CN108264345B - BaTiO3/CoFe2O4/BaTiO3Preparation method of nano multilayer composite magnetoelectric ceramic - Google Patents

BaTiO3/CoFe2O4/BaTiO3Preparation method of nano multilayer composite magnetoelectric ceramic Download PDF

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CN108264345B
CN108264345B CN201810101854.7A CN201810101854A CN108264345B CN 108264345 B CN108264345 B CN 108264345B CN 201810101854 A CN201810101854 A CN 201810101854A CN 108264345 B CN108264345 B CN 108264345B
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ceramic
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CN108264345A (en
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柳阳
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Hubei University of Technology
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2666—Other ferrites containing nickel, copper or cobalt
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]

Abstract

The invention provides a BaTiO3/CoFe2O4/BaTiO3The preparation method of nano multilayer composite magnetoelectric ceramic uses nano cobalt ferrite and submicron barium titanate as raw materials, and utilizes plasma discharge sintering technique to prepare high-density BaTiO3/CoFe2O4/BaTiO3Multilayer composite magnetoelectric ceramics. The method of the invention utilizes the low-temperature rapid forming characteristic of plasma discharge sintering, and the sintered ceramic has high density and avoids the generation of impurity phases and the coupling dislocation between two phases, thereby ensuring that the ceramic has good magnetoelectric coupling performance and anisotropy. The ceramic prepared by the method has good application prospect in the aspects of information storage, integrated circuits, magnetic sensors, spinning electronic devices and the like.

Description

BaTiO3/CoFe2O4/BaTiO3Preparation method of nano multilayer composite magnetoelectric ceramic
Technical Field
The invention belongs to the field of electronic information component materials, and particularly relates to a preparation method of a BaTiO3/CoFe2O4/BaTiO3 nano multilayer composite magnetoelectric ceramic.
Background
The multiferroic material has ferromagnetism and ferroelectricity at the same time, and has attractive application prospects in the aspects of information storage, integrated circuits, magnetic sensors, spinning electronic devices and the like, thereby arousing great interest of people. Wherein, CoFe2O4-BaTiO3Composite materials have been extensively studied over the past few decades because of their ferroelectric, ferromagnetic, and magnetoelectric coupling properties at room temperature. In 1972, the magnetoelectric coupling characteristic in a ferromagnetic/ferroelectric composite system was first proposed. Shortly afterwards, scientists in Philips laboratories successfully synthesized CoFe with large magnetoelectric effect at room temperature in a five-element solution of Fe-Co-Ti-Ba-O2O4-BaTiO3A eutectic ceramic system. In recent years, multilayer magnetoelectric materials have been proved to have optimal magnetoelectric effects, but the application thereof is mainly based on thin film materials. However, the thin film material has complex preparation process, high cost and is not beneficial to the post processing. In contrast, multilayer ceramic materials have better plasticity and three-dimensional ductility and are considered to have great practical potential. In the last 90 s, the subject group of Newnhamd and Russian scientists prepared a series of magnetoelectric ceramics by using a common solid-phase sintering method. Although the solid-phase sintering method for preparing the magnetoelectric ceramic has lower cost and is convenient to realize, the magnetoelectric effect of the ceramic prepared by the method is smaller due to the impurity phase and the coupling dislocation generated along with the preparation. Thus how to prepare a multilayer with good magnetoelectric properties in a simple, convenient and low-cost mannerMagnetoelectric ceramic materials have become an important research direction. More and more processes are being used to prepare CoFe2O4-BaTiO3Composite ceramics, some magnetoelectric materials prepared by the process also have good magnetoelectric performance, but the process is complex and is not easy to repeat with higher cost. BaTiO preparation by plasma discharge sintering technology3/CoFe2O4/BaTiO3Multilayer composite ceramics are not described in both domestic and foreign literature.
Disclosure of Invention
The invention provides BaTiO3/CoFe2O4/BaTiO3Preparation method of nano multilayer composite magnetoelectric ceramic and BaTiO obtained by method3/CoFe2O4/BaTiO3The ceramic has a large magnetoelectric coupling coefficient and significant magnetoelectric anisotropy.
The invention is realized by the following technical scheme:
BaTiO3/CoFe2O4/BaTiO3The preparation method of the nano multilayer composite magnetoelectric ceramic comprises the following steps:
(1) mixing CoFe2O4Putting the mixture into a carbon grinding tool, putting the grinding tool into a plasma discharge sintering machine for presintering, and applying pressure to press and form a piece;
(2) mixing BaTiO3Putting the mixture into a carbon grinding tool, putting the grinding tool into a plasma discharge sintering machine for presintering, and applying pressure to press and form a piece;
(3) pre-pressed shaped CoFe2O4Sheet and BaTiO3Sheet according to BaTiO3/CoFe2O4/BaTiO3The raw materials are sequentially put into a carbon grinding tool with the inner diameter of 10mm and the outer diameter of 40 mm;
(4) putting the grinding tool with the BaTiO3/CoFe2O4/BaTiO3 three-layer sheet structure into a plasma discharge sintering machine, applying pressure, heating to 600 ℃ within 10 minutes, heating to 1100 ℃ within 1 minute, heating to 1150 ℃ within 5 minutes, then keeping the temperature for 5 minutes, naturally cooling to room temperature, removing external pressure, and taking out a sample;
(5) placing the sintered sample into a muffle furnaceAnnealing at 600 ℃ for 5 hours to remove carbon to obtain BaTiO3/ CoFe2O4/BaTiO3Multilayer composite magnetoelectric ceramics.
Preferably, CoFe in step (1)2O4The particle size of (A) is 30 to 50 nm.
Preferably, BaTiO in step (2)3The particle size of (A) is 500 to 600 nm.
Preferably, BaTiO in step (3)3/CoFe2O4/BaTiO3The thickness ratio between the three-layer sheet structure is 1: (0.5-3) 1.
Preferably, infrared temperature control is adopted in the sintering process in the step (4).
Preferably, the pressure applied in the steps (1), (2) and (4) is 40-80 MPa.
Preferably, the temperature of the presintering in the steps (1) and (2) is 600 ℃, and the sintering time is 30 min.
By consulting a large number of literatures, no report is made on the preparation of the multilayer composite magnetoelectric ceramic by using a plasma discharge process. The multilayer composite magnetoelectric ceramic sintered by the traditional process usually needs very long sintering time and sintering temperature of about 2000 ℃ to be compact into sheets, but the higher sintering temperature and the longer sintering time can cause layer-to-layer mutual reaction and mutual permeation, the boundary between layers is fuzzy, and the crystal boundary/interface coupling is seriously influenced, so that the multilayer composite ceramic prepared by the traditional sintering process is greatly damaged, and the requirement of practical application cannot be met.
The invention creatively prepares the BaTiO by adopting a prepressing presintering-plasma discharging sintering process for the first time3/ CoFe2O4/BaTiO3Multilayer composite magnetoelectric ceramics. Obtaining single-layer BaTiO through pre-pressing and pre-sintering treatment3And CoFe2O4The single-layer sheet can obtain inward residual stress in the step, the boundary of each layer is tightened, and the purpose of clear layer-to-layer boundary in the subsequent plasma discharge sintering process is achieved.
It is worth noting that all substances in the plasma discharge sintering are in a semi-molten state under the maximum external pressureWill be tightly bonded together. Therefore, only short sintering time and low sintering temperature are needed to sinter the ceramics, and simultaneously, different substances have no time to generate chemical reaction, thereby ensuring that BaTiO near the interface3And CoFe2O4No impurity phase and atom interpenetration occur. BaTiO thus prepared3/ CoFe2O4/BaTiO3The multilayer composite magnetoelectric ceramic has clear boundary between layers, no impurity phase and mutual permeation, and has extremely high density. The interface coupling effect between layers is ensured to the maximum extent, so that the magnetoelectric property of the multilayer ceramic is greatly improved.
Compared with the prior art, the prior art uses BaTiO3And CoFe2O4The two phases are mechanically mixed and then sintered into a sheet by plasma discharge, so that the improvement of the magnetoelectric effect is achieved. However, in the mechanically mixed sample, a great leakage phenomenon exists, and the piezoelectric performance of the composite ceramic is reduced. At the same time, the magnetostrictive effect is greatly limited due to the clamping effect inside the mixed material. The magnetoelectric effect of the composite material is proportional to the piezoelectric property and the magnetostrictive effect, so that BaTiO3And CoFe2O4The magnetoelectric property of the sintered composite ceramic after the two phases are mechanically mixed can not be optimized. Compared with the prior art, the three-layer composite ceramic in the scheme has better magnetostrictive effect and piezoelectric property, and the interface coupling of two substances is optimized clearly and greatly. BaTiO prepared by the invention3/CoFe2O4/BaTiO3The multilayer composite magnetoelectric ceramic has the largest magnetoelectric effect in the known magnetoelectric composite ceramics.
The prepared ceramic has no impure phase, high density, huge magnetoelectric coupling coefficient and obvious magnetoelectric anisotropy, and is a ferroelectric-ferromagnetic-magnetoelectric multifunctional ceramic material with wide application prospect; compared with the traditional solid phase reaction method, the preparation method of the invention has the advantages that the sintering phase forming temperature of the ceramic is obviously reduced, and the preparation method is a low-temperature ceramic sintering process.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows the thickness ratios (t) of three layers in examples 1 to 4B:tC:tB1:0.5:1,1:1:1, 1:2:1 and 1:3:1) XRD patterns of assembled and plasma discharge sintered BaTiO3/CoFe2O4/BaTiO3 multilayer composite magnetoelectric ceramic samples;
FIG. 2 is a scanning electron micrograph and an X-ray spectrum of a BaTiO3/CoFe2O4/BaTiO3 multilayer ceramic sample sintered in example 1.
FIG. 3 shows the thickness ratios (t) of three layers in examples 1 to 4B:tC:tBMagnetoelectric coupling coefficient-applied direct current magnetic field (a) of BaTiO3/CoFe2O4/BaTiO3 layer composite magnetoelectric ceramic samples assembled and plasma discharge sintered (1: 0.5:1,1:1:1, 1:2:1 and 1:3:1)E-H) graph.
FIG. 4 is the magneto-electric effect anisotropy (. alpha.) of the BaTiO3/CoFe2O4/BaTiO3 multilayer composite magneto-electric ceramic sample sintered in example 3E- θ) curve.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A certain amount of CoFe with the particle size of about 30nm2O4Loading into carbon grinding tool with inner diameter of 10mm and outer diameter of 40mm,putting the grinding tool into a plasma discharge sintering machine, and applying a pressure of 60MPa to compact the powder into a sheet, wherein CoFe filled into the grinding tool is controlled in the step2O4The amount of (c) controls the thickness of the sheet. Adding a certain amount of BaTiO with the particle size of about 600nm3Charging into carbon grinding tool with inner diameter of 10mm and outer diameter of 40mm, placing the grinding tool into plasma discharge sintering machine, and applying pressure of 60MPa to compact the powder into tablet, wherein BaTiO charged into the grinding tool is controlled3The amount of (c) controls the thickness of the sheet. Pre-pressed shaped CoFe2O4And BaTiO3Sheet according to BaTiO3/CoFe2O4/BaTiO3By controlling the amount of the powder in the steps (1) and (2), BaTiO is made to be in a state that the powder is sequentially charged into a carbon grinding tool with an inner diameter of 10mm and an outer diameter of 40mm3/CoFe2O4/BaTiO3The thickness ratio between the three layers is tB:tC:tB1:0.5: 1. Will be filled with BaTiO3/CoFe2O4/BaTiO3And (3) placing the grinding tool with the three-layer structure into a plasma discharge sintering machine, controlling the temperature by infrared rays in the sintering process, heating to 600 ℃ within 10 minutes, heating to 1100 ℃ within one minute, heating to 1150 ℃ within 5 minutes, keeping the temperature for 5 minutes, naturally cooling to room temperature, removing external pressure, and taking out a sample. Putting the sintered sample into a muffle furnace to anneal for 5 hours at 600 ℃ for decarbonization to obtain BaTiO3/CoFe2O4/BaTiO3Multilayer composite magnetoelectric ceramics.
BaTiO prepared by example 13/CoFe2O4/BaTiO3XRD of the multilayer composite magnetoelectric ceramic is shown in figure 1, and the removal of CoFe in the ceramic can be seen from figure 12O4And BaTiO3The crystal phase of (A) has no other impurity phase. BaTiO prepared by example 13/CoFe2O4/BaTiO3The TEM and EDX of the multilayer composite magnetoelectric ceramic are shown in figure 2, and it can be seen from figure 2 that the boundaries between layers in the ceramic are clear, no interpenetration and miscellaneous items are generated, and the interior of the ceramic has high compactness. Mixing BaTiO3/CoFe2O4/BaTiO3Multilayer composite magnetoelectric ceramic silver-coated brazed electrode, method for producing the same, and method for producing the sameRelationship between magnetoelectric coupling effect and external DC magnetic field (alpha)E-H) is as shown in FIG. 3. Example 1 the curve shown in fig. 1 and 3 is Sample a.
Example 2
A certain amount of CoFe with the particle size of about 40nm2O4Charging into carbon grinding tool with inner diameter of 10mm and outer diameter of 40mm, placing the grinding tool into plasma discharge sintering machine, and applying pressure of 60MPa to compact the powder into pieces, wherein CoFe charged into the grinding tool is controlled in the step2O4The amount of (c) controls the thickness of the sheet. Adding a certain amount of BaTiO with the particle size of about 500nm3Charging into carbon grinding tool with inner diameter of 10mm and outer diameter of 40mm, placing the grinding tool into plasma discharge sintering machine, and applying pressure of 60MPa to compact the powder into tablet, wherein BaTiO charged into the grinding tool is controlled3The amount of (c) controls the thickness of the sheet. Pre-pressed shaped CoFe2O4And BaTiO3Sheet according to BaTiO3/CoFe2O4/BaTiO3By controlling the amount of the powder in the steps (1) and (2), BaTiO is made to be in a state that the powder is sequentially charged into a carbon grinding tool with an inner diameter of 10mm and an outer diameter of 40mm3/CoFe2O4/BaTiO3The thickness ratio between the three layers is tB:tC:tB1:1: 1. Will be filled with BaTiO3/CoFe2O4/BaTiO3And (3) placing the grinding tool with the three-layer structure into a plasma discharge sintering machine, controlling the temperature by infrared rays in the sintering process, heating to 600 ℃ within 10 minutes, heating to 1100 ℃ within one minute, heating to 1150 ℃ within 5 minutes, keeping the temperature for 5 minutes, naturally cooling to room temperature, removing external pressure, and taking out a sample. Putting the sintered sample into a muffle furnace to anneal for 5 hours at 600 ℃ for decarbonization to obtain BaTiO3/CoFe2O4/BaTiO3Multilayer composite magnetoelectric ceramics.
BaTiO prepared by example 23/CoFe2O4/BaTiO3XRD of the multilayer composite magnetoelectric ceramic is shown in figure 1, and the removal of CoFe in the ceramic can be seen from figure 12O4And BaTiO3The crystal phase of (A) has no other impurity phase. Mixing BaTiO3/CoFe2O4/BaTiO3Multilayer compositeThe magnetoelectric ceramic is coated with silver paste to weld an electrode, and the relationship (alpha) between the magnetoelectric coupling effect of the sample and an external direct current magnetic fieldE-H) is as shown in FIG. 3. Example 2 the curve shown in fig. 1 and 3 is Sample B.
Example 3
Adding a certain amount of CoFe with the particle size of about 50nm2O4Charging into carbon grinding tool with inner diameter of 10mm and outer diameter of 40mm, placing the grinding tool into plasma discharge sintering machine, and applying pressure of 60MPa to compact the powder into pieces, wherein CoFe charged into the grinding tool is controlled in the step2O4The amount of (c) controls the thickness of the sheet. Adding a certain amount of BaTiO with the particle size of about 500nm3Charging into carbon grinding tool with inner diameter of 10mm and outer diameter of 40mm, placing the grinding tool into plasma discharge sintering machine, and applying pressure of 60MPa to compact the powder into tablet, wherein BaTiO charged into the grinding tool is controlled3The amount of (c) controls the thickness of the sheet. Pre-pressed shaped CoFe2O4And BaTiO3Sheet according to BaTiO3/CoFe2O4/BaTiO3By controlling the amount of the powder in the steps (1) and (2), BaTiO is made to be in a state that the powder is sequentially charged into a carbon grinding tool with an inner diameter of 10mm and an outer diameter of 40mm3/CoFe2O4/BaTiO3The thickness ratio between the three layers is tB:tC:tB1:2: 1. Will be filled with BaTiO3/CoFe2O4/BaTiO3And (3) placing the grinding tool with the three-layer structure into a plasma discharge sintering machine, controlling the temperature by infrared rays in the sintering process, heating to 600 ℃ within 10 minutes, heating to 1100 ℃ within one minute, heating to 1150 ℃ within 5 minutes, keeping the temperature for 5 minutes, naturally cooling to room temperature, removing external pressure, and taking out a sample. Putting the sintered sample into a muffle furnace to anneal for 5 hours at 600 ℃ for decarbonization to obtain BaTiO3/CoFe2O4/BaTiO3Multilayer composite magnetoelectric ceramics.
BaTiO prepared by example 33/CoFe2O4/BaTiO3XRD of the multilayer composite magnetoelectric ceramic is shown in figure 1, and the removal of CoFe in the ceramic can be seen from figure 12O4And BaTiO3The crystal phase of (A) has no other impurity phase. Mixing BaTiO3/CoFe2O4/BaTiO3The relationship (alpha) between the magnetoelectric coupling effect of the sample and the applied DC magnetic fieldE-H) and the relation (alpha) of the direction of the applied magnetic fieldE- θ) as shown in fig. 3 and 4. Example 3 the curve shown in figures 1 and 3 is Sample C.
Example 4
A certain amount of CoFe with the particle size of about 30nm2O4Charging into carbon grinding tool with inner diameter of 10mm and outer diameter of 40mm, placing the grinding tool into plasma discharge sintering machine, and applying pressure of 60MPa to compact the powder into pieces, wherein CoFe charged into the grinding tool is controlled in the step2O4The amount of (c) controls the thickness of the sheet. Adding a certain amount of BaTiO with the particle size of about 500nm3Charging into carbon grinding tool with inner diameter of 10mm and outer diameter of 40mm, placing the grinding tool into plasma discharge sintering machine, and applying pressure of 60MPa to compact the powder into tablet, wherein BaTiO charged into the grinding tool is controlled3The amount of (c) controls the thickness of the sheet. Pre-pressed shaped CoFe2O4And BaTiO3Sheet according to BaTiO3/CoFe2O4/BaTiO3By controlling the amount of the powder in the steps (1) and (2), BaTiO is made to be in a state that the powder is sequentially charged into a carbon grinding tool with an inner diameter of 10mm and an outer diameter of 40mm3/CoFe2O4/BaTiO3The thickness ratio between the three layers is tB:tC:tB1:3: 1. Will be filled with BaTiO3/CoFe2O4/BaTiO3And (3) placing the grinding tool with the three-layer structure into a plasma discharge sintering machine, controlling the temperature by infrared rays in the sintering process, heating to 600 ℃ within 10 minutes, heating to 1100 ℃ within one minute, heating to 1150 ℃ within 5 minutes, keeping the temperature for 5 minutes, naturally cooling to room temperature, removing external pressure, and taking out a sample. Putting the sintered sample into a muffle furnace to anneal for 5 hours at 600 ℃ for decarbonization to obtain BaTiO3/CoFe2O4/BaTiO3Multilayer composite magnetoelectric ceramics.
BaTiO prepared by example 43/CoFe2O4/BaTiO3XRD of the multilayer composite magnetoelectric ceramic is shown in figure 1, and the ceramic can be seen from figure 1Removing CoFe2O4And BaTiO3The crystal phase of (A) has no other impurity phase. Mixing BaTiO3/CoFe2O4/BaTiO3The relationship (alpha) between the magnetoelectric coupling effect of the sample and the applied DC magnetic fieldE-H) is as shown in FIG. 3. Example 4 the curve shown in figures 1 and 3 is Sample D.
BaTiO prepared by the above method3/CoFe2O4/BaTiO3The multilayer composite magnetoelectric ceramic has no impurity phase, high density and large magnetoelectric coupling coefficient, is a ferroelectric-ferromagnetic-magnetoelectric multifunctional ceramic material with wide application prospect, and can be used as a component of an electronic sensor, a mass data storage component and the like. And (3) characterizing the microstructure of the sample, and analyzing the phase and the micro-morphology of the sample by using an X-ray diffractometer (XRD) and a Scanning Electron Microscope (SEM). And measuring the magnetoelectric coupling property of the sample by adopting a room-temperature magnetoelectric coupling coefficient tester.
FIG. 1 shows the thickness ratios (t) between the three layers in examples 1 to 4B:tC:tB1:0.5:1,1:1:1, 1:2:1 and 1:3:1) assembled and SPS sintered BaTiO3/CoFe2O4/BaTiO3The multilayer composite magnetoelectric ceramic sample has XRD pattern, and the ceramic crystal sintered by the method is perfect without impurity phase generation.
The SEM and EDX patterns of the sample of example 1 are shown in FIG. 2, and the SEM pictures of the cross section of the sample in FIGS. 2(a), (b) and (c) show that the boundaries between layers are clear after sintering, the particles inside the sample are tightly packed, and the plasma discharge sintered ceramic sample has high compactness. FIGS. 2(d), (e) are EDX maps scanned along line A and line B in FIG. 2(c), respectively. The EDX results indicate no interpenetration between the two phases and no formation of a hetero-phase.
FIG. 3 shows the thickness ratios (t) between the three layers in examples 1 to 4B:tC:tB1:0.5:1,1:1:1, 1:2:1 and 1:3:1) assembled and plasma discharge sintered BaTiO3/CoFe2O4/BaTiO3Magnetoelectric coupling effect and external application of multilayer composite magnetoelectric ceramic sampleAnd (3) a relationship diagram of the direct current magnetic field. It can be seen that the sample shows good magnetoelectric coupling effect when BaTiO3/CoFe2O4/BaTiO3The magnetoelectric coupling effect reaches the maximum when the thickness ratio is 1:2: 1. For the same sample aE33Has a value of more than alphaE31The magneto-electric coupling effect is shown to have anisotropy.
Fig. 4 is a graph of anisotropy of magnetoelectric coupling effects for the sample in example 3. The method shows that the direction of the external magnetic field has very obvious influence on the magnetoelectric coupling effect, and the experimental data and the theoretical calculation data of the anisotropy of the magnetoelectric effect of the sample are very consistent. The above data indicate that plasma discharge sintering is a very suitable magnetoelectric ceramic preparation process, and can be popularized as a common method for preparing magnetoelectric ceramics.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. BaTiO3/CoFe2O4/BaTiO3The preparation method of the nano multilayer composite magnetoelectric ceramic is characterized by comprising the following steps:
(1) mixing CoFe2O4Putting the mixture into a carbon grinding tool, putting the grinding tool into a plasma discharge sintering machine for presintering, and applying pressure to press and form a piece;
(2) mixing BaTiO3Putting the mixture into a carbon grinding tool, putting the grinding tool into a plasma discharge sintering machine for presintering, and applying pressure to press and form a piece;
(3) pre-pressed shaped CoFe2O4Sheet and BaTiO3Sheet according to BaTiO3/ CoFe2O4/ BaTiO3The raw materials are sequentially put into a carbon grinding tool with the inner diameter of 10mm and the outer diameter of 40 mm;
(4) will be filled with BaTiO3/CoFe2O4/BaTiO3Putting the grinding tool with the three-layer sheet structure into a plasma discharge sintering machine, applying pressure, heating to 600 ℃ within 10 minutes, and then heatingHeating to 1100 ℃ after 1 minute, then heating to 1150 ℃ after 5 minutes, then preserving heat for 5 minutes, naturally cooling to room temperature, removing external pressure, and taking out a sample;
(5) putting the sintered sample into a muffle furnace to anneal for 5 hours at 600 ℃ for decarbonization to obtain BaTiO3/ CoFe2O4/ BaTiO3Multilayer composite magnetoelectric ceramics;
BaTiO in step (3)3/ CoFe2O4/ BaTiO3The thickness ratio between the three-layer sheet structure is 1: (0.5-3) 1.
2. A BaTiO compound of claim 13/CoFe2O4/BaTiO3The preparation method of the nano multilayer composite magnetoelectric ceramic is characterized in that CoFe in the step (1)2O4The particle size of (A) is 30 to 50 nm.
3. A BaTiO compound of claim 13/CoFe2O4/BaTiO3The preparation method of the nano multilayer composite magnetoelectric ceramic is characterized in that BaTiO in the step (2)3The particle size of (A) is 500 to 600 nm.
4. A BaTiO compound of claim 13/CoFe2O4/BaTiO3The preparation method of the nano multilayer composite magnetoelectric ceramic is characterized in that infrared temperature control is adopted in the sintering process in the step (4).
5. A BaTiO compound of claim 13/CoFe2O4/BaTiO3The preparation method of the nano multilayer composite magnetoelectric ceramic is characterized in that the pressure applied in the steps (1), (2) and (4) is 40-80 MPa.
6. A BaTiO compound of claim 13/CoFe2O4/BaTiO3The preparation method of the nano multilayer composite magnetoelectric ceramic is characterized in that the steps (1) and (2) areThe presintering temperature is 600 ℃, and the sintering time is 30 min.
CN201810101854.7A 2018-02-01 2018-02-01 BaTiO3/CoFe2O4/BaTiO3Preparation method of nano multilayer composite magnetoelectric ceramic Expired - Fee Related CN108264345B (en)

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CN104692828A (en) * 2015-03-06 2015-06-10 西安电子科技大学 Method for preparing and transferring multilayer barium titanate and multilayer cobalt ferrite magnetoelectric composite film
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CN1810720A (en) * 2006-02-24 2006-08-02 中国科学院上海硅酸盐研究所 Prepn process of SiN ceramic with high heat conductivity
CN101269967A (en) * 2008-05-13 2008-09-24 武汉理工大学 Method for preparing boron carbide ceramic
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