CN102586952A - Method for preparing graphene-reinforced polyacrylonitrile carbon fibers - Google Patents
Method for preparing graphene-reinforced polyacrylonitrile carbon fibers Download PDFInfo
- Publication number
- CN102586952A CN102586952A CN201210005004XA CN201210005004A CN102586952A CN 102586952 A CN102586952 A CN 102586952A CN 201210005004X A CN201210005004X A CN 201210005004XA CN 201210005004 A CN201210005004 A CN 201210005004A CN 102586952 A CN102586952 A CN 102586952A
- Authority
- CN
- China
- Prior art keywords
- graphene
- polyacrylonitrile
- carbon fiber
- solution
- water
- 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.)
- Pending
Links
Images
Abstract
The invention relates to a method for preparing graphene-reinforced polyacrylonitrile carbon fibers. The method comprises the following steps of: (1) preparing graphene or graphene oxide; (2) preparing a graphene/polyacrylonitrile spinning solution; (3) preparing graphene/polyacrylonitrile-based composite fibers; and (4) preparing graphene/polyacrylonitrile-based carbon. By the method, the dispersibility and interface bonding strength of the graphene oxide in a polymer matrix are effectively improved, and the comprehensive performance of the carbon fibers is further improved; the mechanical properties of the prepared carbon fibers are obviously improved, and the prepared carbon fibers can be used in the fields such as material reinforcement, electric conduction, anti-static electricity and heat conduction; and moreover, the preparation process is simple, easy to control and low in cost.
Description
Technical field
The invention belongs to the preparation field of polyacrylonitrile carbon fiber, particularly a kind of preparation method of Graphene RPP nitrile carbon fiber.
Background technology
Polyacrylonitrile is the fiber of being processed through spinning process for the polymer of main chain structure unit by acrylonitrile, is that the carbon fiber combination property of presoma preparation is best with the polyacrylonitrile fibril, and output accounts for more than 90%.Polyacrylonitrile-based carbon fibre integrates high mechanical properties, high-modulus, low-gravity, high temperature resistant, chemical resistance and good electricity physical and mechanical properties; Its good performance and unique function, Aeronautics and Astronautics, weapons, naval vessels, automobile, machine-building, through spin, fields such as industrial circle such as chemical industry, electronics, communication, medical equipment and physical culture have opened up application prospects.
Along with constant development of economy, the whole world constantly increases having demand special or that improve the tencel of function, and the fiber that especially has high strength, electric conductivity is applied to fields such as reinforcing material, function dress ornament, electromagnetic field, military affairs gradually by exploration.Graphene is SP between the carbon atom
2Hydridization Cheng Jian is arranged in the monoatomic layer flat crystal of bi-dimensional cellular shape lattice, has bigger serface, excellent electricity, calorifics and mechanical property.At present, it is its excellent mechanical property that Graphene attracts researcher's characteristic most, and Graphene is the highest material of human known strength, and is also harder than diamond, taller last 100 times of the best in the world iron and steel of strength ratio.Use Graphene and compound preparation composite of matrix polymer or fiber, can obviously improve the performance of material,, improve electricity, heat resistance etc. as improving physical-mechanical properties.
About the existing report of the technology of preparing of Graphene hybrid polymer thing composite; For example: Chinese patent; The old Yongsheng of CN101474897 etc.; " Graphene-organic material layered assembling film and preparation method thereof ", its characteristic comprises: with grapheme material and organic material is raw material, through method for manufacturing thin film such as spin coating, spraying, dipping-the lift film forming that is layering.The old Yongsheng of Chinese patent CN200910067708.8 etc.; " Graphene and carbon fibre composite and preparation method thereof "; Its principal character comprises: it is to be raw material with Graphene and carbon fibre material, forms in carbon fibre material surface-coated Graphene production of coatings through the method that applies, and the product of this method preparation is mainly the film product; And owing to only adopt the good carbon fiber surface combination of the carbonization of coating limited, it is inevitable also influenced that performance strengthens degree.Patent (ZL200810034458.3, a kind of preparation method of CNT enhanced polypropylene itrile group carbon fiber) discloses the technology of CNT being added to preparation carbon fiber in the polyacrylonitrile.
Existing data is illustrated in utilizes Graphene enhancing polymer properties aspect to do a lot of effort really, but utilizes the preparation method and the technology of Graphene RPP itrile group carbon fiber but not to appear in the newspapers.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of Graphene RPP nitrile carbon fiber; This method has improved dispersion and the interface binding power of graphene oxide in polymeric matrix effectively; Further improved the combination property of carbon fiber, the mechanical property of prepared carbon fiber is improved significantly.
The preparation method of a kind of Graphene RPP nitrile carbon fiber of the present invention comprises:
(1) be raw material with native graphite or Delanium, earlier with the centrifugal 2-10 of the speed of 4000-6000rpm minute, collect upper solution after ultrasonic 1-60 minute, again with the centrifugal 1-5 of the speed of 12000-15000rpm minute, collecting precipitation, vacuumize promptly gets Graphene;
Be raw material perhaps, adopt Hummer method, Staudenmaier method or Brodie legal system to be equipped with graphite oxide with native graphite or Delanium; Graphite oxide is scattered in the water, and centrifugal after sonicated, washing, 50-60 ℃ vacuumize obtain graphene oxide; Graphene oxide is scattered in the organic solvent, ultrasonic at normal temperatures, obtain graphene oxide suspension;
(2) polyacrylonitrile is joined in the organic solvent, 0～15 ℃ of following swelling 4～5h is heated to 70～75 ℃ and continues to stir 2～3h, and cooling obtains polyacrylonitrile solution; With above-mentioned Graphene or graphene oxide suspension and polyacrylonitrile solution blend, stir 5～6h under the room temperature, after filtration, deaeration, obtain Graphene/polyacrylonitrile spinning solution;
(3) above-mentioned spinning solution is made Graphene/polyacrylonitrile composite fiber through wet method or dry-wet spinning technology; Wherein, spinning temperature is 30～50 ℃, and the aperture of spinneret orifice is 0.08～0.5mm, and the temperature of coagulating bath is 25～30 ℃, and draw speed is 5-20m/min, and draw ratio is 2～15 times;
(4) with above-mentioned composite fibre process pre-oxidation and carbonization, obtain Graphene enhanced polypropylene base carbon fibre.
Ultrasonic power in the said step (1) is 60-500W.
Organic solvent in said step (1) and (2) is N, N '-dimethyl formamide (DMF), N, one or more in N '-dimethylacetylamide (DMAc), N-Methyl pyrrolidone (NMP), the dimethyl sulfoxide (DMSO) (DMSO).
The percentage by weight that the middle polyacrylonitrile of said step (2) accounts for spinning solution is 5～35%, and Graphene or graphene oxide are 0.1～20% with respect to the percentage by weight of polyacrylonitrile.
The used coagulating bath of wet spinning in the said step (3) is methyl alcohol, ethanol, butanols, ethylene glycol, acetone, butanone, N, N '-dimethyl formamide, N, any one in N '-dimethylacetylamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) and the water; Perhaps methyl alcohol, ethanol, butanols, ethylene glycol, acetone, butanone, N, N '-dimethyl formamide, N, the mixed solution of any one in N '-dimethylacetylamide, N-Methyl pyrrolidone, the dimethyl sulfoxide (DMSO) or two kinds and water; When coagulating bath is methyl alcohol, ethanol, butanols, ethylene glycol, acetone, butanone, N; N '-dimethyl formamide, N; During the mixed solution of any one and water, the volume ratio of organic solvent and water is 2: 8～8: 2 in N '-dimethylacetylamide, N-Methyl pyrrolidone, the dimethyl sulfoxide (DMSO); When coagulating bath is methyl alcohol, ethanol, butanols, ethylene glycol, acetone, butanone, N; N '-dimethyl formamide, N; During any two kinds of mixed solutions with water in N '-dimethylacetylamide, N-Methyl pyrrolidone, the dimethyl sulfoxide (DMSO), the volume ratio of first kind of organic solvent, second kind of organic solvent and water is x: y: z, x+y+z=10; X+y=2～8, z=8～2.
Said coagulating bath is N, N '-dimethyl formamide, N, the mixed solution of one or both in N '-dimethylacetylamide, N-Methyl pyrrolidone, the dimethyl sulfoxide (DMSO) and water.
The technological parameter of pre-oxidation is in the said step (4): in oxidation furnace, take gradient heating, oxidizing temperature is respectively 180,210,230,250,270 ℃, and oxidization time is 0.5～1 hour under each temperature, air atmosphere.
The technological parameter of carbonization is in the said step (4): 500～700 ℃ in low-carbon (LC) stove, and the time is 40 minutes; 900～1100 ℃ in high-carbon stove, the time is 10～30 minutes, nitrogen atmosphere.
Principle of the present invention is at first native graphite to be carried out oxidation processes; And peel off and obtain graphene oxide, again graphene oxide is dispersed in the organic solvent uniformly, and then passes through solution blending; Make it be distributed in the polyacrylonitrile solution uniformly; Prepare spinning solution, through wet method or dry-wet spinning prepared graphene oxide finely disseminated composite fibre in the PAN matrix, prepare Graphene enhanced polypropylene itrile group carbon fibre composite through pre-oxidation and carbonization technique at last.
Beneficial effect
The present invention has improved dispersion and the interface binding power of graphene oxide in polymeric matrix effectively; Further improved the combination property of carbon fiber; The mechanical property of prepared carbon fiber is improved significantly, and can be used for a plurality of fields such as material enhancing, conduction, antistatic, heat conduction, and preparation technology of the present invention is simple; Easy to control, cost is low.
Description of drawings
Fig. 1 is the uv-visible absorption spectrum figure of 0.1mg/ml graphite oxide and graphene suspension for concentration; Wherein, (a) graphite oxide, (b) Graphene;
Fig. 2 is wet spinning device sketch map (this device can through being modified to dry spinning or dry-wet spinning).
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) with the native graphite is raw material, adopts the Hummer legal system to be equipped with graphite oxide.Be about to the 92ml concentrated sulfuric acid and join in the three-neck flask, ice-water bath is stirred to temperature and reduces to 0 ℃～3 ℃, adds 4g native graphite powder and 2g sodium nitrate (NaNO again
3), stir then, when stirred on the limit, the limit slowly added 60g potassium permanganate (KMnO
4), and guarantee temperature less than 20 ℃, and after reinforced the completion, solution is heated to 35 ± 3 ℃, and keeps 30min, next slowly add distilled water, and temperature is controlled in 100 ℃; Behind the 15min, through adding the hydrogen peroxide (H of a large amount of distilled water and 10ml30%
2O
2), with reaction terminating.Mixture through centrifugal treating, is filtered, and repeatedly wash,, obtain the graphite oxide sample 50～60 ℃ of vacuumizes with the aqueous solution that contains 5%HCl; Get the 2.5g graphite oxide again and be dispersed in 100ml N, among the N '-dimethylacetylamide (DMAc), obtain Huang-brown dispersion liquid, behind the ultrasonic 30min, what obtain peeling off is dispersed in the graphene oxide suspension among the DMAc.
(2) 24.5g polyacrylonitrile powder is joined in 100ml DMAC N,N (DMAc) solvent, 0 ℃ of following swelling 4 hours, water-bath slowly is heated to 70 ℃, continues to stir 2h, obtains uniform polyacrylonitrile (PAN) solution.
(3) get the graphene oxide suspension that 20ml prepares, join in the polyacrylonitrile solution of 100ml, stir 4.5h under the room temperature, after filtration, standing and defoaming, make Graphene/polyacrylonitrile spinning solution that graphene oxide content is 2wt%.Utilize the wet spinning device spinning shown in the accompanying drawing 2 to prepare Graphene/polyacrylonitrile composite fiber, wherein spinning temperature is 25 ℃, and the aperture of spinneret orifice is 0.08mm, and the temperature of coagulating bath is 25 ℃, and coagulation bath composition is DMAc/H
2O (1: 1) solution, draft speed is 5m/min, stretches 4 times, promptly gets Graphene/polyacrylonitrile composite fiber.
(4) Graphene/polyacrylonitrile composite fiber obtains the carbon fibre material that Graphene strengthens through pre-oxidation and carbonization.Wherein pre-oxidation process is: oxidation furnace is taked gradient heating, and oxidizing temperature is respectively 180,210,230,250,270 ℃, and oxidization time is 0.5h under each temperature, air atmosphere.Carbonization technique: 600 ℃ in low-carbon (LC) stove, the time is 40 minutes; 1000 ℃ in high-carbon stove, the time is 15 minutes, protective gas is a high pure nitrogen.Finally obtain the carbon fiber that the graphene oxide mass percent is 2wt%.The prepared carbon fiber surface of this implementation method is smooth, and fibre-forming performance is good, and intensity 2.8Gpa, extension at break are 1.8%.
Embodiment 2
(1) with the native graphite is raw material, adopts the Staudenmaier legal system to be equipped with graphite oxide.Graphite oxide is scattered in the water, and ultrasonic power is 500W, after ultrasonic 60 minutes with the speed of 5000rpm centrifugal 4 minutes earlier, collects upper solution, centrifugal 2 minutes again with the speed of 15000rpm, and collecting precipitation, 60 ℃ of vacuumizes obtain the graphene oxide powder.Get the 2.5g graphene oxide and be dispersed in 100ml N, among the N '-dimethylacetylamide (DMAc), obtain Huang-brown dispersion liquid, behind the ultrasonic 40min, what obtain peeling off is dispersed in the graphene oxide suspension among the DMAc.
(2) 16.2g polyacrylonitrile powder is joined in 100ml DMAC N,N (DMAc) solvent, 15 ℃ of following swellings 4 hours, water-bath slowly is heated to 70 ℃, continues to stir 1.5h, obtains uniform polyacrylonitrile (PAN) solution.
(3) get the graphene oxide suspension that 20ml prepares, join in the polyacrylonitrile solution of 100ml, stir 4.5h under the room temperature, after filtration, standing and defoaming, make Graphene/polyacrylonitrile spinning solution that graphene oxide content is 3wt%.Utilize wet spinning device shown in the drawings spinning to prepare Graphene/polyacrylonitrile composite fiber, wherein spinning temperature is 25 ℃, and the aperture of spinneret orifice is 0.08mm, and the temperature of coagulating bath is 25 ℃, and coagulation bath composition is DMAc/H
2O (3: 7) solution, draft speed is 20m/min, stretches 3.5 times, promptly gets Graphene/polyacrylonitrile composite fiber.
(4) Graphene/polyacrylonitrile composite fiber obtains the carbon fibre material that Graphene strengthens through pre-oxidation and carbonization.Wherein pre-oxidation process is: oxidation furnace is taked gradient heating, and oxidizing temperature is respectively 180,210,230,250,270 ℃, and oxidization time is 40min under each temperature, air atmosphere.Carbonization technique: 700 ℃ in low-carbon (LC) stove, the time is 40 minutes; 900 ℃ in high-carbon stove, the time is 30 minutes, protective gas is a high pure nitrogen.Finally obtain the carbon fiber that the graphene oxide mass percent is 3wt%.The prepared carbon fiber surface of this implementation method is smooth, and fibre-forming performance is good, and intensity 2.7Gpa, extension at break are 1.8%.
Embodiment 3
(1) with the native graphite is raw material, adopts the Brodie legal system to be equipped with graphite oxide.Graphite oxide is scattered in the water, and ultrasonic power is 500W, after ultrasonic 60 minutes with the speed of 5000rpm centrifugal 4 minutes earlier, collects upper solution, centrifugal 2 minutes again with the speed of 15000rpm, and collecting precipitation, 60 ℃ of vacuumizes obtain the graphene oxide powder.Get the 2g graphene oxide and be dispersed in 100mlN, among the N '-dimethylacetylamide (DMAc), obtain Huang-brown dispersion liquid, behind the ultrasonic 40min, what obtain peeling off is dispersed in the graphene oxide suspension among the DMAc.
(2) 19.5g polyacrylonitrile powder is joined in 100ml DMAC N,N (DMAc) solvent, 8 ℃ of following swellings 4 hours, water-bath slowly is heated to 70 ℃, continues to stir 1.5h, obtains uniform polyacrylonitrile (PAN) solution.
(3) get the graphene oxide suspension that 25ml prepares, join in the polyacrylonitrile solution of 100ml, stir 4.5h under the room temperature, after filtration, standing and defoaming, make Graphene/polyacrylonitrile spinning solution that graphene oxide content is 2.5wt%.Utilize the wet spinning device spinning shown in the accompanying drawing 2 to prepare Graphene/polyacrylonitrile composite fiber, wherein spinning temperature is 25 ℃, and spinning head is 50 holes, aperture 0.1mm, and the temperature of coagulating bath is 25 ℃, coagulation bath composition is DMAc/H
2O (5: 5) solution, draft speed is 15m/min, stretches 4 times, promptly gets Graphene/polyacrylonitrile composite fiber.
(4) Graphene/polyacrylonitrile composite fiber obtains the carbon fibre material that Graphene strengthens through pre-oxidation and carbonization.Wherein pre-oxidation process is: oxidation furnace is taked gradient heating, and oxidizing temperature is respectively 180,210,230,250,270 ℃, and oxidization time is 40min under each temperature, air atmosphere.Carbonization technique: 700 ℃ in low-carbon (LC) stove, the time is 40 minutes; 1100 ℃ in high-carbon stove, the time is 10 minutes, protective gas is a high pure nitrogen.Finally obtain the carbon fiber that the graphene oxide mass percent is 2.5wt%.The prepared carbon fiber surface of this implementation method is smooth, and fibre-forming performance is good, and intensity 2.69Gpa, extension at break are 1.38%.
Embodiment 4
(1) with the electrographite is raw material, adopts the Hummer legal system to be equipped with graphite oxide.Be about to the 92ml concentrated sulfuric acid and join in the three-neck flask, ice-water bath is stirred to temperature and reduces to 0 ℃～3 ℃, adds 4g native graphite powder and 2g sodium nitrate (NaNO3) again, stirs then, and when stirred on the limit, the limit slowly added 60g potassium permanganate (KMnO
4), and guarantee temperature less than 20 ℃, and after reinforced the completion, solution is heated to 35 ± 3 ℃, and keeps 30min, next slowly add distilled water, and temperature is controlled in 100 ℃; Behind the 15min, through adding the hydrogen peroxide (H of a large amount of distilled water and 10ml30%
2O
2), with reaction terminating.Mixture through centrifugal treating, is filtered, and repeatedly wash,, obtain the graphite oxide sample 50～60 ℃ of vacuumizes with the aqueous solution that contains 5%HCl; Get the 2.5g graphite oxide and be dispersed in 100ml N, among the N '-dimethyl formamide (DMF), obtain Huang-brown dispersion liquid, behind the ultrasonic 30min, what obtain peeling off is dispersed in the graphene oxide suspension among the DMF.
(2) 24.5g polyacrylonitrile powder is joined 100ml N, in dinethylformamide (DMF) solvent, 10 ℃ of following swellings 4 hours, water-bath slowly is heated to 70 ℃, continues to stir 2h, obtains uniform polyacrylonitrile (PAN) solution.
(3) get the graphene oxide suspension that 20ml prepares, join in the polyacrylonitrile solution of 100ml, stir 4.5h under the room temperature, after filtration, standing and defoaming, make Graphene/polyacrylonitrile spinning solution that graphene oxide content is 2wt%.Utilize the wet spinning device spinning shown in the accompanying drawing 2 to prepare Graphene/polyacrylonitrile composite fiber, wherein spinning temperature is 25 ℃, and spinning head is 50 holes, aperture 0.1mm, and the temperature of coagulating bath is 25 ℃, coagulation bath composition is DMF/H
2O (1: 1) solution, draft speed is 15m/min, stretches 4 times, promptly gets Graphene/polyacrylonitrile composite fiber.
(4) Graphene/polyacrylonitrile composite fiber obtains the carbon fibre material that Graphene strengthens through pre-oxidation and carbonization.Wherein pre-oxidation process is: oxidation furnace is taked gradient heating, and oxidizing temperature is respectively 180,210,230,250,270 ℃, and oxidization time is 0.5h under each temperature, air atmosphere.Carbonization technique: 600 ℃ in low-carbon (LC) stove, the time is 40 minutes; 1000 ℃ in high-carbon stove, the time is 15 minutes, protective gas is a high pure nitrogen.Finally obtain the carbon fiber that the graphene oxide mass percent is 2wt%.The prepared carbon fiber surface of this implementation method is smooth, and fibre-forming performance is good, and intensity 3.0Gpa, extension at break are 1.0%.
Embodiment 5
(1) with the electrographite is raw material, adopts the Hummer legal system to be equipped with graphite oxide.Be about to the 92ml concentrated sulfuric acid and join in the three-neck flask, ice-water bath is stirred to temperature and reduces to 0 ℃～3 ℃, adds 4g native graphite powder and 2g sodium nitrate (NaNO3) again, stirs then, and when stirred on the limit, the limit slowly added 60g potassium permanganate (KMnO
4), and guarantee temperature less than 20 ℃, and after reinforced the completion, solution is heated to 35 ± 3 ℃, and keeps 30min, next slowly add distilled water, and temperature is controlled in 100 ℃; Behind the 15min, through adding the hydrogen peroxide (H of a large amount of distilled water and 10ml30%
2O
2), with reaction terminating.Mixture through centrifugal treating, is filtered, and repeatedly wash,, obtain the graphite oxide sample 50～60 ℃ of vacuumizes with the aqueous solution that contains 5%HCl; Get the 2.5g graphite oxide and be dispersed in 100ml N, among the N '-dimethyl formamide (DMF), obtain Huang-brown dispersion liquid, behind the ultrasonic 30min, what obtain peeling off is dispersed in the graphene oxide suspension among the DMF.
(2) 24g polyacrylonitrile powder is joined 150ml N, in dinethylformamide (DMF) solvent, 15 ℃ of following swellings 4 hours, water-bath slowly is heated to 65 ℃, continues to stir 2h, obtains uniform polyacrylonitrile (PAN) solution.
(3) get the graphene oxide suspension that 40ml prepares, join in the polyacrylonitrile solution of 150ml, stir 5h under the room temperature, after filtration, standing and defoaming, make Graphene/polyacrylonitrile spinning solution that graphene oxide content is 4wt%.Utilize the wet spinning device spinning shown in the accompanying drawing 2 to prepare Graphene/polyacrylonitrile composite fiber, wherein spinning temperature is 25 ℃, and spinning head is 50 holes, aperture 0.1mm, and the temperature of coagulating bath is 25 ℃, coagulation bath composition is DMF/H
2O (3: 7) solution, draft speed is 5-20m/min, stretches 4 times, promptly gets Graphene/polyacrylonitrile composite fiber.
(4) Graphene/polyacrylonitrile composite fiber obtains the carbon fibre material that Graphene strengthens through pre-oxidation and carbonization.Wherein pre-oxidation process is: oxidation furnace is taked gradient heating, and oxidizing temperature is respectively 180,210,230,250,270 ℃, and oxidization time is 0.5h under each temperature, air atmosphere.Carbonization technique: 600 ℃ in low-carbon (LC) stove, the time is 40 minutes; 1000 ℃ in high-carbon stove, the time is 15 minutes, protective gas is a high pure nitrogen.Finally obtain the carbon fiber that the graphene oxide mass percent is 4wt%.The prepared carbon fiber surface of this implementation method is smooth, and fibre-forming performance is good, and intensity 3.1Gpa, extension at break are 1.18%.
Embodiment 6
(1) is raw material with the electrographite, it is scattered in the water that ultrasonic power is 500W, after ultrasonic 60 minutes with the speed of 5000rpm centrifugal 4 minutes earlier; Collect upper solution, centrifugal 2 minutes again with the speed of 15000rpm, collecting precipitation; 60 ℃ of vacuumizes obtain graphene powder.Get the 2g Graphene and be dispersed in the 100ml N-Methyl pyrrolidone (NMP), obtain Huang-brown dispersion liquid, behind the ultrasonic 40min, what obtain peeling off is dispersed in the graphene suspension among the NMP.
(2) 19.5g polyacrylonitrile powder is joined in 100ml N-Methyl pyrrolidone (NMP) solvent, 15 ℃ of following swellings 4 hours, water-bath slowly is heated to 70 ℃, continues to stir 1.5h, obtains uniform polyacrylonitrile (PAN) solution.
(3) get the graphene suspension that 25ml prepares, join in the polyacrylonitrile solution of 100ml, stir 4.5h under the room temperature, after filtration, standing and defoaming, make Graphene/polyacrylonitrile spinning solution that Graphene content is 4wt%.Utilize wet spinning device shown in the drawings spinning to prepare Graphene/polyacrylonitrile composite fiber, wherein spinning temperature is 25 ℃, and spinning head is 50 holes, aperture 0.1mm, and the temperature of coagulating bath is 25 ℃, coagulation bath composition is NMP/H
2O (5: 5) solution, draft speed is 20m/min, stretches 5 times, promptly gets Graphene/polyacrylonitrile composite fiber.
(4) Graphene/polyacrylonitrile composite fiber obtains the carbon fibre material that Graphene strengthens through pre-oxidation and carbonization.Wherein pre-oxidation process is: oxidation furnace is taked gradient heating, and oxidizing temperature is respectively 180,210,230,250,270 ℃, and oxidization time is 40min under each temperature, air atmosphere.Carbonization technique: 600 ℃ in low-carbon (LC) stove, the time is 40 minutes; 1000 ℃ in high-carbon stove, the time is 15 minutes, protective gas is a high pure nitrogen.Finally obtain the carbon fiber that the Graphene mass percent is 4wt%.The prepared carbon fiber surface of this implementation method is smooth, and fibre-forming performance is good, intensity 2.38Gpa.
Claims (8)
1. the preparation method of a Graphene RPP nitrile carbon fiber comprises:
(1) be raw material with native graphite or Delanium, earlier with the centrifugal 2-10 of the speed of 4000-6000rpm minute, collect upper solution after ultrasonic 1-60 minute, again with the centrifugal 1-5 of the speed of 12000-15000rpm minute, collecting precipitation, vacuumize promptly gets Graphene;
Be raw material perhaps, adopt Hummer method, Staudenmaier method or Brodie legal system to be equipped with graphite oxide with native graphite or Delanium; Graphite oxide is scattered in the water, and centrifugal after sonicated, washing, vacuumize obtain graphene oxide; Graphene oxide is scattered in the organic solvent, ultrasonic at normal temperatures, obtain graphene oxide suspension;
(2) polyacrylonitrile is joined in the organic solvent, 0～15 ℃ of following swelling 4～5h is heated to 70～75 ℃ and continues to stir 2～3h, and cooling obtains polyacrylonitrile solution; With above-mentioned Graphene or graphene oxide suspension and polyacrylonitrile solution blend, stir 5～6h under the room temperature, after filtration, deaeration, obtain Graphene/polyacrylonitrile spinning solution;
(3) above-mentioned spinning solution is made Graphene/polyacrylonitrile composite fiber through wet method or dry-wet spinning technology; Wherein, spinning temperature is 30～50 ℃, and the aperture of spinneret orifice is 0.08～0.5mm, and the temperature of coagulating bath is 25～30 ℃, and draw speed is 5-20m/min, and draw ratio is 2～15 times;
(4) with above-mentioned composite fibre process pre-oxidation and carbonization, obtain Graphene enhanced polypropylene base carbon fibre.
2. the preparation method of a kind of Graphene RPP nitrile carbon fiber according to claim 1 is characterized in that: the ultrasonic power in the said step (1) is 60-500W.
3. the preparation method of a kind of Graphene RPP nitrile carbon fiber according to claim 1; It is characterized in that: the organic solvent in said step (1) and (2) is N; N '-dimethyl formamide, N, one or more in N '-dimethylacetylamide, N-Methyl pyrrolidone, the dimethyl sulfoxide (DMSO).
4. the preparation method of a kind of Graphene RPP nitrile carbon fiber according to claim 1; It is characterized in that: the percentage by weight that the middle polyacrylonitrile of said step (2) accounts for spinning solution is 5～35%, and Graphene or graphene oxide are 0.1～20% with respect to the percentage by weight of polyacrylonitrile.
5. the preparation method of a kind of Graphene RPP nitrile carbon fiber according to claim 1; It is characterized in that: the used coagulating bath of the wet spinning in the said step (3) is methyl alcohol, ethanol, butanols, ethylene glycol, acetone, butanone, N; N '-dimethyl formamide, N, any one in N '-dimethylacetylamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) and the water; Perhaps methyl alcohol, ethanol, butanols, ethylene glycol, acetone, butanone, N, N '-dimethyl formamide, N, the mixed solution of any one in N '-dimethylacetylamide, N-Methyl pyrrolidone, the dimethyl sulfoxide (DMSO) or two kinds and water; When coagulating bath is methyl alcohol, ethanol, butanols, ethylene glycol, acetone, butanone, N; N '-dimethyl formamide, N; During the mixed solution of any one and water, the volume ratio of organic solvent and water is 2: 8～8: 2 in N '-dimethylacetylamide, N-Methyl pyrrolidone, the dimethyl sulfoxide (DMSO); When coagulating bath is methyl alcohol, ethanol, butanols, ethylene glycol, acetone, butanone, N; N '-dimethyl formamide, N; During any two kinds of mixed solutions with water in N '-dimethylacetylamide, N-Methyl pyrrolidone, the dimethyl sulfoxide (DMSO), the volume ratio of first kind of organic solvent, second kind of organic solvent and water is x: y: z, x+y+z=10; X+y=2～8, z=8～2.
6. the preparation method of a kind of Graphene RPP nitrile carbon fiber according to claim 5; It is characterized in that: said coagulating bath is N; N '-dimethyl formamide, N, the mixed solution of one or both in N '-dimethylacetylamide, N-Methyl pyrrolidone, the dimethyl sulfoxide (DMSO) and water.
7. the preparation method of a kind of Graphene RPP nitrile carbon fiber according to claim 1; It is characterized in that: the technological parameter of pre-oxidation is in the said step (4): in oxidation furnace; Take gradient heating; Oxidizing temperature is respectively 180,210,230,250,270 ℃, and oxidization time is 0.5～1 hour under each temperature, air atmosphere.
8. the preparation method of a kind of Graphene RPP nitrile carbon fiber according to claim 1 is characterized in that: the technological parameter of carbonization is in the said step (4): 500～700 ℃ in low-carbon (LC) stove, and the time is 40 minutes; 900～1100 ℃ in high-carbon stove, the time is 10～30 minutes, nitrogen atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210005004XA CN102586952A (en) | 2012-01-09 | 2012-01-09 | Method for preparing graphene-reinforced polyacrylonitrile carbon fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210005004XA CN102586952A (en) | 2012-01-09 | 2012-01-09 | Method for preparing graphene-reinforced polyacrylonitrile carbon fibers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102586952A true CN102586952A (en) | 2012-07-18 |
Family
ID=46476162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210005004XA Pending CN102586952A (en) | 2012-01-09 | 2012-01-09 | Method for preparing graphene-reinforced polyacrylonitrile carbon fibers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102586952A (en) |
Cited By (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102828267A (en) * | 2012-09-10 | 2012-12-19 | 浙江大学 | Preparation method of conductive high-strength graphene-reinforced polymer fiber |
| CN102926020A (en) * | 2012-11-14 | 2013-02-13 | 浙江大学 | Preparation method for polymer-grafted graphene laminated fiber with electrical conductivity and high-strength |
| CN102936764A (en) * | 2012-11-27 | 2013-02-20 | 天津工业大学 | Preparation method of polyacrylonitrile-based carbon nanofibers |
| CN103215693A (en) * | 2013-02-01 | 2013-07-24 | 清华大学 | Graphene-oxide-modified phenolic-resin-based ultrafine porous carbon fiber and preparation method thereof |
| CN103569997A (en) * | 2013-11-20 | 2014-02-12 | 东北师范大学 | Preparation method for flexible graphene-modified knittable carbon nanofiber |
| CN103696239A (en) * | 2013-12-05 | 2014-04-02 | 西安航空制动科技有限公司 | Preparation method of carbon nano-fiber film |
| CN103746130A (en) * | 2014-01-15 | 2014-04-23 | 天津工业大学 | Preparation method of hollow fiber tube for fuel batteries |
| CN103768864A (en) * | 2014-01-24 | 2014-05-07 | 中国科学院重庆绿色智能技术研究院 | Method for preparing anti-static and high-performance flue gas purification filter material |
| CN104037393A (en) * | 2013-03-06 | 2014-09-10 | 佛山市顺德宇红纳米科技有限公司 | Preparation method for tin/graphene/carbon fiber composite lithium battery cathode material |
| CN104846466A (en) * | 2015-04-09 | 2015-08-19 | 浙江泰索科技有限公司 | High thermal conductivity polyacrylonitrile fiber and preparation method thereof |
| CN104862828A (en) * | 2015-04-09 | 2015-08-26 | 浙江泰索科技有限公司 | High thermal conductivity carbon fiber and preparation method thereof |
| CN104862807A (en) * | 2015-04-09 | 2015-08-26 | 浙江泰索科技有限公司 | High thermal conductivity acrylic fiber and preparation method thereof |
| CN105392930A (en) * | 2013-06-21 | 2016-03-09 | 可隆工业株式会社 | Polyacrylonitrile-based precursor fiber for carbon fibre, and production method therefor |
| CN105384989A (en) * | 2015-12-02 | 2016-03-09 | 安徽创奇乐智能游乐设备有限公司 | Waterproof rubber material |
| CN105400009A (en) * | 2015-12-02 | 2016-03-16 | 安徽创奇乐智能游乐设备有限公司 | High damping environmentally friendly rubber material |
| CN105463620A (en) * | 2016-01-15 | 2016-04-06 | 东华大学 | Graphene/polyethylene terephthalate composite fiber and preparation method thereof |
| CN105544020A (en) * | 2016-01-28 | 2016-05-04 | 东华大学 | Graphene-doped polyacrylonitrile mesopore activated carbon fiber and preparation method thereof |
| WO2016127465A1 (en) * | 2015-02-09 | 2016-08-18 | 上海史墨希新材料科技有限公司 | Preparation method for high-strength polyacrylonitrile nano composite fibres |
| CN106012110A (en) * | 2016-06-30 | 2016-10-12 | 东华大学 | Flexible carbon fiber and preparation method thereof |
| CN106192048A (en) * | 2016-08-01 | 2016-12-07 | 青岛大学 | A kind of preparation method of graphene oxide modified polypropylene fiber |
| CN106350883A (en) * | 2016-08-08 | 2017-01-25 | 青岛大学 | Preparation method of graphene oxide/polyacrylonitrile composite fiber |
| CN106567157A (en) * | 2016-08-17 | 2017-04-19 | 重庆大学 | Preparation method of graphene nanoribbon in situ toughened nano carbon fiber |
| CN106676678A (en) * | 2016-12-30 | 2017-05-17 | 苏州高通新材料科技有限公司 | Graphene modified composite carbon fibers as well as preparation method and application thereof |
| CN106835332A (en) * | 2016-09-14 | 2017-06-13 | 济南圣泉集团股份有限公司 | Compound para-aramid fiber of high performance Graphene and preparation method thereof, application |
| US20170166722A1 (en) * | 2015-12-10 | 2017-06-15 | Aruna Zhamu | Chemical-free production of graphene-reinforced polymer matrix composites |
| CN107475793A (en) * | 2016-06-08 | 2017-12-15 | 南京理工大学 | A kind of preparation method of graphene oxide parcel polyacrylonitrile composite nano fiber |
| CN108085766A (en) * | 2017-12-13 | 2018-05-29 | 华南理工大学 | A kind of cellulose nanometer fibril enhancing acrylic fiber and preparation method and application |
| CN108538630A (en) * | 2017-10-08 | 2018-09-14 | 北京化工大学 | A kind of preparation method of biomass carbon/graphene flexible compound film |
| KR101919658B1 (en) * | 2016-10-10 | 2018-11-16 | 한양대학교 산학협력단 | Graphene/polymer composite fiber and the manufacturing method therefor |
| CN109294388A (en) * | 2018-08-02 | 2019-02-01 | 无锡泰科纳米新材料有限公司 | A kind of graphene anticorrosive paint and preparation method thereof |
| CN109355735A (en) * | 2018-08-30 | 2019-02-19 | 北京化工大学 | Graphene carbon fiber and preparation method thereof |
| CN109369185A (en) * | 2018-09-26 | 2019-02-22 | 南通大学 | A kind of preparation method of nitrogen-doped graphene complex carbon material |
| CN109440231A (en) * | 2018-11-14 | 2019-03-08 | 中国地质大学（北京） | A kind of graphene/carbon composite micro-nano rice fiber and preparation method thereof |
| CN109608949A (en) * | 2018-11-29 | 2019-04-12 | 广州市领格汽车零件制造有限公司 | A kind of high temperature resistant vehicle spare and accessory parts rust-proof coating and preparation method thereof |
| CN109881286A (en) * | 2019-01-14 | 2019-06-14 | 常州兴烯石墨烯科技有限公司 | A kind of graphene flame-retardant acrylic fibre fiber and preparation method thereof |
| CN110917902A (en) * | 2019-12-26 | 2020-03-27 | 广州康滤净化科技有限公司 | Graphene polyacrylonitrile hollow fiber membrane and preparation method thereof |
| CN112030256A (en) * | 2020-09-07 | 2020-12-04 | 吉祥三宝高科纺织有限公司 | Preparation method of carbon nano tube reinforced polyacrylonitrile composite material |
| CN112323262A (en) * | 2020-09-30 | 2021-02-05 | 苏州大学 | Electrostatic spinning porous carbon material and preparation method thereof |
| US10981791B2 (en) | 2015-04-13 | 2021-04-20 | Garmor Inc. | Graphite oxide reinforced fiber in hosts such as concrete or asphalt |
| US10995002B2 (en) | 2013-03-08 | 2021-05-04 | University Of Central Florida Research Foundation, Inc. | Large scale oxidized graphene production for industrial applications |
| US11214658B2 (en) | 2016-10-26 | 2022-01-04 | Garmor Inc. | Additive coated particles for low cost high performance materials |
| US11361877B2 (en) | 2013-03-08 | 2022-06-14 | Asbury Graphite Of North Carolina, Inc. | Graphene entrainment in a host |
| US11466380B2 (en) | 2011-10-27 | 2022-10-11 | Asbury Graphite Of North Carolina, Inc. | Composite graphene structures |
| CN115233320A (en) * | 2022-08-04 | 2022-10-25 | 青岛大学 | Preparation method of high-conductivity profiled composite fiber |
| US11772975B2 (en) | 2015-12-03 | 2023-10-03 | Global Graphene Group, Inc. | Chemical-free production of graphene materials |
| US11791061B2 (en) | 2019-09-12 | 2023-10-17 | Asbury Graphite North Carolina, Inc. | Conductive high strength extrudable ultra high molecular weight polymer graphene oxide composite |
| US11916264B2 (en) | 2015-09-21 | 2024-02-27 | Asbury Graphite Of North Carolina, Inc. | Low-cost, high-performance composite bipolar plate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245500A (en) * | 2008-03-25 | 2008-08-20 | 东华大学 | Attapulgite nano-particle modified polyacrylonitrile-based carbon fiber protofilament and production method |
| CN101250770A (en) * | 2008-03-11 | 2008-08-27 | 东华大学 | Method for manufacturing polyacrylonitrile-based carbon fiber with enganced carbon nano-tube |
| CN101619509A (en) * | 2009-08-14 | 2010-01-06 | 东华大学 | Carbon nanotube modified polyacrylonitrile-based carbon fibre precursor and preparation method thereof |
| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
-
2012
- 2012-01-09 CN CN201210005004XA patent/CN102586952A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250770A (en) * | 2008-03-11 | 2008-08-27 | 东华大学 | Method for manufacturing polyacrylonitrile-based carbon fiber with enganced carbon nano-tube |
| CN101245500A (en) * | 2008-03-25 | 2008-08-20 | 东华大学 | Attapulgite nano-particle modified polyacrylonitrile-based carbon fiber protofilament and production method |
| CN101619509A (en) * | 2009-08-14 | 2010-01-06 | 东华大学 | Carbon nanotube modified polyacrylonitrile-based carbon fibre precursor and preparation method thereof |
| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
Non-Patent Citations (1)
| Title |
|---|
| 李鹏洲: "碳纳米管/聚丙烯腈碳纤维的制备及其结构与性能的研究", 《东华大学硕士学位论文》, 15 August 2010 (2010-08-15) * |
Cited By (60)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11466380B2 (en) | 2011-10-27 | 2022-10-11 | Asbury Graphite Of North Carolina, Inc. | Composite graphene structures |
| CN102828267A (en) * | 2012-09-10 | 2012-12-19 | 浙江大学 | Preparation method of conductive high-strength graphene-reinforced polymer fiber |
| CN102828267B (en) * | 2012-09-10 | 2014-05-07 | 浙江大学 | Preparation method of conductive high-strength graphene-reinforced polymer fiber |
| CN102926020A (en) * | 2012-11-14 | 2013-02-13 | 浙江大学 | Preparation method for polymer-grafted graphene laminated fiber with electrical conductivity and high-strength |
| CN102936764A (en) * | 2012-11-27 | 2013-02-20 | 天津工业大学 | Preparation method of polyacrylonitrile-based carbon nanofibers |
| CN103215693A (en) * | 2013-02-01 | 2013-07-24 | 清华大学 | Graphene-oxide-modified phenolic-resin-based ultrafine porous carbon fiber and preparation method thereof |
| CN104037393A (en) * | 2013-03-06 | 2014-09-10 | 佛山市顺德宇红纳米科技有限公司 | Preparation method for tin/graphene/carbon fiber composite lithium battery cathode material |
| US10995002B2 (en) | 2013-03-08 | 2021-05-04 | University Of Central Florida Research Foundation, Inc. | Large scale oxidized graphene production for industrial applications |
| US11361877B2 (en) | 2013-03-08 | 2022-06-14 | Asbury Graphite Of North Carolina, Inc. | Graphene entrainment in a host |
| CN105392930A (en) * | 2013-06-21 | 2016-03-09 | 可隆工业株式会社 | Polyacrylonitrile-based precursor fiber for carbon fibre, and production method therefor |
| CN103569997A (en) * | 2013-11-20 | 2014-02-12 | 东北师范大学 | Preparation method for flexible graphene-modified knittable carbon nanofiber |
| CN103696239B (en) * | 2013-12-05 | 2015-10-21 | 西安航空制动科技有限公司 | A kind of preparation method of carbon nano-fiber film |
| CN103696239A (en) * | 2013-12-05 | 2014-04-02 | 西安航空制动科技有限公司 | Preparation method of carbon nano-fiber film |
| CN103746130A (en) * | 2014-01-15 | 2014-04-23 | 天津工业大学 | Preparation method of hollow fiber tube for fuel batteries |
| CN103746130B (en) * | 2014-01-15 | 2015-11-18 | 天津工业大学 | A kind of preparation method of fuel cell hollow fiber conduit |
| CN103768864A (en) * | 2014-01-24 | 2014-05-07 | 中国科学院重庆绿色智能技术研究院 | Method for preparing anti-static and high-performance flue gas purification filter material |
| CN103768864B (en) * | 2014-01-24 | 2015-11-04 | 中国科学院重庆绿色智能技术研究院 | A kind of preparation method of antistatic high-performance gas cleaning filtrate |
| WO2016127465A1 (en) * | 2015-02-09 | 2016-08-18 | 上海史墨希新材料科技有限公司 | Preparation method for high-strength polyacrylonitrile nano composite fibres |
| CN104862807A (en) * | 2015-04-09 | 2015-08-26 | 浙江泰索科技有限公司 | High thermal conductivity acrylic fiber and preparation method thereof |
| CN104862828A (en) * | 2015-04-09 | 2015-08-26 | 浙江泰索科技有限公司 | High thermal conductivity carbon fiber and preparation method thereof |
| CN104846466A (en) * | 2015-04-09 | 2015-08-19 | 浙江泰索科技有限公司 | High thermal conductivity polyacrylonitrile fiber and preparation method thereof |
| US10981791B2 (en) | 2015-04-13 | 2021-04-20 | Garmor Inc. | Graphite oxide reinforced fiber in hosts such as concrete or asphalt |
| US11916264B2 (en) | 2015-09-21 | 2024-02-27 | Asbury Graphite Of North Carolina, Inc. | Low-cost, high-performance composite bipolar plate |
| CN105400009A (en) * | 2015-12-02 | 2016-03-16 | 安徽创奇乐智能游乐设备有限公司 | High damping environmentally friendly rubber material |
| CN105384989A (en) * | 2015-12-02 | 2016-03-09 | 安徽创奇乐智能游乐设备有限公司 | Waterproof rubber material |
| US11772975B2 (en) | 2015-12-03 | 2023-10-03 | Global Graphene Group, Inc. | Chemical-free production of graphene materials |
| US9926427B2 (en) | 2015-12-10 | 2018-03-27 | Nanotek Instruments, Inc. | Chemical-free production of graphene-reinforced polymer matrix composites |
| CN108602675B (en) * | 2015-12-10 | 2023-08-18 | 纳米技术仪器公司 | Chemical-free production of graphene-reinforced polymer matrix composites |
| US20170166722A1 (en) * | 2015-12-10 | 2017-06-15 | Aruna Zhamu | Chemical-free production of graphene-reinforced polymer matrix composites |
| WO2017100294A1 (en) * | 2015-12-10 | 2017-06-15 | Nanotek Instruments, Inc. | Chemical-free production of graphene-reinforced polymer matrix composites |
| CN108602675A (en) * | 2015-12-10 | 2018-09-28 | 纳米技术仪器公司 | The polymer matrix composites of graphene enhancing are produced without chemicals formula |
| CN105463620A (en) * | 2016-01-15 | 2016-04-06 | 东华大学 | Graphene/polyethylene terephthalate composite fiber and preparation method thereof |
| CN105544020A (en) * | 2016-01-28 | 2016-05-04 | 东华大学 | Graphene-doped polyacrylonitrile mesopore activated carbon fiber and preparation method thereof |
| CN107475793A (en) * | 2016-06-08 | 2017-12-15 | 南京理工大学 | A kind of preparation method of graphene oxide parcel polyacrylonitrile composite nano fiber |
| CN106012110A (en) * | 2016-06-30 | 2016-10-12 | 东华大学 | Flexible carbon fiber and preparation method thereof |
| CN106192048B (en) * | 2016-08-01 | 2020-10-13 | 青岛大学 | Preparation method of graphene oxide modified polypropylene fiber |
| CN106192048A (en) * | 2016-08-01 | 2016-12-07 | 青岛大学 | A kind of preparation method of graphene oxide modified polypropylene fiber |
| CN106350883A (en) * | 2016-08-08 | 2017-01-25 | 青岛大学 | Preparation method of graphene oxide/polyacrylonitrile composite fiber |
| CN106567157B (en) * | 2016-08-17 | 2022-03-08 | 重庆大学 | Preparation method of graphene nanoribbon in-situ toughening carbon nanofibers |
| CN106567157A (en) * | 2016-08-17 | 2017-04-19 | 重庆大学 | Preparation method of graphene nanoribbon in situ toughened nano carbon fiber |
| CN106835332A (en) * | 2016-09-14 | 2017-06-13 | 济南圣泉集团股份有限公司 | Compound para-aramid fiber of high performance Graphene and preparation method thereof, application |
| KR101919658B1 (en) * | 2016-10-10 | 2018-11-16 | 한양대학교 산학협력단 | Graphene/polymer composite fiber and the manufacturing method therefor |
| US11214658B2 (en) | 2016-10-26 | 2022-01-04 | Garmor Inc. | Additive coated particles for low cost high performance materials |
| CN106676678A (en) * | 2016-12-30 | 2017-05-17 | 苏州高通新材料科技有限公司 | Graphene modified composite carbon fibers as well as preparation method and application thereof |
| CN108538630A (en) * | 2017-10-08 | 2018-09-14 | 北京化工大学 | A kind of preparation method of biomass carbon/graphene flexible compound film |
| CN108538630B (en) * | 2017-10-08 | 2020-01-07 | 北京化工大学 | Preparation method of biomass charcoal/graphene flexible composite membrane |
| CN108085766A (en) * | 2017-12-13 | 2018-05-29 | 华南理工大学 | A kind of cellulose nanometer fibril enhancing acrylic fiber and preparation method and application |
| CN109294388A (en) * | 2018-08-02 | 2019-02-01 | 无锡泰科纳米新材料有限公司 | A kind of graphene anticorrosive paint and preparation method thereof |
| CN109355735A (en) * | 2018-08-30 | 2019-02-19 | 北京化工大学 | Graphene carbon fiber and preparation method thereof |
| CN109369185A (en) * | 2018-09-26 | 2019-02-22 | 南通大学 | A kind of preparation method of nitrogen-doped graphene complex carbon material |
| CN109440231A (en) * | 2018-11-14 | 2019-03-08 | 中国地质大学（北京） | A kind of graphene/carbon composite micro-nano rice fiber and preparation method thereof |
| CN109608949A (en) * | 2018-11-29 | 2019-04-12 | 广州市领格汽车零件制造有限公司 | A kind of high temperature resistant vehicle spare and accessory parts rust-proof coating and preparation method thereof |
| CN109881286A (en) * | 2019-01-14 | 2019-06-14 | 常州兴烯石墨烯科技有限公司 | A kind of graphene flame-retardant acrylic fibre fiber and preparation method thereof |
| US11791061B2 (en) | 2019-09-12 | 2023-10-17 | Asbury Graphite North Carolina, Inc. | Conductive high strength extrudable ultra high molecular weight polymer graphene oxide composite |
| CN110917902A (en) * | 2019-12-26 | 2020-03-27 | 广州康滤净化科技有限公司 | Graphene polyacrylonitrile hollow fiber membrane and preparation method thereof |
| CN112030256B (en) * | 2020-09-07 | 2022-06-17 | 吉祥三宝高科纺织有限公司 | Preparation method of carbon nano tube reinforced polyacrylonitrile composite material |
| CN112030256A (en) * | 2020-09-07 | 2020-12-04 | 吉祥三宝高科纺织有限公司 | Preparation method of carbon nano tube reinforced polyacrylonitrile composite material |
| CN112323262A (en) * | 2020-09-30 | 2021-02-05 | 苏州大学 | Electrostatic spinning porous carbon material and preparation method thereof |
| CN115233320B (en) * | 2022-08-04 | 2024-01-09 | 青岛大学 | Preparation method of high-conductivity special-shaped composite fiber |
| CN115233320A (en) * | 2022-08-04 | 2022-10-25 | 青岛大学 | Preparation method of high-conductivity profiled composite fiber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102586952A (en) | Method for preparing graphene-reinforced polyacrylonitrile carbon fibers | |
| CN101250770B (en) | Method for manufacturing polyacrylonitrile-based carbon fiber with enganced carbon nano-tube | |
| Chen et al. | Carbon-based fibers for advanced electrochemical energy storage devices | |
| Hiremath et al. | Recent developments in carbon fibers and carbon nanotube-based fibers: a review | |
| Zhu et al. | Engineering cross-linking by coal-based graphene quantum dots toward tough, flexible, and hydrophobic electrospun carbon nanofiber fabrics | |
| CN104882613B (en) | A kind of preparation method of flexible High-conductivity composite carbon fiber cloth | |
| CN104695040A (en) | Preparation method of high-strength polyacrylonitrile nano-composite fiber | |
| CN111101371B (en) | High-performance carbon nanotube/carbon composite fiber and rapid preparation method thereof | |
| CN101956252A (en) | Method for preparing carbon fibers from boron modified polyacrylonitrile precursors | |
| CN105696114B (en) | Controllable carbon fibre material aperture and the preparation method and carbon fibre material of porosity | |
| CN104838051A (en) | Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof | |
| CN111074381A (en) | Preparation method of high-strength medium-modulus aviation carbon fiber based on dry jet wet spinning | |
| CN106567157B (en) | Preparation method of graphene nanoribbon in-situ toughening carbon nanofibers | |
| KR20130131003A (en) | Graphite nanofiber comprising graphene and producing method thereof and electrode materials in li-rechargeable batteries using the same | |
| CN113308754B (en) | Method for preparing high-orientation aramid fiber based on wet spinning | |
| CN106319934A (en) | Silicon carbide nanowire in-situ enhanced silicon carbide fiber material and preparation method thereof | |
| CN106120027A (en) | A kind of preparation method of high porosity mesopore nano-graphene fiber | |
| CN111748906A (en) | Waste silk-based flexible carbon nanofiber membrane and preparation method thereof | |
| CN105544020A (en) | Graphene-doped polyacrylonitrile mesopore activated carbon fiber and preparation method thereof | |
| CN109755033A (en) | A kind of carbon fiber loaded cobalt/cobalt oxide composite material and preparation method and application | |
| CN111118671B (en) | Preparation method of 25k large-tow carbon fiber | |
| CN106987925B (en) | Functionalized graphene preparation method based on ion exchange | |
| Wenrui et al. | Fabrication and specific functionalisation of carbon fibers for advanced flexible biosensors | |
| Qu et al. | Design of a ductile carbon nanofiber/ZrB2 nanohybrid film with entanglement structure fabricated by electrostatic spinning | |
| CN110144643A (en) | A kind of preparation method of high-performance intermediate phase pitch-based graphite fibre |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120718 |