CN104130753A - High-thermal-conductivity high-electrical-conductivity carbon nano-grade composite material and preparation method thereof - Google Patents
High-thermal-conductivity high-electrical-conductivity carbon nano-grade composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-thermal-conductivity high-electrical-conductivity carbon nano-grade composite material. The material is characterized in that a polymer with a mass percentage of 3-30% is stuck and coated on the surface of carbon-based micro-nano powder with a mass percentage of 70-97%, and press molding is carried out, such that the material is obtained. According to the composite material, a layer of polymer is coated on the surface of high-thermal-conductivity high-electrical-conductivity carbon-based micro-nano powder with a water suspension method, such that the high-thermal-conductivity high-electrical-conductivity carbon nano-grade composite material powder is prepared. Preparation efficiency is high. When the method provided by the invention is used in preparing the high-thermal-conductivity high-electrical-conductivity carbon nano-grade composite material, the method is simple and feasible. The content of the carbon-based micro-nano powder filling material is high. The method can satisfy actual requirements of large-batch productions. The prepared high-thermal-conductivity carbon nano-grade material has good electrical conductivity and thermal conductivity, and can be applied in 3D printing materials, chemical equipment heat exchangers, laptops, high-power LED lightings, flat panel displays, digital cameras, mobile communication products, and fields of related miniaturized and high speed electronic components.
Description
Technical field
The invention belongs to carbon-based polymer matrix material, relate to a kind of high heat-conductivity conducting carbon nano-composite material and preparation method thereof.Be particularly related to and utilize the coated one layer of polymeric binding agent of water suspension method to prepare electric-conductivity heat-conductivity high carbon nano-composite material on high heat-conductivity conducting carbon back micro-nano powder surface.High heat-conductivity conducting carbon nano-composite material of the present invention is mainly used in interchanger, notebook computer, high-power LED illumination, flat-panel monitor, Digital Video and mobile communication product and relevant microminiaturization and the electronic devices and components field of high speed of 3D printed material, chemical industry equipment.
Background technology
Carbon back micro-nano powder has thermal characteristics and the electrical property of high specific surface area, mechanical property, brilliance, and wherein carbon back filler, as graphite (209Wm
-1k
-1), carbon nanotube (3100～3500Wm
-1k
-1), diamond (2000Wm
-1k
-1), Graphene (4840～5300Wm
-1k
-1) etc. there is the thermal conductivity of superelevation, the thermal conductivity that uses it to improve matrix material enjoys the favor of academia and industry member.In recent years, people are successfully by carbon nanotube (as: multi-walled carbon nano-tubes, Single Walled Carbon Nanotube), carbon nanofiber, the carbon materials such as soccerballene are as filler, with metal-powder or metal and ceramic mixed powder etc. be base material, prepare various novel electric-conductivity heat-conductivity high carbon nanomaterials, the functionalized carbon based composites of gained has high heat conduction and electroconductibility simultaneously, good mechanical property, and good workability, value has a wide range of applications in fields such as biological medicine, micro-nano electronics, high performance composite.Chinese patent CN101707911A discloses a kind of " highly thermally conductive composite material ", system is used in the base material that the discharge plasma sintered compact of metal-powder or metal and ceramic mixed powder or ceramic powder forms, form and exist the fibrous carbon material that multilayer is made up of superfine tubular body structure, this superfine tubular body structure is made up of the Graphene of single or multiple lift; The fibrous carbon material that forms each layer is to be formed by the mixture that in the particle size fiber that is 500nm～100um in mean diameter, a small amount of mixing mean diameter is the small diameter fiber below 100nm; In the method, relate to the problem that particle size fibre orientation and small diameter fiber are not orientated, in process, need to be by particle size fiber and small diameter fiber in proportion at dispersion liquid from processing, and then by apply magnetic field, electric field or directly in dispersion liquid slow stretching be orientated, this process is not easy to operation, complex steps, consume energy larger, and cannot ensure the degree of orientation of fiber, therefore can have a great impact the thermal conductivity of product.
Summary of the invention
Object of the present invention is intended to overcome deficiency of the prior art, a kind of high heat-conductivity conducting carbon nano-composite material and preparation method thereof is provided, the invention provides a kind of easy, method of preparing efficiently electric-conductivity heat-conductivity high carbon nanomaterial, can effectively improve the content of carbon back filler in carbon-based polymer matrix material, significantly improve the mechanical property of polymer materials, give polymer materials many new functions simultaneously, show especially the high thermal conductivity aspect of material, thereby realize multi-functional high-strength composite material.
Content of the present invention is: a kind of high heat-conductivity conducting carbon nano-composite material, it is characterized in that: the carbon back micro nano powder filler that is 70～97% by mass percent, the polymeric binder that be coated on carbon back micro nano powder filler, mass percent is 3～30% composition.
In content of the present invention: described carbon back micro nano powder filler can be:
Single Walled Carbon Nanotube (can be Timestub
tM-high-purity Single Walled Carbon Nanotube, Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences produces, model: TNS, outside diameter OD is 1～2nm, purity (Purity>=90wt%), length is 5～30 μ m, specific surface area SSA>=380m
2/ g, ash content≤1.5wt%, electric conductivity EC>=100s/cm, bulk density (Tap Density) is 0.14g/cm
3),
Multi-walled carbon nano-tubes (can be that Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences produces, model: TNM1, outside diameter OD>=50nm, purity (Purity>=90wt%), length is 10～30 μ m, specific surface area SSA>=40m
2/ g, ash content≤5wt%, electric conductivity EC>=100s/cm, bulk density (Tap Density) is 0.27g/cm
3),
Graphene (can be TimesGraph
tM-Graphene, Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences produces, purity (Purity>=95wt%), specific surface area SSA>=554.364m
2/ g, diameter is 0.5～3 μ m, and the number of plies is 1～10 layer, and thickness is 0.55～3.74nm; Or soccerballene C
60, purity (Purity>=98wt%), fusing point>=280 DEG C, burning-point>=94 DEG C) or
Carbon nanofiber (can be: C-25 carbon nanofiber, Anshan Sinocrab Carbon Fiber Co., Ltd. produces, specific surface area SSA>=1000m
2/ g).
The particle diameter of described carbon back micro nano powder filler is 0.5 μ m～50 μ m preferably.
In content of the present invention: described polymeric binder can be that polymethylmethacrylate (is called for short PMMA, manufacturing enterprise has: SUMITOMO CHEMICAL, trade mark HT03Y, France Arkema, trade mark V04l resin), (manufacturing enterprise has viton: middle Wu Chenguang chemical institute etc., trade mark FPM2606 resin) or nylon (abbreviation PA, manufacturing enterprise has: Shen Ma engineering plastics company etc., nylon-66, nylon-6) etc. resin, be common commercial commercialization high molecular synthetic resin.
Described polymeric binder (for example PMMA, PA's etc.) number-average molecular weight is 100,000～200,000.
Another content of the present invention is: the preparation method of high heat-conductivity conducting carbon nano-composite material, and it is characterized in that adopting following water suspension method to be prepared from, step is as follows:
A, 1～5g carbon back micro nano powder filler is joined in the distilled water of 40～200ml and disperses the ultrasonic dispersion of method of ultrasonic dispersion (can adopt 3～6 hours), then carbon back micro nano powder filler/aqueous systems is warming up to 50～80 DEG C, heat while stirring, in system, add tensio-active agent 0.05～0.2ml again, continue to stir 5～10min;
B, 0.125～0.625g polymeric binder is dissolved in 5～15ml organic solvent, again polymeric binder/organic solvent system (with given pace) is added drop-wise in above-mentioned carbon back micro nano powder filler/aqueous systems, time for adding is 5～15min, stir on dropping limit, limit, mixed system is warming up to 55～85 DEG C, continue again to stir 10～20min, be formed with particle;
C, be cooled to room temperature (discharging), after filtering, get solids and be placed in air dry oven forced air drying 3～4h at the temperature of 40～50 DEG C, obtain the coccoid particle of dry black; Filtering out particle size range is the small-particle of 10 μ m～90 μ m, the phenomenon that grain diameter is larger is because the reunion of carbon back micro nano powder filler causes, make polymer overmold poor effect, can affect heat conduction, conductivity and other relevant mechanical properties etc. of matrix material, the coccoid carbon back micro nano powder filler/polymeric binder of the black particle obtaining (can again through grinding, hot-forming) is high heat-conductivity conducting carbon nano-composite material powder.
In another content of the present invention: the coccoid carbon back micro nano powder filler/polymeric binder of the black particle obtaining described in step c can also be again through hot-forming, hot-forming processing parameter is: the pressure of compression moulding is 20～120KN, temperature when hot pressing is 200～400 DEG C, time is 10～600min, the concrete same prior art of mode, object is to make polymeric binder melt-flow in the process of compacting, fully fill the space between small-particle, thereby the gravitation between enhancing small-particle and adhesive power, strengthen the heat conduction of profiled member, conductivity and other relevant mechanical properties etc., after hot-forming, obtain high heat-conductivity conducting carbon nano-composite material.
The thermal conductivity of the described high heat-conductivity conducting carbon nano-composite material obtaining (test sample) is 1～30Wm
-1k
-1, specific conductivity is 0.5～5S/m, and ultimate compression strength is 5～25MPa, and tensile strength is 2～10MPa.
In another content of the present invention: the carbon back micro nano powder filler described in step a is: Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, Graphene or carbon nanofiber; Polymeric binder described in step b is polymethylmethacrylate, viton or nylon.
In another content of the present invention: described carbon back micro nano powder filler can be:
Single Walled Carbon Nanotube (Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences produces, model: TNS, and outside diameter OD is 1～2nm, purity (Purity>=90wt%), length is 5～30 μ m, specific surface area SSA>=380m
2/ g, ash content≤1.5wt%, electric conductivity EC>=100s/cm, bulk density (Tap Density) is 0.14g/cm
3),
Multi-walled carbon nano-tubes (Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences produces, model: TNM1, and outside diameter OD>=50nm, purity (Purity>=90wt%), length is 10～30 μ m, specific surface area SSA>=40m
2/ g, ash content≤5wt%, electric conductivity EC>=100s/cm, bulk density (Tap Density) is 0.27g/cm
3),
Graphene (can be TimesGraph
tM-Graphene, Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences produces, purity (Purity>=95wt%), specific surface area SSA>=554.364m
2/ g, diameter is 0.5～3 μ m, and the number of plies is 1～10 layer, and thickness is 0.55～3.74nm; Or soccerballene C
60, purity (Purity>=98wt%), fusing point>=280 DEG C, burning-point>=94 DEG C) or
Carbon nanofiber (can be: C-25 carbon nanofiber, Anshan Sinocrab Carbon Fiber Co., Ltd. produces, specific surface area SSA>=1000m
2/ g);
The particle diameter of described carbon back micro nano powder filler is 0.5 μ m～50 μ m preferably.
In another content of the present invention: described polymeric binder can be that polymethylmethacrylate (is called for short PMMA, manufacturing enterprise has: SUMITOMO CHEMICAL, trade mark HT03Y, France Arkema, trade mark V04l resin), (manufacturing enterprise has viton: middle Wu Chenguang chemical institute etc., trade mark FPM2606 resin) or nylon (abbreviation PA, manufacturing enterprise has: Shen Ma engineering plastics company etc., nylon-66, nylon-6) etc. resin, be common commercial commercialization high molecular synthetic resin;
Described polymeric binder (for example PMMA, PA's etc.) number-average molecular weight is 100,000～200,000.
In another content of the present invention: the tensio-active agent described in step a (water-in-oil-type tensio-active agent) is tween-80 (English name Tween-80) or span-80 (Span-80) etc. preferably, or other common commercial commercialization nonionic agent.
In another content of the present invention: the organic solvent described in step b is chloroform, ethyl acetate or methylene dichloride etc. preferably, or other and the immiscible organic solvent of water.
Compared with prior art, the present invention has following feature and beneficial effect:
(1) adopt the present invention, utilize the coated one layer of polymeric of water suspension method to prepare electric-conductivity heat-conductivity high carbon nanomaterial, preparation efficiency is high, and the electric-conductivity heat-conductivity high carbon nanomaterial heat-conductivity conducting excellent property of preparing;
(2) adopt the present invention, the thermal conductivity of the high heat-conductivity conducting carbon nano-composite material making is that 1～30W/ (mK), specific conductivity are that 0.5～5S/m, ultimate compression strength are that 5～25MPa, tensile strength are 2～10MPa; The content of electric-conductivity heat-conductivity high carbon back micro-nano powder filler is high, can reach 70～97wt%, simple and feasible, can meet the actual requirement of production in enormous quantities;
(3) high heat-conductivity conducting carbon nano-composite material of the present invention is mainly used in interchanger, notebook computer, high-power LED illumination, flat-panel monitor, Digital Video and the mobile communication product of 3D printed material, chemical industry equipment and the relevant association area such as microminiaturization and the electronic devices and components of high speed;
(4) product preparation process of the present invention is simple, and operation is easy, and feasibility is high, practical.
Embodiment
The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1:
High heat-conductivity conducting carbon nano-composite material consists of: mass percent consists of carbon nanotube (can be Single Walled Carbon Nanotube or multi-walled carbon nano-tubes) 94.3wt%, polymethylmethacrylate 5.7wt%.
The preparation method of high heat-conductivity conducting carbon nano-composite material, step is as follows:
A, by carbon nanotube in appropriate distilled water, adopt ultrasonic 3～6 hours of the method for ultrasonic dispersion;
B, above-mentioned carbon nanotube/aqueous systems is heated to 60 DEG C, violent stirring, then add appropriate water-in-oil-type tensio-active agent tween 80, stir 5～10min;
C, polymethylmethacrylate is dissolved in appropriate chloroform, is made into the solution of 15% left and right;
D, the above-mentioned chloroformic solution dropping funnel that is dissolved with polymethylmethacrylate is splashed in above-mentioned carbon nanotube/aqueous systems, violent stirring, is warming up to 62 DEG C, the form of carbon nanotube in observe system, and reaction is carried out stopping after 20min;
E, be cooled to room temperature, then carry out suction filtration, then put into vacuum drying oven dry 2 hours, through screening, grind, obtain the coccoid particle of black;
F, coccoid the black of gained particle is adopted to hot-forming mode, the temperature when pressure of compression moulding is 120KN, hot pressing is that 210 DEG C, time are 60min, object is to make polymeric binder melt-flow in the process of compacting, fully fill the space between small-particle, thereby the gravitation between enhancing small-particle and adhesive power, heat conduction, conductivity and other the relevant mechanical properties etc. that strengthen profiled member, by hot-forming, obtain high heat-conductivity conducting carbon nano-composite material;
The composite property test data obtaining is as follows: thermal conductivity: 8.5Wm
-1k
-1, ultimate compression strength: 23.37MPa, tensile strength: 6.89MPa.
Embodiment 2:
The high heat-conductivity conducting carbon nano-composite material mass percent of the present embodiment forms with embodiment 1; Preparation technology is with reference to embodiment 1, and compared with embodiment 1, its processing parameter is basic identical, and the hot pressing temperature, the temperature that change in hot-forming process are 160 DEG C, the other the same as in Example 1;
The composite property test data obtaining is as follows: thermal conductivity: 8.2Wm
-1k
-1, ultimate compression strength: 21.68MPa, tensile strength: 5.93MPa.
Embodiment 3:
The high heat-conductivity conducting carbon nano-composite material mass percent of the present embodiment forms with embodiment 1; Preparation technology is with reference to embodiment 1, and compared with embodiment 1, its processing parameter is basic identical, and the hot pressing temperature, the temperature that change in hot-forming process are 25 DEG C of room temperatures, the other the same as in Example 1;
The composite property test data obtaining is as follows: thermal conductivity: 7.5Wm
-1k
-1, ultimate compression strength: 15.70MPa, tensile strength: 2.51MPa.
Embodiment 4:
The high heat-conductivity conducting carbon nano-composite material mass percent of the present embodiment forms with embodiment 1; Preparation technology is with reference to embodiment 1, and compared with embodiment 1, its processing parameter is basic identical, and the pressing pressure, the pressure that change in hot-forming process are 60KN, the other the same as in Example 1;
The composite property test data obtaining is as follows: thermal conductivity: 7.8Wm
-1k
-1, ultimate compression strength: 18.93MPa, tensile strength: 3.17MPa.
Embodiment 5:
A kind of high heat-conductivity conducting carbon nano-composite material, the carbon back micro nano powder filler that is 70% by mass percent, the polymeric binder that be coated on carbon back micro nano powder filler, mass percent is 30% composition.
Embodiment 6:
A kind of high heat-conductivity conducting carbon nano-composite material, the carbon back micro nano powder filler that is 97% by mass percent, the polymeric binder that be coated on carbon back micro nano powder filler, mass percent is 3% composition.
Embodiment 7:
A kind of high heat-conductivity conducting carbon nano-composite material, the carbon back micro nano powder filler that is 83% by mass percent, the polymeric binder that be coated on carbon back micro nano powder filler, mass percent is 16% composition.
Embodiment 8～14:
A kind of high heat-conductivity conducting carbon nano-composite material, the carbon back micro nano powder filler that is 70～97% by mass percent, the polymeric binder that be coated on carbon back micro nano powder filler, mass percent is 3～30% composition; In each embodiment, the concrete mass percent consumption of each component raw material sees the following form:
Embodiment 15:
A preparation method for high heat-conductivity conducting carbon nano-composite material, adopts water suspension method to be prepared from, and step is as follows:
A, 1g carbon back micro nano powder filler is joined in the distilled water of 40ml and disperses the ultrasonic dispersion of method of ultrasonic dispersion (can adopt 3 hours), then carbon back micro nano powder filler/aqueous systems is warming up to 50 DEG C, heat while stirring, in system, add tensio-active agent 0.05ml again, continue to stir 10min;
B, 0.125g polymeric binder is dissolved in 5ml organic solvent, again polymeric binder/organic solvent system (with given pace) is added drop-wise in above-mentioned carbon back micro nano powder filler/aqueous systems, time for adding is 5min, stir on dropping limit, limit, mixed system is warming up to 55 DEG C, continue again to stir 20min, be formed with particle;
C, be cooled to room temperature (discharging), after filtering, the solids of getting filtration is placed in air dry oven forced air drying 4h at the temperature of 40 DEG C, obtains the coccoid particle of dry black; Filtering out particle size range is the small-particle of 10 μ m～90 μ m, the phenomenon that grain diameter is larger is because the reunion of carbon back micro nano powder filler causes, make polymer overmold poor effect, can affect heat conduction, conductivity and other relevant mechanical properties etc. of matrix material, the coccoid carbon back micro nano powder filler/polymeric binder of the black particle obtaining (can again through grinding, hot-forming) is high heat-conductivity conducting carbon nano-composite material powder.
The coccoid carbon back micro nano powder filler/polymeric binder of the black particle obtaining described in step c can also be again through hot-forming, hot-forming processing parameter is: the pressure of compression moulding is 20KN, temperature when hot pressing is 200 DEG C, time is 300min, object is to make polymeric binder melt-flow in the process of compacting, fully fill the space between small-particle, thereby the gravitation between enhancing small-particle and adhesive power, strengthen the heat conduction of profiled member, conductivity and other relevant mechanical properties etc., after hot-forming, obtain high heat-conductivity conducting carbon nano-composite material.
Embodiment 16:
A preparation method for high heat-conductivity conducting carbon nano-composite material, adopts water suspension method to be prepared from, and step is as follows:
A, 5g carbon back micro nano powder filler is joined in the distilled water of 200ml and disperses the ultrasonic dispersion of method of ultrasonic dispersion (can adopt 6 hours), then carbon back micro nano powder filler/aqueous systems is warming up to 80 DEG C, heat while stirring, in system, add tensio-active agent 0.2ml again, continue to stir 5min;
B, 0.625g polymeric binder is dissolved in 15ml organic solvent, again polymeric binder/organic solvent system (with given pace) is added drop-wise in above-mentioned carbon back micro nano powder filler/aqueous systems, time for adding is 15min, stir on dropping limit, limit, mixed system is warming up to 85 DEG C, continue again to stir 10min, be formed with particle;
C, be cooled to room temperature (discharging), after filtering, the solids of getting filtration is placed in air dry oven forced air drying 3h at the temperature of 50 DEG C, obtains the coccoid particle of dry black; Filtering out particle size range is the small-particle of 10 μ m～90 μ m, the phenomenon that grain diameter is larger is because the reunion of carbon back micro nano powder filler causes, make polymer overmold poor effect, can affect heat conduction, conductivity and other relevant mechanical properties etc. of matrix material, the coccoid carbon back micro nano powder filler/polymeric binder of the black particle obtaining (can again through grinding, hot-forming) is high heat-conductivity conducting carbon nano-composite material powder.
The coccoid carbon back micro nano powder filler/polymeric binder of the black particle obtaining described in step c can also be again through hot-forming, hot-forming processing parameter is: the pressure of compression moulding is 120KN, temperature when hot pressing is 400 DEG C, time is 300min, object is to make polymeric binder melt-flow in the process of compacting, fully fill the space between small-particle, thereby the gravitation between enhancing small-particle and adhesive power, strengthen the heat conduction of profiled member, conductivity and other relevant mechanical properties etc., after hot-forming, obtain high heat-conductivity conducting carbon nano-composite material.
Embodiment 17:
A preparation method for high heat-conductivity conducting carbon nano-composite material, adopts water suspension method to be prepared from, and step is as follows:
A, 3g carbon back micro nano powder filler is joined in the distilled water of 120ml and disperses the ultrasonic dispersion of method of ultrasonic dispersion (can adopt 4.5 hours), then carbon back micro nano powder filler/aqueous systems is warming up to 65 DEG C, heat while stirring, in system, add tensio-active agent 0.12ml again, continue to stir 8min;
B, 0.375g polymeric binder is dissolved in 10ml organic solvent, again polymeric binder/organic solvent system (with given pace) is added drop-wise in above-mentioned carbon back micro nano powder filler/aqueous systems, time for adding is 10min, stir on dropping limit, limit, mixed system is warming up to 70 DEG C, continue again to stir 15min, be formed with particle;
C, be cooled to room temperature (discharging), after filtering, get solids and be placed in air dry oven forced air drying 3.5h at the temperature of 45 DEG C, obtain the coccoid particle of dry black; Filtering out particle size range is the small-particle of 10 μ m～90 μ m, the phenomenon that grain diameter is larger is because the reunion of carbon back micro nano powder filler causes, make polymer overmold poor effect, can affect heat conduction, conductivity and other relevant mechanical properties etc. of matrix material, the coccoid carbon back micro nano powder filler/polymeric binder of the black particle obtaining (can again through grinding, hot-forming) is high heat-conductivity conducting carbon nano-composite material powder.
The coccoid carbon back micro nano powder filler/polymeric binder of the black particle obtaining described in step c can also be again through hot-forming, hot-forming processing parameter is: the pressure of compression moulding is 70KN, temperature when hot pressing is 300 DEG C, time is 300min, object is to make polymeric binder melt-flow in the process of compacting, fully fill the space between small-particle, thereby the gravitation between enhancing small-particle and adhesive power, strengthen the heat conduction of profiled member, conductivity and other relevant mechanical properties etc., after hot-forming, obtain high heat-conductivity conducting carbon nano-composite material.
Embodiment 18:
A preparation method for high heat-conductivity conducting carbon nano-composite material, adopts water suspension method to be prepared from, and step is as follows:
A, 1～5g carbon back micro nano powder filler is joined in the distilled water of 40～200ml and disperses the ultrasonic dispersion of method of ultrasonic dispersion (can adopt 3～6 hours), then carbon back micro nano powder filler/aqueous systems is warming up to 50～80 DEG C, heat while stirring, in system, add tensio-active agent 0.05～0.2ml again, continue to stir 5～10min;
B, 0.125～0.625g polymeric binder is dissolved in 5～15ml organic solvent, again polymeric binder/organic solvent system (with given pace) is added drop-wise in above-mentioned carbon back micro nano powder filler/aqueous systems, time for adding is 5～15min, stir on dropping limit, limit, mixed system is warming up to 55～85 DEG C, continue again to stir 10～20min, be formed with particle;
C, be cooled to room temperature (discharging), after filtering, get solids and be placed in air dry oven forced air drying 3～4h at the temperature of 40～50 DEG C, obtain the coccoid particle of dry black; Filtering out particle size range is the small-particle of 10 μ m～90 μ m, the phenomenon that grain diameter is larger is because the reunion of carbon back micro nano powder filler causes, make polymer overmold poor effect, can affect heat conduction, conductivity and other relevant mechanical properties etc. of matrix material, the coccoid carbon back micro nano powder filler/polymeric binder of the black particle obtaining (can again through grinding, hot-forming) is high heat-conductivity conducting carbon nano-composite material powder;
The coccoid carbon back micro nano powder filler/polymeric binder of the black particle obtaining described in step c can also be again through hot-forming, hot-forming processing parameter is: the pressure of compression moulding is 20～120KN, temperature when hot pressing is 200～400 DEG C, time is 10～600min, object is to make polymeric binder melt-flow in the process of compacting, fully fill the space between small-particle, thereby the gravitation between enhancing small-particle and adhesive power, strengthen the heat conduction of profiled member, conductivity and other relevant mechanical properties etc., after hot-forming, obtain high heat-conductivity conducting carbon nano-composite material.
In above-described embodiment 5～18: described carbon back micro nano powder filler can be:
Single Walled Carbon Nanotube (can be Timestub
tM-high-purity Single Walled Carbon Nanotube, Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences produces, model: TNS, outside diameter OD is 1～2nm, purity (Purity>=90wt%), length is 5～30 μ m, specific surface area SSA>=380m
2/ g, ash content≤1.5wt%, electric conductivity EC>=100s/cm, bulk density (Tap Density) is 0.14g/cm
3),
Multi-walled carbon nano-tubes (can be Timestub
tM-high-purity Single Walled Carbon Nanotube, Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences produces, model: TNM1, outside diameter OD>=50nm, purity (Purity>=90wt%), length is 10～30 μ m, specific surface area SSA>=40m
2/ g, ash content≤5wt%, electric conductivity EC>=100s/cm, bulk density (Tap Density) is 0.27g/cm
3),
Graphene (can be TimesGraph
tM-Graphene, Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences produces, purity (Purity>=95wt%), specific surface area SSA>=554.364m
2/ g, diameter is 0.5～3 μ m, and the number of plies is 1～10 layer, and thickness is 0.55～3.74nm; Or soccerballene C
60, purity (Purity>=98wt%), fusing point>=280 DEG C, burning-point>=94 DEG C) or
Carbon nanofiber (can be: C-25 carbon nanofiber, Anshan Sinocrab Carbon Fiber Co., Ltd. produces, specific surface area SSA>=1000m
2/ g).
The particle diameter of described carbon back micro nano powder filler is 0.5 μ m～50 μ m preferably.
In above-described embodiment 5～18: described polymeric binder can be that polymethylmethacrylate (is called for short PMMA, manufacturing enterprise has: SUMITOMO CHEMICAL, trade mark HT03Y, France Arkema, trade mark V04l resin), (manufacturing enterprise has viton: middle Wu Chenguang chemical institute etc., trade mark FPM2606 resin) or nylon (abbreviation PA, manufacturing enterprise has: Shen Ma engineering plastics company etc., nylon-66, nylon-6) etc. resin, be common commercial commercialization high molecular synthetic resin.
Described polymeric binder (for example PMMA, PA's etc.) number-average molecular weight is 100,000～200,000.
In above-described embodiment 5～18: the tensio-active agent described in step a is tween-80 (English name Tween-80) or span-80 (Span-80) etc. preferably, or other common commercial commercialization nonionic agent.
In above-described embodiment 5～18: the organic solvent described in step b can be chloroform, ethyl acetate or methylene dichloride etc., or other and the immiscible organic solvent of water.
The performance test data of the described high heat-conductivity conducting carbon nano-composite material obtaining is 1～30Wm in thermal conductivity
-1k
-1, specific conductivity is 0.5～5S/m, ultimate compression strength is 5～25MPa, in the scope that tensile strength is 2～10MPa.
In above-described embodiment: the each component raw material adopting is commercially available prod.
In above-described embodiment: in the percentage adopting, do not indicate especially, be quality (weight) percentage or well known to a person skilled in the art percentage; Described quality (weight) part can be all gram or kilogram; Symbol wt% is weight (quality) percentage.
In above-described embodiment: processing parameter (temperature, time, concentration, pressure etc.) and each amounts of components numerical value etc. in each step is scope, and any point is all applicable.
The not concrete same prior art of technology contents of narrating in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, all can implement and have described good result described in content of the present invention.
Claims (10)
1. a high heat-conductivity conducting carbon nano-composite material, is characterized in that: the carbon back micro nano powder filler that is 70～97% by mass percent, the polymeric binder that be coated on carbon back micro nano powder filler, mass percent is 3～30% composition.
2. by high heat-conductivity conducting carbon nano-composite material described in claim 1, it is characterized in that: described carbon back micro nano powder filler is: Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, Graphene or carbon nanofiber.
3. by high heat-conductivity conducting carbon nano-composite material described in claim 1 or 2, it is characterized in that: the particle diameter of described carbon back micro nano powder filler is 0.5 μ m～50 μ m.
4. by high heat-conductivity conducting carbon nano-composite material described in claim 1, it is characterized in that: described polymeric binder is polymethylmethacrylate, viton or nylon.
5. by high heat-conductivity conducting carbon nano-composite material described in claim 1, it is characterized in that: described polymeric binder number-average molecular weight is 100,000～200,000.
6. a preparation method for high heat-conductivity conducting carbon nano-composite material, is characterized in that step is as follows:
A, 1～5g carbon back micro nano powder filler is joined in the distilled water of 40～200ml and disperse, then carbon back micro nano powder filler/aqueous systems is warming up to 50～80 DEG C, heat while stirring, then add tensio-active agent 0.05～0.2ml in system, continue to stir 5～10min;
B, 0.125～0.625g polymeric binder is dissolved in 5～15ml organic solvent, again polymeric binder/organic solvent system is added drop-wise in above-mentioned carbon back micro nano powder filler/aqueous systems, time for adding is 5～15min, stir on dropping limit, limit, mixed system is warming up to 55～85 DEG C, then continues to stir 10～20min;
C, be cooled to room temperature, after filtering, the solids of getting filtration is placed in air dry oven forced air drying 3～4h at the temperature of 40～50 DEG C, obtains the coccoid particle of dry black; Filtering out particle size range is the small-particle of 10 μ m～90 μ m, the coccoid carbon back micro nano powder of black obtaining.
7. by the preparation method of high heat-conductivity conducting carbon nano-composite material described in claim 6, it is characterized in that: the coccoid carbon back micro nano powder filler/polymeric binder of the black particle obtaining described in step c is again through hot-forming, hot-forming processing parameter is: the temperature when pressure of compression moulding is 20～120KN, hot pressing is that 200～400 DEG C, time are 10～600min, obtains high heat-conductivity conducting carbon nano-composite material after hot-forming.
8. by the preparation method of high heat-conductivity conducting carbon nano-composite material described in claim 6 or 7, it is characterized in that: the carbon back micro nano powder filler described in step a is: Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, Graphene or carbon nanofiber; Polymeric binder described in step b is polymethylmethacrylate, viton or nylon.
9. by the preparation method of high heat-conductivity conducting carbon nano-composite material described in claim 6 or 7, it is characterized in that: the tensio-active agent described in step a is tween-80 or span-80.
10. by the preparation method of high heat-conductivity conducting carbon nano-composite material described in claim 6 or 7, it is characterized in that: the organic solvent described in step b is chloroform, ethyl acetate or methylene dichloride.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546579A (en) * | 2003-12-04 | 2004-11-17 | 上海交通大学 | Polymer thin layer coated carbon nanometer tube and its preparation method |
| CN101381511A (en) * | 2008-10-24 | 2009-03-11 | 南开大学 | Mono-layer graphite and polymer compound material and preparation and application thereof |
-
2014
- 2014-07-15 CN CN201410336463.5A patent/CN104130753A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546579A (en) * | 2003-12-04 | 2004-11-17 | 上海交通大学 | Polymer thin layer coated carbon nanometer tube and its preparation method |
| CN101381511A (en) * | 2008-10-24 | 2009-03-11 | 南开大学 | Mono-layer graphite and polymer compound material and preparation and application thereof |
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