CN108264345A - A kind of BaTiO3/CoFe2O4/BaTiO3The preparation method of nanometer multilayer compound magnetoelectric ceramics - Google Patents
A kind of BaTiO3/CoFe2O4/BaTiO3The preparation method of nanometer multilayer compound magnetoelectric ceramics Download PDFInfo
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- 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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Abstract
The present invention proposes a kind of BaTiO3/CoFe2O4/BaTiO3The preparation method of nanometer multilayer compound magnetoelectric ceramics is raw material using the cobalt ferrite of nano-scale and the barium titanate of submicron-scale, and the BaTiO of high-compactness is prepared using spark plasma sintering technology3/CoFe2O4/BaTiO3Multilayered compound magnetoelectricity ceramics.The method of the present invention utilizes the low temperature rapid shaping characteristic of spark plasma sintering, coupling dislocation between the ceramic generation that dephasign is avoided while with high-compactness of sintering and two-phase, so as to ensure that ceramics have good magneto-electric coupled performance and anisotropy.The ceramics that the method for the present invention is prepared have good application prospect in information storage, integrated circuit, Magnetic Sensor and spin electric device etc..
Description
Technical field
The invention belongs to field of electronic information component materials, more particularly to a kind of BaTiO3/CoFe2O4/
The preparation method of BaTiO3 nanometer multilayers compound magnetoelectric ceramics.
Background technology
Multi-iron material is provided simultaneously with ferromagnetism and ferroelectricity, in information storage, integrated circuit, Magnetic Sensor and spin electricity
Sub- device etc. has tempting application prospect, thus causes the great interest of people.Wherein, CoFe2O4-BaTiO3It is compound
Material is ground extensively in the past few decades due to having ferroelectricity, ferromagnetism and magneto-electric coupled characteristic simultaneously at room temperature
Study carefully.1972, the magneto-electric coupled characteristic in ferromagnetic/ferroelectricity compound system was put forward for the first time.Soon later, Philip laboratory
Scientist has successfully synthesized the CoFe at room temperature with larger magnetoelectric effect in five yuan of solution of Fe-Co-Ti-Ba-O2O4-
BaTiO3Eutectic ceramic system.In recent years, multilayer magnetoelectric material is proved to have optimal magnetoelectric effect, but its application mainly with
Based on thin-film material.However thin-film material preparation process is complicated, it is of high cost and be unfavorable for post-production.In contrast, multilayer is made pottery
Ceramic material has better plasticity and three-dimensional ductility, is considered having huge practical potentiality.The nineties in last century,
The seminar of Newnhamd and the scientists of Russia have prepared a series of magnetoelectric ceramic with common solid sintering technology.
Although prepared by solid sintering technology, magnetoelectric ceramic cost is relatively low to be easy to implement, and the dephasign generated therewith and coupling dislocation cause this
Ceramic magnetoelectric effect prepared by method is smaller.Therefore how to be prepared with the method for simple and convenient low cost has good magnetic electricity performance
Multilayer magnetoelectric ceramic material have become as important research direction.More and more methods are used to prepare CoFe2O4-BaTiO3
Composite ceramics, magnetoelectric material prepared by some techniques also has good magnetic electricity performance, but cost is not easy compared with high technology complexity
In repetition.At present BaTiO is prepared with spark plasma sintering technology3/CoFe2O4/BaTiO3Multi-layer composite ceramic is at home and state
It is not recorded in outer document.
Invention content
The present invention proposes a kind of BaTiO3/CoFe2O4/BaTiO3The preparation method of nanometer multilayer compound magnetoelectric ceramics, we
The BaTiO that method obtains3/CoFe2O4/BaTiO3Ceramics have larger magneto-electric coupled coefficient and significant magnetoelectricity anisotropy.
What the present invention was realized particular by following technical scheme：
A kind of BaTiO3/CoFe2O4/BaTiO3The preparation method of nanometer multilayer compound magnetoelectric ceramics, includes the following steps：
(1) by CoFe2O4It is fitted into carbon grinding tool, grinding tool is put into spark plasma sintering machine and is pre-sintered, and applies pressure
Pressure forms piece；
(2) by BaTiO3It is fitted into carbon grinding tool, grinding tool is put into spark plasma sintering machine and is pre-sintered, and applies pressure
Pressure forms piece；
(3) by the CoFe of pre-molding2O4Piece and BaTiO3Piece is according to BaTiO3/CoFe2O4/BaTiO3Sequence be packed into
Diameter 10mm, outer diameter 40mm carbon grinding tool in；
(4) grinding tool equipped with BaTiO3/CoFe2O4/BaTiO3 three-layer tablet structures is put into spark plasma sintering machine,
Apply pressure, be warming up to 600 DEG C within 10 minutes, 1100 DEG C were warming up to using 1 minute, be warming up to 1150 DEG C within 5 minutes later, then
Heat preservation 5 minutes, naturally cools to room temperature, cancels additional pressure, takes out sample；
(5) sample of sintering is put into the annealing 5 hours of 600 DEG C of Muffle furnace except carbon, obtains BaTiO3/CoFe2O4/BaTiO3
Multilayered compound magnetoelectricity ceramics.
Preferably, CoFe in step (1)2O4Particle size be 30~50nm.
Preferably, BaTiO in step (2)3Particle size be 500~600nm.
Preferably, BaTiO in step (3)3/CoFe2O4/BaTiO3Thickness ratio between three-layer tablet structure is 1：(0.5~
3):1。
Preferably, sintering process uses infrared temperature control in step (4).
Preferably, the pressure applied in step (1), (2), (4) is 40~80MPa.
Preferably, the temperature being pre-sintered in step (1), (2) is 600 DEG C, sintering time 30min.
By consulting lot of documents, there is no the reports that multilayered compound magnetoelectricity ceramics are prepared using plasma discharge techniques at present
Road.The multilayered compound magnetoelectricity ceramics being sintered using traditional handicraft usually require the sintering time grown very much and 2000 DEG C or so of sintering
Temperature can be fine and close in blocks, but higher sintering temperature and longer sintering time are bound to cause to occur between layers
It reacts to each other and interpenetrates, boundary obscures between layers, has seriously affected crystal boundary/interface coupling so that conventional sintering work
Multi-layer composite ceramic magnetic electricity performance prepared by skill is greatly destroyed, and can not meet the needs of practical application.
Novelty of the invention is prepared for BaTiO using precompressed pre-burning-spark plasma sintering technique for the first time3/CoFe2O4/
BaTiO3Multilayered compound magnetoelectricity ceramics.It handles to obtain individual layer BaTiO by precompressed pre-sintering3And CoFe2O4Piece, this step can be with
Single-layer sheet is made to obtain inside residual stress, the boundary of each layer of tightening is realized in follow-up spark plasma sintering process middle level
The clear-cut between layer.
It is worth noting that, all substances are all semi-molten states in spark plasma sintering, in greatly outer plus pressure
Under can closely be combined together.Therefore very short sintering time and relatively low sintering temperature is only needed to be sintered ceramics, together
When but also have little time to chemically react between different material, ensure that near interface BaTiO3And CoFe2O4It will not generate miscellaneous
Mutually interpenetrated with atom.The BaTiO so prepared3/CoFe2O4/BaTiO3Multilayered compound magnetoelectricity is ceramic, between layers boundary
Limit without dephasign and interpenetrates clearly, and with high consistency.It ensure that interface coupling between layers to greatest extent
Close effect so that multi-layer ceramics magnetic electricity performance greatly improves.
It compares and the prior art, the prior art is by BaTiO3And CoFe2O4Two-phase mechanical mixture, is then put using plasma
Electricity sintering is in blocks, has reached the promotion of magnetoelectric effect.But in the sample of mechanical mixture, there are great leakies, reduce
The piezoelectric properties of composite ceramics.Simultaneously because the clamp effect inside mixing material, magnetostrictive effect are greatly limited
System.And the magnetoelectric effect of composite material is proportional to piezoelectric property and magnetostrictive effect, thus BaTiO3And CoFe2O4Two cameras
The composite ceramics magnetic electricity performance being sintered after tool mixing is unable to reach optimization.In contrast, three layers of composite ceramics tool in this programme
There are better magnetostrictive effect and piezoelectric property, and the interface coupling of two kinds of substances has clearly been greatly optimized in interface.The present invention
BaTiO obtained3/CoFe2O4/BaTiO3Multilayered compound magnetoelectricity ceramics have magnetoelectricity effect maximum in known magnetoelectric ceramic
It should.
The ceramics that the present invention is prepared are without dephasign, consistency is high and has huge magneto-electric coupled coefficient and significant magnetic
Electrical anisotropy is a kind of ferroelectric-ferromagnetic-magnetoelectricity multifunctional ceramic material with broad prospect of application；The preparation of the present invention
Compared with traditional solid reaction process, the ceramic phase temperature that sinters into significantly reduces method, is a kind of low-temp ceramics sintering process,
In addition, this preparation process has easy to operate, the period is short, of low cost, environment-protecting and non-poisonous, the features such as without special atmosphere.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is by different-thickness ratio (t between three layers in embodiment 1 to embodiment 4B:tC:tB=1:0.5:1,1:1:1,1:
2:1 and 1:3:1) the BaTiO3/CoFe2O4/BaTiO3 multilayered compound magnetoelectricity ceramics samples of assembling and spark plasma sintering
XRD spectrum；
Fig. 2 is by the BaTiO3/CoFe2O4/BaTiO3 multi-layer ceramics Sample Scan electron microscopes that are sintered in embodiment 1
Photo and X-ray energy spectrum.
Fig. 3 is by different-thickness ratio (t between three layers in embodiment 1 to embodiment 4B:tC:tB=1:0.5:1,1:1:1,1:
2:1 and 1:3:1) the BaTiO3/CoFe2O4/BaTiO3 layer compound magnetoelectric ceramics samples of assembling and spark plasma sintering
Magneto-electric coupled coefficient-applying dc magnetic field (aE- H) curve graph.
Fig. 4 is by the magnetoelectricity of BaTiO3/CoFe2O4/BaTiO3 multilayered compound magnetoelectricity ceramics samples that is sintered in embodiment 3
Effect anisotropy (αE- θ) curve.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
The CoFe for being about 30nm by a certain amount of particle size2O4It is fitted into the carbon grinding tool of internal diameter 10mm outer diameters 40mm, by grinding tool
It is put into spark plasma sintering machine, and powder pressure is formed piece by the pressure for applying 60MPa, is packed into this step by controlling
Grinding tool CoFe2O4Amount control sheet thickness.The BaTiO for being about 600nm by a certain amount of particle size3It is packed into internal diameter 10mm outer diameters
In the carbon grinding tool of 40mm, grinding tool is put into spark plasma sintering machine, and powder pressure is formed piece by the pressure for applying 60MPa,
Grinding tool BaTiO is packed by control in this step3Amount control sheet thickness.By the CoFe of pre-molding2O4And BaTiO3Piece
According to BaTiO3/CoFe2O4/BaTiO3Sequence be fitted into the carbon grinding tool of internal diameter 10mm outer diameters 40mm, pass through rate-determining steps (1)
(2) amount of powder in so that BaTiO3/CoFe2O4/BaTiO3Thickness ratio between three layers is tB:tC:tB=1:0.5:1.It will
Equipped with BaTiO3/CoFe2O4/BaTiO3The grinding tool of three-decker is put into spark plasma sintering machine, and sintering process is using infrared
Temperature control, is warming up to 600 DEG C in 10 minutes, and 1100 DEG C were warming up to using one minute, is warming up to 1150 DEG C within 5 minutes later, Ran Houbao
Temperature 5 minutes, naturally cools to room temperature, cancels additional pressure, takes out sample.The sample of sintering is put into 600 DEG C of annealing 5 of Muffle furnace
Hour except carbon, obtains BaTiO3/CoFe2O4/BaTiO3Multilayered compound magnetoelectricity ceramics.
BaTiO is prepared using embodiment 13/CoFe2O4/BaTiO3XRD such as Fig. 1 institutes of multilayered compound magnetoelectricity ceramics
Show, remove CoFe in ceramics as can be seen from Figure 12O4And BaTiO3Crystalline phase it is outer without other dephasigns.It is prepared using embodiment 1
BaTiO3/CoFe2O4/BaTiO3The TEM and EDX of multilayered compound magnetoelectricity ceramics are as shown in Fig. 2, as can be seen from Figure 2 in ceramics
Distinct between layers has very high consistency without interpenetrating with miscellaneous generation, ceramics inside.By BaTiO3/
CoFe2O4/BaTiO3Multilayered compound magnetoelectricity ceramics coat elargol and burn-on electrode, the magnetoelectric effect and external dc of the sample
Relationship (the α in magnetic fieldE- H) as shown in Figure 3.The curve that embodiment 1 represents in Fig. 1 and Fig. 3 is Sample A.
Embodiment 2
The CoFe for being about 40nm by a certain amount of particle size2O4It is fitted into the carbon grinding tool of internal diameter 10mm outer diameters 40mm, by grinding tool
It is put into spark plasma sintering machine, and powder pressure is formed piece by the pressure for applying 60MPa, is packed into this step by controlling
Grinding tool CoFe2O4Amount control sheet thickness.The BaTiO for being about 500nm by a certain amount of particle size3It is packed into internal diameter 10mm outer diameters
In the carbon grinding tool of 40mm, grinding tool is put into spark plasma sintering machine, and powder pressure is formed piece by the pressure for applying 60MPa,
Grinding tool BaTiO is packed by control in this step3Amount control sheet thickness.By the CoFe of pre-molding2O4And BaTiO3Piece
According to BaTiO3/CoFe2O4/BaTiO3Sequence be fitted into the carbon grinding tool of internal diameter 10mm outer diameters 40mm, pass through rate-determining steps (1)
(2) amount of powder in so that BaTiO3/CoFe2O4/BaTiO3Thickness ratio between three layers is tB:tC:tB=1:1:1.It will dress
There is BaTiO3/CoFe2O4/BaTiO3The grinding tool of three-decker is put into spark plasma sintering machine, and sintering process uses infrared control
Temperature, is warming up to 600 DEG C in 10 minutes, and 1100 DEG C were warming up to using one minute, is warming up to 1150 DEG C within 5 minutes later, then keeps the temperature 5
Minute, room temperature is naturally cooled to, cancels additional pressure, takes out sample.It is small that the sample of sintering is put into 600 DEG C of annealing 5 of Muffle furnace
When except carbon, obtain BaTiO3/CoFe2O4/BaTiO3Multilayered compound magnetoelectricity ceramics.
BaTiO is prepared using embodiment 23/CoFe2O4/BaTiO3XRD such as Fig. 1 institutes of multilayered compound magnetoelectricity ceramics
Show, remove CoFe in ceramics as can be seen from Figure 12O4And BaTiO3Crystalline phase it is outer without other dephasigns.By BaTiO3/CoFe2O4/
BaTiO3Multilayered compound magnetoelectricity ceramics coat elargol and burn-on electrode, the magnetoelectric effect of the sample and the pass of applying dc magnetic field
It is (αE- H) as shown in Figure 3.The curve that embodiment 2 represents in Fig. 1 and Fig. 3 is Sample B.
Embodiment 3
The CoFe for being about 50nm by a certain amount of particle size2O4It is fitted into the carbon grinding tool of internal diameter 10mm outer diameters 40mm, by grinding tool
It is put into spark plasma sintering machine, and powder pressure is formed piece by the pressure for applying 60MPa, is packed into this step by controlling
Grinding tool CoFe2O4Amount control sheet thickness.The BaTiO for being about 500nm by a certain amount of particle size3It is packed into internal diameter 10mm outer diameters
In the carbon grinding tool of 40mm, grinding tool is put into spark plasma sintering machine, and powder pressure is formed piece by the pressure for applying 60MPa,
Grinding tool BaTiO is packed by control in this step3Amount control sheet thickness.By the CoFe of pre-molding2O4And BaTiO3Piece
According to BaTiO3/CoFe2O4/BaTiO3Sequence be fitted into the carbon grinding tool of internal diameter 10mm outer diameters 40mm, pass through rate-determining steps (1)
(2) amount of powder in so that BaTiO3/CoFe2O4/BaTiO3Thickness ratio between three layers is tB:tC:tB=1:2:1.It will dress
There is BaTiO3/CoFe2O4/BaTiO3The grinding tool of three-decker is put into spark plasma sintering machine, and sintering process uses infrared control
Temperature, is warming up to 600 DEG C in 10 minutes, and 1100 DEG C were warming up to using one minute, is warming up to 1150 DEG C within 5 minutes later, then keeps the temperature 5
Minute, room temperature is naturally cooled to, cancels additional pressure, takes out sample.It is small that the sample of sintering is put into 600 DEG C of annealing 5 of Muffle furnace
When except carbon, obtain BaTiO3/CoFe2O4/BaTiO3Multilayered compound magnetoelectricity ceramics.
BaTiO is prepared using embodiment 33/CoFe2O4/BaTiO3XRD such as Fig. 1 institutes of multilayered compound magnetoelectricity ceramics
Show, remove CoFe in ceramics as can be seen from Figure 12O4And BaTiO3Crystalline phase it is outer without other dephasigns.By BaTiO3/CoFe2O4/
BaTiO3Multilayered compound magnetoelectricity ceramics coat elargol and burn-on electrode, the magnetoelectric effect of the sample and the pass of applying dc magnetic field
It is (αE- H) and externally-applied magnetic field direction relationship (αE- θ) as shown in Figure 3 and Figure 4.The curve that embodiment 3 represents in Fig. 1 and Fig. 3
For Sample C.
Embodiment 4
The CoFe for being about 30nm by a certain amount of particle size2O4It is fitted into the carbon grinding tool of internal diameter 10mm outer diameters 40mm, by grinding tool
It is put into spark plasma sintering machine, and powder pressure is formed piece by the pressure for applying 60MPa, is packed into this step by controlling
Grinding tool CoFe2O4Amount control sheet thickness.The BaTiO for being about 500nm by a certain amount of particle size3It is packed into internal diameter 10mm outer diameters
In the carbon grinding tool of 40mm, grinding tool is put into spark plasma sintering machine, and powder pressure is formed piece by the pressure for applying 60MPa,
Grinding tool BaTiO is packed by control in this step3Amount control sheet thickness.By the CoFe of pre-molding2O4And BaTiO3Piece
According to BaTiO3/CoFe2O4/BaTiO3Sequence be fitted into the carbon grinding tool of internal diameter 10mm outer diameters 40mm, pass through rate-determining steps (1)
(2) amount of powder in so that BaTiO3/CoFe2O4/BaTiO3Thickness ratio between three layers is tB:tC:tB=1:3:1.It will dress
There is BaTiO3/CoFe2O4/BaTiO3The grinding tool of three-decker is put into spark plasma sintering machine, and sintering process uses infrared control
Temperature, is warming up to 600 DEG C in 10 minutes, and 1100 DEG C were warming up to using one minute, is warming up to 1150 DEG C within 5 minutes later, then keeps the temperature 5
Minute, room temperature is naturally cooled to, cancels additional pressure, takes out sample.It is small that the sample of sintering is put into 600 DEG C of annealing 5 of Muffle furnace
When except carbon, obtain BaTiO3/CoFe2O4/BaTiO3Multilayered compound magnetoelectricity ceramics.
BaTiO is prepared using embodiment 43/CoFe2O4/BaTiO3XRD such as Fig. 1 institutes of multilayered compound magnetoelectricity ceramics
Show, remove CoFe in ceramics as can be seen from Figure 12O4And BaTiO3Crystalline phase it is outer without other dephasigns.By BaTiO3/CoFe2O4/
BaTiO3Multilayered compound magnetoelectricity ceramics coat elargol and burn-on electrode, the magnetoelectric effect of the sample and the pass of applying dc magnetic field
It is (αE- H) as shown in Figure 3.The curve that embodiment 4 represents in Fig. 1 and Fig. 3 is Sample D.
The BaTiO prepared using above method3/CoFe2O4/BaTiO3Multilayered compound magnetoelectricity ceramics are without dephasign consistency height
And there is big magneto-electric coupled coefficient, it is a kind of ferroelectric-ferromagnetic-magnetoelectricity multifunctional ceramic material with broad prospect of application,
It can be used as the component of electronic sensor, mass data reservoir part etc..To the characterization of sample microstructure, using X-ray diffraction
Instrument (XRD) and surface sweeping formula electron microscope (SEM) analyze its object phase and micromorphology.Using the magneto-electric coupled coefficient tester of room temperature
Measure the magneto-electric coupled property of sample.
Fig. 1 is given in embodiment 1 to embodiment 4 by different-thickness ratio (t between three layersB:tC:tB=1:0.5:1,1:1:
1,1:2:1 and 1:3:1) BaTiO of assembling and SPS sintering3/CoFe2O4/BaTiO3The XRD of multilayered compound magnetoelectricity ceramics sample
Collection of illustrative plates, the ceramic complete crystallization being according to said method sintered are generated without dephasign.
Fig. 2 gives the SEM photograph of the sample in embodiment 1 and EDX collection of illustrative plates, and Fig. 2 (a), (b), (c) is sample in cross section
SEM photograph, it is seen that be sintered later distinct between layers, sample interior particle packing is close, illustrates that plasma discharge is burnt
The ceramics sample of knot has very high consistency.Fig. 2 (d), (e) are line A and the line B-scans along Fig. 2 (c) respectively
EDX collection of illustrative plates.Nothing is interpenetrated and is generated without dephasign between EDX results illustrate two-phase.
Fig. 3 is given in embodiment 1 to embodiment 4 by different-thickness ratio (t between three layersB:tC:tB=1:0.5:1,1:1:
1,1:2:1 and 1:3:1) BaTiO of assembling and spark plasma sintering3/CoFe2O4/BaTiO3Multilayered compound magnetoelectricity Ceramic Like
The magnetoelectric effect of product and the relational graph of applying dc magnetic field.It can be seen that sample shows good magnetoelectric effect,
Work as BaTiO3/CoFe2O4/BaTiO3Thickness ratio is 1:2:When 1, magnetoelectric effect reaches maximum.For same sample αE33
Value be more than αE31, illustrate that magnetoelectric effect has anisotropy.
Fig. 4 is the magnetoelectric effect anisotropy figure of the sample in embodiment 3.The direction of externally-applied magnetic field is shown to magnetic
The influence of coupling effect is extremely apparent, and the anisotropic experimental data of sample magnetoelectric effect and theoretical calculation data are extremely kissed
It closes.Data above illustrates that spark plasma sintering is a kind of magnetoelectric ceramic preparation process being particularly suitable for, and can be extended to magnetic
The common method of the preparation of electroceramics.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (7)
1. a kind of BaTiO3/CoFe2O4/BaTiO3The preparation method of nanometer multilayer compound magnetoelectric ceramics, which is characterized in that including with
Lower step：
(1) by CoFe2O4It is fitted into carbon grinding tool, grinding tool is put into spark plasma sintering machine and is pre-sintered, and apply pressure pressure knot
In flakes；
(2) by BaTiO3It is fitted into carbon grinding tool, grinding tool is put into spark plasma sintering machine and is pre-sintered, and apply pressure pressure knot
In flakes；
(3) by the CoFe of pre-molding2O4Piece and BaTiO3Piece is according to BaTiO3/CoFe2O4/BaTiO3Sequence be packed into internal diameter
10mm, outer diameter 40mm carbon grinding tool in；
(4) grinding tool equipped with BaTiO3/CoFe2O4/BaTiO3 three-layer tablet structures is put into spark plasma sintering machine, applied
Pressure, is warming up to 600 DEG C in 10 minutes, and 1100 DEG C were warming up to using 1 minute, is warming up to 1150 DEG C within 5 minutes later, then keeps the temperature
5 minutes, room temperature is naturally cooled to, cancels additional pressure, takes out sample；
(5) sample of sintering is put into the annealing 5 hours of 600 DEG C of Muffle furnace except carbon, obtains BaTiO3/CoFe2O4/BaTiO3Multilayer is answered
Close magnetoelectric ceramic.
2. a kind of BaTiO as described in claim 13/CoFe2O4/BaTiO3The preparation method of nanometer multilayer compound magnetoelectric ceramics,
It is characterized in that, CoFe in step (1)2O4Particle size be 30~50nm.
3. a kind of BaTiO as described in claim 13/CoFe2O4/BaTiO3The preparation method of nanometer multilayer compound magnetoelectric ceramics,
It is characterized in that, BaTiO in step (2)3Particle size be 500~600nm.
4. a kind of BaTiO as described in claim 13/CoFe2O4/BaTiO3The preparation method of nanometer multilayer compound magnetoelectric ceramics,
It is characterized in that, BaTiO in step (3)3/CoFe2O4/BaTiO3Thickness ratio between three-layer tablet structure is 1：(0.5~3):1.
5. a kind of BaTiO as described in claim 13/CoFe2O4/BaTiO3The preparation method of nanometer multilayer compound magnetoelectric ceramics,
It is characterized in that, sintering process uses infrared temperature control in step (4).
6. a kind of BaTiO as described in claim 13/CoFe2O4/BaTiO3The preparation method of nanometer multilayer compound magnetoelectric ceramics,
It is characterized in that, the pressure applied in step (1), (2), (4) is 40~80MPa.
7. a kind of BaTiO as described in claim 13/CoFe2O4/BaTiO3The preparation method of nanometer multilayer compound magnetoelectric ceramics,
It is characterized in that, the temperature being pre-sintered in step (1), (2) is 600 DEG C, sintering time 30min.
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