CN107936292A - Carbon nanotubes carbon nano rod PTFE micro-nano composite materials and preparation method thereof - Google Patents
Carbon nanotubes carbon nano rod PTFE micro-nano composite materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of carbon nanotubes carbon nano rod PTFE micro-nano composite materials and preparation method thereof, the composite material is obtained by the pulverulent mixture of carbon nanotubes and carbon nano rod and polytetrafluoroethylpowder powder after crushing and micro-nano composite granule is made by twin-screw extruder molding granulation, gained composite material tensile strength adds 30 40%, bending strength adds 5 10%, friction coefficient reduces by 5 10%, and wear rate reduces by 90 98%.The carbon nanomaterial of two kinds of property of carbon nanotubes carbon nano rod can realize cooperative effect, mutually make up to it is sub- the shortcomings that, realize polymer performance General Promotion；Come from the effect of filling, the performance boost after filling is more notable；The mechanical performance and wear-resisting property of composite material are all obviously improved.
Description
Technical field
The invention belongs to the field of polymers, more particularly to a kind of carbon nanotubes-carbon nano rod-PTFE micro-nanos composite material and
Its preparation method.
Background technology
Polytetrafluoroethylene (PTFE)（PTFE）It is a kind of by the aggregated high crystallinity polymer formed of tetrafluoroethylene monomer, there is " modeling
The good name of material king ", is a kind of indispensable engineering plastics.PTFE has excellent, special physicochemical properties, in chemical industry
Field and some other relevant industries application are quite extensive, are the fluororesin of current production rate maximum.But due to PTFE some
Inherent shortcoming, it is wear-resistant it is poor, hardness is low, creep resistant official post its application is subject to a definite limitation.
In order to improve the comprehensive performance of PTFE, the self-defect people for making up PTFE are directed to the study on the modification of PTFE.Mesh
It is several big that preceding PTFE often can be divided into modified surface, filling-modified, blending and modifying, chemical modification, structurally-modified etc. with method of modifying
Class:（1）Surface is modified, and the structural symmetry of PTFE strands makes it that electroneutral be presented, and molecule is nonpolarity, becomes surface
The extremely low material of power.On the one hand the surface of PTFE is modified mainly makes its surface go after fluorine by the method for various pretreatments
Some polar groups or polymer are grafted, to improve its cementability；On the other hand, core/shell type structure wraps up PTFE surfaces
The of a relatively high polymer of layer of surface energy, causes the cementability of PTFE and other materials to strengthen;(2) it is filling-modified:
Filling-modified is pure to improve and overcome by filling inorganic, metal class, organic polymer class filler in PTFE resins
The defects of PTFE, on the basis of original advantage is kept, improve the resistance to pressure of PTFE, wearability and cold using complex effect
Fluidity;(3) blending and modifying:Blending and modifying is mainly to carry out Alloying Treatment to some resins using the excellent characteristics of PTFE,
Make general engineering plastic functionalization, so that the application range of widening project plastics;(4) chemical modification:Since PTFE has height
Crystallinity（92%~98%）, super high molecular weight, cause material that there is high melting viscosity, it is difficult to melt-processed.Chemical modification
Principle is that the more huge side base of volume is introduced on polymeric linear strand, molecular weight can be reduced, reduce melt viscosity and
Crystallinity is reduced, while can still keep the traditional excellent properties of PTFE.Common chemical modification method include copolymerization, crosslinking,
Block, grafting etc.;(5) it is structurally-modified:Structure modified technology is mainly by the change in moulding process, is formed in material
Make PTFE that there is the microstructure different from traditional PTFE in the case of not changing, so that it shows and tradition
PTFE has the macro property of larger difference, its physical mechanical property is got a promotion, and its medium-resistance is from any shadow
Ring.
In above-mentioned method of modifying, filling-modified is most industrialization representativeness, has more operability than other methods
And practicality.And other method of modifying have complicated, of high cost, environmental pollution, it is difficult to the defects of industrializing.Many
In packing material, carbon nanotubes has obvious advantage in terms of polymer is strengthened.Carbon nano-tube filled polytetrafluoroethylene (PTFE)（CNT
/ PTFE）Composite material the result shows that, carbon nanotubes significantly increases the abrasion resistance properties of PTFE composite and significantly drops
Low its friction coefficient [J.R. Vail, et al.Multifunctionality of single-walled carbon
Nanotube-polytetrafluoroethylene, nanocomposites, Wear 267 (2009) 619-624].So
And traditional carbon nanotubes manufacture cost is higher, for filled polymer, although getting a promotion in performance enhancement, can lead
Cause the cost of polymer composites to increase considerably, be unfavorable for market-oriented promotion and application.
The content of the invention
A kind of the present invention is intended to provide carbon nanotubes-carbon nano rod-PTFE micro-nano composite materials and preparation method thereof.
Realizing the technical solution of the object of the invention is：A kind of carbon nanotubes-carbon nano rod-PTFE micro-nano composite woods
Material, is passed through by the pulverulent mixture of carbon nanotubes and carbon nano rod and PTFE powders after high speed crushes obtained micro-nano composite granule
Twin-screw extruder molding granulation obtains.
Further, carbon nanotubes-carbon nano rod pulverulent mixture accounts for the 0.5-2% of the composite material gross weight.
Further, the composite material tensile strength adds 30-40%, and bending strength adds 5-10%, friction
Coefficient reduces 5-10%, and wear rate reduces 90-98 %.
The preparation method of above-mentioned composite material, includes the following steps：
(1) dehydration, 100-120 DEG C of drying temperature are first dried to nano-pore mould material, when the time is 3-6 small, does
After dry, under 0.05-0.02MPa vacuum, method that certain density macromolecule polymer solution is poured by nanometer
Be cast in nano-pore mould material, nano-pore placing temperature be 60-80 DEG C, pour the time for 1-3 it is small when, it is extensive after pouring
Normal pressure state is arrived again, when then drying process 12-16 is small at 80-110 DEG C of normal pressure, is obtained nano-pore and is poured high molecular polymer
Inorganic-organic nanocomposite；
(2) above-mentioned composite material is placed in tubular type Muffle furnace, heating rate is 5 DEG C -10 DEG C/min, and calcination temperature is rank
Terraced temperature, 20-50min is kept from room temperature to 260-300 DEG C, is continued to be warming up to 400-500 DEG C when keeping 1-3 small, is continued to heat up
When keeping 4-6 small to 900-1000 DEG C, the inorganic-organic composite material after being carbonized；
(3) it is 10-20wt%HF or HNO the material after above-mentioned carbonization to be put into concentration3When middle etching processing 5-8 is small, residue passes through
Be put into after filtering and washing temperature for freeze-drying process 2-6 at subzero 5-10 DEG C it is small when, obtain carbon nanotubes-carbon nano rod and mix
Compound/carbon nano material；
(4) carbon nanotubes-carbon nano rod mixing carbon nanomaterial and PTFE master batch powders are put into high speed powder machine and handle 1-3
Hour, the rotating speed of powder machine is 1000-3000r/min, and carbon nanotubes-carbon nano rod-PTFE micro-nano composite granules are made；
(5) that micro-nano composite material powder is prepared into nanotube carbon nanotubes-carbon nano rod-PTFE with double screw extruder is compound
Material, screw speed are 100 r/min, 160 DEG C of preheating temperature, the temperature from hopper to mould is respectively 150,200,200,
220、220、220、220℃。
Further, the nano-pore mould material is natural galapectite or porous aluminum, its aperture is 20-30nm, long
Spend for 2-5 microns.
Further, the high molecular polymer be PVA, PMMA and PAN in one kind or arbitrary proportion it is several.
Further, the concentration of the macromolecule polymer solution is 20-40wt%, its solute is water or DMF.
Further, the volume ratio of the high molecular polymer and nano-pore mould material is 1：1-2.
Further, the sour volume that the etching uses is 3-5 times of composite material volume.
Further, the carbon nanotubes-carbon nano rod mixing nano-carbon material accounts for the composite material gross weight
0.5-2%.
Further, a diameter of 15-20nm of carbon nanotubes-carbon nano rod mixing carbon nanomaterial, 1-3 μm of length.
Compared with prior art, the advantage of the invention is that：（1）Carbon nanotubes-carbon nano rod mixing nano-carbon material
Preparation process is simple, it can be achieved that large-scale production；（2）The carbon nanomaterial of two kinds of property of carbon nanotubes-carbon nano rod can be real
Existing cooperative effect, mutually make up to it is sub- the shortcomings that, realize polymer performance General Promotion；Come from the effect of filling, after filling
Performance boost is more notable；（3）From preparation process, technique is simple, non-environmental-pollution, can produce in enormous quantities, cost
It is low.（4）The mechanical performance and wear-resisting property of composite material are all obviously improved.
Brief description of the drawings
Fig. 1 is the SEM of carbon nanotubes made from embodiment 3-carbon nano rod mixing nano-carbon material（A）With TEM (B, C, D)
Photo.
Embodiment
Embodiment 1
The method that the PVA solution of concentration 20% is poured by nanometer is cast in the porous aluminum material of nano-pore, it is true to pour
Sky is lower to carry out.In vacuum drying oven, vacuum 0.05MPa, starts dry dehydration, 100 DEG C of drying temperature, time 6
Hour；Injected slurry volume ratio is 1 after drying:1 PVA aqueous solutions of polymers, nano-pore placing temperature are 80 DEG C, pour the time
For 3 it is small when, pour terminate vacuum return to normal pressure state, be then placed in normal pressure oven temperature for 110 DEG C of drying process 12 it is small
When, obtain the inorganic-organic nanocomposite that nano-pore pours high molecular polymer.Above-mentioned composite material is placed on tubular type
In Muffle furnace, heating rate is 10 DEG C/min, and calcination temperature is step temperature, from room temperature to 260 DEG C of holding 20min, after of continuing rising
Temperature to 500 DEG C keep 1 it is small when, continue to be warming up to 1000 DEG C keep 4 it is small when, the inorganic-organic composite material after being carbonized.Will
Material after above-mentioned carbonization be put into volume make its 3 times concentration for 20wt.%HF etching processings 8 it is small when, residue by filtering and wash
Wash be put into temperature afterwards three times for be freeze-dried subzero 5 DEG C of drying process 6 it is small when, obtain black powder solid, that is, obtain carbon and receive
Mitron-carbon nano rod mixing carbon nanomaterial.
Above-mentioned mixing carbon nano-tube material number is 0.5 part and 99.5 parts of PTFE, pour into powder machine processing 1 it is small when, turn
Speed is 3000r/min, and nanotube-carbon nano rod-PTFE micro-nano composite granules are finally made（Micro-nano composite granule refers to be more than
The mixture of the micron-scale powder of 100nm and the nano-scale powder of 0-100nm）.By micro-nano composite material powder pair spiral shells
Bar extruder is prepared into nanotube carbon nanotubes-carbon nano rod-PTFE composite, and screw speed is 100 r/min, preheating temperature
160 DEG C of degree, the temperature from hopper to mould are respectively：150/ 200/ 200/ 220/ 220/ 220/ 220 DEG C, sample carbon
The mechanical performance of nanotube-carbon nano rod-PTFE is in table 1.
Embodiment 2
The method that the PAN solution of concentration 40% is poured by nanometer is cast in the porous aluminum material of nano-pore, it is true to pour
Sky is lower to carry out.In vacuum drying oven, vacuum 0.02MPa, starts dry dehydration, 120 DEG C of drying temperature, time 3
Hour；Injected slurry volume ratio is 1 after drying:2 PVA polymer/DMF solutions, nano-pore placing temperature is 60 DEG C, when pouring
Between for 6 it is small when, pour terminate vacuum return to normal pressure state, be then placed in normal pressure oven temperature for 80 DEG C of drying process 16 it is small
When, obtain the inorganic-organic nanocomposite that nano-pore pours high molecular polymer.Above-mentioned composite material is placed on tubular type
In Muffle furnace, heating rate is 5 DEG C/min, and calcination temperature is step temperature, from room temperature to 300 DEG C of holding 50min, after of continuing rising
Temperature to 400 DEG C keep 3 it is small when, continue to be warming up to 900 DEG C keep 6 it is small when, the inorganic-organic composite material after being carbonized.Will
Material after above-mentioned carbonization, which is put into volume, makes its 5 times concentration be 40%HNO3When etching processing 5 is small, residue is by filtering and washes
Wash be put into temperature afterwards three times for be freeze-dried subzero 10 DEG C of drying process 2 it is small when, obtain black powder solid, that is, obtain carbon and receive
Mitron-carbon nano rod mixing carbon nanomaterial.
Above-mentioned mixing carbon nano-tube material number is 2 parts and 98 parts of PTFE, pour into powder machine processing 5 it is small when, rotating speed is
3000r/min, is finally made carbon nanotubes-carbon nano rod-PTFE micro-nano composite granules.By micro-nano composite material powder pair spiral shells
Bar extruder is prepared into nanotube carbon nanotubes-carbon nano rod-PTFE composite, and screw speed is 100 r/min, preheating temperature
140 DEG C of degree, the temperature from hopper to mould are respectively：140/ 200/ 200/ 220/ 220/ 220/ 220 DEG C, sample carbon
The mechanical performance of nanotube-carbon nano rod-PTFE is in table 1.
Embodiment 3
The method that the PMMA solution of concentration 30% is poured by nanometer is cast in the galapectite material of nano-pore, pour be
Carried out under vacuum.In vacuum drying oven, vacuum 0.03MPa, starts dry dehydration, 110 DEG C of drying temperature, time
For 5 it is small when；Injected slurry volume ratio is 1 after drying:1 PMMA polymer DMF solution, nano-pore placing temperature are 70 DEG C, are poured
Build the time for 5 it is small when, pour and terminate vacuum and return to normal pressure state, be then placed in normal pressure oven temperature for 100 DEG C it is dry at
Manage 15 it is small when, obtain the inorganic-organic nanocomposite that nano-pore pours high molecular polymer.Above-mentioned composite material is placed
In tubular type Muffle furnace, heating rate is 6 DEG C/min, and calcination temperature is step temperature, from room temperature to 280 DEG C of holding 40min,
Continue to be warming up to 450 DEG C keep 2 it is small when, continue to be warming up to 940 DEG C keep 5 it is small when, the inorganic-organic hybrid material after being carbonized
Material.By the material after above-mentioned carbonization be put into volume make its 4 times concentration for 10%HF etching processings 6 it is small when, residue by filtering and
Washing be put into temperature afterwards three times for be freeze-dried subzero 6 DEG C of drying process 5 it is small when, obtain black powder solid, that is, obtain carbon
Nanotube-carbon nano rod mixing carbon nanomaterial.
Above-mentioned mixing carbon nano-tube material number is 1 part and 99 parts of PTFE, pour into powder machine processing 1 it is small when, rotating speed is
3000r/min, is finally made carbon nanotubes-carbon nano rod-PTFE micro-nano composite granules.By micro-nano composite material powder pair spiral shells
Bar extruder is prepared into nanotube galapectite-PTFE composite, and screw speed is 100 r/min, 160 DEG C of preheating temperature, from
The temperature of hopper to mould is respectively：150/ 200/ 200/ 220/ 220/ 220/ 220 DEG C, sample carbon nanotubes-carbon is received
The mechanical performance of rice rod-PTFE is in table 1.
Embodiment 4
The method that the PAN solution of concentration 30% is poured by nanometer is cast in the galapectite material of nano-pore, it is true to pour
Sky is lower to carry out.In vacuum drying oven, vacuum 0.03MPa, starts dry dehydration, 120 DEG C of drying temperature, time 3
Hour；Injected slurry volume ratio is 1 after drying:1 PMMA polymer DMF solution, nano-pore placing temperature is 60 DEG C, when pouring
Between for 6 it is small when, pour terminate vacuum return to normal pressure state, be then placed in normal pressure oven temperature for 80 DEG C of drying process 16 it is small
When, obtain the inorganic-organic nanocomposite that nano-pore pours high molecular polymer.Above-mentioned composite material is placed on tubular type
In Muffle furnace, heating rate is 10 DEG C/min, and calcination temperature is step temperature, from room temperature to 300 DEG C of holding 50min, after of continuing rising
Temperature to 400 DEG C keep 3 it is small when, continue to be warming up to 900 DEG C keep 6 it is small when, the inorganic-organic composite material after being carbonized.Will
Material after above-mentioned carbonization be put into volume make its 3 times concentration for 10%HF etching processings 5 it is small when, residue by filtering and washing
Be put into temperature afterwards three times for be freeze-dried subzero 10 DEG C of drying process 2 it is small when, obtain black powder solid, that is, obtain carbon nanometer
Pipe-carbon nano rod mixing carbon nanomaterial.
Above-mentioned mixing carbon nano-tube material number is 1 part and 99 parts of PTFE, pour into powder machine processing 2 it is small when, rotating speed is
1000r/min, is finally made carbon nanotubes-carbon nano rod-PTFE micro-nano composite granules.By micro-nano composite material powder pair spiral shells
Bar extruder is prepared into nanotube carbon nanotubes-carbon nano rod-PTFE composite, and screw speed is 100 r/min, preheating temperature
140 DEG C of degree, the temperature from hopper to mould are respectively：140/ 200/ 200/ 220/ 220/ 220/ 220 DEG C, sample carbon
The mechanical performance of nanotube-carbon nano rod-PTFE is in table 1.
Embodiment 5
The method that the PVA solution of concentration 30% is poured by nanometer is cast in the galapectite material of nano-pore, it is true to pour
Sky is lower to carry out.In vacuum drying oven, vacuum 0.02MPa, starts dry dehydration, 100 DEG C of drying temperature, time 6
Hour；Injected slurry volume ratio is 1 after drying:2 PVA aqueous solutions of polymers, nano-pore placing temperature are 80 DEG C, pour the time
For 3 it is small when, pour terminate vacuum return to normal pressure state, be then placed in normal pressure oven temperature for 110 DEG C of drying process 12 it is small
When, obtain the inorganic-organic nanocomposite that nano-pore pours high molecular polymer.Above-mentioned composite material is placed on tubular type
In Muffle furnace, heating rate is 10 DEG C/min, and calcination temperature is step temperature, from room temperature to 260 DEG C of holding 20min, after of continuing rising
Temperature to 500 DEG C keep 1 it is small when, continue to be warming up to 1000 DEG C keep 4 it is small when, the inorganic-organic composite material after being carbonized.Will
Material after above-mentioned carbonization, which is put into volume, makes its 4 times concentration be 40%HNO3When etching processing 8 is small, residue is by filtering and washes
Wash be put into temperature afterwards three times for be freeze-dried subzero 5 DEG C of drying process 6 it is small when, obtain black powder solid, that is, obtain carbon and receive
Mitron-carbon nano rod mixing carbon nanomaterial.
Above-mentioned mixing carbon nano-tube material number is 1.5 parts and 98.5 parts of PTFE, pour into powder machine processing 1 it is small when, turn
Speed is 2000r/min, and nanotube-carbon nano rod-PTFE micro-nano composite granules are finally made.Micro-nano composite material powder is used double
Screw extruder is prepared into nanotube carbon nanotubes-carbon nano rod-PTFE composite, and screw speed is 100 r/min, preheating
160 DEG C of temperature, the temperature from hopper to mould are respectively：150/ 200/ 200/ 220/ 220/ 220/ 220 DEG C, sample
The mechanical performance of carbon nanotubes-carbon nano rod-PTFE is in table 1.
Embodiment 6
The method that the PMMA solution of concentration 30% is poured by nanometer is cast in the porous aluminum material of nano-pore, pour be
Carried out under vacuum.In vacuum drying oven, vacuum 0.03MPa, starts dry dehydration, 110 DEG C of drying temperature, time
For 5 it is small when；Injected slurry volume ratio is 1 after drying:2 PMMA polymer DMF solution, nano-pore placing temperature are 70 DEG C, are poured
Build the time for 5 it is small when, pour and terminate vacuum and return to normal pressure state, be then placed in normal pressure oven temperature for 100 DEG C it is dry at
Manage 15 it is small when, obtain the inorganic-organic nanocomposite that nano-pore pours high molecular polymer.Above-mentioned composite material is placed
In tubular type Muffle furnace, heating rate is 6 DEG C/min, and calcination temperature is step temperature, from room temperature to 280 DEG C of holding 40min,
Continue to be warming up to 450 DEG C keep 2 it is small when, continue to be warming up to 940 DEG C keep 5 it is small when, the inorganic-organic hybrid material after being carbonized
Material.Material after above-mentioned carbonization is put into volume makes its 3 times concentration be 40%HNO3When etching processing 6 is small, residue is by filtering
Be put into temperature afterwards three times with washing for be freeze-dried subzero 6 DEG C of drying process 5 it is small when, obtain black powder solid, that is, obtain
Carbon nanotubes-carbon nano rod mixing carbon nanomaterial.
Above-mentioned mixing carbon nano-tube material number is 2 parts and 98 parts of PTFE, pour into powder machine processing 1 it is small when, rotating speed is
3000r/min, is finally made carbon nanotubes-carbon nano rod-PTFE micro-nano composite granules.By micro-nano composite material powder pair spiral shells
Bar extruder is prepared into nanotube galapectite-PTFE composite, and screw speed is 100 r/min, 160 DEG C of preheating temperature, from
The temperature of hopper to mould is respectively：150/ 200/ 200/ 220/ 220/ 220/ 220 DEG C, sample carbon nanotubes-carbon is received
The mechanical performance of rice rod-PTFE is in table 1.
.The test condition of embodiment sample frictional behaviour test：Load：200N；Rotating speed：200r/m；Test temperature：Room temperature；Phase
To humidity: 50±10%.
Claims (10)
1. carbon nanotubes-carbon nano rod-PTFE micro-nano composite materials, it is characterised in that by carbon nanotubes and the powder of carbon nano rod
Shape mixture is obtained with polytetrafluoroethylpowder powder after crushing and micro-nano composite granule is made by twin-screw extruder molding granulation.
2. micro-nano composite material as claimed in claim 1, it is characterised in that carbon nanotubes-carbon nano rod pulverulent mixture accounts for
The 0.5-2% of the composite material gross weight.
3. micro-nano composite material as claimed in claim 1, it is characterised in that the composite material tensile strength adds 30-
40%, bending strength adds 5-10%, and friction coefficient reduces 5-10%, and wear rate reduces 90-98 %.
4. the preparation method of carbon nanotubes-carbon nano rod-PTFE micro-nano composite materials, it is characterised in that include the following steps：
(1) dehydration first is dried to nano-pore mould material, after drying, will under 0.05-0.02MPa vacuum
The method that macromolecule polymer solution is poured by nanometer is cast in nano-pore mould material, and nano-pore placing temperature is 60-
80 DEG C, pour the time for 1-3 it is small when, normal pressure state is returned to after pouring, then the drying process at 80-110 DEG C of normal pressure
When 12-16 is small, the inorganic-organic nanocomposite that nano-pore pours high molecular polymer is obtained；
(2) above-mentioned composite material is placed in tubular type Muffle furnace, heating rate is 5 DEG C -10 DEG C/min, and calcination temperature is rank
Terraced temperature, 20-50min is kept from room temperature to 260-300 DEG C, is continued to be warming up to 400-500 DEG C when keeping 1-3 small, is continued to heat up
When keeping 4-6 small to 900-1000 DEG C, the inorganic-organic composite material after being carbonized；
(3) when by the material after above-mentioned carbonization, etching processing 5-8 is small in acid solution, residue is put into after filtering and washing
When temperature is that freeze-drying process 2-6 is small at subzero 5-10 DEG C, carbon nanotubes-carbon nano rod mixing carbon nanomaterial is obtained；
(4) carbon nanotubes-carbon nano rod mixing carbon nanomaterial and PTFE powders are crushed at a high speed and carbon nanotubes-carbon nanometer is made
Rod-PTFE micro-nano composite granules；
(5) that micro-nano composite material powder is prepared into nanotube carbon nanotubes-carbon nano rod-PTFE with double screw extruder is compound
Material, screw speed are 100 r/min, 160 DEG C of preheating temperature, the temperature from hopper to mould is respectively 150,200,200,
220、220、220、220℃。
5. preparation method as claimed in claim 4, it is characterised in that the nano-pore mould material for natural galapectite or
Porous aluminum, its aperture are 20-30nm, and length is 2-5 microns.
6. preparation method as claimed in claim 4, it is characterised in that the high molecular polymer is PVA, PMMA and PAN
In one kind or arbitrary proportion it is several.
7. preparation method as claimed in claim 4, it is characterised in that the concentration of the macromolecule polymer solution is 20-
40wt%, its solute are water or DMF.
8. preparation method as claimed in claim 4, it is characterised in that the high molecular polymer and nano-pore mould material
Volume ratio be 1：1-2.
9. preparation method as claimed in claim 4, it is characterised in that the sour volume that the etching uses is composite material
3-5 times of volume.
10. preparation method as claimed in claim 4, it is characterised in that step（4）In, carbon nanotubes-carbon nano rod is mixed
Carbon nanomaterial is put into when processing 1-3 is small in high speed powder machine with PTFE powders and carries out high speed crushing, and the rotating speed of powder machine is
1000-3000r/min。
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