CN102219389B - Preparation method of carbon film obtained by self assembly of graphene oxide or its derivatives - Google Patents
Preparation method of carbon film obtained by self assembly of graphene oxide or its derivatives Download PDFInfo
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- CN102219389B CN102219389B CN 201110104353 CN201110104353A CN102219389B CN 102219389 B CN102219389 B CN 102219389B CN 201110104353 CN201110104353 CN 201110104353 CN 201110104353 A CN201110104353 A CN 201110104353A CN 102219389 B CN102219389 B CN 102219389B
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Abstract
The invention discloses a carbon film obtained by self assembly of graphene oxide or its derivatives and a preparation method thereof, and relates to a preparation method for a highly ordered carbon film. The objective of the invention is to solve the problems existing in the prior art that the combination between a carbon film and a substrate is poor, the preparation technology is complex, the cost is high, and the thickness of carbon films is difficult to control in the process of preparation. The carbon film provided in the invention uses graphene oxide or its derivatives as the raw material and is obtained through the process of self assembly. The carbon film is prepared by the following steps: dispersing graphene oxide or its derivatives in a solvent so as to obtain a solution, immersing a substrate into the solution and allowing the solution to stand at a constant temperature for assembly, wherein the temperature is in a range of 50 to 100 DEG C. The carbon film prepared in the invention has smooth surfaces, strong bonding force to the substrate and good light transmittance and mechanical properties; the modulus of the carbon film is 80 to 120 GPa, and the hardness is 7 to 9 Gpa; the carbon film is orderly orientated along the surface of the substrate, and the thickness of the carbon film is 10 nm to 2 mu m. The preparation process is controllable and concise and produces products with controllable thickness. The carbon film provided in the invention has broad application prospects in such fields as electrode materials, electronic chips, solar cells and high efficient catalysis.
Description
Technical field
The present invention relates to a kind of preparation method of high-sequential carbon film.
Background technology
The carbon film material is the mould material that a class has the important application prospect; mainly contain quasi-diamond type and class graphite mould two classes; have the characteristics such as high strength, wear-resisting, corrosion-resistant, photoelectric properties are good, be widely used as the fields such as hot protecting materials, high-abrasive material, electrophotographic film and high temperature semiconductors material.The technology of preparing of carbon film comprises physical vapor deposition and chemical vapour deposition; as magnetron sputtering, ion beam sputtering; technique for atomic layer deposition etc. are difficult to control with these technology ubiquity deposit thickness, easy fold; internal stress is large; the problems such as substrate bonding intensity is not firm, the shortcomings such as the while equipment cost is high, the protected material surface of difficult uniform fold.
The polymer precursor film carbonization that present directed carbon film mainly contains preliminary draft prepares, perhaps by chemical Vapor deposition process (CVD) in catalyst surface growth, and the physical deposition methods such as magnetron sputtering, plasma sputtering obtain on substrate.Wherein there are the defectives such as pore in the film of carbonization acquisition, and planarization is relevant with thickness, usually is difficult to obtain high-quality directed carbon film.And chemistry or physical vaporous deposition, apparatus expensive and processing condition are strict, obtaining thicker film needs very long depositing time, and need to could obtain the carbon film of good orientation on specific substrate, and the existence of these shortcomings has affected widespread use and the use of carbon film material.
Summary of the invention
The objective of the invention is for solve existing carbon film be combined with substrate poor, complicated process of preparation, cost are high, and carbon film thickness problem rambunctious in preparation process, the invention provides a kind of carbon film that utilizes graphene oxide or derivatives thereof self-assembly acquisition and preparation method thereof.
The carbon film that utilizes the self-assembly of graphene oxide or derivatives thereof to obtain of the present invention is take the graphene oxide or derivatives thereof as raw material, obtains by the self-assembly film forming, and the specific conductivity of carbon film is 1～10
3S/cm.
The preparation method of the carbon film that the self-assembly of graphene oxide or derivatives thereof obtains that utilizes of the present invention realizes by following steps: one, with graphene oxide (or derivatives thereof) ultra-sonic dispersion in dispersion medium, getting concentration is graphene oxide (or derivatives thereof) solution of 0.01～3mg/mL, wherein dispersion medium is water or organic solvent, and the graphite oxide ene derivative utilizes organic amine or organic alcohols that graphene oxide is modified and prepares; Two, the graphene oxide that step 1 is got (or derivatives thereof) solution is placed in open container, then the substrate with surface cleaning inserts in graphene oxide (or derivatives thereof) solution, the top of controlling substrate exceeds liquid level of solution, again open container is placed under the condition of 50～100 ℃ constant temperature standing, treat that liquid level of solution is lower than three/for the moment of initial liquid level, take out substrate, get surperficial baseplate material with carbon film, wherein keep the angle of substrate and horizontal plane greater than 45 ° in the standing process of constant temperature; Three, the surface that step 2 is got has the substrate of carbon film and does the reduction processing, namely obtains carbon film on substrate, completes the preparation method of the carbon film that utilizes graphene oxide or derivatives thereof self-assembly acquisition.
In the preparation method who utilizes the carbon film that the self-assembly of graphene oxide or derivatives thereof obtains of the present invention, in step 1 with when graphene oxide (or derivatives thereof) ultra-sonic dispersion is in dispersion medium, add nanoparticle or strengthen composite nanometer particle, and self-assembly prepares the carbon film that contains nanoparticle or strengthen composite nanometer particle.Described nanoparticle or enhancing composite nanometer particle are semi-conductor SeS, CdS, CdTe, Fe
3O
4, TiO
2Nanocrystalline or quantum dot.The particle diameter of described nanoparticle or enhancing composite nanometer particle is 1～20nm.
In step 1 of the present invention, graphene oxide is the commercially available prod, perhaps utilize existing chemical oxidization method to prepare, wherein existing chemical oxidization method is Humers method (vitriol oil+potassium permanganate), and ozone, hydrogen peroxide oxidation method or the vitriol oil are combined the methods such as oxidation with Potcrate.
Described in step 1 of the present invention, the preparation method of graphite oxide ene derivative is as follows: the organic amine that the quality such as adds in the graphene oxide, stir, then insulation reaction 60～180min under the condition of 85～95 ℃, carry out substitution reaction and get the graphite oxide ene derivative that amino hydro carbons is modified; Perhaps, the organic alcohols of quality such as add in the graphene oxide, stir, then insulation reaction 60～150min under the condition of 85～95 ℃, add diluted acid catalysis again after esterification, gets the graphite oxide ene derivative that the Fatty Alcohol(C12-C14 and C12-C18) side group is modified.Two kinds of Graphene derivatives that more than prepare can obtain highly purified Graphene derivative through washing, filtration, carry out self-assembly and prepare carbon film.
The graphene oxide solution that step 1 of the present invention obtains is the solution of graphene oxide particle or the stabilising system of suspension.
In step 2 of the present invention, substrate is sheet glass, quartz (SiO
2), oxide ceramics or silicon carbide ceramics.Substrate can be replaced by the base material of other shape, the material that has smooth surface structure as tubular, spherical etc.
Reduction described in step 3 of the present invention is treated to thermal reduction: in inert gas atmosphere, the substrate that the surface that step 2 is got has carbon film is incubated 3～5h under the condition of 200～300 ℃, naturally cool to room temperature.
Reduction described in step 3 of the present invention is processed and can also be chemical reduction: the substrate that the surface that step 2 is got has carbon film is placed in reducing gas atmosphere or hydrazine solution, and reduction 180～360min gets final product.
The present invention utilizes the self-assembly of step 2 and the reduction in step 3 to process, and obtains carbon film of the present invention.The carbon film surfacing that utilizes the self-assembly of graphene oxide or derivatives thereof to obtain of the present invention is smooth, good light transmission and mechanical property are preferably arranged, and modulus is 80～120GPa, hardness 7～9Gpa; Carbon film is oriented and ordered, and along the substrate surface orientation, thickness is 10nm～2 μ m.
The method that self-assembly method of the present invention prepares carbon film can have at flat board, sphere, right cylinder etc. the carbon film surface that material surface Quick uniform generation directional property is good, the matrix bonding strength is high of smooth surface structure, preparation technology's controllability is good, process is succinct, and thickness is controlled.The carbon film smooth surface of preparation, light transmission and mechanical property are preferably arranged.
Carbon film of the present invention and preparation method thereof has following advantage:
1) experiment condition is gentle, and the process environmental protection can obtain the film of superperformance;
2) can repeatedly assemble the acquisition lamination;
3) composite structure is regular, and material is finer and close;
4) the convenient structure properties that adds other nanoparticles or altered contents reinforced composite of mixing in assembling process, obtain the new functions such as photoelectromagnetism, and the Application Areas of widening material has good technical foundation;
5) it is poor that the carbon film that is prepared into is combined with substrate, and preparation technology is simple, cost is low.
Of the present inventionly utilize carbon film that the self-assembly of graphene oxide or derivatives thereof obtains application prospect very widely to be arranged electrode materials, electronic chip, solar cell, efficient catalytic etc. are multi-field.
Description of drawings
Fig. 1 is the sub-spectrogram of X-ray photoelectric that utilizes the carbon film that the self-assembly of graphene oxide or derivatives thereof obtains that embodiment 22 prepares; Fig. 2 is the scanning electronic microscope cross-section photograph that surface that embodiment 22 step 2 obtain has the carbon film on the substrate of carbon film; Fig. 3 is the electron scanning micrograph of 2000 times of the amplifications of the carbon film that obtains of embodiment 22 step 2; Fig. 4 is the electron scanning micrograph of 10000 times of the amplifications of the carbon film that obtains of embodiment 22 step 2; Fig. 5 is the electron scanning micrograph of the carbon film that obtains of embodiment 22.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is the carbon film that utilizes the self-assembly of graphene oxide or derivatives thereof to obtain, and it is take the graphene oxide or derivatives thereof as raw material, obtains by the self-assembly film forming, and the specific conductivity of carbon film is 1～10
3S/cm, wherein the graphite oxide ene derivative utilizes organic amine or organic alcohols that graphene oxide is modified to prepare.
The carbon film surfacing of present embodiment is smooth, good light transmission and mechanical property are preferably arranged, and modulus is 80～120GPa, hardness 7～9Gpa; Carbon film is oriented and ordered, and along the substrate surface orientation, thickness is 50nm～2 μ m.
Graphene oxide raw material in present embodiment is the commercially available prod, or adopts existing open chemical oxidization method to prepare.
Embodiment two: present embodiment is different from embodiment one is that the specific conductivity of carbon film is 1 * 10
2～9 * 10
2S/cm.Other parameter is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one is that the specific conductivity of carbon film is 6 * 10
2S/cm.Other parameter is identical with embodiment one.
Embodiment four: present embodiment is the preparation method who utilizes the carbon film of graphene oxide or derivatives thereof self-assembly acquisition as described in embodiment one, it is realized by following steps: one, with graphene oxide (or derivatives thereof) ultra-sonic dispersion in dispersion medium, getting concentration is graphene oxide (or derivatives thereof) solution of 0.01～3mg/mL, wherein dispersion medium is water or organic solvent, and the graphite oxide ene derivative utilizes organic amine or organic alcohols that graphene oxide is modified and prepares; Two, the graphene oxide that step 1 is got (or derivatives thereof) solution is placed in open container, then the substrate with surface cleaning inserts in graphene oxide (or derivatives thereof) solution, the top of controlling substrate exceeds liquid level of solution, again open container is placed under the condition of 50～100 ℃ constant temperature standing, treat that liquid level of solution is lower than three/for the moment of initial liquid level, take out substrate, get surperficial baseplate material with carbon film, wherein keep the angle of substrate and horizontal plane greater than 45 ° in the standing process of constant temperature; Three, the surface that step 2 is got has the substrate of carbon film and does the reduction processing, namely obtains carbon film on substrate, completes the preparation method of the carbon film that utilizes graphene oxide or derivatives thereof self-assembly acquisition.
The preparation technology of present embodiment is simple, cost is low.The method that the self-assembly method of present embodiment prepares carbon film can have at flat board, sphere, right cylinder etc. the carbon film surface that material surface Quick uniform generation directional property is good, the matrix bonding strength is high of smooth surface structure, preparation technology's controllability is good, process is succinct, and thickness is controlled.The carbon film smooth surface of preparation, light transmission and mechanical property are preferably arranged.Obtain the substrate of surface uniform carbon film coating.
The carbon film surfacing that present embodiment prepares utilizes the self-assembly of graphene oxide or derivatives thereof to obtain is smooth, good light transmission and mechanical property are preferably arranged, and modulus is 80～120GPa, hardness 7～9Gpa; Carbon film is oriented and ordered, and along the substrate surface orientation, thickness is 10nm～2 μ m.The specific conductivity of carbon film is 1～10
3S/cm.
Graphene oxide raw material described in the present embodiment step 1 adopts existing open chemical oxidization method to prepare.In step 1, the organic solvent dispersion medium is ethanol, acetone, dimethyl formamide, methyl-sulphoxide etc.
Embodiment five: what present embodiment was different from embodiment four is that graphene oxide described in step 1 utilizes chemical oxidization method to prepare, wherein, chemical oxidization method is Humers method (vitriol oil+potassium permanganate), ozone, hydrogen peroxide oxidation method, perhaps the vitriol oil is combined the methods such as oxidation with Potcrate.Other step and parameter are identical with embodiment four.
Embodiment six: present embodiment is different from embodiment four or five is that the preparation method of graphite oxide ene derivative in step 1 is as follows: the organic amine that the quality such as adds in the graphene oxide, stir, then insulation reaction 60～180min under the condition of 85～95 ℃, carry out substitution reaction and get the graphite oxide ene derivative that amino hydro carbons is modified; Perhaps, the organic alcohols of quality such as add in the graphene oxide, stir, then insulation reaction 60～150min under the condition of 85～95 ℃, add diluted acid catalysis again after esterification, gets the graphite oxide ene derivative that the Fatty Alcohol(C12-C14 and C12-C18) side group is modified.Other step and parameter are identical with embodiment four or five.
Two kinds of graphite oxide ene derivatives that present embodiment will prepare are washed successively and filter, and after purifying, are prepared into the solution that concentration is 0.1～2mg/mL, and are standby.
Organic amine described in present embodiment is amino dodecane, cetylamine or sulfanilic amide, and described organic alcohols is butanols, amylalcohol or hexalin.
Embodiment seven: present embodiment and embodiment four, five or six different be in step 1 concentration be graphene oxide (or derivatives thereof) solution of 0.5～2.5mg/mL.Other step and parameter and embodiment four, five or six identical.
Embodiment eight: present embodiment and embodiment four, five or six different be in step 1 concentration be graphene oxide (or derivatives thereof) solution of 1～2mg/mL.Other step and parameter and embodiment four, five or six identical.
Embodiment nine: present embodiment and embodiment four, five or six different be in step 1 concentration be graphene oxide (or derivatives thereof) solution of 1.5mg/mL.Other step and parameter and embodiment four, five or six identical.
Embodiment ten: present embodiment is different from one of embodiment four to nine is in step 2, the substrate of surface cleaning to be inserted in graphene oxide (or derivatives thereof) solution, and the length that the top of controlling substrate exceeds liquid level of solution is 1/10th to 1/9th of substrate.Other step and parameter are identical with one of embodiment four to nine.
Embodiment 11: present embodiment is different from one of embodiment four to ten is that in step 2, open container to be placed under the condition of 60～90 ℃ constant temperature standing.Other step and parameter are identical with one of embodiment four to ten.
Embodiment 12: present embodiment is different from one of embodiment four to ten is that in step 2, open container to be placed under the condition of 80 ℃ constant temperature standing.Other step and parameter are identical with one of embodiment four to ten.
Embodiment 13: present embodiment is different from one of embodiment four to 12 is that to keep the angle of substrate and horizontal plane in the standing process of constant temperature in step 2 be 45 °～90 °.Other step and parameter are identical with one of embodiment four to 12.
More optimizedly keeping the angle of substrate and horizontal plane in the standing process of constant temperature in step 2 in present embodiment is 60 °～90 °.
Embodiment 14: what present embodiment was different from one of embodiment four to 13 is that in step 2, substrate is sheet glass, quartz (SiO
2), oxide ceramics or silicon carbide ceramics.Other step and parameter are identical with one of embodiment four to 13.
In present embodiment, substrate can be replaced by the base material of other shape, the material that has smooth surface structure as tubular, spherical etc.
Embodiment 15: what present embodiment was different from one of embodiment four to 14 is that described in step 3, reduction is treated to thermal reduction: in inert gas atmosphere, the substrate that the surface that step 2 is got has carbon film is incubated 3～5h under the condition of 200～300 ℃, naturally cool to room temperature.Other step and parameter are identical with one of embodiment four to 14.
Embodiment 16: what present embodiment was different from embodiment 15 is that described in step 3, reduction is treated to thermal reduction: in inert gas atmosphere, the substrate that the surface that step 2 is got has carbon film is incubated 4h under the condition of 250 ℃, naturally cool to room temperature.Other step and parameter are identical with embodiment 15.
Embodiment 17: present embodiment is different from one of embodiment four to 14 is that reduction described in step 3 is processed and can also be chemical reduction: the substrate that the surface that step 2 is got has carbon film is placed in reducing gas atmosphere or hydrazine solution, reduction 180～360min gets final product.Other step and parameter are identical with one of embodiment four to 14.
Embodiment 18: present embodiment is different from embodiment 17 is that reduction described in step 3 is processed and can also be chemical reduction: the substrate that the surface that step 2 is got has carbon film is placed in reducing gas atmosphere or hydrazine solution, reductase 12 40min gets final product.Other step and parameter are identical with embodiment 17.
Embodiment 19: present embodiment is different from one of embodiment four to 18 be in step 1 with when graphene oxide (or derivatives thereof) ultra-sonic dispersion is in dispersion medium, add nanoparticle or strengthen composite nanometer particle.Other step and parameter are identical with one of embodiment four to 18.
The quality of the nanoparticle that adds in present embodiment or enhancing composite nanometer particle is 1%～10% of graphene oxide (or derivatives thereof) quality.
The present embodiment self-assembly prepares the carbon film that contains nanoparticle or strengthen composite nanometer particle.Make the carbon film that obtains obtain the new function such as light, electricity, magnetic, the Application Areas of widening material has good technical foundation.
Embodiment 20: what present embodiment was different from embodiment 19 is that described nanoparticle or enhancing composite nanometer particle are semi-conductor SeS, CdS, CdTe, Fe
3O
4, TiO
2Nanocrystalline or quantum dot.Other step and parameter are identical with embodiment 19.
Embodiment 21: what present embodiment was different from embodiment 19 is that described nanoparticle or the particle diameter that strengthens composite nanometer particle are 1～20nm.Other step and parameter are identical with embodiment 19.
embodiment 22: present embodiment is to utilize the preparation method of the carbon film of graphene oxide or derivatives thereof self-assembly acquisition, it is realized by following steps: one, with graphite oxide ene derivative ultra-sonic dispersion in dispersion medium, getting concentration is the graphene oxide derivative solution of 0.5mg/mL, wherein dispersion medium is water, the preparation method of graphite oxide ene derivative is as follows: the amino dodecane that the quality such as adds in the graphene oxide, stir, then insulation reaction 120min under the condition of 90 ℃, carry out substitution reaction and get the graphite oxide ene derivative that amino dodecyl is modified, two, the graphene oxide derivative solution that step 1 is got is placed in open container, then the sheet glass with surface cleaning inserts in the graphene oxide derivative solution, the top of controlling substrate exceeds liquid level of solution, again open container is placed under the condition of 80 ℃ constant temperature standing, when solution evaporation is complete, take out substrate, get surperficial baseplate material with carbon film, wherein keeping the angle of substrate and horizontal plane in the standing process of constant temperature is 90 °, three, the surface that step 2 is got has the substrate of carbon film and does the thermal reduction processing: in inert gas atmosphere, the substrate that the surface that step 2 is got has carbon film is incubated 4h under the condition of 250 ℃, naturally cool to room temperature, namely obtain carbon film on substrate, complete the preparation method of the carbon film that utilizes graphene oxide or derivatives thereof self-assembly acquisition.
In the present embodiment step 1, graphene oxide is the commercially available prod.
In the present embodiment step 2, the cleaning mode of the sheet glass of surface cleaning is: the oily matter of a, use acetone ultrasonic cleaning glass pane surface, and ultrasonic time is 20min; B, with the sheet glass after step a processes under 40～60 ℃ of conditions, soak 5～10min with 10wt.% chromic acid solution or acid permanganate soln, remove reducing substances and unnecessary organism on sheet glass; C, in distilled water ultrasonic cleaning 20min, change distilled water and repeat ultrasonic cleaning 2～3 times, then dry getting final product.
The sub-spectrogram of X-ray photoelectric of the carbon film that utilizes graphene oxide or derivatives thereof self-assembly acquisition that present embodiment prepares as shown in Figure 1, as can be known, mainly formed by carbon, and there is a small amount of oxygen to exist, this is because airborne oxygen absorption causes, and also there is a small amount of oxygen-containing functional group the carbon film the inside simultaneously.
The surface that the present embodiment step 2 obtains has the scanning electronic microscope cross-section photograph of the carbon film on the substrate of carbon film, and as shown in Figure 2, as seen, carbon film is fine and close, and thickness is 500nm.
The surface that the present embodiment step 2 obtains have the carbon film on the substrate of carbon film 2000 times of amplifications electron scanning micrograph as shown in Figure 3, amplify the electron scanning micrograph of 10000 times as shown in Figure 4, as seen, carbon film surface surfacing is smooth, carbon film is oriented and ordered, is orientated along substrate surface.
The electron scanning micrograph of the carbon film that the present embodiment step 3 obtains through reduction as shown in Figure 5, as seen, the carbon film surface after reduction is processed is finer and close, more smooth smooth.
The carbon film that present embodiment is obtained on substrate carries out Mechanics Performance Testing, and testing method is: Using Nanoindentation is measured, and uses the Berkovich diamond penetrator of rhizoma sparganic taper, strain rate 0.05s
-1, speed is 5nm/s, depth of indentation is 0.4 micron.The modulus that test obtains the carbon film of present embodiment is 120Gpa, and hardness is 8.5Gpa; Light transmission is good.
The carbon film that present embodiment is obtained on substrate carries out the specific conductivity performance test, and testing method is: two electrode methods or four electrode method are measured.The specific conductivity that test obtains carbon film is 6 * 10
2S/cm.
Embodiment 23: present embodiment is different from embodiment 22 be in step 1 with the graphene oxide ultra-sonic dispersion in dispersion medium, getting concentration is the graphene oxide solution of 3mg/mL, wherein dispersion medium is water.Other step and parameter are identical with embodiment 22.
The thickness of the carbon film that present embodiment prepares on glass sheet substrate is 2 μ m.
Adopt mechanical property and the specific conductivity performance of the described testing method test of embodiment 22 carbon film, test result is: the modulus of carbon film is 80GPa, and hardness is 7GPa; Specific conductivity is 100S/cm.
Embodiment 24: present embodiment is different from embodiment 22 be in step 1 with graphite oxide ene derivative ultra-sonic dispersion in dispersion medium, getting concentration is the graphene oxide derivative solution of 0.1mg/mL, wherein dispersion medium is water, the preparation method of graphite oxide ene derivative is as follows: the butanols that the quality such as adds in the graphene oxide, stir, then insulation reaction 120min under the condition of 90 ℃, carry out substitution reaction and get the graphite oxide ene derivative that butoxy is modified.Other step and parameter are identical with embodiment 22.
The thickness of the carbon film that present embodiment prepares on glass sheet substrate is 100nm.
Adopt mechanical property and the specific conductivity performance of the described testing method test of embodiment 22 carbon film, test result is: the modulus of carbon film is 100GPa, and hardness is 8GPa; Specific conductivity is 600S/cm.
Embodiment 25: present embodiment is to utilize the preparation method of the carbon film that the graphene oxide derivative self-assembled obtains, and it is realized by following steps: one, with the Fe of graphite oxide ene derivative and 10～20nm
3O
4Nanocrystalline nanoparticle ultra-sonic dispersion is in dispersion medium, getting concentration is the graphite oxide ene derivative mixing solutions of 3mg/mL, wherein dispersion medium is water, the preparation method of graphite oxide ene derivative is as follows: the amino dodecane that the quality such as adds in the graphene oxide, stir, then insulation reaction 120min under the condition of 90 ℃, carry out substitution reaction and get the graphite oxide ene derivative that amino dodecyl is modified; Two, the graphite oxide ene derivative mixing solutions that step 1 is got is placed in open container, then the sheet glass with surface cleaning inserts in the graphene oxide derivative solution, the top of controlling substrate exceeds liquid level of solution, again open container is placed under the condition of 80 ℃ constant temperature standing, treat that the liquid level of solution in open container is lower than three/for the moment of initial liquid level, take out substrate, get surperficial baseplate material with carbon film, wherein keeping the angle of substrate and horizontal plane in the standing process of constant temperature is 90 °; Three, the surface that step 2 is got has the substrate of carbon film and does the thermal reduction processing: in inert gas atmosphere, the substrate that the surface that step 2 is got has carbon film is incubated 4h under the condition of 250 ℃, naturally cool to room temperature, namely obtain carbon film on substrate, complete the preparation method of the carbon film that utilizes graphene oxide or derivatives thereof self-assembly acquisition.
The Fe of 10～20nm in the present embodiment step 1
3O
4Nanocrystalline nanoparticle quality is 5%～8% of graphene oxide derivative quality.
The carbon film that present embodiment prepares has ferromegnetism, at necks such as magnetic recording medium, magnetic device and magneticsensors.
Claims (4)
1. utilize the preparation method of the carbon film of graphene oxide derivative self-assembled acquisition, wherein carbon film is take the graphite oxide ene derivative as raw material, obtains by the self-assembly film forming; It is characterized in that utilizing the preparation method of the carbon film that the graphene oxide derivative self-assembled obtains to realize by following steps: one, with graphite oxide ene derivative ultra-sonic dispersion in dispersion medium, getting concentration is the graphene oxide derivative solution of 0.01～3mg/mL, wherein dispersion medium is water or organic solvent, and the graphite oxide ene derivative utilizes organic amine or organic alcohols that graphene oxide is modified and prepares; Two, the graphene oxide derivative solution that step 1 is got is placed in open container, then the substrate with surface cleaning inserts in the graphene oxide derivative solution, the top of controlling substrate exceeds liquid level of solution, again open container is placed under the condition of 50～100 ℃ constant temperature standing, treat that the liquid level of solution height is reduced to lower than three/for the moment of initial liquid level, take out substrate, get surperficial baseplate material with carbon film, wherein keep the angle of substrate and horizontal plane greater than 45 ° in the standing process of constant temperature; Three, the surface that step 2 is got has the substrate of carbon film and does the reduction processing, namely obtains carbon film on substrate, completes the preparation method of the carbon film that utilizes the acquisition of graphene oxide derivative self-assembled; The specific conductivity of carbon film is 1～10
3S/cm; Modulus is 80～120GPa, hardness 7～9GPa; Thickness is 10nm～2 μ m; In step 1, the preparation method of graphite oxide ene derivative is as follows: the organic amine that the quality such as adds in the graphene oxide, stir, then insulation reaction 60～180min under the condition of 85～95 ℃, carry out substitution reaction and get the graphite oxide ene derivative that amino hydro carbons is modified; Perhaps, the organic alcohols of quality such as add in the graphene oxide, stir, then insulation reaction 60～150min under the condition of 85～95 ℃, add diluted acid catalysis again after esterification, gets the graphite oxide ene derivative that the Fatty Alcohol(C12-C14 and C12-C18) side group is modified; Reduction described in step 3 is treated to thermal reduction or chemical reduction: thermal reduction is in inert gas atmosphere, and the substrate that the surface that step 2 is got has carbon film is incubated 3～5h under the condition of 200～300 ℃, naturally cool to room temperature; Chemical reduction is placed in reducing gas atmosphere or hydrazine solution for the substrate that the surface that step 2 is got has carbon film, and reduction 180～360min gets final product.
2. the preparation method who utilizes the carbon film of graphene oxide derivative self-assembled acquisition according to claim 1, is characterized in that getting concentration in step 1 is the graphene oxide derivative solution of 0.5～2.5mg/mL.
3. the preparation method who utilizes the carbon film of graphene oxide derivative self-assembled acquisition according to claim 1, is characterized in that getting concentration in step 1 is the graphene oxide derivative solution of 1～2mg/mL.
4. the preparation method who utilizes the carbon film that the graphene oxide derivative self-assembled obtains according to claim 1, it is characterized in that in step 1 adding nanoparticle or strengthening composite nanometer particle with when graphite oxide ene derivative ultra-sonic dispersion is in dispersion medium.
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| CN102584334A (en) * | 2012-01-13 | 2012-07-18 | 上海交通大学 | Method for preparing graphene composite thin film on surface of silicon slice |
| CN102534586B (en) * | 2012-02-15 | 2013-12-11 | 上海交通大学 | Method for preparing rare earth modified reduction-oxidation graphene film on surface of titanium alloy |
| CN105985140A (en) * | 2015-03-06 | 2016-10-05 | 于有海 | Graphene and ceramic composite film and preparation method thereof |
| CN106669447A (en) * | 2015-11-08 | 2017-05-17 | 于有海 | Production method of graphene/ceramic composite filter membrane |
| CN106116580B (en) * | 2016-06-30 | 2018-07-17 | 东华大学 | A kind of flexibility carbon film and preparation method thereof |
| CN106365689A (en) * | 2016-08-31 | 2017-02-01 | 安徽斯迈尔电子科技有限公司 | Preparation method of carbon film for resistor |
| CN113247946B (en) * | 2021-04-22 | 2022-07-05 | 哈尔滨工业大学 | Self-assembled nano biocatalyst, preparation method thereof and application thereof in butanol production |
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