WO2020062618A1 - 一种优良温度稳定性的铁电材料及其制备方法与应用 - Google Patents

一种优良温度稳定性的铁电材料及其制备方法与应用 Download PDF

Info

Publication number
WO2020062618A1
WO2020062618A1 PCT/CN2018/121725 CN2018121725W WO2020062618A1 WO 2020062618 A1 WO2020062618 A1 WO 2020062618A1 CN 2018121725 W CN2018121725 W CN 2018121725W WO 2020062618 A1 WO2020062618 A1 WO 2020062618A1
Authority
WO
WIPO (PCT)
Prior art keywords
ferroelectric material
temperature stability
ball milling
excellent temperature
preparing
Prior art date
Application number
PCT/CN2018/121725
Other languages
English (en)
French (fr)
Inventor
齐西伟
张敏
杜强
张晓燕
Original Assignee
东北大学
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 东北大学 filed Critical 东北大学
Publication of WO2020062618A1 publication Critical patent/WO2020062618A1/zh

Links

Images

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
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2675—Other ferrites containing rare earth metals, e.g. rare earth ferrite garnets
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C04B2235/3234—Titanates, not containing zirconia
    • C04B2235/3236—Alkaline earth titanates
    • 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
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time

Definitions

  • the invention relates to the field of ferroelectric materials, in particular to a ferroelectric material with excellent temperature stability, a preparation method and application thereof.
  • Ferroelectric materials have various properties such as ferroelectricity, ferroelasticity, dielectric properties, pyroelectricity, and piezoelectricity, as well as the coupling properties between them, such as force-electric-thermal coupling properties, and electro-acoustic-optical properties. Coupling properties, switching characteristics, etc., have made ferroelectric materials widely used, and set off increasing researches on ferroelectric materials. At present, countries are investing more and more in the research of ferroelectric materials, and related research results are constantly emerging.
  • 0.7BiFeO 3 –0.3BaTiO 3 has very excellent ferroelectric properties.
  • the 0.7BiFeO 3 –0.3BaTiO 3 ceramic system modified by solid solution of LaFeO 3 has a ferroelectric, Both ferromagnetic and magnetoelectric coupling performance have been significantly improved.
  • 0.675BiFeO 3 -0.3BaTiO 3 -0.025LaFeO 3 material has very good properties, its temperature is not stable enough and cannot meet the practical application. By doping MnO 2 in this system, its temperature stability has been significantly improved.
  • no report about 0.675BiFeO 3 -0.3BaTiO 3 -0.025LaFeO 3 -x% MnO 2 has been reported.
  • the present invention provides a ferroelectric material with excellent temperature stability, and a preparation method and application thereof.
  • the ferroelectric material with excellent temperature stability of the present invention has excellent temperature stability and can be applied to a sensor or a memory.
  • a ferroelectric material with excellent temperature stability according to the present invention has a general chemical composition formula: 0.675BiFeO 3 -0.3BaTiO 3 -0.025LaFeO 3 -x% MnO 2 , 0 ⁇ x ⁇ 4.
  • the method for preparing a ferroelectric material with excellent temperature stability of the present invention includes the following steps:
  • the debinding temperature is 500-600 ° C, and the debinding time is 2-5h to obtain the demineralized ceramic sheet;
  • the sintered ceramic sheet is sintered at a high temperature, the sintering temperature is 900-1100 ° C, and the sintering time is 2-5h to obtain a ferroelectric material with excellent temperature stability.
  • the starting materials include Bi 2 O 3 , La 2 O 3 , Fe 2 O 3 , BaCO 3 , TiO 2 and MnO 2 .
  • the ball mill is preferably a ball mill tank, and the material of the ball mill tank is preferably polytetrafluoroethylene.
  • the ball milling time is preferably 18 hours.
  • the calcination temperature is preferably 750 ° C.
  • the calcination time is 2-4 hours, and preferably 3 hours.
  • the solvent is preferably anhydrous ethanol; the molar volume ratio corresponds to the initial raw material used to prepare the 0.06mol ferroelectric material, and the solvent used is 30-40mL.
  • the binder is an aqueous PVA solution, and the mass concentration of PVA in the aqueous PVA solution is 3% to 7%, and preferably 5%.
  • the ball milling time is preferably 10 hours.
  • the screening purpose is to screen particles smaller than 90 mesh.
  • the tabletting is preferably 2 MPa.
  • the debinding temperature is preferably 550 ° C
  • the debinding time is preferably 3h
  • the debonding heating rate is 1-2 ° C / min.
  • the sintering temperature is preferably 1000 ° C.
  • the sintering time is preferably 3 h
  • the sintering heating rate is 3-5 ° C./min.
  • An application of a ferroelectric material with excellent temperature stability is to use the material in a sensor or a memory.
  • the ferroelectric material with excellent temperature stability and the preparation method and application thereof have the following beneficial effects:
  • the ferroelectric material with excellent temperature stability prepared by the preparation method of the invention has stable structure, excellent ferroelectric performance, and can Used in sensors or memories.
  • FIG. 1 is an X-ray diffraction pattern of a ferroelectric material obtained in a comparative example of the present invention and Examples 1 to 5;
  • Example 3 is a hysteresis loop of the ferroelectric material obtained in Example 1 of the present invention at different test temperatures;
  • Fig. 4 is a graph showing changes in the residual polarization intensity of the ferroelectric materials obtained in the comparative example and Examples 1 to 5 of the present invention with the test temperature.
  • the method for preparing the ferroelectric material includes the following steps:
  • the pre-synthesized powder is further subjected to wet ball milling for 10 hours. After drying, a second ball milling powder is obtained;
  • the pressed ceramic sheet is heated to a temperature of 2 ° C / min to a temperature of 550 ° C for 3 hours, and the ceramic sheet after debinding is obtained.
  • the temperature is increased, and the temperature is increased to a high temperature of 1000 ° C at a temperature of 5 ° C / min. Sintered for 3 hours to obtain a ferroelectric material.
  • a method for preparing a ferroelectric material with excellent temperature stability includes the following steps:
  • the pre-synthesized powder is further subjected to wet ball milling for 10 hours. After drying, a second ball milling powder is obtained;
  • the pressed ceramic sheet is heated to a temperature of 2 ° C / min to a temperature of 550 ° C for 3 hours, and the ceramic sheet after debinding is obtained.
  • the temperature is increased, and the temperature is increased to a high temperature of 1000 ° C at a temperature of 5 ° C / min. Sintered for 3 hours to obtain a ferroelectric material.
  • a method for preparing a ferroelectric material with excellent temperature stability includes the following steps:
  • the pre-synthesized powder is further subjected to wet ball milling for 10 hours. After drying, a second ball milling powder is obtained;
  • the pressed ceramic sheet is heated to a temperature of 2 ° C / min to a temperature of 550 ° C for 3 hours, and the ceramic sheet after debinding is obtained.
  • the temperature is increased, and the temperature is increased to a high temperature of 1000 ° C at a temperature of 5 ° C / min. Sintered for 3 hours to obtain a ferroelectric material.
  • a method for preparing a ferroelectric material with excellent temperature stability includes the following steps:
  • the pre-synthesized powder is further subjected to wet ball milling for 10 hours. After drying, a second ball milling powder is obtained;
  • the pressed ceramic sheet is heated to a temperature of 2 ° C / min to a temperature of 550 ° C for 3 hours, and the ceramic sheet after debinding is obtained.
  • the temperature is increased, and the temperature is increased to a high temperature of 1000 ° C at a temperature of 5 ° C / min. Sintered for 3 hours to obtain a ferroelectric material.
  • a method for preparing a ferroelectric material with excellent temperature stability includes the following steps:
  • the pre-synthesized powder is further subjected to wet ball milling for 10 hours. After drying, a second ball milling powder is obtained;
  • the pressed ceramic sheet is heated to a temperature of 2 ° C / min to a temperature of 550 ° C for 3 hours, and the ceramic sheet after debinding is obtained.
  • the temperature is increased, and the temperature is increased to a high temperature of 1000 ° C at a temperature of 5 ° C / min. Sintered for 3 hours to obtain a ferroelectric material.
  • a method for preparing a ferroelectric material with excellent temperature stability includes the following steps:
  • the pre-synthesized powder is further subjected to wet ball milling for 10 hours. After drying, a second ball milling powder is obtained;
  • the pressed ceramic sheet is heated to a temperature of 2 ° C / min to a temperature of 550 ° C for 3 hours, and the ceramic sheet after debinding is obtained.
  • the temperature is increased, and the temperature is increased to 5 ° C / min to a high temperature of 1000 ° C Sintered for 3 hours to obtain a ferroelectric material.
  • the structure of the ceramic is determined:
  • the present invention is based on finding a ferroelectric material with excellent temperature stability.
  • BiFeO 3 -BaTiO 3 -LaFeO 3 (referred to as BFO-BTO-LFO), as a multiferroic material with both ferroelectricity and antiferromagnetism, has great research value and application value.
  • the first is the ceramic synthesis process. Through repeated experimental exploration, the optimal sintering temperature and sintering time are explored, and finally the ceramic sample with the best performance is obtained. The structure is determined by an X-ray diffractometer. Then, the iron at different test temperatures is determined.
  • the test results of the ferroelectric performance of Comparative Example and Example 1 are shown in FIG. 2 and FIG. 3.
  • the ferroelectric material (comparative example) not doped with MnO 2 increased 65 ° C from 25 ° C, and the residual polarization intensity increased sharply, from 26mC / cm 2 to 42mC / cm 2 with a change rate of 61.5%.
  • the stability is poor.
  • the slope of the highest point of the curve is negative, indicating that there is a space charge effect.
  • the ferroelectric material doped with 0.5% MnO 2 (Example 1), when the test temperature is 25-110 ° C, the change of the residual polarization intensity is small (the maximum change rate is 6.4%), which indicates the incorporation of MnO 2 .
  • the temperature stability of the system is significantly improved, but as the doped amount of MnO 2 is increased, as shown in FIG. 4, wherein 0, 0.5, 1, 2, 3, and 4 in the figure correspond to the comparative examples, Example 1, Example 2, Example 3, Example 4 and Example 5.
  • the amount of MnO 2 added increases, the temperature stability of the system decreases.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

一种优良温度稳定性的铁电材料及其制备方法与应用，属于铁电材料领域。该铁电材料的化学组成通式为：0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2，0＜x≤4。其制备方法为：按照铁电材料成分的化学计量比，称量初始原料；将初始原料放入球磨罐中，加入溶剂球磨，然后烘干，再于720-780℃预烧，得到预合成粉体；将预合成粉体继续湿法球磨，烘干后，加入粘结剂，混合均匀后，过筛，压片，将得到陶瓷片于500-600℃排胶，再于900-1100℃烧结，得到优良温度稳定性的铁电材料。

Description

一种优良温度稳定性的铁电材料及其制备方法与应用 技术领域
本发明涉及铁电材料领域，具体而言，涉及一种优良温度稳定性的铁电材料及其制备方法及应用。
背景技术
铁电材料同时具有铁电性、铁弹性、介电性、热释电性及压电性等多种性质以及它们之间的耦合性质，如力-电-热耦合性质、电-声-光耦合性质、开关特性等，这些性质使铁电材料获得了广泛的应用，掀起了对于铁电材料与日俱增的投入研究。目前，各国对于铁电材料的研究的投入越来越多，相关的研究成果也在不断地涌现。
在众多铁电材料中，0.7BiFeO 3–0.3BaTiO 3具有非常优异的铁电性质，在前期的研究中，通过LaFeO 3固溶改性的0.7BiFeO 3–0.3BaTiO 3陶瓷体系，其铁电、铁磁和磁电耦合性能都有明显改善和提高。虽然0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3材料具有非常好的性质，但其温度稳定不佳，无法满足实际的应用。通过对该体系进行掺杂MnO 2,其温度稳定性得到了显著提高，然而，目前尚未见到0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2相关的体系的报道。
发明内容
针对现有技术的不足，本发明提供一种优良温度稳定性的铁电材料及其制备方法与应用。本发明的优良温度稳定性的铁电材料具有优良的温度稳定性，能够应用于传感器或存储器中。
本发明的一种优良温度稳定性的铁电材料，该材料的化学组成通式为：0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2，0＜x≤4。
所述的优良温度稳定性的铁电材料，作为优选x＝0.5-1。
本发明的一种优良温度稳定性的铁电材料的制备方法，包括以下步骤：
(1)按照优良温度稳定性的铁电材料化学式的成分计量比，称量初始原料；
(2)将称量好的初始原料放入球磨罐中，加入溶剂，采用湿法球磨的方法进行球磨，球磨时间为16-20h，得到球磨后的混合物，将混合物进行烘干，得到粉料；将粉料于720-780℃进行预烧，得到预合成粉体；
(3)将预合成粉体继续湿法球磨，球磨时间为6-14h，烘干后，得到第二次球磨粉体；
向第二次球磨粉体中加入粘结剂，混合均匀后，过筛，在1-3MPa下压片，得到陶瓷片；其中，按质量比，铁电材料：粘结剂＝1g：(0.18-0.24)g；
(4)将压好的陶瓷片进行排胶，排胶温度为500-600℃，排胶时间为2-5h，得到排胶后的 陶瓷片；
将排胶后的陶瓷片进行高温烧结，烧结温度为900-1100℃，烧结时间为2-5h，得到优良温度稳定性的铁电材料。
所述的步骤(1)中，初始原料包括Bi 2O 3，La 2O 3，Fe 2O 3，BaCO 3，TiO 2和MnO 2。
所述的步骤(2)中，所述的球磨优选为球磨罐，所述的球磨罐的材质优选为聚四氟乙烯。
所述的步骤(2)中，所述的球磨参数为：球磨转速为150-200r/min，料球质量比为，料：球＝1：(5-10)；
所述的步骤(2)中，所述的球磨时间优选为18h。
所述的步骤(2)中，所述的预烧温度优选为750℃，预烧时间为2-4h，优选为3h。
所述的步骤(2)中，所述的湿法球磨中，溶剂优选为无水乙醇；按摩尔体积比，对应制备0.06mol铁电材料所用的初始原料，所用溶剂为30-40mL。
所述的步骤(3)中，所述的粘结剂为PVA水溶液，PVA水溶液中PVA的质量浓度为3％-7％，优选为5％。
所述的步骤(3)中，所述的湿法球磨中，溶剂优选为无水乙醇；按摩尔体积比，对应制备0.06mol铁电材料所用的初始原料：溶剂＝0.06mol：30-40mL。
所述的步骤(3)中，所述的湿法球磨，球磨时间优选为10h。
所述的步骤(3)中，所述的过筛目的在于筛选小于90目的颗粒。
所述的步骤(3)中，所述的压片，优选为2MPa。
所述的步骤(4)中，排胶温度优选为550℃，排胶时间优选为3h，排胶升温速度为1-2℃/min。
所述的步骤(4)中，所述的烧结温度优选为1000℃，烧结时间优选为3h，烧结升温速度为3-5℃/min。
一种优良温度稳定性的铁电材料的应用，为将该材料用在传感器或存储器中。
本发明的一种优良温度稳定性的铁电材料及其制备方法与应用，其具有以下有益效果：本发明制备方法制备的优良温度稳定性的铁电材料具有结构稳定、铁电性能优良，能够应用于传感器或存储器中。
附图说明
图1是本发明对比例和实施例1至实施例5所得出的铁电材料的X射线衍射图谱；
图2是本发明对比例所得出的铁电材料在不同测试温度下的电滞回线；
图3是本发明实施例1所得出的铁电材料在不同测试温度下的电滞回线；
图4是本发明对比例和实施例1至实施例5所得出的铁电材料的剩余极化强度随测试温 度变化图。
此处的附图被并入说明书并构成本说明书的一部分，示出了符合本发明的实施例，并与说明书一起用于解释本发明的原理。
具体实施方式
以下通过具体的实施例并结合附图对本发明作进一步的介绍。
以下实施例中，除特殊说明，所用试剂均为市售产品，分析纯。
对比例
一种铁电材料，其化学组分为0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2的铁电材料；其中，x＝0。
该铁电材料的制备方法，包括以下步骤：
(1)按照0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2分子式的化学计量比准确称量初始原料Bi 2O 3，La 2O 3，Fe 2O 3，BaCO 3，TiO 2和MnO 2，称取量为0.06mol该铁电材料所对应的初始原料的总量；具体为Bi 2O 3为9.4357g，La 2O 3为0.2444g，Fe 2O 3为3.3535g，BaCO 3为3.5521g，TiO 2为1.4377g和MnO 2为0g；
(2)将称好的初始原料放入装有氧化锆球的球磨罐中，加入30mL无水乙醇作溶剂进行湿法球磨，球磨转速为150r/min，料球质量比为1:5，球磨时间为18h，得到球磨后的混合物，将混合物倒入托盘中烘干，并在750℃下预烧，得到预合成粉体；
(3)将预合成粉体继续湿法球磨10h，烘干后，得到第二次球磨粉体；
向第二次球磨粉体中加入质量浓度为5％的PVA作为粘结剂，混合均匀后，过90目筛子，将小于90目的颗粒，在2MPa下压片，得到陶瓷片；其中，1g铁电材料对应所加入的PVA量为0.18-0.24g；
(4)将压好的陶瓷片以2℃/min的升温速度加热到550℃排胶3h，得到排胶后的陶瓷片；继续升温，以5℃/min的升温速度加热到1000℃高温中烧结3h，得到铁电材料。
实施例1
一种优良温度稳定性的铁电材料，该材料的化学组分0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2的铁电材料；其中，x＝0.5。
一种优良温度稳定性的铁电材料的制备方法，包括以下步骤：
(1)按照0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2分子式的化学计量比准确称量初始原料Bi 2O 3，La 2O 3，Fe 2O 3，BaCO 3，TiO 2和MnO 2，称取量为0.06mol该铁电材料所对应的初始原料的总量；其中，具体为Bi 2O 3为9.4357g，La 2O 3为0.2444g，Fe 2O 3为3.3535g，BaCO 3为3.5521g，TiO 2为1.4377g和MnO 2为0.0264g；
(2)将称好的初始原料放入装有氧化锆球的球磨罐中，加入30mL无水乙醇作溶剂进行湿法球磨，球磨转速为150r/min，料球质量比为1:5，球磨时间为18h，得到球磨后的混合物，将混合物球磨后倒入托盘中烘干，并在750℃下预烧，得到预合成粉体；
(3)将预合成粉体继续湿法球磨10h，烘干后，得到第二次球磨粉体；
向第二次球磨粉体中加入质量浓度为5％的PVA作为粘结剂，混合均匀后，过90目筛子，将小于90目的颗粒，在2MPa下压片，得到陶瓷片；其中，1g铁电材料对应所加入的PVA量为0.18-0.24g；
(4)将压好的陶瓷片以2℃/min的升温速度加热到550℃排胶3h，得到排胶后的陶瓷片；继续升温，以5℃/min的升温速度加热到1000℃高温中烧结3h，得到铁电材料。
实施例2
一种优良温度稳定性的铁电材料，该材料的化学组分为0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2的铁电材料；其中，x＝1。
一种优良温度稳定性的铁电材料的制备方法，包括以下步骤：
(1)按照0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2分子式的化学计量比准确称量初始原料Bi 2O 3，La 2O 3，Fe 2O 3，BaCO 3，TiO 2和MnO 2，称取量为0.06mol该铁电材料所对应的初始原料的总量；其中，具体为Bi 2O 3为9.4357g，La 2O 3为0.2444g，Fe 2O 3为3.3535g，BaCO 3为3.5521g，TiO 2为1.4377g和MnO 2为0.0528g；
(2)将称好的初始原料放入装有氧化锆球的球磨罐中，加入30mL无水乙醇作溶剂进行湿法球磨，球磨转速为150r/min，料球质量比为1:5，球磨时间为18h，得到球磨后的混合物，将混合物球磨后倒入托盘中烘干，并在750℃下预烧，得到预合成粉体；
(3)将预合成粉体继续湿法球磨10h，烘干后，得到第二次球磨粉体；
向第二次球磨粉体中加入质量浓度为5％的PVA作为粘结剂，混合均匀后，过90目筛子，将小于90目的颗粒，在2MPa下压片，得到陶瓷片；其中，1g铁电材料对应所加入的PVA量为0.18-0.24g；
(4)将压好的陶瓷片以2℃/min的升温速度加热到550℃排胶3h，得到排胶后的陶瓷片；继续升温，以5℃/min的升温速度加热到1000℃高温中烧结3h，得到铁电材料。
实施例3
一种优良温度稳定性的铁电材料，该材料的化学组分为0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2的铁电材料；其中x＝2。
一种优良温度稳定性的铁电材料的制备方法，包括以下步骤：
(1)按照0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2分子式的化学计量比准确称量初 始原料Bi 2O 3，La 2O 3，Fe 2O 3，BaCO 3，TiO 2和MnO 2，称取量为0.06mol该铁电材料所对应的初始原料的总量；其中，具体为Bi 2O 3为9.4357g，La 2O 3为0.2444g，Fe 2O 3为3.3535g，BaCO 3为3.5521g，TiO 2为1.4377g和MnO 2为0.1056g；
(2)将称好的初始原料放入装有氧化锆球的球磨罐中，加入30mL无水乙醇作溶剂进行湿法球磨，球磨转速为150r/min，料球质量比为1:5，球磨时间为18h，得到球磨后的混合物，将混合物球磨后倒入托盘中烘干，并在750℃下预烧，得到预合成粉体；
(3)将预合成粉体继续湿法球磨10h，烘干后，得到第二次球磨粉体；
向第二次球磨粉体中加入质量浓度为5％的PVA作为粘结剂，混合均匀后，过90目筛子，将小于90目的颗粒，在2MPa下压片，得到陶瓷片；其中，1g铁电材料对应所加入的PVA量为0.18-0.24g；
(4)将压好的陶瓷片以2℃/min的升温速度加热到550℃排胶3h，得到排胶后的陶瓷片；继续升温，以5℃/min的升温速度加热到1000℃高温中烧结3h，得到铁电材料。
实施例4
一种优良温度稳定性的铁电材料，该材料的化学组分为0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2的铁电材料；其中x＝3。
一种优良温度稳定性的铁电材料的制备方法，包括以下步骤：
(1)按照0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2分子式的化学计量比准确称量初始原料Bi 2O 3，La 2O 3，Fe 2O 3，BaCO 3，TiO 2和MnO 2，称取量为0.06mol该铁电材料所对应的初始原料的总量；其中，具体为Bi 2O 3为9.4357g，La 2O 3为0.2444g，Fe 2O 3为3.3535g，BaCO 3为3.5521g，TiO 2为1.4377g和MnO 2为0.1584g；
(2)将称好的初始原料放入装有氧化锆球的球磨罐中，加入30mL无水乙醇作溶剂进行湿法球磨，球磨转速为150r/min，料球质量比为1:5，球磨时间为18h，得到球磨后的混合物，将混合物球磨后倒入托盘中烘干，并在750℃下预烧，得到预合成粉体；
(3)将预合成粉体继续湿法球磨10h，烘干后，得到第二次球磨粉体；
向第二次球磨粉体中加入质量浓度为5％的PVA作为粘结剂，混合均匀后，过90目筛子，将小于90目的颗粒，在2MPa下压片，得到陶瓷片；其中，1g铁电材料对应所加入的PVA量为0.18-0.24g；
(4)将压好的陶瓷片以2℃/min的升温速度加热到550℃排胶3h，得到排胶后的陶瓷片；继续升温，以5℃/min的升温速度加热到1000℃高温中烧结3h，得到铁电材料。
实施例5
一种优良温度稳定性的铁电材料，该材料的化学组分为 0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2的铁电材料；其中x＝4。
一种优良温度稳定性的铁电材料的制备方法，包括以下步骤：
(1)按照0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2分子式的化学计量比准确称量初始原料Bi 2O 3，La 2O 3，Fe 2O 3，BaCO 3，TiO 2和MnO 2，称取量为0.06mol该铁电材料所对应的初始原料的总量；其中，具体为Bi 2O 3为9.4357g，La 2O 3为0.2444g，Fe 2O 3为3.3535g，BaCO 3为3.5521g，TiO 2为1.4377g和MnO 2为0.2112g；
(2)将称好的初始原料放入装有氧化锆球的球磨罐中，加入30mL无水乙醇作溶剂进行湿法球磨，球磨转速为150r/min，料球质量比为1:5，球磨时间为18h，得到球磨后的混合物，将混合物球磨后倒入托盘中烘干，并在750℃下预烧，得到预合成粉体；
(3)将预合成粉体继续湿法球磨10h，烘干后，得到第二次球磨粉体；
向第二次球磨粉体中加入质量浓度为5％的PVA作为粘结剂，混合均匀后，过90目筛子，将小于90目的颗粒，在2MPa下压片，得到陶瓷片；其中，1g铁电材料对应所加入的PVA量为0.18-0.24g；
(4)将压好的陶瓷片以2℃/min的升温速度加热到550℃排胶3h，得到排胶后的陶瓷片；继续升温，以5℃/min的升温速度加热到1000℃高温中烧结3h，得到铁电材料。
下面以制备实施例1到实施例5、以及对比例所得的优良温度稳定性的铁电材料为实验对象，通过实验分析所制备的铁电材料的性质以及性能，具体如下：
实验例一
陶瓷的结构确定：
不同物质都有特定的原子种类、原子排列方式和点阵参数，在X射线作用下晶体的不同晶面发生各自的衍射，呈现出特定的衍射花样。采用X射线粉末衍射，确定陶瓷的结构。采用的仪器是日本理学SmartLab型X射线衍射仪，其扫描角度范围：2θ＝20-80°，扫描速度为4°/min，步长为0.01°，得到的粉末衍射结果如图1所示，其中，图中x＝0、x＝0.5、x＝1、x＝2、x＝3和x＝4分别对应对比例，实施例1，实施例2，实施例3、实施例4和实施例5。
实验例二
陶瓷的变温铁电性能测量：
a)陶瓷片磨薄、抛光，两面涂上银浆，为电学性质的测试做准备。
b)铁电性质的测量：所用仪器为美国Radiant铁电测试系统，测试条件为:室温-155℃，频率为1Hz。
本发明是基于寻找优良温度稳定性的铁电材料而进行的。BiFeO 3–BaTiO 3–LaFeO 3(简称BFO-BTO-LFO)作为同时具有铁电性和反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，最终得到性能最佳的陶瓷样品，用X射线衍射仪确定结构，然后，对其不同测试温度的铁电性能测量分析，其中，对比例所得出的铁电材料在不同测试温度下(25℃、50℃、60℃)的电滞回线见图2；实施例1所得出的铁电材料在不同测试温度下(25℃、50℃、80℃、110℃、135℃、155℃)的电滞回线见图3。
制备实施例1至实施例5、以及对比例的晶体结构的测试结果，如图1所示。经XRD测试分析可得，制备实施例1至实施例5、以及对比例的铁电材料为纯的钙钛矿结构。
制备对比例和实施例1的铁电性能的测试结果，如图2和图3所示。未掺杂MnO 2的铁电材料(对比例)，随测试温度从25℃增加65℃，剩余极化强度急剧增加，从26mC/cm 2增加到42mC/cm 2，变化率为61.5％，温度稳定性较差，在测试温度为65℃时，曲线最高点的斜率为负，说明存在空间电荷效应。掺杂了0.5％MnO 2的铁电材料(实施例1)，在测试温度为25-110℃时，剩余极化强度变化很小(变化率最大为6.4％)，说明MnO 2的掺入，明显提高了体系的温度稳定性，但是随着MnO 2掺入量的增加，如图4所示，其中，图中0、0.5、1、2、3和4分别对应对比例，实施例1，实施例2，实施例3、实施例4和实施例5。通过对比，随着MnO 2掺入量的增加，体系的温度稳定性有所下降。
由于其具有上述优良性能，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。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围内。

Claims (11)

  1. 一种优良温度稳定性的铁电材料，其特征在于，该材料的化学组成通式为：0.675BiFeO 3-0.3BaTiO 3-0.025LaFeO 3-x％MnO 2，0＜x≤4。
  2. 如权利要求1所述的优良温度稳定性的铁电材料，其特征在于，所述的优良温度稳定性的铁电材料，x＝0.5-1。
  3. 权利要求1或2所述的优良温度稳定性的铁电材料的制备方法，其特征在于，包括以下步骤：
    (1)按照优良温度稳定性的铁电材料化学式的成分计量比，称量初始原料；
    (2)将称量好的初始原料放入球磨罐中，加入溶剂，采用湿法球磨的方法进行球磨，球磨时间为16-20h，得到球磨后的混合物，将混合物进行烘干，得到粉料；将粉料于720-780℃进行预烧，得到预合成粉体；
    (3)将预合成粉体继续湿法球磨，球磨时间为6-14h，烘干后，得到第二次球磨粉体；
    向第二次球磨粉体中加入粘结剂，混合均匀后，过筛，在1-3MPa下压片，得到陶瓷片；其中，按质量比，铁电材料：粘结剂＝1g：(0.18-0.24)g；
    (4)将压好的陶瓷片进行排胶，排胶温度为500-600℃，排胶时间为2-5h，得到排胶后的陶瓷片；
    将排胶后的陶瓷片继续进行高温烧结，烧结温度为900-1100℃，烧结时间为2-5h，得到优良温度稳定性的铁电材料。
  4. 如权利要求3所述的优良温度稳定性的铁电材料的制备方法，其特征在于，所述的步骤(1)中，初始原料包括Bi 2O 3，La 2O 3，Fe 2O 3，BaCO 3，TiO 2和MnO 2。
  5. 如权利要求3所述的优良温度稳定性的铁电材料的制备方法，其特征在于，所述的步骤(2)中，所述的球磨参数为：球磨转速为150-200r/min，料球质量比为，料：球＝1：(5-10)。
  6. 如权利要求3所述的优良温度稳定性的铁电材料的制备方法，其特征在于，所述的步骤(3)中，所述的粘结剂为PVA水溶液，PVA水溶液中PVA的质量浓度为3％-7％。
  7. 如权利要求3所述的优良温度稳定性的铁电材料的制备方法，其特征在于，所述的湿法球磨中，溶剂为无水乙醇；按摩尔体积比，对应制备0.06mol铁电材料所用的初始原料，所用溶剂为30-40mL。
  8. 如权利要求3所述的优良温度稳定性的铁电材料的制备方法，其特征在于，所述的步骤(3)中，所述的过筛为筛选小于90目的颗粒。
  9. 如权利要求3所述的优良温度稳定性的铁电材料的制备方法，其特征在于，所述的步骤(4)中，排胶升温速度为1-2℃/min。
  10. 如权利要求3所述的优良温度稳定性的铁电材料的制备方法，其特征在于，所述的步 骤(4)中，烧结升温速度为3-5℃/min。
  11. 一种优良温度稳定性的铁电材料的应用，其特征在于，将优良温度稳定性的铁电材料用在传感器或存储器中。
PCT/CN2018/121725 2018-09-28 2018-12-18 一种优良温度稳定性的铁电材料及其制备方法与应用 WO2020062618A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811135814.0A CN108947514B (zh) 2018-09-28 2018-09-28 一种优良温度稳定性的铁电材料及其制备方法与应用
CN201811135814.0 2018-09-28

Publications (1)

Publication Number Publication Date
WO2020062618A1 true WO2020062618A1 (zh) 2020-04-02

Family

ID=64472614

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/121725 WO2020062618A1 (zh) 2018-09-28 2018-12-18 一种优良温度稳定性的铁电材料及其制备方法与应用

Country Status (2)

Country Link
CN (1) CN108947514B (zh)
WO (1) WO2020062618A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108947514B (zh) * 2018-09-28 2020-03-31 东北大学 一种优良温度稳定性的铁电材料及其制备方法与应用
CN114671678A (zh) * 2022-03-30 2022-06-28 哈尔滨理工大学 一种低损耗BiFeO3-BaTiO3高温无铅压电陶瓷及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102205721A (zh) * 2010-03-12 2011-10-05 精工爱普生株式会社 液体喷射头、液体喷射装置以及压电元件
CN103708817A (zh) * 2013-12-19 2014-04-09 桂林电子科技大学 一种高耐压无铅高温铁电陶瓷及其制备方法
CN104402425A (zh) * 2014-11-27 2015-03-11 桂林电子科技大学 一种低损耗铁酸铋-钛酸钡基压电陶瓷的制备方法
CN104961451A (zh) * 2015-07-01 2015-10-07 西北工业大学 铁酸镧铋陶瓷及其制备方法
CN108947514A (zh) * 2018-09-28 2018-12-07 东北大学 一种优良温度稳定性的铁电材料及其制备方法与应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105948737B (zh) * 2016-05-11 2019-01-04 武汉理工大学 一种CaTiO3基线性储能介质陶瓷材料及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102205721A (zh) * 2010-03-12 2011-10-05 精工爱普生株式会社 液体喷射头、液体喷射装置以及压电元件
CN103708817A (zh) * 2013-12-19 2014-04-09 桂林电子科技大学 一种高耐压无铅高温铁电陶瓷及其制备方法
CN104402425A (zh) * 2014-11-27 2015-03-11 桂林电子科技大学 一种低损耗铁酸铋-钛酸钡基压电陶瓷的制备方法
CN104961451A (zh) * 2015-07-01 2015-10-07 西北工业大学 铁酸镧铋陶瓷及其制备方法
CN108947514A (zh) * 2018-09-28 2018-12-07 东北大学 一种优良温度稳定性的铁电材料及其制备方法与应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LUO, LINGLING ET AL.: "Phase Transition, Piezoelectric, and Multiferroic Properties of La(Co0.5Mn0.5)O3-Modified BiFeO3-BaTiO3 Lead-Free Ceramics", PHYS. STATUS SOLIDI A, vol. 212, no. 9, 28 April 2015 (2015-04-28), pages 2012 - 2022, XP055706321 *
ZHANG, MIN ET AL.: "Enhanced Ferroelectric, Magnetic and Magnetoelectric Properties of Multiferroic BiFeO3-BaTiO3-LaFeO3 Ceramics", CERAMICS INTERNATIONAL, vol. 44, 18 August 2018 (2018-08-18), XP055706315 *

Also Published As

Publication number Publication date
CN108947514A (zh) 2018-12-07
CN108947514B (zh) 2020-03-31

Similar Documents

Publication Publication Date Title
Sunder et al. Investigation of tetragonal distortion in the PbTiO3–BiFeO3 system by high-temperature X-ray diffraction
CN109180181A (zh) 一种无铅弛豫反铁电陶瓷储能材料及其制备方法
CN106810235A (zh) 铁酸铋‑钛酸铅‑钛酸钡三元体系高温压电陶瓷及其制备方法
WO2020062618A1 (zh) 一种优良温度稳定性的铁电材料及其制备方法与应用
CN113292329B (zh) 一种铁酸铋-钛酸钡二元高温压电陶瓷材料及其制备方法和应用
CN109704762A (zh) 一种铌酸锶基类反铁电陶瓷及其制备方法和应用
CN103981573B (zh) 提高钙钛矿结构铁电材料居里温度的方法
CN106145941A (zh) 一种富锆锆钛酸铅‑铁酸铋多铁性陶瓷材料
Bendahhou et al. Structural, electrical, and dielectric study of the influence of 3.4% lanthanide (Ln 3+= Sm 3+ and La 3+) insertion in the A-site of perovskite Ba 0.95 Ln 0.034 Ti 0.99 Zr 0.01 O 3
US6403053B1 (en) Preparation of translucent strontium barium niobate ceramics using reaction sintering
CN104692800A (zh) 一种温度稳定型无铅巨介电常数陶瓷材料
JP3295018B2 (ja) チタン酸バリウム粉末の製造方法
CN107512910A (zh) 一种三元弛豫铁电压电材料铌镥酸铅‑铌镍酸铅‑钛酸铅及其制备方法和应用
CN105314982A (zh) 三元多铁性材料、该材料的制备方法及应用
CN112537952B (zh) 一种具有优异磁电性能的铁酸铋基陶瓷及其制备方法
CN114956815A (zh) 一种新型高应变高居里温度铌酸钾钠基铁电陶瓷的制备方法
CN107311643A (zh) 宽工作温区高介电性能的无铅电子陶瓷材料及制备方法
JP3629285B2 (ja) 圧電セラミックの製法
CN106518055B (zh) 高介电常数铥、锶掺杂钛酸钡陶瓷材料及其制备方法
Bhatt et al. Temperature dependence of dielectric properties of sodium potassium niobate ceramics
Wang et al. Effect of PbO excess on sintering and piezoelectric properties of 12Pb (Ni1/3Sb2/3) O3–40PbZrO3–48PbTiO3 ceramics
Fang et al. Structural and dielectric properties of Ba6M0. 67Nb9. 33O30 (M= Zn and Ni) ceramics
JP3194994B2 (ja) 誘電体磁器組成物の誘電特性制御方法
CN110240478B (zh) 一种具有优异压电性能材料的制备方法
JPH04114919A (ja) 複合ペロブスカイト型誘電体磁器粉末の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18934796

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18934796

Country of ref document: EP

Kind code of ref document: A1