CN102993645A - Preparation method for graphene/DBSA (dodecyl benzene sulphonic acid)-modified carbon nanotube/polythiophene composite wave-absorbing additive - Google Patents
Preparation method for graphene/DBSA (dodecyl benzene sulphonic acid)-modified carbon nanotube/polythiophene composite wave-absorbing additive Download PDFInfo
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Abstract
The invention provides a preparation method for a graphene/DBSA (dodecyl benzene sulphonic acid)-modified carbon nanotube/polythiophene composite wave-absorbing additive. The preparation method provided by the invention comprises the following steps of: modifying a multi-wall carbon nanotube by dodecyl benzene sulphonic acid (DBSA) at first, and then preparing the graphene/DBSA-modified carbon nanotube/polythiophene composite wave-absorbing additive by taking the modified carbon nanotube, graphene, thiophene monomer as raw materials via in-situ polymerization. The composite material additive has good electromagnetic performance, and an important application value in the field of microwave absorption.
Description
Technical field
The invention belongs to the electromagnetic wave absorbent material preparation field, particularly the preparation method of a kind of Graphene/DBSA modified carbon nano-tube/Polythiophene composite wave-suction material additive.
Background technology
The crystalline network of Graphene is very stable, and the movement velocity of its electronics has reached 15000cm/Vs, is equivalent to 1/300 of the light velocity, considerably beyond the movement velocity of electronics in general conductor.Graphene has excellent mechanical property, under external force, because the distortion of the self-adaptation of atomic plane, the C-C key is not easy to disconnect, the Graphene crystalline network can keep relative stability, and therefore shows as the intensity height in macroscopic view, the phenomenon that difficult generation fractures, punctures, tears.
Carbon nanotube had both had the intrinsic person's character of carbon materials, had again conduction and the thermal conductivity of metallic substance, heat-resisting, the erosion resistance of stupalith, the stitchability of textile fibres, and the lightweight of macromolecular material, workability.Carbon nanotube can make matrix material show good intensity, elasticity, fatigue resistance and isotropy as composite material reinforcement body, so Carbon Nanotubes Reinforced Composites may bring the once leap of composite property.
Therefore, the present invention prepares the thienyl composite wave-suction material take Graphene, carbon nanotube as strengthening body, and this matrix material has excellent conductivity, has important using value in fields such as electromagnetic absorption, electronic devices and components, safety precautions.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of Graphene/DBSA modified carbon nano-tube/Polythiophene composite wave-suction material additive, this composite density is little, thin thickness, bandwidth, absorption are strong, can use as the absorbing material additive of different field.
The present invention is achieved like this, and its preparation method is:
(1) preparation of DBSA modified carbon nano-tube: carbon nanotube and DBSA mass ratio are 1:2, are that the multi-walled carbon nano-tubes of 20～30nm joins in the aqueous solution with the 1.0g caliber, behind the ultra-sonic dispersion 1h, add 2.0g DBSA again, react 2.5h in ice-water bath.React complete extremely neutral by deionized water wash, 50 ℃ of lower vacuum-dryings obtain the DBSA modified carbon nano-tube.
(2) preparation of Graphene: 1.0g graphite scale, 0.5g SODIUMNITRATE and the 25mL vitriol oil are mixed under condition of ice bath, slowly add 3.0g potassium permanganate under the restir, remain on below 10 ℃ and stir 1h, then at 35 ℃ of lower 0.5h that stir, add again the dilution of 50mL deionized water under the ice-water bath, make temperature be lower than 100 ℃, continue to stir 0.5h, after adding again the further dilution of 200mL deionized water, add 10mL 30% H
2O
2, standing demix removes supernatant liquor, and standing demix after the adding 100mL absolute ethyl alcohol and stirring removes supernatant liquor, 3～4 times so repeatedly, obtains the graphite oxide suspension liquid.The graphite oxide suspension liquid that makes is distributed in the 100mL dehydrated alcohol, behind the supersound process 30min, adds 50mL hydrazine hydrate, 50mL ammoniacal liquor, 95 ℃ of backflow 1h again after mixing, suction filtration, absolute ethanol washing filter cake 3～4 times, after 60 ℃ of vacuum-dryings, grind and obtain Graphene.
(3) preparation of Graphene/DBSA modified carbon nano-tube/polythiophene composite material additive: with Xg(X=0.20～0.40) Graphene, Yg(Y=0.20～0.40) DBSA modified carbon nano-tube, 2.0mL thiophene monomer add in the 80mL trichloromethane, ultrasonic 30min, add the 8.0g FERRIC CHLORIDE ANHYDROUS, suction filtration behind the stirring reaction 10h, methanol wash, deionized water wash to filtrate is colourless, 60 ℃ of vacuum-drying 24h obtain Graphene/DBSA modified carbon nano-tube/polythiophene composite material additive.
With the HITACHI/SU1510 of Hitachi scanning electronic microscope particle form and the size of Graphene/DBSA modified carbon nano-tube/Polythiophene composite wave-suction material additive are observed.Take Graphene/DBSA modified carbon nano-tube/Polythiophene mixture (X=0.20, Y=0.20) as example, carbon nanotube, graphene uniform is scattered in the polythiophene matrix in the mixture.
With the four point probe conductivity meter specific conductivity of Graphene/DBSA modified carbon nano-tube/Polythiophene composite wave-suction material additive is measured.Take Graphene/DBSA modified carbon nano-tube/Polythiophene mixture (X=0.30, Y=0.30) as example, the mixture specific conductivity is 1.9428S/cm.
With vibrating sample magnetometer (VSM) Graphene/DBSA modified carbon nano-tube/Polythiophene composite wave-suction material additive is carried out magnetism testing.So that Graphene/DBSA modified carbon nano-tube/Polythiophene mixture (X=0.40, Y=0.40) is as example, test result is: coercive force is 526.3Oe, and saturation magnetization is 96.42emug
-1, residual magnetization is 84.09emug
-1
Adopt Agilent 8722ES vector network analyzer test Graphene/DBSA modified carbon nano-tube/Polythiophene composite wave-suction material additive, at the reflectivity of 2～18GHz.So that Graphene/DBSA modified carbon nano-tube/Polythiophene mixture (X=0.40, Y=0.40) is as example, test result is: maximum absorption band appears in the 12.2GHz place, and peak value is-54dB, and reflectivity loss value is lower than-the wide 14.2GHz of reaching of absorption band of 10dB.
Advantage of the present invention: the present invention adopts first Witco 1298 Soft Acid (DBSA) that multi-walled carbon nano-tubes is carried out modification, and take this modified carbon nano-tube, Graphene, thiophene monomer as raw material, by in-situ polymerization, prepare Graphene/DBSA modified carbon nano-tube/Polythiophene composite wave-suction material additive.The advantage of the comprehensive carbon nanotube of this composite additives, Graphene, Polythiophene, coercive force is less, density is lighter, impedance matching is better, absorption characteristic is good, can be widely used in the absorbing material additive in various fields, has important using value in the microwave absorbing field.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1
(1) is that the multi-walled carbon nano-tubes of 20～30nm joins in the aqueous solution with the 1.0g caliber, behind the ultra-sonic dispersion 1h, adds again 2.0g DBSA, in ice-water bath, react 2.5h.React complete extremely neutral by deionized water wash, 50 ℃ of lower vacuum-dryings obtain the DBSA modified carbon nano-tube.
(2) 1.0g graphite scale, 0.5g SODIUMNITRATE and the 25mL vitriol oil are mixed under condition of ice bath, stir the lower 3.0g potassium permanganate that slowly adds, remain on below 10 ℃ and stir 1h, then at 35 ℃ of lower 0.5h that stir, add the dilution of 50mL deionized water under the ice-water bath, make temperature be lower than 100 ℃, continue to stir 0.5h, add again the 200mL deionized water and further dilute, add 10mL 30% H
2O
2, standing demix removes supernatant liquor, and standing demix after the adding 100mL absolute ethyl alcohol and stirring removes supernatant liquor, 3～4 times so repeatedly, obtains the graphite oxide suspension liquid.The graphite oxide suspension liquid that makes is distributed in the 100mL dehydrated alcohol, behind the supersound process 30min, adds 50mL hydrazine hydrate, 50mL ammoniacal liquor, 95 ℃ of backflow 1h again after mixing, suction filtration, absolute ethanol washing 3～4 times, 60 ℃ of vacuum-dryings are ground and are obtained Graphene.
(3) 0.20g Graphene, 0.20g DBSA modified carbon nano-tube, 2.0mL thiophene monomer are added in the 80mL trichloromethane, supersound process 30min, add the 8.0g FERRIC CHLORIDE ANHYDROUS, suction filtration behind the stirring reaction 10h, methanol wash, deionized water wash to filtrate is colourless, 60 ℃ of vacuum-drying 24h, obtain Graphene/DBSA modified carbon nano-tube/polythiophene composite material additive (X=0.20, Y=0.20).Prepared composite additives is lower than in 2～18GHz internal reflection rate loss value-and the frequency span of 10dB reaches 16.3GHz, and minimum reflectance loss value can reach-47dB.
Embodiment 2
The preparation method of DBSA modified carbon nano-tube, Graphene is respectively with embodiment 1 step (1), step (2).Take by weighing 0.30g Graphene, 0.30g DBSA modified carbon nano-tube, the preparation method prepares Graphene/DBSA modified carbon nano-tube/polythiophene composite material additive (X=0.30, Y=0.30) with embodiment 1 step (3).Prepared composite additives is lower than in 2 ~ 18GHz internal reflection rate loss value-and the frequency span of 10dB reaches 15.4GHz, and minimum reflectance loss value can reach-51dB.
Embodiment 3
The preparation method of DBSA modified carbon nano-tube, Graphene is respectively with embodiment 1 step (1), step (2).Take by weighing 0.40g Graphene, 0.40g DBSA modified carbon nano-tube, the preparation method prepares Graphene/DBSA modified carbon nano-tube/polythiophene composite material additive (X=0.40, Y=0.40) with embodiment 1 step (3).Prepared composite additives is lower than in 2～18GHz internal reflection rate loss value-and the frequency span of 10dB reaches 14.2GHz, and minimum reflectance loss value can reach-54dB.
Claims (2)
1. the preparation method of Graphene/DBSA modified carbon nano-tube/Polythiophene composite wave-suction material additive is characterized in that the preparation method is as follows:
(1) preparation of DBSA modified carbon nano-tube: carbon nanotube and DBSA mass ratio are 1:2, are that the multi-walled carbon nano-tubes of 20～30nm joins in the aqueous solution with the 1.0g caliber, behind the ultra-sonic dispersion 1h, add 2.0g DBSA again, react 2.5h in ice-water bath; React complete extremely neutral by deionized water wash, 50 ℃ of lower vacuum-dryings obtain the DBSA modified carbon nano-tube;
(2) preparation of Graphene: 1.0g graphite scale, 0.5g SODIUMNITRATE and the 25mL vitriol oil are mixed under condition of ice bath, slowly add 3.0g potassium permanganate under the restir, remain on below 10 ℃ and stir 1h, then at 35 ℃ of lower 0.5h that stir, add again the dilution of 50mL deionized water under the ice-water bath, make temperature be lower than 100 ℃, continue to stir 0.5h, after adding again the further dilution of 200mL deionized water, add 10mL 30% H
2O
2, standing demix removes supernatant liquor, and standing demix after the adding 100mL absolute ethyl alcohol and stirring removes supernatant liquor, 3～4 times so repeatedly, obtains the graphite oxide suspension liquid;
The graphite oxide suspension liquid that makes is distributed in the 100mL dehydrated alcohol, behind the supersound process 30min, adds 50mL hydrazine hydrate, 50mL ammoniacal liquor, 95 ℃ of backflow 1h again after mixing, suction filtration, absolute ethanol washing filter cake 3～4 times, after 60 ℃ of vacuum-dryings, grind and obtain Graphene;
(3) preparation of Graphene/DBSA modified carbon nano-tube/polythiophene composite material additive: with Xg(X=0.20～0.40) Graphene, Yg(Y=0.20～0.40) DBSA modified carbon nano-tube, 2.0mL thiophene monomer add in the 80mL trichloromethane, ultrasonic 30min, add the 8.0g FERRIC CHLORIDE ANHYDROUS, suction filtration behind the stirring reaction 10h, methanol wash, deionized water wash to filtrate is colourless, 60 ℃ of vacuum-drying 24h obtain Graphene/DBSA modified carbon nano-tube/polythiophene composite material additive.
2. the preparation method of a kind of Graphene according to claim 1/DBSA modified carbon nano-tube/Polythiophene composite wave-suction material additive, be further characterized in that described composite wave-suction material additive be lower than in 2～18GHz internal reflection rate loss value-frequency span of 10dB reaches 14.2～16.3GHz, minimum reflectance loss value can reach-47～-54dB.
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| CN104212131A (en) * | 2014-07-21 | 2014-12-17 | 中国人民解放军理工大学 | Graphene-polythiophene three-dimensional self-assembling-structured wave-absorbing material and preparation method thereof |
| CN104744895A (en) * | 2014-09-24 | 2015-07-01 | 郑州大学 | Conductive polymer and halloysite nanotube composite wave-absorbing material and preparation method thereof |
| CN106468680A (en) * | 2015-08-19 | 2017-03-01 | Sk新技术株式会社 | The method for evaluating quality of CNT |
| CN106986983A (en) * | 2017-04-25 | 2017-07-28 | 安徽博硕科技有限公司 | A kind of preparation method of polythiophene/graphene/attapulgite conductive composite material |
| CN108948672A (en) * | 2018-06-07 | 2018-12-07 | 高博通信（上海）有限公司 | A kind of preparation method of composite wave-suction material |
| CN109456031A (en) * | 2017-09-06 | 2019-03-12 | 南开大学 | Microwave absorbing material and preparation method thereof comprising carbon nanotube and graphene oxide |
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| CN104212131A (en) * | 2014-07-21 | 2014-12-17 | 中国人民解放军理工大学 | Graphene-polythiophene three-dimensional self-assembling-structured wave-absorbing material and preparation method thereof |
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| CN109456031A (en) * | 2017-09-06 | 2019-03-12 | 南开大学 | Microwave absorbing material and preparation method thereof comprising carbon nanotube and graphene oxide |
| CN108948672A (en) * | 2018-06-07 | 2018-12-07 | 高博通信（上海）有限公司 | A kind of preparation method of composite wave-suction material |
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