CN102690426A - Method for preparing graphene/polymer composite material based on infrared irradiation - Google Patents
Method for preparing graphene/polymer composite material based on infrared irradiation Download PDFInfo
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Abstract
The invention discloses a method for preparing a graphene/polymer composite material based on infrared irradiation. The method comprises the following steps: 1) mixing a graphite oxide solution with a polymer solution or polymer emulsion to obtain a mixed solution, casting or spinning, and drying until the weight percentage of the total solvent is less than or equal to 50 percent so as to obtain a composite product; and 2) removing the solvent from the composite product under the irradiation of an infrared heating lamp, and performing reduction reaction of graphite oxide to obtain the graphene/polymer composite material. By the preparation method, the graphene/polymer composite material is prepared under the irradiation of the infrared heating lamp, the process is simple and convenient, the production cost is low, the method is suitable for large-scale industrial production, different polymers can be selected for preparing different graphene/polymer composite materials so as to meet the production and use requirements, and the graphene/polymer composite material has a wide application prospect in the fields such as conductive polymer composite materials, films and fibers.
Description
Technical field
The present invention relates to the preparation field of Graphene/polymer composites, be specifically related to a kind of preparation method of the Graphene/polymer composites based on infrared irridiation.
Background technology
Graphene is a kind of monolayer carbon material that is made up of carbon atom.A.K.Geim of University of Manchester in 2004 and co-worker thereof report that for the first time the method for graphite being peeled off with plastic adhesive tape obtains Graphene (K.S.Novoselov, A.K.Geim, S.V.Morozov, D.Jiang; Y.Zhang, S.V.Dubonos, I.V.Grigorieva, A.A.Firsov; Electric Field Effect in Atomically Thin Carbon Films, Science, 306; 22,2004,666-669).Subsequently, Graphene begins to receive whole world investigator's favor.
Graphene has bigger specific surface area (2360m
2G
-1), higher electronic mobility (200000cm
2V
-1S
-1), higher Young's modulus (1.0TPa), higher thermal conductivity (5000Wm
-1K
-1) and light transmission (97.7%), (Yanwu Zhu, Shanthi Murali have broad application prospects at aspects such as field-effect transistor, transmitter, transparent conductive film, Graphene battery, electron detection device, heat transfer equipment and polymer matrix composites; Weiwei Cai, Xuesong Li, Ji Won Suk; Jeffrey R.Potts; Rodney S.Ruoff, Graphene and Graphene Oxide:Synthesis, Properties; And Applications, Adv.Mater.2010).
Mainly contain six kinds of methods at present and prepare Graphene:
One, epitaxy Graphene; Promptly make Graphene be grown in the metallic surface of orientation through chemical gaseous phase depositing process; Can accomplish the Graphene thin layer of endless, non-constant width on this theoretical method, but need high temperature and Graphene needs from the process that metallic substrate surface is peeled off are being used corrosive chemical;
Two, micromechanics stripping means, this method are applicable to the electrical property and other performances of research Graphene, but resulting Graphene lamella size of this method and thickness also are difficult to control at present, and are not suitable for preparing in a large number Graphene;
Three, the chemical reduction method of graphite oxide promptly reduces graphite oxide with chemical process and obtains Graphene (also being reduction-oxidation graphite) in solution.The reductive agent that adopts at present mainly contains Hydrazine Hydrate 80, Peng Qinghuana, glucose, xitix, sodium hydroxide and Pottasium Hydroxide etc.These methods prepare that reduction-oxidation graphite speed is slow, and energy consumption is higher, and employed some chemical reagent has higher toxicity;
Four, the high temperature pyrolysis reduction method of graphite oxide is about to graphite oxide and under protection of inert gas, heats and make graphite oxide deviate from oxy radical to be reduced into Graphene.The temperature of reduction reaction is generally 500 ℃ to 1200 ℃.This method can prepare Graphene in enormous quantities, but has the matrix shortcomings such as (like plastics, textiless) that energy consumption is high, the heating and cooling cycle is long, be not suitable for non-refractory;
Five, (publication number is the one Chinese patent application of CN 101559941A to the electron beam irradiation method for Zhao Bing etc., the method for preparing graphite alkenyl nanometer materials by electron beam irradiation method; Chen Wufeng, Yan Lifeng, Prakriti R.Bangal; Preparation of graphene by the rapid and mild thermal reduction of graphene oxide induced by microwaves, Carbon, 48; 2010,1146-1152).This method need be used expensive rumbatron, and the cost of its preparation is higher, is unfavorable for industrialization promotion and production;
Six, xenon lamp irradiation reduction method (Laura J.Cote; Rodolfo Cruz-Silva; Jiaxing Huang, Flash Reduction and Patterning of Graphite Oxide and Its Polymer Composite, J.Am.Chem.Soc.2009.131.11207-11032).This method reduction rate is very fast, but only is fit to the reduction of graphite oxide film, and its operating process simultaneously is step, is difficult to carry out the reduction processing of serialization, is difficult to satisfy the reduction demand of big area or a large amount of graphite oxides.
Aspect the preparation of Graphene/polymer composites, how with Graphene and polymkeric substance evenly compound be the key that obtains high-performance Graphene/polymer composites.Normally adopt earlier at present graphite oxide is reduced, compound with polymkeric substance again, but owing to the Graphene self of reduction-oxidation graphite method preparation is easy to reunite, so be difficult to obtain finely dispersed Graphene/polymer composites.
Summary of the invention
The invention provides a kind of preparation method of the Graphene/polymer composites based on infrared irridiation, its preparation is simple fast, can be continuously produced.
A kind of preparation method of the Graphene/polymer composites based on infrared irridiation may further comprise the steps:
1) graphite oxide solution is mixed with polymers soln or polymer emulsion, obtain mixed solution, cast or spinning, the weight percentage that is dried to total solvent obtains combination product smaller or equal to 50%;
Described mixed solution comprises total soluble matters and total solvent; Total soluble matters is graphite oxide and polymkeric substance; Total solvent is solvent and the solvent sum in the polymers soln in the graphite oxide solution, and in the drying process, the weight of total solvent can reduce thereupon in the mixed solution; The weight percentage that is total solvent can reduce accordingly, the weight percentage of total solvent=dried total solvent weight/(dried total solvent weight+dried total soluble matters weight);
2) under infrared heating lamp irradiation, the solvent in the combination product in the step 1) removed and carry out the reduction reaction of graphite oxide, obtain Graphene/polymer composites.
The preparation of graphite oxide is referring to disclosed preparation method (Laura J.Cote in " xenon lamp reduction, patterning and the polymer composite thereof of graphite oxide "; Franklin Kim; And Jiaxing Huang, Flash Reduction and Patterning of Graphite Oxide and Its Polymer Composite, J.Am.Chem.Soc.2009; 131,10431049).The preparation process can brief overview be with graphite in the vitriol oil, SODIUMNITRATE and potassium permanganate, disperse, intercalation, heated oxide then, again through overpickling, washing filtering, separation, it is for use to take out throw out, throw out is graphite oxide.
In the step 1), as preferably, the weight ratio of described graphite oxide and polymkeric substance is 0.001 ~ 40: 1, and the weight ratio of raw material is limited in the suitable scope, and it is compound preferably to help reduction-oxidation graphite and polymkeric substance.
For graphite oxide solution and polymers soln or polymer emulsion have the better mixing effect; And help follow-up processing; The weight percentage of graphite oxide is 0.1% ~ 2% in the described graphite oxide solution, and the weight percentage of polymkeric substance is 0.5% ~ 20% in described polymers soln or the polymer emulsion.Further preferred, the weight percentage of graphite oxide is 0.1% ~ 0.5% in the described graphite oxide solution, and the weight percentage of polymkeric substance is 1% ~ 10% in described polymers soln or the polymer emulsion.
Solvent in the described graphite oxide solution is water, N,N-DIMETHYLACETAMIDE or N; Primary solvent in described polymers soln or the polymer emulsion is water, N,N-DIMETHYLACETAMIDE or N; Help graphite oxide and polymkeric substance are evenly dispersed in the solvent on the one hand; On the other hand, these solvents are removed in the preparation process easily.
Described polymers soln or polymer emulsion are dimethylacetamide solution, ptfe emulsion, perfluoroethylene-propylene emulsion, organic silicon emulsion, polyaryletherketone emulsion, polyetherimide emulsion or the polyethersulfone emulsion of polyvinyl alcohol water solution, polyamic acid.These polymkeric substance all can be compound preferably with reduction-oxidation graphite, obtains the Graphene/polymer composites of excellent property.
As preferably, the weight percentage that is dried to total solvent is 5% ~ 50%, helps under infrared heating lamp irradiation, carrying out the reduction reaction of graphite oxide.Step 2) in; As preferably, the power of described infrared heating lamp is 5W to 10kW, and the time of described infrared heating lamp irradiation is 10 seconds to 60 minutes; During infrared heating lamp irradiation, the distance of described infrared heating lamp and combination product is 1 millimeter to 1000 millimeters; Under this condition, the infrared heating lamp can reduce graphite oxide preferably, and makes that reduction-oxidation graphite (being Graphene) and polymkeric substance are compound more equably, and the Graphene/polymer composites that obtains embodies preferable performance.
Compared with prior art, have the following advantages:
Infrared irridiation heating have thermal conversion efficiency height, heat-up rate fast, be easy to advantages such as serialization, mass-producing, in industrial and agricultural production and daily life, be widely used in purposes such as heating, drying.Among the preparation method of the present invention, utilize preparation Graphene/polymer composites under the infrared heating lamp irradiation, technology is very easy, production cost is very low, helps large-scale industrialization production, has broad application prospects.Among the preparation method of the present invention; Polymkeric substance can be selected different kinds; Can prepare different Graphene/polymer composites; Can satisfy different production and request for utilization, help utilization and extention, have broad application prospects in fields such as conductive polymer composite and film, fibers.
Compare with the electron beam irradiation method of reducing, preparation method of the present invention does not need expensive equipment, and the production cost of Graphene/polymer composites is lower; Compare with chemical reduction method, preparation method of the present invention need not add any catalyzer or chemical reducing agent, and a step can obtain reduction-oxidation graphite, and preparation is very easy; Compare with the Pintsch process reduction method, preparing method's reduction temperature of the present invention is low, the heating and cooling cycle short, be easy to mass-producing, is suitable for the preparation of the lower polymer composites of thermotolerance.
Description of drawings
Fig. 1 is the electron scanning micrograph of the reduction-oxidation graphite in the preparation example 1;
Fig. 2 is the X-ray diffractogram of graphite oxide (curve 1) and reduction-oxidation graphite (curve 2) in the preparation example 1;
Fig. 3 is electron-microscope scanning (SEM) photo of the reduction-oxidation graphite/polyvinyl alcohol compound film of embodiment 1 preparation;
Fig. 4 is square resistance and the relation curve of transmittance of the reduction-oxidation graphite/polyvinyl alcohol compound film of each different thickness among the embodiment 2;
Fig. 5 is electron-microscope scanning (SEM) photo of the reduction-oxidation graphite/tetrafluoroethylene laminated film of embodiment 3 preparations.
Embodiment
Below be the embodiment that the present invention provides, invention is further introduced, need to prove, the invention is not restricted to following examples.Umber among the embodiment is weight part.Volume specific resistance in the present embodiment and square resistance all use four probe method (RTS-2 type four point probe tester, Guangzhou four point probe Science and Technology Ltd.) to measure.
Preparation example 1
Descend reaction after 2 hours at 35 ℃ in 3g graphite, 3g SODIUMNITRATE, the 60mL vitriol oil (98%) and 6g potassium permanganate; Add the 100mL deionized water; Add the hydrogen peroxide weight percentage then and be 3% aqueous hydrogen peroxide solution 200mL, pickling and washing obtain the graphite oxide jelly after leaving standstill 12 hours.The graphite oxide jelly places 25 ℃ of following vacuum-dryings of room temperature or lyophilize, obtains oxidation graphite solid.Use power to adjust the distance 10 millimeters places of oxidation graphite solid to its irradiation 1 minute, reduction reaction promptly takes place, obtain the reduction-oxidation graphite solid as the infrared heating lamp of 275W.The electron scanning micrograph of reduction-oxidation graphite solid is as shown in Figure 1, and is visible, and loose, the porous of reduction-oxidation graphite-structure that obtains with this understanding explains that reduction process is more violent, discharges a large amount of gases.The X-ray diffractogram of oxidation graphite solid is shown in curve among Fig. 21, and the X-ray diffractogram of reduction-oxidation graphite solid is shown in curve among Fig. 22.As shown in Figure 2, diffraction peak disappears after the reduction of graphite oxide infrared radiation, explains that reduction process is relatively more violent, discharges gas and graphite flake layer is peeled off.
The graphite oxide aqueous solution among the embodiment 1 ~ 16 all obtains after the preparation oxidation graphite solid is dissolved in deionized water among the embodiment 1.
1) be 200 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of Z 150PH with the weight percentage of graphite oxide be that 10% polyvinyl alcohol water solution mixes for 10 parts; Wherein the number-average molecular weight of Z 150PH is 1799, obtains mixed solution after stirring, and is cast in the sample cell; Drying is 12 hours in 70 ℃ baking oven; The weight percentage that is dried to total solvent equals 35%, obtains graphite oxide/polyvinyl alcohol compound film (combination product), and this laminated film is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) 100 millimeters places of graphite oxide/polyvinyl alcohol compound film to its irradiation 30 minutes; Obtain the reduction-oxidation graphite/polyvinyl alcohol compound film (being Graphene/polymer composites) of 1.5 parts conduction, volume specific resistance is 1.1 * 10
3Ω cm, the electron-microscope scanning picture of the reduction-oxidation graphite/polyvinyl alcohol compound film of preparation is as shown in Figure 3.As shown in Figure 3, the thickness of film is approximately 800 nanometers, and section structure is dense not to have tangible pore.
1) be 100 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of Z 150PH with the weight percentage of graphite oxide be that 10% the aqueous solution mixes for 1 part; Wherein the number-average molecular weight of Z 150PH is 5000; Obtain mixed solution after stirring; The weight percentage that mixed solution is diluted with water to graphite oxide in the mixed solution respectively is 0.01%, 0.02%, 0.05%, 0.1%, 0.2% and 0.4%; Get 10 portions of mixed solutions after the dilution respectively and be cast on the silica glass surface, drying is 12 hours in 70 ℃ baking oven, and the weight percentage that is dried to total solvent equals 25%; Obtain graphite oxide/polyvinyl alcohol compound film (combination product), this laminated film is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) 100 millimeters places of graphite oxide/polyvinyl alcohol compound film to its irradiation 30 minutes; Obtain having the reduction-oxidation graphite/polyvinyl alcohol compound film (being Graphene/polymer composites) of each different thickness certain transparency, conduction; Survey the square resistance (ohm/sq) and the transmittance of the reduction-oxidation graphite/polyvinyl alcohol compound film of each different thickness then respectively; Its test result is as shown in Figure 4, among Fig. 4 from left to right point successively the weight percentage of corresponding graphite oxide be 0.01%, 0.02%, 0.05%, 0.1%, 0.2% and 0.4%.The electroconductibility of reduction-oxidation graphite/polyvinyl alcohol compound film significantly increases along with the increase of thickness, and this is because graphite oxide under the irradiation of infrared light reduction has taken place, and changes into the good Graphene of electroconductibility.
Embodiment 3
1) be 200 parts of 0.5% the graphite oxide aqueous solution with weight percentage with the weight percentage of graphite oxide be that 1% ptfe emulsion (adding the deionized water dilution by Daikin D210 ptfe emulsion obtains) mixes for 2.5 parts; Obtain mixed solution after stirring; Be cast in the sample cell; Drying is 2 hours in 70 ℃ baking oven; The weight percentage that is dried to total solvent equals 43%, obtains graphite oxide/tetrafluoroethylene laminated film (combination product), and this laminated film is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) graphite oxide/100 millimeters places of tetrafluoroethylene laminated film to its irradiation 10 minutes; Obtain the reduction-oxidation graphite/tetrafluoroethylene laminated film (being Graphene/polymer composites) of 0.5 part conduction; Volume specific resistance is 106 Ω cm; The electron-microscope scanning picture of the reduction-oxidation graphite/tetrafluoroethylene laminated film of preparation is as shown in Figure 5, and this product is that thickness is the densification about 6 microns, imperforate film.
Embodiment 4
1) be 100 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of tetrafluoroethylene with the weight percentage of graphite oxide be that 1% ptfe emulsion (adding the deionized water dilution by Daikin D210 ptfe emulsion obtains) mixes for 2.5 parts; Obtain mixed solution after stirring; Be cast in the sample cell; Drying is 2 hours in 70 ℃ baking oven; The weight percentage that is dried to total solvent equals 40%, obtains graphite oxide/tetrafluoroethylene laminated film (combination product), and this laminated film is nonconducting;
2) use power as the infrared heating lamp of 5W in apart from step 1) graphite oxide/1 millimeter place of tetrafluoroethylene laminated film to its irradiation 60 minutes; Obtain reduction-oxidation graphite/tetrafluoroethylene laminated film (being Graphene/polymer composites) of 0.2 part, volume specific resistance is 3.4 * 10
8Ω cm.
Embodiment 5
1) be 2000 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of perfluoroethylene-propylene with the weight percentage of graphite oxide be that 10% perfluoroethylene-propylene emulsion (adding the deionized water dilution by hugeization F46 emulsion) is mixed for 5 parts; Obtain mixed solution after stirring; Be cast in the sample cell; Drying is 2 hours in 70 ℃ baking oven; The weight percentage that is dried to total solvent equals 45%, obtains graphite oxide/perfluoroethylene-propylene laminated film (combination product), and this laminated film is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) graphite oxide/100 millimeters places of perfluoroethylene-propylene laminated film to its irradiation 10 minutes; Obtain reduction-oxidation graphite/perfluoroethylene-propylene laminated film (being Graphene/polymer composites) of 5 parts, volume specific resistance is 1.1 Ω cm.
Embodiment 6
1) be 1000 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of perfluoroethylene-propylene with the weight percentage of graphite oxide be that 10% perfluoroethylene-propylene emulsion is mixed (adding the deionized water dilution by hugeization F46 emulsion) for 5 parts; Obtain mixed solution after stirring; Be cast in the sample cell; Drying is 2 hours in 70 ℃ baking oven; The weight percentage that is dried to total solvent equals 40%, obtains graphite oxide/perfluoroethylene-propylene laminated film (combination product), and this laminated film is nonconducting;
2) use power as the infrared heating lamp of 10kW in apart from step 1) graphite oxide/50 millimeters places of perfluoroethylene-propylene laminated film to its irradiation 10 seconds; Obtain reduction-oxidation graphite/perfluoroethylene-propylene laminated film (being Graphene/polymer composites) of 3 parts, volume specific resistance is 250 Ω cm.
Embodiment 7
1) be 20 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of graphite oxide and organosilyl weight percentage is 10% organic silicon emulsion (Wacker; E101CN) 1000 parts of mixing obtain mixed solution after stirring, and are cast in the sample cell; Drying is 2 hours in 70 ℃ baking oven; Be dried to that the weight of solvent equals 37% of mixed solution gross weight in the mixed solution, obtain graphite oxide/organosilicon laminated film (combination product), this laminated film is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) graphite oxide/100 millimeters places of organosilicon laminated film to its irradiation 10 minutes; Obtain reduction-oxidation graphite/organosilicon laminated film (being Graphene/polymer composites) of 98.7 parts, volume specific resistance is 1.1 * 10
11Ω cm.
Embodiment 8
1) be 20 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of graphite oxide and organosilyl weight percentage is 10% organic silicon emulsion (Wacker; E101CN) 500 parts of mixing obtain mixed solution after stirring, and are cast in the sample cell; Drying is 2 hours in 70 ℃ baking oven; The weight percentage that is dried to total solvent equals 33%, obtains graphite oxide/organosilicon laminated film (combination product), and this laminated film is nonconducting;
2) use power as the infrared heating lamp of 10kW in apart from step 1) graphite oxide/1000 millimeters places of organosilicon laminated film to its irradiation 60 minutes; Obtain reduction-oxidation graphite/organosilicon laminated film (being Graphene/polymer composites) of 49 parts, volume specific resistance is 1.1 * 10
11Ω cm.
Embodiment 9
1) be that 20 parts of weight percentages with polyethersulfone (German BASF E2010) of the graphite oxide aqueous solution of 0.5% are that 10% polyethersulfone emulsion is mixed for 18 parts with the weight percentage of graphite oxide; Obtain mixed solution after stirring; Be cast in the sample cell, drying is 2 hours in 70 ℃ baking oven, and the weight percentage that is dried to total solvent equals 30%; Obtain graphite oxide/polyethersulfone laminated film (combination product), this laminated film is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) graphite oxide/100 millimeters places of polyethersulfone laminated film to its irradiation 10 minutes; Obtain reduction-oxidation graphite/polyethersulfone laminated film (being Graphene/polymer composites) of 1.8 parts, volume specific resistance is 1.1 * 10
5Ω cm.
1) be 20 parts of 0.5% the graphite oxide aqueous solution and polyaryletherketone (012P with the weight percentage of graphite oxide; Changchun Jida special plastic engineering Co., Ltd) weight percentage is 15 parts of mixing of polyaryletherketone emulsion of 10%, obtains mixed solution after stirring, and is cast in the sample cell; Drying is 2 hours in 70 ℃ baking oven; The weight percentage that is dried to total solvent equals 29%, obtains graphite oxide/polyaryletherketone laminated film (combination product), and this laminated film is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) graphite oxide/100 millimeters places of polyaryletherketone laminated film to its irradiation 10 minutes; Obtain reduction-oxidation graphite/polyaryletherketone laminated film (being Graphene/polymer composites) of 1.4 parts, volume specific resistance is 1.1 * 10
10Ω cm.
Embodiment 11
1) be that 20 parts of weight percentages with polyetherimide (GE ULTEM 1000) of the graphite oxide aqueous solution of 0.5% are that 10% polyetherimide emulsion is mixed for 10 parts with the weight percentage of graphite oxide; Obtain mixed solution after stirring; Be cast in the sample cell, drying is 2 hours in 70 ℃ baking oven, and the weight percentage that is dried to total solvent equals 28%; Obtain graphite oxide/polyetherimide laminated film (combination product), this laminated film is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) graphite oxide/100 millimeters places of polyetherimide laminated film to its irradiation 10 minutes; Obtain reduction-oxidation graphite/polyetherimide laminated film (being Graphene/polymer composites) of 0.9 part, volume specific resistance is 2.7 * 10
3Ω cm.
Embodiment 12
1) be that 20 parts of weight percentages with polyamic acid of dimethylacetamide solution of 0.2% graphite oxide are the dimethylacetamide solution (ZKPI-305IA of 1% polyamic acid with the weight percentage of graphite oxide; Beijing Bomi Sci. & Tech. Co., Ltd.) 20 parts of mixing; Obtain mixed solution after stirring; Be cast in the sample cell, drying is 48 hours in 120 ℃ baking oven, and the weight percentage that is dried to total solvent equals 5%; Obtain graphite oxide/polyamic acid laminated film (combination product), this laminated film is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) graphite oxide/100 millimeters places of polyamic acid laminated film to its irradiation 10 minutes; Obtain reduction-oxidation graphite/polyamic acid laminated film (being Graphene/polymer composites) of 0.14 part, volume specific resistance is 6.4 * 10
5Ω cm.
Embodiment 13
1) be that 100 parts of weight percentages with polyamic acid of dimethyl formamide solution of 0.5% graphite oxide are the dimethylacetamide solution (ZKPI-305IA of 10% polyamic acid with the weight percentage of graphite oxide; Beijing Bomi Sci. & Tech. Co., Ltd.) 100 parts of mixing; Obtain mixed solution after stirring; Spinning, drying is 2 hours in 160 ℃ baking oven, and the weight percentage that is dried to total solvent equals 5%; Obtain graphite oxide/polyamic acid conjugated fibre (combination product), this conjugated fibre is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) graphite oxide/100 millimeters places of polyamic acid conjugated fibre to its irradiation 30 minutes; Obtain reduction-oxidation graphite/polyamic acid conjugated fibre (being Graphene/polymer composites) of 7.6 parts, volume specific resistance is 2.6 * 10
3Ω cm.
Embodiment 14
1) is that 100 parts of weight percentages with polyaryletherketone (012P, Changchun Jida special plastic engineering Co., Ltd) of the graphite oxide aqueous solution of 0.1% are 100 parts of mixing of polyaryletherketone emulsion of 10% with the weight percentage of graphite oxide, obtains mixed solution after stirring; Again while stirring 70 ℃ of heating; Along with the volatilization of water, form the graphite oxide/polyaryletherketone mixture of colloidal, mixture is watered in the sample cell; Drying is 24 hours in 70 ℃ baking oven; The weight percentage that is dried to total solvent equals 20%, obtains graphite oxide/polyaryletherketone matrix material (combination product), and this matrix material is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) graphite oxide/100 millimeters places of polyaryletherketone matrix material to its irradiation 10 minutes; Obtain reduction-oxidation graphite/polyaryletherketone matrix material (being Graphene/polymer composites) of 1.4 parts, volume specific resistance is 5.3 * 10
4Ω cm.
Embodiment 15
1) be that 100 parts of weight percentages with polyetherimide (GE ULTEM 1000) of the graphite oxide aqueous solution of 0.1% are that 1% polyetherimide emulsion is mixed for 10 parts with the weight percentage of graphite oxide; Obtain mixed solution after stirring, more while stirring 70 ℃ of heating, along with the volatilization of water; Form the graphite oxide/polyetherimide amine mixt of colloidal; Mixture is watered in the sample cell, and drying is 24 hours in 70 ℃ baking oven, and the weight percentage that is dried to total solvent equals 17%; Obtain graphite oxide/polyetherimide composite material (combination product), this matrix material is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) 100 millimeters places of graphite oxide/polyetherimide composite material to its irradiation 10 minutes; Obtain reduction-oxidation graphite/polyetherimide composite material (being Graphene/polymer composites) of 0.15 part, volume specific resistance is 3.8 * 10
2Ω cm.
Embodiment 16
1) be 100 parts of 0.1% the graphite oxide aqueous solution with the weight percentage of polyethersulfone with the weight percentage of graphite oxide be that 10% polyethersulfone (BASF Ultrason E3010) emulsion is mixed for 100 parts; Obtain mixed solution after stirring, more while stirring 70 ℃ of heating, along with the volatilization of water; Form the graphite oxide/polyethersulfone mixture of colloidal; Mixture is watered in the sample cell, and drying is 24 hours in 70 ℃ baking oven, and the weight percentage that is dried to total solvent equals 25%; Obtain graphite oxide/polyethersulfone matrix material (combination product), this matrix material is nonconducting;
2) use power as the infrared heating lamp of 275W in apart from step 1) graphite oxide/100 millimeters places of polyethersulfone matrix material to its irradiation 10 minutes; Obtain reduction-oxidation graphite/polyethersulfone matrix material (being Graphene/polymer composites) of 9.8 parts, volume specific resistance is 2.9 * 10
2Ω cm.
Claims (8)
1. preparation method based on the Graphene/polymer composites of infrared irridiation may further comprise the steps:
1) graphite oxide solution is mixed with polymers soln or polymer emulsion, obtain mixed solution, cast or spinning, the weight percentage that is dried to total solvent obtains combination product smaller or equal to 50%;
2) under infrared heating lamp irradiation, the solvent in the combination product in the step 1) removed and carry out the reduction reaction of graphite oxide, obtain Graphene/polymer composites.
2. preparation method according to claim 1 is characterized in that, the weight ratio of described graphite oxide and polymkeric substance is 0.001 ~ 40: 1.
3. preparation method according to claim 1 is characterized in that, the weight percentage of graphite oxide is 0.1% ~ 2% in the described graphite oxide solution, and the weight percentage of polymkeric substance is 0.5% ~ 20% in described polymers soln or the polymer emulsion.
4. preparation method according to claim 3 is characterized in that, the weight percentage of graphite oxide is 0.1% ~ 0.5% in the described graphite oxide solution, and the weight percentage of polymkeric substance is 1% ~ 10% in described polymers soln or the polymer emulsion.
5. preparation method according to claim 1 is characterized in that, the solvent in the described graphite oxide solution is water, N,N-DIMETHYLACETAMIDE or N.
6. preparation method according to claim 1; It is characterized in that described polymers soln or polymer emulsion are dimethylacetamide solution, ptfe emulsion, perfluoroethylene-propylene emulsion, organic silicon emulsion, polyaryletherketone emulsion, polyetherimide emulsion or the polyethersulfone emulsion of polyvinyl alcohol water solution, polyamic acid.
7. preparation method according to claim 1 is characterized in that, the weight percentage that is dried to total solvent is 5% ~ 50%.
8. preparation method according to claim 1; It is characterized in that; The power of described infrared heating lamp is 5W to 10kW, and the time of described infrared heating lamp irradiation is 10 seconds to 60 minutes, and the distance of described infrared heating lamp and combination product is 1 millimeter to 1000 millimeters.
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