CN101585959B - Conductive polymer wave-absorbing material - Google Patents
Conductive polymer wave-absorbing material Download PDFInfo
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- CN101585959B CN101585959B CN2008101120791A CN200810112079A CN101585959B CN 101585959 B CN101585959 B CN 101585959B CN 2008101120791 A CN2008101120791 A CN 2008101120791A CN 200810112079 A CN200810112079 A CN 200810112079A CN 101585959 B CN101585959 B CN 101585959B
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Abstract
The invention belongs to the technical field of wave-absorbing materials, and in particular relates to a conductive polymer wave-absorbing material. The material consists of poly(3,4-ethylenedioxythiophene) (PEDOT) microspheres and epoxy resin or organic binder such as polyurethane and the like, wherein the content of the conductive polymer poly(3,4-ethylenedioxythiophene) microspheres in the conductive polymer wave-absorbing material is 20 to 80 percent by mass percentage. The conductive polymer wave-absorbing material has the remarkable advantages of thin coating, light weight and the like, has good wave-absorbing performance on a frequency band of between 2 and 18GHz, has the maximum absorption of -21dB at the frequency of 16GHz particularly, and has good prospect as a radar wave-absorbing material.
Description
Technical field
The invention belongs to the absorbing material technical field, particularly conductive polymer wave-absorbing material.
Background technology
Absorbing material is can absorb to project its surperficial electromagnetic wave energy, and changes a class material of heat energy into by the loss of material.In recent years, along with to the expansion of radar absorbing research and deeply, various novel wave-absorbing materials continue to bring out, and are intended to improve the existence, prominent anti-of stealthy weapon, especially the deep strike ability.At aspect such as satisfy that material (layer) is thin, (matter) is light, (frequently) is wide, (absorbing property) strong, conductive polymers has good application prospects as a kind of novel absorbing material.
Conductive polymers is meant process chemistry with л conjugation backbone or the polymer materials that electrochemical doping can conduct electricity.Mainly contain polyaniline, polypyrrole, Polythiophene etc., they have not only that the general polymer density of material is little, light weight, easily processing, advantage such as inexpensive, conductivity can be regulated and control between isolator, semi-conductor, conductor as required simultaneously, the electrical loss of utilizing it to have, can be used as absorbing material etc., it has caused the people's concern.
Chinese patent 03117132.X discloses the conductive polymers polyaniline and has been coated on magnetic particle Fe
3O
4, Fe
2O
3, Co
2O
3, on the NiO, have electroconductibility and magnetic, provided the saturation magnetization value, but do not had the absorbing property data.Chinese patent 200610037966.8 discloses polyaniline clad nano TiO
2Or TiO
2Whisker modified cyanate under the situation that does not change specific inductivity, increases dielectric loss, and certain wave absorbtion is arranged.Chinese patent 98111335.X discloses electrochemical production polypyrrole/ferrite/composite polypyrrole film, has electroconductibility and magnetic, provided electric conductivity, tensile strength, the saturation magnetization value of film, but it does not provide the absorbing property data yet.Chinese patent 03121536.X and Chinese patent 200410009428.9 disclose Fe, Co, Ni powder and the electrically conductive polyaniline of soft magnetic metal particle Fe, Co, Ni last coating polyaniline and 95% and organic binder bond blend respectively as suction ripple and electromagnetic shielding material, reflectivity preferably reaches-17dB, less than the 1.5GHz frequency range, shielding is higher than 50dB.Document Polym.Adv.Tech. (2001,12,1～7) has reported the electromagnetic performance of the electrically conductive polyaniline of granule-morphology and microtubule pattern, and microtubule pattern polyaniline not only has electrical loss and has magnetic loss simultaneously, can be used as novel wave-absorbing material.
Poly-(3, the 4-dioxoethyl) thiophene (PEDOT) is in conductive polymers family, have high conductivity, low band gaps width, outstanding stability, realizing commercial applications aspect anti-static coating, the solid capacitor, but do not seeing that aspect absorbing material document and patent report are arranged.
Summary of the invention
The purpose of this invention is to provide a kind of conductive polymer wave-absorbing material with advantages such as density are light, absorbing property is good.
A further object of the present invention provides the method that is used to prepare poly-(3, the 4-dioxoethyl) thiophene (PEDOT) microballoon of conductive polymer wave-absorbing material.
Conductive polymer wave-absorbing material of the present invention, by poly-(3, the 4-dioxoethyl) organic binder bonds such as thiophene (PEDOT) microballoon and Resins, epoxy or urethane are formed, wherein the quality percentage composition of the conductive polymer poly in the conductive polymer wave-absorbing material (3, the 4-dioxoethyl) thiophene (PEDOT) microballoon is 20～80%.
The conductive polymer wave-absorbing material that obtains is coated on the thick aluminium sheet of 2～5mm of 180mm * 180mm size, and glue spread is 0.5kg/m
2～5kg/m
2, 1kg/m preferably
2～3kg/m
2, the coating back is solidified dry down in 40～100 ℃; Test its performance, conductive polymer wave-absorbing material of the present invention has absorbing property on 2～18GHz frequency band, and maximum absorption (reflectivity) reaches-21dB.
The particle diameter of described poly-(3, the 4-dioxoethyl) thiophene microballoon is between 50nm～10 μ m, and specific conductivity is 1 * 10
-4～100S/cm.
Described poly-(3, the 4-dioxoethyl) thiophene microballoon is solid microsphere and/or tiny balloon.
The particle diameter of described poly-(3, the 4-dioxoethyl) thiophene solid microsphere is between 50nm～10 μ m, and specific conductivity is 1 * 10
-2Between～the 100S/cm.
The particle diameter of described poly-(3, the 4-dioxoethyl) thiophene tiny balloon is between 100nm～10 μ m, and specific conductivity is 1 * 10
-4Between～the 10S/cm.
Described Resins, epoxy can be commercially available epoxy resin-based paint.
Described urethane can be commercially available polyurethane paint.
The preparation method of conductive polymer wave-absorbing material of the present invention is: will gather (3, the 4-dioxoethyl) thiophene (PEDOT) microballoon is dispersed in the organic binder bonds such as Resins, epoxy or urethane, obtain conductive polymer wave-absorbing material, wherein the quality percentage composition of poly-(3, the 4-dioxoethyl) thiophene (PEDOT) microballoon in the conductive polymer wave-absorbing material is 20～80%.
Poly-(3, the 4-dioxoethyl) thiophene (PEDOT) microballoon among the present invention prepares by method of emulsion polymerization, and this method may further comprise the steps:
1) be solvent with water and acetonitrile mixed solution, the preparation mass concentration is 1%～10% water-soluble polymer solution, and wherein: the volume ratio of water and acetonitrile is 1: 2～20: 1, is preferably 2: 1～5: 1;
2) oxygenant is joined in the water-soluble polymer solution of step 1) preparation, stirring and dissolving, the volumetric molar concentration of oxygenant in water-soluble polymer solution is 1.0 * 10
-3～1.0mol/L obtains the mixed solution of water-soluble polymer solution and oxygenant;
3) under agitation condition, sour doping agent is joined step 2) in the mixed solution that obtains, the concentration of acid doping agent in mixed solution is 0.1～0.5mol/L, after stirring, add 3,4-dioxoethyl thiophene (EDOT), wherein: 3 of adding, the molar weight of 4-dioxoethyl thiophene (EDOT) is a step 2) in 0.05～3 times of the oxygenant molar weight that adds; At room temperature continue stirring reaction 12 hours～72 hours, obtain containing the black emulsion of conductive polymer poly (3, the 4-dioxoethyl) thiophene (PEDOT) solid microsphere;
4) the black emulsion that contains conductive polymer poly (3, the 4-dioxoethyl) thiophene (PEDOT) solid microsphere that step 3) is obtained obtains the Dark grey blocks of solid 40～80 ℃ of oven dry down; This solid is ground, cross 120 mesh sieves, obtain dark gray powder; To soak 0.5～2 hour in this dark gray powder immersion water and the ethanol mixed solvent; Suction filtration then, and with an amount of water and alcohol mixed solvent drip washing, colourless substantially up to leacheate, the filter cake that obtains has obtained graphite glossy black powder at 40～90 ℃ of following vacuum dryings; Above-mentioned black powder promptly is the conductive polymer poly described in the present invention (3, the 4-dioxoethyl) thiophene (PEDOT) solid microsphere, its particle diameter between 50nm～10 μ m, 100nm～2 μ m preferably.Its specific conductivity is 1 * 10
-2Between～the 100S/cm; Or
A) be solvent with water and acetonitrile mixed solution, the preparation mass concentration is 1%～10% water-soluble polymer solution; Wherein: the volume ratio of water and acetonitrile is 1: 2～20: 1, is preferably 2: 1～5: 1;
B) oxygenant is joined in the water-soluble polymer solution of step a) preparation, stirring and dissolving, the volumetric molar concentration of oxygenant in water-soluble polymer solution is 1.0 * 10
-3～1.0mol/L obtains the mixed solution of water-soluble polymer solution and oxygenant;
C) under agitation condition, with 3,4-dioxoethyl thiophene (EDOT) joins in the mixed solution that step b) obtains, wherein: 3 of adding, the molar weight of 4-dioxoethyl thiophene (EDOT) are 0.2～10 times of the oxygenant molar weight that adds in the step b); At room temperature continue stirring reaction 12 hours～72 hours, and obtained containing the black emulsion of conductive polymer poly (3, the 4-dioxoethyl) thiophene (PEDOT) tiny balloon;
D) the black emulsion that contains conductive polymer poly (3, the 4-dioxoethyl) thiophene (PEDOT) tiny balloon that step c) is obtained obtains the Dark grey blocks of solid 40～80 ℃ of oven dry down; This solid is ground, cross 120 mesh sieves, obtain dark gray powder; To soak 0.5～2 hour in this dark gray powder immersion water and the ethanol mixed solvent; Suction filtration then, and with an amount of water and alcohol mixed solvent drip washing, colourless substantially up to leacheate, the filter cake that obtains has obtained graphite glossy black powder at 40～90 ℃ of following vacuum dryings; Above-mentioned black powder promptly is the conductive polymer poly described in the present invention (3, the 4-dioxoethyl) thiophene (PEDOT) tiny balloon, its particle diameter between 100nm～10 μ m, 200nm～2 μ m preferably.Its specific conductivity is 1 * 10
-4Between～the 10S/cm.
Described water-soluble polymer comprises polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP) or polyoxyethylene glycol (PEG) etc.
Described oxygenant is, iron trichloride, hydrochloro-auric acid, ammonium persulphate or Potassium Persulphate etc.; Preferably when preparation conductive polymer poly (3, the 4-dioxoethyl) thiophene solid microsphere, use ammonium persulphate, iron trichloride or hydrochloro-auric acid; When preparation conductive polymer poly (3, the 4-dioxoethyl) thiophene tiny balloon with ammonium persulphate or Potassium Persulphate.
Described sour doping agent can be beta-naphthalenesulfonic-acid, tosic acid or camphorsulfonic acid etc.
Described water and alcoholic acid volume ratio are 1: 1.
Poly-(3, the 4-dioxoethyl) thiophene (PEDOT) microballoon that the present invention utilizes emulsion polymerization to prepare as radar absorbing, is principal character of the present invention with it.It is thin that conductive polymer wave-absorbing material of the present invention has coating, the outstanding advantage of grade in light weight, and it reaches maximum absorption (reflectivity)-21dB when the 16GHz frequency.
Description of drawings
Fig. 1. the SEM photo of poly-(3, the 4-dioxoethyl) thiophene (PEDOT) microballoon of the embodiment of the invention 1 preparation.
Fig. 2. the SEM photo of poly-(3, the 4-dioxoethyl) thiophene (PEDOT) microballoon of the embodiment of the invention 2 preparations.
Embodiment
Embodiment 1
1) be that 10: 1 the water and the mixed solution of acetonitrile are solvent with volume ratio, the preparation mass concentration is 3% water-soluble polymer polyvinyl alcohol (PVA) solution.
2) in the water-soluble polymer solution of step 1) preparation, add the oxygenant iron trichloride, stirring and dissolving, the volumetric molar concentration of iron trichloride in polyvinyl alcohol (PVA) aqueous solution is 0.05mol/L, obtains the mixed solution of iron trichloride and polyvinyl alcohol (PVA).
3) under agitation condition, sour doping agent beta-naphthalenesulfonic-acid is joined step 2) in the mixed solution that obtains, the volumetric molar concentration of acid doping agent beta-naphthalenesulfonic-acid in mixed solution is 0.3mol/L, after stirring, add 3,4-dioxoethyl thiophene (EDOT), wherein: 3 of adding, the molar weight of 4-dioxoethyl thiophene (EDOT) is a step 2) in 0.5 times of the iron trichloride molar weight that adds.At room temperature continue stirring reaction 24 hours, obtain containing the black emulsion of conductive polymer poly (3, the 4-dioxoethyl) thiophene (PEDOT) solid microsphere.
4) the black emulsion in the step 3) is dried down at 60 ℃, obtain the Dark grey blocks of solid.This solid is ground, cross 120 mesh sieves, obtain dark gray powder.This dark gray powder is immersed 20 times of immersions 2 hours in the water of its quality and ethanol mixed solvent (volume ratio is 1: 1), suction filtration then, and with an amount of water and ethanol mixed solvent (volume ratio is 1: 1) drip washing, colourless substantially up to leacheate, the filter cake that obtains is at 70 ℃ of following vacuum dryings, obtained graphite glossy black powder, it is conductive polymer poly (3, the 4-dioxoethyl) thiophene (PEDOT) solid microsphere, its stereoscan photograph such as Fig. 1, particle is even-grained sphere, and particle diameter is about 100nm, and the surface is coarse slightly.Recording specific conductivity is 3.8S/cm.
5) poly-(3, the 4-dioxoethyl) thiophene (PEDOT) solid microsphere that step 4) is prepared is dispersed in and obtains conductive polymer wave-absorbing material in the epoxy adhesive, and wherein the quality percentage composition of poly-(3, the 4-dioxoethyl) thiophene (PEDOT) is 30%.This absorbing material is coated on the thick aluminium sheet of the 3mm of 180mm * 180mm size, and glue spread is 1kg/m
2, the coating back is solidified dry down in 80 ℃, and the about 1mm of thickness has certain absorbing property on 2.0～18GHz frequency band, and wherein at peak value 5GHz place, reflectivity is-5dB.
Embodiment 2
1). with volume ratio is that 5: 1 the water and the mixture of acetonitrile are solvent, and the preparation mass concentration is 5% polyvinylpyrrolidone (PVP) solution.
2). add ammonium persulphate as oxygenant in polyvinylpyrrolidone (PVP) solution of step 1) preparation, stirring and dissolving is even, and the volumetric molar concentration of ammonium persulphate in solution is 0.1mol/L, obtains ammonium persulphate and the polyvinylpyrrolidone (mixed solution of PVP.
3) under agitation condition, with 3,4-dioxoethyl thiophene (EDOT) joins step 2) in the mixed solution that obtains, wherein: 3 of adding, the molar weight of 4-dioxoethyl thiophene (EDOT) is a step 2) in 2 times of the ammonium persulphate molar weight that adds, at room temperature continue stirring reaction 72 hours, obtain containing poly-(3, the 4-dioxoethyl) thiophene (PEDOT) tiny balloon black emulsion.
4) the black emulsion in the step 3) is dried down at 40 ℃, obtain the Dark grey blocks of solid.This solid is ground, cross 120 mesh sieves, obtain dark gray powder.This dark gray powder is immersed 20 times of immersions 1 hour in the water of its quality and ethanol mixed solvent (volume ratio is 1: 1), suction filtration then, and with an amount of water and ethanol mixed solvent (volume ratio is 1: 1) drip washing, colourless substantially up to leacheate, the filter cake that obtains is at 50 ℃ of following vacuum dryings, obtained graphite glossy black powder, it is conductive polymer poly (3, the 4-dioxoethyl) thiophene (PEDOT) tiny balloon, stereoscan photograph such as Fig. 2, particle are tiny balloon shape, smooth surface, local granule has recessed flat phenomenon, the about 500nm of granular size～1.2 μ m.Recording specific conductivity is 1.3 * 10
-1S/cm.
5). gather (3 with what obtain in the step 4), the 4-dioxoethyl) thiophene (PEDOT) tiny balloon is evenly dispersed in the polyurethane paint, obtain conductive polymer wave-absorbing material, wherein gather (3, the 4-dioxoethyl) mass percentage concentration of thiophene (PEDOT) microballoon is 50%, it is coated on the thick aluminium sheet of the 3mm of 180mm * 180mm size, and glue spread is 2kg/m
2, coating back is solidified the about 2mm of dry film thickness down in 70 ℃, on the broadband of 13.0～18GHz reflectivity-more than the 10dB, wherein at maximum absorption 16GHz place, reflectivity can reach-21dB, shows the absorbing property of excellence.
Embodiment 3
1) be that 6: 1 the water and the mixed solution of acetonitrile are solvent with volume ratio, the preparation mass concentration is 2% water-soluble polymer polyvinylpyrrolidone (PVP) solution.
2) in the water-soluble polymer solution of step 1) preparation, add the oxidants chlorine auric acid, stirring and dissolving, the volumetric molar concentration of hydrochloro-auric acid in polyvinylpyrrolidone (PVP) aqueous solution is 0.3mol/L, obtains the mixed solution of hydrochloro-auric acid and polyvinylpyrrolidone (PVP).
3) under agitation condition, sour doping agent tosic acid is joined step 2) in the mixed solution that obtains, the volumetric molar concentration of acid doping agent tosic acid in mixed solution is 0.1mol/L, after stirring, add 3,4-dioxoethyl thiophene (EDOT), wherein: 3 of adding, the molar weight of 4-dioxoethyl thiophene (EDOT) is a step 2) in 3 times of the iron trichloride molar weight that adds.At room temperature continue stirring reaction 48 hours, obtain containing the black emulsion of conductive polymer poly (3, the 4-dioxoethyl) thiophene (PEDOT) solid microsphere.
4) the black emulsion in the step 3) is dried down at 50 ℃, obtain the Dark grey blocks of solid.This solid is ground, cross 120 mesh sieves, obtain dark gray powder.This dark gray powder is immersed 20 times of immersions 2 hours in the water of its quality and ethanol mixed solvent (volume ratio is 1: 1), suction filtration then, and with an amount of water and ethanol mixed solvent (volume ratio is 1: 1) drip washing, colourless substantially up to leacheate, the filter cake that obtains is at 50 ℃ of following vacuum dryings, obtained graphite glossy black powder, it is conductive polymer poly (3, the 4-dioxoethyl) thiophene (PEDOT) solid microsphere, particle is even-grained sphere, particle diameter is about 130nm, and recording specific conductivity is 6.3S/cm.Standby.
5). with volume ratio is that 8: 1 the water and the mixture of acetonitrile are solvent, and the preparation mass concentration is 4% polyvinyl alcohol (PVA) solution.
6). add Potassium Persulphate as oxygenant in polyvinyl alcohol (PVA) solution of step 5) preparation, stirring and dissolving is even, and the volumetric molar concentration of Potassium Persulphate in solution is 0.1mol/L, obtains the mixed solution of Potassium Persulphate and polyvinyl alcohol (PVA).
7) under agitation condition, with 3,4-dioxoethyl thiophene (EDOT) joins in the mixed solution that step 6) obtains, wherein: 3 of adding, the molar weight of 4-dioxoethyl thiophene (EDOT) is a step 2) in 6 times of the ammonium persulphate molar weight that adds, at room temperature continue stirring reaction 24 hours, obtain containing the black emulsion of poly-(3, the 4-dioxoethyl) thiophene (PEDOT) tiny balloon.
8) the black emulsion in the step 7) is dried down at 40 ℃, obtain the Dark grey blocks of solid.This solid is ground, cross 120 mesh sieves, obtain dark gray powder.This dark gray powder is immersed 20 times of immersions 1 hour in the water of its quality and ethanol mixed solvent (volume ratio is 1: 1), suction filtration then, and with an amount of water and ethanol mixed solvent (volume ratio is 1: 1) drip washing, colourless substantially up to leacheate, the filter cake that obtains is at 60 ℃ of following vacuum dryings, obtained graphite glossy black powder, it is conductive polymer poly (3, the 4-dioxoethyl) thiophene (PEDOT) tiny balloon, smooth surface, the about 700nm of granular size～1.0 μ m, recording specific conductivity is 1.9 * 10
-2/ cm.Standby.
9). gather (3 with what obtain in the step 4), what the 4-dioxoethyl) thiophene (PEDOT) solid microsphere and step 8) obtained gathers (3, the 4-dioxoethyl) thiophene (PEDOT) tiny balloon is evenly dispersed in the polyurethane paint, obtain conductive polymer wave-absorbing material, wherein gather (3, the 4-dioxoethyl) mass percentage concentration of thiophene (PEDOT) solid microsphere is 20%, poly-(3, the 4-dioxoethyl) mass percentage concentration of thiophene (PEDOT) hollow ball is 40%, it is coated on the thick aluminium sheet of the 3mm of 180mm * 180mm size, and glue spread is about 3kg/m
2, coating back is solidified the about 3mm of dry film thickness down in 70 ℃, on the broadband of 8.0～14GHz reflectivity-more than the 10dB, wherein at the about 10GHz of maximum absorption place, reflectivity can reach-17dB, shows the absorbing property of excellence.
Claims (3)
1. conductive polymer wave-absorbing material, it is characterized in that, this material is by poly-(3, the 4-dioxoethyl) thiophene tiny balloon and Resins, epoxy or urethane organic binder bond are formed, wherein the quality percentage composition of the conductive polymer poly in the conductive polymer wave-absorbing material (3, the 4-dioxoethyl) thiophene tiny balloon is 20～80%;
Described poly-(3, the 4-dioxoethyl) thiophene tiny balloon prepares by method of emulsion polymerization, and this method may further comprise the steps:
A) be solvent with water and acetonitrile mixed solution, the preparation mass concentration is 1%～10% water-soluble polymer solution; Wherein: the volume ratio of water and acetonitrile is 1: 2～20: 1;
B) oxygenant is joined in the water-soluble polymer solution of step a) preparation, stirring and dissolving, the volumetric molar concentration of oxygenant in water-soluble polymer solution is 1.0 * 10
-3～1.0mol/L obtains water-soluble polymer solution and oxygenant mixed solution;
C) under agitation condition, with 3,4-dioxoethyl thiophene joins in the mixed solution that step b) obtains, wherein: 3 of adding, the molar weight of 4-dioxoethyl thiophene are 0.2～10 times of the oxygenant molar weight that adds in the step b); At room temperature continue stirring reaction, obtain containing the emulsion of conductive polymer poly (3, the 4-dioxoethyl) thiophene tiny balloon;
D) emulsion that contains conductive polymer poly (3, the 4-dioxoethyl) thiophene tiny balloon that step c) is obtained obtains solid 40～80 ℃ of oven dry down; This solid is ground, cross 120 mesh sieves, obtain powder; To soak in this powder immersion and the ethanol mixed solvent; Suction filtration, and water then and alcohol mixed solvent drip washing, the filter cake that obtains obtain conductive polymer poly (3, the 4-dioxoethyl) thiophene tiny balloon at 40～90 ℃ of following vacuum dryings;
The particle diameter of described poly-(3, the 4-dioxoethyl) thiophene tiny balloon is between 100nm～10 μ m, and specific conductivity is 1 * 10
-4Between～the 10S/cm.
2. conductive polymer wave-absorbing material according to claim 1, it is characterized in that: described by poly-(3, the 4-dioxoethyl) conductive polymer wave-absorbing material of thiophene tiny balloon and Resins, epoxy or urethane organic binder bond composition is on 2～18GHz frequency band, have absorbing property, maximum absorption reaches-21dB.
3. conductive polymer wave-absorbing material according to claim 1 is characterized in that: described water-soluble polymer is polyvinyl alcohol, polyvinylpyrrolidone or polyoxyethylene glycol;
Described oxygenant is iron trichloride, hydrochloro-auric acid, ammonium persulphate or Potassium Persulphate.
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| CN102344648B (en) * | 2010-08-02 | 2014-01-08 | 中国科学院理化技术研究所 | Conductive polymer-magnetic material composite absorbing material |
| CN102344552B (en) * | 2010-08-02 | 2012-10-03 | 中国科学院理化技术研究所 | Preparation method of three-dimensional chrysanthemum-shaped poly (3, 4-ethylenedioxythiophene) nanostructural material |
| CN102634169B (en) * | 2011-02-15 | 2014-08-20 | 中国科学院理化技术研究所 | Wave-absorbing material composited by magnetic material and conducting polymer as well as preparation method thereof |
| CN102250324B (en) * | 2011-05-20 | 2012-09-12 | 中国科学院理化技术研究所 | Preparation method of poly(3,4-ethylenedioxythiophene) (PEDOT)-coated carbon nanotube composite material |
| CN105017509A (en) * | 2014-04-22 | 2015-11-04 | 中国人民解放军理工大学 | Preparation method of polythiophene wave-absorbing material |
| CN103965586B (en) * | 2014-05-19 | 2016-02-10 | 哈尔滨工业大学 | A kind of preparation method of the Wave suction composite material as coating or packing layer |
| CN105153883B (en) * | 2015-09-17 | 2017-10-27 | 中国科学院理化技术研究所 | A kind of polythiophene composition metal anticorrosive paint of pattern influence, preparation method and applications |
| CN106028767B (en) * | 2016-05-11 | 2018-09-14 | 合肥师范学院 | A kind of composite electromagnetic absorption material and preparation method thereof |
| CN109971243B (en) * | 2017-12-27 | 2021-03-02 | 中国科学院化学研究所 | Ink for wave-absorbing coating, wave-absorbing coating material and preparation method thereof |
| CN109233743B (en) * | 2018-10-25 | 2021-11-09 | 中北大学 | Light wave-absorbing composite material with coal ash-based core-shell structure and preparation method thereof |
| CN115595797A (en) * | 2021-07-08 | 2023-01-13 | 天津工业大学（Cn） | Polypyrrole/polyethylene geotextile wave-absorbing material for building and preparation method thereof |
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