CN110230129A - A kind of surfaces externally and internally growth carbon nanotube contains Fe3Hollow Compound carbon fiber of C and preparation method thereof - Google Patents
A kind of surfaces externally and internally growth carbon nanotube contains Fe3Hollow Compound carbon fiber of C and preparation method thereof Download PDFInfo
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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Abstract
A kind of surfaces externally and internally growth carbon nanotube contains Fe3Hollow Compound carbon fiber of C and preparation method thereof, it is related to hollow fibre shielding material and preparation method thereof.It is the technical problem that solve existing carbon fiber and carbon nano tube compound material electromagnet shield effect difference.Surfaces externally and internally growth carbon nanotube of the invention contains Fe3The structure of the Hollow Compound carbon fiber of C is containing magnetic Fe3The carbon fibre hollow pipe of C nano particle is carrier, has carbon nanotube in the inner and outer surfaces growth of hollow pipe.Preparation method: one, Fe is prepared3O4- PAN/PMMA hollow fibre；Two, in Fe3O4- PAN hollow fibre surfaces externally and internally grows carbon nanotube.Surfaces externally and internally growth carbon nanotube of the invention contains Fe3The electromagnet shield effect of the Hollow Compound carbon fiber of C can reach 80dB, can be used for being electromagnetically shielded field.
Description
Technical field
The present invention relates to hollow fibre shielding materials and preparation method thereof.
Background technique
Currently, electromagnetic pollution has become the fifth-largest pollution sources polluted after atmosphere pollution, water pollution, noise pollution, soil,
Trend through harmful physical and mental health.Unlike other pollutants, big gas and water, noise, soil pollution be all visible, can
It is target-seeking, can directly observe, people can also be fully recognized that the harm of these pollutions, but electromagnetic radiation is that no mark can be sought
, it is a kind of energy contamination, it is more covert to the damage ratio of environment.In daily life, when electromagnetic radiation intensity is more than safety and sanitation
After standard limited value, negative effect can be generated to human body, the symptoms such as headache, insomnia occur.The harm of electromagnetic radiation has become various countries
The focal point of health organization, therefore, development shielding and absorbing material have the harm for preventing electromagnetic pollution from bringing
Significance.
Carbon-based material is a kind of common shielding material, this kind of material mainly have carbon fiber-containing, silicon carbide, electrically conductive graphite,
Carbon nanotube and mesoporous carbon etc..Carbon fiber-containing reaches decaying electromagnetic wave mainly due to the eddy-current loss that skin effect generates
Purpose；Simultaneously after electromagnetic wave incident, it may appear that fractional phase cancellation phenomenon, can equally decay electromagnetic wave.But pure carbon system material
The electromagnet shield effect of material is typically small, can improve it by being modified to carbon-based material at present and be electromagnetically shielded effect, such as
Metal, plating SiC or deposition graphite carbon granules are coated in carbon fiber surface, the electromagnet shield effect of obtained composite material is generally 30
~40dB；By the compound rear electromagnet shield effect of carbon nanotube (CNT) and organic polymer about between 40~50dB.Electromagnetic shielding
Efficiency is still lower.
Summary of the invention
The present invention is to solve the technical problem of existing carbon fiber and carbon nano tube compound material electromagnet shield effect difference,
And provide a kind of surfaces externally and internally growth carbon nanotube contains Fe3Hollow Compound carbon fiber of C and preparation method thereof.
Surfaces externally and internally growth carbon nanotube of the invention contains Fe3The Hollow Compound carbon fiber of C, structure are containing magnetic
Property Fe3The carbon fibre hollow pipe of C nano particle is carrier, has carbon nanotube in the inner and outer surfaces growth of hollow pipe.
Above-mentioned surfaces externally and internally growth carbon nanotube contains Fe3The preparation method of the Hollow Compound carbon fiber of C, by following
Step carries out:
One, Fe is prepared3O4- PAN/PMMA hollow fibre:
A, by Fe3O4Nanoparticle is dispersed in dimethyl sulfoxide, obtains Fe3O4Nanoparticle dispersion liquid；By polyacrylonitrile
It is added in DMSO and dissolves by heating, obtain polyacrylonitrile solution；By Fe3O4Nanoparticle dispersion liquid is mixed with polyacrylonitrile solution, is obtained
To mixed liquor；Partial solvent is evaporated under reduced pressure, obtains shell solution；
B, the DMSO solution for preparing polymethyl methacrylate (PMMA), obtains sandwich layer solution；
C, using DMSO aqueous solution as coagulating bath, sandwich layer solution is passed through to the center cavity of the coaxial spinning head of spinning machine binary channels
In, shell solution is passed through in the annular chamber of the coaxial spinning head of spinning machine binary channels, carries out spinning using dry-jet wet-spinning technique；
D, spun fiber filament is immersed in the methanol that temperature is -30~-20 DEG C and is impregnated to remove the solvent in fiber,
Obtain Fe3O4- PAN/PMMA core-skin fibre；
E, by Fe3O4- PAN/PMMA core-skin fibre, which is immersed in acetone, to be impregnated, and during which intermittence is ultrasonically treated, to remove fibre
PMMA in dimension, obtains Fe3O4- PAN hollow fibre；
Two, in Fe3O4- PAN hollow fibre surfaces externally and internally grows carbon nanotube:
F, by Fe3O4- PAN hollow fibre, which is immersed in the toluene solution of ferrocene, to be impregnated, and during which intermittence is ultrasonically treated,
It g, will be through step f treated Fe3O4After the drying of-PAN hollow fibre, it is put into CVD tube furnace, and in fiber two
End applies tension；
H, CVD tube furnace is warming up to 200~300 DEG C and 1~2h is kept to carry out pre-oxidation treatment to fiber；It then passes to
1~1.2h of argon gas, followed by be continuously heating to 600~620 DEG C and keep be passed through at this temperature hydrogen react 30~60min；
The toluene for being passed through ferrocene using argon gas/hydrogen mixed gas as carrier it is further heated up to 800~820 DEG C and at this temperature is molten
Liquid reacts 1~4h, grows carbon nanotube simultaneously in the surfaces externally and internally of hollow fibre during this, Fe3O4Presoma is changed into
Fe3C is down to room temperature, and obtain surfaces externally and internally growth carbon nanotube contains Fe3The hollow compound fibre of C.
Surfaces externally and internally growth carbon nanotube of the invention contains Fe3The Hollow Compound carbon fiber of C, is first with binary channels
Spinning head prepares nano-magnetic Fe3O4Polyacrylonitrile (PAN)/polymethyl methacrylate (PMMA) skin-core structure fiber, it is molten
PMMA is gone to obtain doping Fe3O4The hollow PAN fiber of presoma grows carbon nanotube, preparation in hollow fibre surfaces externally and internally later
Surfaces externally and internally growth carbon nanotube contains magnetic Fe out3The hollow carbon fiber material of C nano particle.Hollow Fe3C- carbon fiber
Surfaces externally and internally grows carbon nanotube (CNT), and dielectric loss will occur when passing through, be easier at fiber and CNT node for electromagnetic wave
It is lost, electromagnetic intensity is decayed；Magnetic Fe3C nano particle adjusts the magnetic property of material, and material is made integrally to reach Jie
Dielectric loss and magnetic loss matching, electromagnetic intensity are further decayed.By high temperature cabonization, PAN is changed into carbon, is formed one-dimensional
The carbon fiber of hollow tubular structures, electromagnetic wave equally carry out multiple reflections in hollow cavity, cause the further of electromagnetic intensity
Decaying.These special structures make material have excellent electromagnetic shielding performance.
Surfaces externally and internally growth carbon nanotube of the invention contains Fe3The Hollow Compound carbon fiber of C, wherein high conductivity
CNT is used for reinforcing material to the dielectric loss of electromagnetic wave, without the ferromagnetic Fe to fall off3It is permanent that C particle imparts material
Magnetic property simultaneously has the characteristics that magnetic loss, by the synergistic effect of three, the shielding properties of material is made to reach best.Of the invention
Surfaces externally and internally growth carbon nanotube contains Fe3The electromagnet shield effect of the Hollow Compound carbon fiber of C can reach 80dB or more,
It can be used for being electromagnetically shielded field.
Detailed description of the invention
Fig. 1 is the Fe that embodiment 1 is obtained through step d3O4The stereoscan photograph on-PAN/PMMA core-skin fibre surface；
Fig. 2 is the Fe that embodiment 1 is obtained through step d3O4The stereoscan photograph in-PAN/PMMA core-skin fibre section；
Fig. 3 is the Fe that embodiment 1 is obtained through step e3O4The stereoscan photograph of-PAN hollow fibre；
Fig. 4 be embodiment 1 through step h obtain obtain surfaces externally and internally growth carbon nanotube contain Fe3The Hollow Compound of C
The stereoscan photograph of the outer surface of carbon fiber；
Fig. 5 be embodiment 1 through step h obtain obtain surfaces externally and internally growth carbon nanotube contain Fe3The Hollow Compound of C
The stereoscan photograph of the inner surface of carbon fiber；
Fig. 6 be embodiment 1 through step h obtain obtain surfaces externally and internally growth carbon nanotube contain Fe3The Hollow Compound of C
The XRD curve graph of carbon fiber；
Fig. 7 be embodiment 1 through step h obtain obtain surfaces externally and internally growth carbon nanotube contain Fe3The Hollow Compound of C
The electromagnet shield effect curve of carbon fiber.
Specific embodiment
Specific embodiment 1: the surfaces externally and internally growth carbon nanotube of present embodiment contains Fe3The Hollow Compound carbon of C
Fiber, structure are containing magnetic Fe3The carbon fibre hollow pipe of C nano particle is carrier, raw in the inner and outer surfaces of hollow pipe
With carbon nanotube.
Specific embodiment 2: the surfaces externally and internally growth carbon nanotube of present embodiment contains Fe3The Hollow Compound carbon of C
The preparation method of fiber, sequentially includes the following steps:
One, Fe is prepared3O4- PAN/PMMA hollow fibre:
A, by Fe3O4Nanoparticle is dispersed in dimethyl sulfoxide, obtains Fe3O4Nanoparticle dispersion liquid；By polyacrylonitrile
It is added in DMSO and dissolves by heating, obtain polyacrylonitrile solution；By Fe3O4Nanoparticle dispersion liquid is mixed with polyacrylonitrile solution, is obtained
To mixed liquor；Partial solvent will be evaporated under reduced pressure, obtain shell solution；
B, the DMSO solution for preparing polymethyl methacrylate (PMMA), obtains sandwich layer solution；
C, using DMSO aqueous solution as coagulating bath, sandwich layer solution is passed through to the center cavity of the coaxial spinning head of spinning machine binary channels
In, shell solution is passed through in the annular chamber of the coaxial spinning head of spinning machine binary channels, carries out spinning using dry-jet wet-spinning technique；
D, spun fiber filament is immersed in the methanol that temperature is -30~-20 DEG C and is impregnated to remove the solvent in fiber,
Obtain Fe3O4- PAN/PMMA core-skin fibre；
E, by Fe3O4- PAN/PMMA core-skin fibre, which is immersed in acetone, to be impregnated, and during which intermittence is ultrasonically treated, to remove fibre
PMMA in dimension, obtains Fe3O4- PAN hollow fibre；
Two, in Fe3O4- PAN hollow fibre surfaces externally and internally grows carbon nanotube:
F, by Fe3O4- PAN hollow fibre, which is immersed in the toluene solution of ferrocene, to be impregnated, and during which intermittence is ultrasonically treated,
It g, will be through step f treated Fe3O4After the drying of-PAN hollow fibre, it is put into CVD tube furnace, and in fiber two
End applies tension；
H, CVD tube furnace is warming up to 200~300 DEG C and 1~2h is kept to carry out pre-oxidation treatment to fiber；It then passes to
1~1.2h of argon gas, followed by be continuously heating to 600~620 DEG C and keep be passed through at this temperature hydrogen react 30~60min；
The toluene for being passed through ferrocene using argon gas/hydrogen mixed gas as carrier it is further heated up to 800~820 DEG C and at this temperature is molten
Liquid reacts 1~4h, grows carbon nanotube simultaneously in the surfaces externally and internally of hollow fibre during this, Fe3O4Presoma is changed into
Fe3C is down to room temperature, and obtain surfaces externally and internally growth carbon nanotube contains Fe3The hollow compound fibre of C.
Specific embodiment 3: present embodiment and magnetic Fe in step 1 unlike specific embodiment two3O4Nanometer
Particle the preparation method comprises the following steps: by 1.35~2.7g FeCl3·6H2O, 3.6~7.2g anhydrous sodium acetate, 0~1g polyethylene glycol and
The mixing of 80ml ethylene glycol, ultrasound stirs, is put into ptfe autoclave, react 8 at 190~210 DEG C~
Then 10h is cleaned up with ethyl alcohol, dry in vacuum drying oven, obtains magnetic Fe3O4Nanoparticle.Other and specific embodiment party
Formula two is identical.
Specific embodiment 4: present embodiment is unlike specific embodiment two or three in step 1 a, mixed liquor
In, Fe3O4The quality of nanoparticle accounts for Fe3O4The 5%~30% of nanoparticle and polyacrylonitrile gross mass.Other and specific reality
It is identical to apply mode two or three.
Specific embodiment 5: subtracting in step 1 a unlike one of present embodiment and specific embodiment two to four
The concentration of polyacrylonitrile reaches 250~350g/L after pressure evaporation section solvent.Other phases one of with specific embodiment two to four
Together.
Specific embodiment 6: unlike one of present embodiment and specific embodiment two to five in step 1 b, core
In layer solution, the concentration of polymethyl methacrylate is 500~700g/L.Other phases one of with specific embodiment two to five
Together.
Specific embodiment 7: making unlike one of present embodiment and specific embodiment two to six in step 1 c
Mass percentage concentration for the DMSO aqueous solution of coagulating bath is 40%~50%.Other phases one of with specific embodiment two to six
Together.
Specific embodiment 8: unlike one of present embodiment and specific embodiment two to seven in step 1 d, it is fine
Tieing up the soaking time of silk in methyl alcohol is 3~5 days.It is other identical as one of specific embodiment two to seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment two to eight in step 1 e,
Fe3O4The soaking time of-PAN/PMMA core-skin fibre in acetone is 3~4 days.One of other and specific embodiment two to eight
It is identical.
Specific embodiment 10: unlike one of present embodiment and specific embodiment two to nine in step 1 e,
Having a rest property ultrasonic treatment refers to be ultrasonically treated 10~15 minutes every 2~4 hours.Other phases one of with specific embodiment two to nine
Together.
Specific embodiment 11: unlike one of present embodiment and specific embodiment two to ten in step 2 f,
Fe3O4The time that-PAN hollow fibre impregnates in the toluene solution of ferrocene is 2~3 days.It is other with specific embodiment two to
One of ten is identical.
Specific embodiment 12: present embodiment and step 2 f unlike specific embodiment two to one of 11
In, the mass percentage concentration of ferrocene is 5%~10wt% in the toluene solution of ferrocene.It is other with specific embodiment two to
One of 11 is identical.
Specific embodiment 13: present embodiment and step 2 f unlike specific embodiment two to one of 12
In, intermittence ultrasonic treatment refers to be ultrasonically treated 10~15 minutes every 2~4 hours.Other and specific embodiment two to ten
One of two is identical.
Beneficial effects of the present invention are verified with the following examples:
Embodiment 1: the surfaces externally and internally growth carbon nanotube of the present embodiment contains Fe3The system of the Hollow Compound carbon fiber of C
Preparation Method sequentially includes the following steps:
One, Fe is prepared3O4- PAN/PMMA hollow fibre:
A, by 3gFe3O4Nanoparticle ultrasonic disperse obtains Fe in 100ml dimethyl sulfoxide3O4Nanoparticle dispersion
Liquid；110 DEG C are heated in the polyacrylonitrile addition 100ml DMSO for being 48000~50000 by 27g molecular weight to make it dissolve, and are obtained
To polyacrylonitrile solution；By Fe3O4Nanoparticle dispersion liquid is mixed with polyacrylonitrile solution, then Fe3O4The quality of nanoparticle accounts for
Fe3O4The 10% of nanoparticle and polyacrylonitrile gross mass is evaporated under reduced pressure solvent, the concentration of polyacrylonitrile is made to reach 30g/
100ml obtains shell solution；
B, by the DMSO for being added to 100ml of 60g polymethyl methacrylate (PMMA), dissolution obtains sandwich layer solution；
Wherein the concentration of polymethyl methacrylate is 60g/100ml；
C, sandwich layer solution is passed through spinning machine binary channels as coagulating bath by the DMSO aqueous solution for being 50% using mass percentage concentration
In the center cavity of coaxial spinning head, shell solution is passed through in the annular chamber of the coaxial spinning head of spinning machine binary channels, utilizes dry spray
Wet-spinning techniques carry out spinning；The volume flow ratio of shell solution and sandwich layer solution is 1:1；
D, spun fiber filament is immersed in the low-temp methanol that temperature is -20 DEG C and is kept for 3 days, to remove in fiber
Solvent obtains Fe3O4- PAN/PMMA core-skin fibre；
E, by Fe3O4- PAN/PMMA core-skin fibre is immersed in acetone 3 days, during which intermittent 10 points ultrasonic every 4 hours
Clock obtains Fe to remove PMMA in fiber3O4- PAN hollow fibre；
Two, in Fe3O4- PAN hollow fibre surfaces externally and internally grows carbon nanotube:
F, by Fe3O4- PAN hollow fibre, which is immersed in the toluene solution of ferrocene, to be impregnated 2 days, during which every 4 hours intervals
Property ultrasound 10 minutes, the mass percentage concentration of ferrocene is 10% in the toluene solution of ferrocene；
It g, will be through step f treated Fe3O4After the drying of-PAN hollow fibre, it is put into CVD tube furnace, and fiber both ends
Apply tension；
H, CVD tube furnace is warming up to 240 DEG C and keeps 1h, 285 DEG C of holding 30min carry out pre-oxidation treatment to fiber；
Then pass to argon gas 1h, followed by be continuously heating to 600 DEG C and keep be passed through at this temperature hydrogen reaction 30min；It is further continued for
It is warming up to 800 DEG C and is passed through the toluene solution of ferrocene using argon gas/hydrogen mixed gas as carrier at this temperature, react 4h, this
Carbon nanotube is grown simultaneously in the surfaces externally and internally of hollow carbon fibre in the process, Fe3O4Presoma is changed into Fe3C is down to room temperature,
Obtain surfaces externally and internally growth carbon nanotube contains Fe3The Hollow Compound carbon fiber of C.
Wherein magnetic Fe in step 13O4Nanoparticle the preparation method comprises the following steps:
By 2.7g FeCl3·6H2O, 7.2g anhydrous sodium acetate, 1.0g polyethylene glycol and the mixing of 80ml ethylene glycol, ultrasound are filled
Divide stirring that it is made within 30 minutes to be uniformly then placed in ptfe autoclave, 8h is reacted at 200 DEG C, it is then clear with ethyl alcohol
It washes three times, it is 12 hours dry under conditions of temperature is 60 DEG C in vacuum drying oven, obtain magnetic Fe3O4Nanoparticle.
In the present embodiment, the Fe that is obtained through step d3O4The stereoscan photograph such as Fig. 1 on-PAN/PMMA core-skin fibre surface
Shown, the stereoscan photograph in section is as shown in Fig. 2, it will be seen from figure 1 that fiber surface is more smooth, and wherein spot is Fe3O4
It flocks together and to be formed.Figure it is seen that fiber is more equal with the clearly thickness of skin-core structure and case fibre
One, illustrate the successful preparation of core-skin fibre.
In the present embodiment, the Fe that is obtained through step e3O4The stereoscan photograph of-PAN hollow fibre is as shown in figure 3, from Fig. 3
As can be seen that PAN hollow fibre thickness is uniform, Cross Section Morphology is regular.The PMMA of fibrous inside has been completely removed simultaneously.
In the present embodiment, contain Fe through the surfaces externally and internally growth carbon nanotube that obtains that step h is obtained3The Hollow Compound of C
The stereoscan photograph of the outer surface of carbon fiber as shown in figure 4, from fig. 4, it can be seen that CNT is coated on the surface of fiber completely,
One layer thicker of CNT shell is formed in hollow fibre outer surface.The stereoscan photograph of inner surface is as shown in figure 5, can be with from Fig. 5
Find out, CNT also has growth in fiber inner surface, shows that the surfaces externally and internally of hollow fibre all grown CNT.
Carbon nanotube is grown simultaneously in the surfaces externally and internally of hollow carbon fibre in step h, Fe therein3O4Presoma turns
Become Fe3C, as shown in fig. 6, surfaces externally and internally growth carbon nanotube contains Fe3The XRD spectra of the Hollow Compound carbon fiber of C and
Fe3O4Spectrogram control, discovery characteristic peak occur significant change, there is Fe between 30~50 °3The characteristic peak of C.
Surfaces externally and internally manufactured in the present embodiment growth carbon nanotube is contained into Fe3The Hollow Compound carbon fiber of C is cut into
The staple fiber of 10mm, and mixed for 20% with paraffin by the mass percentage of staple fiber, length × width × height is made using mold
=22.9mm × 10.2mm × h mm test sample, wherein h=0.5mm, 1mm, 1.5mm and 2mm, the test to different-thickness
Sample carries out electromagnetic shielding performance test, as a result as shown in Figure 7.From figure 7 it can be seen that fibre-bearing 20% with a thickness of 2mm's
The electromagnetic wave shielding of material can reach 80dB.
In the present embodiment, after electromagnetic wave incident to Hollow Compound carbon fiber, hollow Fe3The surfaces externally and internally of C- carbon fiber is raw
Dielectric loss will occur when passing through for long carbon nanotube (CNT), electromagnetic wave, be easier to be lost at fiber and CNT node, electricity
Magnetic wave intensity is decayed；Magnetic Fe3C nano particle adjusts the magnetic property of material, and material is made to have magnetic loss performance, electromagnetic wave
Intensity is further decayed.By high temperature cabonization, PAN is changed into carbon, the carbon fiber of one-dimensional hollow tubular structures, and electromagnetic wave exists
Multiple reflections are carried out in hollow cavity, cause the further decaying of electromagnetic intensity.These special structures have material excellent
Electromagnetic shielding performance.
In the present embodiment, surfaces externally and internally growth carbon nanotube contains Fe3Fe in the Hollow Compound carbon fiber of C3C is logical
It crosses and Fe is added during the spinning process3O4Presoma is changed into ferromagnetic Fe at high temperature3C, it improves magnetic particles
Son prevents it from falling off in the stability of material internal, and magnetism of material is enable to keep for a long time, so that performance be made to stablize.
Claims (10)
1. a kind of surfaces externally and internally growth carbon nanotube contains Fe3The Hollow Compound carbon fiber of C, it is characterised in that the knot of the fiber
Structure is containing magnetic Fe3The carbon fibre hollow pipe of C nano particle is carrier, has carbon to receive in the inner and outer surfaces growth of hollow pipe
Mitron.
2. prepare a kind of surfaces externally and internally growth carbon nanotube described in claim 1 contains Fe3The Hollow Compound carbon fiber of C
Method, it is characterised in that this method sequentially includes the following steps:
One, Fe is prepared3O4- PAN/PMMA hollow fibre:
A, by Fe3O4Nanoparticle is dispersed in dimethyl sulfoxide, obtains Fe3O4Nanoparticle dispersion liquid；Polyacrylonitrile is added
It is dissolved by heating in DMSO, obtains polyacrylonitrile solution；By Fe3O4Nanoparticle dispersion liquid is mixed with polyacrylonitrile solution, is mixed
Close liquid；Partial solvent is evaporated under reduced pressure, obtains shell solution；
B, the DMSO solution for preparing polymethyl methacrylate, obtains sandwich layer solution；
C, using DMSO aqueous solution as coagulating bath, sandwich layer solution is passed through in the center cavity of the coaxial spinning head of spinning machine binary channels, it will
Shell solution is passed through in the annular chamber of the coaxial spinning head of spinning machine binary channels, carries out spinning using dry-jet wet-spinning technique；
D, spun fiber filament is immersed in the methanol that temperature is -30~-20 DEG C and is impregnated to remove the solvent in fiber, obtained
Fe3O4- PAN/PMMA core-skin fibre；
E, by Fe3O4- PAN/PMMA core-skin fibre, which is immersed in acetone, to be impregnated, and during which intermittence is ultrasonically treated, to remove in fiber
PMMA obtains Fe3O4- PAN hollow fibre；
Two, in Fe3O4- PAN hollow fibre surfaces externally and internally grows carbon nanotube:
F, by Fe3O4- PAN hollow fibre, which is immersed in the toluene solution of ferrocene, to be impregnated, and during which intermittence is ultrasonically treated；
It g, will be through step f treated Fe3O4After the drying of-PAN hollow fibre, it is put into CVD tube furnace, and applied at fiber both ends
Add tension；
H, CVD tube furnace is warming up to 200~300 DEG C and 1~2h is kept to carry out pre-oxidation treatment to fiber；Then pass to argon gas
1~1.2h, followed by be continuously heating to 600~620 DEG C and keep be passed through at this temperature hydrogen react 30~60min；Followed by
The continuous toluene solution for being warming up to 800~820 DEG C and be passed through ferrocene using argon gas/hydrogen mixed gas as carrier at this temperature, instead
1~4h is answered, grows carbon nanotube simultaneously in the surfaces externally and internally of hollow fibre during this, Fe3O4Presoma is changed into Fe3C, drop
To room temperature, obtain surfaces externally and internally growth carbon nanotube contains Fe3The hollow compound fibre of C.
3. a kind of surfaces externally and internally growth carbon nanotube according to claim 2 contains Fe3The Hollow Compound carbon fiber of C
Preparation method, it is characterised in that magnetic Fe in step 13O4Nanoparticle the preparation method comprises the following steps: by 1.35~2.7g FeCl3·
6H2O, 3.6~7.2g anhydrous sodium acetate, 0~1g polyethylene glycol and the mixing of 80ml ethylene glycol, ultrasonic agitation uniformly, are put into poly- four
In vinyl fluoride reaction kettle, 8~10h is reacted at 190~210 DEG C, is then cleaned up with ethyl alcohol, it is dry in vacuum drying oven,
Obtain magnetic Fe3O4Nanoparticle.
4. a kind of surfaces externally and internally growth carbon nanotube according to claim 2 or 3 contains Fe3The Hollow Compound carbon fiber of C
Preparation method, it is characterised in that in step 1 a, in mixed liquor, Fe3O4The quality of nanoparticle accounts for Fe3O4Nanoparticle and poly-
The 5%~30% of acrylonitrile gross mass.
5. a kind of surfaces externally and internally growth carbon nanotube according to claim 2 or 3 contains Fe3The Hollow Compound carbon fiber of C
Preparation method, it is characterised in that in step 1 a, the concentration of polyacrylonitrile reaches 250~350g/ after partial solvent is evaporated under reduced pressure
L。
6. a kind of surfaces externally and internally growth carbon nanotube according to claim 2 or 3 contains Fe3The Hollow Compound carbon fiber of C
Preparation method, it is characterised in that in step 1 b, in sandwich layer solution, the concentration of polymethyl methacrylate is 500~700g/
L。
7. a kind of surfaces externally and internally growth carbon nanotube according to claim 2 or 3 contains Fe3The Hollow Compound carbon fiber of C
Preparation method, it is characterised in that in step 1 c, the mass percentage concentration of the DMSO aqueous solution as coagulating bath is 40%~
50%.
8. a kind of surfaces externally and internally growth carbon nanotube according to claim 2 or 3 contains Fe3The Hollow Compound carbon fiber of C
Preparation method, it is characterised in that in step 1 e, intermittence ultrasonic treatment refers to every 2~4 hours be ultrasonically treated 10~15 points
Clock.
9. a kind of surfaces externally and internally growth carbon nanotube according to claim 2 or 3 contains Fe3The Hollow Compound carbon fiber of C
Preparation method, it is characterised in that in step 2 f, in the toluene solution of ferrocene the mass percentage concentration of ferrocene be 5%~
10wt%.
10. a kind of surfaces externally and internally growth carbon nanotube according to claim 2 or 3 contains Fe3The Hollow Compound carbon fiber of C
The preparation method of dimension, it is characterised in that in step 2 f, intermittence ultrasonic treatment, which refers to, was ultrasonically treated 10~15 every 2~4 hours
Minute.
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