CN107840659A - A kind of tungsten bronze pure phase room temperature multiferroic ceramics and preparation method thereof - Google Patents

A kind of tungsten bronze pure phase room temperature multiferroic ceramics and preparation method thereof Download PDF

Info

Publication number
CN107840659A
CN107840659A CN201711262299.8A CN201711262299A CN107840659A CN 107840659 A CN107840659 A CN 107840659A CN 201711262299 A CN201711262299 A CN 201711262299A CN 107840659 A CN107840659 A CN 107840659A
Authority
CN
China
Prior art keywords
bsfn
ceramics
room temperature
tungsten bronze
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201711262299.8A
Other languages
Chinese (zh)
Other versions
CN107840659B (en
Inventor
郑兴华
罗国仕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuzhou University
Original Assignee
Fuzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuzhou University filed Critical Fuzhou University
Priority to CN201711262299.8A priority Critical patent/CN107840659B/en
Publication of CN107840659A publication Critical patent/CN107840659A/en
Application granted granted Critical
Publication of CN107840659B publication Critical patent/CN107840659B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/638—Removal thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Abstract

The invention discloses a kind of tungsten bronze pure phase room temperature multiferroic ceramics and preparation method thereof.The present invention is quickly prepared for room temperature multiferroic tungsten bronze pure phase ceramics by microwave sintering.It has excellent ferroelectric properties and ferromagnetic property at room temperature, and has strong magnetoelectric effect.It is multiferroic ceramic raw material wide material sources provided by the invention, cheap, environmentally friendly；Preparation technology is simple, excellent performance, has great industrial application value.

Description

A kind of tungsten bronze pure phase room temperature multiferroic ceramics and preparation method thereof
Technical field
The present invention relates to a kind of tungsten bronze pure phase room temperature multiferroic ceramics and its and preparation method thereof.
Background technology
Multi-ferroic material refers to have simultaneously in three kinds of ferroelectricity, ferromagnetism and ferroelasticity characteristics the characteristic of two kinds and the above And the effect of intercoupling between this basic iron be present and produce a kind of important functional material of new effect, its essential characteristic It is with ferroelectricity, ferromagnetism, it has piezo-electric effect, ferroelectric effect, pyroelectric effect, non-linear under conditions of external electric field The several physicals such as optical effect, magnetoelectric effect.These particular characteristics cause multi-ferroic material to be widely used in piezoelectricity The important materials of the materials such as sonar, ferroelectric film memory, sensor, electrooptic light valve.
Present multi-ferroic material mainly has ferroelectricity and ferromagnetism simultaneously, and its spontaneous polarization and Spontaneous Magnetic Moments are mutual It can intercouple, regulate and control.But it is this while have ferroelectricity and ferromagnetic single-phase compounds rare, mainly due to same When have the point group of spontaneous polarization and spontaneous manetization have and only 1,2,2, m, m, 3m, 3,4m m, 4, m m 2, m m2, This 13 kinds of 6m m 13 and 6.Such as perovskite structure (ABO3) material, oxygen octahedra center Nb5+、W6+And Ti4+Deng ferroelectric activity from The d0 electron configurations of son play very important effect in terms of the stability that ferroelectricity distorts.But come for magnetic oxide Say, then require that its track needs the Fe not being fully filled with3+、Ni2+、Gr3+Deng transition metal ions.If oxygen octahedra center is by d Magnetic ion that rail portion is filled up filling, then the Central Symmetry of the lattice is not inclined to destroyed, and also implying that will not There is spontaneous polarization, therefore single-phase multi-ferroic material is very rare.In addition, the high density of states more than fermi level often causes Ferromagnet shows metallic conductivity, but ferroelectric material then requires it is insulator.Because the electric conductor under DC Electric Field It is electric current rather than electric polarization caused by inside, so the difference of electric conductivity requirement is also to cause single-phase multi-ferroic material to be difficult to One of the reason for preparation.
It is low that all there is ferromagnetic Curie temperature than relatively low, magnetoelectric effect temperature occurs for most of single-phase multi-ferroic material The defects of, so as to limit its application actually, rank is explored so being merely resting at present for single-phase multi-ferroic material Section.It is BiFeO wherein by the single-phase multi-ferroic material of numerous studies3（BFO）, but its resistivity it is relatively low it is smaller, leakage lead it is excessive Seriously hinder its ferroelectricity and the practice of ferromagnetic property.In addition, due to BFO ferroelectricitys and ferromagnetic source not Together, also cause its magnetoelectric effect weaker.And BFO be difficult to synthesize it is single-phase.Because above mentioned problem, there is an urgent need to research and develop New single-phase multi-ferroic material.One of which method is that magnetic ion is incorporated into ferroelectric, forms ferroelectricity and ferromagnetism and is total to It is stored in integral solid solution.Such as Pb (Fe1/2 3+Nb1/2 5+) (PFN), its ferroelectrie Curie temperature and antiferromagnetic temperature are 385K respectively With 143K, therefore at a lower temperature just simultaneously there is ferromagnetism and ferroelectricity：.Research shows that different cations is PFN magnetic Property and ferroelectricity source, Nb5+Ion is ferroelectricity active ions and Fe3+Ion is magnetic active ions, therefore magnetoelectric effect is low Basic reason.Recent years researcher exploration and analysis Ba4Ln2Fe2Nb8O30 (Ln=La, Pr, Nd, Sm, Eu, Y) Serial tungsten bronze multi-ferroic material, although having nothing in common with each other for the result of different researchers research, all shows Ba4 Ln2Fe2Nb8O30(Ln=Nd, Sm, Eu) ceramics have room temperature ferroelectricity and ferromagnetism.But the series ceramic is all observed less Measure LnNbO4、BaFe12O19Dephasign, and all its ferromagnetism is attributed in ceramics and a small amount of ferrite BaFe be present12O19Dephasign. In addition, current Ba4 Ln2Fe2Nb8O30(Ln=Nd, Sm, Eu) Tungsten Bronze Ceramic is all sintered using conventional solid-state method, crystal grain Cheng Zhu Shape.And it is unfavorable for improving ferromagnetism according to the nonequiaxial crystal grain such as the ferromagnetism and ferroelectricity feature of multi-ferroic material, column.
Because single-phase multiferroic ceramics are considerably less, and it is difficult to prepare, therefore some researchers are used ferroelectric bulk ceramic With ferromagnet Ceramic Composite, multiferroic composite ceramics is prepared.Such as a kind of preparation method of multiferroic composite ceramics of patent （CN201611246516.X）With a kind of Bi2Fe4O9/BaFe12O19Composite ceramics and preparation method thereof （CN201511024110.2）Using microwave-hydrothermal method elder generation synthetising nanometre powder body, then microwave sintering is prepared for BaTiO respectively3- BaFe12O19、Bi2Fe4O9/BaFe12O19Multiferroic composite ceramics.Both composite ceramicses are two kinds of different ferroelectric phases and ferromagnetic Mutually coexist, there is stronger ferromagnetism, but ferroelectric properties is very weak.Also reported in Anhui University of Science and Technology's Chen Chen academic dissertations micro- Ripple sintering prepares Ni1-xZnxFe2O4-Sr1-xCaxTiO3Composite ceramics prepares and performance study, and there is also same problem.Although this A little document reports microwave sintering prepares relevant multiferroic composite ceramics, compound compared to the similar multiferroic prepared with conventional sintering Ceramics have obvious shortening on sintering time, but performance is not lifted, and corresponding several between ferroelectric phase and ferromagnetic phase Do not react.And use microwave-hydrothermal method elder generation synthetising nanometre powder body in these reports more, complex process, raw material be present Expensive, the problems such as cost is high.There is no relevant report also in pure phase multiferroic ceramics at present.Therefore, it is blue or green to research and develop a kind of tungsten Copper pure phase room temperature multiferroic ceramics and preparation method thereof, not only contribute to verify the multiferroic essence of tungsten bronze BSFN ceramics；And And the ferroelectric properties and ferromagnetic property of BSFN ceramics can be improved；Be advantageous to its practical application.In addition, accelerating to burn till speed, save The about energy and resource, reach energy-saving and emission-reduction, the effect of environmental protection；And production efficiency is improved, production cost is considerably reduced, Significantly improve the economic benefit and social benefit of enterprise.
The content of the invention
The technical problem to be solved in the present invention is, for current Ba4Sm2Fe2Nb8O30(BSFN) ceramics are difficult to obtain in preparing Pure phase, the deficiencies of ferromagnetism is poor；And the BSFN microstructure of ceramics that current sintering method is obtained is mostly columnar grain The characteristics of, it is unfavorable for improving ferromagnetism.It is proposed a kind of tungsten bronze pure phase room temperature multiferroic ceramics and preparation method thereof.
The technical scheme that the present invention takes is as follows：
A kind of tungsten bronze pure phase room temperature multiferroic ceramics, the chemical composition expression formula Ba of the multiferroic ceramics4Sm2Fe2Nb8O30 (BSFN), its preparation method comprises the following steps：
1）With BaCO3、Sm2O3、Nb2O5、Fe2O3Electron level powder weighs dispensing to prepare the raw material of ceramics, according to molecular formula, High-energy ball milling 4-24 hours in deionized water or alcohol, in 1100-1200 after dryingoC is incubated 2-6 hours, synthesizes tungsten bronze Single-phase BSFN powders；
2）By BSFN powders high-energy ball milling 2-8 hours in deionized water or alcohol again, the poly- second of 1-3wt% is added after drying Enol binding agent is granulated, and the powder being granulated is pressed into BSFN base substrates under 100-150MPa.
3）After BSFN base substrate dumpings, in 1200-1300oC microwave sintering methods（2.45GHz）Insulation -1 hour 15 minutes, Cool to room temperature with the furnace, obtain the tungsten bronze pure phase room temperature multiferroic ceramics BSFN.
The crystal structure of the multiferroic one-component ceramic BSFN is tungsten bronze structure, and microstructure forms for equi-axed crystal.
The dielectric constant (f=1kHz) of the multiferroic ceramics BSFN>120；Remanent polarization Pr>1.80μC/cm2, rectify Stupid field Ec>5.00kV/cm；Remanent magnetization Mr>0.40emu/g, coercive field Hc>2000Oe。
The technical contribution of the present invention：1）Using conventional solid react synthesis BSFN powders, without using hydro-thermal method the methods of Synthetising nanometre powder body, technique is simple, and cost is low；2）BSFN tungsten bronze pure phase room temperatures multiferroic pottery is prepared using microwave sintering method Porcelain, sintering time is short, can avoid Fe3+Reduction and LnNbO4、BaFe12O19Dephasign occurs；3）The BSFN ceramics of preparation are isometric Crystal grain, it is suppressed that the preferential growth of tungsten bronze crystal grain is into column.
The BSFN ceramics prepared through the inventive method are with tungsten bronze is single-phase, uniformly tiny, microstructure is isometric to crystal grain Crystal grain and excellent room temperature ferromagnetic and ferroelectric properties.It is intrinsic room temperature multiferroic monophase materialses that this, which has not only verified BSFN, and A kind of simple effective method is provided for the application of BSFN sills.
Brief description of the drawings
Fig. 1 is the typical ferroelectric hysteresis loop of tungsten bronze pure phase room temperature multiferroic ceramics prepared by the present embodiment 3；
Fig. 2 is the typical hysteresis curve of the tungsten bronze pure phase room temperature multiferroic ceramics of the present invention；
Fig. 3 is the electromicroscopic photograph of tungsten bronze pure phase room temperature multiferroic ceramics prepared by the present embodiment 3；
Fig. 4 is the XRD spectrum of the tungsten bronze pure phase room temperature multiferroic ceramics of the present invention.
Embodiment
In order that content of the present invention easily facilitates understanding, with reference to embodiment to of the present invention Technical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
Chemical composition expression formula Ba4Sm2Fe2Nb8O30(BSFN).With BaCO3、Sm2O3、Nb2O5、Fe2O3Electron level powder is preparation The raw material of ceramics, dispensing is weighed according to molecular formula, in deionized water high-energy ball milling 4 hours, 1150 after dryingoC insulations 4 are small When, synthesize the single-phase BSFN powders of tungsten bronze；By BSFN powders high-energy ball milling 2 hours in deionized water again, added after drying 1wt% polyvinyl alcohol adhesives are granulated, and the powder being granulated is pressed into BSFN base substrates under 100MPa.By BSFN base substrates After dumping, 1250oC microwave sintering methods（2.45GHz）Insulation 30 minutes, cools to room temperature with the furnace.
The BSFN multiferroic one-component ceramics of acquisition, its crystal structure are tungsten bronze structure, and microstructure is that size is no more than 2 The equi-axed crystal composition of micron.Its room-temperature property is as follows：Dielectric constant (f=1kHz)=156；Remanent polarization Pr=1.82μC/ cm2, coercive field Ec=5.86kV/cm；Remanent magnetization=0.42emu/g, coercive field Hc=2030Oe。
Embodiment 2
Chemical composition expression formula Ba4Sm2Fe2Nb8O30(BSFN).With BaCO3、Sm2O3、Nb2O5、Fe2O3Electron level powder is preparation The raw material of ceramics, dispensing, high-energy ball milling 6 hours in alcohol, 1150 after drying are weighed according to molecular formulaoC is incubated 2 hours, Synthesize the single-phase BSFN powders of tungsten bronze；By BSFN powders high-energy ball milling 2 hours in alcohol again, the poly- second of 1wt% is added after drying Enol binding agent is granulated, and the powder being granulated is pressed into BSFN base substrates under 150MPa.After BSFN base substrate dumpings, 1250oC microwave sintering methods（2.45GHz）Insulation 30 minutes, cools to room temperature with the furnace.
The BSFN multiferroic one-component ceramics of acquisition, its crystal structure are tungsten bronze structure, and microstructure is that size is no more than 2 The equi-axed crystal composition of micron.Its room-temperature property is as follows：Dielectric constant (f=1kHz)=165；Remanent polarization Pr=2. 05μ C/cm2, coercive field Ec=6.56kV/cm；Remanent magnetization=0.43emu/g, coercive field Hc=2630Oe。
Embodiment 3
Chemical composition expression formula Ba4Sm2Fe2Nb8O30(BSFN).With BaCO3、Sm2O3、Nb2O5、Fe2O3Electron level powder is preparation The raw material of ceramics, dispensing is weighed according to molecular formula, in deionized water high-energy ball milling 16 hours, 1100 after dryingoC insulations 4 Hour, synthesize the single-phase BSFN powders of tungsten bronze；By BSFN powders high-energy ball milling 4 hours in deionized water again, add after drying Add 1wt% polyvinyl alcohol adhesives to be granulated, the powder being granulated is pressed into BSFN base substrates under 100MPa.By BSFN bases After body dumping, 1250oC microwave sintering methods（2.45GHz）Insulation 15 minutes, cools to room temperature with the furnace.The more iron of BSFN of acquisition Property one-component ceramic, its crystal structure is tungsten bronze structure, microstructure be size no more than 2 microns equi-axed crystal form.Its Room-temperature property is as follows：Dielectric constant (f=1kHz)=180；Remanent polarization Pr=2.28μC/cm2, coercive field Ec=6.86kV/ cm；Remanent magnetization=0.45emu/g, coercive field Hc=3000Oe。
Embodiment 4
Chemical composition expression formula Ba4Sm2Fe2Nb8O30(BSFN).With BaCO3、Sm2O3、Nb2O5、Fe2O3Electron level powder is preparation The raw material of ceramics, dispensing is weighed according to molecular formula, in deionized water high-energy ball milling 16 hours, 1100 after dryingoC insulations 6 Hour, synthesize the single-phase BSFN powders of tungsten bronze；By BSFN powders high-energy ball milling 6 hours in deionized water again, add after drying Add 1wt% polyvinyl alcohol adhesives to be granulated, the powder being granulated is pressed into BSFN base substrates under 100MPa.By BSFN bases After body dumping, 1200oC microwave sintering methods（2.45GHz）Insulation 1 hour, cools to room temperature with the furnace.
The BSFN multiferroic one-component ceramics of acquisition, its crystal structure are tungsten bronze structure, and microstructure is that size is no more than 2 The equi-axed crystal composition of micron.Its room-temperature property is as follows：Dielectric constant (f=1kHz)=162；Remanent polarization Pr=2.08μC/ cm2, coercive field Ec=6.25kV/cm；Remanent magnetization=0.46emu/g, coercive field Hc=3120Oe。
Embodiment 5
Chemical composition expression formula Ba4Sm2Fe2Nb8O30(BSFN).With BaCO3、Sm2O3、Nb2O5、Fe2O3Electron level powder is preparation The raw material of ceramics, dispensing is weighed according to molecular formula, in deionized water high-energy ball milling 24 hours, 1200 after dryingoC insulations 2 Hour, synthesize the single-phase BSFN powders of tungsten bronze；By BSFN powders high-energy ball milling 8 hours in deionized water again, add after drying Add 1wt% polyvinyl alcohol adhesives to be granulated, the powder being granulated is pressed into BSFN base substrates under 100MPa.By BSFN bases After body dumping, 1300oC microwave sintering methods（2.45GHz）Insulation 15 minutes, cools to room temperature with the furnace.The more iron of BSFN of acquisition Property one-component ceramic, its crystal structure is tungsten bronze structure, microstructure be size no more than 2 microns equi-axed crystal form.Its Room-temperature property is as follows：Dielectric constant (f=1kHz)=186；Remanent polarization Pr=2.38μC/cm2, coercive field Ec=6.02kV/ cm；Remanent magnetization=0.41emu/g, coercive field Hc=2320Oe。
Fig. 1 is ceramic typical ferroelectric hysteresis loop prepared by the present embodiment 3, and it has high remanent polarization residual polarization Intensity PrWith coercive field Ec, show that the ceramics have typical ferroelectric hysteresis loop, be at room temperature typical ferroelectric.Fig. 2 hysteresis curves BSFN ceramics prepared by the microwave sintering for illustrating to prepare have strong ferromagnetism：High remanent magnetization=0.45emu/g and rectify Magnetic remanence field Hc=3000Oe；Illustrate it for typical ferromagnet at room temperature.Fig. 3 show the tungsten bronze pure phase of the preparation of the present embodiment 3 The electromicroscopic photograph of room temperature multiferroic ceramics, as seen from the figure its there is fine and close microstructure, it is made up of equi-axed crystal, is not as Conventional solid sintering process prepares the columnar grain of Tungsten Bronze Ceramic.All diffraction maximums correspond to four directions in XRD spectrum shown in Fig. 4 Tungsten bronze, show ceramics of the invention for tungsten bronze pure phase ceramics.Show that ceramic material prepared by the present invention is by information above Tungsten bronze pure phase room temperature multi-ferroic material, and with excellent room temperature ferroelectricity, ferromagnetic property.
The invention mainly relates to multi-ferroic material field, and various forms of devices can be made as needed.It is described above only For presently preferred embodiments of the present invention, all equivalent changes and modifications done according to scope of the present invention patent, it should all belong to the present invention Covering scope.

Claims (4)

  1. A kind of 1. preparation method of tungsten bronze pure phase room temperature multiferroic ceramics, it is characterised in that：The chemistry of the multiferroic ceramics Form expression formula Ba4Sm2Fe2Nb8O30, abridge BSFN, and its preparation method comprises the following steps：
    1）With BaCO3、Sm2O3、Nb2O5、Fe2O3Electron level powder weighs dispensing to prepare the raw material of ceramics, according to molecular formula, High-energy ball milling 4-24 hours in deionized water or alcohol, in 1100-1200 after dryingoC is incubated 2-6 hours, synthesizes tungsten bronze Single-phase BSFN powders；
    2）By BSFN powders high-energy ball milling 2-8 hours in deionized water or alcohol again, the poly- second of 1-3wt% is added after drying Enol binding agent is granulated, and the powder being granulated is pressed into BSFN base substrates under 100-150MPa；
    3）After BSFN base substrate dumpings, using microwave sintering method, in 1200-1300oC is incubated -1 hour 15 minutes, cools to the furnace Room temperature, obtain the tungsten bronze pure phase room temperature multiferroic ceramics BSFN, wherein microwave sintering frequency 2.45GHz.
  2. 2. the preparation method of tungsten bronze pure phase room temperature multiferroic ceramics according to claim 1, it is characterised in that：It is described more Iron ceramics BSFN crystal structure is tungsten bronze structure, and microstructure is the equi-axed crystal composition no more than 2 microns.
  3. 3. the preparation method of tungsten bronze pure phase room temperature multiferroic ceramics according to claim 1, it is characterised in that：It is described more Iron ceramics BSFN dielectric constant (f=1kHz)>120；Remanent polarization Pr>1.80μC/cm2, coercive field Ec>5.00kV/ cm；Remanent magnetization Mr>0.40emu/g, coercive field Hc>2000Oe。
  4. 4. tungsten bronze pure phase room temperature multiferroic ceramics made from the preparation method as described in claim 1-3 is any.
CN201711262299.8A 2017-12-04 2017-12-04 Tungsten bronze pure-phase room-temperature multiferroic ceramic and preparation method thereof Active CN107840659B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711262299.8A CN107840659B (en) 2017-12-04 2017-12-04 Tungsten bronze pure-phase room-temperature multiferroic ceramic and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711262299.8A CN107840659B (en) 2017-12-04 2017-12-04 Tungsten bronze pure-phase room-temperature multiferroic ceramic and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107840659A true CN107840659A (en) 2018-03-27
CN107840659B CN107840659B (en) 2021-03-30

Family

ID=61664478

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711262299.8A Active CN107840659B (en) 2017-12-04 2017-12-04 Tungsten bronze pure-phase room-temperature multiferroic ceramic and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107840659B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108675789A (en) * 2018-06-27 2018-10-19 桂林理工大学 A kind of new iron-based ceramic capacitor material and preparation method thereof
CN109516795A (en) * 2018-11-28 2019-03-26 中国科学技术大学 A kind of 0-3 ferrous acid bismuthino magnetic electric compound material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8803264B1 (en) * 2010-05-27 2014-08-12 University Of Puerto Rico Room-temperature magnetoelectric multiferroic thin films and applications thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8803264B1 (en) * 2010-05-27 2014-08-12 University Of Puerto Rico Room-temperature magnetoelectric multiferroic thin films and applications thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
M. JOSSE: ""The Ba2LnFeNb4O15 "Tetragonal Tungsten Bronze"：towards RT composite multiferroics"", 《SOLID STATE SCIENCES》 *
蔡苇等: ""微波烧结制备铁酸铋陶瓷的介电性和铁电性"", 《人工晶体学报》 *
骆统领等: ""退火对含铁钨青铜型铌酸盐结构和性能的影响"", 《金属热处理》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108675789A (en) * 2018-06-27 2018-10-19 桂林理工大学 A kind of new iron-based ceramic capacitor material and preparation method thereof
CN109516795A (en) * 2018-11-28 2019-03-26 中国科学技术大学 A kind of 0-3 ferrous acid bismuthino magnetic electric compound material and preparation method thereof

Also Published As

Publication number Publication date
CN107840659B (en) 2021-03-30

Similar Documents

Publication Publication Date Title
Chen et al. Room temperature multiferroic properties of Ni-doped Aurivillus phase Bi5Ti3FeO15
Miah et al. Synthesis and enhancement of multiferroic properties of (x) Ba0. 95Sr0. 05TiO3–(1− x) BiFe0. 90Dy0. 10O3 ceramics
Jain et al. Tuning the dielectric, ferroelectric and electromechanical properties of Ba0. 83Ca0. 10Sr0. 07TiO3–MnFe2O4 multiferroic composites
Rawat et al. Structural, dielectric, ferroelectric and magnetic properties of (x) CoFe 2 O 4-(1-x) BaTiO 3 composite
Bai et al. Enhanced ferroelectricity and magnetism of quenched (1− x) BiFeO 3-x BaTiO 3 ceramics
Jain et al. Improvement in dielectric, ferroelectric and ferromagnetic characteristics of Ba0. 9Sr0. 1Zr0. 1Ti0. 9O3-NiFe2O4 composites
Li et al. Enhanced Multiferroic and Magnetocapacitive Properties of (1− x) Ba 0.7 Ca 0.3 TiO 3–x BiFeO 3 Ceramics
Srinivas et al. Room temperature multiferroism and magnetoelectric coupling in BaTiO3–BaFe12O19 system
Li et al. Structure, ferroelectric, piezoelectric, and ferromagnetic properties of BiFeO3‐BaTiO3‐Bi0. 5Na0. 5TiO3 lead‐free multiferroic ceramics
Chen et al. Room-temperature magnetoelectric coupling in Bi4 (Ti1Fe2) O12− δ system
Kulkarni et al. Dielectric and magnetoelectric properties of (x) Ni0. 8Co0. 1Cu0. 1Fe2O4/(1− x) PbZr0. 8Ti0. 2O3 composites
Kaswan et al. Crystal structure refinement, enhanced magnetic and dielectric properties of Na0. 5Bi0. 5TiO3 modified Bi0. 8Ba0. 2FeO3 ceramics
Dai et al. Structural, dielectric and magnetic properties of Mn modified xBiFeO3-(1− x) BaTiO3 ceramics
Li et al. Structural and multiferroic properties of Nd and Mn co-doped 0.55 BiFeMnO3-0.45 BaTiO3 ceramics with high energy storage efficiency
Peng et al. Multi-phase structure and electrical properties of Bi 0.5 Li 0.5 ZrO 3 doping K 0.48 Na 0.56 NbO 3 lead-free piezoelectric ceramics
Kim et al. Multiferroic property and crystal structural transition of BiFeO 3-SrTiO 3 ceramics
CN107840659A (en) A kind of tungsten bronze pure phase room temperature multiferroic ceramics and preparation method thereof
CN107417267B (en) Bismuth ferrite multiferroic ceramic and preparation method thereof
Zhou et al. Structural, magnetic and ferroelectric properties of Sm and Mn co-substituted BiFeO3 ceramics with composition near the morphotropic phase boundary
US20220199298A1 (en) Room-temperature multiferroicity material, method for preparing same, and electronic device comprising same
Kanamadi et al. Synthesis and characterization of CoFe 2 O 4–Ba 0.9 Sr 0.1 TiO 3 magnetoelectric composites with dielectric and magnetic properties
CN107986784A (en) A kind of tungsten bronze pure phase room temperature multiferroic ceramic thick film and preparation method thereof
Das et al. Rietveld refined crystal structure, magnetic, dielectric, and electric properties of Li-substituted Ni–Cu–Zn ferrite and Sm, Dy co-doped BaTiO3 multiferroic composites
CN106242546A (en) A kind of Novel Room Temperature many ferrum pottery of high polarization intensity and preparation method thereof
Belavi et al. Resistivity and grain size dependent magnetoelectric effect in (Y) Ni0. 85Cd0. 1Cu0. 05Fe2O4+(1-Y) Batio3 ME composites

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant