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CN102391831A - Carbon nanotube composite material modified by magnetic nanoparticles, its preparation method and application - Google Patents

Carbon nanotube composite material modified by magnetic nanoparticles, its preparation method and application Download PDF

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Publication number
CN102391831A
CN102391831A CN2011104021944A CN201110402194A CN102391831A CN 102391831 A CN102391831 A CN 102391831A CN 2011104021944 A CN2011104021944 A CN 2011104021944A CN 201110402194 A CN201110402194 A CN 201110402194A CN 102391831 A CN102391831 A CN 102391831A
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carbon nanotube
preparation
modified
electromagnetic shielding
magnetic
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车仁超
陈华骏
刘继伟
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Fudan University
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Fudan University
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Abstract

The invention, belonging to the technical field of electromagnetic shielding materials, particularly discloses a carbon nanotube composite material modified by magnetic nanoparticles, its preparation method and application. The preparation method comprises the following steps: firstly, heating a carbon nanotube in mixed acid to reflux, introducing carbonyl, carboxyl or hydroxy and other function groups on the carbon nanotube; next, using ferric trichloride as the iron source, adding 1,6-hexylenediamine, anhydrous sodium acetate and ethanol to react in a high temperature reaction vessel to obtain nano magnetic particles with a surface carrying amino; and finally, dissolving the modified carbon nanotube and magnetic particles in a solution of 1-ethyl-(3-dimethyl amino propyl) carbonyl diimine and N-hydroxy succinimide at room temperature, and carrying out stirring and centrifugation to obtain a final product. The composite material can be used as an electromagnetic shielding material. The prepared electromagnetic shielding material has characteristics of electrical loss and magnetic loss, and has the advantages of strong absorption, wide frequency band, light weight and good stability.

Description

The carbon nano tube compound material that a kind of magnetic nanoparticle is modified
Technical field
The invention belongs to the inorganic nano composite material field, be specifically related to a kind of electromagnetic shielding material and method of manufacture thereof and application.
Background technology
Electromagnetic shielding material is meant and can absorbs the electromagnetic wave energy that projects its surface, and makes electromagnetic wave energy be converted into one type of material of heat energy or other form energies through the dielectric loss of material.Nowadays, the electromagnetic radiation pollution problem that the electronic industry fast development brings is serious day by day, and the research of therefore carrying out the absorbing material preparation has far reaching significance.Carbon nanotube shows special electromagnetic property, makes its application on stealthy absorbing material that very big potentiality arranged.Carbon nanotube; It is the seamless accurate one dimension hollow tubular nanostructure that the graphite face curls and forms; It is then less to tens nanometer internal diameters that O.D.T. is generally several nanometers, and just about 1nm, pipe range can reach tens microns even longer sometimes. and the specific surface area of carbon nanotube is big, length-to-diameter ratio is high and particular structural such as small size; Also have its special electromagnetic property that shows, make its application on stealthy absorbing material that very big potentiality arranged.Compare with traditional absorbing material; Yet carbon nanotube possesses such as the character as the high-quality wave-absorbing coating material such as light weight, oxidation-resistance, high stability.; Though researcher has poured into a large amount of energy in the research of carbon nanotube absorbing material, also have a lot of difficult problems to need to solve.Therefore, on the basis of existing absorbing material technology, the exploratory development of actively developing the absorbing material of new kind, new ideas, new technology approach seems very important.
Summary of the invention
The purpose of this invention is to provide a kind of carbon nano tube compound material and method of manufacture thereof that absorbs strong, bandwidth, in light weight, good stability, and the application of this matrix material aspect electromagnetic shielding.
Carbon nano tube compound material provided by the invention is a kind of carbon nano tube compound material of Z 250 finishing, is promptly evenly modifying nano magnetic particle on the external diameter of carbon nanotube, and the molecular formula of this nano magnetic particle is Fe 3O 4
The present invention also provides the preparation method of the carbon nano tube compound material of above-mentioned magnetic nanoparticle modification, comprises with commercial multi-walled carbon nano-tubes being the carbon nanotube of feedstock production surface-treated; With the iron trichloride is source of iron, 1, and the 6-hexanediamine is the ammonia source, ethanol is the amino nano magnetic particle of reductive agent preparation surface band; At last through organic crosslinked matrix material for preparing.Concrete steps are following:
(1) surface of carbon nanotube changes surname; 0.1-0.2 gram carbon nanotube is dispersed in the mixing solutions that the 35--45 milliliter is made up of for 1:2.5-1:3.5 nitric acid and sulfuric acid by volume; Stirred 3.5-4.5 hours down at 65--75 degree centigrade; Arrive neutrality, spinning again with washed with de-ionized water to pH value then;
(2) preparation of ferroferric oxide nano granules adds 1--2 gram iron trichloride, 7--9 gram 1 in beaker; The 6-hexanediamine, 2-3 gram sodium acetate, anhydrous and 30--40 milliliter ethanol are transferred in the pyroreaction still after 45--55 degree centigrade is fully stirred down; Reaction is 5--7 hour under the 190--200 degrees celsius; Obtain the amino nano magnetic particle of surface band, behind cool to room temperature, separate, clean the back oven dry with deionized water with magnet;
(3) carbon nanotube of the surface-treated of step (1) preparation is put into beaker; Add nano magnetic particle, 5--7 milligram 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimine and 7.5-8.5 milligrams of N-hydroxy-succinamides that the 30--35 milligram is prepared by step (2), at room temperature vibrated 4--5 hour; Carry out spinning, and use washed with de-ionized water, promptly obtain title product.
The inventive method realizes the coating of magnetic-particle in carbon nano tube surface, thereby reaches the unification of electrical loss and magnetic loss, and the enhancing of capability of electromagnetic shielding can be used as electromagnetic shielding material.
Description of drawings
Fig. 1 is preparing method's flow process diagram of matrix material of the present invention.
Fig. 2 is the image of matrix material of the present invention.Wherein, a) images of transmissive electron microscope of the carbon nanotube of surface-treated; B) scanning electron microscope image of Z 250/carbon nanotube composite electromagnetic shield materials can find out that carbon nano tube surface magnetic-particle charge capacity is big from figure, the pattern homogeneous is about 20-40nm; C) the projection sem image of Z 250/carbon nanotube composite electromagnetic shield materials; D) the high-resolution-ration transmission electric-lens lattice fringe picture of Z 250/carbon nanotube structural interface place's carbon nanotube and Z 250 can find out that the spacing of magnetic-particle is 0.25nm, corresponding to (311) face of Z 250 from figure.
Fig. 3 is the magnetic hysteresis loop of matrix material of the present invention.Wherein, a) carbon nanotube, b) Z 250, c), d) adopt the magnetic hysteresis loop of the carbon nanotube composite materials of the present invention's preparation at 300K.
Fig. 4 is the capability of electromagnetic shielding test pattern of matrix material of the present invention.Wherein, a) carbon nanotube, b) Z 250, c), d) adopt the capability of electromagnetic shielding test pattern of carbon nanotube composite materials in the 2-18Ghz frequency range of the present invention's preparation.Figure floating coat thickness is 2mm, and maximum reflection loss reaches when 9.5Ghz-11dB.
Embodiment
Following instance will combine accompanying drawing that the present invention is described further.Present embodiment provided detailed embodiment and process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.The experimental technique of unreceipted actual conditions in the following example is usually according to normal condition.
Embodiment 1
(1) 0.1 gram carbon nanotube being dispersed in 40 milliliters of concentrated nitric acids and vitriol oil volume ratio is in the mixing solutions of 1:3. this mixture takes out after 4 hours 70 degrees centigrade of mechanical stirring, with the spinning afterwards of washed with de-ionized water to pH value arrival neutrality.
(2) in beaker, add 1 gram iron trichloride; 7 grams 1,6-hexanediamine, 2 gram sodium acetate, anhydrous and 30 milliliters of ethanol; Fully transfer to the pyroreaction still after the stirring at 50 degrees centigrade; Reaction obtained the amino nano magnetic particle of surface band in 6 hours under 190 degrees celsius, behind cool to room temperature, separated with magnet, cleaned the back oven dry with deionized water.
(3) carbon nanotube of above-mentioned surface-treated is put into beaker; Add 30 milligrams of nano magnetic particle, 5 milligrams of 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimines and 7.5 milligrams of N-hydroxy-succinamides that prepare by (2); At room temperature vibrated 4 hours; Through spinning, and repeatedly obtain title product with washed with de-ionized water.
Adopt the capability of electromagnetic shielding of carbon nanotube composite materials in the 2-18Ghz frequency range of the present invention's preparation to be-8dB~-11dB.
The present invention provided a kind of simple and easy, effectively, repeatably prepare the method for carbon nanotube/magnetic-particle composite electromagnetic shield materials.In the composite nano materials that obtains, monodispersed magnetic-particle is coated on carbon nano tube surface equably.And the charge capacity of magnetic-particle can be regulated through changing experiment parameter, thereby changes the shielding properties and the mass density of this matrix material.Final this matrix material of capability of electromagnetic shielding test proof has the excellent shielding properties that is superior to independent carbon nanotube or magnetic-particle.

Claims (3)

1. the carbon nano tube compound material that magnetic nanoparticle is modified is characterized in that on the external diameter of carbon nanotube, evenly being modified with nano magnetic particle, and described nano magnetic particle is a Z 250, and molecular formula is Fe 3O 4
2. the preparation method of the carbon nano tube compound material that magnetic nanoparticle according to claim 1 is modified is characterized in that concrete steps are following:
(1) surface-treated of carbon nanotube; 0.1-0.2 gram carbon nanotube is dispersed in the mixing solutions that the 35--45 milliliter is made up of for 1:2.5-1:3.5 nitric acid and sulfuric acid by volume; Stirred 3.5-4.5 hours down at 65--75 degree centigrade; Arrive neutrality, spinning again with washed with de-ionized water to pH value then;
(2) preparation of ferroferric oxide nano granules adds 1--2 gram iron trichloride, 7--9 gram 1 in beaker; The 6-hexanediamine, 2-3 gram sodium acetate, anhydrous and 30--40 milliliter terepthaloyl moietie are transferred in the pyroreaction still after 45--55 degree centigrade is fully stirred down; Reaction is 5--7 hour under the 190--200 degrees celsius; Obtain the amino nano magnetic particle of surface band, behind cool to room temperature, separate, clean the back oven dry with deionized water with magnet;
(3) carbon nanotube of the surface-treated of step (1) preparation is put into beaker; Add nano magnetic particle, 5--7 milligram 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimine and 7.5-8.5 milligrams of N-hydroxy-succinamides that the 30--35 milligram is prepared by step (2), at room temperature vibrated 4--5 hour; Carry out spinning, and use washed with de-ionized water, promptly obtain title product.
3. the carbon nano tube compound material that magnetic nanoparticle as claimed in claim 1 is modified is as the application of electromagnetic shielding material.
CN2011104021944A 2011-12-07 2011-12-07 Carbon nanotube composite material modified by magnetic nanoparticles, its preparation method and application Pending CN102391831A (en)

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CN103115947A (en) * 2013-03-05 2013-05-22 济南大学 Preparation method and application of carbon-doped mesoporous metal oxide acetone sensor
CN104479626A (en) * 2014-12-05 2015-04-01 吉林大学 Graphitization multiwall carbon nanotube/nano-particle composite absorbing agent and preparation method thereof
CN104882346A (en) * 2015-04-02 2015-09-02 天津师范大学 Method for preparing field emission cathode of carbon nanotube array coated with carbon nanoparticles
CN105749881A (en) * 2016-03-10 2016-07-13 江苏省农业科学院 Preparation method and application of carbon nanotube polyvinyl alcohol magnetic microspheres
CN106047290A (en) * 2016-06-24 2016-10-26 中国科学院理化技术研究所 Method for uniformly coating carbon nano tube with nano ferroferric oxide magnetic particles
CN107010613A (en) * 2017-02-22 2017-08-04 延边大学 The preparation method of conductive magneto-conductive nano-functional material
CN108031440A (en) * 2017-12-15 2018-05-15 中国科学院烟台海岸带研究所 A kind of composite material and its preparation and absorption, remove water body in chromium application
CN108199150A (en) * 2017-12-30 2018-06-22 吴迪 A kind of preparation method of the carbon-based absorbing material of strong absorbent
CN108246258A (en) * 2018-01-29 2018-07-06 浙江海洋大学 A kind of preparation method of magnetism aminated carbon nano tube
CN108558328A (en) * 2018-04-04 2018-09-21 北京工业大学 A kind of Electromagnetically shielding cement based composites and preparation method thereof
CN109806868A (en) * 2018-07-02 2019-05-28 陈天仪 A kind of organic wastewater degraded agent of recyclable recycling
CN110559935A (en) * 2019-10-25 2019-12-13 青岛科技大学 Preparation method of one-dimensional nano magnetons with stable solution dispersibility
CN111116992A (en) * 2019-12-27 2020-05-08 洛阳尖端装备技术有限公司 Modified carbon fiber, preparation method and application
CN111534278A (en) * 2019-12-25 2020-08-14 江西悦安新材料股份有限公司 Preparation method of carbon nano tube composite wave-absorbing material
CN111770958A (en) * 2017-10-11 2020-10-13 钢筋分子设计有限责任公司 Shielding formulations using discrete carbon nanotubes with targeted oxidation levels and formulations thereof
CN112839500A (en) * 2020-12-04 2021-05-25 浙江工业大学 Yolk shell hollow ferroferric oxide @ air @ carbon nano composite wave-absorbing material and preparation method thereof

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Cited By (20)

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Publication number Priority date Publication date Assignee Title
CN103115947A (en) * 2013-03-05 2013-05-22 济南大学 Preparation method and application of carbon-doped mesoporous metal oxide acetone sensor
CN103115947B (en) * 2013-03-05 2014-04-23 济南大学 Preparation method and application of carbon-doped mesoporous metal oxide acetone sensor
CN104479626A (en) * 2014-12-05 2015-04-01 吉林大学 Graphitization multiwall carbon nanotube/nano-particle composite absorbing agent and preparation method thereof
CN104882346A (en) * 2015-04-02 2015-09-02 天津师范大学 Method for preparing field emission cathode of carbon nanotube array coated with carbon nanoparticles
CN105749881A (en) * 2016-03-10 2016-07-13 江苏省农业科学院 Preparation method and application of carbon nanotube polyvinyl alcohol magnetic microspheres
CN106047290A (en) * 2016-06-24 2016-10-26 中国科学院理化技术研究所 Method for uniformly coating carbon nano tube with nano ferroferric oxide magnetic particles
CN107010613A (en) * 2017-02-22 2017-08-04 延边大学 The preparation method of conductive magneto-conductive nano-functional material
CN111770958A (en) * 2017-10-11 2020-10-13 钢筋分子设计有限责任公司 Shielding formulations using discrete carbon nanotubes with targeted oxidation levels and formulations thereof
CN108031440A (en) * 2017-12-15 2018-05-15 中国科学院烟台海岸带研究所 A kind of composite material and its preparation and absorption, remove water body in chromium application
CN108199150A (en) * 2017-12-30 2018-06-22 吴迪 A kind of preparation method of the carbon-based absorbing material of strong absorbent
CN108246258A (en) * 2018-01-29 2018-07-06 浙江海洋大学 A kind of preparation method of magnetism aminated carbon nano tube
CN108558328A (en) * 2018-04-04 2018-09-21 北京工业大学 A kind of Electromagnetically shielding cement based composites and preparation method thereof
CN109806868A (en) * 2018-07-02 2019-05-28 陈天仪 A kind of organic wastewater degraded agent of recyclable recycling
CN109806868B (en) * 2018-07-02 2021-10-26 陈天仪 Recyclable and reusable organic wastewater degrading agent
CN110559935A (en) * 2019-10-25 2019-12-13 青岛科技大学 Preparation method of one-dimensional nano magnetons with stable solution dispersibility
CN111534278A (en) * 2019-12-25 2020-08-14 江西悦安新材料股份有限公司 Preparation method of carbon nano tube composite wave-absorbing material
CN111116992A (en) * 2019-12-27 2020-05-08 洛阳尖端装备技术有限公司 Modified carbon fiber, preparation method and application
CN111116992B (en) * 2019-12-27 2021-11-30 洛阳尖端装备技术有限公司 Modified carbon fiber, preparation method and application
CN112839500A (en) * 2020-12-04 2021-05-25 浙江工业大学 Yolk shell hollow ferroferric oxide @ air @ carbon nano composite wave-absorbing material and preparation method thereof
CN112839500B (en) * 2020-12-04 2022-04-08 浙江工业大学 Yolk shell hollow ferroferric oxide @ air @ carbon nano composite wave-absorbing material and preparation method thereof

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Application publication date: 20120328