CN108203813A - A kind of preparation method of in-situ preparation graphene - Google Patents
A kind of preparation method of in-situ preparation graphene Download PDFInfo
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- CN108203813A CN108203813A CN201711390206.XA CN201711390206A CN108203813A CN 108203813 A CN108203813 A CN 108203813A CN 201711390206 A CN201711390206 A CN 201711390206A CN 108203813 A CN108203813 A CN 108203813A
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- graphene
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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
- 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
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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
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0254—Physical treatment to alter the texture of the surface, e.g. scratching or polishing
- C23C16/0263—Irradiation with laser or particle beam
Abstract
The invention discloses a kind of preparation methods of in-situ preparation graphene.This method utilizes plasma enhanced chemical vapor deposition technology, and using steel ball as base material, by the use of argon gas, nitrogen and methane as air source, graphene is prepared in situ in substrate under the collective effect of radio-frequency power supply and pulsed negative bias.Its main feature is that：Equipment is simple, temperature is low, yield is high, production cost is low, it is reproducible, be easy to operate and control, between substrate and polishing stainless steel steel disc friction coefficient lower it is with obvious effects.And it can effectively avoid graphene low with substrate bond strength in this way, lubricant effect not had so as to cause the graphene of substrate surface.The method is applicable not only to stainless steel surface, is equally applicable, has broad application prospects in Material Fields such as cast iron, alloy, ceramics, high molecular materials.Therefore the method application potential that graphene is prepared in situ that the invention is provided is huge.
Description
Technical field
The present invention relates to a kind of preparation methods of in-situ preparation graphene, belong to chemical vapor deposition field.The present invention can be used for
Metal, ceramics and the wear-resistant and reduction friction coefficient on polymerizable material surface.
Background technology
For mechanical moving element, friction and wear is still the principal mode of energy dissipation, this also leads to material
Unnecessary loss.Lubriation material technology is to reduce friction, reduce or avoid wearing, extend equipment life, improve working efficiency
Most effective means.Data is shown according to statistics, and the nearly 1/3 disposable energy is for overcoming friction, and more than 50% mechanized equipment
Serious accident results from lubrication failure and excessive wear.Efforts To Develop lubriation material is studied can significantly energy saving and money with application
Source is improved the ecological environment, and is eliminated safe hidden trouble, and improves quality of life.Therefore, the resource increasingly sharpened, the energy are faced in the whole world
And under the severe situation of the problems such as environment, wear-resistant and reduction friction becomes an important indicator of material.For example,《Country
Medium-term and long-term science and technology development planning outline》（2006-2020）In 16 key special subjects listed, empty day and ocean skill
Art, large aircraft, equipment manufacturing, manned space flight and moon exploration program, electronic product power-saving technology etc. are close with high-performance lubriation material
Cut phase is closed, lubriation material technology become above-mentioned key special subjects successful implementation and the most important guarantee of long-life reliability service it
One.Two-dimensional material is attracted wide attention because of the weak model ylid bloom action of its interlayer and excellent tribological property in recent years.And stone
Black alkene has excellent mechanical property, optical property, electric property, thermal property, chemical property etc., is well suited as protection and applies
Layer.It is with a wide range of applications simultaneously in fields such as electrochemistry, machinery, tribology, nuclear energy, aerospaces.
However a great problem is always existed in graphene development and application, graphene is limited to material, leads to it
It is expensive, while graphene surface is smooth, is unfavorable for the combination with other functional materials, which greatly limits stones
The popularization and application of black alkene.At present, scientists from all over the world and industrial circle personage have been attempted through such as micromechanics stripping, chemical stripping, outer
The methods of epitaxial growth, graphite intercalation, redox, prepares graphene.And these method preparation conditions are harsh（High temperature, high pressure）, into
This height causes serious pollution to the environment（201110204967.8 and 201610704984 .0 of patent）.The reason of leading to weak binding power is
It since graphene surface does not have activating functional group, is chemically bonded it is difficult to be formed with substrate so that graphene and substrate bond strength
It reduces.
Chemical deposition is chemically reacted under higher temperature conditions in gaseous state by reactive material, and annealing generation is solid
State electrodeposition substance is in substrate surface.This method is considered as the graphene for being most hopeful to prepare high quality, large area, is production
The most potential industrialization method of graphene film.
Chemical deposition prepares the temperature of graphene between 500 ~ 1300 DEG C at present（Patent 201110204967.8）, and
And the process prepared produces environment pollution.
In conclusion the preparation of research graphene and generalization have important scientific meaning and application prospect.
Invention content
Problem to be solved by this invention is overcome the deficiencies in the prior art, and using plasma enhances chemical vapor deposition
Method, provides that a kind of equipment is simple, temperature is low, yield is high, production cost is low, the reproducible, graphite that is easy to operate and control
The preparation method of alkene.
A kind of preparation method of in-situ preparation graphene, includes the following steps：
1) substrate is cleaned
Substrate after advance cleaning is put into acetone, ethyl alcohol and is cleaned by ultrasonic each 20 ~ 40 minutes, is then dried with non-dust cloth；
2) it is packed into sample
Substrate after cleaning is transferred to vacuum chamber, is placed on the substrate disk of lower part, substrate disk and negative bias pulsed power phase
Even；
3) it vacuumizes and cleans again
Intracavitary is vacuumized successively using mechanical pump, lobe pump and molecular pump, until intracavitary vacuum is less than 1.0 × 10-3Pa；It closes
Molecular pump is closed, intracavitary is passed through argon gas, and plasma is carried out under conditions of the V of pulsed bias -800 ~ -600, duty ratio 50 ~ 70%
Cleaning 20 ~ 50 minutes, to remove the burr of remained on surface and pollutant；
4) plasma low temperature nitriding
Be passed through nitrogen, under conditions of the V of pulsed bias -900 ~ -400, about 10 ~ 30 Pa of deposition pressure, duty ratio 50 ~ 70% Hong
Hit substrate 1 ~ 3 hour, vacuum chamber diameter and height are all 200 ~ 500 mm, top crown diameter and bottom crown a diameter of 100 ~ 600
Mm, the distance between they are 30 ~ 110 mm；
5) graphene film is prepared
Methane is passed through, is prepared under conditions of the V of pulsed bias -800 ~ -300, about 5 ~ 30 Pa of deposition pressure, duty ratio 50 ~ 70%
Graphene 0.5 ~ 3 hour.
The volume flow of the argon gas is 100 ~ 300 SCCM；The volume flow of nitrogen is 10 ~ 40 SCCM；The body of methane
Product flow is 5 ~ 30 SCCM.
Power supply used unconventional single radio-frequency power supply for radio-frequency power supply and the pulse power.In this system, radio frequency
Power supply can control the density of plasma, and DC negative bias voltage can control the energy of plasma and the pulse power that can prepare
The graphene of itself excellent properties is not destroyed, and triplicity is excellent to achieve the effect that.
The substrate is stainless steel, cast iron, alloy, ceramics or high molecular material.
The present invention can control the temperature for preparing graphene between 200 ~ 400 DEG C, can effectively reduce the group of matrix
Knit variation.The Basement surge that the present invention is handled is greatly lowered, and increases work longevity of the substrate under high intensity work condition environment
Life.
For the present invention using plasma enhanced chemical vapor deposition technology in-situ preparation graphene, the method has technique letter
It is single, temperature is low, yield is high, production cost is low, advantages, the tissue that can effectively reduce matrix such as reproducible, easily operated become
Change, while preparation method is convenient and efficient, excellent properties at low cost and not destroying graphene itself.Therefore, the invention application back of the body
Scape is extensive and plays an important role.
Description of the drawings
Fig. 1 is the Raman spectrogram of in-situ preparation graphene.
Fig. 2 is the friction coefficient comparison diagram that surface in situ generates graphene steel ball and original steel ball.
Specific embodiment
The present invention proposes a kind of preparation method of in-situ preparation graphene, below the invention will be further described.
Embodiment 1：
The steel ball five of any surface finish is selected first, with dilute hydrochloric acid solution prerinse, it is waited to put it into acetone, second again after drying
It is cleaned by ultrasonic in alcohol each 20 minutes, takes out steel ball, be transferred to rapidly in vacuum chamber substrate after being dried with non-dust cloth, start to vacuumize.
Secondly, treat that vacuum is extracted into less than 1.0 × 10-3During Pa, it is passed through argon gas（150 SCCM）, adjustment air pressure is about 30 Pa, in pulse
In the case that -600 V of bias, duty ratio are 60%, plasma clean is carried out, continues 40 minutes.After the completion of cleaning, it is passed through nitrogen
Gas（30 SCCM）, it is about 25 Pa to adjust air pressure, bombards steel ball surface under conditions of -500 V of pulsed bias, duty ratio 60%,
Time is 1.5 hours.Finally it is passed through methane（25 SCCM）, it is about 25 Pa to adjust air pressure, in -600 V of pulsed bias, duty ratio
Graphene is prepared in situ under conditions of 60%, the time is 1 hour.
Embodiment 2：
The steel ball three of any surface finish is selected first, then to these three steel ball surface in-situ preparation graphenes.As Fig. 1 institutes
Show, Raman spectrum shows prepared graphene, and there are three apparent characteristic peak, as D peaks, G peaks and 2D peaks, wave number difference
It is 1360,1600 and 2920.It tests in triplicate, to ensure the accuracy of experimental result.
Embodiment 3：
The steel ball nine of any surface finish is selected first, then to this nine steel ball surface in-situ preparation graphenes.Steel ball is carried out
Friction test, as shown in Figure 2, average friction coefficient can between the surface in situ generation steel ball of graphene and polishing stainless steel steel disc
To reach 0.028 or so, and average friction coefficient is up between the steel ball and polishing stainless steel steel disc handled without the method
0.08 or so.It tests in triplicate, it is ensured that the accuracy of experimental result shows that surface in situ generation graphene method can be substantially
Degree reduces the friction coefficient between steel base and polishing stainless steel steel disc, and friction coefficient is reduced 65%.
Claims (4)
1. a kind of preparation method of in-situ preparation graphene, it is characterised in that include the following steps：
1) substrate is cleaned
Substrate after advance cleaning is put into acetone, ethyl alcohol and is cleaned by ultrasonic each 20 ~ 40 minutes, is then dried with non-dust cloth；
2) it is packed into sample
Substrate after cleaning is transferred to vacuum chamber, is placed on the substrate disk of lower part, substrate disk and negative bias pulsed power phase
Even；
3) it vacuumizes and cleans again
Intracavitary is vacuumized successively using mechanical pump, lobe pump and molecular pump, until intracavitary vacuum is less than 1.0 × 10-3Pa；It closes
Molecular pump is closed, intracavitary is passed through argon gas, and plasma is carried out under conditions of the V of pulsed bias -800 ~ -600, duty ratio 50 ~ 70%
Cleaning 20 ~ 50 minutes, to remove the burr of remained on surface and pollutant；
4) plasma low temperature nitriding
Be passed through nitrogen, under conditions of the V of pulsed bias -900 ~ -400, about 10 ~ 30 Pa of deposition pressure, duty ratio 50 ~ 70% Hong
Hit substrate 1 ~ 3 hour, vacuum chamber diameter and height are all 200 ~ 500 mm, top crown diameter and bottom crown a diameter of 100 ~ 600
Mm, the distance between they are 30 ~ 110 mm；
5) graphene film is prepared
Methane is passed through, is prepared under conditions of the V of pulsed bias -800 ~ -300, about 5 ~ 30 Pa of deposition pressure, duty ratio 50 ~ 70%
Graphene 0.5 ~ 3 hour.
2. preparation method as described in claim 1, it is characterised in that the volume flow of the argon gas is 100 ~ 300 SCCM；Nitrogen
The volume flow of gas is 10 ~ 40 SCCM；The volume flow of methane is 5 ~ 30 SCCM.
3. preparation method as described in claim 1, it is characterised in that power supply used is radio-frequency power supply and the pulse power.
4. preparation method as described in claim 1, it is characterised in that the substrate is stainless steel, cast iron, alloy, ceramics or height
Molecular material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711390206.XA CN108203813A (en) | 2017-12-21 | 2017-12-21 | A kind of preparation method of in-situ preparation graphene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711390206.XA CN108203813A (en) | 2017-12-21 | 2017-12-21 | A kind of preparation method of in-situ preparation graphene |
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| CN108203813A true CN108203813A (en) | 2018-06-26 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108796176A (en) * | 2018-08-15 | 2018-11-13 | 江苏大学 | A method of induction spheroidal graphite cast-iron in-situ authigenic graphene |
| CN110970289A (en) * | 2018-10-01 | 2020-04-07 | 三星电子株式会社 | Method of forming graphene |
| WO2021109813A1 (en) * | 2019-12-04 | 2021-06-10 | 江苏菲沃泰纳米科技有限公司 | Coating apparatus and application thereof |
| CN115519840A (en) * | 2022-09-22 | 2022-12-27 | 北京石墨烯技术研究院有限公司 | Metal graphene composite material, preparation method and application thereof, and electronic component |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665942A (en) * | 2008-09-04 | 2010-03-10 | 中国科学院兰州化学物理研究所 | Method for preparing ultra-lubricating compound carbon film material |
| CN102260858A (en) * | 2010-05-26 | 2011-11-30 | 中国科学院物理研究所 | Method for directly growing graphine on various substrates |
| CN104561909A (en) * | 2015-01-27 | 2015-04-29 | 大连理工常州研究院有限公司 | Ionitriding/arc ion plating surface composite modification apparatus and method |
-
2017
- 2017-12-21 CN CN201711390206.XA patent/CN108203813A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665942A (en) * | 2008-09-04 | 2010-03-10 | 中国科学院兰州化学物理研究所 | Method for preparing ultra-lubricating compound carbon film material |
| CN102260858A (en) * | 2010-05-26 | 2011-11-30 | 中国科学院物理研究所 | Method for directly growing graphine on various substrates |
| CN104561909A (en) * | 2015-01-27 | 2015-04-29 | 大连理工常州研究院有限公司 | Ionitriding/arc ion plating surface composite modification apparatus and method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108796176A (en) * | 2018-08-15 | 2018-11-13 | 江苏大学 | A method of induction spheroidal graphite cast-iron in-situ authigenic graphene |
| CN110970289A (en) * | 2018-10-01 | 2020-04-07 | 三星电子株式会社 | Method of forming graphene |
| CN110970289B (en) * | 2018-10-01 | 2024-04-05 | 三星电子株式会社 | Method for forming graphene |
| WO2021109813A1 (en) * | 2019-12-04 | 2021-06-10 | 江苏菲沃泰纳米科技有限公司 | Coating apparatus and application thereof |
| CN115519840A (en) * | 2022-09-22 | 2022-12-27 | 北京石墨烯技术研究院有限公司 | Metal graphene composite material, preparation method and application thereof, and electronic component |
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Application publication date: 20180626 |