CN109438927A - A kind of chitosan-modified ferrite filling multi-walled carbon nanotube/polythiophene composite wave-suction material preparation method - Google Patents
A kind of chitosan-modified ferrite filling multi-walled carbon nanotube/polythiophene composite wave-suction material preparation method Download PDFInfo
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Abstract
The present invention provides a kind of chitosan-modified ferrite filling multi-walled carbon nanotube/polythiophene composite wave-suction material preparation method.The present invention first uses nitration mixture oxidizing process to prepare the carbon nanotube that ferrite is filled, analyze the structure of ferrite filling carbon nano-pipe, after chitosan-modified, then again with thiophene monomer by in-situ polymerization, chitosan-modified ferrite filling multi-walled carbon nanotube/polythiophene composite material is prepared.The composite material is compounded with the suction wave advantage of ferrite, carbon nanotube, conduction high polymer, with good electromagnetic performance, there is important application value in field of microwave absorption, can satisfy the new demands such as absorption band in modern project field is wide, light-weight, thickness is thin, absorption is strong and physical mechanical property is good.
Description
Technical field
The invention belongs to electromagnetic wave absorbent material preparation field, in particular to a kind of chitosan-modified ferrite filling is more
Wall carbon nano tube/polythiophene composite wave-suction material preparation method.
Background technique
Although the development of absorbing material has achieved certain achievement with exploitation, narrow, low efficiency that there is also frequency bands, face are close
The disadvantages of big is spent, application range is subject to certain restrictions.Therefore, broadband absorbent is developed, develops multiband compatible type and inhales wave
Material realizes that efficient absorption is the future developing trend of absorbing material.Simultaneously, it is desirable that the physical and chemical performance of material is stablized, i.e.,
Absorbent keeps stablizing under the conditions of various physical chemistry (the long-term electromagnetic irradiation of such as photo-thermal).
With the development of various new electromagnetic wave absorption mechanisms and model, the absorbing material of " thin, light, wide, strong " will be by
The various aspects developed and be applied to military and civilian gradually.Conducting polymer-inorganic nano material composite material is
The forward position of current material science is a kind of very promising absorbing material.
Summary of the invention
The purpose of the present invention is to provide a kind of chitosan-modified ferrite filling multi-walled carbon nanotube/polythiophene is compound
The preparation method of absorbing material and chitosan-modified ferrite prepared by the above method fill multi-wall carbon nano-tube
Pipe/polythiophene composite wave-suction material.
A kind of chitosan-modified ferrite filling multi-walled carbon nanotube/polythiophene composite wave-suction material preparation method,
Include the following steps:
(1) preparation of the multi-wall carbon nano-tube composite material of ferrite filling: multi-walled carbon nanotube (MWNTs) is added to
Dense H2SO4With dense HNO3(volume ratio of the two is 3 to 1), agitated ultrasonic disperse, heated at constant temperature, condensing reflux in mixed solution
After be cooled to room temperature；Then filtered with miillpore filter, filter gained solid matter it is washed, it is dry, grind after, obtain acid
Carbon nano tube；
It disperses acidification carbon nanotube in deionized water, divalent iron salt and trivalent iron salt mixture is added after ultrasound, makes
Divalent iron salt and trivalent iron salt are completely dissolved, 10~12h of reaction under the conditions of 120~140 DEG C, the washed suction filtration of products therefrom,
Powder is ground into after freeze-day with constant temperature；Gained powder is rinsed and filtered with dilute HCl, then will be ground after gained solid matter drying will be filtered
Powder is worn into, the multi-wall carbon nano-tube composite material of ferrite filling is obtained；
(2) multi-walled carbon nanotube/polythiophene composite wave-suction material preparation of ferrite filling: the multi wall of ferrite filling
Carbon nano tube compound material is added in chloroform, and thiophene monomer is added after ultrasonic disperse, and anhydrous ferric trichloride is added and causes
Polymerization reaction filters to obtain solid matter, obtains the compound suction of multi-walled carbon nanotube/polythiophene of ferrite filling after washing, drying
Wave material；
(3) chitosan-modified ferrite fills the preparation of multi-walled carbon nanotube/polythiophene composite wave-suction material: shell is gathered
Sugar is dissolved in the acetic acid solution of 2% (mass fraction), after ultrasonic treatment, obtains chitosan solution；By the more of ferrite filling
Wall carbon nano tube/polythiophene composite wave-suction material is dissolved in the water, and is then added in chitosan solution, magnetic agitation；Finally, through
Magneto separate, it is dry after being washed with 1% acetic acid solution, obtain chitosan-modified ferrite filling multi-walled carbon nanotube/poly- thiophene
Pheno composite wave-suction material.
The divalent iron salt can be FeSO4·7H2O, the trivalent iron salt can be Fe (NO3)3·9H2O。
The purity of the multi-walled carbon nanotube (MWNTs) is 95%, and diameter is 60~100nm, and length is 5~15 μm.
The chitosan-modified ferrite of preparation of the present invention fills multi-walled carbon nanotube/polythiophene composite wave-suction material
In frequency bandwidth of 2~18GHz internal reflection rate penalty values lower than -25dB up to 3.5~18.6GHz, minimum reflectance penalty values can
Up to -60dB.The composite material has good electromagnetic performance, has important application value in field of microwave absorption.
The invention has the advantages that the present invention provides prepare chitosan-modified ferrite filling multi-walled carbon nanotube/poly-
The method of thiophene composite wave-suction material, it is excellent that the composite material of preparation is compounded with ferrite, carbon nanotube, the suction wave of conduction high polymer
Point has good electromagnetic performance, has important application value in field of microwave absorption, can satisfy in modern project field
Absorption band is wide, the new demands such as light-weight, thickness is thin, absorption is strong and physical mechanical property is good.
Specific embodiment
Below by embodiment, the invention will be further described.
(1) ferritic preparation:
1) drug needed for preparing: Fe is kept3+: Fe2+=1.75:1, total 0.12ml；
A. 31.32g ferric nitrate (Fe (NO is taken3)3·9H2O, molecular weight 404, content 98.5%, 0.0764mol), it adds water to
1. 250ml, configuration solution are；
B. 12.24g ferrous sulfate (FeSO is taken4·7H2O, molecular weight 278.03, content 99%, 0.0436mol), it adds water to
250ml, 2. preparing solution is；
C. concentrated ammonia liquor 50ml is taken, 3. label solution is；
D. 82.02g ferric nitrate (Fe (NO is taken3)3·9H2O, molecular weight 404, content 98.5%, 0.2mol), it adds water to
500ml, 4. preparing solution is；
2) preparation of nano ferriferrous oxide granule: it 1. will 2. be mixed, and rapidly join under nitrogen atmosphere 3., make system
PH=10~11, stir 30min, Magneto separate, stand 4h or more；It is cleared up with deionized water to ph=7, will 4. be poured into again, boiled
30min is risen, Magneto separate to natural cooling loses supernatant, is cleaned twice with acetone, Magneto separate, removes supernatant, is dried in vacuo
It two days, pulverizes.Theoretically obtain Fe3O4There is 0.04mol (quality 9.2g).
(2) preparation of ferrite filling multi-wall carbon nano-tube composite material:
Test multi-walled carbon nanotube (MWNTs, purity 95%, diameter are 60~100nm, and length is 5~15Lm),
His chemical reagent is that analysis is pure.
2g multi-walled carbon nanotube is weighed with electronic balance first, is put into equipped with the dense H of 80mL2SO4With dense HNO3Mixed solution
In the conical flask of (3:1, volume ratio), ultrasonic disperse 1.5h after mixing evenly.It is diluted with a large amount of acetone, precipitating is collected by centrifugation
Object.Then gained sediment is washed with deionized, is filtered by the miillpore filter that aperture is 0.22 μm, washing operation is extremely repeatedly
The ph value of solution finally removes water evaporation close to 7, is placed in DZF6000 type vacuum oven and is dried in vacuo at 60 DEG C
12h to get arrive Carboxylation MWNTs.
Hydro-thermal reaction carries out in the stainless steel hydrothermal reaction kettle of 100mL polytetrafluoroethylliner liner.Weigh 250mg's first
Carboxylation MWNTs is scattered in 95ml and contains Fe2(SO4)3(0.1mol/L) and Fe (NH4)2(SO4)2·6H2O (0.1mol/L) go from
In sub- aqueous solution, and in N2Ultrasonic reaction 30min in atmosphere；Then in ultrasonic procedure, 4% ammonia spirit is added drop-wise to dropwise
It fills in the liner of mixed molysite, the final ph for adjusting solution is 11；Finally mixed solution is heated separately in reaction system
140 DEG C and isothermal reaction 12h.Product attracts separation by additional magnetic force, is washed repeatedly with deionized water and dehydrated alcohol, to wash
Surface is gone not have reacted foreign ion, adjusting solution ph with deionized water is about 7, and 60 DEG C of product are dried in vacuo
6h.It is weighed after grinding.
(3) preparation of the carbon nano-tube/poly thiophene composite wave-suction material of ferrite filling:
The multi-walled carbon nanotube 250mg for weighing ferrite filling is added in 80mL chloroform, and ultrasonic 30min makes carbon receive
Mitron is dispersed in chloroform, and thiophene monomer 2.5mL is added, and continues to stir 1h, and 4.0g anhydrous ferric trichloride is added and draws
Polymerization reaction is sent out, continues stirring at room temperature for 24 hours, filtering is washed with methanol and secondary distilled water repeatedly until filtrate becomes nothing
Until color, product is finally dried in vacuo 6h at 50 DEG C, obtains multi-walled carbon nanotube-polythiophene composite wood of ferrite filling
Material.
(4) preparation of the carbon nano-tube/poly thiophene composite wave-suction material of chitosan-modified ferrite filling:
200mg chitosan is dissolved in the acetic acid solution of 100mL 2% (mass fraction), ultrasonication 30min.Claim
(the carbon nano-tube/poly thiophene composite wave-suction material of the ferrite filling of acidification) of amount 200mg is dissolved in 200mL aqueous solution
In, it is added into chitosan solution, magnetic agitation 4h.Finally, composite material (receive by the carbon of chitosan-modified ferrite filling
Mitron/polythiophene composite wave-suction material) through Magneto separate, product washes away unreacted chitosan with 1% acetic acid solution, at 40 DEG C
It is dried in vacuo 8h.Grinding obtains product.The prepared composite wave-suction material 2~18GHz internal reflection rate penalty values lower than-
The frequency bandwidth of 25dB is up to 3.5~18.6GHz, the reachable -60dB of minimum reflectance penalty values.
In conclusion the present invention, which prepares chitosan-modified ferrite from the angle of composite material, fills multi-wall carbon nano-tube
Pipe/polythiophene composite wave-suction material, the composite material by conducting polymer, carbon nanotube, ferrite three synergy
Effect obtains more superior absorbing property, has important scientific meaning and good application prospect, to the state for promoting China
Anti- strength, the fight capability for enhancing airborne weapon and reduction electromagnetic wave have major contribution to the pollution of environment.
Claims (6)
1. a kind of chitosan-modified ferrite fills multi-walled carbon nanotube/polythiophene composite wave-suction material preparation method, packet
Include following steps:
(1) preparation of the multi-wall carbon nano-tube composite material of ferrite filling: multi-walled carbon nanotube (MWNTs) is added to dense
H2SO4With dense HNO3In mixed solution, room temperature is cooled to after agitated ultrasonic disperse, heated at constant temperature, condensing reflux；Then with micro-
Hole filter membrane is filtered, filter gained solid matter it is washed, it is dry, grinding after, obtain be acidified carbon nanotube；
It disperses acidification carbon nanotube in deionized water, divalent iron salt and trivalent iron salt mixture is added after ultrasound, makes divalent
Molysite and trivalent iron salt are completely dissolved, and 10~12h, the washed suction filtration of products therefrom, constant temperature are reacted under the conditions of 120~140 DEG C
Powder is ground into after drying；Gained powder is rinsed and filtered with dilute HCl, then will be ground into after gained solid matter drying will be filtered
Powder obtains the multi-wall carbon nano-tube composite material of ferrite filling；
(2) multi-walled carbon nanotube/polythiophene composite wave-suction material preparation of ferrite filling: the multi wall carbon that ferrite is filled
Nanometer tube composite materials are added in chloroform, and thiophene monomer is added after ultrasonic disperse, and it is poly- that anhydrous ferric trichloride initiation is added
Reaction is closed, solid matter is filtered to obtain, obtains multi-walled carbon nanotube/polythiophene composite wave-absorbing of ferrite filling after washing, drying
Material；
(3) chitosan-modified ferrite fills the preparation of multi-walled carbon nanotube/polythiophene composite wave-suction material: chitosan is molten
Solution after ultrasonic treatment, obtains chitosan solution in the acetic acid solution that mass fraction is 2%；The multi wall carbon that ferrite is filled
Nanotube/polythiophene composite wave-suction material is dissolved in the water, and is then added in chitosan solution, magnetic agitation；Finally, through magnetic point
From, it is dry after being washed with 1% acetic acid solution, it is multiple to obtain chitosan-modified ferrite filling multi-walled carbon nanotube/polythiophene
Close absorbing material.
2. according to the method described in claim 1, it is characterized by: dense H2SO4With dense HNO3Volume ratio both in mixed solution
It is 3 to 1.
3. according to the method described in claim 1, it is characterized by: the divalent iron salt is FeSO4·7H2O, described three
Valence molysite is Fe (NO3)3·9H2O。
4. according to the method described in claim 1, it is characterized by: the purity of the multi-walled carbon nanotube (MWNTs) is
95%, diameter is 60~100nm, and length is 5~15 μm.
5. a kind of chitosan-modified ferrite fills multi-walled carbon nanotube/polythiophene composite wave-suction material, it is characterised in that: root
It is prepared according to method described in Claims 1 to 4 any claim.
6. chitosan-modified ferrite according to claim 5 fills multi-walled carbon nanotube/polythiophene composite wave-absorbing material
Expect the application in field of microwave absorption.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115286843A (en) * | 2022-08-18 | 2022-11-04 | 彗晶新材料科技(杭州)有限公司 | Yb 3+ /Sm 3+ -Ti 3 C 2 T x Preparation method of/PPy @ multi-walled carbon nanotube composite material |
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| CN102627834A (en) * | 2012-04-05 | 2012-08-08 | 南昌航空大学 | Preparation method of chitosan modification barium ferrite filling multi-walled carbon nanotube/poly 3-methylthiophene composite wave-absorbing material |
| CN104086953A (en) * | 2014-06-26 | 2014-10-08 | 南昌航空大学 | Preparation method for chitosan-modified ferrite-filled multi-wall carbon nano tube/polythiophene composite wave-absorbing material |
| CN104098874A (en) * | 2014-06-26 | 2014-10-15 | 南昌航空大学 | Composite wave-absorbing material preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627834A (en) * | 2012-04-05 | 2012-08-08 | 南昌航空大学 | Preparation method of chitosan modification barium ferrite filling multi-walled carbon nanotube/poly 3-methylthiophene composite wave-absorbing material |
| CN104086953A (en) * | 2014-06-26 | 2014-10-08 | 南昌航空大学 | Preparation method for chitosan-modified ferrite-filled multi-wall carbon nano tube/polythiophene composite wave-absorbing material |
| CN104098874A (en) * | 2014-06-26 | 2014-10-15 | 南昌航空大学 | Composite wave-absorbing material preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286843A (en) * | 2022-08-18 | 2022-11-04 | 彗晶新材料科技(杭州)有限公司 | Yb 3+ /Sm 3+ -Ti 3 C 2 T x Preparation method of/PPy @ multi-walled carbon nanotube composite material |
| CN115286843B (en) * | 2022-08-18 | 2023-03-28 | 彗晶新材料科技(杭州)有限公司 | Yb 3+ /Sm 3+ -Ti 3 C 2 T x Preparation method of/PPy @ multi-walled carbon nanotube composite material |
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