CN103951916B - Polyvinylidene difluoride (PVDF) composite wave-suction material that a kind of RGO/ ferric oxide is filled and preparation method thereof - Google Patents

Polyvinylidene difluoride (PVDF) composite wave-suction material that a kind of RGO/ ferric oxide is filled and preparation method thereof Download PDF

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CN103951916B
CN103951916B CN201410176439.XA CN201410176439A CN103951916B CN 103951916 B CN103951916 B CN 103951916B CN 201410176439 A CN201410176439 A CN 201410176439A CN 103951916 B CN103951916 B CN 103951916B
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rgo
ferric oxide
pvdf
polyvinylidene difluoride
shell structure
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CN103951916A (en
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陈德志
权红英
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Nanchang Hangkong University
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Nanchang Hangkong University
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Abstract

The invention discloses polyvinylidene difluoride (PVDF) composite wave-suction material of a kind of RGO/ ferric oxide filling and preparation method thereof, composite wave-suction material comprises RGO/ ferric oxide core-shell structure nanometer particle, polyvinylidene difluoride (PVDF); In RGO/ ferric oxide core-shell structure nanometer particle, RGO and ferric oxide mass ratio are 20% ﹕ 80%, in composite wave-suction material, RGO/ ferric oxide core-shell structure nanometer particle is 1 ~ 20%, polyvinylidene difluoride (PVDF) is 80-99%, RGO/ ferric oxide core-shell structure nanometer particle is filled in polyvinylidene difluoride (PVDF) by the present invention, when inorganic nano-particle mass ratio is 5%, maximum reflection loss when inorganic/organic composite absorbing material thickness is 2mm is issued to-39.43dB at frequency 14Hz, and reflection loss reaches 6.0GHz (11.28 ~ 17.28GHz) lower than the bandwidth of-10dB.Advantage of the present invention is: this composite wave-suction material has the features such as quality is light, corrosion-resistant, absorbing property is good, easy processing, and preparation method is simple simultaneously, easily realizes suitability for industrialized production.

Description

Polyvinylidene difluoride (PVDF) composite wave-suction material that a kind of RGO/ ferric oxide is filled and preparation method thereof
Technical field
The present invention relates to inorganic/organic composite absorbing material and preparation method thereof, be specifically related to polyvinylidene difluoride (PVDF) composite wave-suction material of a kind of RGO/ ferric oxide filling and preparation method thereof.
Technical background
The investigation and application of material obsorbing radar waves (abbreviation absorbing material) is the key factor of stealthy technique development.Along with the development of the radar exploration technique, huge challenge is proposed to absorbing material, in the urgent need to the multifunctional ceiling wave material of the advantage the whole bodys such as collection " thickness is thin, quality is light, frequency range is wide, absorptions strong ".Often there is the shortcomings such as frequency band is narrow, density is large, matching thickness is large in traditional absorbing material, is difficult to meet above-mentioned composite request.
Graphene (graphene) be grow up recent years a kind of by carbon atom with the two-dimensional and periodic honeycomb lattice structural carbon material of sp2 hydridization bonding.Graphene has a large amount of electron channels, effectively microwave energy can be changed into heat energy, is a kind of potential lightweight microwave absorbing material [X.Sun, J.He, G.Li, J.Tang, T.Wang, Y.GuoandH.Xue, JournalofMaterialsChemistryC2013,1,765-777.].Utilize graphite for starting material, by chemistry redox method, graphene-based nanometer sheet RGO(can be prepared on a large scale and have another name called: the graphene oxide of reduction).Based on the oxy radical of its remained on surface and defect and suitable electroconductibility, compare graphite, carbon nanotube and high-quality graphene, RGO shows more excellent microwave absorbing property [C.Wang, X.Han, P.Xu, X.Zhang, Y.Du, S.Hu, J.WangandX.Wang, AppliedPhysicsLetters2011,98,072906.].But due to the Van der Waals force that sheet interlayer is stronger, RGO easily assembles, and has a strong impact on its performance.
Summary of the invention
The object of the invention is to solve prior art Problems existing, provide the polyvinylidene difluoride (PVDF) composite wave-suction material that a kind of RGO/ ferric oxide is filled, this material has the advantages that quality is light, corrosion-resistant, absorbing property is good and easily process; Preparation method is simple, is applicable to suitability for industrialized production.
Technical scheme of the present invention is: the polyvinylidene difluoride (PVDF) composite wave-suction material that a kind of RGO/ ferric oxide core-shell structure nanometer particle is filled, and this material comprises: RGO/ ferric oxide core-shell structure nanometer particle is polymeric matrix as inorganic non-metallic weighting agent, polyvinylidene difluoride (PVDF); It is characterized in that shared by each composition, mass ratio is: RGO/ ferric oxide core-shell structure nanometer particle 1-20%, polyvinylidene difluoride (PVDF) 80-99%; In described RGO/ ferric oxide nano particles, ferric oxide is wrapped in formation nucleocapsid structure by RGO; The thickness of RGO is 0.37nm-5nm, and structure is single or multiple lift; The particle diameter of ferric oxide is 120nm-200nm, and shape is polyhedron, and structure is monocrystalline.
RGO/ ferric oxide core-shell structure nanometer particle of the present invention, comprising: RGO nanoscale twins and ferric oxide, and its mass ratio is 20% ﹕ 80%.
The present invention preferably consists of RGO/ ferric oxide core-shell structure nanometer particle 5%, polyvinylidene difluoride (PVDF) 95%; During this composition, the maximum reflection loss of composite wave-suction material when thickness is 2mm is issued to-39.43dB at frequency 14Hz, and reflection loss reaches 6.0GHz (11.28 ~ 17.28GHz) lower than the bandwidth of-10dB.
The present invention's RGO/ ferric oxide core-shell structure nanometer particle used is prepared by simple wet chemical method, and polyvinylidene difluoride (PVDF) is Industrial products, without any process, so this matrix material is prepared simple, with low cost, is applicable to suitability for industrialized production.
The concrete preparation method of the polyvinylidene difluoride (PVDF) composite wave-suction material that RGO/ ferric oxide core-shell structure nanometer particle of the present invention is filled:
Step one: RGO/ ferric oxide core-shell structure nanometer particle; In 2L three-necked flask under strong stirring, successively the 80wt% hydrazine hydrate solution of 0.555g polypyrrole alkane ketone and 4mL is joined in the 0.25mg/mL graphene oxide solution of 1.5L, 90 DEG C and isothermal reaction add 30mL 2.5M ferric chloride Solution after 2 hours is heated under agitation condition, then 100 DEG C of isothermal reactions 24 hours are warming up to, be cooled to room temperature subsequently, by filtering separation, and fully wash rear 60 DEG C of dryings 24 hours with deionized water, collect black product;
Step 2: take the RGO/ ferric oxide core-shell structure nanometer particle of 1-20% and the polyvinylidene difluoride (PVDF) (each component sum is 100%) of 80-99% in mass ratio, add N, N-dimethylformamide, sonic oscillation 1h, makes RGO/ ferric oxide core-shell structure nanometer particle and polyvinylidene difluoride (PVDF) mix and naturally to dry afterwards;
Step 3: the compound of step 2 gained is loaded in mould, on thermocompressor, 180-200 DEG C, mold pressing 30min under 10-20MPa, then pressurize cooling, namely prepare the polyvinylidene difluoride (PVDF) composite wave-suction material that RGO/ ferric oxide core-shell structure nanometer particle is filled;
The invention has the advantages that: the matrix material prepared by (1) the present invention has unique structure and physico-chemical property, as: inorganic non-metallic weighting agent RGO/ ferric oxide uniqueness nucleocapsid structure between inorganic/inorganic interface that has and RGO/ polyvinylidene difluoride (PVDF) inorganic/organic interface structure, the thermal conductivity of RGO excellence and electric conductivity and the abundant oxy radical of RGO/ iron oxide surface and unsaturated outstanding key be all conducive to electromagnetic absorption and decay; (2) this matrix material has strong and wide electromagnetic absorption effect to 2-18GHz hertzian wave; (3) this matrix material quality is light; (4) in this matrix material, polymer-based carbon phase content is high, and the good processability of matrix material can be prepared into required shape.
Accompanying drawing explanation
Fig. 1 is RGO/ ferric oxide nucleocapsid structure SEM photo figure in the present invention.
Fig. 2 is the SEM photo figure of matrix material section in the embodiment of the present invention 3.
Fig. 3 is the reflection of electromagnetic wave extinction curve of matrix material when thickness is 2.0mm in embodiment 3 under room temperature.
Embodiment
Embodiment 1: preparation RGO/ ferric oxide core-shell structure nanometer particle mass ratio is the matrix material of 1wt%, and concrete steps are as follows:
(1): preparation RGO/ ferric oxide core-shell structure nanometer particle;
(2): take the RGO/ ferric oxide core-shell structure nanometer particle of 1% and the polyvinylidene difluoride (PVDF) of 99% in mass ratio, add DMF, sonic oscillation 1h, RGO/ ferric oxide core-shell structure nanometer particle and polyvinylidene difluoride (PVDF) are mixed;
(3): loaded in mould by the compound of above gained, on thermocompressor, 180 DEG C, mold pressing 30min under 15MPa, then pressurize cooling, namely preparing massfraction is the polyvinylidene difluoride (PVDF) composite wave-suction material that 1%RGO/ ferric oxide core-shell structure nanometer particle is filled.
Embodiment 2: preparation Fe 2o 3nanoparticle mass ratio is the matrix material of 2%, and concrete steps are as follows:
(1): preparation RGO/ ferric oxide core-shell structure nanometer particle;
(2): take the RGO/ ferric oxide core-shell structure nanometer particle of 2% and the polyvinylidene difluoride (PVDF) of 98% in mass ratio, add DMF, sonic oscillation 1h, RGO/ ferric oxide core-shell structure nanometer particle and polyvinylidene difluoride (PVDF) are mixed;
(3): loaded in mould by the compound of above gained, on thermocompressor, 180 DEG C, mold pressing 30min under 15MPa, then pressurize cooling, namely preparing massfraction is the polyvinylidene difluoride (PVDF) composite wave-suction material that 2%RGO/ ferric oxide core-shell structure nanometer particle is filled.
Embodiment 3: preparation RGO/ ferric oxide core-shell structure nanometer particle mass ratio is the matrix material of 5%, and concrete steps are as follows:
(1): preparation RGO/ ferric oxide core-shell structure nanometer particle;
(2): take the RGO/ ferric oxide core-shell structure nanometer particle of 5% and the polyvinylidene difluoride (PVDF) of 95% in mass ratio, add DMF, sonic oscillation 1h, RGO/ ferric oxide core-shell structure nanometer particle and polyvinylidene difluoride (PVDF) are mixed;
(3): loaded in mould by the compound of above gained, on thermocompressor, 180 DEG C, mold pressing 30min under 15MPa, then pressurize cooling, namely preparing massfraction is the polyvinylidene difluoride (PVDF) composite wave-suction material that 5%RGO/ ferric oxide core-shell structure nanometer particle is filled.
Embodiment 4: preparation RGO/ ferric oxide core-shell structure nanometer particle mass ratio is the matrix material of 10%, and concrete steps are as follows:
(1): preparation RGO/ ferric oxide core-shell structure nanometer particle; ;
(2): take the RGO/ ferric oxide core-shell structure nanometer particle of 10% and the polyvinylidene difluoride (PVDF) of 90% in mass ratio, add DMF, sonic oscillation 1h, RGO/ ferric oxide core-shell structure nanometer particle and polyvinylidene difluoride (PVDF) are mixed;
(3): loaded in mould by the compound of above gained, on thermocompressor, 180 DEG C, mold pressing 30min under 15MPa, then pressurize cooling, namely preparing massfraction is the polyvinylidene difluoride (PVDF) composite wave-suction material that 10%RGO/ ferric oxide core-shell structure nanometer particle is filled.
Embodiment 5: preparation RGO/ ferric oxide core-shell structure nanometer particle mass ratio is the matrix material of 15%, and concrete steps are as follows:
(1): preparation RGO/ ferric oxide core-shell structure nanometer particle;
(2): take the RGO/ ferric oxide core-shell structure nanometer particle of 15% and the polyvinylidene difluoride (PVDF) of 85% in mass ratio, add DMF, sonic oscillation 1h, RGO/ ferric oxide core-shell structure nanometer particle and polyvinylidene difluoride (PVDF) are mixed;
(3): loaded in mould by the compound of above gained, on thermocompressor, 180 DEG C, mold pressing 30min under 15MPa, then pressurize cooling, namely preparing massfraction is the polyvinylidene difluoride (PVDF) composite wave-suction material that 15%RGO/ ferric oxide core-shell structure nanometer particle is filled.
Embodiment 6: preparation RGO/ ferric oxide core-shell structure nanometer particle mass ratio is the matrix material of 20%, and concrete steps are as follows:
(1): preparation RGO/ ferric oxide core-shell structure nanometer particle;
(2): take the RGO/ ferric oxide core-shell structure nanometer particle of 20% and the polyvinylidene difluoride (PVDF) of 80% in mass ratio, add DMF, sonic oscillation 1h, RGO/ ferric oxide core-shell structure nanometer particle and polyvinylidene difluoride (PVDF) are mixed;
(3): loaded in mould by the compound of above gained, on thermocompressor, 180 DEG C, mold pressing 30min under 15MPa, then pressurize cooling, namely preparing massfraction is the polyvinylidene difluoride (PVDF) composite wave-suction material that 20%RGO/ ferric oxide core-shell structure nanometer particle is filled.

Claims (1)

1. a preparation method for the polyvinylidene difluoride (PVDF) composite wave-suction material of RGO/ ferric oxide filling, is characterized in that:
The polyvinylidene difluoride (PVDF) composite wave-suction material that described RGO/ ferric oxide is filled, it comprises: RGO/ ferric oxide core-shell structure nanometer particle is polymeric matrix as inorganic non-metallic weighting agent, polyvinylidene difluoride (PVDF); Wherein: shared by each composition, mass ratio is: RGO/ ferric oxide core-shell structure nanometer particle 1-20%, polyvinylidene difluoride (PVDF) 80-99%; In described RGO/ ferric oxide core-shell structure nanometer particle, ferric oxide is wrapped in formation nucleocapsid structure by RGO; The thickness of RGO is 0.37nm-5nm, and structure is single or multiple lift; The particle diameter of ferric oxide is 120nm-200nm, and shape is polyhedron, and structure is monocrystalline; And: described RGO/ ferric oxide core-shell structure nanometer particle, comprises RGO nanoscale twins and ferric oxide, and its mass ratio is 20%:80%;
Described preparation method's step is as follows:
The preparation of step (1) described RGO/ ferric oxide core-shell structure nanometer particle: in 2L three-necked flask under strong stirring, successively 80% hydrazine hydrate solution of 0.555g polypyrrole alkane ketone and 4mL is joined in the 0.25mg/mL graphene oxide solution of 1.5L, 90 DEG C and isothermal reaction add 30mL 2.5M ferric chloride Solution after 2 hours is heated under agitation condition, then 100 DEG C of isothermal reactions 24 hours are warming up to, be cooled to room temperature subsequently, pass through filtering separation, and fully wash rear 60 DEG C of dryings 24 hours with deionized water, collect black product;
Step (2): the nanoparticle that above-mentioned steps (1) prepares is mixed with organic polymer polyvinylidene difluoride (PVDF).
CN201410176439.XA 2014-04-29 2014-04-29 Polyvinylidene difluoride (PVDF) composite wave-suction material that a kind of RGO/ ferric oxide is filled and preparation method thereof Expired - Fee Related CN103951916B (en)

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