CN111995830B - Polymer-based composite medium with ferromagnetic anisotropy and preparation method thereof - Google Patents

Polymer-based composite medium with ferromagnetic anisotropy and preparation method thereof Download PDF

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CN111995830B
CN111995830B CN202010710612.5A CN202010710612A CN111995830B CN 111995830 B CN111995830 B CN 111995830B CN 202010710612 A CN202010710612 A CN 202010710612A CN 111995830 B CN111995830 B CN 111995830B
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trfe
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CN111995830A (en
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冯宇
张煜
迟庆国
梁剑
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Harbin University of Science and Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

A polymer-based composite medium with ferromagnetic anisotropy and a preparation method thereof belong to the technical field of preparation of multiferroic composite media. The invention aims to solve the technical problem that the complex preparation process of the material structure has harsh growth conditions and is difficult to adjust and control. The method comprises the steps of firstly preparing an inorganic fiber filling phase with a large length-diameter ratio by adopting a sol-gel method and an electrostatic spinning technology, then coating the inorganic fiber filling phase with barium titanate by adopting a hydrothermal synthesis method, and then compounding the inorganic fiber filling phase with P (VDF-TrFE) and carrying out hot-pressing treatment to obtain the compact high-orientation nano fiber polyvinylidene fluoride flexible multiferroic composite medium with the one-dimensional core-shell structure. According to the invention, by applying magnetic fields in different directions in the composite medium surface, the composite medium is observed to have obvious magnetic anisotropy, and has larger saturation magnetization and residual magnetization in the fiber direction in the surface than in the direction perpendicular to the fiber direction. This property allows for more unique application potential of the composite media.

Description

Polymer-based composite medium with ferromagnetic anisotropy and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of multiferroic composite media; in particular to a polymer-based composite medium with ferromagnetic anisotropy and a preparation method thereof.
Background
With the advent of the big data age, the amount of information generated continuously is increasing explosively, and a serious challenge is posed to the storage capacity (capacity, speed) of data. Magnetic memory is the most important memory technology at present, and the memory speed approaches the limit due to the principle of magnetic writing and reading and the limitation of microelectronic technology, so how to improve the access speed is an important problem at present. Therefore, research and development of a novel "read/write" technology has become an important trend in domestic and foreign research, and among many read/write technologies, an "electromagnetic write" technology using a multiferroic material magnetoelectric coupling effect (the electrical property of a material can be changed by a magnetic field, and the magnetism of the material can be regulated and controlled by an electric field) is concerned about the advantages of high speed, low power consumption, non-volatility and the like. Meanwhile, multiferroic materials with strong magnetic-electric coupling effect at room temperature are the premise and the basis for realizing the technology of 'electromagnetic writing and reading', wherein ferroelectric ferromagnetic materials are the multiferroic materials which are most discussed at present.
The composite multiferroic media are mainly divided into three types according to communication: 0-3 type particle composite, 2-2 type laminated structure and 1-3 type columnar structure. The ferromagnetic phase is embedded in the ferroelectric material matrix as a one-dimensional columnar shape to obtain the composite medium. The communication structure increases the contact area of two phases of the ferroelectric phase and the ferromagnetic phase, and is beneficial to generating strong magnetoelectric coupling. However, at present, the preparation process of the structure is complex, and the growth conditions are harsh and difficult to adjust and control, so that the structure is greatly limited in practical application.
Disclosure of Invention
The invention aims to provide a polymer-based composite medium with ferromagnetic anisotropy and a preparation method thereof, wherein the polymer-based composite medium has strong process controllability, is easy to operate and has better multiferroic performance.
The invention is realized by the following technical scheme:
a method for preparing a polymer-based composite media having ferromagnetic anisotropy, comprising the steps of:
step a, preparation of CoFe2O4A nanofiber;
step b, preparing core-shell structure CoFe2O4@BaTiO3A nanofiber;
step c, preparation of CoFe2O4@BaTiO3-a P (VDF-TrFE) based composite medium;
and d, preparing a polymer-based composite medium with ferromagnetic anisotropy.
The invention relates to a preparation method of a polymer-based composite medium with ferromagnetic anisotropy, wherein in the step a, CoFe2O4The preparation method of the nanofiber comprises the following steps:
step a1, weighing a certain mass of cobalt hexahydrate, ferric nitrate nonahydrate and citric acid according to the mass ratio of substances for later use;
step a2, adding cobalt nitrate hexahydrate and ferric nitrate nonahydrate weighed in the step a1 into an ethanol solution, adding citric acid after uniformly stirring, and continuously stirring until the mixed solution is clear to obtain a mixed solution for later use;
step a3, continuously adding polyvinylpyrrolidone into the mixed solution obtained in the step a2, wherein the material-to-liquid ratio of the mixed solution to the polyvinylpyrrolidone is 10 ml/0.4-0.6 g, and continuously stirring at normal temperature for 10-12 hours to obtain CoFe2O4Adding the precursor solution into an injector for electrostatic spinning to obtain CoFe2O4Precursor fibers;
step a4, CoFe obtained in the step a32O4Sintering the precursor fiber in a muffle furnace to obtain CoFe2O4And (3) nano fibers.
The invention relates to a preparation method of a polymer-based composite medium with ferromagnetic anisotropy, wherein in the step a1, the mass ratio of cobalt nitrate hexahydrate, ferric nitrate nonahydrate and citric acid is 1:2: 3; and b, uniformly stirring the mixture of the cobalt hexahydrate and the ferric nitrate nonahydrate in the step a2 and an ethanol solution to obtain a mixed solution, wherein the concentration of cobalt ions in the mixed solution is 0.2-0.3 mol/L, and the concentration of the ethanol solution is 70 vol%.
The invention relates to a preparation method of a polymer-based composite medium with ferromagnetic anisotropy, which comprises the steps of electrostatic spinning in step a3, setting the advancing speed of an injector to be 0.1-0.2 mm/min, the rotating speed of a receiver to be 60-100 r/min, setting the distance from the injector to the receiver to be 10-20 cm, and setting the electrostatic pulse voltage V of the injector+10-20 kV, and receiving electrostatic pulse voltage V of the roller－10-20 kV; in the step a4, the muffle furnace sintering temperature is 500-700 ℃, and the sintering time is 2-4 h.
The invention relates to a preparation method of a polymer-based composite medium with ferromagnetic anisotropy, and in the step b, CoFe with a core-shell structure2O4@BaTiO3The preparation method of the nanofiber comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, cetyl trimethyl ammonium bromide, n-butyl alcohol and distilled water, mixing n-butyl alcohol, cetyl trimethyl ammonium bromide and distilled water uniformly, adding weighed CoFe2O4Carrying out ultrasonic dispersion on the nanofiber uniformly to obtain CoFe2O4Mixing the nanofiber solution for later use;
step b2, CoFe according to step b12O4Weighing tetrabutyl titanate with a certain mass according to a mass ratio of 1:2, adding the weighed tetrabutyl titanate into n-butanol, stirring for 20-40 min, and slowly dripping CoFe obtained in the step b1 under the stirring condition2O4Mixing the solution with nano-fiber to obtain CoFe2O4@TiO2Washing and drying the nano-fibers with absolute ethyl alcohol for later use;
step b3, weighing a certain mass of barium hydroxide octahydrate according to the mass ratio of tetrabutyl titanate to barium hydroxide octahydrate in step b2 of 1:1.2, and then adding CoFe obtained in step b22O4@TiO2Adding the nano-fiber, barium hydroxide octahydrate and distilled water into a hydrothermal reaction kettle, then putting the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 200 ℃, and preserving heat for 4 hours to obtain core-shell structure CoFe2O4@BaTiO3And (3) nano fibers.
The invention relates to a preparation method of a polymer-based composite medium with ferromagnetic anisotropy, namely CoFe in step b12O4The feed-liquid ratio of the nano-fibers, the cetyl trimethyl ammonium bromide, the n-butyl alcohol and the distilled water is 0.459-6.36 g, 0.4-5 g, 150-2000 ml and 10-100 ml; n-butanol in step b2 and CoFe obtained in step b12O4Nanofiber blendThe volume ratio of the mixed solution is 4-50: 16-210; the addition amount of the distilled water in the step b3 is 2/3 of the volume of the hydrothermal reaction kettle.
The invention relates to a preparation method of a polymer-based composite medium with ferromagnetic anisotropy, and CoFe in step c2O4@BaTiO3The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step c1 CoFe as used in step b12O4Weighing a certain mass of P (VDF-TrFE) powder and a certain volume of N, N-dimethylformamide solution for later use;
step c2, preparing the core-shell structure CoFe prepared in step b2O4@BaTiO3Adding the nano-fibers into the N, N-dimethylformamide solution weighed in the step c1, carrying out ultrasonic oscillation until the nano-fibers are uniformly dispersed, then adding the P (VDF-TrFE) powder weighed in the step c1, and carrying out ultrasonic uniform treatment to obtain CoFe2O4@BaTiO3A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step c3, CoFe obtained in step c22O4@BaTiO3Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite wet membrane, ready for use;
step c4, CoFe obtained in step c32O4@BaTiO3Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite media.
The invention relates to a preparation method of a polymer-based composite medium with ferromagnetic anisotropy, which comprises the step c1 of using CoFe used in the step b12O4Weighing P (VDF-TrFE) powder and N, N-dimethylformamide solution according to the mass of the nanofiber and the feed-liquid ratio of the P (VDF-TrFE) powder to the N, N-dimethylformamide solution of 0.459-6.36 g:5g:50 ml; c2, controlling the ultrasonic oscillation frequency to be 60W and the ultrasonic oscillation time to be 5-30 min; the rotating speed of the high-speed directional electrostatic spinning receiver in the step c3 is 2000 to 3000r/min, the advancing speed of the injector is set to be 0.1 to 0.2mm/min, the distance from the injector to the receiver is 10 to 20cm, and the electrostatic pulse voltage V of the injector is set+12-20 kV, and receiving electrostatic pulse voltage V of the roller－Is 12-20 kV; in the step c4, the vacuum drying temperature is 60-80 ℃, and the drying time is 6-24 h.
The invention relates to a preparation method of a polymer-based composite medium with ferromagnetic anisotropy, which comprises the step of preparing CoFe prepared in the step c2O4@BaTiO3And (2) placing the-P (VDF-TrFE) based composite medium in a vulcanizing press for hot pressing, wherein the hot pressing pressure is 15MPa, the hot pressing temperature is 140-170 ℃, the hot pressing time is 15-25 min, then quickly cooling to room temperature through water cooling, and maintaining the pressure at 1-10 MPa for 1-10 min to obtain the polymer based composite medium with ferromagnetic anisotropy.
The polymer-based composite medium with the ferromagnetic anisotropy, which is prepared by the preparation method of the polymer-based composite medium with the ferromagnetic anisotropy, is CoFe2O4@BaTiO3The content of the nanofiber filling phase in the polymer-based composite medium with ferromagnetic anisotropy is 3-30 vol%.
The polymer-based composite medium with ferromagnetic anisotropy prepared by the preparation method provided by the invention has the thickness of 10-30 mu m.
The invention has the beneficial effects that:
compared with the situation that the fibers are arranged in a disordered manner in the polymer matrix under the low-speed receiving condition of the rotating speed of 60-100 r/min, the fibers are subjected to the combined action of the tensile force and the electrostatic force of the electric field when the rotating speed is up to 2000-3000 r/min, so that the inorganic fibers are arranged in a highly parallel manner, the orientation of the fibers in the matrix is kept consistent, and the regular fibers in the material are vertical to the direction of the external electric field when the material is applied under the external electric field, so that the leakage current of the composite medium is reduced.
The polymer-based composite medium with ferromagnetic anisotropy, which is prepared by the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, is CoFe with a core-shell structure2O4@BaTiO3The nano fibers are highly parallel to each other in the polymer matrix, and the macroscopic performance of the nano fibers is tested, so that the anisotropy of the polymer-based composite medium with the ferromagnetic anisotropy in different directions can be detected, and the polymer-based composite medium is perpendicular to the direction of an external electric field in the application process.
According to the polymer-based composite medium with the ferromagnetic anisotropy prepared by the preparation method, magnetic fields in the fiber direction and the direction perpendicular to the fiber direction are respectively applied along the surface of the composite medium in the plane, so that the difference of residual magnetization, saturated magnetization, coercive force and the like is found, and obvious magnetic anisotropy is reflected. This property allows the polymer-based composite media with ferromagnetic anisotropy to have more unique application potential.
According to the polymer-based composite medium with ferromagnetic anisotropy prepared by the preparation method, the core-shell structure fibers in high directional arrangement are embedded in a ferroelectric material P (VDF-TrFE) phase matrix as a one-dimensional columnar shape, and the 1-3 communication structure enables the contact area of two phases of a ferroelectric phase and a ferromagnetic phase to be increased, so that strong magnetoelectric coupling is generated. And in CoFe2O4The surface of the fiber is coated with a layer of BaTiO3A grain shell layer for limiting leakage current and coating BaTiO3The shell layer is used as a ferroelectric material, so that the electric polarization of the composite medium can be further increased, and the magnetoelectric effect is further causedAnd meanwhile, the preparation method has the advantages of low equipment price, simple process and easy realization.
The invention relates to a preparation method of a polymer-based composite medium with ferromagnetic anisotropy, which comprises the steps of firstly preparing an inorganic fiber filling phase with a large length-diameter ratio by adopting a sol-gel method and an electrostatic spinning technology, then coating the inorganic fiber filling phase with barium titanate by adopting a hydrothermal synthesis method, then compounding the inorganic fiber filling phase with P (VDF-TrFE) and carrying out hot pressing treatment to obtain the compact polymer-based composite medium with ferromagnetic anisotropy in high orientation.
The polymer-based composite medium with the ferromagnetic anisotropy, which is prepared by the preparation method of the polymer-based composite medium with the ferromagnetic anisotropy, is CoFe2O4@BaTiO3NFs is core-shell fiber structure, with the core layer being cobalt ferrite and the shell layer being barium titanate.
The polymer-based composite medium with ferromagnetic anisotropy prepared by the preparation method of the polymer-based composite medium with ferromagnetic anisotropy has the advantages of simple operation, easy preparation, excellent ferroelectric and ferromagnetic properties, effective solving of the possible leakage current problem of the composite film, and flexibility which is not possessed by inorganic multiferroic materials.
Drawings
FIG. 1 shows P (VDF-TrFE) and CoFe2O4The nanofiber and the polymer-based composite medium with ferromagnetic anisotropy prepared by the method of the embodiment one have an X-ray diffraction contrast map;
FIG. 2 is a cross-sectional SEM photograph of a polymer-based composite media having ferromagnetic anisotropy made by a method according to one embodiment;
FIG. 3 is a SEM photograph of a cross-section of P (VDF-TrFE);
FIG. 4 is a comparison of the hysteresis loops of P (VDF-TrFE) and a polymer-based composite media with ferromagnetic anisotropy made by the method of one embodiment.
FIG. 5 is a hysteresis loop curve of a polymer-based composite media with ferromagnetic anisotropy under different magnetic field directions prepared by a method according to an embodiment;
FIG. 6 shows CoFe with core-shell structure prepared by the method of the first embodiment2O4@BaTiO3TEM photograph of the nanofibers;
FIG. 7 is a CoFe prepared by the method of one embodiment2O4TEM images of nanofibers.
Detailed Description
The present invention is further described in detail with reference to the drawings, but the invention is not limited thereto, and modifications and equivalent substitutions may be made to the present invention without departing from the spirit and scope of the present invention.
The first embodiment is as follows:
a method for preparing a polymer-based composite media having ferromagnetic anisotropy, comprising the steps of:
step a, preparation of CoFe2O4A nanofiber;
step b, preparing core-shell structure CoFe2O4@BaTiO3A nanofiber;
step c, preparation of CoFe2O4@BaTiO3-a P (VDF-TrFE) based composite medium;
and d, preparing the polymer-based composite medium with the ferromagnetic anisotropy.
In the method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe is used in step a2O4The preparation method of the nanofiber comprises the following steps:
step a1, weighing a certain mass of cobalt hexahydrate, ferric nitrate nonahydrate and citric acid according to the mass ratio of substances for later use;
step a2, adding cobalt nitrate hexahydrate and ferric nitrate nonahydrate weighed in the step a1 into an ethanol solution, adding citric acid after uniformly stirring, and continuously stirring until the mixed solution is clear to obtain a mixed solution for later use;
step a3, adding the mixed solution obtained in the step a2 continuouslyPolyvinylpyrrolidone, the material-to-liquid ratio of the mixed solution to the polyvinylpyrrolidone is 10ml/0.5g, and the mixture is continuously stirred for 12 hours at normal temperature to obtain CoFe2O4Adding the precursor solution into an injector for electrostatic spinning to obtain CoFe2O4Precursor fibers;
step a4, CoFe obtained in the step a32O4Sintering the precursor fiber in a muffle furnace to obtain CoFe2O4And (3) nano fibers.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, the amount ratio of the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the citric acid in the step a1 is 1:2: 3; and b, uniformly stirring the mixture of the cobalt hexahydrate and the ferric nitrate nonahydrate in the step a2 and an ethanol solution to obtain a mixed solution, wherein the concentration of cobalt ions in the mixed solution is 0.2mol/L, and the concentration of the ethanol solution is 70 vol%.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, step a3 is performed by electrostatic spinning, the advancing speed of the injector is set to be 0.14mm/min, the rotating speed of the receiver is 100r/min, the distance from the injector to the receiver is 15cm, and the voltage V of the electrostatic pulse of the injector is set+Is 14kV, receives the electrostatic pulse voltage V of the roller－Is-14 kV; in the step a4, the muffle furnace sintering temperature is 700 ℃, and the sintering time is 2 h. And selecting a 23G metal needle to prepare for electrostatic spinning.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, in step b, the core-shell structure of CoFe2O4@BaTiO3The preparation method of the nanofiber comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, cetyl trimethyl ammonium bromide, n-butyl alcohol and distilled water, mixing n-butyl alcohol, cetyl trimethyl ammonium bromide and distilled water uniformly, adding weighed CoFe2O4Carrying out ultrasonic dispersion on the nanofiber uniformly to obtain CoFe2O4Mixing the nanofiber solution for later use；
Step b2, CoFe according to step b12O4Weighing tetrabutyl titanate with a certain mass according to a mass ratio of 1:2, adding the weighed tetrabutyl titanate into n-butanol, stirring for 30min, and slowly dripping CoFe obtained in the step b1 under the stirring condition2O4Stirring the nanofiber mixed solution for 12 hours to obtain CoFe2O4@TiO2Washing and drying the nano-fibers with absolute ethyl alcohol for later use;
step b3, weighing a certain mass of barium hydroxide octahydrate according to the mass ratio of tetrabutyl titanate to barium hydroxide octahydrate in step b2 of 1:1.2, and then adding CoFe obtained in step b22O4@TiO2Adding the nano-fiber, barium hydroxide octahydrate and distilled water into a hydrothermal reaction kettle, then putting the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 200 ℃, and preserving heat for 4 hours to obtain core-shell structure CoFe2O4@BaTiO3And (3) nano fibers.
The method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to this embodiment, CoFe in step b12O4The feed-liquid ratio of the nano-fiber, the hexadecyl trimethyl ammonium bromide, the normal butanol and the distilled water is 0.781:0.6g:250ml:20 ml; n-butanol in step b2 and CoFe obtained in step b12O4The volume ratio of the nanofiber mixed solution is 6: 27; the addition amount of the distilled water in the step b3 is 2/3 of the volume of the hydrothermal reaction kettle.
In the method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe is used in step c2O4@BaTiO3The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step c1 CoFe as used in step b12O4Weighing a certain mass of P (VDF-TrFE) powder and a certain volume of N, N-dimethylformamide solution for later use;
step c2, and step b to obtain core-shell structure CoFe2O4@BaTiO3Adding the nano-fiber into the N, N-dimethyl methyl weighed in the step c1Ultrasonically oscillating the mixture to be uniformly dispersed in an amide solution, then adding the P (VDF-TrFE) powder weighed in the step c1, and ultrasonically uniformly stirring to obtain CoFe2O4@BaTiO3A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step c3, CoFe obtained in step c22O4@BaTiO3Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite wet membrane, ready for use;
step c4, CoFe obtained in step c32O4@BaTiO3Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite media.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe used in step b1 in step c12O4Weighing P (VDF-TrFE) powder and N, N-dimethylformamide solution with the mass of the nanofiber and the feed-liquid ratio of the P (VDF-TrFE) powder to the N, N-dimethylformamide solution being 0.781g:5g:50 ml; c2, controlling the ultrasonic oscillation frequency to be 60W and the ultrasonic oscillation time to be 20 min; in the step c3, the rotating speed of the high-speed directional electrostatic spinning receiver is 2000r/min, the propelling speed of the injector is set to be 0.1mm/min, the distance from the injector to the receiver is 15cm, and the electrostatic pulse voltage V of the injector is set+Is 14kV, receives the electrostatic pulse voltage V of the roller－Is-14 kV; in step c4, the vacuum drying temperature is 70 ℃, and the drying time is 12 h.
In the method for preparing the polymer-based composite media with ferromagnetic anisotropy in the embodiment, the method for preparing the polymer-based composite media with ferromagnetic anisotropy in the step d is to use the CoFe prepared in the step c2O4@BaTiO3Placing the-P (VDF-TrFE) based composite medium in a plate vulcanizing machine for hot pressing treatment, wherein the hot pressing pressure is 15MPa, the hot pressing temperature is 160 ℃, the hot pressing time is 20min, then rapidly cooling to room temperature through water cooling, and maintaining the pressure at 5MPa for 3min to obtain the productA polymer-based composite media having ferromagnetic anisotropy.
In the method for preparing a polymer-based composite media with ferromagnetic anisotropy according to the embodiment, the content of the prepared polymer-based composite media with ferromagnetic anisotropy is 5 vol%.
The X-ray diffraction contrast spectrum of the polymer-based composite medium with ferromagnetic anisotropy prepared by the method for preparing the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment is shown in fig. 1, and as can be seen from fig. 1, the one-dimensional CoFe prepared by the embodiment2O4The nano-fiber crystal phase is of a spinel structure and has no other impurities; the polymer-based composite medium with ferromagnetic anisotropy is characterized and analyzed in crystal structure through an X-ray diffraction pattern (XRD), and the filled phase CoFe is detected in the XRD2O4、BaTiO3The diffraction peak of (A) and the crystal structure of P (VDF-TrFE) indicate that the inorganic phase and the matrix are successfully compounded.
In the polymer-based composite media with ferromagnetic anisotropy prepared by the method for preparing the polymer-based composite media with ferromagnetic anisotropy according to the embodiment, the SEM photograph of the cross section is shown in fig. 2, the SEM photograph of the cross section of P (VDF-TrFE) is shown in fig. 3, and as can be seen from the comparison between fig. 2 and fig. 3, the polymer-based composite media with ferromagnetic anisotropy according to the embodiment has a thickness of 20 μm, and the P (VDF-TrFE) alone has a thickness of 24 μm, so that CoFe can be clearly observed2O4@BaTiO3The nano-fibers are highly directionally arranged in the polymer-based composite medium with ferromagnetic anisotropy and are uniformly distributed.
The method for preparing a polymer-based composite media with ferromagnetic anisotropy according to the present embodiment is used to prepare a polymer-based composite media with ferromagnetic anisotropy, the tested hysteresis loop is shown in fig. 4, and it can be seen from fig. 4 that the polymer-based composite media with ferromagnetic anisotropy has larger maximum polarization and remanent polarization compared with pure P (VDF-TrFE) media under the same electric field, so as to obtain a polymer-based composite media with ferromagnetic anisotropyThe coercive field is small, and the ferroelectric property is improved; in addition, because of BaTiO3The shell layer belongs to ferroelectrics, so that the polarization strength of the polymer-based composite medium with ferromagnetic anisotropy can be further increased, and the generation of leakage current is limited.
In the polymer-based composite media with ferromagnetic anisotropy prepared by the method for preparing a polymer-based composite media with ferromagnetic anisotropy according to the embodiment, magnetic fields in the fiber direction and the direction perpendicular to the fiber direction are respectively applied along the surface of the composite media in the plane, as shown in fig. 5, the direction a is the in-plane fiber direction, and the direction b is the in-plane perpendicular to the fiber direction. As is apparent from the figure, the saturation magnetization and remanent magnetization are clearly smaller in the b direction than in the a direction. Exhibiting significant magnetic anisotropy. And is coated with BaTiO3After the shell layer is formed, the polymer-based composite medium with ferromagnetic anisotropy still has good ferromagnetic performance. As can also be seen from fig. 4 and 5, the polymer-based composite medium with ferromagnetic anisotropy prepared by the preparation method of the embodiment has good ferroelectric property and ferromagnetic property, ensures good flexibility of the polymer matrix, and realizes excellent multiferroic property under low content of inorganic fiber with a one-dimensional core-shell structure.
CoFe, a polymer-based composite medium with ferromagnetic anisotropy prepared by the method of preparing a polymer-based composite medium with ferromagnetic anisotropy according to this embodiment2O4@BaTiO3TEM photograph of the composite fiber is shown in FIG. 6, CoFe2O4The TEM photograph of the fiber is shown in FIG. 7, and CoFe can be seen in FIG. 62O4The surface of the fiber is evenly and completely coated with a layer of BaTiO3Shell, CoFe in core-shell structure2O4Diameter of about 300nm, BaTiO3The cladding layer is about 30 nm.
In the polymer-based composite medium with ferromagnetic anisotropy, by applying magnetic fields in the fiber direction and perpendicular to the fiber direction along the surface of the composite medium in the plane, the differences of residual magnetization, saturated magnetization, coercive force and the like are found, and obvious magnetic anisotropy is reflected. This property allows the polymer-based composite media with ferromagnetic anisotropy to have more unique application potential.
The second embodiment is as follows:
a method for preparing a polymer-based composite media having ferromagnetic anisotropy, comprising the steps of:
step a, preparation of CoFe2O4A nanofiber;
step b, preparing core-shell structure CoFe2O4@BaTiO3A nanofiber;
step c, preparation of CoFe2O4@BaTiO3-a P (VDF-TrFE) based composite medium;
and d, preparing a polymer-based composite medium with ferromagnetic anisotropy.
In the method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe is used in step a2O4The preparation method of the nanofiber comprises the following steps:
step a1, weighing a certain mass of cobalt hexahydrate, ferric nitrate nonahydrate and citric acid according to the mass ratio of substances for later use;
step a2, adding cobalt nitrate hexahydrate and ferric nitrate nonahydrate weighed in the step a1 into an ethanol solution, adding citric acid after uniformly stirring, and continuously stirring until the mixed solution is clear to obtain a mixed solution for later use;
step a3, continuously adding polyvinylpyrrolidone into the mixed solution obtained in the step a2, and mixing the mixed solution with polyethyleneThe material-liquid ratio of the vinylpyrrolidone is 10ml/0.4g, and the stirring is continued for 10 hours at normal temperature to obtain CoFe2O4Adding the precursor solution into an injector for electrostatic spinning to obtain CoFe2O4Precursor fibers;
step a4, CoFe obtained in the step a32O4Sintering the precursor fiber in a muffle furnace to obtain CoFe2O4And (3) nano fibers.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, the amount ratio of the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the citric acid in the step a1 is 1:2: 3; and b, uniformly stirring the mixture of the cobalt hexahydrate and the ferric nitrate nonahydrate in the step a2 and an ethanol solution to obtain a mixed solution, wherein the concentration of cobalt ions in the mixed solution is 0.2mol/L, and the concentration of the ethanol solution is 70 vol%.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, step a3 is performed by electrostatic spinning, the advancing speed of the injector is set to be 0.1mm/min, the rotating speed of the receiver is 60r/min, the distance from the injector to the receiver is 10cm, and the voltage V of the electrostatic pulse of the injector is set+Is 10kV, receives the electrostatic pulse voltage V of the roller－Is 10 kV; in the step a4, the muffle furnace sintering temperature is 500 ℃, and the sintering time is 4 h.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, in step b, the core-shell structure of CoFe2O4@BaTiO3The preparation method of the nanofiber comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, cetyl trimethyl ammonium bromide, n-butyl alcohol and distilled water, mixing n-butyl alcohol, cetyl trimethyl ammonium bromide and distilled water uniformly, adding weighed CoFe2O4Carrying out ultrasonic dispersion on the nanofiber uniformly to obtain CoFe2O4Mixing the nanofiber solution for later use;
step b2, CoFe according to step b12O4And tetra (titanic acid)Weighing tetrabutyl titanate with a certain mass according to a mass ratio of 1:2, adding the weighed tetrabutyl titanate into n-butanol, stirring for 20min, and slowly dripping CoFe obtained in the step b1 under the stirring condition2O4Mixing the solution with nano-fiber to obtain CoFe2O4@TiO2Washing and drying the nano-fibers with absolute ethyl alcohol for later use;
step b3, weighing a certain mass of barium hydroxide octahydrate according to the mass ratio of tetrabutyl titanate to barium hydroxide octahydrate in step b2 of 1:1.2, and then adding CoFe obtained in step b22O4@TiO2Adding the nano-fiber, barium hydroxide octahydrate and distilled water into a hydrothermal reaction kettle, then putting the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 200 ℃, and preserving heat for 4 hours to obtain core-shell structure CoFe2O4@BaTiO3And (3) nano fibers.
The method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to this embodiment, CoFe in step b12O4The feed-liquid ratio of the nano-fiber, the hexadecyl trimethyl ammonium bromide, the n-butanol and the distilled water is 0.459g to 0.4g to 150ml to 10 ml; n-butanol in step b2 and CoFe obtained in step b12O4The volume ratio of the nanofiber mixed solution is 4: 16; the addition amount of the distilled water in the step b3 is 2/3 of the volume of the hydrothermal reaction kettle.
In the method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe is used in step c2O4@BaTiO3The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step c1 CoFe as used in step b12O4Weighing a certain mass of P (VDF-TrFE) powder and a certain volume of N, N-dimethylformamide solution for later use;
step c2, preparing the core-shell structure CoFe prepared in step b2O4@BaTiO3Adding the nano-fibers into the N, N-dimethylformamide solution weighed in the step c1, carrying out ultrasonic oscillation until the nano-fibers are uniformly dispersed, then adding the P (VDF-TrFE) powder weighed in the step c1, and carrying out ultrasonic oscillation until the nano-fibers are uniformly dispersedTo obtain CoFe2O4@BaTiO3A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step c3, CoFe obtained in step c22O4@BaTiO3Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite wet membrane, ready for use;
step c4, CoFe obtained in step c32O4@BaTiO3Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite media.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe used in step b1 in step c12O4Weighing P (VDF-TrFE) powder and N, N-dimethylformamide solution according to the mass of the nanofiber and the feed-liquid ratio of the P (VDF-TrFE) powder to the N, N-dimethylformamide solution of 0.459g:5g:50 ml; c2, controlling the ultrasonic oscillation frequency to be 60W and the ultrasonic oscillation time to be 5-30 min; in the step c3, the rotating speed of the high-speed directional electrostatic spinning receiver is 2000r/min, the propelling speed of the injector is set to be 0.16mm/min, the distance from the injector to the receiver is 10cm, and the electrostatic pulse voltage V of the injector is set+12kV, receiving electrostatic pulse voltage V of the roller－Is 12 kV; in step c4, the vacuum drying temperature is 60 ℃, and the drying time is 24 h.
In the method for preparing the polymer-based composite media with ferromagnetic anisotropy in the embodiment, the method for preparing the polymer-based composite media with ferromagnetic anisotropy in the step d is to use the CoFe prepared in the step c2O4@BaTiO3And (2) placing the-P (VDF-TrFE) based composite medium in a vulcanizing press for hot pressing, wherein the hot pressing pressure is 15MPa, the hot pressing temperature is 140 ℃, the hot pressing time is 25min, then quickly cooling to room temperature through water cooling, and maintaining the pressure at 1MPa for 10min to obtain the polymer based composite medium with ferromagnetic anisotropy.
Described in the present embodimentPreparation method of polymer-based composite medium with ferromagnetic anisotropy, and CoFe2O4@BaTiO3The content of the nanofiber filler phase in a polymer-based composite medium having ferromagnetic anisotropy was 3 vol%.
The preparation method of the polymer-based composite medium with ferromagnetic anisotropy, which is described in the embodiment, is core-shell structure CoFe2O4@BaTiO3The nano fibers are highly parallel to each other in the polymer matrix, and the macroscopic performance of the nano fibers is tested, so that the anisotropy of the polymer-based composite medium with the ferromagnetic anisotropy in different directions can be detected, and the polymer-based composite medium is perpendicular to the direction of an external electric field in the application process.
In the polymer-based composite medium with ferromagnetic anisotropy prepared by the preparation method of the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, the core-shell structure fibers in highly directional arrangement are embedded in the ferroelectric material P (VDF-TrFE) phase matrix as a one-dimensional columnar shape, and the 1-3 communication structure increases the contact area of two phases of a ferroelectric phase and a ferromagnetic phase, thereby being beneficial to generating strong magnetoelectric coupling. And in CoFe2O4The surface of the fiber is coated with a layer of BaTiO3A grain shell layer for limiting leakage current and coating BaTiO3The shell layer is used as a ferroelectric material, so that the electric polarization of the composite medium can be further increased, the magnetoelectric effect is further increased, and meanwhile, the preparation method has the advantages of low price of required equipment, simple process and easy realization.
In the polymer-based composite medium with ferromagnetic anisotropy, by applying magnetic fields in the fiber direction and perpendicular to the fiber direction along the surface of the composite medium in the plane, the differences of residual magnetization, saturated magnetization, coercive force and the like are found, and obvious magnetic anisotropy is reflected. This property allows the polymer-based composite media with ferromagnetic anisotropy to have more unique application potential.
The third concrete implementation mode:
a method for preparing a polymer-based composite media having ferromagnetic anisotropy, comprising the steps of:
step a, preparation of CoFe2O4A nanofiber;
step b, preparing core-shell structure CoFe2O4@BaTiO3A nanofiber;
step c, preparation of CoFe2O4@BaTiO3-a P (VDF-TrFE) based composite medium;
and d, preparing a polymer-based composite medium with ferromagnetic anisotropy.
In step a, the method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to this embodiment uses CoFe2O4The preparation method of the nanofiber comprises the following steps:
step a1, weighing a certain mass of cobalt hexahydrate, ferric nitrate nonahydrate and citric acid according to the mass ratio of substances for later use;
step a2, adding cobalt nitrate hexahydrate and ferric nitrate nonahydrate weighed in the step a1 into an ethanol solution, adding citric acid after uniformly stirring, and continuously stirring until the mixed solution is clear to obtain a mixed solution for later use;
step a3, continuously adding polyvinylpyrrolidone into the mixed solution obtained in the step a2, wherein the material-to-liquid ratio of the mixed solution to the polyvinylpyrrolidone is 10ml/0.6g, and continuously stirring at normal temperature for 12 hours to obtain CoFe2O4Adding the precursor solution into an injector for electrostatic spinning to obtain CoFe2O4Precursor fibers;
step a4, CoFe obtained in the step a32O4Sintering the precursor fiber in a muffle furnace to obtain CoFe2O4And (3) nano fibers.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, the amount ratio of the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the citric acid in the step a1 is 1:2: 3; and b, uniformly stirring the mixture of the cobalt hexahydrate and the ferric nitrate nonahydrate in the step a2 and an ethanol solution to obtain a mixed solution, wherein the concentration of cobalt ions in the mixed solution is 0.2mol/L, and the concentration of the ethanol solution is 70 vol%.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, step a3 is performed by electrostatic spinning, the advancing speed of the injector is set to be 0.2mm/min, the rotating speed of the receiver is 100r/min, the distance from the injector to the receiver is 20cm, and the voltage V of the electrostatic pulse of the injector is set+Is 20kV, receives the electrostatic pulse voltage V of the roller－Is 20 kV; in the step a4, the muffle furnace sintering temperature is 700 ℃, and the sintering time is 2 h.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, in step b, the core-shell structure of CoFe2O4@BaTiO3The preparation method of the nanofiber comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, cetyl trimethyl ammonium bromide, n-butyl alcohol and distilled water, mixing n-butyl alcohol, cetyl trimethyl ammonium bromide and distilled water uniformly, adding weighed CoFe2O4Carrying out ultrasonic dispersion on the nanofiber uniformly to obtain CoFe2O4Mixing the nanofiber solution for later use;
step b2, CoFe according to step b12O4Weighing tetrabutyl titanate with a certain mass according to a mass ratio of 1:2, adding the weighed tetrabutyl titanate into n-butanol, stirring for 40min, and slowly dripping CoFe obtained in the step b1 under the stirring condition2O4Mixing the nanofiber mixed solution and stirring for 12 hours to obtain CoFe2O4@TiO2Washing and drying the nano-fibers with absolute ethyl alcohol for later use;
step b3, weighing a certain mass of barium hydroxide octahydrate according to the mass ratio of tetrabutyl titanate to barium hydroxide octahydrate in step b2 of 1:1.2, and then adding CoFe obtained in step b22O4@TiO2Adding the nano-fiber, barium hydroxide octahydrate and distilled water into a hydrothermal reaction kettle, then putting the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 200 ℃, and preserving heat for 4 hours to obtain core-shell structure CoFe2O4@BaTiO3And (3) nano fibers.
The method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to this embodiment, CoFe in step b12O4The feed-liquid ratio of the nano-fiber, the cetyl trimethyl ammonium bromide, the n-butanol and the distilled water is 1.65g to 1.5g to 500ml to 30 ml; n-butanol in step b2 and CoFe obtained in step b12O4The volume ratio of the nanofiber mixed solution is 12: 53; the addition amount of the distilled water in the step b3 is 2/3 of the volume of the hydrothermal reaction kettle.
In the method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe is used in step c2O4@BaTiO3The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step c1 CoFe as used in step b12O4Weighing a certain mass of P (VDF-TrFE) powder and a certain volume of N, N-dimethylformamide solution for later use;
step c2, preparing the core-shell structure CoFe prepared in step b2O4@BaTiO3Adding the nano-fibers into the N, N-dimethylformamide solution weighed in the step c1, carrying out ultrasonic oscillation until the nano-fibers are uniformly dispersed, then adding the P (VDF-TrFE) powder weighed in the step c1, and carrying out ultrasonic uniform treatment to obtain CoFe2O4@BaTiO3A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step c3, CoFe obtained in step c22O4@BaTiO3Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite wet membrane, ready for use;
step c4, CoFe obtained in step c32O4@BaTiO3Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite media.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe used in step b1 in step c12O4Weighing P (VDF-TrFE) powder and N, N-dimethylformamide solution according to the mass of the nanofiber and the feed-liquid ratio of the P (VDF-TrFE) powder to the N, N-dimethylformamide solution of 1.65g:5g:50 ml; c2, controlling the ultrasonic oscillation frequency to be 60W and the ultrasonic oscillation time to be 15 min; in the step c3, the rotating speed of the high-speed directional electrostatic spinning receiver is 2000r/min, the propelling speed of the injector is set to be 0.15mm/min, the distance from the injector to the receiver is 16cm, and the electrostatic pulse voltage V of the injector is set+15kV, receiving electrostatic pulse voltage V of the roller－Is-14 kV; in step c4, the vacuum drying temperature is 80 ℃ and the drying time is 10 h.
In the method for preparing a polymer-based composite media with ferromagnetic anisotropy in step d, the method for preparing a polymer-based composite media with ferromagnetic anisotropy according to the embodiment is to use CoFe prepared in step c2O4@BaTiO3And (2) placing the-P (VDF-TrFE) based composite medium in a vulcanizing press for hot pressing, wherein the hot pressing pressure is 15MPa, the hot pressing temperature is 160 ℃, the hot pressing time is 20min, then rapidly cooling to room temperature through water cooling, and maintaining the pressure at 10MPa for 2min to obtain the polymer based composite medium with ferromagnetic anisotropy.
The polymer-based composite medium with ferromagnetic anisotropy prepared by the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, which is described in the embodiment, is CoFe2O4@BaTiO3The content of the nanofiber loading phase in a polymer-based composite media with ferromagnetic anisotropy was 10 vol%.
A magnet having a ferromagnetic property according to the present embodimentPreparation method of anisotropic polymer-based composite medium, and CoFe prepared by same2O4@BaTiO3NFs is core-shell fiber structure, with the core layer being cobalt ferrite and the shell layer being barium titanate.
The polymer-based composite medium with ferromagnetic anisotropy prepared by the preparation method of the polymer-based composite medium with ferromagnetic anisotropy in the embodiment has the advantages of simple operation, easy preparation, excellent ferroelectric and ferromagnetic properties, effective solution to the problem of leakage current of the composite film, and flexibility which is not possessed by inorganic multiferroic materials.
In the polymer-based composite medium with ferromagnetic anisotropy, by applying magnetic fields in the fiber direction and perpendicular to the fiber direction along the surface of the composite medium in the plane, the differences of residual magnetization, saturated magnetization, coercive force and the like are found, and obvious magnetic anisotropy is reflected. This property allows the polymer-based composite media with ferromagnetic anisotropy to have more unique application potential.
The fourth concrete implementation mode:
a method for preparing a polymer-based composite media having ferromagnetic anisotropy, comprising the steps of:
step a, preparation of CoFe2O4A nanofiber;
step b, preparing core-shell structure CoFe2O4@BaTiO3A nanofiber;
step c, preparation of CoFe2O4@BaTiO3-a P (VDF-TrFE) based composite medium;
and d, preparing a polymer-based composite medium with ferromagnetic anisotropy.
In the method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe is used in step a2O4The preparation method of the nanofiber comprises the following steps:
step a1, weighing a certain mass of cobalt hexahydrate, ferric nitrate nonahydrate and citric acid according to the mass ratio of substances for later use;
step a2, adding cobalt nitrate hexahydrate and ferric nitrate nonahydrate weighed in the step a1 into an ethanol solution, adding citric acid after uniformly stirring, and continuously stirring until the mixed solution is clear to obtain a mixed solution for later use;
step a3, continuously adding polyvinylpyrrolidone into the mixed solution obtained in the step a2, wherein the material-to-liquid ratio of the mixed solution to the polyvinylpyrrolidone is 10ml/0.45g, and continuously stirring for 10 hours at normal temperature to obtain CoFe2O4Adding the precursor solution into an injector for electrostatic spinning to obtain CoFe2O4Precursor fibers;
step a4, CoFe obtained in the step a32O4Sintering the precursor fiber in a muffle furnace to obtain CoFe2O4And (3) nano fibers.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, the ratio of the amounts of cobalt hexahydrate, iron nitrate nonahydrate and citric acid in step a1 is 1:2: 3; and b, uniformly stirring the mixture of the cobalt hexahydrate and the ferric nitrate nonahydrate in the step a2 and an ethanol solution to obtain a mixed solution, wherein the concentration of cobalt ions in the mixed solution is 0.2-0.3 mol/L, and the concentration of the ethanol solution is 70 vol%.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, step a3 is performed by electrostatic spinning, the advancing speed of the injector is set to be 0.1mm/min, the rotating speed of the receiver is 80r/min, the distance from the injector to the receiver is 16cm, and the voltage V of the electrostatic pulse of the injector is set+15kV, receiving electrostatic pulse voltage V of the roller－Is-16 kV; step a4, the muffle furnace sintering temperature is 600 ℃, and the sintering time is 4 hours.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, in step b, the core-shell structure of CoFe2O4@BaTiO3The preparation method of the nanofiber comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, cetyl trimethyl ammonium bromide, n-butyl alcohol and distilled water, mixing n-butyl alcohol, cetyl trimethyl ammonium bromide and distilled water uniformly, adding weighed CoFe2O4Carrying out ultrasonic dispersion on the nanofiber uniformly to obtain CoFe2O4Mixing the nanofiber solution for later use;
step b2, CoFe according to step b12O4Weighing tetrabutyl titanate with a certain mass according to a mass ratio of 1:2, adding the weighed tetrabutyl titanate into n-butanol, stirring for 30min, and slowly dripping CoFe obtained in the step b1 under the stirring condition2O4Mixing the solution with nano-fiber to obtain CoFe2O4@TiO2Washing and drying the nano-fibers with absolute ethyl alcohol for later use;
step b3, weighing a certain mass of barium hydroxide octahydrate according to the mass ratio of tetrabutyl titanate to barium hydroxide octahydrate in step b2 of 1:1.2, and then adding CoFe obtained in step b22O4@TiO2Adding the nano-fiber, barium hydroxide octahydrate and distilled water into a hydrothermal reaction kettle, then putting the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 200 ℃, and preserving heat for 4 hours to obtain core-shell structure CoFe2O4@BaTiO3And (3) nano fibers.
The method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to this embodiment, CoFe in step b12O4The feed-liquid ratio of the nano-fiber, the cetyl trimethyl ammonium bromide, the n-butanol and the distilled water is 3.71g:3g:1200ml:60 ml; n-butanol in step b2 and CoFe obtained in step b12O4The volume ratio of the nanofiber mixed solution is 30: 126; steaming in step b3The distilled water is added in 2/3 volume of the hydrothermal reaction kettle.
In step c, the method for preparing a polymer-based composite media with ferromagnetic anisotropy according to the embodiment2O4@BaTiO3The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step c1 CoFe as used in step b12O4Weighing a certain mass of P (VDF-TrFE) powder and a certain volume of N, N-dimethylformamide solution for later use;
step c2, preparing the core-shell structure CoFe prepared in step b2O4@BaTiO3Adding the nano-fibers into the N, N-dimethylformamide solution weighed in the step c1, carrying out ultrasonic oscillation until the nano-fibers are uniformly dispersed, then adding the P (VDF-TrFE) powder weighed in the step c1, and carrying out ultrasonic uniform treatment to obtain CoFe2O4@BaTiO3A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step c3, CoFe obtained in step c22O4@BaTiO3Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite wet membrane, ready for use;
step c4, CoFe obtained in step c32O4@BaTiO3Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite media.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe used in step b1 in step c12O4Weighing P (VDF-TrFE) powder and N, N-dimethylformamide solution according to the mass of the nanofiber and the feed-liquid ratio of the P (VDF-TrFE) powder to the N, N-dimethylformamide solution of 3.71g:5g:50 ml; c2, controlling the ultrasonic oscillation frequency to be 60W and the ultrasonic oscillation time to be 30 min; the rotating speed of the high-speed directional electrostatic spinning receiver in the step c3 is 3000r/min, the propelling speed of the injector is set to be 0.2mm/min, and the injection is carried outThe distance from the device to the receiver is 20cm, and the voltage V of the electrostatic pulse of the injector is set+15kV, receiving electrostatic pulse voltage V of the roller－Is-16 kV; in step c4, the vacuum drying temperature is 80 ℃ and the drying time is 6 h.
In the method for preparing the polymer-based composite media with ferromagnetic anisotropy in the embodiment, the method for preparing the polymer-based composite media with ferromagnetic anisotropy in the step d is to use the CoFe prepared in the step c2O4@BaTiO3And (2) placing the-P (VDF-TrFE) based composite medium in a vulcanizing press for hot pressing, wherein the hot pressing pressure is 15MPa, the hot pressing temperature is 170 ℃, the hot pressing time is 25min, then quickly cooling to room temperature through water cooling, and maintaining the pressure at 10MPa for 2min to obtain the polymer based composite medium with ferromagnetic anisotropy.
The polymer-based composite medium with ferromagnetic anisotropy, which is prepared by the method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, is CoFe2O4@BaTiO3The content of the nanofiber filler phase in a polymer-based composite media with ferromagnetic anisotropy was 20 vol%.
In the polymer-based composite medium with ferromagnetic anisotropy prepared by the preparation method of the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, the core-shell structure fibers in highly directional arrangement are embedded in the ferroelectric material P (VDF-TrFE) phase matrix as a one-dimensional columnar shape, and the 1-3 communication structure increases the contact area of two phases of the ferroelectric phase and the ferromagnetic phase, thereby being beneficial to generating strong magnetoelectric coupling. And in CoFe2O4The surface of the fiber is coated with a layer of BaTiO3A grain shell layer for limiting leakage current and coating BaTiO3The shell layer is used as a ferroelectric material, so that the electric polarization of the composite medium can be further increased, the magnetoelectric effect is further increased, and meanwhile, the preparation method has the advantages of low price of required equipment, simple process and easy realization.
In the polymer-based composite medium with ferromagnetic anisotropy, by applying magnetic fields in the fiber direction and perpendicular to the fiber direction along the surface of the composite medium in the plane, the differences of residual magnetization, saturated magnetization, coercive force and the like are found, and obvious magnetic anisotropy is reflected. This property allows the polymer-based composite media with ferromagnetic anisotropy to have more unique application potential.
The fifth concrete implementation mode:
a method for preparing a polymer-based composite media having ferromagnetic anisotropy, comprising the steps of:
step a, preparation of CoFe2O4A nanofiber;
step b, preparing core-shell structure CoFe2O4@BaTiO3A nanofiber;
step c, preparation of CoFe2O4@BaTiO3-a P (VDF-TrFE) based composite medium;
and d, preparing a polymer-based composite medium with ferromagnetic anisotropy.
In the method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe is used in step a2O4The preparation method of the nanofiber comprises the following steps:
step a1, weighing a certain mass of cobalt hexahydrate, ferric nitrate nonahydrate and citric acid according to the mass ratio of substances for later use;
step a2, adding cobalt nitrate hexahydrate and ferric nitrate nonahydrate weighed in the step a1 into an ethanol solution, adding citric acid after uniformly stirring, and continuously stirring until the mixed solution is clear to obtain a mixed solution for later use;
step a3, adding the poly into the mixed solution obtained in the step a2The material-to-liquid ratio of the mixed solution to the polyvinylpyrrolidone is 10ml/0.55g, and the mixture is continuously stirred for 10 hours at normal temperature to obtain CoFe2O4Adding the precursor solution into an injector for electrostatic spinning to obtain CoFe2O4Precursor fibers;
step a4, CoFe obtained in the step a32O4Sintering the precursor fiber in a muffle furnace to obtain CoFe2O4And (3) nano fibers.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, the amount ratio of the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the citric acid in the step a1 is 1:2: 3; and b, uniformly stirring the mixture of the cobalt hexahydrate and the ferric nitrate nonahydrate in the step a2 and an ethanol solution to obtain a mixed solution, wherein the concentration of cobalt ions in the mixed solution is 0.3mol/L, and the concentration of the ethanol solution is 70 vol%.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, step a3 is performed by electrostatic spinning, the advancing speed of the injector is set to be 0.2mm/min, the rotating speed of the receiver is 90r/min, the distance from the injector to the receiver is 11cm, and the voltage V of the electrostatic pulse of the injector is set+12kV, receiving electrostatic pulse voltage V of the roller－Is-12 kV; in the step a4, the muffle furnace sintering temperature is 700 ℃, and the sintering time is 2 h.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, in step b, the core-shell structure of CoFe2O4@BaTiO3The preparation method of the nanofiber comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, cetyl trimethyl ammonium bromide, n-butyl alcohol and distilled water, mixing n-butyl alcohol, cetyl trimethyl ammonium bromide and distilled water uniformly, adding weighed CoFe2O4Carrying out ultrasonic dispersion on the nanofiber uniformly to obtain CoFe2O4Mixing the nanofiber solution for later use;
step b2, according to the stepb1 CoFe2O4Weighing tetrabutyl titanate with a certain mass according to a mass ratio of 1:2, adding the weighed tetrabutyl titanate into n-butanol, stirring for 40min, and slowly dripping CoFe obtained in the step b1 under the stirring condition2O4Mixing the solution with nano-fiber to obtain CoFe2O4@TiO2Washing and drying the nano-fibers with absolute ethyl alcohol for later use;
step b3, weighing a certain mass of barium hydroxide octahydrate according to the mass ratio of tetrabutyl titanate to barium hydroxide octahydrate in step b2 of 1:1.2, and then adding CoFe obtained in step b22O4@TiO2Adding the nano-fiber, barium hydroxide octahydrate and distilled water into a hydrothermal reaction kettle, then putting the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 200 ℃, and preserving heat for 4 hours to obtain core-shell structure CoFe2O4@BaTiO3And (3) nano fibers.
The method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to this embodiment, CoFe in step b12O4The feed-liquid ratio of the nano-fiber, the cetyl trimethyl ammonium bromide, the n-butanol and the distilled water is 6.36g:5g:2000ml:100 ml; n-butanol in step b2 and CoFe obtained in step b12O4The volume ratio of the nanofiber mixed solution is 50: 210; the addition amount of the distilled water in the step b3 is 2/3 of the volume of the hydrothermal reaction kettle.
In the method for preparing a polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe is used in step c2O4@BaTiO3The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step c1 CoFe as used in step b12O4Weighing a certain mass of P (VDF-TrFE) powder and a certain volume of N, N-dimethylformamide solution for later use;
step c2, preparing the core-shell structure CoFe prepared in step b2O4@BaTiO3Adding the nano-fibers into the N, N-dimethylformamide solution weighed in the step c1, performing ultrasonic oscillation until the nano-fibers are uniformly dispersed, and then adding the nano-fibers into the step c1Weighing P (VDF-TrFE) powder, and obtaining CoFe after ultrasonic homogenization2O4@BaTiO3A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step c3, CoFe obtained in step c22O4@BaTiO3Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite wet membrane, ready for use;
step c4, CoFe obtained in step c32O4@BaTiO3Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite media.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, CoFe used in step b1 in step c12O4Weighing P (VDF-TrFE) powder and N, N-dimethylformamide solution according to the mass of the nanofiber and the material-to-liquid ratio of the P (VDF-TrFE) powder to the N, N-dimethylformamide solution of 6.36g:5g:50 ml; c2, controlling the ultrasonic oscillation frequency to be 60W and the ultrasonic oscillation time to be 30 min; in the step c3, the rotating speed of the high-speed directional electrostatic spinning receiver is 3000r/min, the propelling speed of the injector is set to be 0.2mm/min, the distance from the injector to the receiver is 20cm, and the electrostatic pulse voltage V of the injector is set+Is 20kV, receives the electrostatic pulse voltage V of the roller－Is-20 kV; in step c4, the vacuum drying temperature is 80 ℃, and the drying time is 12 h.
In the method for preparing the polymer-based composite media with ferromagnetic anisotropy in the embodiment, the method for preparing the polymer-based composite media with ferromagnetic anisotropy in the step d is to use the CoFe prepared in the step c2O4@BaTiO3And (2) placing the-P (VDF-TrFE) based composite medium in a vulcanizing press for hot pressing, wherein the hot pressing pressure is 15MPa, the hot pressing temperature is 170 ℃, the hot pressing time is 25min, then quickly cooling to room temperature through water cooling, and maintaining the pressure at 1MPa for 10min to obtain the polymer based composite medium with ferromagnetic anisotropy.
The polymer-based composite medium with ferromagnetic anisotropy prepared by the preparation method of the polymer-based composite medium with ferromagnetic anisotropy, which is described in the embodiment, is CoFe2O4@BaTiO3The content of the nanofiber loading phase in a polymer-based composite media with ferromagnetic anisotropy was 30 vol%.
In the preparation method of the polymer-based composite medium with ferromagnetic anisotropy according to the embodiment, the core-shell structure fibers arranged in a highly oriented manner are embedded in the ferroelectric material P (VDF-TrFE) phase matrix as a one-dimensional columnar shape, and the 1-3 connected structure increases the contact area between the ferroelectric phase and the ferromagnetic phase, thereby facilitating the generation of strong magnetoelectric coupling. And in CoFe2O4The surface of the fiber is coated with a layer of BaTiO3A grain shell layer for limiting leakage current and coating BaTiO3The shell layer is used as a ferroelectric material, so that the electric polarization of the composite medium can be further increased, the magnetoelectric effect is further increased, and meanwhile, the preparation method has the advantages of low price of required equipment, simple process and easy realization.
In the polymer-based composite medium with ferromagnetic anisotropy, by applying magnetic fields in the fiber direction and perpendicular to the fiber direction along the surface of the composite medium in the plane, the differences of residual magnetization, saturated magnetization, coercive force and the like are found, and obvious magnetic anisotropy is reflected. This property allows the polymer-based composite media with ferromagnetic anisotropy to have more unique application potential.

Claims (5)

1. A method for preparing a polymer-based composite medium with ferromagnetic anisotropy is characterized in that: the method comprises the following steps:
step a, preparation of CoFe2O4A nanofiber;
CoFe2O4the preparation method of the nanofiber comprises the following steps:
step a1, weighing cobalt nitrate hexahydrate, ferric nitrate nonahydrate and citric acid with certain mass according to the mass ratio of the substances for later use;
step a2, adding cobalt nitrate hexahydrate and ferric nitrate nonahydrate weighed in the step a1 into an ethanol solution, adding citric acid after uniformly stirring, and continuously stirring until a mixed solution is clarified to obtain a mixed solution for later use;
step a3, continuously adding polyvinylpyrrolidone into the mixed solution obtained in the step a2, wherein the material-to-liquid ratio of the mixed solution to the polyvinylpyrrolidone is 10 ml/0.4-0.6 g, and continuously stirring at normal temperature for 10-12 hours to obtain CoFe2O4Adding the precursor solution into an injector for electrostatic spinning to obtain CoFe2O4Precursor fibers;
step a4, CoFe obtained in the step a32O4Sintering the precursor fiber in a muffle furnace to obtain CoFe2O4A nanofiber;
step b, preparing core-shell structure CoFe2O4@BaTiO3A nanofiber;
core-shell structure CoFe2O4@BaTiO3The preparation method of the nanofiber comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, cetyl trimethyl ammonium bromide, n-butyl alcohol and distilled water, mixing n-butyl alcohol, cetyl trimethyl ammonium bromide and distilled water uniformly, adding weighed CoFe2O4Carrying out ultrasonic dispersion on the nanofiber uniformly to obtain CoFe2O4Mixing the nanofiber solution for later use;
step b2, CoFe according to step b12O4The amount of the substance to be mixed with tetrabutyl titanate is 1:2, a certain mass of tetrabutyl titanate is weighed, andadding weighed tetrabutyl titanate into n-butanol, stirring for 20-40 min, and slowly dripping CoFe obtained in the step b1 under the stirring condition2O4Mixing the solution with nano-fiber to obtain CoFe2O4@TiO2Washing and drying the nano-fibers by using absolute ethyl alcohol for later use;
step b3, weighing a certain mass of barium hydroxide octahydrate according to the mass ratio of tetrabutyl titanate to barium hydroxide octahydrate in step b2 of 1:1.2, and then adding CoFe obtained in step b22O4@TiO2Adding the nano-fiber, barium hydroxide octahydrate and distilled water into a hydrothermal reaction kettle, then putting the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 200 ℃, and preserving heat for 4 hours to obtain core-shell structure CoFe2O4@BaTiO3A nanofiber;
step c, preparation of CoFe2O4@BaTiO3-a P (VDF-TrFE) based composite medium;
CoFe2O4@BaTiO3the preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step c1 CoFe as used in step b12O4Weighing a certain mass of P (VDF-TrFE) powder and a certain volume of N, N-dimethylformamide solution for later use;
step c2, preparing the core-shell structure CoFe prepared in step b2O4@BaTiO3Adding the nano-fibers into the N, N-dimethylformamide solution weighed in the step c1, carrying out ultrasonic oscillation until the nano-fibers are uniformly dispersed, then adding the P (VDF-TrFE) powder weighed in the step c1, and carrying out ultrasonic uniform treatment to obtain CoFe2O4@BaTiO3A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step c3, CoFe obtained in step c22O4@BaTiO3Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4@BaTiO3-P (VDF-TrFE) based composite wet membrane, ready for use; the rotating speed of the high-speed directional electrostatic spinning receiver is 2000-3000 r/min;
step c4, step cCoFe obtained from c32O4@BaTiO3Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4@BaTiO3-a P (VDF-TrFE) based composite medium;
step d, preparing a polymer-based composite medium with ferromagnetic anisotropy;
the preparation method of the polymer-based composite medium with ferromagnetic anisotropy comprises the step of preparing the CoFe prepared in the step c2O4@BaTiO3Placing the-P (VDF-TrFE) based composite medium in a vulcanizing press for hot pressing treatment, wherein the hot pressing pressure is 15MPa, the hot pressing temperature is 140-170 ℃, the hot pressing time is 15-25 min, then rapidly cooling to room temperature through water cooling, and maintaining the pressure at 1-10 MPa for 1-10 min to obtain the polymer based composite medium with ferromagnetic anisotropy, wherein the CoFe2O4@BaTiO3The content of the nanofiber filling phase in the polymer-based composite medium with ferromagnetic anisotropy is 3-30 vol%.
2. The method of claim 1, wherein the polymer-based composite media having ferromagnetic anisotropy comprises: the mass ratio of the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the citric acid in the step a1 is 1:2: 3; and b, uniformly stirring the mixture of the cobalt nitrate hexahydrate and the ferric nitrate nonahydrate in the step a2 and an ethanol solution to obtain a mixed solution, wherein the concentration of cobalt ions in the mixed solution is 0.2-0.3 mol/L, and the concentration of the ethanol solution is 70 vol%.
3. The method of claim 1, wherein the polymer-based composite media having ferromagnetic anisotropy comprises: in the electrostatic spinning in the step a3, the advancing speed of an injector is set to be 0.1-0.2 mm/min, the rotating speed of a receiver is 60-100 r/min, the distance from the injector to the receiver is 10-20 cm, and the electrostatic pulse voltage V of the injector is set+10-20 kV, and receiving electrostatic pulse voltage V of the roller－10-20 kV; in the step a4, the muffle furnace sintering temperature is 500-700 ℃, and the sintering time is 2-4 h.
4. The method of claim 1, wherein the polymer-based composite media having ferromagnetic anisotropy comprises: CoFe in step b12O4The feed-liquid ratio of the nano-fibers, the cetyl trimethyl ammonium bromide, the n-butyl alcohol and the distilled water is 0.459-6.36 g, 0.4-5 g, 150-2000 ml and 10-100 ml; n-butanol in step b2 and CoFe obtained in step b12O4The volume ratio of the nanofiber mixed solution is 4-50: 16-210; the addition amount of the distilled water in the step b3 is 2/3 of the volume of the hydrothermal reaction kettle.
5. The method of claim 1, wherein the polymer-based composite media having ferromagnetic anisotropy comprises: CoFe used in step c1 according to step b12O4Weighing P (VDF-TrFE) powder and N, N-dimethylformamide solution according to the mass of the nanofiber and the feed-liquid ratio of the P (VDF-TrFE) powder to the N, N-dimethylformamide solution of 0.459-6.36 g:5g:50 ml; c2, controlling the ultrasonic oscillation frequency to be 60W and the ultrasonic oscillation time to be 5-30 min; in the step c3, the advancing speed of the injector is set to be 0.1-0.2 mm/min, the distance from the injector to the receiver is 10-20 cm, and the electrostatic pulse voltage V of the injector is set+12-20 kV, and receiving electrostatic pulse voltage V of the roller－Is 12-20 kV; in the step c4, the vacuum drying temperature is 60-80 ℃, and the drying time is 6-24 h.
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