CN108976718A - A kind of epoxy resin base electro-magnetic screen composite material and preparation method thereof - Google Patents
A kind of epoxy resin base electro-magnetic screen composite material and preparation method thereof Download PDFInfo
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- CN108976718A CN108976718A CN201810914287.7A CN201810914287A CN108976718A CN 108976718 A CN108976718 A CN 108976718A CN 201810914287 A CN201810914287 A CN 201810914287A CN 108976718 A CN108976718 A CN 108976718A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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Abstract
The present invention provides a kind of epoxy resin base electro-magnetic screen composite materials and preparation method thereof.The method comprises the steps of firstly, preparing amination ferroso-ferric oxide-graphite oxide aerogels；Then it handles to obtain amination ferroso-ferric oxide-redox graphene aeroge by thermal reduction；Amination ferroso-ferric oxide-redox graphene aeroge is poured using epoxy resin liquid in a mold again, vacuum defoamation and solidification is then successively carried out, obtains epoxy resin base electro-magnetic screen composite material.The present invention makes graphene form the graphene aerogel with three-dimensional structure by self assembly, to effectively prevent its reunion in resin matrix；Conductive network of the three-dimensional structure network of graphene as epoxy inner simultaneously, can significantly improve the electromagnetic shielding performance of composite material；Amination ferroso-ferric oxide is supported in graphene aerogel simultaneously, and magnetic hystersis loss can be also generated to electromagnetic wave, further promotes the electromagnetic shielding performance of composite material.
Description
Technical field
The present invention relates to the technical field of electromagnetic shielding material, in particular to a kind of epoxy resin base electro-magnetic screen composite wood
Material and preparation method thereof.
Background technique
With the high speed development of modern electronics industry, electromagnetic interference and electromagnetic radiation pollution are increasingly severe, in order to anti-
Only interference and leakage caused by electromagnetic radiation, carrying out shielding using electromagnetic shielding material is one of main prevention method.Tradition
Electromagnetic shielding material be metal material, such as copper, aluminium, steel metal product, but metal electromagnetic shielding material density is big, intolerant to
Corrosion, thus limit its application.
Conductive carbon/polymer composites are because light weight, corrosion-resistant and with certain shielding properties and by science
The extensive concern on boundary and industry.Graphene has high specific surface area, excellent electric conductivity, is expected to as electromagnetic shielding
Candidate materials, but graphene disperses bad, easy reunion in polymer resin matrix, and single graphene/polymer matrix is multiple
The electromagnetic shielding performance of condensation material is not high, is not able to satisfy requirement of the existing electronic equipment to electromagnetic shielding performance.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of epoxy resin base electro-magnetic screen composite material and its preparation sides
Method.Composite material electromagnetic shielding performance provided by the invention is good, and graphene is not in agglomeration.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of preparation method of epoxy resin base electro-magnetic screen composite material, comprising the following steps:
Ultrasound and heating stirring are successively carried out after amination ferroso-ferric oxide, graphene oxide and water are mixed, and obtain ammonia
Base ferroso-ferric oxide-graphene oxide dispersion；
It is successively carried out at gelation after the amination ferroso-ferric oxide-graphene oxide dispersion and reducing agent are mixed
Reason and freeze-drying, obtain amination ferroso-ferric oxide-graphite oxide aerogel；
Amination ferroso-ferric oxide-the graphite oxide aerogel is subjected to thermal reduction processing, obtains four oxygen of amination
Change three-iron-redox graphene aeroge；
Amination ferroso-ferric oxide-redox graphene the aeroge is placed in mold, epoxy resin liquid is used
Amination ferroso-ferric oxide-redox graphene the aeroge is poured, makes the amination ferroso-ferric oxide-also
Former graphite oxide aerogel is immersed in epoxy resin liquid, is then successively carried out vacuum defoamation and solidification, is obtained epoxy resin
Base electro-magnetic screen composite material；It include epoxy resin and curing agent in the epoxy resin liquid.
Preferably, the reducing agent includes one or more of L-AA, ethylenediamine and sodium hydrogensulfite.
Preferably, the mass ratio of the amination ferroso-ferric oxide, graphene oxide and water is 0.5~2:3.8~3.9:
30；
The mass ratio of the water and reducing agent is 30:7.6~7.8.
Preferably, the temperature of the gelation processing is 30~50 DEG C, and the time is 11~13hrs.
Preferably, the temperature of the freeze-drying is -50~-60 DEG C, and the time is 36~48hrs.
Preferably, the thermal reduction processing carries out in a nitrogen atmosphere；The temperature of the thermal reduction processing is 750~850
DEG C, the time is 25~35min.
Preferably, the mass ratio of the epoxy resin in the epoxy resin liquid and graphene oxide is 100:3.8~3.9；
The mass ratio of epoxy resin and curing agent in the epoxy resin liquid is 100:26~27.
Preferably, the temperature of the vacuum defoamation is 100~105 DEG C, and the time is 1~2hrs.
Preferably, the cured temperature is 120~125 DEG C, and the time is 5~6hrs.
The present invention provides the epoxy resin base electro-magnetic screen composite materials of the preparation of preparation method described in above scheme, including
Epoxy resin-base, the redox graphene aeroge being cast in inside the epoxy resin-base and be supported on it is described also
Amination ferroso-ferric oxide in former graphite oxide aerogel.
The present invention provides a kind of preparation methods of epoxy resin base electro-magnetic screen composite material, comprising the following steps: first
Ultrasound and heating stirring are successively carried out after will first amination ferroso-ferric oxide, graphene oxide and water being mixed, obtains amination
Ferroso-ferric oxide-graphene oxide dispersion；Then amination ferroso-ferric oxide-graphene oxide dispersion and reducing agent are mixed
Gelation processing and freeze-drying are successively carried out after conjunction, obtain amination ferroso-ferric oxide-graphite oxide aerogel；Then lead to
Overheat reduction treatment obtains amination ferroso-ferric oxide-redox graphene aeroge；Use epoxy resin in a mold again
Liquid is poured the amination ferroso-ferric oxide-redox graphene aeroge, then successively carry out vacuum defoamation and
Solidification, obtains epoxy resin base electro-magnetic screen composite material.The present invention, which is constructed by self-assembly method using graphene, has three-dimensional
The graphene aerogel of structure, to effectively prevent its reunion in resin matrix, low stone is may be implemented in three-dimensional net structure
The efficient formation of resin matrix inner conductive network under black alkene loading；The three-dimensional structure network of graphene is as asphalt mixtures modified by epoxy resin simultaneously
Conductive network inside rouge can greatly improve multiple absorption, reflection and interior scattering of the composite material to incident electromagnetic wave, from
And significantly improve the electromagnetic shielding performance of composite material；Amination ferroso-ferric oxide is supported in graphene aerogel simultaneously,
Also magnetic hystersis loss can be generated to electromagnetic wave, further improves the electromagnetic shielding performance of composite material.Embodiment the result shows that, this
The electromagnet shield effect for inventing the composite material provided is 28~35dB, meets existing electronic equipment to electromagnetic shielding performance
It is required that.
Detailed description of the invention
Fig. 1 is the SEM figure of amination ferroferric oxide/reduced graphene oxide aeroge prepared by the embodiment of the present invention 1.
Specific embodiment
The present invention provides a kind of preparation methods of epoxy resin base electro-magnetic screen composite material, comprising the following steps:
Ultrasound and heating stirring are successively carried out after amination ferroso-ferric oxide, graphene oxide and water are mixed, and obtain ammonia
Base ferroso-ferric oxide-graphene oxide dispersion；
It is successively carried out at gelation after the amination ferroso-ferric oxide-graphene oxide dispersion and reducing agent are mixed
Reason and freeze-drying, obtain amination ferroso-ferric oxide-graphite oxide aerogel；
Amination ferroso-ferric oxide-the graphite oxide aerogel is subjected to thermal reduction processing, obtains four oxygen of amination
Change three-iron-redox graphene aeroge；
Amination ferroso-ferric oxide-redox graphene the aeroge is placed in mold, epoxy resin liquid is used
Amination ferroso-ferric oxide-redox graphene the aeroge is poured, makes the amination ferroso-ferric oxide-also
Former graphite oxide aerogel is immersed in epoxy resin liquid, is then successively carried out vacuum defoamation and solidification, is obtained epoxy resin
Base electro-magnetic screen composite material；It include epoxy resin and curing agent in the epoxy resin liquid.
The present invention is to the amination ferroso-ferric oxide (NH2-Fe3O4) source there is no particular/special requirement, in tool of the invention
In body embodiment, using commercially available amination ferroso-ferric oxide or voluntarily prepare, in the present invention, four oxygen of amination
Change three-iron to be preferably prepared by following steps:
Ferroso-ferric oxide, ammonium persulfate, acrylic acid and water are mixed, acrylic acid is performed etching to ferroso-ferric oxide, obtains
To carboxylated ferroso-ferric oxide；
The carboxylated ferroso-ferric oxide, water and polyamines are mixed, the carboxylic of polyamines and carboxylated ferroso-ferric oxide surface is made
Base carries out amidation process, obtains amination ferroso-ferric oxide.
In the present invention, the mass ratio of the ferroso-ferric oxide, ammonium persulfate, water and acrylic acid is preferably 0.4~1.6:
0.25~1:100:2.5~10, more preferably 0.5~1.2:0.3~0.5:100:3~8.In the present invention, the water is preferred
For deionized water；The temperature of the etching is preferably 70~80 DEG C, and more preferably 75 DEG C, the time of the etching is preferably 3~
4hrs, more preferably 3.5hrs；The present invention preferably carries out acrylic acid to the etching of ferroso-ferric oxide, the present invention under agitation
There is no particular/special requirement to the revolving speed of the stirring, uses speed of agitator well known to those skilled in the art.
Ferroso-ferric oxide and ammonium persulfate are preferably added to the water progress ultrasound at room temperature by the present invention, obtain four oxidations three
Then ferroso-ferric oxide dispersion liquid is warming up to etching temperature, then ferroso-ferric oxide dispersion liquid is added in acrylic acid by iron dispersion liquid
In.In the present invention, the power of the ultrasound is preferably 200W, and the time of the ultrasound is preferably 20~30min, more preferably
25min, the present invention make ferroso-ferric oxide be uniformly dispersed by ultrasound.
After the completion of etching, present invention preferably uses magnet adsorbed products, obtain carboxylated ferroso-ferric oxide.
After obtaining carboxylated ferroso-ferric oxide, the present invention mixes the carboxylated ferroso-ferric oxide, water and polyamines, makes more
Amine and the carboxyl on carboxylated ferroso-ferric oxide surface carry out amidation process, obtain amination ferroso-ferric oxide.In the present invention,
The mass ratio of the carboxylated ferroso-ferric oxide, water and polyamines is preferably 0.6~1.4:100:4~16；The water is preferably gone
Ionized water, the polyamines are preferably ethylenediamine, triethylamine or hexamethylene diamine；The temperature of the amidation process is preferably 70~80
DEG C, more preferably 75 DEG C, the time of the amidation process is preferably 3~4hrs, more preferably 3.5hrs.
The carboxylated ferroso-ferric oxide is preferably added to the water by the present invention, obtains carboxylated ferroso-ferric oxide dispersion liquid,
Then carboxylated ferroso-ferric oxide dispersion liquid is warming up to 70~80 DEG C, then carboxylated ferroso-ferric oxide dispersion liquid is added in polyamines
Middle carry out amidation process.
After the completion of amidation process, the present invention preferably uses magnet adsorbed product, and then successively product is washed and done
It is dry, obtain amination ferroso-ferric oxide (NH2-Fe3O4).The present invention is to the volume and washing times of the water scouring water without spy
It is different to require, the impurity of surface can be cleaned up；In the present invention, the temperature of the drying is preferably 60~70
DEG C, more preferably 65 DEG C, the time of the drying is preferably 12~rs, more preferably 15~20hrs for 24 hours.
The present invention does not have particular/special requirement to the source of the graphene oxide (GO), in a specific embodiment of the present invention,
It is preferred that preparing graphene oxide by Hummers method, the present invention prepares the Hummers method using natural graphite flakes as raw material
The method of graphene oxide does not have particular/special requirement, uses Hummers method well known to those skilled in the art.
After obtaining amination ferroso-ferric oxide and graphene oxide, the present invention will be by amination ferroso-ferric oxide, oxidation stone
Ultrasound and heating stirring are successively carried out after black alkene and water mixing, obtains amination ferroso-ferric oxide-graphene oxide dispersion.?
In the present invention, the water is preferably deionized water, and the mass ratio of the amination ferroso-ferric oxide, graphene oxide and water is preferred
For 0.5~2:3.8~3.9:30, more preferably 1~1.5:3.85:30.In the present invention, the power of the ultrasound is preferably
The time of 450W, the ultrasound are preferably 20~30min, more preferably 25min.The present invention makes ferroso-ferric oxide point by ultrasound
It dissipates uniform.
In the present invention, the temperature of the heating stirring be 70~90 DEG C, more preferably 80 DEG C, the heating stirring when
Between preferably 2~3hrs, more preferably 2hrs；The present invention does not have particular/special requirement to the revolving speed of the stirring, uses this field skill
Speed of agitator known to art personnel.In the present invention, the surface of graphene oxide contains the oxygen-containing groups such as carboxyl, is adding
During thermal agitation, the amino and the carboxyl of surface of graphene oxide on amination ferroso-ferric oxide surface etc. react, thus
It is supported on ferroso-ferric oxide on graphene oxide, ferroso-ferric oxide can increase magnetic hystersis loss, further increase epoxidation tree
The electromagnetic shielding performance of resin-based composite.In the present invention, the revolving speed of the stirring is preferably 450rpm, and the present invention is by stirring
Mixing dissolves reducing agent sufficiently.
After obtaining amination ferroso-ferric oxide-graphene oxide dispersion, the present invention is by the amination ferroso-ferric oxide-
Gelation processing and freeze-drying are successively carried out after graphene oxide dispersion and reducing agent mixing, obtains the oxidation of amination four three
Iron-graphite oxide aerogel.In the present invention, the reducing agent preferably includes L-AA, ethylenediamine and bisulfite
One or more of sodium, more preferably L-AA；The mass ratio of the reducing agent and water is preferably 7.6~7.8:30.
Preferably reducing agent is added again after amination ferroso-ferric oxide-graphene oxide dispersion is cooling by the present invention.
In the present invention, the temperature of gelation processing is preferably 30~50 DEG C, and more preferably 40 DEG C, the time is preferably
11~13hrs, more preferably 12hrs.The present invention preferably passes through standing and carries out gelation processing, in gelation treatment process,
Graphene oxide is issued in reducing agent effect is born from assembling, forms the amination ferroso-ferric oxide-oxygen with three-dimensional net structure
Graphite alkene hydrogel.
After obtaining hydrogel, the hydrogel is freeze-dried by the present invention, obtains amination ferroso-ferric oxide-oxidation
Graphene aerogel.In the present invention, the temperature of the freeze-drying is preferably -50~-60 DEG C, more preferably -56 DEG C, described
The time of freeze-drying is preferably 36~48hrs, more preferably 48hrs.The present invention will be in the hydrogel by freeze-drying
Water removal.
After obtaining amination ferroso-ferric oxide-graphite oxide aerogel, the present invention is by the amination ferroso-ferric oxide-
Graphite oxide aerogel carries out thermal reduction processing, obtains amination ferroso-ferric oxide-redox graphene aeroge (NH2-
Fe3O4/TAGA).In the present invention, the thermal reduction processing preferably carries out in a nitrogen atmosphere；The temperature of the thermal reduction processing
The time of preferably 750~850 DEG C, more preferably 800 DEG C, the thermal reduction processing is preferably 25~35min, more preferably
30min.In the present invention, the graphene oxide electric conductivity is poor, and the present invention is handled graphene oxide also by thermal reduction
It originally was the graphene of good conductivity.
After obtaining amination ferroso-ferric oxide-redox graphene aeroge, the present invention aoxidizes the amination four
Three-iron-redox graphene aeroge is placed in mold, using epoxy resin liquid to the amination ferroso-ferric oxide-reduction
Graphite oxide aerogel is poured, and the amination ferroso-ferric oxide-redox graphene aeroge is made to be immersed in ring
In oxygen resin liquid, vacuum defoamation and solidification are then successively carried out, epoxy resin base electro-magnetic screen composite material (NH is obtained2-
Fe3O4/ TAGA/ epoxy resin electromagnetic shielding composite material).In the present invention, in the epoxy resin liquid include epoxy resin and
The mass ratio of curing agent, epoxy resin and graphene oxide in the epoxy resin liquid is preferably 100:3.8~3.9, more excellent
It is selected as 100:3.85；The mass ratio of epoxy resin and curing agent in the epoxy resin liquid is preferably 100:26~27, more excellent
It is selected as 100:26.5；The present invention does not have particular/special requirement to the curing agent, uses epoxy resin well known to those skilled in the art
Curing agent, preferably curing agent EK3402.
The present invention is stirred after preferably mixing epoxy resin and curing agent, obtains epoxy resin liquid.In the present invention,
The temperature of the stirring is preferably 70~80 DEG C, and more preferably 75 DEG C；The time of the stirring is preferably 20~30min, more excellent
It is selected as 25min；The revolving speed of the stirring is preferably 200rpm.
The present invention does not have particular/special requirement to the size of the mold, in a specific embodiment of the present invention, preferably according to ammonia
Base ferroso-ferric oxide-redox graphene aeroge volume determines the size of mold；The present invention makes epoxy by casting
The aeroge is coated on inside by resin liquid, so that aeroge is formed the three-dimensional conductive network inside epoxy resin-base, simultaneously
Epoxy resin liquid can also enter in aeroge duct in casting process, avoid graphene in conventional method and be not easy to disperse, and be easy
The problem of reunion.
After casting complete, casting system is successively carried out vacuum defoamation and solidification by the present invention, obtains epoxy resin-matrix electromagnetism
Shielding composite.In the present invention, the temperature of the vacuum defoamation is preferably 100~105 DEG C, more preferably 100 DEG C, described
The time of vacuum defoamation is preferably 1~2hrs, more preferably 1.5hrs；The cured temperature is preferably 120~125 DEG C, more
Preferably 120 DEG C, the cured time is preferably 5~6hrs, more preferably 5hrs.
After the completion of solidification, epoxy resin-matrix electromagnetism is can be obtained in die sinking after cured product is preferably cooled to room temperature by the present invention
Shielding composite；In a specific embodiment of the present invention, various sizes of epoxy resin-matrix electromagnetic screen can be obtained by polishing
Cover composite sample.
The present invention provides the epoxy resin base electro-magnetic screen composite materials of the preparation of preparation method described in above scheme, including
Epoxy resin-base, the redox graphene aeroge being cast in inside the epoxy resin-base and be supported on it is described also
Amination ferroso-ferric oxide in former graphite oxide aerogel.In the present invention, the redox graphene is with aeroge
Form is present in inside epoxy resin-base, to effectively prevent its reunion in resin；The three-dimensional structure of aeroge simultaneously
Network can greatly improve multiple absorption, reflection and interior scattering of the composite material to incident electromagnetic wave as conductive network, thus
Significantly improve the electromagnetic shielding performance of composite material；Load has amination ferroso-ferric oxide in graphene aerogel simultaneously,
Magnetic hystersis loss can be generated to electromagnetic wave, further promote the electromagnetic shielding performance of composite material.Composite material provided by the invention
Electromagnet shield effect be 28~35dB, meet requirement of the existing electronic equipment to electromagnetic shielding performance.
Below with reference to embodiment to epoxy resin base electro-magnetic screen composite material provided by the invention and preparation method thereof into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) preparation of graphene oxide: by the natural graphite flakes of 0.5 parts by weight, 0.75 parts by weight potassium peroxydisulfate, 0.75 weight
98% concentrated sulfuric acid for measuring part phosphorus pentoxide and 4 parts by weight is uniformly mixed, and 75 DEG C are stirred to react 5hrs, and 100 weight are then added
Part deionized water, is filtered.Under condition of ice bath, products therefrom after suction filtration is mixed with 98% concentrated sulfuric acid of 20 parts by weight
It is even, the potassium permanganate of 2 parts by weight is added, stirs 20min；It is warming up to 35 DEG C to continue to stir 2hrs, adds going for 20 parts by weight
Ionized water stirs 10min, continues thereafter with the aqueous hydrogen peroxide solution of deionized water and 5 parts by weight 35% that 30 parts by weight are added,
Solution becomes golden yellow；Dilute hydrochloric acid washing, the centrifugation of deionized water, 10 parts by weight by 100 parts by weight, freeze at -56 DEG C
After dry 48hrs, GO is made.
(2) preparation of amination ferroso-ferric oxide: by the Fe of 0.4 parts by weight3O4It is added to 0.25 parts by weight ammonium persulfate
In the deionized water of 100 parts by weight, with the power ultrasound 30min of 200W, 80 DEG C are warming up to, 2.5 parts by weight of acrylic acid, machine is added
Tool stirs 4hrs and removes supernatant with magnet adsorbed product；Product is added in the deionization of 100 parts by weight and is warming up to 80
DEG C, 4 parts by weight ethylenediamines are added, mechanical stirring 4hrs washs 3 with magnet adsorbed product and with the deionized water of 200 parts by weight
Secondary, NH is made in 60 DEG C of dry 12hrs2-Fe3O4。
(3) amination ferroso-ferric oxide-redox graphene aeroge preparation: by 0.5 parts by weight NH2-Fe3O4With 3.8
Parts by weight GO is added in the deionization of 30 parts by weight, with the power ultrasound 30min of 450W, is then stirred to react at 80 DEG C
2hrs obtains amination ferroso-ferric oxide-redox graphene dispersion liquid, 7.6 parts by weight is added into dispersion liquid after cooling
L-AA, at normal temperature with the revolving speed mechanical stirring 20min of 400rpm, then in 40 DEG C of reaction 12hrs, finally at -56 DEG C
Lower freeze-drying 48hrs obtains amination ferroso-ferric oxide-graphite oxide aerogel；
(4) thermal reduction is handled: under the atmosphere of nitrogen, by amination ferroso-ferric oxide-redox graphene aeroge
30min is heat-treated at 800 DEG C, NH is made2-Fe3O4/ redox graphene aeroge (NH2-Fe3O4/TAGA)；
(5) it is poured: by NH2-Fe3O4/ TAGA is placed in mold, then by 100 parts by weight epoxy resin and 26.5 parts by weight
Curing agent (EK3402), with the revolving speed mechanical stirring 30min of 200rpm, is then poured into mold at 70 DEG C, true at 100 DEG C
Then empty deaeration 1hr is solidified by 120 DEG C/5hrs technique, be cooled to room temperature to be opened and answer up to epoxy resin base electro-magnetic screen
Condensation material (NH2-Fe3O4/ TAGA/ epoxy resin electromagnetic shielding composite material).
Gained NH2-Fe3O4/ redox graphene aeroge (NH2-Fe3O4/ TAGA) SEM figure as shown in Figure 1, according to
Fig. 1 can be seen that aeroge with three-dimensional net structure.
After tested, prepared NH2-Fe3O4/ TAGA/ epoxy resin electromagnetic shielding composite material electromagnetic shielding performance is
28dB。
Embodiment 2
(1) graphene oxide (GO) is prepared according to the method for embodiment 1.
(2) amination ferroso-ferric oxide (NH is prepared according to the method for embodiment 12-Fe3O4)。
(3) amination ferroso-ferric oxide-redox graphene aeroge preparation: by 0.97 parts by weight NH2-Fe3O4With
3.87 parts by weight GO are added in the deionization of 30 parts by weight, with power 20~30min of ultrasound of 450W, are then stirred at 80 DEG C
Reaction 2h is mixed, amination ferroso-ferric oxide-redox graphene dispersion liquid is obtained, 7.7 weights is added into dispersion liquid after cooling
Part L-AA is measured, at normal temperature with revolving speed 15~20min of mechanical stirring of 400rpm, then in 40 DEG C of reaction 12hrs, finally
It is freeze-dried 48hrs at -56 DEG C, obtains amination ferroso-ferric oxide-graphite oxide aerogel；
(4) thermal reduction is handled: in a nitrogen atmosphere, by amination ferroso-ferric oxide-graphite oxide aerogel at 800 DEG C
NH is made in lower thermal reduction 30min2-Fe3O4/ redox graphene aeroge (NH2-Fe3O4/TAGA)；
(5) it is poured: by NH2-Fe3O4/ TAGA is placed in mold, then by 100 parts by weight epoxy resin and 26.5 parts by weight
Curing agent (EK3402), with revolving speed 20~30min of mechanical stirring of 200rpm, is then poured into mold, 100 DEG C at 70 DEG C
Then lower vacuum defoamation 1hr is solidified by 120 DEG C/5hrs technique, be cooled to room temperature and be opened up to NH2-Fe3O4/ TAGA/ ring
Oxygen resin electromagnetic shielding composite material.
After tested, prepared NH2-Fe3O4/ TAGA/ epoxy resin electromagnetic shielding composite material electromagnetic shielding performance is
31dB。
Embodiment 3
(1) graphene oxide (GO) is prepared according to the method for embodiment 1.
(2) amination ferroso-ferric oxide (NH is prepared according to the method for embodiment 12-Fe3O4)。
(3) amination ferroso-ferric oxide-redox graphene aeroge preparation: by 2 parts by weight NH2-Fe3O4With 3.9 weights
Amount part GO is added in the deionization of 30 parts by weight, with power 20~30min of ultrasound of 450W, is then stirred to react at 80 DEG C
2hrs obtains amination ferroso-ferric oxide-redox graphene dispersion liquid, 7.8 parts by weight is added into dispersion liquid after cooling
L-AA, at normal temperature with revolving speed 15~20min of mechanical stirring of 400rpm, then in 40 DEG C of reaction 12hrs, finally-
It is freeze-dried 48hrs at 56 DEG C, obtains amination ferroso-ferric oxide-graphite oxide aerogel；
(4) thermal reduction is handled: under the atmosphere of nitrogen, by amination ferroso-ferric oxide -800 DEG C of graphite oxide aerogel
NH is made in lower thermal reduction 30min2-Fe3O4/ thermal reduction graphite oxide aerogel (NH2-Fe3O4/TAGA)；
(5) it is poured: by NH2-Fe3O4/ TAGA is placed in mold, then by 100 parts by weight epoxy resin and 26.5 parts by weight
Curing agent (EK3402), with revolving speed 20~30min of mechanical stirring of 200rpm, is then poured into mold, 100 DEG C at 70 DEG C
Then lower vacuum defoamation 1hr is solidified by 120 DEG C/5hrs technique, be cooled to room temperature and be opened up to NH2-Fe3O4/ TAGA/ ring
Oxygen resin electromagnetic shielding composite material.
After tested, prepared NH2-Fe3O4/ TAGA/ epoxy resin electromagnetic shielding composite material electromagnetic shielding performance is
35dB。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of epoxy resin base electro-magnetic screen composite material, comprising the following steps:
Ultrasound and heating stirring are successively carried out after amination ferroso-ferric oxide, graphene oxide and water are mixed, and obtain amination
Ferroso-ferric oxide-graphene oxide dispersion；
Will the amination ferroso-ferric oxide-graphene oxide dispersion and reducing agent mix after successively carry out gelation processing and
Freeze-drying, obtains amination ferroso-ferric oxide-graphite oxide aerogel；
Amination ferroso-ferric oxide-the graphite oxide aerogel is subjected to thermal reduction processing, obtains the oxidation of amination four three
Iron-redox graphene aeroge；
Amination ferroso-ferric oxide-redox graphene the aeroge is placed in mold, using epoxy resin liquid to institute
It states amination ferroso-ferric oxide-redox graphene aeroge to be poured, makes the amination ferroso-ferric oxide-oxygen reduction
Graphite alkene aeroge is immersed in epoxy resin liquid, then successively carries out vacuum defoamation and solidification, obtains epoxy resin-matrix electricity
Magnetic screen composite material；It include epoxy resin and curing agent in the epoxy resin liquid.
2. preparation method according to claim 1, which is characterized in that the reducing agent includes L-AA, ethylenediamine
One or more of with sodium hydrogensulfite.
3. preparation method according to claim 1 or 2, which is characterized in that the amination ferroso-ferric oxide, graphite oxide
The mass ratio of alkene and water is 0.5~2:3.8~3.9:30；
The mass ratio of the water and reducing agent is 30:7.6~7.8.
4. preparation method according to claim 1, which is characterized in that the temperature of the gelation processing is 30~50 DEG C,
Time is 11~13hrs.
5. preparation method according to claim 1, which is characterized in that the temperature of the freeze-drying is -50~-60 DEG C,
Time is 36~48hrs.
6. preparation method according to claim 1, which is characterized in that the thermal reduction processing carries out in a nitrogen atmosphere；
The temperature of the thermal reduction processing is 750~850 DEG C, and the time is 25~35min.
7. preparation method according to claim 1, which is characterized in that epoxy resin and oxidation in the epoxy resin liquid
The mass ratio of graphene is 100:3.8~3.9；
The mass ratio of epoxy resin and curing agent in the epoxy resin liquid is 100:26~27.
8. preparation method according to claim 1, which is characterized in that the temperature of the vacuum defoamation is 100~105 DEG C,
Time is 1~2hrs.
9. preparation method according to claim 1, which is characterized in that the cured temperature is 120~125 DEG C, the time
For 5~6hrs.
10. the epoxy resin base electro-magnetic screen composite material of the preparation of preparation method described in claim 1~9 any one, including
Epoxy resin-base, the redox graphene aeroge being cast in inside the epoxy resin-base and be supported on it is described also
Amination ferroso-ferric oxide in former graphite oxide aerogel.
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| CN109928713A (en) * | 2019-04-09 | 2019-06-25 | 天津大学 | MXene hydrogel and its liquid phase assemble method |
| CN110562962A (en) * | 2019-08-28 | 2019-12-13 | 同济大学 | super-elastic magnetic graphene aerogel and preparation method thereof |
| CN111542213A (en) * | 2020-05-11 | 2020-08-14 | 向怀珍 | Manganese-zinc ferrite-graphene composite electromagnetic shielding material and preparation method thereof |
| CN111592376A (en) * | 2020-06-08 | 2020-08-28 | 北京化工大学 | Composite aerogel functional material based on ferroferric oxide nanowire/graphene oxide interpenetrating structure and preparation method thereof |
| CN113015422A (en) * | 2021-02-22 | 2021-06-22 | 山东大学 | Cobalt-nickel alloy/reduced graphene oxide nanocomposite for shielding high-frequency electromagnetic waves, and preparation method and application thereof |
| CN113930055A (en) * | 2021-11-04 | 2022-01-14 | 合肥晋怡科技有限公司 | Preparation method of anti-lightning antistatic epoxy resin |
| CN113980427A (en) * | 2021-11-01 | 2022-01-28 | 陕西工业职业技术学院 | Epoxy resin-based biomass charcoal electromagnetic shielding composite material and preparation method thereof |
| CN115212814A (en) * | 2022-07-14 | 2022-10-21 | 北京旭碳新材料科技有限公司 | Graphene composite aerogel composition, graphene composite aerogel, and preparation method and application thereof |
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| CN109928713A (en) * | 2019-04-09 | 2019-06-25 | 天津大学 | MXene hydrogel and its liquid phase assemble method |
| CN110562962A (en) * | 2019-08-28 | 2019-12-13 | 同济大学 | super-elastic magnetic graphene aerogel and preparation method thereof |
| CN110562962B (en) * | 2019-08-28 | 2021-07-06 | 同济大学 | Super-elastic magnetic graphene aerogel and preparation method thereof |
| CN111542213A (en) * | 2020-05-11 | 2020-08-14 | 向怀珍 | Manganese-zinc ferrite-graphene composite electromagnetic shielding material and preparation method thereof |
| CN111592376A (en) * | 2020-06-08 | 2020-08-28 | 北京化工大学 | Composite aerogel functional material based on ferroferric oxide nanowire/graphene oxide interpenetrating structure and preparation method thereof |
| CN113015422A (en) * | 2021-02-22 | 2021-06-22 | 山东大学 | Cobalt-nickel alloy/reduced graphene oxide nanocomposite for shielding high-frequency electromagnetic waves, and preparation method and application thereof |
| CN113980427A (en) * | 2021-11-01 | 2022-01-28 | 陕西工业职业技术学院 | Epoxy resin-based biomass charcoal electromagnetic shielding composite material and preparation method thereof |
| CN113930055A (en) * | 2021-11-04 | 2022-01-14 | 合肥晋怡科技有限公司 | Preparation method of anti-lightning antistatic epoxy resin |
| CN115212814A (en) * | 2022-07-14 | 2022-10-21 | 北京旭碳新材料科技有限公司 | Graphene composite aerogel composition, graphene composite aerogel, and preparation method and application thereof |
| CN115212814B (en) * | 2022-07-14 | 2023-11-03 | 北京旭碳新材料科技有限公司 | Graphene composite aerogel composition, graphene composite aerogel, and preparation method and application thereof |
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