CN102977601A - Preparation method of manganese-zinc-ferrite-coated DBSA-modified carbon-nanotube-polyaniline composite wave-absorbing material - Google Patents
Preparation method of manganese-zinc-ferrite-coated DBSA-modified carbon-nanotube-polyaniline composite wave-absorbing material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000011358 absorbing material Substances 0.000 title abstract description 7
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 title abstract 4
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 title abstract 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 38
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 4
- 229910000859 α-Fe Inorganic materials 0.000 claims description 58
- 230000004048 modification Effects 0.000 claims description 52
- 238000012986 modification Methods 0.000 claims description 52
- 239000002041 carbon nanotube Substances 0.000 claims description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 238000005303 weighing Methods 0.000 claims description 22
- -1 carbon nano tube compound Chemical class 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000004448 titration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 abstract 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 abstract 2
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 7
- 230000005291 magnetic effect Effects 0.000 description 5
- 230000009102 absorption Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
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- 230000005389 magnetism Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Carbon And Carbon Compounds (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention provides a preparation method of a manganese-zinc-ferrite-coated DBSA-modified carbon-nanotube-polyaniline composite wave-absorbing material. According to the invention, multi-wall carbon nanotube is modified by using dodecylbenzene sulfonic acid (DBSA); the modified carbon nanotube, MnSO4.H2O, Zn(NO3)2.6H2O, and Fe(NO3)3.9H2O are adopted as raw materials, and a manganese-zinc-ferrite-coated DBSA-modified carbon-nanotube composite material is prepared with a hydrothermal synthesis method; and the material is subjected to in-situ polymerization with aniline monomer, such that the manganese-zinc-ferrite-coated DBSA-modified carbon-nanotube-polyaniline composite wave-absorbing material is prepared. The composite material overcomes defects such as high density and poor dielectric loss of previous wave-absorbing materials, and has excellent impedance matching and loss characteristics. The material has important application value in the field of microwave absorption.
Description
?
Technical field
The invention belongs to the electromagnetic wave absorbent material preparation field, particularly a kind of Mn-Zn ferrite coats the preparation method of the carbon naotube-polyaniline composite wave-suction material of DBSA modification.
Background technology
The nonmetal composite oxides with spinel structure that Mn-Zn ferrite is comprised of manganese, zinc, iron, it is a kind of very important basic function material in the national economic development, compare with metallicl magnetic material of the same type, under high frequency, have the physical and chemical performances such as high magnetic permeability, high resistivity, high saturation and magnetic intensity, low-coercivity and low-loss, be widely used in the industries such as electronics and information industry, electrical appliance industry, network of communication and terminal and instrument.
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.
Polyaniline is cheap with monomer whose, synthesis technique is simple, mechanism of doping effect is special, conductivity is good, stable good and special light, electricity, magnetic property and get more and more people's extensive concerning, and is considered to the most promising a kind of conducting polymer.People are synthetic to it, structure, characteristic and application oneself done a large amount of work, and obtained a series of important achievements, be widely used in many fields.Nowadays, the research of people's p-poly-phenyl amine no longer has been confined to electricity field, find polyaniline and magneticsubstance is compound after, show special optics, magnetics and electric property.
Therefore, the Mn-Zn ferrite that goes out take polyaniline conductive polymer as matrix composition coats DBSA modified carbon nano-tube-polyaniline composite material, dual nature with magnetic and electroconductibility, be to integrate the advanced composite material that ferrite is inhaled ripple, carbon nanotube suction ripple, conducting polymer suction ripple, have broad application prospects at aspects such as sensing technology, electromagnetic shielding and radar absorptions.
Summary of the invention
The purpose of this invention is to provide the preparation method that a kind of Mn-Zn ferrite coats DBSA modified carbon nano-tube-polyaniline compound wave-absorbing material, adding by modified carbon nano-tube, and compound with the layer/polyaniline conductive polymkeric substance, regulate and control the impedance matching property of composites, overcome the large defective of traditional absorbing material density.
The present invention is achieved like this, and its preparation method is as follows:
(1) preparation of DBSA modified carbon nano-tube: be 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, carbon nanotube and DBSA mass ratio are 1:2.React complete extremely neutral by deionized water wash, obtain the DBSA modified carbon nano-tube after 50 ℃ of lower vacuum-dryings.
(2) Mn-Zn ferrite coats the preparation of the carbon nano tube compound material of DBSA modification: at first according to stoichiometric ratio Mn
xZn
1-xFe
2O
4(X=0.3～0.9) takes by weighing respectively 0.10～0.30g MnSO
4H
2O, 0.06～0.42g Zn (NO
3)
26H
2O, 1.60g Fe (NO
3)
39H
2O is dissolved in an amount of distilled water, and ultra-sonic dispersion is processed the 30min dissolve complete, then adds 1.0g DBSA modified carbon nano-tube, behind the supersound process 30min, under magnetic stirring apparatus rapid stirring condition, is titrated to the pH value greater than 8 with 10mol/L NaOH solution again.After titration was finished, standing demix was removed upper clear supernate, and rest part all moves in the reactor, reacts 12h under the temperature 60 C.Be cooled to room temperature, filter, the distilled water wash filter cake is used washing with alcohol 1～2 time again to neutral, and 70～80 ℃ lower dry, obtains the carbon nano tube compound material that Mn-Zn ferrite coats the DBSA modification.
(3) preparation of the carbon naotube-polyaniline composite material of Mn-Zn ferrite coating DBSA modification: take by weighing respectively Yg(Y=0.05～0.15) Mn-Zn ferrite coats the carbon nanotube of DBSA modification, the 1mL aniline monomer, add and fill in the there-necked flask of 35mL 0.1mol/L hydrochloric acid soln, ultra-sonic dispersion 30min, then the 2.50g ammonium persulphate is dissolved in the 15mL 0.1mol/L hydrochloric acid soln, slowly splash in the above-mentioned mixing solutions with dropping funnel, constantly stir lower reaction 12h, filter, use respectively 0.1mol/L hydrochloric acid, deionized water wash product to filtrate is colourless, 60 ℃ of lower vacuum-drying 24h obtain the carbon naotube-polyaniline composite wave-suction material that Mn-Zn ferrite coats the DBSA modification.
With the H-600 transmission electron microscope particle form and size that Mn-Zn ferrite coats the carbon naotube-polyaniline composite wave-suction material of DBSA modification are observed, operating voltage is 75kV.The carbon naotube-polyaniline mixture (X=0.90, Y=0.15) that coats the DBSA modification take Mn-Zn ferrite is as example, and the mixture particle diameter is about 100nm.
With the four point probe conductivity meter specific conductivity that Mn-Zn ferrite coats the carbon naotube-polyaniline composite wave-suction material of DBSA modification is measured.The carbon naotube-polyaniline mixture (X=0.30, Y=0.10) that coats the DBSA modification take Mn-Zn ferrite is as example, and the mixture specific conductivity is 9.59 * 10
-2S/cm.
With vibrating sample magnetometer (VSM) the carbon naotube-polyaniline composite wave-suction material that Mn-Zn ferrite coats the DBSA modification is carried out magnetism testing.The carbon naotube-polyaniline mixture (X=0.30, Y=0.10) that coats the DBSA modification take Mn-Zn ferrite is as example, and test result is: coercive force is 2345.70Oe, and saturation magnetization is 62.95emug
-1, residual magnetization is 39.09emug
-1
Adopt Agilent 8722ES vector network analyzer test Mn-Zn ferrite to coat the carbon naotube-polyaniline composite wave-suction material of DBSA modification at the reflectivity of 2 ~ 18GHz.Coat the carbon naotube-polyaniline mixture (X=0.30 of DBSA modification with Mn-Zn ferrite, Y=0.15) be example, test result is: maximum absorption band appears in the 14.6GHz place, and peak value is-45dB, and reflectivity loss value is lower than-the wide 12.3GHz of reaching of absorption band of 10dB.
Advantage of the present invention:
The present invention at first carries out modification to carbon nanotube and reduces reunion, strengthens the dispersiveness of carbon nanotube, according to Mn
xZn
1-xFe
2O
4The stoichiometric of (X=0.3,0.6,0.9) adopts hydrothermal synthesis method to prepare Mn-Zn ferrite and coats the DBSA modified carbon nano-tube; Then coat the mass ratio 1～3:20 of DBSA modified carbon nano-tube and aniline monomer with Mn-Zn ferrite, adopt situ aggregation method to prepare the carbon naotube-polyaniline composite wave-suction material that Mn-Zn ferrite coats the DBSA modification, this matrix material has overcome the defective that absorbing material density was large in the past, dielectric loss is poor, have excellent impedance matching and loss characteristic, have broad application prospects at aspects such as sensing technology, electromagnetic shielding and radar absorptions.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1
(1) be 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, carbon nanotube and DBSA mass ratio are 1:2.React complete extremely neutral by deionized water wash, 50 ℃ of lower vacuum-dryings obtain the DBSA modified carbon nano-tube.
(2) take by weighing respectively 0.10g MnSO
4H
2O, 0.42g Zn (NO
3)
26H
2O, 1.60g Fe (NO
3)
39H
2O is dissolved in an amount of distilled water, and then supersound process 30min dissolve complete adds 1.0g DBSA modified carbon nano-tube, again behind the supersound process 30min, under magnetic stirring apparatus rapid stirring condition, is titrated to the pH value greater than 8 with 10mol/L NaOH solution.After titration was finished, standing demix was removed upper clear supernate, and all the other all move in the reactor, under 60 ℃, and reaction 12h.Be cooled to room temperature, filter, distilled water is washed till neutrality, washing with alcohol 1～2 time, and 70～80 ℃ are lower dry, obtain the carbon nano tube compound material that Mn-Zn ferrite coats the DBSA modification.
(3) take by weighing respectively the carbon nanotube that the 0.05g Mn-Zn ferrite coats the DBSA modification, the 1mL aniline monomer, add and fill in the there-necked flask of 35mL 0.1mol/L hydrochloric acid soln, ultra-sonic dispersion 30min, then the 2.50g ammonium persulphate is dissolved in the 15mL 0.1mol/L hydrochloric acid soln, slowly splash in the above-mentioned mixing solutions with dropping funnel, constantly stir lower reaction 12h, filter, use respectively 0.1mol/L hydrochloric acid, deionized water wash product to filtrate is colourless, 60 ℃ of lower vacuum-drying 24h, obtain the carbon naotube-polyaniline composite material (X=0.30, Y=0.05) that Mn-Zn ferrite coats the DBSA modification.Prepared matrix material 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-41dB.
Embodiment 2
The preparation method of DBSA modified carbon nano-tube is with embodiment 1 step (1).Accurately take by weighing 0.10g MnSO
4H
2O, 0.42g Zn (NO
3)
26H
2O, 1.60g Fe (NO
3)
39H
2O, preparation method obtain the carbon nano tube compound material that Mn-Zn ferrite coats the DBSA modification with embodiment 1 step (2).Accurately take by weighing carbon nano tube compound material, 1mL aniline monomer that the 0.10g Mn-Zn ferrite coats the DBSA modification, the preparation method is with embodiment 1 step (3), obtain the carbon naotube-polyaniline composite material (X=0.30, Y=0.10) that Mn-Zn ferrite coats the DBSA modification.Prepared matrix material is lower than in 2～18GHz internal reflection rate loss value-and the frequency span of 10dB reaches 13.6GHz, and minimum reflectance loss value can reach-42dB.
Embodiment 3
The preparation method of DBSA modified carbon nano-tube is with embodiment 1 step (1).Accurately take by weighing 0.10g MnSO
4H
2O, 0.42g Zn (NO
3)
26H
2O, 1.60g Fe (NO
3)
39H
2O, preparation method obtain the carbon nano tube compound material that Mn-Zn ferrite coats the DBSA modification with embodiment 1 step (2).Accurately take by weighing carbon nano tube compound material, 1mL aniline monomer that the 0.15g Mn-Zn ferrite coats the DBSA modification, the preparation method is with embodiment 1 step (3), obtain the carbon naotube-polyaniline composite material (X=0.30, Y=0.15) that Mn-Zn ferrite coats the DBSA modification.Prepared matrix material is lower than in 2～18GHz internal reflection rate loss value-and the frequency span of 10dB reaches 12.3GHz, and minimum reflectance loss value can reach-45dB.
Embodiment 4
The preparation method of DBSA modified carbon nano-tube is with embodiment 1 step (1).Accurately take by weighing 0.20g MnSO
4H
2O, 0.24g Zn (NO
3)
26H
2O, 1.60g Fe (NO
3)
39H
2O, preparation method obtain the carbon nano tube compound material that Mn-Zn ferrite coats the DBSA modification with embodiment 1 step (2).Accurately take by weighing carbon nano tube compound material, 1mL aniline monomer that the 0.05g Mn-Zn ferrite coats the DBSA modification, the preparation method is with embodiment 1 step (3), obtain the carbon naotube-polyaniline composite material (X=0.60, Y=0.05) that Mn-Zn ferrite coats the DBSA modification.Prepared matrix material 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-46dB.
Embodiment 5
The preparation method of DBSA modified carbon nano-tube is with embodiment 1 step (1).Accurately take by weighing 0.20g MnSO
4H
2O, 0.24g Zn (NO
3)
26H
2O, 1.60g Fe (NO
3)
39H
2O, preparation method obtain the carbon nano tube compound material that Mn-Zn ferrite coats the DBSA modification with embodiment 1 step (2).Accurately take by weighing carbon nano tube compound material, 1mL aniline monomer that the 0.10g Mn-Zn ferrite coats the DBSA modification, the preparation method is with embodiment 1 step (3), obtain the carbon naotube-polyaniline composite material (X=0.60, Y=0.10) that Mn-Zn ferrite coats the DBSA modification.Prepared matrix material is lower than in 2～18GHz internal reflection rate loss value-and the frequency span of 10dB reaches 15.2GHz, and minimum reflectance loss value can reach-49dB.
Embodiment 6
The preparation method of DBSA modified carbon nano-tube is with embodiment 1 step (1).Accurately take by weighing 0.20g MnSO
4H
2O, 0.24g Zn (NO
3)
26H
2O, 1.60g Fe (NO
3)
39H
2O, preparation method obtain the carbon nano tube compound material that Mn-Zn ferrite coats the DBSA modification with embodiment 1 step (2).Accurately take by weighing carbon nano tube compound material, 1mL aniline monomer that the 0.15g Mn-Zn ferrite coats the DBSA modification, the preparation method is with embodiment 1 step (3), obtain the carbon naotube-polyaniline composite material (X=0.60, Y=0.15) that Mn-Zn ferrite coats the DBSA modification.Prepared matrix material is lower than in 2～18GHz internal reflection rate loss value-and the frequency span of 10dB reaches 14.7GHz, and minimum reflectance loss value can reach-50dB.
Embodiment 7
The preparation method of DBSA modified carbon nano-tube is with embodiment 1 step (1).Accurately take by weighing 0.30g MnSO
4H
2O, 0.06g Zn (NO
3)
26H
2O, 1.60g Fe (NO
3)
39H
2O, preparation method obtain the carbon nano tube compound material that Mn-Zn ferrite coats the DBSA modification with embodiment 1 step (2).Accurately take by weighing carbon nano tube compound material, 1mL aniline monomer that the 0.05g Mn-Zn ferrite coats the DBSA modification, the preparation method is with embodiment 1 step (3), obtain the carbon naotube-polyaniline composite material (X=0.90, Y=0.05) that Mn-Zn ferrite coats the DBSA modification.Prepared matrix material is lower than in 2～18GHz internal reflection rate loss value-and the frequency span of 10dB reaches 16.8GHz, and minimum reflectance loss value can reach-48dB.
Embodiment 8
The preparation method of DBSA modified carbon nano-tube is with embodiment 1 step (1).Accurately take by weighing 0.30g MnSO
4H
2O, 0.06g Zn (NO
3)
26H
2O, 1.60g Fe (NO
3)
39H
2O, preparation method obtain the carbon nano tube compound material that Mn-Zn ferrite coats the DBSA modification with embodiment 1 step (2).Accurately take by weighing carbon nano tube compound material, 1mL aniline monomer that the 0.10g Mn-Zn ferrite coats the DBSA modification, the preparation method is with embodiment 1 step (3), obtain the carbon naotube-polyaniline composite material (X=0.90, Y=0.10) that Mn-Zn ferrite coats the DBSA modification.Prepared matrix material is lower than in 2～18GHz internal reflection rate loss value-and the frequency span of 10dB reaches 15.3GHz, and minimum reflectance loss value can reach-51dB.
Embodiment 9
The preparation method of DBSA modified carbon nano-tube is with embodiment 1 step (1).Accurately take by weighing 0.30g MnSO
4H
2O, 0.06g Zn (NO
3)
26H
2O, 1.60g Fe (NO
3)
39H
2O, preparation method obtain the carbon nano tube compound material that Mn-Zn ferrite coats the DBSA modification with embodiment 1 step (2).Accurately take by weighing carbon nano tube compound material, 1mL aniline monomer that the 0.15g Mn-Zn ferrite coats the DBSA modification, the preparation method is with embodiment 1 step (3), obtain the carbon naotube-polyaniline composite material (X=0.90, Y=0.15) that Mn-Zn ferrite coats the DBSA modification.Prepared matrix material is lower than in 2～18GHz internal reflection rate loss value-and the frequency span of 10dB reaches 14.8GHz, and minimum reflectance loss value can reach-55dB.
Claims (2)
1. a Mn-Zn ferrite coats the preparation method of the carbon naotube-polyaniline composite wave-suction material of DBSA modification, it is characterized in that the preparation method is as follows:
(1) preparation of DBSA modified carbon nano-tube: be 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, carbon nanotube and DBSA mass ratio are 1:2;
React complete extremely neutral by deionized water wash, obtain the DBSA modified carbon nano-tube after 50 ℃ of lower vacuum-dryings;
(2) Mn-Zn ferrite coats the preparation of the carbon nano tube compound material of DBSA modification: at first according to stoichiometric ratio Mn
xZn
1-xFe
2O
4(X=0.3～0.9) takes by weighing respectively 0.10～0.30g MnSO
4H
2O, 0.06～0.42g Zn (NO
3)
26H
2O, 1.60g Fe (NO
3)
39H
2O is dissolved in an amount of distilled water, and ultra-sonic dispersion is processed the 30min dissolve complete, then adds 1.0g DBSA modified carbon nano-tube, behind the supersound process 30min, under magnetic stirring apparatus rapid stirring condition, is titrated to the pH value greater than 8 with 10mol/L NaOH solution again;
After titration was finished, standing demix was removed upper clear supernate, and rest part all moves in the reactor, reacts 12h under the temperature 60 C;
Be cooled to room temperature, filter, the distilled water wash filter cake is used washing with alcohol 1～2 time again to neutral, and 70～80 ℃ lower dry, obtains the carbon nano tube compound material that Mn-Zn ferrite coats the DBSA modification;
(3) Mn-Zn ferrite coats the preparation of the carbon naotube-polyaniline composite material of DBSA modification: the control Mn-Zn ferrite coats the mass ratio 1～3:20 of DBSA modified carbon nano-tube and aniline monomer, taking by weighing respectively Yg(Y=0.05～0.15) Mn-Zn ferrite coats the carbon nanotube of DBSA modification, the 1mL aniline monomer, add and fill in the there-necked flask of 35mL 0.1mol/L hydrochloric acid soln, ultra-sonic dispersion 30min, then the 2.50g ammonium persulphate is dissolved in the 15mL 0.1mol/L hydrochloric acid soln, slowly splash in the above-mentioned mixing solutions with dropping funnel, constantly stir lower reaction 12h, filter, use respectively 0.1mol/L hydrochloric acid, deionized water wash product to filtrate is colourless, 60 ℃ of lower vacuum-drying 24h obtain the carbon naotube-polyaniline composite wave-suction material that Mn-Zn ferrite coats the DBSA modification.
2. a kind of Mn-Zn ferrite according to claim 1 coats the preparation method of the carbon naotube-polyaniline composite wave-suction material of DBSA modification, prepared Mn-Zn ferrite coats the carbon naotube-polyaniline composite wave-suction material of DBSA modification, prepared matrix material is lower than in 2～18GHz internal reflection rate loss value-and the frequency span of 10dB reaches 12.3～16.8GHz, and minimum reflectance loss value can reach-41～-55dB.
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