CN104559920A - Nano-particle composite with double-shell microstructure and application of nano-particle composite - Google Patents

Nano-particle composite with double-shell microstructure and application of nano-particle composite Download PDF

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Publication number
CN104559920A
CN104559920A CN201310497223.9A CN201310497223A CN104559920A CN 104559920 A CN104559920 A CN 104559920A CN 201310497223 A CN201310497223 A CN 201310497223A CN 104559920 A CN104559920 A CN 104559920A
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nano
dielectric oxide
bivalve layer
oxide
shell
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CN104559920B (en
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李达
姜菁菁
李少杰
耿殿禹
王振华
刘伟
张志东
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Institute of Metal Research of CAS
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Abstract

The invention discloses a nano-particle composite wave-absorbing material with a double-shell microstructure so as to solve the defect that absorption frequency bands of the current wave absorbing materials are narrow. The nano-particle composite wave-absorbing material is characterized in that the composite wave-absorbing material is in a double-shell microstructure, an external shell is made of dielectric oxides, an internal shell is made of carbon, and an inner core is made of ferromagnetic materials. The nano-particle composite wave-absorbing material has the advantages that gradual impedance gradation is generated through the structural change of dielectric oxide shell-carbon shell-magnetic metal particle core, so that electromagnetic waves can maximumly transmit into the material, and the reflection of the electromagnetic waves is lowered; besides, the characteristics of resistance loss, dielectric loss and magnetic loss of the composite material, and ample interfacial polarization in the double-shell microstructure are utilized, so that the electromagnetic waves entering into the interior of the material rapidly attenuate. The composite material has the advantages of small density and wide frequency bands. The composite material has a wide application prospect in electromagnetic shielding, electrorheological fluids, functional coatings and the like.

Description

A kind of nano-particle complex and application thereof with bivalve layer microstructure
Technical field
The invention belongs to electromagnetic wave absorption field, provide a kind of especially and there is the nano-particle complex of bivalve layer microstructure and absorb the method for microwave.
Background technology
The effect of microwave absorbing material is absorbed into be mapped to microwave in material, can change microwave electromagnetic into heat energy, thus reduce microwave reflection cross section.This kind of material has been widely used in military affairs, the civil areas such as electromagnetic pollution shielding and stealth technology.The material obsorbing radar waves that current use is comparatively general, can be divided into electrical loss, magnetic loss two kinds according to electromagnetic consumable mechanism.According to the difference of application mode, coating-type absorbing materials, structural type composite wave-suction material can be divided into, put on a suit of armour shield formula stealth material etc.Wherein, coating-type absorbing materials has the plurality of advantages such as easy construction, material cost are relatively low, the coating that is suitable for various surfaces of complex shape, more can not affect contour structures and the using function of equipment of having shaped, become the first-selection of weaponry stealth material.Conventional absorbents kind is more, has graphite powder, conducting high polymers thing, silicon carbide fibre, conductive metallic fiber, magnetic powder etc.The ceramic materials such as carborundum are mainly used in high temperature sorbent.Conducting polymer absorption band is narrow, and the adhesive matched with it is less.Magnetic powder comprises ferrite and magnetic metal powder, and ferromagnetic resonance makes it have larger magnetic loss angle.Although ferrite has higher magnetic permcability, there is the shortcomings such as theoretical surface density is large, coating is thicker.Magnetic metal micro mist absorbent has that temperature stabilization performance is good, magnetic conductivity is higher, Curie temperature comparatively advantages of higher, is the main development direction of absorbent of new generation.Dielectric material and magnetic nano-particle are combined, can reach and open up wide band object, make electromagnetic parameter convergence optimum Match, reduce reflection, increase and absorb.As: application for a patent for invention 200910011350.7 discloses a kind of preparation method of carbon-wrapped iron-cobalt nano wave-absorbing material.It has utilized plasma arc legal system to make outer shell for carbon shell, and ferrocobalt is as the Nano capsule of kernel, and its absorbing property is better than most ferrites.Application for a patent for invention 201310261578.8 discloses a kind of method using porous nickel acid lanthanum powder preparation dielectric/ferromagnetic absorption microwave composite material.
Summary of the invention
The object of this invention is to provide a kind of nano-particle complex adopting bivalve layer microstructure and the method absorbing microwave thereof, absorb the narrow deficiency of frequency range to solve single kind absorbing material.
The present invention specifically provides a kind of nano-particle complex with bivalve layer microstructure, it is characterized in that: described compound has bivalve layer microstructure, outer shell is made up of dielectric oxide, interior shell is carbon, kernel is made up of ferrimagnet, preferred ferromagnetic nanoparticle, as ferrocobalt nano particle.
The nano-particle complex with bivalve layer microstructure of the present invention, is characterized in that: described outer shell dielectric oxide is barium titanate, aluminium oxide, zinc oxide, titanium oxide, nickel oxide, cobalt oxide, or ferrite magnetic oxide.The described outer shell be made up of dielectric oxide can regulate the electromagnetic parameter of nano-complex.
The nano-particle complex with bivalve layer microstructure of the present invention, it is characterized in that: the mass percentage of described outer shell dielectric oxide is the 20-80wt.% of composite total amount, and the mass percentage of magnetic carbon Nano capsule is the 80-20wt.% of composite total amount.
The novel nano-particles reinforcement absorbing material with bivalve layer microstructure of the present invention's design, its advantage can produce mild impedance transition mechanism by the structure change of dielectric oxide shell-carbon shell-magnetic metal particle core, make electromagnetic wave incide material internal to greatest extent, reduce reflection of electromagnetic wave; Play resistance loss, dielectric loss, magnetic loss characteristic that this kind of composite has simultaneously, and interfacial polarization abundant in the layer microstructure of bivalve, the electromagnetic wave entering material internal is attenuated rapidly.
There is described in present invention also offers the preparation method of the nano-particle complex of bivalve layer microstructure, it is characterized in that: carbon parcel ferrimagnet kernel forms magnetic carbon Nano capsule, by sol-gal process, dielectric oxide gel is wrapping to the carbon-coating surface of magnetic metal carbon Nano capsule, pass through heat treatment, make dielectric oxide crystallization, obtain the nano-particle complex with bivalve layer microstructure.
The concrete preparation process with the nano-particle complex of bivalve layer microstructure of the present invention is as follows:
(1) sol-gal process is adopted to obtain dielectric oxide gel;
(2) magnetic carbon Nano capsule is dispersed in n-hexane, forms magnetic carbon Nano capsule-n-hexane suspension;
(3) aqueous solution of preparation containing n-hexane, water, ethanol and polyvinylpyrrolidone;
(4) by magnetic carbon Nano capsule-n-hexane suspension and aqueous solution, prepare o/w type microemulsion (o: oil, w: water) by ultrasonic method, wherein polyvinylpyrrolidone is emulsifying agent.
(5) dielectric oxide gel is added in o/w type microemulsion, is formed the precursor solution of dispersed magnetic carbon Nano capsule-dielectric oxide colloidal sol by sonic oscillation;
(6) by dry in atmosphere for the precursor solution of magnetic carbon Nano capsule-dielectric oxide colloidal sol, dry composite powder is obtained.Wash composite powder by deionized water again, remove polyvinylpyrrolidone wherein, after drying, obtain the magnetic carbon Nano capsule compound of dielectric oxide forerunner soma glue parcel.
(7) the magnetic carbon Nano capsule compound that dielectric oxide forerunner soma glue wraps up is placed in vacuum, obtains described bivalve layer Encapsulation nanoparticle compound microwave absorbing material through heat treatment.
There is described in present invention also offers the application of nano-particle complex as composite microwave absorbing material of bivalve layer microstructure.Described composite can join in base matter with the addition of 30wt% ~ 50wt% mass percent and make microwave absorbing coating, and the electromagnetic wave of this microwave absorbing coating to 1-18GHz scope has absorption.
Microwave absorbing coating as above, it measures the base matter adopted is paraffin.
Advantage of the present invention: the present invention is wrapping to magnetic carbon Nano capsule carbon shell layer surface by adopting dielectric oxide, forms the method with the microwave absorbing material of bivalve layer microstructure and is not reported.Instant invention overcomes the difficulty that polarity dielectric oxide Gel Precursor is coated to the nonpolar carbon shell layer surface of nano magnetic capsule.Nano combined microwave absorbing material prepared by the present invention, has density little, absorbs the advantage that frequency range is wide and absorption intensity is large, has broad application prospects in electromagnetic shielding, electro rheological fluids, functional paint etc.
Accompanying drawing explanation
Barium titanate (the BaTiO that Fig. 1 the present invention obtains 3) X-ray diffractogram of oxide coated magnetic carbon-wrapped iron-cobalt nano capsule (FeCo/C) composite wave-suction material;
Fig. 2 is the barium titanate (BaTiO that the present invention obtains 3) transmission electron microscope photo of oxide coated magnetic carbon-wrapped iron-cobalt nano capsule (FeCo/C) composite wave-suction material;
Fig. 3 is the barium titanate (BaTiO that the present invention obtains 3) the high-resolution-ration transmission electric-lens photo of oxide coated magnetic carbon-wrapped iron-cobalt nano capsule (FeCo/C) composite wave-suction material;
Fig. 4 be the barium titanate oxide coated magnetic carbon-wrapped iron-cobalt nano capsule composite (barium titanate: carbon-wrapped iron-cobalt nano capsule=20:80) that the present invention obtains complex permittivity with frequency variation curve (ε ' be the real part of complex permittivity, ε " imaginary part for complex permittivity)
Fig. 5 be the barium titanate oxide coated magnetic carbon-wrapped iron-cobalt nano capsule composite (barium titanate: carbon-wrapped iron-cobalt nano capsule=20:80) that the present invention obtains complex permeability number with frequency variation curve (μ ' be the real part of complex permeability, μ " imaginary part for complex permeability);
Fig. 6 is the barium titanate oxide coated magnetic carbon-wrapped iron-cobalt nano capsule composite (barium titanate: carbon-wrapped iron-cobalt nano capsule=20:80) that the present invention obtains is 1.5-7.5 millimeter at absorber thickness, the reflection loss figure of frequency range 1-18GHz;
Fig. 7 is the barium titanate oxide coated magnetic carbon-wrapped iron-cobalt nano capsule composite (barium titanate: carbon-wrapped iron-cobalt nano capsule=50:50) that the present invention obtains is 1.5-7.5 millimeter at absorber thickness, the reflection loss figure of frequency range 1-18GHz;
Fig. 8 is the barium titanate oxide coated magnetic carbon-wrapped iron-cobalt nano capsule composite (barium titanate: carbon-wrapped iron-cobalt nano capsule=80:20) that the present invention obtains is 1.5-6 millimeter at absorber thickness, the reflection loss figure of frequency range 1-18GHz.
Detailed description of the invention
Following examples will be further described the present invention, but therefore not limit the present invention.
Embodiment 1
Described bivalve layer Encapsulation nanoparticle compound microwave absorbing material, its step prepared is:
(1) adopt sol-gal process, using barium acetate and isopropyl titanate as raw starting material, prepare barium titanate gel;
(2) by magnetic carbon wrapped iron-cobalt nano capsules disperse in n-hexane, form magnetic carbon wrapped iron-cobalt nano capsule-n-hexane suspension;
(3) aqueous solution of preparation containing n-hexane, water, ethanol and polyvinylpyrrolidone;
(4) by magnetic carbon wrapped iron-cobalt nano capsule-n-hexane suspension and aqueous solution, prepare o/w type microemulsion by ultrasonic method, wherein polyvinylpyrrolidone is emulsifying agent;
(5) dielectric oxide gel is added in o/w type microemulsion, is formed the precursor solution of dispersed magnetic carbon wrapped iron-cobalt nano capsule-dielectric oxide colloidal sol by sonic oscillation;
(6) by dry in atmosphere for the precursor solution of magnetic carbon wrapped iron-cobalt nano capsule-dielectric oxide colloidal sol, dry composite powder is obtained; Wash composite powder by deionized water again, remove polyvinylpyrrolidone wherein, after drying, obtain the magnetic iron clad cobalt carbon Nano capsule compound of dielectric oxide forerunner soma glue parcel;
(7) the magnetic carbon wrapped iron-cobalt nano bladder compound that dielectric oxide forerunner soma glue wraps up is placed in vacuum, bivalve layer Encapsulation nanoparticle compound microwave absorbing material is obtained through heat treatment, wherein barium titanate: carbon-wrapped iron-cobalt nano capsule quality is than being 20wt.%:80wt.%, and its thing phase composition as shown in Figure 1.As shown in Figure 2, Fig. 3 is the high resolution electron microscopy photo of its microstructure to its microstructure.
Inhale the preparation of ripple sample:
The 0.4g bivalve layer Encapsulation nanoparticle compound microwave absorbing material (barium titanate: carbon-wrapped iron-cobalt nano capsule is 20wt.%:80wt.%) of preparation is mixed (composite inhale the mass fraction in ripple sample be 40wt%) with 0.6g paraffin even, grinding tool is utilized to be pressed into internal diameter for 3.04mm, external diameter is 7mm, and thickness is the annulus of 2mm.After tested, the complex permittivity of described composite in 1-18GHz frequency (f) scope (ε r=ε '+i ε ") and complex permeability (μ r=μ '+i μ ") as shown in Figure 4 and Figure 5.By regulating absorber thickness, reflection loss (RL) all has the absorption (see figure 6) lower than-15dB at different frequencies.
Embodiment 2
Difference from Example 1 is: barium titanate: carbon-wrapped iron-cobalt nano capsule quality is than being 50wt.%:50wt.%.By regulating absorber thickness, reflection loss (RL) all has the absorption (see figure 7) lower than-20dB at different frequencies.
Embodiment 3
Difference from Example 1 is: barium titanate: carbon-wrapped iron-cobalt nano capsule quality is than being 80wt.%:20wt.%.After tested, gained composite reflection loss (RL) all has the absorption (see figure 8) lower than-15dB at different frequencies.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims (10)

1. there is a nano-particle complex for bivalve layer microstructure, it is characterized in that: described compound has bivalve layer microstructure, and outer shell is made up of dielectric oxide, and interior shell is carbon, and kernel is made up of ferrimagnet.
2. according to the nano-particle complex described in claim 1 with bivalve layer microstructure, it is characterized in that: described outer shell dielectric oxide is barium titanate, aluminium oxide, zinc oxide, titanium oxide, nickel oxide, cobalt oxide or ferrite magnetic oxide.
3. according to the nano-particle complex described in claim 1 with bivalve layer microstructure, it is characterized in that: described kernel is made up of ferromagnetic nanoparticle.
4. according to the nano-particle complex described in claim 1 with bivalve layer microstructure, it is characterized in that: the mass percentage of described dielectric oxide is the 20-80wt.% of composite total amount.
5. one kind has the preparation method of the nano-particle complex of bivalve layer microstructure as claimed in claim 1, it is characterized in that: carbon parcel ferrimagnet kernel forms magnetic carbon Nano capsule, by sol-gal process, dielectric oxide gel is wrapping to the carbon-coating surface of magnetic carbon Nano capsule, pass through heat treatment, make dielectric oxide crystallization, obtain the nano-particle complex with bivalve layer microstructure.
6., according to the preparation method of nano-particle complex described in claim 5 with bivalve layer microstructure, it is characterized in that, preparation process is as follows:
(1) sol-gal process is adopted to obtain dielectric oxide gel;
(2) magnetic carbon Nano capsule is dispersed in n-hexane, forms magnetic carbon Nano capsule-n-hexane suspension;
(3) aqueous solution of preparation containing n-hexane, water, ethanol and polyvinylpyrrolidone;
(4) by magnetic carbon Nano capsule-n-hexane suspension and aqueous solution, prepare o/w type microemulsion by ultrasonic method, wherein polyvinylpyrrolidone is emulsifying agent;
(5) dielectric oxide gel is added in o/w type microemulsion, is formed the precursor solution of dispersed magnetic carbon Nano capsule-dielectric oxide colloidal sol by sonic oscillation;
(6) by dry in atmosphere for the precursor solution of magnetic carbon Nano capsule-dielectric oxide colloidal sol, dry composite powder is obtained; Wash composite powder by deionized water again, remove polyvinylpyrrolidone wherein, after drying, obtain the magnetic carbon Nano capsule compound of dielectric oxide forerunner soma glue parcel;
(7) the magnetic carbon Nano capsule compound that dielectric oxide forerunner soma glue wraps up is placed in vacuum, obtains bivalve layer Encapsulation nanoparticle compound microwave absorbing material through heat treatment.
7. a nano-particle complex as claimed in claim 1 with bivalve layer microstructure is applied as microwave absorbing material.
8. the microwave absorbing coating that the nano-particle complex as claimed in claim 1 with bivalve layer microstructure is made, is characterized in that: described composite microwave absorbing material joins in base matter with the addition of 30wt.% ~ 50wt.% mass percent and makes microwave absorbing coating.
9. according to the microwave absorbing coating that the nano-particle complex described in claim 8 with bivalve layer microstructure is made, it is characterized in that: described base matter is paraffin.
10. one kind as claimed in claim 8 microwave absorbing coating as the application of the electromagnetic absorbing material aspect of 1-18GHz scope.
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CN105110315A (en) * 2015-07-28 2015-12-02 大连理工大学 Method for synthesis of double-casing layer carbon nanometer hollow polyhedron by metal-organic framework as template
CN107151332A (en) * 2017-06-30 2017-09-12 南京航空航天大学 A kind of electromagnetic wave absorption agent using titanium-based metal organic framework materials as presoma and preparation method thereof
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CN109321328A (en) * 2018-09-27 2019-02-12 安徽省华腾农业科技有限公司 A kind of ER fluid and preparation method thereof
CN109321328B (en) * 2018-09-27 2021-06-25 安徽省华腾农业科技有限公司 Electrorheological fluid and preparation method thereof
CN114801381A (en) * 2022-03-29 2022-07-29 四川盈乐威科技有限公司 Multilayer wave-absorbing material and preparation method thereof

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