CN111587055A - Ni-doped ZnFe2O4-carbon nano fiber-epoxy resin wave-absorbing material and preparation method thereof - Google Patents

Ni-doped ZnFe2O4-carbon nano fiber-epoxy resin wave-absorbing material and preparation method thereof Download PDF

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CN111587055A
CN111587055A CN202010364473.5A CN202010364473A CN111587055A CN 111587055 A CN111587055 A CN 111587055A CN 202010364473 A CN202010364473 A CN 202010364473A CN 111587055 A CN111587055 A CN 111587055A
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carbon nanofiber
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黄礼辉
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked

Abstract

The invention relates to the technical field of wave-absorbing materials and discloses Ni-doped ZnFe2O4The carbon nanofiber-epoxy resin wave-absorbing material comprises the following formula raw materials and components: epoxy resin and carboxylated carbon nanofiber coated Ni-doped ZnFe2O4An activator, a catalyst and a polyetheramine. The Ni-doped ZnFe2O4The hollow structure of the-carbon nanofiber-epoxy resin wave-absorbing material is beneficial to reducing ZnFe2O4Density, magnetic Ni2+Doped with substituted Zn2+Lattice of (2) improved ZnFe2O4The ferromagnetism of the material is enhanced, the magnetic loss performance of the material is enhanced, and the dielectric loss is excellent2O4The impedance matching performance of the material can be improved by compounding, and the Ni-doped ZnFe is coated on the polyetheramine grafted carbon nanofiber2O4In the process of epoxy resin curing, the carbon nano-fiber is coated with Ni through ring-opening crosslinking reaction with an epoxy groupHetero ZnFe2O4Has strong crosslinking property and compatibility with the epoxy resin, and endows the epoxy resin with excellent wave-absorbing property.

Description

Ni-doped ZnFe2O4-carbon nano fiber-epoxy resin wave-absorbing material and preparation method thereof
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to Ni-doped ZnFe2O4-carbon nanofiber-epoxy resin wave-absorbing material and a preparation method thereof.
Background
Electromagnetic radiation is a phenomenon that energy is emitted to a space in an electromagnetic wave mode, along with the rapid development of broadcasting, television and microwave technologies, the power and the electromagnetic radiation of radio frequency equipment are greatly increased, electromagnetic pollution is caused by excessive electromagnetic radiation, the human body is in long-term contact with the electromagnetic radiation, the health of the human body is harmed through spinning of thermal effect, non-thermal effect, accumulative effect and the like, the immunologic function is reduced, disorders of a cardiovascular system, a reproductive system and the like are caused, and the normal work of a navigation system, an electronic precision instrument and the like is influenced by the excessive electromagnetic radiation, so that the development of a novel efficient wave-absorbing material becomes a research hotspot.
The wave-absorbing material mainly comprises carbon-series wave-absorbing materials such as graphene, carbon nano tubes and the like; iron-based wave-absorbing materials such as ferrite and magnetic iron nano-materials; the ceramic wave-absorbing material such as silicon carbide can absorb and lose electromagnetic waves in the modes of dielectric loss, magnetic loss, resistance type loss and the like, wherein ZnFe2O4Spinel-like ferrite has the advantages of high saturation magnetization, large complex permeability, good chemical stability and the like, can absorb and consume electromagnetic waves through magnetic loss, is a wave-absorbing material with great development potential, but ZnFe2O4High density, low dielectric constant, poor impedance matching performance, single ZnFe2O4It is difficult to efficiently dissipate electromagnetic and electromagnetic radiation.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a Ni-doped ZnFe2O4The wave-absorbing material of-carbon nanofiber-epoxy resin and the preparation method thereof solve the problem of ZnFe2O4The impedance matching performance and the wave absorbing performance of the material are poor.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: ni-doped ZnFe2O4The carbon nanofiber-epoxy resin wave-absorbing material comprises the following raw materials and components: epoxy resin, namely carboxylated carbon nanofiber coated with Ni-doped ZnFe with the mass ratio of 100:10-40:5-15:2-42O4An activator, a catalyst and a polyetheramine.
Preferably, the activator is 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the catalyst is 4-dimethylaminopyridine.
Preferably, the Ni is doped ZnFe2O4The preparation method of the-carbon nanofiber-epoxy resin wave-absorbing material comprises the following steps:
(1) adding glycol solvent, ferric chloride, zinc chloride and nickel chloride into a reaction bottle, and uniformly stirringAdding sodium acetate and polyethylene glycol after the mixture is mixed, heating to 40-60 ℃, stirring at a constant speed for 1-3h, transferring the solution into a micro reaction kettle, placing the micro reaction kettle into a reaction kettle heater, heating to 180 ℃ plus 210 ℃, stirring at a constant speed for reaction for 10-20h, filtering the solution, washing a solid product with ethanol and distilled water, and fully drying to prepare the Ni-doped ZnFe2O4Nano hollow microspheres.
(2) Adding N, N-dimethylformamide and Ni-doped ZnFe into a reaction bottle2O4Adding polyacrylonitrile and polymethyl methacrylate after ultrasonic dispersion, stirring at constant speed for 10-20h to form a spinning solution, pouring the spinning solution into an injector for electrostatic spinning, wherein the spinning voltage is 20-22kV, the spinning flow rate is 0.04-0.08mL/h, placing a nanofiber precursor in an atmosphere resistance furnace, the heating rate is 2-5 ℃/min, heating to 280-320 ℃ in the air atmosphere, carrying out heat preservation treatment for 1-1.5h, then heating to 850-950 ℃ in the argon atmosphere, carrying out heat preservation calcination for 1-1.5h, placing a calcined product in a potassium hydroxide solution with the mass fraction of 5-10%, stirring at constant speed for 2-5h, carrying out vacuum drying on the solution to remove a solvent, placing a solid mixed product in the atmosphere resistance furnace, and heating at the heating rate of 2-5 ℃/min, heating to 800 ℃ under the argon atmosphere, carrying out heat preservation treatment for 1-1.5h, washing the solid calcined product by using distilled water until the calcined product is neutral, and preparing the porous carbon nanofiber-coated Ni-doped ZnFe2O4。
(3) Adding concentrated nitric acid solution and porous carbon nanofiber coated Ni-doped ZnFe into a reaction bottle2O4Performing ultrasonic dispersion treatment, stirring at a constant speed at 70-90 ℃ for reaction for 3-6h, filtering the solution to remove the solvent, washing the product with distilled water until the product is neutral, and drying to prepare the carboxylated carbon nanofiber-coated Ni-doped ZnFe2O4。
(4) Distilled water solvent and carboxylated carbon nanofiber coated Ni-doped ZnFe are added into a reaction bottle2O4Adding polyether amine, an activating agent 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and a catalyst 4-dimethylaminopyridine after ultrasonic dispersion is uniform, stirring at a constant speed at 80-100 ℃ for reaction for 5-10h, filtering, washing and drying the solution to prepare the modified polyether amine modified ureaNi-doped ZnFe coated by polyetheramine grafted carbon nanofiber2O4。
(5) Adding epoxy resin and polyetheramine grafted carbon nanofiber into a reaction bottle to coat Ni-doped ZnFe2O4And epoxy resin curing agent, uniformly stirring, pouring into a mould for thermosetting film forming, and preparing to obtain the Ni-doped ZnFe2O4Carbon nanofiber-epoxy resin wave-absorbing material.
Preferably, the reation kettle heater includes heating collar, reation kettle heater inner wall both sides fixedly connected with rotary device, and rotary device swing joint has swivel bearing, swivel bearing fixedly connected with axis of rotation, and axis of rotation fixedly connected with governing valve, governing valve swing joint have the regulation pole, adjust pole swing joint have level regulator, level regulator swing joint have the bracing piece, and the bracing piece top is provided with miniature reation kettle.
Preferably, the mass ratio of the ferric chloride, the zinc chloride, the nickel chloride, the sodium acetate and the polyethylene glycol is 100:35-40:2.5-7.5:430-480: 110-150.
Preferably, the Ni is doped ZnFe2O4The mass ratio of the nano hollow microspheres to the polyacrylonitrile to the polymethyl methacrylate is 10:5-12: 15-45.
Preferably, the epoxy resin and the polyetheramine grafted carbon nanofiber are coated with Ni-doped ZnFe2O4And the epoxy resin curing agent in a mass ratio of 100:2-6: 30-35.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the Ni-doped ZnFe2O 4-carbon nanofiber-epoxy resin wave-absorbing material is prepared by taking polyethylene glycol as a template agent to obtain spinel type Ni-doped ZnFe2O4The hollow structure of the nano hollow microsphere is beneficial to reducing ZnFe2O4Density of material, and magnetic Ni2+Doped with substituted Zn2+The lattice increases the ion logarithm of the super exchange effect of the A-B position, enhances the spin coupling effect, and leads Ni to be doped with ZnFe2O4Shows stronger ferromagnetismThereby enhancing the magnetic loss performance of the material.
The Ni-doped ZnFe2O4-carbon nanofiber-epoxy resin wave-absorbing material, polyacrylonitrile, polymethyl methacrylate and Ni-doped ZnFe2O4Compounding hollow nano-microspheres, and preparing the porous carbon nanofiber-coated Ni-doped ZnFe through electrostatic spinning, high-temperature thermal cracking and strong base etching2O4The porous carbon nanofiber has low density, light weight, suitable resistivity and excellent dielectric loss, and is doped with Ni and ZnFe2O4The impedance matching performance of the material can be improved through compounding, the electromagnetic wave absorption performance of the material is optimized, a large number of active carboxyl groups are generated through oxidizing the porous carbon nanofibers by strong acid, and condensation reaction is carried out on the active carboxyl groups and amino groups of polyetheramine under the action of an activating agent and a catalyst to obtain the polyetheramine grafted carbon nanofiber coated Ni-doped ZnFe2O4During the curing process of the epoxy resin, a large number of amino groups of the polyetheramine and epoxy groups carry out ring-opening crosslinking reaction, so that the carbon nanofiber is coated with the Ni-doped ZnFe2O4Has strong crosslinking property and compatibility with epoxy resin, and reduces the Ni-doped ZnFe coated by the carbon nano-fiber2O4The phenomenon of agglomeration and caking in the epoxy resin endows the epoxy resin with excellent wave-absorbing performance.
Drawings
FIG. 1 is a schematic front view of a reactor heater;
FIG. 2 is an enlarged schematic view of the adjustment lever;
fig. 3 is a schematic view of adjustment lever adjustment.
1. A reactor heater; 2. heating a ring; 3. a rotating device; 4. a rotating bearing; 5. a rotating shaft; 6. adjusting a valve; 7. adjusting a rod; 8. a level adjuster; 9. a support bar; 10. and (5) a reaction kettle.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: ni-doped ZnFe2O4The carbon nanofiber-epoxy resin wave-absorbing material comprises the following raw materials and components: epoxy resin, massCarboxylated carbon nanofiber coated with Ni doped ZnFe in the mass ratio of 100:10-40:5-15:2-42O4The activator is 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the catalyst is 4-dimethylaminopyridine and polyether amine.
Ni-doped ZnFe2O4The preparation method of the-carbon nanofiber-epoxy resin wave-absorbing material comprises the following steps:
(1) adding a glycol solvent, ferric chloride, zinc chloride and nickel chloride into a reaction bottle, uniformly stirring, adding sodium acetate and polyethylene glycol, heating to 40-60 ℃, uniformly stirring for 1-3h, transferring the solution into a micro reaction kettle, placing the micro reaction kettle into a reaction kettle heater, wherein the reaction kettle heater comprises a heating ring, rotating devices are fixedly connected to two sides of the inner wall of the reaction kettle heater, the rotating devices are movably connected with rotating bearings, the rotating bearings are fixedly connected with rotating shafts, regulating valves are fixedly connected with the rotating shafts, regulating rods are movably connected with the regulating rods, horizontal regulators are movably connected with supporting rods, a micro reaction kettle is arranged above the supporting rods, heating to 180-210 ℃, stirring at constant speed for reaction for 10-20h, filtering the solution, washing the solid product with ethanol and distilled water, and fully drying to obtain Ni-doped ZnFe2O4Nano hollow microspheres.
(2) Adding N, N-dimethylformamide and Ni-doped ZnFe into a reaction bottle2O4Adding polyacrylonitrile and polymethyl methacrylate after ultrasonic dispersion uniformly, the mass ratio of the three is 10:5-12:15-45, stirring at constant speed for 10-20h to form a spinning solution, pouring the spinning solution into an injector to carry out electrostatic spinning process, the spinning voltage is 20-22kV, the spinning flow rate is 0.04-0.08mL/h, placing a nanofiber precursor in an atmosphere resistance furnace, the heating rate is 2-5 ℃/min, heating to 280 plus materials 320 ℃ under the air atmosphere, carrying out heat preservation treatment for 1-1.5h, then heating to 850 plus materials 950 ℃ under the argon atmosphere, carrying out heat preservation calcination for 1-1.5h, placing the calcined product in 5-10% potassium hydroxide solution, stirring at constant speed for 2-5h, carrying out vacuum drying on the solution to remove the solvent, placing the solid mixed product in the atmosphere resistance furnace, rate of temperature riseHeating to 700-2O4。
(3) Adding concentrated nitric acid solution and porous carbon nanofiber coated Ni-doped ZnFe into a reaction bottle2O4Performing ultrasonic dispersion treatment, stirring at a constant speed at 70-90 ℃ for reaction for 3-6h, filtering the solution to remove the solvent, washing the product with distilled water until the product is neutral, and drying to prepare the carboxylated carbon nanofiber-coated Ni-doped ZnFe2O4。
(4) Distilled water solvent and carboxylated carbon nanofiber coated Ni-doped ZnFe are added into a reaction bottle2O4Adding polyetheramine, an activating agent 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and a catalyst 4-dimethylaminopyridine after uniform ultrasonic dispersion, stirring at a constant speed at 80-100 ℃ for reaction for 5-10h, filtering, washing and drying the solution to obtain the polyetheramine grafted carbon nanofiber coated Ni-doped ZnFe2O4。
(5) Adding epoxy resin and polyetheramine grafted carbon nanofiber into a reaction bottle to coat Ni-doped ZnFe2O4And epoxy resin curing agent with the mass ratio of 100:2-6:30-35, uniformly stirring, pouring into a mold, and performing thermosetting film forming to prepare the Ni-doped ZnFe2O4Carbon nanofiber-epoxy resin wave-absorbing material.
Example 1
(1) Preparation of Ni-doped ZnFe2O4The nano hollow microsphere component 1: adding a glycol solvent, ferric chloride, zinc chloride and nickel chloride into a reaction bottle, uniformly stirring, adding sodium acetate and polyethylene glycol, heating to 40 ℃, uniformly stirring for 1h, transferring the solution into a micro reaction kettle, placing the micro reaction kettle into a reaction kettle heater, wherein the reaction kettle heater comprises a heating ring, two sides of the inner wall of the reaction kettle heater are fixedly connected with rotating devices, the rotating devices are movably connected with rotating bearings, the rotating bearings are fixedly connected with rotating shafts, and the rotating shafts are fixedly connected with regulating valves and adjusting valvesThe joint valve is movably connected with an adjusting rod, the adjusting rod is movably connected with a horizontal regulator, the horizontal regulator is movably connected with a supporting rod, a micro reaction kettle is arranged above the supporting rod, the temperature is increased to 180 ℃, the reaction is carried out for 10 hours under uniform stirring, the solution is filtered, the solid product is washed by ethanol and distilled water and is fully dried, and the Ni-doped ZnFe is prepared2O4And (3) a nano hollow microsphere component 1.
(2) Preparation of porous carbon nanofiber coated Ni-doped ZnFe2O4Component 1: adding N, N-dimethylformamide and Ni-doped ZnFe into a reaction bottle2O4Uniformly dispersing a nano hollow microsphere component 1 by ultrasonic, adding polyacrylonitrile and polymethyl methacrylate, uniformly stirring for 10h at a mass ratio of 10:5:15 to form a spinning solution, pouring the spinning solution into an injector to perform an electrostatic spinning process, wherein the spinning voltage is 20kV, the spinning flow rate is 0.04mL/h, placing a nanofiber precursor in an atmosphere resistance furnace at a heating rate of 2 ℃/min, heating to 280 ℃ in the air atmosphere, carrying out heat preservation treatment for 1h, then heating to 850 ℃ in the argon atmosphere, carrying out heat preservation calcination for 1h, placing a calcined product in a potassium hydroxide solution with the mass fraction of 5%, uniformly stirring for 2h, carrying out vacuum drying on the solution to remove a solvent, placing a solid mixed product in the atmosphere resistance furnace at a heating rate of 2 ℃/min, heating to 700 ℃ in the argon atmosphere, carrying out heat preservation treatment for 1h, washing the solid calcined product with distilled water until the solid calcined product is neutral, preparing to obtain porous carbon nanofiber coated Ni-doped ZnFe2O4And (3) component 1.
(3) Preparation of carboxylated carbon nanofiber-coated Ni-doped ZnFe2O4Component 1: adding concentrated nitric acid solution and porous carbon nanofiber coated Ni-doped ZnFe into a reaction bottle2O4Performing ultrasonic dispersion treatment on the component 1, performing uniform stirring reaction at 70 ℃ for 3 hours, filtering the solution to remove the solvent, washing the product with distilled water until the product is neutral and drying to prepare the carboxylated carbon nanofiber coated Ni-doped ZnFe2O4And (3) component 1.
(4) Preparation of polyetheramine grafted carbon nanofiber coated Ni-doped ZnFe2O4Component 1: distilled water solvent and carboxylated carbon nanofiber are added into a reaction bottle for coatingNi-doped ZnFe2O4Uniformly dispersing the component 1 by ultrasonic, adding the polyether amine, an activating agent 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride and a catalyst 4-dimethylaminopyridine in a mass ratio of 100:10:5:2, uniformly stirring and reacting for 5 hours at 80 ℃, filtering, washing and drying the solution to obtain the polyether amine grafted carbon nanofiber coated Ni-doped ZnFe2O4And (3) component 1.
(5) Preparation of Ni-doped ZnFe2O4Carbon nanofiber-epoxy resin wave-absorbing material 1: adding epoxy resin and polyetheramine grafted carbon nanofiber into a reaction bottle to coat Ni-doped ZnFe2O4The component 1 and the epoxy resin curing agent with the mass ratio of 100:2:30 are uniformly stirred and poured into a mold for thermosetting film forming to prepare the Ni-doped ZnFe2O4Carbon nanofiber-epoxy resin wave-absorbing material 1.
Example 2
(1) Preparation of Ni-doped ZnFe2O4Nano hollow microsphere component 2: adding a glycol solvent, ferric chloride, zinc chloride and nickel chloride into a reaction bottle, uniformly stirring, adding sodium acetate and polyethylene glycol, heating to 60 ℃, uniformly stirring for 1h, transferring the solution into a micro reaction kettle, placing the micro reaction kettle into a reaction kettle heater, wherein the mass ratio of the five components is 100:36:7:440:120, the reaction kettle heater comprises a heating ring, two sides of the inner wall of the reaction kettle heater are fixedly connected with rotating devices, the rotating devices are movably connected with rotating bearings, the rotating shafts are fixedly connected with adjusting valves, the adjusting valves are movably connected with adjusting rods, the adjusting rods are movably connected with horizontal regulators, the horizontal regulators are movably connected with supporting rods, the micro reaction kettle is arranged above the supporting rods, heating to 180 ℃, uniformly stirring for 20h, filtering the solution, washing solid products with ethanol and distilled water, and fully drying, preparing to obtain Ni-doped ZnFe2O4And (3) a nano hollow microsphere component 2.
(2) Preparation of porous carbon nanofiber coated Ni-doped ZnFe2O4And (2) component: adding N, N-dimethylformamide and Ni-doped ZnFe into a reaction bottle2O4Nano meterThe preparation method comprises the following steps of adding polyacrylonitrile and polymethyl methacrylate after ultrasonic dispersion of a hollow microsphere component 2 is uniform, stirring the three components at a constant mass ratio of 10:6:20 for 20 hours to form a spinning solution, pouring the spinning solution into an injector for electrostatic spinning, wherein the spinning voltage is 22kV, the spinning flow rate is 0.05mL/h, placing a nanofiber precursor in an atmosphere resistance furnace, the heating rate is 5 ℃/min, heating to 320 ℃ in the air atmosphere, carrying out heat preservation treatment for 1 hour, then heating to 850 ℃ in the argon atmosphere, carrying out heat preservation calcination for 1.5 hours, placing a calcined product in a potassium hydroxide solution with the mass fraction of 10%, stirring at a constant velocity for 5 hours, carrying out vacuum drying on the solution to remove a solvent, placing a solid mixed product in the atmosphere resistance furnace, heating to 800 ℃ in the argon atmosphere, carrying out heat preservation treatment for 1.5 hours, washing the solid calcined product with distilled water until the solid calcined product is neutral, preparing to obtain porous carbon nanofiber coated Ni-doped ZnFe2O4And (3) component 2.
(3) Preparation of carboxylated carbon nanofiber-coated Ni-doped ZnFe2O4And (2) component: adding concentrated nitric acid solution and porous carbon nanofiber coated Ni-doped ZnFe into a reaction bottle2O4Performing ultrasonic dispersion treatment on the component 2, stirring at a constant speed at 90 ℃ for reaction for 3 hours, filtering the solution to remove the solvent, washing the product with distilled water until the product is neutral and drying to prepare the carboxylated carbon nanofiber-coated Ni-doped ZnFe2O4And (3) component 2.
(4) Preparation of polyetheramine grafted carbon nanofiber coated Ni-doped ZnFe2O4And (2) component: distilled water solvent and carboxylated carbon nanofiber coated Ni-doped ZnFe are added into a reaction bottle2O4And (2) after uniformly dispersing by ultrasonic, adding polyetheramine, an activating agent 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride and a catalyst 4-dimethylaminopyridine in a mass ratio of 100:15:7:2.5, reacting for 10 hours at a constant speed at 100 ℃, filtering, washing and drying the solution to obtain the polyetheramine grafted carbon nanofiber coated Ni-doped ZnFe2O4And (3) component 2.
(5) Preparation of Ni-doped ZnFe2O4Carbon nanofiber-epoxy resin wave-absorbing material 2: adding epoxy resin and polyether into a reaction bottleNi-doped ZnFe coated with amine grafted carbon nanofiber2O4The component 2 and the epoxy resin curing agent with the mass ratio of 100:3:31 are uniformly stirred and poured into a mold for thermosetting film forming to prepare the Ni-doped ZnFe2O4Carbon nanofiber-epoxy resin wave-absorbing material 2.
Example 3
(1) Preparation of Ni-doped ZnFe2O4The nano hollow microsphere component 3: adding a glycol solvent, ferric chloride, zinc chloride and nickel chloride into a reaction bottle, uniformly stirring, adding sodium acetate and polyethylene glycol, heating to 60 ℃, uniformly stirring for 3 hours, transferring the solution into a micro reaction kettle, placing the micro reaction kettle into a reaction kettle heater, wherein the mass ratio of the sodium acetate to the polyethylene glycol is 100:37:6:450:135, the reaction kettle heater comprises a heating ring, two sides of the inner wall of the reaction kettle heater are fixedly connected with rotating devices, the rotating devices are movably connected with rotating bearings, the rotating shafts are fixedly connected with adjusting valves, the adjusting valves are movably connected with adjusting rods, the adjusting rods are movably connected with horizontal regulators, the horizontal regulators are movably connected with supporting rods, the micro reaction kettle is arranged above the supporting rods, heating to 200 ℃, uniformly stirring for 15 hours, filtering the solution, washing solid products with ethanol and distilled water, and fully drying, preparing to obtain Ni-doped ZnFe2O4And (3) a nano hollow microsphere component.
(2) Preparation of porous carbon nanofiber coated Ni-doped ZnFe2O4And (3) component: adding N, N-dimethylformamide and Ni-doped ZnFe into a reaction bottle2O4Uniformly dispersing a nano hollow microsphere component 3 by ultrasonic, adding polyacrylonitrile and polymethyl methacrylate at a mass ratio of 10:8:25, uniformly stirring for 15h to form a spinning solution, pouring the spinning solution into an injector to perform an electrostatic spinning process, wherein the spinning voltage is 22kV, the spinning flow rate is 0.06mL/h, placing a nanofiber precursor in an atmosphere resistance furnace at a heating rate of 4 ℃/min, heating to 300 ℃ in the air atmosphere, carrying out heat preservation treatment for 1.2h, then heating to 900 ℃ in the argon atmosphere, carrying out heat preservation calcination for 1.2h, placing a calcined product in a potassium hydroxide solution with the mass fraction of 8%, uniformly stirring for 4h, and carrying out vacuum drying on the solution to remove a solventPlacing the solid mixed product in an atmosphere resistance furnace, heating to 750 ℃ at the heating rate of 3 ℃/min under the argon atmosphere, carrying out heat preservation treatment for 1.2h, washing the solid calcined product to be neutral by using distilled water, and preparing to obtain the porous carbon nanofiber coated Ni-doped ZnFe2O4And (3) component.
(3) Preparation of carboxylated carbon nanofiber-coated Ni-doped ZnFe2O4And (3) component: adding concentrated nitric acid solution and porous carbon nanofiber coated Ni-doped ZnFe into a reaction bottle2O4Performing ultrasonic dispersion treatment on the component 3, stirring at a constant speed at 80 ℃ for reaction for 4 hours, filtering the solution to remove the solvent, washing the product with distilled water until the product is neutral, and drying to prepare the carboxylated carbon nanofiber-coated Ni-doped ZnFe2O4And (3) component.
(4) Preparation of polyetheramine grafted carbon nanofiber coated Ni-doped ZnFe2O4And (3) component: distilled water solvent and carboxylated carbon nanofiber coated Ni-doped ZnFe are added into a reaction bottle2O4Uniformly dispersing the component 3 by ultrasonic, adding the polyether amine, an activating agent 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and a catalyst 4-dimethylaminopyridine in a mass ratio of 100:25:10:3, uniformly stirring and reacting at 90 ℃ for 8 hours, filtering, washing and drying the solution to obtain the polyether amine grafted carbon nanofiber coated Ni-doped ZnFe2O4And (3) component.
(5) Preparation of Ni-doped ZnFe2O4Carbon nanofiber-epoxy resin wave-absorbing material 3: adding epoxy resin and polyetheramine grafted carbon nanofiber into a reaction bottle to coat Ni-doped ZnFe2O4The component 3 and the epoxy resin curing agent with the mass ratio of 100:4:32 are uniformly stirred and poured into a mould for thermosetting film forming to prepare the Ni-doped ZnFe2O4Carbon nanofiber-epoxy resin wave-absorbing material 3.
Example 4
(1) Preparation of Ni-doped ZnFe2O4The nano hollow microsphere component 4: adding glycol solvent, ferric chloride, zinc chloride and nickel chloride into a reaction bottle, stirring uniformly, adding sodium acetate, polyethylene glycol and pentaHeating to 60 ℃, stirring at a constant speed for 3 hours, transferring the solution into a micro reaction kettle, placing the solution into a reaction kettle heater, wherein the reaction kettle heater comprises a heating ring, rotating devices are fixedly connected to two sides of the inner wall of the reaction kettle heater, the rotating devices are movably connected with rotating bearings, the rotating bearings are fixedly connected with rotating shafts, regulating valves are fixedly connected with the rotating shafts, regulating rods are movably connected with the regulating valves, horizontal regulators are movably connected with the regulating rods, supporting rods are movably connected with the horizontal regulators, the micro reaction kettle is arranged above the supporting rods, heating to 210 ℃, stirring at a constant speed for 10 hours, filtering the solution, washing a solid product with ethanol and distilled water, and drying fully to prepare the Ni-doped ZnFe2O4And 4, a nano hollow microsphere component.
(2) Preparation of porous carbon nanofiber coated Ni-doped ZnFe2O4And (4) component: adding N, N-dimethylformamide and Ni-doped ZnFe into a reaction bottle2O4Uniformly dispersing a nano hollow microsphere component 4 by ultrasonic, adding polyacrylonitrile and polymethyl methacrylate, stirring the three components at a mass ratio of 10:12:15 for 10 hours at a constant speed to form a spinning solution, pouring the spinning solution into an injector to perform an electrostatic spinning process, wherein the spinning voltage is 22kV, the spinning flow rate is 0.06mL/h, placing a nanofiber precursor in an atmosphere resistance furnace at a heating rate of 3 ℃/min, heating the solution to 280 ℃ in the air atmosphere, performing heat preservation treatment for 1.5 hours, then heating the solution to 950 ℃ in the argon atmosphere, performing heat preservation calcination for 1.5 hours, placing a calcined product in a potassium hydroxide solution with the mass fraction of 8%, stirring the solution at a constant speed for 4 hours, drying the solution in vacuum to remove a solvent, placing a solid mixed product in the atmosphere resistance furnace at a heating rate of 3 ℃/min, heating the solution to 780 ℃ in the argon atmosphere, performing heat preservation treatment for 1.4 hours, washing the solid calcined product with distilled water until, preparing to obtain porous carbon nanofiber coated Ni-doped ZnFe2O4And (4) component.
(3) Preparation of carboxylated carbon nanofiber-coated Ni-doped ZnFe2O4And (4) component: adding concentrated nitric acid solution and porous carbon nanofiber coated Ni-doped ZnFe into a reaction bottle2O4Component 4, ultrasonic dispersing treatment is carried out, and the mixture is stirred at a constant speed at 90 DEG CReacting for 5h, filtering the solution to remove the solvent, washing the product with distilled water until the product is neutral and drying to prepare the carboxylated carbon nanofiber-coated Ni-doped ZnFe2O4And (4) component.
(4) Preparation of polyetheramine grafted carbon nanofiber coated Ni-doped ZnFe2O4And (4) component: distilled water solvent and carboxylated carbon nanofiber coated Ni-doped ZnFe are added into a reaction bottle2O4And (4) after uniformly dispersing by ultrasonic, adding polyetheramine, an activating agent 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride and a catalyst 4-dimethylaminopyridine in a mass ratio of 100:35:13:3.5, uniformly stirring and reacting for 10 hours at 100 ℃, filtering, washing and drying the solution to obtain the polyetheramine grafted carbon nanofiber coated Ni-doped ZnFe2O4And (4) component.
(5) Preparation of Ni-doped ZnFe2O4-carbon nanofiber-epoxy resin wave-absorbing material 4: adding epoxy resin and polyetheramine grafted carbon nanofiber into a reaction bottle to coat Ni-doped ZnFe2O4The component 4 and the epoxy resin curing agent with the mass ratio of 100:5:34 are evenly stirred and poured into a mould for thermosetting film forming to prepare the Ni-doped ZnFe2O4Carbon nanofiber-epoxy resin wave-absorbing material 4.
Example 5
(1) Preparation of Ni-doped ZnFe2O4The nano hollow microsphere component 5: adding a glycol solvent, ferric chloride, zinc chloride and nickel chloride into a reaction bottle, uniformly stirring, adding sodium acetate and polyethylene glycol, heating to 60 ℃, uniformly stirring for 3 hours, transferring the solution into a micro reaction kettle, placing the micro reaction kettle into a reaction kettle heater, wherein the mass ratio of the five components is 100:40:7.5:480:150, the reaction kettle heater comprises a heating ring, two sides of the inner wall of the reaction kettle heater are fixedly connected with rotating devices, the rotating devices are movably connected with rotating bearings, the rotating bearings are fixedly connected with rotating shafts, the rotating shafts are fixedly connected with regulating valves, the regulating valves are movably connected with regulating rods, the regulating rods are movably connected with horizontal regulators, the horizontal regulators are movably connected with supporting rods, the micro reaction kettle is arranged above the supporting rods, heating is carried out to 210 ℃, and the solution isStirring the mixture quickly to react for 20 hours, filtering the solution, washing the solid product with ethanol and distilled water, and fully drying the solid product to prepare the Ni-doped ZnFe2O4And (5) a nano hollow microsphere component.
(2) Preparation of porous carbon nanofiber coated Ni-doped ZnFe2O4And (5) component: adding N, N-dimethylformamide and Ni-doped ZnFe into a reaction bottle2O4Adding polyacrylonitrile and polymethyl methacrylate after uniformly dispersing the nano hollow microsphere component 5 by ultrasonic, stirring the mixture for 20 hours at a constant mass ratio of 10:12:45 to form a spinning solution, pouring the spinning solution into an injector to perform an electrostatic spinning process, wherein the spinning voltage is 22kV, the spinning flow rate is 0.08mL/h, placing a nanofiber precursor in an atmosphere resistance furnace at a heating rate of 5 ℃/min, heating the nanofiber precursor to 320 ℃ in the air atmosphere, carrying out heat preservation treatment for 1.5 hours, then heating the nanofiber precursor to 950 ℃ in the argon atmosphere, carrying out heat preservation calcination for 1.5 hours, placing a calcined product in a potassium hydroxide solution with the mass fraction of 10%, stirring the solution at a constant velocity for 5 hours, drying the solution in vacuum to remove the solvent, placing a solid mixed product in the atmosphere resistance furnace at a heating rate of 5 ℃/min, heating the solid mixed product to 800 ℃ in the argon atmosphere, carrying out heat preservation treatment for 1.5 hours, washing the solid calcined product with, preparing to obtain porous carbon nanofiber coated Ni-doped ZnFe2O4And (5) component.
(3) Preparation of carboxylated carbon nanofiber-coated Ni-doped ZnFe2O4And (5) component: adding concentrated nitric acid solution and porous carbon nanofiber coated Ni-doped ZnFe into a reaction bottle2O4Performing ultrasonic dispersion treatment on the component 5, stirring at a constant speed at 90 ℃ for reaction for 6 hours, filtering the solution to remove the solvent, washing the product with distilled water until the product is neutral, and drying to prepare the carboxylated carbon nanofiber-coated Ni-doped ZnFe2O4And (5) component.
(4) Preparation of polyetheramine grafted carbon nanofiber coated Ni-doped ZnFe2O4And (5) component: distilled water solvent and carboxylated carbon nanofiber coated Ni-doped ZnFe are added into a reaction bottle2O4Component 5, after ultrasonic dispersion, adding polyether amine, activator 1-ethyl- (3-dimethyl amino propyl) carbonyl diimine hydrochloride and catalyst 4-bisMethylamino pyridine with the mass ratio of 100:40:15:4, stirring at a constant speed at 100 ℃ for reaction for 10 hours, filtering, washing and drying the solution to prepare the polyetheramine grafted carbon nanofiber coated Ni-doped ZnFe2O4And (5) component.
(5) Preparation of Ni-doped ZnFe2O4-carbon nanofiber-epoxy resin wave-absorbing material 5: adding epoxy resin and polyetheramine grafted carbon nanofiber into a reaction bottle to coat Ni-doped ZnFe2O4The component 5 and the epoxy resin curing agent with the mass ratio of 100:6:35 are uniformly stirred and poured into a mold for thermosetting film forming to prepare the Ni-doped ZnFe2O4Carbon nanofiber-epoxy resin wave-absorbing material 5.
Testing of Ni-doped ZnFe Using TTR506A vector network Analyzer2O4The electromagnetic property and the wave absorbing property of the carbon nanofiber-epoxy resin wave absorbing material 1-5.
Figure BDA0002476112860000131
In summary, the Ni-doped ZnFe2O4Preparing spinel Ni-doped ZnFe through adopting polyethylene glycol as a template agent and adopting-carbon nanofiber-epoxy resin wave-absorbing material2O4The hollow structure of the nano hollow microsphere is beneficial to reducing ZnFe2O4Density of material, and magnetic Ni2+Doped with substituted Zn2+The lattice increases the ion logarithm of the super exchange effect of the A-B position, enhances the spin coupling effect, and leads Ni to be doped with ZnFe2O4The material has stronger ferromagnetism, thereby enhancing the magnetic loss performance of the material.
Polyacrylonitrile, polymethyl methacrylate and Ni-doped ZnFe2O4Compounding hollow nano-microspheres, and preparing the porous carbon nanofiber-coated Ni-doped ZnFe through electrostatic spinning, high-temperature thermal cracking and strong base etching2O4The porous carbon nanofiber has low density, light weight, suitable resistivity and excellent dielectric loss, and is doped with Ni and ZnFe2O4Composite can be liftedThe impedance matching performance of the material is high, the electromagnetic wave absorption performance of the material is optimized, a large number of active carboxyl groups are generated by oxidizing the porous carbon nanofibers with strong acid, and the active carboxyl groups and the amino groups of the polyetheramine are subjected to condensation reaction under the action of an activating agent and a catalyst to obtain the polyetheramine grafted carbon nanofiber coated Ni-doped ZnFe2O4During the curing process of the epoxy resin, a large number of amino groups of the polyetheramine and epoxy groups carry out ring-opening crosslinking reaction, so that the carbon nanofiber is coated with the Ni-doped ZnFe2O4Has strong crosslinking property and compatibility with epoxy resin, and reduces the Ni-doped ZnFe coated by the carbon nano-fiber2O4The phenomenon of agglomeration and caking in the epoxy resin endows the epoxy resin with excellent wave-absorbing performance.

Claims (7)

1. Ni-doped ZnFe2O4The carbon nanofiber-epoxy resin wave-absorbing material comprises the following raw materials and components, and is characterized in that: epoxy resin, namely carboxylated carbon nanofiber coated with Ni-doped ZnFe with the mass ratio of 100:10-40:5-15:2-42O4An activator, a catalyst and a polyetheramine.
2. The Ni-doped ZnFe of claim 12O4-carbon nanofiber-epoxy resin wave-absorbing material, characterized in that: the activating agent is 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, and the catalyst is 4-dimethylaminopyridine.
3. The Ni-doped ZnFe of claim 12O4-carbon nanofiber-epoxy resin wave-absorbing material, characterized in that: the Ni is doped with ZnFe2O4The preparation method of the-carbon nanofiber-epoxy resin wave-absorbing material comprises the following steps:
(1) adding ferric chloride, zinc chloride, nickel chloride, sodium acetate and polyethylene glycol into ethylene glycol solvent, heating to 40-60 ℃, stirring for 1-3h, transferring the solution into a micro reaction kettle, placing the micro reaction kettle in a reaction kettle heater, heating to 180 ℃ and 210 ℃, reacting for 10-20h, filtering, washing and drying to prepare the nano-composite materialDoping of ZnFe to Ni2O4Nano hollow microspheres;
(2) adding Ni-doped ZnFe into N, N-dimethylformamide2O4Adding polyacrylonitrile and polymethyl methacrylate after uniform ultrasonic dispersion into nano hollow microspheres, stirring for 10-20h to form a spinning solution, pouring the spinning solution into an injector for electrostatic spinning, wherein the spinning voltage is 20-22kV, the spinning flow rate is 0.04-0.08mL/h, placing a nanofiber precursor in an atmosphere resistance furnace, the heating rate is 2-5 ℃/min, heating to 280-10 ℃ and 320 ℃ in the air atmosphere, carrying out heat preservation treatment for 1-1.5h, then heating to 850-5 ℃ and 950 ℃ in the argon atmosphere, carrying out heat preservation and calcination for 1-1.5h, placing a calcined product in a potassium hydroxide solution with the mass fraction of 5-10%, stirring at a constant speed for 2-5h, washing and drying a solid mixed product, placing in the atmosphere resistance furnace, heating at the heating rate of 2-5 ℃/min, heating to 700-10 ℃ and 800 ℃ in the argon atmosphere, preserving heat for 1-1.5h, washing the solid calcined product by using distilled water until the calcined product is neutral, and preparing the porous carbon nanofiber coated Ni-doped ZnFe2O4；
(3) Adding porous carbon nanofiber coated Ni-doped ZnFe into concentrated nitric acid solution2O4Performing ultrasonic dispersion treatment, reacting for 3-6h at 70-90 ℃, filtering, washing and drying to prepare the carboxylated carbon nanofiber-coated Ni-doped ZnFe2O4；
(4) Adding carboxylated carbon nanofiber coated Ni-doped ZnFe into distilled water solvent2O4Adding polyetheramine, an activating agent 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and a catalyst 4-dimethylaminopyridine after uniform ultrasonic dispersion, reacting for 5-10h at 80-100 ℃, filtering, washing and drying to prepare the polyetheramine grafted carbon nanofiber coated Ni-doped ZnFe2O4；
(5) Adding epoxy resin and polyetheramine grafted carbon nanofiber into a reaction bottle to coat Ni-doped ZnFe2O4And epoxy resin curing agent, uniformly stirring, pouring into a mould for thermosetting film forming, and preparing to obtain the Ni-doped ZnFe2O4Carbon nanofiber-epoxy resin wave-absorbing material.
4. A Ni doped ZnFe according to claim 22O4-carbon nanofiber-epoxy resin wave-absorbing material, characterized in that: the reaction kettle heater comprises a heating ring, a rotating device fixedly connected to two sides of the inner wall of the reaction kettle heater, a rotating bearing is movably connected to the rotating device, a rotating shaft is fixedly connected to the rotating bearing, a regulating valve and a regulating valve are fixedly connected to the rotating shaft, a regulating rod is movably connected to the regulating valve, a horizontal regulator and a supporting rod are movably connected to the regulating rod, and a miniature reaction kettle is arranged above the supporting rod.
5. A Ni doped ZnFe according to claim 22O4-carbon nanofiber-epoxy resin wave-absorbing material, characterized in that: the mass ratio of the ferric chloride to the zinc chloride to the nickel chloride to the sodium acetate to the polyethylene glycol is 100:35-40:2.5-7.5:430-480: 110-150.
6. A Ni doped ZnFe according to claim 22O4-carbon nanofiber-epoxy resin wave-absorbing material, characterized in that: the Ni is doped with ZnFe2O4The mass ratio of the nano hollow microspheres to the polyacrylonitrile to the polymethyl methacrylate is 10:5-12: 15-45.
7. A Ni doped ZnFe according to claim 22O4-carbon nanofiber-epoxy resin wave-absorbing material, characterized in that: the epoxy resin and the polyether amine grafted carbon nanofiber are coated with Ni-doped ZnFe2O4And the epoxy resin curing agent in a mass ratio of 100:2-6: 30-35.
CN202010364473.5A 2020-04-30 2020-04-30 Ni-doped ZnFe2O4-carbon nano fiber-epoxy resin wave-absorbing material and preparation method thereof Withdrawn CN111587055A (en)

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CN112281259A (en) * 2020-10-30 2021-01-29 西安工程大学 Preparation method of hollow carbon microsphere-loaded carbon fiber fabric composite material
CN112391833A (en) * 2020-11-16 2021-02-23 江苏科技大学 Light high-efficiency wave-absorbing material SnFe2O4/C composite nanofiber, wave-absorbing coating and preparation method
CN113999489A (en) * 2021-11-09 2022-02-01 齐盛时代(广州)科技有限公司 High-power microwave resistant shielding film and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112281259A (en) * 2020-10-30 2021-01-29 西安工程大学 Preparation method of hollow carbon microsphere-loaded carbon fiber fabric composite material
CN112281259B (en) * 2020-10-30 2023-03-14 西安工程大学 Preparation method of hollow carbon microsphere-loaded carbon fiber fabric composite material
CN112391833A (en) * 2020-11-16 2021-02-23 江苏科技大学 Light high-efficiency wave-absorbing material SnFe2O4/C composite nanofiber, wave-absorbing coating and preparation method
CN112391833B (en) * 2020-11-16 2022-11-08 江苏科技大学 Light high-efficiency wave-absorbing material SnFe 2 O 4 /C composite nanofiber, wave-absorbing coating and preparation method
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