WO2022127067A1 - Bifeo3-bi0.5na0.5tio3-based ceramic solid solution having magnetoelectric coupling, preparation method therefor and application thereof - Google Patents

Bifeo3-bi0.5na0.5tio3-based ceramic solid solution having magnetoelectric coupling, preparation method therefor and application thereof Download PDF

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WO2022127067A1
WO2022127067A1 PCT/CN2021/102615 CN2021102615W WO2022127067A1 WO 2022127067 A1 WO2022127067 A1 WO 2022127067A1 CN 2021102615 W CN2021102615 W CN 2021102615W WO 2022127067 A1 WO2022127067 A1 WO 2022127067A1
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bifeo
solid solution
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黄文娟
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常州工学院
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/46—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
    • C04B35/475—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 bismuth titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets

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  • the invention relates to the technical field of preparation of a novel multiferroic BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based material, in particular to a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution and a preparation method and application thereof .
  • Multiferroic materials are a special class of solid-state compounds that contain at least two order parameters of magnetic order, ferroelectric order or piezoelastic order parameters.
  • magneto-electric or magneto-electric-strain coexist, and this magnetoelectric effect enables the energy stored between the magnetic field and the electric field to be converted into each other, and there is a magneto-electric cross-regulation effect. That is, by applying an electric field to control the magnetization or applying a magnetic field to control the ferroelectric polarization, this provides a way to read or write information on the storage medium by different means, and it is possible to develop a new concept of next-generation information storage. functional device.
  • multiferroic materials In addition to data storage, multiferroic materials also have a wide range of potential applications in sensors, actuators, and more. Therefore, the study of multiferroic materials has become a research hotspot in the field of current international functional materials.
  • Bi 0.5 Na 0.5 TiO 3 and BiFeO 3 both showed rhombohedral R3c structure at room temperature, and the obtained full-component solid solution BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 system showed rhombohedral R3c structure at room temperature.
  • Previous studies have shown that the structure, electrical and magnetic properties of quasi-homomorphic phase boundaries can be tailored through compositional control in solid solutions. Therefore, how to construct a BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 based solid solution quasi-isotype phase boundary and tailor its magnetoelectric coupling effect on the basis of improving the leakage current of the ceramic bulk deserves further study.
  • the purpose of the present invention is to provide a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution
  • the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution of the present invention has stable structure, electrical properties, It has excellent magnetic properties and magnetoelectric coupling properties, and can be used in sensors or memories
  • another object of the present invention is to provide a simple method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution.
  • the magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution (ternary multiferroic material) provided by the invention has stable structure, excellent electrical properties, magnetic properties and magnetoelectric coupling properties.
  • An application of magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution characterized in that the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution (ie (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 ternary solid solution) used in sensors or memories.
  • a method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution characterized in that the method comprises the following steps:
  • the obtained ceramic sheet is sintered for a second time, and then quenched after sintering to obtain a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, which is (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 ternary multiferroic material.
  • the bismuth source described in step (1) is bismuth nitrate pentahydrate (Bi(NO 3 ) 3 .5H 2 O); the iron source is ferric nitrate nonahydrate (Fe(NO 3 ) 3 .9H) 2 O); the sodium source is sodium acetate (Na(CH 3 COO)); the titanium source is tetrabutyl titanate; the calcium source is calcium acetate (Ca(CH 3 COO) 2 ) .
  • step (2) is citric acid monohydrate (C 6 H 8 O 7 ⁇ H 2 O).
  • the mol ratio of the addition amount of the complexing agent described in the step (2) and the sum of the cations is 1.6:1; the stirring time is 3-5 hours; the glacial acetic acid, the acetylacetone and the The volume ratio of the ethanolamine is 5:1:1, and the mass ratio of the raw material to the mixed solution is 1:3.
  • the molar ratio of the added amount of the complexing agent (citric acid monohydrate) to the sum of metal cations in the raw material is 1.6:1.
  • the drying temperature in step (3) is 80-90°C, and the drying time is 8-12 hours; the pre-sintering temperature is 400-800° C., and the pre-sintering time is 3 -12 hours.
  • step (4) the obtained precursor powder is manually ground in an agate mortar for 0.5-1 hour, and the ground precursor powder is pressed under a pressure of 15-20 MPa to obtain a diameter of 8-12 mm and a thickness of 8-12 mm. For 1-2 mm ceramic pieces.
  • step ( 5 ) the obtained ceramic sheet is sintered at 1050-1250° C. for a second time, and the sintering time is 2-5 hours.
  • Bi 0.5 Na 0.5 TiO 3 based ceramic solid solution To prevent the generation of impurity phases and optimize the sample properties, the sintered samples were quenched with deionized water.
  • CaTiO 3 with orthogonal Pbnm structure is introduced into BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 solid solution, and BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -CaTiO 3 ternary solid solution is obtained, and the orthogonal structure is constructed through component control / rhombohedral quasi-homotype phase boundary, the ceramic block was prepared by pechini method, quenched with deionized water to reduce the leakage current of the system, and a BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 based ceramic solid solution with room temperature magnetoelectric coupling effect was obtained.
  • the invention adopts the improved pechini method to prepare the precursor powder, introduces a quenching process when sintering the ceramic block, and finally enhances the room temperature magnetoelectric coupling effect by preparing a ternary solid solution system.
  • the precursor powder is prepared by the improved pechini method, the inorganic salt raw materials are more easily dissolved, the raw materials can be uniformly mixed at the molecular level, and the synthesis and sintering temperature can be reduced; and the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 prepared by the quenching process
  • the base ceramic solid solution is denser and the leakage current is smaller.
  • the quasi-homomorphic phase boundary of the system is regulated, and a multiferroic quasi-homomorphic phase boundary with room temperature ferromagnetism is realized.
  • the room temperature magnetoelectric coupling effect of BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is realized.
  • the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution (ternary multiferroic material) with room temperature magnetoelectric coupling provided by the invention has stable structure, excellent electrical properties, magnetic properties and magnetoelectric coupling properties, and can be applied to sensor or memory.
  • Fig. 1 is the X-ray diffraction pattern of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Examples 1-3 of the present invention
  • Fig. 2 is the X-ray diffraction pattern of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Examples 4-12 of the present invention
  • FIG. 9 shows the magneto-dielectric properties of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Examples 13-15 of the present invention.
  • a method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution comprising the following specific steps:
  • a method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution comprising the following specific steps:
  • a method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution comprising the following specific steps:
  • a method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution comprising the following specific steps:
  • a method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution comprising the following specific steps:
  • the obtained precursor powder was manually ground in an agate mortar for 0.6 hours, and then pressed under the pressure of 18MPa to obtain a ceramic sheet with a diameter of 12mm and a thickness of 2mm;
  • a method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution comprising the following specific steps:
  • the obtained precursor powder was manually ground in an agate mortar for 1 hour, and then pressed under the pressure of 16MPa to obtain a ceramic sheet with a diameter of 12mm and a thickness of 1mm;
  • Example 7 and Example 1 are the same as Example 1 except that the ratio of raw materials is different, and other preparation conditions are the same.
  • Example 8 and Example 2 are the same as Example 2 except that the raw material ratio is different, and other preparation conditions are the same.
  • Example 9 Except that the ratio of raw materials is different from Example 9 and Example 3, all other preparation conditions are the same as Example 3.
  • Example 10 and Example 4 are the same as Example 4 except that the ratio of raw materials is different.
  • Example 11 and Example 5 are the same as Example 5 except that the raw material ratio is different, and other preparation conditions are the same.
  • Example 12 and Example 6 are the same as Example 6 except that the ratio of raw materials is different.
  • Example 13 and Example 1 are the same as Example 1 except that the ratio of raw materials is different, and other preparation conditions are the same.
  • Example 14 and Example 2 are the same as Example 2 except that the raw material ratio is different, and other preparation conditions are the same.
  • Example 15 and Example 3 are the same as Example 3 except that the raw material ratio is different, and other preparation conditions are the same.
  • Example 16 and Example 1 are the same as Example 1 except that the ratio of raw materials is different, and other preparation conditions are the same.
  • Example 17 and Example 2 are the same as Example 2 except that the raw material ratio is different, and other preparation conditions are the same.
  • Example 18 and Example 3 are the same as Example 3 except that the ratio of raw materials is different.
  • the structure of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling obtained in the above examples 1-18 was tested by X-ray powder diffraction: the instrument used was the model PhilipsX'pertPRO, and the target material was Cu target, the wavelength ⁇ is 0.15406nm, the scanning range is 10°-90°, and the scanning rate is 10°/min.
  • Example 1 the test results of Examples 1-3 are shown in Figure 1; the test results of Examples 4-12 are shown in Figure 2; the test results of Examples 13-15 are shown in Figure 3; The test results are shown in Figure 4; it can be seen from the above Figures 1-4 that the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Example 1-18 is a pure perovskite
  • the four series of examples all experienced a structural transition from rhombohedral phase to orthorhombic phase with the increase of y value (CaTiO 3 content), and the rhombohedral-orthomorphic phase boundary was constructed by composition control.
  • Examples 7, 8, 13, 14, 16, and 17 are located near the rhombohedral-orthogonal quasi-isotype phase boundary, and the test results of their PE loops are shown in Figure 5 (a in the figure corresponds to Examples 7, b Corresponding to Example 8, c corresponds to Example 13, d corresponds to Example 14, e corresponds to Example 16, and f corresponds to Example 17); the ferroelectric properties near the phase boundary are significantly better than other samples, and with Bi 0.5 Na With the increase of 0.5 TiO 3 content, the leakage current decreases significantly. In Examples 14 and 16, the remanent polarization can reach 33.67 ⁇ C/cm 2 and 30.91 ⁇ C/cm 2 .
  • the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution ((1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 ) with room temperature magnetoelectric coupling prepared by the invention has stable structure, electrical It has excellent performance, magnetic properties and magnetoelectric coupling properties, so it can be used in sensors or memories to replace existing ferroelectric materials.
  • the present invention is based on the search for new multiferroic BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 based materials.
  • BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -CaTiO 3 (BFO-BNTO-CTO for short), as a multiferroic material with both room temperature ferroelectricity and ferromagnetism, has good research value and application value.
  • the first is the synthesis process of ceramics. Through repeated experimental exploration, the optimal sintering temperature and sintering time are explored, and finally a ceramic sample with the largest magnetoelectric coupling at room temperature is obtained.
  • the structure is determined by an X-ray diffractometer, and then its ferroelectric properties, Measurement and analysis of magnetic properties and magnetoelectric coupling properties.

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Abstract

Disclosed are a BiFeO3-Bi0.5Na0.5TiO3-based ceramic solid solution having room temperature magnetoelectric coupling, a preparation method therefor and an application thereof. The chemical composition of the ceramic solid solution is (1.0-x-y)BiFeO3-xBi0.5Na0.5TiO3-yCaTiO3, wherein x=0-0.3 and y=0-0.4. The preparation method comprises: (1) accurately weighing a bismuth source, an iron source, a sodium source, a titanium source and a calcium source according to the stoichiometric ratio of (1.0-x-y)BiFeO3-xBi0.5Na0.5TiO3-yCaTiO3; (2) adding a raw material to a mixed solution of glacial acetic acid, acetylacetone, a complexing agent and ethanolamine, and stirring same to obtain a clear sol; (3) first drying the sol, and then pre-sintering same to obtain a precursor powder; (4) grinding the precursor powder and then pressing same to obtain a ceramic sheet; and (5) sintering the ceramic sheet for a second time, and quenching same after sintering so as to obtain a BiFeO3-Bi0.5Na0.5TiO3-based ceramic solid solution having room temperature magnetoelectric coupling. The BiFeO3-Bi0.5Na0.5TiO3-based ceramic solid solution having room temperature magnetoelectric coupling provided in the present invention has a stable structure and excellent electrical properties, magnetic properties and magnetoelectric coupling properties, and may be applied in a sensor or a memory; in addition, the preparation method of the present invention is simple.

Description

磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体及其制备方法与应用 Magnetoelectrically coupled BiFeO 3-Bi 0.5Na 0.5TiO 3-base ceramic solid solution and its preparation method and application 技术领域technical field
本发明涉及一种新型多铁性BiFeO 3-Bi 0.5Na 0.5TiO 3基材料的制备技术领域，具体涉及一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体及其制备方法与应用。 The invention relates to the technical field of preparation of a novel multiferroic BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based material, in particular to a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution and a preparation method and application thereof .
背景技术Background technique
多铁性材料是一类特殊的固态化合物，其中至少包含磁有序、铁电有序或压弹序参量中的两个序参量。而在磁电耦合多铁性材料中，磁-电或磁-电-应变共存，且这种磁电效应使得储存在磁场和电场之间的能量能够相互转化，存在磁-电交叉调控效应，即通过施加电场来调控磁化强度或施加磁场来调控铁电极化强度，这就提供了用不同手段在存储介质上读取或写入信息的途径，就有可能开发出全新概念的下一代信息存储功能器件。除数据存储外，多铁性材料在传感器、制动器等方面也具有广泛的潜在应用价值。因此，对多铁性材料的研究已成为当前国际功能材料等领域中的一个研究热点。Multiferroic materials are a special class of solid-state compounds that contain at least two order parameters of magnetic order, ferroelectric order or piezoelastic order parameters. In magnetoelectrically coupled multiferroic materials, magneto-electric or magneto-electric-strain coexist, and this magnetoelectric effect enables the energy stored between the magnetic field and the electric field to be converted into each other, and there is a magneto-electric cross-regulation effect. That is, by applying an electric field to control the magnetization or applying a magnetic field to control the ferroelectric polarization, this provides a way to read or write information on the storage medium by different means, and it is possible to develop a new concept of next-generation information storage. functional device. In addition to data storage, multiferroic materials also have a wide range of potential applications in sensors, actuators, and more. Therefore, the study of multiferroic materials has become a research hotspot in the field of current international functional materials.
BiFeO 3-Bi 0.5Na 0.5TiO 3固溶体相较于室温单相多铁性材料BiFeO 3，Bi 0.5Na 0.5TiO 3的引入打破了螺旋型自旋结构被，磁性改善明显。关于BiFeO 3-Bi 0.5Na 0.5TiO 3固溶体体系多铁性的研究已引发了广泛的关注。但是，在陶瓷块体烧结过程中Bi和Na易挥发，漏电流大，电铁性改进有限。且Bi 0.5Na 0.5TiO 3和BiFeO 3室温都表现为菱方R3c结构，得到的全组分固溶的BiFeO 3-Bi 0.5Na 0.5TiO 3体系室温均表现为菱方R3c结构。已有研究表明，在固溶体中通过组分调控构建准同型相界，其结构、 电学、磁学性质都可以进行剪裁。因此，如何在改善陶瓷块体的漏电流的基础上，构建BiFeO 3-Bi 0.5Na 0.5TiO 3基固溶体准同型相界，剪裁其磁电耦合效应值得深入研究。 Compared with the room temperature single-phase multiferroic material BiFeO 3 , the introduction of Bi 0.5 Na 0.5 TiO 3 breaks the helical spin structure of BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 solid solution, and the magnetic properties are improved significantly. The research on the multiferroicity of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 solid solution system has attracted extensive attention. However, Bi and Na are easily volatilized during the sintering process of ceramic bulk, the leakage current is large, and the improvement of ferroelectricity is limited. And Bi 0.5 Na 0.5 TiO 3 and BiFeO 3 both showed rhombohedral R3c structure at room temperature, and the obtained full-component solid solution BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 system showed rhombohedral R3c structure at room temperature. Previous studies have shown that the structure, electrical and magnetic properties of quasi-homomorphic phase boundaries can be tailored through compositional control in solid solutions. Therefore, how to construct a BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 based solid solution quasi-isotype phase boundary and tailor its magnetoelectric coupling effect on the basis of improving the leakage current of the ceramic bulk deserves further study.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，本发明的磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，其结构稳定，电学性能，磁学性能以及磁电耦合性能优异，能有应用于传感器或存储器中；本发明的另一目的在于提供一种简单的磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法。 The purpose of the present invention is to provide a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution of the present invention has stable structure, electrical properties, It has excellent magnetic properties and magnetoelectric coupling properties, and can be used in sensors or memories; another object of the present invention is to provide a simple method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution.
本发明是通过如下技术方案实现的：The present invention is achieved through the following technical solutions:
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，其特征在于，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0-0.3，y＝0-0.4。本发明所提供的磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体(三元多铁性材料)其结构稳定，电学性能，磁学性能以及磁电耦合性能优异。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, characterized in that the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0-0.3, y=0-0.4. The magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution (ternary multiferroic material) provided by the invention has stable structure, excellent electrical properties, magnetic properties and magnetoelectric coupling properties.
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的应用，其特征在于，将所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体(即(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3三元固溶体)用于传感器或存储器中。 An application of magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, characterized in that the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution (ie (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 ternary solid solution) used in sensors or memories.
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，其特征在于，该方法包括如下步骤： A method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, characterized in that the method comprises the following steps:
(1)按照(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3分子式的化 学计量比准确称取铋源、铁源、钠源、钛源和钙源作为原料； (1) Accurately weigh bismuth source, iron source, sodium source, titanium source and calcium source as raw materials according to the stoichiometric ratio of (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 molecular formula;
(2)将上述称取好的原料加入到冰醋酸(CH 3COOH)、乙酰丙酮(CH 3COCH 2COCH 3)、络合剂和乙醇胺(C 2H 7NO)的混合溶液中，并搅拌得到澄清的溶胶； (2) adding the above-weighed raw materials to the mixed solution of glacial acetic acid (CH 3 COOH), acetylacetone (CH 3 COCH 2 COCH 3 ), complexing agent and ethanolamine (C 2 H 7 NO), and stirring A clear sol is obtained;
(3)将所得溶胶烘干，然后预烧结，得到前驱体粉末；(3) drying the obtained sol, and then pre-sintering to obtain the precursor powder;
(4)将所得前驱体粉末研磨，然后压制，得到陶瓷片；(4) the obtained precursor powder is ground and then pressed to obtain a ceramic sheet;
(5)将所得到的陶瓷片进行二次烧结，烧结后淬火处理，即可得到磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，即为(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3三元多铁性材料。 (5) The obtained ceramic sheet is sintered for a second time, and then quenched after sintering to obtain a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, which is (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 ternary multiferroic material.
进一步地，步骤(1)中所述的铋源为五水合硝酸铋(Bi(NO 3) 3·5H 2O)；所述的铁源为九水合硝酸铁(Fe(NO 3) 3·9H 2O)；所述的钠源为乙酸钠(Na(CH 3COO))；所述的钛源为钛酸四丁酯；所述的钙源为乙酸钙(Ca(CH 3COO) 2)。 Further, the bismuth source described in step (1) is bismuth nitrate pentahydrate (Bi(NO 3 ) 3 .5H 2 O); the iron source is ferric nitrate nonahydrate (Fe(NO 3 ) 3 .9H) 2 O); the sodium source is sodium acetate (Na(CH 3 COO)); the titanium source is tetrabutyl titanate; the calcium source is calcium acetate (Ca(CH 3 COO) 2 ) .
进一步地，步骤(2)中所述的络合剂为一水合柠檬酸(C 6H 8O 7·H 2O)。 Further, the complexing agent described in step (2) is citric acid monohydrate (C 6 H 8 O 7 ·H 2 O).
进一步地，步骤(2)中所述的络合剂的添加量与阳离子总和的摩尔比为1.6:1；所述的搅拌时间为3-5小时；所述冰醋酸、所述乙酰丙酮和所述乙醇胺的体积比为5:1:1，且所述原料与所述混合溶液的质量比为1:3。具体的，所述络合剂(一水合柠檬酸)的添加量与所述原料中金属阳离子总和的摩尔比为1.6:1。Further, the mol ratio of the addition amount of the complexing agent described in the step (2) and the sum of the cations is 1.6:1; the stirring time is 3-5 hours; the glacial acetic acid, the acetylacetone and the The volume ratio of the ethanolamine is 5:1:1, and the mass ratio of the raw material to the mixed solution is 1:3. Specifically, the molar ratio of the added amount of the complexing agent (citric acid monohydrate) to the sum of metal cations in the raw material is 1.6:1.
进一步地，步骤(3)中所述的烘干温度为80-90℃，且烘干时间为8-12小时；所述的预烧结的温度为400-800℃，且预烧结的时间为3-12小时。Further, the drying temperature in step (3) is 80-90°C, and the drying time is 8-12 hours; the pre-sintering temperature is 400-800° C., and the pre-sintering time is 3 -12 hours.
进一步地，步骤(4)将所得前驱体粉末在玛瑙研钵中手动研磨0.5-1小时，将研磨后的前驱体粉末在15-20MPa的压强下压制成形，得到直径为8-12毫米、厚度为1-2毫米的陶瓷片。Further, in step (4), the obtained precursor powder is manually ground in an agate mortar for 0.5-1 hour, and the ground precursor powder is pressed under a pressure of 15-20 MPa to obtain a diameter of 8-12 mm and a thickness of 8-12 mm. For 1-2 mm ceramic pieces.
进一步地，步骤(5)将所得陶瓷片在1050-1250℃下进行二次烧结，且烧结时间为2-5小时，烧结后用去离子水进行淬火处理，即可得到磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体。为了防止杂相的产生和优化样品性能，烧结样品采用去离子水淬火处理。 Further, in step ( 5 ), the obtained ceramic sheet is sintered at 1050-1250° C. for a second time, and the sintering time is 2-5 hours. Bi 0.5 Na 0.5 TiO 3 based ceramic solid solution. To prevent the generation of impurity phases and optimize the sample properties, the sintered samples were quenched with deionized water.
本发明将正交Pbnm结构的CaTiO 3引入到BiFeO 3-Bi 0.5Na 0.5TiO 3固溶体中，得到了BiFeO 3-Bi 0.5Na 0.5TiO 3-CaTiO 3三元固溶体，并通过组分调控构建正交/菱方准同型相界，用pechini法制备陶瓷块体，用去离子水淬火处理，减小体系漏电流，得到了具有室温磁电耦合效应BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体。 In the present invention, CaTiO 3 with orthogonal Pbnm structure is introduced into BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 solid solution, and BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -CaTiO 3 ternary solid solution is obtained, and the orthogonal structure is constructed through component control / rhombohedral quasi-homotype phase boundary, the ceramic block was prepared by pechini method, quenched with deionized water to reduce the leakage current of the system, and a BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 based ceramic solid solution with room temperature magnetoelectric coupling effect was obtained.
本发明的有益效果：Beneficial effects of the present invention:
本发明采用改进的pechini法制备前驱体粉末，在烧结陶瓷块体时引入了淬火工艺，最后通过制备三元固溶体体系来增强室温磁电耦合效应。采用改进的pechini法制备前驱体粉末时，无机盐原料更容易溶解，可以使原料达到分子水平的均匀混合，并且降低合成烧结温度；且采用淬火工艺，制备的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体更致密，漏电流更小；最后通过制备三元固溶体，来调控体系的准同型相界，实现具有室温铁磁性的多铁性准同型相界。通过本发明的这一方法，实现了BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的室温磁电耦合效应。 The invention adopts the improved pechini method to prepare the precursor powder, introduces a quenching process when sintering the ceramic block, and finally enhances the room temperature magnetoelectric coupling effect by preparing a ternary solid solution system. When the precursor powder is prepared by the improved pechini method, the inorganic salt raw materials are more easily dissolved, the raw materials can be uniformly mixed at the molecular level, and the synthesis and sintering temperature can be reduced; and the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 prepared by the quenching process The base ceramic solid solution is denser and the leakage current is smaller. Finally, by preparing a ternary solid solution, the quasi-homomorphic phase boundary of the system is regulated, and a multiferroic quasi-homomorphic phase boundary with room temperature ferromagnetism is realized. By this method of the present invention, the room temperature magnetoelectric coupling effect of BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is realized.
本发明提供的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷 固溶体(三元多铁性材料)其结构稳定，电学性能，磁学性能与磁电耦合性能优异，能够应用于传感器或存储器中。 The BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution (ternary multiferroic material) with room temperature magnetoelectric coupling provided by the invention has stable structure, excellent electrical properties, magnetic properties and magnetoelectric coupling properties, and can be applied to sensor or memory.
附图说明Description of drawings
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域的技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他附图。In order to illustrate the technical solutions of the embodiments of the present invention more clearly, the following briefly introduces the accompanying drawings used in the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those skilled in the art, other drawings can also be obtained from these drawings without any creative effort.
图1为本发明中实施例1-3所制备的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的X射线衍射图； Fig. 1 is the X-ray diffraction pattern of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Examples 1-3 of the present invention;
图2为本发明中实施例4-12所制备的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的X射线衍射图； Fig. 2 is the X-ray diffraction pattern of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Examples 4-12 of the present invention;
图3为本发明中实施例13-15所制备的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的X射线衍射图； 3 is an X-ray diffraction pattern of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Examples 13-15 of the present invention;
图4为本发明中实施例16-18所制备的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的X射线衍射图； 4 is the X-ray diffraction pattern of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Examples 16-18 of the present invention;
图5为本发明中实施例7、8、13、14、16、17所制备的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体在不同电场下的电滞回线； 5 is the hysteresis loops of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solutions with room temperature magnetoelectric coupling prepared in Examples 7, 8, 13, 14, 16, and 17 of the present invention under different electric fields;
图6为本发明中实施例4、6、8、10、12所制备的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的磁滞回线； 6 is the hysteresis loop of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Examples 4, 6, 8, 10, and 12 of the present invention;
图7为本发明中实施例13-15所制备的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的磁滞回线； 7 is the hysteresis loop of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Examples 13-15 of the present invention;
图8为本发明中实施例16-18所制备的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的磁滞回线； 8 is the hysteresis loop of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Examples 16-18 of the present invention;
图9为本发明中实施例13-15所制备的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的磁介电性能。 FIG. 9 shows the magneto-dielectric properties of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Examples 13-15 of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本发明及其应用或使用的任何限制。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0，y＝0.15。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0, y=0.15.
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，包括如下具体步骤： A method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, comprising the following specific steps:
(1)按照(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3(其中x＝0，y＝0.15)分子式的化学计量比准确称取五水合硝酸铋(Bi(NO 3) 3·5H 2O)、九水合硝酸铁(Fe(NO 3) 3·9H 2O)、乙酸钠(Na(CH 3COO))、钛酸四丁酯和乙酸钙(Ca(CH 3COO) 2)作为原料；且称取量为0.06mol该三元多铁性材料所对应的初始原料的总量； (1) Accurately weigh bismuth nitrate pentahydrate (Bi(NO 3 ) 3 according to the stoichiometric ratio of the molecular formula of (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 (wherein x=0, y=0.15) 5H 2 O), ferric nitrate nonahydrate (Fe(NO 3 ) 3 9H 2 O), sodium acetate (Na(CH 3 COO)), tetrabutyl titanate and calcium acetate (Ca(CH 3 COO) 2 ) as a raw material; and the weighing amount is 0.06mol of the total amount of initial raw materials corresponding to the ternary multiferroic material;
(2)将上述称取好的原料加入到冰醋酸(CH 3COOH)、乙酰丙酮(CH 3COCH 2COCH 3)、一水合柠檬酸(C 6H 8O 7·H 2O)和乙醇胺(C 2H 7NO)的混合溶液中，并搅拌4小时，得到澄清的溶胶；其中：一水合柠檬酸的添加量与上述原料中金属阳离子总和的摩尔比为1.6：1；所述冰醋酸、所述乙酰丙酮和所述乙醇胺的体积比为5:1:1，且所述原料与所述混合溶液的质量比为1:3； (2) The above-mentioned raw materials were weighed into glacial acetic acid (CH 3 COOH), acetylacetone (CH 3 COCH 2 COCH 3 ), citric acid monohydrate (C 6 H 8 O 7 ·H 2 O) and ethanolamine ( C 2 H 7 NO) mixed solution, and stirred for 4 hours to obtain a clear sol; wherein: the molar ratio of the addition of citric acid monohydrate and the sum of metal cations in the above raw materials is 1.6:1; the glacial acetic acid, The volume ratio of described acetylacetone and described ethanolamine is 5:1:1, and the mass ratio of described raw material and described mixed solution is 1:3;
(3)将所得溶胶在90℃的烘箱中烘干12小时，烘干后在800℃下预烧结3小时，即得到前驱体粉末；(3) drying the obtained sol in an oven at 90° C. for 12 hours, and pre-sintering at 800° C. for 3 hours after drying to obtain the precursor powder;
(4)将所得到的前驱体粉末在玛瑙研钵中手动研磨0.5小时，然后在15MPa的压强下压制成形，得到直径10mm、厚1mm的陶瓷片；(4) manually grinding the obtained precursor powder in an agate mortar for 0.5 hours, and then press-forming under a pressure of 15MPa to obtain a ceramic sheet with a diameter of 10mm and a thickness of 1mm;
(5)将陶瓷片在1050℃下进行二次烧结2小时，烧结后用去离子水淬火处理，得到具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，即(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3其中：x＝0，y＝0.15。 (5) The ceramic sheet was sintered at 1050°C for 2 hours, and quenched with deionized water after sintering to obtain a BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling, namely (1.0- xy) BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 where: x=0, y=0.15.
实施例2Example 2
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0，y＝0.20。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0, y=0.20.
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，包括如下具体步骤： A method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, comprising the following specific steps:
(1)按照(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3(其中x＝0，y＝0.20)分子式的化学计量比准确称取五水合硝酸铋(Bi(NO 3) 3·5H 2O)、九水合硝酸铁(Fe(NO 3) 3·9H 2O)、乙酸钠(Na(CH 3COO))、钛酸四丁酯 和乙酸钙(Ca(CH 3COO) 2)作为原料；且称取量为0.06mol该三元多铁性材料所对应的初始原料的总量； (1) Accurately weigh bismuth nitrate pentahydrate (Bi(NO 3 ) 3 according to the stoichiometric ratio of the molecular formula of (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 (wherein x=0, y=0.20) 5H 2 O), ferric nitrate nonahydrate (Fe(NO 3 ) 3 9H 2 O), sodium acetate (Na(CH 3 COO)), tetrabutyl titanate and calcium acetate (Ca(CH 3 COO) 2 ) as a raw material; and the weighing amount is 0.06mol of the total amount of initial raw materials corresponding to the ternary multiferroic material;
(2)将上述称取好的原料加入到冰醋酸(CH 3COOH)、乙酰丙酮(CH 3COCH 2COCH 3)、一水合柠檬酸(C 6H 8O 7·H 2O)和乙醇胺(C 2H 7NO)的混合溶液中，并搅拌3小时，得到澄清的溶胶；其中：一水合柠檬酸的添加量与上述原料中金属阳离子总和的摩尔比为1.6：1；所述冰醋酸、所述乙酰丙酮和所述乙醇胺的体积比为5:1:1，且所述原料与所述混合溶液的质量比为1:3； (2) The above-mentioned raw materials were weighed into glacial acetic acid (CH 3 COOH), acetylacetone (CH 3 COCH 2 COCH 3 ), citric acid monohydrate (C 6 H 8 O 7 ·H 2 O) and ethanolamine ( C 2 H 7 NO) mixed solution, and stirred for 3 hours to obtain a clear sol; wherein: the molar ratio of the addition of citric acid monohydrate and the sum of metal cations in the above raw materials is 1.6:1; the glacial acetic acid, The volume ratio of described acetylacetone and described ethanolamine is 5:1:1, and the mass ratio of described raw material and described mixed solution is 1:3;
(3)将所得溶胶在80℃的烘箱中烘干10小时，烘干后在400℃下预烧结12小时，即得到前驱体粉末；(3) drying the obtained sol in an oven at 80° C. for 10 hours, and pre-sintering at 400° C. for 12 hours after drying to obtain the precursor powder;
(4)将所得到的前驱体粉末在玛瑙研钵中手动研磨1小时，然后在15MPa的压强下压制成形，得到直径10mm、厚1mm的陶瓷片；(4) manually grinding the obtained precursor powder in an agate mortar for 1 hour, and then pressing and forming under a pressure of 15MPa to obtain a ceramic sheet with a diameter of 10mm and a thickness of 1mm;
(5)将陶瓷片在1100℃下进行二次烧结5小时，烧结后用去离子水淬火处理，得到具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，即(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0，y＝0.20。 (5) Secondary sintering of the ceramic sheet at 1100° C. for 5 hours, quenching with deionized water after sintering, to obtain a BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling, namely (1.0- xy) BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0, y=0.20.
实施例3Example 3
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0，y＝0.25。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0, y=0.25.
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，包括如下具体步骤： A method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, comprising the following specific steps:
(1)按照(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3(其中x＝0，y＝0.25)分子式的化学计量比准确称取五水合硝酸铋(Bi(NO 3) 3·5H 2O)、九水合硝酸铁(Fe(NO 3) 3·9H 2O)、乙酸钠(Na(CH 3COO))、钛酸四丁酯和乙酸钙(Ca(CH 3COO) 2)作为原料；且称取量为0.06mol该三元多铁性材料所对应的初始原料的总量； (1) Accurately weigh bismuth nitrate pentahydrate (Bi(NO 3 ) 3 according to the stoichiometric ratio of the molecular formula of (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 (where x=0, y=0.25) 5H 2 O), ferric nitrate nonahydrate (Fe(NO 3 ) 3 9H 2 O), sodium acetate (Na(CH 3 COO)), tetrabutyl titanate and calcium acetate (Ca(CH 3 COO) 2 ) as a raw material; and the weighing amount is 0.06mol of the total amount of initial raw materials corresponding to the ternary multiferroic material;
(2)将上述称取好的原料加入到冰醋酸(CH 3COOH)、乙酰丙酮(CH 3COCH 2COCH 3)、一水合柠檬酸(C 6H 8O 7·H 2O)和乙醇胺(C 2H 7NO)的混合溶液中，并搅拌5小时，得到澄清的溶胶；其中：一水合柠檬酸的添加量与上述原料中金属阳离子总和的摩尔比为1.6：1；所述冰醋酸、所述乙酰丙酮和所述乙醇胺的体积比为5:1:1，且所述原料与所述混合溶液的质量比为1:3； (2) The above-mentioned raw materials were weighed into glacial acetic acid (CH 3 COOH), acetylacetone (CH 3 COCH 2 COCH 3 ), citric acid monohydrate (C 6 H 8 O 7 ·H 2 O) and ethanolamine ( C 2 H 7 NO) mixed solution, and stirred for 5 hours to obtain a clear sol; wherein: the molar ratio of the addition of citric acid monohydrate and the sum of metal cations in the above raw materials is 1.6:1; the glacial acetic acid, The volume ratio of described acetylacetone and described ethanolamine is 5:1:1, and the mass ratio of described raw material and described mixed solution is 1:3;
(3)将所得溶胶在85℃的烘箱中烘干8小时，烘干后在600℃下预烧结8小时，即得到前驱体粉末；(3) drying the obtained sol in an oven at 85° C. for 8 hours, and pre-sintering at 600° C. for 8 hours after drying to obtain the precursor powder;
(4)将所得到的前驱体粉末在玛瑙研钵中手动研磨0.8小时，然后在20MPa的压强下压制成形，得到直径10mm、厚1mm的陶瓷片；(4) manually grinding the obtained precursor powder in an agate mortar for 0.8 hours, and then pressing under the pressure of 20MPa to obtain a ceramic sheet with a diameter of 10mm and a thickness of 1mm;
(5)将陶瓷片在1150℃下进行二次烧结3小时，烧结后用去离子水淬火处理，得到具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，即(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0，y＝0.25。 (5) Secondary sintering of the ceramic sheet at 1150°C for 3 hours, quenching with deionized water after sintering, to obtain a BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling, namely (1.0- xy) BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0, y=0.25.
实施例4Example 4
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为： (1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.1，y＝0。 A magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.1, y=0.
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，包括如下具体步骤： A method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, comprising the following specific steps:
(1)按照(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3(其中x＝0.1，y＝0)分子式的化学计量比准确称取五水合硝酸铋(Bi(NO 3) 3·5H 2O)、九水合硝酸铁(Fe(NO 3) 3·9H 2O)、乙酸钠(Na(CH 3COO))、钛酸四丁酯和乙酸钙(Ca(CH 3COO) 2)作为原料；且称取量为0.06mol该三元多铁性材料所对应的初始原料的总量； (1) Accurately weigh bismuth nitrate pentahydrate (Bi(NO 3 ) 3 according to the stoichiometric ratio of the molecular formula of (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 (where x=0.1, y=0) 5H 2 O), ferric nitrate nonahydrate (Fe(NO 3 ) 3 9H 2 O), sodium acetate (Na(CH 3 COO)), tetrabutyl titanate and calcium acetate (Ca(CH 3 COO) 2 ) as a raw material; and the weighing amount is 0.06mol of the total amount of initial raw materials corresponding to the ternary multiferroic material;
(2)将上述称取好的原料加入到冰醋酸(CH 3COOH)、乙酰丙酮(CH 3COCH 2COCH 3)、一水合柠檬酸(C 6H 8O 7·H 2O)和乙醇胺(C 2H 7NO)的混合溶液中，并搅拌3小时，得到澄清的溶胶；其中：一水合柠檬酸的添加量与上述原料中金属阳离子总和的摩尔比为1.6：1；所述冰醋酸、所述乙酰丙酮和所述乙醇胺的体积比为5:1:1，且所述原料与所述混合溶液的质量比为1:3； (2) The above-mentioned raw materials were weighed into glacial acetic acid (CH 3 COOH), acetylacetone (CH 3 COCH 2 COCH 3 ), citric acid monohydrate (C 6 H 8 O 7 ·H 2 O) and ethanolamine ( C 2 H 7 NO) mixed solution, and stirred for 3 hours to obtain a clear sol; wherein: the molar ratio of the addition of citric acid monohydrate and the sum of metal cations in the above raw materials is 1.6:1; the glacial acetic acid, The volume ratio of described acetylacetone and described ethanolamine is 5:1:1, and the mass ratio of described raw material and described mixed solution is 1:3;
(3)将所得溶胶在90℃的烘箱中烘干10小时，烘干后在700℃下预烧结10小时，即得到前驱体粉末；(3) drying the obtained sol in an oven at 90° C. for 10 hours, and pre-sintering at 700° C. for 10 hours after drying to obtain the precursor powder;
(4)将所得到的前驱体粉末在玛瑙研钵中手动研磨0.6小时，然后在18MPa的压强下压制成形，得到直径8mm、厚1mm的陶瓷片；(4) manually grinding the obtained precursor powder in an agate mortar for 0.6 hours, then press-forming under a pressure of 18MPa to obtain a ceramic sheet with a diameter of 8mm and a thickness of 1mm;
(5)将陶瓷片在1150℃下进行二次烧结2小时，烧结后用去离子水淬火处理，得到具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，即(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中x＝0.1，y＝0。 (5) The ceramic sheet was sintered at 1150°C for 2 hours, and quenched with deionized water after sintering to obtain a BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling, namely (1.0- xy) BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where x=0.1, y=0.
实施例5Example 5
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.1，y＝0.05。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.1, y=0.05.
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，包括如下具体步骤： A method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, comprising the following specific steps:
(1)按照(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3(其中x＝0.1，y＝0.05)分子式的化学计量比准确称取五水合硝酸铋(Bi(NO 3) 3·5H 2O)、九水合硝酸铁(Fe(NO 3) 3·9H 2O)、乙酸钠(Na(CH 3COO))、钛酸四丁酯和乙酸钙(Ca(CH 3COO) 2)作为原料；且称取量为0.06mol该三元多铁性材料所对应的初始原料的总量； (1) Accurately weigh bismuth nitrate pentahydrate (Bi(NO 3 ) 3 according to the stoichiometric ratio of the molecular formula of (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 (where x=0.1, y=0.05) 5H 2 O), ferric nitrate nonahydrate (Fe(NO 3 ) 3 9H 2 O), sodium acetate (Na(CH 3 COO)), tetrabutyl titanate and calcium acetate (Ca(CH 3 COO) 2 ) as a raw material; and the weighing amount is 0.06mol of the total amount of initial raw materials corresponding to the ternary multiferroic material;
(2)将上述称取好的原料加入到冰醋酸(CH 3COOH)、乙酰丙酮(CH 3COCH 2COCH 3)、一水合柠檬酸(C 6H 8O 7·H 2O)和乙醇胺(C 2H 7NO)的混合溶液中，并搅拌4小时，得到澄清的溶胶；其中：一水合柠檬酸的添加量与上述原料中金属阳离子总和的摩尔比为1.6：1；所述冰醋酸、所述乙酰丙酮和所述乙醇胺的体积比为5:1:1，且所述原料与所述混合溶液的质量比为1:3； (2) The above-mentioned raw materials were weighed into glacial acetic acid (CH 3 COOH), acetylacetone (CH 3 COCH 2 COCH 3 ), citric acid monohydrate (C 6 H 8 O 7 ·H 2 O) and ethanolamine ( C 2 H 7 NO) mixed solution, and stirred for 4 hours to obtain a clear sol; wherein: the molar ratio of the addition of citric acid monohydrate and the sum of metal cations in the above raw materials is 1.6:1; the glacial acetic acid, The volume ratio of described acetylacetone and described ethanolamine is 5:1:1, and the mass ratio of described raw material and described mixed solution is 1:3;
(3)将所得溶胶在80℃的烘箱中烘干9小时，烘干后在500℃下预烧结12小时，即得到前驱体粉末；(3) drying the obtained sol in an oven at 80° C. for 9 hours, and pre-sintering at 500° C. for 12 hours after drying to obtain the precursor powder;
(4)将所得到的前驱体粉末在玛瑙研钵中手动研磨0.6小时，然后在18MPa的压强下压制成形，得到直径12mm、厚2mm的陶瓷片；(4) the obtained precursor powder was manually ground in an agate mortar for 0.6 hours, and then pressed under the pressure of 18MPa to obtain a ceramic sheet with a diameter of 12mm and a thickness of 2mm;
(5)将陶瓷片在1250℃下进行二次烧结3小时，烧结后用去离子水淬火处理，得到具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷 固溶体，即(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.1，y＝0.05。 (5) The ceramic sheet was sintered at 1250°C for 3 hours, and then quenched with deionized water after sintering to obtain a BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling, namely (1.0- xy) BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.1, y=0.05.
实施例6Example 6
一种磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.1，y＝0.10。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.1, y=0.10.
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，包括如下具体步骤： A method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, comprising the following specific steps:
(1)按照(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3(其中x＝0.1，y＝0.10)分子式的化学计量比准确称取五水合硝酸铋(Bi(NO 3) 3·5H 2O)、九水合硝酸铁(Fe(NO 3) 3·9H 2O)、乙酸钠(Na(CH 3COO))、钛酸四丁酯和乙酸钙(Ca(CH 3COO) 2)作为原料；且称取量为0.06mol该三元多铁性材料所对应的初始原料的总量； (1) Accurately weigh bismuth nitrate pentahydrate (Bi(NO 3 ) 3 according to the stoichiometric ratio of the molecular formula of (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 (where x=0.1, y=0.10) 5H 2 O), ferric nitrate nonahydrate (Fe(NO 3 ) 3 9H 2 O), sodium acetate (Na(CH 3 COO)), tetrabutyl titanate and calcium acetate (Ca(CH 3 COO) 2 ) as a raw material; and the weighing amount is 0.06mol of the total amount of initial raw materials corresponding to the ternary multiferroic material;
(2)将上述称取好的原料加入到冰醋酸(CH 3COOH)、乙酰丙酮(CH 3COCH 2COCH 3)、一水合柠檬酸(C 6H 8O 7·H 2O)和乙醇胺(C 2H 7NO)的混合溶液中，并搅拌3小时，得到澄清的溶胶；其中：一水合柠檬酸的添加量与上述原料中金属阳离子总和的摩尔比为1.6：1；所述冰醋酸、所述乙酰丙酮和所述乙醇胺的体积比为5:1:1，且所述原料与所述混合溶液的质量比为1:3； (2) The above-mentioned raw materials were weighed into glacial acetic acid (CH 3 COOH), acetylacetone (CH 3 COCH 2 COCH 3 ), citric acid monohydrate (C 6 H 8 O 7 ·H 2 O) and ethanolamine ( C 2 H 7 NO) mixed solution, and stirred for 3 hours to obtain a clear sol; wherein: the molar ratio of the addition of citric acid monohydrate and the sum of metal cations in the above raw materials is 1.6:1; the glacial acetic acid, The volume ratio of described acetylacetone and described ethanolamine is 5:1:1, and the mass ratio of described raw material and described mixed solution is 1:3;
(3)将所得溶胶在85℃的烘箱中烘干8小时，烘干后在650℃下预烧结11小时，即得到前驱体粉末；(3) drying the obtained sol in an oven at 85°C for 8 hours, and pre-sintering at 650°C for 11 hours after drying to obtain the precursor powder;
(4)将所得到的前驱体粉末在玛瑙研钵中手动研磨1小时，然 后在16MPa的压强下压制成形，得到直径12mm、厚1mm的陶瓷片；(4) the obtained precursor powder was manually ground in an agate mortar for 1 hour, and then pressed under the pressure of 16MPa to obtain a ceramic sheet with a diameter of 12mm and a thickness of 1mm;
(5)将陶瓷片在1200℃下进行二次烧结4小时，烧结后用去离子水淬火处理，得到具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，即(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.1，y＝0.10。 (5) The ceramic sheet was sintered at 1200°C for 4 hours, and then quenched with deionized water after sintering to obtain a BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling, namely (1.0- xy) BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.1, y=0.10.
实施例7Example 7
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.1，y＝0.15。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.1, y=0.15.
实施例7与实施例1除原料配比不同外，其余制备条件均与实施例1相同。Example 7 and Example 1 are the same as Example 1 except that the ratio of raw materials is different, and other preparation conditions are the same.
实施例8Example 8
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.1，y＝0.20。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.1, y=0.20.
实施例8与实施例2除原料配比不同外，其余制备条件均与实施例2相同。Example 8 and Example 2 are the same as Example 2 except that the raw material ratio is different, and other preparation conditions are the same.
实施例9Example 9
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.1，y＝0.25。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.1, y=0.25.
实施例9与实施例3除原料配比不同外，其余制备条件均与实施 例3相同。Except that the ratio of raw materials is different from Example 9 and Example 3, all other preparation conditions are the same as Example 3.
实施例10Example 10
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.1，y＝0.30。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.1, y=0.30.
实施例10与实施例实施例4除原料配比不同外，其余制备条件均与实施例4相同。Example 10 and Example 4 are the same as Example 4 except that the ratio of raw materials is different.
实施例11Example 11
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.1，y＝0.35。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.1, y=0.35.
实施例11与实施例实施例5除原料配比不同外，其余制备条件均与实施例5相同。Example 11 and Example 5 are the same as Example 5 except that the raw material ratio is different, and other preparation conditions are the same.
实施例12Example 12
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.1，y＝0.40。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.1, y=0.40.
实施例12与实施例实施例6除原料配比不同外，其余制备条件均与实施例6相同。Example 12 and Example 6 are the same as Example 6 except that the ratio of raw materials is different.
实施例13Example 13
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为： (1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.2，y＝0.15。 A magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.2, y=0.15.
实施例13与实施例实施例1除原料配比不同外，其余制备条件均与实施例1相同。Example 13 and Example 1 are the same as Example 1 except that the ratio of raw materials is different, and other preparation conditions are the same.
实施例14Example 14
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.2，y＝0.20。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.2, y=0.20.
实施例14与实施例实施例2除原料配比不同外，其余制备条件均与实施例2相同。Example 14 and Example 2 are the same as Example 2 except that the raw material ratio is different, and other preparation conditions are the same.
实施例15Example 15
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.2，y＝0.25。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.2, y=0.25.
实施例15与实施例实施例3除原料配比不同外，其余制备条件均与实施例3相同。Example 15 and Example 3 are the same as Example 3 except that the raw material ratio is different, and other preparation conditions are the same.
实施例16Example 16
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.3，y＝0.15。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.3, y=0.15.
实施例16与实施例实施例1除原料配比不同外，其余制备条件均与实施例1相同。Example 16 and Example 1 are the same as Example 1 except that the ratio of raw materials is different, and other preparation conditions are the same.
实施例17Example 17
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.3，y＝0.20。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.3, y=0.20.
实施例17与实施例实施例2除原料配比不同外，其余制备条件均与实施例2相同。Example 17 and Example 2 are the same as Example 2 except that the raw material ratio is different, and other preparation conditions are the same.
实施例18Example 18
一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0.3，y＝0.25。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0.3, y=0.25.
实施例18与实施例实施例3除原料配比不同外，其余制备条件均与实施例3相同。Example 18 and Example 3 are the same as Example 3 except that the ratio of raw materials is different.
测试例1Test Example 1
采用X射线粉末衍射测试上述实施例1-18所制得的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的结构：采用的仪器是型号是PhilipsX’pertPRO，靶材为Cu靶，波长λ为0.15406nm，扫描范围是10°-90°，扫描速率是10°/min。其中：实施例1-3的测试结果如图1所示；实施例4-12的测试结果如图2所示；实施例13-15的测试结果如图3所示；实施例16-18的测试结果如图4所示；从上述图1-4中可以看出，实施例1-18制备的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体为纯的钙钛矿结构，且四个系列的实施例随y值(CaTiO 3含量)的增大都经历了从菱方相到正交相的结构转变，通过组分调控构造了菱方-正交准同型相界。 The structure of the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling obtained in the above examples 1-18 was tested by X-ray powder diffraction: the instrument used was the model PhilipsX'pertPRO, and the target material was Cu target, the wavelength λ is 0.15406nm, the scanning range is 10°-90°, and the scanning rate is 10°/min. Among them: the test results of Examples 1-3 are shown in Figure 1; the test results of Examples 4-12 are shown in Figure 2; the test results of Examples 13-15 are shown in Figure 3; The test results are shown in Figure 4; it can be seen from the above Figures 1-4 that the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in Example 1-18 is a pure perovskite The four series of examples all experienced a structural transition from rhombohedral phase to orthorhombic phase with the increase of y value (CaTiO 3 content), and the rhombohedral-orthomorphic phase boundary was constructed by composition control.
测试例2 Test case 2
分别取上述实施例7、实施例8、实施例13、实施例14、实施例16和实施例17所制得的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，并将其分别磨薄、抛光、两面涂上银浆，为电学性质的测试做准备；然后进行铁电性质的测量：选用仪器为美国Radiant铁电测试系统，型号是Precision Premier II，Radiant Technologies，测试条件为：室温，频率为10Hz。实施例7、8、13、14、16、17的组分位于菱方-正交准同型相界附近，其P-E回线的测试结果如图5所示(图中a对应实施例7、b对应实施例8、c对应实施例13、d对应实施例14、e对应实施例16、f对应实施例17)；相界附近的铁电性能要明显优于其它样品，且随着Bi 0.5Na 0.5TiO 3含量的增加，漏电流显著减小。在实施例14、16中剩余极化强度可达33.67μC/cm 2和30.91μC/cm 2。 Take the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in the above Example 7, Example 8, Example 13, Example 14, Example 16 and Example 17, respectively, and Thin, polish, and coat silver paste on both sides to prepare for the test of electrical properties; then measure the ferroelectric properties: the instrument selected is the American Radiant ferroelectric test system, the model is Precision Premier II, Radiant Technologies, testing Conditions are: room temperature, frequency 10 Hz. The components of Examples 7, 8, 13, 14, 16, and 17 are located near the rhombohedral-orthogonal quasi-isotype phase boundary, and the test results of their PE loops are shown in Figure 5 (a in the figure corresponds to Examples 7, b Corresponding to Example 8, c corresponds to Example 13, d corresponds to Example 14, e corresponds to Example 16, and f corresponds to Example 17); the ferroelectric properties near the phase boundary are significantly better than other samples, and with Bi 0.5 Na With the increase of 0.5 TiO 3 content, the leakage current decreases significantly. In Examples 14 and 16, the remanent polarization can reach 33.67 μC/cm 2 and 30.91 μC/cm 2 .
测试例3Test case 3
分别取上述实施例4、6、8、10、12-18所制得的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体进行磁性质的测量：采用超导量子干涉仪(Quantum Design superconducting quantum interface device，SQUID)磁性测量系统(Physical Properties Measurement System，PPMS，2K≤T≤400K，0T≤H≤5T)测量样品在300K时的磁滞回线(M-H)。其中实施例4、6、8、10、12的室温M-H测试结果如图6所示，实施例13-15的室温M-H测试结果如图7所示，实施例16-18的室温M-H测试结果如图8所示；可以看出实施例6的剩 余磁化强度约为M r＝0.18emu/g。 Take the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling obtained in the above Examples 4, 6, 8, 10, 12-18 respectively to measure the magnetic properties: using a superconducting quantum interferometer The (Quantum Design superconducting quantum interface device, SQUID) magnetic measurement system (Physical Properties Measurement System, PPMS, 2K≤T≤400K, 0T≤H≤5T) measures the hysteresis loop (MH) of the sample at 300K. The room temperature MH test results of Examples 4, 6, 8, 10, and 12 are shown in Figure 6, the room temperature MH test results of Examples 13-15 are shown in Figure 7, and the room temperature MH test results of Examples 16-18 are as follows 8; it can be seen that the residual magnetization of Example 6 is about Mr = 0.18 emu/ g .
测试例4Test Example 4
分别取上述实施例13、14、15所制得的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体进行磁介电性质测量：将TH2828S型宽频阻抗分析测试仪(LCR)与Quantum Design公司的物性系统(Physical Property Measurement system，PPMS)连接，可以测试样品的介电常数随磁场的变化(0T≤H≤8T)。实施例13-15的室温磁介电结果如图9(a)和9(b)所示，发现菱方-正交准同型相界共存的实施例14的磁介电系数最大。 Take the BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution with room temperature magnetoelectric coupling prepared in the above-mentioned Examples 13, 14 and 15 respectively to measure the magneto-dielectric properties: a TH2828S broadband impedance analyzer (LCR) It is connected with the Physical Property Measurement system (PPMS) of Quantum Design Company, and the change of the dielectric constant of the sample with the magnetic field (0T≤H≤8T) can be measured. The room-temperature magneto-dielectric results of Examples 13-15 are shown in Figures 9(a) and 9(b), and it was found that Example 14 with the coexistence of rhombohedral-orthogonal phase boundaries had the largest magneto-dielectric coefficient.
本发明制得的具有室温磁电耦合的BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体((1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3)，由于其具有结构稳定，电学性能，磁学性能以及磁电耦合性能优异的优良性能，因此能够应用于传感器或存储器中，以替代现有的铁电材料。 The BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution ((1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 ) with room temperature magnetoelectric coupling prepared by the invention has stable structure, electrical It has excellent performance, magnetic properties and magnetoelectric coupling properties, so it can be used in sensors or memories to replace existing ferroelectric materials.
本发明是基于寻找新的多铁性BiFeO 3-Bi 0.5Na 0.5TiO 3基材料而进行的。BiFeO 3-Bi 0.5Na 0.5TiO 3-CaTiO 3(简称BFO-BNTO-CTO)作为同时具有室温铁电性和铁磁性的多铁性材料，具有很好的研究价值和使用价值。首先是陶瓷的合成过程，通过反复的实验探索，探究出最佳的烧结温度和烧结时间，最终得到室温磁电耦合最大的陶瓷样品，用X射线衍射仪确定结构，然后对其铁电性能、磁性质和磁电耦合性质测量分析。 The present invention is based on the search for new multiferroic BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 based materials. BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -CaTiO 3 (BFO-BNTO-CTO for short), as a multiferroic material with both room temperature ferroelectricity and ferromagnetism, has good research value and application value. The first is the synthesis process of ceramics. Through repeated experimental exploration, the optimal sintering temperature and sintering time are explored, and finally a ceramic sample with the largest magnetoelectric coupling at room temperature is obtained. The structure is determined by an X-ray diffractometer, and then its ferroelectric properties, Measurement and analysis of magnetic properties and magnetoelectric coupling properties.
上述为本发明的较佳实施例仅用于解释本发明，并不用于限定本发明。凡由本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之中。The above-mentioned preferred embodiments of the present invention are only used to explain the present invention, and are not intended to limit the present invention. Any obvious changes or changes derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims (9)

  1. 一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体，其特征在于，所述磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的化学组成为：(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3，其中：x＝0-0.3，y＝0-0.4。 A magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution, characterized in that the chemical composition of the magneto-electrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution is: (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 , where: x=0-0.3, y=0-0.4.
  2. 根据权利要求1所述的一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的应用，其特征在于，在传感器或存储器中的应用。 The application of a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution according to claim 1, characterized in that it is used in a sensor or a memory.
  3. 根据权利要求1所述的一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，其特征在于，该方法包括如下步骤： The method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution according to claim 1, wherein the method comprises the following steps:
    (1)按照(1.0-x-y)BiFeO 3-xBi 0.5Na 0.5TiO 3-yCaTiO 3分子式的化学计量比准确称取铋源、铁源、钠源、钛源和钙源作为原料； (1) Accurately weigh bismuth source, iron source, sodium source, titanium source and calcium source as raw materials according to the stoichiometric ratio of (1.0-xy)BiFeO 3 -xBi 0.5 Na 0.5 TiO 3 -yCaTiO 3 molecular formula;
    (2)将称取好的原料加入到冰醋酸、乙酰丙酮、络合剂和乙醇胺的混合溶液中，并搅拌得到溶胶；(2) the raw material taken by weighing is added to the mixed solution of glacial acetic acid, acetylacetone, complexing agent and ethanolamine, and stirred to obtain a sol;
    (3)将所得溶胶烘干，然后预烧结，得到前驱体粉末；(3) drying the obtained sol, and then pre-sintering to obtain the precursor powder;
    (4)将所得前驱体粉末研磨，然后压制，得到陶瓷片；(4) the obtained precursor powder is ground and then pressed to obtain a ceramic sheet;
    (5)将所得陶瓷片二次烧结，然后淬火，得到磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体。 (5) Secondary sintering of the obtained ceramic sheet, followed by quenching, to obtain a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution.
  4. 根据权利要求3所述的一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，其特征在于，步骤(1)中所述的铋源为五水合硝酸铋；所述的铁源为九水合硝酸铁；所述的钠源为乙酸钠；所述的钛源为钛酸四丁酯；所述的钙源为乙酸钙。 The method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution according to claim 3, wherein the bismuth source described in step (1) is bismuth nitrate pentahydrate; the The iron source is ferric nitrate nonahydrate; the sodium source is sodium acetate; the titanium source is tetrabutyl titanate; the calcium source is calcium acetate.
  5. 根据权利要求3所述的一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，其特征在于，步骤(2)中所述的络合剂为一水合柠檬酸。 The method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution according to claim 3, wherein the complexing agent described in step (2) is citric acid monohydrate.
  6. 根据权利要求3所述的一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，其特征在于，步骤(2)中所述的络合剂的添加量与阳离子总和的摩尔比为1.6:1；所述的搅拌时间为3-5小时；所述冰醋酸、所述乙酰丙酮和所述乙醇胺的体积比为5:1:1，且所述原料与所述混合溶液的质量比为1:3。 The method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution according to claim 3, wherein the amount of the complexing agent added in the step (2) is equal to the sum of the cations The molar ratio is 1.6:1; the stirring time is 3-5 hours; the volume ratio of the glacial acetic acid, the acetylacetone and the ethanolamine is 5:1:1, and the raw material and the mixed solution are The mass ratio is 1:3.
  7. 根据权利要求3所述的一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，其特征在于，步骤(3)中所述的烘干温度为80-90℃，且烘干时间为8-12小时；所述的预烧结的温度为400-800℃，且预烧结的时间为3-12小时。 The method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution according to claim 3, wherein the drying temperature in step (3) is 80-90° C., and The drying time is 8-12 hours; the pre-sintering temperature is 400-800° C., and the pre-sintering time is 3-12 hours.
  8. 根据权利要求3所述的一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，其特征在于，步骤(4)将所得前驱体粉末在玛瑙研钵中手动研磨0.5-1小时，将研磨后的前驱体粉末在15-20MPa的压强下压制成形，得到直径为8-12毫米、厚度为1-2毫米的陶瓷片。 The method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution according to claim 3, wherein in step (4), the obtained precursor powder is manually ground in an agate mortar for 0.5- For 1 hour, the ground precursor powder is pressed and formed under a pressure of 15-20 MPa to obtain a ceramic sheet with a diameter of 8-12 mm and a thickness of 1-2 mm.
  9. 根据权利要求3所述的一种磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体的制备方法，其特征在于，步骤(5)将所得陶瓷片在1050-1250℃下进行二次烧结，且烧结时间为2-5小时，烧结后用去离子水进行淬火处理，即可得到磁电耦合BiFeO 3-Bi 0.5Na 0.5TiO 3基陶瓷固溶体。 The method for preparing a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution according to claim 3, wherein in step (5), the obtained ceramic sheet is sintered at 1050-1250° C. , and the sintering time is 2-5 hours. After sintering, deionized water is used for quenching treatment to obtain a magnetoelectrically coupled BiFeO 3 -Bi 0.5 Na 0.5 TiO 3 -based ceramic solid solution.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101941838A (en) * 2010-02-22 2011-01-12 华中科技大学 BiFeO3-Bi0.5Na0.5TiO3 base multiferroic solid solution ceramic and preparation method thereof
US20110007115A1 (en) * 2009-07-09 2011-01-13 Fujifilm Corporation Perovskite oxide material, ferroelectric compound, piezoelectric body, piezoelectric device, and liquid discharge device
CN107112412A (en) * 2014-12-26 2017-08-29 精工爱普生株式会社 The equipment of piezoelectric and its manufacture method and piezoelectric element and application piezoelectric element

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110007115A1 (en) * 2009-07-09 2011-01-13 Fujifilm Corporation Perovskite oxide material, ferroelectric compound, piezoelectric body, piezoelectric device, and liquid discharge device
CN101941838A (en) * 2010-02-22 2011-01-12 华中科技大学 BiFeO3-Bi0.5Na0.5TiO3 base multiferroic solid solution ceramic and preparation method thereof
CN107112412A (en) * 2014-12-26 2017-08-29 精工爱普生株式会社 The equipment of piezoelectric and its manufacture method and piezoelectric element and application piezoelectric element

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHAKRABARTI CHIRANJIB; FU QINGSHAN; PAUL BIPLAB KUMAR; CHEN XINGHAN; ZHENG JIA; YIN HONGXIA; ALI WAJAHAT; QIU YANG; ROY PRADIP KUM: "Ferromagnetic, dielectric, and ferroelectric characteristic near the morphotropic phase boundary in (1-x)(0.7BiFeO3-0.3BiNa0.5Ti O3)-x(CaTiO3) solid solution", CERAMICS INTERNATIONAL, vol. 47, no. 14, 8 April 2021 (2021-04-08), NL , pages 20268 - 20275, XP086636378, ISSN: 0272-8842, DOI: 10.1016/j.ceramint.2021.04.035 *
HUANG WENJUAN: "Multiferroic and Magntodielectric Studies of BiFeO3-based Solid Solutions", CHINESE DOCTORAL DISSERTATIONS FULL-TEXT DATABASE, UNIVERSITY OF CHINESE ACADEMY OF SCIENCES, CN, 15 October 2018 (2018-10-15), CN , XP055943074, ISSN: 1674-022X *
KUMAR PAWAN; KAR MANORANJAN: "Effect of structural transition on magnetic and optical properties of Ca and Ti co-substituted BiFeO3ceramics", JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE., CH, vol. 584, 24 September 2013 (2013-09-24), CH , pages 566 - 572, XP028761968, ISSN: 0925-8388, DOI: 10.1016/j.jallcom.2013.09.107 *
W.J.HUANG ET AL.: "Room-temperature multiferrocity and magnetodielectric properties of ternary BiFeO3–Bi0.5Na0.5TiO3–CaTiO3 ceramics across the rhombohedral–orthorhombic phase boundary", JOURNAL OF MATERIALS SCIENCE: MATERIALS IN ELECTRONICS, vol. 32, no. 9, 10 April 2021 (2021-04-10), XP037454136, ISSN: 1573-482X, DOI: 10.1007/s10854-021-05729-5 *

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