CN107354500B - A kind of nanoscale Fe3O4The glass fiber compound material and preparation method thereof of grapheme modified cladding - Google Patents
A kind of nanoscale Fe3O4The glass fiber compound material and preparation method thereof of grapheme modified cladding Download PDFInfo
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- CN107354500B CN107354500B CN201710569523.1A CN201710569523A CN107354500B CN 107354500 B CN107354500 B CN 107354500B CN 201710569523 A CN201710569523 A CN 201710569523A CN 107354500 B CN107354500 B CN 107354500B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
Abstract
The invention discloses a kind of nanoscale Fe3O4The glass fiber compound material of grapheme modified cladding, comprising the following steps: (1) glass fibre is put into Muffle furnace and is calcined, be sequentially placed into acetone, handle in lye；(2) by the aqueous solution of treated glass fibre is placed in silane coupling agent, infiltrate in bovine serum albumin solution after taking out cleaning, clean be placed in graphene oxide suspension again, it after drying, is put into sodium borohydride alkaline solution, heats, stirring, it is dry；(3) using redox graphene/glass fibre as anode, tiselius apparatus is constructed by cathode of carbon-point, with Fe3O4Suspension is plating solution, carries out electrophoretic deposition to graphene/glass fibre, composite material is made.The invention discloses the composite materials of this method preparation simultaneously.Composite material prepared by the present invention has higher magnetic conductivity under the premise of guaranteeing conductive capability, can promote its performance in terms of electromagnetic shielding.
Description
Technical field
The present invention relates to a kind of composite material, in particular to a kind of nanoscale Fe3O4The glass fibre of grapheme modified cladding
Composite material and preparation method.
Background technique
With the development of science and technology and electronics industry, various electronic equipments using increasing, form electromagnetic pollution.
Electromagenetic wave radiation can not only damage human health, interfere the normal work of electronic instrument, also will cause the leakage of confidential information, because
This, research and develop High Performance Shielding material, reduce electromagnetic pollution to for us social life and national defense construction all have it is important
Meaning.
Graphene be one kind by carbon atom with sp2The honeycomb flat film that hybrid form is formed, be it is a kind of only one
There is the quasi- two-dimensional material of atomic layer level thickness good conductive, heating conduction and mechanical property, electron mobility can reach 2
×105cm2/ VS, temperature stability is high, and for conductivity up to 108 Ω/m, surface resistance is about 31 Ω/sq(310 Ω/m2), compare copper
Or silver is lower, is conductive best material at room temperature.And large specific surface area (2630m2/g), thermal conductivity (are at room temperature
5000W·m-1·K-1) it is 36 times of silicon, 20 times of GaAs are copper (401WmK at room temperature) more than ten times.Single layer stone
The thermal coefficient of black alkene is up to 5300W/mK, or even some researches show that its thermal coefficients to be up to 6600W/mK.Graphene is existing
The most hard and highest material of intensity, elasticity modulus 1.1Tpa, tensile strength 125Gpa in material.
Glass fibre as a kind of technical fiber material, be by glass raw material under high temperature fused state wire drawing preparation and
At with a series of excellent performance energy such as high temperature resistant, resist chemical, intensity height, modulus height.Glass fibre has become resin base
One of most important reinforcing material of composite material has obtained abundant application in fields such as Aeronautics and Astronautics, naval vessel, chemical industry metallurgicals.
Ferroso-ferric oxide is a kind of oxide of iron, chemical formula Fe3O4.Ferroso-ferric oxide has ferromagnetism, such as fruit shape
At particle radius in Nano grade, referred to as magnetic particles of ferroferric oxide.In contemporary electrified and informationized society, magnetic material
Expect very widely used.Fe 3 O 4 magnetic material is inhaled as a kind of multifunction magnetic material in the treatment of tumour, microwave
Receipts material, catalyst carrier, cell separation, magnetic recording material, magnetic fluid, medicine and other fields have been widely used.
Summary of the invention
The invention discloses a kind of nanoscale Fe3O4The preparation method of the glass fiber compound material of grapheme modified cladding,
The composite material of this method preparation improves the technique that graphene is coated in fiberglass surfacing, and with electrophoretic deposition in stone
Nanoscale ferroso-ferric oxide is deposited on black alkene/glass fibre, high magnetic permeability graphene coated glass fibre is made, and is had better
Electromagnetic shielding performance.
A kind of nanoscale Fe3O4The preparation method of the glass fiber compound material of grapheme modified cladding, including following step
It is rapid:
(1) surface treatment of glass fibre: glass fibre being put into Muffle furnace and is calcined, and is sequentially placed into acetone, in lye
Processing；
(2) graphene oxide/glass fibre preparation: by step (1), treated, and glass fibre is placed in silane coupling agent
Aqueous solution, take out cleaning after infiltrate in bovine serum albumin solution, again cleaning be placed on graphene oxide suspend
It in liquid, after drying, is put into sodium borohydride alkaline solution, heats, stir, it is dry, graphene oxide/glass fibre is made；
(3) modification of magnetic material: using manufactured graphene oxide/glass fibre in step (2) as anode, it is with carbon-point
Cathode constructs tiselius apparatus, with the Fe of 1.0-1.5mg/ml3O4Suspension is plating solution, carries out electrophoresis to graphene oxide/glass fibre
Deposition, is made nanoscale Fe3O4The glass fiber compound material of grapheme modified cladding.
Preferably, it is 455-500 DEG C that glass fibre is put into the temperature calcined in Muffle furnace in the step (1), calcining
Time is 1-2 hours；The concentration of lye is 1wt.%-30wt.% in the step (1), and the processing time is 0.5-6 hours.
It is highly preferred that step (1) lye is sodium hydroxide solution, concentration 25wt.%.
Preferably, in the step (2), the aqueous solution of silane coupling agent is the aqueous solution of kh550, concentration 1wt.%-
5wt.%, the time being placed in silane coupling agent aqueous solution are 5min-10min.The treatment process of silane coupling agent can obviously increase
The solidification effect of BSA.
Preferably, the concentration of bovine serum albumin solution is 1-1.5wt.% in the step (2), and infiltration is pure to ox blood
Time in protein solution is 4h.
Preferably, the concentration of graphene oxide suspension is 0.08-0.12wt.%, the temperature of drying in the step (2)
It is 60 DEG C, drying time is 0.5 hour.
Preferably, the concentration of sodium borohydride alkaline solution is 1.5g/L, pH value 10-13, hydroboration in the step (2)
The temperature of sodium alkaline solution is 80 DEG C, time 3h, dry temperature 60 C, time 1h.
Preferably, in the step (3), Fe3O4Nano-scale particle, partial size 60-100nm are prepared for hydro-thermal method.
Preferably, in the step (3), the DC voltage of electrophoresis is 12v-21v, and the electrophoretic deposition time is 60min.
The present invention discloses the composite materials of above-mentioned preparation method preparation.
Beneficial effects of the present invention
The present invention provides a kind of nanoscale Fe3O4The preparation method of the glass fiber compound material of grapheme modified cladding, will
Graphene is compound with glass fibre, is modified with ferroso-ferric oxide, selects suitable experimental condition, the composite material of preparation, relatively
Than other binary composites, electromagnetic shielding performance with higher.
Detailed description of the invention
Fig. 1 is Fe prepared by embodiment 13O4Graphene-glass fiber compound material SEM figure；
Fig. 2 is Fe prepared by embodiment 13O4Graphene-glass fiber compound material EDS test；
Fig. 3 is that the composite material of embodiment preparation and unmodified composite material electromagnet shield effect compare.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
(1) glass fibre is calcined into 455 DEG C of Muffle furnaces 60min, removes surface size, then glass fibre exists
Cleaning treatment in acetone, it is finally modified to fiberglass surfacing with 25wt.% sodium hydroxide solution liquid.
(2) 15min in the aqueous solution for the kh550 that glass fibre handled by step (1) is placed in 2.5wt.% takes out cleaning
4h in 1.5wt.% bovine serum albumin solution is infiltrated afterwards, and cleaning is placed on the suspension of 0.12wt.% graphene oxide again
60min in liquid, deionized water cleaning, drying, the temperature of drying are 60 DEG C, and drying time is 0.5 hour, then is dipped in
1.5g/L, pH value 10,3h in the sodium borohydride alkaline solution that temperature is 80 DEG C, take out dry temperature 60 C, time 1h.
(3) using graphene-glass as anode, tiselius apparatus is constructed by cathode of carbon-point, is 80nm ferroso-ferric oxide by partial size
1.5mg/ml suspension is made in nano particle ultrasonic disperse in deionized water, as plating solution, to graphene-under 15V voltage
Glass carries out electrophoretic deposition 60min, nanoscale Fe3O4The glass fiber compound material of grapheme modified cladding.
Attached drawing 1 is Fe prepared by embodiment 13O4Graphene-glass fiber compound material SEM figure；Attached drawing 2 is embodiment
The Fe of 1 preparation3O4Graphene-glass fiber compound material EDS test.
Embodiment 2
(1) glass fibre is calcined into 460 DEG C of Muffle furnaces 60min, removes surface size, then glass fibre exists
Cleaning treatment in acetone, it is finally modified to fiberglass surfacing with 15wt.% sodium hydroxide solution liquid.
(2) 15min in the aqueous solution for the kh550 that glass fibre handled by step (1) is placed in 4wt.%, after taking out cleaning
4h in 1.5wt.% bovine serum albumin solution is infiltrated, cleaning is placed in 0.1wt.% graphene oxide suspension again
60min, deionized water cleaning, drying, the temperature of drying are 60 DEG C, and drying time is 0.5 hour, then be dipped in 1.5g/L,
3h in the sodium borohydride alkaline solution that pH value is 13, temperature is 80 DEG C, takes out dry temperature 60 C, time 1h.
(3) using graphene-glass fibre as anode, tiselius apparatus is constructed by cathode of carbon-point, is that 60nm tetra- is aoxidized by partial size
1.0mg/ml suspension is made in three iron nano-particle ultrasonic disperses in deionized water, as plating solution, to graphite under 18V voltage
Alkene/glass carries out electrophoretic deposition 60min, nanoscale Fe3O4The glass fiber compound material of grapheme modified cladding.
Embodiment 3
(1) glass fibre is calcined into 500 DEG C of Muffle furnaces 60min, removes surface size, then glass fibre exists
Cleaning treatment in acetone, it is finally modified to fiberglass surfacing with 20wt.% sodium hydroxide solution liquid.
(2) glass fibre handled by step (1) is placed in 15min in the aqueous solution of 2.5wt.% silane coupling agent, taken out clear
4h in 1.0wt.% bovine serum albumin solution is infiltrated after washing, it is outstanding to be placed on 0.08wt.% graphene oxide for cleaning again
60min in supernatant liquid, deionized water cleaning, drying, the temperature of drying are 60 DEG C, and drying time is 0.5 hour, then is dipped in
1.5g/L, pH value 12,3h in the sodium borohydride alkaline solution that temperature is 80 DEG C, take out dry temperature 60 C, time 1h.
(3) using graphene-glass as anode, tiselius apparatus is constructed by cathode of carbon-point, is 100nm ferroso-ferric oxide by partial size
1.5mg/ml suspension is made in nano particle ultrasonic disperse in deionized water, as plating solution, to graphene-under 21V voltage
Glass carries out electrophoretic deposition 60min, nanoscale Fe3O4The glass fiber compound material of grapheme modified cladding.
Comparative example 1
(1) glass fibre is placed in in 400 DEG C of Muffle furnace thermal cleaning and handles 50min, then in turn through acetone,
The hydrochloric acid solution of 6mol/L, deionized water cleaning are subsequently placed in spare after drying in 60 DEG C of baking oven；
(2) it will be put in the bovine serum albumin(BSA) 50ml solution that mass fraction is 1.0% by pretreated glass fibre
Immersion treatment 60min, it is during which, primary every 5min lifting；
(3) at room temperature, the ultrapure aqueous dispersions 50ml of graphite oxide that mass fraction is 0.1% is prepared, by bovine serum albumin
The glass fibre of white functionalization impregnation 30min in graphite oxide dispersion takes out, and is rinsed with deionized water；Then
It is placed in 55 DEG C of baking ovens and is dried for standby；
(4) hydroiodic acid, acetic acid solution 10ml is prepared with the ratio of volume ratio 1:2 to be placed in sealing container, while will
To graphite oxide cladding glass fibre fixed on the upper layer of closed container, reduction-oxidation graphite 20min, obtains at 40 DEG C
Graphene coated glass fiber compound material.
Comparative example 2
(1) graphene oxide water solution is prepared, and it is molten that the dispersion of 0.1mg/ml graphene oxide is obtained after ultrasonic disperse processing
Liquid；Compound concentration is the ferrous sulfate aqueous solution of 0.2mol/L again；
(2) the graphene oxide dispersion solution of step (1) is heated to 50 DEG C and continual ultrasonic 30min, by ferrous sulfate
Aqueous solution is slowly dropped to graphene oxide dispersion solution, and rate of addition 5ml/min obtains precursor mixed solution；
(3) precursor mixed solution of step (2) is heated to 90 DEG C and continual ultrasonic 30min, is added 30ml's
The sodium hydrate aqueous solution of 0.1mol/L, regulation system pH value are 10；
(4) after reaction system is maintained at 90 DEG C and continual ultrasonic reaction 120min, reaction product is obtained, rear Magneto separate is multiple
It is dried in vacuo 8h at 60 DEG C later, obtained black powder is ferroso-ferric oxide/graphene oxide composite material.
Comparative example 3
(1) glass fibre is calcined into 400 DEG C of Muffle furnaces 50min, removes surface size, successively by acetone,
The hydrochloric acid solution of 6mol/L, deionized water cleaning are subsequently placed in spare after drying in 60 DEG C of baking oven.
(2) it will be put in the bovine serum albumin(BSA) 50ml solution that mass fraction is 1.0% by pretreated glass fibre
Immersion treatment 60min, it is during which, primary every 5min lifting.At room temperature, it is ultrapure to prepare the graphite oxide that mass fraction is 0.1%
Aqueous dispersions 50ml, by the glass fibre of bovine serum albumin(BSA) functionalization in graphite oxide dispersion impregnation 30min, take
Out, and with deionized water it rinses；It is subsequently placed in 55 DEG C of baking ovens and is dried for standby.
(3) using graphene-glass as anode, tiselius apparatus is constructed by cathode of carbon-point, is 80nm ferroso-ferric oxide by partial size
1.5mg/ml suspension is made in nano particle ultrasonic disperse in deionized water, as plating solution, to graphene-under 15V voltage
Glass carries out electrophoretic deposition 60min, the glass fiber compound material of the grapheme modified cladding of nanoscale Fe3O4.Fig. 3 is embodiment
The composite material of preparation and unmodified composite material electromagnet shield effect compare.
Claims (10)
1. a kind of nanoscale Fe3O4The preparation method of the glass fiber compound material of grapheme modified cladding, which is characterized in that packet
Include following steps:
(1) surface treatment of glass fibre: glass fibre being put into Muffle furnace and is calcined, and is sequentially placed into acetone, is handled in lye；
(2) graphene oxide/glass fibre preparation: by step (1), treated that glass fibre is placed in the water-soluble of silane coupling agent
Liquid is infiltrated in bovine serum albumin solution after taking out cleaning, and cleaning is placed in graphene oxide suspension again, is dried
It after dry, is put into sodium borohydride alkaline solution, heats, stir, it is dry, graphene oxide/glass fibre is made；
(3) modification of magnetic material: using graphene oxide/glass fibre in step (2) as anode, electricity is constructed by cathode of carbon-point
Swimming pool, with the Fe of 1.0-1.5mg/ml3O4Suspension is plating solution, carries out electrophoretic deposition to graphene oxide/glass fibre, is made
Nanoscale Fe3O4The glass fiber compound material of grapheme modified cladding.
2. preparation method as described in claim 1, glass fibre in being put into Muffle furnace by feature in the step (1)
The temperature of calcining is 455-500 DEG C, and calcination time is 1-2 hours；
The concentration of lye is 1wt.%-30wt.% in the step (1), and the processing time is 0.5-6 hours.
3. preparation method as described in claim 1, feature is in step (1) lye is sodium hydroxide solution, and concentration is
25wt.%。
4. preparation method as described in claim 1, feature is in the step (2), the aqueous solution of silane coupling agent is
The aqueous solution of kh550, concentration 1wt.%-5wt.%, the time being placed in silane coupling agent aqueous solution are 5min-15min.
5. preparation method as described in claim 1, feature is in the concentration of bovine serum albumin solution in the step (2)
For 1-1.5wt.%, the time infiltrated into bovine serum albumin solution is 4h.
6. preparation method as described in claim 1, feature is in the concentration of graphene oxide suspension in the step (2)
For 0.08-0.12wt.%, the temperature of drying is 60 DEG C, and drying time is 0.5 hour.
7. preparation method as described in claim 1, feature is in the concentration of sodium borohydride alkaline solution in the step (2)
For 1.5g/L, pH value 10-13, the temperature of sodium borohydride alkaline solution is 80 DEG C, time 3h, dry temperature 60 C, when
Between be 1h.
8. preparation method as described in claim 1, feature in, in the step (3), Fe3O4Nanometer is prepared for hydro-thermal method
Grade particles, partial size 60-100nm.
9. preparation method as described in claim 1, feature is in the step (3), the DC voltage of electrophoresis is 12v-
21v, electrophoretic deposition time are 60min.
10. the nanoscale Fe of the preparation of preparation method described in a kind of one of claim 1-93O4The glass of grapheme modified cladding
Fibrous composite.
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| CN109706737A (en) * | 2019-01-22 | 2019-05-03 | 重庆纤维研究设计院股份有限公司 | Based on the modified glass fibre guard glass fibre cotton and preparation method thereof with thermal insulation performance of bovine serum albumin(BSA) and graphene oxide |
| CN109867455B (en) * | 2019-03-06 | 2020-04-21 | 内蒙古世环新材料股份有限公司 | High-modulus environment-friendly glass fiber and processing technology thereof |
| CN112047646A (en) * | 2020-08-27 | 2020-12-08 | 泰山玻璃纤维有限公司 | Preparation method of graphene-coated glass fiber |
| CN112055528A (en) * | 2020-09-15 | 2020-12-08 | 福州大学 | Preparation method of graphene-coated glass fiber reinforced plastic |
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| CN104163578A (en) * | 2014-07-22 | 2014-11-26 | 杭州杭复新材料科技有限公司 | Preparation method of graphene coated composite glass fiber |
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| CN104163578A (en) * | 2014-07-22 | 2014-11-26 | 杭州杭复新材料科技有限公司 | Preparation method of graphene coated composite glass fiber |
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