CN107311661A - A kind of composite stone ink film and its preparation method and application - Google Patents

A kind of composite stone ink film and its preparation method and application Download PDF

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CN107311661A
CN107311661A CN201710546896.7A CN201710546896A CN107311661A CN 107311661 A CN107311661 A CN 107311661A CN 201710546896 A CN201710546896 A CN 201710546896A CN 107311661 A CN107311661 A CN 107311661A
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film
warming
nano diamond
stone ink
constant temperature
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CN107311661B (en
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白云飞
李娜
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BEIJING XINGKEDI ELECTRONIC TECHNOLOGY Research Institute
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Beijing Kaben Billion New Mstar Technology Ltd
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Abstract

The invention discloses a kind of composite stone ink film and its preparation method and application, including：Prepare the polyimide composite film formed by Nano diamond and polyimides；Under inert gas shielding, it is carbonized and graphitization processing, then removes graphite paper, obtains the composite stone ink film formed by Nano diamond and polyimides.In carbonization and graphitizing process, Nano diamond promotes carbonization and the graphitization of polyimides as nucleus, degree of graphitization and carbonization yield is improved, so as to improve the heat conductivility of compound carbon film, electric conductivity.

Description

A kind of composite stone ink film and its preparation method and application
Technical field
The invention belongs to graphite film field, and in particular to a kind of composite graphite formed by Nano diamond and polyimides Film and its preparation method and application.
Background technology
As electronic product constantly develops towards the direction of precise treatment, precision and energy-conservation, to composition electronic product The requirement of electronic device is also improved constantly.The graphite of highly directional layer structure due to good thermal conductivity, electric conductivity, and by Extensively using on the electronic devices.Tradition prepare highly directional structure graphite method be by pyrolytic carbon under stress high temperature Pyrolysis is obtained, and the graphite of the highly directional structure prepared by this kind of method is referred to as highly oriented pyrolytic graphite.But above-mentioned preparation technology It is complex so that the graphite price with highly directional structure is high, greatly limit its application.In order to overcome above-mentioned ask Topic, people finally found that polyimides (PI) under inert gas shielding by trial and prolonged research and probe for several times, pass through The graphite of gained is as highly directional pyrolysis carbon graphite-structure after high temperature cabonization and graphitization processing, with good orientation knot layer Shape structure.Being prepared using polyimides, there is high starch breeding greatly to simplify preparation technology, has saved cost, has greatly reduced The cost of high starch breeding.But use polyimides made from high starch breeding there is certain defect, for example its Easily crimped in carbonization or graphitizing process, cause final products fragility big, carbonizing degree is low, be broken while also existing The defect of intensity difference, heat conduction and poorly conductive, these problems significantly limit its application.
Therefore, a kind of manufacture methods of high heat conduction graphite film of Chinese patent CN103011141A, disclosed in the manufacture method Using Kapton as raw material, Kapton and graphite paper are cut into fixed dimension, established practice will be cut Determination height is put into the polyimide film layer stacking being sized, and graphite paper is added between each strata imide membrane；Will Between be separated with the cross layered rear Kapton of graphite paper and be put into carbide furnace, under inert gas shielding, respectively in 1000- It is carbonized and graphitization at 1400 DEG C, and at 2500-3000 DEG C, obtains the graphite film of high heat conduction.Above-mentioned technology by Graphite paper is superimposed between Kapton, the bending resistance of graphite film is enhanced, the fragility of graphite film is reduced, but it is right Carbonizing degree, fracture strength, electric conductivity and the thermal conductivity of graphite film are not improved.
The content of the invention
Therefore, the technical problem to be solved in the present invention be to overcome it is of the prior art have polyimides prepare electric conductivity and The defect of poor thermal conductivity, so as to provide a kind of composite stone ink film and its preparation method and application；
The invention solves the problems that another technical problem be the carbonization for overcoming polyimides graphite film of the prior art Degree and the low defect of fracture strength, so as to provide a kind of composite stone ink film and its preparation method and application.
A kind of preparation method of composite stone ink film, comprises the following steps：
(1) polyimide composite film (Nano diamond/polyamides Asia formed by Nano diamond and polyimides is prepared Amine laminated film)；
(2) polyimide composite film is placed between two graphite papers, under inert gas shielding, be carbonized And graphitization processing, the graphite paper is then removed, the composite stone ink film formed by Nano diamond and polyimides is obtained.
Preferably, in described preparation method, in the step (1),
Nano diamond is scattered in organic solvent, nanodiamond suspension is formed；
Under inert gas shielding, 4,4 '-diaminodiphenyl ether, in stirring shape are added into the diamond suspension liquid Under state, pyromellitic dianhydride is added several times, and home position polymerization reaction is carried out at -10-10 DEG C, is obtained containing Nano diamond Polyamic acid solution；
Film is made in the polyamic acid solution, hot imidization processing is carried out to the film, the polyamides is obtained sub- Amine laminated film.
Preferably, in described preparation method, the organic solvent is aprotic polar organic solvent.
Preferably, in described preparation method, described 4,4 '-diaminodiphenyl ether and the pyromellitic acid anhydride Mol ratio is 1:(1-1.5).
Preferably, in described preparation method, in the polyamic acid solution, the content of the Nano diamond is The 4,4 '-diaminodiphenyl ether and the 0.1wt%-10wt% of the pyromellitic acid anhydride quality sum；
The particle diameter of the Nano diamond is 5-100nm.
Preferably, in described preparation method, the condition of the hot imidization processing is：With 3-5 DEG C/min speed, 100 DEG C, 200 DEG C and 300 DEG C are warming up to successively and 0.5-2h is kept respectively at the corresponding temperature, then to be warming up to 330- again 400 DEG C of processing 0.5-1h.
Preferably, in described preparation method, the graphite paper thickness is 20-30 μm；The polyimides THIN COMPOSITE The thickness of film is 20-30 μm.
Preferably, in described preparation method, the condition of the carbonization treatment is：With (5-10) DEG C/min heating speed Rate, is warming up to 800-1500 DEG C, then constant temperature processing 1-2h；
The condition of the graphitization processing is：With (1-20) DEG C/min heating rate, 2400-2800 DEG C is warming up to, and Constant temperature handles 1-2h afterwards.
A kind of composite stone ink film as made from preparation method of the present invention.
A kind of composite stone ink film prepared by preparation method of the present invention conductive field, heat conduction field and The application in wear-resisting field.
Technical solution of the present invention, has the following advantages that：
1. the preparation method of composite stone ink film of the present invention, uses gathering for being formed by Nano diamond and polyimides Material based on acid imide laminated film (Nano diamond/Kapton), in carbonization and graphitizing process, nanogold Hard rock promotes carbonization and the graphitization of polyimides as nucleus, improves the carbonization rate of graphite film, and then improve compound carbon film Heat conductivility, electric conductivity and fracture strength；Tests prove that, the electrical conductivity of composite stone ink film prepared by the present invention reaches 1.81×104S·m-1, thermal conductivity can arrive 1056W (mK)-1, carbonization rate is up to 59.06%, and fracture strength is reachable 6.92MPa；
2. the preparation method of composite stone ink film of the present invention, on the one hand by pyromellitic dianhydride and 4,4 '-diaminourea Diphenyl ether is added in Nano diamond suspension, on the other hand, in the adition process of polymerized monomer, equal benzene is added several times Tetracarboxylic acid dianhydride, while ensureing that polymerisation occurs completely, further increases the dispersiveness of Nano diamond, while on State three kinds of composition mixing direct polycondensations and ultimately form the Kapton containing Nano diamond, further ensure that and receive Rice diamond is scattered in polyimide acid mixed solution, improves it in Nano diamond poly- containing Nano diamond It is scattered in imide membrane, so that film subsequently carbonization and graphited degree are improved, so as to further increase compound The thermal conductivity and electric conductivity of film；Further, since high dispersive of the Nano diamond in the polyimide film containing Nano diamond Degree, improves the thermal conductivity and tensile strength of the Kapton prepared, and then makes the fracture of composite stone ink film strong Degree is improved.
3. the preparation method of composite stone ink film of the present invention, polar organic solvent is added directly into by Nano diamond In, nanodiamond suspension is ultimately formed by dispersing modes such as ultrasounds；On add hybrid mode, without extra coupling agent And dispersant, not only save cost, and reduce contamination gas during follow-up hot imidization, carbonization and graphitization processing The discharge capacity of body, while avoiding due to the defect for the structure that above-mentioned organic solvent is caused in high temperature overflow process, and then really The performance of composite stone ink film is protected.
4. composite stone ink film of the present invention, is combined with polyimides from Nano diamond, utilizes Nano diamond Huge specific surface area, and its fault of construction and surface oxygen functional group, Kapton is added to by Nano diamond In, its surface is contained a large amount of oxygen-containing functional groups and form strong interaction with polyimides, not only obtain wearability Improve, fragility reduction, and in carbonization and graphitizing process, also promote carbonization and the graphitization of polyimides, improve carbonization Yield and degree of graphitization, so as to improve thermal conductivity, electric conductivity and the fracture strength of final composite stone ink film.
Embodiment
Technical scheme will be clearly and completely described below, it is clear that described embodiment is this hair Bright a part of embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not having There is the every other embodiment made and obtained under the premise of creative work, belong to the scope of protection of the invention.In addition, below Just can be mutual as long as the technical characteristic involved by described different embodiments of the present invention does not constitute conflict each other With reference to.
Graphite paper of the present invention can be that any commercial available graphite paper or this area routinely prepare graphite paper preparation method Obtained graphite paper, for the ease of comparing, the graphite paper used in following embodiment 1-7 and comparative example 1-3 is bought from Qingdao Three with graphite Co., Ltd.
Embodiment 1
A kind of preparation method of composite stone ink film, comprises the following steps：
(1) selection is a diameter of takes particle diameter to be 5nm Nano diamonds, is added to as DMA (DMAc) solution In, ultrasonic disperse forms nanodiamond suspension to without obvious graininess；
(2) nitrogen is passed through to nanodiamond suspension, adds 1mol 4,4 '-diaminodiphenyl ether is stirred to completely molten Solution, then under stirring, 1mol pyromellitic dianhydrides are added in three times, under stirring, and low temperature contracts at -10 DEG C Poly- reaction 10h, obtains the polyamic acid solution containing Nano diamond, Nano diamond wherein in polyamic acid mixed solution Content is the 0.1wt% of 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride quality sum；
(3) by polyamic acid solution coating on a glass, at 80 DEG C, constant temperature 2h removes film, film is fixed on On shelf, it is placed in baking oven, the heating rate of regulation baking oven is 3 DEG C/min, 100 DEG C is first warming up to, at such a temperature at constant temperature 0.5h is managed, 200 DEG C, then constant temperature processing 0.5h is then warming up to, 300 DEG C are then heated to, constant temperature processing 0.5h is finally warming up to 330 DEG C, constant temperature processing 0.5h obtains the polyimides THIN COMPOSITE formed by Nano diamond and polyimides that thickness is 20 μm Film；
(4) graphite paper that two thickness are 30 μm is superimposed upon polyimide composite film both sides, is then placed in carbonization Stove, is passed through argon gas, with 5 DEG C/min heating rate, is warming up to 800 DEG C, constant temperature 1h；Then take out, be placed in graphitizing furnace, lead to Enter argon gas, with 20 DEG C/min heating rate, be warming up to 2800 DEG C, constant temperature 2h naturally cools to room temperature, removes two graphite Paper, obtains composite stone ink film A.
Embodiment 2
A kind of preparation method of composite stone ink film, comprises the following steps：
(1) selection is a diameter of takes particle diameter to be 100nm Nano diamonds, is added in DMAc solution, ultrasonic disperse is to without bright Aobvious particle, forms nanodiamond suspension；
(2) argon gas is passed through to nanodiamond suspension, adds 1mol 4,4 '-diaminodiphenyl ether is stirred to completely molten Solution, then under stirring, 1.5mol pyromellitic dianhydrides are added in five times, under stirring, the low temperature at 10 DEG C Polycondensation reaction 2h, obtains the polyamic acid solution containing Nano diamond, and Nano diamond contains wherein in polyamic acid solution Measure the 10wt% for 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride quality sum；
(3) by polyamic acid solution coating on a glass, at 80 DEG C, constant temperature 2h removes film, film is fixed on On shelf, it is placed in baking oven, the heating rate for controlling baking oven is 5 DEG C/min, 100 DEG C is first warming up to, at such a temperature at constant temperature 2h is managed, 200 DEG C, then constant temperature processing 2h is then warming up to, 300 DEG C are then heated to, constant temperature processing 2h is finally warming up to 400 DEG C, Constant temperature handles 0.5h, obtains the polyimide composite film that thickness is 30 μm；
(4) graphite paper that two thickness are 20 μm is superimposed upon polyimide composite film both sides, is then placed in carbonization Stove, is passed through argon gas, with 10 DEG C/min heating rate, is warming up to 1500 DEG C, constant temperature 2h；Then take out, be placed in graphitizing furnace, Argon gas is passed through, with 1 DEG C/min heating rate, 2400 DEG C are warming up to, constant temperature 1h naturally cools to room temperature, removes two graphite Paper, obtains composite stone ink film B.
Embodiment 3
A kind of preparation method of composite stone ink film, comprises the following steps：
(1) selection is a diameter of takes particle diameter to be 50nm Nano diamonds, is added in DMAc solution, ultrasonic disperse is to without substantially Particle, forms nanodiamond suspension；
(2) argon gas is passed through to nanodiamond suspension, adds 1mol 4,4 '-diaminodiphenyl ether is stirred to completely molten Solution, then under stirring, 1.02mol pyromellitic dianhydrides are added in five times, under stirring, the low temperature at -5 DEG C Polycondensation reaction 6h, obtains the polyamic acid solution containing Nano diamond, and Nano diamond contains wherein in polyamic acid solution Measure the 0.5wt% for 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride quality sum；
(3) by polyamic acid solution curtain coating on a glass, at 80 DEG C, constant temperature 2h removes film, film is fixed on On shelf, it is placed in baking oven, the heating rate for controlling baking oven is 4 DEG C/min, 100 DEG C is first warming up to, at such a temperature at constant temperature 1h is managed, 200 DEG C, then constant temperature processing 1h is then warming up to, 300 DEG C are then heated to, constant temperature processing 1h is finally warming up to 350 DEG C, Constant temperature handles 0.5h, obtains the polyimide composite film that thickness is 30 μm；
(4) graphite paper that two thickness are 30 μm is superimposed upon polyimide composite film both sides, is then placed in carbonization Stove, is passed through argon gas, with 8 DEG C/min heating rate, is warming up to 1000 DEG C, constant temperature 1h；Then take out, be placed in graphitizing furnace, Argon gas is passed through, with 10 DEG C/min heating rate, 2800 DEG C are warming up to, constant temperature 1h naturally cools to room temperature, removes two graphite Paper, obtains composite stone ink film C.
Embodiment 4
A kind of preparation method of composite stone ink film, comprises the following steps：
(1) selection is a diameter of takes particle diameter to be 20nm Nano diamonds, is added in DMAc solution, ultrasonic disperse is to without substantially Particle, forms nanodiamond suspension；
(2) argon gas is passed through to nanodiamond suspension, adds 1mol 4,4 '-diaminodiphenyl ether is stirred to completely molten Solution, then under stirring, 1.2mol pyromellitic dianhydrides are added in seven times, under stirring, and low temperature contracts at 5 DEG C Poly- reaction 6h, obtains the polyamic acid solution containing Nano diamond, the content of Nano diamond wherein in polyamic acid solution For 4,4 '-diaminodiphenyl ether and the 1wt% of pyromellitic acid anhydride quality sum；
(3) by polyamic acid solution coating on a glass, at 80 DEG C, constant temperature 2h removes film, film is fixed on On shelf, it is placed in baking oven, it is 5 DEG C to control baking oven heating rate, is first warming up to 100 DEG C, at such a temperature constant temperature processing 1h, and After be warming up to 200 DEG C, then constant temperature processing 1h then heats to 300 DEG C, constant temperature processing 1h is finally warming up to 350 DEG C, at constant temperature 0.5h is managed, the polyimide composite film that thickness is 30 μm is obtained；
(4) graphite paper that two thickness are 30 μm is superimposed upon polyimide composite film both sides, is then placed in carbonization Stove, is passed through argon gas, with 7 DEG C/min heating rate, is warming up to 1000 DEG C, constant temperature 1h；Then take out, be placed in graphitizing furnace, Argon gas is passed through, with 10 DEG C/min heating rate, 2800 DEG C are warming up to, constant temperature 1h naturally cools to room temperature, removes two graphite Paper, obtains composite stone ink film D.
Embodiment 5
A kind of preparation method of Nano diamond/polyimides composite stone ink film, comprises the following steps：
(1) selection is a diameter of takes particle diameter to be 80nm Nano diamonds, is added in DMAc solution, ultrasonic disperse is to without substantially Particle, forms nanodiamond suspension；
(2) argon gas is passed through to nanodiamond suspension, adds 1mol 4,4 '-diaminodiphenyl ether is stirred to completely molten Solution, then under stirring, 1.3mol pyromellitic dianhydrides are added in seven times, under stirring, and low temperature contracts at 0 DEG C Poly- reaction 6h, obtains the polyamic acid solution containing Nano diamond, the content of Nano diamond wherein in polyamic acid solution For 4,4 '-diaminodiphenyl ether and the 5wt% of pyromellitic acid anhydride quality sum；
(3) by polyamic acid solution coating on a glass, at 80 DEG C, constant temperature 2h removes film, film is fixed on On shelf, it is placed in baking oven, the heating rate for controlling baking oven is 5 DEG C/min, 100 DEG C is first warming up to, at such a temperature at constant temperature 0.5h is managed, 200 DEG C, then constant temperature processing 0.5h is then warming up to, 300 DEG C are then heated to, constant temperature processing 1h is finally warming up to 400 DEG C, constant temperature processing 1h obtains the polyimide composite film that thickness is 20 μm；
(4) graphite paper that two thickness are 30 μm is superimposed upon polyimide composite film both sides, is then placed in carbonization Stove, is passed through argon gas, with 10 DEG C/min heating rate, is warming up to 1300 DEG C, constant temperature 1.5h；Then take out, be placed in graphitizing furnace In, argon gas is passed through, with 10 DEG C/min heating rate, 2500 DEG C are warming up to, constant temperature 1.5h naturally cools to room temperature, removes two Graphite paper is opened, composite stone ink film E is obtained.
Embodiment 6
A kind of preparation method of composite stone ink film, comprises the following steps：
(1) selection is a diameter of takes particle diameter to be 40nm Nano diamonds, is added in DMAc solution, ultrasonic disperse is to without substantially Particle, forms nanodiamond suspension；
(2) argon gas is passed through to nanodiamond suspension, adds 1mol 4,4 '-diaminodiphenyl ether is stirred to completely molten Solution, then under stirring, 1.4mol pyromellitic dianhydrides are added in seven times, under stirring, the low temperature at -3 DEG C Polycondensation reaction 6h, obtains the polyamic acid solution containing Nano diamond, and Nano diamond contains wherein in polyamic acid solution Measure the 7wt% for 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride quality sum；
(3) by the coating of polyimide acid mixed solution on a glass, at 80 DEG C, constant temperature 2h removes film, by film Fixed to be placed on the top of the shelf in baking oven, the heating rate for controlling baking oven is 5 DEG C/min, is first warming up to 100 DEG C, constant temperature processing 1.5h, is then warming up to 200 DEG C, constant temperature processing 1.5h then heats to 300 DEG C, constant temperature processing 1.5h is finally warming up to 350 DEG C, constant temperature processing 0.5h, it is 25 μm of polyimide composite films containing Nano diamond to obtain thickness；
(4) graphite paper that two thickness are 30 μm is superimposed upon polyimide composite film both sides, is then placed in carbonization Stove, is passed through argon gas, with 10 DEG C/min heating rate, is warming up to 1000 DEG C, constant temperature 1h；Then take out, be placed in graphitizing furnace, Argon gas is passed through, with 10 DEG C/min heating rate, 2500 DEG C are warming up to, constant temperature 1h naturally cools to room temperature, removes two graphite Paper, obtains composite stone ink film F.
Embodiment 7
A kind of preparation method of polyimides composite stone ink film, comprises the following steps：
(1) argon gas is passed through into DMAc solution, 1mol 4 is added, 4 '-diaminodiphenyl ether is stirred to being completely dissolved, so Afterwards under stirring, 1.02mol pyromellitic dianhydrides are added, under stirring, the low temperature poly condensation 6h at -5 DEG C, and It is afterwards that 50nm Nano diamonds, vinyltrimethoxy silane and silane coupler are added by particle diameter, ultrasonic disperse is to without substantially Particle, obtains the polyamic acid solution containing Nano diamond, and the content of Nano diamond is 4 wherein in polyamic acid solution, The 0.5wt% of 4 '-diaminodiphenyl ether and pyromellitic acid anhydride quality sum, it is vinyltrimethoxy silane, silane coupled Agent and DMAc mass ratioes are：1:1:23；
(2) by polyamic acid solution coating on a glass, at 80 DEG C, constant temperature 2h removes film, film is fixed on On shelf, it is placed in baking oven, the heating rate for controlling baking oven is 4 DEG C/min, is first warming up to 100 DEG C, constant temperature processing 1h then rises Temperature is to 200 DEG C, and constant temperature processing 1h then heats to 300 DEG C, constant temperature processing 1h is finally warming up to 350 DEG C, constant temperature handles 0.5h, It is 30 μm of polyimide composite films containing Nano diamond to obtain thickness；
(3) graphite paper that two thickness are 30 μm is superimposed upon polyimide composite film both sides, is then placed in carbonization Stove, is passed through argon gas, with 8 DEG C/min heating rate, is warming up to 1000 DEG C, constant temperature 1h；Then take out, be placed in graphitizing furnace, Argon gas is passed through, with 10 DEG C/min heating rate, 2800 DEG C are warming up to, constant temperature 1h naturally cools to room temperature, removes two graphite Film, obtains composite stone ink film G.
Comparative example 1
A kind of preparation method of composite stone ink film, comprises the following steps：
(1) selection is a diameter of takes particle diameter to be 50nm nano-graphites, is added in DMAc solution, ultrasonic disperse is to without obvious Grain, forms nano-graphite suspension；
(2) argon gas is passed through to nano-graphite suspension, adds 1mol 4,4 '-diaminodiphenyl ether is stirred to completely molten Solution, then under stirring, 1.02mol pyromellitic dianhydrides are added in five times, under stirring, the low temperature at -5 DEG C Polycondensation reaction 6h, obtains the polyamic acid solution containing nano-graphite, wherein being received in the polyamic acid solution containing nano-graphite Meter Shi Mo content is 4,4 '-diaminodiphenyl ether and the 0.5wt% of pyromellitic acid anhydride quality sum；
(3) by the polyamic acid solution coating containing nano-graphite on a glass, at 80 DEG C, constant temperature 2h removes thin Film, film is fixed on the top of the shelf, is placed in baking oven, and the heating rate for controlling baking oven is 4 DEG C/min, is first warming up to 100 DEG C, perseverance Temperature processing 1h, is then warming up to 200 DEG C, constant temperature processing 1h then heats to 300 DEG C, constant temperature processing 1h is finally warming up to 350 DEG C, constant temperature processing 0.5h, it is 30 μm of polyimide composite films containing nano-graphite to obtain thickness；
(4) graphite paper that two thickness are 30 μm is superimposed upon the polyimide composite film two containing nano-graphite Side, is then placed in carbide furnace, is passed through argon gas, with 8 DEG C/min heating rate, is warming up to 1000 DEG C, constant temperature 1h；Then take out, It is placed in graphitizing furnace, is passed through argon gas, with 10 DEG C/min heating rate, is warming up to 2800 DEG C, constant temperature 1h naturally cools to room Temperature, removes two graphite papers, obtains composite stone ink film H.
Comparative example 2
A kind of preparation method of polyimides composite stone ink film, comprises the following steps：
(1) argon gas is passed through into DMAc solution, 1mol 4 is added, 4 '-diaminodiphenyl ether is stirred to being completely dissolved, so Afterwards under stirring, 1.02mol pyromellitic dianhydrides are added, under stirring, the low temperature poly condensation 6h at -5 DEG C, and It is afterwards that 50nm nano-graphites, vinyltrimethoxy silane and silane coupler are added by particle diameter, ultrasonic disperse is to without obvious Grain, obtains the polyamic acid solution containing nano-graphite, wherein nano-graphite in the polyamic acid solution containing nano-graphite Content is 4,4 '-diaminodiphenyl ether and the 0.5wt% of pyromellitic acid anhydride quality sum, vinyltrimethoxy silane, Silane coupler and DMAc mass ratioes are：1:1:23；
(2) by the polyamic acid solution coating containing nano-graphite on a glass, at 80 DEG C, constant temperature 2h removes thin Film, film is fixed on the top of the shelf, is placed in baking oven, and the heating rate for controlling baking oven is 4 DEG C/min, is first warming up to 100 DEG C, perseverance Temperature processing 1h, is then warming up to 200 DEG C, constant temperature processing 1h then heats to 300 DEG C, constant temperature processing 1h is finally warming up to 350 DEG C, constant temperature processing 0.5h, it is 30 μm of polyimide composite films containing nano-graphite to obtain thickness；
(3) graphite paper that two thickness are 30 μm is superimposed upon the polyimide composite film two containing nano-graphite Side, is then placed in carbide furnace, is passed through argon gas, with 8 DEG C/min heating rate, is warming up to 1000 DEG C, constant temperature 1h；Then take out, It is placed in graphitizing furnace, is passed through argon gas, with 10 DEG C/min heating rate, is warming up to 2800 DEG C, constant temperature 1h naturally cools to room Temperature, removes two graphite films, obtains composite stone ink film I.
Comparative example 3
(1) it is passed through argon gas into DMAc, adds 1mol 4,4 '-diaminodiphenyl ether, stirring is to being completely dissolved, Ran Hou Under stirring, 1.02mol pyromellitic dianhydrides are added in five times, under stirring, the low temperature poly condensation at -5 DEG C 6h, obtains polyamic acid solution；
(2) by polyamic acid solution coating on a glass, at 80 DEG C, constant temperature 2h removes film, film is fixed on On shelf, it is placed in baking oven, the heating rate for controlling baking oven is 4 DEG C/min, is first warming up to 100 DEG C, constant temperature processing 1h then rises Temperature is to 200 DEG C, and constant temperature processing 1h then heats to 300 DEG C, constant temperature processing 1h is finally warming up to 350 DEG C, constant temperature handles 0.5h, Obtain the polyimide composite film that thickness is 30 μm；
(3) graphite paper that two thickness are 30 μm is superimposed upon polyimide composite film both sides, is then placed in carbonization Stove, is passed through argon gas, with 8 DEG C/min heating rate, is warming up to 1000 DEG C, constant temperature 1h；Then take out, be placed in graphitizing furnace, Argon gas is passed through, with 10 DEG C/min heating rate, 2800 DEG C are warming up to, constant temperature 1h naturally cools to room temperature, removes two graphite Film, obtains composite stone ink film J.
Compliance test result
1. composite stone ink film A-J prepared by couple embodiment 1-7 and comparative example 1-3 electric conductivity, thermal conductivity, carbonization rate with And fracture strength is detected；
Conductance is carried out with four-point probe to composite stone ink film A-J to test, testing result is shown in Table 1；
With German LFA447Nanofalsh laser methods conductometer being carried out towards thermal diffusion coefficient to composite stone ink film A-J Detection, and according to the thermal conductivity that composite stone ink film A-J is calculated towards thermal diffusion coefficient detected, the results are shown in Table 1；
Testing result, which is shown in Table 1, to be detected to composite stone ink film A-J fracture strength using universal electrical testing machine；
Composite stone ink film A-J carbonization rate (C%) is detected, the detection method of every composite stone ink film is：Weigh polyamides The weight of imines laminated film, is designated as W1, the weight of composite stone ink film is weighed, W is designated as2, calculated and be carbonized according to following formula Yield, the results are shown in Table 1.
C%=(W2/W1) × 100%
Table 1
2. the embodiment 1-7 and comparative example 1-3 polyimide composite films prepared are passed through into DRL-II type heat conduction respectively Coefficient tester carries out thermal conductivity test, and carries out tensile strength test by universal electrical testing machine, the results are shown in Table 2.
Table 2
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or Among changing still in the protection domain of the invention.

Claims (10)

1. a kind of preparation method of composite stone ink film, comprises the following steps：
(1) polyimide composite film formed by Nano diamond and polyimides is prepared；
(2) polyimide composite film is placed between two graphite papers, under inert gas shielding, be carbonized and stone Blackization processing, then removes the graphite paper, obtains the composite stone ink film formed by Nano diamond and polyimides.
2. preparation method according to claim 1, it is characterised in that in the step (1),
Nano diamond is scattered in organic solvent, nanodiamond suspension is formed；
Under inert gas shielding, 4,4 '-diaminodiphenyl ether, in stirring are added into the diamond suspension liquid Under, pyromellitic dianhydride is added several times, home position polymerization reaction is carried out at -10-10 DEG C, obtains poly- containing Nano diamond Acid amides acid solution；
Film is made in the polyamic acid solution, hot imidization processing is carried out to the film, the polyimides is obtained and answers Close film.
3. preparation method according to claim 2, it is characterised in that the organic solvent is that aprotonic polar is organic molten Agent.
4. the preparation method according to Claims 2 or 3, it is characterised in that described 4,4 '-diaminodiphenyl ether with it is described The mol ratio of PMDA is 1:(1-1.5).
5. according to any described preparation methods of claim 2-4, it is characterised in that described in the polyamic acid solution The content of Nano diamond is the 4,4 '-diaminodiphenyl ether and the 0.1wt%- of the pyromellitic acid anhydride quality sum 10wt%；
The particle diameter of the Nano diamond is 5-100nm.
6. according to any described preparation methods of claim 1-5, it is characterised in that the condition of the hot imidization processing is： With 3-5 DEG C/min speed, 100 DEG C, 200 DEG C and 300 DEG C are warming up to successively and 0.5-2h is kept respectively at the corresponding temperature, so Afterwards 0.5-1h is handled to be warming up to 330-400 DEG C again.
7. according to any described preparation methods of claim 1-6, it is characterised in that the graphite paper thickness is 20-30 μm；Institute The thickness for stating polyimide composite film is 20-30 μm.
8. according to any described preparation methods of claim 1-7, it is characterised in that the condition of the carbonization treatment is：With (5- DEG C 10)/min heating rate, is warming up to 800-1500 DEG C, then constant temperature processing 1-2h；
The condition of the graphitization processing is：With (1-20) DEG C/min heating rate, 2400-2800 DEG C is warming up to, it is then permanent Temperature processing 1-2h.
9. the composite stone ink film as made from the preparation method described in claim any one of 1-8.
10. the composite stone ink film that a kind of any described preparation methods of claim 1-8 are prepared is led in conductive field, heat conduction Domain and the application in wear-resisting field.
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