CN111491501A - Electromagnetic shielding material with conductive polymer coated with nickel ferrite and preparation method thereof - Google Patents
Electromagnetic shielding material with conductive polymer coated with nickel ferrite and preparation method thereof Download PDFInfo
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- CN111491501A CN111491501A CN202010334409.2A CN202010334409A CN111491501A CN 111491501 A CN111491501 A CN 111491501A CN 202010334409 A CN202010334409 A CN 202010334409A CN 111491501 A CN111491501 A CN 111491501A
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- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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Abstract
The invention relates to the technical field of electromagnetic shielding materials, and discloses an electromagnetic shielding material of conductive polymer coated nickel ferrite, which comprises the following formula raw materials and components: hollow aminated ferrite balls, pyrrole, aniline and ammonium persulfate. The electromagnetic shielding material of the conductive polymer coated nickel ferrite aminates amino and Ni in polystyrene2+And Fe3+Complexing is carried out, samarium is doped with nickel ferrite nano hollow microspheres, samarium replaces partial crystal lattices of iron, the magnetic conductivity and saturation magnetization are improved, a large number of hydrogen bond networks are formed between the aminated nickel ferrite hollow spheres and imino groups of pyrrole, polypyrrole is formed to coat the samarium doped nickel ferrite, polyaniline and polypyrrole have good compatibility, and the polyaniline and the polypyrrole are used as secondary coating layers to coat the nickel ferrite with the polypyrrole to form a shell-core structure,dielectric loss performance and resistance loss performance of polypyrrole and polyaniline and good impedance matching performance of samarium-doped nickel ferrite with excellent magnetic loss performance are formed.
Description
Technical Field
The invention relates to the technical field of electromagnetic shielding materials, in particular to an electromagnetic shielding material of conductive polymer coated nickel ferrite and a preparation method thereof.
Background
The electromagnetic wave has the electromagnetic radiation characteristic, the electromagnetic radiation is divided into radio wave, microwave, infrared ray, visible light and ultraviolet ray from low frequency to high frequency, substances or particles generally higher than absolute zero degree all have electromagnetic radiation, the radiation quantity is larger when the temperature is higher, the electromagnetic radiation is a mode for transferring energy, the radiation types comprise free radiation, non-free radiation with thermal effect, non-free radiation without thermal effect, base station electromagnetic wave absolutely non-free radiation wave and the like, the mechanism of the electromagnetic radiation harming the human body mainly comprises the thermal effect, the non-thermal effect and accumulation effect, the long-term contact with the high-energy electromagnetic wave radiation can cause serious harm to the central nervous system, the organism immune function, the cardiovascular system and the reproductive system of the human body even if the power and the frequency are very low, the symptoms of the human body such as immunity reduction, metabolism disorder, memory impairment and the like can be caused, and the electromagnetic radiation can also cause, The key point for solving the problems is to develop efficient wave-absorbing and electromagnetic shielding materials.
The existing wave-absorbing and electromagnetic shielding materials mainly comprise carbon-based electromagnetic shielding materials such as graphene, carbon nanotubes, carbon fibers and the like; iron-based electromagnetic shielding materials such as ferrite and magnetic nano-iron; the electromagnetic shielding material is made of conductive polymers such as polyaniline and polypyrrole, wherein the nickel ferrite has high magnetic conductivity and can absorb electromagnetic waves, and the electromagnetic waves are converted into heat energy for dissipation through the modes of magnetic polarization effect, resonant loss and the like, but the nickel ferrite has poor impedance matching performance and does not have dielectric loss and resistance loss, and the electromagnetic waves are difficult to be fully absorbed and consumed only by the magnetic loss of the nickel ferrite material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a conductive polymer coated nickel ferrite electromagnetic shielding material and a preparation method thereof, and solves the problems that the nickel ferrite electromagnetic shielding material does not have dielectric loss and resistance loss capability and has poor impedance matching performance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: an electromagnetic shielding material of conductive polymer coated nickel ferrite comprises the following formula raw materials and components in parts by weight: 28-35 parts of aminated nickel ferrite hollow spheres, 12-18 parts of pyrrole, 8-14 parts of aniline and 33-52 parts of ammonium persulfate.
Preferably, the preparation method of the aminated nickel ferrite hollow sphere comprises the following steps:
(1) introducing nitrogen into a reaction bottle to discharge air, adding a methanol solvent, polyvinylpyrrolidone and 4-aminostyrene, placing the reaction bottle into a constant-temperature water bath, heating to 60-80 ℃, adding an initiator potassium persulfate, stirring at a constant speed for reaction for 15-25h, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the aminated polystyrene microsphere.
(2) Distilled water, aminated polystyrene microsphere and Ni (NO) are added into a reaction bottle3)2、Fe(NO3)3And Sm (NO)3)3Placing a reaction bottle in a constant-temperature water bath kettle, uniformly stirring and reacting for 40-60h at 30-40 ℃, heating to 70-90 ℃, adding sodium hydroxide to adjust the pH value of the solution to 11-12, uniformly stirring and reacting for 4-8h, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and fully drying, placing the solid product in a resistance furnace, heating at the rate of 2-10 ℃/min, and carrying out heat preservation and calcination at 480-540 ℃ for 2-4h to obtain the calcined product, namely the samarium-doped nickel ferrite.
(3) Adding an ethylene glycol solvent, samarium-doped nickel ferrite and hexamethylene diamine into a reaction bottle, after uniform ultrasonic dispersion, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the reaction kettle into a blast drier, heating to 180-260 ℃, reacting for 10-15h, carrying out vacuum drying on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the hexamethylene diamine modified aminated nickel ferrite hollow sphere.
Preferably, the mass ratio of the polyvinylpyrrolidone to the 4-aminostyrene to the potassium persulfate is 1:28-35: 15-22.
Preferably, the Ni (NO)3)2、Fe(NO3)3And Sm (NO)3)3The mass ratio of the samarium doped nickel ferrite is 1:1.93-1.98:0.02-0.07, and the chemical expression of the samarium doped nickel ferrite is NiSm0.02-0.07Fe1.93-1.98O4。
Preferably, the mass ratio of the samarium-doped nickel ferrite to the hexamethylene diamine is 1: 4-8.
Preferably, the preparation method of the electromagnetic shielding material with the conductive polymer coating the nickel ferrite comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 4-6:1, adding 28-35 parts of hollow aminated nickel ferrite spheres and 12-18 parts of pyrrole, performing ultrasonic dispersion uniformly, stirring at a constant speed for 15-25h at 50-80 ℃, cooling to 0-5 ℃, adding hydrochloric acid to adjust the pH of the solution to 4-5, stirring at a constant speed for reaction for 4-8h, performing centrifugal separation on the solution to remove the solvent, washing the product with distilled water and ethanol, and fully drying to prepare the polypyrrole modified hollow nickel ferrite spheres.
(2) Adding distilled water, polypyrrole modified nickel ferrite hollow spheres and 8-14 parts of aniline into a reaction bottle, after uniform ultrasonic dispersion, adding hydrochloric acid at 0-5 ℃ to adjust the pH value of the solution to 4-5, then adding 33-52 parts of ammonium persulfate, stirring at a constant speed to react for 20-30h, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the conductive polymer coated nickel ferrite electromagnetic shielding material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the electromagnetic shielding material of the conductive polymer coated nickel ferrite aminates amino and Ni in polystyrene nano hollow microspheres2+And Fe3+Complexing is carried out to Ni2+And Fe3+The samarium-doped nickel ferrite nano hollow microspheres are uniformly adsorbed on the surfaces of polystyrene microspheres, prepared by a hydrothermal synthesis method and a thermal cracking method, have a hollow structure and a huge specific surface area, are more favorable for absorbing electromagnetic waves, replace part of the crystal lattices of iron with samarium, improve the magnetic permeability and saturation magnetization of the nickel ferrite, and have stronger magnetic loss capacity and magnetic polarization effect compared with common nickel ferrite.
The electromagnetic shielding material with the conductive polymer coating the nickel ferrite has the advantages that the specific surface area of the nickel ferrite nano hollow microspheres is large, the ethylene diamine modification process is accelerated by a high-pressure hot solvent method to obtain aminated nickel ferrite hollow spheres, a large number of hydrogen bond networks are formed by amino groups and imino groups of pyrrole, the pyrrole is uniformly attached to the surface of the nickel ferrite hollow spheres, and then a part of the nickel ferrite is made to produce Fe through an in-situ polymerization method and hydrochloric acid is added to produce Fe through a part of the nickel ferrite3+In-situ polymerization of pyrrole on the surface of the nickel ferrite hollow sphere is initiated as an oxidant to form polypyrrole-coated samarium-doped nickel ferriteThe polyaniline and polypyrrole which are easy to obtain have good compatibility, and form a shell-core structure with polypyrrole-coated nickel ferrite as a secondary coating layer, so that the dispersion and compatibility of inorganic samarium-doped nickel ferrite in polyaniline are greatly improved, and the electromagnetic shielding material with conductive polymer-coated nickel ferrite is obtained.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: an electromagnetic shielding material of conductive polymer coated nickel ferrite comprises the following formula raw materials and components in parts by weight: 28-35 parts of aminated nickel ferrite hollow spheres, 12-18 parts of pyrrole, 8-14 parts of aniline and 33-52 parts of ammonium persulfate.
The preparation method of the aminated nickel ferrite hollow sphere comprises the following steps:
(1) introducing nitrogen into a reaction bottle to discharge air, adding a methanol solvent, polyvinylpyrrolidone and 4-aminostyrene, placing the reaction bottle into a constant-temperature water bath, heating to 60-80 ℃, adding an initiator potassium persulfate, stirring at a constant speed for reaction for 15-25h, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the aminated polystyrene microsphere.
(2) Adding distilled water and aminated polystyrene microsphere into a reaction flask, wherein the mass ratio of Ni (NO) is 1:1.93-1.98:0.02-0.073)2、Fe(NO3)3And Sm (NO)3)3Placing a reaction bottle in a constant-temperature water bath kettle, reacting at 30-40 deg.C for 40-60h under uniform stirring, heating to 70-90 deg.C, adding sodium hydroxide to adjust pH to 11-12, reacting at uniform stirring for 4-8h, centrifuging the solution to remove solvent, washing with distilled waterFully drying the solid product, placing the solid product in a resistance furnace, heating at a rate of 2-10 ℃/min, and calcining at 480-540 ℃ for 2-4h to obtain a samarium-doped nickel ferrite with a chemical expression of NiSm0.02-0.07Fe1.93-1.98O4。
(3) Adding an ethylene glycol solvent, samarium-doped nickel ferrite and hexamethylene diamine in a mass ratio of 1:4-8 into a reaction bottle, after uniform ultrasonic dispersion, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle into a blast drier, heating to 260 ℃ for reaction for 10-15h, carrying out vacuum drying on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the hexamethylenediamine modified aminated nickel ferrite hollow sphere.
The preparation method of the electromagnetic shielding material with conductive polymer coated with nickel ferrite comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 4-6:1, adding 28-35 parts of hollow aminated nickel ferrite spheres and 12-18 parts of pyrrole, performing ultrasonic dispersion uniformly, stirring at a constant speed for 15-25h at 50-80 ℃, cooling to 0-5 ℃, adding hydrochloric acid to adjust the pH of the solution to 4-5, stirring at a constant speed for reaction for 4-8h, performing centrifugal separation on the solution to remove the solvent, washing the product with distilled water and ethanol, and fully drying to prepare the polypyrrole modified hollow nickel ferrite spheres.
(2) Adding distilled water, polypyrrole modified nickel ferrite hollow spheres and 8-14 parts of aniline into a reaction bottle, after uniform ultrasonic dispersion, adding hydrochloric acid at 0-5 ℃ to adjust the pH value of the solution to 4-5, then adding 33-52 parts of ammonium persulfate, stirring at a constant speed to react for 20-30h, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the conductive polymer coated nickel ferrite electromagnetic shielding material.
Example 1
(1) Preparing an aminated polystyrene microsphere component 1: introducing nitrogen into a reaction bottle to discharge air, adding a methanol solvent, polyvinylpyrrolidone and 4-aminostyrene, placing the reaction bottle into a constant-temperature water bath, heating to 60 ℃, adding an initiator potassium persulfate, stirring at a constant speed for reaction for 15 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the aminated polystyrene microsphere component 1.
(2) Preparing samarium-doped nickel ferrite component 1: distilled water and aminated polystyrene microsphere component 1 were added to a reaction flask in an amount of Ni (NO) in a ratio of 1:1.98:0.023)2、Fe(NO3)3And Sm (NO)3)3Placing a reaction bottle in a constant-temperature water bath kettle, stirring at a constant speed at 30 ℃ for 40h for reaction, heating to 70 ℃, adding sodium hydroxide to adjust the pH of the solution to 11, stirring at a constant speed for reaction for 4h, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and fully drying, placing the solid product in a resistance furnace, heating at a rate of 2 ℃/min, and calcining at 480 ℃ for 2h to obtain a samarium-doped nickel ferrite component 1, wherein the chemical expression of the samarium-doped nickel ferrite is NiSm0.02Fe1.98O4。
(3) Preparing a hexanediamine modified aminated nickel ferrite hollow sphere component 1: adding an ethylene glycol solvent, samarium-doped nickel ferrite component 1 and hexamethylenediamine in a mass ratio of 1:4 into a reaction bottle, after uniform ultrasonic dispersion, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle into a blast drier, heating to 180 ℃, reacting for 10 hours, carrying out vacuum drying on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the hexamethylenediamine-modified aminated nickel ferrite hollow sphere component 1.
(4) Preparing a polypyrrole modified nickel ferrite hollow sphere component 1: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 4:1, adding 28 parts of aminated nickel ferrite hollow sphere component 1 and 12 parts of pyrrole, performing ultrasonic dispersion uniformly, stirring at 50 ℃ for 15h at a constant speed, cooling to 5 ℃, adding hydrochloric acid to adjust the pH value of the solution to 5, stirring at a constant speed for reaction for 4h, performing centrifugal separation on the solution to remove the solvent, washing the product with distilled water and ethanol, and fully drying to prepare polypyrrole modified nickel ferrite hollow sphere component 1.
(5) Preparing an electromagnetic shielding material 1 of conductive polymer coated nickel ferrite: adding distilled water and 1 part of polypyrrole modified nickel ferrite hollow sphere component and 8 parts of aniline into a reaction bottle, after uniform ultrasonic dispersion, adding hydrochloric acid at 5 ℃ to adjust the pH value of the solution to 5, then adding 52 parts of ammonium persulfate, stirring at a constant speed for reaction for 20 hours, carrying out centrifugal separation on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the electromagnetic shielding material 1 with the conductive polymer coated with the nickel ferrite.
Example 2
(1) Preparing an aminated polystyrene microsphere component 2: introducing nitrogen into a reaction bottle to discharge air, adding a methanol solvent, polyvinylpyrrolidone and 4-aminostyrene, placing the reaction bottle into a constant-temperature water bath, heating to 80 ℃, adding an initiator potassium persulfate, stirring at a constant speed for reaction for 15 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the aminated polystyrene microsphere component 2.
(2) Preparing samarium-doped nickel ferrite component 2: distilled water and aminated polystyrene microsphere component 2 were added to a reaction flask in an amount of Ni (NO) in a ratio of 1:1.97:0.033)2、Fe(NO3)3And Sm (NO)3)3Placing a reaction bottle in a constant-temperature water bath kettle, stirring at a constant speed at 40 ℃ for 40h for reaction, heating to 90 ℃, adding sodium hydroxide to adjust the pH of the solution to 12, stirring at a constant speed for reaction for 8h, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and fully drying, placing the solid product in a resistance furnace, heating at a rate of 10 ℃/min, and calcining at 480 ℃ for 4h to obtain a samarium-doped nickel ferrite component 2, wherein the chemical expression of the samarium-doped nickel ferrite is NiSm0.03Fe1.97O4。
(3) Preparing a hexanediamine modified aminated nickel ferrite hollow sphere component 2: adding an ethylene glycol solvent, samarium-doped nickel ferrite component 2 and hexamethylenediamine in a mass ratio of 1:4 into a reaction bottle, after uniform ultrasonic dispersion, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle into a blast drier, heating to 180 ℃, reacting for 15h, carrying out vacuum drying on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the hexamethylenediamine-modified aminated nickel ferrite hollow sphere component 2.
(4) Preparing a polypyrrole modified nickel ferrite hollow sphere component 2: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 6:1, adding 29 parts of aminated nickel ferrite hollow sphere component 2 and 13 parts of pyrrole, performing ultrasonic dispersion uniformly, stirring at 80 ℃ for 15h at a constant speed, cooling to 5 ℃, adding hydrochloric acid to adjust the pH value of the solution to 4, stirring at a constant speed for reaction for 8h, performing centrifugal separation on the solution to remove the solvent, washing the product with distilled water and ethanol, and fully drying to prepare polypyrrole modified nickel ferrite hollow sphere component 2.
(5) Preparing the electromagnetic shielding material 2 with conductive polymer coated with nickel ferrite: adding distilled water, 2 parts of polypyrrole modified nickel ferrite hollow sphere component and 9 parts of aniline into a reaction bottle, after uniform ultrasonic dispersion, adding hydrochloric acid at 0 ℃ to adjust the pH value of the solution to 5, then adding 49 parts of ammonium persulfate, stirring at a constant speed for reaction for 30 hours, carrying out centrifugal separation on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the electromagnetic shielding material 2 with the conductive polymer coated with the nickel ferrite.
Example 3
(1) Preparing an aminated polystyrene microsphere component 3: introducing nitrogen into a reaction bottle to discharge air, adding a methanol solvent, polyvinylpyrrolidone and 4-aminostyrene, placing the reaction bottle into a constant-temperature water bath, heating to 70 ℃, adding an initiator potassium persulfate, stirring at a constant speed for reaction for 20 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the aminated polystyrene microsphere component 3.
(2) Preparing samarium-doped nickel ferrite component 3: distilled water and aminated polystyrene microsphere component 3 were added to a reaction flask in an amount of Ni (NO) in a ratio of 1:1.96:0.043)2、Fe(NO3)3And Sm (NO)3)3Placing the reaction bottle in a constant-temperature water bath, stirring at constant speed at 35 ℃ for reaction for 50h, heating to 80 ℃, adding sodium hydroxide to adjust the pH value of the solution to 12,stirring at constant speed for reaction for 6h, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and fully drying, placing the solid product in a resistance furnace, heating at the rate of 5 ℃/min, and calcining at 520 ℃ for 3h to obtain a samarium-doped nickel ferrite component 3, wherein the chemical expression of the samarium-doped nickel ferrite is NiSm0.04Fe1.96O4。
(3) Preparing a hexanediamine modified aminated nickel ferrite hollow sphere component 3: adding an ethylene glycol solvent, samarium-doped nickel ferrite component 3 and hexamethylenediamine in a mass ratio of 1:6 into a reaction bottle, after uniform ultrasonic dispersion, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle into a blast drier, heating to 220 ℃, reacting for 12h, carrying out vacuum drying on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the hexamethylenediamine-modified aminated nickel ferrite hollow sphere component 3.
(4) Preparing a polypyrrole modified nickel ferrite hollow sphere component 3: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 5:1, adding 31 parts of aminated nickel ferrite hollow sphere component 3 and 15 parts of pyrrole, performing ultrasonic dispersion uniformly, stirring at a constant speed of 65 ℃ for 20h, cooling to 2 ℃, adding hydrochloric acid to adjust the pH value of the solution to 5, stirring at a constant speed for reaction for 6h, performing centrifugal separation on the solution to remove the solvent, washing the product with distilled water and ethanol, and fully drying to prepare polypyrrole modified nickel ferrite hollow sphere component 3.
(5) Preparing an electromagnetic shielding material 3 of conductive polymer coated nickel ferrite: adding distilled water, 3 parts of polypyrrole modified nickel ferrite hollow sphere components and 10 parts of aniline into a reaction bottle, after uniform ultrasonic dispersion, adding hydrochloric acid at 3 ℃ to adjust the pH value of the solution to 5, adding 44 parts of ammonium persulfate, stirring at a constant speed for reaction for 25 hours, carrying out centrifugal separation on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the electromagnetic shielding material 3 with the conductive polymer coated with the nickel ferrite.
Example 4
(1) Preparing an aminated polystyrene microsphere component 4: introducing nitrogen into a reaction bottle to discharge air, adding a methanol solvent, polyvinylpyrrolidone and 4-aminostyrene, placing the reaction bottle into a constant-temperature water bath, heating to 60 ℃, adding an initiator potassium persulfate, stirring at a constant speed for reaction for 25 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the aminated polystyrene microsphere component 4.
(2) Preparing samarium-doped nickel ferrite component 4: distilled water and aminated polystyrene microsphere component 4 were added to a reaction flask in an amount of Ni (NO) in a ratio of 1:1.94:0.063)2、Fe(NO3)3And Sm (NO)3)3Placing a reaction bottle in a constant-temperature water bath kettle, stirring at a constant speed at 40 ℃ for 60 hours for reaction, heating to 90 ℃, adding sodium hydroxide to adjust the pH of the solution to 12, stirring at a constant speed for 4 hours for reaction, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and fully drying, placing the solid product in a resistance furnace, heating at a rate of 10 ℃/min, and calcining at 540 ℃ for 4 hours to obtain a samarium-doped nickel ferrite component 4, wherein the chemical expression of the samarium-doped nickel ferrite is NiSm0.04Fe1.96O4。
(3) Preparing a hexanediamine modified aminated nickel ferrite hollow sphere component 4: adding an ethylene glycol solvent, samarium-doped nickel ferrite component 4 and hexamethylenediamine in a mass ratio of 1:8 into a reaction bottle, after uniformly ultrasonic dispersing, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle into a blast drier, heating to 180 ℃, reacting for 15h, carrying out vacuum drying on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the hexamethylenediamine modified aminated nickel ferrite hollow sphere component 4.
(4) Preparing a polypyrrole modified nickel ferrite hollow sphere component 4: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 4:1, adding 33.5 parts of aminated nickel ferrite hollow sphere component 4 and 16.5 parts of pyrrole, performing ultrasonic dispersion uniformly, stirring at a constant speed for 25h, cooling to 5 ℃, adding hydrochloric acid to adjust the pH value of the solution to 5, stirring at a constant speed for reaction for 4h, performing centrifugal separation on the solution to remove the solvent, washing a product with distilled water and ethanol, and fully drying to prepare polypyrrole-modified nickel ferrite hollow sphere component 4.
(5) Preparing the electromagnetic shielding material 4 of conductive polymer coated nickel ferrite: adding distilled water, 4 parts of polypyrrole modified nickel ferrite hollow sphere component and 13 parts of aniline into a reaction bottle, after uniform ultrasonic dispersion, adding hydrochloric acid at 0 ℃ to adjust the pH value of the solution to 4, then adding 38 parts of ammonium persulfate, stirring at a constant speed for reaction for 30 hours, carrying out centrifugal separation on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the electromagnetic shielding material 4 with the conductive polymer coated with the nickel ferrite.
Example 5
(1) Preparing an aminated polystyrene microsphere component 5: introducing nitrogen into a reaction bottle to discharge air, adding a methanol solvent, polyvinylpyrrolidone and 4-aminostyrene, placing the reaction bottle into a constant-temperature water bath, heating to 80 ℃, adding an initiator potassium persulfate, stirring at a constant speed for reaction for 25 hours, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the aminated polystyrene microsphere component 5.
(2) Preparing samarium-doped nickel ferrite component 5: distilled water and aminated polystyrene microsphere component 5 were added to a reaction flask in an amount of Ni (NO) in a ratio of 1:1.93:0.073)2、Fe(NO3)3And Sm (NO)3)3Placing a reaction bottle in a constant-temperature water bath kettle, stirring at a constant speed at 40 ℃ for 60 hours for reaction, heating to 90 ℃, adding sodium hydroxide to adjust the pH of the solution to 12, stirring at a constant speed for 8 hours, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water and fully drying, placing the solid product in a resistance furnace, heating at a rate of 10 ℃/min, and calcining at 540 ℃ for 4 hours to obtain a samarium-doped nickel ferrite component 5, wherein the chemical expression of the samarium-doped nickel ferrite is NiSm0.07Fe1.93O4。
(3) Preparing a hexanediamine modified aminated nickel ferrite hollow sphere component 5: adding an ethylene glycol solvent, samarium-doped nickel ferrite component 5 and hexamethylenediamine in a mass ratio of 1:8 into a reaction bottle, after uniform ultrasonic dispersion, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle into a blast drier, heating to 260 ℃, reacting for 15h, carrying out vacuum drying on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the hexamethylenediamine-modified aminated nickel ferrite hollow sphere component 5.
(4) Preparing a polypyrrole modified nickel ferrite hollow sphere component 5: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 6:1, adding 35 parts of aminated nickel ferrite hollow sphere component 5 and 18 parts of pyrrole, performing ultrasonic dispersion uniformly, stirring at 80 ℃ for 25h at a constant speed, cooling to 0 ℃, adding hydrochloric acid to adjust the pH value of the solution to 4, stirring at a constant speed for reaction for 8h, performing centrifugal separation on the solution to remove the solvent, washing the product with distilled water and ethanol, and fully drying to prepare polypyrrole modified nickel ferrite hollow sphere component 5.
(5) Preparing the electromagnetic shielding material 5 with conductive polymer coated with nickel ferrite: adding distilled water, 5 parts of polypyrrole modified nickel ferrite hollow sphere components and 14 parts of aniline into a reaction bottle, after uniform ultrasonic dispersion, adding hydrochloric acid at 0 ℃ to adjust the pH value of the solution to 4, adding 33 parts of ammonium persulfate, stirring at a constant speed for reaction for 30 hours, carrying out centrifugal separation on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the electromagnetic shielding material 5 with the conductive polymer coated with the nickel ferrite.
To sum up, the electromagnetic shielding material of the conductive polymer coated nickel ferrite aminates amino and Ni in polystyrene nano hollow microspheres2+And Fe3+Complexing is carried out to Ni2+And Fe3+The samarium-doped nickel ferrite nano hollow microspheres are uniformly adsorbed on the surfaces of polystyrene microspheres, prepared by a hydrothermal synthesis method and a thermal cracking method, have a hollow structure and a huge specific surface area, are more favorable for absorbing electromagnetic waves, replace part of the crystal lattices of iron with samarium, improve the magnetic permeability and saturation magnetization of the nickel ferrite, and have stronger magnetic loss capacity and magnetic polarization effect compared with common nickel ferrite.
The specific surface area of the nickel ferrite nano hollow microsphere is large, and the nickel ferrite nano hollow microsphere passes through high pressureThe hot solvent method accelerates the modification process of ethylenediamine to obtain the aminated nickel ferrite hollow sphere, the amino group and the imino group of the pyrrole form a large amount of hydrogen bond networks to ensure that the pyrrole is uniformly attached to the surface of the nickel ferrite hollow sphere, and then the hydrochloric acid is added to ensure that part of the nickel ferrite produces Fe through the in-situ polymerization method3+The polypyrrole and polyaniline which are conductive can enhance the dielectric loss performance and the resistance loss performance of the material, and the polyaniline-polypyrrole coating layer with the shell-core structure can enable incident electromagnetic waves to penetrate into the shield to the maximum extent, and electromagnetic waves are reflected for multiple times, and the samarium-doped nickel ferrite nano hollow microspheres with excellent magnetic loss performance form good impedance matching performance, so that the material is endowed with excellent wave absorption and electromagnetic shielding energy absorption.
Claims (6)
1. The electromagnetic shielding material of the conductive polymer coated nickel ferrite comprises the following formula raw materials and components in parts by weight, and is characterized in that: 28-35 parts of aminated nickel ferrite hollow spheres, 12-18 parts of pyrrole, 8-14 parts of aniline and 33-52 parts of ammonium persulfate.
2. The conductive polymer-clad nickel ferrite electromagnetic shielding material as claimed in claim 1, wherein: the preparation method of the aminated nickel ferrite hollow sphere comprises the following steps:
(1) adding polyvinylpyrrolidone and 4-aminostyrene into a methanol solvent, heating to 60-80 ℃ in a nitrogen atmosphere, adding an initiator potassium persulfate, reacting for 15-25h, performing centrifugal separation, washing and drying to prepare aminated polystyrene microspheres;
(2) adding aminated polystyrene microsphere and Ni (N) into distilled waterO3)2、Fe(NO3)3And Sm (NO)3)3Stirring at constant speed at 30-40 ℃ for reaction for 40-60h, heating to 70-90 ℃, adding sodium hydroxide to adjust the pH value of the solution to 11-12, reacting for 4-8h, centrifugally separating, washing and drying, placing the solid product in a resistance furnace, heating at the rate of 2-10 ℃/min, and calcining at 480-540 ℃ for 2-4h to obtain a calcined product, namely samarium-doped nickel ferrite;
(3) adding samarium-doped nickel ferrite and hexamethylene diamine into an ethylene glycol solvent, after uniform ultrasonic dispersion, transferring the solution into a hydrothermal reaction kettle, heating to 180-260 ℃, reacting for 10-15h, removing the solvent, washing and drying to prepare the hexamethylene diamine modified aminated nickel ferrite hollow sphere.
3. The conductive polymer-clad nickel ferrite electromagnetic shielding material as claimed in claim 2, wherein: the mass ratio of the polyvinylpyrrolidone to the 4-aminostyrene to the potassium persulfate is 1:28-35: 15-22.
4. The conductive polymer-clad nickel ferrite electromagnetic shielding material as claimed in claim 2, wherein: the Ni (NO)3)2、Fe(NO3)3And Sm (NO)3)3The mass ratio of the samarium doped nickel ferrite is 1:1.93-1.98:0.02-0.07, and the chemical expression of the samarium doped nickel ferrite is NiSm0.02-0.07Fe1.93-1.98O4。
5. The conductive polymer-clad nickel ferrite electromagnetic shielding material as claimed in claim 2, wherein: the mass ratio of the samarium-doped nickel ferrite to the hexamethylene diamine is 1: 4-8.
6. The conductive polymer-clad nickel ferrite electromagnetic shielding material as claimed in claim 1, wherein: the preparation method of the electromagnetic shielding material with the conductive polymer coated with the nickel ferrite comprises the following steps:
(1) adding 28-35 parts of aminated nickel ferrite hollow sphere and 12-18 parts of pyrrole into a mixed solvent of distilled water and ethanol with a volume ratio of 4-6:1, uniformly dispersing by ultrasonic, stirring at a constant speed of 50-80 ℃ for 15-25h, cooling to 0-5 ℃, adding hydrochloric acid to adjust the pH value of the solution to 4-5, reacting for 4-8h, centrifugally separating, washing and drying to prepare the polypyrrole modified nickel ferrite hollow sphere;
(2) and adding polypyrrole modified nickel ferrite hollow spheres and 8-14 parts of aniline into distilled water, performing ultrasonic dispersion uniformly, adding hydrochloric acid at 0-5 ℃ to adjust the pH value of the solution to 4-5, adding 33-52 parts of ammonium persulfate, reacting for 20-30h, performing centrifugal separation, washing and fully drying to prepare the electromagnetic shielding material of the conductive polymer coated nickel ferrite.
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| CN115213396A (en) * | 2022-08-16 | 2022-10-21 | 湖南金天铝业高科技股份有限公司 | Electromagnetic shielding material and preparation method thereof |
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