CN110041571A - A kind of preparation method of high thermal conductivity graphene composite material - Google Patents
A kind of preparation method of high thermal conductivity graphene composite material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of high thermal conductivity graphene composite material, specially by the method in graphene nanometer sheet/natural rubber dispersion liquid insertion chemical vapour deposition technique preparation three-dimensional graphene foam, the graphene composite material that this method obtains can be used as lateral heat conducting and heat radiating fin and hot interface cooling fin.The preparation method, which specifically includes that disperse graphene nanometer sheet in natural rubber solution, prepares graphene nanometer sheet/natural rubber dispersion liquid；Dispersion liquid is poured into the mold equipped with three-dimensional graphene foam, spontaneously dries or heating is dried, prepare graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material；High thermal conductivity graphene composite material is obtained by hot-press vulcanization.Present invention process is simple, solves original Heat Conduction Material and heat filling is excessively used, such as: aluminum oxide, aluminium nitride, silicon carbide, copper, silver, caused by mechanical properties decrease and shortage of resources, the problems such as expensive and the device is complicated.
Description
Technical field
The present invention relates to graphene nanometer sheet, three-dimensional graphene foam, natural rubber, graphene nanometer sheets/natural rubber
It is embedded in the manufacture craft field of three-dimensional graphene foam pore structure, the vulcanization of rubber, specially a kind of high thermal conductivity graphene composite wood
The preparation method of material, the graphene composite material that this method obtains can be used as lateral heat conducting and heat radiating fin and hot interface cooling fin.
Background technique
Heat-conductive composite material is important component indispensable in high power consumption electronic device, is to guarantee that electronic device is long
The key run under time normal operation or high power consumption.Heat-conductive composite material be heat filling is evenly dispersed into it is polymer-based
A kind of composite material formed in body.Heat-conductive composite material mainly includes two aspect content of heat filling and macromolecule matrix,
Middle heat filling is usually by Al2O3, AlN, SiC, MgO, ZnO composition, and the highest aluminium oxide thermal coefficient of frequency of use~
30W/mK, i.e., the common general thermal coefficient of heat filling is low, and filler loading is big (50wt%~70wt%).
Heat-conductive composite material is widely used for the medium between electronic device and radiator, such as: semiconductor power device
In part, integrated circuit, LED encapsulation, high power power module, high-speed memory chip and communication apparatus.Various high power electronics
Interconnection technique between device or easy heat generating device and radiator is all radiated using to heat-conductive composite material with meeting this kind of material
Demand.Graphene Heat Conduction Material has many advantages, such as that such as: the intrinsic thermal conductivity of graphene is more than compared with traditional Heat Conduction Material
5000W/mK, flexible, light weight, filler additive amount is few, corrosion-resistant, easily with basis material machine-shaping.
And use traditional heat filling (such as: Al2O3, AlN, SiC etc.), cause filler additive amount big, difficulty of processing is big,
Mechanical properties decrease limits its application field.Use graphene as heat filling, not only heating conduction is made to get a promotion, and
And technique can be made to simplify, reduce equipment cost etc..With the continuous deepening of research, just gradually substitution passes graphene Heat Conduction Material
System Heat Conduction Material, constantly expansion application field, become the mainstream Heat Conduction Material of a new generation.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of high thermal conductivity graphene composite material, this method preparation processes
Simply, high-efficient, without vacuum, easy to operate, it is big and be difficult to constitute complete to solve heat filling additive amount in macromolecule matrix
Thermal conducting path the problem of.
Technical solution of the present invention:
A kind of preparation method of high thermal conductivity graphene composite material, it is embedding using graphene nanometer sheet/natural rubber dispersion liquid
Enter three-dimensional graphene foam, specifically includes that
(1) natural rubber is dissolved in the case where heating stirring using toluene solvant, form natural rubber solution；
(2) it is dispersed graphene nanometer sheet in toluene using ultrasonic wave, forms graphene nanometer sheet dispersion liquid；By graphite
Alkene nanometer sheet dispersion liquid is added in natural rubber solution, forms graphene nanometer sheet/natural rubber dispersion liquid；
(3) graphene nanometer sheet/natural rubber is added in stearic acid, sulphur, dibenzothiazyl disulfide and zinc oxide to disperse
In liquid；
(4) solution that (3) obtain is poured into the Teflon mould equipped with three-dimensional graphene foam, using naturally dry
Dry or heating drying removal toluene solvant, obtains graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material；
(5) high thermal conductivity graphene nanometer sheet/three-dimensional graphene foam/natural rubber composite wood is obtained by hot-press vulcanization
Material.
The preparation method of the high thermal conductivity graphene composite material in step (1), dissolves the technique ginseng of natural rubber
Number: temperature is 40~70 DEG C, and magnetic agitation speed is 200~1000r/min, and mixing time is 3~8h.
The preparation method of the high thermal conductivity graphene composite material, 3~5 μm of graphene nanometer sheet size, the number of plies
≤ 10, three-dimensional graphene foam is prepared using chemical vapour deposition technique, porosity of=99.58%, and hole size is 400~600 μm.
The preparation method of the high thermal conductivity graphene composite material, natural rubber are the natural rubber rubber smoked sheet of level-one.
The preparation method of the high thermal conductivity graphene composite material prepares graphene nanometer sheet/natural rubber dispersion liquid
When, the concentration of natural rubber solution is 12~40mg/ml, and the concentration of graphene nanometer sheet dispersion liquid is 6~12mg/ml, by weight
Graphene nanometer sheet dispersion liquid is added in natural rubber solution amount ratio 1:10~1:2, then through 60~90 DEG C of temperature, revolving speed
The heating stirring 2 of 600~1500r/min~for 24 hours, that is, obtain graphene nanometer sheet/natural rubber dispersion liquid.
The preparation method of the high thermal conductivity graphene composite material, in the solution that (3) obtain, stearic acid, sulphur, two sulphur
Change weight percent shared by bisbenzothiazole and zinc oxide and is respectively as follows: 1~5%, 2~8%, 0.2~0.7%, 3~10%.
The preparation method of the high thermal conductivity graphene composite material, in step (4), the natural drying time is 12~72h,
Heating drying are as follows: 30~90 DEG C of drying times are 6~12h, and graphene nanometer sheet/natural rubber is made to be embedded into three-dimensional grapheme bubble
In foam.
The preparation method of the high thermal conductivity graphene composite material, in step (5), graphene nanometer sheet/three-dimensional graphite
Alkene foam/native rubber composite material, which is put into cast iron die, carries out hot-press vulcanization: 140~170 DEG C of temperature, pressure 5~
15MPa, 1~5h of time align graphene nanometer sheet and composite material densification, and thermal conductivity is promoted.
The preparation method of the high thermal conductivity graphene composite material, in high thermal conductivity graphene nanometer sheet/three-dimensional grapheme
In foam/native rubber composite material, graphene content is 8~25wt%, 8~12W/mK of thermal conductivity in face, vertical thermal conductivity 2
~4W/mK.
Design philosophy of the invention is:
The method of the present invention, which specifically includes that disperse graphene nanometer sheet in natural rubber solution, prepares graphene nano
The right rubber dispersion of tablet per day；Dispersion liquid is poured into the mold equipped with three-dimensional graphene foam, spontaneously dries or heating is dried,
Prepare graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material；High thermal conductivity graphite is obtained by hot-press vulcanization
Alkene composite material.Graphene nanometer sheet/natural rubber dispersion liquid is embedded in the three of chemical vapour deposition technique (CVD) preparation by the present invention
It ties up in grapheme foam, and the system by the method for hot-press vulcanization, suitable for lateral quick conductive cooling fin, hot interface cooling fin
Standby and relative high power consumption electronic product rapid cooling component packaging technology.
The invention has the advantages and beneficial effects that:
1, the present invention proposes graphene direct construction three-dimensional network thermal conducting path in macromolecule matrix, with traditional filler
Compared to (Al2O3, AlN, SiC), filler additive amount reduces, and thermal conductivity dramatically increases, provide one be applied to about graphene it is thermally conductive
The new approaches of composite material.Thermal conducting path is to prepare heat-conductive composite material, realizes that three-dimensional grapheme thermal conducting path exists
It is complete in macromolecule matrix, furthermore graphene nanometer sheet is along three-dimensional graphene foam hole formation thermal conducting path and orientation row
Column, thermal conducting path increase.
2, preparation process of the present invention is simple, and required equipment requirement is low, easy large-scale production, and it is excessive to solve original Heat Conduction Material
Using heat filling, such as: aluminum oxide (Al2O3), aluminium nitride (AlN), silicon carbide (SiC), copper (Cu), silver-colored (Ag) etc., cause
Mechanical properties decrease and shortage of resources, the problems such as expensive and the device is complicated.
Detailed description of the invention
Fig. 1 is flow diagram of the present invention using three-dimensional network building preparation high thermal conductivity graphene composite material method.
Fig. 2 (a) is high thermal conductivity graphene composite material shape appearance figure, and Fig. 2 (b) is graphene nanometer sheet/natural rubber and three
Grapheme foam framework morphology figure is tieed up, Fig. 2 (c) is to align graphene nanometer sheet shape appearance figure.
Specific embodiment
As shown in Figure 1, in a specific embodiment, the preparation method of high thermal conductivity graphene composite material of the present invention, specifically
Process is as follows:
(1) natural rubber is completely dissolved in the case where heating stirring (temperature is 40~70 DEG C, magnetic using toluene solvant
Power stirring rate is 200~1000r/min, and mixing time is 6~8h), then graphene nanometer sheet is dispersed in by ultrasonic wave
In toluene, graphene nanometer sheet dispersion liquid is added in natural rubber solution, (temperature is 60~90 under condition of heating and stirring
DEG C, stirring rate be 600~1500r/min, the time be 2~for 24 hours) obtain graphene nanometer sheet/natural rubber dispersion liquid, then
Stearic acid, sulphur, dibenzothiazyl disulfide (DM), zinc oxide are sequentially added, stearic acid and zinc oxide role are activity
Respectively role is vulcanizing agent and accelerator respectively for agent, sulphur and dibenzothiazyl disulfide (DM).
(2) graphene nanometer sheet/natural rubber dispersion liquid is poured into the polytetrafluoroethylene (PTFE) equipped with three-dimensional graphene foam
(PTFE) in mold, graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material is obtained, utilizes natural drying 12
~72h or 30~90 DEG C of 6~12h of drying removes toluene solvant.
(3) densification is carried out to composite material using hot-press vulcanization and graphene nanometer sheet orients, hot-press vulcanization condition is
140~170 DEG C, pressure is 5~15MPa, and the time is 1~5h.To obtain high thermal conductivity graphene nanometer sheet/three-dimensional grapheme bubble
Foam/native rubber composite material.
The preparation of three-dimensional graphene foam of the present invention: Chinese patent application (publication number: CN102674321A is used；Invention
A kind of title: grapheme foam and its magnanimity preparation method with three-dimensional full-mesh network；The applying date: March 10 in 2011
Day), graphene is grown on nickel foam porous metals surface, after etching away nickel foam, obtains three-dimensional graphene foam.
In the following, the present invention is described in further detail by embodiment and attached drawing.
Embodiment 1
In the present embodiment, high thermal conductivity graphene composite material the preparation method is as follows:
80~150ml toluene solvant is taken to dissolve 3g natural rubber in the case where heating stirring, temperature is 40 DEG C, magnetic force
Stirring rate is 300r/min, mixing time 6h, forms natural rubber solution.300~600mg of graphene nanometer sheet is taken, it will
Graphene nanometer sheet is dispersed in 60ml toluene by ultrasonic wave, forms graphene nanometer sheet dispersion liquid.By graphene nanometer sheet
Dispersion liquid is added in natural rubber solution, and heating stirring obtains graphene nanometer sheet/natural rubber dispersion liquid, and sequentially adds
0.03g stearic acid, 0.15g sulphur, 0.006g DM and 0.09g zinc oxide.Temperature is 60 DEG C, stirring rate 800r/min, the time
For 12h.
30ml graphene nanometer sheet/natural rubber dispersion liquid is taken to pour into the PTFE mold equipped with three-dimensional graphene foam,
Toluene solvant is removed using spontaneously drying, obtains graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material.
Densification is carried out to composite material using hot-press vulcanization and graphene nanometer sheet orients, hot-press vulcanization condition is 140
DEG C, pressure 10MPa, time 1h, so that it is compound to obtain high thermal conductivity graphene nanometer sheet/three-dimensional graphene foam/natural rubber
Material.Graphene content is 8~15wt%, thermal conductivity~10.0W/mK, vertical thermal conductivity~3.0W/mK in face.
As shown in Fig. 2 (a), smooth, fine and close, the nothing that can be seen that sample surfaces from high thermal conductivity graphene composite material pattern
Hole.
As shown in Fig. 2 (b), it can be seen that from graphene nanometer sheet/natural rubber and three-dimensional graphene foam framework morphology
Grapheme foam skeleton is combined closely with graphene nanometer sheet/natural rubber.
As shown in Fig. 2 (c), graphene nanometer sheet can be seen that along same from graphene nanometer sheet shape appearance figure is aligned
Direction arrangement, facilitates the promotion of this direction thermal conductivity.
Embodiment 2
In the present embodiment, high thermal conductivity graphene composite material the preparation method is as follows:
90ml toluene solvant is taken to dissolve 3g natural rubber in the case where heating stirring, temperature is 40 DEG C, magnetic agitation
Rate is 200r/min, mixing time 8h, forms natural rubber solution.Graphene nanometer sheet 400mg is taken, by graphene nano
Piece is dispersed in 80ml toluene by ultrasonic wave, forms graphene nanometer sheet dispersion liquid.Graphene nanometer sheet dispersion liquid is added
In natural rubber solution, heating stirring obtains graphene nanometer sheet/natural rubber dispersion liquid, and sequentially add 0.12g stearic acid,
0.15g sulphur, 0.021g DM and 0.09g zinc oxide.Temperature is 60 DEG C, stirring rate 800r/min, time 12h.
25ml graphene nanometer sheet/natural rubber dispersion liquid is taken to pour into the PTFE mold equipped with three-dimensional graphene foam,
Toluene solvant is removed using spontaneously drying, obtains graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material.
Densification is carried out to composite material using hot-press vulcanization and graphene nanometer sheet orients, hot-press vulcanization condition is 150
DEG C, pressure 15MPa, time 3h, so that it is compound to obtain high thermal conductivity graphene nanometer sheet/three-dimensional graphene foam/natural rubber
Material.Graphene content is 10wt%, thermal conductivity~8.0W/mK, vertical thermal conductivity~2.0W/mK in face.
Embodiment 3
In the present embodiment, high thermal conductivity graphene composite material the preparation method is as follows:
120ml toluene solvant is taken to dissolve 3g natural rubber in the case where heating stirring, temperature is 40 DEG C, magnetic agitation
Rate is 300~600r/min, and mixing time is 6~8h, forms natural rubber solution.Graphene nanometer sheet 500mg is taken, by stone
Black alkene nanometer sheet is dispersed in 100ml toluene by ultrasonic wave, forms graphene nanometer sheet dispersion liquid.By graphene nanometer sheet point
Dispersion liquid is added in natural rubber solution, and heating stirring obtains graphene nanometer sheet/natural rubber dispersion liquid, and sequentially adds
0.03g stearic acid, 0.12g sulphur, 0.021g DM and 0.24g zinc oxide.Temperature is 60 DEG C, stirring rate 1000r/min, when
Between be 12h.
30ml graphene nanometer sheet/natural rubber dispersion liquid is taken to be added in the PTFE mold equipped with three-dimensional graphene foam,
Toluene solvant is removed using spontaneously drying, obtains graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material.
Densification is carried out to composite material using hot-press vulcanization and graphene nanometer sheet orients, hot-press vulcanization condition is 150
DEG C, pressure 15MPa, time 3h obtain high thermal conductivity graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material.
Graphene content is 12wt%, thermal conductivity~10.5W/mK, vertical thermal conductivity~3.0W/mK in face.
Embodiment 4
In the present embodiment, high thermal conductivity graphene composite material the preparation method is as follows:
100ml toluene solvant is taken to dissolve 2g natural rubber in the case where heating stirring, temperature is 50 DEG C, magnetic agitation
Rate is 500r/min, and mixing time is 6~8h, forms natural rubber solution.400~500mg of graphene nanometer sheet is taken, by stone
Black alkene nanometer sheet is dispersed in 70ml toluene by ultrasonic wave, forms graphene nanometer sheet dispersion liquid.By graphene nanometer sheet point
Dispersion liquid is added in natural rubber solution, and heating stirring obtains graphene nanometer sheet/natural rubber dispersion liquid, and sequentially adds
0.03g stearic acid, 0.03g sulphur, 0.009g DM and 0.05g zinc oxide.Temperature is 80 DEG C, stirring rate 800r/min, the time
For 8~12h.
Take 35~40ml graphene nanometer sheet/natural rubber dispersion liquid that the PTFE mold that three-dimensional graphene foam is housed is added
In, toluene solvant is removed using spontaneously drying, obtains graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material.
Densification is carried out to composite material using hot-press vulcanization and graphene nanometer sheet orients, hot-press vulcanization condition is 160
DEG C, 9~10MPa of pressure, time 5h obtain high thermal conductivity graphene nanometer sheet/three-dimensional graphene foam/natural rubber composite wood
Material.Graphene content is 18~25wt%, thermal conductivity~9.0W/mK, vertical thermal conductivity~2.2W/mK in face.
Embodiment 5
In the present embodiment, high thermal conductivity graphene composite material the preparation method is as follows:
80 toluene solvants are taken to dissolve 2g natural rubber in the case where heating stirring, temperature is 70 DEG C, magnetic agitation speed
Rate is 600r/min, mixing time 8h, forms natural rubber solution.350~400mg of graphene nanometer sheet is taken, by graphene
Nanometer sheet is dispersed in 60ml toluene by ultrasonic wave, forms graphene nanometer sheet dispersion liquid.By graphene nanometer sheet dispersion liquid
It is added in natural rubber solution, heating stirring obtains graphene nanometer sheet/natural rubber dispersion liquid, and it is hard to sequentially add 0.03g
Resin acid, 0.02g sulphur, 0.005g DM and 0.06g zinc oxide.Temperature be 70 DEG C, stirring rate 900r/min, the time be 8~
12h。
Take 35~40ml graphene nanometer sheet/natural rubber dispersion liquid that the PTFE mold that three-dimensional graphene foam is housed is added
In, toluene solvant is removed using 90 DEG C of heating, dryings, it is compound to obtain graphene nanometer sheet/three-dimensional graphene foam/natural rubber
Material.
Densification is carried out to composite material using hot-press vulcanization and graphene nanometer sheet orients, hot-press vulcanization condition is 170
DEG C, pressure 15MPa, time 1h obtain high thermal conductivity graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material.
Graphene content is 15~19wt%, thermal conductivity~8.5W/mK, vertical thermal conductivity~2.8W/mK in face.
Embodiment 6
In the present embodiment, high thermal conductivity graphene composite material the preparation method is as follows:
120~150ml toluene solvant is taken to dissolve 4g natural rubber in the case where heating stirring, temperature is 50 DEG C, magnetic
Power stirring rate is 1000r/min, and mixing time is 6~8h, forms natural rubber solution.Take graphene nanometer sheet 500~
Graphene nanometer sheet is dispersed in 120ml toluene by 700mg by ultrasonic wave, forms graphene nanometer sheet dispersion liquid.By graphite
Alkene nanometer sheet dispersion liquid is added in natural rubber solution, and heating stirring obtains graphene nanometer sheet/natural rubber dispersion liquid, and according to
Secondary addition 0.09g stearic acid, 0.08g sulphur, 0.018g DM and 0.15g zinc oxide.Temperature is 70 DEG C, stirring rate 1000r/
Min, time are 8~12h.
40ml graphene nanometer sheet/natural rubber dispersion liquid is taken to be added in the PTFE mold equipped with three-dimensional graphene foam,
Toluene solvant is removed using spontaneously drying, obtains graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material.
Densification is carried out to composite material using hot-press vulcanization and graphene nanometer sheet orients, hot-press vulcanization condition is 150
DEG C, it is compound to obtain high thermal conductivity graphene nanometer sheet/three-dimensional graphene foam/natural rubber by 8~10MPa of pressure, time 1.5h
Material.Graphene content is 10~17wt%, thermal conductivity~10.5W/mK, vertical thermal conductivity~3.5W/mK in face.
Embodiment 7
In the present embodiment, high thermal conductivity graphene composite material the preparation method is as follows:
120~150ml toluene solvant is taken to dissolve 4g natural rubber in the case where heating stirring, temperature is 40 DEG C, magnetic
Power stirring rate is 300r/min, mixing time 8h, forms natural rubber solution.Graphene nanometer sheet 700mg is taken, by graphite
Alkene nanometer sheet is dispersed in 100ml toluene by ultrasonic wave, forms graphene nanometer sheet dispersion liquid.Graphene nanometer sheet is dispersed
Liquid is added in natural rubber solution, and heating stirring obtains graphene nanometer sheet/natural rubber dispersion liquid, and sequentially adds 0.15g
Stearic acid, 0.09g sulphur, 0.028g DM and 0.2g zinc oxide.Temperature be 60 DEG C, stirring rate 1500r/min, the time be 8~
12h。
25ml graphene nanometer sheet/natural rubber dispersion liquid is taken to be added in the PTFE mold equipped with three-dimensional graphene foam,
Toluene solvant is removed using spontaneously drying, obtains graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material.
Densification is carried out to composite material using hot-press vulcanization and graphene nanometer sheet orients, hot-press vulcanization condition is 140
DEG C, pressure 12MPa, time 1h obtain high thermal conductivity graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material.
Graphene content is 16wt%, thermal conductivity~11.0W/mK, vertical thermal conductivity~4.0W/mK in face.
Embodiment 8
In the present embodiment, high thermal conductivity graphene composite material the preparation method is as follows:
180ml toluene solvant is taken to dissolve 5g natural rubber in the case where heating stirring, temperature is 70 DEG C, magnetic agitation
Rate is 800r/min, and mixing time is 6~8h, forms natural rubber solution.Graphene nanometer sheet 800mg is taken, by graphene
Nanometer sheet is dispersed in 100ml toluene by ultrasonic wave, forms graphene nanometer sheet dispersion liquid.By graphene nanometer sheet dispersion liquid
It is added in natural rubber solution, heating stirring obtains graphene nanometer sheet/natural rubber dispersion liquid, and sequentially adds 0.2g tristearin
Acid, 0.2g sulphur, 0.025g DM and 0.2g zinc oxide.Temperature is 70 DEG C, stirring rate 1000r/min, and the time is 8~12h.
30ml graphene nanometer sheet/natural rubber dispersion liquid is taken to be added in the PTFE mold equipped with three-dimensional graphene foam,
Toluene solvant is removed using 50 DEG C of heating, dryings, obtains graphene nanometer sheet/three-dimensional graphene foam/natural rubber composite wood
Material.
Densification is carried out to composite material using hot-press vulcanization and graphene nanometer sheet orients, hot-press vulcanization condition is 160
DEG C, pressure 15MPa, time 5h obtain high thermal conductivity graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material.
Graphene content is 14wt%, thermal conductivity~11.2W/mK, vertical thermal conductivity~4.0W/mK in face.
Embodiment 9
In the present embodiment, high thermal conductivity graphene composite material the preparation method is as follows:
200ml toluene solvant is taken to dissolve 5g natural rubber in the case where heating stirring, temperature is 50 DEG C, magnetic agitation
Rate is 400r/min, mixing time 8h, forms natural rubber solution.Graphene nanometer sheet 800mg is taken, by graphene nano
Piece is dispersed in 120ml toluene by ultrasonic wave, forms graphene nanometer sheet dispersion liquid.Graphene nanometer sheet dispersion liquid is added
In natural rubber solution, heating stirring obtains graphene nanometer sheet/natural rubber dispersion liquid, and sequentially add 0.15g stearic acid,
0.15g sulphur, 0.021g DM and 0.15g zinc oxide.Temperature is 50 DEG C, stirring rate 1000r/min, and the time is 8~12h.
Take 35~45ml graphene nanometer sheet/natural rubber dispersion liquid that the PTFE mold that three-dimensional graphene foam is housed is added
In, toluene solvant is removed using 50 DEG C of heating, dryings, it is compound to obtain graphene nanometer sheet/three-dimensional graphene foam/natural rubber
Material.
Densification is carried out to composite material using hot-press vulcanization and graphene nanometer sheet orients, hot-press vulcanization condition is 150
DEG C, pressure 10MPa, time 2h obtain high thermal conductivity graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material.
Graphene content is 12wt%, thermal conductivity~11.0W/mK, vertical thermal conductivity~3.5W/mK in face.
Embodiment 10
In the present embodiment, high thermal conductivity graphene composite material the preparation method is as follows:
260~300ml toluene solvant is taken to dissolve 5g natural rubber in the case where heating stirring, temperature is 60 DEG C, magnetic
Power stirring rate is 400r/min, mixing time 6h, forms natural rubber solution.Graphene nanometer sheet 1500mg is taken, by stone
Black alkene nanometer sheet is dispersed in 90ml toluene by ultrasonic wave, forms graphene nanometer sheet dispersion liquid.By graphene nanometer sheet point
Dispersion liquid is added in natural rubber solution, and heating stirring obtains graphene nanometer sheet/natural rubber dispersion liquid, and sequentially adds
0.20g stearic acid, 0.15g sulphur, 0.012g DM and 0.20g zinc oxide.Temperature is 60 DEG C, stirring rate 1000r/min, when
Between be 8~12h.
30ml graphene nanometer sheet/natural rubber dispersion liquid is taken to be added in the PTFE mold equipped with three-dimensional graphene foam,
Toluene solvant is removed using 80 DEG C of heating, dryings, obtains graphene nanometer sheet/three-dimensional graphene foam/natural rubber composite wood
Material.
Densification is carried out to composite material using hot-press vulcanization and graphene nanometer sheet orients, hot-press vulcanization condition is 140
DEG C, pressure 10MPa, time 5h obtain high thermal conductivity graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material.
Graphene content is 25wt%, thermal conductivity~11.6W/mK, vertical thermal conductivity~3.8W/mK in face.
Embodiment the result shows that, the present invention realize in macromolecule matrix low content heat filling direct construction three dimentional heat conduction
Access, resulting graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material have high thermal conductivity.
Claims (9)
1. a kind of preparation method of high thermal conductivity graphene composite material, which is characterized in that utilize graphene nanometer sheet/natural rubber
Dispersion liquid is embedded in three-dimensional graphene foam, specifically includes that
(1) natural rubber is dissolved in the case where heating stirring using toluene solvant, form natural rubber solution；
(2) it is dispersed graphene nanometer sheet in toluene using ultrasonic wave, forms graphene nanometer sheet dispersion liquid；Graphene is received
Rice piece dispersion liquid is added in natural rubber solution, forms graphene nanometer sheet/natural rubber dispersion liquid；
(3) stearic acid, sulphur, dibenzothiazyl disulfide and zinc oxide are added in graphene nanometer sheet/natural rubber dispersion liquid；
(4) by (3) obtain solution pour into the Teflon mould equipped with three-dimensional graphene foam, using spontaneously dry or
Heating drying removal toluene solvant, obtains graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material；
(5) high thermal conductivity graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material is obtained by hot-press vulcanization.
2. the preparation method of high thermal conductivity graphene composite material described in accordance with the claim 1, which is characterized in that in step (1),
Dissolve the technological parameter of natural rubber: temperature is 40~70 DEG C, and magnetic agitation speed is 200~1000r/min, and mixing time is
3~8h.
3. the preparation method of high thermal conductivity graphene composite material described in accordance with the claim 1, which is characterized in that graphene nano
3~5 μm of chip size size, the number of plies≤10, three-dimensional graphene foam is prepared using chemical vapour deposition technique, porosity of=
99.58%, hole size is 400~600 μm.
4. the preparation method of high thermal conductivity graphene composite material described in accordance with the claim 1, which is characterized in that natural rubber is
The natural rubber rubber smoked sheet of level-one.
5. the preparation method of high thermal conductivity graphene composite material described in accordance with the claim 1, which is characterized in that prepare graphene
When nanometer sheet/natural rubber dispersion liquid, the concentration of natural rubber solution is 12~40mg/ml, graphene nanometer sheet dispersion liquid
Concentration is 6~12mg/ml, and graphene nanometer sheet dispersion liquid is added in natural rubber solution ratio 1:10~1:2 by weight, then
Through 60~90 DEG C of temperature, the heating stirring 2 of 600~1500r/min of revolving speed~for 24 hours, i.e. acquisition graphene nanometer sheet/natural rubber
Dispersion liquid.
6. according to the preparation method of high thermal conductivity graphene composite material described in claim 1 and 3, which is characterized in that obtained in (3)
Solution in, weight percent shared by stearic acid, sulphur, dibenzothiazyl disulfide and zinc oxide is respectively as follows: 1~5%, 2~
8%, 0.2~0.7%, 3~10%.
7. the preparation method of high thermal conductivity graphene composite material described in accordance with the claim 1, which is characterized in that in step (4),
The natural drying time is 12~72h, heating drying are as follows: 30~90 DEG C of drying times are 6~12h, make graphene nanometer sheet/natural
Rubber is embedded into three-dimensional graphene foam.
8. the preparation method of high thermal conductivity graphene composite material described in accordance with the claim 1, which is characterized in that in step (5),
Graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material, which is put into cast iron die, carries out hot-press vulcanization: temperature
140~170 DEG C, 5~15MPa of pressure, 1~5h of time, align graphene nanometer sheet and composite material densification, thermal conductivity
Rate is promoted.
9. according to the preparation method of high thermal conductivity graphene composite material described in claim 1 or 8, which is characterized in that led in height
In hot graphene nanometer sheet/three-dimensional graphene foam/native rubber composite material, graphene content is 8~25wt%, heat in face
Conductance 8~12W/mK, vertical 2~4W/mK of thermal conductivity.
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