CN104085143B - Preparation method and the product of Graphene composite guide hotting mask - Google Patents
Preparation method and the product of Graphene composite guide hotting mask Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and product of Graphene composite guide hotting mask, described preparation method comprises the following steps: S1, the mixed liquor that crystalline flake graphite or graphite powder is placed in to the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide soaks diel, and then suction filtration drying, completes pre-oxidation; S2, the graphite after adopting Hummers method to pre-oxidation is further oxidized, and in the concentrated sulfuric acid and potassium permanganate, is fully oxidized, and then adds deionized water dilution, after cyclic washing suction filtration, obtains graphite oxide aqueous solution; S3, adopts hot spray process that graphite oxide aqueous solution is sprayed on substrate, and deposition obtains graphene oxide film; S4, reduces to graphene oxide film, obtains graphene film; S5, carries out overlay film processing to graphene film, obtains Graphene composite guide hotting mask. Compared with prior art, preparation technology of the present invention is simple, with low cost, and the heat dispersion of the Graphene composite guide hotting mask making is good.
Description
Technical field
The present invention relates to a kind of preparation method and product of Graphene composite guide hotting mask, particularly a kind of loose for electronics and IT productsPreparation method and the product of the Graphene composite guide hotting mask in the fields such as thermal device, chip overheating protection, heat conduction dielectric surface material, belong toElectronic functional material technical field.
Background technology
For electronic product, its all parts effectively heat radiation obtains lower operating temperature to its service life and operationSpeed can produce extremely important impact. Along with scientific and technological development and progress, particularly computer chip multinucleation becomesFor main flow, and the speed of service constantly accelerates, and power also increases thereupon, and effectively heat radiation plays very important to its speed of serviceEffect. At present, the heat radiation main product on market is graphite-like heat conducting film, but its heat dispersion can not meet electronics far awayThe radiating requirements of information products radiating element, becomes the heat radiation bottleneck of most electronic product.
At present, the preparation method of graphite-like heat conducting film mainly contains rubbing method, suction method and CVD method. Coating process comprise lift,The method such as spin coating, scraper, its difficult point is how to be configured to a kind of stable and Graphene slurry of not reuniting, this just need to be at slurryThe auxiliary agents such as middle interpolation thickener, surfactant, binding agent, but these auxiliary agents can make Graphene or the graphene oxide can not be fineLink together; And due to the steric hindrance of auxiliary agent, can not make Graphene be parallel to from level to level substrate orderly taking like thatBe connected together, can greatly reduce the heat conductivility of heat dissipation film; In addition, spin-coating method is not suitable for the large-area film of preparation, suction filtrationConsuming time and the bad control film thickness of method. CVD legal system is higher for the cost of heat conducting film, and general Graphene is raw at substrate by CVD methodLong one or more layers Graphene, the graphene layer that more difficult formation is very thick, is generally hundreds of nanometer thickness, is therefore not suitable for preparation looseHotting mask, and be mainly used in conducting film; While CVD prepares heat conducting film and also faces the problem that a transfer could be used, must be from goldBelong on substrate and transfer on required substrate and could use processing device, and transfer meeting brings more defect to heat conducting film.
Except said method, normal LB (Langmuir-Blodgett) embrane method, solution casting, the tape casting etc. of adopting in laboratoryMethod is prepared graphene film, but the complex process of these laboratory methods, and valuable product, is unsuitable for Graphene thinThe large-scale industrial production of film.
Summary of the invention
The object of the invention is to, a kind of preparation method and product of Graphene composite guide hotting mask is provided, its preparation technology is simple,With low cost, its heat conducting film product of preparing has good heat dispersion.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A preparation method for Graphene composite guide hotting mask, comprises the following steps:
S1, the mixed liquor that crystalline flake graphite or graphite powder is placed in to the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide soaks diel, thenSuction filtration is also dried, and completes pre-oxidation;
S2, the graphite after adopting Hummers method to pre-oxidation is further oxidized, and in the concentrated sulfuric acid and potassium permanganate, carries out abundant oxygenChange, then add deionized water dilution, after cyclic washing suction filtration, obtain graphite oxide aqueous solution;
S3, adopts hot spray process that graphite oxide aqueous solution is sprayed on substrate, and deposition obtains graphene oxide film;
S4, reduces to graphene oxide film, obtains graphene film;
S5, carries out overlay film processing to graphene film, obtains Graphene composite guide hotting mask.
A preparation method for Graphene composite guide hotting mask, comprises the following steps:
S11, the mixed liquor that crystalline flake graphite or graphite powder is placed in to the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide soaks diel, soRear suction filtration is also dried, and completes pre-oxidation;
S12, the graphite after adopting Hummers method to pre-oxidation is further oxidized, and in the concentrated sulfuric acid and potassium permanganate, carries out abundant oxygenChange, then add deionized water dilution, after cyclic washing suction filtration, obtain graphite oxide aqueous solution;
S13, adopts hot spray process that graphite oxide aqueous solution is sprayed on Copper Foil substrate, and deposition obtains graphene oxide film;
S14, reduces to graphene oxide film, obtains graphene film;
S15, at graphene film surface brush coating adhesive, by binding agent, release liners, heat insulation layer is sticky with graphene film respectivelyKnot, obtains Graphene composite guide hotting mask.
A preparation method for Graphene composite guide hotting mask, comprises the following steps:
S21, the mixed liquor that crystalline flake graphite or graphite powder is placed in to the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide soaks diel, soRear suction filtration is also dried, and completes pre-oxidation;
S22, the graphite after adopting Hummers method to pre-oxidation is further oxidized, and in the concentrated sulfuric acid and potassium permanganate, carries out abundant oxygenChange, then add deionized water dilution, after cyclic washing suction filtration, obtain graphite oxide aqueous solution;
S23 brushes binding agent in flexible substrate;
S24, adopts hot spray process graphite oxide aqueous solution to be sprayed in the flexible substrate of brushing in advance binding agent, and deposition obtains oxygenFunctionalized graphene film;
S25, reduces to graphene oxide film, obtains graphene film;
S26, brushes binding agent in the Graphene one side of graphene film,, obtains release liners and graphene film bonding by binding agentTo Graphene composite guide hotting mask.
Aforementioned flexible substrate mainly refers to the flexible organic material of some thin polymer films, as PET (polyethylene terephthalateEster), PEN (polyethylene naphthalate), PC (Merlon), PVC (polyvinyl chloride), PS (polystyrene),PMMA (polymethyl methacrylate), PBT (polybutylene terephthalate (PBT)), PES (poly-to benzene diethyl sulfone), also bagDraw together some metallic films except Copper Foil, as stainless steel film, titanium foil etc., also have ultra-thin glass etc.
Aforementioned binding agent plays the bilevel effect of bonding, can be acrylic, cellulose base, epoxy radicals and silica gel base etc.Binding agent.
In the preparation method of aforesaid Graphene composite guide hotting mask, in step S1, S11 and S21, dense sulphur in described mixed liquorThe mass ratio of acid, potassium peroxydisulfate and phosphorus pentoxide is 0.5-3:1-4:1-4.
In the preparation method of aforesaid Graphene composite guide hotting mask, in step S2, S12 and S22, the concentrated sulfuric acid, potassium permanganate andThe mass ratio of the graphite after pre-oxidation is 0.5-10:250-400:15-75.
In the preparation method of aforesaid Graphene composite guide hotting mask, before spraying, in graphite oxide aqueous solution, add adjuvant;Adjuvant can be controlled the viscosity of spraying stoste, and increases between graphene oxide sheet and sheet and be connected in film after spraying, to increaseAdd film heat conductivility, increase the adhesion of substrate and film simultaneously, control thin film strength; Adjuvant can adopt nanometerMetallic particles, nano-oxide, polymer monomer (as epoxy monomer), oligomer (polyvinyl alcohol, cellulose esters) etc.
In the preparation method of aforesaid Graphene composite guide hotting mask, before spraying, in graphite oxide aqueous solution, add zinc oxide orCNT.
In the preparation method's of aforesaid Graphene composite guide hotting mask step S13, the height of spraying be from substrate 40～60cm,Temperature is 100～200 DEG C; When spraying, the spraying equipment of employing comprises 3 pressure regulator valve A, F, P, and P is switch, controls wholeThe air-flow size of individual gas circuit, air pressure is 0.2～0.8MPa, A, F are respectively main control valve, auxiliary valve, control spray-coating surfaceLong-pending, air pressure is 0.1～0.7MPa.
In the preparation method's of aforesaid Graphene composite guide hotting mask step S24, the height of spraying is from substrate 40-60cm, temperatureDegree is 80-150 DEG C; When spraying, the spraying equipment of employing comprises 3 pressure regulator valve A, F, P, and P is switch, controls whole gasThe air-flow size on road, air pressure is 0.2～0.8MPa, A, F are respectively main control valve, auxiliary valve, control spray area, gasPressure is 0.1～0.7MPa.
In the preparation method of aforesaid Graphene composite guide hotting mask, before spraying, adopt oxygen plasma method or ultraviolet-smell oxygen method pairSubstrate surface carries out hydrophilic treated.
In the preparation method of aforesaid Graphene composite guide hotting mask, the method for reducing of step S14 is specially: adopt electron tubes typeStove, under the high temperature of 1000 DEG C, passes into H2 and reduces, and obtains graphene film.
In the preparation method of aforesaid Graphene composite guide hotting mask, the method for reducing of step S25 is specially: under zero degree low temperature, addEnter reducing agent, in the flexible substrate of 100-200 DEG C, spray, then in vacuum or protective atmosphere, 300-400 DEG C temperatureUnder heat-treat, to the further deoxygenation of graphene oxide film, obtain graphene film.
In the preparation method of aforesaid Graphene composite guide hotting mask, described reducing agent is urea and/or ascorbic acid; Urea and anti-Bad hematic acid is nontoxic reagent, environmental friendliness, and simultaneously reducing power is also gentleer controlled, and is easy to decompose and removes. Except urineElement and ascorbic acid, as outside reducing agent, can also adopt hydrazine class (hydrazine hydrate etc.), metal hydride (sodium borohydride, hydrogenationAluminium lithium etc.), halogen acids (hydrogen iodide, hydrobromic acid etc.) and the reproducibility reagent such as alcohols and sulfur-containing compound.
In the preparation method of aforesaid Graphene composite guide hotting mask, graphene oxide film is reduced and is specially: will be oxidized stoneChina ink alkene film is immersed in 45% HF solution, is heated to 80 DEG C, is incubated 6 hours, and deionized water is cleaned and cryogenic vacuum is doneDry, obtain the graphene film of high-carbon/oxygen ratio.
In the preparation method of aforesaid Graphene composite guide hotting mask, graphene oxide film is reduced and is specially: by what obtainGraphene oxide film carries out microwave and light radiation reduction, obtains graphene film.
In the preparation method of aforesaid Graphene composite guide hotting mask, the graphene film that reduction is obtained carries out surface cure processing(for example ultra-violet curing, heat cure, catalytic curing processing), obtains Graphene composite guide hotting mask.
A Graphene composite guide hotting mask that adopts preceding method to prepare, comprise successively bonding heat insulation layer 3～10 μ m,Tack coat A, graphene layer 50 μ m, Copper Foil substrate 12～70 μ m, tack coat B and release liners, tack coat A, tack coat BAll below 10 μ m.
A Graphene composite guide hotting mask that adopts preceding method to prepare, comprise successively the flexible substrate 3 of bonding～12 μ m, tack coat C, graphene layer 50 μ m, tack coat D and release liners, tack coat C, tack coat D all 10 μ m withUnder.
Compared with prior art, the present invention has the following advantages:
(1) Graphene is the highest material of known thermal conductivity factor, but current high-quality Graphene (1-3 layer) output is less;The present invention, by raw material are carried out to pre-oxidation, makes oxidizing process below more thorough, and the interlamellar spacing of graphite oxide is become moreGreatly, ultrasonic peel off more easily and more thorough, the less graphene oxide of individual layer or the number of plies is more, then obtains stone by reductionChina ink alkene, improves the output of graphene oxide and the object of quality thereby realize.
(2) utilize graphene oxide dispersion liquid as spray coating liquor, avoid directly using Graphene spraying. Because Graphene has neitherHydrophilic also not close oil properties, more difficult well dispersion in solution, easily reunites, thereby causes spraying out thin uniformlyFilm, and Graphene cost is also high, is domesticly also difficult to provide stay-in-grade Graphene industrialization product; Therefore directly utilize stoneThe graphite oxide aqueous solution that China ink makes is as raw material, both cost-saving, can ensure again the quality of raw material, simultaneous oxidation graphiteAlkene has oxy radical, has hydrophily, stronger than Graphene with substrate adhesion, makes more flexible of rete.
(3) the horizontal thermal conductivity factor of graphene film is relevant with the arrangement mode of Graphene particulate, and therefore the present invention is by controlling substrateTemperature and air-flow and the shape of spraying, Graphene particulate unfolded be naturally laid on substrate, improve graphene filmDensity.
(4) conventional graphite alkene film, because Graphene is discontinuous in surface distributed, makes its heat conduction discontinuous, has reduced Graphene thinThe overall heat-conducting effect of film; Therefore, the present invention carries out oleophylic according to the surface-active effects on surface of Graphene or hydrophilic surface is repaiiedDecorations, according to effect and the huge specific surface of Graphene of blind date, the nanostructured of the substrate surface that change Graphene distributes, makesObtain Graphene at substrate surface drawout; Or by the modification to graphene film, add such as zinc oxide, CNT etc.Material, makes Graphene in the substrate surface serialization that distributes, and improves its heat-conducting effect.
(5) although being reduced into Graphene, graphene oxide has several different methods, due to the oxygen content of the product thermal conductivity to GrapheneCan be able to produce a very large impact, therefore the present invention has optimized the reducing process of graphene film, is immersed in by graphene oxide film45% HF solution, is heated to 80 DEG C, is incubated 6 hours, and deionized water is cleaned and low-temperature vacuum drying, obtains high-carbon/oxygen ratioThe graphene film of example.
To sum up, the Graphene composite guide hotting mask that the present invention makes is as highly heat-conductive material of new generation, have lightweight, high heat conduction,The characteristic such as temperature tolerance, pliability, can be widely used in all parts that each electronic product need to dispel the heat, as mobile phone, flat boardLiquid crystal panel, mainboard, battery, back of the body lid and computer chip etc. in computer, notebook. With the like product phase on existing marketRatio, performance is more excellent, price is cheaper, product index is reached advanced world standards, contribute to solve electronics and IT products andThe technical barrier of LED industry, promotes the great-leap-forward development of whole industry.
Brief description of the drawings
Fig. 1 is the process chart of the embodiment of the present invention;
Fig. 2 is the structural representation of the Graphene composite guide hotting mask of Copper Foil series;
Fig. 3 is the structural representation of the Graphene composite guide hotting mask of flexible material series.
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated.
Detailed description of the invention
Embodiments of the invention 1: a kind of preparation method of Graphene composite guide hotting mask, as shown in Figure 1, comprises the following steps:
S1, is placed in crystalline flake graphite or graphite powder mixed liquor (the dense sulphur of described mixed liquor of the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxideThe mass ratio of acid, potassium peroxydisulfate and phosphorus pentoxide is 0.5-3:1-4:1-4) the middle diel that soaks, then suction filtration oven dry,Complete pre-oxidation;
S2, the graphite after adopting Hummers method to pre-oxidation is further oxidized, and in the concentrated sulfuric acid and potassium permanganate, carries out abundant oxygenChange, the mass ratio of the graphite after the concentrated sulfuric acid, potassium permanganate and pre-oxidation is 0.5-10:250-400:15-75, then addsIonized water dilution, after cyclic washing suction filtration, obtains graphite oxide aqueous solution;
S3, adopts hot spray process that graphite oxide aqueous solution is sprayed on substrate, and deposition obtains graphene oxide film;
S4, is immersed in graphene oxide film 45% HF solution, is heated to 80 DEG C, is incubated 6 hours, and deionized water is cleaned alsoLow-temperature vacuum drying, obtains the graphene film of high-carbon/oxygen ratio;
S5, carries out overlay film processing to graphene film, then the surface of graphene film is cured to processing (for example ultra-violet curing, heatCuring, catalytic curing processing), finally obtain Graphene composite guide hotting mask.
Embodiments of the invention 2: a kind of preparation method of Graphene composite guide hotting mask, as shown in Figure 1, comprises the following steps:
S11, crystalline flake graphite or graphite powder are placed in to the mixed liquor of the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide, and (described mixed liquor is denseThe mass ratio of sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide is 0.5-1.5:1-2:1-2) the middle diel that soaks, then suction filtration bakingDry, complete pre-oxidation;
S12, the graphite after adopting Hummers method to pre-oxidation is further oxidized, and in the concentrated sulfuric acid and potassium permanganate, carries out abundant oxygenChange, the mass ratio of the graphite after the concentrated sulfuric acid, potassium permanganate and pre-oxidation is 0.5-3:250-280:15-30, then add fromSub-water dilution, after cyclic washing suction filtration, obtains graphite oxide aqueous solution;
S13, adopts hot spray process that graphite oxide aqueous solution is sprayed on Copper Foil substrate, and deposition obtains graphene oxide film; SprayThe height being coated with is is 100～150 DEG C from substrate 40～50cm, temperature; When spraying, the spraying equipment of employing comprises 3 pressure regulationValve A, F, P, P is switch, controls the air-flow size of whole gas circuit, and air pressure is 0.2～0.5MPa, and A, F are respectively master controlValve processed, auxiliary valve, control spray area, and air pressure is 0.1～0.4MPa;
S14, adopts vacuum tube furnace, under the high temperature of 1000 DEG C, passes into H2 graphene oxide film is reduced, and obtains graphiteAlkene film;
S15, at graphene film surface brush coating adhesive, by binding agent, release liners, heat insulation layer is sticky with graphene film respectivelyKnot, then ultra-violet curing or heat cure processing are carried out in the surface of graphene film, finally obtain Graphene composite guide hotting mask.
Embodiments of the invention 3: a kind of preparation method of Graphene composite guide hotting mask, as shown in Figure 1, comprises the following steps:
S11, crystalline flake graphite or graphite powder are placed in to the mixed liquor of the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide, and (described mixed liquor is denseThe mass ratio of sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide is 1.5-3:2-4:2-4) the middle diel that soaks, then suction filtration bakingDry, complete pre-oxidation;
S12, the graphite after adopting Hummers method to pre-oxidation is further oxidized, and in the concentrated sulfuric acid and potassium permanganate, carries out abundant oxygenChange, the mass ratio of the graphite after the concentrated sulfuric acid, potassium permanganate and pre-oxidation is 3-10:280-400:30-75, then add fromSub-water dilution, after cyclic washing suction filtration, obtains graphite oxide aqueous solution;
S13, adopts hot spray process that graphite oxide aqueous solution is sprayed on Copper Foil substrate, and deposition obtains graphene oxide film; SprayThe height being coated with is is 150～200 DEG C from substrate 50～60cm, temperature; When spraying, the spraying equipment of employing comprises 3 pressure regulationValve A, F, P, P is switch, controls the air-flow size of whole gas circuit, and air pressure is 0.5～0.8MPa, and A, F are respectively master controlValve processed, auxiliary valve, control spray area, and air pressure is 0.4～0.7MPa;
S14, is immersed in graphene oxide film 45% HF solution, is heated to 80 DEG C, is incubated 6 hours, and deionized water is cleaned alsoLow-temperature vacuum drying, obtains the graphene film of high-carbon/oxygen ratio;
S15, at graphene film surface brush coating adhesive, by binding agent, release liners, heat insulation layer is sticky with graphene film respectivelyKnot, then catalytic curing processing is carried out in the surface of graphene film, finally obtain Graphene composite guide hotting mask.
Embodiment 2 and 3 is methods of preparing Graphene composite guide hotting mask for Copper Foil substrate, and 4 and 5 of that embodiment are pinsTo another common backing material---flexible substrate is prepared Graphene composite guide hotting mask, and wherein flexible substrate mainly refers to some polymerizationsThe flexible organic material of thing film, as (poly-to naphthalenedicarboxylic acid ethylene glycol in PET (PETG), PENEster), PC (Merlon), PVC (polyvinyl chloride), PS (polystyrene), PMMA (polymethyl methacrylate), PBT(polybutylene terephthalate (PBT)), PES (poly-to benzene diethyl sulfone), also comprise some metallic films except Copper Foil, asStainless steel film, titanium foil etc., also have ultra-thin glass etc.
Embodiments of the invention 4: a kind of preparation method of Graphene composite guide hotting mask, as shown in Figure 1, comprises the following steps:
S21, crystalline flake graphite or graphite powder are placed in to the mixed liquor of the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide, and (described mixed liquor is denseThe mass ratio of sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide is 0.5-1:1-2.5:1-2.5) the middle diel that soaks, then suction filtration is alsoDry, complete pre-oxidation;
S22, the graphite after adopting Hummers method to pre-oxidation is further oxidized, and in the concentrated sulfuric acid and potassium permanganate, carries out abundant oxygenChange, the mass ratio of the graphite after the concentrated sulfuric acid, potassium permanganate and pre-oxidation is 0.5-2:250-300:15-40, then add fromSub-water dilution, after cyclic washing suction filtration, obtains graphite oxide aqueous solution;
S23 brushes binding agent in flexible substrate;
S24, adopts hot spray process that the spraying of graphite oxide aqueous solution is brushed in the flexible substrate of binding agent in advance, and deposition is oxidizedGraphene film; The height of spraying is is 80～110 DEG C from substrate 40～55cm, temperature; When spraying, the spraying equipment of employingComprise 3 pressure regulator valve A, F, P, P is switch, controls the air-flow size of whole gas circuit, and air pressure is 0.2～0.6MPa,A, F are respectively main control valve, auxiliary valve, control spray area, and air pressure is 0.1～0.5MPa;
S25 adds urea and/or ascorbic acid under zero degree low temperature, sprays, then in vacuum in the flexible substrate of 100-200 DEG COr in protective atmosphere, heat-treat at 300-350 DEG C temperature, to the further deoxygenation of graphene oxide film, obtain graphiteAlkene film;
S26, brushes binding agent in the Graphene one side of graphene film, by binding agent, release liners and graphene film bondd, thenUltra-violet curing processing is carried out in the surface of graphene film, finally obtain Graphene composite guide hotting mask.
Embodiments of the invention 5: a kind of preparation method of Graphene composite guide hotting mask, as shown in Figure 1, comprises the following steps:
S21, crystalline flake graphite or graphite powder are placed in to the mixed liquor of the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide, and (described mixed liquor is denseThe mass ratio of sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide is 1-3:2.5-4:2.5-4) the middle diel that soaks, then suction filtration bakingDry, complete pre-oxidation;
S22, the graphite after adopting Hummers method to pre-oxidation is further oxidized, and in the concentrated sulfuric acid and potassium permanganate, carries out abundant oxygenChange, the mass ratio of the graphite after the concentrated sulfuric acid, potassium permanganate and pre-oxidation is 2-10:300-400:40-75, then add fromSub-water dilution, after cyclic washing suction filtration, obtains graphite oxide aqueous solution;
S23 brushes binding agent in flexible substrate;
S24, adopts hot spray process that the spraying of graphite oxide aqueous solution is brushed in the flexible substrate of binding agent in advance, and deposition is oxidizedGraphene film; The height of spraying is is 110～150 DEG C from substrate 55～60cm, temperature; When spraying, the spraying of employing is establishedFor comprising 3 pressure regulator valve A, F, P, P is switch, controls the air-flow size of whole gas circuit, and air pressure is 0.6～0.8MPa,A, F are respectively main control valve, auxiliary valve, control spray area, and air pressure is 0.5～0.7MPa;
S25, is immersed in graphene oxide film 45% HF solution, is heated to 80 DEG C, is incubated 6 hours, and deionized water is cleaned alsoLow-temperature vacuum drying, obtains the graphene film of high-carbon/oxygen ratio;
S26, brushes binding agent in the Graphene one side of graphene film, by binding agent, release liners and graphene film bondd, thenHeat cure or catalytic curing processing are carried out in the surface of graphene film, finally obtain Graphene composite guide hotting mask.
In embodiment 1-5, described binding agent plays the bilevel effect of bonding, can be acrylic, cellulose base, ringThe binding agents such as oxygen base and silica gel base; Before spraying, can in graphite oxide aqueous solution, add adjuvant (such as nano metalGrain, nano-oxide, polymer monomer (as epoxy monomer), oligomer (polyvinyl alcohol, cellulose esters) etc.) controlThe viscosity of spraying stoste, the adhesion of increase heat conductivility and substrate and film, controls thin film strength; Before spraying, canIn graphite oxide aqueous solution, add zinc oxide or CNT; Before spraying, can adopt oxygen plasma method or ultraviolet-smell oxygenMethod is carried out hydrophilic treated to substrate surface; If graphene oxide is not dispersed in water, but be dispersed in ethyl acetate, firstIn the non-polar solven such as benzene, cyclohexane, need to carry out oleophylic processing to Copper Foil and flexible substrate, by the substrate after hydrophilic treatedBe immersed in the silane coupler solution of 0.1%-10% and carry out modification.
Step S4, S14 and S25 can adopt following method of reducing to replace: by the graphene oxide film obtaining carry out microwave andLight radiation reduction, obtains graphene film.
Embodiments of the invention 6: the Graphene composite guide hotting mask that described in a kind of embodiment of employing 2, method prepares, as Fig. 2Shown in, comprise successively bonding heat insulation layer 3～5 μ m, tack coat A, graphene layer 50 μ m, Copper Foil substrate 12～45 μ m,Tack coat B and release liners, tack coat A, tack coat B are all below 10 μ m; Wherein, graphene layer and Copper Foil substrate are commonForm the graphene film in embodiment 2.
Embodiments of the invention 7: the Graphene composite guide hotting mask that described in a kind of embodiment of employing 3, method prepares, as Fig. 2Shown in, comprise successively heat insulation layer 5～10 μ m, tack coat A, graphene layer 50 μ m, the Copper Foil substrate 45 of bonding～70 μ m, tack coat B and release liners, tack coat A, tack coat B are all below 10 μ m; Wherein, graphene layer and Copper FoilSubstrate forms the graphene film in embodiment 3 jointly.
Embodiments of the invention 8: the Graphene composite guide hotting mask that a kind of method shown in embodiment of employing 4 prepares, as Fig. 3Shown in, comprise flexible substrate 3～6 μ m, tack coat C, graphene layer 50 μ m, the tack coat D and release of bonding successivelyPaper, tack coat C, tack coat D are all below 10 μ m; Wherein, flexible substrate, tack coat C and graphene layer form jointlyGraphene film in embodiment 4.
Embodiments of the invention 9: the Graphene composite guide hotting mask that a kind of method shown in embodiment of employing 5 prepares, as Fig. 3Shown in, comprise flexible substrate 6～12 μ m, tack coat C, graphene layer 50 μ m, the tack coat D and release of bonding successivelyPaper, tack coat C, tack coat D are all below 10 μ m; Wherein, flexible substrate, tack coat C and graphene layer form jointlyGraphene film in embodiment 5.
Claims (9)
1. a preparation method for Graphene composite guide hotting mask, is characterized in that, comprises the following steps:
S1, the mixed liquor that graphite powder is placed in to the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide soaks diel, and then suction filtration oven dry, complete pre-oxidation; Wherein, in mixed liquor, the mass ratio of the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide is 0.5-3:1-4:1-4;
S2, the graphite after adopting Hummers method to pre-oxidation is further oxidized, and in the concentrated sulfuric acid and potassium permanganate, is fully oxidized, and then adds deionized water dilution, after cyclic washing suction filtration, obtains graphite oxide aqueous solution;
S3, adopts hot spray process that graphite oxide aqueous solution is sprayed on substrate, and deposition obtains graphene oxide film; Wherein, before spraying, in graphite oxide aqueous solution, add zinc oxide or CNT; When spraying, control the air-flow size of whole gas circuit and control spray area;
S4, reduces to graphene oxide film, obtains graphene film;
S5, carries out overlay film processing to graphene film, obtains Graphene composite guide hotting mask.
2. the preparation method of Graphene composite guide hotting mask according to claim 1, is characterized in that, comprises the following steps:
S11, the mixed liquor that graphite powder is placed in to the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide soaks diel, and then suction filtration oven dry, complete pre-oxidation;
S12, the graphite after adopting Hummers method to pre-oxidation is further oxidized, and in the concentrated sulfuric acid and potassium permanganate, is fully oxidized, and then adds deionized water dilution, after cyclic washing suction filtration, obtains graphite oxide aqueous solution;
S13, adopts hot spray process that graphite oxide aqueous solution is sprayed on Copper Foil substrate, and deposition obtains graphene oxide film;
S14, reduces to graphene oxide film, obtains graphene film;
S15, at graphene film surface brush coating adhesive, bonds release liners, heat insulation layer respectively by binding agent with graphene film, obtain Graphene composite guide hotting mask.
3. the preparation method of Graphene composite guide hotting mask according to claim 1, is characterized in that, comprises the following steps:
S21, the mixed liquor that graphite powder is placed in to the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide soaks diel, and then suction filtration oven dry, complete pre-oxidation;
S22, the graphite after adopting Hummers method to pre-oxidation is further oxidized, and in the concentrated sulfuric acid and potassium permanganate, is fully oxidized, and then adds deionized water dilution, after cyclic washing suction filtration, obtains graphite oxide aqueous solution;
S23 brushes binding agent in flexible substrate;
S24, adopts hot spray process graphite oxide aqueous solution to be sprayed in the flexible substrate of brushing in advance binding agent, and deposition obtains graphene oxide film;
S25, reduces to graphene oxide film, obtains graphene film;
S26, brushes binding agent in the Graphene one side of graphene film, by release liners and graphene film bonding, obtains Graphene composite guide hotting mask by binding agent.
4. according to the preparation method of the Graphene composite guide hotting mask described in claim 1 or 2 or 3, it is characterized in that: in step S2, S12 and S22, the mass ratio of the graphite after the concentrated sulfuric acid, potassium permanganate and pre-oxidation is 0.5-10:250-400:15-75.
5. the preparation method of Graphene composite guide hotting mask according to claim 2, is characterized in that, the method for reducing of step S14 is specially: adopt vacuum tube furnace, under the high temperature of 1000 DEG C, pass into H2Reduce, obtain graphene film.
6. the preparation method of Graphene composite guide hotting mask according to claim 3, it is characterized in that, the method of reducing of step S25 is specially: under zero degree low temperature, add reducing agent, in the flexible substrate of 100-200 DEG C, spray, then in vacuum or protective atmosphere, heat-treat at 300-400 DEG C temperature, to the further deoxygenation of graphene oxide film, obtain graphene film; Described reducing agent is urea and/or ascorbic acid.
7. according to the preparation method of the Graphene composite guide hotting mask described in claim 1 or 2 or 3, it is characterized in that, graphene oxide film is reduced and is specially: graphene oxide film is immersed in to 45% HF solution, be heated to 80 DEG C, be incubated 6 hours, deionized water is cleaned and low-temperature vacuum drying, obtains the graphene film of high-carbon/oxygen ratio.
8. one kind adopts the Graphene composite guide hotting mask that method prepares described in claim 2,4,5 or 7, it is characterized in that: comprise heat insulation layer 3～10 μ m, tack coat A, graphene layer 50 μ m, Copper Foil substrate 12～70 μ m, tack coat B and the release liners of bonding successively, tack coat A, tack coat B are all below 10 μ m.
9. one kind adopts the Graphene composite guide hotting mask that method prepares described in claim 3,4,6 or 7, it is characterized in that: comprise flexible substrate 3～12 μ m, tack coat C, graphene layer 50 μ m, tack coat D and the release liners of bonding successively, tack coat C, tack coat D are all below 10 μ m.
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