CN103396586A - 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 PDFInfo
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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
Technical field
The present invention relates to the 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, good application prospect be arranged, 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, more successful case is being arranged at present, but only having spinning and two kinds of methods of mold aspect fiber, 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 clamp-on graphene oxide crystalline state solution in the NaOH/ methanol solution of 5wt%, after obtaining the graphene oxide filament, put into again the acid iodide heat reduction, namely 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; 20 ℃～60 ℃ dryings, the dehydration of aqueous graphite feed alkene fiber is shunk and is obtained graphene fiber (Dong ZL, Jiang CC with described aqueous graphite feed alkene fiber, 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 the graphene fiber of the present invention's preparation 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:
The graphite oxide aqueous solution is carried out freezing curing in liquid nitrogen, then carry out lyophilize and process, obtain the 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) the graphite oxide aqueous solution is carried out freezing curing in liquid nitrogen, then carry out lyophilize and process, obtain the graphene oxide fiber; Described graphene oxide makes according to chemical oxidization method;
2) described graphene oxide fiber being carried out thermal reduction processes;
3) with step 2) be cured after the graphene oxide fiber that obtains and mixed with resin, obtain the 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 that then obtains with step 1) carries out compound, and is at 60～80 ℃ of insulation 1～2h, after then being warming up to 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 the chemical oxidization method preparation, its degree of oxidation is very high, contains abundant oxygen-containing functional group, and wetting ability is fine; In the process for preparing the graphene oxide fiber reinforcement, at first with the freezing curing in liquid nitrogen of graphite oxide aqueous solution, in the 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 the nanometer ice crystal; Then the graphene oxide after freezing curing is carried out lyophilize, ice between the graphene oxide of tridimensional network is distilled, make graphene oxide fiber reinforcement original position preserve, the graphene oxide fiber that obtains is tridimensional network, and the Fibre diameter of the graphene oxide fiber reinforcement of the present invention's preparation is 100～500nm.Prepared the reinforced epoxy matrix material based on this material, test-results shows, can make its tensile strength improve 85% after compound with epoxy resin, with the carbon fiber Non crimp fabric reinforced epoxy of same matrix, homogenous quantities mark, compare, tensile strength improves 38%.
Description of drawings
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 embodiment of the invention discloses a kind of preparation method of graphene oxide fiber, comprising:
The graphite oxide aqueous solution is carried out freezing curing in liquid nitrogen, then carry out lyophilize and process, obtain the graphene oxide fiber; Described graphene oxide makes according to chemical oxidization method.
In the process for preparing the graphene oxide fiber reinforcement, at first the present invention carries out the graphite oxide aqueous solution freezing curing in liquid nitrogen.Graphene oxide is that crystalline flake graphite is through chemical oxidation and the product 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 the 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 the 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 derivative carboxylic acid group is arranged 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 form stable in water, 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, is uniformly dispersed in water.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 the 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 the fiber reinforcement structure, the present invention carries out the graphite oxide aqueous solution freezing curing in liquid nitrogen.The present invention carries out freezing curing in liquid nitrogen, be mainly to make graphene oxide be 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 the 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, does not dissolve graphene oxide, and temperature is extremely low, and commercialization, abundant raw material, cheapness.Therefore liquid nitrogen is the ideal chose of the freezing curing of graphene oxide.
According to the present invention, then the graphene oxide of freezing curing is preferably carried out in freeze drier lyophilize and process, obtain the graphene oxide fiber reinforcement.Above-mentioned lyophilize is not carried out once freezing again, but keeps not melting and getting final product on former freezing basis.It is to utilize the principle of distillation to carry out dry technology that lyophilize is processed, and is the material quick freezing at low temperatures that will be dried, the process that then makes the water molecules that freezes directly distil and overflow under vacuum environment.The present invention adopts cryodesiccated method to distil through the ice in the graphene oxide of freezing curing, thereby graphene oxide fiber reinforcement structure original position remains, and obtains three-dimensional netted graphene oxide fiber.
On the basis for preparing the graphene oxide fiber, the present invention also provides the preparation method of graphene oxide fibre composite, comprises the following steps:
1) the graphite oxide aqueous solution is carried out freezing curing in liquid nitrogen, then carry out lyophilize and process, obtain the graphene oxide fiber; Described graphene oxide makes according to chemical oxidization method;
2) described graphene oxide fiber being carried out thermal reduction processes;
3) with step 2) be cured after the graphene oxide fiber that obtains and mixed with resin, obtain the graphene oxide fibre composite.
Method according to above-mentioned graphene oxide fiber prepares the graphene oxide fiber, then the graphene oxide fiber being carried out thermal reduction processes, further to improve the intensity of graphene oxide fiber, increasing its oil loving while can also keep 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 the JL-236 high strength epoxy resin.Solidifying agent is preferentially selected the 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.The process of described curing is specially: after the mixture of graphene oxide fiber reinforcement and epoxy resin and solidifying agent is compound, be warming up to 60～80 ℃ of insulation 1～2h, and after then being warming up to 100～120 ℃ of insulation 1～2h, 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 of the present invention's preparation has tridimensional network as seen from the figure.
The invention provides a kind of preparation method of graphene oxide fiber reinforcement.In the process for preparing the graphene oxide fiber reinforcement, the present invention is at first with the freezing curing in liquid nitrogen of graphite oxide aqueous solution, form the graphene oxide of tridimensional network, then the graphene oxide after freezing curing is carried out lyophilize, make the ice distillation of the graphene oxide of tridimensional network, thereby obtain the graphene oxide fiber reinforcement.Particularly the standby graphene oxide degree of oxidation of Hummers legal system is very high due to graphene oxide, contains abundant oxygen-containing functional group, and wetting ability is fine, and therefore in the process of freezing curing, graphene oxide sheet is joined together to form tridimensional network; Then lyophilize, with the distillation of the ice on graphene oxide surface, thereby remain the structure of graphene oxide fiber reinforcement, obtains three-dimensional netted graphene oxide fiber reinforcement.The test-results surface, the diameter of the graphene oxide fiber of the present invention's preparation 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) with the 1g natural graphite, 1.2g saltpetre, join the vitriol oil that 46ml concentration is 98wt%, stirred 10 minutes, then add 6g potassium permanganate, heat up simultaneously 40 ℃, heated and stirred 6h, add the 80ml deionized water afterwards, and temperature is raised to 80 ℃, add 200ml deionized water, 6ml hydrogen peroxide after heated and stirred 0.5h, reactant becomes golden yellow, and reaction stops.Repeatedly clean to supernatant liquor pH and be neutral with deionized water under the high speed centrifugation condition finally, obtain the graphene oxide concentrated solution.
(2) the graphene oxide concentrated solution of step (1) is mixed with 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 liquid nitrogen, the graphite oxide dilute solution quick freezing in mould is solidified.
(4) adopt freeze drier to carry out lyophilize to the graphite oxide aqueous solution that solidifies in step (3) and process, obtain the complete three-dimensional netted graphene oxide fiber reinforcement of 120mg.
(5) skeleton that obtains in step (4) is carried out 200 ℃ of thermal reductions and process 3～5h, obtain the three-dimensional netted skeleton of Graphene.As can be known, the diameter of the graphene oxide fiber reinforcement of the present invention's preparation is 100～500nm to stereoscan photograph (SEM) as shown in Figure 1, Figure 2;
(6) with 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 that obtains with step (5) in mass ratio 800:1 carry out compound.Adopt vacuum assistant resin infused, three-dimensional netted graphene oxide skeleton directly is laid on the mould that scribbles demoulding material, then paving is covered the auxiliary materials of technique such as demoulding medium, permeable medium successively, coat, seal by flexible vacuum bag, suck thermoplastic resin-impregnated fibers after vacuumizing the gas of getting rid of in airtight die cavity, after last resin solidification, the demoulding becomes composite product again.Curing process is: room temperature is warming up to 70 ℃ of insulation 2h, then is warming up to 110 ℃ of insulation 2h.Experimental result shows: the tensile strength of the matrix material that obtains after curing is 152MPa.
Embodiment 2
(1) obtain 1.25mg/ml graphite oxide aqueous solution with the Hummers legal system.
(2) the 60ml graphite oxide aqueous solution that step (1) is obtained is poured long 20cm into, and wide 10cm, in the mould of thick 3mm.
(3) mould is immersed rapidly liquid nitrogen, the graphite oxide dilute solution quick freezing in mould is solidified.
(4) with freeze drier, the graphite oxide aqueous solution that solidifies in step (3) is carried out lyophilize and process, obtain the complete three-dimensional netted graphene oxide fiber reinforcement of 75mg.
(5) skeleton that step (4) is 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 with JL-236 high strength epoxy resin and JH-239 epoxy hardener according to mass ratio mixes, the more three-dimensional netted skeleton of Graphene that obtains with step (5) in mass ratio 500:1 solidify compound.Curing process: room temperature is warming up to 60 ℃ of insulation 2h, then is warming up to 120 ℃ of insulation 2h, is cooled to the room temperature demoulding.Experimental result shows: the tensile strength of the matrix material that obtains after curing is 139MPa.
Embodiment 3
(1) obtain 0.8mg/ml graphite oxide aqueous solution with the Hummers legal system.
(2) the 60ml graphite oxide aqueous solution that step (1) is obtained is poured long 20cm into, and wide 10cm, in the mould of thick 3mm.
(3) mould is immersed rapidly liquid nitrogen, the graphite oxide dilute solution quick freezing in mould is solidified.
(4) carry out lyophilize with the graphite oxide aqueous solution that freeze drier solidifies step (3) and process, obtain the complete three-dimensional netted graphene oxide fiber reinforcement of 48mg.
(5) skeleton that step (4) is 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 with JL-236 high strength epoxy resin and JH-239 epoxy hardener according to mass ratio mixes, the more three-dimensional netted skeleton of Graphene that obtains with step (5) to be according to mass ratio that 1250:1 solidifies compound.Curing process: room temperature is warming up to 80 ℃ of insulation 1h, then is 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 that obtains after curing is 115MPa.
Embodiment 4
(1) obtain 0.2mg/ml graphite oxide aqueous solution with the Hummers legal system.
(2) the 60ml graphite oxide aqueous solution that step (1) is obtained is poured long 20cm into, and wide 10cm, in the mould of thick 3mm.
(3) mould is immersed rapidly liquid nitrogen, the graphene oxide solution quick freezing in mould is solidified.
(4) with freeze drier, the graphite oxide aqueous solution that solidifies in step (3) is carried out lyophilize and process, obtain the complete three-dimensional netted graphene oxide fiber reinforcement of 12mg.
(5) skeleton that step (4) is 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 that obtains with step 5) in mass ratio 5000:1 solidify compound.Curing process: room temperature is warming up to 75 ℃ of insulation 2h, then is warming up to 115 ℃ of insulation 2h, is cooled to the room temperature demoulding.Experimental result shows: the tensile strength of the matrix material that obtains after curing is 105MPa.
Comparative Examples 1
In employing and embodiment 1, epoxy resin carries out compound with the reinforcement equal in quality than 1:800.
Adopting mass ratio is JL-236 high strength epoxy resin and the JH-239 epoxy hardener of 10:3, with four-axial, without the flexing carbon fabric, mixes, and room temperature is warming up to 70 ℃ of insulation 2h, then is 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 that obtains after curing only is 110MPa.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.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.
, to the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent for those skilled in the art, and General Principle as defined herein can be in the situation that do not break away from the spirit or scope of the present invention, realization 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 (10)
1. a graphene oxide fiber, is characterized in that, the diameter of described graphene oxide fiber is 100～500nm.
2. the preparation method of the described graphene oxide fiber of claim 1 comprises:
The graphite oxide aqueous solution is carried out freezing curing in liquid nitrogen, then carry out lyophilize and process, obtain the graphene oxide fiber; Described graphene oxide makes according to chemical oxidization method.
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. the preparation method of a graphene oxide fibre composite comprises the following steps:
1) the graphite oxide aqueous solution is carried out freezing curing in liquid nitrogen, then carry out lyophilize and process, obtain the graphene oxide fiber; Described graphene oxide makes according to chemical oxidization method;
2) described graphene oxide fiber being carried out thermal reduction processes;
3) with step 2) be cured after the graphene oxide fiber that obtains and mixed with resin, obtain the 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, the temperature that described thermal reduction is processed is 50 ℃～200 ℃, and the time that described thermal reduction is processed is 0.5～10h.
9. preparation method according to claim 5, is characterized in that, described resin is epoxy resin.
10. preparation method according to claim 5, is characterized in that, step 3) is specially:
Epoxy resin is mixed with solidifying agent, and the graphene oxide fiber that then obtains with step 1) carries out compound, and is at 60～80 ℃ of insulation 1～2h, after then being warming up to 100～120 ℃ of insulation 1～2h, cooling.
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