CN113897591A - Metal protection method and application - Google Patents
Metal protection method and application Download PDFInfo
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- CN113897591A CN113897591A CN202111171976.1A CN202111171976A CN113897591A CN 113897591 A CN113897591 A CN 113897591A CN 202111171976 A CN202111171976 A CN 202111171976A CN 113897591 A CN113897591 A CN 113897591A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 70
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 239000007769 metal material Substances 0.000 claims abstract description 25
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 16
- 239000000835 fiber Substances 0.000 claims description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 37
- 229910052802 copper Inorganic materials 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
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- 229910052786 argon Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052790 beryllium Inorganic materials 0.000 claims description 3
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- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000004377 microelectronic Methods 0.000 abstract description 3
- 230000003746 surface roughness Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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Images
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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
Abstract
The invention discloses a metal protection method, which comprises the following steps: providing a metal material; and growing the vertical graphene coating on the surface of the metal material through plasma enhanced chemical vapor deposition. Also disclosed is a device comprising the structure prepared by the method. According to the invention, the vertical graphene coating is grown on the surface of the metal material, and the surface roughness of the vertical graphene coating is larger, so that the excellent hydrophobic characteristic can be shown, and an air layer is reserved between the hydrophobic vertical graphene layer and corrosive liquid, so that a corrosive medium can be effectively isolated and prevented from further permeating into the metal surface. The vertical graphene coating can also realize the corrosion resistance of metal materials in severe environments such as high temperature, corrosion and the like, so that the vertical graphene coating is expected to be applied to the fields of high-power wires and cables, microelectronic devices, high-temperature electromagnetic shielding and the like. In addition, the method for preparing the vertical graphene coating on the metal material substrate is simple and effective, and is convenient to popularize to large-scale production.
Description
Technical Field
The invention relates to the field of application of graphene, in particular to application of graphene in the field of metal corrosion prevention.
Background
Metal corrosion is an important problem in modern society and is widespread in many fields. It is a conservative estimate that economic losses due to metal corrosion worldwide reach hundreds of billions of dollars each year. The surface coating method is the most common and effective metal protection method at present, i.e. a layer of protective film is covered on the metal surface to prevent the metal from directly contacting with corrosive media in the environment, so as to reduce the probability of chemical or electrochemical reaction of the metal. Traditional surface protective coatings, such as organic and high molecular materials, have poor heat and electricity conducting capability, and will affect the intrinsic physical properties of metals; in addition, the moisture absorption characteristics of the material limit its ability to protect against moisture.
Graphene as a novel two-dimensional material can obstruct oxygen, moisture, corrosive liquid and the like from reaching the surface of a metal matrix, thereby showing excellent protective performance. Compared with the traditional surface coating, the graphene has unique and excellent thermal, electrical and mechanical properties, does not have negative influence on the intrinsic physical properties of metal, and is expected to become a new generation of optimal metal protection material. In the past, people are continuously dedicated to exploring the protection capability of graphene on metals. Prasai et al reduced the electrochemical corrosion rate of the copper foil in a sodium sulfate solution by about 7 times by growing horizontal graphene on the surface of the copper foil (ACS Nano 2012,6, 1102-1108). Roy et al relieved the oxidation of copper foil at 200 ℃ by increasing the size and number of graphene domains (Roy, s.s.et al. adv.funct.mater.2013,23, 3638-3644).
However, some studies report that levels of graphene exacerbate metal corrosion instead. For example, Schriver et al found that graphene-coated copper foil corroded more severely in air than bare copper foil for a longer period of time. The reasons for this may be: substances such as oxygen and moisture in the air come into contact with the metal through edges, defects, wrinkles, breakage, and the like of the graphene, and the copper foil and the graphene constitute a galvanic cell, promoting corrosion of the copper foil in the air. Therefore, the protective effect of horizontal graphene still needs to be further improved.
Disclosure of Invention
In order to overcome the defects, the invention provides a metal protection method and application thereof.
The invention provides a metal protection method, which comprises the following steps: providing a metal material; and growing the vertical graphene coating on the surface of the metal material through plasma enhanced chemical vapor deposition.
According to an embodiment of the present invention, the growth temperature of the pecvd is 500 to 800 ℃; the heating rate is 1 ℃/min to 100 ℃/min; the plasma source power of the plasma enhanced chemical vapor deposition is 10W-500W.
According to another embodiment of the present invention, the carbon source gas for the plasma enhanced chemical vapor deposition is selected from one or more of methane, ethane, ethylene, acetylene, methanol, and ethanol, and the flow rate of the carbon source gas is 0.05sccm to 100 sccm; preferably, the method further comprises introducing an inert gas or a reducing gas into the plasma enhanced chemical vapor deposition system, wherein the inert gas is selected from one or more of argon and nitrogen, and the reducing gas is hydrogen.
According to another embodiment of the present invention, the plasma source is one of rf, microwave, dc plasma source or a combination thereof; the power of the plasma source is 10W-500W.
According to another embodiment of the invention, the metallic material is in the form of a block, a film, a foil, a fiber or a foam.
According to another embodiment of the present invention, the material of the metal material is pure metal or alloy.
According to another embodiment of the present invention, the metal material contains one or more elements selected from the group consisting of aluminum, beryllium, cadmium, cobalt, gold, hafnium, indium, iridium, iron, lead, molybdenum, nickel, platinum, palladium, rhenium, silver, tantalum, titanium, tungsten, vanadium, zinc, zirconium, bismuth, copper, manganese, magnesium, chromium, rhodium, ruthenium, and aluminum.
The invention also provides a device comprising the structure prepared by the method.
According to an embodiment of the present invention, the thickness of the vertical graphene coating is 10nm to 100 μm.
According to another embodiment of the present invention, the lateral dimension of the vertical graphene in the vertical graphene coating is 10nm to 2 μm.
According to the invention, the purpose of protecting the metal material is realized by growing the vertical graphene coating on the surface of the metal material. Different from horizontal graphene coating, vertical orientation graphene coating surface roughness is bigger, can show more excellent hydrophobic characteristic to it has the air bed to make to have between hydrophobic vertical graphene layer and the corrosive liquid, therefore can effectively completely cut off corrosive medium and hinder it further to permeate to the metal surface. The vertical graphene coating can also realize the corrosion resistance of metal materials in severe environments such as high temperature, corrosion and the like, so that the vertical graphene coating is expected to be widely applied to the fields of high-power wires and cables, microelectronic devices, high-temperature electromagnetic shielding and the like. In addition, the preparation method provided by the invention has the advantages that the vertical graphene coating is prepared on the metal material substrate, the method is simple and effective, and the method is convenient to popularize to large-scale production.
Drawings
Fig. 1 is a schematic structural view of a metal fiber with a vertical graphene coating grown prepared in example 1.
Fig. 2 is a scanning electron microscope image of the composite fiber prepared in example 1.
Fig. 3 is a cross-sectional electron microscope image of the composite fiber prepared in example 1.
Fig. 4 is a raman spectrum of the composite fiber prepared in example 1.
Fig. 5 is a potentiodynamic polarization curve for bare copper fibers before forming a vertical graphene coating and composite fibers after forming a vertical graphene coating in example 1.
Fig. 6 is nyquist curves for bare copper fibers before forming a vertical graphene coating and composite fibers after forming a vertical graphene coating in example 1.
Fig. 7 is a scanning electron microscope photograph of the bare copper fiber after heat treatment for 6 hours before forming the vertical graphene coating in example 1.
Fig. 8 is a scanning electron microscope photograph of the copper fiber after the composite fiber after the vertical graphene coating was formed in example 1 and the coating was removed after heat treatment for 6 hours.
FIG. 9 is a Raman spectrum of the composite fiber prepared in example 1 after heat treatment for 6 hours.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below in the specification. It is to be understood that the invention is capable of various modifications in various embodiments, all without departing from the scope of the invention.
The term "vertical graphene" in this patent refers to a three-dimensional morphology of graphene grown by plasma-enhanced chemical vapor deposition, which is different from the conventional two-dimensional horizontal graphene parallel to the growth substrate.
The metal protection method provided by the invention comprises the following steps: providing a metal material; and growing the vertical graphene coating on the surface of the metal material through plasma enhanced chemical vapor deposition. In a plasma enhanced chemical vapor deposition system, graphene exhibits a vertical growth characteristic under the combined action of lattice mismatch, thermal mismatch, plasma bombardment, a sheath electric field and the like in a growth process, so that a vertical graphene layer can be formed. The surface roughness of the vertically-oriented graphene coating is larger, and more excellent hydrophobic characteristics can be shown, so that an air layer is reserved between the hydrophobic vertical graphene layer and corrosive liquid, and therefore corrosive media can be effectively isolated and prevented from further permeating into the metal surface. The vertical graphene coating can also realize the oxidation resistance and corrosion resistance of metal materials in severe environments such as high temperature, corrosion and the like, so that the vertical graphene coating is expected to be widely applied to the fields of high-power wires and cables, microelectronic devices, high-temperature electromagnetic shielding and the like.
In an alternative embodiment, the carbon source gas is selected from one or more of methane, ethane, ethylene, acetylene, methanol, ethanol, and the like, and the flow rate of the carbon source gas is 0.05sccm to 100sccm, such as, but not limited to, 2sccm, 10sccm, 50sccm, and the like. Preferably, the method further comprises introducing an inert gas or a reducing gas into the plasma enhanced chemical vapor deposition system, wherein the inert gas is one or more selected from argon and nitrogen, and the reducing gas is hydrogen.
In an alternative embodiment, the growth temperature of the PECVD deposition is 500-800 deg.C, such as, but not limited to, 550 deg.C, 600 deg.C, 650 deg.C. The heating rate is 1 ℃/min to 100 ℃/min, for example, but not limited to, 10 ℃/min, 30 ℃/min, 50 ℃/min, 70 ℃/min, 90 ℃/min, and the like. Preferably, the plasma source is one or a combination of radio frequency, microwave and direct current plasma sources; the plasma source power is 10W-500W, such as, but not limited to, 50W, 150W, 300W, etc.
In alternative embodiments, the metallic material may be in the form of, but is not limited to, a block, a film, a foil, a fiber, or a foam.
In an alternative embodiment, the metal material is a pure metal or an alloy. The metal material may contain one or more elements selected from aluminum, beryllium, cadmium, cobalt, gold, hafnium, indium, iridium, iron, lead, molybdenum, nickel, platinum, palladium, rhenium, silver, tantalum, titanium, tungsten, vanadium, zinc, zirconium, bismuth, copper, manganese, magnesium, chromium, rhodium, ruthenium, and aluminum.
The invention also provides a device comprising the structure prepared by the method.
In an alternative embodiment, the thickness of the vertical graphene coating is 10nm to 100 μm. When the thickness of the vertical graphene coating is less than 10nm, the protection effect on metal is limited and effective protection cannot be achieved; however, if the thickness of the vertical graphene coating is greater than 100 μm, the coating is easy to fall off.
In an alternative embodiment, the lateral dimension of the vertical graphene in the vertical graphene coating is 10nm to 2 μm. The transverse size of the vertical graphene in the coating is less than 10nm, so that the protective effect on metal is limited; when the transverse dimension is larger than 2 mu m, the protection effect is not obviously enhanced along with the increase of the thickness, but the growth consumes time and energy seriously.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, reagents, materials and the like used in the present invention are commercially available.
Example 1
Vertical graphene growth was performed on copper fibers using the rf plasma enhanced chemical vapor deposition apparatus shown in fig. 1. Providing a copper fiber as a growth substrate, fixing the copper fiber on a quartz carrier and placing the copper fiber in a heating area of a chemical vapor deposition furnace of a quartz tube, wherein the copper fiber is positioned on an axial line of the quartz tube under the support of the quartz carrier, and the copper fiber plays a role in uniformly distributing plasma on the surface of the copper fiber. Wherein the copper fiber has a diameter of 100 μm and a length of 10 cm.
And heating the chemical vapor deposition furnace under the hydrogen atmosphere with the flow of 100sccm, wherein the heating rate is 20 ℃/min. And after the temperature of the system reaches the growth temperature of 650 ℃, continuously annealing for 30min in a hydrogen atmosphere to remove impurities such as oxides on the surface of the copper fiber. And closing hydrogen, and introducing 10sccm methane gas, wherein the system pressure is 25 Pa. Meanwhile, a radio frequency alternating current power supply is started to perform vertical graphene growth, the radio frequency power is 150W, and the growth time is 60 min. And after the growth is finished, closing the alternating current radio frequency power supply, stopping introducing methane gas, introducing 50sccm hydrogen and 300sccm argon, and cooling the chemical vapor deposition furnace to obtain the composite fiber.
Performance testing
As can be seen from the scanning electron microscope photograph of FIG. 2, the vertical graphene is in a three-dimensional shape, and the transverse dimension is 1-2 μm. It can be seen from the cross-sectional electron micrograph of fig. 3 that the thickness of the vertical graphene plating layer is about 1.25 μm.
It can be seen from the raman spectrum of fig. 4 that the vertical graphene coating exhibits an D, G, 2D raman peak typical of graphene. For bare copper fiberAnd the prepared composite fiber is 0.1mol/L Na2SO4Electrochemical tests were performed in solution, and the results are shown in fig. 5 and 6. From the potentiodynamic polarization curve, it can be seen that the corrosion current density of the copper fiber with vertical graphene protection is reduced by about one order of magnitude compared to the bare copper fiber. From the nyquist curve, it can be seen that the arc-resistant radius of the copper fiber protected by the vertical graphene is significantly larger than that of the bare copper fiber, which indicates that the vertical graphene can effectively protect the copper fiber from electrochemical corrosion.
Bare copper fibers and the composite fibers prepared in example 1 were heated on a 200 ℃ hot plate for 6 hours for oxidation resistance testing. The heat treated composite fiber prepared in example 1 was sonicated in ethanol to remove the vertical graphene coating and expose the copper fiber surface, and the bare copper fiber was sonicated in the same way as a control. The scanning electron micrographs are shown in FIGS. 7 and 8, and the Raman spectrum is shown in FIG. 9. As can be seen from fig. 7 and 8, the surface of the bare copper fiber after 6 hours of heat treatment is severely oxidized, while the surface of the copper fiber protected by the vertical graphene coating is not significantly oxidized, which indicates that the vertical graphene can effectively protect the copper fiber from oxidation. From the raman spectrum of fig. 9, it can also be seen that the bare copper fiber after 6h of heat treatment exhibits a significant raman characteristic peak of copper oxide/cuprous oxide, and the characteristic peak of the copper fiber protected by the vertical graphene coating is not significantly observed.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A method of metal protection, comprising:
providing a metal material; and
and growing the vertical graphene coating on the surface of the metal material through plasma enhanced chemical vapor deposition.
2. The method of claim 1, wherein the growth temperature of the PECVD deposition is 500-800 ℃; the heating rate is 1 ℃/min to 100 ℃/min; the plasma source power of the plasma enhanced chemical vapor deposition is 10W-500W.
3. The method of claim 2, wherein the carbon source gas for the plasma enhanced chemical vapor deposition is selected from one or more of methane, ethane, ethylene, acetylene, methanol, and ethanol, and the flow rate of the carbon source gas is 0.05sccm to 100 sccm; preferably, the method further comprises introducing an inert gas or a reducing gas into the plasma enhanced chemical vapor deposition system, wherein the inert gas is selected from one or more of argon and nitrogen, and the reducing gas is hydrogen.
4. The method of claim 2, wherein the plasma source is one of a radio frequency, microwave, direct current plasma source, or a combination thereof.
5. The method of claim 1, wherein the metallic material is in the form of a block, film, foil, fiber, or foam.
6. The method of claim 1, wherein the metallic material is a pure metal or an alloy.
7. The method according to claim 1, wherein the metal material contains one or more elements selected from the group consisting of aluminum, beryllium, cadmium, cobalt, gold, hafnium, indium, iridium, iron, lead, molybdenum, nickel, platinum, palladium, rhenium, silver, tantalum, titanium, tungsten, vanadium, zinc, zirconium, bismuth, copper, manganese, magnesium, chromium, rhodium, ruthenium, and aluminum.
8. A device comprising a structure prepared by the method of any one of claims 1-7.
9. The apparatus of claim 8, wherein the vertical graphene coating has a thickness of 10nm to 100 μm.
10. The apparatus of claim 8, wherein the lateral dimension of the vertical graphene in the vertical graphene coating is 10nm to 2 μm.
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