CN107840659B - Tungsten bronze pure-phase room-temperature multiferroic ceramic and preparation method thereof - Google Patents
Tungsten bronze pure-phase room-temperature multiferroic ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses tungsten bronze pure-phase room-temperature multiferroic ceramic and a preparation method thereof. The room temperature multiferroic tungsten bronze pure-phase ceramic is rapidly prepared by microwave sintering. The material has excellent ferroelectric and ferromagnetic properties at room temperature, and has strong magnetoelectric coupling effect. The multiferroic ceramic provided by the invention has the advantages of wide raw material source, low price and environmental protection; the preparation process is simple, the performance is excellent, and the industrial application value is great.
Description
Technical Field
The invention relates to tungsten bronze pure-phase room-temperature multiferroic ceramic and a preparation method thereof.
Background
The multiferroic material is an important functional material which has two or more of ferroelectricity, ferromagnetism and ferroelasticity and has a new effect due to mutual coupling among the basic ferroelectricity, and is basically characterized by having ferroelectricity and ferromagnetism and having various physical effects such as piezoelectric effect, ferroelectric effect, pyroelectric effect, nonlinear optical effect, magnetoelectric coupling effect and the like under the condition of an external electric field. These specific properties make the multiferroic material widely used as important material for piezoelectric sonar, ferroelectric film memory, sensor, electrooptical light valve, etc.
At present, the multiferroic material mainly has ferroelectricity and ferromagnetism, and spontaneous polarization and spontaneous magnetic moment of the multiferroic material can be mutually coupled and regulated. However, such single-phase compounds having both ferroelectricity and ferromagnetism are rare, mainly due to the fact that the group of points having both spontaneous polarization and spontaneous magnetization has only 13 kinds of 1, 2 ΄, 2, m ΄, m, 3m ΄, 3, 4m ΄ m ΄, 4, m ΄ m ΄ 2 ΄, m ΄ m2 ΄, 6m ΄ m ΄ 13 and 6. Such as perovskite structure (ABO)3) Material, oxygen octahedral center Nb5+、W6+And Ti4+The d0 electronic configuration of the isoferroelectric active ion plays a very important role in the stability of ferroelectric distortion. However, for magnetic oxides, it is required that the track thereof needs Fe which is not completely filled3+、Ni2+、Gr3+And (3) waiting for transition metal ions. Provided that the oxygen octahedron center is partially filled with d orbitalsFull magnetic ion filling, the centrosymmetry of the crystal lattice tends not to be broken, meaning that spontaneous polarization does not occur, and thus single-phase multiferroic materials are rare. In addition, high state densities above the fermi level tend to make ferromagnets exhibit metallic conductivity, whereas ferroelectric materials require insulators. Because the current is generated inside the electric conductor under the action of the external electric field, but not the electric polarization, the difference of the requirements of the electric conductivity is also one of the reasons for the difficulty in preparing the single-phase multiferroic material.
Most of single-phase multiferroic materials have the defects of low ferromagnetic Curie temperature, low temperature generated by magnetoelectric coupling effect and the like, so that the application of the materials in practice is limited, and the single-phase multiferroic materials are only in an exploration stage at present. Among the single-phase multiferroic materials that have been extensively studied is BiFeO3(BFO), but its resistivity is low and small, and its leakage conductance is too large, so that it can seriously inhibit the practical application of its ferroelectric and ferromagnetic properties. In addition, the BFO has a weak magnetoelectric coupling effect due to different ferroelectric and ferromagnetic sources. BFO is also difficult to synthesize into a single phase. Because of the above problems, research and development of a novel single-phase multiferroic material is urgently required. One of the methods is to introduce magnetic ions into a ferroelectric to form a solid solution in which ferroelectricity and ferromagnetism coexist in one body. Such as Pb (Fe)1/2 3+Nb1/2 5+) (PFN) with ferroelectric curie and antiferromagnetic temperatures of 385K and 143K, respectively, thus having both ferromagnetic and ferroelectric properties at lower temperatures: . Studies have shown that different cations are the source of PFN magnetism and ferroelectricity, Nb5+The ions being ferroelectric active ions of Fe3+Ions are magnetically active ions, so the magnetoelectric coupling effect is low. In recent years researchers have investigated and analyzed Ba4Ln2Fe2Nb8O30 (Ln = La, Pr, Nd, Sm, Eu, Y) series tungsten bronze multiferroic materials, although the results of the studies by different researchers vary, all show Ba4Ln2Fe2Nb8O30The (Ln = Nd, Sm, Eu) ceramic has room temperature ferroelectricity and ferromagnetism. However, a small amount of LnN was observed in the ceramic seriesbO4、BaFe12O19Hetero-phase, and all attribute their ferromagnetism to the presence of small amounts of ferrite BaFe in the ceramic12O19And (3) impurity phase. In addition, Ba is currently available4 Ln2Fe2Nb8O30The (Ln = Nd, Sm, Eu) tungsten bronze ceramics are sintered by a traditional solid phase method, and crystal grains are columnar. According to the characteristics of ferromagnetism and ferroelectricity of the multiferroic material, columnar and other non-isometric crystal grains are not beneficial to improving the ferromagnetism.
Since single-phase multiferroic ceramics are very few and difficult to prepare, some researchers have used ferroelectric ceramics and ferromagnetic ceramics to prepare multiferroic composite ceramics by compounding them. For example, a method for preparing a multiferroic composite ceramic (CN201611246516. X) and a Bi compound2Fe4O9/BaFe12O19The composite ceramic and the preparation method (CN 201511024110.2) adopt a microwave hydrothermal method to synthesize nano-powder, and then prepare BaTiO respectively by microwave sintering3-BaFe12O19、Bi2Fe4O9/BaFe12O19Multiferroic composite ceramics. The two composite ceramics are two different ferroelectric phases and ferromagnetic phases which coexist, and have stronger ferromagnetism but weak ferroelectric property. The Chencheng academic paper of Anhui university also reports the preparation of Ni by microwave sintering1-xZnxFe2O4-Sr1-xCaxTiO3The same problems exist in the preparation and performance research of the composite ceramic. Although these documents report that the sintering time of the microwave sintering process for preparing multiferroic composite ceramics is significantly shortened as compared with the sintering time of the same multiferroic composite ceramics prepared by conventional sintering processes, the performance is not improved, and the corresponding ferroelectric phase and ferromagnetic phase hardly react with each other. In addition, in these reports, the microwave hydrothermal method is mostly adopted to synthesize the nano-powder first, which has the problems of complex process, expensive raw materials, high cost and the like. At present, no relevant report exists in pure-phase multiferroic ceramics. Therefore, the research and development of the tungsten bronze pure-phase room-temperature multiferroic ceramic and the preparation method thereof are beneficial to exploring the multiferroic nature of the tungsten bronze BSFN ceramic; and can improve BSFN ceramicsFerroelectric and ferromagnetic properties; is beneficial to the practical application. In addition, the firing speed is accelerated, energy and resources are saved, and the effects of energy conservation, emission reduction and environmental protection are achieved; and the production efficiency is improved, the production cost is greatly reduced, and the economic benefit and the social benefit of an enterprise are obviously improved.
Disclosure of Invention
The invention aims at solving the technical problem of the current Ba4Sm2Fe2Nb8O30The (BSFN) ceramic has the defects of difficult acquisition of pure phase, poor ferromagnetism and the like in the preparation process; and the BSFN ceramic obtained by the existing sintering method has the characteristic that the microstructure is mostly columnar grains, which is not beneficial to improving the ferromagnetism. Provides a tungsten bronze pure-phase room-temperature multiferroic ceramic and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
tungsten bronze pure-phase room-temperature multiferroic ceramic, wherein the chemical composition expression of the multiferroic ceramic is Ba4Sm2Fe2Nb8O30(BSFN), the preparation method comprising the steps of:
1) with BaCO3、Sm2O3、Nb2O5、Fe2O3The electronic grade powder is used as a raw material for preparing the ceramic, the materials are weighed according to a molecular formula, are subjected to high-energy ball milling in deionized water or alcohol for 4 to 24 hours, and are dried and then are subjected to high-energy ball milling in a temperature range of 1100-1200 DEG CoC, preserving heat for 2-6 hours to synthesize tungsten bronze single-phase BSFN powder;
2) and (3) performing high-energy ball milling on the BSFN powder in deionized water or alcohol for 2-8 hours, drying, adding 1-3wt% of polyvinyl alcohol binder for granulation, and pressing the granulated powder under the pressure of 100-150MPa to prepare a BSFN blank.
3) After the BSFN blank is subjected to glue removal, the BSFN blank is subjected to glue removal at 1200-1300oAnd (3) preserving the heat for 15 minutes to 1 hour by using a C microwave sintering method (2.45 GHz), and cooling to room temperature along with the furnace to obtain the tungsten bronze pure-phase room-temperature multiferroic ceramic BSFN.
The multiferroic single-phase ceramic BSFN has a tungsten bronze structure and an equiaxed grain composition as a microstructure.
Of said multiferroic ceramic BSFNDielectric constant (f =1kHz)>120 of a solvent; remanent polarization Pr>1.80μC/cm2Coercive field Ec>5.00 kV/cm; remanent magnetization Mr>0.40emu/g, coercive field Hc>2000Oe。
The technical contribution of the invention is as follows: 1) BSFN powder is synthesized by adopting the traditional solid-phase reaction, and nano powder is synthesized without adopting methods such as a hydrothermal method and the like, so that the process is simple and the cost is low; 2) the BSFN tungsten bronze pure-phase room-temperature multiferroic ceramic is prepared by a microwave sintering method, the sintering time is short, and Fe can be avoided3+Reduction and LnNbO4、BaFe12O19Appearance of mixed phases; 3) the prepared BSFN ceramic is equiaxial, and the preferential growth of tungsten bronze phase grains into columnar shape is inhibited.
The BSFN ceramic prepared by the method has a tungsten bronze single phase, uniform and fine crystal grains, equiaxial crystal grains in a microstructure and excellent room-temperature ferromagnetic and ferroelectric properties. This not only proves that BSFN is an intrinsic room temperature multiferroic single-phase material, but also provides a simple and effective method for application of BSFN-based materials.
Drawings
FIG. 1 is a typical hysteresis loop of a pure-phase room temperature multiferroic tungsten bronze ceramic prepared in example 3;
FIG. 2 is a typical hysteresis loop of a tungsten bronze pure phase room temperature multiferroic ceramic of the present invention;
FIG. 3 is an electron micrograph of a pure phase room temperature multiferroic tungsten bronze ceramic prepared according to example 3;
FIG. 4 is an XRD spectrum of a pure phase room temperature multiferroic tungsten bronze ceramic of the present invention.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Chemical composition expression Ba4Sm2Fe2Nb8O30(BSFN). With BaCO3、Sm2O3、Nb2O5、Fe2O3Electronic grade powder is used as raw material for preparing ceramic, the raw material is weighed according to molecular formula, is subjected to high-energy ball milling in deionized water for 4 hours, and is dried and then is added in 1150oC, preserving heat for 4 hours, and synthesizing tungsten bronze single-phase BSFN powder; and (3) performing high-energy ball milling on the BSFN powder in deionized water for 2 hours, drying, adding 1wt% of polyvinyl alcohol binder for granulation, and pressing the granulated powder under 100MPa to obtain a BSFN green body. After the BSFN green body is de-gummed, at 1250oAnd C, preserving the heat for 30 minutes by a microwave sintering method (2.45 GHz), and cooling to room temperature along with the furnace.
The BSFN multiferroic single-phase ceramic obtained has a tungsten bronze structure as a crystal structure and a microstructure consisting of equiaxed grains with a size not exceeding 2 microns. The room temperature properties are as follows: dielectric constant (f =1kHz) = 156; remanent polarization Pr=1.82μC/cm2Coercive field Ec=5.86 kV/cm; remanent magnetization =0.42emu/g, coercive field Hc=2030Oe。
Example 2
Chemical composition expression Ba4Sm2Fe2Nb8O30(BSFN). With BaCO3、Sm2O3、Nb2O5、Fe2O3Electronic grade powder is used as raw material for preparing ceramic, the raw material is weighed according to molecular formula, is subjected to high-energy ball milling in alcohol for 6 hours, and is dried and then is added in 1150oC, preserving heat for 2 hours, and synthesizing tungsten bronze single-phase BSFN powder; and (3) performing high-energy ball milling on the BSFN powder in alcohol for 2 hours again, drying, adding 1wt% of polyvinyl alcohol binder for granulation, and pressing the granulated powder under 150MPa to prepare a BSFN blank. After the BSFN green body is de-gummed, at 1250oAnd C, preserving the heat for 30 minutes by a microwave sintering method (2.45 GHz), and cooling to room temperature along with the furnace.
The BSFN multiferroic single-phase ceramic obtained has a tungsten bronze structure as a crystal structure and a microstructure consisting of equiaxed grains with a size not exceeding 2 microns. The room temperature properties are as follows: dielectric constant (f =1kHz) = 165; remanent polarization Pr=2. 05μC/cm2Coercive field Ec=6.56 kV/cm; remanent magnetization =0.43emu/g, coercive field Hc=2630Oe。
Example 3
Chemical composition expression Ba4Sm2Fe2Nb8O30(BSFN). With BaCO3、Sm2O3、Nb2O5、Fe2O3Electronic grade powder is used as raw material for preparing ceramic, the raw material is weighed according to molecular formula, is subjected to high-energy ball milling in deionized water for 16 hours, and is dried and then is processed at 1100 DEG CoC, preserving heat for 4 hours, and synthesizing tungsten bronze single-phase BSFN powder; and (3) performing high-energy ball milling on the BSFN powder in deionized water for 4 hours, drying, adding 1wt% of polyvinyl alcohol binder for granulation, and pressing the granulated powder under 100MPa to obtain a BSFN green body. After the BSFN green body is de-gummed, at 1250oAnd C, preserving the heat for 15 minutes by a microwave sintering method (2.45 GHz), and cooling to room temperature along with the furnace. The BSFN multiferroic single-phase ceramic obtained has a tungsten bronze structure as a crystal structure and a microstructure consisting of equiaxed grains with a size not exceeding 2 microns. The room temperature properties are as follows: dielectric constant (f =1kHz) = 180; remanent polarization Pr=2.28μC/cm2Coercive field Ec=6.86 kV/cm; remanent magnetization =0.45emu/g, coercive field Hc=3000Oe。
Example 4
Chemical composition expression Ba4Sm2Fe2Nb8O30(BSFN). With BaCO3、Sm2O3、Nb2O5、Fe2O3Electronic grade powder is used as raw material for preparing ceramic, the raw material is weighed according to molecular formula, is subjected to high-energy ball milling in deionized water for 16 hours, and is dried and then is processed at 1100 DEG CoC, preserving heat for 6 hours, and synthesizing tungsten bronze single-phase BSFN powder; and (3) performing high-energy ball milling on the BSFN powder in deionized water for 6 hours, drying, adding 1wt% of polyvinyl alcohol binder for granulation, and pressing the granulated powder under 100MPa to obtain a BSFN green body. After the BSFN green body is de-gummed, at 1200oAnd C, preserving heat for 1 hour by a microwave sintering method (2.45 GHz), and cooling to room temperature along with the furnace.
The BSFN multiferroic single-phase ceramic obtained has a tungsten bronze structure as a crystal structure and a microstructure consisting of equiaxed grains with a size not exceeding 2 microns. The room temperature properties are as follows: dielectric constant (f =1kHz) = 162; the residue is leftRemanent polarization Pr=2.08μC/cm2Coercive field Ec=6.25 kV/cm; remanent magnetization =0.46emu/g, coercive field Hc=3120Oe。
Example 5
Chemical composition expression Ba4Sm2Fe2Nb8O30(BSFN). With BaCO3、Sm2O3、Nb2O5、Fe2O3Electronic grade powder is used as raw material for preparing ceramic, the raw material is weighed according to molecular formula, is subjected to high-energy ball milling in deionized water for 24 hours, and is dried and then is processed at 1200 DEG CoC, preserving heat for 2 hours, and synthesizing tungsten bronze single-phase BSFN powder; and (3) performing high-energy ball milling on the BSFN powder in deionized water for 8 hours, drying, adding 1wt% of polyvinyl alcohol binder for granulation, and pressing the granulated powder under 100MPa to obtain a BSFN green body. After the BSFN green body is de-gummed, at 1300oAnd C, preserving the heat for 15 minutes by a microwave sintering method (2.45 GHz), and cooling to room temperature along with the furnace. The BSFN multiferroic single-phase ceramic obtained has a tungsten bronze structure as a crystal structure and a microstructure consisting of equiaxed grains with a size not exceeding 2 microns. The room temperature properties are as follows: dielectric constant (f =1kHz) = 186; remanent polarization Pr=2.38μC/cm2Coercive field Ec=6.02 kV/cm; remanent magnetization =0.41emu/g, coercive field Hc=2320Oe。
FIG. 1 is a typical hysteresis loop of the ceramic prepared in this example 3, which has a high remanent polarization PrAnd coercive field EcThe ceramic is shown to have a typical hysteresis loop and is a typical ferroelectric at room temperature. Fig. 2 shows the hysteresis loop that the prepared BSFN ceramic prepared by microwave sintering has strong ferromagnetism: high remanent magnetization =0.45emu/g and coercive field Hc=3000 Oe; which is illustrated as a typical ferromagnet at room temperature. Fig. 3 is an electron micrograph of the pure-phase room temperature multiferroic tungsten bronze ceramic prepared according to example 3, which shows that the pure-phase room temperature multiferroic tungsten bronze ceramic has a dense microstructure composed of equiaxed grains, unlike the columnar grains of tungsten bronze ceramic prepared by the conventional solid-phase sintering method. All diffraction peaks in the XRD pattern shown in FIG. 4 correspond to the tetragonal tungsten bronze phase, indicating the ceramics of the present inventionIs tungsten bronze pure phase ceramic. The information shows that the ceramic material prepared by the invention is a tungsten bronze pure-phase room-temperature multiferroic material and has excellent room-temperature ferroelectric and ferromagnetic properties.
The invention mainly relates to the field of multiferroic materials, and devices in different forms can be manufactured according to requirements. The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (2)
1. A preparation method of tungsten bronze pure-phase room-temperature multiferroic ceramic is characterized by comprising the following steps: the chemical composition expression of the multiferroic ceramic is Ba4Sm2Fe2Nb8O30Abbreviated BSFN, the preparation method comprises the steps of:
1) with BaCO3、Sm2O3、Nb2O5、Fe2O3The electronic grade powder is used as a raw material for preparing the ceramic, the materials are weighed according to a molecular formula, are subjected to high-energy ball milling in deionized water or alcohol for 4 to 24 hours, and are dried and then are subjected to high-energy ball milling in a temperature range of 1100-1200 DEG CoC, preserving heat for 2-6 hours to synthesize tungsten bronze single-phase BSFN powder;
2) performing high-energy ball milling on the BSFN powder in deionized water or alcohol for 2-8 hours, drying, adding 1-3wt% of polyvinyl alcohol binder for granulation, and pressing the granulated powder under the pressure of 100-150MPa to prepare a BSFN blank;
3) after the BSFN blank is subjected to glue discharge, a microwave sintering method is adopted to carry out the steps of 1200-1300oC, preserving the heat for 15 minutes to 1 hour, and cooling to room temperature along with the furnace to obtain the tungsten bronze pure-phase room-temperature multiferroic ceramic BSFN, wherein the microwave sintering frequency is 2.45 GHz;
the multiferroic ceramic BSFN is in a tungsten bronze structure, and the microstructure is composed of equiaxed grains not more than 2 microns; a dielectric constant of the multiferroic ceramic BSFN at f =1kHz>120 of a solvent; remanent polarization Pr>1.80μC/cm2Coercive field Ec>5.00 kV/cm; remanent magnetization Mr>0.40emu/g, coercive field Hc>2000Oe。
2. The tungsten bronze pure-phase room-temperature multiferroic ceramic produced by the production method according to claim 1.
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