CN105482110A - PANI (polyaniline)/CoFe2O4/PVDF (polyvinylidene fluoride) wave-absorbing material and preparation method - Google Patents

PANI (polyaniline)/CoFe2O4/PVDF (polyvinylidene fluoride) wave-absorbing material and preparation method Download PDF

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CN105482110A
CN105482110A CN201511018217.6A CN201511018217A CN105482110A CN 105482110 A CN105482110 A CN 105482110A CN 201511018217 A CN201511018217 A CN 201511018217A CN 105482110 A CN105482110 A CN 105482110A
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pvdf
pani
cofe
absorbing material
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CN105482110B (en
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杨海波
韩宁
林营
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Abstract

The invention provides a PANI (polyaniline)/CoFe2O4/PVDF (polyvinylidene fluoride) wave-absorbing material and a preparation method. The preparation method comprises the following steps: adding PVDF and CoFe2O4 powder to hydrochloric acid, adding PANI after mixing the materials uniformly, stirring the materials in an ice bath for 30-60 minutes, naturally cooling the materials to be below zero, dropwise adding an ammonium persulfate solution and stirring the materials in the ice water bath for 8-10 hours after dropwise adding is completed, thus obtaining a mixed solution; carrying out suction filtration on the mixed solution, repeatedly washing the filtrate with ultrapure water until the filtrate is colorless to obtain a black product and drying the black product, thus obtaining the PANI/CoFe2O4/PVDF wave-absorbing material. The PANI/CoFe2O4/PVDF wave-absorbing material has the beneficial effects that an in-situ compound method is adopted and ammonium persulfate is compounded with CoFe2O4 and BaSr0.6Ti0.4O3 powder when inducing PANI to form a long molecular chain, thus being beneficial to matching of dielectric loss and magnetic loss and ensuring better wave absorbing properties of the wave-absorbing material; the prepared composite material has excellent wave absorbing properties and has maximum reflection loss of -27.4dB; the preparation process of the composite material is simple.

Description

A kind of PANI/CoFe 2o 4/ PVDF absorbing material and preparation method
Technical field
The invention belongs to material science, relate to a kind of PANI/CoFe 2o 4/ PVDF absorbing material and preparation method.
Background technology
Along with development that is scientific and technical and electronic industry, the harm of electromagnetic radiation is day by day serious, and the NEW TYPE OF COMPOSITE absorbing material simultaneously with magnetic loss and electrical loss becomes the focus of current research.Traditional electromagnetic shielding material, mainly by reflecting the object reaching shielding to hertzian wave.But, still can the normal work of electron device and the health of human body be had an impact to external world by the hertzian wave reflected.Therefore, be necessary, according to Electromagnetic theory and material and electromagnetic interaction principle, to carry out the compound of multiple different filler, develop, to hertzian wave, there is high-selenium corn, the electromagnetic shielding material of low reflection potential, i.e. absorbing material.At present, absorbing material towards being " thin, light, wide, strong ", namely require the coat-thickness of absorbing material thin, than important light, future development that absorption band is wide.But density is greatly a bottle item of ferrite application scope, therefore always finds wide, that absorptive character good and cost the is low microwave ferrite absorbing material of absorption frequency range in reality and seem very urgent.Improve the absorbing property of ferrite wave-absorbing material, reduce match materials thickness and application in low frequency field, mainly contain two kinds of approach at present: one is the multilayered structure by preparing material, make full use of the absorbing property of differing materials under different frequency range, composite wave-suction material is made to obtain optimum combination to greatest extent, thus meet multiband, the absorption of multimachine system, meet the over-all properties requirement of modern society to absorbing material.Two is improve material electromagnetic parameter value by the method such as ion substitution, preparation technology, increases loss with thinning coat-thickness.
CoFe 2o 4absorbing material is cheap because of it, and absorbing property is good, even if at low frequency, still has good absorbing property under the fickle condition of thickness, is one of absorbing material that research is more ripe at present, is still widely used so far from the fifties.CoFe 2o 4its dielectric is because the self poling effect of molecule causes, magnetic is then caused by the natural resonance of material, wherein natural resonance is that ferrite inhales the main mechanism of ripple, research find ferritic absorbing property and composition, technique, shape and frequency used closely related.In electric property, the resistivity of Ferrite Material is comparatively large, has higher dielectric properties; In magnetic property, ferrite has obvious ferrimagnetism, has higher magnetic permeability when high frequency.In recent years, along with multi-disciplinary crossing research, absorbing material has had larger space in the selection of material, and particularly with the compound with different qualities material, the absorbing property of absorbing material has had larger raising.PANI (aniline) and PVDF (poly-two vinylidenes) is how to make PANI and PVDF and matrix material thereof play maximum wave-sucking performance as electromagnetic-wave absorbent institute problems faced.On the one hand, the microwave electrical loss of PANI and PVDF and matrix material thereof is improved; On the other hand, good microwave absorbing is reached in conjunction with magnetic loss.For absorbing material, in succession carry out the research of conduction high polymer radar absorbing both at home and abroad, and made some progress.But with current range of application, simple magnetic loss type or dielectric loss type all can not meet the needs of application completely, and the people such as Jiang Junjun prepare polyaniline/CoFe by coordination-oxypolymerization-hydrothermal method 2o 4nano-complex and have studied its absorbing property, research finds that mixture is multilevel hierarchy, wherein CoFe 2o 4for cubic, median size is less than 20mm, when composite thickness is 2mm, is-16.71dB in the maximum reflection loss of 16.01GHz place.
The developing direction of following absorbing material is the composite wave absorption material integrating magnetic loss and electrical loss as can be seen here.Compound prepares organic/inorganic polynary nanometer matrix material, due to its surface effects, quantum effect and synergistic existence, the Effective Regulation to matrix material electricity, magnetic property can be realized, having the advantage that cannot replace than single polymkeric substance or inorganic nano material, is one of the desirable route of exploitation light weight, wideband, high-efficiency electromagnetic absorbing material.
Summary of the invention
The object of the present invention is to provide a kind of PANI/CoFe 2o 4/ PVDF absorbing material and preparation method, this absorbing material has excellent absorbing property, and maximum reflection loss reaches-27.4dB, and preparation technology is simple.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of PANI/CoFe 2o 4/ PVDF absorbing material, Reactive Synthesis expression formula is PANI/xCoFe 2o 4/ (1-x) PVDF, wherein x is 0.1 ~ 0.9.
Reactive Synthesis expression formula is PANI/xCoFe 2o 4/ (1-x) PVDF, wherein x is 0.3 ~ 0.9.
Reactive Synthesis expression formula is PANI/xCoFe 2o 4/ (1-x) PVDF, wherein x is 0.6 ~ 0.9.
A kind of PANI/CoFe 2o 4the preparation method of/PVDF absorbing material, comprises the following steps:
1) by PVDF and CoFe 2o 4powder joins in hydrochloric acid, adds aniline after mixing, under ice bath, stir 30-60min, and Temperature fall, to subzero, drips ammonium persulfate solution, drips after finishing and stir 8-10h in ice-water bath, obtain mixing solutions; Wherein, PVDF and CoFe 2o 4the mass ratio of powder is (1-x): x, x are 0.1 ~ 0.9, aniline and PVDF, CoFe 2o 4the ratio of the total mass of powder is (1 ~ 1.5): 1; Ammonium persulphate in ammonium persulfate solution and the mol ratio of aniline are (1 ~ 1.5): 1;
2) by mixing solutions suction filtration, with ultrapure water repetitive scrubbing until filtrate is colourless, obtain black product, obtain PANI/CoFe by after black product drying 2o 4/ PVDF absorbing material absorbing material.
Described concentration of hydrochloric acid is 1 ~ 2mol/L; PVDF, CoFe 2o 4the total mass of powder and the ratio of hydrochloric acid are 2g:50mL.
Mix and carry out under ultrasonic.
Rate of addition is 3s to 5s one.
Ammonium persulfate solution is obtained by being dissolved in by ammonium persulphate in hydrochloric acid, and concentration is 0.21mol/L.
Described drying is in vacuum drying oven, dry 18-24h under 60 DEG C of conditions.
Compared with prior art, the beneficial effect that the present invention has: the present invention adopts chemical oxidization method to prepare doped hydrochloride electrically conductive polyaniline, situ aggregation method preparation conduction PANI/CoFe 2o 4/ PVDF matrix material, obtains the matrix material simultaneously with electroconductibility, magnetic and nano effect.In addition, the present invention adopts the method for In-situ reaction, and ammonium persulphate brings out time aniline forms long molecular chain and CoFe 2o 4, BaSr 0.6ti 0.4o 3powder generation compound, is conducive to dielectric loss and magnetic loss reaches coupling, makes its absorbing property better.The matrix material that the present invention obtains has excellent absorbing property, and maximum reflection loss reaches-27.4dB, and the preparation technology of this matrix material is simple.Along with CoFe 2o 4the minimizing of content, saturation magnetization reduces 15.9-2.9emu/g gradually, and residual magnetization also reduces 7.9-1.5emu/g gradually; Work as CoFe 2o 4content is 90%, PVDF content when being 10%, and absorbing property is best, and maximum absorption can reach-27.4dB, and the absorption band width of below-10dB is 3.4GHz (7.2 ~ 10.6GHz).PANI/CoFe prepared by the present invention 2o 4/ PVDF absorbing material may be used for absorbing material and electrostatic shielding materials, the feature such as while possessing good suction wave energy, have both that quality is light, thickness is thin, broadband, compatible good and erosion resistance are strong.
Accompanying drawing explanation
Fig. 1 is concentration of hydrochloric acid is 2mol/mL, and aniline and ammonium persulphate mol ratio are 1:1, stir the XRD figure of gained powder PANI under condition of ice bath.
Fig. 2 is PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4mass percent composite granule XRD figure spectrum when be the mass percent of 90%, PVDF being 10%.
Fig. 3 is PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4mass percent composite granule XRD figure spectrum when be the mass percent of 70%, PVDF being 30%.
Fig. 4 is PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4mass percent composite granule XRD figure spectrum when be the mass percent of 50%, PVDF being 50%.
Fig. 5 is PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4mass percent composite granule XRD figure spectrum when be the mass percent of 30%, PVDF being 90%.
Fig. 6 is PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4mass percent composite granule XRD figure spectrum when be the mass percent of 10%, PVDF being 90%.
Fig. 7 is for work as PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4the magnetic hysteresis loop of mass percent composite granule when be the mass percent of 90%, PVDF being 10%.
Fig. 8 is for work as PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4the magnetic hysteresis loop of mass percent composite granule when be the mass percent of 70%, PVDF being 30%.
Fig. 9 is for work as PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4the magnetic hysteresis loop of mass percent composite granule when be the mass percent of 50%, PVDF being 50%.
Figure 10 is for work as PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4the magnetic hysteresis loop of mass percent composite granule when be the mass percent of 30%, PVDF being 70%.
Figure 11 is for work as PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4the magnetic hysteresis loop of mass percent composite granule when be the mass percent of 10%, PVDF being 90%.
Figure 12 is for work as PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4the reflection loss figure of mass percent composite granule when be the mass percent of 90%, PVDF being 10%.
Figure 13 is for work as PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4the reflection loss figure of mass percent composite granule when be the mass percent of 70%, PVDF being 30%.
Figure 14 is for work as PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4the reflection loss figure of mass percent composite granule when be the mass percent of 50%, PVDF being 50%.
Figure 15 is for work as PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4the reflection loss figure of mass percent composite granule when be the mass percent of 30%, PVDF being 70%.
Figure 16 is for work as PANI:(CoFe 2o 4+ PVDF) mass ratio=1:1 time, CoFe 2o 4the reflection loss figure of mass percent composite granule when be the mass percent of 10%, PVDF being 90%.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
The present invention is by aniline and ammonium persulphate according to mol ratio 1:1, and join in the hydrochloric acid of 50mL2mol/L, then under condition of ice bath, stir 8-10h, obtain PANI, wherein, aniline is 1g; Carried out XRD test to PANI, see Fig. 1, as can be seen from Figure 1, the PANI diffraction angle of synthesis is greatly about 22, about 27 degree, consistent with the peak of standard P ANI, illustrates that the PANI in embodiment of the present invention 1-7 is consistent with the peak of standard P ANI.
Embodiment 1
1) by PVDF and CoFe 2o 4powder joins in the hydrochloric acid of 2mol/L, adds aniline, under ice bath, stir 30min after mixing under ultrasonic, and Temperature fall is to subzero, and drip ammonium persulfate solution, rate of addition is 3s mono-, drips after finishing and stir 10h in ice-water bath, obtain mixing solutions; Wherein, PVDF (poly-two vinylidenes) and CoFe 2o 4the mass ratio of powder is (1-x): x, x are mass percent, and x is 0.9, aniline and PVDF, CoFe 2o 4the ratio of the total mass of powder is 1:1; Ammonium persulphate in ammonium persulfate solution and the mol ratio of aniline are 1:1; Ammonium persulfate solution is obtained by being dissolved in by ammonium persulphate in hydrochloric acid, and concentration is 0.21mol/L; PVDF, CoFe 2o 4the total mass of powder and the ratio of hydrochloric acid are 2g:50mL.
2) by mixing solutions suction filtration, with ultrapure water repetitive scrubbing until filtrate is colourless, obtain black product, by black product in vacuum drying oven, under 60 DEG C of conditions, dry 18h, obtains PANI/CoFe 2o 4/ PVDF absorbing material absorbing material.
As can be seen from Figure 2, CoFe 2o 4, PANI and PVDF characteristic diffraction peak, represent in composite granule the existence having three.
As can be seen from Figure 7, coercive field is 1709.1 (Oe), and saturation magnetization is 15.9 (emu/g), and residual magnetization is 7.9 (emu/g).
As can be seen from Figure 12, the maximum absorption of the matrix material that 3mm is thick can reach-27.4dB, and the absorption band width of below-10dB is 3.4GHz (7.2 ~ 10.6GHz).
Embodiment 2
1) by PVDF and CoFe 2o 4powder joins in the hydrochloric acid of 2mol/L, adds aniline, under ice bath, stir 30min after mixing under ultrasonic, and Temperature fall is to subzero, and drip ammonium persulfate solution, rate of addition is 4s mono-, drips after finishing and stir 8h in ice-water bath, obtain mixing solutions; Wherein, PVDF (poly-two vinylidenes) and CoFe 2o 4the mass ratio of powder is (1-x): x, x are mass percent, and x is 0.7, aniline and PVDF, CoFe 2o 4the ratio of the total mass of powder is 1:1; Ammonium persulphate in ammonium persulfate solution and the mol ratio of aniline are 1:1; Ammonium persulfate solution is obtained by being dissolved in by ammonium persulphate in hydrochloric acid, and concentration is 0.21mol/L; PVDF, CoFe 2o 4the total mass of powder and the ratio of hydrochloric acid are 2g:50mL.
2) by mixing solutions suction filtration, with ultrapure water repetitive scrubbing until filtrate is colourless, obtain black product, by black product in vacuum drying oven, under 60 DEG C of conditions, dry 20h, obtains PANI/CoFe 2o 4/ PVDF absorbing material absorbing material.
As can be seen from Figure 3 CoFe 2o 4, PANI and PVDF characteristic diffraction peak, represent in composite granule the existence having three.
As can be seen from Figure 8 coercive field is 1685.2 (Oe), and saturation magnetization is 13.3 (emu/g), and residual magnetization is 6.5 (emu/g).
As can be seen from Figure 13, the maximum absorption of the matrix material that 3mm is thick can reach-21.7dB, and the absorption band width of below-10dB is 3.3GHz (8.1 ~ 11.4GHz).
Embodiment 3
1) by PVDF and CoFe 2o 4powder joins in the hydrochloric acid of 2mol/L, adds aniline, under ice bath, stir 30min after mixing under ultrasonic, and Temperature fall is to subzero, and drip ammonium persulfate solution, rate of addition is 5s mono-, drips after finishing and stir 9h in ice-water bath, obtain mixing solutions; Wherein, PVDF (poly-two vinylidenes) and CoFe 2o 4the mass ratio of powder is (1-x): x, x are mass percent, and x is 0.5, aniline and PVDF, CoFe 2o 4the ratio of the total mass of powder is 1:1; Ammonium persulphate in ammonium persulfate solution and the mol ratio of aniline are 1:1; Ammonium persulfate solution is obtained by being dissolved in by ammonium persulphate in hydrochloric acid, and concentration is 0.21mol/L; PVDF, CoFe 2o 4the total mass of powder and the ratio of hydrochloric acid are 2g:50mL.
2) by mixing solutions suction filtration, with ultrapure water repetitive scrubbing until filtrate is colourless, obtain black product, by black product in vacuum drying oven, under 60 DEG C of conditions, dry 22h, obtains PANI/CoFe 2o 4/ PVDF absorbing material absorbing material.
As can be seen from Figure 4 CoFe 2o 4, PANI and PVDF characteristic diffraction peak, represent in composite granule the existence having three.
As can be seen from Figure 9 coercive field is 1709.1 (Oe), and saturation magnetization is 10.1 (emu/g), and residual magnetization is 4.9 (emu/g).
As can be seen from Figure 14, the maximum absorption of the matrix material that 3mm is thick can reach-15.9dB, and the absorption band width of below-10dB is 3.1GHz (7.4 ~ 10.5GHz).
Embodiment 4
1) by PVDF and CoFe 2o 4powder joins in the hydrochloric acid of 2mol/L, adds aniline, under ice bath, stir 30min after mixing under ultrasonic, and Temperature fall is to subzero, and drip ammonium persulfate solution, rate of addition is 3s mono-, drips after finishing and stir 8h in ice-water bath, obtain mixing solutions; Wherein, PVDF (poly-two vinylidenes) and CoFe 2o 4the mass ratio of powder is (1-x): x, x are mass percent, and x is 0.3, aniline and PVDF, CoFe 2o 4the ratio of the total mass of powder is 1:1; Ammonium persulphate in ammonium persulfate solution and the mol ratio of aniline are 1:1; Ammonium persulfate solution is obtained by being dissolved in by ammonium persulphate in hydrochloric acid, and concentration is 0.21mol/L; PVDF, CoFe 2o 4the total mass of powder and the ratio of hydrochloric acid are 2g:50mL.
2) by mixing solutions suction filtration, with ultrapure water repetitive scrubbing until filtrate is colourless, obtain black product, by black product in vacuum drying oven, under 60 DEG C of conditions, dry 24h, obtains PANI/CoFe 2o 4/ PVDF absorbing material absorbing material.
As can be seen from Figure 5 CoFe 2o 4, PANI and PVDF characteristic diffraction peak, represent in composite granule the existence having three.
As can be seen from Figure 10 coercive field is 1609.3 (Oe), and saturation magnetization is 6.9 (emu/g), and residual magnetization is 3.3 (emu/g).
As can be seen from Figure 15, the maximum absorption of the matrix material that 3mm is thick can reach-15.8dB, and the absorption band width of below-10dB is 5.2GHz (10.9 ~ 16.1GHz).
Embodiment 5
1) by PVDF and CoFe 2o 4powder joins in the hydrochloric acid of 2mol/L, adds aniline, under ice bath, stir 30min after mixing under ultrasonic, and Temperature fall is to subzero, and drip ammonium persulfate solution, rate of addition is 4s mono-, drips after finishing and stir 10h in ice-water bath, obtain mixing solutions; Wherein, PVDF (poly-two vinylidenes) and CoFe 2o 4the mass ratio of powder is (1-x): x, x are mass percent, and x is 0.1, aniline and PVDF, CoFe 2o 4the ratio of the total mass of powder is 1:1; Ammonium persulphate in ammonium persulfate solution and the mol ratio of aniline are 1:1; Ammonium persulfate solution is obtained by being dissolved in by ammonium persulphate in hydrochloric acid, and concentration is 0.21mol/L; PVDF, CoFe 2o 4the total mass of powder and the ratio of hydrochloric acid are 2g:50mL.
2) by mixing solutions suction filtration, with ultrapure water repetitive scrubbing until filtrate is colourless, obtain black product, by black product in vacuum drying oven, under 60 DEG C of conditions, dry 21h, obtains PANI/CoFe 2o 4/ PVDF absorbing material absorbing material.
As can be seen from Figure 6 CoFe 2o 4, PANI and PVDF characteristic diffraction peak, represent in composite granule the existence having three.
As can be seen from Figure 11 coercive field is 1671.5 (Oe), and saturation magnetization is 2.9 (emu/g), and residual magnetization is 1.5 (emu/g).
As can be seen from Figure 16, the maximum absorption of the matrix material that 3mm is thick can reach-17.5dB, and the absorption band width of below-10dB is 3.5GHz (7.4 ~ 10.9GHz).
Embodiment 6
1) by PVDF and CoFe 2o 4powder joins in the hydrochloric acid of 1mol/L, adds aniline, under ice bath, stir 45min after mixing under ultrasonic, and Temperature fall is to subzero, and drip ammonium persulfate solution, rate of addition is 4s mono-, drips after finishing and stir 8.5h in ice-water bath, obtain mixing solutions; Wherein, PVDF (poly-two vinylidenes) and CoFe 2o 4the mass ratio of powder is (1-x): x, x are mass percent, and x is 0.4, aniline and PVDF, CoFe 2o 4the ratio of the total mass of powder is 1.2:1; Ammonium persulphate in ammonium persulfate solution and the mol ratio of aniline are 1.5:1; Ammonium persulfate solution is obtained by being dissolved in by ammonium persulphate in hydrochloric acid, and concentration is 0.21mol/L; PVDF, CoFe 2o 4the total mass of powder and the ratio of hydrochloric acid are 2g:50mL.
2) by mixing solutions suction filtration, with ultrapure water repetitive scrubbing until filtrate is colourless, obtain black product, by black product in vacuum drying oven, under 60 DEG C of conditions, dry 23h, obtains PANI/CoFe 2o 4/ PVDF absorbing material absorbing material.
Embodiment 7
1) by PVDF and CoFe 2o 4powder joins in the hydrochloric acid of 1.5mol/L, adds aniline, under ice bath, stir 60min after mixing under ultrasonic, Temperature fall is to subzero, and drip ammonium persulfate solution, rate of addition is 5s mono-, drip after finishing and stir 9.5h in ice-water bath, obtain mixing solutions; Wherein, PVDF (poly-two vinylidenes) and CoFe 2o 4the mass ratio of powder is (1-x): x, x are mass percent, and x is 0.8, aniline and PVDF, CoFe 2o 4the ratio of the total mass of powder is 1.5:1; Ammonium persulphate in ammonium persulfate solution and the mol ratio of aniline are 1.3:1; Ammonium persulfate solution is obtained by being dissolved in by ammonium persulphate in hydrochloric acid, and concentration is 0.21mol/L; PVDF, CoFe 2o 4the total mass of powder and the ratio of hydrochloric acid are 2g:50mL.
2) by mixing solutions suction filtration, with ultrapure water repetitive scrubbing until filtrate is colourless, obtain black product, by black product in vacuum drying oven, under 60 DEG C of conditions, dry 20h, obtains PANI/CoFe 2o 4/ PVDF absorbing material absorbing material.
Sorbing material of the present invention has excellent absorbing property, and maximum reflection loss reaches-27.4dB.The preparation technology of this matrix material is simple.Along with CoFe 2o 4the minimizing of content, saturation magnetization reduces 15.9-2.9emu/g gradually, and residual magnetization also reduces 7.9-1.5emu/g gradually; Work as CoFe 2o 4content is 90%, PVDF content when being 10%, and absorbing property is best, and maximum absorption can reach-27.4dB, and the absorption band width of below-10dB is 3.4GHz (7.2 ~ 10.6GHz).

Claims (9)

1. a PANI/CoFe 2o 4/ PVDF absorbing material, is characterized in that, Reactive Synthesis expression formula is PANI/xCoFe 2o 4/ (1-x) PVDF, wherein x is 0.1 ~ 0.9.
2. PANI/CoFe according to claim 1 2o 4/ PVDF absorbing material, is characterized in that, Reactive Synthesis expression formula is PANI/xCoFe 2o 4/ (1-x) PVDF, wherein x is 0.3 ~ 0.9.
3. PANI/CoFe according to claim 1 2o 4/ PVDF absorbing material, is characterized in that, Reactive Synthesis expression formula is PANI/xCoFe 2o 4/ (1-x) PVDF, wherein x is 0.6 ~ 0.9.
4. a PANI/CoFe 2o 4the preparation method of/PVDF absorbing material, is characterized in that, comprises the following steps:
1) by PVDF and CoFe 2o 4powder joins in hydrochloric acid, adds aniline after mixing, under ice bath, stir 30-60min, and Temperature fall, to subzero, drips ammonium persulfate solution, drips after finishing and stir 8-10h in ice-water bath, obtain mixing solutions; Wherein, PVDF and CoFe 2o 4the mass ratio of powder is (1-x): x, x are 0.1 ~ 0.9, aniline and PVDF, CoFe 2o 4the ratio of the total mass of powder is (1 ~ 1.5): 1; Ammonium persulphate in ammonium persulfate solution and the mol ratio of aniline are (1 ~ 1.5): 1;
2) by mixing solutions suction filtration, with ultrapure water repetitive scrubbing until filtrate is colourless, obtain black product, obtain PANI/CoFe by after black product drying 2o 4/ PVDF absorbing material absorbing material.
5. a kind of PANI/CoFe according to claim 4 2o 4the preparation method of/PVDF absorbing material, is characterized in that, described concentration of hydrochloric acid is 1 ~ 2mol/L; PVDF, CoFe 2o 4the total mass of powder and the ratio of hydrochloric acid are 2g:50mL.
6. a kind of PANI/CoFe according to claim 4 2o 4the preparation method of/PVDF absorbing material, is characterized in that, mixes and carries out under ultrasonic.
7. a kind of PANI/CoFe according to claim 4 2o 4the preparation method of/PVDF absorbing material, is characterized in that, rate of addition is 3s to 5s one.
8. a kind of PANI/CoFe according to claim 4 2o 4the preparation method of/PVDF absorbing material, is characterized in that, ammonium persulfate solution is obtained by being dissolved in by ammonium persulphate in hydrochloric acid, and concentration is 0.21mol/L.
9. a kind of PANI/CoFe according to claim 4 2o 4the preparation method of/PVDF absorbing material, is characterized in that, described drying is in vacuum drying oven, dry 18-24h under 60 DEG C of conditions.
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