CN107188526B - The preparation method of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation - Google Patents

The preparation method of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation Download PDF

Info

Publication number
CN107188526B
CN107188526B CN201710257639.1A CN201710257639A CN107188526B CN 107188526 B CN107188526 B CN 107188526B CN 201710257639 A CN201710257639 A CN 201710257639A CN 107188526 B CN107188526 B CN 107188526B
Authority
CN
China
Prior art keywords
carbon
carbon fiber
composite
nanotube array
cold
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.)
Active
Application number
CN201710257639.1A
Other languages
Chinese (zh)
Other versions
CN107188526A (en
Inventor
封伟
吕峰
冯奕钰
纪滕霄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University
Original Assignee
Tianjin University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tianjin University filed Critical Tianjin University
Priority to CN201710257639.1A priority Critical patent/CN107188526B/en
Publication of CN107188526A publication Critical patent/CN107188526A/en
Application granted granted Critical
Publication of CN107188526B publication Critical patent/CN107188526B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B30/00—Compositions for artificial stone, not containing binders
    • C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/022—Carbon
    • C04B14/026—Carbon of particular shape, e.g. nanotubes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38—Fibrous materials; Whiskers
    • C04B14/386—Carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
    • C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors

Abstract

The present invention relates to a kind of preparation methods of thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation；Chopped carbon fiber is added in pure ethyl orthosilicate solvent, drying is filtered, obtains the carbon fiber that silica coating is contained on surface；It is subsequently placed in vacuum tube furnace heating, obtains silica/carbon fiber material；Complex catalyst precursor liquid is at the uniform velocity pushed into the growth for carrying out carbon nano-tube fibre beam, obtains carbon fiber/carbon nanotube array composite powder；Carbon nano pipe array/carbon fiber composite powder is added in cold stamping die, it is cold-pressed with the pressure loading room temperature of 200~300MPa, the carbon nano pipe array of the one-way orientation of acquisition/carbon fiber pipe block is overturn 180 °, then it rejoins in cold stamping die, the cold pressing of uniform pressure load room temperature, obtains the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation.Thermal conductivity is axially greater than 300W/ (mK) along material, is radially greater than 70W/ (mK).

Description

The preparation method of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation
Technical field
The present invention relates to the preparation method of the rigid thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation, tools Say to body it is one kind vertical-growth carbon nano pipe array and utilization cold pressing orientation high thermal conductivity carbon fiber/carbon nanotube on carbon fiber The preparation method of array.
Background technique
The raising and heat dissipation of thermal conductivity become the critical problem in thermal management materials field in recent decades.Heat generating device During arrangement works, because of effects or external environment influences such as the resistance of device itself, thermal resistance, electronics vortex, build up Amount of heat, especially narrow in components very high density, heat-dissipating space position, heat flow density can be especially big, thus Cause integral device Temperature Distribution extremely uneven, this proposes increasingly higher demands to Heat Conduction Material, and device heat production energy Whether uniform high-efficiency greatly affected the quality, performance and service life of electronic equipment for no timely discharge, device heat dissipation.In order to timely By these heat derives, we need in a hurry, and development quality is lighter, thermal conductivity is higher, more excellent performance of thermally conductive novel-section Material.
Carbon fiber is a kind of fibre obtained by asphaltic base or acrylonitrile group organic fiber by pre-oxidation and high temperature graphitization Tie up shape monodimension nanometer material.Carbon fiber lacks in face since with regular orderly graphite atomic layer, the obstruction of phonon conduction is less Fall into less, heat transfer efficiency is very high, thus prepares carbon-based highly heat-conductive material using carbon fiber and become the emphasis of people's research, also goes out The authorization or openly of similar patent is showed.State Intellectual Property Office of the People's Republic of China's grant number be CN105274698A, The patents of invention such as CN105972685A, CN106304444A disclose the technology that heat-conductive composite material is prepared using carbon fiber.
Above-described patent of invention merely illustrates traditional carbon fiber production method and combination process, is only had There is the graphite heat conducting material of anisotropic heat conductivity.And for the graphite flake layer of carbon fiber, the lattice vibration of carbon atom is that material is led Heat basis, therefore in carbon fibre material phonon transmitting can only along graphite crystal face, that is, carbon fiber axle to carry out travel at high speeds, and For between graphite wafer surface layer, distance too far has severely impacted the conduction of phonon.It is handled by Organic Ingredients fiber-forming process Afterwards, graphene crystal face is under external force along fiber axial orientation, thus only has upwards along fiber axis in the carbon fibers High heat conductance (is greater than 900W/ (mK)), and very low along fiber radial thermal conductivity, less than 15W/ (mK).The patent Shen of China Please the announcements such as CN105274698A, CN105972685A carbon fiber guiding hot material along axial thermal conductivity all at 10W/ (mK) Below.Therefore, the higher anisotropy of thermal coefficient of existing the obtained material of published patent of invention is big far from meeting The requirement to the Heat Conduction Material capacity of heat transmission such as type computer, highly integrated electronic device, is developed on the basis of carbon material is advantageous It is a kind of while having both axially and radially that the high thermal conductivity in direction, the material of less anisotropy are particularly important.
Summary of the invention
The too low deficiency of the thermally conductive sheet through-thickness thermal conductivity that the present invention is prepared for existing carbon fiber or carbon nanotube, There is provided it is a kind of axially and radially all have high thermal conductivity energy along material, i.e., the carbon-carbon composite of low anisotropic heat conductivity and Preparation method.Along the axial carbon-to-carbon composite wood for respectively reaching 300W/ (mK) and 70W/ (mK) with radial thermal conductivity of material Material, this thermal conductivity have apparent advantage compared to other carbon material.As shown in Figure 1.
The invention adopts the following technical scheme:
A kind of preparation method of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation, its step are as follows:
1) chopped carbon fiber that length is 1~3mm is added in pure ethyl orthosilicate solvent, volume ratio is 1:3 room temperature It stirs, filter cake is placed in drying in air dry oven after suction filtration, the carbon fiber that silica coating is contained on surface is prepared；
2) obtained silica coating/carbon fiber is placed in vacuum tube furnace, is passed through argon gas as protection after being evacuated to vacuum Gas is heated up by process control, is at the uniform velocity warming up to 1100~1400 DEG C with 10~15 DEG C/min and is kept the temperature 0.5~2 hour, wait cool down Silica/carbon fiber material is obtained after to room temperature；
3) ferrocene is dissolved in xylene solution and the complex catalyst precursor liquid that concentration is 0.02~0.05g/ml is made, by step 2) silica coating/carbon fiber material being prepared is placed in the flat-temperature zone of vacuum tube furnace, is passed through argon gas work after being evacuated to vacuum To protect gas, is heated up by process control, be at the uniform velocity warming up to 700~900 DEG C with 10~15 DEG C/min, at the uniform velocity by complex catalyst precursor liquid Be pushed into vacuum tube furnace in and stablize heat preservation, carry out carbon nano-tube fibre beam growth, obtained after being cooled to room temperature carbon fiber/ Carbon nano pipe array composite powder；
4) carbon nano pipe array/carbon fiber composite powder is added in cold stamping die, is carried with the pressure of 200~300MPa The carbon nano pipe array of the one-way orientation of acquisition/carbon fiber pipe block is overturn 180 °, then rejoined by the cold pressing of lotus room temperature In cold stamping die, it is cold-pressed with the pressure loading room temperature of 200~300MPa, it is thermally conductive obtains carbon fiber/carbon nanotube array double orientation Carbon-carbon composite.
With 300~600r/min stirring at normal temperature 10~30 minutes in the step 1).
The vacuum degree condition of the tubular type stove evacuation are as follows: air pressure is lower than 20Pa in tube furnace.
Complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube furnace with 0.2~0.6ml/min in the step 3) and is stablized Heat preservation 10~60 minutes.
Being cold-pressed the time twice respectively in the step 4) is 0.5~2 hour.
The thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation of method preparation of the invention, by being received with carbon The blocks of solid heat-conducting pad that mitron array/carbon fiber orientation is arranged to make up；The composite material is mentioned by the carbon fiber of axial orientation For composite material along axial thermal conducting path, and composite material leading radially is provided by radial oriented carbon nano pipe array Hot property；Thermal conductivity is axially greater than 300W/ (mK) along material, is radially greater than 70W/ (mK).
It is described as follows:
(1) growth of carbon nano pipe array: adjusting process parameter prepare length be greater than 20 μm, array density be greater than 2 × 108cm-2Directional carbon nanotube array；
Since carbon fiber has high thermal conductivity coefficient along axial, and radial thermal coefficient is very low, grows carbon in carbon fiber surface After nano-tube array, carbon nano pipe array will be led perpendicular to carbon fiber, the height using carbon nano pipe array along carbon fiber radial direction The hot transmitting for being able to achieve the thermally conductive carbon-carbon composite radial heat flows of carbon fiber/carbon nanotube array double orientation, this is highly beneficial In improving the capacity of heat transmission of composite material radially, its anisotropic heat conductivity is reduced；
It is real by the cold pressing orientation of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation of above step The carbon nano pipe array radially along the axial carbon fiber with high thermal conductivity and along carbon fiber with high thermal conductivity is showed Double orientation, heat-flow meter method measure thermal conductivity and are axially greater than 300W/ (mK) along material, and radially the height greater than 70W/ (mK) is led Hot carbon-carbon composite.
Advantages of the present invention: matrix material carbon fiber of the invention is easy to get, and the growth of carbon nano pipe array is simply controllable.This Microstructure ordering, stratification, graphitization and material molding can be completed efficiently in invention, and having for can obtaining is lower thermally conductive each Anisotropy can carbon-carbon composite, the capacity of heat transmission be far superior to traditional carbon fiber paper coiled material and other carbon fibers with Carbon nano-tube array composite material.
Detailed description of the invention:
Fig. 1 is the microcosmic schematic diagram of high thermal conductivity carbon-carbon composite of the invention, including complex form and thermally conductive direction；
Fig. 2 is the scanning electron microscopic picture for the carbon fiber samples that surface growth has carbon nano pipe array；
Fig. 3 is the digital photograph of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation.
Specific embodiment
A kind of preparation method of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation, steps are as follows:
1) the commercially available chopped carbon fiber that length is 1~3mm is added in pure ethyl orthosilicate solvent, volume ratio is 1:3 Filter cake was placed in air dry oven after suction filtration by (based on being totally submerged) with 300~600r/min stirring at normal temperature 10~30 minutes It is 3~5 hours dry with 50~70 DEG C, the carbon fiber that silica coating is contained on surface is prepared；
2) silica coating/carbon fiber that the first step is prepared is placed in vacuum tube furnace, 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 1100~1400 DEG C with 10~15 DEG C/min and is kept the temperature 0.5~2 Hour, silica/carbon fiber material is obtained after being cooled to room temperature；
3) ferrocene is dissolved in xylene solution and the complex catalyst precursor liquid that concentration is 0.02~0.05g/ml is made, by second The flat-temperature zone that the silica coating/carbon fiber material being prepared is placed in vacuum tube furnace is walked, is passed through argon gas work after being evacuated to vacuum To protect gas, is heated up by process control, be at the uniform velocity warming up to 700~900 DEG C, after reaching set temperature with 10~15 DEG C/min, answer With injector for medical purpose by complex catalyst precursor liquid under the action of delicate flow pump (or similar can accurately control flow velocity equipment) Heat preservation 10~60 minutes is at the uniform velocity pushed into vacuum tube furnace and stablized with 0.2~0.6ml/min, carries out carbon nano-tube fibre beam Growth, obtains carbon fiber/carbon nanotube array composite powder, as shown in Figure 2 after being cooled to room temperature；
4) 1~2g (is adjusted into) carbon nano pipe array/carbon fiber composite powder at any time with mold bearing capacity and is added to cold pressing In mold, it is cold-pressed 0.5~2 hour with the pressure loading room temperature of 200~300MPa, by the carbon nano-pipe array of the one-way orientation of acquisition Column/carbon fiber pipe block overturns 180 °, then rejoins in cold stamping die, with the pressure loading room temperature of 200~300MPa Cold pressing 0.5~2 hour, finally obtains the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation, (photomacrograph is such as Shown in Fig. 3).
5) the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation being finally prepared is by being received with carbon The blocks of solid heat-conducting pad that mitron array/carbon fiber orientation is arranged to make up.The composite material is mentioned by the carbon fiber of axial orientation For composite material along axial thermal conducting path, and composite material leading radially is provided by radial oriented carbon nano pipe array Hot property.
5 embodiments of the invention are given below, are that rather than model of the invention is limited to further explanation of the invention It encloses.
Embodiment 1
The commercially available chopped carbon fiber that length is 1mm is added in pure ethyl orthosilicate solvent and is impregnated 0.5 hour, 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, oxygen is prepared SiClx/carbon fiber；Silica/carbon fiber that the first 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, 1100 DEG C is at the uniform velocity warming up to 10 DEG C/min and keeps the temperature 0.5 hour, to Silicon carbide/carbon fibrous raw material is obtained after being cooled to room temperature；It is 0.02g/ml's that ferrocene, which is dissolved in xylene solution concentration is made, The silicon carbide/carbon fibrous raw material that second step is prepared is placed in the flat-temperature zone of vacuum tube furnace by complex catalyst precursor liquid, is evacuated to true It is passed through argon gas after sky as protection gas, is heated up by process control, is at the uniform velocity warming up to 700 DEG C with 10 DEG C/min, reaches set temperature Afterwards, complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube with 0.2ml/min under the action of delicate flow pumps using injector for medical purpose In formula furnace and stablize heat preservation 10 minutes, carries out the growth of carbon nano-tube fibre beam, carbon fiber/carbon is obtained after being cooled to room temperature and is received Mitron array composite powder；1g carbon nano pipe array/carbon fiber composite powder is added in cold stamping die, with the pressure of 200MPa Power load room temperature is cold-pressed 0.5 hour, and the carbon nano pipe array of the one-way orientation of acquisition/carbon fiber pipe block is overturn, is then weighed It is newly added in cold stamping die, is cold-pressed 0.5 hour with the pressure loading room temperature of 200~300MPa, finally obtains carbon fiber/carbon and receive The thermally conductive carbon-carbon composite of mitron array double orientation, testing thermal conductivity along material is axially 300W/ (mK), radially for 70W/(m·K)。
Embodiment 2
The commercially available chopped carbon fiber that length is 3mm is added in pure ethyl orthosilicate solvent and is impregnated 0.5 hour, with 600r/min stirring at normal temperature 30 minutes, will be 5 hours dry with 70 DEG C in filter cake merging air dry oven after suction filtration, oxygen is prepared SiClx/carbon fiber；Silica/carbon fiber that the first 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, 1400 DEG C is at the uniform velocity warming up to 15 DEG C/min and keeps the temperature 2 hours, wait drop Silicon carbide/carbon fibrous raw material is obtained after warming to room temperature；It is urging for 0.05g/ml that ferrocene, which is dissolved in xylene solution concentration is made, The silicon carbide/carbon fibrous raw material that second step is prepared is placed in the flat-temperature zone of vacuum tube furnace, is evacuated to vacuum by agent precursor liquid After be passed through argon gas as protection gas, heated up by process control, be at the uniform velocity warming up to 900 DEG C, after reaching set temperature with 15 DEG C/min, Complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube furnace with 0.6ml/min under the action of delicate flow pumps using injector for medical purpose In and stablize heat preservation 60 minutes, carry out carbon nano-tube fibre beam growth, carbon fiber/carbon nanotube is obtained after being cooled to room temperature Array composite powder；2g carbon nano pipe array/carbon fiber composite powder is added in cold stamping die, is carried with the pressure of 300MPa Lotus room temperature is cold-pressed 2 hours, and the carbon nano pipe array of the one-way orientation of acquisition/carbon fiber pipe block is overturn, is then rejoined It into cold stamping die, is cold-pressed 2 hours with the pressure loading room temperature of 300MPa, finally obtains carbon fiber/carbon nanotube array pair and take To thermally conductive carbon-carbon composite, it is radially 150W/ (mK) that testing thermal conductivity along material, which is axially 350W/ (mK),.
Embodiment 3
The commercially available chopped carbon fiber that length is 2mm is added in pure ethyl orthosilicate solvent and is impregnated 0.5 hour, with 500r/min stirring at normal temperature 20 minutes, will be 4 hours dry with 60 DEG C in filter cake merging air dry oven after suction filtration, oxygen is prepared SiClx/carbon fiber；Silica/carbon fiber that the first 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, 1350 DEG C is at the uniform velocity warming up to 13 DEG C/min and keeps the temperature 1 hour, wait drop Silicon carbide/carbon fibrous raw material is obtained after warming to room temperature；It is urging for 0.03g/ml that ferrocene, which is dissolved in xylene solution concentration is made, The silicon carbide/carbon fibrous raw material that second step is prepared is placed in the flat-temperature zone of vacuum tube furnace, is evacuated to vacuum by agent precursor liquid After be passed through argon gas as protection gas, heated up by process control, be at the uniform velocity warming up to 800 DEG C, after reaching set temperature with 13 DEG C/min, Complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube furnace with 0.4ml/min under the action of delicate flow pumps using injector for medical purpose In and stablize heat preservation 40 minutes, carry out carbon nano-tube fibre beam growth, carbon fiber/carbon nanotube is obtained after being cooled to room temperature Array composite powder；1.5g carbon nano pipe array/carbon fiber composite powder is added in cold stamping die, with the pressure of 250MPa Load room temperature is cold-pressed 1 hour, and the carbon nano pipe array of the one-way orientation of acquisition/carbon fiber pipe block is overturn, and is then added again Enter into cold stamping die, be cold-pressed 1 hour with the pressure loading room temperature of 250MPa, it is double to finally obtain carbon fiber/carbon nanotube array It is orientated thermally conductive carbon-carbon composite, it is radially 80W/ (mK) that testing thermal conductivity along material, which is axially 400W/ (mK),.
Embodiment 4
The commercially available chopped carbon fiber that length is 1mm is added in pure ethyl orthosilicate solvent and is impregnated 0.5 hour, with 500r/min stirring at normal temperature 16 minutes, will be 3 hours dry with 60 DEG C in filter cake merging air dry oven after suction filtration, oxygen is prepared SiClx/carbon fiber；Silica/carbon fiber that the first 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, 1100 DEG C is at the uniform velocity warming up to 11 DEG C/min and keeps the temperature 2 hours, wait drop Silicon carbide/carbon fibrous raw material is obtained after warming to room temperature；It is urging for 0.04g/ml that ferrocene, which is dissolved in xylene solution concentration is made, The silicon carbide/carbon fibrous raw material that second step is prepared is placed in the flat-temperature zone of vacuum tube furnace, is evacuated to vacuum by agent precursor liquid After be passed through argon gas as protection gas, heated up by process control, be at the uniform velocity warming up to 850 DEG C, after reaching set temperature with 10 DEG C/min, Complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube furnace with 0.3ml/min under the action of delicate flow pumps using injector for medical purpose In and stablize heat preservation 26 minutes, carry out carbon nano-tube fibre beam growth, carbon fiber/carbon nanotube is obtained after being cooled to room temperature Array composite powder；1g carbon nano pipe array/carbon fiber composite powder is added in cold stamping die, is carried with the pressure of 220MPa Lotus room temperature is cold-pressed 2 hours, and the carbon nano pipe array of the one-way orientation of acquisition/carbon fiber pipe block is overturn, is then rejoined It into cold stamping die, is cold-pressed 0.5 hour with the pressure loading room temperature of 300MPa, it is double to finally obtain carbon fiber/carbon nanotube array It is orientated thermally conductive carbon-carbon composite, it is radially 91W/ (mK) that testing thermal conductivity along material, which is axially 370W/ (mK),.
Embodiment 5
The commercially available chopped carbon fiber that length is 3mm is added in pure ethyl orthosilicate solvent and is impregnated 0.5 hour, with 500r/min stirring at normal temperature 15 minutes, will be 3 hours dry with 70 DEG C in filter cake merging air dry oven after suction filtration, oxygen is prepared SiClx/carbon fiber；Silica/carbon fiber that the first 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 14 DEG C/min and keeps the temperature 1.5 hours, to Silicon carbide/carbon fibrous raw material is obtained after being cooled to room temperature；It is 0.02g/ml's that ferrocene, which is dissolved in xylene solution concentration is made, The silicon carbide/carbon fibrous raw material that second step is prepared is placed in the flat-temperature zone of vacuum tube furnace by complex catalyst precursor liquid, is evacuated to true It is passed through argon gas after sky as protection gas, is heated up by process control, is at the uniform velocity warming up to 900 DEG C with 15 DEG C/min, reaches set temperature Afterwards, complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube with 0.6ml/min under the action of delicate flow pumps using injector for medical purpose In formula furnace and stablize heat preservation 60 minutes, carries out the growth of carbon nano-tube fibre beam, carbon fiber/carbon is obtained after being cooled to room temperature and is received Mitron array composite powder；1.5g carbon nano pipe array/carbon fiber composite powder is added in cold stamping die, with 300MPa's Pressure loading room temperature is cold-pressed 2 hours, and the carbon nano pipe array of the one-way orientation of acquisition/carbon fiber pipe block is overturn, is then weighed It is newly added in cold stamping die, is cold-pressed 0.5 hour with the pressure loading room temperature of 200MPa, finally obtains carbon fiber/carbon nanotube The thermally conductive carbon-carbon composite of array double orientation, it is radially 100W/ that testing thermal conductivity along material, which is axially 400W/ (mK), (m·K)。

Claims (6)

1. a kind of preparation method of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation, it is characterized in that step is such as Under:
1) chopped carbon fiber that length is 1~3mm being added in pure ethyl orthosilicate solvent, volume ratio is 1:3 stirring at normal temperature, Filter cake is placed in drying in air dry oven after suction filtration, the carbon fiber that silica coating is contained on surface is prepared；
2) obtained silica coating/carbon fiber is placed in vacuum tube furnace, is passed through argon gas conduct protection gas after being evacuated to vacuum, by Process control 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, room to be cooled to Silica/carbon fiber material is obtained after temperature；
3) ferrocene is dissolved in xylene solution and the complex catalyst precursor liquid that concentration is 0.02~0.05g/ml is made, step 2) is made Standby obtained silica/carbon fiber material is placed in the flat-temperature zone of vacuum tube furnace, is passed through argon gas conduct protection gas after being evacuated to vacuum, It is heated up by process control, is at the uniform velocity warming up to 700~900 DEG C with 10~15 DEG C/min, complex catalyst precursor liquid is at the uniform velocity pushed into vacuum In tube furnace and stablize heat preservation, carries out the growth of carbon nano-tube fibre beam, carbon fiber/carbon nanotube is obtained after being cooled to room temperature Array composite powder；
4) carbon fiber/carbon nanotube array composite powder is added in cold stamping die, it is normal with the pressure loading of 200~300MPa The carbon fiber/carbon nanotube array block of the one-way orientation of acquisition is overturn 180 °, then rejoins cold stamping die by temperature cold pressing It in tool, is cold-pressed with the pressure loading room temperature of 200~300MPa, it is multiple to obtain the thermally conductive carbon-to-carbon of carbon fiber/carbon nanotube array double orientation Condensation material.
2. the method as described in claim 1, it is characterized in that with 300~600r/min stirring at normal temperature 10~30 in the step 1) Minute.
3. the method as described in claim 1, it is characterized in that the vacuum degree condition of the tubular type stove evacuation are as follows: gas in tube furnace It forces down in 20Pa.
4. the method as described in claim 1, it is characterized in that by complex catalyst precursor liquid with 0.2~0.6ml/ in the step 3) Min is at the uniform velocity pushed into vacuum tube furnace and stablizes heat preservation 10~60 minutes.
5. the method as described in claim 1, it is characterized in that being cold-pressed the time twice respectively in the step 4) is 0.5~2 hour.
6. the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation of method preparation described in claim 1, It is characterized in the blocks of solid heat-conducting pad by being constituted with carbon fiber/carbon nanotube array orientations；The composite material is by axial direction The carbon fiber of orientation provides composite material along axial thermal conducting path, and compound by radial oriented carbon nano pipe array offer The heating conduction of material radially；Thermal conductivity is axially greater than 300 W/ (mK) along material, is radially greater than 70W/ (mK).
CN201710257639.1A 2017-04-19 2017-04-19 The preparation method of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation Active CN107188526B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710257639.1A CN107188526B (en) 2017-04-19 2017-04-19 The preparation method of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710257639.1A CN107188526B (en) 2017-04-19 2017-04-19 The preparation method of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation

Publications (2)

Publication Number Publication Date
CN107188526A CN107188526A (en) 2017-09-22
CN107188526B true CN107188526B (en) 2019-09-17

Family

ID=59871648

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710257639.1A Active CN107188526B (en) 2017-04-19 2017-04-19 The preparation method of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation

Country Status (1)

Country Link
CN (1) CN107188526B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108440006A (en) * 2018-04-13 2018-08-24 山东理工大学 The method that transition metal element regulates and controls carbon fibre reinforced ceramics based composite material interface

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9156700B2 (en) * 2013-02-25 2015-10-13 Nanotek Instruments, Inc. Process for producing unitary graphene materials
US20140356613A1 (en) * 2013-05-31 2014-12-04 Materials Sciences Corporation Carbon nanotube studded carbon fiber tow and matrix prepreg
CN105645962B (en) * 2016-01-06 2018-07-13 天津大学 A kind of preparation method of fire-resistant oxidation resistant heat conduction carbon fiber/composite material of silicon carbide
CN105948776B (en) * 2016-04-28 2018-08-28 天津大学 A kind of preparation method of array carbon nano-tube/carbon fiber/silicon carbide heat-conductive composite material

Also Published As

Publication number Publication date
CN107188526A (en) 2017-09-22

Similar Documents

Publication Publication Date Title
CN104943223B (en) There is graphite flake and the preparation method of high thermal conductivity coefficient along plane and thickness direction simultaneously
CN109554168A (en) Carbon nano pipe array/graphene heat-conductive composite material and preparation method thereof
CN107141803A (en) The preparation method of carbon fiber carbon nano-tube array/silicones heat-conductive composite material
CN106543979B (en) Graphite/carbon nanotube fibers beam/graphene thermally conductive laminated film preparation method
CN105503227B (en) A kind of preparation method of stereo fabric enhancing silicon carbide diamond composite
CN111234502A (en) Efficient and uniform heat conduction polymer-based heat conduction material and preparation method thereof
CN105236982B (en) The enhanced graphite-base composite material of aluminium nitride and preparation technology
CN104961464B (en) Through-thickness has high resilience and high thermal conductivity coefficient C-base composte material and preparation method
CN102030556B (en) Method for preparing diamond/silicon carbide ceramic matrix composite material
CN105948776B (en) A kind of preparation method of array carbon nano-tube/carbon fiber/silicon carbide heat-conductive composite material
CN106010469A (en) Carbon nanotube array/graphene paper heat-conducting composite material and preparation method
CN102176436B (en) Process for preparing high-performance Diamond/SiC electronic packaging material
CN105859291B (en) The preparation method of three-dimensional highly-conductive hot carbon based composites
CN108796397A (en) A kind of preparation method of graphene/carbon SiClx/aluminium composite material
CN109928756A (en) A kind of SiC reinforcement C-base composte material and preparation method
CN107188526B (en) The preparation method of the thermally conductive carbon-carbon composite of carbon fiber/carbon nanotube array double orientation
CN109987954A (en) A kind of tungsten carbide enhancing graphite-base composite material and preparation method
CN105016773B (en) The method that reaction-sintered and low-level oxidation treatment prepare porous silicon carbide ceramic
Wang et al. MXene reconciles concurrent enhancement of thermal conductivity and mechanical robustness of SiC-based thermal energy storage composites
CN108611511B (en) A kind of three-dimensional intercommunication CNTs/Cu composite material and preparation method
CN113666748B (en) Preparation method of graphite material and graphite material
CN110421918A (en) A kind of heat management graphite film-Ti lamina block composite material and preparation method
CN110436949A (en) A kind of preparation method of high thermal conductivity pitch based carbon fiber/composite material of silicon carbide
CN106565263B (en) A kind of preparation method of carbon nanotube/silicon carbide heat-conductive composite material
WO2003072526A1 (en) Energy converting c/c-composite and method of making the same

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
GR01 Patent grant
GR01 Patent grant