阅读说明：本技术 一种SiO2包覆镍锌铁氧体接枝聚苯胺吸波材料及其制法 (SiO (silicon dioxide)2Coated nickel-zinc ferrite grafted polyaniline wave-absorbing material and preparation method thereof ) 是由 陈由根 于 2020-05-20 设计创作，主要内容包括：本发明涉及吸波材料技术领域,且公开了一种SiO<Sub>2</Sub>包覆镍锌铁氧体接枝聚苯胺吸波材料,包括以下配方原料及组分：功能化SiO<Sub>2</Sub>包覆钴掺杂镍锌铁氧体、对苯二胺、苯胺、过硫酸铵、对甲苯磺酸。该一种SiO<Sub>2</Sub>包覆镍锌铁氧体接枝聚苯胺吸波材料,钴掺杂镍锌铁氧体中空微球具有更高的磁性质和磁损耗性能,SiO<Sub>2</Sub>包覆钴掺杂镍锌铁氧体,环氧基硅烷偶联剂对其表面改性,进一步将苯胺结构引入SiO<Sub>2</Sub>包覆钴掺杂镍锌铁氧体粒子的表面,苯胺结构与苯胺分子原位聚合,改善了SiO<Sub>2</Sub>包覆钴掺杂镍锌铁氧与聚苯胺的相容性,分散均匀的SiO<Sub>2</Sub>包覆钴掺杂镍锌铁氧体与聚苯胺之间产生界面极化效应和偶极极化效应,使材料表现出优异的阻抗匹配性能、介电损耗和磁损耗性能。(The invention relates to the technical field of wave-absorbing materials and discloses SiO 2 The nickel-zinc-coated ferrite-grafted polyaniline wave-absorbing material comprises the following formula raw materials and components: functionalized SiO 2 Cladding cobalt-doped nickel-zinc ferrite, p-phenylenediamine, aniline, ammonium persulfate and p-toluenesulfonic acid. The SiO 2 The coated nickel-zinc ferrite grafted polyaniline wave-absorbing material, the cobalt-doped nickel-zinc ferrite hollow microsphere has higher magnetic property and magnetic loss performance, and SiO 2 Coating cobalt-doped nickel-zinc ferrite, modifying the surface of the cobalt-doped nickel-zinc ferrite by using an epoxy silane coupling agent, and further introducing an aniline structure into SiO 2 The surface of the cobalt-doped nickel-zinc ferrite particles is coated, the aniline structure and aniline molecules are polymerized in situ, and SiO is improved 2 SiO coated with cobalt-doped nickel-zinc ferrite and polyaniline with compatibility and uniform dispersion 2 An interface electrode is generated between the cobalt-doped nickel-zinc ferrite and the polyanilineThe polarization effect and the dipole polarization effect enable the material to show excellent impedance matching performance, dielectric loss and magnetic loss performance.)

1. SiO (silicon dioxide)₂The coated nickel-zinc ferrite grafted polyaniline wave-absorbing material comprises the following raw materials and components, and is characterized in that: functionalized SiO₂Coating cobalt-doped nickel-zinc ferrite, p-phenylenediamine, aniline, ammonium persulfate and p-toluenesulfonic acid in a mass ratio of 80-120:2-6:100:240-260: 0.5-3.

2. An SiO as claimed in claim 1₂The nickel-zinc-coated ferrite grafted polyaniline wave-absorbing material is characterized in that: the SiO₂The preparation method of the coated nickel-zinc ferrite grafted polyaniline wave-absorbing material comprises the following steps:

(1) adding ferric nitrate, nickel nitrate, zinc nitrate, cobalt nitrate, ammonium acetate and sodium dodecyl sulfate into an ethylene glycol solvent, pouring the solution into a hydrothermal reaction kettle after ultrasonic dispersion is uniform, placing the hydrothermal reaction kettle into a reaction kettle heating instrument, heating to 220 ℃ for reaction for 40-50h, centrifugally separating, washing and drying, placing a solid product into a muffle furnace, and carrying out heat preservation and calcination for 2-4h at 600 ℃ for 550 ℃ to obtain the cobalt-doped nickel-zinc ferrite hollow microsphere;

(2) adding cobalt-doped nickel-zinc ferrite hollow microspheres into a mixed solvent of distilled water and ethanol with a volume ratio of 1:3-5, adding concentrated ammonia water after ultrasonic dispersion is uniform to adjust the pH of the solution to 10-11, adding tetraethoxysilane, reacting at room temperature for 15-25h, filtering, washing and drying to prepare SiO₂Coating cobalt-doped nickel zinc ferrite;

(3) adding SiO to toluene solvent₂Coating cobalt-doped nickel zinc ferrite, adding a silane coupling agent after ultrasonic dispersion is uniform, heating to 110-130 ℃, reacting for 5-10h, filtering, washing and drying to prepare the epoxy group modified functional SiO₂Coating cobalt-doped nickel zinc ferrite;

(4) adding functional SiO into distilled water solvent₂Coating cobalt-doped nickel-zinc ferrite, adding p-phenylenediamine after ultrasonic dispersion is uniform, reacting for 2-8h, adding aniline, adding salt to adjust the pH of the solution to 1-2, slowly dropwise adding an ammonium persulfate aqueous solution at 0-5 ℃, reacting for 10-15h, and filteringFiltering and washing, placing the solid product in an ethanol solvent, adding p-toluenesulfonic acid as proton doping acid, stirring at constant speed for 10-20h, filtering, washing, drying and pressing into a film to prepare SiO₂Coating nickel-zinc ferrite graft polyaniline wave-absorbing material.

3. An SiO as claimed in claim 2₂The nickel-zinc-coated ferrite grafted polyaniline wave-absorbing material is characterized in that: the reation kettle heating appearance in step (1) includes heat preservation, the inside top fixedly connected with bearing of heat preservation, bearing swing joint has the rotation axis, rotation axis swing joint has rotary device, the rotation axis surface is provided with the card annular groove, draw-in groove swing joint has the snap ring, snap ring fixed connection has horizontal cardboard, rotation axis fixedly connected with base, the base top is until having reation kettle, the base surface is provided with the card groove, card groove swing joint has fixture block, the perpendicular cardboard of fixture block fixedly connected with.

4. An SiO as claimed in claim 2₂The nickel-zinc-coated ferrite grafted polyaniline wave-absorbing material is characterized in that: the mass ratio of the ferric nitrate, the nickel nitrate, the zinc nitrate, the cobalt nitrate, the ammonium acetate and the sodium dodecyl sulfate in the step (1) is 2:0.6:0.34-0.38:0.02-0.06:6-12: 3-5.

5. An SiO as claimed in claim 2₂The nickel-zinc-coated ferrite grafted polyaniline wave-absorbing material is characterized in that: the mass ratio of the cobalt-doped nickel-zinc ferrite hollow microspheres to the ethyl orthosilicate in the step (2) is 2.5-3.5: 1.

6. An SiO as claimed in claim 2₂The nickel-zinc-coated ferrite grafted polyaniline wave-absorbing material is characterized in that: the silane coupling agent is 3-glycidoxy propyl trimethoxy silane or 3- [ (2,3) -glycidoxy]Any one of propyl methyl dimethoxy silane and SiO₂The mass ratio of the cladding cobalt doped nickel zinc ferrite is 1: 6-10.

Technical Field

The invention relates to the technical field of wave-absorbing materials, in particular to SiO₂A nickel-zinc-coated ferrite grafted polyaniline wave-absorbing material and a preparation method thereof.

Background

With the wide application of radio technology, electromagnetic radiation pollution, air pollution, noise pollution and water pollution are four public hazards, excessive electromagnetic radiation can not only interfere with the normal operation of various electronic devices, but also has great harm to human health, so that the development of a novel efficient electromagnetic shielding material with light weight and small density to reduce the electromagnetic radiation pollution and protect human health becomes a research hotspot.

The existing electromagnetic shielding and wave absorbing materials mainly comprise carbon-series wave absorbing materials, iron-series wave absorbing materials, ceramic-series wave absorbing materials, conductive polymer materials and the like, electromagnetic radiation can be absorbed and lost through magnetic loss, resistance type loss and dielectric loss, ferrite materials such as manganese zinc ferrite, nickel zinc ferrite and the like have good magnetic properties and magnetic loss properties and are widely applied to the wave absorbing materials, but the traditional nickel zinc ferrite wave absorbing materials do not have the dielectric loss effect, the impedance matching performance is poor, and the single nickel zinc ferrite material is difficult to effectively absorb the electromagnetic radiation.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides SiO₂The coated nickel-zinc ferrite grafted polyaniline wave-absorbing material and the preparation method thereof solve the problems that the nickel-zinc ferrite wave-absorbing material has no dielectric loss and has poor impedance matching performance.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: SiO (silicon dioxide)₂The coated nickel-zinc ferrite grafted polyaniline wave-absorbing material comprises the following raw materials and components, and is characterized in that: functionalized SiO₂Coating cobalt-doped nickel-zinc ferrite, p-phenylenediamine, aniline, ammonium persulfate and p-toluenesulfonic acid in a mass ratio of 80-120:2-6:100:240-260: 0.5-3.

Preferably, the SiO₂The preparation method of the coated nickel-zinc ferrite grafted polyaniline wave-absorbing material comprises the following steps:

(1) adding an ethylene glycol solvent, ferric nitrate, nickel nitrate, zinc nitrate, cobalt nitrate, ammonium acetate and sodium dodecyl sulfate into a reaction bottle, pouring the solution into a hydrothermal reaction kettle after uniform ultrasonic dispersion, placing the hydrothermal reaction kettle into a reaction kettle heating instrument, heating to 220 ℃ for reaction for 40-50h, centrifugally separating the solution to remove the solvent, washing a solid product by using distilled water and ethanol, drying, placing the solid product in a muffle furnace, and performing heat preservation and calcination at 600 ℃ for 2-4h to prepare the cobalt-doped nickel-zinc ferrite hollow microsphere.

(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 1:3-5, and adding cobalt-doped nickel-zinc ferriteUltrasonically dispersing hollow microspheres uniformly, adding concentrated ammonia water to adjust the pH value of the solution to 10-11, adding ethyl orthosilicate, stirring at a constant speed at room temperature for 15-25h, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and drying to obtain SiO₂Cladding cobalt-doped nickel zinc ferrite.

(3) Adding toluene solvent and SiO into a reaction bottle₂Coating cobalt-doped nickel-zinc ferrite, adding a silane coupling agent after uniform ultrasonic dispersion, placing the mixture in an oil bath pot, heating to 110 ℃ and 130 ℃, stirring at a constant speed for reaction for 5-10 hours, filtering the solution to remove the solvent, washing the solid product with ethanol, and drying to prepare the epoxy group modified functional SiO₂Cladding cobalt-doped nickel zinc ferrite.

(4) Adding distilled water solvent and functional SiO into a reaction bottle₂Coating cobalt-doped nickel-zinc ferrite, adding p-phenylenediamine after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 2-8h, adding aniline, adding salt to adjust the pH value of the solution to 1-2, slowly dropwise adding an aqueous solution of ammonium persulfate at 0-5 ℃, stirring at a constant speed for reaction for 10-15h, filtering the solution to remove the solvent, washing the solid product with ethanol and distilled water, drying, placing the solid product in an ethanol solvent, adding p-toluenesulfonic acid as proton-doped acid after uniform stirring, stirring at a constant speed for 10-20h, filtering the solution, washing, drying and pressing into a film to prepare the SiO-doped nickel-zinc ferrite₂Coating nickel-zinc ferrite graft polyaniline wave-absorbing material.

Preferably, the reation kettle heating appearance in step (1) includes heat preservation, the inside top fixedly connected with bearing of heat preservation, bearing swing joint has the rotation axis, rotation axis swing joint has rotary device, the rotation axis surface is provided with the card annular groove, draw-in groove swing joint has the snap ring, snap ring fixed connection has horizontal cardboard, rotation axis fixedly connected with base, the base top is until having reation kettle, the base surface is provided with the card piece groove, card piece groove swing joint has fixture block, the perpendicular cardboard of fixture block fixedly connected with.

Preferably, the mass ratio of the ferric nitrate, the nickel nitrate, the zinc nitrate, the cobalt nitrate, the ammonium acetate and the sodium dodecyl sulfate in the step (1) is 2:0.6:0.34-0.38:0.02-0.06:6-12: 3-5.

Preferably, the mass ratio of the cobalt-doped nickel zinc ferrite hollow microspheres to the tetraethoxysilane in the step (2) is 2.5-3.5: 1.

Preferably, the silane coupling agent is 3-glycidoxypropyltrimethoxysilane or 3- [ (2,3) -glycidoxy]Any one of propyl methyl dimethoxy silane and SiO₂The mass ratio of the cladding cobalt doped nickel zinc ferrite is 1: 6-10.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

the SiO₂The coated nickel-zinc ferrite grafted polyaniline wave-absorbing material is prepared by taking sodium dodecyl sulfate as a surfactant to obtain cobalt-doped nickel-zinc ferrite hollow microspheres, Co³⁺By substitution of part of Zn²⁺Lattice of (C), Co³⁺Occupies the B site of the octahedron of the nickel zinc ferrite crystal, increases the magnetic moment of the crystal, and achieves the effect of stabilizing the domain wall by compensating the negative anisotropy of the nickel zinc ferrite, so the magnetic property and the magnetic loss performance of the cobalt-doped nickel zinc ferrite hollow microsphere are more excellent.

The SiO₂Coating nickel-zinc ferrite grafted polyaniline wave-absorbing material, and forming SiO by in-situ coating method₂Coating cobalt-doped nickel-zinc ferrite, performing surface modification by using epoxy silane coupling agent, performing ring-opening reaction on epoxy group and amino group of p-phenylenediamine, and introducing an aniline structure into SiO₂Coating the surface of the cobalt-doped nickel-zinc ferrite particle, and carrying out in-situ polymerization on the aniline structure on the surface of the particle and aniline molecules by an in-situ polymerization method to obtain SiO₂Coating nickel-zinc ferrite grafted polyaniline wave-absorbing material, and grafting SiO by covalent bond₂The coated cobalt-doped nickel-zinc ferrite particles are introduced into the molecular chain of polyaniline, so that SiO is improved₂The compatibility of the cobalt-doped nickel-zinc ferrite and polyaniline is coated, the conductivity and impedance matching performance of the polyaniline can be improved by doping the protonic acid with toluenesulfonic acid, and the uniformly dispersed SiO can be obtained by regulating the proportion of the components₂Coated cobalt doped nickel zinc ferriteInterface polarization effect and dipole polarization effect are generated between the SiO and polyaniline₂The coated nickel-zinc ferrite grafted polyaniline material has excellent impedance matching performance, and can efficiently absorb and lose electromagnetic radiation through dielectric loss and magnetic loss performance.

Drawings

FIG. 1 is a schematic view of a reactor heater;

FIG. 2 is an enlarged schematic view of the rotation axis;

FIG. 3 is a schematic view of vertical card adjustment;

FIG. 4 is a scanning electron microscope SEM image of cobalt doped nickel zinc ferrite hollow microspheres;

FIG. 5 is a functionalized SiO₂TEM image of transmission electron microscope coated with Co-doped Ni-Zn ferrite.

1-a reaction kettle heating instrument; 2-insulating layer; 3-a bearing; 4-a rotating shaft; 5-a rotating device; 6-a clamping ring groove; 7-a snap ring; 8-horizontal snap gauge; 9-a base; 10-a block slot; 11-a fixture block; 12-vertical cardboard;

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: SiO (silicon dioxide)₂The coated nickel-zinc ferrite grafted polyaniline wave-absorbing material comprises the following raw materials and components, and is characterized in that: functionalized SiO₂Coating cobalt-doped nickel-zinc ferrite, p-phenylenediamine, aniline, ammonium persulfate and p-toluenesulfonic acid in a mass ratio of 80-120:2-6:100:240-260: 0.5-3.

SiO₂The preparation method of the coated nickel-zinc ferrite grafted polyaniline wave-absorbing material comprises the following steps:

(1) adding ethylene glycol solvent, ferric nitrate, nickel nitrate, zinc nitrate, cobalt nitrate, ammonium acetate and sodium dodecyl sulfate into a reaction bottle, wherein the mass ratio of the six substances is 2:0.6:0.34-0.38:0.02-0.06:6-12:3-5, pouring the solution into a hydrothermal reaction kettle after ultrasonic dispersion is uniform, placing the hydrothermal reaction kettle into a reaction kettle heating instrument, wherein the reaction kettle heating instrument comprises a heat insulation layer, a bearing is fixedly connected above the heat insulation layer, the bearing is movably connected with a rotating shaft, the rotating shaft is movably connected with a rotating device, a clamping ring groove is arranged on the surface of the rotating shaft, the clamping ring is movably connected with a clamping ring, the clamping ring is fixedly connected with a horizontal clamping plate, the rotating shaft is fixedly connected with a base, the base is arranged above the reaction kettle, a clamping block groove is arranged on the surface of the base, the clamping block groove is movably connected, and reacting for 40-50h, centrifugally separating the solution to remove the solvent, washing the solid product by using distilled water and ethanol, drying, placing the solid product in a muffle furnace, and performing heat preservation and calcination at the temperature of 550-600 ℃ for 2-4h to prepare the cobalt-doped nickel-zinc ferrite hollow microsphere.

(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 1:3-5, adding cobalt-doped nickel-zinc ferrite hollow microspheres, adding concentrated ammonia water after ultrasonic dispersion is uniform to adjust the pH value of the solution to 10-11, adding tetraethoxysilane, the mass ratio of the tetraethoxysilane to the cobalt-doped nickel-zinc ferrite hollow microspheres is 1:2.5-3.5, stirring at a constant speed at room temperature for reaction for 15-25h, filtering to remove the solvent, washing a solid product with distilled water and ethanol, and drying to prepare SiO, thus obtaining the product₂Cladding cobalt-doped nickel zinc ferrite.

(3) Adding toluene solvent and SiO into a reaction bottle₂Coating cobalt-doped nickel-zinc ferrite, adding 3-glycidol ether oxy propyl trimethoxy silane or 3- [ (2,3) -epoxy propoxy after uniform ultrasonic dispersion]In propyl methyl dimethoxy silane, with SiO₂Coating cobalt-doped nickel-zinc ferrite with the mass ratio of 1:6-10, placing the coated cobalt-doped nickel-zinc ferrite in an oil bath pot, heating the coated cobalt-doped nickel-zinc ferrite to 110-₂Cladding cobalt-doped nickel zinc ferrite.

(4) Adding distilled water solvent and functional SiO into a reaction bottle₂Coating cobalt-doped nickel-zinc ferrite, adding p-phenylenediamine after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 2-8h, adding aniline, adding salt to adjust the pH value of the solution to 1-2, slowly dropwise adding an aqueous solution of ammonium persulfate at 0-5 ℃, stirring at a constant speed for reaction for 10-15h, filtering the solution to remove the solvent, washing the solid product with ethanol and distilled water, drying, placing the solid product in an ethanol solvent, adding p-toluenesulfonic acid as proton-doped acid after uniform stirring, stirring at a constant speed and stirring for reaction for 10-15hStirring for 10-20h, filtering, washing, drying and pressing the solution into a film to prepare SiO₂Coating nickel-zinc ferrite graft polyaniline wave-absorbing material.