CN104085143A - Preparation method of composite heat conduction graphene film and composite heat conduction graphene film - Google Patents
Preparation method of composite heat conduction graphene film and composite heat conduction graphene film Download PDFInfo
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Abstract
The invention discloses a preparation method of a composite heat conduction graphene membrane and the composite heat conduction graphene film. The preparation method comprises the following steps: S1, putting crystalline flake graphite or graphite powder into a mixed solution of concentrated sulfuric acid, potassium persulfate and phosphorus pentoxide, soaking for a day and a night, then carrying out suction filtration, drying, and carrying out pre-oxidizing; S2, oxidizing pre-oxidized graphite further by adopting a Hummers method, that is, oxidizing fully in concentrated sulfuric acid and potassium permanganate, then adding deionized water for diluting, and carrying out repeated washing and suction filtration, so as to obtain an oxidized graphene aqueous solution; S3, spraying the oxidized graphene aqueous solution on a substrate by adopting a thermal spray method, and depositing, so as to obtain an oxidized graphene film; S4, reducing the oxidized graphene film, so as to obtain the graphene film; and S5, laminating the graphene film, so as to obtain the composite heat conduction graphene film. Compared with the prior art, the preparation method is simple, the cost is low, and the prepared composite heat conduction graphene film has a favorable heat conduction performance.
Description
Technical field
The present invention relates to a kind of preparation method and product of Graphene composite guide hotting mask; particularly, for preparation method and the product of the Graphene composite guide hotting mask in the fields such as electronics and IT products radiating element, chip overheating protection, heat conduction dielectric surface material, belong to electronic functional material technical field.
Background technology
For electronic product, its all parts effectively heat radiation obtains lower operating temperature to its service life and the speed of service producing extremely important impact.Along with scientific and technological development and progress, particularly computer chip multinucleation has become main flow, and the speed of service constantly accelerates, and power also increases thereupon, and effectively heat radiation plays a part very important to its speed of service.At present, the heat radiation main product on market is graphite-like heat conducting film, but its heat dispersion can not meet the radiating requirements of electronics and IT products radiating element far away, 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 add the auxiliary agents such as thickener, surfactant, binding agent in slurry, but these auxiliary agents can make Graphene or graphene oxide well not link together; And due to the steric hindrance of auxiliary agent, can not make Graphene be parallel to from level to level substrate orderly overlapping like that, 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, the consuming time and bad control film thickness of suction method.CVD legal system is higher for the cost of heat conducting film, and general Graphene is by CVD method at substrate one or more layers Graphene of growing, and the graphene layer that more difficult formation is very thick, is generally hundreds of nanometer thickness, is therefore not suitable for preparing heat dissipation film, and is mainly used in conducting film; While CVD prepares heat conducting film and also faces the problem that a transfer could be used, and must transfer on required substrate and could use processing device from metal substrate, and transfer meeting brings more defect to heat conducting film.
Except said method, in laboratory, the normal methods such as LB (Langmuir-Blodgett) embrane method, solution casting, the tape casting that adopt are prepared graphene film, but the complex process of these laboratory methods, valuable product, is unsuitable for the large-scale industrial production of graphene 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, and 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, 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.
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, and then suction filtration drying, 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, 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.
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, and then suction filtration drying, 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, 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.
Aforementioned flexible substrate mainly refers to the flexible organic material of some thin polymer films, as PET (PETG), PEN (polyethylene naphthalate), 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, as stainless steel film, titanium foils etc., also have ultra-thin glass etc.
Aforementioned binding agent plays the bilevel effect of bonding, can be the binding agents such as acrylic, cellulose base, epoxy radicals and silica gel base.
In the preparation method of aforesaid Graphene composite guide hotting mask, in step S1, S11 and S21, in described mixed liquor, the mass ratio of the concentrated sulfuric 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 mass ratio of the graphite after the concentrated sulfuric acid, potassium permanganate and 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 increase film heat conductivility, increases the adhesion of substrate and film simultaneously, controls thin film strength; Adjuvant can adopt nano-metal particle, 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 or CNT.
In the preparation method's of aforesaid Graphene composite guide hotting mask step S13, the height of spraying is is 100～200 DEG C from substrate 40～60cm, temperature; When spraying, the spraying equipment of employing comprises 3 pressure regulator valve A, F, P, and P is switch, controls the air-flow size of whole gas circuit, and air pressure is 0.2～0.8MPa, and A, F are respectively main control valve, auxiliary valve, controls spray area, and 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 is 80-150 DEG C from substrate 40-60cm, temperature; When spraying, the spraying equipment of employing comprises 3 pressure regulator valve A, F, P, and P is switch, controls the air-flow size of whole gas circuit, and air pressure is 0.2～0.8MPa, and A, F are respectively main control valve, auxiliary valve, controls spray area, and air pressure is 0.1～0.7MPa.
In the preparation method of aforesaid Graphene composite guide hotting mask, before spraying, adopt oxygen plasma method or ultraviolet-smelling oxygen method carries out hydrophilic treated to substrate surface.
In the preparation method of aforesaid Graphene composite guide hotting mask, the method for reducing of step S14 is specially: adopt vacuum tube furnace, under the high temperature of 1000 DEG C, pass into H2 and reduce, obtain graphene film.
In the preparation method of aforesaid Graphene composite guide hotting mask; 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.
In the preparation method of aforesaid Graphene composite guide hotting mask, described reducing agent is urea and/or ascorbic acid; Urea and ascorbic acid are nontoxic reagent, environmental friendliness, and simultaneously reducing power is also gentleer controlled, and is easy to decompose and removes.Except urea and ascorbic acid are as reducing agent, can also adopt the reproducibility reagent such as hydrazine class (hydrazine hydrate etc.), metal hydride (sodium borohydride, lithium aluminium hydride reduction etc.), halogen acids (hydrogen iodide, hydrobromic acid etc.) and alcohols and sulfur-containing compound.
In the preparation method of aforesaid Graphene composite guide hotting mask, graphene oxide film is reduced and is specially: graphene oxide film is immersed in to 45% HF solution, is 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.
In the preparation method of aforesaid Graphene composite guide hotting mask, graphene oxide film is reduced and is specially: the graphene oxide film obtaining is carried out to microwave and light radiation reduction, obtain 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 kind of Graphene composite guide hotting mask that adopts preceding method to prepare, 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.
A Graphene composite guide hotting mask that adopts preceding method to prepare, comprises flexible substrate 3～12 μ m, tack coat C, graphene layer 50 μ m, tack coat D and the release liners of bonding successively, and tack coat C, tack coat D are all below 10 μ m.
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 is by carrying out pre-oxidation to raw material, make oxidizing process below more thorough, make the interlamellar spacing of graphite oxide become larger, ultrasonic peeling off more easily with more thorough, the less graphene oxide of individual layer or the number of plies is more, obtain Graphene by reduction again, improve 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 neither hydrophilic also not close oil properties, more difficultly in solution, well disperse, easily reunite, thereby cause spraying out uniform film, and Graphene cost is also high, is domesticly also difficult to provide stay-in-grade Graphene industrialization product; Therefore directly utilize graphite oxide aqueous solution that graphite-made obtains as raw material, both cost-saving, can ensure again the quality of raw material, simultaneous oxidation Graphene 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, therefore the present invention is by controlling air-flow and the shape of substrate temperature and spraying, Graphene particulate is unfolded naturally and be laid on substrate, improve the density of graphene film.
(4) conventional graphite alkene film, because Graphene is discontinuous in surface distributed, makes its heat conduction discontinuous, has reduced the overall heat-conducting effect of graphene film; Therefore, the present invention carries out oleophylic or hydrophilic finishing according to the surface-active effects on surface of Graphene, according to effect and the huge specific surface of Graphene of blind date, the nanostructured of the substrate surface that change Graphene distributes, makes Graphene at substrate surface drawout; Or by the modification to graphene film, add such as the material such as zinc oxide, CNT, make Graphene in the substrate surface serialization that distributes, improve its heat-conducting effect.
(5) although being reduced into Graphene, graphene oxide has several different methods, but because the oxygen content of product can produce a very large impact the heat conductivility of Graphene, therefore the present invention has optimized the reducing process of graphene film, be immersed in 45% HF solution by graphene oxide film, 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.
To sum up, the Graphene composite guide hotting mask that the present invention makes is as highly heat-conductive material of new generation, there is the characteristics such as lightweight, high heat conduction, temperature tolerance, pliability, can be widely used in all parts that each electronic product need to dispel the heat, as liquid crystal panel, mainboard, battery, back of the body lid and computer chip etc. in mobile phone, panel computer, notebook.Compared with like product on existing market, performance is more excellent, price is cheaper, product index is reached advanced world standards, and contributes to solve the technical barrier of electronics and IT products and 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, the mixed liquor (mass ratio of the described mixed liquor concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide is 0.5-3:1-4:1-4) that crystalline flake graphite or graphite powder is placed in to the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide soaks diel, then suction filtration oven dry, complete pre-oxidation;
S2, graphite after adopting Hummers method to pre-oxidation is further oxidized, in the concentrated sulfuric acid and potassium permanganate, be fully oxidized, 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 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, is immersed in graphene oxide film 45% HF solution, is heated to 80 DEG C, is incubated 6 hours, and deionized water is cleaned and low-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, heat cure, catalytic curing processing), finally obtains 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, the mixed liquor (mass ratio of the described mixed liquor concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide is 0.5-1.5:1-2:1-2) that crystalline flake graphite or graphite powder is placed in to the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide soaks diel, then suction filtration oven dry, complete pre-oxidation;
S12, graphite after adopting Hummers method to pre-oxidation is further oxidized, in the concentrated sulfuric acid and potassium permanganate, be fully oxidized, 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 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; The height of spraying is is 100～150 DEG C from substrate 40～50cm, temperature; When spraying, the spraying equipment of employing comprises 3 pressure regulator valve A, F, P, and 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 main control valve, auxiliary valve, controls 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 graphene film;
S15, at graphene film surface brush coating adhesive, bonds release liners, heat insulation layer respectively by binding agent, then ultra-violet curing or heat cure processing is carried out in the surface of graphene film with 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, the mixed liquor (mass ratio of the described mixed liquor concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide is 1.5-3:2-4:2-4) that crystalline flake graphite or graphite powder is placed in to the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide soaks diel, then suction filtration oven dry, complete pre-oxidation;
S12, graphite after adopting Hummers method to pre-oxidation is further oxidized, in the concentrated sulfuric acid and potassium permanganate, be fully oxidized, 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 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; The height of spraying is is 150～200 DEG C from substrate 50～60cm, temperature; When spraying, the spraying equipment of employing comprises 3 pressure regulator valve A, F, P, and 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 main control valve, auxiliary valve, controls 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 and low-temperature vacuum drying, obtains the graphene film of high-carbon/oxygen ratio;
S15, at graphene film surface brush coating adhesive, bonds release liners, heat insulation layer respectively by binding agent, then catalytic curing processing is carried out in the surface of graphene film with 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, 4 and 5 of that embodiment are for another common backing material---flexible substrate is prepared Graphene composite guide hotting mask, wherein flexible substrate mainly refers to the flexible organic material of some thin polymer films, as PET (PETG), PEN (polyethylene naphthalate), 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, as stainless steel film, titanium foil etc., also has 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, the mixed liquor (mass ratio of the described mixed liquor concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide is 0.5-1:1-2.5:1-2.5) that crystalline flake graphite or graphite powder is placed in to the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide soaks diel, then suction filtration oven dry, complete pre-oxidation;
S22, graphite after adopting Hummers method to pre-oxidation is further oxidized, in the concentrated sulfuric acid and potassium permanganate, be fully oxidized, 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 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 that the spraying of graphite oxide aqueous solution is brushed in the flexible substrate of binding agent in advance, and deposition obtains graphene oxide film; The height of spraying is is 80～110 DEG C from substrate 40～55cm, temperature; When spraying, the spraying equipment of employing comprises 3 pressure regulator valve A, F, P, and P is switch, controls the air-flow size of whole gas circuit, and air pressure is 0.2～0.6MPa, and A, F are respectively main control valve, auxiliary valve, controls spray area, and air pressure is 0.1～0.5MPa;
S25, under zero degree low temperature, add urea and/or ascorbic acid, in the flexible substrate of 100-200 DEG C, spray, then in vacuum or protective atmosphere, heat-treat at 300-350 DEG C temperature, to the further deoxygenation of graphene oxide film, obtain graphene film;
S26, brushes binding agent in the Graphene one side of graphene film, by binding agent, release liners and graphene film is bondd, then ultra-violet curing processing is carried out in the surface of graphene film, finally obtains 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, the mixed liquor (mass ratio of the described mixed liquor concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide is 1-3:2.5-4:2.5-4) that crystalline flake graphite or graphite powder is placed in to the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide soaks diel, then suction filtration oven dry, complete pre-oxidation;
S22, graphite after adopting Hummers method to pre-oxidation is further oxidized, in the concentrated sulfuric acid and potassium permanganate, be fully oxidized, 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 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 that the spraying of graphite oxide aqueous solution is brushed in the flexible substrate of binding agent in advance, and deposition obtains graphene oxide film; The height of spraying is is 110～150 DEG C from substrate 55～60cm, temperature; When spraying, the spraying equipment of employing comprises 3 pressure regulator valve A, F, P, and P is switch, controls the air-flow size of whole gas circuit, and air pressure is 0.6～0.8MPa, and A, F are respectively main control valve, auxiliary valve, controls 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 and low-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 is bondd, then heat cure or catalytic curing processing are carried out in the surface of graphene film, finally obtains Graphene composite guide hotting mask.
In embodiment 1-5, described binding agent plays the bilevel effect of bonding, can be the binding agents such as acrylic, cellulose base, epoxy radicals and silica gel base; Before spraying, can in graphite oxide aqueous solution, add adjuvant (such as nano-metal particle, nano-oxide, polymer monomer (as epoxy monomer), oligomer (polyvinyl alcohol, cellulose esters) etc.) control spraying stoste viscosity, increase the adhesion of heat conductivility and substrate and film, control thin film strength; Before spraying, can in graphite oxide aqueous solution, add zinc oxide or CNT; Before spraying, can adopt that oxygen plasma method or ultraviolet-smelling oxygen method carries out hydrophilic treated to substrate surface; If graphene oxide is not dispersed in water, but be dispersed in the non-polar solvens such as ethyl acetate, toluene, cyclohexane, need to carry out oleophylic processing to Copper Foil and flexible substrate, be immersed in by the substrate after hydrophilic treated 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: the graphene oxide film obtaining is carried out to microwave and light radiation reduction, obtain 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 shown in Figure 2, comprise 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 the release liners of bonding successively, tack coat A, tack coat B are all below 10 μ m; Wherein, graphene layer and Copper Foil substrate form the graphene film in embodiment 2 jointly.
Embodiments of the invention 7: the Graphene composite guide hotting mask that described in a kind of embodiment of employing 3, method prepares, as shown in Figure 2, comprise heat insulation layer 5～10 μ m, tack coat A, graphene layer 50 μ m, Copper Foil substrate 45～70 μ m, tack coat B and the release liners of bonding successively, tack coat A, tack coat B are all below 10 μ m; Wherein, graphene layer and Copper Foil substrate form 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 shown in Figure 3, comprise flexible substrate 3～6 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; Wherein, flexible substrate, tack coat C and graphene layer form the graphene film in embodiment 4 jointly.
Embodiments of the invention 9: the Graphene composite guide hotting mask that a kind of method shown in embodiment of employing 5 prepares, as shown in Figure 3, comprise flexible substrate 6～12 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; Wherein, flexible substrate, tack coat C and graphene layer form the graphene film in embodiment 5 jointly.
Claims (10)
1. a preparation method for Graphene composite guide hotting mask, is characterized in that, 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.
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 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;
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 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;
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 S1, S11 and S21, in described mixed liquor, the mass ratio of the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide is 0.5-3:1-4:1-4.
5. 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.
6. 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 H2 and reduce, obtain graphene film.
7. 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.
8. 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.
9. one kind adopts the Graphene composite guide hotting mask that method prepares described in claim 2,4,5,6 or 8, 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.
10. one kind adopts the Graphene composite guide hotting mask that method prepares described in claim 3,4,5,7 or 8, 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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