into vacuum chamber, vacuum chamber both sides sealing door is closed, is then turned on vacuum pump group, it will
Vacuum system is extracted into 5 × 10 by atmospheric condition-3Pa, starting heating device make the temperature in vacuum furnace be heated to 250 DEG C, are then charged with
Argon gas, partial pressure of ar gas 0.5Pa open heated filament heating power supply, and heater current is gradually promoted to 40A by 10A, is then turned on heated filament
Grid bias power supply, voltage are set as -40V, are then turned on film plating machine workpiece bias, and bias sets are -400V, and duty ratio is set as
70%, substrate surface ion sputtering and etching activation are carried out, 60min is continued；Successively closed after then workpiece bias, heated filament bias,
Heated filament heating power supply, reduction partial pressure of ar gas are 0.5Pa, are then turned on workpiece bias power supply, and bias sets are -800V, duty ratio
It is set as 40%, is then turned on titanium alloy target and tungsten alloy target material, titanium alloy target target arc stream is set as 80A, tungsten alloy target
Material target arc stream is set as 80A, carries out metal ion and bombards process, strengthens bombardment etching and activation effect, continues 15min；
Then argon gas is kept continually and steadily to input afterwards, partial pressure of ar gas maintains 0.5Pa, keeps workpiece bias power supply to be in and opens
State is opened, is -150V by bias sets, duty ratio 35% keeps titanium alloy target and tungsten alloy target material in the open state, titanium
Alloy target material arc stream is set as 80A, and tungsten alloy target material arc stream is set as 80A, continues 10min, completes anti-corrosion transition zone deposition；
It then keeps workpiece bias power supply in the open state afterwards, is -150V by bias sets, duty ratio 40% closes nitrogen
Gas keeps argon gas to be continually fed into, while adjusting accordingly to partial pressure of ar gas, so that total pressure maintains 0.5Pa in vacuum chamber,
Tungsten alloy target material, titanium alloy target are closed, graphite target is opened, target arc stream is set as 80A, carries out superconduction electric layer deposition, holds
Continuous 15min.
The coating according to prepared by above-described embodiment is under 0.6MPa pressure test, contact resistance 2m Ω cm2, graphene
Content is 4%, and corrosion electric current density is 6 × 10 under simulation application corrosion working conditions-7A/cm2。
The embodiment of the present invention three：
The titanium alloy group for forming anti-corrosion transition zone is divided into the titanium alloy containing titanium 30wt%, and wherein titanium is β phase, other additions
Ingredient can be one of vanadium, tantalum, nickel, chromium, zirconium or a variety of, such as titanium and vanadium, titanium and tantalum, titanium and chromium, titanium and chromium and nickel institute group
At binary, ternary even multicomponent alloy, the alloy as composed by 80wt% titanium, 10wt% vanadium, 10wt% chromium, and be formed by conjunction
Gold be BCC structure, form self-healing layer another alloy, component include 80wt% tungsten, other adding ingredients can be titanium, vanadium,
One of niobium, chromium, zirconium are a variety of, such as tungsten and vanadium, tungsten and titanium, tungsten and zirconium, tungsten and niobium and chromium, as 80wt% tungsten, 10wt% niobium,
Alloy composed by 10wt% chromium.
In the present embodiment, 2 in anti-corrosion transition zone involved in titanium alloy and tungsten alloy target material there is frozen composition ratio,
Wherein titanium alloy target is the titanium comprising 70wt%, the tantalum of 20wt% and 10wt% vanadium, and tungsten alloy target material includes 20wt% tungsten, 40wt%
Chromium and 40wt% niobium.
It puts the workpiece in ultrasonic cleaning device and successively carries out ultrasonic oil removing cleaning, pure water ultrasonic cleaning, pure water rinsing, removes
Water, hydrocarbon solvent vacuum ultrasonic cleaning, vacuum and heating drying, hydrocarbon solvent vacuum ultrasonic cleaning Cleaning Process vacuum degree are
200Pa, it is 90 DEG C that vacuum degree, which is 100Pa heating temperature, during vacuum and heating drying；It puts the workpiece in and is equipped with after the completion of cleaning
It is impregnated in the thermostatic container of depassivation coating solution, temperature is maintained at 80 DEG C, continues 30 minutes；Then put the workpiece in clear water into
Row rinsing, is then removed water, and is then charged on specific fixture etc. to be coated；
Fixture equipped with workpiece is fitted into vacuum chamber, vacuum chamber both sides sealing door is closed, is then turned on vacuum pump group, it will
Vacuum system is extracted into 5 × 10 by atmospheric condition-3Pa, starting heating device make the temperature in vacuum furnace be heated to 250 DEG C, are then charged with
Argon gas, partial pressure of ar gas 0.5Pa open heated filament heating power supply, and heater current is gradually promoted to 60A by 10A, is then turned on heated filament
Grid bias power supply, voltage are set as -60V, are then turned on film plating machine workpiece bias, and bias sets are -800V, and duty ratio is set as
80%, substrate surface ion sputtering and etching activation are carried out, 120min is continued；It is inclined that workpiece bias, heated filament are successively closed after then
Pressure, heated filament heating power supply, reduction partial pressure of ar gas are 0.5Pa, are then turned on workpiece bias power supply, and bias sets are -1000V, are accounted for
Empty ratio is set as 80%, is then turned on titanium alloy target and tungsten alloy target material, and titanium alloy target target arc stream is set as 70A, and tungsten closes
Gold target material target arc stream is set as 70A, carries out metal ion and bombards process, strengthens bombardment etching and activation effect, continues
30min；
Then argon gas is kept continually and steadily to input afterwards, partial pressure of ar gas maintains 0.5Pa, keeps workpiece bias power supply to be in and opens
State is opened, is -400V by bias sets, duty ratio 60% keeps titanium alloy target and tungsten alloy target material in the open state, titanium
Alloy target material arc stream is set as 100A, and tungsten alloy target material arc stream is set as 100A, continues 30min, completes anti-corrosion transition zone deposition；
It then keeps workpiece bias power supply in the open state afterwards, is -350V by bias sets, duty ratio 60% closes nitrogen
Gas keeps argon gas to be continually fed into, while adjusting accordingly to partial pressure of ar gas, so that total pressure maintains 0.5Pa in vacuum chamber,
Tungsten alloy target material, titanium alloy target are closed, graphite target is opened, target arc stream is set as 100A, carries out superconduction electric layer deposition, holds
Continuous 30min.
The coating according to prepared by above-described embodiment is under 0.6MPa pressure test, contact resistance 1m Ω cm2, graphene
Content is 10%, and corrosion electric current density is 5 × 10 under simulation application corrosion working conditions-8A/cm2。
Described above to be merely exemplary for the purpose of the present invention, and not restrictive, those of ordinary skill in the art understand,
In the case where not departing from spirit and scope as defined in the appended claims, many modifications, variation or equivalent can be made, but all
It will fall within the scope of protection of the present invention.
Claims (4)
1. a kind of superconduction graphene coating material, characterized in that the coating material includes anti-corrosion transition zone（2）With superconduction electric layer
（3）, anti-corrosion transition zone（2）It is made of titanium alloy and tungsten alloy, superconduction electric layer（3）Include graphene and graphite, superconduction electric layer（3）
In graphene content be 2%-10%, anti-corrosion transition zone（2）Middle titanium alloy include titanium and one of vanadium, tantalum, nickel, chromium, zirconium or
A variety of, wherein Ti content is 30wt%-80wt%；Tungsten alloy includes tungsten and one of titanium, vanadium, niobium, chromium, zirconium or a variety of, wherein
W content is 5wt%-80wt%.
2. superconduction graphene coating material according to claim 1, characterized in that anti-corrosion transition zone（2）With a thickness of
30nm-500nm, anti-corrosion transition zone（2）It in use can be at pin hole or mechanical injuries（4）Automatically form filler
（5）, at pin hole or mechanical injuries（4）It is easy to react with oxygen due to being exposed to outer, automatically forms oxidation filler
（5）, be formed by oxidation product with preferable corrosion resisting property and preferable conductive capability, thus prevent corrosion reaction into one
Step occurs.
3. superconduction graphene coating material according to claim 1, characterized in that superconduction electric layer（3）It is pressed in 0.6MPa
Under power test, the contact resistance 1m Ω cm2-3m Ω cm2 with carbon paper.
4. a kind of preparation method of any one of manufacturing claims 1-3 superconduction graphene coating material, characterized in that coating material
The anti-corrosion transition zone of material（2）With superconduct layer by layer（3）It is to be set in the Magnetic filter arc ion plating for being equipped with heated filament assisting ion source
Completion is disposably deposited in standby, filming equipment target is respectively distributed to vacuum furnace body two sides, and same level possesses at least 3
A target rigging position, wherein side installation titanium alloy doping target or tungsten alloy adulterate target, other side graphite target, including
Following processing step：
Step 1：Workpiece pre-treatment：It puts the workpiece in ultrasonic cleaning device and successively carries out ultrasonic oil removing cleaning, pure water ultrasound clearly
It washes, pure water rinsing, water removal, hydrocarbon solvent vacuum ultrasonic cleaning, vacuum and heating drying, during hydrocarbon solvent vacuum ultrasonic cleaning
Cleaning vacuum degree is 200Pa-500Pa, and it is 90 DEG C that vacuum degree, which is 100Pa-200Pa heating temperature, during vacuum and heating drying；
It puts the workpiece in the thermostatic container equipped with depassivation coating solution and impregnates after the completion of cleaning, temperature is maintained at 80 DEG C, continues 30 points
Clock；Then it puts the workpiece in clear water and is rinsed, then removed water, is then charged on specific fixture etc. to be coated；
Step 2：Plated film pre-treatment：Fixture equipped with workpiece is fitted into vacuum chamber, closes vacuum chamber both sides sealing door, then
Vacuum pump group is opened, vacuum system is extracted into 5 × 10 by atmospheric condition-3Pa, starting heating device heat the temperature in vacuum furnace
To 200 DEG C -350 DEG C, be then charged with argon gas, partial pressure of ar gas 0.4Pa-1.0Pa opens heated filament heating power supply, heater current by
10A is gradually promoted to 30A-60A, is then turned on heated filament grid bias power supply, and voltage is set as -30V--60V, is then turned on coating machine
Workpiece bias, bias sets are -200V--800V, and duty ratio is set as 60%-80%, carry out substrate surface ion sputtering and etching
Activation continues 10min-120min；Workpiece bias, heated filament bias, heated filament heating power supply are successively closed after then, reduce argon gas point
Pressure is 0.2Pa-0.8Pa, is then turned on workpiece bias power supply, and bias sets are -600V--1000V, and duty ratio is set as 10%-
80%, it is then turned on titanium alloy target and tungsten alloy target material, titanium alloy target target arc stream is set as 50A-120A, tungsten alloy target
Material target arc stream is set as 50A-120A, carries out metal ion and bombards process, strengthens bombardment etching and activation effect, continues
5min-30min；
Step 3：Anti-corrosion transition zone deposition：Then argon gas is kept continually and steadily to input afterwards, partial pressure of ar gas maintains 0.2Pa-
0.8Pa keeps workpiece bias power supply in the open state, is -30V--800V, duty ratio 10%-80% by bias sets, keeps
Titanium alloy target is in the open state with tungsten alloy target material, and titanium alloy target arc stream is set as 50A-120A, tungsten alloy target material arc
Stream is set as 50A-120A, continues 1min-30min, completes anti-corrosion transition zone deposition；
Step 4：Superconduction electric layer deposition：It then keeps workpiece bias power supply in the open state afterwards, is -30V-- by bias sets
800V, duty ratio 10%-80% close nitrogen, keep argon gas to be continually fed into, while adjusting accordingly to partial pressure of ar gas, so that
Total pressure maintains 0.2Pa-0.8Pa in vacuum chamber, closes tungsten alloy target material, titanium alloy target, opens graphite target, target arc
Stream is set as 50A-120A, carries out superconduction electric layer deposition, continues 1min-30min.
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