CN106987017A - A kind of construction method of graphenic surface fold - Google Patents

A kind of construction method of graphenic surface fold Download PDF

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CN106987017A
CN106987017A CN201710273923.8A CN201710273923A CN106987017A CN 106987017 A CN106987017 A CN 106987017A CN 201710273923 A CN201710273923 A CN 201710273923A CN 106987017 A CN106987017 A CN 106987017A
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rubber
fold
construction method
graphene oxide
graphenic surface
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CN106987017B (en
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楚增勇
谭银龙
蒋振华
李公义
胡天娇
宋嘉
李义和
王清华
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National University of Defense Technology
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/06Coating with compositions not containing macromolecular substances
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/20Graphene characterized by its properties
    • C01B2204/32Size or surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2307/00Characterised by the use of natural rubber
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/02Copolymers with acrylonitrile

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
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  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

A kind of construction method of graphenic surface fold, comprises the following steps:(1)Graphene oxide dispersion is configured;(2)Substrate surface processing;(3)Substrate is pre-stretched;(4)Surface is coated;(5)Substrate Contraction;(6)Graphene oxide is reduced.It is prepared by the disposable three-dimensional shrinkage of gained graphenic surface fold of the invention, folding degree is high, hydrophobicity is good, it is stretchable, it is flexible, available for the dynamic device of solvent response type deformation intelligence for building compound bending, quick response, deep camber deformation, available for assembling high sensitivity, low potential driving, long-life strain transducer, had a good application prospect in wearable smart machine field.

Description

A kind of construction method of graphenic surface fold
Technical field
The invention belongs to the field of constructing of surface micro-nano structure, more particularly to a kind of side of constructing of graphenic surface fold Method.
Background technology
Regulating microstructure based on macromolecule matrix surface is the great research topic in nano science field, particularly bullet Elastomeric surface biomimetic features are constructed and regulated and controled.Researcher obtains inspiration from the surface microstructure in the Nature, in laboratory Construct bionic surface fold.1998, Bowden et al. obtained the pleated structure of metallic film by the thermal contraction of substrate, opens The new page of surface folding is constructed in laboratory(Nature 1998, 393: 146-149).According to constructing surface folding forerunner The difference of body, constructing mainly for surface folding has three kinds of strategies:(1)Surface folding based on the double-deck system of film/substrate is constructed; (2)Surface folding based on gradation type substrate is constructed;(3)Surface folding based on homogeneity substrate is constructed(Prog. Polym. Sci. 2015, 42: 1-41).
Graphene is due to the uniqueness of itself structure, such as:The two dimensional crystal of the honeycomb of monoatomic layer thickness, It is to have now been found that the Two Dimensional Free state crystal uniquely existed, and this causes it to have extremely excellent electricity, magnetics, catalysis, heat Learn and the physical and chemical performance such as mechanics so that it have in new energy materialses, sensor and all kinds of field of compound material it is extremely wide General application prospect.Graphene is built into wrinkled surface to assign its more excellent performance.Wang et al.(ACS Nano 2011, 5: 3645-3650)Preprepared graphene is transferred to the planar structure polydimethylsiloxanes for applying tension In alkane flexible substrate, by the stress in release liners, graphene is set to recover the process of nature in dimethyl silicone polymer Middle formation corrugated foldable structure, gained wrinkled surface has good stress response characteristic.
Although in constructing and its application field for the micro- fold of graphenic surface, having been achieved for preliminary achievement in research, There is also some limitations and deficiency:On the one hand, worked and be mainly based upon the surface construction graphene fold of two-dimentional matrix, lacked Weary real three-dimensional construction method, yet there are no the document report constructed based on hollow sphere and cylindrical base graphene fold Road;On the other hand, Graphite During The Process alkene surface folding generally pre-stretching rate is constructed at present smaller, it is difficult to obtain height folded state, Or need to obtain height folded state by multistep transfer, process is extremely cumbersome.Do not find also at present by disposable three-dimensional Shrink and prepare the report that height folds graphene fold.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art there is provided a kind of without shifting, can highly roll over The construction method of folded graphenic surface fold.
The technical scheme that the present invention solves the use of its technical problem is that a kind of construction method of graphenic surface fold is wrapped Include following steps:
(1)Dispersion liquid is configured:By graphene oxide powder, scattered in deionized water, ultrasonic disperse more than 0.5 hour, is configured dense Spend for 0.2 ~ 8.0 mg/ml(It is preferred that 1.0 ~ 5.0 mg/mls)Graphene oxide dispersion;
The graphene oxide number of plies is 1 ~ 3 layer, and lamella size is 0.2 ~ 30 micron(It is preferred that 1 ~ 20 micron).
Research shows, deionized water can be to configure high concentration dispersion, and with rubber polymer-based end without mutual Effect.
The ultrasonic disperse time, the longer the better.The concentration influence coating layer thickness of dispersion liquid, the too low generation coating layer thickness mistake of concentration It is thin;The dispersion liquid of high concentration is difficult to configure, and coating layer thickness can be made uneven.
(2)Substrate surface processing:Hollow sphere or cylindrical rubber polymer-based end are put into absolute ethyl alcohol, are cleaned by ultrasonic 10 ~ 60 minutes(It is preferred that 30 minutes), it is dried in vacuo more than 1 hour at room temperature.
Purity >=99% of the absolute ethyl alcohol(Mass percent).
The hollow sphere or cylindrical rubber polymer-based end, substrate thickness >=20 micron.
The rubber polymer-based end refers to elongation strain up to more than 500% macromolecule, including natural rubber, butylbenzene rubber Glue, butadiene rubber, isoprene rubber, EP rubbers, nitrile rubber, neoprene, chloro rubber, fluorubber, epichlorohydrin rubber, silicon rubber At least one of glue, polyurethane rubber.
Research shows that a kind of selection rubber polymer-based end of any of the above does not influence constructing for final pattern.
(3)Substrate is pre-stretched:To through step(2)Sky is filled with the hollow sphere or cylindrical rubber polymer-based end of processing Gas, makes it be expanded to prestrain degree, fixed;
Hollow sphere rubber polymer-based end ring prestretching stretching strain is between 20 ~ 500%(It is preferred that 100 ~ 400%);
Hollow cylindrical rubber polymer-based end ring prestretching stretching strain is between 20 ~ 500%(It is preferred that 100 ~ 400%), axial prestretching Stretching strain is between 20 ~ 500%(It is preferred that 100 ~ 400%).
The elasticity of rubber polymer-based end allows elongation strain in interior change in a big way, and prestretching stretching strain can shape 20% Into fold, the fold formed when prestretching stretching strain is more than 100% is more notable.
(4)Surface is coated:By step(1)The graphene oxide dispersion configured is coated uniformly on through step(3)Processing Hollow sphere or the polymer-based basal surface of cylindrical rubber, at 20 ~ 60 DEG C(It is preferred that 30 ~ 40 DEG C)Rotary drying in air, is obtained Thickness is 0.2 ~ 20 micron of graphite oxide ene coatings;
The rotary speed is preferably 5 ~ 60 revs/min(More preferably 20 ~ 40 revs/min).
(5)Substrate Contraction:Will be through step(4)Air in the hollow sphere or cylindrical rubber polymer-based end of processing is released Put, obtain surface of graphene oxide fold;
Air release time >=2 minute.
If the too fast uniformity that can influence fold pattern of air rate of release, stability, and coating shedding may be caused.
(6)Graphene oxide is reduced:By step(5)Gained surface of graphene oxide fold is placed in hydrazine hydrate steam and carried out Reduction, produces graphenic surface fold.
Hydrazine hydrate solution purity >=85% used(Mass percent);
The reduction temperature is 80 ~ 100 DEG C(It is preferred that 85 ~ 95 DEG C), the recovery time is 10 ~ 24 hours(It is preferred that 15 ~ 20 hours).
Beneficial effect of the present invention:
(1)The present invention realizes that height folds graphenic surface by disposable three-dimensional shrinkage in hollow sphere and cylindrical base Constructing and Morphological control for fold, sets up a kind of simple, efficiently, inexpensive micro- pattern construction technology of graphene.
(2)Gained height fold graphene/rubber polymer-based end compound system of the invention, it is disposable to prepare, fold journey Degree is high, and hydrophobicity is good, stretchable, flexible, available for the solvent response for building compound bending, quick response, deep camber deformation Type deformation intelligence moves device, two-way available for building available for assembling high sensitivity, low potential driving, long-life strain transducer Bending, quick response, the solvent response type deformation intelligence of deep camber deformation move device, have well in wearable smart machine field Application prospect.
Brief description of the drawings
Fig. 1 is the SEM figures of the gained graphenic surface fold of the embodiment of the present invention 1;
Fig. 2 is the SEM figures of the gained graphenic surface fold of the embodiment of the present invention 8.
Embodiment
With reference to embodiment, the invention will be further described, but must not be construed to these embodiments to present invention guarantor Protect the limitation of scope.
Embodiment 1
The present embodiment comprises the following steps:
(1)Dispersion liquid is configured:By 200 milligrams of graphene oxide powders(Individual layer, lamella size is 4 microns)It is dispersed in 100 milliliters In deionized water, ultrasonic disperse 1 hour, configuration concentration is the graphene oxide dispersion of 2.0 mg/mls;
(2)Substrate surface processing:By hollow sphere natural rubber substrate(Substrate thickness is 200 microns)It is put into absolute ethyl alcohol, It is cleaned by ultrasonic 30 minutes, is dried in vacuo 1 hour at room temperature;
The purity of the absolute ethyl alcohol is 99%(Mass percent).
(3)Substrate is pre-stretched:To through step(2)Air is filled with the hollow sphere rubber polymer-based end of processing, makes it It is 300% to be expanded to spherical substrate ring prestretching stretching strain, fixed;
(4)Surface is coated:By step(1)The graphene oxide dispersion configured is coated in through step(3)The hollow ball of processing The polymer-based basal surface of shape rubber, in air at a temperature of 40 DEG C, with 30 revs/min of rotary speed Rotary drying, obtains thickness Spend the graphite oxide ene coatings for 2.0 microns;
(5)Substrate Contraction:Will be through step(4)Air release in the hollow sphere rubber polymer-based end of processing, release time For 10 minutes, surface of graphene oxide fold is obtained;
(6)Graphene oxide is reduced:By step(5)Gained surface of graphene oxide fold, which is placed in hydrazine hydrate steam, to be gone back Original, redox graphene surface folding 20 hours at a temperature of 90 DEG C, produces graphenic surface fold.
Hydrazine hydrate solution purity used is 85%(Mass percent).
It is 5.8, a width of 5.8 microns of fold, fold a height of 30.2 that graphenic surface fold obtained by the present embodiment, which folds index, Micron, water contact angle is 115 degree.
The detection method and instrument of each parameter in the present embodiment:The appearance of hollow ball or cylinder when folding index=inflation The external surface area of hollow ball or cylinder after area/deflation, calculates after being measured with ruler and obtains relevant surfaces product.Calculate fold wide It is high:First taken pictures with SEM, then according to photo scale by the wide height of software statistics fold.The test of water contact angle Determined using water contact angle tester.Following embodiment is same.
Embodiment 2
The present embodiment difference from Example 1 is, step(1)In, graphene is individual layer, and lamella size is 2 microns, configuration Graphene oxide concentration is 3.0 mg/mls;Step(2)In, rubber constituent is butadiene rubber, and substrate thickness is 300 microns; Step(4)In, obtain the graphite oxide ene coatings that thickness is 3.0 microns.Remaining parameter is same as Example 1.
It is 5.6 that gained graphenic surface fold, which folds index, a width of 6.3 microns of fold, a height of 32.5 microns of fold, and water connects Feeler is 110 degree.
Embodiment 3
The present embodiment difference from Example 1 is, step(1)In, graphene is three layers, and lamella size is 20 microns, is matched somebody with somebody Graphene oxide concentration is put for 5.0 mg/mls;Step(2)In, rubber constituent is nitrile rubber, and substrate thickness is 100 micro- Rice;Step(4)In, obtain the graphite oxide ene coatings that thickness is 3.5 microns.Remaining parameter is same as Example 1.
It is 5.0 that gained graphenic surface fold, which folds index, a width of 6.6 microns of fold, a height of 35.5 microns of fold, and water connects Feeler is 102 degree.
Embodiment 4
The present embodiment difference from Example 1 is, step(1)In, graphene is bilayer, and lamella size is 10 microns, is matched somebody with somebody Graphene oxide concentration is put for 7.0 mg/mls;Step(4)In, obtain the graphite oxide ene coatings that thickness is 10.5 microns. Remaining parameter is same as Example 1.
It is 5.4 that gained graphenic surface fold, which folds index, a width of 7.5 microns of fold, a height of 42.8 microns of fold, and water connects Feeler is 107 degree.
Embodiment 5
The present embodiment difference from Example 1 is, step(3)In, it is 100% to control spherical substrate pre-stretching rate;Step (4)In, drying condition is with 60 revs/min of rotary speed Rotary drying in 60 DEG C of air.Remaining parameter and the phase of embodiment 1 Together.
It is 2.6 that gained graphenic surface fold, which folds index, a width of 9.6 microns of fold, a height of 23.0 microns of fold, and water connects Feeler is 85 degree.
Embodiment 6
The present embodiment difference from Example 1 is, step(3)In, it is 140% to control spherical substrate pre-stretching rate;Step (6)In, reducing condition is redox graphene surface folding 24 hours at a temperature of 80 DEG C of hydrazine hydrate steam.Remaining parameter and reality Apply example 1 identical.
It is 3.3 that gained graphenic surface fold, which folds index, a width of 6.7 microns of fold, a height of 27.0 microns of fold, and water connects Feeler is 95 degree.
Embodiment 7
The present embodiment difference from Example 1 is, step(3)In, it is 500% to control spherical substrate pre-stretching rate;Step (6)In, reducing condition is reduction 12 hours at 100 DEG C of hydrazine hydrate steam.Remaining parameter is same as Example 1.
It is 8.9 that gained graphenic surface fold, which folds index, a width of 2.3 microns of fold, a height of 36.4 microns of fold, and water connects Feeler is 120 degree.
Embodiment 8
The present embodiment comprises the following steps:
(1)Dispersion liquid is configured:By 300 milligrams of graphene oxide powders(Individual layer, lamella size is 10 microns)It is dispersed in 100 milliliters In deionized water, ultrasonic disperse 2 hours, configuration concentration is the graphene oxide dispersion of 3.0 mg/mls;
(2)Substrate surface processing:Hollow cylindrical silicone rubber substrate is put into absolute ethyl alcohol, ultrasonic cleaning 30 minutes, at room temperature Vacuum drying 1 hour;
The purity of the absolute ethyl alcohol is 99.5%(Mass percent).
The hollow cylindrical rubber polymer-based end, substrate thickness is 350 microns.
(3)Substrate is pre-stretched:To through step(2)Air is filled with the hollow cylindrical silicone rubber substrate of processing, it is expanded It is 300% to ring prestretching stretching strain, axial prestretching stretching strain is 400%, fixed;
(4)Surface is coated:By step(1)The graphene oxide dispersion configured is coated uniformly on through step(3)In processing Void column shape silicone rubber substrate surface, with 50 revs/min of rotary speed Rotary drying in 20 DEG C of air, it is 4.0 to obtain thickness The graphite oxide ene coatings of micron;
(5)Substrate Contraction:Will be through step(4)Air release in the hollow cylindrical silicone rubber substrate of processing, release time is 20 Minute, obtain surface of graphene oxide fold;
(6)Graphene oxide is reduced:By step(5)The surface of graphene oxide fold of processing hangs on lower section and hydrazine hydrate is housed In flask, using hydrazine hydrate steam at a temperature of 90 DEG C redox graphene surface folding 12 hours, produce graphenic surface Fold.
Hydrazine hydrate solution purity used is 88%(Mass percent).
It is 8.1 that gained graphenic surface fold, which folds index, a width of 0.2 micron of fold, a height of 2.2 microns of fold, and water connects Feeler is 138 degree.
Embodiment 9
The present embodiment difference from Example 8 is, step(1)In, graphene is individual layer, and lamella size is 20 microns, is surpassed Sound is scattered 4 hours, and configuration graphene oxide concentration is 8.0 mg/mls;Step(4)In, obtain the oxygen that thickness is 16.6 microns Graphite ene coatings.Remaining parameter is same as Example 8.
It is 6.0 that gained graphenic surface fold, which folds index, a width of 0.8 micron of fold, a height of 6.5 microns of fold, and water connects Feeler is 111 degree.
Embodiment 10
The present embodiment difference from Example 8 is, step(1)In, configuration graphene oxide concentration is 5.0 mg/mls; Step(3)In, hollow cylindrical rubber polymer-based end ring prestretching stretching strain is 100%, and axial prestretching stretching strain is 400%;Step Suddenly(4)In, obtain the graphite oxide ene coatings that thickness is 7.2 microns.Remaining parameter is same as Example 8.
It is 4.4 that gained graphenic surface fold, which folds index, a width of 0.2 micron of fold, a height of 3.5 microns of fold, and water connects Feeler is 126 degree.
Embodiment 11
The present embodiment difference from Example 8 is, step(3)In, the pre-stretching of hollow cylindrical rubber polymer-based end ring Strain as 500%, axial prestretching stretching strain is 500%;Step(5)In, gas release time is 40 minutes.Remaining parameter is with implementing Example 8 is identical.
It is 11.8 that gained graphenic surface fold, which folds index, a width of 0.1 micron of fold, a height of 4.0 microns of fold, and water connects Feeler is 160 degree.
Embodiment 12
The present embodiment difference from Example 8 is, step(3)In, the pre-stretching of hollow cylindrical rubber polymer-based end ring Strain as 400%, axial prestretching stretching strain is 100%;Step(6)In, reducing condition is small for reduction 18 at 85 DEG C of hydrazine hydrate steam When.Remaining parameter is same as Example 8.
It is 6.8 that gained graphenic surface fold, which folds index, a width of 0.2 micron of fold, a height of 2.8 microns of fold, and water connects Feeler is 105 degree.

Claims (10)

1. a kind of construction method of graphenic surface fold, it is characterised in that comprise the following steps:
(1)Dispersion liquid is configured:By graphene oxide powder, scattered in deionized water, ultrasonic disperse more than 0.5 hour, is configured dense Spend for the graphene oxide dispersion of 0.2 ~ 8.0 mg/ml;
(2)Substrate surface processing:Hollow sphere or cylindrical rubber polymer-based end are put into absolute ethyl alcohol, ultrasonic cleaning 10 ~ 60 minutes, it is dried in vacuo more than 1 hour at room temperature;
(3)Substrate is pre-stretched:To through step(2)Air is filled with the hollow sphere or cylindrical rubber polymer-based end of processing, is made It is expanded to predetermined degree of strain, fixed;
Hollow sphere rubber polymer-based end ring prestretching stretching strain is between 20 ~ 500%;
Hollow cylindrical rubber polymer-based end ring prestretching stretching strain is between 20 ~ 500%, and axial prestretching stretching strain is 20 ~ 500% Between;
(4)Surface is coated:By step(1)The graphene oxide dispersion configured is coated uniformly on through step(3)In processing The polymer-based basal surface of empty spherical or cylindrical rubber, the Rotary drying in 20 ~ 60 DEG C of air, it is 0.2 ~ 20 micron to obtain thickness Graphite oxide ene coatings;
(5)Substrate Contraction:Will be through step(4)Air release in the hollow sphere or cylindrical rubber polymer-based end of processing, is obtained To surface of graphene oxide fold;
(6)Graphene oxide is reduced:By step(5)Gained surface of graphene oxide fold is with hydrazine hydrate steam to graphene oxide Surface folding is reduced, and produces graphenic surface fold.
2. the construction method of graphenic surface fold according to claim 1, it is characterised in that step(1)In, the oxygen The graphite alkene number of plies is 1 ~ 3 layer, and lamella size is 0.2 ~ 30 micron.
3. the construction method of graphenic surface fold according to claim 1 or 2, it is characterised in that step(1)In, institute The time for stating graphene oxide ultrasonic disperse is more than 0.5 hour.
4. the construction method of graphenic surface fold according to claim 1 or 2, it is characterised in that step(2)In, institute State hollow sphere or cylindrical rubber polymer-based end, substrate thickness >=20 micron.
5. the construction method of graphenic surface fold according to claim 1 or 2, it is characterised in that step(2)In, institute Rubber polymer-based end is stated for natural rubber, butadiene-styrene rubber, butadiene rubber, isoprene rubber, EP rubbers, nitrile rubber, neoprene At least one of rubber, chloro rubber, fluorubber, epichlorohydrin rubber, silicon rubber, polyurethane rubber.
6. the construction method of graphenic surface fold according to claim 1 or 2, it is characterised in that step(3)In, in Empty spherical rubber polymer-based end ring prestretching stretching strain is 100 ~ 400%.
7. the construction method of graphenic surface fold according to claim 1 or 2, it is characterised in that step(3)In, in Empty cylindrical rubber polymer-based end ring prestretching stretching strain is 100 ~ 400%, and axial prestretching stretching strain is 100 ~ 400%.
8. the construction method of graphenic surface fold according to claim 1 or 2, it is characterised in that step(4)In, institute Rotary speed is stated for 5 ~ 60 revs/min.
9. the construction method of graphenic surface fold according to claim 1 or 2, it is characterised in that step(5)In, institute State air release time >=2 minute.
10. the construction method of graphenic surface fold according to claim 1 or 2, it is characterised in that step(6)In, institute With hydrazine hydrate solution purity >=85%;The reduction temperature is 80 ~ 100 DEG C, and the recovery time is 10 ~ 24 hours.
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