CN107740118A - A kind of method for the graphene protection metal erosion that crystal face relies on - Google Patents
A kind of method for the graphene protection metal erosion that crystal face relies on Download PDFInfo
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- CN107740118A CN107740118A CN201710961693.4A CN201710961693A CN107740118A CN 107740118 A CN107740118 A CN 107740118A CN 201710961693 A CN201710961693 A CN 201710961693A CN 107740118 A CN107740118 A CN 107740118A
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- copper foil
- autoxidation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F15/00—Other methods of preventing corrosion or incrustation
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Abstract
A kind of method of the graphene protection metal erosion relied on the invention provides crystal face.Graphene is covered in metal foil surface by methods described using the methods of chemical vapor deposition; utilize not penetrability and the interaction between metal substrate completely of graphene; to autoxidation, hot water and steam is smoked and briny environment under metal protect, protect metal not to be corroded.Method proposed by the present invention, solve the problems, such as metal oxide etch, by very simple method, realize protection of the graphene to metal.
Description
Technical field
A kind of method of the graphene protection metal erosion relied on the present invention relates to crystal face.
Background technology
Copper is a kind of nonferrous materials having been widely cited, and has good electric conductivity, thermal conductivity, ductility, and molten
Point is relatively low, is easy to smelt, is easy to extensive, inexpensive industrial production to process, therefore is widely used in electrical industry, light industry
Industry, machinery manufacturing industry, building industry, national defense industry etc..In the application of copper, one is that copper contains oxygen corrosion the problem of serious：
When copper is exposed in air for a long time, oxygen and vapor in air can react with copper, generate the oxide of copper, so as to
The quality of copper product is greatly influenceed, or even directly affects the normal function of copper product.At present, people are oxygen-containing in order to avoid copper
Corrosion, often use and plate other metals, organic matter protective layer, protective oxide film etc., but their often conductive, heat conduction
Property is poor, and thicker, translucency is poor, protects the defects of incomplete.Because the application of copper is extremely wide, every year because of copper oxide etch
Lose hundreds of millions of.Therefore, a kind of low cost, high quality, ultra-thin and with more preferable anti-corrosion effects new protective layer material are found
Material has highly important practical value and economy, environment protection significance.
Graphene is the monoatomic layer thing with regular hexagon lattice structure that a kind of carbon atom by sp2 hydridization is formed
Matter.It has the advantages that high conductivity, high-termal conductivity, high mechanical properties, at room temperature high light transmittance, high chemical stability.At present,
Using chemical gaseous phase depositing process, can on single crystal Cu surface extensive, high efficiency, grow the monocrystalline stone of high quality at low cost
Black alkene.This causes graphene to have the great potential as monoatomic layer thickness anti oxidation layer.
Before this, it has been found that, although graphene protective layer can protect copper not to be corroded in the short period at high temperature,
Long-term, by electrochemical corrosion effects, it on the contrary can accelerated corrosion.Therefore, can people be used as long-term sudden and violent to graphene
Suspection was once being responded with the effective anticorrosive protection for the copper product being exposed under atmospheric environment.
The content of the invention
The method of the graphene protection metal erosion relied on present invention firstly provides a kind of crystal face, by graphene growth in spy
Determine on the tinsel of crystal face, protect tinsel not to be corroded.Graphene is to be grown in metal foil with chemical vapour deposition technique
On piece, or metal foil surface covered by branch mode.The tinsel includes copper foil, nickel foil etc., preferably
Copper foil.The specific copper crystal face is Cu (111), Cu (311) etc. and preferably all crystal faces of graphene Lattice Matching.
The present invention grows graphene using conventional chemical gaseous phase depositing process in copper foil surface, utilizes special copper crystal face
Close coupling effect between graphene, is protected to copper foil.Method proposed by the present invention, solve the metals such as copper and be oxidized
The problem of corrosion wastes, by very simple method, realizes the protection to metal.
The advantage of the invention is that：
1. the method for the graphene protection metal erosion relied on present invention firstly provides crystal face；
2. present invention graphene in copper foil surface covering using conventional chemical gaseous phase depositing process, process is simple, pole
The earth reduces cost；
3. the present invention can use identical method protection copper foil, nickel foil etc. all stronger with graphene interlayer coupling
Metal crystal face.
4. the inventive method is simple, effective, cost is low, the practical application for contributing to tinsel to protect.
Brief description of the drawings
Cu (111) sample autoxidation optical pictures one year after of the Fig. 1 (a) covered with graphene；Fig. 1 (b) covered with
Raman results of Cu (111) the sample autoxidation of graphene after 1 year.Low-energy electron corresponding to Fig. 1 (c) Cu (111) copper foil
Diffraction (LEED) result.
Fig. 2 (a) is optical picture of Cu (311) the sample autoxidation after 1 year covered with graphene；Fig. 2 (b) Cu
(311) low-energy electron diffraction corresponding to copper foil (LEED) result.
Fig. 3 (a) is optical picture of Cu (100) the sample autoxidation after 1 year covered with graphene；Fig. 3 (b) Cu
(100) low-energy electron diffraction corresponding to copper foil (LEED) result.
Fig. 4 (a) is optical picture of Cu (410) the sample autoxidation after 1 year covered with graphene；Fig. 4 (b) Cu
(410) low-energy electron diffraction corresponding to copper foil (LEED) result.
Embodiment
The present invention is described in further details with reference to specific embodiment, the raw material can unless otherwise instructed
Obtained from open commercial sources.
Embodiment one：A kind of method for the graphene protection metal erosion that crystal face relies on, comprises the following steps：
(1) graphene, is grown in copper foil surface with the method for aumospheric pressure cvd；
(2) copper foil sample that, will be covered with graphene is positioned in air, autoxidation, and the time is 1 month~2 years；
(3), after sample autoxidation, with optics microscope direct observing, you can see that protection of the graphene to copper foil is made
With.
Wherein, graphene is to be grown in chemical vapour deposition technique on tinsel, or is covered by branch mode
Metal foil surface.The tinsel includes copper foil, nickel foil etc., preferably copper foil.The specific copper crystal face is Cu
(111), Cu (311) etc. and preferably all crystal faces of graphene Lattice Matching.
By the paillon foil of above-mentioned Cu (111) crystal face covered with graphene prepared, autoxidation 1 year in air is placed.
After oxidation, optical picture is as shown in Figure 1a.Copper foil carries out Raman sign after oxidation, as a result as shown in Figure 1 b.From Fig. 1 a,
Copper foil of the autoxidation after 1 year, there is the region that graphene covers completely without oxidized.Exposed copper foil region is oxidized to
Kermesinus.Copper foils of Fig. 1 b covered with graphene does not see Raman peaks corresponding to cuprous oxide, further confirms that copper foil by very
Protect well, be not oxidized.As can be seen here, can be in nature by graphene growth on the copper foil of Cu (111) crystal face
Under conditions of oxidation, copper foil is protected not to be corroded well.
Experiment one：The method for the graphene protection metal erosion that a kind of crystal face of this experiment relies on is to enter according to the following steps
OK：
(1), graphene is grown in the copper foil surface of Cu (111) crystal face with the method for aumospheric pressure cvd；
(2) copper foil sample that, will be covered with graphene is positioned in air, autoxidation, and the time is 2 years；
(3), after sample autoxidation, with optics microscope direct observing, you can see that protection of the graphene to copper foil is made
With.
Under this experimental condition, graphene serves extraordinary protective effect to Cu (111).
Experiment two：The method for the graphene protection metal erosion that a kind of crystal face of this experiment relies on is to enter according to the following steps
OK：
(1), graphene is grown in the copper foil surface of Cu (311) crystal face with the method for aumospheric pressure cvd；
(2) copper foil sample that, will be covered with graphene is positioned in air, autoxidation, and the time is 2 years；
(3), after sample autoxidation, with optics microscope direct observing, you can see that protection of the graphene to copper foil is made
With.
Under this experimental condition, graphene serves extraordinary protective effect to Cu (311).It can see, cover by Fig. 2 a
The copper foil for being stamped graphene is not oxidized corrosion.
Experiment three：The method for the graphene protection metal erosion that a kind of crystal face of this experiment relies on is to enter according to the following steps
OK：
(1), graphene is grown in the copper foil surface of Cu (111) crystal face with the method for aumospheric pressure cvd；
(2) copper foil sample that, will be covered with graphene is placed on above water-bath, is smoked with hot water and steam, temperature is about 50
DEG C, time 8h；
(3) after, sample has been smoked, with optics microscope direct observing, you can see protective effect of the graphene to copper foil.
Under this experimental condition, graphene serves extraordinary protective effect to Cu (111).Copper foil covered with graphene
It is not oxidized corrosion.
Experiment four：The method for the graphene protection metal erosion that a kind of crystal face of this experiment relies on is to enter according to the following steps
OK：
(1), graphene is grown in the copper foil surface of Cu (311) crystal face with the method for aumospheric pressure cvd；
(2) copper foil sample that, will be covered with graphene is placed on above water-bath, is smoked with hot water and steam, temperature is about 50
DEG C, time 8h；
(3) after, sample has been smoked, with optics microscope direct observing, you can see protective effect of the graphene to copper foil.
Under this experimental condition, graphene serves extraordinary protective effect to Cu (311).Copper foil covered with graphene
It is not oxidized corrosion.
Above-mentioned experiment one is to the method for experiment four, and selection is matched preferably with graphene crystal face, and coupling is stronger
Copper foil crystal face.It can be seen that on these crystal faces, either autoxidation or hot water and steam is smoked, and graphene can be very
Good protection copper foil, not oxidized corrosion.
Comparative example：From with graphene lattice mismatch, the weaker copper crystal face of coupling, research graphene to they
Protective effect, carry out according to the following steps：
Experiment one：The method for the graphene protection metal erosion that a kind of crystal face of this experiment relies on is to enter according to the following steps
OK：
(1), graphene is grown in the copper foil surface of Cu (100) crystal face with the method for aumospheric pressure cvd；
(2) copper foil sample that, will be covered with graphene is positioned in air, autoxidation, and the time is 2 years；
(3), after sample autoxidation, with optics microscope direct observing, you can see that protection of the graphene to copper foil is made
With.
Under this experimental condition, graphene does not play a protective role to Cu (100).It can see by Fig. 3 a, covered with stone
The copper foil of black alkene is oxidized seriously corroded.
Experiment two：The method for the graphene protection metal erosion that a kind of crystal face of this experiment relies on is to enter according to the following steps
OK：
(1), graphene is grown in the copper foil surface of Cu (410) crystal face with the method for aumospheric pressure cvd；
(2) copper foil sample that, will be covered with graphene is positioned in air, autoxidation, and the time is 2 years；
(3), after sample autoxidation, with optics microscope direct observing, you can see that protection of the graphene to copper foil is made
With.
Under this experimental condition, graphene does not play a protective role to Cu (410).It can see by Fig. 4 a, covered with stone
The copper foil of black alkene is oxidized seriously corroded.
To the above results, it can be seen that mismatched from Cu (100) or Cu (410) are this with graphene lattice, coupling
Weaker copper crystal face, graphene can not provide protective effect, and the copper covered with graphene is corroded seriously.Graphene is to copper foil
Protective effect shows very strong crystal face dependence.
Claims (9)
1. the method for the graphene protection metal erosion that a kind of crystal face relies on, it is characterised in that by graphene growth in specific crystalline substance
On the tinsel in face, tinsel is protected not to be corroded.
2. according to the method for claim 1, it is characterised in that graphene is to be grown in metal foil with chemical vapour deposition technique
On piece, or metal foil surface covered by branch mode.
3. according to the method for claim 2, it is characterised in that graphene high-temperature heating, autoxidation, vapor smoke or
Copper foil is protected not to be corroded under the environment such as person's seawater.
4. according to the method for claim 1, it is characterised in that the tinsel includes copper foil, nickel foil etc., preferably
Copper foil.
5. according to the method for claim 1, it is characterised in that the specific copper crystal face be Cu (111), Cu (311) etc. with
Preferably all crystal faces of graphene Lattice Matching.
6. according to any described methods of claim 1-5, it is characterised in that methods described comprises the following steps：
(1) graphene, is grown in copper foil surface with the method for aumospheric pressure cvd；
(2) copper foil sample that, will be covered with graphene is positioned in air, autoxidation；
(3), after sample autoxidation, directly observe, you can see protective effect of the graphene to copper foil.
7. according to the method for claim 6, it is characterised in that methods described comprises the following steps：
(1) graphene, is grown in copper foil surface with the method for aumospheric pressure cvd；
(2) copper foil sample that, will be covered with graphene is positioned in air, autoxidation, and the time is 1 month~2 years；
(3), after sample autoxidation, with optics microscope direct observing, you can see protective effect of the graphene to copper foil.
8. according to the method described in claim any one of 1-6, it is characterised in that graphene can be provided 1 month to 2 copper foil
The anti-corrosion protection of year autoxidation process.
9. the method for the graphene protection metal erosion that a kind of crystal face relies on, it is characterised in that the anti-corrosion method is by right
It is required that described in method described in any one of 1-9, the graphene can provide 1 month to 2 years autoxidation process to graphene
Anti-corrosion protection.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109930156A (en) * | 2019-03-04 | 2019-06-25 | 无锡广兴东茂科技有限公司 | A method of for fashioned iron derusting anti-corrosive |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104807810A (en) * | 2014-01-23 | 2015-07-29 | 中国科学院上海微系统与信息技术研究所 | Method for using graphene to determining copper substrate surface crystal orientation |
| CN105819429A (en) * | 2016-03-10 | 2016-08-03 | 北京大学 | Preparation method of wrinkle-free graphene |
| CN106584976A (en) * | 2016-08-10 | 2017-04-26 | 上海交通大学 | High-conductivity graphene/copper-based layered composite material and preparation method thereof |
| CN206217267U (en) * | 2016-10-28 | 2017-06-06 | 史广洲 | A kind of Graphene Copper Foil diaphragm |
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2017
- 2017-10-17 CN CN201710961693.4A patent/CN107740118B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104807810A (en) * | 2014-01-23 | 2015-07-29 | 中国科学院上海微系统与信息技术研究所 | Method for using graphene to determining copper substrate surface crystal orientation |
| CN105819429A (en) * | 2016-03-10 | 2016-08-03 | 北京大学 | Preparation method of wrinkle-free graphene |
| CN106584976A (en) * | 2016-08-10 | 2017-04-26 | 上海交通大学 | High-conductivity graphene/copper-based layered composite material and preparation method thereof |
| CN206217267U (en) * | 2016-10-28 | 2017-06-06 | 史广洲 | A kind of Graphene Copper Foil diaphragm |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109930156A (en) * | 2019-03-04 | 2019-06-25 | 无锡广兴东茂科技有限公司 | A method of for fashioned iron derusting anti-corrosive |
| CN109930156B (en) * | 2019-03-04 | 2021-02-05 | 无锡广兴东茂科技有限公司 | Method for rust removal and corrosion prevention of section steel |
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| CN107740118B (en) | 2019-07-19 |
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