CN106219531B - A kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film - Google Patents
A kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film Download PDFInfo
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- CN106219531B CN106219531B CN201610614188.8A CN201610614188A CN106219531B CN 106219531 B CN106219531 B CN 106219531B CN 201610614188 A CN201610614188 A CN 201610614188A CN 106219531 B CN106219531 B CN 106219531B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
Abstract
The present invention relates to a kind of graphite/nanometer carbon pipe array composite heat conduction film preparation methods, include the following steps: (1) in the catalyst-loaded layer of graphite film surface or catalyst precursor layer；(2) graphite film of step (1) is placed in chemical vapor depsotition equipment, the deposition of nanometer carbon pipe array is carried out after reduction treatment, obtain the conduction graphite film of surface deposition nanometer carbon pipe array；(3) conduction graphite film of surface deposition nanometer carbon pipe array is subjected to graphitization processing, obtains graphite/nanometer carbon pipe array composite heat conduction film.The present invention has this specific process of high directivity nanometer carbon pipe array by surface deposition, significantly increase the effective radiating area of conduction graphite film, reduce the interface resistance between heat conducting film and air, to significantly improve the heat exchange amount of the surrounding enviroment such as unit area heat conducting film and air, achieve the effect that for heat to be quickly diffused into the surrounding enviroment such as air from heat conducting film.
Description
Technical field
The invention belongs to thermally conductive and technical field of heat dissipation, are related to a kind of system of graphite/nanometer carbon pipe array composite heat conduction film
Preparation Method.
Background technique
In recent years, graphite film material was answered extensively because of its excellent high thermal conductivity, heat-resisting, the corrosion-resistant and characteristics such as highly conductive
For technical fields such as electronic product heat dissipation, heat-resistant seal material, heaters.And the graphite film with high thermal conductivity is even more
It is widely used under smart phone and tablet computer equidimension, in the handheld terminals such as electronic component is intensive, calorific value is big, passes through height
Thermal conductivity realizes heat sinking function.
Currently, can be had by selecting organic polymer thin-film material directly to carry out carbonization and graphitization processing
High-termal conductivity, high conductivity, the graphite film material of resistance to bend(ing) (104445174 A of CN 102838107 B, CN etc.), and
It is widely used in handheld terminal.Although the type conduction graphite film can be by heating device easy in handheld terminal
Heat conduct rapidly in entire graphite film, but being limited swept area causes it heat promptly cannot be radiated week
In collarette border, as a result, the cruising ability of heat dissipation is insufficient.Cause heat dissipation cruising ability insufficient main reason is that thermally conductive
The lesser swept area of film, and thereby result between heat conducting film and air that there are biggish interface resistances.
Carbon nanotubes has the excellent characteristics such as high heat conductance, high conductivity, high-specific surface area and high intensity, in macromolecule
The fields such as material, metal material, ceramic material play significant reinforcing effect.By the way that carbon nanotubes is mutually tied with graphite film
It closes, can effectively enhance the thermal conductive contact between substrate, and the adhesive force and splitting resistance of Heat Conduction Material can be improved
Can, so as to improve the overall performance of thin-film material.
In this regard, 104810336 A of Chinese patent CN discloses a kind of heat transmission carbon nanotube composite stone ink film, in graphite
The direct carbon nano-tube coating layer of film surface (carbon nanotube heat dissipating layer includes carbon nano-tube material, auxiliary agent and binding resin) increases
The capacity of heat transmission of vertical direction, while improving the mechanical property and flexility of heat conducting film.But due to carbon nanotubes and stone
The active force on ink film surface is poor, carbon nanotubes random distribution and cause to orient it is poor, and coating carbon nanotubes it is easy to reunite
And effective swept area cannot be increased by causing specific surface area reasons, the gained composite stone ink film such as substantially to decline.Chinese patent CN
105110312 A disclose carbon nanotube graphite composite material and preparation method thereof and device, pass through carbon using complete wet filtration method
Composite membrane is made in nanotube dispersion liquid and graphite dispersing solution, and it is thin to solve the problems, such as that natural graphite is difficult to, increases simultaneously
The capacity of heat transmission of vertical direction.However, the material has the following deficiencies: that only abutment surface adhesive force connects carbon nanotubes with graphite flake
Even, final products globality and continuity are poor；The graphite flake of carbon nanotubes and low specific surface area mutually coats and easy to reunite, leads
It causes whole specific surface area to reduce, not can increase effective swept area；Carbon nanotubes random distribution, directionality is poor, heat without
Method is conducted towards preset direction and is spread.104029461 A of Chinese patent CN discloses a kind of graphene/carbon nano-tube/graphite film
Composite material and preparation method prepares nickel Catalytic Layer in graphite film surface using magnetic control sputtering system, and be vapor-deposited graphene
With carbon nanotubes particle, the three-dimensional net structure of graphene and carbon nanotubes preferably promotes the heating conduction of material.But
Granular graphene and carbon nanotubes causes specific surface area to reduce significantly because it reunites the shortcomings that, and effective radiating area cannot get
It is obviously improved；In addition, the random distribution of graphene and carbon nanotubes causes poor directionality to cause in three-dimensional net structure
Heat radiation is difficult to carry out towards preset direction.
It can be seen that existing graphite and the composite film material of carbon nanotubes are focused on how to promote material plane direction
Or the thermal coefficient of vertical direction, and for how heat to be quickly directionally diffused into this technology in the surrounding enviroment such as air
Problem, which then rarely has, to be related to.In the preparation method of existing graphite and carbon nanotubes composite film material, cladding process and complete wet filtration method
Since carbon nanotubes passes through the randomness that dispersion causes distribution, the nanometer carbon pipe array and graphite of high orientation cannot be formed
The composite film material of film；And the random distribution for the carbon nanotubes particle that is vapor-deposited, the astaticism of carbon nanotubes is caused, together
Sample cannot form the nanometer carbon pipe array of high orientation and the composite film material of graphite film.This has just been doomed the above material not
Effective swept area can be significantly increased, so quickly heat directionally cannot be diffused into the surrounding enviroment such as air.In addition,
The composite film material of existing graphite and carbon nanotubes introduces carbon nanotubes on the basis of molding graphite film,
Its process is complex, larger for the change of original process units, is unfavorable for continuous production.
Summary of the invention
The object of the present invention is to provide a kind of graphite/nanometer carbon pipe array composite heat conduction film preparation methods, in graphite film
Surface deposition has the nanometer carbon pipe array of high directivity, the effective radiating area of conduction graphite film is significantly increased, reduction is led
Interface resistance between hotting mask and air significantly improves the heat exchange amount of the surrounding enviroment such as unit area heat conducting film and air, reach by
Heat is quickly diffused into the effect in the surrounding enviroment such as air from heat conducting film.
Technical scheme is as follows:
A kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film, includes the following steps:
(1) in the catalyst-loaded layer of graphite film surface or catalyst precursor layer；
(2) graphite film of step (1) is placed in chemical vapor depsotition equipment, carbon nanotubes battle array is carried out after reduction treatment
The deposition of column obtains the conduction graphite film of surface deposition nanometer carbon pipe array；
(3) conduction graphite film of surface deposition nanometer carbon pipe array is subjected to graphitization processing, obtains graphite/carbon nanotubes battle array
Column composite heat conduction film.
Specifically, catalyst described in step (1) is one or more of iron, cobalt, nickel, copper, platinum, palladium, Jin Heyin, institute
State one or more of oxide, inorganic salts and the organo-metallic compound that catalyst precursor is metal.
Specifically, the loading method of catalyst described in step (1) or catalyst precursor is infusion process, sedimentation, sinks
Shallow lake method or sputtering method.
Specifically, the graphite film in step (1) is carried out to following locate before supported catalyst oxidant layer or catalyst precursor layer
Reason: it is warming up to 200-500 DEG C in air atmosphere and keeps 10-180min.
Specifically, the graphite film in step (1) is carried out to following locate before supported catalyst oxidant layer or catalyst precursor layer
Reason: graphite film is placed in CO2It is warming up to 800-1200 DEG C in atmosphere and keeps 10-180min.
Specifically, reduction treatment condition in step (2) are as follows: temperature is 300-600 DEG C, reducing atmosphere Ar/H2、He/H2Or
N2/H2, recovery time 0.5-20h.
Specifically, in step (2) deposition of nanometer carbon pipe array condition are as follows: temperature is 400-1200 DEG C, and atmosphere is
CH4、C2H4、C2H6、C3H8、C6H6、C2H5The mixed gas of one or more of OH or CO gas and reducing atmosphere, sedimentation time
For 0.5-20h.
Specifically, in step (2) deposition of nanometer carbon pipe array condition further include: be passed through sulfur-bearing auxiliary agent, the sulfur-bearing
Auxiliary agent is thiophene or H2S。
Specifically, step (4) the graphitization processing condition are as follows: temperature is 2400-3300 DEG C.
Specifically, step (4) the graphitization processing condition are as follows: temperature is 2600-3100 DEG C.
The beneficial effects of the present invention are:
The graphite film of a kind of graphite/nanometer carbon pipe array composite heat conduction film preparation method preparation of the invention, in graphite
Film surface deposition has the nanometer carbon pipe array of high directivity, and the swept area of conduction graphite film is significantly increased, and reduces thermally conductive
Interface resistance between film and air significantly improves the heat exchange amount of the surrounding enviroment such as unit area heat conducting film and air, and reaching will be hot
Measure the effect being quickly diffused into from heat conducting film in the surrounding enviroment such as air.
Detailed description of the invention
Fig. 1 is graphite of the invention/nanometer carbon pipe array composite heat conduction film structural schematic diagram；
In figure: 11. nanometer carbon pipe arrays, 12. graphite films.
Specific embodiment
In order to which the object of the invention, technical solution and advantage is more clearly understood, below in conjunction with example, the present invention is carried out
It is further to be described in detail.
Embodiment I
As shown in Fig. 1 (a), a kind of graphite/nanometer carbon pipe array composite heat conduction film, comprising: graphite film 12 and vertical life
The nanometer carbon pipe array in graphite film upper surface is grown, wherein the thickness of graphite film can be 10-100 μm, nanometer carbon pipe array
Thickness can be 1-200 μm, in this embodiment, graphite film with a thickness of 100 μm, nanometer carbon pipe array with a thickness of
200μm。
Embodiment II
As shown in Figure 1, a kind of graphite/nanometer carbon pipe array composite heat conduction film, comprising: graphite film 12 and vertical-growth exist
The nanometer carbon pipe array of graphite film upper and lower surfaces, wherein the thickness of graphite film can be 10-100 μm, carbon nanotubes battle array
The thickness of column can be 1-200 μm, in this embodiment, graphite film with a thickness of 10 μm, the thickness of nanometer carbon pipe array
It is 1 μm.
Preferably, graphite film and nanometer carbon pipe array are generated using one-step method.
A kind of specific embodiment of the preparation method of nanometer carbon pipe array/graphite composite heat conduction film is as follows:
Embodiment 1
In this example, it uses iron for catalyst, it is as follows to support implementation process:
Iron catalyst layer is supported on a wherein surface for graphite film using magnetron sputtering technique；This graphite film is placed in gas
Phase cvd furnace flat-temperature zone, in reducing atmosphere Ar/H2Lower temperature programming is to 400 DEG C and keeps 2h, carries out the reduction treatment of catalyst,
Wherein Ar/H2Flow be 900mL/min, H2Volume fraction be 20%.
Gas is switched to carbon-source gas C to after 800 DEG C by temperature programming2H4/Ar/H22h is kept, carbon nanotubes battle array is carried out
The deposition of column, after switch to reducing atmosphere Ar/H2And it is down to room temperature, wherein C2H4/Ar/H2Flow be 900mL/min,
C2H4And H2Volume fraction be 25%.
Graphitization processing is carried out at 2600-3000 DEG C again, finally obtains graphite/nanometer carbon pipe array composite heat conduction film.
There are nanometer carbon pipe arrays on one of surface of heat conducting film.
After tested it is found that obtained graphite/nanometer carbon pipe array composite heat conduction film, the thermal coefficient of horizontal direction are
1863-1879 W/ (K m), the thermal coefficient of vertical direction are 453-461 W/ (K m), effective radiating area 178-188
m2/g。
Embodiment 2
In this example, used catalyst precursor is nickel nitrate, and it is as follows to support implementation process:
Nickel nitrate is dissolved in ethanol solution, control content is 10wt%；Graphite film is completely immersed in nickel nitrate/ethyl alcohol
In solution and keep 12h；It takes out graphite film and is placed in air atmosphere and dry, support nickel nitrate on two surfaces of graphite film.
This graphite film is placed in gaseous phase deposition stove flat-temperature zone, in reducing atmosphere Ar/H2Lower temperature programming is to 450 DEG C and keeps
2h carries out the reduction treatment of catalyst, wherein He/H2Flow be 1000mL/min, H2Volume fraction be 30%.
Gas is switched to carbon-source gas C to after 850 DEG C by temperature programming2H4/He/H22h is kept, carbon nanotubes battle array is carried out
The deposition of column, after switch to reducing atmosphere Ar/H2And it is down to room temperature, wherein C2H4/He/H2Flow be 1000mL/min,
C2H4And H2Volume fraction be respectively 30% and 20%.
Graphitization processing is carried out at 2600-3000 DEG C again, finally obtains graphite/nanometer carbon pipe array composite heat conduction film.
There is nanometer carbon pipe array on two surfaces of heat conducting film.
After tested it is found that obtained nanometer carbon pipe array/graphite composite heat conduction film, the thermal coefficient of horizontal direction are
1883-1902 W/ (K m), the thermal coefficient of vertical direction are 468-485 W/ (K m), effective radiating area 204-219
m2/g。
Embodiment 3
In this example, used catalyst precursor is ferrocene, and it is as follows to support implementation process:
Ferrocene is supported on two surfaces of graphite film in a manner of being vapor-deposited, this graphite film material is placed in gas
Phase cvd furnace flat-temperature zone, in reducing atmosphere Ar/H2Lower temperature programming is to 500 DEG C and keeps 1.5h, carries out the also original place of catalyst
It manages, wherein N2/H2Flow be 2000mL/min, H2Volume fraction be 30%.
Gas is switched to carbon-source gas CH to after 830 DEG C by temperature programming4/ N2/H21h is kept, carbon nanotubes battle array is carried out
The deposition of column, after switch to reducing atmosphere Ar/H2And it is down to room temperature, wherein CH4/N2/H2Flow be 2000mL/min,
CH4And H2Volume fraction be respectively 35% and 20%.
Graphitization processing is carried out at 2600-3000 DEG C again, finally obtains graphite/nanometer carbon pipe array composite heat conduction film.
There is nanometer carbon pipe array on two surfaces of heat conducting film.
After tested it is found that obtained graphite/nanometer carbon pipe array composite heat conduction film, the thermal coefficient of horizontal direction are
1948-1975 W/ (K m), the thermal coefficient of vertical direction are 474-492 W/ (K m), effective radiating area 238-253
m2/g。
Embodiment 4
In this example, used catalyst precursor is ferric carbonate, and it is as follows to support implementation process:
Ferric nitrate is dissolved in deionized water, control content is 15wt%；By graphite film material be completely immersed in nickel nitrate/
In aqueous solution, after being gradually added into ammonium bicarbonate aqueous solution under magnetic stirring, stand for 24 hours；Graphite film material drying is taken out, in stone
Two surfaces of ink film have supported ferric carbonate.
This graphite film is placed in gaseous phase deposition stove flat-temperature zone, in reducing atmosphere Ar/H2Lower temperature programming is to 500 DEG C and keeps
1.5h carries out the reduction treatment of catalyst, wherein Ar/H2Flow be 1800mL/min, H2Volume fraction be 30%.
Gas is switched to carbon-source gas C to after 750 DEG C by temperature programming3H6/Ar/H21h is kept, carbon nanotubes battle array is carried out
The deposition of column, after switch to reducing atmosphere Ar/H2And it is down to room temperature, wherein C3H6/Ar/H2Flow be 1800mL/min,
C3H6And H2Volume fraction be respectively 20% and 30%.
Graphitization processing is carried out at 2600-3000 DEG C again, finally obtains graphite/nanometer carbon pipe array composite heat conduction film.
There is nanometer carbon pipe array on two surfaces in heat conducting film.
After tested it is found that obtained graphite/nanometer carbon pipe array composite heat conduction film, the thermal coefficient of horizontal direction are
1898-1915 W/ (K m), the thermal coefficient of vertical direction are 464-482 W/ (K m), effective radiating area 198-223
m2/g。
As a comparison, 104810336 A of patent CN is respectively adopted, in 104029461 A of CN 105110312 A and CN
The method, prepares graphite/nanometer carbon pipe array composite heat conduction film respectively, and with and patent in embodiment 1-4 it is prepared
Composite heat conduction film carry out performance comparison, the results are shown in tables 1.
By the comparison of table 1 it is found that high-specific surface area, high directionality nanometer carbon pipe array and the stone obtained through the invention
The composite heat-conducting thin-film material of ink not only both horizontally and vertically has apparent advantage, but also its effective radiating surface
Product is with more the advantage on the order of magnitude.
Table 1
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (8)
1. a kind of graphite/nanometer carbon pipe array composite heat conduction film preparation method, it is characterised in that include the following steps:
(1) in the catalyst-loaded layer of graphite film surface or catalyst precursor layer；
(2) graphite film of step (1) is placed in chemical vapor depsotition equipment, nanometer carbon pipe array is carried out after reduction treatment
Deposition obtains the conduction graphite film of surface deposition nanometer carbon pipe array；
(3) conduction graphite film of surface deposition nanometer carbon pipe array is subjected to graphitization processing, it is multiple obtains graphite/nanometer carbon pipe array
Close heat conducting film；
Reduction treatment condition in step (2) are as follows: temperature is 300-600 DEG C, reducing atmosphere Ar/H2、He/H2Or N2/H2, when reduction
Between be 0.5-20h；
Step (3) the graphitization processing condition are as follows: temperature is 2400-3300 DEG C.
2. a kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film according to claim 1, feature exist
In: catalyst described in step (1) is one or more of iron, cobalt, nickel, copper, platinum, palladium, Jin Heyin, the complex catalyst precursor
Body is one or more of oxide, inorganic salts and the organo-metallic compound of metal.
3. a kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film according to claim 1, feature exist
In: the loading method of catalyst described in step (1) or catalyst precursor is infusion process, sedimentation, the precipitation method or sputtering method.
4. a kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film according to claim 1, feature exist
In: the graphite film in step (1) is carried out the following processing before supported catalyst oxidant layer or catalyst precursor layer: in air atmosphere
In be warming up to 200-500 DEG C and keep 10-180min.
5. a kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film according to claim 1, feature exist
In: the graphite film in step (1) is carried out the following processing before supported catalyst oxidant layer or catalyst precursor layer: graphite film is set
In CO2It is warming up to 800-1200 DEG C in atmosphere and keeps 10-180min.
6. a kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film according to claim 1, feature exist
In: the condition of the deposition of nanometer carbon pipe array in step (2) are as follows: temperature is 400-1200 DEG C, atmosphere CH4、C2H4、C2H6、
C3H8、C6H6、C2H5The mixed gas of one or more of OH or CO gas and reducing atmosphere, sedimentation time 0.5-20h.
7. a kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film according to claim 6, feature exist
In the condition of the deposition of nanometer carbon pipe array in step (2) further include: be passed through sulfur-bearing auxiliary agent, the sulfur-bearing auxiliary agent be thiophene or
H2S。
8. a kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film according to claim 1, feature exist
In: step (3) the graphitization processing condition are as follows: temperature is 2600-3100 DEG C.
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| CN107059004B (en) * | 2017-04-19 | 2021-09-24 | 江苏联科纳米科技有限公司 | High-radiance radiating metal foil and preparation method and application thereof |
| CN110777532A (en) * | 2019-11-29 | 2020-02-11 | 山东大学 | Control method for uniformly growing carbon nanotubes on surface of graphite fiber film cloth |
| CN111925735B (en) * | 2020-08-18 | 2022-06-10 | 南京工程学院 | Directional heat dissipation composite adhesive film and preparation method thereof |
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