CN107419365A - 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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- CN107419365A CN107419365A CN201710456507.1A CN201710456507A CN107419365A CN 107419365 A CN107419365 A CN 107419365A CN 201710456507 A CN201710456507 A CN 201710456507A CN 107419365 A CN107419365 A CN 107419365A
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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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
- 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
Abstract
The invention belongs to technical field of function materials.Using carbon fiber precursor polyacrylonitrile as carrier, chemical bonding is produced using Technology for Heating Processing and graphene and magnetic material function ingredients, anisotropy is assigned 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 turns into：0.5~15 part of graphene, 1~25 part of magnetic material, the solid part of polyacrylonitrile 100, 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, is related to electromagnetic wave absorbent material technology, and more particularly to graphene absorbs
Agent technology.
Background technology
Absorbing material be refer to absorb, the energy for incident electromagnetic wave of decaying, and by material by electromagnetic energy rapid translating
Into heat energy or a kind of functional material of other form of energy.Traditional ferromagnetic class absorbent mainly includes metal fine powder, ferrite
Deng, the problems such as density is big, structure design is difficult, environment resistant poor be present in these materials, make its application be extremely restricted.Carbon is fine
The fiber-like absorbent such as dimension, polycrystalline iron fiber, silicon carbide fibre, because it has, unique electromagnetic performance, density be small, addition
Low advantage, it has also become the focus of current research.Graphene is due to skin effect, quantum size effect, Hall effect etc.
Special performance, and the small easy processing of density, got most of the 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, the requirement of absorbing material can not be met.
Related graphene mainly inhales the flakelike powder of graphenic surface carried magnetic material as the report of absorbent
Receive agent or magnetic material and graphene direct combination are prepared into polynary graphene composite powder absorbent.
The A of CN 105647468 disclose a kind of absorbing material based on graphene and preparation method thereof, will using ball-milling method
Graphite composite powder and ferrite, the one of which in three kinds of magnetizing mediums section bar material of carbonyl iron dust or super-fine metal powder or several doping,
A few hours are ground after being mixed 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
Beneficial 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 in graphenic surface deposited metal, then by high-temperature oxydation, metal is changed into oxide, prepares nanometer
Graphene/metal oxide Wave suction composite material.The method can make metal oxide particle overcome boundary by electrochemical method
Face effect is combined together well, but because graphene size is smaller, and it is relatively low to deposit metal oxide content therein, to inhaling
The magnetic loss contribution for receiving agent is few.
The A of CN 104690289 disclose 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 the hot method of agent.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 up of graphene and magnetic material, and magnetic material improves graphite to a certain extent
The absorbing property of alkene, but due to the difference of electromagnetic property between each functional component, still suffer from impedance mismatch characteristic, cause to absorb
Agent overall absorption frequency band is narrow, and global density is larger.
The content of the invention
It is an object of the invention to provide a kind of graphene composite fibre suction for having dielectric loss, dielectric loss and magnetic loss concurrently
Agent is received, while its preparation method is 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 N, O, H active element and the oxygen-containing functional group in grapheme material and magnetic material on middle polyacrylonitrile strand is anti-
Should, graphene, carbon and each functional component of magnetic material is produced chemical bonding, absorbent is assigned respectively to different using spining technology
Property, binding fiber draw ratio, improve absorbability of the absorbent to 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 turns into：
0.5~15 part of graphene,
1~25 part of magnetic material,
The solid part of polyacrylonitrile 100；
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 is nanoscale ferromagnetic metal powder or its change
At least one of compound.
Graphene composite fibre absorbent of the present invention, the quality group of effective material component turn into：
2~10 parts of graphene,
5~15 parts of magnetic material,
The solid part of polyacrylonitrile 100.
Graphene composite fibre absorbent of the present invention, the quality group of effective material component turn into：
5~12 parts of graphene,
10~20 parts of magnetic material,
The solid part of polyacrylonitrile 100.
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 are itaconic acid, acrylic acid, itaconic acid amine, methyl acrylate, one kind in methacrylic acid or wherein
Several mixed systems.
Graphene composite fibre absorbent of the present invention, the polyacrylonitrile are 15wt%~30wt% dimethyl
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：
It is prepared by spinning solution：Grapheme material is distributed in solvent；Magnetic material is dispersed in polyacrylonitrile polymer fluid；45~65
DEG C both are mixed and are uniformly dispersed, obtain 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 30~100mm；
Pre-oxidation：Pre-oxidizing conditions be 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
Close, add magnetic material and be 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, there is excellent thunderstorm activity characteristic, 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, technique is simple, reproducible, controllability
By force, it is easy to mass produce.
Embodiment
With reference to embodiment, the invention will be further described, however technical solution of the present invention be but not limited to it is following
Cited embodiment.Those skilled in the art according to the content of foregoing invention make some it is nonessential change and
Adjustment, belongs to protection scope of the present invention.
Embodiment one
0.5g graphenes and 100mL dimethyl sulphoxide solutions are mixed, at room temperature magnetic agitation 15min, ultrasonication
60min, obtain graphene dispersing solution；
1g Nano ferric hydroxides are doped into the acrylonitrile itaconic acid of the 100g containing polyacrylonitrile（Mass ratio 98:2）/ dimethyl
Sulfoxide is copolymerized stoste（15%wt）In, mechanical agitation 45min is uniformly dispersed；Under the conditions of 45~50 DEG C, graphene dispersing solution is added,
60min is stirred, obtains blend spinning liquid；
Using wet spinning technology spinning, 45 DEG C of spinning temperature, coagulating bath 35%（wt%）Dimethyl sulfoxide (DMSO)-deionized water,
25 DEG C of coagulation bath temperature, 30 μm of spinneret orifice internal diameter, obtains compound protofibre；
Compound protofibre, which is put into pre-oxidation furnace, to be pre-oxidized and carbonizing reduction, pre-oxidizing conditions：Air atmosphere, exist respectively
180 DEG C, 225 DEG C and 270 DEG C pre-oxidation 20min；Carbonizing reduction condition：Blanket of nitrogen, it is 700 DEG C/10min, 900 DEG C/5min, natural
Room temperature is cooled to, obtains nano-magnetic iron system of the present invention（Fe3O4、Fe4N）Graphene composite fibre absorbent.Fiber is straight
5 μm of footpath, density 1.9g/cm3。
After composite fibre is cut（Draw ratio 400）With paraffin（Mass ratio 1:1）Thickness 2mm sample is mixed with, 2
~ 18GHz microwave frequency band internal reflection loss peaks are -11.8dB, and below reflection loss -10dB Absorber Bandwidth is 1.1GHz.
Embodiment two
2g graphene oxides and 200mL dimethylacetamide solutions are mixed, at room temperature magnetic agitation 30min, ultrasonication
75min, obtain graphene oxide dispersion；
5g ferric acetyl acetonades are doped into polyacrylonitrile/dimethylacetamide solution of the 100g containing polyacrylonitrile（18%wt）In, machine
Tool stirring 45min is uniformly dispersed；Under the conditions of 55~60 DEG C, graphene oxide dispersion is added, stirs 60min, mixing is obtained and spins
Silk liquid；
Spinning is carried out using dry-jet wet spinning process, spinning temperature is 55 DEG C, coagulating bath 35%（wt%）Dimethyl acetamide-go
Ionized water, 30 DEG C of coagulation bath temperature, 50 μm of spinneret orifice internal diameter, obtain compound protofibre；
Compound protofibre, which is put into pre-oxidation furnace, to be pre-oxidized and carbonizing reduction, pre-oxidizing conditions：Air atmosphere, 180 DEG C/
15min, 235 DEG C/25min and 270 DEG C/30min；Carbonizing reduction condition：Blanket of nitrogen, 800 DEG C/10min, naturally cool to room
Temperature, obtain nano-magnetic iron system of the present invention（Fe、Fe3O4、Fe4N）Graphene composite fibre absorbent.The μ of fibre diameter 12
M, density 2.1g/cm3。
After composite fibre is cut（Draw ratio 200）With paraffin（Mass ratio 1:1）Thickness 2mm sample is mixed with, 2
~ 18GHz microwave frequency band internal reflection loss peaks are -14.5dB, and below reflection loss -10dB Absorber Bandwidth is 2.8GHz.
Embodiment three
5g graphenes and 350mL dimethyl sulphoxide solutions are mixed, at room temperature magnetic agitation 30min, ultrasonication 90min,
Obtain graphene dispersing solution；
10g nano-nickel powders are doped into acrylonitrile itaconic acid-methyl acrylate of the 100g containing polyacrylonitrile（Mass ratio 95:2:
3）/ dimethyl sulfoxide (DMSO) is copolymerized stoste（23%wt）In, mechanical agitation 60min is uniformly dispersed；Under the conditions of 60~65 DEG C, graphite is added
Alkene dispersion liquid, 60min is stirred, obtains blend spinning liquid；
Using wet spinning technology spinning, 65 DEG C of spinning temperature, coagulating bath 25%（wt%）Dimethyl sulfoxide (DMSO)-deionized water,
50 DEG C of coagulation bath temperature, 50 μm of spinneret orifice internal diameter, obtains compound protofibre；
Compound protofibre, which is put into pre-oxidation furnace, to be pre-oxidized and carbonizing reduction, pre-oxidizing conditions：Blanket of nitrogen, 190 DEG C of guarantors
Warm 30min, 260 DEG C of insulation 20min are warming up to through 50min, heat treatment time is 100min altogether；Carbonizing reduction condition：Blanket of nitrogen,
700 DEG C/5min, room temperature is naturally cooled to, obtains nano-magnetic nickel system of the present invention（Ni、NiO）Graphene composite fibre
Absorbent.15 μm of fibre diameter, density 2.9g/cm3。
After composite fibre is cut（Draw ratio 100）With paraffin（Mass ratio 1:1）Thickness 2mm sample is mixed with, 2
~ 18GHz microwave frequency band internal reflection loss peaks are -22.1dB, and below reflection loss -10dB Absorber Bandwidth is up to 4.2GHz.
Example IV
8g graphene oxides and 300mL N'N dimethyl formamide solutions are mixed, at room temperature magnetic agitation 30min, ultrasonic wave
90min is handled, obtains graphene oxide dispersion；
12g nano ferrous oxalates are doped into polyacrylonitrile/N'N dimethyl formamide solutions of the 100g containing polyacrylonitrile（28%
wt）In, mechanical agitation 75min is uniformly dispersed；Under the conditions of 60~65 DEG C, graphene oxide dispersion is added, 60min is stirred, obtains
To blend spinning liquid；
Spinning, 65 DEG C of spinning temperature, coagulating bath 15% are carried out using dry-jet wet spinning process（wt%）N'N dimethylformamides-
Deionized water, 45 DEG C of coagulation bath temperature, 80 μm of spinneret orifice internal diameter, obtain compound protofibre；
Compound protofibre, which is put into pre-oxidation furnace, to be pre-oxidized and carbonizing reduction, pre-oxidizing conditions：Air atmosphere, 150 DEG C/
20min, 215 DEG C/25min and 270 DEG C/30min；Carbonizing reduction condition：Blanket of nitrogen, 650 DEG C/18min, naturally cool to room
Temperature, obtain nano-magnetic iron system of the present invention（Fe3O4）Graphene composite fibre absorbent.28 μm of fibre diameter, density
2.3g/cm3。
After composite fibre is cut（Draw ratio 50）With paraffin（Mass ratio 1:1）Thickness 2mm sample is mixed with, 2 ~
18GHz microwave frequency band internal reflection loss peaks are -15.3dB, and below reflection loss -10dB Absorber Bandwidth is up to 3.3GHz.
Embodiment five
10g graphene oxides and 350mL dimethyl sulphoxide solutions are mixed, at room temperature magnetic agitation 30min, ultrasonication
90min, obtain graphene oxide dispersion；
15g nanometer iron powders are doped into the acrylonitrile itaconic acid of the 100g containing polyacrylonitrile（Mass ratio 97:3）/ dimethyl sulfoxide (DMSO) is common
Poly- stoste（20%wt）In, mechanical agitation 60min is uniformly dispersed；Under the conditions of 60~65 DEG C, graphene oxide dispersion is added, is stirred
90min is mixed, obtains blend spinning liquid；
Using wet spinning technology spinning, 60 DEG C of spinning temperature, coagulating bath 25%（wt%）Dimethyl sulfoxide (DMSO)-deionized water,
35 DEG C of coagulation bath temperature, 80 μm of spinneret orifice internal diameter, obtains compound protofibre；
Compound protofibre, which is put into pre-oxidation furnace, to be pre-oxidized and carbonizing reduction, pre-oxidizing conditions：Air atmosphere, 190 DEG C/
20min, 245 DEG C/30min and 270 DEG C/30min；Carbonizing reduction condition：Blanket of nitrogen, 750 DEG C/15min, naturally cool to room
Temperature, obtain nano-magnetic iron system of the present invention（Fe、Fe3O4、Fe4N）Graphene composite fibre absorbent.The μ of fibre diameter 25
M, density 3.1g/cm3。
After composite fibre is cut（Draw ratio 40,80,120 and 160）With paraffin（Mass ratio 1:1）It is mixed with thickness
2mm sample, the test reflectivity in 2 ~ 18GHz microwave frequency bands.The sample reflection loss peak that draw ratio is 40 for-
16.7dB, below reflection loss -10dB Absorber Bandwidth are up to 3.5GHz；The sample reflection loss peak that draw ratio is 80 for-
19.5dB, below reflection loss -10dB Absorber Bandwidth are up to 4.3GHz；The sample reflection loss peak that draw ratio is 120 for-
23.5dB, below reflection loss -10dB Absorber Bandwidth are up to 5.3GHz.The sample reflection loss peak that draw ratio is 160 for-
12.5dB, below reflection loss -10dB Absorber Bandwidth are 2.1GHz.
Comparative example
With embodiment five, spinning technique is changed to press mold technique and prepares absorbent for film-type absorbent, component ratio and process conditions
Film, 100 μm of film thickness, density 3.1g/cm3。
After laminated film is ground with paraffin（Mass ratio 1:1）The sample that thickness is 2mm is made after mixing, in 2 ~ 18GHz
Microwave frequency band internal reflection loss peak is -21.5dB, and below reflection loss -10dB Absorber Bandwidth is up to 4.1GHz.
Embodiment six
12g graphene oxides and 400mLN'N dimethyl formamide solutions are mixed, at room temperature magnetic agitation 30min, ultrasonic wave
90min is handled, obtains graphene oxide dispersion；
20g nano-cobalt powders are doped into polyacrylonitrile/N'N dimethyl formamide solutions of the 100g containing polyacrylonitrile（25%wt）In,
Mechanical agitation 75min is uniformly dispersed；Under the conditions of 60~65 DEG C, graphene oxide dispersion is added, 90min is stirred, is mixed
Spinning solution；
Spinning, 63 DEG C of spinning temperature, coagulating bath 10% are carried out using dry-jet wet spinning process（wt%）N'N dimethylformamides-
Deionized water, 40 DEG C of coagulation bath temperature, 80 μm of spinneret orifice internal diameter, obtain compound protofibre；
Compound protofibre, which is put into pre-oxidation furnace, to be pre-oxidized and carbonizing reduction, pre-oxidizing conditions：Blanket of nitrogen, 185 DEG C of guarantors
Warm 40min, 265 DEG C are warming up to through 40min, is incubated 40min, heat treatment time is 120min altogether；Carbonizing reduction condition：Nitrogen
Atmosphere, 700 DEG C/20min, room temperature is naturally cooled to, obtain nano-magnetic cobalt system of the present invention（Co、Co3O4）Graphene is compound
Fibrous absorber.22 μm of fibre diameter, density 3.5g/cm3。
After composite fibre is cut（Draw ratio 80）With paraffin（Mass ratio 1:1）Thickness 2mm sample is mixed with, 2 ~
18GHz microwave frequency band internal reflection loss peaks are -21.6dB, and below reflection loss -10dB Absorber Bandwidth is up to 4.5GHz.
Embodiment seven
12g graphene oxides, 3g graphenes and 500mL dimethyl sulphoxide solutions are mixed, at room temperature magnetic agitation 45min, surpassed
Sonicated 90min, obtain admixed graphite alkene material dispersion liquid；
25g nanometer iron powders are doped into acrylonitrile itaconic acid-acrylic acid of the 100g containing polyacrylonitrile（Mass ratio 96:2:2）/ bis-
Methyl sulfoxide is copolymerized stoste（30%wt）In, mechanical agitation 90min is uniformly dispersed；Under the conditions of 60~70 DEG C, admixed graphite alkene is added
Material dispersion liquid, 120min is stirred, 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, spinneret orifice
100 μm of internal diameter, obtains compound protofibre；
Compound protofibre, which is put into pre-oxidation furnace, to be pre-oxidized and carbonizing reduction, pre-oxidizing conditions：Air atmosphere, exist respectively
190 DEG C, 230 DEG C and 270 DEG C pre-oxidation 30min；Carbonizing reduction condition：Blanket of nitrogen, 600 DEG C/30min, room temperature is naturally cooled to,
Obtain nano-magnetic iron system of the present invention（Fe、Fe3O4）Graphene composite fibre absorbent.30 μm of fibre diameter, density
3.5g/cm3。
After composite fibre is cut（Draw ratio 60）With paraffin（Mass ratio 1:1）Thickness 2mm sample is mixed with, 2 ~
18GHz microwave frequency band internal reflection loss peaks are -19.7dB, and below reflection loss -10dB Absorber Bandwidth is up to 3.9GHz.
Embodiment eight
By graphene oxide, acrylonitrile, itaconic acid and methacrylic acid（Mass ratio 1:94:3:3）It is stirred, dimethyl sulfoxide (DMSO)
For solvent, graphene oxide-polyacrylonitrile polymer fluid is obtained after polymerisation in solution（21% wt）；
By nanoflakes and cobalt hydroxide（Cobalt hydroxide and graphene oxide mass ratio are 8:1）It is doped into graphene oxide-polyacrylonitrile
In polymer fluid, under the conditions of 50~60 DEG C, mechanical agitation 90min, blend spinning liquid is obtained；
Using wet spinning technology spinning, 50 DEG C of spinning temperature, coagulating bath 5%（wt%）Dimethyl sulfoxide (DMSO)-deionized water, coagulate
Gu 25 DEG C of bath temperature, 30 μm of spinneret orifice internal diameter, obtain compound protofibre；
Compound protofibre, which is put into pre-oxidation furnace, to be pre-oxidized and carbonizing reduction, pre-oxidizing conditions：Blanket of nitrogen, 160 DEG C/
20min, 200 DEG C/25min is warming up to through 15min, is warming up to 270 DEG C/25min through 20min, heat treatment time is 105min altogether；
Carbonizing reduction condition：Blanket of nitrogen, 850 DEG C/25min, room temperature is naturally cooled to, obtain nano-magnetic cobalt system of the present invention
（Co3O4）Graphene composite fibre absorbent.10 μm of fibre diameter, density 2.5g/cm3。
After composite fibre is cut（Draw ratio 250）With paraffin（Mass ratio 1:1）Thickness 2mm sample is mixed with, 2
~ 18GHz microwave frequency band internal reflection loss peaks are -13.7dB, and below reflection loss -10dB Absorber Bandwidth is up to 3.1GHz.
Claims (9)
1. a kind of graphene composite fibre absorbent, using polyacrylonitrile-based carbon fibre as carrier, fibre diameter between 5~30 μm it
Between, density is not more than 3.5g/cm3, the quality group of material active principle turns into：
0.5~15 part of graphene,
1~25 part of magnetic material,
The solid part of polyacrylonitrile 100；
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 is nanoscale ferromagnetic metal powder or its change
At least one in compound.
2. graphene composite fibre absorbent according to claim 1, the quality group of effective material component turn into：
2~10 parts of graphene,
5~15 parts of magnetic material,
The solid part of polyacrylonitrile 100.
3. graphene composite fibre absorbent according to claim 1, the quality group of effective material component turn into：
5~12 parts of graphene,
10~20 parts of magnetic material,
The solid part of polyacrylonitrile 100.
4. the graphene composite fibre absorbent according to claims 1 to 3 any one, Fiber Aspect Ratio between 40~
Between 400.
5. the graphene composite fibre absorbent according to claims 1 to 3 any one, 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 kind or wherein several mixed systems in acid.
6. the graphene composite fibre absorbent according to claims 1 to 3 any one, the polyacrylonitrile is 15wt%
~30wt% dimethyl sulfoxide (DMSO), dimethyl acetamide or N'N dimethylformamide solution.
7. the preparation method of the graphene composite fibre absorbent according to claims 1 to 3 any one, including spinning solution
Preparation, spinning, pre-oxidation treatment and carbonizing reduction process, it is characterised in that：
It is prepared by spinning solution：Grapheme material is distributed in solvent；Magnetic material is dispersed in polyacrylonitrile polymer fluid；45~65
DEG C both are mixed and are uniformly dispersed, obtain 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 30~100mm；
Pre-oxidation：Pre-oxidizing conditions be air or nitrogen atmosphere, 150~270 DEG C/60~120min；
Carbonizing reduction：Carbonization Conditions are inert atmosphere, 600~900 DEG C/5~30min.
8. the preparation method of graphene composite fibre absorbent according to claim 7, it is characterised in that：It is prepared by spinning solution
Method is grapheme material, acrylonitrile and comonomer combined polymerization, adds magnetic material and is uniformly dispersed.
9. the preparation method of graphene composite fibre absorbent according to claim 7, it is characterised in that：Carbonizing reduction mistake
The inert atmosphere of journey is nitrogen atmosphere.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108315834A (en) * | 2018-01-26 | 2018-07-24 | 渤海大学 | A kind of preparation method of array magnetizing reduction graphene oxide-carbon nanofibers |
| 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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| CN110656403B (en) * | 2019-11-07 | 2022-04-05 | 武汉纺织大学 | Easily-conductive metal-doped polyacrylonitrile carbon fiber and preparation method thereof |
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| CN111050536B (en) * | 2019-12-27 | 2021-02-26 | 南昌联能科技有限公司 | Shielding film of cable and method for connecting cable and connector |
| CN111676548A (en) * | 2020-07-21 | 2020-09-18 | 和爱电磁兼容科技(安徽)有限公司 | Carbon material high-temperature wave-absorbing composite material and preparation method thereof |
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| CN113652769B (en) * | 2021-08-30 | 2023-08-22 | 中国工程物理研究院激光聚变研究中心 | Core-shell Fe 3 Preparation of C/C fiber composite wave absorber and application thereof in microwave absorption |
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