CN103396586B - Graphene oxide fiber, preparation method, and preparation method of graphene oxide fiber composite material - Google Patents

Graphene oxide fiber, preparation method, and preparation method of graphene oxide fiber composite material Download PDF

Info

Publication number
CN103396586B
CN103396586B CN201310346323.1A CN201310346323A CN103396586B CN 103396586 B CN103396586 B CN 103396586B CN 201310346323 A CN201310346323 A CN 201310346323A CN 103396586 B CN103396586 B CN 103396586B
Authority
CN
China
Prior art keywords
graphene oxide
fiber
preparation
oxide fiber
aqueous solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310346323.1A
Other languages
Chinese (zh)
Other versions
CN103396586A (en
Inventor
周旭峰
刘兆平
张良忠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Ningbo Institute of Material Technology and Engineering of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ningbo Institute of Material Technology and Engineering of CAS filed Critical Ningbo Institute of Material Technology and Engineering of CAS
Priority to CN201310346323.1A priority Critical patent/CN103396586B/en
Publication of CN103396586A publication Critical patent/CN103396586A/en
Application granted granted Critical
Publication of CN103396586B publication Critical patent/CN103396586B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention provides a graphene oxide fiber, a preparation method of the graphene oxide fiber, and a preparation method of a graphene oxide fiber skeleton based composite material. The preparation method of the graphene oxide fiber comprises the following steps: carrying out quenching setting of an aqueous graphene oxide solution in liquid nitrogen, extruding the graphene oxide between nanometer ice crystals to form a fiber skeleton having a tridimensional network structure, and lyophilizing for sublimating the ice crystals between the graphene oxide in order to realize the in-situ preservation of the fiber skeleton having a tridimensional network structure. The fiber diameter of the prepared graphene oxide fiber skeleton is 100-500nm, and the tensile strength of the graphene oxide fiber compounded with an epoxy resin is 85% higher than that of the graphene oxide fiber, and is 38% higher than that of carbon fiber non-crimp fabric reinforced epoxy resin having a same matrix and a same mass fraction.

Description

The preparation method of graphene oxide fiber, preparation method and matrix material thereof
Technical field
The present invention relates to Graphene technical field, relate in particular to the preparation method of a kind of graphene oxide fiber, its preparation method and matrix material thereof.
Background technology
Graphene is by the former molecular two dimensional crystal of monolayer carbon, the excellent performances such as physical strength with superhigh specific surface area, good conduction, heat conductivility and superelevation, therefore make it in a lot of fields, have good application prospect, such as: the fields such as field-effect transistor, high-frequency element, super microprocessor and single-molecule detection device, controlled air-permeable envelope, anisotropy ion-conducting material, ultracapacitor.Yet a large obstruction problem of Graphene application is exactly the assembling of Graphene macrostructure.Aspect graphene film and block assembling, there iing more successful case at present, but aspect fiber, only having spinning and two kinds of methods of mold, and can only obtain single graphene fiber.
Utilize at present Graphene to construct in the technology of fiber, the method that the high superfine people of Zhejiang University prepares graphene fiber is specially: will in the NaOH/ methanol solution of 5wt%, clamp-on graphene oxide crystalline state solution, obtain after graphene oxide filament, put into again acid iodide heat reduction, obtain graphene fiber (the Xu Z that diameter is about 50~100 μ m, Gao C.NATURE COMMUNICATIONS 2011,10:1038).The method that the people such as the Qu Liangti of Beijing Institute of Technology prepare graphene fiber is specially: certain density graphite oxide aqueous solution is injected into linear reactor, in 100 ℃~1000 ℃ heater wire shaped reaction device 1h~6h, graphene oxide is reduced to aqueous graphite feed alkene fiber; Described aqueous graphite feed alkene fiber is dried at 20 ℃~60 ℃, and the dehydration of aqueous graphite feed alkene fiber is shunk and is obtained graphene fiber (Dong ZL, Jiang CC, Cheng HH, Zhao Y, Shi GQ, Jiang L, Qu LT.Adv.Mater.2012,24:1856 1861).The graphene fiber diameter that aforesaid method obtains is larger, and diameter is about 33 μ m, and once can only obtain single fiber, thereby has limited its application in industry.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of graphene oxide fiber, and the diameter of graphene fiber prepared by the present invention is less and have a continuous skeleton structure.
In view of this, the invention provides a kind of graphene oxide fiber, the diameter of described graphene oxide fiber is 100~500nm.
The present invention also provides the preparation method of described graphene oxide fiber, comprising:
Graphite oxide aqueous solution is carried out in liquid nitrogen to freezing solidifying, then carry out lyophilize processing, obtain graphene oxide fiber; Described graphene oxide makes according to chemical oxidization method.
Preferably, the concentration of described graphite oxide aqueous solution is 0.2~2.0mg/mL.
Preferably, the concentration of described graphite oxide aqueous solution is 0.8~1.25mg/mL.
The present invention also provides a kind of preparation method of graphene oxide fibre composite, comprises the following steps:
1) graphite oxide aqueous solution is carried out in liquid nitrogen to freezing solidifying, then carry out lyophilize processing, obtain graphene oxide fiber; Described graphene oxide makes according to chemical oxidization method;
2) described graphene oxide fiber is carried out to thermal reduction processing;
3) by step 2) be cured after the graphene oxide fiber that obtains and mixed with resin, obtain graphene oxide fibre composite.
Preferably, the concentration of described graphite oxide aqueous solution is 0.2~2.0mg/mL.
Preferably, the concentration of described graphite oxide aqueous solution is 0.8~1.25mg/mL.
Preferably, the temperature that described thermal reduction is processed is 50 ℃~200 ℃, and the time that described thermal reduction is processed is 0.5~10h.
Preferably, described resin is epoxy resin.
Preferably, step 3) is specially:
Epoxy resin is mixed with solidifying agent, and the graphene oxide fiber then obtaining with step 1) carries out compound, at 60~80 ℃ of insulation 1~2h, is then warming up to after 100~120 ℃ of insulation 1~2h, cooling.
Compared with prior art, the invention provides the preparation method of a kind of graphene oxide fiber reinforcement, preparation method and matrix material thereof.Because graphene oxide in the present invention adopts chemical oxidization method preparation, its degree of oxidation is very high, contains abundant oxygen-containing functional group, and wetting ability is fine; In preparing the process of graphene oxide fiber reinforcement, first by graphite oxide aqueous solution freezing solidifying in liquid nitrogen, in quick freezing solidification process, the explosive crystallization of liquid water, form rapidly a large amount of nanometer ice crystals uniformly, graphene oxide is compressed in the fiber reinforcement that forms tridimensional network between nanometer ice crystal; Then the graphene oxide after freezing solidifying is carried out to lyophilize, by the ice distillation between the graphene oxide of tridimensional network, graphene oxide fiber reinforcement original position is preserved, the graphene oxide fiber obtaining is tridimensional network, and the Fibre diameter of graphene oxide fiber reinforcement prepared by the present invention is 100~500nm.Based on this material, prepared reinforced epoxy matrix material, test-results shows, after compound with epoxy resin, can make its tensile strength improve 85%, compare with the carbon fiber Non crimp fabric reinforced epoxy of same matrix, homogenous quantities mark, tensile strength improves 38%.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph (SEM) of the embodiment of the present invention 1 graphene oxide fiber reinforcement;
Fig. 2 is the stereoscan photograph (SEM) of the embodiment of the present invention 1 graphene oxide fiber reinforcement.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The preparation method who the embodiment of the invention discloses a kind of graphene oxide fiber, comprising:
Graphite oxide aqueous solution is carried out in liquid nitrogen to freezing solidifying, then carry out lyophilize processing, obtain graphene oxide fiber; Described graphene oxide makes according to chemical oxidization method.
In preparing the process of graphene oxide fiber reinforcement, first the present invention carries out graphite oxide aqueous solution freezing solidifying in liquid nitrogen.Graphene oxide is the product of crystalline flake graphite through chemical oxidation and after peeling off.The preparation method of graphene oxide has three kinds: Brodie method, Staudenmaier method and Hummers method.The graphene oxide degree of oxidation standby due to Hummers legal system is higher, contain more oxygen-containing functional group, therefore graphite oxide aqueous solution of the present invention is preferably standby according to Hummers legal system, the method is method well known to those skilled in the art, the present invention has no particular limits, the method is to adopt potassium permanganate in the vitriol oil and crystalline flake graphite after oxidizing reaction, obtain the brown graphite flake that has derivative carboxylic acid group and be mainly in the plane phenolic hydroxyl group and epoxide group at edge, described graphite flake layer can be peeled off as graphene oxide through ultrasonic or high-shear vigorous stirring, and in water, form stable, the graphene oxide suspension of light brown.The present invention adopts the standby graphene oxide degree of oxidation of Hummers legal system high, contain abundant oxygen-containing functional group, so wetting ability is fine, in water, is uniformly dispersed.Therefore in the atmosphere of liquid nitrogen in freezing icing process, the explosive crystallization of liquid water, form rapidly a large amount of nanometer ice crystals uniformly, graphene oxide is compressed between nanometer ice crystal, and homodisperse graphene oxide sheet is joined together to form tridimensional network.The concentration of graphite oxide aqueous solution of the present invention is preferably 0.2~2.0mg/mL, more preferably 0.8~1.25mg/mL.
In order to make graphene oxide can access fiber reinforcement structure, the present invention carries out graphite oxide aqueous solution freezing solidifying in liquid nitrogen.The present invention carries out freezing solidifying in liquid nitrogen, be mainly to make graphene oxide in an extremely low low temperature environment, yet low temperature organic liquid saturated vapor pressure is too low, and viscosity is too large; Inorganic-liquid is known from experience dissolved oxygen Graphene; Air cooling does not reach so low temperature, and rapidly cooling not, can not get tridimensional network.And liquid nitrogen viscosity is little, volatile, do not dissolve graphene oxide, temperature is extremely low, and commercialization, abundant raw material, cheapness.Therefore liquid nitrogen is the freezing curing ideal chose of graphene oxide.
According to the present invention, then freezing curing graphene oxide is preferably carried out to lyophilize processing in freeze drier, obtain graphene oxide fiber reinforcement.Above-mentioned lyophilize is not carried out once freezing again, but keeps not melting on former freezing basis.It is to utilize the principle of distillation to carry out dry technology that lyophilize is processed, and is by the material being dried quick freezing at low temperatures, the process that the water molecules that then makes to freeze under vacuum environment directly distils and overflows.The present invention adopts cryodesiccated method by the ice distillation through in freezing curing graphene oxide, thereby graphene oxide fiber reinforcement structure original position remains, and obtains three-dimensional netted graphene oxide fiber.
Preparing on the basis of graphene oxide fiber, the present invention also provides the preparation method of graphene oxide fibre composite, comprises the following steps:
1) graphite oxide aqueous solution is carried out in liquid nitrogen to freezing solidifying, then carry out lyophilize processing, obtain graphene oxide fiber; Described graphene oxide makes according to chemical oxidization method;
2) described graphene oxide fiber is carried out to thermal reduction processing;
3) by step 2) be cured after the graphene oxide fiber that obtains and mixed with resin, obtain graphene oxide fibre composite.
According to the method for above-mentioned graphene oxide fiber, prepare graphene oxide fiber, then graphene oxide fiber is carried out to thermal reduction processing, further to improve the intensity of graphene oxide fiber, increasing its oil loving while can also retain appropriate oxygen-containing functional group, is easy to and epoxy resin cure, compound.The temperature that described thermal reduction is processed is preferably 180 ℃~220 ℃, and the time of described thermal reduction is preferably 3~5h.Epoxy resin is preferentially selected JL-236 high strength epoxy resin.Solidifying agent is preferentially selected JH-239 epoxy hardener
Finally that the mixture solidified of the graphene oxide fiber reinforcement after thermal reduction and epoxy resin and solidifying agent is compound.Due to the abundant oxygen-containing functional group of graphene oxide, thereby make the wetting property of it and resin matrix good, easily compound.Described curing process is specially: after the mixture of graphene oxide fiber reinforcement and epoxy resin and solidifying agent is compound, is warming up to 60~80 ℃ of insulation 1~2h, is then warming up to after 100~120 ℃ of insulation 1~2h, and cooling.
It is a kind of by the prepared graphene oxide fiber of such scheme that the present invention also provides.The Fibre diameter of described graphene oxide fiber reinforcement is 100~500nm.As shown in Figures 1 and 2, Fig. 1 and Fig. 2 are the stereoscan photograph of graphene oxide fiber reinforcement, and the graphene oxide fiber reinforcement that as seen from the figure prepared by the present invention has tridimensional network.
The invention provides a kind of preparation method of graphene oxide fiber reinforcement.In preparing the process of graphene oxide fiber reinforcement, the present invention is first by graphite oxide aqueous solution freezing solidifying in liquid nitrogen, form the graphene oxide of tridimensional network, then the graphene oxide after freezing solidifying is carried out to lyophilize, make the ice distillation of the graphene oxide of tridimensional network, thereby obtain graphene oxide fiber reinforcement.Due to graphene oxide, particularly the standby graphene oxide degree of oxidation of Hummers legal system is very high, contains abundant oxygen-containing functional group, and wetting ability is fine, and therefore, in freezing curing process, graphene oxide sheet is joined together to form tridimensional network; Then lyophilize, by the ice distillation on graphene oxide surface, thereby remains the structure of graphene oxide fiber reinforcement, obtains three-dimensional netted graphene oxide fiber reinforcement.Test-results surface, the diameter of graphene oxide fiber prepared by the present invention is 100~500nm.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of graphene oxide fiber reinforcement provided by the invention is elaborated, protection scope of the present invention is not limited by the following examples.
Embodiment 1
(1) by 1g natural graphite, 1.2g saltpetre, joins the vitriol oil that 46ml concentration is 98wt%, stirs 10 minutes, then add 6g potassium permanganate, heat up 40 ℃, heated and stirred 6h, adds 80ml deionized water afterwards simultaneously, and temperature is raised to 80 ℃, after heated and stirred 0.5h, add 200ml deionized water, 6ml hydrogen peroxide, reactant becomes golden yellow, and reaction stops.Finally under high speed centrifugation condition, with deionized water, repeatedly clean to supernatant liquor pH and be neutral, obtain graphene oxide concentrated solution.
(2) the graphene oxide concentrated solution of step (1) is mixed with to the aqueous solution of concentration 2mg/ml, then gets wherein 60ml and pour long 20cm into, wide 10cm, in the mould of thick 3mm.
(3) mould is immersed rapidly to liquid nitrogen, the graphite oxide dilute solution quick freezing in mould is solidified.
(4) adopt freeze drier to carry out lyophilize processing to graphite oxide aqueous solution curing in step (3), obtain the three-dimensional netted graphene oxide fiber reinforcement that 120mg is complete.
(5) skeleton obtaining in step (4) is carried out to 200 ℃ of thermal reductions and process 3~5h, obtain the three-dimensional netted skeleton of Graphene.Stereoscan photograph (SEM) is known as shown in Figure 1, Figure 2, and the diameter of graphene oxide fiber reinforcement prepared by the present invention is 100~500nm;
(6) by JL-236 high strength epoxy resin and JH-239 epoxy hardener 10:3 mixing homogeneous in mass ratio, the more three-dimensional netted skeleton of Graphene obtaining with step (5) in mass ratio 800:1 carry out compound.Adopt vacuum assistant resin infused, three-dimensional netted graphene oxide skeleton is directly laid on the mould that scribbles demoulding material, then paving is covered the auxiliary materials of technique such as demoulding medium, permeable medium successively, by flexible vacuum bag, be coated, seal, after vacuumizing the gas of getting rid of in airtight die cavity, suck thermoplastic resin-impregnated fibers, after last resin solidification, the demoulding becomes composite product again.Curing process is: room temperature is warming up to 70 ℃ of insulation 2h, is then warming up to 110 ℃ of insulation 2h.Experimental result shows: the tensile strength of the matrix material obtaining after solidifying is 152MPa.
Embodiment 2
(1) by Hummers legal system, obtain 1.25mg/ml graphite oxide aqueous solution.
(2) 60ml graphite oxide aqueous solution step (1) being obtained is poured long 20cm into, and wide 10cm, in the mould of thick 3mm.
(3) mould is immersed rapidly to liquid nitrogen, the graphite oxide dilute solution quick freezing in mould is solidified.
(4) with freeze drier, graphite oxide aqueous solution curing in step (3) is carried out to lyophilize processing, obtain the three-dimensional netted graphene oxide fiber reinforcement that 75mg is complete.
(5) skeleton step (4) being obtained carries out 50 ℃ of thermal reductions and processes 0.5~5h, obtains the three-dimensional netted skeleton of Graphene.
(6) ratio that is 10:3 by JL-236 high strength epoxy resin and JH-239 epoxy hardener according to mass ratio mixes, the more three-dimensional netted skeleton of Graphene obtaining with step (5) in mass ratio 500:1 solidify compound.Curing process: room temperature is warming up to 60 ℃ of insulation 2h, is then warming up to 120 ℃ of insulation 2h, is cooled to the room temperature demoulding.Experimental result shows: the tensile strength of the matrix material obtaining after solidifying is 139MPa.
Embodiment 3
(1) by Hummers legal system, obtain 0.8mg/ml graphite oxide aqueous solution.
(2) 60ml graphite oxide aqueous solution step (1) being obtained is poured long 20cm into, and wide 10cm, in the mould of thick 3mm.
(3) mould is immersed rapidly to liquid nitrogen, the graphite oxide dilute solution quick freezing in mould is solidified.
(4) with freeze drier, the curing graphite oxide aqueous solution of step (3) is carried out to lyophilize processing, obtain the three-dimensional netted graphene oxide fiber reinforcement that 48mg is complete.
(5) skeleton step (4) being obtained carries out 100 ℃ of thermal reductions and processes 5~10h, obtains the three-dimensional netted skeleton of Graphene.
(6) ratio that is 10:3 by JL-236 high strength epoxy resin and JH-239 epoxy hardener according to mass ratio mixes, the more three-dimensional netted skeleton of Graphene obtaining with step (5) according to mass ratio, to be that 1250:1 solidifies compound.Curing process: room temperature is warming up to 80 ℃ of insulation 1h, is then warming up to 100 ℃ of insulation 1.5h, is cooled to the room temperature demoulding.Experimental result shows: the tensile strength of the matrix material obtaining after solidifying is 115MPa.
Embodiment 4
(1) by Hummers legal system, obtain 0.2mg/ml graphite oxide aqueous solution.
(2) 60ml graphite oxide aqueous solution step (1) being obtained is poured long 20cm into, and wide 10cm, in the mould of thick 3mm.
(3) mould is immersed rapidly to liquid nitrogen, the graphene oxide solution quick freezing in mould is solidified.
(4) with freeze drier, graphite oxide aqueous solution curing in step (3) is carried out to lyophilize processing, obtain the three-dimensional netted graphene oxide fiber reinforcement that 12mg is complete.
(5) skeleton step (4) being obtained carries out 150 ℃ of thermal reductions and processes 8h, obtains the three-dimensional netted skeleton of Graphene.
(6) JL-236 high strength epoxy resin and JH-239 epoxy hardener are mixed according to mass ratio 10:3, the more three-dimensional netted skeleton of Graphene obtaining with step 5) in mass ratio 5000:1 solidify compound.Curing process: room temperature is warming up to 75 ℃ of insulation 2h, is then warming up to 115 ℃ of insulation 2h, is cooled to the room temperature demoulding.Experimental result shows: the tensile strength of the matrix material obtaining after solidifying is 105MPa.
Comparative example 1
In employing and embodiment 1, epoxy resin carries out compound with reinforcement equal in quality than 1:800.
Adopt JL-236 high strength epoxy resin and JH-239 epoxy hardener that mass ratio is 10:3, mix without flexing carbon fabric with four-axial, room temperature is warming up to 70 ℃ of insulation 2h, is then warming up to 110 ℃ of insulation 2h and is cured reaction, is cooled to the room temperature demoulding.Experimental result shows: the tensile strength of the matrix material obtaining after solidifying is only 110MPa.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.

Claims (9)

1. a graphene oxide fiber, is characterized in that, the diameter of described graphene oxide fiber is 100~500nm;
Described graphene oxide fiber is prepared in accordance with the following methods:
Graphite oxide aqueous solution is carried out in liquid nitrogen to freezing solidifying, then carry out lyophilize processing, obtain graphene oxide fiber; Described graphene oxide makes according to chemical oxidization method.
2. the preparation method of graphene oxide fiber described in claim 1, comprising:
Graphite oxide aqueous solution is carried out in liquid nitrogen to freezing solidifying, then carry out lyophilize processing, obtain graphene oxide fiber; Described graphene oxide makes according to chemical oxidization method; The diameter of described graphene oxide fiber is 100~500nm.
3. preparation method according to claim 2, is characterized in that, the concentration of described graphite oxide aqueous solution is 0.2~2.0mg/mL.
4. preparation method according to claim 3, is characterized in that, the concentration of described graphite oxide aqueous solution is 0.8~1.25mg/mL.
5. a preparation method for graphene oxide fibre composite, comprises the following steps:
1) graphite oxide aqueous solution is carried out in liquid nitrogen to freezing solidifying, then carry out lyophilize processing, obtain graphene oxide fiber; Described graphene oxide makes according to chemical oxidization method; The diameter of described graphene oxide fiber is 100~500nm;
2) described graphene oxide fiber is carried out to thermal reduction processing, described thermal reduction process temperature be 180 ℃~220 ℃, the time that described thermal reduction is processed is 3~5h;
3) by step 2) be cured after the graphene oxide fiber that obtains and mixed with resin, obtain graphene oxide fibre composite.
6. preparation method according to claim 5, is characterized in that, the concentration of described graphite oxide aqueous solution is 0.2~2.0mg/mL.
7. preparation method according to claim 6, is characterized in that, the concentration of described graphite oxide aqueous solution is 0.8~1.25mg/mL.
8. preparation method according to claim 5, is characterized in that, described resin is epoxy resin.
9. preparation method according to claim 5, is characterized in that step 3) be specially:
Epoxy resin being mixed with solidifying agent, then with step 1) the graphene oxide fiber that obtains carries out compoundly, at 60~80 ℃ of insulation 1~2h, is then warming up to after 100~120 ℃ of insulation 1~2h, cooling.
CN201310346323.1A 2013-08-09 2013-08-09 Graphene oxide fiber, preparation method, and preparation method of graphene oxide fiber composite material Active CN103396586B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310346323.1A CN103396586B (en) 2013-08-09 2013-08-09 Graphene oxide fiber, preparation method, and preparation method of graphene oxide fiber composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310346323.1A CN103396586B (en) 2013-08-09 2013-08-09 Graphene oxide fiber, preparation method, and preparation method of graphene oxide fiber composite material

Publications (2)

Publication Number Publication Date
CN103396586A CN103396586A (en) 2013-11-20
CN103396586B true CN103396586B (en) 2014-11-26

Family

ID=49560332

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310346323.1A Active CN103396586B (en) 2013-08-09 2013-08-09 Graphene oxide fiber, preparation method, and preparation method of graphene oxide fiber composite material

Country Status (1)

Country Link
CN (1) CN103396586B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3040307A1 (en) * 2015-01-05 2016-07-06 The Boeing Company Graphene fiber for aerospace composites
US9421739B2 (en) 2015-01-05 2016-08-23 The Boeing Company Graphene aerospace composites
US9434826B2 (en) 2015-01-05 2016-09-06 The Boeing Company Graphene-augmented carbon fiber for aerospace composites
US9518160B2 (en) 2015-01-05 2016-12-13 The Boeing Company Graphene-augmented composite materials
US10266677B2 (en) 2015-01-05 2019-04-23 The Boeing Company Graphene-augmented composite materials

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104692364B (en) * 2013-12-06 2016-05-25 中国科学院兰州化学物理研究所 A kind of liquid nitrogen cold quenching is prepared the method for the loose Graphene of oversubscription
CN104229782B (en) * 2014-09-10 2016-03-30 浙江碳谷上希材料科技有限公司 A kind of preparation method of Graphene ordered porous membrane
CN105947973B (en) * 2016-06-16 2018-04-24 哈尔滨工程大学 Feeler type graphene nano construction unit and graphene-based composite material and preparation method with topological structure
CN106867199B (en) * 2017-02-16 2019-03-05 嘉兴学院 A kind of orientation graphene oxide modified carbon fiber composite material and preparation method
CN109277560A (en) * 2018-05-09 2019-01-29 兰州交通大学 A kind of preparation method of high-strength and high ductility graphene/metallic composite
CN108727820B (en) * 2018-06-12 2023-04-11 四川大学 Polyphenylene sulfide composite material with high mechanical property
CN109467928A (en) * 2018-11-29 2019-03-15 圣盟(廊坊)新材料研究院有限公司 A kind of preparation method of graphene/composite conducting polymer material
CN112477309A (en) * 2020-10-30 2021-03-12 中国科学院金属研究所 Laminated composite material with graphene interpenetrating network structure
CN112500731A (en) * 2020-12-22 2021-03-16 张可新 Anti-cracking putty powder and preparation method thereof
CN115262035A (en) * 2021-04-30 2022-11-01 中国科学院宁波材料技术与工程研究所 Graphene nanofiber material and preparation method and application thereof
CN115805181B (en) * 2022-12-20 2023-08-29 西南交通大学 Preparation method of flexible electrothermal super-hydrophobic layer PDMS-TiO2@GFs

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101935035B (en) * 2010-09-02 2012-10-03 中国科学院宁波材料技术与工程研究所 Ultra-low temperature thermal expansion preparation method of high specific area graphene
CN101987908B (en) * 2010-09-21 2012-01-25 中国科学院长春应用化学研究所 Method for preparing graphene-epoxy resin composite material
CN103058179B (en) * 2013-01-21 2014-12-10 张家港市东大工业技术研究院 Method for preparing spongy graphene oxide by using freeze-drying method

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3040307A1 (en) * 2015-01-05 2016-07-06 The Boeing Company Graphene fiber for aerospace composites
US9421739B2 (en) 2015-01-05 2016-08-23 The Boeing Company Graphene aerospace composites
US9434826B2 (en) 2015-01-05 2016-09-06 The Boeing Company Graphene-augmented carbon fiber for aerospace composites
US9518160B2 (en) 2015-01-05 2016-12-13 The Boeing Company Graphene-augmented composite materials
US9963562B2 (en) 2015-01-05 2018-05-08 The Boeing Company Graphene-augmented composite materials
US10266677B2 (en) 2015-01-05 2019-04-23 The Boeing Company Graphene-augmented composite materials

Also Published As

Publication number Publication date
CN103396586A (en) 2013-11-20

Similar Documents

Publication Publication Date Title
CN103396586B (en) Graphene oxide fiber, preparation method, and preparation method of graphene oxide fiber composite material
CN103483516B (en) Preparation method of graphene oxide-boron-modified phenolic resin
US10926331B2 (en) Method for reinforcing metal material by means of graphene
CN106189088B (en) A kind of preparation method of carbon nanotube-graphene oxide hybrid reinforced composite material
CN103665769B (en) The preparation method of the multiple dimensioned fiber prepreg material of nano-micrometre
CN101456277B (en) Method for preparing carbon nanotube composite material
CN103172973B (en) High thermal-conductivity polymer composite material and preparation method thereof
CN107057283B (en) A kind of carbon fiber enhancement resin base composite material and preparation method thereof
CN105968717A (en) Preparation of carbon fiber/graphene/carbon nanotube/epoxy resin prepreg and carbon fiber composite material
CN105778510A (en) Method for preparing thermally conductive composite material with directivity
CN107586537B (en) Composite phase-change material and preparation method thereof
CN104277421A (en) Preparation method of multicomponent-modified carbon-fiber-reinforced epoxy resin composite material
CN103951916A (en) RGO (Reduced Graphene oxide)/ferric oxide-filled polyvinylidene fluoride composite wave-absorbing material and preparation method thereof
CN104151775A (en) Preparation method of three-dimensional cross-linked graphene foam structure reinforced resin composite material
CN103980668B (en) A kind of preparation method of CNT/amorphous carbon/epoxy resin composite material
CN105860431B (en) A kind of polyether-ether-ketone/multi-walled carbon nanotube composite powder material and preparation method thereof for Selective Laser Sintering
CN104451959B (en) A kind of graphene fiber of porous surface high-specific surface area and preparation method thereof
CN106566156B (en) The preparation method of graphene nanobelt/PMMA fretting map nanocomposites
CN104231624A (en) Modified cyanate resin heat-conducting composite material and preparation method thereof
CN113416334B (en) Hydroxyethyl cellulose/boron nitride nano composite film and preparation method thereof
CN106910894A (en) A kind of preparation method of mesoporous nano carbon microspheres graphene interlayers composite
CN112357910A (en) Preparation method of oriented graphene composite macroscopic body
CN103921368A (en) High-orientation carbon nano tube compound prefabricated body and preparation method thereof
CN106044753A (en) Method for preparing high orientation graphene film
CN104860293A (en) Carbon nanotube three-dimensional network architecture and polymer composite material thereof, and preparation methods thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant