CN105802589A - High-strength heat-conducting film and preparation method thereof - Google Patents
High-strength heat-conducting film and preparation method thereof Download PDFInfo
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- CN105802589A CN105802589A CN201610301081.8A CN201610301081A CN105802589A CN 105802589 A CN105802589 A CN 105802589A CN 201610301081 A CN201610301081 A CN 201610301081A CN 105802589 A CN105802589 A CN 105802589A
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Abstract
The invention provides a high-strength heat-conducting film and a preparation method thereof. The high-strength heat-conducting film is prepared by the steps of uniformly mixing heat-conducting powder with nanomaterals and/or fiber materials, and carrying out one or more manners of solvent evaporation, suction-filtration film formation, roll-press film formation and the like. According to the preparation method, the heat-conducting powder is composited with the nanomaterals and/or the fiber materials, so that the mechanical strength of the heat-conducting film is improved when high heat conductivity coefficient is guaranteed, furthermore, the anisotropy of the heat conductivity coefficient is very obvious; and by virtue of the characteristics, the heat-conducting film has obvious superiorities in actual application. The in-plane heat conductivity coefficient of the high-strength heat-conducting film provided by the invention is 100W/m.K-2000W/m.K, the tensile strength is 50Mpa-300Mpa, the thickness is 5-100 microns, and the density is 0.5g/cm<3>-2.0g/cm<3>.
Description
Technical field
The present invention relates to a kind of high intensity heat conducting film and preparation method thereof, belong to heat conduction and heat radiation field of material technology.
Background technology
Current electronic equipment quickly grows, usual being significantly increased along with power consumption while electronic device performance boost.For solving the heat dissipation problem that power consumption increase causes, the production preparation of all kinds of heat-conducting interface material and heat conducting film increasingly comes into one's own.But, heat conducting film on the market generally adopts simple graphite or the simple calendering process of metal material to prepare at present, and the usual mechanical strength of heat conducting film of preparation is relatively low, and its application receives restriction.
CN104592950A discloses a kind of high thermal conductivity graphene-based polymer bond's film, its preparation method and application.This preparation method includes: graphene microchip and high molecular polymer is sufficiently mixed in varing proportions uniformly, then makes thin film, prepares described high thermal conductivity graphene-based polymer bond's film then through carbonization and graphitization.Graphene microchip therein includes graphene oxide, oxidoreduction Graphene, high-quality thin graphene etc.；High molecular polymer can include polyvinylpyrrolidone etc..The heat conducting film thickness that the method prepares is 5～20 μm, and thermal conductivity is 1500～2000W/m K.The method adopts high molecular polymer and conduction powder compound, and such thermal conductivity of composite materials is generally relatively low.Additionally, the process employs high temperature and high molecular polymer composite membrane has been carried out carbonization treatment, in this course, high molecular polymer component decomposes in complex, thus losing original supporting role, the heat conducting film mechanical strength obtained after process greatly reduces, and does not possess the condition of practical application.
CN104232027A discloses a kind of Graphene heat conducting film and preparation method thereof, this preparation method is by graphene oxide or the Graphene that is modified by macromolecule matrix materials such as polyvinyl alcohol, polystyrene and celluloses, i.e. functionalization graphene, it is dispersed in solvent with Graphene, stabilizer, obtain mixed slurry, then, by above-mentioned mixed slurry after roller process, by film and Matrix separation, Graphene heat conducting film is being finally obtained.Stabilizer therein can include polyvinylpyrrolidone, Carboxymethyl cellulose sodium etc.；Solvent can include water, ethanol, acetone etc..The thickness of the heat conducting film that the method prepares is 5～30 μm, and heat conductivity is 830～890W/m K, and mechanical stretch intensity is 46.4～50.2Mpa.The method is adopt macromolecular material and conduction powder compound equally, but the method and CN104592950A are distinctive in that, macromolecular material therein is not used as matrix material to be existed, disperse conduction powder just with these macromolecular materials more, forming process ensures the homogeneous film formation of conduction powder.The same mechanical strength of heat conducting film that this method prepares is relatively low, and actual application is easily broken.
Conduction powder will be produced the effect of cladding by macromolecular material that CN104592950A and CN104592950A adopts after shaping.In actual conduction process, between conduction powder, heat transmission requires over the polymer material layer of this layer of cladding.The conduction powder such as graphite rely primarily on lattice vibration transmission heat, and the usual crystal formation of macromolecular material is poor, heat conductivity is very low, very big thermal contact resistance is there is, so the existence of this polymer material layer largely reduces the heat conductivity of complex between conduction powder and macromolecular material.
Therefore, develop a kind of high intensity heat conducting film and preparation method thereof, be still one of this area problem demanding prompt solution.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of high intensity heat conducting film and preparation method thereof.This preparation method adopt conduction powder with nanometer and/or fibrous material compound, the mechanical strength of heat conducting film can also be improved when ensureing high thermal conductivity coefficient.
For reaching above-mentioned purpose, the preparation method that the invention provides a kind of high intensity heat conducting film, it comprises the following steps:
By conduction powder with nanometer and/or fibrous material mix homogeneously after make thin film, obtain described high intensity heat conducting film.
In above-mentioned preparation method, preferably, described conduction powder includes the combination of one or more in aluminium nitride powder of graphene powder, boron nitride powder, aluminium nitride powder etc. and the graphene powder of functionalization, the boron nitride powder of functionalization, functionalization etc..It is highly preferred that the particle diameter of described conduction powder is 1～300 μm.Additionally, the Graphene of described functionalization can include the Graphene with functional group such as Graphene (i.e. carboxylated Graphene) of graphene oxide, acid treatment；The boron nitride of described functionalization can include surface with functional group or the boron nitride that is connected with surfactant；The aluminium nitride of described functionalization can include surface with functional group or the aluminium nitride that is connected with surfactant.
In above-mentioned preparation method, it is preferable that described nanometer and/or fibrous material include the combination of one or more in nanofibrils cellulose, nanocrystalline cellulose (NCC), carbon fiber and CNT etc..It is highly preferred that the diameter of described nanometer and/or fibrous material is 1～100nm, length is 0.5～1000 μm.
In above-mentioned preparation method, it is preferable that the mass ratio of described conduction powder and described nanometer and/or fibrous material is 9.9:0.1～5:5.
In above-mentioned preparation method, preferably, by conduction powder with nanometer and/or fibrous material mix homogeneously after make the step of thin film and include: by conduction powder with nanometer and/or the mixed liquor of fibrous material, make thin film in one or more modes in solvent evaporation, sucking filtration film forming, roll-in film forming, be more preferably and make thin film in the way of sucking filtration film forming.Wherein, the solvent in described mixed liquor can include the combination of one or more in water, ethanol, acetone, isopropanol, normal hexane and hexamethylene etc..It is highly preferred that above-mentioned steps farther includes: after making thin film in one or more modes in solvent evaporation, sucking filtration film forming, roll-in film forming, this thin film applied certain pressure and keeps a period of time, obtaining described high intensity heat conducting film.Wherein, the pressure that this thin film is applied can be 1～30MPa, and the time of maintenance can be 1～30 minute.Additionally, above-mentioned steps can further include high-temperature heat treatment (can carry out in heating furnace), namely thin film is being made in one or more modes in solvent evaporation, sucking filtration film forming, roll-in film forming, and after this thin film being applied certain pressure and keeping a period of time, the heat conducting film that obtains can be processed 0.5～2 hour in the atmosphere of 900～1200 DEG C and hydrogen and/or argon, obtain described high intensity heat conducting film.Wherein, described hydrogen and/or the atmosphere of argon are preferably the mixed atmosphere of hydrogen and argon, it is more preferred to, the volume ratio of hydrogen and argon is 1:9～5:5；Further, the gas flow of described hydrogen and/or argon can be 50-100mL/min.
Additionally, above-mentioned conduction powder with nanometer and/or the mixed liquor of fibrous material can pass through first to prepare the dispersion liquid of conduction powder and nanometer and/or the dispersion liquid of fibrous material, then the two mix homogeneously is prepared.Wherein, the dispersion liquid of conduction powder and nanometer and/or the dispersion liquid of fibrous material in solvent such as above-mentioned mixed liquor in solvent, repeat no more herein；By the dispersion liquid of conduction powder and nanometer and/or the mode of dispersion liquid mix homogeneously of fibrous material can adopt the mode of high-speed stirred, mixing speed can be 50～5000r/min.
In above-mentioned preparation method, preferably, the mode of described solvent evaporation comprises the following steps: by described conduction powder with nanometer and/or the mixed liquor of fibrous material pour in open-top receptacle, a period of time is kept to make solvent evaporate under certain vacuum degree and uniform temperature, continue to keep a period of time after solvent all evaporates, obtain described heat conducting film.Wherein, described conduction powder with nanometer and/or the concentration of mixed liquor of fibrous material can be 0.1～100g/L, it is preferred to 1～10g/L (in conduction powder with nanometer and/or the gross mass of fibrous material)；Described vacuum (absolute pressure) can be 10～101KPa (i.e. 0.1～1atm)；Described temperature can be 30～100 DEG C；Making solvent evaporate the time kept completely is 0.5～12 hour；The time that solvent continues after all evaporating to keep is 0.5～1 hour.The step of above-mentioned solvent evaporation can carry out in vacuum drying oven, is cooled to room temperature, it is possible to taken out from container by the heat conducting film of molding after taking out open-top receptacle.
In above-mentioned preparation method, preferably, the mode of described sucking filtration film forming comprises the following steps: by described conduction powder with nanometer and/or the mixed liquor of fibrous material be 0.1～10atm (be preferably 0.1～1atm), sucking filtration time carry out sucking filtration when being 0.5～24 hour at sucking filtration pressure, obtain described heat conducting film.Wherein, described conduction powder with nanometer and/or the concentration of mixed liquor of fibrous material can be 0.01～10g/L, it is preferred to 1～10g/L (in conduction powder with nanometer and/or the gross mass of fibrous material).The Suction filtration device that the step of above-mentioned sucking filtration can adopt this area conventional carries out.
In above-mentioned preparation method, preferably, the mode of described roll-in film forming comprises the following steps: by described conduction powder with nanometer and/or the mixed liquor of fibrous material prepare form slurry, described slurry is carried out roller process, the calendering time is 0.5～10 hour, obtains described heat conducting film.Wherein, described conduction powder with nanometer and/or the mixed liquor of fibrous material prepare form slurry mode can centrifugal treating, to remove major part solvent.
The preparation method that the preparation method of high intensity heat conducting film provided by the invention is different from existing heat conducting film, adopt nanofibrils cellulose, nanocrystalline cellulose etc. nanometer and/or fibrous material and conduction powder compound, these nanometers and/or fibrous material have bigger difference with macromolecular material of the prior art on configuration, the one-dimensional linear structure of such as nanofibrils cellulose is while being woven into network offer skeletal support, contact between conduction powder also is not affected by intercepting, therefore method provided by the invention is adopted to prepare heat conducting film when having higher mechanical strength, heat conductivity is not greatly reduced.In addition, the mode preferably employing sucking filtration film forming in the preparation method of the present invention makes heat conducting film molding, in sucking filtration process, the powder body of the laminated structure such as Graphene can ordered stacks, the structure of this parallel accumulation and unordered accumulative facies ratio, in face, thermal conductance thermal conductance bigger, vertical is less, the anisotropy of heat conductivity becomes apparent from, and this is advantageous in the process of heat conducting film practical application.
Present invention also offers a kind of high intensity heat conducting film, it is the preparation method by above-mentioned high intensity heat conducting film and prepares.
According to the specific embodiment of the present invention, it is preferable that in the face of described high intensity heat conducting film, heat conductivity is 100～2000W/m K, hot strength is 50～300Mpa, and thickness is 5～100 μm, and density is 0.5～2.0g/cm3.It is highly preferred that heat conductivity is 200～500W/m K in the face of described high intensity heat conducting film, hot strength is 130～300Mpa, and thickness is 20～50 μm, and density is 1.2～2.0g/cm3。
In sum, the present invention provides can a kind of high intensity heat conducting film and preparation method thereof, this preparation method adopt conduction powder with nanometer and/or fibrous material compound, the mechanical strength of heat conducting film is also improved when ensureing high thermal conductivity coefficient, and the anisotropy making heat conductivity is fairly obvious, these features make heat conducting film provided by the invention have obvious advantage in actual applications.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, existing technical scheme is carried out described further below, but it is not intended that to the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide a kind of high intensity heat conducting film, it prepares by the following method: (step of acid treatment is: mixed with 80mL concentrated nitric acid and 240mL concentrated sulphuric acid by 1g Graphene to take graphene powder acid-treated for 0.9g, 1000W supersound process 1 hour, filters, cleans, dries；The particle diameter of the graphene powder obtained is 10 μm, and the thickness of Graphene is 3nm, and two-dimensional slice footpath is of a size of 10 μm, and phosphorus content is more than 99.8wt%) it is scattered in 100mL water, stirring is so as to be uniformly dispersed；Taking 0.1g nanocrystalline cellulose (diameter is 20nm, and length is 300 μm) and be dissolved in 50mL water, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；It is subsequently poured in open-top receptacle, and put into vacuum drying oven, keep making solvent evaporate in 2 hours when vacuum be 0.9atm, temperature is 50 DEG C, after solvent all evaporates, continue maintenance 0.5 hour, it is cooled to room temperature after taking out open-top receptacle, the heat conducting film of molding is taken out from container；Mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute afterwards；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 213W/m K, and vertical thermal conductivity is 1.2W/m K, and hot strength is 150Mpa, and thickness is 34 μm, and density is 1.4g/cm3。
Embodiment 2
Present embodiments provide a kind of high intensity heat conducting film, it prepares by the following method: (step of acid treatment is with embodiment 1 to take graphene powder acid-treated for 0.5g, the particle diameter of the graphene powder obtained is 10 μm, the thickness of Graphene is 3nm, two-dimensional slice footpath is of a size of 10 μm, phosphorus content is more than 99.8wt%) it is scattered in 50mL water, stirring is so as to be uniformly dispersed；Taking 0.5g nanocrystalline cellulose (diameter is 20nm, and length is 300 μm) and be dissolved in 100mL water, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；It is subsequently poured in open-top receptacle, and put into vacuum drying oven, keep making solvent evaporate in 1.5 hours when vacuum be 0.7atm, temperature is 60 DEG C, after solvent all evaporates, continue maintenance 0.5 hour, it is cooled to room temperature after taking out open-top receptacle, the heat conducting film of molding is taken out from container；Mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute afterwards；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 150W/m K, and vertical thermal conductivity is 1.3W/m K, and hot strength is 220Mpa, and thickness is 27 μm, and density is 1.6g/cm3。
Embodiment 3
Present embodiments provide a kind of high intensity heat conducting film, it prepares by the following method: (step of acid treatment is with embodiment 1 to take graphene powder acid-treated for 0.9g, the particle diameter of the graphene powder obtained is 10 μm, the thickness of Graphene is 3nm, two-dimensional slice footpath is of a size of 10 μm, phosphorus content is more than 99.8wt%) it is scattered in 100mL water, stirring is so as to be uniformly dispersed；Taking 0.1g nanocrystalline cellulose (diameter is 20nm, and length is 300 μm) and be dissolved in 50mL water, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；Adopting the Suction filtration device mixed liquor to obtaining to carry out sucking filtration, sucking filtration pressure is 0.8atm, and the sucking filtration time is 2 hours, obtains heat conducting film；Then mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute；Testing coefficient in the thermal conductive surface of the heat conducting film obtaining preparation is 278W/m K, and vertical thermal conductivity is 1.3W/m K, and hot strength is 178Mpa, and thickness is 33 μm, and density is 1.4g/cm3。
Embodiment 4
Present embodiments provide a kind of high intensity heat conducting film, it prepares by the following method: (step of acid treatment is with embodiment 1 to take graphene powder acid-treated for 0.9g, the particle diameter of the graphene powder obtained is 10 μm, the thickness of Graphene is 3nm, two-dimensional slice footpath is of a size of 10 μm, phosphorus content is more than 99.8wt%) it is scattered in 100mL water, stirring is so as to be uniformly dispersed；Taking 0.1g nanocrystalline cellulose (diameter is 20nm, and length is 300 μm) and be dissolved in 50mL water, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；Adopting the Suction filtration device mixed liquor to obtaining to carry out sucking filtration, sucking filtration pressure is 0.5atm, and the sucking filtration time is 2 hours, obtains heat conducting film；Then mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 255W/m K, and vertical thermal conductivity is 1.1W/m K, and hot strength is 168Mpa, and thickness is 38 μm, and density is 1.2g/cm3。
Embodiment 5
Present embodiments provide a kind of high intensity heat conducting film, it prepares by the following method: (step of acid treatment is with embodiment 1 to take graphene powder acid-treated for 0.9g, the particle diameter of the graphene powder obtained is 10 μm, the thickness of Graphene is 3nm, two-dimensional slice footpath is of a size of 10 μm, phosphorus content is more than 99.8wt%) it is scattered in 100mL water, stirring is so as to be uniformly dispersed；Taking 0.1g nanocrystalline cellulose (diameter is 20nm, and length is 300 μm) and be dissolved in 50mL water, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；Being removed a large amount of solvents in above-mentioned mixed liquor by centrifugal treating, retain slurry fractions, the slurry obtained carries out roller process, the calendering time is 1 hour, obtains heat conducting film；Then mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 195W/m K, and vertical thermal conductivity is 1.7W/m K, and hot strength is 167Mpa, and thickness is 34 μm, and density is 1.4g/cm3。
Embodiment 6
Present embodiments provide a kind of high intensity heat conducting film, it prepares by the following method: (step of ultrasonic stripping is: take 100g boron nitride powder to take the boron nitride powder after the ultrasonic stripping of 0.9g, add 500mL water, 1000W supersound process 24 hours, take the supernatant after standing 0.5 hour, filter, clean, dry；The particle diameter of the boron nitride powder obtained is 15 μm, and the thickness of boron nitride is 5nm, and diameter is 15 μm) it is scattered in 100mL water, stirring is so as to be uniformly dispersed；Taking 0.1g nanocrystalline cellulose (diameter is 20nm, and length is 300 μm) and be dissolved in 50mL water, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；Adopting the Suction filtration device mixed liquor to obtaining to carry out sucking filtration, sucking filtration pressure is 0.8atm, and the sucking filtration time is 2 hours, obtains heat conducting film；Then mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 278W/m K, and vertical thermal conductivity is 1.5W/m K, and hot strength is 178Mpa, and thickness is 33 μm, and density is 1.4g/cm3。
Embodiment 7
Present embodiments provide a kind of high intensity heat conducting film, it prepares by the following method: (step of ultrasonic stripping is with embodiment 6 to take the boron nitride powder after the ultrasonic stripping of 0.9g, the particle diameter of the boron nitride powder obtained is 15 μm, the thickness of boron nitride is 5nm, diameter is 15 μm) it is scattered in 100mL water, stirring is so as to be uniformly dispersed；Taking 0.1g nanofibrils cellulose (diameter is 20nm, and length is 300 μm) and be dissolved in 50mL water, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；Adopting the Suction filtration device mixed liquor to obtaining to carry out sucking filtration, sucking filtration pressure is 0.8atm, and the sucking filtration time is 2 hours, obtains heat conducting film；Then mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 346W/m K, and vertical thermal conductivity is 1.8W/m K, and hot strength is 267Mpa, and thickness is 28 μm, and density is 1.7g/cm3。
Embodiment 8
Present embodiments provide a kind of high intensity heat conducting film, it prepares by the following method: (step of ultrasonic stripping is with embodiment 6 to take the aluminium nitride powder after the ultrasonic stripping of 0.9g, the particle diameter of the aluminium nitride powder obtained is 15 μm, the thickness of aluminium nitride is 5nm, diameter is 15 μm) it is scattered in 100mL water, stirring is so as to be uniformly dispersed；Taking 0.1g nanofibrils cellulose (diameter is 20nm, and length is 300 μm) and be dissolved in 50mL water, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；Adopting the Suction filtration device mixed liquor to obtaining to carry out sucking filtration, sucking filtration pressure is 0.8atm, and the sucking filtration time is 2 hours, obtains heat conducting film；Then mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 165W/m K, and vertical thermal conductivity is 1.4W/m K, and hot strength is 265Mpa, and thickness is 28 μm, and density is 1.6g/cm3。
Embodiment 9
Present embodiments provide a kind of high intensity heat conducting film, it prepares by the following method: (step of acid treatment is with embodiment 1 to take the graphene powder after 0.9g acid treatment, the particle diameter of the graphene powder obtained is 10 μm, the thickness of Graphene is 3nm, two-dimensional slice footpath is of a size of 10 μm, phosphorus content is more than 99.8wt%) it is scattered in 100mL water, stirring is so as to be uniformly dispersed；(step of acid treatment is with the acid treatment step of above-mentioned Graphene to take the multi-walled carbon nano-tubes after 0.1g acid treatment, the diameter of the multi-walled carbon nano-tubes obtained is 10nm, length is 100 μm) it is dissolved in 50mL water, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；Adopting the Suction filtration device mixed liquor to obtaining to carry out sucking filtration, sucking filtration pressure is 0.8atm, and the sucking filtration time is 2 hours, obtains heat conducting film；Then mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 397W/m K, and vertical thermal conductivity is 5.8W/m K, and hot strength is 137Mpa, and thickness is 38 μm, and density is 1.8g/cm3。
Embodiment 10
Present embodiments provide a kind of high intensity heat conducting film, it prepares by the following method: (step of acid treatment is with embodiment 1 to take the graphene powder after 0.9g acid treatment, the particle diameter of the graphene powder obtained is 10 μm, the thickness of Graphene is 3nm, two-dimensional slice footpath is of a size of 10 μm, phosphorus content is more than 99.8wt%) it is scattered in 100mL water, stirring is so as to be uniformly dispersed；(step of acid treatment is with the acid treatment step of above-mentioned Graphene to take the carbon fiber after 0.1g acid treatment, the diameter of the carbon fiber obtained is 500nm, length is 300 μm) it is dissolved in 50mL water, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；Adopting the Suction filtration device mixed liquor to obtaining to carry out sucking filtration, sucking filtration pressure is 0.8atm, and the sucking filtration time is 2 hours, obtains heat conducting film；Then mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 450W/m K, and vertical thermal conductivity is 6.9W/m K, and hot strength is 159Mpa, and thickness is 35 μm, and density is 1.8g/cm3。
Embodiment 11
Present embodiments provide a kind of high intensity heat conducting film, it prepares by the following method: be placed in heating furnace by the heat conducting film that embodiment 1 prepares, passing into the hydrogen of 10v/v% and the argon of 90v/v%, gas flow is 10mL/min, and 900 DEG C process 2 hours.Testing heat conductivity in the face of the heat conducting film obtaining preparation is 1650W/m K, and vertical thermal conductivity is 5.7W/m K, and hot strength is 59Mpa, and thickness is 27 μm, and density is 1.6g/cm3。
Embodiment 12
Present embodiments provide a kind of high intensity heat conducting film, it prepares by the following method: (step of acid treatment is with embodiment 1 to take graphene powder acid-treated for 0.5g, the particle diameter of the graphene powder obtained is 10 μm, the thickness of Graphene is 3nm, two-dimensional slice footpath is of a size of 10 μm, phosphorus content is more than 99.8wt%) and 0.4g graphene oxide powder (thickness is 3nm, two-dimensional slice footpath is of a size of 10 μm) it is scattered in 100mL water, stirring is so as to be uniformly dispersed；Taking 0.1g nanocrystalline cellulose (diameter is 20nm, and length is 300 μm) and be dissolved in 50mL water, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；It is subsequently poured in open-top receptacle, and put into vacuum drying oven, keep making solvent evaporate in 1.5 hours when vacuum be 0.9atm, temperature is 50 DEG C, after solvent all evaporates, continue maintenance 0.5 hour, it is cooled to room temperature after taking out open-top receptacle, the heat conducting film of molding is taken out from container；Mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute afterwards；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 178W/m K, and hot strength is 276Mpa, and thickness is 33 μm, and density is 1.4g/cm3。
Comparative example 1
This comparative example provides a kind of heat conducting film, it prepares by the following method: (step of acid treatment is with embodiment 1 to take graphene powder acid-treated for 0.9g, the particle diameter of the graphene powder obtained is 10 μm, the thickness of Graphene is 3nm, two-dimensional slice footpath is of a size of 10 μm, phosphorus content is more than 99.8wt%) it is scattered in 100mL water, stirring is so as to be uniformly dispersed；Taking 0.1g polyvinyl alcohol (PVA) and be dissolved in 50mL water, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；It is subsequently poured in open-top receptacle, and put into vacuum drying oven, keep making solvent evaporate in 2 hours when vacuum be 0.9atm, temperature is 50 DEG C, after solvent all evaporates, continue maintenance 0.5 hour, it is cooled to room temperature after taking out open-top receptacle, the heat conducting film of molding is taken out from container；Mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute afterwards；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 13W/m K, and vertical thermal conductivity is 4.3W/m K, and hot strength is 25Mpa, and thickness is 28 μm, and density is 1.6g/cm3。
Comparative example 2
This comparative example provides a kind of heat conducting film, it prepares by the following method: (step of acid treatment is with embodiment 1 to take graphene powder acid-treated for 0.9g, the particle diameter of the graphene powder obtained is 10 μm, the thickness of Graphene is 3nm, two-dimensional slice footpath is of a size of 10 μm, phosphorus content is more than 99.8wt%) it is scattered in 100mL acetone, stirring is so as to be uniformly dispersed；Taking 0.1g epoxy resin and be dissolved in 50mL acetone, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；It is subsequently poured in open-top receptacle, and put into vacuum drying oven, keep making solvent evaporate in 1.5 hours when vacuum be 0.9atm, temperature is 50 DEG C, after solvent all evaporates, continue maintenance 0.5 hour, it is cooled to room temperature after taking out open-top receptacle, the heat conducting film of molding is taken out from container；Mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute afterwards；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 7.8W/m K, and hot strength is 19Mpa, and thickness is 32 μm, and density is 1.5g/cm3。
To heat conducting film obtained above 1400 DEG C of carbonization treatment 24 hours, it is then placed in 2800 DEG C of high temperature furnaces and processes 24 hours, take out calendering afterwards, in the face of the heat conducting film obtained, heat conductivity is 158W/m K, hot strength is 18MPa, and thickness is 22 μm, and density is 1.7g/cm3。
Comparative example 3
This comparative example provides a kind of heat conducting film, it prepares by the following method: (step of acid treatment is with embodiment 1 to take graphene powder acid-treated for 0.5g, the particle diameter of the graphene powder obtained is 10 μm, the thickness of Graphene is 3nm, two-dimensional slice footpath is of a size of 10 μm, phosphorus content is more than 99.8wt%) and 0.4g graphene oxide powder (thickness is 3nm, and two-dimensional slice footpath is of a size of 10 μm) be scattered in 100mL water, stirring so as to be uniformly dispersed；Taking 0.1g polyvinylpyrrolidone and be dissolved in 50mL ethanol, ultrasonic (power is 100W, and frequency is 50KHz) processes 30 minutes；By above-mentioned two dispersion liquid mix homogeneously under high-speed stirred (mixing speed is 1000r/min)；It is subsequently poured in open-top receptacle, and put into vacuum drying oven, keep making solvent evaporate in 1.5 hours when vacuum be 0.9atm, temperature is 50 DEG C, after solvent all evaporates, continue maintenance 0.5 hour, it is cooled to room temperature after taking out open-top receptacle, the heat conducting film of molding is taken out from container；Mechanical pressurization device is adopted this heat conducting film to be applied the pressure of 10MPa and keeps 1 minute afterwards；Testing heat conductivity in the face of the heat conducting film obtaining preparation is 18W/m K, and hot strength is 20Mpa, and thickness is 28 μm, and density is 1.5g/cm3。
Claims (10)
1. a preparation method for high intensity heat conducting film, it comprises the following steps: by conduction powder with nanometer and/or fibrous material mix homogeneously after make thin film, obtain described high intensity heat conducting film.
2. the preparation method of high intensity heat conducting film according to claim 1, wherein, described conduction powder includes the combination of one or more in the aluminium nitride powder of the graphene powder of graphene powder, boron nitride powder, aluminium nitride powder and functionalization, the boron nitride powder of functionalization, functionalization.
3. the preparation method of high intensity heat conducting film according to claim 1, wherein, described nanometer and/or fibrous material include the combination of one or more in nanofibrils cellulose, nanocrystalline cellulose, carbon fiber and CNT.
4. the preparation method of the high intensity heat conducting film according to any one of claim 1-3, wherein, the mass ratio of described conduction powder and described nanometer and/or fibrous material is 9.9:0.1～5:5.
5. the preparation method of high intensity heat conducting film according to claim 1, wherein, by conduction powder with nanometer and/or fibrous material mix homogeneously after make the step of thin film and include: by conduction powder with nanometer and/or the mixed liquor of fibrous material, thin film is made, it will be preferred that in the way of sucking filtration film forming, make thin film in one or more modes in solvent evaporation, sucking filtration film forming, roll-in film forming.
6. the preparation method of high intensity heat conducting film according to claim 5, it farther includes: after making thin film in one or more modes in solvent evaporation, sucking filtration film forming, roll-in film forming, this thin film applied certain pressure and keeps a period of time, obtaining described high intensity heat conducting film；Preferably, the pressure that this thin film is applied is 1～30MPa, and the time of maintenance is 1～30 minute.
7. the preparation method of high intensity heat conducting film according to claim 5, wherein, the mode of described solvent evaporation comprises the following steps: by described conduction powder with nanometer and/or the mixed liquor of fibrous material pour in open-top receptacle, a period of time is kept to make solvent evaporate under certain vacuum degree and uniform temperature, continue to keep a period of time after solvent all evaporates, obtain described heat conducting film；Preferably, described conduction powder with nanometer and/or the concentration of mixed liquor of fibrous material be 0.1～100g/L, described vacuum is 10～101KPa, described temperature is 30～100 DEG C, making solvent evaporate the time kept completely is 0.5～12 hour, and the time that solvent continues after all evaporating to keep is 0.5～1 hour；
The mode of described sucking filtration film forming comprises the following steps: by described conduction powder with nanometer and/or the mixed liquor of fibrous material be 0.1～10atm, sucking filtration time carry out sucking filtration when being 0.5～24 hour at sucking filtration pressure, obtain described heat conducting film；Preferably, described conduction powder with nanometer and/or the concentration of mixed liquor of fibrous material be 0.01～10g/L；
The mode of described roll-in film forming comprises the following steps: by described conduction powder with nanometer and/or the mixed liquor of fibrous material prepare form slurry, described slurry is carried out roller process, the calendering time is 0.5～10 hour, obtains described heat conducting film.
8. the preparation method of high intensity heat conducting film according to claim 6, it farther includes high-temperature heat treatment, namely thin film is being made in one or more modes in solvent evaporation, sucking filtration film forming, roll-in film forming, and after this thin film being applied certain pressure and keeping a period of time, the heat conducting film that obtains is processed 0.5～2 hour in the atmosphere of 900～1200 DEG C and hydrogen and/or argon, obtains described high intensity heat conducting film.
9. a high intensity heat conducting film, it is the preparation method of high intensity heat conducting film according to any one of claim 1-8 and prepares.
10. high intensity heat conducting film according to claim 9, in its face, heat conductivity is 100～2000W/m K, and hot strength is 50～300Mpa, and thickness is 5～100 μm, and density is 0.5～2.0g/cm3；Preferably, in the face of described high intensity heat conducting film, heat conductivity is 200～500W/m K, and hot strength is 130～300Mpa, and thickness is 20～50 μm, and density is 1.2～2.0g/cm3。
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