CN110342497A - Vertical orientation carbon nano pipe array and Graphene composite thin film material and preparation method thereof - Google Patents
Vertical orientation carbon nano pipe array and Graphene composite thin film material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of vertical orientation carbon nano pipe array and Graphene composite thin film materials and preparation method thereof.Vertical orientation carbon nano pipe array of the present invention and Graphene composite thin film material include graphene and equally distributed vertical orientation carbon nano pipe array wherein.Solution is made in graphene oxide, the vertical orientation carbon nano pipe array after filling graphical and densification, redox graphene, obtains vertical orientation carbon nano pipe array and graphene composite structure film at high temperature.Wherein directional carbon nanotube array structure can provide additional longitudinal thermal conducting path for laminated film, and graphene can effectively fill the gap of the vertical orientation carbon nano pipe array after graphical and densification, provide lateral thermal conducting path for it.Using vertical orientation carbon nano pipe array and grapheme material characteristic, the two performance obtains good complementation, can improve effective hot horizontal and vertical heating conduction of interface heat sink material, be suitably applied a variety of dissipation from electronic devices fields.
Description
Technical field
The present invention relates to a kind of thermally conductive composite film materials and preparation method thereof, radiate more particularly to a kind of hot interface multiple
Thin-film material and preparation method thereof is closed, LED, microelectronics, intelligent electronic device technical field of heat dissipation are applied to.
Background technique
With the progress of science and technology, the packaging density of the component on electronic circuit board increasingly increases, while component
Power density is continuously improved again, so that electronic chip heat flow density increases.If the heat of component can not conduct rapidly,
It is research electronics that chip temperature, which increases the hot interface heat sink material that will lead to product failure, therefore find a kind of quick high thermal conductivity,
One important topic of encapsulation.
Graphene has that thermal conductivity is good, mechanical performance is excellent, acid and alkali-resistance etc. is a variety of excellent as a kind of novel two-dimensional material
Benign energy.The thermal conductivity of suspension single-layer graphene at room temperature is up to 5300W/mk, is mesh considerably beyond graphite and diamond
The highest material of preceding known thermal coefficient.However, graphene-based film interlayer Van der Waals force results in its biggish interlayer thermal resistance,
So that its longitudinal thermal conductivity more than 2 order of magnitude lower than transverse thermal conductivity perpendicular to in-plane, shows apparent each
Anisotropy heat transfer limits its application in terms of thermal interfacial material to a certain extent.And vertical orientation carbon nano-pipe array
Column longitudinal direction has high thermal conductivity, the experimental results showed that, the theoretical axial thermal conductivity rate of single single-walled carbon nanotube is reachable
5800W/mk, and the axial thermal conductivity of some multi-walled carbon nanotubes also can exceed that 3000W/mk.In conjunction with graphene transverse direction thermal conductivity
The high and high characteristic of vertical orientation carbon nano pipe array longitudinal direction thermal conductivity, designs the higher hot interface of horizontal and vertical thermal conductivity
Heat sink material.Vertical orientation carbon nano pipe array provides additional longitudinal thermal conducting path in laminated film, thus guaranteeing
It is improved on the basis of higher transverse thermal conductivity in longitudinal thermal conductivity.Graphene can fill hanging down graphically and after densification
The gap of straight directional carbon nanotube array.The structure and performance of the two in this way obtain good complementation, collaboration between the two
Effect can effectively improve the hot horizontal and vertical heating conduction of interface heat sink material.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Graphene oxide is made solution, filled out by vertical orientation carbon nano pipe array and Graphene composite thin film material and preparation method thereof
The vertical orientation carbon nano pipe array after graphical and densification is filled, then redox graphene at high temperature, obtained
To vertical orientation carbon nano pipe array and Graphene composite thin film material.Wherein vertical orientation carbon nano tube array structure forms multiple
It closes film and additional longitudinal thermal conducting path is provided, and graphene then provides lateral thermal conducting path for it.It is received using vertical orientation carbon
Mitron array and grapheme material characteristic, the performance of the two obtain good complementation, effectively improve laminated film longitudinal direction and
Lateral thermal conductivity energy.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of vertical orientation carbon nano pipe array and Graphene composite thin film material, including graphene and wherein uniformly point
The vertical orientation carbon nano pipe array of cloth；Wherein, vertical orientation carbon nano tube array structure provides for composite film material ontology
Additional longitudinal thermal conducting path forms longitudinal thermal conducting path between graphene layer；And graphene is then composite film material ontology
Lateral thermal conducting path is provided；Using the orientation passage of heat of vertical orientation carbon nano pipe array and grapheme material, it is vertically fixed to make
Solid netted passage of heat structure is formed to carbon nano pipe array and grapheme material, the longitudinal direction of laminated film is thermally conductive and lateral
Thermally conductive realization is complementary, and vertical orientation carbon nano pipe array forms thermally-conductive interface with the contact position of graphene or junction and connects knot
Structure.
As currently preferred technical solution, wherein graphene layer spacing is 0.5~3 μm, and graphene is with a thickness of 0.8
~1.2nm, the carbon nanotube height of vertical orientation carbon nano pipe array are 100~200 μm.
As currently preferred technical solution, graphite oxide solution is made in graphene oxide, then using oxidation stone
Black solution fills the vertical orientation carbon nano pipe array after graphical and densification, and removes vertical orientation carbon nanotube
The liquid solvent of graphite oxide solution in the carbon nano tube bundle gap of array makes the gap filling between every cluster carbon nanotube
Graphene oxide, then redox graphene at high temperature, obtains vertical orientation carbon nano pipe array and graphene THIN COMPOSITE
Film.
As currently preferred technical solution, carbon nanotube is subjected to densification, the described of densification is formed and hangs down
Straight directional carbon nanotube array structure；The obtained vertical orientation carbon nano pipe array and graphene composite film with a thickness of
150~250 μm.
A kind of preparation method of vertical orientation carbon nano pipe array and Graphene composite thin film material of the present invention, step is such as
Under:
A. the catalyst that graphical treatment is crossed in substrate is utilized, the growth of vertical directional carbon nanotube array in substrate；
B. densification is carried out to the vertical orientation carbon nano pipe array prepared in the step a, obtaining has cause
The vertical orientation carbon nano pipe array of densifying structure；
C. it adds graphene oxide into deionized water, graphene oxide solution is made in centrifugal mixer；It will be in the step
Vertical orientation carbon nano pipe array in rapid b after densification, which is placed on heated at constant temperature platform, carries out heated at constant temperature, will
Obtained graphene oxide solution drop coating enters in the vertical orientation carbon nano pipe array after densification, and evaporates and remove water
Point, then apply pressure on obtained vertical orientation carbon nano pipe array and graphene composite thin film and is compacted into
Type makes the gap filling graphene oxide between every cluster carbon nanotube, obtains vertical orientation carbon nano pipe array and oxidation stone
Black alkene laminated film；
D. the vertical orientation carbon nano pipe array obtained in the step c and graphene composite thin film are peelled off into base
Bottom, to obtain structure of composite membrane material precursor；
E. the structure of composite membrane material precursor obtained in the step d is placed in high-temperature tubular quartz furnace, in inertia
Under gas shield, gradually heating heat treatment is carried out, control temperature schedule is as follows:
50~400 DEG C first is heated to structure of composite membrane material precursor, carry out first stage heat preservation heat treatment 30~
60min；
400~600 DEG C is warming up to structure of composite membrane material precursor again, carry out second stage heat preservation heat treatment 30~
60min；
600~800 DEG C is warming up to structure of composite membrane material precursor again, carry out phase III heat preservation heat treatment 30min~
60min；
800~1000 DEG C is warming up to structure of composite membrane material precursor, carry out phase III heat preservation heat treatment 30min~
60min；
1000~1200 DEG C is warming up to structure of composite membrane material precursor, carry out phase III heat preservation heat treatment 30min~
60min；
1400 DEG C is warming up to structure of composite membrane material precursor again, carry out fourth stage heat preservation heat treatment 120min~
180min, to obtain vertical orientation carbon nano pipe array and graphene composite film.
As currently preferred technical solution, in above-mentioned steps a, in substrate growing height 100~250 μm it
Between vertical orientation carbon nano pipe array.
As currently preferred technical solution, in above-mentioned steps b, the time for carrying out densification is 15~25s.
It is added graphene oxide into deionized water in above-mentioned steps c as currently preferred technical solution,
The revolving speed for carrying out centrifugal mixer is not less than 500r/min, and mixing time is 60~120min；
As currently preferred technical solution, in above-mentioned steps c, the temperature of control heated at constant temperature platform heating is not higher than
100 DEG C, and evaporate and remove moisture；
As currently preferred technical solution, in above-mentioned steps c, compaction moulding vertical orientation carbon nano-pipe array is carried out
The pressure of the pressurization of column and graphene composite thin film is 20~30Mpa.
As currently preferred technical solution, in the step e, the inert gas includes in argon gas and nitrogen
Any one gas or the two mixed gas, control gas flow be 100~150sccm, control tubular quartz furnace liter
The rate of temperature is 5~10 DEG C/min.
As currently preferred technical solution, in the step e, the vertical orientation with a thickness of 150~250 μm is obtained
Carbon nano pipe array and graphene composite film.
As currently preferred technical solution, in the step e, when carrying out the heat preservation heat treatment of the 6th stage, it is divided into 6
Step carries out gradually heating heat treatment, and control temperature schedule is as follows:
800~1000 DEG C first are warming up to the structure of composite membrane material precursor of second stage heat preservation heat treatment, carries out hot place
Reason is no less than 30min；
1200 DEG C are warming up to structure of composite membrane material precursor again, heat preservation heat treatment is carried out and is no less than 30min；
1400 DEG C are warming up to structure of composite membrane material precursor again, heat preservation heat treatment is carried out and is no less than 120min, thus
To vertical orientation carbon nano pipe array and graphene composite film.
It is preferred that above-mentioned carbon nanotube includes single-walled carbon nanotube or multi-walled carbon nanotube.
It is preferred that above-mentioned graphene oxide filling thickness is higher than vertical orientation carbon nano pipe array height.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the present invention is compound by vertical orientation carbon nano pipe array and graphene, aligned carbon nanotube and stone have been given full play to
Excellent heat conductivity performance of the black alkene in vertical and horizontal both direction, to enable carbon nanotube and graphene composite film conduct
Vertical and horizontal while the good composite film material of heating conduction；
2. carbon nanotube of the present invention and the carbon nanotube of graphene composite film are vertical orientation carbon nano pipe array, uniformly
It is distributed in laminated film, graphene is all filled between every cluster carbon nanotube, vertical orientation carbon nano pipe array passes through cause
After densification process, its porosity further reduced；And by the way that after graphical treatment, therefore the gap between every cluster carbon pipe is expanded
Greatly, it is able to more fully filled graphite alkene, vertical orientation carbon nano-pipe array, which is listed in laminated film, provides longitudinal passage, is promoted
Composite membrane heating conduction；
2. the method for the present invention is simple, easy to operate, reaction condition is mild, and preparation flow is easily controllable, is suitble to promote and apply.
Detailed description of the invention
Fig. 1 is one vertical orientation carbon nano pipe array of the embodiment of the present invention and Graphene composite thin film material preparation method stream
Cheng Tu.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as
Under:
Embodiment one:
In the present embodiment, a kind of vertical orientation carbon nano pipe array and Graphene composite thin film material, including graphene
Equally distributed vertical orientation carbon nano pipe array wherein；Wherein, vertical orientation carbon nano tube array structure is THIN COMPOSITE
Membrane material ontology provides additional longitudinal thermal conducting path, forms longitudinal thermal conducting path between graphene layer；And graphene is then multiple
It closes thin-film material ontology and lateral thermal conducting path is provided；Orientation using vertical orientation carbon nano pipe array and grapheme material is thermally conductive
Channel makes vertical orientation carbon nano pipe array and grapheme material form solid netted passage of heat structure, laminated film
Longitudinal thermally conductive and lateral thermally conductive realization is complementary, and the contact position or junction of vertical orientation carbon nano pipe array and graphene are formed
Thermally-conductive interface connection structure.
In the present embodiment, graphene layer spacing is 0.5~3 μm, and graphene is with a thickness of 0.8~1.2nm, vertical orientation carbon
The carbon nanotube height of nano-tube array is 100 μm；The present embodiment vertical orientation carbon nano pipe array and graphene composite film
With a thickness of 150 μm.Carbon nanotube uses multi-walled carbon nanotube.The present embodiment vertical orientation carbon nano pipe array and graphene are multiple
Film is closed, wherein directional carbon nanotube array can provide additional longitudinal thermal conducting path for laminated film, and graphene is then
It provides lateral thermal conducting path.The present embodiment utilizes vertical orientation carbon nano pipe array and graphene characteristic, and the performance of the two obtains
To good complementation, the vertical and horizontal heating conduction of laminated film can effectively improve.
In the present embodiment, referring to Fig. 1, a kind of the present embodiment vertical orientation carbon nano pipe array and graphene composite film
The preparation method of material, its step are as follows:
A. the catalysis that graphical treatment is crossed on silicon wafer is utilized using silicon wafer as substrate by chemical vapor deposition method
Agent, in silicon wafer, the carbon nanotube that upper growing height is 100 μm, growth time 30min, growth temperature is 650 DEG C, thus
Vertical orientation carbon nano pipe array is obtained on silicon wafer；
B. densification is carried out to the vertical orientation carbon nano pipe array prepared in the step a on silicon wafer, it will
The silicon chip substrate for being loaded with carbon nanotube is placed in 60 DEG C of acetone steam, carries out 20s densification to carbon nanotube, is had
There is the vertical orientation carbon nano pipe array of densified structure；
C. 500mg graphene oxide is placed in the beaker of 50ml, the 40ml deionized water being added into beaker, centrifuge
Tool stirs 60min, and the revolving speed of centrifugal mixer is 500r/min, and finely dispersed graphene oxide solution is made；It will be in the step
Vertical orientation carbon nano pipe array in rapid b after densification is placed on 100 DEG C of constant temperature of progress on heated at constant temperature platform and adds
Graphene oxide solution drop coating obtained is entered in the vertical orientation carbon nano pipe array after densification, and steamed by heat
Hair remove moisture, then on obtained vertical orientation carbon nano pipe array and graphene composite thin film apply 20Mpa~
The pressure of 30Mpa carries out compaction moulding, makes the gap filling graphene oxide between every cluster carbon nanotube, and it is vertically fixed to obtain
To carbon nano pipe array and graphene composite thin film；
D. the vertical orientation carbon nano pipe array obtained in the step c and graphene composite thin film are taken out,
Then silicon wafer substrate is peelled off, thus before obtaining vertical orientation carbon nano pipe array and graphene composite thin film structural material
Body；
E. the complex thin film structure material precursor obtained in the step d is placed in high-temperature tubular quartz furnace, in argon
Under the inert gas shielding of gas, control argon gas flow is 100sccm, carries out gradually heating heat treatment, controls temperature schedule
It is as follows:
First with the heating rate of 5 DEG C/min, 400 DEG C are heated to structure of composite membrane material precursor, carries out the first rank
Duan Baowen is heat-treated 30min；
First with the heating rate of 5 DEG C/min, 600 DEG C are heated to structure of composite membrane material precursor, carries out second-order
Duan Baowen is heat-treated 30min
Again with the heating rate of 5 DEG C/min, 800 DEG C are warming up to structure of composite membrane material precursor, carries out phase III guarantor
Warm processing 30min；
Again with the heating rate of 5 DEG C/min, 1000 DEG C are warming up to structure of composite membrane material precursor, heat preservation heat treatment
30min；Continue with the heating rate of 5 DEG C/min, 1200 DEG C is warming up to structure of composite membrane material precursor, heat preservation heat treatment
30min；Finally with the heating rate of 5 DEG C/min, 1400 DEG C are warming up to structure of composite membrane material precursor, heat preservation heat treatment
120min makes graphene oxide that high temperature reduction reaction occur, to obtain the vertical orientation carbon nano pipe array with a thickness of 150 μm
And graphene composite film.
Experimental test and analysis
The present embodiment combination graphene transverse direction thermal conductivity height and the high spy of vertical orientation carbon nano pipe array longitudinal direction thermal conductivity
Property, prepare a kind of higher hot interface heat sink material of horizontal and vertical thermal conductivity.The vertical orientation carbon nanometer in laminated film
Pipe array provides additional longitudinal thermal conducting path, to improve it on the basis of guaranteeing higher transverse thermal conductivity in longitudinal direction
Thermal conductivity.Graphene can fill the gap of the vertical orientation carbon nano pipe array after graphical and densification.Both in this way
Structure and performance obtain good complementation, synergistic effect between the two can effectively improve hot interface heat sink material laterally and
Longitudinal heating conduction.The present embodiment answers the vertical orientation carbon nano pipe array that graphene and densification and graphical treatment are crossed
It closes.Vertical orientation carbon nano pipe array can provide additional longitudinal thermal conducting path for laminated film, and graphene then mentions for it
For lateral thermal conducting path.Using vertical orientation carbon nano pipe array and graphene characteristic, the performance of the two obtains good complementation,
The vertical and horizontal heating conduction that can effectively improve laminated film, in conjunction with the experimental program of this patent, lateral thermally conductive rate theory
On can achieve 700~750W/mk, longitudinal thermal conductivity can achieve 25~30W/mk.The present embodiment vertical orientation carbon nanotube
Array and graphene composite film heating conduction are high, good mechanical performance, particularly suitable for LED, microelectronics, smart electronics
Device field of radiating.
Embodiment two:
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, a kind of vertical orientation carbon nano pipe array and Graphene composite thin film material, including graphene
Equally distributed vertical orientation carbon nano pipe array wherein；Wherein, vertical orientation carbon nano tube array structure is THIN COMPOSITE
Membrane material ontology provides additional longitudinal thermal conducting path, forms longitudinal thermal conducting path between graphene layer；And graphene is then multiple
It closes thin-film material ontology and lateral thermal conducting path is provided；Orientation using vertical orientation carbon nano pipe array and grapheme material is thermally conductive
Channel makes vertical orientation carbon nano pipe array and grapheme material form solid netted passage of heat structure, laminated film
Longitudinal thermally conductive and lateral thermally conductive realization is complementary, and the contact position or junction of vertical orientation carbon nano pipe array and graphene are formed
Thermally-conductive interface connection structure.
In the present embodiment, graphene layer spacing is 0.5~3 μm, and graphene is with a thickness of 0.8~1.2nm, vertical orientation carbon
The carbon nanotube height of nano-tube array is 200 μm；The present embodiment vertical orientation carbon nano pipe array and graphene composite film
With a thickness of 250 μm.Carbon nanotube uses multi-walled carbon nanotube.The present embodiment vertical orientation carbon nano pipe array and graphene are multiple
Film is closed, wherein directional carbon nanotube array can provide additional longitudinal thermal conducting path for laminated film, and graphene is then
It provides lateral thermal conducting path.The present embodiment utilizes vertical orientation carbon nano pipe array and graphene characteristic, and the performance of the two obtains
To good complementation, the vertical and horizontal heating conduction of laminated film can effectively improve.
In the present embodiment, a kind of system of the present embodiment vertical orientation carbon nano pipe array and Graphene composite thin film material
Preparation Method, its step are as follows:
A. the catalysis that graphical treatment is crossed on silicon wafer is utilized using silicon wafer as substrate by chemical vapor deposition method
Agent, in silicon wafer, the carbon nanotube that upper growing height is 200 μm, growth time 30min, growth temperature is 650 DEG C, thus
Vertical orientation carbon nano pipe array is obtained on silicon wafer；
B. densification is carried out to the vertical orientation carbon nano pipe array prepared in the step a on silicon wafer, it will
The silicon chip substrate for being loaded with carbon nanotube is placed in 60 DEG C of acetone steam, carries out 25s densification to carbon nanotube, is had
There is the vertical orientation carbon nano pipe array of densified structure；
C. 600mg graphene oxide is placed in the beaker of 50ml, the 40ml deionized water being added into beaker, centrifuge
Tool stirs 120min, and the revolving speed of centrifugal mixer is 500r/min, and finely dispersed graphene oxide solution is made；It will be in the step
Vertical orientation carbon nano pipe array in rapid b after densification is placed on 100 DEG C of constant temperature of progress on heated at constant temperature platform and adds
Graphene oxide solution drop coating obtained is entered in the vertical orientation carbon nano pipe array after densification, and steamed by heat
Hair remove moisture, then on obtained vertical orientation carbon nano pipe array and graphene composite thin film apply 20Mpa~
The pressure of 30Mpa carries out compaction moulding, makes the gap filling graphene oxide between every cluster carbon nanotube, and it is vertically fixed to obtain
To carbon nano pipe array and graphene composite thin film；
D. the vertical orientation carbon nano pipe array obtained in the step c and graphene composite thin film are taken out,
Then silicon wafer substrate is peelled off, thus before obtaining vertical orientation carbon nano pipe array and graphene composite thin film structural material
Body；
E. the complex thin film structure material precursor obtained in the step d is placed in high-temperature tubular quartz furnace, in nitrogen
Under the inert gas shielding of gas, the gas flow for controlling nitrogen is 150sccm, carries out gradually heating heat treatment, controls temperature system
It spends as follows:
Again with the heating rate of 10 DEG C/min, 400 DEG C are warming up to structure of composite membrane material precursor, carries out second stage guarantor
Warm processing 60min；
Again with the heating rate of 10 DEG C/min, 600 DEG C are warming up to structure of composite membrane material precursor, carries out phase III guarantor
Warm processing 60min；
Again with the heating rate of 10 DEG C/min, 800 DEG C are warming up to structure of composite membrane material precursor, heat preservation heat treatment
60min；Again with the heating rate of 10 DEG C/min, 1000 DEG C are warming up to structure of composite membrane material precursor, heat preservation heat treatment
60min；Continue with the heating rate of 10 DEG C/min, 1200 DEG C is warming up to structure of composite membrane material precursor, heat preservation heat treatment
60min；Finally with the heating rate of 5 DEG C/min, 1400 DEG C are warming up to structure of composite membrane material precursor, heat preservation heat treatment
180min makes graphene oxide that high temperature reduction reaction occur, to obtain the vertical orientation carbon nano pipe array with a thickness of 250 μm
And graphene composite film.
Experimental test and analysis
The present embodiment vertical orientation carbon nano pipe array and Graphene composite thin film material, including graphene and wherein
The vertical orientation carbon nano pipe array of even distribution.Solution is made in graphene oxide, filling is graphically and after densification
Vertical orientation carbon nano pipe array, then redox graphene at high temperature, obtains vertical orientation carbon nano pipe array and stone
Black alkene compound structure film.Wherein it is thermally conductive logical can to provide additional longitudinal direction for laminated film for directional carbon nanotube array structure
Road, and graphene then provides lateral thermal conducting path for it.Using vertical orientation carbon nano pipe array and graphene characteristic, the two
Performance obtains good complementation, can effectively improve the vertical and horizontal heating conduction of laminated film.The present embodiment is by graphene
The vertical orientation carbon nano pipe array crossed with densification and graphical treatment is compound.Vertical orientation carbon nano pipe array can be multiple
It closes film and additional longitudinal thermal conducting path is provided, and graphene then provides lateral thermal conducting path for it.It is received using vertical orientation carbon
Mitron array and graphene characteristic, the performance of the two obtain good complementation, can effectively improve longitudinal direction and the cross of laminated film
To heating conduction, in conjunction with the experimental program of this patent, lateral thermal conductivity theoretically can achieve 600~700W/mk, longitudinal thermally conductive
Rate can achieve 15~25W/mk.The present embodiment vertical orientation carbon nano pipe array and graphene composite film heating conduction are high,
Good mechanical performance, particularly suitable for LED, microelectronics, intelligent electronic device field of radiating.
To sum up described in embodiment, vertical orientation carbon nano pipe array and Graphene composite thin film material and preparation method thereof
This vertical orientation carbon nano pipe array and Graphene composite thin film material, including graphene and equally distributed vertical wherein
Directional carbon nanotube array.Solution is made in graphene oxide, filling is graphically received with the vertical orientation carbon after densification
Mitron array, then redox graphene at high temperature, obtains vertical orientation carbon nano pipe array and graphene composite structure
Film.Wherein directional carbon nanotube array structure can provide additional longitudinal thermal conducting path for laminated film, and graphene can
To fill the gap of the vertical orientation carbon nano pipe array graphically and after densification, lateral thermal conducting path is provided for it.It utilizes
Vertical orientation carbon nano pipe array and grapheme material characteristic, the performance of the two obtain good complementation, and effective heat can be improved
The horizontal and vertical heating conduction of interface heat sink material.Above-described embodiment graphene oxide filling thickness is above vertical orientation carbon and receives
Mitron array heights have given full play to the high advantage of the axial thermal conductivity rate of carbon nanotube, and have saved material.Above-described embodiment carbon is received
Mitron adopts multi-walled carbon nanotube, and the vertical orientation carbon nano pipe array of preparation and the composite membrane thermal conductivity of graphene are high, when this
Invention carbon nanotube adopts single-walled carbon nanotube, the vertical orientation carbon nano pipe array of preparation and the composite membrane thermal conductivity of graphene
It can be further improved, due to single-walled carbon nanotube chemical inertness with higher, surface wants purer, is received using single wall carbon
The vertical orientation carbon nano pipe array of mitron preparation and the composite membrane of graphene are particularly suitable for application to the precision of extreme environment
The heat dissipation of electronic device is of great significance in aerospace accurate device technical field.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
It is former without departing from the technology of vertical orientation carbon nano pipe array of the present invention and Graphene composite thin film material and preparation method thereof
Reason and inventive concept, belong to protection scope of the present invention.
Claims (10)
1. a kind of vertical orientation carbon nano pipe array and Graphene composite thin film material, it is characterised in that: including graphene and
Wherein equally distributed vertical orientation carbon nano pipe array；Wherein, vertical orientation carbon nano tube array structure is THIN COMPOSITE membrane material
Expect that ontology provides additional longitudinal thermal conducting path, forms longitudinal thermal conducting path between graphene layer；And graphene is then THIN COMPOSITE
Membrane material ontology provides lateral thermal conducting path；It is thermally conductive logical using the orientation of vertical orientation carbon nano pipe array and grapheme material
Road, makes vertical orientation carbon nano pipe array and grapheme material form solid netted passage of heat structure, and laminated film is indulged
To thermally conductive and laterally thermally conductive realization complementation, the contact position or junction of vertical orientation carbon nano pipe array and graphene, which are formed, is led
Hot interface connection structure.
2. vertical orientation carbon nano pipe array and Graphene composite thin film material according to claim 1, it is characterised in that: its
In, graphene layer spacing is 0.5~3 μm, and graphene is with a thickness of 0.8~1.2nm, the carbon nanometer of vertical orientation carbon nano pipe array
Pipe height is 100~200 μm.
3. vertical orientation carbon nano pipe array and Graphene composite thin film material according to claim 1, it is characterised in that: will
Graphite oxide solution is made in graphene oxide, hanging down after then filling graphical and densification using graphite oxide solution
Straight directional carbon nanotube array, and remove the graphite oxide solution in the carbon nano tube bundle gap of vertical orientation carbon nano pipe array
Liquid solvent, make the gap filling graphene oxide between every cluster carbon nanotube, then reduction-oxidation graphite at high temperature
Alkene obtains vertical orientation carbon nano pipe array and graphene composite film.
4. vertical orientation carbon nano pipe array and Graphene composite thin film material according to claim 4, it is characterised in that: will
Carbon nanotube carries out densification, forms the vertical orientation carbon nano tube array structure of densification；What is obtained is described vertical
Straight directional carbon nanotube array and graphene composite film with a thickness of 150~250 μm.
5. the preparation method of vertical orientation carbon nano pipe array and Graphene composite thin film material described in a kind of claim 1,
It is characterized in that, steps are as follows:
A. the catalyst that graphical treatment is crossed in substrate is utilized, the growth of vertical directional carbon nanotube array in substrate；
B. densification is carried out to the vertical orientation carbon nano pipe array prepared in the step a, obtaining has densification
The vertical orientation carbon nano pipe array of structure；
C. it adds graphene oxide into deionized water, graphene oxide solution is made in centrifugal mixer；It will be in the step b
The middle vertical orientation carbon nano pipe array after densification, which is placed on heated at constant temperature platform, carries out heated at constant temperature, will obtain
Graphene oxide solution drop coating enter in the vertical orientation carbon nano pipe array after densification, and evaporate remove moisture,
Then apply pressure on obtained vertical orientation carbon nano pipe array and graphene composite thin film and carry out compaction moulding, make
Gap filling graphene oxide between every cluster carbon nanotube, obtains vertical orientation carbon nano pipe array and graphene oxide is multiple
Close film；
D. the vertical orientation carbon nano pipe array obtained in the step c and graphene composite thin film are peelled off into substrate,
To obtain structure of composite membrane material precursor；
E. the structure of composite membrane material precursor obtained in the step d is placed in high-temperature tubular quartz furnace, in inert gas
Under protection, gradually heating heat treatment is carried out, control temperature schedule is as follows:
50~400 DEG C first is heated to structure of composite membrane material precursor, carry out first stage heat preservation heat treatment 30~
60min；
400~600 DEG C are warming up to structure of composite membrane material precursor, carries out 30~60min of second stage heat preservation heat treatment；
600~800 DEG C are warming up to structure of composite membrane material precursor, carries out phase III heat preservation heat treatment 30min~60min；
800~1000 DEG C are warming up to structure of composite membrane material precursor, carries out phase III heat preservation heat treatment 30min~60min；
1000~1200 DEG C is warming up to structure of composite membrane material precursor, carry out phase III heat preservation heat treatment 30min~
60min；
1400 DEG C are warming up to structure of composite membrane material precursor again, carries out fourth stage heat preservation heat treatment 120min~180min,
To obtain vertical orientation carbon nano pipe array and graphene composite film.
6. the preparation method of vertical orientation carbon nano pipe array and Graphene composite thin film material according to claim 5,
It is characterized in that: in the step a, vertical orientation carbon nano-pipe array of the growing height between 100~250 μm in substrate
Column.
7. the preparation method of vertical orientation carbon nano pipe array and Graphene composite thin film material according to claim 5,
Be characterized in that: in the step b, the time for carrying out densification is 15~25s.
8. the preparation method of vertical orientation carbon nano pipe array and Graphene composite thin film material according to claim 5,
It is characterized in that: in the step c, adding graphene oxide into deionized water, the revolving speed for carrying out centrifugal mixer is not less than
500r/min, mixing time are 60~120min；
Alternatively, the temperature of control heated at constant temperature platform heating is not higher than 100 DEG C, and evaporates and remove moisture；
Alternatively, the pressure for carrying out the pressurization of compaction moulding vertical orientation carbon nano pipe array and graphene composite thin film is 20
~30Mpa.
9. the preparation method of vertical orientation carbon nano pipe array and Graphene composite thin film material according to claim 5,
Be characterized in that: in the step e, the inert gas includes any one gas or the two in argon gas and nitrogen
Mixed gas, control gas flow are 100~150sccm, and the rate of control tubular quartz furnace heating is 5~10 DEG C/min；From
And obtain the vertical orientation carbon nano pipe array and graphene composite film with a thickness of 150~250 μm.
10. the preparation method of vertical orientation carbon nano pipe array and Graphene composite thin film material according to claim 5,
It is characterized in that: in the step e, when carrying out the heat preservation heat treatment of the 6th stage, being divided into six steps and carry out gradually heating heat treatment, control
Temperature schedule processed is as follows: being first warming up to 400~600 DEG C to structure of composite membrane material precursor, carries out heat preservation heat treatment and be no less than
30min；
600~800 DEG C are warming up to structure of composite membrane material precursor again, heat preservation heat treatment is carried out and is no less than 30min；
800~1000 DEG C are warming up to structure of composite membrane material precursor again, heat preservation heat treatment is carried out and is no less than 30min；
The structure of composite membrane material precursor for keeping the temperature heat treatment again is warming up to 800~1000 DEG C, is heat-treated no less than 30min；
1200 DEG C are warming up to structure of composite membrane material precursor again, heat preservation heat treatment is carried out and is no less than 30min；
Structure of composite membrane material precursor is warming up to not higher than 1400 DEG C again, heat preservation heat treatment is carried out and is no less than 120min, thus
Obtain vertical orientation carbon nano pipe array and graphene composite film.
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