CN109554168A - Carbon nano pipe array/graphene heat-conductive composite material and preparation method thereof - Google Patents
Carbon nano pipe array/graphene heat-conductive composite material and preparation method thereof Download PDFInfo
- Publication number
- CN109554168A CN109554168A CN201710867364.3A CN201710867364A CN109554168A CN 109554168 A CN109554168 A CN 109554168A CN 201710867364 A CN201710867364 A CN 201710867364A CN 109554168 A CN109554168 A CN 109554168A
- Authority
- CN
- China
- Prior art keywords
- graphene
- carbon nano
- pipe array
- nano pipe
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/08—Interconnection of layers by mechanical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/025—Particulate layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/042—Bituminous or tarry substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/107—Ceramic
- B32B2264/108—Carbon, e.g. graphite particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
Abstract
The invention discloses a kind of carbon nano pipe array/graphene heat-conductive composite material preparation methods, carbon nano pipe array and Bidirectional hot press oriented moulding heat conductive graphite piece are grown on graphene, realize directional carbon nanotube array along axial with high thermal conductivity in the compound of graphene of the in-plane with high thermal conductivity, by Bidirectional hot press composite material is densified, it obtains thermal conductivity and is greater than 500W/ (mK) along in-plane, through-thickness is greater than the graphite composite heat conducting sheet of 20W/ (mK).
Description
Technical field
The present invention relates to carbon nano pipe array/graphene heat-conductive composite material preparation method, specifically one kind exists
The preparation method of carbon nano pipe array and Bidirectional hot press oriented moulding heat conductive graphite piece is grown on graphene.
Background technique
Science and technology achieves the development of high speed since 21st century, and efficient heat transfer and heat dissipation become heat management
The critical problem of Material Field.Such as during heat generating device arrangement works, because of the resistance of device itself, thermal resistance, electricity
The effects such as son vortex, build up amount of heat, especially at the position that component density is high, heat-dissipating space is narrow, hot-fluid is close
Degree can be especially big, extremely uneven so as to cause integral member temperature.Most of microelectronic chip surface temperature must be maintained at
(such as 100 DEG C of silicon device ﹤) just can ensure that its high performance operation under lower level, and many electronic components are needed at 40~60 DEG C
At a temperature of could work normally, this proposes increasingly higher demands to Heat Conduction Material, and can device heat production be discharged in time, device
Part heat dissipation whether uniform high-efficiency be electronic device can fast and stable work deciding factor, greatly affected electronic equipment
Performance and quality.In order to by these heat derives, need in a hurry in time development quality is lighter, thermal conductivity is higher, performance more
Excellent thermally conductive new material.
Graphene is a kind of planar sheet nano material obtained by natural flake graphite through peroxidating, intercalation, removing.Stone
Black alkene is since with regular orderly graphite atomic layer, the obstruction of phonon conduction is less, and in-plane defects are less, and heat transfer efficiency is very
Height, thus using graphene or graphene paper prepare carbon-based highly heat-conductive material become people research emphasis, also there is class
Like the authorization or openly of patent.State Intellectual Property Office of the People's Republic of China's grant number be CN103449421B,
The patents of invention such as CN103805144A, CN102573413A disclose the technology using graphene preparation thermally-conductive sheet.
Above-described patent of invention discloses only traditional graphene preparation method and combination process, is only had
There is the graphene Heat Conduction Material of anisotropic heat conductivity.And for graphene sheet layer, the lattice vibration of carbon atom is material conducts heat
Basis, therefore phonon transmitting can only carry out travel at high speeds along graphite crystal face in graphene paper material, and for graphite wafer surface layer
Between due to hypertelorism, seriously affect the conduction of phonon.After graphene filter membrane process, graphene crystal face is in hot pressing
It is orientated under effect along in-plane, thus only along in-plane there is high heat conductance (to be greater than in graphene thermally conductive sheet
1000W/ (mK)), and through-thickness thermal conductivity is very low, less than 20W/ (mK) (Balandin AA.Thermal
properties of graphene and nanostructured carbon materials.[J].Nature
Material,2011,10(10):569-81.).The announcements such as patent application CN103449421B, CN103805144A of China
The thermal conductivity of graphene heat-conducting plate through-thickness all 10W/ (mK) below.Therefore, existing published patent of invention institute
The through-thickness thermal coefficient for obtaining material leads Heat Conduction Material far from mainframe computer, highly integrated electronic device etc. is met
The requirement of thermal energy power, developed on the basis of carbon material is advantageous it is a kind of and meanwhile have along the high thermal conductivity of thickness and in-plane,
The material of less anisotropy is particularly important.
Summary of the invention
The graphite paper thermally conductive sheet through-thickness thermal conductivity that the present invention is prepared for existing cool molded graphite alkene or expanded graphite
Too low deficiency, provide it is a kind of along plane and thickness direction all have high thermal conductivity can i.e. low anisotropic heat conductivity thermally conductive stone
Ink sheet and preparation method thereof.500-550W/ (mK) and 20-50W/ (mK) are respectively reached along plane and thickness direction thermal conductivity
Graphite heat-conducting fin, as shown in Figure 1.
The technical solution adopted to achieve the purpose of the present invention is:
A kind of preparation method of carbon nano pipe array/graphene heat-conductive composite material, comprising the following steps:
Mesophase pitch is dissolved in dimethylbenzene, the dipping solution that concentration is 0.3~0.7mg/ml is made, by carbon nano-pipe array
Column/graphene composite powder, which immerses in maceration extract, is placed in vacuum oven progress air drying after vacuum impregnation 24~48 hours
24~36 hours, the dried powder of acquisition is placed in compacting tool set, with 300~800 DEG C and 5~20MPa in argon atmosphere
Pressure at right angle and 5~20MPa horizontal pressure force synergy under carry out hot-forming, and pressure maintaining 0.5~5 hour, obtain
The carbon nano pipe array arrived/graphene heat-conductive composite material, the carbon nano pipe array/graphene heat-conductive composite material be by with
The graphene of growth carbon nano pipe array is the chip solid structure that structural unit carries out that connection stacking obtains layer by layer, and described
Microcosmic fold occurs for carbon nano pipe array-graphene sheet layer.
Preferably, the preparation of the carbon nano pipe array/graphene composite powder is the following steps are included: by poly dimethyl silicon
Oxygen alkane/graphene powder is placed in the flat-temperature zone of vacuum tube furnace, is passed through argon gas as protection gas, by process control after being evacuated to vacuum
Heating is at the uniform velocity warming up to 1100~1400 DEG C with 10~15 DEG C/min and keeps the temperature 0.5~2 hour, it is former to obtain silicon carbide/graphene
Ferrocene is dissolved in xylene solution and the complex catalyst precursor liquid that concentration is 0.02~0.05g/ml is made, by vacuum tube furnace by material
Cooled down by process control, 700~900 DEG C, after reaching set temperature is at the uniform velocity cooled to 10~15 DEG C/min, by complex catalyst precursor
Liquid is at the uniform velocity pushed into vacuum tube furnace with 0.2~0.6ml/min and stablizes heat preservation 10~60 minutes, carries out carbon nano pipe array
Growth, obtains carbon nano pipe array/graphene composite powder, the carbon nano pipe array/graphene is multiple after being cooled to room temperature
Closing powder is the graphene for growing carbon nano pipe array.
Preferably, the preparation of the dimethyl silicone polymer/graphene powder is the following steps are included: by dry graphene
Powder is immersed in the xylene solution that dimethyl silicone polymer concentration is 0.1~0.3g/ml, with 300~600r/min room temperature
Stirring 10~30 minutes, will be 3~5 hours dry with 50~70 DEG C in filter cake merging air dry oven after suction filtration, is prepared poly-
Dimethyl siloxane/graphene powder.
Preferably, the graphene powder preparation the following steps are included: by expanded graphite be add to deionized water into
Row ultrasound removing, is removed 0.5~2 hour with the power room temperature of 200~300W, then using vacuum filter membrane to graphite obtained
Alkene-aqueous mixtures are filtered, separation graphene filter cake and vacuum filter membrane, and filter cake merging vacuum oven is carried out air drying
18~24 hours, obtain dry graphene powder.
Preferably, the preparation method of the expanded graphite is as follows, using commercially available expansible graphite through 900-1100 DEG C of high temperature
After expanding 5-15s, expanded graphite is obtained.
Preferably, the length of carbon nanotube is greater than 20 μm in the carbon nano pipe array/graphene composite powder, and array is close
Degree is greater than 2 × 108cm-2。
Preferably, the vacuum-impregnated vacuum condition is that air pressure is lower than 20Pa.
Preferably, the vacuum condition of the vacuum filtration is that air pressure is lower than 20Pa.
Preferably, the vacuum filter sizes are 0.2~1 μm.
Another aspect of the present invention further includes that carbon nano pipe array/graphene for being obtained by the preparation method is thermally conductive multiple
Condensation material stacks obtained chip solid to carry out connection layer by layer by structural unit of the graphene for growing carbon nano pipe array
Structure, and microcosmic fold occurs for the carbon nano pipe array-graphene sheet layer.
Preferably, the carbon nano pipe array/graphene heat-conductive composite material is 430- along the thermal conductivity of in-plane
550W/ (mK), preferably 500-550W/ (mK), through-thickness thermal conductivity are 20-50W/ (mK), preferably 40-
50W/(m·K)。
Compared with prior art, the beneficial effects of the present invention are:
1, due to graphene, direction has high thermal conductivity coefficient along face, and normal direction thermal coefficient is very low.It is grown on its surface
Directional carbon nanotube array and graphene will generate the pleat for being intended to stand vertically during subsequent Bidirectional hot press
Wrinkle increases the mechanical strength of thickness direction passage of heat and composite material.Using carbon nanotube along axial direction and graphene along face
Interior high-termal conductivity is able to achieve the transmitting of hot-fluid between graphene layer, this is very beneficial for improving leading for composite material through-thickness
Thermal energy power reduces its anisotropic heat conductivity.
2, it is formed by the compound and Bidirectional hot press of the graphene of above step and directional carbon nanotube array, realizes edge
The axial directional carbon nanotube array with high thermal conductivity in the compound of graphene of the in-plane with high thermal conductivity,
By Bidirectional hot press composite material is densified, obtains thermal conductivity along in-plane and be greater than 500W/ (mK), through-thickness
Greater than the graphite composite heat conducting sheet of 20W/ (mK).
3, matrix material expanded graphite of the invention is cheap and easy to get, and the growth of directional carbon nanotube array is simply controllable.This
Microstructure ordering, densification, graphitization and material molding can be completed efficiently in invention, and having for can obtaining is lower thermally conductive each
The C-base composte material thermally conductive sheet of anisotropy energy, the capacity of heat transmission are far superior to traditional expanded graphite coiled material and other graphite
Alkene and carbon fibre composite.
Detailed description of the invention
Fig. 1 is the microcosmic schematic diagram of thermally conductive sheet of the invention, including complex form and hot pressing direction；
Fig. 2 is macroscopical picture of expanded graphite；
Fig. 3 is carbon nano pipe array/graphene heat-conductive composite material scanning electron microscopic picture.
Specific embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.It should be appreciated that described herein
Specific embodiment be only used to explain the present invention, be not intended to limit the present invention.
Embodiment 1
1g expanded graphite (as shown in Figure 2) is add to deionized water the ultrasonic removing of progress, with the power room temperature of 200W
Then removing 0.5 hour filters graphene-aqueous mixtures obtained using vacuum filter membrane, separation graphene filter cake with
Filter cake merging vacuum oven is carried out air drying 18 hours, obtains dry graphene powder by vacuum filter membrane；
Dry graphene powder is immersed in the xylene solution that dimethyl silicone polymer concentration is 0.1g/ml, with
300r/min stirring at normal temperature 10 minutes, will be 3 hours dry with 50 DEG C in filter cake merging air dry oven after suction filtration, it is prepared poly-
Dimethyl siloxane/graphene powder；
Dimethyl silicone polymer/graphene powder that second step is prepared is placed in the flat-temperature zone of vacuum tube furnace, takes out
It is passed through argon gas after to vacuum as protection gas, is heated up by process control, is at the uniform velocity warming up to 1100 DEG C with 10 DEG C/min and keeps the temperature 0.5
Hour, obtain silicon carbide/graphene raw material.By ferrocene be dissolved in xylene solution be made concentration be 0.02g/ml catalyst before
Liquid is driven, vacuum tube furnace is cooled down by process control, is at the uniform velocity cooled to 700 DEG C, after reaching set temperature with 10 DEG C/min, application
Complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube furnace simultaneously by injector for medical purpose under the action of delicate flow pumps with 0.2ml/min
Stablize heat preservation 10 minutes, carries out the growth of carbon nano pipe array, it is multiple that carbon nano pipe array/graphene is obtained after being cooled to room temperature
Close powder；
Mesophase pitch is dissolved in dimethylbenzene, the dipping solution that concentration is 0.3mg/ml is made, by carbon nano pipe array/stone
Black alkene composite powder tailpiece, which immerses, is placed in vacuum oven progress air drying 24 hours after vacuum impregnation 24 hours in maceration extract,
By in the dried powder of acquisition merging compacting tool set, with 300 DEG C and 5MPa of pressure at right angle and 5MPa in argon atmosphere
It carries out hot-forming under the synergy of horizontal pressure force, and pressure maintaining 2 hours, obtains carbon nano pipe array/graphene composite material,
The microcosmic schematic diagram of the composite material is as shown in Figure 1, testing along in-plane thermal conductivity is 439W/ (mK), along thickness side
It is 26W/ (mK) to thermal conductivity, the test of the thermal conductivity of the present embodiment and following embodiment is to utilize Linseis LFA
What 1000 laser thermal conductivity test instrument were completed.
As shown in figure 3, the intermediate graphene sheet layer of the composite material is squeezed out fold, there is bending pattern to generate, two
Side all grown vertical carbon nano pipe array
Embodiment 2
2g expanded graphite is add to deionized water the ultrasonic removing of progress, with the removing of power room temperature 2 hours of 300W, so
Graphene-aqueous mixtures obtained are filtered using vacuum filter membrane afterwards, separation graphene filter cake and vacuum filter membrane, by filter cake
It is placed in vacuum oven to carry out air drying 20 hours, obtains dry graphene powder；Dry graphene powder is immersed
It, will after suction filtration with 300r/min stirring at normal temperature 20 minutes in the xylene solution for being 0.2g/ml to dimethyl silicone polymer concentration
It is 4 hours dry with 60 DEG C in filter cake merging air dry oven, dimethyl silicone polymer/graphene powder is prepared；By second
The flat-temperature zone that the dimethyl silicone polymer/graphene powder being prepared is placed in vacuum tube furnace is walked, is passed through argon after being evacuated to vacuum
Gas is heated up as protection gas by process control, is at the uniform velocity warming up to 1100 DEG C with 10 DEG C/min and is kept the temperature 0.5 hour, is carbonized
Silicon/graphene raw material.Ferrocene is dissolved in xylene solution, the complex catalyst precursor liquid that concentration is 0.02g/ml is made, by vacuum tube
Formula furnace is cooled down by process control, is at the uniform velocity cooled to 700 DEG C, after reaching set temperature with 10 DEG C/min, is existed using injector for medical purpose
Complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube furnace with 0.2ml/min under the action of delicate flow pump and stablizes 30 points of heat preservation
Clock, carries out the growth of carbon nano pipe array, and carbon nano pipe array/graphene composite powder is obtained after being cooled to room temperature；Will in
Between asphalt phase be dissolved in dimethylbenzene, be made concentration be 0.3mg/ml dipping solution, by carbon nano pipe array/graphene composite powder
Piece, which immerses, is placed in vacuum oven progress air drying 30 hours after vacuum impregnation 24 hours in maceration extract, by the drying of acquisition
Powder is placed in compacting tool set, with the horizontal pressure force of 500 DEG C and 10MPa of pressure at right angle and 100MPa in argon atmosphere
Carry out hot-forming under synergy, and pressure maintaining 3 hours, test was 486W/ (mK) along in-plane thermal conductivity, along thickness side
It is 42W/ (mK) to thermal conductivity.
Embodiment 3
1g expanded graphite is add to deionized water the ultrasonic removing of progress, it is small with the power room temperature removing 0.5~2 of 300W
When, then graphene-aqueous mixtures obtained are filtered using vacuum filter membrane, separation graphene filter cake and vacuum filter membrane,
Filter cake merging vacuum oven is carried out air drying 24 hours, dry graphene powder is obtained；By dry Graphene powder
End is immersed in the xylene solution that dimethyl silicone polymer concentration is 0.2g/ml, with 500r/min stirring at normal temperature 30 minutes, is taken out
Will be 4 hours dry with 50 DEG C in filter cake merging air dry oven after filter, dimethyl silicone polymer/graphene powder is prepared；
Dimethyl silicone polymer/graphene powder that second step is prepared is placed in the flat-temperature zone of vacuum tube furnace, after being evacuated to vacuum
Argon gas is passed through as protection gas, is heated up by process control, 1200 DEG C is at the uniform velocity warming up to 15 DEG C/min and keeps the temperature 0.5 hour, obtain
To silicon carbide/graphene raw material.Ferrocene is dissolved in xylene solution, the complex catalyst precursor liquid that concentration is 0.02g/ml is made, it will
Vacuum tube furnace is cooled down by process control, 800 DEG C, after reaching set temperature is at the uniform velocity cooled to 10 DEG C/min, using medical injection
Complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube furnace with 0.5ml/min under the action of delicate flow pumps and is stablized and protected by emitter
Temperature 10 minutes, carries out the growth of carbon nano pipe array, carbon nano pipe array/graphene composite powder is obtained after being cooled to room temperature
End；Mesophase pitch is dissolved in dimethylbenzene, the dipping solution that concentration is 0.5mg/ml is made, by carbon nano pipe array/graphene
Composite powder tailpiece, which immerses, is placed in vacuum oven progress air drying 36 hours after vacuum impregnation 36 hours in maceration extract, will obtain
In the dried powder merging compacting tool set obtained, with 400 DEG C and 20MPa of pressure at right angle and the water of 20MPa in argon atmosphere
Carry out hot-forming under the synergy of concora crush power, and pressure maintaining 3 hours, test was 530W/ (mK) along in-plane thermal conductivity,
Through-thickness thermal conductivity is 46W/ (mK).
Embodiment 4
1~2g expanded graphite is add to deionized water the ultrasonic removing of progress, it is small with the power room temperature removing 0.5 of 200W
When, then graphene-aqueous mixtures obtained are filtered using vacuum filter membrane, separation graphene filter cake and vacuum filter membrane,
Filter cake merging vacuum oven is carried out air drying 18 hours, dry graphene powder is obtained；By dry Graphene powder
End is immersed in the xylene solution that dimethyl silicone polymer concentration is 0.3g/ml, with 600r/min stirring at normal temperature 30 minutes, is taken out
Will be 4 hours dry with 50 DEG C in filter cake merging air dry oven after filter, dimethyl silicone polymer/graphene powder is prepared；
Dimethyl silicone polymer/graphene powder that second step is prepared is placed in the flat-temperature zone of vacuum tube furnace, after being evacuated to vacuum
Argon gas is passed through as protection gas, is heated up by process control, 1300 DEG C is at the uniform velocity warming up to 12 DEG C/min and keeps the temperature 0.5 hour, obtain
To silicon carbide/graphene raw material.Ferrocene is dissolved in xylene solution, the complex catalyst precursor liquid that concentration is 0.04g/ml is made, it will
Vacuum tube furnace is cooled down by process control, 880 DEG C, after reaching set temperature is at the uniform velocity cooled to 11 DEG C/min, using medical injection
Complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube furnace with 0.25ml/min under the action of delicate flow pumps and is stablized by emitter
Heat preservation 10 minutes, carries out the growth of carbon nano pipe array, carbon nano pipe array/graphene composite powder is obtained after being cooled to room temperature
End；Mesophase pitch is dissolved in dimethylbenzene, the dipping solution that concentration is 0.5mg/ml is made, by carbon nano pipe array/graphene
Composite powder tailpiece, which immerses, is placed in vacuum oven progress air drying 24 hours after vacuum impregnation 24 hours in maceration extract, will obtain
In the dried powder merging compacting tool set obtained, with 300 DEG C and 5MPa of pressure at right angle and the level of 5MPa in argon atmosphere
Carry out hot-forming under the synergy of pressure, and pressure maintaining 2 hours, test was 471W/ (mK), edge along in-plane thermal conductivity
Thickness direction thermal conductivity is 46W/ (mK).
Embodiment 5
1g expanded graphite is add to deionized water the ultrasonic removing of progress, is removed 0.5 hour with the power room temperature of 200W,
Then graphene-aqueous mixtures obtained are filtered using vacuum filter membrane, separation graphene filter cake and vacuum filter membrane will be filtered
Cake is placed in vacuum oven and carries out air drying 18 hours, obtains dry graphene powder；Dry graphene powder is soaked
Enter in the xylene solution for being 0.25g/ml to dimethyl silicone polymer concentration, with 500r/min stirring at normal temperature 20 minutes, filters
Afterwards will be 3 hours dry with 60 DEG C in filter cake merging air dry oven, dimethyl silicone polymer/graphene powder is prepared；It will
Dimethyl silicone polymer/graphene powder that second step is prepared is placed in the flat-temperature zone of vacuum tube furnace, leads to after being evacuated to vacuum
Enter argon gas as protection gas, heated up by process control, is at the uniform velocity warming up to 1050 DEG C with 10 DEG C/min and keeps the temperature 0.5 hour, obtain
Silicon carbide/graphene raw material.Ferrocene is dissolved in xylene solution, the complex catalyst precursor liquid that concentration is 0.02g/ml is made, it will be true
Empty tube furnace is cooled down by process control, 850 DEG C, after reaching set temperature is at the uniform velocity cooled to 10 DEG C/min, using medical injection
Complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube furnace with 0.2ml/min under the action of delicate flow pumps and stablizes heat preservation by device
30 minutes, the growth of carbon nano pipe array is carried out, carbon nano pipe array/graphene composite powder is obtained after being cooled to room temperature；
Mesophase pitch is dissolved in dimethylbenzene, the dipping solution that concentration is 0.6mg/ml is made, carbon nano pipe array/graphene is compound
Sheets of powder, which immerses, is placed in vacuum oven progress air drying 24 hours after vacuum impregnation 36 hours in maceration extract, by acquisition
Dried powder is placed in compacting tool set, with 500 DEG C and 8MPa of pressure at right angle and the horizontal pressure force of 8MPa in argon atmosphere
Synergy under carry out hot-forming, and pressure maintaining 2 hours, test was 434W/ (mK) along in-plane thermal conductivity, along thickness
Direction thermal conductivity is 47W/ (mK).
The above is only a preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of carbon nano pipe array/graphene heat-conductive composite material preparation method, which comprises the following steps:
Mesophase pitch is dissolved in dimethylbenzene, be made concentration be 0.3~0.7mg/ml dipping solution, by carbon nano pipe array/
Graphene composite powder, which immerses in maceration extract, is placed in vacuum oven progress air drying 24 after vacuum impregnation 24~48 hours
~36 hours, the dried powder of acquisition is placed in compacting tool set, with 300~800 DEG C and 5~20MPa in argon atmosphere
It carries out hot-forming under the synergy of the horizontal pressure force of pressure at right angle and 5~20MPa, and pressure maintaining 0.5~5 hour, obtains
Carbon nano pipe array/graphene heat-conductive composite material, the carbon nano pipe array/graphene heat-conductive composite material is by with life
The graphene of long carbon nano pipe array is that structural unit progress connection layer by layer stacks obtained chip solid structure, and the carbon
Microcosmic fold occurs for nano-tube array-graphene sheet layer.
2. a kind of preparation method of carbon nano pipe array/graphene heat-conductive composite material according to claim 1, feature
It is, the preparation of the carbon nano pipe array/graphene composite powder is the following steps are included: by dimethyl silicone polymer/graphite
Alkene powder is placed in the flat-temperature zone of vacuum tube furnace, is passed through argon gas as protection gas after being evacuated to vacuum, is heated up by process control, with 10
~15 DEG C/min is at the uniform velocity warming up to 1100~1400 DEG C and keeps the temperature 0.5~2 hour, obtains silicon carbide/graphene raw material, Jiang Ermao
Iron is dissolved in xylene solution and the complex catalyst precursor liquid that concentration is 0.02~0.05g/ml is made, by vacuum tube furnace by process control
Cooling, is at the uniform velocity cooled to 700~900 DEG C, after reaching set temperature with 10~15 DEG C/min, by complex catalyst precursor liquid with 0.2~
0.6ml/min is at the uniform velocity pushed into vacuum tube furnace and stablizes heat preservation 10~60 minutes, the growth of carbon nano pipe array is carried out, wait drop
Carbon nano pipe array/graphene composite powder is obtained after warming to room temperature.
3. a kind of preparation method of carbon nano pipe array/graphene heat-conductive composite material according to claim 2, feature
It is, the preparation of the dimethyl silicone polymer/graphene powder is the following steps are included: dry graphene powder is immersed in
Dimethyl silicone polymer concentration is in the xylene solution of 0.1~0.3g/ml, with 300~600r/min stirring at normal temperature 10~30
Minute, it will be 3~5 hours dry with 50~70 DEG C in filter cake merging air dry oven after suction filtration, polydimethylsiloxanes are prepared
Alkane/graphene powder.
4. a kind of preparation method of carbon nano pipe array/graphene heat-conductive composite material according to claim 3, feature
It is, the preparation of the graphene powder carries out ultrasonic removing the following steps are included: expanded graphite is add to deionized water,
Remove 0.5~2 hour with the power room temperature of 200~300W, then using vacuum filter membrane to graphene-aqueous mixtures obtained into
Row filters, separation graphene filter cake and vacuum filter membrane, and filter cake merging vacuum oven is carried out air drying 18~24 hours, is obtained
To dry graphene powder.
5. a kind of preparation method of carbon nano pipe array/graphene heat-conductive composite material according to claim 4, feature
Be, the preparation method of the expanded graphite is as follows, using commercially available expansible graphite through 900-1100 DEG C of high-temperature expansion 5-15s it
Afterwards, expanded graphite is obtained.
6. a kind of preparation method of carbon nano pipe array/graphene heat-conductive composite material according to claim 1, feature
Be, in the carbon nano pipe array/graphene composite powder the length of carbon nanotube be greater than 20 μm, array density be greater than 2 ×
108cm-2。
7. a kind of preparation method of carbon nano pipe array/graphene heat-conductive composite material according to claim 1, feature
It is, the vacuum-impregnated vacuum condition are as follows: air pressure is lower than 20Pa.
8. a kind of preparation method of carbon nano pipe array/graphene heat-conductive composite material according to claim 4, feature
It is, the vacuum condition of the vacuum filtration is that air pressure is lower than 20Pa, and the vacuum filter sizes are 0.2~1 μm.
9. carbon nano pipe array/graphene the heat-conductive composite material being prepared such as any one of claim 1-8 the method.
10. carbon nano pipe array as claimed in claim 9/graphene heat-conductive composite material, which is characterized in that the carbon nanometer
Pipe array/graphene heat-conductive composite material is 430-550W/ (mK), preferably 500-550W/ along the thermal conductivity of in-plane
(mK), through-thickness thermal conductivity is 20-50W/ (mK), preferably 40-50W/ (mK).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710867364.3A CN109554168A (en) | 2017-09-22 | 2017-09-22 | Carbon nano pipe array/graphene heat-conductive composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710867364.3A CN109554168A (en) | 2017-09-22 | 2017-09-22 | Carbon nano pipe array/graphene heat-conductive composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109554168A true CN109554168A (en) | 2019-04-02 |
Family
ID=65861780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710867364.3A Pending CN109554168A (en) | 2017-09-22 | 2017-09-22 | Carbon nano pipe array/graphene heat-conductive composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109554168A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110342497A (en) * | 2019-07-05 | 2019-10-18 | 上海大学 | Vertical orientation carbon nano pipe array and Graphene composite thin film material and preparation method thereof |
| CN113278406A (en) * | 2020-02-19 | 2021-08-20 | 国家能源投资集团有限责任公司 | Heat-conducting film composite material and preparation method thereof |
| CN114410115A (en) * | 2022-01-26 | 2022-04-29 | 常州富烯科技股份有限公司 | Graphene composite heat conduction gasket, preparation method and mold |
| CN114715884A (en) * | 2022-05-07 | 2022-07-08 | 广东墨睿科技有限公司 | Construction method of Z-axis heat conduction enhanced graphene heat conduction film, graphene heat conduction film and application of graphene heat conduction film |
| CN115368594A (en) * | 2022-09-02 | 2022-11-22 | 哈尔滨工业大学 | Oriented carbon-based electrothermal composite film and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104943223B (en) * | 2015-06-17 | 2016-09-07 | 天津大学 | There is graphite flake and the preparation method of high thermal conductivity coefficient along plane and thickness direction simultaneously |
| CN106010469A (en) * | 2016-05-16 | 2016-10-12 | 天津大学 | Carbon nanotube array/graphene paper heat-conducting composite material and preparation method |
| CN106086811A (en) * | 2016-06-14 | 2016-11-09 | 南昌大学 | A kind of simple and easy method preparing carbon nano pipe array Graphene mixed structure |
| CN107141803A (en) * | 2017-04-19 | 2017-09-08 | 天津大学 | The preparation method of carbon fiber carbon nano-tube array/silicones heat-conductive composite material |
-
2017
- 2017-09-22 CN CN201710867364.3A patent/CN109554168A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104943223B (en) * | 2015-06-17 | 2016-09-07 | 天津大学 | There is graphite flake and the preparation method of high thermal conductivity coefficient along plane and thickness direction simultaneously |
| CN106010469A (en) * | 2016-05-16 | 2016-10-12 | 天津大学 | Carbon nanotube array/graphene paper heat-conducting composite material and preparation method |
| CN106086811A (en) * | 2016-06-14 | 2016-11-09 | 南昌大学 | A kind of simple and easy method preparing carbon nano pipe array Graphene mixed structure |
| CN107141803A (en) * | 2017-04-19 | 2017-09-08 | 天津大学 | The preparation method of carbon fiber carbon nano-tube array/silicones heat-conductive composite material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110342497A (en) * | 2019-07-05 | 2019-10-18 | 上海大学 | Vertical orientation carbon nano pipe array and Graphene composite thin film material and preparation method thereof |
| CN113278406A (en) * | 2020-02-19 | 2021-08-20 | 国家能源投资集团有限责任公司 | Heat-conducting film composite material and preparation method thereof |
| CN114410115A (en) * | 2022-01-26 | 2022-04-29 | 常州富烯科技股份有限公司 | Graphene composite heat conduction gasket, preparation method and mold |
| CN114715884A (en) * | 2022-05-07 | 2022-07-08 | 广东墨睿科技有限公司 | Construction method of Z-axis heat conduction enhanced graphene heat conduction film, graphene heat conduction film and application of graphene heat conduction film |
| CN115368594A (en) * | 2022-09-02 | 2022-11-22 | 哈尔滨工业大学 | Oriented carbon-based electrothermal composite film and preparation method and application thereof |
| CN115368594B (en) * | 2022-09-02 | 2024-01-26 | 哈尔滨工业大学 | Directional carbon-based electric heating composite film and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109554168A (en) | Carbon nano pipe array/graphene heat-conductive composite material and preparation method thereof | |
| Liu et al. | Graphene foam-embedded epoxy composites with significant thermal conductivity enhancement | |
| Liu et al. | 3D lamellar-structured graphene aerogels for thermal interface composites with high through-plane thermal conductivity and fracture toughness | |
| CN106010469A (en) | Carbon nanotube array/graphene paper heat-conducting composite material and preparation method | |
| CN104943223B (en) | There is graphite flake and the preparation method of high thermal conductivity coefficient along plane and thickness direction simultaneously | |
| Wu et al. | Epoxy composites with high cross-plane thermal conductivity by constructing all-carbon multidimensional carbon fiber/graphite networks | |
| CN106543979B (en) | Graphite/carbon nanotube fibers beam/graphene thermally conductive laminated film preparation method | |
| CN107141803A (en) | The preparation method of carbon fiber carbon nano-tube array/silicones heat-conductive composite material | |
| CN104961464B (en) | Through-thickness has high resilience and high thermal conductivity coefficient C-base composte material and preparation method | |
| CN105859291B (en) | The preparation method of three-dimensional highly-conductive hot carbon based composites | |
| CN105110779B (en) | It is a kind of to weld the method that whisker prepares mullite porous ceramic | |
| CN108796397A (en) | A kind of preparation method of graphene/carbon SiClx/aluminium composite material | |
| CN113771443A (en) | Graphene heat conduction gasket enhanced by sintered graphene foam block and preparation method thereof | |
| CN109246977A (en) | A kind of preparation method of high thermal conductivity graphite composite material | |
| CN106565263B (en) | A kind of preparation method of carbon nanotube/silicon carbide heat-conductive composite material | |
| Wan et al. | Enhanced in-plane thermal conductivity and mechanical strength of flexible films by aligning and interconnecting Si3N4 nanowires | |
| Zhang et al. | Radially oriented functional thermal materials prepared by flow field-driven self-assembly strategy | |
| Dang et al. | Pore structure, thermal insulation and compressive property of ZrO2 nanofiber aerogels with carbon junction fabricated by freeze drying | |
| CN102211766B (en) | Rapid low-cost preparation method of high heat conduction carbon material | |
| CN107188526B (en) | The preparation method of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation | |
| Han et al. | Tetris-Style Stacking Process to Tailor the Orientation of Carbon Fiber Scaffolds for Efficient Heat Dissipation | |
| CN109627029B (en) | Preparation method of high-thermal-conductivity CNTs (carbon nanotubes) oriented modified ceramic matrix composite | |
| Zhan et al. | High thermally conductive shape-stabilized phase change composites with dual-aligned carbon nanofiber scaffolds | |
| CN110894338B (en) | Controllable deformation accurate regulation and control composite material based on super-elastic network and preparation method and application thereof | |
| CN113896428B (en) | Nematic liquid crystal orientation Kevlar/silicon carbide composite heat-conducting film, preparation method thereof and application thereof in electronic device heat management |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190402 |