CN102787488B - Method for preparing graphene oxide grafting surface modification carbon fiber - Google Patents
Method for preparing graphene oxide grafting surface modification carbon fiber Download PDFInfo
- Publication number
- CN102787488B CN102787488B CN2012102682260A CN201210268226A CN102787488B CN 102787488 B CN102787488 B CN 102787488B CN 2012102682260 A CN2012102682260 A CN 2012102682260A CN 201210268226 A CN201210268226 A CN 201210268226A CN 102787488 B CN102787488 B CN 102787488B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- graphene oxide
- graphite
- grafting
- surface modification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A method for preparing a graphene oxide grafting surface modification carbon fiber relates to a carbon fiber modification method, and is used for solving the technical problems that the existing carbon fiber has low surface activity, reduced surface tension and poor wettability with a resin matrix, and the interlaminar shear strength of a composite material is caused to reduce. The method comprises the steps as follows: 1, graphite oxidization; 2, separation of graphite oxide mother liquor; 3, functionalization of graphite oxide; 4, carbon fiber surface functionalization; and 5, carbon fiber surface graphite oxide treatment. The graphite oxide uniformly covers the carbon fiber surface, the roughness of the carbon fiber surface can be greatly improved, and accordingly, the interfacial properties of a carbon fiber reinforced composite material can be improved by an anchoring action. The interfacial shear strength of the surface grafting graphene oxide carbon fiber/carbon composite material which is prepared through graphene oxide grafting modification can be improved by 25% in comparison with that of the untreated surface grafting graphene oxide carbon fiber/carbon composite material.
Description
Technical field
The present invention relates to a kind of method of modifying of carbon fiber.
Background technology
Carbon fiber, as its name suggests, it not only has the intrinsic intrinsic property of material with carbon element, and the soft machinability that has textile fabric concurrently is arranged again, is fortifying fibre of new generation.Carbon fiber is through carbonization and graphitization processing and the micro crystal graphite material obtained by organic fiber.The similar Delanium of the microstructure of carbon fiber is random graphits structure.Carbon fiber is a kind of new material of mechanical property excellence, and its proportion is less than 1/4 of steel, carbon fiber resin composite material tensile strength generally all more than 3500Mpa, be the 7-9 of steel doubly, tensile modulus of elasticity is that 230~430Gpa is also higher than steel.Therefore the specific strength of CFRP is that the intensity of material can reach 2000MPa/ (g/cm with the ratio of its density
3) more than, and the specific strength of A3 steel is only 59Mpa/ (g/cm
3) left and right, its specific modulus is also high than steel.The specific strength of material is higher, and member dead weight is less, and specific modulus is higher, and the rigidity of member is larger.The outstanding performance just because of it, it obtains a wide range of applications in many new and high technology cold receptions such as Aeronautics and Astronautics, automobile, motions.
Yet, because carbon fiber is that the phosphorus content that makes through 1300 ℃~1600 ℃ high temperature cabonizations is up to the new carbon more than 93%, carbonization in high temperature inert gas, enrichment along with runaway and the carbon of non-carbon, its surface-activity is reduced, surface tension descends, with resin matrix wettability variation.In addition, for the TENSILE STRENGTH that improves carbon fiber need to reduce blemish as far as possible, therefore, its surface area is also less.Level and smooth like this surface and the grappling effect between matrix resin are also poor, cause the interlaminar shear strength of composite to reduce, and can not reach the use designing requirement.Therefore, when adopting carbon fiber, be reinforcing material while preparing composite, at first carbon fiber all will pass through surface modification treatment, to improve its interface between matrix material, is combined.
Summary of the invention
The present invention is low in order to solve existing carbon fiber surface activity, and surface tension descends, and with resin matrix wettability variation, causes the technical problem of the interlaminar shear strength reduction of composite, and a kind of method of graphene oxide grafting surface modification carbon fiber is provided.
The method of graphene oxide grafting surface modification carbon fiber is carried out according to the following steps:
One, graphite oxidation:
Graphite is joined in the mixture of strong oxidizing acid and nitrate, be cooled to-5 ℃~0 ℃, stir and add containing the potassium strong oxidizer under the speed of 50rpm~200rpm, and 4h~12h is stirred in continuation, obtain mixed liquor, mixed liquor is poured in the water-bath of 10 ℃~50 ℃, continue reaction 40min~60min, then add 90 ℃~100 ℃ hot water, system is seethed with excitement and keep 20min~40min, then add the hydrogen peroxide solution that volumetric concentration is 40%~60%, be stirred under the speed of 100rpm~500rpm fully and dissolve, then adopt ultra-pure water washing 3~6 times, be filtered in filter cake without SO
4 2-, then ,-35 ℃ of lower freeze dryings, obtain graphite oxide,
Wherein graphite is 1 with the mass ratio of strong oxidizing acid: (0.025~5); The mass ratio of graphite and nitrate is 1: (0.2~8); Graphite is 1 with the mass ratio containing the potassium strong oxidizer: (0.1~4); The mass ratio of graphite and hydrogen peroxide is 1: (0.125~4);
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide is dissolved in solvent, and ultrasonic concussion 0.5h~12h under the condition that is 100W~1000W at ultrasonic power, centrifugal under the condition that is then 3000rpm~10000rpm at the centrifuge revolution ,-35 ℃ of freeze dryings, obtain the graphene oxide powder;
Three, graphene oxide functionalization: by 200ml THF solution, 8gNaBH
4with 0.1g I
2join in flask, stirring and dissolving, then add 0.5g graphene oxide powdered reaction 2h, freeze drying 24h, obtain the carboxylic-oxidized Graphene;
Take 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in beaker, add again the 5ml silane resin acceptor kh-550, at 75 ℃ of water bath with thermostatic control reaction 6h, then with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, then add oxolane with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, collect amidized graphene oxide viscous fluid freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the square glass frame is immersed and fills in the beaker of nitration mixture, described nitration mixture is comprised of red fuming nitric acid (RFNA) and the concentrated sulfuric acid, wherein the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1, then beaker is placed on magnetic stirring apparatus, normal-temperature reaction 8h, it is neutral with deionized water, washing to washing lotion, then at 100 ℃ of vacuumize 24h, obtain the acid oxidase carbon fiber;
The acid oxidase carbon fiber is fixed with glass fiber, then acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide that will be fixing with glass fiber join in there-necked flask, there-necked flask is reacted to 48h under 70 ℃ of water bath condition, it is neutral with acetone, washing to washing lotion, at 70 ℃ of vacuumize 24h, obtain the chloride carbon fiber;
Five, the carbon fiber surface graphene oxide is processed:
After being dissolved in dimethyl formamide by the amination graphene oxide, pour in there-necked flask, the chloride carbon fiber that adds the step 4 gained, wherein the mol ratio of amidized graphene oxide and chloride carbon fiber is 1: 1, at 70 ℃ of water bath with thermostatic control heating 48h, wash to filtrate and be neutral with acetone, obtain the grafting carbon fiber, by 150ml acetone backflow 24h for the grafting carbon fiber, then at 60 ℃ of lower vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide.
The present invention has overcome that prior art equipment is complicated, the high in cost of production shortcoming, adopt the method for chemical graft realize graphene oxide carbon fiber surface evenly, firmly cover.Simple, the easy row of the method, cheap, be applicable to produce in enormous quantities.Uniform fold by graphene oxide at carbon fiber surface, can improve the roughness of carbon fiber surface greatly, thereby improve the interface performance of carbon fibre reinforced composite by the grappling effect.The carbon fiber of the surface grafting graphene oxide prepared after the graphene oxide graft modification/carbon composite interface shear strength is more untreated improves 25%.
The accompanying drawing explanation
Fig. 1 is the SEM surface topography map of testing the carbon fiber of a surface grafting graphene oxide prepared;
Fig. 2 is the SEM surface topography map of testing the carbon fiber of the two surface grafting graphene oxides that prepare;
Fig. 3 is the SEM surface topography map of testing the carbon fiber of the three surface grafting graphene oxides that prepare;
Fig. 4 is the SEM surface topography enlarged drawing of testing the carbon fiber of the three surface grafting graphene oxides that prepare;
Fig. 5 is the SEM surface topography map of testing the carbon fiber of the four surface grafting graphene oxides that prepare.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the method for present embodiment graphene oxide grafting surface modification carbon fiber is carried out according to the following steps:
One, graphite oxidation:
Graphite is joined in the mixture of strong oxidizing acid and nitrate, be cooled to-5 ℃~0 ℃, stir and add containing the potassium strong oxidizer under the speed of 50rpm~200rpm, and 4h~12h is stirred in continuation, obtain mixed liquor, mixed liquor is poured in the water-bath of 10 ℃~50 ℃, continue reaction 40min~60min, then add 90 ℃~100 ℃ hot water, system is seethed with excitement and keep 20min~40min, then add the hydrogen peroxide solution that volumetric concentration is 40%~60%, be stirred under the speed of 100rpm~500rpm fully and dissolve, then adopt ultra-pure water washing 3~6 times, be filtered in filter cake without SO
4 2-, then ,-35 ℃ of lower freeze dryings, obtain graphite oxide,
Wherein graphite is 1 with the mass ratio of strong oxidizing acid: (0.025~5); The mass ratio of graphite and nitrate is 1: (0.2~8); Graphite is 1 with the mass ratio containing the potassium strong oxidizer: (0.1~4); The mass ratio of graphite and hydrogen peroxide is 1: (0.125~4);
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide is dissolved in solvent, and ultrasonic concussion 0.5h~12h under the condition that is 100W~1000W at ultrasonic power, centrifugal under the condition that is then 3000rpm~10000rpm at the centrifuge revolution ,-35 ℃ of freeze dryings, obtain the graphene oxide powder;
Three, graphene oxide functionalization: by 200ml THF solution, 8gNaBH
4with 0.1g I
2join in flask, stirring and dissolving, then add 0.5g graphene oxide powdered reaction 2h, freeze drying 24h, obtain the carboxylic-oxidized Graphene;
Take 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in beaker, add again the 5ml silane resin acceptor kh-550, at 75 ℃ of water bath with thermostatic control reaction 6h, then with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, then add oxolane with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, collect amidized graphene oxide viscous fluid freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the square glass frame is immersed and fills in the beaker of nitration mixture, described nitration mixture is comprised of red fuming nitric acid (RFNA) and the concentrated sulfuric acid, wherein the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1, then beaker is placed on magnetic stirring apparatus, normal-temperature reaction 8h, it is neutral with deionized water, washing to washing lotion, then at 100 ℃ of vacuumize 24h, obtain acid oxidase carbon fiber (this step is mainly the active function groups that can react in the carbon fiber surface generation of inertia, is mainly carboxyl and hydroxyl);
The acid oxidase carbon fiber is fixed to (purpose be prevent in course of reaction carbon fiber is wound around mutually be difficult to process) with glass fiber, then acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide that will be fixing with glass fiber join in there-necked flask, there-necked flask is reacted to 48h under 70 ℃ of water bath condition, it is neutral with acetone, washing to washing lotion, at 70 ℃ of vacuumize 24h, obtain the chloride carbon fiber;
Five, the carbon fiber surface graphene oxide is processed:
After being dissolved in dimethyl formamide by the amination graphene oxide, pour in there-necked flask, the chloride carbon fiber that adds the step 4 gained, wherein the mol ratio of amidized graphene oxide and chloride carbon fiber is 1: 1, at 70 ℃ of water bath with thermostatic control heating 48h, wash to filtrate and be neutral with acetone, obtain the grafting carbon fiber, by 150ml acetone backflow 24h for the grafting carbon fiber, then at 60 ℃ of lower vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide.
The specific embodiment two: what present embodiment was different from the specific embodiment one is that the strong oxidizing acid described in step 1 is the concentrated sulfuric acid or perchloric acid.Other is identical with the specific embodiment one.
The specific embodiment three: present embodiment is different from the specific embodiment one or two is described in step 1 containing the potassium strong oxidizer, to be potassium permanganate or potassium hyperchlorate.Other is identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment was different from one of specific embodiment one to three is that the nitrate described in step 1 is potassium nitrate, sodium nitrate, magnesium nitrate or calcium nitrate.Other is identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different from one of specific embodiment one to four is that the solvent described in step 2 is water, ethanol, acetone, ether, chloroform, benzene, toluene, ethylene glycol, oxolane, DMF, benzinum, methyl acetate, ethyl acetate, carbon tetrachloride, organic chloride, pyridine, ethylenediamine or carbon disulfide.Other is identical with one of specific embodiment one to four.
The specific embodiment six: what present embodiment was different from one of specific embodiment one to five is to be cooled to-3 ℃ in step 1.Other is identical with one of specific embodiment one to five.
The specific embodiment seven: what present embodiment was different from one of specific embodiment one to six is that in step 1, graphite is 1: 3 with the mass ratio of strong oxidizing acid; The mass ratio of graphite and nitrate is 1: 2; Graphite is 1: 2 with the mass ratio containing the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide is 1: 2.Other is identical with one of specific embodiment one to six.
The specific embodiment eight: what present embodiment was different from one of specific embodiment one to seven is to add the hydrogen peroxide solution that volumetric concentration is 50% in step 1.Other is identical with one of specific embodiment one to seven.
The specific embodiment nine: present embodiment is different from one of specific embodiment one to eight is ultrasonic concussion under the condition that is 500W at ultrasonic power in step 2.Other is identical with one of specific embodiment one to eight.
The specific embodiment ten: present embodiment is different from one of specific embodiment one to nine is centrifugal under the condition that is 5000rpm at the centrifuge revolution in step 2.Other is identical with one of specific embodiment one to nine.
Adopt following experimental verification effect of the present invention:
Experiment one:
The method of graphene oxide grafting surface modification carbon fiber is carried out according to the following steps:
One, graphite oxidation:
Graphite is joined in the mixture of perchloric acid and potassium nitrate, be cooled to-5 ℃, under the speed of 50rpm, stir and add potassium hyperchlorate, and 4h is stirred in continuation, mixed liquor, mixed liquor is poured in the water-bath of 10 ℃, continue reaction 40min, then add 95 ℃ of hot water, system seethed with excitement and keep 30min, then adding the hydrogen peroxide solution that volumetric concentration is 50%, being stirred under the speed of 150rpm fully and dissolving, then adopt ultra-pure water washing 5 times, be filtered in filter cake without SO
4 2-, then ,-35 ℃ of lower freeze dryings, obtain graphite oxide;
Wherein graphite is 1: 0.1 with the mass ratio of strong oxidizing acid; The mass ratio of graphite and nitrate is 1: 0.2; Graphite is 1: 0.1 with the mass ratio containing the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide is 1: 0.125;
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide is dissolved in solvent, and ultrasonic concussion 3h under the condition that is 200W at ultrasonic power, centrifugal under the condition that is then 5000rpm at the centrifuge revolution ,-35 ℃ of freeze dryings, obtain the graphene oxide powder;
Three, graphene oxide functionalization: by 200ml THF solution, 8g NaBH
4with 0.1g I
2join in flask, stirring and dissolving, then add 0.5g graphene oxide powdered reaction 2h, freeze drying 24h, obtain the carboxylic-oxidized Graphene;
Take 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in beaker, add again the 5ml silane resin acceptor kh-550, at 75 ℃ of water bath with thermostatic control reaction 6h, then with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, then add oxolane with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, collect amidized graphene oxide viscous fluid freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the square glass frame is immersed and fills in the beaker of nitration mixture, described nitration mixture is comprised of red fuming nitric acid (RFNA) and the concentrated sulfuric acid, wherein the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1, then beaker is placed on magnetic stirring apparatus, normal-temperature reaction 8h, it is neutral with deionized water, washing to washing lotion, then at 100 ℃ of vacuumize 24h, obtain the acid oxidase carbon fiber;
The acid oxidase carbon fiber is fixed with glass fiber, then acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide that will be fixing with glass fiber join in there-necked flask, there-necked flask is reacted to 48h under 70 ℃ of water bath condition, it is neutral with acetone, washing to washing lotion, at 70 ℃ of vacuumize 24h, obtain the chloride carbon fiber;
Five, the carbon fiber surface graphene oxide is processed:
After being dissolved in dimethyl formamide by the amination graphene oxide, pour in there-necked flask, the chloride carbon fiber that adds the step 4 gained, wherein the mol ratio of amidized graphene oxide and chloride carbon fiber is 1: 1, at 70 ℃ of water bath with thermostatic control heating 48h, wash to filtrate and be neutral with acetone, obtain the grafting carbon fiber, by 150ml acetone backflow 24h for the grafting carbon fiber, then at 60 ℃ of lower vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide.
The more untreated raising 23% of the carbon fiber of the surface grafting graphene oxide prepared after the graft modification of this experiment graphene oxide/carbon composite interface shear strength.
Experiment two:
The method of graphene oxide grafting surface modification carbon fiber is carried out according to the following steps:
One, graphite oxidation:
Graphite is joined in the mixture of perchloric acid and potassium nitrate, be cooled to-5 ℃, under the speed of 50rpm, stir and add potassium hyperchlorate, and 4h is stirred in continuation, mixed liquor, mixed liquor is poured in the water-bath of 10 ℃, continue reaction 40min, then add 95 ℃ of hot water, system seethed with excitement and keep 30min, then adding the hydrogen peroxide solution that volumetric concentration is 50%, being stirred under the speed of 150rpm fully and dissolving, then adopt ultra-pure water washing 5 times, be filtered in filter cake without SO
4 2-, then ,-35 ℃ of lower freeze dryings, obtain graphite oxide;
Wherein graphite is 1: 0.048 with the mass ratio of strong oxidizing acid; The mass ratio of graphite and nitrate is 1: 0.2; Graphite is 1: 0.1 with the mass ratio containing the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide is 1: 0.125;
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide is dissolved in solvent, and ultrasonic concussion 3h under the condition that is 200W at ultrasonic power, centrifugal under the condition that is then 5000rpm at the centrifuge revolution ,-35 ℃ of freeze dryings, obtain the graphene oxide powder;
Three, graphene oxide functionalization: by 200ml THF solution, 8g NaBH
4with 0.1g I
2join in flask, stirring and dissolving, then add 0.5g graphene oxide powdered reaction 2h, freeze drying 24h, obtain the carboxylic-oxidized Graphene;
Take 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in beaker, add again the 5ml silane resin acceptor kh-550, at 75 ℃ of water bath with thermostatic control reaction 6h, then with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, then add oxolane with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, collect amidized graphene oxide viscous fluid freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the square glass frame is immersed and fills in the beaker of nitration mixture, described nitration mixture is comprised of red fuming nitric acid (RFNA) and the concentrated sulfuric acid, wherein the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1, then beaker is placed on magnetic stirring apparatus, normal-temperature reaction 8h, it is neutral with deionized water, washing to washing lotion, then at 100 ℃ of vacuumize 24h, obtain the acid oxidase carbon fiber;
The acid oxidase carbon fiber is fixed with glass fiber, then acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide that will be fixing with glass fiber join in there-necked flask, there-necked flask is reacted to 48h under 70 ℃ of water bath condition, it is neutral with acetone, washing to washing lotion, at 70 ℃ of vacuumize 24h, obtain the chloride carbon fiber;
Five, the carbon fiber surface graphene oxide is processed:
After being dissolved in dimethyl formamide by the amination graphene oxide, pour in there-necked flask, the chloride carbon fiber that adds the step 4 gained, wherein the mol ratio of amidized graphene oxide and chloride carbon fiber is 1: 1, at 70 ℃ of water bath with thermostatic control heating 48h, wash to filtrate and be neutral with acetone, obtain the grafting carbon fiber, by 150ml acetone backflow 24h for the grafting carbon fiber, then at 60 ℃ of lower vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide.
The carbon fiber of the surface grafting graphene oxide prepared after the graft modification of this experiment graphene oxide/carbon composite interface shear strength is more untreated improves 24%.
Experiment three:
The method of graphene oxide grafting surface modification carbon fiber is carried out according to the following steps:
One, graphite oxidation:
Graphite is joined in the mixture of perchloric acid and potassium nitrate, be cooled to-5 ℃, under the speed of 50rpm, stir and add potassium hyperchlorate, and 4h is stirred in continuation, mixed liquor, mixed liquor is poured in the water-bath of 10 ℃, continue reaction 40min, then add 95 ℃ of hot water, system seethed with excitement and keep 30min, then adding the hydrogen peroxide solution that volumetric concentration is 50%, being stirred under the speed of 150rpm fully and dissolving, then adopt ultra-pure water washing 5 times, be filtered in filter cake without SO
4 2-, then ,-35 ℃ of lower freeze dryings, obtain graphite oxide;
Wherein graphite is 1: 0.025 with the mass ratio of strong oxidizing acid; The mass ratio of graphite and nitrate is 1: 0.2; Graphite is 1: 0.1 with the mass ratio containing the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide is 1: 0.125;
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide is dissolved in solvent, and ultrasonic concussion 3h under the condition that is 200W at ultrasonic power, centrifugal under the condition that is then 5000rpm at the centrifuge revolution ,-35 ℃ of freeze dryings, obtain the graphene oxide powder;
Three, graphene oxide functionalization: by 200ml THF solution, 8g NaBH
4with 0.1g I
2join in flask, stirring and dissolving, then add 0.5g graphene oxide powdered reaction 2h, freeze drying 24h, obtain the carboxylic-oxidized Graphene;
Take 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in beaker, add again the 5ml silane resin acceptor kh-550, at 75 ℃ of water bath with thermostatic control reaction 6h, then with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, then add oxolane with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, collect amidized graphene oxide viscous fluid freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the square glass frame is immersed and fills in the beaker of nitration mixture, described nitration mixture is comprised of red fuming nitric acid (RFNA) and the concentrated sulfuric acid, wherein the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1, then beaker is placed on magnetic stirring apparatus, normal-temperature reaction 8h, it is neutral with deionized water, washing to washing lotion, then at 100 ℃ of vacuumize 24h, obtain the acid oxidase carbon fiber;
The acid oxidase carbon fiber is fixed with glass fiber, then acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide that will be fixing with glass fiber join in there-necked flask, there-necked flask is reacted to 48h under 70 ℃ of water bath condition, it is neutral with acetone, washing to washing lotion, at 70 ℃ of vacuumize 24h, obtain the chloride carbon fiber;
Five, the carbon fiber surface graphene oxide is processed:
After being dissolved in dimethyl formamide by the amination graphene oxide, pour in there-necked flask, the chloride carbon fiber that adds the step 4 gained, wherein the mol ratio of amidized graphene oxide and chloride carbon fiber is 1: 1, at 70 ℃ of water bath with thermostatic control heating 48h, wash to filtrate and be neutral with acetone, obtain the grafting carbon fiber, by 150ml acetone backflow 24h for the grafting carbon fiber, then at 60 ℃ of lower vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide.
The more untreated raising 25% of the carbon fiber of the surface grafting graphene oxide prepared after the graft modification of this experiment graphene oxide/carbon composite interface shear strength.
Experiment four:
The method of graphene oxide grafting surface modification carbon fiber is carried out according to the following steps:
One, graphite oxidation:
Graphite is joined in the mixture of perchloric acid and potassium nitrate, be cooled to-5 ℃, under the speed of 50rpm, stir and add potassium hyperchlorate, and 4h is stirred in continuation, mixed liquor, mixed liquor is poured in the water-bath of 10 ℃, continue reaction 40min, then add 95 ℃ of hot water, system seethed with excitement and keep 30min, then adding the hydrogen peroxide solution that volumetric concentration is 50%, being stirred under the speed of 150rpm fully and dissolving, then adopt ultra-pure water washing 5 times, be filtered in filter cake without SO
4 2-, then ,-35 ℃ of lower freeze dryings, obtain graphite oxide;
Wherein graphite is 1: 0.0125 with the mass ratio of strong oxidizing acid; The mass ratio of graphite and nitrate is 1: 0.2; Graphite is 1: 0.1 with the mass ratio containing the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide is 1: 0.125;
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide is dissolved in solvent, and ultrasonic concussion 3h under the condition that is 200W at ultrasonic power, centrifugal under the condition that is then 5000rpm at the centrifuge revolution ,-35 ℃ of freeze dryings, obtain the graphene oxide powder;
Three, graphene oxide functionalization: by 200ml THF solution, 8g NaBH
4with 0.1g I
2join in flask, stirring and dissolving, then add 0.5g graphene oxide powdered reaction 2h, freeze drying 24h, obtain the carboxylic-oxidized Graphene;
Take 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in beaker, add again the 5ml silane resin acceptor kh-550, at 75 ℃ of water bath with thermostatic control reaction 6h, then with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, then add oxolane with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, collect amidized graphene oxide viscous fluid freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the square glass frame is immersed and fills in the beaker of nitration mixture, described nitration mixture is comprised of red fuming nitric acid (RFNA) and the concentrated sulfuric acid, wherein the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1, then beaker is placed on magnetic stirring apparatus, normal-temperature reaction 8h, it is neutral with deionized water, washing to washing lotion, then at 100 ℃ of vacuumize 24h, obtain the acid oxidase carbon fiber;
The acid oxidase carbon fiber is fixed with glass fiber, then acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide that will be fixing with glass fiber join in there-necked flask, there-necked flask is reacted to 48h under 70 ℃ of water bath condition, it is neutral with acetone, washing to washing lotion, at 70 ℃ of vacuumize 24h, obtain the chloride carbon fiber;
Five, the carbon fiber surface graphene oxide is processed:
After being dissolved in dimethyl formamide by the amination graphene oxide, pour in there-necked flask, the chloride carbon fiber that adds the step 4 gained, wherein the mol ratio of amidized graphene oxide and chloride carbon fiber is 1: 1, at 70 ℃ of water bath with thermostatic control heating 48h, wash to filtrate and be neutral with acetone, obtain the grafting carbon fiber, by 150ml acetone backflow 24h for the grafting carbon fiber, then at 60 ℃ of lower vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide.
Claims (9)
1. the method for graphene oxide grafting surface modification carbon fiber is characterized in that the method for graphene oxide grafting surface modification carbon fiber is carried out according to the following steps:
One, graphite oxidation:
Graphite is joined in the mixture of the concentrated sulfuric acid and nitrate, be cooled to-5 ℃~0 ℃, stir and add containing the potassium strong oxidizer under the speed of 50rpm~200rpm, and 4h~12h is stirred in continuation, obtain mixed liquor, mixed liquor is poured in the water-bath of 10 ℃~50 ℃, continue reaction 40min~60min, then add 90 ℃~100 ℃ hot water, system is seethed with excitement and keep 20min~40min, then add the hydrogen peroxide solution that volumetric concentration is 40%~60%, be stirred under the speed of 100rpm~500rpm fully and dissolve, then adopt ultra-pure water washing 3~6 times, be filtered in filter cake without SO
4 2-, then ,-35 ℃ of lower freeze dryings, obtain graphite oxide,
Wherein the mass ratio of graphite and the concentrated sulfuric acid is 1 ﹕ (0.025~5); The mass ratio of graphite and nitrate is 1 ﹕ (0.2~8); Graphite is 1 ﹕ (0.1~4) with the mass ratio containing the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide is 1 ﹕ (0.125~4);
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide is dissolved in solvent, and ultrasonic concussion 0.5h~12h under the condition that is 100W~1000W at ultrasonic power, centrifugal under the condition that is then 3000rpm~10000rpm at the centrifuge revolution ,-35 ℃ of freeze dryings, obtain the graphene oxide powder;
Three, graphene oxide functionalization: by 200ml THF solution, 8g NaBH
4with 0.1g I
2join in flask, stirring and dissolving, then add 0.5g graphene oxide powdered reaction 2h, freeze drying 24h, obtain the carboxylic-oxidized Graphene;
Take 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in beaker, add again the 5ml silane resin acceptor kh-550, at 75 ℃ of water bath with thermostatic control reaction 6h, then with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, then add oxolane with the centrifugal 10min of the rotating speed of 12000 rev/mins, outwell supernatant liquor, collect amidized graphene oxide viscous fluid freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the square glass frame is immersed and fills in the beaker of nitration mixture, described nitration mixture is comprised of red fuming nitric acid (RFNA) and the concentrated sulfuric acid, wherein the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3:1, then beaker is placed on magnetic stirring apparatus, normal-temperature reaction 8h, it is neutral with deionized water, washing to washing lotion, then at 100 ℃ of vacuumize 24h, obtain the acid oxidase carbon fiber;
The acid oxidase carbon fiber is fixed with glass fiber, then acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide that will be fixing with glass fiber join in there-necked flask, there-necked flask is reacted to 48h under 70 ℃ of water bath condition, it is neutral with acetone, washing to washing lotion, at 70 ℃ of vacuumize 24h, obtain the chloride carbon fiber;
Five, the carbon fiber surface graphene oxide is processed:
After being dissolved in dimethyl formamide by the amination graphene oxide, pour in there-necked flask, the chloride carbon fiber that adds the step 4 gained, wherein the mol ratio of amidized graphene oxide and chloride carbon fiber is 1:1, at 70 ℃ of water bath with thermostatic control heating 48h, wash to filtrate and be neutral with acetone, obtain the grafting carbon fiber, by 150ml acetone backflow 24h for the grafting carbon fiber, then at 60 ℃ of lower vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide.
2. the method for graphene oxide grafting surface modification carbon fiber according to claim 1, is characterized in that described in step 1 being potassium permanganate or potassium hyperchlorate containing the potassium strong oxidizer.
3. the method for graphene oxide grafting surface modification carbon fiber according to claim 1, is characterized in that the nitrate described in step 1 is potassium nitrate, sodium nitrate, magnesium nitrate or calcium nitrate.
4. the method for graphene oxide grafting surface modification carbon fiber according to claim 1, it is characterized in that the solvent described in step 2 is water, ethanol, acetone, ether, chloroform, benzene, toluene, ethylene glycol, oxolane, DMF, benzinum, methyl acetate, ethyl acetate, carbon tetrachloride, pyridine, ethylenediamine or carbon disulfide.
5. according to the method for claim 1,2,3 or 4 described graphene oxide grafting surface modification carbon fibers, it is characterized in that being cooled in step 1-3 ℃.
6. according to the method for claim 1,2,3 or 4 described graphene oxide grafting surface modification carbon fibers, it is characterized in that in step 1, the mass ratio of graphite and the concentrated sulfuric acid is 1 ﹕ 3; The mass ratio of graphite and nitrate is 1 ﹕ 2; Graphite is 1:2 with the mass ratio containing the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide is 1 ﹕ 2.
7. according to the method for claim 1,2,3 or 4 described graphene oxide grafting surface modification carbon fibers, it is characterized in that in step 1 adding the hydrogen peroxide solution that volumetric concentration is 50%.
8. according to the method for claim 1,2,3 or 4 described graphene oxide grafting surface modification carbon fibers, it is characterized in that ultrasonic concussion under the condition that is 500W at ultrasonic power in step 2.
9. according to the method for claim 1,2,3 or 4 described graphene oxide grafting surface modification carbon fibers, it is characterized in that under the condition that is 5000rpm at the centrifuge revolution in step 2 centrifugal.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012102682260A CN102787488B (en) | 2012-07-30 | 2012-07-30 | Method for preparing graphene oxide grafting surface modification carbon fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012102682260A CN102787488B (en) | 2012-07-30 | 2012-07-30 | Method for preparing graphene oxide grafting surface modification carbon fiber |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102787488A CN102787488A (en) | 2012-11-21 |
CN102787488B true CN102787488B (en) | 2013-12-25 |
Family
ID=47153063
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2012102682260A Active CN102787488B (en) | 2012-07-30 | 2012-07-30 | Method for preparing graphene oxide grafting surface modification carbon fiber |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102787488B (en) |
Families Citing this family (45)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103015159A (en) * | 2012-12-03 | 2013-04-03 | 天津工业大学 | Method for improving tensile strength of carbon fiber |
CN103850123B (en) * | 2012-12-03 | 2016-02-03 | 中国科学院宁波材料技术与工程研究所 | Carbon fiber/polypropylene composite material of a kind of interface modification and preparation method thereof |
CN103243544B (en) * | 2013-05-07 | 2015-09-02 | 中国科学院山西煤炭化学研究所 | A kind of method of modifying of carbon fiber surface |
CN103225203B (en) * | 2013-05-09 | 2014-12-31 | 西北工业大学 | Preparation method of carbon fiber-graphene oxide-carbon nanotube multi-scale reinforcement |
CN103321035A (en) * | 2013-06-29 | 2013-09-25 | 西北工业大学 | Surface modification method of carbon fibre plasma grafted graphene oxide |
CN103353529B (en) * | 2013-07-25 | 2015-06-10 | 广西壮族自治区兽医研究所 | Electrochemical immunosensor for detecting AIV H7 and preparation method thereof |
CN103422196B (en) * | 2013-07-29 | 2015-07-15 | 中国科学院生态环境研究中心 | Preparation method for graphene and graphite core sheath structured fiber |
CN103469534B (en) * | 2013-09-30 | 2015-05-13 | 哈尔滨工业大学 | Method for chemical grafting modification for surfaces of carbon fibers |
CN103820996B (en) * | 2014-03-04 | 2016-02-17 | 哈尔滨工业大学 | A kind of preparation method of binary graft modification pbo fiber |
CN104047160B (en) * | 2014-06-17 | 2016-06-22 | 哈尔滨工业大学 | A kind of method of surface of graphene oxide graft modification aramid fiber |
CN104088132B (en) * | 2014-07-23 | 2016-11-16 | 昆明理工恒达科技股份有限公司 | A kind of carbon fiber powder surface modifying method |
CN104151581B (en) * | 2014-07-29 | 2017-04-12 | 哈尔滨工业大学 | Preparation method of composite carbon fiber/graphene oxide/organosilicone resin multidimensional hybrid material |
CN104195824B (en) * | 2014-09-15 | 2016-04-27 | 哈尔滨工业大学 | A kind of carbon fiber surface modification method |
CN104894843B (en) * | 2015-05-22 | 2017-08-18 | 哈尔滨唐风科技发展有限公司 | A kind of carbon fiber for wood plastic composite produces the surface treatment method of waste material |
CN105040412A (en) * | 2015-08-24 | 2015-11-11 | 哈尔滨工业大学 | Method for surface modification of carbon fiber through graphene oxide |
CN105239357A (en) * | 2015-08-24 | 2016-01-13 | 哈尔滨工业大学 | Method of chemically-grafting graphene oxide onto surface of carbon fiber |
CN105542227A (en) * | 2015-12-07 | 2016-05-04 | 宁波墨西科技有限公司 | Carbon fiber reinforcement and preparation method thereof |
CN106009144A (en) * | 2016-03-16 | 2016-10-12 | 盐城市翔盛碳纤维科技有限公司 | High-thermal-conductivity polyolefin resin based composite material and preparation method thereof |
CN105778502A (en) * | 2016-03-24 | 2016-07-20 | 中国科学院理化技术研究所 | Preparation method for graphene oxide treated hybrid chopped fiber reinforced polyether sulfone composite material |
CN106044748A (en) * | 2016-05-12 | 2016-10-26 | 安徽大学 | Method for preparing boron-doped graphene |
CN106115671B (en) * | 2016-06-23 | 2019-02-19 | 常州第六元素材料科技股份有限公司 | A kind of preparation method of alkylation modification graphene |
CN107761375B (en) * | 2017-11-10 | 2020-04-24 | 青岛大学 | Method for grafting branched molecular tannic acid on surface of carbon fiber |
CN108000916B (en) * | 2017-11-15 | 2019-08-02 | 陈川莲 | A kind of preparation method of single layered porous graphene enhancing carbon fiber fishing rod |
CN107903627A (en) * | 2017-11-29 | 2018-04-13 | 西华大学 | A kind of thermoplasticity lightweight composite material and preparation method thereof |
CN109929263A (en) * | 2017-12-15 | 2019-06-25 | 南京机器人研究院有限公司 | Novel carbon fiber composite |
CN108342099A (en) * | 2018-02-08 | 2018-07-31 | 青岛大学 | A kind of method of surface of graphene oxide chemical modification and application |
CN108949025A (en) * | 2018-06-05 | 2018-12-07 | 张芸 | A kind of heat resistant type rust-proofing wax |
CN108841292A (en) * | 2018-06-15 | 2018-11-20 | 汪国亮 | A kind of anti-corrosion epoxy-phenolic hydroxyl group toner coating preparation method of functional graphene oxide filling |
CN110642246B (en) * | 2018-06-26 | 2021-05-28 | 中国石油天然气股份有限公司 | Preparation method of graphene microspheres |
CN108997696A (en) * | 2018-07-12 | 2018-12-14 | 山东佳星环保科技有限公司 | A kind of preparation method of graphene enhancing carbon fibre composite |
CN109112822B (en) * | 2018-07-23 | 2021-01-22 | 河南工业大学 | Method for preparing carbon fiber in-situ growth graphene composite carrier |
CN109133042B (en) * | 2018-09-10 | 2020-06-05 | 宁波革鑫新能源科技有限公司 | Preparation method of large-sheet-diameter graphene sheet |
CN109868647A (en) * | 2019-03-26 | 2019-06-11 | 陕西科技大学 | A method of in the layer-by-layer chemical graft graphene oxide of carbon fiber surface |
CN112409886A (en) * | 2019-03-30 | 2021-02-26 | 刘小龙 | Processing technology of graphene-based anticorrosive coating |
CN109987948B (en) * | 2019-04-15 | 2022-03-08 | 中国科学院宁波材料技术与工程研究所 | Preparation method of pyrolytic carbon interface layer of carbon fiber reinforced ceramic matrix composite |
CN110669347A (en) * | 2019-10-28 | 2020-01-10 | 北京盛广拓再生科技股份有限公司 | Wheel-sticking-free high-viscosity emulsified asphalt |
CN111154144A (en) * | 2020-02-14 | 2020-05-15 | 台州学院 | Preparation method of graphene oxide reinforced carbon fiber material |
CN112442273A (en) * | 2020-11-25 | 2021-03-05 | 界首市兴隆渔具有限公司 | Composite material for preparing carbon fiber fishing rod and preparation method thereof |
CN112430115B (en) * | 2020-12-01 | 2021-12-28 | 江苏星途新材料科技有限公司 | Preparation process of high-performance carbon fiber graphene |
CN112626845B (en) * | 2020-12-18 | 2022-07-22 | 山东非金属材料研究所 | Surface modification method of PBO (poly (p-phenylene benzobisoxazole)) fibers |
CN112830720B (en) * | 2021-01-21 | 2022-07-19 | 广东碧通百年科技有限公司 | Radiation pollution preventing mortar for wall |
CN113652018B (en) * | 2021-06-22 | 2023-05-30 | 浙江邦德管业有限公司 | High-strength polyethylene gas pipeline and preparation method thereof |
CN113666761A (en) * | 2021-09-29 | 2021-11-19 | 江苏脒诺甫纳米材料有限公司 | High-temperature-resistant roller and preparation method thereof |
CN114437467B (en) * | 2022-03-04 | 2023-05-12 | 深圳石墨烯创新中心有限公司 | Preparation method of graphene oxide-polystyrene composite material |
CN115477816B (en) * | 2022-09-06 | 2023-08-18 | 湖北合聚高分子材料有限公司 | Dielectric composite material and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0057492A2 (en) * | 1981-01-05 | 1982-08-11 | BASF Aktiengesellschaft | Process for the surface modification of carbon fibres |
CN101966988A (en) * | 2010-11-17 | 2011-02-09 | 哈尔滨工业大学 | Method for preparing graphene powder |
CN102010218A (en) * | 2010-10-18 | 2011-04-13 | 天津工业大学 | Preparation method of graphene oxide doped unidirectional C/C composite material |
CN102249220A (en) * | 2011-03-18 | 2011-11-23 | 太原理工大学 | Quick preparation method for graphene oxide film |
-
2012
- 2012-07-30 CN CN2012102682260A patent/CN102787488B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0057492A2 (en) * | 1981-01-05 | 1982-08-11 | BASF Aktiengesellschaft | Process for the surface modification of carbon fibres |
CN102010218A (en) * | 2010-10-18 | 2011-04-13 | 天津工业大学 | Preparation method of graphene oxide doped unidirectional C/C composite material |
CN101966988A (en) * | 2010-11-17 | 2011-02-09 | 哈尔滨工业大学 | Method for preparing graphene powder |
CN102249220A (en) * | 2011-03-18 | 2011-11-23 | 太原理工大学 | Quick preparation method for graphene oxide film |
Also Published As
Publication number | Publication date |
---|---|
CN102787488A (en) | 2012-11-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102787488B (en) | Method for preparing graphene oxide grafting surface modification carbon fiber | |
CN102409528B (en) | Preparation method of carbon fiber reinforcement grafted by graphene oxide | |
CN102974838B (en) | Method for preparing graphene loaded nano nickel composite powder material by hydrothermal method | |
CN101781459B (en) | Graphene/polyaniline conductive composite material and preparation method thereof | |
CN106395809A (en) | Method for preparing oxidized graphene at normal temperature | |
CN104403275B (en) | A kind of modified graphene/thermoset ting resin composite and preparation method thereof | |
CN104251753B (en) | Elastic stress sensor based on oxidized grapheme electrospinning PU (polyurethane) film | |
CN105088415A (en) | Graphene oxide solution for wet spinning and preparation method thereof, graphene fiber and preparation method of graphene fiber | |
CN103741264A (en) | Method for preparing graphene fibers through self-assembly of large lamellar graphene oxide | |
CN102826542B (en) | A kind of graphene with high specific surface activity, Its Preparation Method And Use with mesopore | |
CN103146007A (en) | Preparation method for graphene/aramid fibre 1414 nano-fibre composite membrane | |
CN103160826B (en) | Preparation method of continuous carbon fiber surface pyrolytic carbon/nickel composite coating | |
CN102560746A (en) | Preparation method of polyacrylonitrile/graphene composite-based carbon fiber | |
CN113235184B (en) | Preparation method of aramid fiber nano-based composite conductive fiber | |
CN104277421A (en) | Preparation method of multicomponent-modified carbon-fiber-reinforced epoxy resin composite material | |
CN102916168B (en) | Modification method of artificial graphite | |
CN106694048B (en) | A kind of nucleocapsid copper nano-wire-organometallic skeletal composite catalyst and its preparation method and application | |
CN102516771B (en) | Method for modifying methylphenyl silicone resin | |
CN104289249A (en) | Preparation method of Fe and N-doped porous carbon nanofiber applicable to cathode catalyst for polymer fuel cell | |
CN106084179A (en) | A kind of high-strength thermoplastic polyurethane solid-solid phase change energy storage material and preparation method thereof | |
CN104945850A (en) | Preparation method of polymer-modified carbon-nanotube-reinforced mixed resin composite material | |
CN104556021B (en) | A kind of method that large stretch of footpath graphene oxide is prepared with natural flaky graphite | |
CN103820996B (en) | A kind of preparation method of binary graft modification pbo fiber | |
CN102604147A (en) | Preparation method for polypyrrole and graphene oxide based sponge structural material | |
CN103094529B (en) | Preparation method of composite cathode material of helical carbon nanotube/graphite |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |