CN102787488A - Method for preparing graphene oxide grafting surface modification carbon fiber - Google Patents
Method for preparing graphene oxide grafting surface modification carbon fiber Download PDFInfo
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- CN102787488A CN102787488A CN2012102682260A CN201210268226A CN102787488A CN 102787488 A CN102787488 A CN 102787488A CN 2012102682260 A CN2012102682260 A CN 2012102682260A CN 201210268226 A CN201210268226 A CN 201210268226A CN 102787488 A CN102787488 A CN 102787488A
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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 that obtains by organic fiber.The similar Delanium of the microstructure of carbon fiber is a random graphits structure.Carbon fiber is the excellent new material of a kind of mechanical property, and its proportion is less than 1/4 of steel, carbon fiber resin composite material tensile strength generally all more than 3500Mpa, be steel 7-9 doubly, tensile modulus of elasticity is that 230～430Gpa also is higher than steel.Therefore the specific strength of CFRP is that the ratio of intensity and its density of material can reach 2000MPa/ (g/cm
3) more than, and the specific strength of A3 steel is merely 59Mpa/ (g/cm
3) about, its specific modulus is also high than steel.The specific strength of material is higher, and then member dead weight is littler, and specific modulus is higher, and then the rigidity of member is bigger.Just because of its outstanding performance, it has obtained to use widely in many new and high technology cold receptions such as Aeronautics and Astronautics, automobile, motions.
Yet; Owing to 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 along with the enrichment of the runaway and the carbon of non-carbon, reduces its surface-activity; Surface tension descends, with resin matrix wettability variation.In addition, for the TENSILE STRENGTH that improves carbon fiber need reduce blemish as far as possible, therefore, its surface area is also less.Level and smooth like this surface and the grappling effect between the matrix resin are also relatively poor, cause the interlaminar shear strength of composite to reduce, and can not reach the use designing requirement.Therefore, be reinforcing material when preparing composite when adopting carbon fiber, carbon fiber all will at first pass through surface modification treatment, combines with interface between the matrix material to improve it.
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 grafted modified carbon fiber is provided.
The method of graphene oxide grafted modified 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 ℃, under the speed of 50rpm～200rpm, stir adding and contain the potassium strong oxidizer; And continue to stir 4h～12h, mixed liquor, mixed liquor poured in 10 ℃～50 ℃ the water-bath; Continue reaction 40min～60min, add 90 ℃～100 ℃ hot water then, make the system boiling and keep 20min～40min; Add volumetric concentration then and be 40%～60% hydrogen peroxide solution; Under the speed of 100rpm～500rpm, be stirred to dissolving fully, adopt ultra-pure water washing 3～6 times then, being filtered to does not have SO in the filter cake
4 2-,-35 ℃ of following freeze dryings, promptly get graphite oxide then;
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 that contains the potassium strong oxidizer: (0.1～4); The mass ratio of graphite and hydrogen peroxide solution is 1: (0.125～4);
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide being dissolved in the solvent, and being ultrasonic concussion 0.5h～12h under the condition of 100W～1000W at ultrasonic power, is centrifugal under the condition of 3000rpm～10000rpm at the centrifuge revolution then ,-35 ℃ of freeze dryings, promptly gets the graphene oxide powder;
Three, graphene oxide functionalization: with 200ml THF solution, 8gNaBH
4With 0.1g I
2Join in the flask, stirring and dissolving adds 0.5g graphene oxide powdered reaction 2h again, and freeze drying 24h obtains the carboxylic-oxidized Graphene;
Take by weighing 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in the beaker, add the 5ml silane resin acceptor kh-550 again, at 75 ℃ of waters bath with thermostatic control reaction 6h; Then with the centrifugal 10min of 12000 rev/mins rotating speed; Outwell supernatant liquor, add oxolane again, outwell supernatant liquor with the centrifugal 10min of 12000 rev/mins rotating speed; Collect amidized graphene oxide viscous fluid and freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the immersion of square glass frame is filled in the beaker of nitration mixture, said nitration mixture is made up of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid; Wherein the volume ratio of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1; Then beaker is placed on the magnetic stirring apparatus, normal-temperature reaction 8h spends deionised water to washing lotion for neutral; At 100 ℃ of vacuumize 24h, promptly get the acid oxidase carbon fiber then;
The acid oxidase carbon fiber is fixed with glass fiber; To join in the there-necked flask with glass fiber fixing acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide then; There-necked flask is reacted 48h under 70 ℃ of water bath condition; Use washing with acetone to washing lotion to be neutrality,, obtain the chloride carbon fiber at 70 ℃ of vacuumize 24h;
Five, the carbon fiber surface graphene oxide is handled:
Pour in the there-necked flask after being dissolved in the amination graphene oxide in the dimethyl formamide, add the chloride carbon fiber of step 4 gained, the mol ratio of wherein amidized graphene oxide and chloride carbon fiber is 1: 1; At 70 ℃ of water bath with thermostatic control heating 48h; Be neutral with washing with acetone to filtrating, the grafting carbon fiber, with the grafting carbon fiber with 150ml acetone backflow 24h; At 60 ℃ of following vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide then.
The present invention has overcome shortcomings such as prior art complex equipments, cost height, adopts the method for chemical graft to realize even, the firm covering of graphene oxide at carbon fiber surface.Simple, the easy row of the method, cheap is applicable to production in enormous quantities.Through the even covering of graphene oxide, can improve the roughness of carbon fiber surface greatly, thereby improve the interface performance of carbon fibre reinforced composite through the grappling effect at carbon fiber surface.Carbon fiber/carbon composite the interface shear strength of the surface grafting graphene oxide for preparing after the graft modification of process graphene oxide is untreated and can improves 25%.
Description of drawings
Fig. 1 is the SEM surface topography map of carbon fiber of the surface grafting graphene oxide of experiment one preparation;
Fig. 2 is the SEM surface topography map of carbon fiber of the surface grafting graphene oxide of experiment two preparations;
Fig. 3 is the SEM surface topography map of carbon fiber of the surface grafting graphene oxide of experiment three preparations;
Fig. 4 is the SEM surface topography enlarged drawing of carbon fiber of the surface grafting graphene oxide of experiment three preparations;
Fig. 5 is the SEM surface topography map of carbon fiber of the surface grafting graphene oxide of experiment four preparations.
The specific embodiment
Technical scheme of the present invention is not limited to the following cited specific embodiment, also comprises the combination in any between each specific embodiment.
The specific embodiment one: the method for this embodiment graphene oxide grafted modified 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 ℃, under the speed of 50rpm～200rpm, stir adding and contain the potassium strong oxidizer; And continue to stir 4h～12h, mixed liquor, mixed liquor poured in 10 ℃～50 ℃ the water-bath; Continue reaction 40min～60min, add 90 ℃～100 ℃ hot water then, make the system boiling and keep 20min～40min; Add volumetric concentration then and be 40%～60% hydrogen peroxide solution; Under the speed of 100rpm～500rpm, be stirred to dissolving fully, adopt ultra-pure water washing 3～6 times then, being filtered to does not have SO in the filter cake
4 2-,-35 ℃ of following freeze dryings, promptly get graphite oxide then;
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 that contains the potassium strong oxidizer: (0.1～4); The mass ratio of graphite and hydrogen peroxide solution is 1: (0.125～4);
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide being dissolved in the solvent, and being ultrasonic concussion 0.5h～12h under the condition of 100W～1000W at ultrasonic power, is centrifugal under the condition of 3000rpm～10000rpm at the centrifuge revolution then ,-35 ℃ of freeze dryings, promptly gets the graphene oxide powder;
Three, graphene oxide functionalization: with 200ml THF solution, 8gNaBH
4With 0.1g I
2Join in the flask, stirring and dissolving adds 0.5g graphene oxide powdered reaction 2h again, and freeze drying 24h obtains the carboxylic-oxidized Graphene;
Take by weighing 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in the beaker, add the 5ml silane resin acceptor kh-550 again, at 75 ℃ of waters bath with thermostatic control reaction 6h; Then with the centrifugal 10min of 12000 rev/mins rotating speed; Outwell supernatant liquor, add oxolane again, outwell supernatant liquor with the centrifugal 10min of 12000 rev/mins rotating speed; Collect amidized graphene oxide viscous fluid and freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame; Then the immersion of square glass frame is filled in the beaker of nitration mixture, said nitration mixture is made up of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid, and wherein the volume ratio of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1; Then beaker is placed on the magnetic stirring apparatus; Normal-temperature reaction 8h spends deionised water to washing lotion for neutral, then at 100 ℃ of vacuumize 24h; Promptly get acid oxidase carbon fiber (but this step mainly is the carbon fiber surface generation reactive activity functional group in inertia, mainly is carboxyl and hydroxyl);
The acid oxidase carbon fiber is fixed (purpose be prevent in the course of reaction carbon fiber twines each other be difficult to handle) with glass fiber; To join in the there-necked flask with glass fiber fixing acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide then; There-necked flask is reacted 48h under 70 ℃ of water bath condition; Use washing with acetone to washing lotion to be neutrality,, obtain the chloride carbon fiber at 70 ℃ of vacuumize 24h;
Five, the carbon fiber surface graphene oxide is handled:
Pour in the there-necked flask after being dissolved in the amination graphene oxide in the dimethyl formamide, add the chloride carbon fiber of step 4 gained, the mol ratio of wherein amidized graphene oxide and chloride carbon fiber is 1: 1; At 70 ℃ of water bath with thermostatic control heating 48h; Be neutral with washing with acetone to filtrating, the grafting carbon fiber, with the grafting carbon fiber with 150ml acetone backflow 24h; At 60 ℃ of following vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide then.
The specific embodiment two: what this embodiment and the specific embodiment one were different is that the strong oxidizing acid described in the step 1 is the concentrated sulfuric acid or perchloric acid.Other is identical with the specific embodiment one.
The specific embodiment three: what this embodiment was different with the specific embodiment one or two is that the potassium strong oxidizer that contains described in the step 1 is potassium permanganate or potassium hyperchlorate.Other is identical with the specific embodiment one or two.
The specific embodiment four: what this embodiment was different with one of specific embodiment one to three is that the nitrate described in the 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 this embodiment was different with one of specific embodiment one to four is that the solvent described in the step 2 is water, ethanol, acetone, ether, chloroform, benzene, toluene, ethylene glycol, oxolane, N, dinethylformamide, 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 this embodiment was different with one of specific embodiment one to five is to be cooled to-3 ℃ in the step 1.Other is identical with one of specific embodiment one to five.
The specific embodiment seven: this embodiment is different with one of specific embodiment one to six is that the mass ratio of graphite and strong oxidizing acid is 1: 3 in the step 1; The mass ratio of graphite and nitrate is 1: 2; Graphite is 1: 2 with the mass ratio that contains the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide solution is 1: 2.Other is identical with one of specific embodiment one to six.
The specific embodiment eight: this embodiment is different with one of specific embodiment one to seven is that to add volumetric concentration in the step 1 be 50% hydrogen peroxide solution.Other is identical with one of specific embodiment one to seven.
The specific embodiment nine: this embodiment is different with one of specific embodiment one to eight is to be ultrasonic concussion under the condition of 500W at ultrasonic power in the step 2.Other is identical with one of specific embodiment one to eight.
The specific embodiment ten: this embodiment is different with one of specific embodiment one to nine is to be centrifugal under the condition of 5000rpm at the centrifuge revolution in the 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 grafted modified 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 the adding potassium hyperchlorate, and continue to stir 4h; Mixed liquor, mixed liquor poured in 10 ℃ the water-bath, continue reaction 40min; Add 95 ℃ of hot water then, make system boiling and keep 30min, add volumetric concentration then and be 50% hydrogen peroxide solution; Under the speed of 150rpm, be stirred to dissolving fully, adopt ultra-pure water washing 5 times then, being filtered to does not have SO in the filter cake
4 2-,-35 ℃ of following freeze dryings, promptly get graphite oxide then;
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 that contains the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide solution is 1: 0.125;
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide being dissolved in the solvent, and being ultrasonic concussion 3h under the condition of 200W at ultrasonic power, is centrifugal under the condition of 5000rpm at the centrifuge revolution then ,-35 ℃ of freeze dryings, promptly gets the graphene oxide powder;
Three, graphene oxide functionalization: with 200ml THF solution, 8g NaBH
4With 0.1g I
2Join in the flask, stirring and dissolving adds 0.5g graphene oxide powdered reaction 2h again, and freeze drying 24h obtains the carboxylic-oxidized Graphene;
Take by weighing 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in the beaker, add the 5ml silane resin acceptor kh-550 again, at 75 ℃ of waters bath with thermostatic control reaction 6h; Then with the centrifugal 10min of 12000 rev/mins rotating speed; Outwell supernatant liquor, add oxolane again, outwell supernatant liquor with the centrifugal 10min of 12000 rev/mins rotating speed; Collect amidized graphene oxide viscous fluid and freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the immersion of square glass frame is filled in the beaker of nitration mixture, said nitration mixture is made up of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid; Wherein the volume ratio of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1; Then beaker is placed on the magnetic stirring apparatus, normal-temperature reaction 8h spends deionised water to washing lotion for neutral; At 100 ℃ of vacuumize 24h, promptly get the acid oxidase carbon fiber then;
The acid oxidase carbon fiber is fixed with glass fiber; To join in the there-necked flask with glass fiber fixing acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide then; There-necked flask is reacted 48h under 70 ℃ of water bath condition; Use washing with acetone to washing lotion to be neutrality,, obtain the chloride carbon fiber at 70 ℃ of vacuumize 24h;
Five, the carbon fiber surface graphene oxide is handled:
Pour in the there-necked flask after being dissolved in the amination graphene oxide in the dimethyl formamide, add the chloride carbon fiber of step 4 gained, the mol ratio of wherein amidized graphene oxide and chloride carbon fiber is 1: 1; At 70 ℃ of water bath with thermostatic control heating 48h; Be neutral with washing with acetone to filtrating, the grafting carbon fiber, with the grafting carbon fiber with 150ml acetone backflow 24h; At 60 ℃ of following vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide then.
Carbon fiber/carbon composite the interface shear strength of the surface grafting graphene oxide for preparing after the graft modification of this experiment of process graphene oxide is untreated and improves 23%.
Experiment two:
The method of graphene oxide grafted modified 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 the adding potassium hyperchlorate, and continue to stir 4h; Mixed liquor, mixed liquor poured in 10 ℃ the water-bath, continue reaction 40min; Add 95 ℃ of hot water then, make system boiling and keep 30min, add volumetric concentration then and be 50% hydrogen peroxide solution; Under the speed of 150rpm, be stirred to dissolving fully, adopt ultra-pure water washing 5 times then, being filtered to does not have SO in the filter cake
4 2-,-35 ℃ of following freeze dryings, promptly get graphite oxide then;
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 that contains the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide solution is 1: 0.125;
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide being dissolved in the solvent, and being ultrasonic concussion 3h under the condition of 200W at ultrasonic power, is centrifugal under the condition of 5000rpm at the centrifuge revolution then ,-35 ℃ of freeze dryings, promptly gets the graphene oxide powder;
Three, graphene oxide functionalization: with 200ml THF solution, 8g NaBH
4With 0.1g I
2Join in the flask, stirring and dissolving adds 0.5g graphene oxide powdered reaction 2h again, and freeze drying 24h obtains the carboxylic-oxidized Graphene;
Take by weighing 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in the beaker, add the 5ml silane resin acceptor kh-550 again, at 75 ℃ of waters bath with thermostatic control reaction 6h; Then with the centrifugal 10min of 12000 rev/mins rotating speed; Outwell supernatant liquor, add oxolane again, outwell supernatant liquor with the centrifugal 10min of 12000 rev/mins rotating speed; Collect amidized graphene oxide viscous fluid and freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the immersion of square glass frame is filled in the beaker of nitration mixture, said nitration mixture is made up of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid; Wherein the volume ratio of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1; Then beaker is placed on the magnetic stirring apparatus, normal-temperature reaction 8h spends deionised water to washing lotion for neutral; At 100 ℃ of vacuumize 24h, promptly get the acid oxidase carbon fiber then;
The acid oxidase carbon fiber is fixed with glass fiber; To join in the there-necked flask with glass fiber fixing acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide then; There-necked flask is reacted 48h under 70 ℃ of water bath condition; Use washing with acetone to washing lotion to be neutrality,, obtain the chloride carbon fiber at 70 ℃ of vacuumize 24h;
Five, the carbon fiber surface graphene oxide is handled:
Pour in the there-necked flask after being dissolved in the amination graphene oxide in the dimethyl formamide, add the chloride carbon fiber of step 4 gained, the mol ratio of wherein amidized graphene oxide and chloride carbon fiber is 1: 1; At 70 ℃ of water bath with thermostatic control heating 48h; Be neutral with washing with acetone to filtrating, the grafting carbon fiber, with the grafting carbon fiber with 150ml acetone backflow 24h; At 60 ℃ of following vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide then.
Carbon fiber/carbon composite the interface shear strength of the surface grafting graphene oxide for preparing after the graft modification of this experiment of process graphene oxide is untreated and can improves 24%.
Experiment three:
The method of graphene oxide grafted modified 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 the adding potassium hyperchlorate, and continue to stir 4h; Mixed liquor, mixed liquor poured in 10 ℃ the water-bath, continue reaction 40min; Add 95 ℃ of hot water then, make system boiling and keep 30min, add volumetric concentration then and be 50% hydrogen peroxide solution; Under the speed of 150rpm, be stirred to dissolving fully, adopt ultra-pure water washing 5 times then, being filtered to does not have SO in the filter cake
4 2-,-35 ℃ of following freeze dryings, promptly get graphite oxide then;
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 that contains the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide solution is 1: 0.125;
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide being dissolved in the solvent, and being ultrasonic concussion 3h under the condition of 200W at ultrasonic power, is centrifugal under the condition of 5000rpm at the centrifuge revolution then ,-35 ℃ of freeze dryings, promptly gets the graphene oxide powder;
Three, graphene oxide functionalization: with 200ml THF solution, 8g NaBH
4With 0.1g I
2Join in the flask, stirring and dissolving adds 0.5g graphene oxide powdered reaction 2h again, and freeze drying 24h obtains the carboxylic-oxidized Graphene;
Take by weighing 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in the beaker, add the 5ml silane resin acceptor kh-550 again, at 75 ℃ of waters bath with thermostatic control reaction 6h; Then with the centrifugal 10min of 12000 rev/mins rotating speed; Outwell supernatant liquor, add oxolane again, outwell supernatant liquor with the centrifugal 10min of 12000 rev/mins rotating speed; Collect amidized graphene oxide viscous fluid and freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the immersion of square glass frame is filled in the beaker of nitration mixture, said nitration mixture is made up of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid; Wherein the volume ratio of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1; Then beaker is placed on the magnetic stirring apparatus, normal-temperature reaction 8h spends deionised water to washing lotion for neutral; At 100 ℃ of vacuumize 24h, promptly get the acid oxidase carbon fiber then;
The acid oxidase carbon fiber is fixed with glass fiber; To join in the there-necked flask with glass fiber fixing acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide then; There-necked flask is reacted 48h under 70 ℃ of water bath condition; Use washing with acetone to washing lotion to be neutrality,, obtain the chloride carbon fiber at 70 ℃ of vacuumize 24h;
Five, the carbon fiber surface graphene oxide is handled:
Pour in the there-necked flask after being dissolved in the amination graphene oxide in the dimethyl formamide, add the chloride carbon fiber of step 4 gained, the mol ratio of wherein amidized graphene oxide and chloride carbon fiber is 1: 1; At 70 ℃ of water bath with thermostatic control heating 48h; Be neutral with washing with acetone to filtrating, the grafting carbon fiber, with the grafting carbon fiber with 150ml acetone backflow 24h; At 60 ℃ of following vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide then.
Carbon fiber/carbon composite the interface shear strength of the surface grafting graphene oxide for preparing after the graft modification of this experiment of process graphene oxide is untreated and improves 25%.
Experiment four:
The method of graphene oxide grafted modified 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 the adding potassium hyperchlorate, and continue to stir 4h; Mixed liquor, mixed liquor poured in 10 ℃ the water-bath, continue reaction 40min; Add 95 ℃ of hot water then, make system boiling and keep 30min, add volumetric concentration then and be 50% hydrogen peroxide solution; Under the speed of 150rpm, be stirred to dissolving fully, adopt ultra-pure water washing 5 times then, being filtered to does not have SO in the filter cake
4 2-,-35 ℃ of following freeze dryings, promptly get graphite oxide then;
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 that contains the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide solution is 1: 0.125;
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide being dissolved in the solvent, and being ultrasonic concussion 3h under the condition of 200W at ultrasonic power, is centrifugal under the condition of 5000rpm at the centrifuge revolution then ,-35 ℃ of freeze dryings, promptly gets the graphene oxide powder;
Three, graphene oxide functionalization: with 200ml THF solution, 8g NaBH
4With 0.1g I
2Join in the flask, stirring and dissolving adds 0.5g graphene oxide powdered reaction 2h again, and freeze drying 24h obtains the carboxylic-oxidized Graphene;
Take by weighing 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in the beaker, add the 5ml silane resin acceptor kh-550 again, at 75 ℃ of waters bath with thermostatic control reaction 6h; Then with the centrifugal 10min of 12000 rev/mins rotating speed; Outwell supernatant liquor, add oxolane again, outwell supernatant liquor with the centrifugal 10min of 12000 rev/mins rotating speed; Collect amidized graphene oxide viscous fluid and freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the immersion of square glass frame is filled in the beaker of nitration mixture, said nitration mixture is made up of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid; Wherein the volume ratio of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1; Then beaker is placed on the magnetic stirring apparatus, normal-temperature reaction 8h spends deionised water to washing lotion for neutral; At 100 ℃ of vacuumize 24h, promptly get the acid oxidase carbon fiber then;
The acid oxidase carbon fiber is fixed with glass fiber; To join in the there-necked flask with glass fiber fixing acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide then; There-necked flask is reacted 48h under 70 ℃ of water bath condition; Use washing with acetone to washing lotion to be neutrality,, obtain the chloride carbon fiber at 70 ℃ of vacuumize 24h;
Five, the carbon fiber surface graphene oxide is handled:
Pour in the there-necked flask after being dissolved in the amination graphene oxide in the dimethyl formamide, add the chloride carbon fiber of step 4 gained, the mol ratio of wherein amidized graphene oxide and chloride carbon fiber is 1: 1; At 70 ℃ of water bath with thermostatic control heating 48h; Be neutral with washing with acetone to filtrating, the grafting carbon fiber, with the grafting carbon fiber with 150ml acetone backflow 24h; At 60 ℃ of following vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide then.
Claims (10)
1. the method for graphene oxide grafted modified carbon fiber is characterized in that the method for graphene oxide grafted modified 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 ℃, under the speed of 50rpm～200rpm, stir adding and contain the potassium strong oxidizer; And continue to stir 4h～12h, mixed liquor, mixed liquor poured in 10 ℃～50 ℃ the water-bath; Continue reaction 40min～60min, add 90 ℃～100 ℃ hot water then, make the system boiling and keep 20min～40min; Add volumetric concentration then and be 40%～60% hydrogen peroxide solution; Under the speed of 100rpm～500rpm, be stirred to dissolving fully, adopt ultra-pure water washing 3～6 times then, being filtered to does not have SO in the filter cake
4 2-,-35 ℃ of following freeze dryings, promptly get graphite oxide then;
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 that contains the potassium strong oxidizer: (0.1～4); The mass ratio of graphite and hydrogen peroxide solution is 1: (0.125～4);
Two, the graphite oxide mother liquor is peeled off:
Graphite oxide being dissolved in the solvent, and being ultrasonic concussion 0.5h～12h under the condition of 100W～1000W at ultrasonic power, is centrifugal under the condition of 3000rpm～10000rpm at the centrifuge revolution then ,-35 ℃ of freeze dryings, promptly gets the graphene oxide powder;
Three, graphene oxide functionalization: with 200ml THF solution, 8g NaBH
4With 0.1g I
2Join in the flask, stirring and dissolving adds 0.5g graphene oxide powdered reaction 2h again, and freeze drying 24h obtains the carboxylic-oxidized Graphene;
Take by weighing 0.0025g carboxylic-oxidized Graphene and 15ml distilled water joins in the beaker, add the 5ml silane resin acceptor kh-550 again, at 75 ℃ of waters bath with thermostatic control reaction 6h; Then with the centrifugal 10min of 12000 rev/mins rotating speed; Outwell supernatant liquor, add oxolane again, outwell supernatant liquor with the centrifugal 10min of 12000 rev/mins rotating speed; Collect amidized graphene oxide viscous fluid and freeze drying, obtain the amination graphene oxide;
Four, carbon fiber is surface-functionalized:
Carbon fiber is entangled on the square glass frame, then the immersion of square glass frame is filled in the beaker of nitration mixture, said nitration mixture is made up of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid; Wherein the volume ratio of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3: 1; Then beaker is placed on the magnetic stirring apparatus, normal-temperature reaction 8h spends deionised water to washing lotion for neutral; At 100 ℃ of vacuumize 24h, promptly get the acid oxidase carbon fiber then;
The acid oxidase carbon fiber is fixed with glass fiber; To join in the there-necked flask with glass fiber fixing acid oxidase carbon fiber, 160ml thionyl chloride and 20ml dimethyl formamide then; There-necked flask is reacted 48h under 70 ℃ of water bath condition; Use washing with acetone to washing lotion to be neutrality,, obtain the chloride carbon fiber at 70 ℃ of vacuumize 24h;
Five, the carbon fiber surface graphene oxide is handled:
Pour in the there-necked flask after being dissolved in the amination graphene oxide in the dimethyl formamide, add the chloride carbon fiber of step 4 gained, the mol ratio of wherein amidized graphene oxide and chloride carbon fiber is 1: 1; At 70 ℃ of water bath with thermostatic control heating 48h; Be neutral with washing with acetone to filtrating, the grafting carbon fiber, with the grafting carbon fiber with 150ml acetone backflow 24h; At 60 ℃ of following vacuumize 24h, obtain the carbon fiber of surface grafting graphene oxide then.
2. according to the method for the said graphene oxide grafted of claim 1 modified carbon fiber, it is characterized in that the strong oxidizing acid described in the step 1 is the concentrated sulfuric acid or perchloric acid.
3. according to the method for the said graphene oxide grafted of claim 1 modified carbon fiber, it is characterized in that the potassium strong oxidizer that contains described in the step 1 is potassium permanganate or potassium hyperchlorate.
4. according to the method for the said graphene oxide grafted of claim 1 modified carbon fiber, it is characterized in that the nitrate described in the step 1 is potassium nitrate, sodium nitrate, magnesium nitrate or calcium nitrate.
5. according to the method for the said graphene oxide grafted of claim 1 modified carbon fiber; It is characterized in that the solvent described in the step 2 is water, ethanol, acetone, ether, chloroform, benzene, toluene, ethylene glycol, oxolane, N, dinethylformamide, benzinum, methyl acetate, ethyl acetate, carbon tetrachloride, organic chloride, pyridine, ethylenediamine or carbon disulfide.
6. according to the method for claim 1,2,3,4 or 5 said graphene oxide grafted modified carbon fibers, it is characterized in that being cooled in the step 1-3 ℃.
7. according to the method for claim 1,2,3,4 or 5 said graphene oxide grafted modified carbon fibers, it is characterized in that the mass ratio of graphite and strong oxidizing acid is 1: 3 in the step 1; The mass ratio of graphite and nitrate is 1: 2; Graphite is 1: 2 with the mass ratio that contains the potassium strong oxidizer; The mass ratio of graphite and hydrogen peroxide solution is 1: 2.
8. according to the method for claim 1,2,3,4 or 5 said graphene oxide grafted modified carbon fibers, it is characterized in that adding in the step 1 volumetric concentration and be 50% hydrogen peroxide solution.
9. according to the method for claim 1,2,3,4 or 5 said graphene oxide grafted modified carbon fibers, it is characterized in that in the step 2 that at ultrasonic power be ultrasonic concussion under the condition of 500W.
10. according to the method for claim 1,2,3,4 or 5 said graphene oxide grafted modified carbon fibers, it is characterized in that in the step 2 at the centrifuge revolution being centrifugal under the condition of 5000rpm.
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| 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 |
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