CN107419365B - A kind of graphene composite fibre absorbent and preparation method thereof - Google Patents
A kind of graphene composite fibre absorbent and preparation method thereof Download PDFInfo
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- CN107419365B CN107419365B CN201710456507.1A CN201710456507A CN107419365B CN 107419365 B CN107419365 B CN 107419365B CN 201710456507 A CN201710456507 A CN 201710456507A CN 107419365 B CN107419365 B CN 107419365B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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Abstract
The invention belongs to technical field of function materials.Using carbon fiber precursor polyacrylonitrile as carrier, chemical bonding is generated using heat treatment process and graphene and magnetic material function ingredients, assigns anisotropy using spining technology.Graphene composite fibre absorbent of the present invention, using polyacrylonitrile-based carbon fibre as carrier, for fibre diameter between 5~30 μm, density is not more than 3.5g/cm3, the quality group of material active principle becomes: 0.5~15 part of graphene, 1~25 part of magnetic material, and 100 solid part of polyacrylonitrile, by spinning, pre-oxidation treatment and carbonizing reduction process, 150~270 DEG C of 60~120min of pre-oxidation in air or nitrogen atmosphere；Inert atmosphere, 600~900 DEG C of 5~30min of carbonizing reduction are obtained.The graphene composite fibre absorbent, thunderstorm activity excellent, absorption band is wide, and absorbing property is high, and designability is strong.Suitable for absorbing material, anti-static material and electromagnetic shielding field, especially suitable for radar invisible design of absorbing material and processing technique field.
Description
Technical field
The invention belongs to technical field of function materials, are related to electromagnetic wave absorbent material technology, in particular to graphene absorbs
Agent technology.
Background technique
Absorbing material is the energy for referring to absorption, decaying incident electromagnetic wave, and is quickly converted electromagnetic energy by material
At thermal energy or a kind of functional material of other form of energy.Traditional ferromagnetic class absorbent mainly includes metal fine powder, ferrite
The problems such as Deng, these materials there are density big, structure difficult design, environment resistant difference, it is extremely restricted its application.Carbon fiber
The fiber-likes absorbent such as dimension, polycrystalline iron fiber, silicon carbide fibre, due to it with unique electromagnetic performance, density is small, additive amount
Low advantage, it has also become the hot spot of current research.Graphene is due to skin effect, quantum size effect, Hall effect etc.
Special performance, and the small easy processing of density, attracted attention in absorbing material field in recent years.But the absorbent of single lossy is difficult
To adjust two conclusive parameters of dielectric constant and magnetic conductivity simultaneously, it is unable to satisfy the requirement of absorbing material.
Related graphene mainly inhales the flakelike powder of graphene surface carried magnetic material as the report of absorbent
It receives agent or magnetic material and graphene direct combination is prepared into polynary graphene composite powder absorbent.
105647468 A of CN discloses a kind of absorbing material and preparation method thereof based on graphene, will using ball-milling method
One of or several doping in graphite composite powder and three kinds of ferrite, carbonyl iron dust or super-fine metal powder magnetic medium profile material,
A few hours are ground after mixing with dry ice in planetary ball mill, prepare graphene composite absorber.The method is only by graphene
With magnetic material mechanical mixture, although can increase the content of graphene in absorbent, interfacial effect is obvious between its component, no
Conducive to impedance matching.
CN101550003B discloses a kind of nano-graphite alkenyl Wave suction composite material and preparation method thereof, and the material is first
Using electrochemical method deposited metal on the surface of graphene, then by high-temperature oxydation, metal is converted to oxide, prepares nanometer
Graphene/metal oxide Wave suction composite material.The method can oxidize metal composition granule by electrochemical method and overcome boundary
Face effect is combined together well, but since graphene size is smaller, and it is lower to deposit metal oxide content therein, to suction
The magnetic loss contribution for receiving agent is few.
104690289 A of CN discloses a kind of preparation method of graphene-nano nickel absorbing material, and this method passes through molten
Nanometer nickel ion is successfully loaded to graphene film layer surface by agent thermal method.Equally, the method is compound due to the limitation of graphene size
Absorbent magnetic loss is smaller, is unfavorable for the impedance matching of absorbing material.
Though above-mentioned composite absorber is made of graphene and magnetic material, and magnetic material improves to a certain extent
The absorbing property of graphene, but due to the difference of electromagnetic property between each functional component, there are still impedance mismatch characteristics, cause
Absorbent overall absorption frequency band is narrow, and global density is larger.
Summary of the invention
The purpose of the present invention is to provide a kind of graphene composite fibre suctions for having both dielectric loss, dielectric loss and magnetic loss
Agent is received, while preparation method being provided.
The object of the present invention is achieved like this, using carbon fiber precursor polyacrylonitrile as carrier, utilizes heat treatment process
The chemistry of the oxygen-containing functional group and magnetic material in N, O, H active element and grapheme material on middle polyacrylonitrile strand is anti-
It answers, graphene, carbon and each functional component of magnetic material is made to generate chemical bonding, assign absorbent respectively to different using spining technology
Property, binding fiber draw ratio improves absorbent to the absorbability of electromagnetic wave.The dielectric of each functional component in fiber is utilized simultaneously
Loss, magnetic loss, interfacial polarization and spatial polarizations effectively improve absorption efficiency.
Graphene composite fibre absorbent of the present invention, using polyacrylonitrile-based carbon fibre as carrier, fibre diameter is situated between
Between 5~30 μm, density is not more than 3.5g/cm3, the quality group of material active principle becomes:
0.5~15 part of graphene,
1~25 part of magnetic material,
100 solid part of polyacrylonitrile；
Using wet spinning or dry-jet wet spinning process, pre-oxidation and carbonizing reduction technological forming；
The grapheme material is graphene or graphene oxide；The magnetic material be nanoscale ferromagnetic metal powder or
At least one of its compound.
Graphene composite fibre absorbent of the present invention, the quality group of effective material component become:
2~10 parts of graphene,
5~15 parts of magnetic material,
100 solid part of polyacrylonitrile.
Graphene composite fibre absorbent of the present invention, the quality group of effective material component become:
5~12 parts of graphene,
10~20 parts of magnetic material,
100 solid part of polyacrylonitrile.
Graphene composite fibre absorbent of the present invention, Fiber Aspect Ratio is between 40~400.
Graphene composite fibre absorbent of the present invention, the polyacrylonitrile resin are acrylonitrile and comonomer
Copolymerization system, comonomer be one of itaconic acid, acrylic acid, itaconic acid amine, methyl acrylate, methacrylic acid or in which
Several mixed systems.
Graphene composite fibre absorbent of the present invention, the polyacrylonitrile are the dimethyl of 15wt%~30wt%
Sulfoxide, dimethyl acetamide or N'N dimethylformamide solution.
The preparation method of graphene composite fibre absorbent of the present invention, including spinning solution preparation, spinning, pre-oxidation
Processing and carbonizing reduction process, it is characterised in that:
Spinning solution preparation: grapheme material is distributed in solvent；Magnetic material is dispersed in polyacrylonitrile polymer fluid；45
The two is mixed and is uniformly dispersed by~65 DEG C, obtains spinning solution；
Spinning: graphene/nanometer magnetic material/compound original of polyacrylonitrile is prepared using wet spinning or dry-jet wet spinning process
Raw fiber, spinning temperature are 45~65 DEG C, and coagulation bath temperature is 25~50 DEG C, and orifice diameter is between 30~100mm；
Pre-oxidation: pre-oxidizing conditions are air or nitrogen atmosphere, 150~270 DEG C/60~120min；
Carbonizing reduction: Carbonization Conditions are inert atmosphere, 600~900 DEG C/5~30min.
The preparation method of graphene composite fibre absorbent of the present invention, including spinning solution preparation, spinning, pre-oxidation
Processing and carbonizing reduction process, it is characterised in that: spinning liquid and preparation method thereof is grapheme material, acrylonitrile and comonomer
It closes, add magnetic material and is uniformly dispersed.
The preparation method of graphene composite fibre absorbent of the present invention, including spinning solution preparation, spinning, pre-oxidation
Processing and carbonizing reduction process, it is characterised in that: the inert atmosphere of carbonizing reduction process is nitrogen atmosphere.
Graphene composite fibre absorbent of the present invention has excellent thunderstorm activity characteristic, and absorption band is wide,
Absorbing property is high, and designability is strong.Suitable for absorbing material, anti-static material and electromagnetic shielding field, especially suitable for radar
Microwave Absorbing Materials design and processing technique field.
The preparation method of graphene composite fibre absorbent of the present invention, simple process is reproducible, controllability
By force, it is easy to be mass produced.
Specific embodiment
The present invention will be further described with reference to the examples below, however technical solution of the present invention be but not limited to it is following
Cited specific embodiment.Those skilled in the art according to the content of foregoing invention make it is some it is nonessential change and
Adjustment, all belongs to the scope of protection of the present invention.
Embodiment one
0.5g graphene and 100mL dimethyl sulphoxide solution are mixed, at room temperature magnetic agitation 15min, ultrasonication
60min obtains graphene dispersing solution；
1g Nano ferric hydroxide is doped into the acrylonitrile itaconic acid (mass ratio 98:2)/bis- of the 100g containing polyacrylonitrile
Methyl sulfoxide is copolymerized in stoste (15%wt), and mechanical stirring 45min is uniformly dispersed；Under the conditions of 45~50 DEG C, graphene dispersion is added
Liquid stirs 60min, obtains blend spinning liquid；
Using wet spinning technology spinning, 45 DEG C of spinning temperature, coagulating bath 35%(wt%) dimethyl sulfoxide-deionization
Water, 30 μm of spinneret orifice internal diameter, obtains compound protofibre by 25 DEG C of coagulation bath temperature；
Compound protofibre, which is put into pre-oxidation furnace, carries out pre-oxidation and carbonizing reduction, pre-oxidizing conditions: air atmosphere, respectively
In 180 DEG C, 225 DEG C and 270 DEG C pre-oxidation 20min；Carbonizing reduction condition: nitrogen atmosphere, 700 DEG C/10min, 900 DEG C/5min, from
It is so cooled to room temperature, obtains nano-magnetic iron series (Fe of the present invention3O4、Fe4N) graphene composite fibre absorbent.Fiber
5 μm of diameter, density 1.9g/cm3。
(draw ratio 400) and paraffin (mass ratio 1:1) is mixed with the sample of thickness 2mm after composite fibre is cut, 2
~ 18GHz microwave frequency band internal reflection loss peak is -11.8dB, and reflection loss -10dB Absorber Bandwidth below is 1.1GHz.
Embodiment two
2g graphene oxide and 200mL dimethylacetamide solution are mixed, at room temperature magnetic agitation 30min, ultrasonic wave
75min is handled, graphene oxide dispersion is obtained；
5g ferric acetyl acetonade is doped into polyacrylonitrile/dimethylacetamide solution (18%wt) of the 100g containing polyacrylonitrile
In, mechanical stirring 45min is uniformly dispersed；Under the conditions of 55~60 DEG C, graphene oxide dispersion is added, stirs 60min, is mixed
Close spinning solution；
Using dry-jet wet spinning process carry out spinning, spinning temperature be 55 DEG C, coagulating bath 35%(wt%) dimethylacetamide
Amine-deionized water, 50 μm of spinneret orifice internal diameter, obtains compound protofibre by 30 DEG C of coagulation bath temperature；
Compound protofibre, which is put into pre-oxidation furnace, carries out pre-oxidation and carbonizing reduction, pre-oxidizing conditions: air atmosphere, and 180
DEG C/15min, 235 DEG C/25min and 270 DEG C/30min；Carbonizing reduction condition: nitrogen atmosphere, naturally cools to by 800 DEG C/10min
Room temperature obtains nano-magnetic iron series (Fe, Fe of the present invention3O4、Fe4N) graphene composite fibre absorbent.Fibre diameter
12 μm, density 2.1g/cm3。
(draw ratio 200) and paraffin (mass ratio 1:1) is mixed with the sample of thickness 2mm after composite fibre is cut, 2
~ 18GHz microwave frequency band internal reflection loss peak is -14.5dB, and reflection loss -10dB Absorber Bandwidth below is 2.8GHz.
Embodiment three
5g graphene and 350mL dimethyl sulphoxide solution are mixed, at room temperature magnetic agitation 30min, ultrasonication
90min obtains graphene dispersing solution；
By 10g nano-nickel powder be doped into the 100g containing polyacrylonitrile acrylonitrile itaconic acid-methyl acrylate (mass ratio 95:
In 2:3)/dimethyl sulfoxide copolymerization stoste (23%wt), mechanical stirring 60min is uniformly dispersed；Under the conditions of 60~65 DEG C, stone is added
Black alkene dispersion liquid stirs 60min, obtains blend spinning liquid；
Using wet spinning technology spinning, 65 DEG C of spinning temperature, coagulating bath 25%(wt%) dimethyl sulfoxide-deionization
Water, 50 μm of spinneret orifice internal diameter, obtains compound protofibre by 50 DEG C of coagulation bath temperature；
Compound protofibre, which is put into pre-oxidation furnace, carries out pre-oxidation and carbonizing reduction, pre-oxidizing conditions: nitrogen atmosphere, and 190
DEG C heat preservation 30min, be warming up to 260 DEG C of heat preservation 20min through 50min, heat treatment time is 100min altogether；Carbonizing reduction condition: nitrogen
Atmosphere, 700 DEG C/5min, it is compound to obtain nano-magnetic nickel of the present invention system (Ni, NiO) graphene for cooled to room temperature
Fibrous absorber.15 μm of fibre diameter, density 2.9g/cm3。
(draw ratio 100) and paraffin (mass ratio 1:1) is mixed with the sample of thickness 2mm after composite fibre is cut, 2
~ 18GHz microwave frequency band internal reflection loss peak is -22.1dB, and reflection loss -10dB Absorber Bandwidth below is up to 4.2GHz.
Example IV
8g graphene oxide and 300mL N'N dimethyl formamide solution are mixed, at room temperature magnetic agitation 30min, is surpassed
Sonicated 90min, obtains graphene oxide dispersion；
12g nano ferrous oxalate is doped into polyacrylonitrile/N'N dimethyl formamide solution of the 100g containing polyacrylonitrile
In (28%wt), mechanical stirring 75min is uniformly dispersed；Under the conditions of 60~65 DEG C, graphene oxide dispersion, stirring is added
60min obtains blend spinning liquid；
Using dry-jet wet spinning process carry out spinning, 65 DEG C of spinning temperature, coagulating bath 15%(wt%) N'N dimethyl formyl
Amine-deionized water, 80 μm of spinneret orifice internal diameter, obtains compound protofibre by 45 DEG C of coagulation bath temperature；
Compound protofibre, which is put into pre-oxidation furnace, carries out pre-oxidation and carbonizing reduction, pre-oxidizing conditions: air atmosphere, and 150
DEG C/20min, 215 DEG C/25min and 270 DEG C/30min；Carbonizing reduction condition: nitrogen atmosphere, naturally cools to by 650 DEG C/18min
Room temperature obtains nano-magnetic iron series (Fe of the present invention3O4) graphene composite fibre absorbent.28 μm of fibre diameter, density
2.3g/cm3。
(draw ratio 50) and paraffin (mass ratio 1:1) are mixed with the sample of thickness 2mm after composite fibre is cut, 2 ~
18GHz microwave frequency band internal reflection loss peak is -15.3dB, and reflection loss -10dB Absorber Bandwidth below is up to 3.3GHz.
Embodiment five
10g graphene oxide and 350mL dimethyl sulphoxide solution are mixed, at room temperature magnetic agitation 30min, at ultrasonic wave
90min is managed, graphene oxide dispersion is obtained；
Acrylonitrile itaconic acid (mass ratio 97:3)/dimethyl that 15g nanometer iron powder is doped into the 100g containing polyacrylonitrile is sub-
Sulfone is copolymerized in stoste (20%wt), and mechanical stirring 60min is uniformly dispersed；Under the conditions of 60~65 DEG C, graphene oxide dispersion is added
Liquid stirs 90min, obtains blend spinning liquid；
Using wet spinning technology spinning, 60 DEG C of spinning temperature, coagulating bath 25%(wt%) dimethyl sulfoxide-deionization
Water, 80 μm of spinneret orifice internal diameter, obtains compound protofibre by 35 DEG C of coagulation bath temperature；
Compound protofibre, which is put into pre-oxidation furnace, carries out pre-oxidation and carbonizing reduction, pre-oxidizing conditions: air atmosphere, and 190
DEG C/20min, 245 DEG C/30min and 270 DEG C/30min；Carbonizing reduction condition: nitrogen atmosphere, naturally cools to by 750 DEG C/15min
Room temperature obtains nano-magnetic iron series (Fe, Fe of the present invention3O4、Fe4N) graphene composite fibre absorbent.Fibre diameter
25 μm, density 3.1g/cm3。
(draw ratio 40,80,120 and 160) and paraffin (mass ratio 1:1) is mixed with thickness after composite fibre is cut
The sample of 2mm tests reflectivity in 2 ~ 18GHz microwave frequency band.The sample reflection loss peak that draw ratio is 40 be-
16.7dB, reflection loss -10dB Absorber Bandwidth below are up to 3.5GHz；The sample reflection loss peak that draw ratio is 80 be-
19.5dB, reflection loss -10dB Absorber Bandwidth below are up to 4.3GHz；The sample reflection loss peak that draw ratio is 120 be-
23.5dB, reflection loss -10dB Absorber Bandwidth below are up to 5.3GHz.The sample reflection loss peak that draw ratio is 160 be-
12.5dB, reflection loss -10dB Absorber Bandwidth below are 2.1GHz.
Comparative example
With embodiment five, spinning technique is changed to the preparation of press mold technique and inhales for film-type absorbent, component ratio and process conditions
Receipts agent film, 100 μm of film thickness, density 3.1g/cm3。
The sample with a thickness of 2mm is made after mixing after laminated film is ground with paraffin (mass ratio 1:1), in 2 ~ 18GHz
Microwave frequency band internal reflection loss peak is -21.5dB, and reflection loss -10dB Absorber Bandwidth below is up to 4.1GHz.
Embodiment six
12g graphene oxide and 400mLN'N dimethyl formamide solution are mixed, at room temperature magnetic agitation 30min, is surpassed
Sonicated 90min, obtains graphene oxide dispersion；
20g nano-cobalt powder is doped into polyacrylonitrile/N'N dimethyl formamide solution (25% of the 100g containing polyacrylonitrile
Wt in), mechanical stirring 75min is uniformly dispersed；Under the conditions of 60~65 DEG C, graphene oxide dispersion is added, stirs 90min, obtains
To blend spinning liquid；
Using dry-jet wet spinning process carry out spinning, 63 DEG C of spinning temperature, coagulating bath 10%(wt%) N'N dimethyl formyl
Amine-deionized water, 80 μm of spinneret orifice internal diameter, obtains compound protofibre by 40 DEG C of coagulation bath temperature；
Compound protofibre, which is put into pre-oxidation furnace, carries out pre-oxidation and carbonizing reduction, pre-oxidizing conditions: nitrogen atmosphere, and 185
DEG C heat preservation 40min, is warming up to 265 DEG C through 40min, keeps the temperature 40min, heat treatment time is 120min altogether；Carbonizing reduction condition: nitrogen
Atmosphere, 700 DEG C/20min, cooled to room temperature obtains nano-magnetic cobalt of the present invention system (Co, Co3O4) graphene is multiple
Condensating fiber absorbent.22 μm of fibre diameter, density 3.5g/cm3。
(draw ratio 80) and paraffin (mass ratio 1:1) are mixed with the sample of thickness 2mm after composite fibre is cut, 2 ~
18GHz microwave frequency band internal reflection loss peak is -21.6dB, and reflection loss -10dB Absorber Bandwidth below is up to 4.5GHz.
Embodiment seven
12g graphene oxide, 3g graphene and 500mL dimethyl sulphoxide solution are mixed, at room temperature magnetic agitation
45min, ultrasonication 90min obtain admixed graphite alkene material dispersion liquid；
By 25g nanometer iron powder be doped into the 100g containing polyacrylonitrile acrylonitrile itaconic acid-acrylic acid (mass ratio 96:2:
2) in/dimethyl sulfoxide copolymerization stoste (30%wt), mechanical stirring 90min is uniformly dispersed；Under the conditions of 60~70 DEG C, mixing is added
Grapheme material dispersion liquid stirs 120min, obtains blend spinning liquid；
Using wet spinning technology spinning, 60 DEG C of spinning temperature, coagulating bath is deionized water, 25 DEG C of coagulation bath temperature, is sprayed
100 μm of wire hole internal diameter, obtain compound protofibre；
Compound protofibre, which is put into pre-oxidation furnace, carries out pre-oxidation and carbonizing reduction, pre-oxidizing conditions: air atmosphere, respectively
In 190 DEG C, 230 DEG C and 270 DEG C pre-oxidation 30min；Carbonizing reduction condition: nitrogen atmosphere, naturally cools to room by 600 DEG C/30min
Temperature obtains nano-magnetic iron series (Fe, Fe of the present invention3O4) graphene composite fibre absorbent.It is 30 μm of fibre diameter, close
Spend 3.5g/cm3。
(draw ratio 60) and paraffin (mass ratio 1:1) are mixed with the sample of thickness 2mm after composite fibre is cut, 2 ~
18GHz microwave frequency band internal reflection loss peak is -19.7dB, and reflection loss -10dB Absorber Bandwidth below is up to 3.9GHz.
Embodiment eight
Graphene oxide, acrylonitrile, itaconic acid and methacrylic acid (mass ratio 1:94:3:3) are stirred, dimethyl
Sulfoxide is solvent, and graphene oxide-polyacrylonitrile polymer fluid (21% wt) is obtained after polymerisation in solution；
Nanoflakes and cobalt hydroxide (cobalt hydroxide and graphene oxide mass ratio be 8:1) is doped into graphene oxide-poly- third
In alkene nitrile polymer fluid, under the conditions of 50~60 DEG C, mechanical stirring 90min obtains blend spinning liquid；
Using wet spinning technology spinning, 50 DEG C of spinning temperature, coagulating bath 5%(wt%) dimethyl sulfoxide-deionization
Water, 30 μm of spinneret orifice internal diameter, obtains compound protofibre by 25 DEG C of coagulation bath temperature；
Compound protofibre, which is put into pre-oxidation furnace, carries out pre-oxidation and carbonizing reduction, pre-oxidizing conditions: nitrogen atmosphere, and 160
DEG C/20min, it is warming up to 200 DEG C/25min through 15min, is warming up to 270 DEG C/25min through 20min, heat treatment time is altogether
105min；Carbonizing reduction condition: nitrogen atmosphere, 850 DEG C/25min, cooled to room temperature obtains nano magnetic of the present invention
Property cobalt system (Co3O4) graphene composite fibre absorbent.10 μm of fibre diameter, density 2.5g/cm3。
(draw ratio 250) and paraffin (mass ratio 1:1) is mixed with the sample of thickness 2mm after composite fibre is cut, 2
~ 18GHz microwave frequency band internal reflection loss peak is -13.7dB, and reflection loss -10dB Absorber Bandwidth below is up to 3.1GHz.
Claims (8)
1. a kind of graphene composite fibre absorbent, using polyacrylonitrile-based carbon fibre as carrier, fibre diameter between 5~30 μm it
Between, for draw ratio between 40~400, density is not more than 3.5g/cm3, the quality group of material active principle becomes:
0.5~15 part of graphene,
1~25 part of magnetic material,
100 solid part of polyacrylonitrile；
The grapheme material is graphene or graphene oxide；The magnetic material is nanoscale ferromagnetic metal powder or its change
Close at least one of object；
Using wet spinning or dry-jet wet spinning process, pre-oxidation and carbonizing reduction technological forming；Carbonizing reduction condition is indifferent gas
Atmosphere, 600~900 DEG C/5~30min.
2. graphene composite fibre absorbent according to claim 1, the quality group of effective material component become:
2~10 parts of graphene,
5~15 parts of magnetic material,
100 solid part of polyacrylonitrile.
3. graphene composite fibre absorbent according to claim 1, the quality group of effective material component become:
5~12 parts of graphene,
10~20 parts of magnetic material,
100 solid part of polyacrylonitrile.
4. graphene composite fibre absorbent according to any one of claims 1 to 3, the polyacrylonitrile resin is third
The copolymerization system of alkene nitrile and comonomer, comonomer are itaconic acid, acrylic acid, itaconic acid amine, methyl acrylate, metering system
One of acid or in which several mixed systems.
5. graphene composite fibre absorbent according to any one of claims 1 to 3, the polyacrylonitrile is 15wt%
Dimethyl sulfoxide, dimethyl acetamide or the N'N dimethylformamide solution of~30wt%.
6. the preparation method of graphene composite fibre absorbent according to any one of claims 1 to 3, including spinning solution
Preparation, spinning, pre-oxidation treatment and carbonizing reduction process, it is characterised in that:
Spinning solution preparation: grapheme material is distributed in solvent；Magnetic material is dispersed in polyacrylonitrile polymer fluid；45~65
DEG C the two is mixed and is uniformly dispersed, obtains spinning solution；
Spinning: the compound primary fibre of graphene/nanometer magnetic material/polyacrylonitrile is prepared using wet spinning or dry-jet wet spinning process
Dimension, spinning temperature are 45~65 DEG C, and coagulation bath temperature is 25~50 DEG C, and orifice diameter is between 30~100 μm；
Pre-oxidation: pre-oxidizing conditions are air or nitrogen atmosphere, 150~270 DEG C/60~120min；
Carbonizing reduction: Carbonization Conditions are inert atmosphere, 600~900 DEG C/5~30min.
7. the preparation method of graphene composite fibre absorbent according to claim 6, it is characterised in that: spinning solution preparation
Method is grapheme material, acrylonitrile and comonomer combined polymerization, adds magnetic material and is uniformly dispersed.
8. the preparation method of graphene composite fibre absorbent according to claim 6, it is characterised in that: carbonizing reduction mistake
The inert atmosphere of journey is nitrogen atmosphere.
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| CN108315834B (en) * | 2018-01-26 | 2020-04-10 | 渤海大学 | Preparation method of array type magnetic reduced graphene oxide-carbon nanofiber |
| CN109082730A (en) * | 2018-08-09 | 2018-12-25 | 北京化工大学 | Major diameter polyacrylonitrile-based carbon fibre and preparation method thereof |
| CN110295415A (en) * | 2019-06-28 | 2019-10-01 | 南通大学 | A kind of preparation method of intercalated graphite alkene/carbon fiber magnetism Wave suction composite material |
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