CN103101908B - Method for preparing graphene film - Google Patents
Method for preparing graphene film Download PDFInfo
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- CN103101908B CN103101908B CN201310026890.9A CN201310026890A CN103101908B CN 103101908 B CN103101908 B CN 103101908B CN 201310026890 A CN201310026890 A CN 201310026890A CN 103101908 B CN103101908 B CN 103101908B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
- C01B32/192—Preparation by exfoliation starting from graphitic oxides
Abstract
The invention discloses a method for regulating the wetting property of a graphene film. The regulating method comprises the following specific steps of spraying oxidized graphene dispersion liquid on a heated substrate with a spray gun, then carrying out hydrazine steam reduction on an obtained sample. In the process, the surface structure of the graphene film is changed by the change of the substrate temperature, and in order to achieve the super-hydrophobic characteristic, carbon granule modification needs to be conducted on the sample. In short, conversion of hydrophilicity-hydrophobicity-strong hydrophobicity-super-hydrophobicity is realized by changing the surface structure.
Description
Technical field
The present invention relates to a kind of regulate and control the method for graphene film wettability.
Background technology
Along with the discovery of Graphene, the electrical properties of its excellence, mechanical property, thermal property and magnetic property cause the extensive concern of people.The method simultaneously preparing Graphene also emerges in an endless stream, and mainly contains micromechanics stripping method (Novoselov KS, Geim AK, Morozov S V, Jiang D, Zhang Y, Dubonos SV et al.Science2004,306,666), chemical method (Stankovich S, Dikin DA, et al.Carbon2007,45,1558) and epitaxy (Kim KS, ZhaoY, et al.Nature2009,457,706).In addition for the compatible aspect of material and environment, the surface of material serves very important effect.Under many circumstances, although properties of materials seems very excellent for some special application, to carry out processing to meet specific needs (Wang SR accordingly to its surface in a lot of situation, Zhang Y, Abibi N, Cabrales L, Langmuir2009,25,11078).And these seem more particularly important on matrix material, coating and Biomedia.Although have a large amount of work to concentrate in the preparation of Graphene at present, seldom having and the surface property of Graphene is studied, in order to expand the Application Areas of Graphene, must can obtain the Graphene of different surfaces characteristic.
Summary of the invention
Technical problem: the invention provides and a kind ofly can realize the method for graphene film from the regulation and control Graphene wettability of hydrophilic-hydrophobic-hydrophobic-super-hydrophobic transformation by force.
Technical scheme: the method for regulation and control Graphene wettability of the present invention, comprises the following steps:
First graphite oxide is added in solvent, ultrasonic disperse forms the graphene oxide dispersion of 0.1mg/ml to 5mg/l, then substrate is placed on warm table, regulate underlayer temperature, with spray gun, graphene oxide dispersion is sprayed onto on the substrate of heating, obtain graphene oxide film, then hydrazine steam reduction is carried out to gained graphene oxide film, the encloses container filling hydrazine is placed in by graphene oxide film, then 75 to 110 DEG C are heated to, and maintain 5h to 48h, finally carbon granule modification is carried out to hydrazine steam reduction products therefrom.
In the present invention, solvent is any one in water, ethanol, acetone, methyl alcohol, ether, chloroform, tetracol phenixin, benzene, propylene glycol monomethyl ether, butanols, butanone, dimethylbenzene, toluene, tetrahydrofuran (THF), methyl acetate, ethyl acetate, Virahol, normal heptane, normal hexane.
In the present invention, in the preparation process of graphene oxide film, substrate temperature is determined according to solvent species, and the corresponding relation of solvent species and underlayer temperature is: solvent is water, and underlayer temperature is arranged on 25-95 DEG C; Solvent is ethanol, and underlayer temperature is arranged on 25-70 DEG C; Solvent is acetone, and underlayer temperature is arranged on 25-50 DEG C; Solvent is methyl alcohol, and underlayer temperature is arranged on 25-60 DEG C; Solvent is ether, and underlayer temperature is arranged on 25-30 DEG C; Solvent is chloroform, and underlayer temperature is arranged on 25-56 DEG C; Solvent is tetracol phenixin, and underlayer temperature is arranged on 25-70 DEG C; Solvent is benzene, and underlayer temperature is arranged on 25-75 DEG C; Solvent is propylene glycol monomethyl ether, and underlayer temperature is arranged on 25-65 DEG C; Solvent is butanols, and underlayer temperature is arranged on 25-110 DEG C; Solvent is butanone, and underlayer temperature is arranged on 25-75 DEG C; Solvent is dimethylbenzene, and underlayer temperature is arranged on 25-130 DEG C; Solvent is toluene, and underlayer temperature is arranged on 25-105 DEG C; Solvent is tetrahydrofuran (THF), and underlayer temperature is arranged on 25-60 DEG C; Solvent is methyl acetate, and underlayer temperature is arranged on 25-53 DEG C; Solvent is ethyl acetate, and underlayer temperature is arranged on 25-70 DEG C; Solvent is Virahol, and underlayer temperature is arranged on 25-75 DEG C; Solvent is normal heptane, and underlayer temperature is arranged on 25-90 DEG C; Solvent is normal hexane, and underlayer temperature is arranged on 25-65 DEG C.
Carbon granule in the present invention is modified, and is by hydrazine steam reduction products therefrom, is placed in flame calcination completely 2 seconds to 5 seconds.
Carbon granule in the inventive method is modified, and flame is originated as the material of the burning burning generation flame of following arbitrary material is: candle, alcohol, gasoline, diesel oil and various alkane derivative.
In the present invention, the material of substrate is glass, silicon chip, tinsel, polydimethylsiloxane.
The present invention utilizes the change of spraying method bonded substrate temperature, the surface of different degree of roughness can be obtained, and then realize by the transformation of hydrophilic-hydrophobic-hydrophobic by force, in addition, super-hydrophobic in order to realize, must carry out carbon granule modification to its surface, and this process realizes by graphene film being placed in burning on flame.
Beneficial effect: the present invention compared with prior art, has the following advantages:
In existing data, just research graphene film itself has hydrophobic property, and people's research is not by changing the surface tissue of graphene film and then designing the film of different wetting.The present invention utilizes spraying to combine the method for heating first time, achieves the controlled synthesis of graphene film surface tissue, and then obtains the graphene film of different wetting.Graphene is owing to having extraordinary wear resistance, therefore, it has great application prospect in coating, but as coating, wettability will be a very important index, and different fields requires that coating has different wettabilitys, therefore, the present invention, in conjunction with practical situation, utilizes novel method to obtain to have the graphene film of different wetting.The method cost is low, simple, be easy to scale operation.The present invention utilizes temperature to regulate mating surface to modify, thus achieves the controlled modulation of graphene film surface wettability.The method is simple, and cost is low, can also realize scale operation.
Accompanying drawing explanation
The scanning electron microscopic picture of Fig. 1 to be ethanol be solvent, film surface when underlayer temperature is 25 DEG C.
Fig. 2 is the wetting angle test pattern of Fig. 1 sample, and wetting angle is 82 °.
Fig. 3 is ethanol is solvent, and underlayer temperature is the surface scan electron microscopic picture of 50 DEG C.
Fig. 4 is the wetting angle test pattern of sample in Fig. 3, and wetting angle is 105 °.
Fig. 5 is ethanol is solvent, and underlayer temperature is the surface scan electron microscopic picture of 70 DEG C.
Fig. 6 is the wetting angle test pattern of sample in Fig. 5, and wetting angle is 137 °.
Fig. 7 carries out the scanning electron microscopic picture after carbon granule modification to sample in Fig. 5.
Fig. 8 is the wetting angle test pattern of sample in Fig. 7, and wetting angle is 155 °.
Embodiment
Below by embodiment the present invention done and illustrate further.
Embodiment 1:
The first step, gets the graphene oxide alcohol dispersion liquid 200ml of 2mg/ml, and pours in spray gun.
Second step, by glass substrate priority acetone, ethanol, each ultrasonic cleaning of deionized water 30 minutes, then dry and be placed on warm table, temperature is set to 25 DEG C.
3rd step, utilizes spray gun to be sprayed onto on substrate by dispersion liquid, obtains graphene oxide film.
4th step, by the graphene oxide film of gained, puts into the container filling hydrazine hydrate, and good seal, be heated to 95 DEG C and maintain 24h, utilizing hydrazine steam to reduce to it, finally obtain graphene film.Fig. 1 is the surface topography picture of this film.
5th step, has then carried out wetting angle test to obtained graphene film, as shown in Figure 2, can find out, wetting angle is probably 82 °, and this shows that this film is hydrophilic (it is exactly hydrophilic for being less than 90 °).
Embodiment 2:
Regulate and control method is substantially with embodiment 1, and difference is: underlayer temperature is 50 DEG C, and the surperficial picture of gained sample, for shown in Fig. 3, compared to Fig. 1, seems more coarse; Fig. 4 is its wetting angle test pattern, and wetting angle is 105 °, shows hydrophobic property.
Embodiment 3:
Regulate and control method is substantially with embodiment 1, and difference is: underlayer temperature is 70 DEG C, and as shown in Figure 5, surface becomes more coarse compared to Fig. 1, Fig. 3 to the scanning electron microscope of gained sample; Fig. 6 is its wetting angle test pattern, and wetting angle is probably 137 °, presents strong hydrophobic property.Then carry out carbon granule modification to the strong hydrophobic sample obtained, burn by sample as in candle flame, Fig. 7 is its scanning electron microscopic picture, clearly, graphene film adheres to carbon granule; Fig. 8 is the test of its wetting angle, and wetting angle is 155 °, shows superhydrophobic characteristic.
Embodiment 4:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is water, and concentration is 0.1mg/ml, and substrate is silicon chip, and temperature is set to 25 DEG C, and the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 1, Fig. 2.
Embodiment 5:
Regulate and control method is substantially with embodiment 4, and difference is: temperature is set to 65 DEG C, and the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 3, Fig. 4.
Embodiment 6:
Regulate and control method is substantially with embodiment 4, and difference is: temperature is set to 95 DEG C, and the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 5, Fig. 6, carries out carbon granule modification to gained sample, and flame source is candle combustion, acquired results is similar to Fig. 7, Fig. 8.
Embodiment 7:
Regulate and control method is substantially with embodiment 1, difference is: solvent is acetone, graphite oxide dispersion concentration is 5mg/ml, substrate is copper sheet, and preparing in graphene oxide film process, underlayer temperature is set to 25 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test the Fig. 1 be very similar in embodiment 1, Fig. 2 acquired results.
Embodiment 8:
Regulate and control method is substantially with embodiment 7, and difference is: underlayer temperature is set to 35 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test the Fig. 3 be very similar in embodiment 1, Fig. 4 acquired results.
Embodiment 9:
Regulate and control method is substantially with embodiment 7, and difference is: underlayer temperature is set to 50 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test the Fig. 5 be very similar in embodiment 1, Fig. 6 acquired results.Then carry out carbon granule modification to sample, flame source is ethanol combustion, and the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, Fig. 8.
Embodiment 10:
Regulate and control method is substantially with embodiment 1, difference is: solvent is methyl alcohol, temperature in hydrazine steam reduction process is 75 DEG C and maintains 48h, preparing in graphene oxide film process, substrate temperature is set to 25 DEG C, the scanning electron microscopic picture of final gained sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained.
Embodiment 11:
Regulate and control method is substantially with embodiment 10, and difference is: substrate temperature is set to 40 DEG C, and the scanning electron microscopic picture of final gained sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained.
Embodiment 12:
Regulate and control method is substantially with embodiment 10, and difference is: substrate temperature is set to 60 DEG C, and the scanning electron microscopic picture of final gained sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained.Then by sample as on the flame of candle, the scanning electron microscopic picture of gained sample and wetting angle test be very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 13:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is chloroform, and the temperature of reduction is 110 DEG C and maintains 5h, and substrate temperature is set to 25 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained.
Embodiment 14:
Regulate and control method is substantially with embodiment 13, and difference is: substrate temperature is set to 35 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained.
Embodiment 15:
Regulate and control method is substantially with embodiment 13, and difference is: substrate temperature is set to 56 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained.Then be placed on the flame of gasoline combustion by sample, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 16:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is tetracol phenixin, and substrate temperature is set to 25 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained.
Embodiment 17:
Regulate and control method is substantially with embodiment 16, and difference is: substrate temperature is set to 50 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained.
Embodiment 18:
Regulate and control method is substantially with embodiment 16, and difference is: substrate temperature is set to 70 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained.Then sample is placed in the flame of diesel combustion, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 19:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is benzene, and substrate temperature is set to 25 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained.
Embodiment 20:
Regulate and control method is substantially with embodiment 19, and difference is: substrate temperature is set to 55 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained.
Embodiment 21:
Regulate and control method is substantially with embodiment 19, and difference is: substrate temperature is set to 75 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained.Then sample is placed in the flame of methyl hydride combustion, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 22:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is butanols, and substrate is polydimethylsiloxane and temperature is set to 25 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained.
Embodiment 23:
Regulate and control method is substantially with embodiment 22, and difference is: underlayer temperature is set to 85 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained.
Embodiment 24:
Regulate and control method is substantially with embodiment 22, and difference is: underlayer temperature is set to 110 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained.Then sample is placed in ethane burned flame, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 25:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is butanone, and substrate temperature is set to 25 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained.
Embodiment 26:
Regulate and control method is substantially with embodiment 25, and difference is: substrate temperature is set to 55 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained.
Embodiment 27:
Regulate and control method is substantially with embodiment 25, and difference is: substrate temperature is set to 75 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained.Then sample is placed in octane burned flame, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 28:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is toluene, and substrate temperature is set to 25 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained.
Embodiment 29:
Regulate and control method is substantially with embodiment 28, and difference is: substrate temperature is set to 75 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained.
Embodiment 30:
Regulate and control method is substantially with embodiment 28, and difference is: substrate temperature is set to 105 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained.Then sample is placed in hexane burned flame, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 31:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is tetrahydrofuran (THF), and substrate temperature is set to 25 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained.
Embodiment 32:
Regulate and control method is substantially with embodiment 31, and difference is: substrate temperature is set to 45 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained.
Embodiment 33:
Regulate and control method is substantially with embodiment 31, and difference is: substrate temperature is set to 60 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained.Then sample is placed in the flame of ethanol combustion, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 34:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is ethyl acetate, and substrate temperature is set to 25 DEG C, the result of the scanning electron microscopic picture of final sample and very similar Fig. 1, Fig. 2 gained of wetting angle test.
Embodiment 35:
Regulate and control method is substantially with embodiment 34, and difference is: substrate temperature is set to 50 DEG C, the result of the scanning electron microscopic picture of final sample and very similar Fig. 3, Fig. 4 gained of wetting angle test.
Embodiment 36:
Regulate and control method is substantially with embodiment 34, and difference is: substrate temperature is set to 70 DEG C, the result of the scanning electron microscopic picture of final sample and very similar Fig. 5, Fig. 6 gained of wetting angle test.Then sample is placed in dodecane burned flame, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 37:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is Virahol, and substrate temperature is set to 25 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained.
Embodiment 38:
Regulate and control method is substantially with embodiment 37, and difference is: substrate temperature is set to 55 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained.
Embodiment 39:
Regulate and control method is substantially with embodiment 37, and difference is: substrate temperature is set to 75 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained.Then sample is placed in the flame of ethanol combustion, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 40:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is normal hexane, and substrate temperature is set to 25 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained.
Embodiment 41:
Regulate and control method is substantially with embodiment 40, and difference is: substrate temperature is set to 45 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained.
Embodiment 42
Regulate and control method is substantially with embodiment 40, and difference is: substrate temperature is set to 65 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained.Then sample is placed in the flame of candle combustion, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 43
Regulate and control method is substantially with embodiment 1, and difference is: solvent is ether, and substrate temperature is set to 25 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained.
Embodiment 44
Regulate and control method is substantially with embodiment 43, and difference is: substrate temperature is set to 27 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained.
Embodiment 45
Regulate and control method is substantially with embodiment 43, and difference is: substrate temperature is set to 30 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained.Then sample is placed in the flame of candle combustion, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 46:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is propylene glycol monomethyl ether, and substrate temperature is set to 40 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained sample.
Embodiment 47:
Regulate and control method is substantially with embodiment 46, and difference is: substrate temperature is set to 55 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained sample.
Embodiment 48:
Regulate and control method is substantially with embodiment 46, and difference is: substrate temperature is set to 65 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained sample.Then sample is placed in the flame of candle combustion, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 49:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is dimethylbenzene, and substrate temperature is set to 85 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained sample.
Embodiment 50
Regulate and control method is substantially with embodiment 49, and difference is: substrate temperature is set to 105 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained sample.
Embodiment 51
Regulate and control method is substantially with embodiment 49, and difference is: substrate temperature is set to 130 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained sample.Then sample is placed in the flame of candle combustion, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 52
Regulate and control method is substantially with embodiment 1, and difference is: solvent is methyl acetate, and substrate temperature is set to 42 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained sample.
Embodiment 53
Regulate and control method is substantially with embodiment 52, and difference is: substrate temperature is set to 48 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained sample.
Embodiment 54
Regulate and control method is substantially with embodiment 52, and difference is: substrate temperature is set to 53 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained sample.Then sample is placed in the flame of candle combustion, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Embodiment 55:
Regulate and control method is substantially with embodiment 1, and difference is: solvent is normal heptane, and substrate temperature is set to 50 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 1, the result of Fig. 2 gained sample.
Embodiment 56:
Regulate and control method is substantially with embodiment 55, and difference is: substrate temperature is set to 70 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 3, the result of Fig. 4 gained sample.
Embodiment 57:
Regulate and control method is substantially with embodiment 55, and difference is: substrate temperature is set to 90 DEG C, and the scanning electron microscopic picture of final sample and wetting angle test are very similar to Fig. 5, the result of Fig. 6 gained sample.Then sample is placed in the flame of candle combustion, the scanning electron microscopic picture of gained sample and wetting angle test are very similar to Fig. 7, the result of Fig. 8 gained.
Claims (4)
1. prepare a method for graphene film, it is characterized in that, the method comprises the following steps:
First graphite oxide is added in solvent, ultrasonic disperse forms the graphene oxide dispersion of 2mg/ml to 5mg/l, then substrate is placed on warm table, regulate underlayer temperature, with spray gun, described graphene oxide dispersion is sprayed onto on the substrate of heating, obtain graphene oxide film, then hydrazine steam reduction is carried out to gained graphene oxide film, the encloses container filling hydrazine is placed in by graphene oxide film, then 75 to 110 DEG C are heated to, and maintain 5h to 48h, finally carbon granule modification is carried out to described hydrazine steam reduction products therefrom;
Described solvent is any one in ether, chloroform, tetracol phenixin, benzene, propylene glycol monomethyl ether, butanols, butanone, dimethylbenzene, toluene, tetrahydrofuran (THF), methyl acetate, ethyl acetate, Virahol, normal heptane, normal hexane, described carbon granule is modified, be by hydrazine steam reduction products therefrom, be placed in flame calcination completely 2 seconds to 5 seconds.
2. the method preparing graphene film according to claim 1, it is characterized in that, in the preparation process of described graphene oxide film, substrate temperature is determined according to solvent species, the corresponding relation of solvent species and underlayer temperature is: solvent is water, and underlayer temperature is arranged on 25-95 DEG C; Solvent is ethanol, and underlayer temperature is arranged on 25-70 DEG C; Solvent is acetone, and underlayer temperature is arranged on 25-50 DEG C; Solvent is methyl alcohol, and underlayer temperature is arranged on 25-60 DEG C; Solvent is ether, and underlayer temperature is arranged on 25-30 DEG C; Solvent is chloroform, and underlayer temperature is arranged on 25-56 DEG C; Solvent is tetracol phenixin, and underlayer temperature is arranged on 25-70 DEG C; Solvent is benzene, and underlayer temperature is arranged on 25-75 DEG C; Solvent is propylene glycol monomethyl ether, and underlayer temperature is arranged on 25-65 DEG C; Solvent is butanols, and underlayer temperature is arranged on 25-110 DEG C; Solvent is butanone, and underlayer temperature is arranged on 25-75 DEG C; Solvent is dimethylbenzene, and underlayer temperature is arranged on 25-130 DEG C; Solvent is toluene, and underlayer temperature is arranged on 25-105 DEG C; Solvent is tetrahydrofuran (THF), and underlayer temperature is arranged on 25-60 DEG C; Solvent is methyl acetate, and underlayer temperature is arranged on 25-53 DEG C; Solvent is ethyl acetate, and underlayer temperature is arranged on 25-70 DEG C; Solvent is Virahol, and underlayer temperature is arranged on 25-75 DEG C; Solvent is normal heptane, and underlayer temperature is arranged on 25-90 DEG C; Solvent is normal hexane, and underlayer temperature is arranged on 25-65 DEG C.
3. the method preparing graphene film according to claim 1 and 2, is characterized in that, during described carbon granule is modified, flame source is the burning of following arbitrary material: candle, alcohol, gasoline or diesel oil.
4. the method preparing graphene film according to claim 1 and 2, is characterized in that, the material of described substrate is glass, silicon chip, tinsel or polydimethylsiloxane.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310026890.9A CN103101908B (en) | 2013-01-24 | 2013-01-24 | Method for preparing graphene film |
| PCT/CN2013/082523 WO2014114081A1 (en) | 2013-01-24 | 2013-08-29 | Method for preparing graphene film |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310026890.9A CN103101908B (en) | 2013-01-24 | 2013-01-24 | Method for preparing graphene film |
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| CN103101908A CN103101908A (en) | 2013-05-15 |
| CN103101908B true CN103101908B (en) | 2015-06-03 |
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| CN103101908B (en) * | 2013-01-24 | 2015-06-03 | 东南大学 | Method for preparing graphene film |
| CN104698042B (en) | 2013-12-05 | 2017-07-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Biological enzyme sensor that super-hydrophobic solid-liquid-gas three phase coexists and preparation method thereof |
| CN103710685B (en) * | 2013-12-24 | 2016-02-17 | 同济大学 | A kind of spraying method directly preparing transparent graphene conductive film on a flexible substrate |
| CN103924188B (en) * | 2014-05-07 | 2016-06-08 | 山东师范大学 | The method of atmospheric environment lower pair flame method growth in situ Graphene on a dielectric base |
| CN104085143B (en) * | 2014-05-29 | 2016-05-04 | 深圳市铭晶科技有限公司 | Preparation method and the product of Graphene composite guide hotting mask |
| KR102314988B1 (en) * | 2014-12-26 | 2021-10-21 | 솔브레인 주식회사 | Graphene Membrane Film and Method for Solvent Purification and Solvent Purification System using the Same |
| CN104591164B (en) * | 2014-12-30 | 2016-09-07 | 常州碳星科技有限公司 | A kind of preparation method of Graphene microbody |
| CN104609409B (en) * | 2015-01-22 | 2016-11-16 | 东南大学 | A kind of preparation method of Graphene millimeter sheet |
| CN104909580A (en) * | 2015-05-20 | 2015-09-16 | 苏州大学 | Transparent hydrophobic grating glass and preparation method thereof |
| CN105084858B (en) * | 2015-08-07 | 2018-05-18 | 常州富烯科技股份有限公司 | A kind of preparation method of graphene film |
| CN105271209A (en) * | 2015-11-05 | 2016-01-27 | 北京旭碳新材料科技有限公司 | Graphene film and method and device for continuously producing graphene film |
| CN108571913A (en) * | 2017-03-07 | 2018-09-25 | 中国科学院工程热物理研究所 | A kind of super-hydrophobic condensing surface and preparation method thereof |
| CN107640764A (en) * | 2017-10-13 | 2018-01-30 | 南京旭羽睿材料科技有限公司 | A kind of industrial high efficiency prepares big size graphene production technology |
| CN108840320B (en) * | 2018-06-29 | 2020-05-22 | 北京石油化工学院 | Method for preparing carbon film by using water drop stripping mode |
| CN108946709A (en) * | 2018-07-10 | 2018-12-07 | 东南大学 | A kind of preparation method of the three-dimensional high-densit more fold graphene oxides of high-hydroscopicity |
| CN108975316B (en) * | 2018-09-26 | 2020-02-04 | 西北有色金属研究院 | Preparation method of graphene film |
| CN113444470A (en) * | 2021-07-16 | 2021-09-28 | 安徽省奥佳建材有限公司 | Self-adhesive waterproof coiled material |
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