CN107740118B - 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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- CN107740118B CN107740118B CN201710961693.4A CN201710961693A CN107740118B CN 107740118 B CN107740118 B CN 107740118B CN 201710961693 A CN201710961693 A CN 201710961693A CN 107740118 B CN107740118 B CN 107740118B
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- graphene
- copper foil
- crystal face
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- copper
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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
Abstract
The present invention provides a kind of methods for the graphene protection metal erosion that crystal face relies on.Graphene is covered on metal foil surface using the methods of chemical vapor deposition by the method; utilize not penetrability and the interaction between metal substrate completely of graphene; metal to autoxidation, under hot water and steam is smoked and briny environment protects, and metal is protected not to be corroded.Method proposed by the present invention solves the problems, such as metal oxidation corrosion, by very simple method, realizes protection of the graphene to metal.
Description
Technical field
The present invention relates to a kind of methods for the graphene protection metal erosion that crystal face relies on.
Background technique
Copper is a kind of nonferrous materials having been widely cited, and has good electric conductivity, thermal conductivity, ductility, and molten
Point is lower, is easy to smelt, and processes convenient for extensive, inexpensive industrial production, therefore be widely used in electrical industry, light industry
Industry, machinery manufacturing industry, building industry, national defense industry etc..In the application of copper, a serious problem is copper containing oxygen corrosion:
When copper is exposed in air for a long time, oxygen and vapor in air can react with copper, generate the oxide of copper, thus
The quality of copper product is greatly influenced, or even directly affects the normal function of copper product.Currently, people are oxygen-containing in order to avoid copper
Corrosion, often using the other metals of plating, organic matter protective layer, protective oxide film etc., but they are often conductive, thermally conductive
Property is poor, and thicker, translucency is poor, protects the defects of incomplete.Since copper is using extremely wide, every year because of copper oxidation corrosion
It loses 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 a kind of monoatomic layer object with regular hexagon lattice structure that the carbon atom by sp2 hydridization is constituted
Matter.It has many advantages, such as high conductivity, high-termal conductivity, high mechanical strength, high light transmittance, at room temperature high chemical stability.Currently,
Using chemical vapor deposition method, can on single crystal Cu surface extensive, high efficiency, grow the monocrystalline stone of high quality at low cost
Black alkene.This makes graphene 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,
It, instead can accelerated corrosion by electrochemical corrosion effects long-term.Therefore, can people as long-term sudden and violent to graphene
Suspection was once being responded in the effective anticorrosive protection for the copper product being exposed under atmospheric environment.
Summary of the invention
Present invention firstly provides a kind of methods for the graphene protection metal erosion that crystal face relies on, by graphene growth in spy
Determine on the metal foil of crystal face, metal foil is protected not to be corroded.Graphene is to be grown in metal foil with chemical vapour deposition technique
On piece, or metal foil surface is covered by branch mode.The metal foil 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 in copper foil surface using common chemical vapor deposition method, utilizes special copper crystal face
Close coupling effect between graphene, protects copper foil.Method proposed by the present invention solves the metals such as copper and is oxidized
The problem of corrosion waste, by very simple method, realize the protection to metal.
The present invention has the advantages that
1. present invention firstly provides the methods for the graphene protection metal erosion that crystal face relies on；
2. the present invention covers upper graphene in copper foil surface using common chemical vapor deposition method, process is simple, pole
The earth reduces costs；
3. the present invention can protect copper foil, nickel foil etc. all stronger with graphene interlayer coupling with identical method
Metal crystal face.
4. the method for the present invention is simple, effective, at low cost, facilitate the practical application of metal foil protection.
Detailed description of the invention
Fig. 1 (a) is covered with the optical picture of Cu (111) of graphene after sample autoxidation 1 year；Fig. 1 (b) is covered with
Raman results of Cu (111) of graphene after sample autoxidation 1 year.The corresponding low-energy electron of Fig. 1 (c) Cu (111) copper foil
Diffraction (LEED) result.
Fig. 2 (a) is the optical picture for being covered with Cu (311) of graphene after sample autoxidation 1 year；Fig. 2 (b) Cu
(311) the corresponding low-energy electron diffraction of copper foil (LEED) result.
Fig. 3 (a) is the optical picture for being covered with Cu (100) of graphene after sample autoxidation 1 year；Fig. 3 (b) Cu
(100) the corresponding low-energy electron diffraction of copper foil (LEED) result.
Fig. 4 (a) is the optical picture for being covered with Cu (410) of graphene after sample autoxidation 1 year；Fig. 4 (b) Cu
(410) the corresponding low-energy electron diffraction of copper foil (LEED) result.
Specific embodiment
The present invention is described in further details combined with specific embodiments below, the raw material can unless otherwise instructed
It is gotten from open business.
Embodiment one: a kind of method for the graphene protection metal erosion that crystal face relies on includes the following steps:
(1), the method for graphene aumospheric pressure cvd is grown in copper foil surface；
(2), the copper foil sample that will be covered with graphene is placed in atmosphere, autoxidation, and the time is 1 month~2 years；
(3), after sample autoxidation, with optics microscope direct observing, i.e., it can be seen that graphene makees the protection of copper foil
With.
Wherein, graphene is to be grown on metal foil with chemical vapour deposition technique, or covered by branch mode
Metal foil surface.The metal foil 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 of above-mentioned Cu (111) crystal face for being covered with graphene prepared, place in atmosphere autoxidation 1 year.
After oxidation, optical picture is as shown in Figure 1a.Copper foil carries out Raman characterization after oxidation, as a result as shown in Figure 1 b.By Fig. 1 a it is found that
Copper foil after autoxidation 1 year, the region for having graphene to cover absolutely not are oxidized.Exposed copper foil region is oxidized to
Kermesinus.The copper foil that Fig. 1 b is covered with graphene does not see the corresponding Raman peaks of cuprous oxide, further confirms that copper foil by very
It protects well, is not oxidized.It can be seen that by graphene growth on the copper foil of Cu (111) crystal face, it can be in nature
Under conditions of oxidation, copper foil is protected not to be corroded well.
Test one: the method that the graphene that a kind of crystal face of this test relies on protects metal erosion be according to the following steps into
Row:
(1), the method for graphene aumospheric pressure cvd is grown in the copper foil surface of Cu (111) crystal face；
(2), the copper foil sample that will be covered with graphene is placed in atmosphere, autoxidation, and the time is 2 years；
(3), after sample autoxidation, with optics microscope direct observing, i.e., it can be seen that graphene makees the protection of copper foil
With.
Under this experimental condition, graphene plays extraordinary protective effect to Cu (111).
Test two: the method that the graphene that a kind of crystal face of this test relies on protects metal erosion be according to the following steps into
Row:
(1), the method for graphene aumospheric pressure cvd is grown in the copper foil surface of Cu (311) crystal face；
(2), the copper foil sample that will be covered with graphene is placed in atmosphere, autoxidation, and the time is 2 years；
(3), after sample autoxidation, with optics microscope direct observing, i.e., it can be seen that graphene makees the protection of copper foil
With.
Under this experimental condition, graphene plays 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.
Test three: the method that the graphene that a kind of crystal face of this test relies on protects metal erosion be according to the following steps into
Row:
(1), the method for graphene aumospheric pressure cvd is grown in the copper foil surface of Cu (111) crystal face；
(2), the copper foil sample that will be covered with graphene is placed on above water-bath, and 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, i.e., it can be seen that protective effect of the graphene to copper foil.
Under this experimental condition, graphene plays extraordinary protective effect to Cu (111).It is covered with the copper foil of graphene
It is not oxidized corrosion.
Test four: the method that the graphene that a kind of crystal face of this test relies on protects metal erosion be according to the following steps into
Row:
(1), the method for graphene aumospheric pressure cvd is grown in the copper foil surface of Cu (311) crystal face；
(2), the copper foil sample that will be covered with graphene is placed on above water-bath, and 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, i.e., it can be seen that protective effect of the graphene to copper foil.
Under this experimental condition, graphene plays extraordinary protective effect to Cu (311).It is covered with the copper foil of graphene
It is not oxidized corrosion.
Above-mentioned test one is to the method for test four, and selection is matched preferably with graphene crystal face, and coupling is stronger
Copper foil crystal face.It can be seen that either autoxidation or hot water and steam are smoked, and graphene can be very on these crystal faces
Good protection copper foil, not oxidized corrosion.
Comparative example: select with graphene lattice mismatch, the weaker copper crystal face of coupling, research graphene to they
Protective effect sequentially includes the following steps:
Test one: the method that the graphene that a kind of crystal face of this test relies on protects metal erosion be according to the following steps into
Row:
(1), the method for graphene aumospheric pressure cvd is grown in the copper foil surface of Cu (100) crystal face；
(2), the copper foil sample that will be covered with graphene is placed in atmosphere, autoxidation, and the time is 2 years；
(3), after sample autoxidation, with optics microscope direct observing, i.e., it can be seen that graphene makees the protection of copper foil
With.
Under this experimental condition, graphene does not play a protective role to Cu (100).It can see by Fig. 3 a, be covered with stone
The copper foil of black alkene is oxidized seriously corroded.
Test two: the method that the graphene that a kind of crystal face of this test relies on protects metal erosion be according to the following steps into
Row:
(1), the method for graphene aumospheric pressure cvd is grown in the copper foil surface of Cu (410) crystal face；
(2), the copper foil sample that will be covered with graphene is placed in atmosphere, autoxidation, and the time is 2 years；
(3), after sample autoxidation, with optics microscope direct observing, i.e., it can be seen that graphene makees the protection of copper foil
With.
Under this experimental condition, graphene does not play a protective role to Cu (410).It can see by Fig. 4 a, be covered with stone
The copper foil of black alkene is oxidized seriously corroded.
To the above results, it can be seen that select Cu (100) or Cu (410) is this and graphene lattice mismatches, coupling
Weaker copper crystal face, graphene can not provide protective effect, and the copper for being covered with graphene is corroded seriously.Graphene is to copper foil
Protective effect shows very strong crystal face dependence.
Claims (1)
1. a kind of method for the graphene protection metal erosion that crystal face relies on, which is characterized in that by graphene growth in specific crystalline substance
On the metal foil in face, metal foil is protected not to be corroded；
Described method includes following steps:
(1), the method for graphene aumospheric pressure cvd is grown in the copper foil surface of Cu (311) crystal face；
(2), the copper foil sample that will be covered with graphene is placed in atmosphere, autoxidation, and the time is 2 years；
(3), after sample autoxidation, with optics microscope direct observing, i.e., it can be seen that protective effect of the graphene to copper foil；
It is acted on using the close coupling between special copper crystal face and graphene, copper foil is protected；
Wherein, the copper foil for being covered with graphene is not oxidized corrosion.
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| CN107740118B true CN107740118B (en) | 2019-07-19 |
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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***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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- 2017-10-17 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***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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