CN109763213A - Carbon nano-tube fibre and its preparation method and application - Google Patents
Carbon nano-tube fibre and its preparation method and application Download PDFInfo
- Publication number
- CN109763213A CN109763213A CN201811457302.6A CN201811457302A CN109763213A CN 109763213 A CN109763213 A CN 109763213A CN 201811457302 A CN201811457302 A CN 201811457302A CN 109763213 A CN109763213 A CN 109763213A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- tube
- array
- polymer
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Abstract
The present invention relates to a kind of carbon nano-tube fibres and its preparation method and application.The preparation method includes the following steps: under the first protective gas atmosphere; ultraviolet light processing is carried out to carry out graft reaction to polymer and carbon nano pipe array; obtain modified carbon nano-tube array; polymer is selected from least one of aldehyde ketone resin and cyclohexanone derivative; ultraviolet light is the monochromatic narrow band light that illumination wavelength is 198nm~289nm, and irradiation power is 20mW~30mW；Modified carbon nano-tube array is subjected to spinning, obtains modified fibre；Reinforcement is set on modified fibre, and is reacted at 80 DEG C~100 DEG C under the second protective gas atmosphere, carbon nano-tube fibre is obtained, reinforcement is selected from least one of epoxy resin and phenolic resin.The carbon nano-tube fibre that above-mentioned preparation method obtains can be used in the cloth that production has both wearability and elasticity.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of carbon nano-tube fibre and its preparation method and application.
Background technique
Carbon nano-tube fibre is piled up by organic fibers such as flake graphites along fiber axial direction, through carbonization and stone
Microcrystalline graphite material obtained from blackization processing.Carbon nano-tube fibre has high-intensitive and light weight characteristic, is widely used in
The fields such as machine-building, health care, high efficient protected, fine filtering and agricultural.Fiber cloth is also known as carbon fiber sheet, in the world
It is known as " black gold ", it is referred to as " third generation material " after the metals such as stone implement and steel in the world.However, traditional
Carbon nano-tube fibre made of cloth wearability it is poor, and elasticity is lower, the serious use for limiting cloth.
Summary of the invention
Based on this, it is necessary to provide a kind of preparation method of carbon nano-tube fibre, the carbon nanotube which obtains
Fiber can be used in the cloth that production has both wearability and elasticity.
In addition, also providing a kind of carbon nano-tube fibre and its preparation method and application.
A kind of preparation method of carbon nano-tube fibre, includes the following steps:
Under the first protective gas atmosphere, ultraviolet light processing is carried out to carry out to polymer and carbon nano pipe array
Graft reaction, obtains modified carbon nano-tube array, the polymer in aldehyde ketone resin and cyclohexanone derivative at least one
Kind, the structural formula of the cyclohexanone derivative is as follows:The n is
Integer greater than 12；The ultraviolet light is the monochromatic narrow band light that illumination wavelength is 198nm~289nm, irradiation power be 20mW~
30mW；
The modified carbon nano-tube array is subjected to spinning, obtains modified fibre；And
Reinforcement is set on the modified fibre, and anti-at 80 DEG C~100 DEG C under the second protective gas atmosphere
It answers, obtains carbon nano-tube fibre, the reinforcement is selected from least one of epoxy resin and phenolic resin.
The preparation method of above-mentioned carbon nano-tube fibre by ultraviolet light, and sets ultraviolet light as illumination wavelength and is
The monochromatic narrow band light of 198nm~289nm, irradiation power is 20mW~30mW, so that polymer grafts on carbon nano pipe array,
Polymer is selected from least one of aldehyde ketone resin and cyclohexanone derivative, and the structural formula of cyclohexanone derivative is as follows:N is the integer greater than 12, improves the elasticity of carbon nano pipe array；
By the way that reinforcement is arranged on modified carbon nano-tube fiber, reinforcement is selected from least one of epoxy resin and phenolic resin,
Reinforcement can form hydrogen bond with the carbonyl in polymer, to improve carbon nanotube in forming protective film on carbon nano-tube fibre
The wearability of fiber, so that manufactured carbon nano-tube fibre can be used in the cloth that production has higher elasticity and wearability.Through
Verification experimental verification, the elongation of cloth made of the carbon nano-tube fibre for using above-mentioned preparation method to obtain for 4.1%~5.2%,
Effectively abrasion number is 2.03 × 104Secondary~2.7 × 104It is secondary, it can be applied to the product more demanding to elasticity and wearability
In.
It is described under the first protective gas atmosphere in one of the embodiments, to polymer and carbon nano pipe array
Before carrying out the step of ultraviolet light processing is to carry out graft reaction, further include the steps that preparing the carbon nano pipe array:
Catalyst layer is formed in the first substrate, the catalyst is selected from least one of cobalt and nickel；
Under third protective gas atmosphere, first substrate for being formed with the catalyst layer is warming up to 650 DEG C
After~750 DEG C, it is passed through carbon-source gas reaction, obtains the carbon nano pipe array, the carbon-source gas includes ethylene and hexane, institute
The partial pressure ratio for stating ethylene and the hexane is 3:2~4:1.
The catalyst is made of nickel and cobalt in one of the embodiments, and the mass ratio of the nickel and the cobalt is
0.8:1~1.2:1.
It is described under the first protective gas atmosphere in one of the embodiments, to polymer and carbon nano pipe array
Carry out the step of ultraviolet light processing is to carry out graft reaction specifically: the polymer is formed in the second substrate；By shape
It is arranged side by side at first substrate for having the carbon nano pipe array and second substrate for being formed with the polymer；?
Under the first protective gas atmosphere, to first substrate for being formed with the carbon nano pipe array and it is equipped with the polymerization
Second substrate of object carries out ultraviolet light processing, so that the carbon nano pipe array and the polymer be grafted instead
It answers.
The weight average molecular weight of the polymer is 20000~35000 in one of the embodiments,.
The polymer is made of the aldehyde ketone resin and the cyclohexanone derivative in one of the embodiments, and
The aldehyde ketone resin and the molar ratio of the cyclohexanone derivative are 0.8:1~1.13:1.
It is described in one of the embodiments, that the modified carbon nano-tube array is subjected to spinning, obtain modified fibre
Step specifically: the modified carbon nano-tube array is clamped from the edge of the modified carbon nano-tube array, along perpendicular to institute
The direction of growth for stating modified carbon nano-tube array is pulled and is rotated, and the modified fibre is obtained.
The reinforcement is made of epoxy resin and phenolic resin in one of the embodiments, and the epoxy resin
And the molar ratio of the phenolic resin is 0.75:1~1.33:1.
A kind of carbon nano-tube fibre is prepared by the preparation method of above-mentioned carbon nano-tube fibre.
Above-mentioned carbon nano-tube fibre 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.The present invention can be with many not
With form realize, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes to this
The understanding of the disclosure of invention is more thorough and comprehensive.
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 carbon nano-tube fibre of one embodiment, manufactured carbon nano-tube fibre, which can be used in being made, to be had
The cloth of higher elasticity and wearability, to expand the application range of cloth.
It should be noted that carbon nano-tube fibre can be woven into cloth using traditional Weaving method.Traditional spinning
Organization method for example can be flat weaving method or twill.It should be noted that can be spun using single-root carbon nano-tube fiber
It knits, more carbon nano-tube fibres can also be made one in parallel and weaved again.
Specifically, the preparation method of the carbon nano-tube fibre includes the following steps S110~S130:
S110, under the first protective gas atmosphere, ultraviolet light processing is carried out to polymer and carbon nano pipe array
To carry out graft reaction, modified carbon nano-tube array is obtained.Polymer in aldehyde ketone resin and cyclohexanone derivative at least
It is a kind of.The structural formula of cyclohexanone derivative is as follows:N is greater than 12
Integer.Ultraviolet light is the monochromatic narrow band light that illumination wavelength is 198nm~289nm, and irradiation power is 20mW~30mW.
By ultraviolet light, and the monochromatic narrow band light that ultraviolet light is 198nm~289nm as illumination wavelength is set, irradiated
Power is 20mW~30mW, so that polymer grafts on carbon nano pipe array, polymer is selected from aldehyde ketone resin and cyclohexanone spreads out
At least one of biology improves the elasticity of carbon nano-tube fibre.
The weight average molecular weight of polymer is 20000~35000 in one of the embodiments,.Further, polymer
Weight average molecular weight is 25000~30000.
Polymer is made of aldehyde ketone resin and cyclohexanone derivative in one of the embodiments,.Aldehyde ketone resin and hexamethylene
The molar ratio of ketone derivatives is 0.8:1~1.13:1.The polymer of this setting grafts on the surface of carbon nano pipe array, Neng Gouti
The dispersibility of high carbon nano pipe array, to improve the wearability of carbon nano-tube fibre.
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.
The irradiation power of ultraviolet light is 23mW~26mW when carrying out ultraviolet light processing in one of the embodiments,.
Under this irradiation power, be conducive to the fuel factor for improving reaction system, so that system temperature is increased to polymer and forms gaseous state shape
State, and be moved under the action of protective gas air-flow the surface of carbon nano pipe array and carbon nano pipe array that grafting occurs is poly-
Close reaction.
Ultraviolet light is the monochrome that illumination wavelength is 256nm~289nm in one of the embodiments,
(monochromatic) narrow band light.Further, monochromatic narrow band light is the monochromatic light that bandwidth is 198nm~298nm.
Ultraviolet source is 2mm~20mm apart from the distance of polymer and carbon nano pipe array in one of the embodiments,.
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 20min.
The irradiation power of ultraviolet light is 25mW, ultraviolet light when carrying out ultraviolet light processing in one of the embodiments,
For the monochromatic narrow band light of 256nm, the time for carrying out ultraviolet light processing is 20min.With this condition, be conducive to guaranteeing to gather
Destruction of the reduction ultraviolet light to polymer and carbon nano tube array structure in the case where carbon nano pipe array can be grafted to by closing object,
To guarantee the mechanical property of carbon nano pipe array.
Carbon nano-pipe array is classified as single-wall carbon nanotube array in one of the embodiments,.It should be noted that carbon nanometer
Pipe array is also possible to array of multi-walled carbon nanotubes.
The length of carbon nano pipe array is 800 μm~1000 μm in one of the embodiments,.Carbon in carbon nano pipe array
The diameter of nanotube is 10nm~15nm.
In one of the embodiments, in the first protective gas atmosphere, polymer and carbon nano pipe array are carried out
Before the step of ultraviolet light processing is to carry out graft reaction, further include the steps that preparing carbon nano pipe array.Carbon is prepared to receive
The step of mitron array includes S111~S112:
S111, catalyst layer is formed in the first substrate.
It deposits to form catalyst layer on the surface of the first substrate using electron beam evaporation method in one of the embodiments,.
Further, the material of catalyst layer is selected from least one of cobalt and nickel.Further, the material of catalyst layer by nickel and
The mass ratio of cobalt composition, nickel and cobalt is 0.8:1~1.2:1.
In one of the embodiments, catalyst layer with a thickness of 20nm~23nm.
The first substrate is alumina plate in one of the embodiments,.The size of first substrate is 5 feet.Certainly, at it
In his embodiment, the size of the first substrate is also possible to any other size.Further, the first substrate has the first work
Face forms catalyst layer in the first working face.
S112, under third protective gas atmosphere, by the first substrate for being formed with catalyst layer be warming up to 650 DEG C~
After 750 DEG C, then it is passed through carbon-source gas reaction, obtains carbon nano pipe array.Carbon-source gas includes ethylene and hexane, ethylene and hexane
Partial pressure ratio be 3:2~4:1.
In one of the embodiments, by the first substrate for being formed 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 650 DEG C~750 DEG C, so that catalyst layer homogeneous nucleation in the first substrate；Carbon-source gas is passed through thereto again to be reacted.
Further, the flow velocity of carbon-source gas is 8mL/min~12mL/min, be passed through that carbon-source gas reacted when
Between be 10min~25min.It is arranged by this, the better carbon nano pipe array of dispersibility can be obtained, to improve carbon nano-pipe array
The mechanical property of column.
In one of the embodiments, third protective gas in nitrogen, hydrogen, argon gas and helium at least one
Kind.
Further, the step of S110 specifically: form polymer in the second substrate；Carbon nano pipe array will be formed with
The first substrate and be formed with polymer the second substrate be arranged side by side；Under the first protective gas atmosphere, to being formed with carbon
First substrate of nano-tube array and the second substrate for being formed with polymer carry out ultraviolet light processing, so that polymer and carbon
Nano-tube array carries out graft reaction, obtains modified carbon nano-tube array.
The second substrate is silicon wafer, nickel sheet or copper sheet in one of the embodiments,.The main function of second substrate is pair
Carrier polymer, and the stability of silicon wafer, nickel sheet and copper sheet is good, will not react with polymer.Further, the second substrate
Size be 50mm*50mm, certainly, in other embodiments, the size of the second substrate is also possible to any other size.
Polymer is set in the form of a film in the second substrate in one of the embodiments, certainly, in other realities
It applies in example, it can also be in such a way that shear polymer solution material be placed in again in the second substrate.Further, the second substrate has the
Two working faces.Thin polymer film is formed on the second working face.The second working face is completely covered in thin polymer film.
Further, the thin polymer film formed in the second substrate with a thickness of 1mm~5mm.Specifically, it will be formed
Have carbon nano pipe array the first substrate and be formed with polymer the second substrate it is placed side by side so that the side of carbon nano pipe array
The EDGE CONTACT of edge and thin polymer film.
The first substrate for being formed with carbon nano pipe array and the second of polymer will be formed in one of the embodiments,
Substrate is placed in same reaction chamber.Reaction chamber can be closed, and reaction chamber has an air inlet and a gas outlet.It is set in reaction chamber
There is ultraviolet light module, ultraviolet light processing can be carried out to reaction chamber.
Further, the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer are carried out purple
During outer photo-irradiation treatment, firstly, the air inlet of capping chamber and gas outlet, and reaction chamber is carried out to vacuumize place
Reason, makes the air pressure in reaction chamber be down to 10-2Torr or less.Optionally, make air pressure drop in reaction chamber down to 10-6Torr or less.
Secondly, being passed through protective gas into reaction chamber by air inlet until reaching normal atmosphere (An) again, gas outlet is opened, and constantly
It is passed through the pressure that third protective gas keeps system.
In one of the embodiments, to be formed with carbon nano pipe array the first substrate and be formed with the second of polymer
It further include the behaviour that the first substrate is placed in natural cooling under protective gas atmosphere after substrate carries out ultraviolet light processing
Make.It should be noted that in other embodiments, the first substrate to be placed in the operation of natural cooling under protective gas atmosphere
Also it 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 modified fibre.
The step of S120 in one of the embodiments, specifically: using clamping tool from modified carbon nano-tube array
Edge clamps modified carbon nano-tube array, and is pulled and revolved along the direction perpendicular to modified carbon nano-tube array growth
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 modified 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 modified fibre.
Further, the step of S120 specifically: clamp modified carbon nano-tube battle array from the edge of modified carbon nano-tube array
Column, and pulled along the direction perpendicular to modified carbon nano-tube array growth, obtain silky nano pipe array；It is received from filiform
The silky nano pipe array of the edge clamping of mitron array, and revolved along the extending direction perpendicular to silky nano pipe array
Turn and pull, so that silky nano pipe array is stretched, and every silky nano pipe in silky nano pipe array is made to be screwed in one
It rises, obtains modified fibre.
When clamping modified carbon nano-tube array from the edge of modified carbon nano-tube array in one of the embodiments, folder
The width taken is 50 μm~150 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.
Speed when being pulled in one of the embodiments, along the direction of growth perpendicular to modified carbon nano-tube array
Rate is 0.05m/s~0.5mm/s.Further, when being pulled along the direction of growth perpendicular to modified carbon nano-tube array
Rate be 0.1m/s~0.4mm/s.Further, it is dragged along the direction of growth perpendicular to modified carbon nano-tube array
Rate when dragging is 0.2m/s~0.3mm/s.
Turn when being rotated in one of the embodiments, along the direction of growth perpendicular to modified carbon nano-tube array
Speed is 1000rpm~3000rpm.Further, when being rotated along the direction of growth perpendicular to modified carbon nano-tube array
Revolving speed be 2000rpm.
The diameter of modified fibre is 10 μm~200 μm in one of the embodiments,.
The length of modified fibre is 100m~500m in one of the embodiments,.It should be noted that modified fibre
Length is not limited to above-mentioned length, can be configured according to actual needs.
S130, reinforcement is set on modified fibre, and anti-at 80 DEG C~100 DEG C under the second protective gas atmosphere
It answers, obtains carbon nano-tube fibre, reinforcement is selected from least one of epoxy resin and phenolic resin.
By the way that reinforcement is arranged on modified fibre, reinforcement is selected from least one of epoxy resin and phenolic resin,
Reinforcement can form hydrogen bond with the carbonyl in polymer and improve the resistance to of modified fibre to form protective film on modified fibre
Mill property, so that manufactured carbon nano-tube fibre can be used in the cloth that production has higher elasticity and wearability.
It should be noted that the reinforcement in the setting of modified fibre surface can come into full contact with copolymer.Further,
On modified fibre surface, the surface of carbon nano-tube fibre can be completely covered in the reinforcement of setting, to guarantee reinforcement and copolymer
It comes into full contact with.
In one of the embodiments, the second protective gas in nitrogen, helium, neon and argon gas at least one
Kind.
Reinforcement is set on modified fibre in one of the embodiments, and under the second protective gas atmosphere in
The step of being reacted at 80 DEG C~100 DEG C specifically: spray reinforcement on the surface of modified fibre, and in the second protective gas atmosphere
Reaction is 10min~15min at 80 DEG C~100 DEG C under enclosing.Under this setting, reinforcement can be made sufficiently anti-with modified fibre
It answers, to guarantee the wearability of carbon nano-tube fibre.It should be noted that the mode of setting reinforcement is not limited to spray, it can be with
It for other modes, such as can be coating.
Reinforcement is misty or film-form in one of the embodiments,.Such setting enables reinforcement more equal
Even is set on modified fibre.
Reinforcement is made of epoxy resin and phenolic resin in one of the embodiments, and epoxy resin and phenolic aldehyde tree
The molar ratio of rouge is 0.75:1~1.33:1.Such setting can obtain the better carbon nano-tube fibre of wearability.
The preparation method of above-mentioned carbon nano-tube fibre by ultraviolet light, and sets ultraviolet light as illumination wavelength and is
The monochromatic narrow band light of 198nm~289nm, irradiation power is 20mW~30mW, so that polymer grafts on carbon nano pipe array,
Polymer is selected from least one of aldehyde ketone resin and cyclohexanone derivative, improves the elasticity of carbon nano pipe array；By changing
Property carbon nano-tube fibre on reinforcement is set, reinforcement is selected from least one of epoxy resin and phenolic resin, enhances physical efficiency
Carbonyl in enough and polymer forms hydrogen bond, to improve the resistance to of carbon nano-tube fibre in forming protective film on carbon nano-tube fibre
Mill property, so that manufactured carbon nano-tube fibre can be used in the cloth that production has higher elasticity and wearability.Experiment proves that
The elongation of cloth made of the carbon nano-tube fibre for using above-mentioned preparation method to obtain is 4.1%~5.2%, effectively abrasion time
Number is 2.03 × 104Secondary~2.7 × 104It is secondary, it can be applied in the product more demanding to elasticity and wearability.
Above-mentioned preparation method does not need that carbon nano pipe array is dispersed to carry out in a solvent subsequent processing, technique letter
Change, the array structure of carbon nano pipe array will not be destroyed, advantageously ensures that modified carbon nano-tube array and carbon nano-tube fibre
Mechanical property, solvent-free equal residual, the purity of obtained carbon nano-tube fibre are 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.Reinforcement is complete
The surface of all standing modified fibre.Ultraviolet light is the monochromatic light that bandwidth is 298nm.Epoxy resin is bisphenol A type epoxy resin.Ring
The structural formula of hexanone derivative is as follows:
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 0.8:1) of cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace and is led to
Nitrogen is crossed, then is warming up to 650 DEG C, then into chemical vapour deposition reactor furnace is passed through carbon-source gas (carbon-source gas is by ethylene and oneself
Alkane composition, ethylene and the partial pressure of hexane ratio are 4:1) and the flow control of carbon-source gas react 25min at 12L/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 800 μm, and the diameter of carbon nanotube is 15nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the thin polymer film with a thickness of 1mm in the second substrate.Polymer is hexamethylene
Ketone derivatives.The weight average molecular weight of polymer is 20000.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer is placed side by side in anti-
It answers in chamber, the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer are in same level, and
Carbon nano pipe array and polymer contact, reaction chamber are evacuated to air pressure and are down to 10-2It is being passed through nitrogen after Torr, is keeping nitrogen
Flow velocity is 2L/min, carries out ultraviolet light to the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer
Treatment with irradiation, ultraviolet source distance be formed with carbon nano pipe array the first substrate and be formed with polymer the second substrate away from
From for 2mm, the irradiation power of ultraviolet light is 35mW, and ultraviolet light is the monochromatic narrow band light that illumination wavelength is 198nm, and irradiation time is
30min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere down toward natural cooling, obtains modified carbon nano-tube battle array
Column.
(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 modified fibre.From modified carbon nano-tube array
Edge clamp modified carbon nano-tube array when, 150 μm of the width of clamping.The speed of dragging is 0.5mm/s, and revolving speed is
3000rpm。
(5) reinforcement is sprayed on the surface of modified fibre, and reacts 15min at 80 DEG C under a nitrogen, obtain carbon nanometer
Pipe fiber, reinforcement are epoxy resin.
(6) carbon nano-tube fibre 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 1.2:1) of cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace and is led to
Nitrogen is crossed, then is warming up to 750 DEG C, then into chemical vapour deposition reactor furnace is passed through carbon-source gas (carbon-source gas is by ethylene and oneself
The partial pressure ratio of alkane composition, ethylene and hexane is 3:2), and the flow control of carbon-source gas reacts 10min at 8L/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 1000 μm, and the diameter of carbon nanotube is 10nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the thin polymer film with a thickness of 5mm in the second substrate.Polymer is aldehyde ketone
Resin.The weight average molecular weight of polymer is 35000.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer is placed side by side in anti-
It answers in chamber, the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer are in same level, and
Carbon nano pipe array and polymer contact, reaction chamber are evacuated to air pressure and are down to 10-2It is being passed through nitrogen after Torr, is keeping nitrogen
Flow velocity is 3L/min, carries out ultraviolet light to the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer
Treatment with irradiation, ultraviolet source distance be formed with carbon nano pipe array the first substrate and be formed with polymer the second substrate away from
From for 10mm, the irradiation power of ultraviolet light is 20mW, and ultraviolet light is the monochromatic narrow band light that illumination wavelength is 289nm, irradiation time
For 10min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere 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 is rotated, and obtains modified fibre.From modified carbon nano-tube array
Edge clamp modified carbon nano-tube array when, 50 μm of the width of clamping.The speed of dragging is 0.05mm/s, and revolving speed is
1000rpm。
(5) reinforcement is sprayed on the surface of modified fibre, and reacts 10min at 100 DEG C under a nitrogen, obtain carbon nanometer
Pipe fiber, reinforcement are phenolic resin.
(6) carbon nano-tube fibre 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 is by ethylene and hexane
Composition, ethylene and the partial pressure of hexane ratio are 3:1) and the flow control of carbon-source gas react 20min at 10L/min, make
It obtains the first substrate surface and is completely covered with carbon nano pipe array, carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nanotube
The length of array is 900 μm, and the diameter of carbon nanotube is 12nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the thin polymer film with a thickness of 3mm in the second substrate.Polymer is by aldehyde ketone
Resin and cyclohexanone derivative composition.Aldehyde ketone resin and the molar ratio of cyclohexanone derivative are 1:1, the Weight-average molecular of aldehyde ketone resin
Amount is 27100, and the weight average molecular weight of cyclohexanone derivative is 25500.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer is placed side by side in anti-
It answers in chamber, the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer are in same level, and
Carbon nano pipe array and polymer contact, reaction chamber are evacuated to air pressure and are down to 10-2It is being passed through nitrogen after Torr, is keeping nitrogen
Flow velocity is 2.5L/min, is carried out to the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer ultraviolet
Photo-irradiation treatment, ultraviolet source distance are formed with the first substrate of carbon nano pipe array and are formed with the second substrate of polymer
Distance is 5mm, and the irradiation power of ultraviolet light is 25mW, and ultraviolet light is the monochromatic narrow band light that illumination wavelength is 256nm, irradiation time
For 20min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere 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 is rotated, and obtains modified fibre.From modified carbon nano-tube array
Edge clamp modified carbon nano-tube array when, 100 μm of the width of clamping.The speed of dragging is 0.3mm/s, and revolving speed is
2000rpm。
(5) reinforcement is sprayed on the surface of modified fibre, and reacts 12min at 90 DEG C under a nitrogen, obtain carbon nanometer
Pipe fiber, reinforcement are made of epoxy resin and phenolic resin, and it is 1:1 that epoxy resin and phenolic resin, which are mass ratio,.
(6) carbon nano-tube fibre 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: cyclohexanone derivative
And the molar ratio of aldehyde ketone resin is 1:0.8.
Embodiment 5
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: cyclohexanone derivative
And the molar ratio of aldehyde ketone resin is 1:1.13.
Embodiment 6
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: epoxy resin and phenolic aldehyde
Resin is that molar ratio is 0.75:1.
Embodiment 7
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: epoxy resin and phenolic aldehyde
Resin is that molar ratio is 1.33:1.
Embodiment 8
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: polymer is aldehyde ketone
Resin, the weight average molecular weight of aldehyde ketone resin are 27100.
Embodiment 9
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: polymer is hexamethylene
Ketone derivatives, the weight average molecular weight of cyclohexanone derivative are 25500.
Embodiment 10
The preparation process of the cloth of the present embodiment is as follows:
(1) carbon nano pipe array is made 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 100 μm.The speed of dragging is 0.3mm/s, revolving speed 2000rpm.
(3) cloth is made according to (5) the step of embodiment 3~(6) in carbon nano-tube fibre.
Embodiment 11
The preparation process of the cloth of the present embodiment is as follows:
(1) carbon nano pipe array is set in the first substrate.Carbon nano pipe array is purchased from Cnano company Flotube
9110 carbon nano pipe arrays.
(2) according to the operation of (2) the step of embodiment 3~(6), cloth is obtained.
Embodiment 12
The preparation process of the cloth of the present embodiment is as follows:
(1) modified fibre is obtained according to the operation of (1) the step of embodiment 3~(4).
(2) modified fibre is weaved, obtains cloth.
Test:
The wearability and elasticity of 1~12 cloth of embodiment are measured, see Table 1 for details for measurement result.What table 1 indicated is embodiment 1
The wearability and elasticity of~12 cloth.
Specifically, using effective abrasion index of the method test cloth of 1454 prescribed by standard of JIS A, to characterize it
Wear-resisting property, wherein effective abrasion index refer to test material is worn up to there is obvious silk thread breaking state needed for abrasion
Number；
Using the elongation of extension test method measurement cloth, to characterize its elasticity.
Table 1
As it can be seen from table 1 the effective abrasion index for the cloth that Examples 1 to 7 obtains is 2.03 × 104Secondary~2.7 ×
104Secondary, elongation is 4.1%~5.2%, is better than embodiment 10 and embodiment 12, wearability and elasticity with higher, explanation
The carbon nano-tube fibre that above embodiment obtains, which can be used in preparation, has the cloth for having both wearability and elasticity.
Wherein, the effective abrasion index and elongation for the cloth that embodiment 6~7 obtains are below embodiment 3, illustrate aldehyde ketone
The synergistic effect of resin and cyclohexanone derivative is more advantageous to the wearability and elasticity for improving cloth.The cloth that embodiment 11 obtains
Effective abrasion index and elongation be lower than embodiment 3, illustrate using above embodiment prepare carbon nano pipe array more have
The cloth of wearability and elasticity is had both conducive to preparation.
To sum up, the carbon nano-tube fibre that above embodiment is prepared can be used in preparation and have both wearability and elasticity
Cloth can be applied in the product more demanding to elasticity and wearability, and application range is wider.
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 carbon nano-tube fibre, which comprises the steps of:
Under the first protective gas atmosphere, ultraviolet light processing is carried out to be grafted to polymer and carbon nano pipe array
Reaction, obtains modified carbon nano-tube array, and the polymer is selected from least one of aldehyde ketone resin and cyclohexanone derivative, institute
The structural formula for stating cyclohexanone derivative is as follows:The n is greater than 12
Integer；The ultraviolet light is the monochromatic narrow band light that illumination wavelength is 198nm~289nm, and irradiation power is 20mW~30mW；
The modified carbon nano-tube array is subjected to spinning, obtains modified fibre；And
Reinforcement is set on the modified fibre, and is reacted at 80 DEG C~100 DEG C under the second protective gas atmosphere, is obtained
To carbon nano-tube fibre, the reinforcement is selected from least one of epoxy resin and phenolic resin.
2. the preparation method of carbon nano-tube fibre according to claim 1, which is characterized in that described in the first protectiveness gas
Under body atmosphere, before carrying out the step of ultraviolet light processing is to carry out graft reaction to polymer and carbon nano pipe array, also
Include the steps that preparing the carbon nano pipe array:
Catalyst layer is formed in the first substrate, the catalyst is selected from least one of cobalt and nickel；
Under third protective gas atmosphere, first substrate for being formed with the catalyst layer is warming up to 650 DEG C~750
After DEG C, 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 ratio of alkene and the hexane is 3:2~4:1.
3. the preparation method of carbon nano-tube fibre according to claim 2, which is characterized in that the catalyst is by nickel and cobalt
Composition, and the mass ratio of the nickel and the cobalt is 0.8:1~1.2:1.
4. the preparation method of carbon nano-tube fibre according to claim 2, which is characterized in that described in the first protectiveness gas
Under body atmosphere, the step of ultraviolet light processing is to carry out graft reaction is carried out to polymer and carbon nano pipe array specifically:
The polymer is formed in the second substrate；By first substrate for being formed with the carbon nano pipe array and it is formed with described
Second substrate of polymer is arranged side by side；Under the first protective gas atmosphere, to being formed with the carbon nanotube
First substrate of array and second substrate equipped with the polymer carry out ultraviolet light processing, so that the carbon
Nano-tube array and the polymer carry out graft reaction.
5. the preparation method of carbon nano-tube fibre according to claim 1 again, which is characterized in that the polymer is divided equally
Son amount is 20000~35000.
6. the preparation method of carbon nano-tube fibre according to claim 1, which is characterized in that the polymer is by the aldehyde
Ketone resin and cyclohexanone derivative composition, and the aldehyde ketone resin and the molar ratio of the cyclohexanone derivative are 0.8:1
~1.13:1.
7. the preparation method of carbon nano-tube fibre according to claim 1, which is characterized in that described to receive the carbon modified
The step of mitron array carries out spinning, obtains modified fibre specifically: clamp institute from the edge of the modified carbon nano-tube array
Modified carbon nano-tube array is stated, is pulled and is rotated along the direction of growth perpendicular to the modified carbon nano-tube array, obtained
To the modified fibre.
8. the preparation method of carbon nano-tube fibre according to claim 1, which is characterized in that the reinforcement is by asphalt mixtures modified by epoxy resin
Rouge and phenolic resin composition, and the molar ratio of the epoxy resin and the phenolic resin is 0.75:1~1.33:1.
9. a kind of carbon nano-tube fibre, which is characterized in that by the system of carbon nano-tube fibre according to any one of claims 1 to 8
Preparation Method is prepared.
10. carbon nano-tube fibre as claimed in claim 9 is preparing the application in cloth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811457302.6A CN109763213A (en) | 2018-11-30 | 2018-11-30 | Carbon nano-tube fibre and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811457302.6A CN109763213A (en) | 2018-11-30 | 2018-11-30 | Carbon nano-tube fibre and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109763213A true CN109763213A (en) | 2019-05-17 |
Family
ID=66450363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811457302.6A Withdrawn CN109763213A (en) | 2018-11-30 | 2018-11-30 | Carbon nano-tube fibre and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109763213A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111764026A (en) * | 2020-06-08 | 2020-10-13 | 深圳烯湾科技有限公司 | Carbon nanotube fiber hybrid fabric, preparation method thereof and reinforced composite material |
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 |
-
2018
- 2018-11-30 CN CN201811457302.6A patent/CN109763213A/en not_active Withdrawn
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 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111764026A (en) * | 2020-06-08 | 2020-10-13 | 深圳烯湾科技有限公司 | Carbon nanotube fiber hybrid fabric, preparation method thereof and reinforced composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qin et al. | Growing carbon nanotubes by microwave plasma-enhanced chemical vapor deposition | |
| Takahashi et al. | Dispersion and purification of single-wall carbon nanotubes using carboxymethylcellulose | |
| Xu et al. | Functionalization of carbon nanotubes by corona‐discharge induced graft polymerization for the reinforcement of epoxy nanocomposites | |
| Bang et al. | Effects of pH on electrospun PVA/acid-treated MWNT composite nanofibers | |
| Wang et al. | Functionalized carbon nanotube/polyacrylonitrile composite nanofibers: fabrication and properties | |
| WO2015160041A1 (en) | Carbon nanotube fiber and manufacturing method thereof | |
| CN110734053A (en) | Method for producing carbon nanotube and carbon nanotube fiber | |
| JP5257813B2 (en) | Polyvinyl alcohol-based composite fiber and method for producing the same | |
| CN109763213A (en) | Carbon nano-tube fibre and its preparation method and application | |
| WO2008119138A1 (en) | Production of nanotube forests | |
| CN109763206A (en) | Modified carbon nano tube array, carbon nano-fiber and its preparation method and application | |
| CN109704309A (en) | Modified carbon nano-tube array, carbon nano-tube fibre and its preparation method and application | |
| Jingrui et al. | Dispersion characteristics of multi-walled carbon nanotubes and carbon nanoflakes with oxygen plasma | |
| CN109706732A (en) | Nanometer fabric and preparation method thereof | |
| Takikawa et al. | Amorphous carbon fibrilliform nanomaterials prepared by chemical vapor deposition | |
| CN109485030A (en) | Modified carbon nano tube array, carbon nano-fiber and its preparation method and application | |
| CN109680367A (en) | Carbon nano-tube fibre and its preparation method and application | |
| CN109455693A (en) | Modified carbon nano-tube array, carbon nano-tube fibre and its preparation method and application | |
| CN109763207A (en) | Carbon nano-tube fibre and its preparation method and application | |
| CN109735964A (en) | Carbon nano-tube fibre and its preparation method and application | |
| CN109735965A (en) | Modified carbon nano tube fiber and its preparation method and application | |
| CN109455694A (en) | Modified carbon nano-tube array, carbon nano-tube fibre and its preparation method and application | |
| CN109775689A (en) | Modified carbon nano-tube array, carbon nano-tube fibre and its preparation method and application | |
| CN109553087B (en) | Modified carbon nanotube array, carbon nanotube fiber, and preparation method and application thereof | |
| CN109704311A (en) | Modified carbon nano-tube array, carbon nano-tube fibre and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190517 |