CN112030369A - Multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer and preparation method thereof - Google Patents

Multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer and preparation method thereof Download PDF

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CN112030369A
CN112030369A CN202010710600.2A CN202010710600A CN112030369A CN 112030369 A CN112030369 A CN 112030369A CN 202010710600 A CN202010710600 A CN 202010710600A CN 112030369 A CN112030369 A CN 112030369A
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cofe
ferroelectric polymer
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trfe
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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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Abstract

A multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer and a preparation method thereof belong to the technical field of multiferroic film preparation. The invention aims to solve the technical problems of improving multiferroic property of a multiferroic composite medium and reducing leakage current possibly occurring in the composite medium. The invention firstly adopts a sol-gel method and an electrostatic spinning technology to prepareCoFe with a large aspect ratio2O4The preparation method comprises the steps of preparing a nanometer fiber inorganic filling phase, preparing a P (VDF-TrFE) mixed solution with uniformly dispersed nanometer fibers by using a solution method, and finally obtaining a multi-iron composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer in oriented arrangement by using a high-speed oriented spinning technology and a hot pressing method. The composite medium is used in the fields of sensors and nonvolatile memory devices.

Description

Multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer and preparation method thereof
Technical Field
The invention belongs to the technical field of multiferroic film preparation; in particular to a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer and a preparation method thereof.
Background
In order to adapt to the rapid progress of modern science and technology, the requirements on hardware such as electronic devices and the like are higher and higher, the miniaturization and integration are required to be realized in the structure, and the diversity is required in the function, so that the development of a new material with multiple functions is urgent, and it is worth mentioning that multiferroic materials just meet the requirement, and the coupling among different ferroics can generate some new functions. For example, the combination of ferroelectricity and ferromagnetism generates a magnetoelectric coupling effect, so that the magnetic control electrical property or the electric control magnetism becomes possible.
However, although researchers have found various single-phase multiferroic composite materials so far, the magnetoelectric coupling effect at room temperature is weak, and artificial construction of the magnetoelectric multiferroic composite material has become a hot research spot nowadays.
Disclosure of Invention
The invention aims to solve the problems of improving multiferroic property of a multiferroic composite medium and reducing possible leakage current of the composite medium, and provides a flexible multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer and a preparation method thereof, wherein the multiferroic composite medium has strong process controllability and is easy to operate.
The invention is realized by the following technical scheme:
a preparation method of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer comprises the following steps:
step a, preparation of CoFe2O4A nanofiber;
step b, preparation of CoFe2O4-a P (VDF-TrFE) based composite medium;
and c, preparing the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
The invention relates to a preparation method of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, which comprises the step a of preparing 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 multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, wherein the mass ratio of cobalt nitrate hexahydrate, ferric 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%.
The preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer comprises the step a3 of electrostatic spinning, wherein the advancing speed of an injector is set to be 0.15-0.25 mm/min, the rotating speed of a receiver is 70-120 r/min, the distance from the injector to the receiver is 7-20 cm, and the electrostatic pulse voltage V of the injector is set+12-20 kV, receiving static electricity of the rollerPulse voltage V－Is-12 to-20 kV; in the step a4, the muffle furnace sintering temperature is 550-750 ℃, and the sintering time is 2-5 h.
The invention relates to a preparation method of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, in step b, CoFe2O4The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, P (VDF-TrFE) powder and N, N-dimethylformamide solution for standby;
step b2, weighing CoFe in step b12O4Adding the nano-fiber into N, N-dimethylformamide solution, carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed, then adding the P (VDF-TrFE) powder weighed in the step b1, and carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed to obtain the product containing CoFe2O4A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step b3, CoFe contained in the product obtained in step b22O4Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4-P (VDF-TrFE) based composite wet membrane, ready for use;
step b4, CoFe obtained in the step b32O4Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4-P (VDF-TrFE) based composite media.
The invention relates to a preparation method of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, namely CoFe in step b12O4The feed-liquid ratio of the nanofiber, the P (VDF-TrFE) powder and the N, N-dimethylformamide solution is 0.459-6.36 g:5g:50 ml; and b2, controlling the ultrasonic oscillation frequency to be 60W and the ultrasonic oscillation time to be 2-20 min.
The invention relates to a preparation method of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, in the step b3, the rotating speed of a high-speed directional electrostatic spinning receiver is 2000-3000 r/min, the propelling speed of an injector is set to be 0.1-0.2 mm/min, the distance from the injector to the receiver is 10-20 cm,setting the injector electrostatic pulse voltage V+12-20 kV, and receiving electrostatic pulse voltage V of the roller－Is-12 to-20 kV; in the step b4, the vacuum drying temperature is 50-80 ℃, and the drying time is 4-48 h.
The invention relates to a preparation method of a one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium, which comprises the step of preparing the CoFe prepared in the step b2O4And (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 150-180 ℃, the hot pressing time is 10-30 min, then quickly cooling to room temperature through water cooling, and maintaining the pressure at 1-10 MPa for 3-15 min to obtain the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
The invention relates to a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer prepared by the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, and CoFe2O4The content of the nano-fiber filling phase in the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer is 3-30 vol%.
Compared with the method for preparing the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer, the method has the advantages that the fibers are arranged in a disordered manner in the polymer matrix under the low-speed receiving at the rotating speed of 70-120 r/min, and the fibers are subjected to the combined action of the tensile force and the electrostatic force of the electric field when the rotating speed reaches 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 an 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 one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium prepared by the preparation method of the one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium has the thickness of 7-28 micrometers.
The fibers of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer prepared by the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer are highly arranged in parallel in the polymer matrix, and the macroscopic performance of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer is tested, so that the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer can be detected to have anisotropy in different directions and be vertical to the direction of an external electric field in the application process.
The invention has the beneficial effects that:
the invention relates to a preparation method of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, which comprises the steps of firstly preparing CoFe with large length-diameter ratio by adopting a sol-gel method and an electrostatic spinning technology2O4And (3) preparing a P (VDF-TrFE) mixed solution with uniformly dispersed nano fibers by using a solution method, and finally obtaining the one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium in oriented arrangement by using a high-speed oriented spinning technology and a hot pressing method.
According to the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer, the nanofibers which are arranged in a highly oriented mode are embedded in a ferroelectric material P (VDF-TrFE) phase matrix as a one-dimensional columnar shape, the contact area of two phases of a ferroelectric phase and a ferromagnetic phase is increased due to a communicated structure, strong magnetoelectric coupling is favorably generated, the nanofibers are arranged in the P (VDF-TrFE) matrix in a highly oriented mode, leakage current can be improved, and the breakdown strength in the direction of an external electric field is improved.
The preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer has the advantages of low price of required equipment, simple process, easy realization, excellent ferroelectric and ferromagnetic properties, capability of effectively solving the possible leakage current problem of a composite film due to the directionally arranged structure, flexibility which is not possessed by inorganic multiferroic materials, and great application potential in the fields of sensors, nonvolatile memory devices and the like.
Drawings
FIG. 1 shows P (VDF-TrFE) and CoFe2O4Nanofiber and one-dimensional ferromagnetic prepared by method of embodiment oneAn X-ray diffraction contrast spectrum of a multiferroic composite medium of a filler-ferroelectric polymer;
FIG. 2 is a SEM image of a cross-section of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer prepared 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 a multiferroic composite media of P (VDF-TrFE) and a one-dimensional ferromagnetic filler-ferroelectric polymer prepared by the method of one embodiment.
Fig. 5 is a hysteresis loop of a one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium prepared by a method according to an embodiment.
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 preparation method of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer comprises the following steps:
step a, preparation of CoFe2O4A nanofiber;
step b, preparation of CoFe2O4-a P (VDF-TrFE) based composite medium;
and c, preparing the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe 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; CoFe2O4The precursor solution is dark red; the needle head of the syringe is a metal needle head with the model number of 23G;
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 multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer 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 multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment, the electrostatic spinning is performed in step a3, the advancing speed of the injector is set to 0.16mm/min, the rotating speed of the receiver is 120r/min, the distance between the injector and the receiver is 14cm, and the electrostatic pulse voltage V of the injector is set+Is 13kV, receives the electrostatic pulse voltage V of the roller－Is-13 kV; in the step a4, the muffle furnace sintering temperature is 650 ℃, and the sintering time is 3 h.
In the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, CoFe is adopted in step b2O4The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, P (VDF-TrFE) powder and N, N-dimethylformamide solution for standby;
step b2, weighing CoFe in step b12O4Adding the nano-fiber into N, N-dimethylformamide solution, carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed, then adding the P (VDF-TrFE) powder weighed in the step b1, and carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed to obtain the product containing CoFe2O4A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step b3, CoFe contained in the product obtained in step b22O4Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4-P (VDF-TrFE) based composite wet membrane, ready for use;
step b4, CoFe obtained in the step b32O4Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4-P (VDF-TrFE) based composite media.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe in step b12O4The feed-liquid ratio of the nano-fiber, P (VDF-TrFE) powder and N, N-dimethylformamide solution is 0.459g:5g:50 ml; in the step b2, the frequency of the ultrasonic oscillation is 60W, and the time of the ultrasonic oscillation is 8 min.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, in the step b3, the rotating speed of the high-speed directional electrostatic spinning receiver is 2000r/min, the advancing speed of the injector is set to be 0.2mm/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 the step b4, the vacuum drying temperature is 70 ℃, and the drying time is 12 h.
In the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment, the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer in step c is to use CoFe prepared in step b2O4Placing the-P (VDF-TrFE) base composite medium in a vulcanizing press for hot pressing treatment, wherein the hot pressing pressure is 15MPa, the hot pressing temperature is 170 ℃,and the hot pressing time is 25min, then the temperature is rapidly reduced to the room temperature through water cooling, and the pressure is maintained for 5min under the pressure of 5MPa, so that the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer is obtained.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe2O4The content of the nano-fiber filling phase in the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer is 3 vol%.
The multi-iron composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, P (VDF-TrFE) or CoFe, prepared by the method for preparing a multi-iron composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment2O4The X-ray diffraction contrast spectrum of the nano-fiber and the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer prepared by the method of the embodiment is shown in FIG. 1, and as can be seen from FIG. 1, CoFe2O4The nano-fiber crystal phase is in a spinel structure and has no other impurities, and the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer prepared by the embodiment has a filling phase CoFe2O4And the crystal structure of P (VDF-TrFE) illustrate the success of the inorganic phase and the matrix in the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment.
In the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer prepared by the method for preparing a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to the present embodiment, the SEM photograph of the cross section is shown in fig. 2, and the SEM photograph of the cross section is shown in fig. 3P (VDF-TrFE), as can be seen from the comparison between fig. 2 and fig. 3, the thickness of the film layer of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer prepared by the method of the present embodiment is 20 μm, and CoFe can be observed from the SEM photograph of the cross section2O4The nano-fiber has large length-diameter ratio, is highly directionally arranged in a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, and is uniformly distributed.
The ferroelectric hysteresis loop comparison curve of a one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium prepared by the method for preparing a one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium according to the present embodiment, P (VDF-TrFE) and the one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium is shown in fig. 4, and it can be seen from fig. 4 that the one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium has larger maximum polarization and residual polarization and improved ferroelectric properties compared to pure P (VDF-TrFE) medium under the same electric field.
Fig. 5 shows a hysteresis loop curve of a one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium prepared by the method for preparing a one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium according to the present embodiment, and a magnetic field along a fiber direction is applied in a plane during a test, and as can be seen from fig. 5, the one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium has large saturation magnetization and residual magnetization, and is excellent in ferromagnetic property.
The multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer prepared by the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer in the embodiment has good ferroelectric property and ferromagnetic property, and good flexibility of a polymer matrix, and realizes excellent multiferroic property under the condition of low content of inorganic fiber of one-dimensional core-shell structure.
The second embodiment is as follows:
a preparation method of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer comprises the following steps:
step a, preparation of CoFe2O4A nanofiber;
step b, preparation of CoFe2O4-a P (VDF-TrFE) based composite medium;
and c, preparing the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe 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/0.4g, 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 multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer 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 multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment, the electrostatic spinning is performed in step a3, the advancing speed of the injector is set to 0.15mm/min, the rotating speed of the receiver is 70r/min, the distance between the injector and the receiver is 7cm, and the electrostatic pulse voltage V 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 550 ℃, and the sintering time is 5 h.
In the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, CoFe is adopted in step b2O4The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step b1, pressCoFe was weighed separately in the ratio of the control solutions2O4Nano-fiber, P (VDF-TrFE) powder and N, N-dimethylformamide solution for standby;
step b2, weighing CoFe in step b12O4Adding the nano-fiber into N, N-dimethylformamide solution, carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed, then adding the P (VDF-TrFE) powder weighed in the step b1, and carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed to obtain the product containing CoFe2O4A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step b3, CoFe contained in the product obtained in step b22O4Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4-P (VDF-TrFE) based composite wet membrane, ready for use;
step b4, CoFe obtained in the step b32O4Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4-P (VDF-TrFE) based composite media.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe in step b12O4The feed-liquid ratio of the nano-fiber, P (VDF-TrFE) powder and N, N-dimethylformamide solution is 0.781g:5g:50 ml; and b2, controlling the ultrasonic oscillation frequency to be 60W and the ultrasonic oscillation time to be 5 min.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, in the step b3, the rotating speed of the high-speed directional electrostatic spinning receiver is 2000r/min, the advancing speed of the injector is set to be 0.1mm/min, the distance from the injector to the receiver is 10-20 cm, and the electrostatic pulse voltage V of the injector is set+12kV, receiving electrostatic pulse voltage V of the roller－Is-12 kV; in the step b4, the vacuum drying temperature is 50 ℃, and the drying time is 24 h.
In the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment, the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer in step c is to use the Co prepared in step bFe2O4And (3) 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 150 ℃, the hot pressing time is 30min, then quickly cooling to room temperature through water cooling, and maintaining the pressure at 1MPa for 15min to obtain the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe2O4The content of the nano-fiber filling phase in the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer is 5 vol%.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, firstly, the CoFe with a large length-diameter ratio is prepared by adopting a sol-gel method and an electrostatic spinning technology2O4And (3) preparing a P (VDF-TrFE) mixed solution with uniformly dispersed nano fibers by using a solution method, and finally obtaining the one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium in oriented arrangement by using a high-speed oriented spinning technology and a hot pressing method.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, the nanofibers arranged in a highly oriented manner are embedded in the ferroelectric material P (VDF-TrFE) phase matrix as a one-dimensional columnar shape, the connection structure increases the contact area between the ferroelectric phase and the ferromagnetic phase, which is beneficial to generating strong magnetoelectric coupling, and the nanofibers are highly oriented in the P (VDF-TrFE) phase matrix, so that leakage current can be improved, and the breakdown strength in the direction of an external electric field can be improved.
The preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer, which is described by the embodiment, has the advantages of low price of required equipment, simple process, easy realization, excellent ferroelectric and ferromagnetic properties, capability of effectively solving the possible leakage current problem of the composite film due to the directionally arranged structure, flexibility which is not possessed by inorganic multiferroic materials, and great application potential in the fields of sensors, nonvolatile memory devices and the like.
The third concrete implementation mode:
a preparation method of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer comprises the following steps:
step a, preparation of CoFe2O4A nanofiber;
step b, preparation of CoFe2O4-a P (VDF-TrFE) based composite medium;
and c, preparing the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe 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/0.6g, 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 multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer 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 multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment, the electrostatic spinning is performed in step a3, the advancing speed of the injector is set to 0.25mm/min, the rotating speed of the receiver is 120r/min, the distance between the injector and the receiver is 20cm, 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 the step a4, the muffle furnace sintering temperature is 750 ℃, and the sintering time is 2 h.
In the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, CoFe is adopted in step b2O4The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, P (VDF-TrFE) powder and N, N-dimethylformamide solution for standby;
step b2, weighing CoFe in step b12O4Adding the nano-fiber into N, N-dimethylformamide solution, carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed, then adding the P (VDF-TrFE) powder weighed in the step b1, and carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed to obtain the product containing CoFe2O4A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step b3, CoFe contained in the product obtained in step b22O4Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4-P (VDF-TrFE) based composite wet membrane, ready for use;
step b4, CoFe obtained in the step b32O4Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4-P (VDF-TrFE) based composite media.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe in step b12O4The feed-liquid ratio of the nanofiber, P (VDF-TrFE) powder and N, N-dimethylformamide solution is 1.65g:5g:50 ml; step b2 ultrasonic oscillationThe frequency of (2) is 60W, and the time of ultrasonic oscillation is 20 min.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, in the step b3, the rotating speed of the high-speed directional electrostatic spinning receiver is 3000r/min, the advancing 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 13kV, receives the electrostatic pulse voltage V of the roller－Is-13 kV; in the step b4, the vacuum drying temperature is 80 ℃, and the drying time is 4 h.
In the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment, the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer in step c is to use CoFe prepared in step b2O4And (3) 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 180 ℃, the hot pressing time is 10min, then rapidly cooling to room temperature through water cooling, and maintaining the pressure at 10MPa for 3min to obtain the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe2O4The content of the nano-fiber filling phase in the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer is 10 vol%.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, firstly, the CoFe with a large length-diameter ratio is prepared by adopting a sol-gel method and an electrostatic spinning technology2O4And (3) preparing a P (VDF-TrFE) mixed solution with uniformly dispersed nano fibers by using a solution method, and finally obtaining the one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium in oriented arrangement by using a high-speed oriented spinning technology and a hot pressing method.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, the nanofibers arranged in a highly oriented manner are embedded in the ferroelectric material P (VDF-TrFE) phase matrix as a one-dimensional columnar shape, the connection structure increases the contact area between the ferroelectric phase and the ferromagnetic phase, which is beneficial to generating strong magnetoelectric coupling, and the nanofibers are highly oriented in the P (VDF-TrFE) phase matrix, so that leakage current can be improved, and the breakdown strength in the direction of an external electric field can be improved.
The preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer, which is described by the embodiment, has the advantages of low price of required equipment, simple process, easy realization, excellent ferroelectric and ferromagnetic properties, capability of effectively solving the possible leakage current problem of the composite film due to the directionally arranged structure, flexibility which is not possessed by inorganic multiferroic materials, and great application potential in the fields of sensors, nonvolatile memory devices and the like.
The fourth concrete implementation mode:
a preparation method of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer comprises the following steps:
step a, preparation of CoFe2O4A nanofiber;
step b, preparation of CoFe2O4-a P (VDF-TrFE) based composite medium;
and c, preparing the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe 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/0.5g, and continuously stirring for 11 hours at normal temperatureTo 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 multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer 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 0.25mol/L, and the concentration of the ethanol solution is 70 vol%.
In the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment, the electrostatic spinning is performed in step a3, the advancing speed of the injector is set to 0.15mm/min, the rotating speed of the receiver is 100r/min, the distance between the injector and the receiver is 12cm, and the electrostatic pulse voltage V of the injector is set+15kV, receiving electrostatic pulse voltage V of the roller－Is-15 kV; in the step a4, the muffle furnace sintering temperature is 650 ℃, and the sintering time is 3 h.
In the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, CoFe is adopted in step b2O4The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, P (VDF-TrFE) powder and N, N-dimethylformamide solution for standby;
step b2, weighing CoFe in step b12O4Adding the nano-fiber into N, N-dimethylformamide solution, carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed, then adding the P (VDF-TrFE) powder weighed in the step b1, and carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed to obtain the product containing CoFe2O4A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step b3,The product obtained in step b2 contains CoFe2O4Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4-P (VDF-TrFE) based composite wet membrane, ready for use;
step b4, CoFe obtained in the step b32O4Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4-P (VDF-TrFE) based composite media.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe in step b12O4The feed-liquid ratio of the nanofiber, P (VDF-TrFE) powder and N, N-dimethylformamide solution is 3.71g:5g:50 ml; in the step b2, the frequency of the ultrasonic oscillation is 60W, and the time of the ultrasonic oscillation is 10 min.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, in the step b3, the rotating speed of the high-speed directional electrostatic spinning receiver is 2500r/min, the advancing speed of the injector is set to be 0.2mm/min, the distance from the injector to the receiver is 10-20 cm, and the electrostatic pulse voltage V of the injector is set+15kV, receiving electrostatic pulse voltage V of the roller－Is-15 kV; in the step b4, the vacuum drying temperature is 70 ℃, and the drying time is 20 h.
In the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment, the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer in step c is to use CoFe prepared in step b2O4And (3) 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 15min, then rapidly cooling to room temperature through water cooling, and maintaining the pressure at 6MPa for 5min to obtain the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe2O4Multiferroic nano-fiber filled phase in one-dimensional ferromagnetic filler-ferroelectric polymerThe content of the composite medium was 20 vol%.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, firstly, the CoFe with a large length-diameter ratio is prepared by adopting a sol-gel method and an electrostatic spinning technology2O4And (3) preparing a P (VDF-TrFE) mixed solution with uniformly dispersed nano fibers by using a solution method, and finally obtaining the one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium in oriented arrangement by using a high-speed oriented spinning technology and a hot pressing method.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, the nanofibers arranged in a highly oriented manner are embedded in the ferroelectric material P (VDF-TrFE) phase matrix as a one-dimensional columnar shape, the connection structure increases the contact area between the ferroelectric phase and the ferromagnetic phase, which is beneficial to generating strong magnetoelectric coupling, and the nanofibers are highly oriented in the P (VDF-TrFE) phase matrix, so that leakage current can be improved, and the breakdown strength in the direction of an external electric field can be improved.
The preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer, which is described by the embodiment, has the advantages of low price of required equipment, simple process, easy realization, excellent ferroelectric and ferromagnetic properties, capability of effectively solving the possible leakage current problem of the composite film due to the directionally arranged structure, flexibility which is not possessed by inorganic multiferroic materials, and great application potential in the fields of sensors, nonvolatile memory devices and the like.
The fifth concrete implementation mode:
a preparation method of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer comprises the following steps:
step a, preparation of CoFe2O4A nanofiber;
step b, preparation of CoFe2O4-a P (VDF-TrFE) based composite medium;
and c, preparing the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
A one-dimensional ferromagnetic material according to the present embodimentPreparation method of multiferroic composite medium of filler-ferroelectric polymer, CoFe 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/0.55g, 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 multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer 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 multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment, the electrostatic spinning is performed in step a3, the advancing speed of the injector is set to 0.2mm/min, the rotating speed of the receiver is 90r/min, the distance between the injector and the receiver is 14cm, 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 the step a4, the muffle furnace sintering temperature is 700 ℃, and the sintering time is 4 h.
A one-dimensional structure according to the present embodimentPreparation method of multiferroic composite medium of ferromagnetic filler-ferroelectric polymer, CoFe in step b2O4The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, P (VDF-TrFE) powder and N, N-dimethylformamide solution for standby;
step b2, weighing CoFe in step b12O4Adding the nano-fiber into N, N-dimethylformamide solution, carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed, then adding the P (VDF-TrFE) powder weighed in the step b1, and carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed to obtain the product containing CoFe2O4A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step b3, CoFe contained in the product obtained in step b22O4Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4-P (VDF-TrFE) based composite wet membrane, ready for use;
step b4, CoFe obtained in the step b32O4Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4-P (VDF-TrFE) based composite media.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe in step b12O4The feed-liquid ratio of the nanofiber, P (VDF-TrFE) powder and N, N-dimethylformamide solution is 6.36g:5g:50 ml; in the step b2, the frequency of the ultrasonic oscillation is 60W, and the time of the ultrasonic oscillation is 20 min.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, in the step b3, the rotating speed of the high-speed directional electrostatic spinning receiver is 3000r/min, the advancing speed of the injector is set to 0.2mm/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-15 kV; in the step b4, the vacuum drying temperature is 80 ℃, and the drying time is 48 h.
In the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment, the preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer in step c is to use CoFe prepared in step b2O4And (3) 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 180 ℃, the hot pressing time is 20min, then quickly cooling to room temperature through water cooling, and maintaining the pressure for 10min at 8MPa to obtain the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
The preparation method of the multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer according to this embodiment is CoFe2O4The content of the nano-fiber filling phase in the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer is 30 vol%.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, firstly, the CoFe with a large length-diameter ratio is prepared by adopting a sol-gel method and an electrostatic spinning technology2O4And (3) preparing a P (VDF-TrFE) mixed solution with uniformly dispersed nano fibers by using a solution method, and finally obtaining the one-dimensional ferromagnetic filler-ferroelectric polymer multiferroic composite medium in oriented arrangement by using a high-speed oriented spinning technology and a hot pressing method.
In the preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer according to the embodiment, the nanofibers arranged in a highly oriented manner are embedded in the ferroelectric material P (VDF-TrFE) phase matrix as a one-dimensional columnar shape, the connection structure increases the contact area between the ferroelectric phase and the ferromagnetic phase, which is beneficial to generating strong magnetoelectric coupling, and the nanofibers are highly oriented in the PVDF matrix, which can improve leakage current and improve breakdown strength along the direction of an external electric field.
The preparation method of the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer, which is described by the embodiment, has the advantages of low price of required equipment, simple process, easy realization, excellent ferroelectric and ferromagnetic properties, capability of effectively solving the possible leakage current problem of the composite film due to the directionally arranged structure, flexibility which is not possessed by inorganic multiferroic materials, and great application potential in the fields of sensors, nonvolatile memory devices and the like.

Claims (9)

1. A preparation method of a multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer is characterized by comprising the following steps: the method comprises the following steps:
step a, preparation of CoFe2O4A nanofiber;
step b, preparation of CoFe2O4-a P (VDF-TrFE) based composite medium;
and c, preparing the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
2. The method for preparing a multiferroic composite dielectric of one-dimensional ferromagnetic filler-ferroelectric polymer as claimed in claim 1, wherein: CoFe 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 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.
3. The method for preparing a multiferroic composite dielectric of one-dimensional ferromagnetic filler-ferroelectric polymer as claimed in claim 2, wherein: 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 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%.
4. The method for preparing a multiferroic composite dielectric of one-dimensional ferromagnetic filler-ferroelectric polymer as claimed in claim 2, wherein: in the electrostatic spinning in the step a3, the advancing speed of an injector is set to be 0.15-0.25 mm/min, the rotating speed of a receiver is 70-120 r/min, the distance from the injector to the receiver is 7-20 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 to-20 kV; in the step a4, the muffle furnace sintering temperature is 550-750 ℃, and the sintering time is 2-5 h.
5. The method for preparing a multiferroic composite dielectric of one-dimensional ferromagnetic filler-ferroelectric polymer as claimed in claim 1, wherein: CoFe in step b2O4The preparation method of the (E) -P (VDF-TrFE) based composite medium comprises the following steps:
step b1, weighing CoFe according to the material-liquid ratio2O4Nano-fiber, P (VDF-TrFE) powder and N, N-dimethylformamide solution for standby;
step b2, weighing CoFe in step b12O4Adding the nano-fiber into N, N-dimethylformamide solution, carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed, then adding the P (VDF-TrFE) powder weighed in the step b1, and carrying out ultrasonic oscillation until the nano-fiber is uniformly dispersed to obtain the product containing CoFe2O4A P (VDF-TrFE) mixed solution of a nanofiber filling phase for later use;
step b3, CoFe contained in the product obtained in step b22O4Adding the P (VDF-TrFE) mixed solution of the nanofiber filling phase into an injector for high-speed directional electrostatic spinning to obtain CoFe2O4-P(VDF-TrFE) based composite wet film for standby;
step b4, CoFe obtained in the step b32O4Drying the-P (VDF-TrFE) based composite wet film in a vacuum oven to obtain CoFe2O4-P (VDF-TrFE) based composite media.
6. The method for preparing a multiferroic composite dielectric of one-dimensional ferromagnetic filler-ferroelectric polymer as claimed in claim 5, wherein: CoFe in step b12O4The feed-liquid ratio of the nanofiber, the P (VDF-TrFE) powder and the N, N-dimethylformamide solution is 0.459-6.36 g:5g:50 ml; and b2, controlling the ultrasonic oscillation frequency to be 60W and the ultrasonic oscillation time to be 2-20 min.
7. The method for preparing a multiferroic composite dielectric of one-dimensional ferromagnetic filler-ferroelectric polymer as claimed in claim 5, wherein: in the step b3, the rotating speed of the high-speed directional electrostatic spinning receiver is 2000-3000 r/min, the propelling 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 to-20 kV; in the step b4, the vacuum drying temperature is 50-80 ℃, and the drying time is 4-48 h.
8. The method for preparing a multiferroic composite dielectric of one-dimensional ferromagnetic filler-ferroelectric polymer as claimed in claim 1, wherein: the preparation method of the one-dimensional nanofiber polyvinylidene fluoride flexible multiferroic composite medium in the step c comprises the step of mixing the CoFe prepared in the step b2O4And (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 150-180 ℃, the hot pressing time is 10-30 min, then quickly cooling to room temperature through water cooling, and maintaining the pressure at 1-10 MPa for 3-15 min to obtain the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer.
9. A one-dimensional ferromagnetic filler as claimed in any one of claims 1 to 8-preparation method of multiferroic composite medium of ferroelectric polymer-multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer, characterized in that: the CoFe2O4The content of the nano-fiber filling phase in the multiferroic composite medium of the one-dimensional ferromagnetic filler-ferroelectric polymer is 3-30 vol%.
CN202010710600.2A 2020-07-22 2020-07-22 Multiferroic composite medium of one-dimensional ferromagnetic filler-ferroelectric polymer and preparation method thereof Pending CN112030369A (en)

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