CN107936292B - Carbon nanotube-carbon nano rod-PTFE micro-nano composite material and preparation method - Google Patents
Carbon nanotube-carbon nano rod-PTFE micro-nano composite material and preparation method Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a kind of carbon nanotube-carbon nano rod-PTFE micro-nano composite material and preparation methods, the composite material is obtained after crushing and micro-nano composite granule is made by twin-screw extruder molding granulation by the pulverulent mixture and polytetrafluoroethylpowder powder of carbon nanotube and carbon nano rod, gained composite material tensile strength increases 30-40%, bending strength increases 5-10%, coefficient of friction reduces 5-10%, and wear rate reduces 90-98%.The carbon nanomaterial of two kinds of properties of carbon nanotube-carbon nano rod can be realized synergistic effect, mutually makes up to the disadvantage of son, realizes polymer performance General Promotion；Come from the effect of filling, filled performance boost is more significant；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, in particular to a kind of carbon nanotube-carbon nano rod-PTFE micro-nano composite material and
Preparation method.
Background technique
Polytetrafluoroethylene (PTFE) be it is a kind of as tetrafluoroethylene monomer it is aggregated made of high crystallinity polymer, have " 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 maximum fluororesin of current production rate.But it is some due to PTFE
Inherent shortcoming, it is wear-resistant it is poor, hardness is low, creep resistant official post it application be subject to certain restrictions.
In order to improve the comprehensive performance of PTFE, the self-defect people for making up PTFE are dedicated 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 strand 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 to go its surface after fluorine by various pretreated methods
It is grafted some polar groups or polymer, to improve its cementability；On the other hand, core/shell type structure wraps up the surface PTFE
The relatively high polymer of layer of surface energy, causes the cementability of PTFE and other materials to enhance;(2) filling-modified:
Filling-modified is pure to improve and overcome by filling inorganic, metal class, organic polymer class filler in PTFE resin
The defect of PTFE improves the resistance to pressure of PTFE, wearability and cold using complex effect on the basis of keeping original advantage
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, thus the application range of widening project plastics;(4) chemical modification: since PTFE has height
Crystallinity (92%~98%), super high molecular weight cause material to have high melting viscosity, it is difficult to melt-processed.Chemical modification
Principle is that the more huge side group of volume is introduced on polymeric linear strand, molecular weight can be reduced, reduce melt viscosity and
Reduce crystallinity, while the excellent properties that still PTFE can be kept traditional.Common chemical modification method include copolymerization, crosslinking,
Block, grafting etc.;(5) structurally-modified: structure modified technology mainly by the variation in moulding process, is formed in material
Make PTFE that there is the microstructure different from traditional PTFE in the case where not changing, so that it be made to show and tradition
PTFE has the macro property of larger difference, its physical mechanical property is made to get a promotion, and its medium-resistance is not by any shadow
It rings.
In above-mentioned method of modifying, filling-modified is most industrialization representativeness, has more operability than other methods
And practicability.And other method of modifying have complicated for operation, at high cost, environmental pollution, it is difficult to the defects of industrializing.Many
In packing material, carbon nanotube has apparent advantage in terms of enhancing polymer.Carbon nano-tube filled polytetrafluoroethylene (PTFE) (CNT
/ PTFE) composite material the result shows that, carbon nanotube significantly increases the abrasion resistance properties of PTFE composite and significantly drops
Low its coefficient of friction [J.R. Vail, et al.Multifunctionality of single-walled carbon
Nanotube-polytetrafluoroethylene, nanocomposites, Wear 267 (2009) 619-624].So
And traditional carbon nanotube manufacturing cost is relatively high, can lead for filled polymer although getting a promotion in performance enhancement
It causes the cost of polymer composites to increase considerably, is unfavorable for market-oriented promotion and application.
Summary of the invention
The present invention is intended to provide a kind of carbon nanotube-carbon nano rod-PTFE micro-nano composite material and preparation method.
Realizing the technical solution of the object of the invention is: a kind of carbon nanotube-carbon nano rod-PTFE micro-nano composite wood
Material is passed through after high speed crushes and micro-nano composite granule is made by the pulverulent mixture of carbon nanotube and carbon nano rod with PTFE powder
Twin-screw extruder molding granulation obtains.
Further, carbon nanotube-carbon nano rod pulverulent mixture accounts for the 0.5-2% of the composite material total weight.
Further, the composite material tensile strength increases 30-40%, and bending strength increases 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) processing first is dried and dehydrated to nano-pore mould material, 100-120 DEG C of drying temperature, the time is that 3-6 is small
When, after drying, under 0.05-0.02MPa vacuum, certain density macromolecule polymer solution is poured by nanometer
Method is cast in nano-pore mould material, and nano-pore placing temperature is 60-80 DEG C, and pouring the time is 1-3 hours, pours end
After be restored to normal pressure state, be then dried 12-16 hours at 80-110 DEG C of normal pressure, obtain nano-pore and pour polyphosphazene polymer
Close the inorganic-organic nanocomposite of object；
(2) above-mentioned composite material is placed in tubular type Muffle furnace, heating rate is 5 DEG C -10 DEG C/min, maturing temperature
For step temperature, DEG C holding 20-50min, continues to be warming up to 400-500 DEG C of holding 1-3 hours, continue from room temperature to 260-300
It is warming up to 900-1000 DEG C of holding 4-6 hours, the inorganic-organic composite material after being carbonized；
(3) material after above-mentioned carbonization is put into concentration is 10-20wt%HF or HNO3Middle etching processing 5-8 hours, residue
It is to obtain carbon nanotube-carbon nanometer freeze-drying process 2-6 hours at subzero 5-10 DEG C that temperature is put into after filtering and washing
Stick mixing carbon nanomaterial；
(4) carbon nanotube-carbon nano rod mixing carbon nanomaterial and PTFE master batch powder are put into high speed powder machine
Reason 1-3 hours, the revolving speed of powder machine are 1000-3000r/min, and carbon nanotube-carbon nano rod-PTFE micro-nano composite powder is made
Body；
(5) micro-nano composite material powder is prepared into nanotube carbon nanotube-carbon nano rod-PTFE with double screw extruder
Composite material, screw speed are 100 r/min, 160 DEG C of preheating temperature, the temperature from hopper to mold is respectively 150,200,
200、220、220、220、220℃。
Further, the nano-pore mould material is natural galapectite or porous aluminum, and aperture 20-30nm is long
Degree is 2-5 microns.
Further, the high molecular polymer is the several of one of PVA, PMMA and PAN or arbitrary proportion.
Further, the concentration of the macromolecule polymer solution is 20-40wt%, and 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 volume for the acid that the etching uses is 3-5 times of composite material volume.
Further, the carbon nanotube-carbon nano rod mixing nano-carbon material accounts for the composite material total weight
0.5-2%.
Further, carbon nanotube-carbon nano rod mixing carbon nanomaterial diameter be 15-20nm, 1-3 μm of length.
Compared with the prior art, the advantages of the present invention are as follows: (1) carbon nanotube-carbon nano rod mixing nano-carbon material
Preparation process is simple, it can be achieved that large-scale production；(2) carbon nanomaterial of two kinds of property of carbon nanotube-carbon nano rod can be real
Existing synergistic effect mutually makes up to the disadvantage of son, realizes polymer performance General Promotion；Come from the effect of filling, it is filled
Performance boost is more significant；(3) from preparation process, simple process, non-environmental-pollution can be produced in enormous quantities, cost
It is low.(4) mechanical performance of composite material and wear-resisting property are all obviously improved.
Detailed description of the invention
Fig. 1 is carbon nanotube-carbon nano rod mixing nano-carbon material SEM(A made from embodiment 3) and TEM (B, C, D)
Photo.
Specific embodiment
Embodiment 1
The PVA solution of concentration 20% is cast in the porous aluminum material of nano-pore by the method that nanometer pours, pouring is
It carries out under vacuum.In vacuum drying oven, vacuum degree 0.05MPa starts dry dehydration, and 100 DEG C of drying temperature, when
Between be 6 hours；For injected slurry volume than the PVA aqueous solutions of polymers for 1:1, nano-pore placing temperature is 80 DEG C after drying, is poured
Building the time is 3 hours, and pouring, which terminates vacuum degree, is restored to normal pressure state, and being then placed in normal pressure oven temperature is at 110 DEG C dry
Reason 12 hours, obtains 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 10 DEG C/min, and maturing temperature is step temperature, from room temperature to 260 DEG C of holding 20min,
Continue to be warming up to 500 DEG C of holdings 1 hour, continues to be warming up to 1000 DEG C of holdings 4 hours, the inorganic-organic hybrid after being carbonized
Material.Material after above-mentioned carbonization, which is put into volume, makes its 3 times concentration 20wt.%HF etching processing 8 hours, and residue passes through
Filtering and washing are put into temperature afterwards three times and are dried 6 hours to be freeze-dried subzero 5 DEG C, obtain black powder solid, i.e.,
Obtain carbon nanotube-carbon nano rod mixing carbon nanomaterial.
Above-mentioned mixing carbon nano-tube material number is 0.5 part and 99.5 parts of PTFE, pours into powder machine and handles 1 hour, is turned
Speed is 3000r/min, and nanotube-is finally made, and (micro-nano composite granule refers to be greater than carbon nano rod-PTFE micro-nano composite granule
The mixture of the nano-scale powder of the micron-scale powder and 0-100nm of 100nm).By the double spiral shells of micro-nano composite material powder
Bar extruder is prepared into nanotube carbon nanotube-carbon nano rod-PTFE composite, and screw speed is 100 r/min, preheating temperature
160 DEG C of degree, the temperature from hopper to mold is respectively as follows: 150/ 200/ 200/ 220/ 220/ 220/ 220 DEG C, sample carbon
Nanotube-carbon nano rod-PTFE mechanical performance is in table 1.
Embodiment 2
The PAN solution of concentration 40% is cast in the porous aluminum material of nano-pore by the method that nanometer pours, pouring is
It carries out under vacuum.In vacuum drying oven, vacuum degree 0.02MPa starts dry dehydration, and 120 DEG C of drying temperature, when
Between be 3 hours；For injected slurry volume than the PVA polymer/DMF solution for 1:2, nano-pore placing temperature is 60 DEG C after drying, is poured
Building the time is 6 hours, and pouring, which terminates vacuum degree, is restored to normal pressure state, and being then placed in normal pressure oven temperature is 80 DEG C of drying process
16 hours, obtain the inorganic-organic nanocomposite that nano-pore pours high molecular polymer.Above-mentioned composite material is placed on
In tubular type Muffle furnace, heating rate is 5 DEG C/min, and maturing temperature is step temperature, from room temperature to 300 DEG C of holding 50min, after
It is continuous to be warming up to 400 DEG C of holdings 3 hours, continue to be warming up to 900 DEG C of holdings 6 hours, the inorganic-organic hybrid material after being carbonized
Material.Material after above-mentioned carbonization, which is put into volume, makes its 5 times of concentration 40%HNO3Etching processing 5 hours, residue was by filtering
Temperature is put into afterwards three times with washing to be dried 2 hours to be freeze-dried subzero 10 DEG C, obtains black powder solid to get arriving
Carbon nanotube-carbon nano rod mixing carbon nanomaterial.
Above-mentioned mixing carbon nano-tube material number is 2 parts and 98 parts of PTFE, pours into powder machine and handles 5 hours, revolving speed is
Carbon nanotube-carbon nano rod-PTFE micro-nano composite granule is finally made in 3000r/min.By the double spiral shells of micro-nano composite material powder
Bar extruder is prepared into nanotube carbon nanotube-carbon nano rod-PTFE composite, and screw speed is 100 r/min, preheating temperature
140 DEG C of degree, the temperature from hopper to mold is respectively as follows: 140/ 200/ 200/ 220/ 220/ 220/ 220 DEG C, sample carbon
Nanotube-carbon nano rod-PTFE mechanical performance is in table 1.
Embodiment 3
The PMMA solution of concentration 30% is cast in the galapectite material of nano-pore by the method that nanometer pours, is poured
It is to carry out under vacuum.In vacuum drying oven, vacuum degree 0.03MPa starts dry dehydration, and 110 DEG C of drying temperature,
Time is 5 hours；For injected slurry volume than the PMMA polymer DMF solution for 1:1, nano-pore placing temperature is 70 after drying
DEG C, pouring the time is 5 hours, and pouring, which terminates vacuum degree, is restored to normal pressure state, and being then placed in normal pressure oven temperature is 100 DEG C dry
Dry processing 15 hours, obtains the inorganic-organic nanocomposite that nano-pore pours high molecular polymer.By above-mentioned composite material
It is placed in tubular type Muffle furnace, heating rate is 6 DEG C/min, and maturing temperature is step temperature, is kept from room temperature to 280 DEG C
40min continues to be warming up to 450 DEG C of holdings 2 hours, continues to be warming up to 940 DEG C of holdings 5 hours, the inorganic-organic after being carbonized
Composite material.Material after above-mentioned carbonization, which is put into volume, makes its 4 times concentration 10%HF etching processing 6 hours, and residue passes through
Filtering and washing are put into temperature afterwards three times and are dried 5 hours to be freeze-dried subzero 6 DEG C, obtain black powder solid, i.e.,
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, pours into powder machine and handles 1 hour, revolving speed is
Carbon nanotube-carbon nano rod-PTFE micro-nano composite granule is finally made in 3000r/min.By the double spiral shells of micro-nano composite material powder
Bar extruder is prepared into nanotube galapectite-PTFE composite, and screw speed is 100 r/min, and 160 DEG C of preheating temperature, from
The temperature of hopper to mold is respectively as follows: 150/ 200/ 200/ 220/ 220/ 220/ 220 DEG C, and sample carbon nanotube-carbon is received
The mechanical performance of rice stick-PTFE is in table 1.
Embodiment 4
The PAN solution of concentration 30% is cast in the galapectite material of nano-pore by the method that nanometer pours, pouring is
It carries out under vacuum.In vacuum drying oven, vacuum degree 0.03MPa starts dry dehydration, and 120 DEG C of drying temperature, when
Between be 3 hours；For injected slurry volume than the PMMA polymer DMF solution for 1:1, nano-pore placing temperature is 60 DEG C after drying,
Pouring the time is 6 hours, and pouring, which terminates vacuum degree, is restored to normal pressure state, and being then placed in normal pressure oven temperature is at 80 DEG C dry
Reason 16 hours, obtains 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 10 DEG C/min, and maturing temperature is step temperature, from room temperature to 300 DEG C of holding 50min,
Continue to be warming up to 400 DEG C of holdings 3 hours, continues to be warming up to 900 DEG C of holdings 6 hours, the inorganic-organic hybrid material after being carbonized
Material.Material after above-mentioned carbonization, which is put into volume, makes its 3 times concentration 10%HF etching processing 5 hours, residue by filtering and
Washing is put into temperature afterwards three times and is dried 2 hours to be freeze-dried subzero 10 DEG C, obtains black powder solid to get carbon is arrived
Nanotube-carbon nano rod mixing carbon nanomaterial.
Above-mentioned mixing carbon nano-tube material number is 1 part and 99 parts of PTFE, pours into powder machine and handles 2 hours, revolving speed is
Carbon nanotube-carbon nano rod-PTFE micro-nano composite granule is finally made in 1000r/min.By the double spiral shells of micro-nano composite material powder
Bar extruder is prepared into nanotube carbon nanotube-carbon nano rod-PTFE composite, and screw speed is 100 r/min, preheating temperature
140 DEG C of degree, the temperature from hopper to mold is respectively as follows: 140/ 200/ 200/ 220/ 220/ 220/ 220 DEG C, sample carbon
Nanotube-carbon nano rod-PTFE mechanical performance is in table 1.
Embodiment 5
The PVA solution of concentration 30% is cast in the galapectite material of nano-pore by the method that nanometer pours, pouring is
It carries out under vacuum.In vacuum drying oven, vacuum degree 0.02MPa starts dry dehydration, and 100 DEG C of drying temperature, when
Between be 6 hours；For injected slurry volume than the PVA aqueous solutions of polymers for 1:2, nano-pore placing temperature is 80 DEG C after drying, is poured
Building the time is 3 hours, and pouring, which terminates vacuum degree, is restored to normal pressure state, and being then placed in normal pressure oven temperature is at 110 DEG C dry
Reason 12 hours, obtains 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 10 DEG C/min, and maturing temperature is step temperature, from room temperature to 260 DEG C of holding 20min,
Continue to be warming up to 500 DEG C of holdings 1 hour, continues to be warming up to 1000 DEG C of holdings 4 hours, the inorganic-organic hybrid after being carbonized
Material.Material after above-mentioned carbonization, which is put into volume, makes its 4 times of concentration 40%HNO3Etching processing 8 hours, residue passed through
Filter and washing be put into afterwards three times temperature for be freeze-dried it is subzero 5 DEG C be dried 6 hours, obtain black powder solid to get
To carbon nanotube-carbon nano rod mixing carbon nanomaterial.
Above-mentioned mixing carbon nano-tube material number is 1.5 parts and 98.5 parts of PTFE, pours into powder machine and handles 1 hour, is turned
Speed is 2000r/min, and nanotube-carbon nano rod-PTFE micro-nano composite granule is finally made.Micro-nano composite material powder is used double
Screw extruder is prepared into nanotube carbon nanotube-carbon nano rod-PTFE composite, and screw speed is 100 r/min, preheating
160 DEG C of temperature, the temperature from hopper to mold is respectively as follows: 150/ 200/ 200/ 220/ 220/ 220/ 220 DEG C, sample
Carbon nanotube-carbon nano rod-PTFE mechanical performance is in table 1.
Embodiment 6
The PMMA solution of concentration 30% is cast in the porous aluminum material of nano-pore by the method that nanometer pours, is poured
It is to carry out under vacuum.In vacuum drying oven, vacuum degree 0.03MPa starts dry dehydration, and 110 DEG C of drying temperature,
Time is 5 hours；For injected slurry volume than the PMMA polymer DMF solution for 1:2, nano-pore placing temperature is 70 after drying
DEG C, pouring the time is 5 hours, and pouring, which terminates vacuum degree, is restored to normal pressure state, and being then placed in normal pressure oven temperature is 100 DEG C dry
Dry processing 15 hours, obtains the inorganic-organic nanocomposite that nano-pore pours high molecular polymer.By above-mentioned composite material
It is placed in tubular type Muffle furnace, heating rate is 6 DEG C/min, and maturing temperature is step temperature, is kept from room temperature to 280 DEG C
40min continues to be warming up to 450 DEG C of holdings 2 hours, continues to be warming up to 940 DEG C of holdings 5 hours, the inorganic-organic after being carbonized
Composite material.Material after above-mentioned carbonization, which is put into volume, makes its 3 times of concentration 40%HNO3Etching processing 6 hours, residue warp
Filtering and washing are put into temperature afterwards three times and are dried 5 hours to be freeze-dried subzero 6 DEG C, obtain black powder solid,
Obtain carbon nanotube-carbon nano rod mixing carbon nanomaterial.
Above-mentioned mixing carbon nano-tube material number is 2 parts and 98 parts of PTFE, pours into powder machine and handles 1 hour, revolving speed is
Carbon nanotube-carbon nano rod-PTFE micro-nano composite granule is finally made in 3000r/min.By the double spiral shells of micro-nano composite material powder
Bar extruder is prepared into nanotube galapectite-PTFE composite, and screw speed is 100 r/min, and 160 DEG C of preheating temperature, from
The temperature of hopper to mold is respectively as follows: 150/ 200/ 200/ 220/ 220/ 220/ 220 DEG C, and sample carbon nanotube-carbon is received
The mechanical performance of rice stick-PTFE is in table 1.
.The test condition of embodiment sample frictional behaviour test: load: 200N；Revolving speed: 200r/m；Test temperature: room
Temperature；Relative humidity: 50 ± 10%.
Claims (12)
1. carbon nanotube-carbon nano rod-PTFE micro-nano composite material, which is characterized in that by the powder of carbon nanotube and carbon nano rod
Shape mixture and polytetrafluoroethylpowder powder are obtained after crushing and micro-nano composite granule is made by twin-screw extruder molding granulation,
In, carbon nanotube-carbon nano rod pulverulent mixture accounts for the 0.5-2% of the composite material total weight；The composite material stretches strong
Degree increases 30-40%, and bending strength increases 5-10%, and coefficient of friction reduces 5-10%, and wear rate reduces 90-98 %；Including
Following steps:
(1) processing first is dried and dehydrated to nano-pore mould material, it after drying, will under 0.05-0.02MPa vacuum
Macromolecule polymer solution is cast in nano-pore mould material by the method that nanometer pours, and nano-pore placing temperature is 60-
80 DEG C, pouring the time is 1-3 hours, and normal pressure state is restored to after pouring, is then dried at 80-110 DEG C of normal pressure
12-16 hours, obtain the inorganic-organic nanocomposite that nano-pore pours high molecular polymer；
(2) above-mentioned composite material is placed in tubular type Muffle furnace, heating rate is 5 DEG C -10 DEG C/min, and maturing temperature is rank
Terraced temperature, DEG C holding 20-50min, continues to be warming up to 400-500 DEG C of holding 1-3 hours, continues to heat up from room temperature to 260-300
To 900-1000 DEG C holding 4-6 hours, inorganic-organic composite material after being carbonized；
(3) by the material after above-mentioned carbonization etching processing 5-8 hours in acid solution, residue is put into after filtering and washing
Temperature is to obtain carbon nanotube-carbon nano rod mixing carbon nanomaterial freeze-drying process 2-6 hours at subzero 5-10 DEG C；
(4) carbon nanotube-carbon nano rod mixing carbon nanomaterial and PTFE powder high speed are crushed and carbon nanotube-carbon nanometer is made
Stick-PTFE micro-nano composite granule；
(5) micro-nano composite granule is prepared into nanotube carbon nanotube-carbon nano rod-PTFE composite wood with double screw extruder
Material, screw speed are 100 r/min, 160 DEG C of preheating temperature, the temperature from hopper to mold is respectively 150,200,200,
220、220、220、220℃。
2. carbon nanotube as described in claim 1-carbon nano rod-PTFE micro-nano composite material preparation method, feature exist
In including the following steps:
(1) processing first is dried and dehydrated to nano-pore mould material, it after drying, will under 0.05-0.02MPa vacuum
Macromolecule polymer solution is cast in nano-pore mould material by the method that nanometer pours, and nano-pore placing temperature is 60-
80 DEG C, pouring the time is 1-3 hours, and normal pressure state is restored to after pouring, is then dried at 80-110 DEG C of normal pressure
12-16 hours, obtain the inorganic-organic nanocomposite that nano-pore pours high molecular polymer；
(2) above-mentioned composite material is placed in tubular type Muffle furnace, heating rate is 5 DEG C -10 DEG C/min, and maturing temperature is rank
Terraced temperature, DEG C holding 20-50min, continues to be warming up to 400-500 DEG C of holding 1-3 hours, continues to heat up from room temperature to 260-300
To 900-1000 DEG C holding 4-6 hours, inorganic-organic composite material after being carbonized；
(3) by the material after above-mentioned carbonization etching processing 5-8 hours in acid solution, residue is put into after filtering and washing
Temperature is to obtain carbon nanotube-carbon nano rod mixing carbon nanomaterial freeze-drying process 2-6 hours at subzero 5-10 DEG C；
(4) carbon nanotube-carbon nano rod mixing carbon nanomaterial and PTFE powder high speed are crushed and carbon nanotube-carbon nanometer is made
Stick-PTFE micro-nano composite granule；
(5) micro-nano composite granule is prepared into nanotube carbon nanotube-carbon nano rod-PTFE composite wood with double screw extruder
Material, screw speed are 100 r/min, 160 DEG C of preheating temperature, the temperature from hopper to mold is respectively 150,200,200,
220、220、220、220℃。
3. preparation method as claimed in claim 2, which is characterized in that the nano-pore mould material be natural galapectite or
Porous aluminum, aperture 20-30nm, length are 2-5 microns.
4. preparation method as claimed in claim 2, which is characterized in that the high molecular polymer is PVA, PMMA and PAN
One of or arbitrary proportion it is several.
5. preparation method as claimed in claim 2, which is characterized in that the concentration of the macromolecule polymer solution is 20-
40wt%, solute are water or DMF.
6. preparation method as claimed in claim 2, which is characterized in that the high molecular polymer and nano-pore mould material
Volume ratio be 1:1-2.
7. preparation method as claimed in claim 2, which is characterized in that the volume for the acid that the etching uses is composite material
3-5 times of volume.
8. preparation method as claimed in claim 2, which is characterized in that in step (4), carbon nanotube-carbon nano rod is mixed
Carbon nanomaterial and PTFE powder, which are put into high speed powder machine, handles progress high speed crushing in 1-3 hours, and the revolving speed of powder machine is
1000-3000r/min。
9. preparation method as claimed in claim 2, which is characterized in that obtain carbon nanotube-carbon nano rod and mix compound/carbon nano material
The diameter of material be 15-20nm, 1-3 μm of length.
10. preparation method as claimed in claim 2, which is characterized in that the carbon nanotube-carbon nano rod mixes nano-sized carbon
Material accounts for the 0.5-2% of the composite material total weight.
11. preparation method as claimed in claim 2, which is characterized in that in step (1), 100-120 DEG C of drying temperature, the time
It is 3-6 hours.
12. preparation method as claimed in claim 2, which is characterized in that in step (3), acid solution is concentration 10-20wt%
HF or 10-20wt%HNO3。
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