CN104789941A - Method for graphene chemical bonding coating by using chemical vapor deposition method - Google Patents
Method for graphene chemical bonding coating by using chemical vapor deposition method Download PDFInfo
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- CN104789941A CN104789941A CN201510230922.6A CN201510230922A CN104789941A CN 104789941 A CN104789941 A CN 104789941A CN 201510230922 A CN201510230922 A CN 201510230922A CN 104789941 A CN104789941 A CN 104789941A
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Abstract
The invention discloses a method for graphene chemical bonding coating by using a chemical vapor deposition method. The method comprises the following steps: I, preheating graphene oxide at 500-700 DEG C; II, when ethylene and argon are introduced, simultaneously blowing the preheated graphene oxide into a high-temperature reaction cavity; III, performing phi-bond fission on ethylene so as to generate a free radical .CH2-CH2. when the temperature inside the reaction cavity is about 800-1000 DEG C, subsequently under the action of the ethylene free radical, performing high-temperature thermal reduction on oxygen-containing groups hydroxyl and carboxyl carried by graphene oxide so as to generate arene free radicals GP-CH.-CH2. or GP-CH2-CH2., thereby obtaining a substrate with free radicals; IV, performing argon auxiliary deposition on the free radicals at high temperature so as to be adhered to the substrate in the presence of argon; V, discharging the generated byproducts CO2 and H2O along with argon, wherein the preheat of the byproducts high-temperature gases can be used for preheating graphene oxide. Due to the mode that graphene monomers and a graphene monomer and the substrate are both bonded by using chemical bonds, a coated layer is sufficient in bonding force.
Description
Technical field
The invention belongs to graphene film production field, be specifically related to a kind of method that chemical Vapor deposition process carries out Graphene chemical bonding coating.
Background technology
The graphite of Graphene and individual layer is a kind of material of the individual layer sheet structure be made up of carbon atom, is a kind ofly to form with sp2 hybridized orbital the flat film that hexangle type is honeycomb lattice by carbon atom, only has the two-dimensional material of a carbon atom thickness.Graphene had once once been considered to rationalistic material, because think that it can not stable existence.But after the people such as Geim in 2004 have found self-existent Graphene, in succession there is some cut-and-try works current carrier demonstrated in Graphene to be the dirac fermion not having rest mass, from then on started the research boom of Graphene.
At present, Graphene has been proved to be in nano electron device, single-electronic transistor, thermoelectricity, has had good application prospect in conductive film etc.How preparing the large-area graphene film of high quality is on a large scale a research emphasis, and the graphene growth method that institute obtains mainly contains: mechanically peel method, and the Graphene quality obtained is high but area is little, and efficiency is also very low; Oxidation reduction process, simple to operate and cost is low, but Graphene can cause the disappearance of some physical and chemical performances in redox processes, and the Graphene area obtained is also very little; Silicon carbide cracking process, can obtain large-area Graphene, but the quality of Graphene is very large by substrate effect, and growth cost is also higher, needs vacuum environment; Chemical Vapor deposition process, is applicable to preparing Graphene on a large scale, but larger by the constraint of substrate.
Common metal substrate in current chemical Vapor deposition process, as Cu, Ni, Ru etc., for metal substrate, all easily has certain defect in preparation process: sputtering.Because metal at high temperature easily condenses into island particle, preparation and the Graphene area that obtains is too little, and tinsel easily bends generation gauffer in operation, thus affect the planarization of substrate.And use physical bond between graphene film and matrix, easily degrade.Another kind of more common graphene film material Graphene is infiltrated functional film, coating or other functional materialss combined by Van der Waals force and π interorbital reactive force.Graphene film interlayer and the faint non covalent bond be present between graphite and substrate limit their industrial application to a great extent.2012, James professor Lee of Ohio State Univ-Columbus USA waits the erosion of the vacuum pressure hot soarfing of using function graphene nano paper first to obtain a kind of " one-step moulding method " of chemical bonding Graphene coating, in Graphene plating layer research, achieve breakthrough progress.The appearance of chemical bonding Graphene coating substantially improves the atom of edge in conjunction with network structure, can increase the application of Graphene coating well.
The chemical Vapor deposition process that the present invention intends proposing carries out Graphene chemical bonding coating, more existing research has three large outstanding advantages, one is that operation is simple and easy realizes mass production, and two is can carry out arbitrary shape matrix coating under gas is assisted, and three is have very high bonding force between Graphene and matrix.Except this, also having made full use of preheating and the chemical energy of waste gas in reaction process, is comparatively simple, the pollution-free and lower-cost scheme of a kind of technical process.
Summary of the invention
The object of the invention is to realize Graphene chemical bonding coating, solve the problem that Graphene physics coating easily degrades, and the superconductivity of graphene film can be applied to industrial production and carry out optimized production process, realize that technique is simple, practicality is wide, raw material sources are extensive, pollution-free, lower-cost Graphene bonding coating production method.
The concrete grammar realizing such scheme is, a kind of chemical Vapor deposition process carries out the method for Graphene chemical bonding coating, obtains mainly through ethene vacuum high-temperature thermal reduction graphene oxide.The first step, carries out preheating by graphene oxide at 500 ~ 700 DEG C; Second step, along with passing into of ethene and argon gas, enters pyroreaction chamber by the graphene oxide of preheating together drum; 3rd step, reaction chamber cavity temperature is about 800-1000 DEG C, ethene at this temperature, free radical (CH2-CH2) is generated through π bond rupture process, subsequently on graphene oxide with oxy radical hydroxyl (-OH) and carboxyl (-COOH) generated (GP-CH-CH2) or (GP-CH2-CH2) by high-temperature hot reduction, silicon chip also form silicon free radical (-Si) and obtains being with the substrate of free radical; 4th step, free free radical is at high temperature attached on substrate by argon gas assistant depositing, the same with substrate with Graphene, and graphene nano interlayer is that the chemical bond formed by original position is connected; 5th step, the by product CO of generation
2and H
2o discharges with argon gas, and the preheating of by product high-temperature gas can carry out the preheating of graphene oxide.This Graphene coating that high temperature reduction is obtained under argon shield and matrix are fitted more uniformly, more controlled.The reduction of this high-temperature hot obtains Graphene coating and at high temperature deposits, and more can stand high-temperature fusant contact friction, not easily degrade, and true meaning achieves one-step moulding, obtains a kind ofly to realize the controlled novel coating technology of coating performance by air temperature and current.
A kind of chemical Vapor deposition process of the present invention carries out the method for Graphene chemical bonding coating, and the Graphene raw material that the method uses is stannic oxide/graphene nano lamella.
A kind of chemical Vapor deposition process of the present invention carries out the method for Graphene chemical bonding coating, the reducing gas ethene that the method uses or acetylene.
A kind of chemical Vapor deposition process of the present invention carries out the method for Graphene chemical bonding coating, and the assist gas that the method uses is argon gas (Ar).
A kind of chemical Vapor deposition process of the present invention carries out the method for Graphene chemical bonding coating, and the mass ratio of week reduction gas and graphene-containing raw material is (4.5-5.6): 1, optimum quality ratio 5:1.
A kind of chemical Vapor deposition process of the present invention carries out the method for Graphene chemical bonding coating, and the volume ratio of pre-heating fuel and air is (6-7): 1.
A kind of chemical Vapor deposition process of the present invention carries out the method for Graphene chemical bonding coating, and mixed vapour deposition temperature is 800-1000 DEG C.
A kind of chemical Vapor deposition process of the present invention carries out the method for Graphene chemical bonding coating, before mixing, graphene oxide is preheated to 500-700 DEG C.
A kind of chemical Vapor deposition process of the present invention carries out the method for Graphene chemical bonding coating, and preheating high-temperature gas used comprises the by product CO of subsequent oxidation reduction
2with water vapour, react assist gas Ar gas and react remaining ethene (or acetylene), ethene (or acetylene) is simultaneously also as fuel, and hankering oxygenant used is in advance oxygen or air.
A kind of chemical Vapor deposition process of the present invention carries out the method for Graphene chemical bonding coating, and preheating rear oxidation reduction phase uses electrically heated, all needs to carry out vacuumizing process before preheating and heating.
Preheating not only can reduce the consumption of electric energy in subsequent reactions, improves the Graphene reducing degree in product, can also reduce the duration of reaction.Hanker the by product CO that preheating high-temperature gas used comprises subsequent oxidation reduction in advance
2with water vapor, react assist gas Ar gas and react remaining ethene (or acetylene).Because reaction is pyroreaction, the gas of eliminating is also the high-temperature gas that temperature is at least 1000 DEG C, therefore utilizes the discarded remaining temperature of eliminating to carry out preheating.Meanwhile, reacting remaining ethene (or acetylene) is a kind of inflammable substance, directly the emptying waste causing the energy.Be mixed into auxiliary fuel oxygen or air at high temperature, make full use of remaining chemical energy.This three portion gas as pre-heating fuel, was both prevented hot driving, effectively make use of energy again, achieved many things at one stroke by the present invention.
The advantage that the present invention has:
Compared with traditional calcium carbide production method, the present invention adopts chemical vapour deposition (Chemical VaporDeposition, prepared by method CVD) is continuously fine and close and the Graphene coating that thickness is controlled, and the mode wherein between Graphene monomer and Graphene monomer, all by chemical bonding between Graphene monomer and base material guarantees that coating has enough bonding forces.The reductive agent that the method uses without any injury to human body, does not corrode boiler, does not need loaded down with trivial details starting material preparatory phase.Because reductive agent is inflammable gas, reacting remaining raw material can also burn fully, is pre-heating stage heat supply.Whole step of reaction does not have toxic gas to discharge, not atmosphere pollution, free from environmental pollution.In addition, reaction method is more convenient, feeds intake conveniently, reduces the labour intensity of workman, significantly improve work situation, and enterprise is used for the cost of labor force aspect by reducing.In a word, coating linkage force is large, contaminative is low, utilization ratio is high, speed of reaction is fast and operation difficulty is low.
Adopt the nanoscale twins of graphene oxide as oxidic raw materials, on graphene oxide with-COOH and-OH at high temperature just can be reduced, for ensureing the homogeneity of each temperature of reaction, need graphene oxide to carry out preheating at 500 ~ 700 DEG C, the dispersion of Graphene can be promoted and be heated evenly.Adopt the ethene (or acetylene) of gas as reductive agent, increase the contact surface of reactant, sufficient reacting carries out, and improves the utilization ratio of response capacity and raw material.
The high temperature secondary product that reaction is got rid of and flammable ethene (or acetylene) combustion heat supplying comprised thereof, make energy consumption of reaction reduce, and improve the utilization ratio of raw material.
Accompanying drawing explanation
Fig. 1 is that a kind of chemical Vapor deposition process of the present invention carries out Graphene chemical bonding coating reaction process schematic diagram.
In figure: 1-π bond rupture process, 2-high-temperature hot is reduced, and 3-is with the substrate of free radical, 4-argon gas assistant depositing.
Embodiment
A kind of chemical Vapor deposition process of the present invention carries out Graphene chemical bonding coating reaction process as shown in Figure 1.The first step, carries out preheating by graphene oxide at 500-700 DEG C; Second step, along with passing into of ethene and argon gas, enters pyroreaction chamber by the graphene oxide of preheating together drum; 3rd step, reaction chamber cavity temperature is about 800-1000 DEG C, at this temperature, ethene experience π bond rupture process 1 generates free radical (CH2-CH2), subsequently under the effect of ethylene free radical, graphene oxide with oxy radical hydroxyl (-OH) and carboxyl (-COOH) by high-temperature hot reductase 12 generate aromatic hydrocarbons free radical (GP-CH-CH2) or (GP-CH2-CH2).Substrate (as silicon chip) surface also creates the substrate 3 (as-Si) of band free radical; 4th step, free free radical is at high temperature attached on substrate by argon gas assistant depositing 4; 5th step, the by product CO of generation
2and H
2o discharges with argon gas, and the preheating of by product high-temperature gas can carry out the preheating of graphene oxide.
Embodiment 1: Ethylene reduction Graphene scheme
The stannic oxide/graphene nano sheet of 2g is placed in preheating cavity room and is heated to 500-700 DEG C, preset the temperature of high temperature reaction stove to 800-1000 DEG C, stannic oxide/graphene nano sheet after preheating is inserted in high temperature reaction stove, and pass into the ethene of about 320mL and the Ar gas of equivalent, after ethene enters high temperature reaction stove, after π bond rupture process 1, high-temperature hot reductase 12 graphene oxide generates aromatics free radical, after abundant reaction 15min, free radical obtains the Graphene coating that connected by in-situ chemical key through the assistant depositing 4 of argon gas to the substrate 3 of band free radical.Discharge high-temperature gas and ethene remnants, passed into preheater zone of heating after being mixed into about 224mL air, one is remaining temperature preheating, and two is fully react remaining ethene.If transformation efficiency is 100%, estimate that obtaining solid film quality is about 1.2g.
Embodiment 2: Acetylene Reduction Graphene
The stannic oxide/graphene nano lamella of 2g is heated to 500-700 DEG C as in preheating chamber, preset the temperature of high temperature reaction stove to 800-1000 DEG C, stannic oxide/graphene nano sheet after preheating is inserted in high temperature reaction stove, and pass into the acetylene of about 370mL and the Ar gas of equivalent, after ethene enters high temperature reaction stove, after π bond rupture process 1, high-temperature hot reductase 12 graphene oxide generates aromatics free radical, after abundant reaction 15min, free radical obtains the Graphene coating that connected by in-situ chemical key through the assistant depositing 4 of argon gas to the substrate 3 of band free radical.Discharge high-temperature gas and ethene remnants, passed into preheater zone of heating after being mixed into about 186mL air, one is remaining temperature preheating, and two is that fully the remaining second of reaction lacks.If transformation efficiency is 100%, estimate that obtaining solid film quality is still about 1.2g.
Claims (10)
1. chemical Vapor deposition process carries out a method for Graphene chemical bonding coating, it is characterized in that: the first step, and graphene oxide is carried out preheating at 500-700 DEG C; Second step, along with passing into of ethene and argon gas, enters pyroreaction chamber by the graphene oxide of preheating together drum; 3rd step, reaction chamber cavity temperature is at 800-1000 DEG C, and ethene at this temperature, generates free radical CH2-CH2 through π bond rupture process
subsequently on graphene oxide with oxy radical hydroxyl-OH and carboxyl-COOH generated GP-CH-CH2 or GP-CH2-CH2 by high-temperature hot reduction, silicon chip also form silicon free radical-Si and obtains being with the substrate of free radical; 4th step, free free radical is at high temperature attached on substrate by argon gas assistant depositing; 5th step, the by product CO of generation
2and H
2o discharges with argon gas, and the preheating of by product high-temperature gas can carry out the preheating of graphene oxide.
2. a kind of chemical Vapor deposition process according to claim 1 carries out the method for Graphene chemical bonding coating, it is characterized in that: graphene oxide raw material is stannic oxide/graphene nano lamella.
3. a kind of chemical Vapor deposition process according to claim 1 carries out the method for Graphene chemical bonding coating, it is characterized in that: reducing gas is ethene or acetylene.
4. a kind of chemical Vapor deposition process according to claim 1 carries out the method for Graphene chemical bonding coating, it is characterized in that: the mass ratio of week reduction gases argon and graphene-containing raw material is (4.5-5.6): 1.
5. a kind of chemical Vapor deposition process according to claim 4 carries out the method for Graphene chemical bonding coating, it is characterized in that: the mass ratio of week reduction gases argon and graphene-containing raw material is 5:1.
6. a kind of chemical Vapor deposition process according to claim 1 carries out the method for Graphene chemical bonding coating, it is characterized in that: the volume ratio of pre-heating fuel and air is (6-7): 1.
7. a kind of chemical Vapor deposition process according to claim 1 carries out the method for Graphene chemical bonding coating, it is characterized in that: mixed vapour deposition temperature is 800-1000 DEG C.
8. a kind of chemical Vapor deposition process according to claim 1 carries out the method for Graphene chemical bonding coating, it is characterized in that: before mixing, graphene oxide is preheated to 500-700 DEG C.
9. a kind of chemical Vapor deposition process according to claim 1 carries out the method for Graphene chemical bonding coating, it is characterized in that: preheating high-temperature gas used comprises the by product CO of subsequent oxidation reduction
2with water vapour, react assist gas argon gas and react remaining ethene or acetylene, ethene or acetylene are simultaneously also as fuel, and hankering oxygenant used is in advance oxygen or air.
10. a kind of chemical Vapor deposition process according to claim 1 carries out the method for Graphene chemical bonding coating, it is characterized in that: preheating rear oxidation reduction phase uses electrically heated, all needs to carry out vacuumizing process before preheating and heating.
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CN110761070A (en) * | 2018-07-25 | 2020-02-07 | 张文跃 | Preparation device and production process of graphene wire-plated coiled material |
CN110760089A (en) * | 2018-07-25 | 2020-02-07 | 张文跃 | Preparation device and production process of PET graphene coated coiled material |
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WO2014004514A1 (en) * | 2012-06-25 | 2014-01-03 | The Ohio State University | Covalently-bonded graphene coating and its applications thereof |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110761070A (en) * | 2018-07-25 | 2020-02-07 | 张文跃 | Preparation device and production process of graphene wire-plated coiled material |
CN110760089A (en) * | 2018-07-25 | 2020-02-07 | 张文跃 | Preparation device and production process of PET graphene coated coiled material |
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Application publication date: 20150722 |