CN109735965A - Modified carbon nano tube fiber and its preparation method and application - Google Patents
Modified carbon nano tube fiber and its preparation method and application Download PDFInfo
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- CN109735965A CN109735965A CN201811519066.6A CN201811519066A CN109735965A CN 109735965 A CN109735965 A CN 109735965A CN 201811519066 A CN201811519066 A CN 201811519066A CN 109735965 A CN109735965 A CN 109735965A
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Abstract
The present invention relates to a kind of modified carbon nano tube fibers and its preparation method and application.The preparation method of the modified carbon nano tube fiber includes the following steps: to form carbon nano pipe array in the first substrate；High molecular polymer is formed in the second substrate, high molecular polymer is the copolymer of 2- oxazoline class monomer and nitrogen-containing heterocycle class monomer；And under protective gas atmosphere; ultraviolet light processing is carried out to the first substrate and the second substrate, so that high molecular polymer and carbon nano pipe array carry out graft reaction, obtains modified carbon nano-tube array; modified carbon nano-tube array is subjected to spinning, obtains carbon nano-tube fibre；Presoma is sprayed on carbon nano-tube fibre and is reacted under protective gas atmosphere, modified carbon nano tube fiber is obtained, and presoma is selected from least one of epoxy resin, polyurethane resin and polystyrene resin.The modified carbon nano tube fiber that above-mentioned preparation method obtains can be used in preparing the preferable cloth of non-deformability.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of modified carbon nano tube fiber and preparation method thereof and answer
With.
Background technique
Carbon nano-tube fibre is to be prepared by carbon nanotube by spinning, have many abnormal mechanics, electricity and
Chemical property is widely used in middle life and every field, such as cosmetics, coating and the energy of production etc..Especially exist
Textile industry, carbon nano-tube fibre have boundless prospect of the application.However, cloth prepared by traditional carbon nano-tube fibre
Non-deformability it is poor, be not able to satisfy actual needs.
Summary of the invention
Based on this, it is necessary to provide a kind of preparation method of modified carbon nano tube fiber, the carbon modified which obtains
Nanofiber can be used in preparing the preferable cloth of non-deformability.
In addition, also providing a kind of modified carbon nano tube fiber and its preparation method and application.
A kind of preparation method of modified carbon nano tube fiber, includes the following steps:
Carbon nano pipe array is formed in the first substrate；
High molecular polymer is formed in the second substrate, the high molecular polymer is 2- oxazoline class monomer and nitrogen-containing hetero
The copolymer of ring class monomer, the 2- oxazoline class monomer are selected from 2- isopropenyl -2- oxazoline and 4,4'- dimethyl -2- second
At least one of alkenyl -2- oxazoline, the nitrogen-containing heterocycle class monomer are n-vinyl pyrrolidone；
Under the first protective gas atmosphere, to first substrate for being formed with the carbon nano pipe array and it is formed with
Second substrate of the high molecular polymer carries out ultraviolet light processing, so that the high molecular polymer and the carbon
Nano-tube array carries out graft reaction, obtains modified carbon nano-tube array；
The modified carbon nano-tube array is subjected to spinning, obtains carbon nano-tube fibre；
Presoma is sprayed on the carbon nano-tube fibre, and in 140 DEG C~160 DEG C under the second protective gas atmosphere
Reaction, obtains modified carbon nano tube fiber, and the presoma is selected from epoxy resin, polyurethane resin and polystyrene tree
At least one of rouge.
High molecular polymer is grafted to carbon nano-pipe array using ultraviolet light by the preparation method of above-mentioned modified carbon nano tube fiber
The surface of column, and high molecular polymer is the copolymer of 2- oxazoline class monomer and nitrogen-containing heterocycle class monomer, 2- oxazoline class
Monomer is selected from 2- isopropenyl -2- oxazoline and 4, at least one of 4'- dimethyl -2- vinyl -2- oxazoline, nitrogen-containing hetero
Ring class monomer is n-vinyl pyrrolidone, the modified carbon nano-tube array being easily dispersed, and by by the carbon modified
Spray presoma on carbon nano-tube fibre made of nanotube, presoma be selected from epoxy resin, polyurethane resin and
At least one of polystyrene resin, so that presoma reacts with-the NCO (isocyanate group) of high molecular polymer and forms guarantor
Cuticula, so that obtained modified carbon nano tube fiber can make the stronger cloth of ability of anti-deformation.Experiment proves that above-mentioned system
The Young's modulus for the modified carbon nano tube fiber that Preparation Method obtains is 545GPa~730GPa, and ability of anti-deformation is stronger, by the modification
The Young's modulus of the cloth of carbon nano-fiber preparation is 540GPa~640GPa, it may have stronger ability of anti-deformation.
It is described in one of the embodiments, that presoma is sprayed on the carbon nano-tube fibre, and in the second protectiveness
Under atmosphere in 140 DEG C~160 DEG C reactions the step of in, the reaction time is 1h~2h.
The weight average molecular weight of the high molecular polymer is 3500~30000 in one of the embodiments,；And/or
The molar ratio of the 2- oxazoline class monomer and the nitrogen-containing heterocycle class monomer is 0.75~3.2.
The irradiation power of the ultraviolet light is 15mW~35mW in one of the embodiments, and the ultraviolet light is irradiation
Wavelength is the monochromatic narrow band light of 196nm~350nm, and the time of the ultraviolet light processing is 10min~35min.
It is described before the step of forming high molecular polymer in the second substrate in one of the embodiments, further include
The preparation step of the high molecular polymer: the 2- oxazoline class monomer and the nitrogen-containing heterocycle class monomer are passed through into free radical
Polymerization reaction obtains reactant；Solvent is added into the reactant, collects precipitating after separation of solid and liquid, obtains the macromolecule
Polymer.
The 2- oxazoline class monomer and the nitrogen-containing heterocycle class monomer are passed through into free radical in one of the embodiments,
The step of polymerization reaction specifically: the 2- oxazoline class monomer, the nitrogen-containing heterocycle class monomer and initiator are mixed, and in
Raolical polymerizable is carried out at 60 DEG C~65 DEG C, the reaction time is 6h~8h, and the initiator is potassium peroxydisulfate.
The molar ratio of the initiator and the 2- oxazoline class monomer is 1:18~1 in one of the embodiments:
24。
It is described in one of the embodiments, to include: the step of forming carbon nano pipe array in the first substrate
The deposit catalyst layers in first substrate；And
Under protective gas atmosphere, first substrate for being formed with the catalyst layer is warming up to 550 DEG C~900
After DEG C, then it is passed through carbon-source gas reaction, obtains the carbon nano pipe array；The source gas includes ethylene and hexane, the second
The partial pressure of alkene and hexane ratio is 1.25:1~8:1, and the flow velocity of the carbon-source gas is 5mL/min~15mL/min,
Being passed through the time that the carbon-source gas is reacted is 10min~25min.
A kind of modified carbon nano tube fiber is prepared by the preparation method of above-mentioned modified carbon nano tube fiber.
Above-mentioned modified carbon nano tube fiber is preparing the application in cloth.
Specific embodiment
It to facilitate the understanding of the present invention, below will be to invention is more fully described.But the present invention can be to be permitted
Mostly different form is realized, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes
It is more thorough and comprehensive to the understanding of the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
The preparation method of the modified carbon nano tube fiber of one embodiment can prepare the preferable carbon modified of non-deformability and receive
Rice fiber, and then can be applied to the preparation better cloth of quality.The preparation method of the modified carbon nano tube fiber includes following step
Rapid S110~S130:
S110, modified carbon nano-tube array is prepared.
The step of preparing modified carbon nano-tube array in one of the embodiments, includes S111~S113:
S111, the deposition of carbon nanotubes array in the first substrate.
In one of the embodiments, the step of deposition of carbon nanotubes array in the first substrate include S1111~
S1112:
S1111, the deposit catalyst layers in the first substrate.
Catalyst layer is formed on the surface of the first substrate using electron beam evaporation method in one of the embodiments,.Into one
The material on step ground, catalyst layer is selected from least one of iron, cobalt and nickel.Catalyst layer with a thickness of 20nm~23nm.
S1112, under protective gas atmosphere, the first substrate for being formed with catalyst layer is warming up to 550 DEG C~900 DEG C
Afterwards, then it is passed through carbon-source gas reaction, obtains carbon nano pipe array.
In one of the embodiments, by the first substrate for being deposited with catalyst layer be placed in chemical gas phase reaction furnace into
Row reaction.Further, it is first passed through protective gas into chemical gas phase reaction furnace, then increases the temperature of chemical gas phase reaction furnace
To 550 DEG C~900 DEG C, so that catalyst layer homogeneous nucleation in the first substrate；Carbon-source gas is passed through thereto again to be reacted.
Further, carbon-source gas includes ethylene and hexane, and the partial pressure ratio of ethylene and hexane is 1.25:1~8:
1.The flow velocity of carbon-source gas is 5mL/min~15mL/min, and being passed through the time that carbon-source gas is reacted is 10min~25min.
It is arranged by this, the mechanical property of obtained carbon nano pipe array is preferable.
Protective gas is selected from least one of nitrogen, hydrogen, argon gas and helium in one of the embodiments,.
The carbon nano-pipe array deposited in the first substrate in one of the embodiments, is classified as single-walled carbon nanotube battle array
Column.It should be noted that the carbon nano pipe array deposited in the first substrate is also possible to array of multi-walled carbon nanotubes.It needs
It is noted that the surface of single-wall carbon nanotube array is compared with multi wall carbon when using the preparation method of above-mentioned modified carbon nano tube fiber
The surface modification difficulty of nano-tube array is bigger.
The length of the carbon nano pipe array deposited in the first substrate in one of the embodiments, be 650 μm~
1200μm.The diameter of carbon nanotube is 10nm~15nm in carbon nano pipe array.
The first substrate is alumina plate in one of the embodiments,.The main function of first substrate is to carrying carbon
Nano-tube array.The size of the first substrate is 8 feet in one of the embodiments,.Certainly, in other embodiments,
The size of one substrate is also possible to any other size.
The first substrate has the first working face in one of the embodiments, deposits to form carbon nanometer in the first working face
Pipe array layer.
S112, high molecular polymer is deposited in the second substrate.
2- oxazoline class monomer is selected from 2- isopropenyl -2- oxazoline and 4,4'- diformazan in one of the embodiments,
At least one of base -2- vinyl -2- oxazoline, nitrogen-containing heterocycle class monomer are n-vinyl pyrrolidone.
The weight average molecular weight of high molecular polymer is 3500~30000 in one of the embodiments,.Further, high
The weight average molecular weight of Molecularly Imprinted Polymer is 5000~20000.
The molar ratio of 2- oxazoline class monomer and nitrogen-containing heterocycle class monomer is 0.75~3.2 in one of the embodiments,.
The high molecular polymer of such setting is grafted to the surface of carbon nano pipe array, can obtain the better carbon modified of ability of anti-deformation
Nanofiber.
2- oxazoline class monomer is by 2- isopropenyl -2- oxazoline and 4,4 '-dimethyl-in one of the embodiments,
2- vinyl -2- oxazoline composition, and 2- isopropenyl -2- oxazoline and 4,4'- dimethyl -2- vinyl -2- oxazoline
Molar ratio is 0.7~1.3.The high molecular polymer of such setting is grafted to the surface of carbon nano pipe array, can obtain resistance
The better modified carbon nano tube fiber of shape ability.Further, 2- isopropenyl -2- oxazoline and 4,4'- dimethyl -2- ethylene
The molar ratio of base -2- oxazoline is 1.
The second substrate is silicon wafer, nickel sheet or copper sheet in one of the embodiments,.The main function of second substrate is pair
High molecular polymer is carried, and the stability of silicon wafer, nickel sheet and copper sheet is good, will not react with high molecular polymer.
The size of the second substrate is 50mm*50mm in one of the embodiments, certainly, in other embodiments, the
The size of two substrates is also possible to any other size.
The method for forming high molecular polymer in the second substrate in one of the embodiments, can be using in the second base
The mode of high molecular polymer film is formed on bottom, it certainly, in other embodiments, can also be using shearing high molecular polymerization
Object material is placed in the mode in the second substrate again.Further, the high molecular polymer deposited in the second substrate with a thickness of
1mm~3mm.Further, the second substrate has the second working face, and deposition forms high molecular polymer on the second working face
The second working face is completely covered in film, high molecular polymer film.
It further include the preparation step of high molecular polymer in one of the embodiments, before S112: by 2- oxazoline class
Monomer and nitrogen-containing heterocycle class monomer obtain reactant by Raolical polymerizable；Solvent is added into reactant, is separated by solid-liquid separation
Precipitating is collected afterwards, obtains high molecular polymer.
Further, the step of 2- oxazoline class monomer being passed through Raolical polymerizable with nitrogen-containing heterocycle class monomer is specific
Are as follows: 2- oxazoline class monomer, nitrogen-containing heterocycle class monomer and initiator are mixed, and carry out free radical polymerization at 60 DEG C~65 DEG C
Reaction, reaction time are 6h~8h, and initiator is potassium peroxydisulfate.Further, initiator and 2- oxazoline class monomer rub
You are than being 1:18~1:24.
Solvent is selected from least one of carbon tetrachloride, tetrahydrofuran and methylene chloride in one of the embodiments,.
The mode being separated by solid-liquid separation in one of the embodiments, is centrifugation.It should be noted that the mode being separated by solid-liquid separation is not
It is limited to for centrifugation, or other solid-liquid separation methods, such as filter.
It further include being done to precipitating after the step of collecting precipitating after separation of solid and liquid in one of the embodiments,
Dry step, to obtain dry high molecular polymer.It should be noted that if precipitating can satisfy demand, to heavy
The step of shallow lake is dried can be omitted.
S113, under the first protective gas atmosphere, to the first substrate for being formed with carbon nano pipe array and be formed with height
Second substrate of Molecularly Imprinted Polymer carries out ultraviolet light processing, so that high molecular polymer and carbon nano pipe array are grafted
Reaction, obtains modified carbon nano-tube array.
High molecular polymer is grafted to the surface of carbon nano pipe array using ultraviolet light, and high molecular polymer is 2-
The copolymer of oxazoline class monomer and nitrogen-containing heterocycle class monomer, 2- oxazoline class monomer be selected from 2- isopropenyl -2- oxazoline and
At least one of 4,4'- dimethyl -2- vinyl -2- oxazolines, nitrogen-containing heterocycle class monomer are n-vinyl pyrrolidone, are obtained
To the modified carbon nano-tube array being easily dispersed.
By the first substrate for being formed with carbon nano pipe array and it is formed with high molecular polymer in one of the embodiments,
The second substrate be placed in same reaction chamber.Reaction chamber can be closed, and reaction chamber has an air inlet and a gas outlet.Reaction
It is equipped with ultraviolet light module in chamber, ultraviolet light processing can be carried out to reaction chamber.
Further, the first substrate of carbon nano pipe array will be formed with and be formed with the second substrate of high molecular polymer
It is placed side by side in reaction chamber.Further, by the first substrate for being formed with carbon nano pipe array and it is formed with polyphosphazene polymer
The second substrate for closing object is placed side by side, so that carbon nano pipe array and high molecular polymer film contacts.
To the first substrate for being formed with carbon nano pipe array and it is formed with high molecular polymer in one of the embodiments,
The second substrate carry out ultraviolet light processing during, the air inlet of capping chamber and gas outlet first, and to reaction
Chamber carries out vacuumize process, and the air pressure in reaction chamber is made to be down to 10-2Torr or less.Preferably, the air pressure in reaction chamber is reduced
To 10-6Torr or less.Secondly, being passed through the first protective gas into reaction chamber by air inlet until reaching normal atmosphere again
Pressure, open gas outlet, it is not open close enter the first protective gas keep system pressure.
The flow velocity of the first protective gas is 2L/min~3L/min in one of the embodiments,.First protectiveness gas
Body is selected from least one of nitrogen, helium, neon and argon gas.
To the first substrate for being formed with carbon nano pipe array and it is formed with high molecular polymer in one of the embodiments,
The second substrate when carrying out ultraviolet light processing, the irradiation power of ultraviolet light is 15mW~35mW.Under this irradiation power, have
Conducive to the fuel factor for improving reaction system, so that system temperature is increased to high molecular polymer and forms gaseous state, and protecting
Property gas flow under the action of be moved to carbon nano pipe array surface and carbon nano pipe array occur graft polymerization reaction.
Ultraviolet light is the monochrome that illumination wavelength is 196nm~350nm in one of the embodiments,
(monochromatic) narrow band light.Further, monochromatic narrow band light is the monochromatic light that bandwidth is 218nm~298nm.
Ultraviolet source distance is formed with the first substrate of carbon nano pipe array and is formed with height in one of the embodiments,
The distance of second substrate of Molecularly Imprinted Polymer is 2mm~20mm.
The time for carrying out ultraviolet light processing in one of the embodiments, is 10min~35min.One wherein
In embodiment, the time for carrying out ultraviolet light processing is 15min~30min.Ultraviolet light is carried out in one of the embodiments,
The time for the treatment of with irradiation is 23min.
To the first substrate for being formed with carbon nano pipe array and it is formed with high molecular polymer in one of the embodiments,
The second substrate when carrying out ultraviolet light processing, the irradiation power of ultraviolet light is 15mW~35mW, ultraviolet light be 196nm~
The monochromatic narrow band light of 350nm, the time for carrying out ultraviolet light processing is 15min~30min.With this condition, be conducive to
Guarantee high molecular polymer reduces ultraviolet light in the case where capable of being grafted to carbon nano pipe array and receives to high molecular polymer and carbon
The destruction of mitron array structure to guarantee the mechanical property of carbon nano pipe array, and obtains the better carbon nanometer of non-deformability
Pipe fiber.
To the first substrate for being formed with carbon nano pipe array and it is formed with high molecular polymer in one of the embodiments,
The second substrate carry out ultraviolet light processing after, further include the first substrate is placed in it is naturally cold under protective gas atmosphere
But operation.It should be noted that in other embodiments, the first substrate is placed in naturally cold under protective gas atmosphere
But operation also can be omitted.
The first substrate is placed under protective gas atmosphere in the operation of natural cooling in one of the embodiments,
Protective gas is selected from least one of nitrogen, argon gas and helium.By the first substrate be placed under protective gas atmosphere into
Row natural cooling can prevent carbon nano pipe array exposure to be oxidized in air.
S120, spinning is carried out to modified carbon nano-tube array, obtains carbon nano-tube fibre.
In a wherein embodiment, the step of S120 specifically: using clamping tool from modified carbon nano-tube array
Edge clamp modified carbon nano-tube array, and pulled and revolved along the direction of growth perpendicular to modified carbon nano-tube array
Turn, so that modified carbon nano-tube array is stretched, and every modified carbon nano-tube in modified carbon nano-tube array is made to be screwed in one
It rises, obtains carbon nano-tube fibre.
In clamping tool drawing and modifying carbon nano pipe array, modified carbon nano-tube is by Van der Waals force and modification in modification
Non-covalent interaction power between the copolymer on carbon nano pipe array surface or the decomposition product of copolymer drives carbon modified to receive
Mitron array is continuously drawn out and makes modified carbon nano-tube battle array in filiform, then by rotating modified carbon nano-tube array
Every modified carbon nano-tube in column is threaded together, as carbon nano-tube fibre.
Further, the step of S120 specifically: the modified carbon nano-tube clamped from the edge of modified carbon nano-tube array
Array, and pulled along the direction perpendicular to modified carbon nano-tube array growth, obtain silky nano pipe array；From filiform
The silky nano pipe array of the edge clamping of nano-tube array, and along the extending direction progress perpendicular to silky nano pipe array
It rotates and pulls, so that silky nano pipe array is stretched, and be screwed in every silky nano pipe in silky nano pipe array
Together, carbon nano-tube fibre is obtained.
In a wherein embodiment, when clamping modified carbon nano-tube array from the edge of modified carbon nano-tube array,
The width of clamping is 50 μm~200 μm.Further, modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array
When, the width of clamping is 100 μm~150 μm.
In a wherein embodiment, when being pulled along the direction of growth perpendicular to modified carbon nano-tube array
Rate is 0.05m/s~0.5mm/s.Further, it is pulled along the direction of growth perpendicular to modified carbon nano-tube array
When rate be 0.1m/s~0.4mm/s.Further, along the direction of growth progress perpendicular to modified carbon nano-tube array
Rate when dragging is 0.2m/s~0.3mm/s.
In a wherein embodiment, when being rotated along the direction of growth perpendicular to modified carbon nano-tube array
Revolving speed is 1000rpm~3000rpm.Further, it is rotated along the direction of growth perpendicular to modified carbon nano-tube array
When revolving speed be 2000rpm.
In a wherein embodiment, the diameter of carbon nano-tube fibre is 10 μm~200 μm.
In a wherein embodiment, the length of carbon nano-tube fibre is 100m~6000m.It should be noted that carbon
The length of nanotube fibers is not limited to above-mentioned length, can be configured according to actual needs.
S130, presoma is sprayed on carbon nano-tube fibre, and in 140 DEG C~160 under the second protective gas atmosphere
DEG C reaction, obtains modified carbon nano tube fiber, presoma is selected from epoxy resin, polyurethane resin and polystyrene resin
At least one of.
By spraying presoma on carbon nano-tube fibre, and specific presoma is selected, so that presoma and macromolecule
- the NCO of polymer reacts and forms protective film, so that obtained modified carbon nano tube fiber has preferably ability of anti-deformation, with
Guarantee the ability of anti-deformation of carbon nanometer fabric.
It should be noted that the presoma in the spraying of carbon nano-tube fibre surface can sufficiently connect with high molecular polymer
Touching.Further, the surface of carbon nano-tube fibre can be completely covered, in the presoma of carbon nano-tube fibre surface spraying to protect
Card presoma comes into full contact with high molecular polymer.
In one of the embodiments, the second protective gas in nitrogen, helium, neon and argon gas at least one
Kind.
Presoma is sprayed on carbon nano-tube fibre in one of the embodiments, and in the second protective gas atmosphere
Under in 140 DEG C~160 DEG C reactions the step of in, the reaction time is 1h~2h.Under this reaction time, presoma and carbon can be made
Nanotube fibers sufficiently react, to guarantee the mechanical property of modified carbon nano tube fiber.
Presoma is misty or film-form in one of the embodiments,.Such setting enables presoma more equal
Even is coated on carbon nano-tube fibre.
Presoma is selected from epoxy resin, polyurethane resin and polystyrene tree in one of the embodiments,
At least one of rouge.
Presoma is made of epoxy resin and polystyrene resin in one of the embodiments, and epoxy resin and poly-
The molar ratio of styrene resin is 95:1~99:1.Such setting can obtain the more excellent modified carbon nano tube of mechanical property
Fiber.
High molecular polymer is grafted to carbon nano-pipe array using ultraviolet light by the preparation method of above-mentioned modified carbon nano tube fiber
The surface of column, and high molecular polymer is the copolymer of 2- oxazoline class monomer and nitrogen-containing heterocycle class monomer, 2- oxazoline class
Monomer is selected from 2- isopropenyl -2- oxazoline and 4, at least one of 4'- dimethyl -2- vinyl -2- oxazoline, nitrogen-containing hetero
Ring class monomer is n-vinyl pyrrolidone, the modified carbon nano-tube array being easily dispersed, and by by the carbon modified
Spray presoma on carbon nano-tube fibre made of nanotube, presoma be selected from epoxy resin, polyurethane resin and
At least one of polystyrene resin, so that presoma reacts with-the NCO (isocyanate group) of high molecular polymer and forms guarantor
Cuticula, so that obtained modified carbon nano tube fiber can make the stronger cloth of ability of anti-deformation.Experiment proves that above-mentioned system
The Young's modulus for the modified carbon nano tube fiber that Preparation Method obtains is 545GPa~730GPa, and ability of anti-deformation is stronger, by the modification
The Young's modulus of the cloth of carbon nano-fiber preparation is 540GPa~640GPa, it may have stronger ability of anti-deformation.
Furthermore the preparation method of above-mentioned modified carbon nano tube fiber, passes through the height in carbon nano pipe array surface grafting characteristic
Molecularly Imprinted Polymer is capable of increasing the distance between carbon nanotube, reduces the group due to caused by the Van der Waals force between carbon nanotube
Poly-, the modified carbon nano tube fiber made is easily dispersed, and to obtain, fibre density is lower and the stronger carbon modified of ability of anti-deformation
Nanofiber can be applied to the preparation higher cloth of more soft and quality.
Finally, above-mentioned preparation method does not need to disperse carbon nano pipe array to carry out subsequent processing, work in a solvent
Skill simplifies, and will not destroy the array structure of carbon nano pipe array, advantageously ensure that modified carbon nano-tube array and modified carbon nano tube
The mechanical property of fiber, solvent-free equal residual, the purity of obtained modified carbon nano tube fiber are higher.
The cloth of one embodiment, the modified carbon nano tube fiber including above embodiment.
It should be noted that can use traditional Weaving method by modified carbon nano tube fibrous woven at cloth.Traditional
Weaving method for example can be flat weaving method or twill.
It should be noted that can be weaved using single modified carbon nano tube fiber, more carbon modifieds can also be received
Rice fibers parallel is made one and weaves again.
Above-mentioned cloth includes the modified carbon nano tube fiber of above embodiment, since the modified carbon nano tube fiber is with lower
Density and more excellent ability of anti-deformation so that cloth quality with higher.
It is below the part of specific embodiment.
Unless otherwise instructed, following embodiment is without containing other groups not yet explicitly pointed out in addition to inevitable impurity
Point.
Unless otherwise instructed, in following embodiment, the first substrate is alumina plate.Second substrate is copper sheet.Presoma is complete
On all standing carbon nano-tube fibre.Ultraviolet source distance is formed with the first substrate of carbon nano pipe array and is formed with polyphosphazene polymer
When closing the second substrate of object, the bandwidth of ultraviolet source is 256nm.
Embodiment 1
The preparation process of the cloth of the present embodiment is as follows:
(1) take one piece of first substrate, deposition forms the catalyst layer of 20nm thickness in the first substrate, catalyst layer be nickel with
The mixing material (mass ratio of nickel and cobalt is 1:1) of cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace and is passed through
Nitrogen, then be warming up to 900 DEG C, then into chemical vapour deposition reactor furnace be passed through carbon-source gas (carbon-source gas includes ethylene and oneself
The partial pressure ratio of alkane, ethylene and hexane is 1.25:1), and the flow control of carbon-source gas reacts 25min at 15L/min,
So that the first substrate surface is completely covered with carbon nano pipe array, carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nanometer
The length of pipe array is 650 μm, and the diameter of carbon nanotube is 15nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the high molecular polymer film with a thickness of 1mm in the second substrate.Macromolecule
The preparation process of polymer are as follows: 2- oxazoline class monomer is mixed with nitrogen-containing heterocycle class monomer and initiator, and at 65 DEG C into
Row Raolical polymerizable 6h, obtains reactant, and initiator is potassium peroxydisulfate, the molar ratio of initiator and 2- oxazoline class monomer
For 1:18；Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is dried, high molecular polymer is obtained.
2- oxazoline class monomer is 2- isopropenyl -2- oxazoline, and nitrogen-containing heterocycle class monomer is n-vinyl pyrrolidone, 2- oxazoline
The molar ratio of class monomer and nitrogen-containing heterocycle class monomer is 3.2.The weight average molecular weight of high molecular polymer is 3500.Solvent is tetrachloro
Change carbon.
(3) it by the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with high molecular polymer and discharges
It is placed in reaction chamber, is formed with the first substrate of carbon nano pipe array and is formed with the second substrate of high molecular polymer in same
One horizontal plane, and carbon nano pipe array and high molecular polymer contact, reaction chamber are evacuated to air pressure and are down to 10-2Logical after Torr
Enter nitrogen, keeping the flow velocity of nitrogen is 2L/min, to the first substrate for being formed with carbon nano pipe array and is formed with polyphosphazene polymer
The second substrate for closing object carries out ultraviolet light processing, and ultraviolet source distance is formed with the first substrate and shape of carbon nano pipe array
Distance at the second substrate for having high molecular polymer is 2mm, and the irradiation power of ultraviolet light is 35mW, and ultraviolet light is illumination wavelength
For the monochromatic narrow band light of 196nm, irradiation time 35min；Ultraviolet light module is closed, the first substrate is exposed under nitrogen atmosphere
To natural cooling, modified carbon nano-tube array is obtained.
(4) modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array using clamping tool, and along vertical
Directly the direction of growth in modified carbon nano-tube array is pulled and is rotated, and obtains carbon nano-tube fibre.From modified carbon nano-tube
When the edge of array clamps modified carbon nano-tube array, the width of clamping is 200 μm.The speed of dragging is 0.5mm/s, and revolving speed is
3000rpm.The diameter of obtained carbon nano-tube fibre is 10 μm.
(5) presoma is sprayed on carbon nano-tube fibre, and reacts 1h at 140 DEG C in nitrogen atmosphere, is modified
Carbon nano-fiber, presoma are bisphenol A type epoxy resin.
(6) modified carbon nano tube fiber is weaved, obtains cloth.
Embodiment 2
The preparation process of the cloth of the present embodiment is as follows:
(1) take one piece of first substrate, deposition forms the catalyst layer of 23nm thickness in the first substrate, catalyst layer be nickel with
The mixing material (mass ratio of nickel and cobalt is 1:1) of cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace and is passed through
Nitrogen, then be warming up to 550 DEG C, then into chemical vapour deposition reactor furnace be passed through carbon-source gas (carbon-source gas includes ethylene and oneself
The partial pressure ratio of alkane, ethylene and hexane is 8:1), and the flow control of carbon-source gas reacts 10min at 5L/min, so that
First substrate surface is completely covered with carbon nano pipe array, and carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nano-pipe array
The length of column is 1180 μm, and the diameter of carbon nanotube is 10nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the high molecular polymer film with a thickness of 3mm in the second substrate.Macromolecule
The preparation process of polymer are as follows: 2- oxazoline class monomer is mixed with nitrogen-containing heterocycle class monomer and initiator, and at 60 DEG C into
Row Raolical polymerizable 8h, obtains reactant, and initiator is potassium peroxydisulfate, the molar ratio of initiator and 2- oxazoline class monomer
For 1:24；Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is dried, high molecular polymer is obtained.
Wherein, 2- oxazoline class monomer is 4,4'- dimethyl -2- vinyl -2- oxazoline, and nitrogen-containing heterocycle class monomer is N- vinylpyridine
The molar ratio of pyrrolidone, 2- oxazoline class monomer and nitrogen-containing heterocycle class monomer is 0.75.The weight average molecular weight of high molecular polymer
It is 30000.Solvent is tetrahydrofuran.
(3) it by the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with high molecular polymer and discharges
It is placed in reaction chamber, is formed with the first substrate of carbon nano pipe array and is formed with the second substrate of high molecular polymer in same
One horizontal plane, and carbon nano pipe array and high molecular polymer contact, reaction chamber are evacuated to air pressure and are down to 10-2Logical after Torr
Enter nitrogen, keeping the flow velocity of nitrogen is 3L/min, to the first substrate for being formed with carbon nano pipe array and is formed with polyphosphazene polymer
The second substrate for closing object carries out ultraviolet light processing, and ultraviolet source distance is formed with the first substrate and shape of carbon nano pipe array
Distance at the second substrate for having high molecular polymer is 10mm, and the irradiation power of ultraviolet light is 15mW, and ultraviolet light is irradiation wave
The monochromatic narrow band light of a length of 350nm, irradiation time 10min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere
Down toward natural cooling, modified carbon nano-tube array is obtained.
(4) modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array using clamping tool, and along vertical
Directly the direction of growth in modified carbon nano-tube array is pulled and is rotated, and obtains carbon nano-tube fibre.From modified carbon nano-tube
When the edge of array clamps modified carbon nano-tube array, the width of clamping is 50 μm.The speed of dragging is 0.05mm/s, and revolving speed is
1000rpm.The diameter of obtained carbon nano-tube fibre is 200 μm.
(5) presoma is sprayed on carbon nano-tube fibre, and reacts 2h at 160 DEG C under nitrogen atmosphere, is modified
Carbon nano-fiber, presoma are polyurethane resin.
(6) modified carbon nano tube fiber is weaved, obtains cloth.
Embodiment 3
The preparation process of the cloth of the present embodiment is as follows:
(1) take one piece of first substrate, deposition forms the catalyst layer of 21nm thickness in the first substrate, catalyst layer be nickel with
The mixing material (mass ratio of nickel and cobalt is 1:1) of cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace and is passed through
Nitrogen, then be warming up to 700 DEG C, then into chemical vapour deposition reactor furnace be passed through carbon-source gas (carbon-source gas includes ethylene and oneself
The partial pressure ratio of alkane, ethylene and hexane is 4:1), and the flow control of carbon-source gas reacts 20min at 10L/min, so that
First substrate surface is completely covered with carbon nano pipe array, and carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nano-pipe array
The length of column is 800 μm, and the diameter of carbon nanotube is 12nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the high molecular polymer film with a thickness of 2mm in the second substrate.Macromolecule
The preparation process of polymer are as follows: 2- oxazoline class monomer is mixed with nitrogen-containing heterocycle class monomer and initiator, and at 63 DEG C into
Row Raolical polymerizable 7h, obtains reactant, and initiator is potassium peroxydisulfate, the molar ratio of initiator and 2- oxazoline class monomer
For 1:20；Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is dried, high molecular polymer is obtained；
2- oxazoline class monomer is by 2- isopropenyl -2- oxazoline and 4,4 '-dimethyl -2- vinyl -2- oxazolines composition, and 2- is different
The molar ratio of acrylic -2- oxazoline and 4,4'- dimethyl -2- vinyl -2- oxazoline is 1；Nitrogen-containing heterocycle class monomer is N-
Vinyl pyrrolidone；The molar ratio of 2- oxazoline class monomer and nitrogen-containing heterocycle class monomer is 2；High molecular polymer is divided equally again
Son amount is 15000；Solvent is carbon dichloride.
(3) it by the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with high molecular polymer and discharges
It is placed in reaction chamber, is formed with the first substrate of carbon nano pipe array and is formed with the second substrate of high molecular polymer in same
One horizontal plane, and carbon nano pipe array and high molecular polymer contact, reaction chamber are evacuated to air pressure and are down to 10-2Logical after Torr
Enter nitrogen, keeping the flow velocity of nitrogen is 2.5L/min, to the first substrate for being formed with carbon nano pipe array and is formed with macromolecule
Second substrate of polymer carries out ultraviolet light processing, ultraviolet source distance be formed with carbon nano pipe array the first substrate and
The distance for being formed with the second substrate of high molecular polymer is 10mm, and the irradiation power of ultraviolet light is 25mW, and ultraviolet light is irradiation
Wavelength is the monochromatic narrow band light of 256nm, irradiation time 23min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere
It encloses down toward natural cooling, obtains modified carbon nano-tube array.
(4) modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array using clamping tool, and along vertical
Directly the direction of growth in modified carbon nano-tube array is pulled and rotates to obtain carbon nano-tube fibre.From modified carbon nano-tube battle array
When the edge of column clamps modified carbon nano-tube array, the width of clamping is 130 μm.The speed of dragging is 0.3mm/s, and revolving speed is
2000rpm.The diameter of obtained carbon nano-tube fibre is 100 μm.
(5) presoma is sprayed on carbon nano-tube fibre, and reacts 1.5h at 150 DEG C under nitrogen atmosphere, is changed
Property carbon nano-fiber, presoma is made of bisphenol A type epoxy resin and polystyrene resin, and bisphenol A type epoxy resin and poly-
The molar ratio of styrene resin is 98:1.
(6) modified carbon nano tube fiber is weaved, obtains cloth.
Embodiment 4
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: 2- oxazoline class monomer
By 2- isopropenyl -2- oxazoline and 4,4 '-dimethyl -2- vinyl -2- oxazolines composition, 2- isopropenyl -2- oxazoline
And the molar ratio of 4,4'- dimethyl -2- vinyl -2- oxazoline is 0.7；Nitrogen-containing heterocycle class monomer is N- ethenyl pyrrolidone
Ketone.
Embodiment 5
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: 2- oxazoline class monomer
By 2- isopropenyl -2- oxazoline and 4,4 '-dimethyl -2- vinyl -2- oxazolines composition, 2- isopropenyl -2- oxazoline
And the molar ratio of 4,4'- dimethyl -2- vinyl -2- oxazoline is 1.3；Nitrogen-containing heterocycle class monomer is N- ethenyl pyrrolidone
Ketone.
Embodiment 6
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: presoma is by bisphenol-A
Type epoxy resin and polystyrene resin composition, and it is 99:1 that bisphenol A type epoxy resin and polystyrene resin, which are mass ratio,.
Embodiment 7
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: presoma is by bisphenol-A
Type epoxy resin and polystyrene resin composition, and it is 95:1 that bisphenol A type epoxy resin and polystyrene resin, which are mass ratio,.
Embodiment 8
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: by 2- oxazoline class list
Body obtains reactant by Raolical polymerizable；Solvent is added into reactant, collects precipitating after separation of solid and liquid, will precipitate
It is dried, obtains high molecular polymer；Oxazoline class monomer is by 2- isopropenyl -2- oxazoline and 4,4 '-dimethyl -2-
Vinyl -2- oxazoline composition, and 2- isopropenyl -2- oxazoline and 4,4'- dimethyl -2- vinyl -2- oxazoline rubs
You are than being 1.
Embodiment 9
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: by nitrogen-containing heterocycle class list
Body obtains reactant by Raolical polymerizable；Solvent is added into reactant, collects precipitating after separation of solid and liquid, will precipitate
It is dried, obtains high molecular polymer；Nitrogen-containing heterocycle class monomer is n-vinyl pyrrolidone.
Embodiment 10
The preparation process of the cloth of the present embodiment is as follows:
(1) carbon nano pipe array is prepared according to (1) the step of embodiment 3.
(2) carbon nano pipe array is clamped from the edge of carbon nano pipe array using clamping tool, and is received along perpendicular to carbon
The direction of growth of mitron array is pulled and is rotated, and carbon nano-tube fibre is obtained.Carbon is clamped from the edge of carbon nano pipe array
When nano-tube array, the width of clamping is 130 μm.The speed of dragging is 0.3mm/s, revolving speed 2000rpm.Obtained carbon nanometer
The diameter of pipe fiber is 100 μm.
(3) presoma is sprayed on carbon nano-tube fibre, and reacts 1.5h at 150 DEG C in nitrogen, is obtained carbon modified and is received
Rice fiber, presoma is made of bisphenol A type epoxy resin and polystyrene resin, and bisphenol A type epoxy resin and polystyrene
The molar ratio of resin is 98:1.
(4) modified carbon nano tube fiber is weaved, obtains cloth.
Embodiment 11
The preparation process of the cloth of the present embodiment is as follows:
(1) carbon nano-tube fibre is prepared according to (1) the step of embodiment 3~(4).
(2) carbon nano-tube fibre is weaved, obtains cloth.
Embodiment 12
The preparation process of the cloth of the present embodiment is as follows:
(1) carbon nano pipe array is prepared according to (1) the step of embodiment 3.
(2) carbon nano pipe array is clamped from the edge of carbon nano pipe array using clamping tool, and is received along perpendicular to carbon
The direction of growth of mitron array is pulled and is rotated, and carbon nano-tube fibre is obtained.Carbon is clamped from the edge of carbon nano pipe array
When nano-tube array, the width of clamping is 130 μm.The speed of dragging is 0.3mm/s, revolving speed 2000rpm.Obtained carbon nanometer
The diameter of pipe fiber is 100 μm.
(3) carbon nano-tube fibre is weaved, obtains cloth.
Test:
Measure density and the poplar of the modified carbon nano tube fiber of Examples 1 to 10 and the carbon nano-tube fibre of embodiment 11~12
Family name's modulus, and measure the density and Young's modulus of the cloth of embodiment 1~12.See Table 1 for details for measurement result.What table 1 indicated is real
Apply the density and Young's modulus, embodiment 1 of the modified carbon nano tube fiber of example 1~10 and the carbon nano-tube fibre of embodiment 11~12
The density and Young's modulus of~12 cloth.
Specifically, using the density of Archimedes method (canola oil) measurement fiber and cloth；
Using the Young's modulus (GPa) of extension test method test fiber and cloth.
Table 1
As it can be seen from table 1 the Young's modulus of the modified carbon nano tube fiber of Examples 1 to 7 is 645GPa~730GPa, say
The modified carbon nano tube fiber that bright above-mentioned preparation method obtains has stronger ability of anti-deformation, and it is higher to can be used in preparation quality
Cloth, also, the density of the modified carbon nano tube fiber of Examples 1 to 7 is 1.75g/cm2~1.83g/cm2, illustrate above-mentioned preparation
The modified carbon nano tube fiber that method obtains has lower density；Meanwhile the density of the cloth of Examples 1 to 7 is 191g/cm2
~209g/cm2, Young's modulus is 540GPa~640GPa, further proves to prepare using above-mentioned modified carbon nano tube fiber
With stronger ability of anti-deformation and more soft cloth.
Wherein, the ability of anti-deformation of the modified carbon nano tube fiber of embodiment 3 is higher than embodiment 8~9, and illustrates 2- oxazoline
The high molecular polymer that class monomer and nitrogen-containing heterocycle class monomer polymerization are formed is more advantageous to the anti-shape for improving modified carbon nano tube fiber
Change ability.The ability of anti-deformation of the modified carbon nano tube fiber of embodiment 3 be higher than embodiment 10~12, illustrate high molecular polymer with
The reaction of presoma can be improved the ability of anti-deformation of modified carbon nano tube fiber.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of modified carbon nano tube fiber, which comprises the steps of:
Carbon nano pipe array is formed in the first substrate；
High molecular polymer is formed in the second substrate, the high molecular polymer is 2- oxazoline class monomer and nitrogen-containing heterocycle class
The copolymer of monomer, the 2- oxazoline class monomer are selected from 2- isopropenyl -2- oxazoline and 4,4'- dimethyl -2- vinyl -
At least one of 2- oxazoline, the nitrogen-containing heterocycle class monomer are n-vinyl pyrrolidone；
Under the first protective gas atmosphere, to first substrate for being formed with the carbon nano pipe array and it is formed with described
Second substrate of high molecular polymer carries out ultraviolet light processing, so that the high molecular polymer and the carbon nanometer
Pipe array carries out graft reaction, obtains modified carbon nano-tube array；
The modified carbon nano-tube array is subjected to spinning, obtains carbon nano-tube fibre；
Presoma is sprayed on the carbon nano-tube fibre, and anti-in 140 DEG C~160 DEG C under the second protective gas atmosphere
It answers, obtains modified carbon nano tube fiber, the presoma is selected from epoxy resin, polyurethane resin and polystyrene resin
At least one of.
2. the preparation method of modified carbon nano tube fiber according to claim 1, which is characterized in that described in the carbon nanometer
Presoma is sprayed on pipe fiber, and under the second protective gas atmosphere in 140 DEG C~160 DEG C reactions the step of in, when reaction
Between be 1h~2h.
3. the preparation method of modified carbon nano tube fiber according to claim 1, which is characterized in that the high molecular polymer
Weight average molecular weight be 3500~30000；And/or
The molar ratio of the 2- oxazoline class monomer and the nitrogen-containing heterocycle class monomer is 0.75~3.2.
4. the preparation method of modified carbon nano tube fiber according to claim 1, which is characterized in that the irradiation of the ultraviolet light
Power is 15mW~35mW, and the ultraviolet light is the monochromatic narrow band light that illumination wavelength is 196nm~350nm, the ultraviolet lighting
The time for penetrating processing is 10min~35min.
5. the preparation method of modified carbon nano tube fiber according to claim 1, which is characterized in that described in the second substrate
It further include the preparation step of the high molecular polymer: by the 2- oxazoline class before the step of forming high molecular polymer
Monomer and the nitrogen-containing heterocycle class monomer obtain reactant by Raolical polymerizable；Solvent is added into the reactant,
Precipitating is collected after separation of solid and liquid, obtains the high molecular polymer.
6. the preparation method of modified carbon nano tube fiber according to claim 5, which is characterized in that by the 2- oxazoline class
The step of monomer and the nitrogen-containing heterocycle class monomer pass through Raolical polymerizable specifically: by the 2- oxazoline class monomer,
The nitrogen-containing heterocycle class monomer and initiator mixing, and carry out Raolical polymerizable at 60 DEG C~65 DEG C, and the reaction time is
6h~8h, the initiator are potassium peroxydisulfate.
7. the preparation method of modified carbon nano tube fiber according to claim 6, which is characterized in that the initiator with it is described
The molar ratio of 2- oxazoline class monomer is 1:18~1:24.
8. the preparation method of modified carbon nano tube fiber according to claim 1, which is characterized in that described in the first substrate
Formed carbon nano pipe array the step of include:
The deposit catalyst layers in first substrate；And
Under protective gas atmosphere, first substrate for being formed with the catalyst layer is warming up to 550 DEG C~900 DEG C
Afterwards, then it is passed through carbon-source gas reaction, obtains the carbon nano pipe array；The carbon-source gas includes ethylene and hexane, the second
The partial pressure of alkene and hexane ratio is 1.25:1~8:1, and the flow velocity of the carbon-source gas is 5mL/min~15mL/min,
Being passed through the time that the carbon-source gas is reacted is 10min~25min.
9. a kind of modified carbon nano tube fiber, which is characterized in that by modified carbon nano tube fiber according to any one of claims 1 to 8
Preparation method be prepared.
10. modified carbon nano tube fiber as claimed in claim 9 is preparing the application in cloth.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314009A (en) * | 2018-03-30 | 2018-07-24 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano pipe array |
| CN108532287A (en) * | 2018-03-30 | 2018-09-14 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano-tube fibre |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314009A (en) * | 2018-03-30 | 2018-07-24 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano pipe array |
| CN108532287A (en) * | 2018-03-30 | 2018-09-14 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano-tube fibre |
Non-Patent Citations (3)
| Title |
|---|
| FEI DENG 等: "Grafting polymer coatings onto the surfaces of carbon nanotube forests and yarns via a photon irradiation process", 《APPLIED PHYSICS LETTERS》 * |
| 娄春华等: "《聚合物结构与性能》", 31 May 2016, 哈尔滨工程大学出版社 * |
| 王国建等: "《功能高分子材料》", 31 January 2010, 同济大学出版社 * |
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