CN108147813B - 一种高压电系数钛酸铋钠基无铅压电陶瓷及其制备方法 - Google Patents

一种高压电系数钛酸铋钠基无铅压电陶瓷及其制备方法 Download PDF

Info

Publication number
CN108147813B
CN108147813B CN201810124947.1A CN201810124947A CN108147813B CN 108147813 B CN108147813 B CN 108147813B CN 201810124947 A CN201810124947 A CN 201810124947A CN 108147813 B CN108147813 B CN 108147813B
Authority
CN
China
Prior art keywords
powder
piezoelectric ceramic
lead
tio
free piezoelectric
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.)
Active
Application number
CN201810124947.1A
Other languages
English (en)
Other versions
CN108147813A (zh
Inventor
张斗
周学凡
姜超
罗行
周科朝
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.)
Guangzhou Guangding Technology Group Co ltd
Original Assignee
Guangzhou Guangding Technology Group Co ltd
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 Guangzhou Guangding Technology Group Co ltd filed Critical Guangzhou Guangding Technology Group Co ltd
Priority to CN201810124947.1A priority Critical patent/CN108147813B/zh
Publication of CN108147813A publication Critical patent/CN108147813A/zh
Application granted granted Critical
Publication of CN108147813B publication Critical patent/CN108147813B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/475—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on bismuth titanates
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • 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
    • C04B35/62695—Granulation or pelletising
    • 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
    • C04B35/6342—Polyvinylacetals, e.g. polyvinylbutyral [PVB]
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5116—Ag or Au
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/093—Forming inorganic materials
    • H10N30/097—Forming inorganic materials by sintering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H10N30/8561—Bismuth based oxides
    • 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
    • C04B2235/3201—Alkali metal 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
    • C04B2235/3205—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
    • C04B2235/65—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
    • 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
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering

Abstract

本发明公开了一种高压电系数钛酸铋钠基无铅压电陶瓷及其制备方法；所述高压电系数钛酸铋钠基无铅压电陶瓷的化学计量比为：0.85Bi0.5Na0.5TiO3‑0.11Bi0.5K0.5‑xRbxTiO3‑0.04BaTiO3(BNT‑BKT‑BT‑Rbx,x＝0,0.05,0.10,0.20)；其制备方法包括：将Bi2O3,Na2CO3,K2CO3,BaCO3,Rb2CO3和TiO2粉末按照化学计量比混合均匀，经过球磨、烘干，在850℃预烧3h得到预烧粉，再经过二次球磨、烘干、造粒、压制、排胶后，于1160‑1180℃烧结，再经过被银和极化后，制得无铅压电陶瓷。本发明通过将铷元素掺杂在钛酸铋钠基无铅压电陶瓷中，提高了其压电系数d33，BNT‑BKT‑BT‑Rb0.05陶瓷的压电系数达210pC/N，该无铅压电材料在驱动器、传感器等多种领域可以得到良好应用。

Description

一种高压电系数钛酸铋钠基无铅压电陶瓷及其制备方法
技术领域
本发明涉及一种高压电系数钛酸铋钠基无铅压电陶瓷及其制备方法，属于无铅压电陶瓷材料技术领域。
背景技术
压电陶瓷是一种功能陶瓷，其可以实现将电能和机械能相互转化，在电子、机械和通讯等领域都有着不可替代的应用价值，广泛应用于驱动器、传感器、换能器等多种器件的制作。但目前大规模使用的压电陶瓷仍是以PZT等为主的铅基压电陶瓷，但是铅具有毒性，会危害人体健康并对环境造成污染。各主要工业国及我国政府都颁布了相应的法律法规，限制或在不久的将来全面禁止含铅等有害物质在电子信息产品中的使用。因此亟须寻求一种无铅的、环境友好的并且性能优良的压电材料以取代传统的铅基压电材料。无铅压电铁电材料中，钛酸铋钠(Na0.5Bi0.5TiO3，NBT)因其具有较高的剩余极化强度、居里温度、介电常数以及近年来发现的大场致应变而受到重视，被认为是最有希望取代铅基压电铁电材料的无铅体系。为了进一步提高钛酸铋钠基无铅压电陶瓷的性能，通常会添加第二组元进行掺杂改性，发展出了相应的二元、三元体系，其具有比纯NBT陶瓷更加优异的烧结特性和压电性能。然而，总体来说钛酸铋钠基无铅压电陶瓷的压电性能仍需进一步提升，以获得高的压电系数。目前对于钛酸铋钠体系进行Rb等价掺杂的研究还鲜有报道。
发明内容
针对上述问题，本发明的第一个目的是具有良好压电性能的高压电系数钛酸铋钠基无铅压电陶瓷。
本发明的第二个目的是提供上述高压电系数钛酸铋钠基无铅压电陶瓷的制备方法。
为此，本发明提供的第一个技术方案是这样的：
一种高压电系数钛酸铋钠基无铅压电陶瓷，其组分原料及其摩尔百分比含量为0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.5-xRbxTiO3-0.04BaTiO3；
其中：所述x＝0或者0.05或者0.10或者0.20。
本发明提供的第二个技术方案是这样的：
一种高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，依次包括下述步骤：
步骤一：配料合成
根据0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.5-xRbxTiO3-0.04BaTiO3的化学计量比称取原料Bi2O3，Na2CO3，K2CO3，BaCO3，Rb2CO3和TiO2进行配料，将配好的料放入以无水乙醇为介质、氧化锆球为磨球的尼龙罐中球磨，再将球磨后的浆料于75-85℃烘干；
步骤二：预烧
烘干后的粉料过筛后置于氧化铝坩埚中，在750-850℃下预烧2-4h，得到预烧粉，再将预烧粉置于球磨机中进行二次球磨，再于75-85℃烘干；
步骤三：造粒
将步骤二的粉末过筛后，按照质量百分比0.8-1.2％加入聚乙烯醇缩丁醛，充分研磨至粉料呈粒状，得到颗粒均匀的粉料；
步骤四：压制成型
将步骤三中的粉料压制成直径为8-12mm，厚度为1.0-1.4mm的圆柱生坯圆柱生坯；
步骤五：排胶烧结
将上述生坯置于氧化铝坩埚中，利用同等组分的预烧粉埋烧，首先以2℃/min的升温速率至550-650℃保温1h排胶，然后以5℃/min的升温速率至1160-1180℃保温2h烧结，随炉自然冷却，制得无铅压电陶瓷；
步骤六：被银
对烧结好的陶瓷块体进行打磨和抛光，在两面涂覆中温银浆，在500-600℃下保温25-35min烧成银电极；
步骤七：极化
将述被银后的无铅压电陶瓷块体在硅油浴中极化处理，即得到高压电系数钛酸铋钠基无铅压电陶瓷0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.5-xRbxTiO3-0.04BaTiO3。
进一步的，上述的一种高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，步骤一所述的配料、磨球和无水乙醇的质量比为4:2:1。
进一步的，述的一种高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，步骤一和步骤二中的球磨机的转速均为400r/min，步骤一球磨时间为12h，步骤二球磨时间为24h。
进一步的，上述的一种高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，步骤二中预烧粉的预烧时间为3h。
进一步的，上述的一种高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，步骤四中压制生坯时的压制压强为20Mpa，保压时间为5min。
进一步的，上述的一种高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，步骤七中的极化时间为10-30min，极化电场为2-4kV/mm。
与现有技术相比，本发明的有益效果：
本发明将铷元素等价掺杂入钛酸铋钠基无铅压电陶瓷，所制备压电陶瓷无杂相，随着铷掺杂含量的增多，压电陶瓷的性能发生了显著改变，在掺杂量x为0.05时，获得压电系数高达210pC/N。本发明制备的无铅压电陶瓷生产成本低，压电性能好，在驱动器、传感器等多种领域可以得到良好应用。
附图说明
图1为实施例1、2、3、4所制备的不同铷掺杂量的无铅压电陶瓷的XRD检测结；
图2为实施例1、2、3、4所制备的不同铷掺杂量的无铅压电陶瓷的铁电电滞回线(P-E loops)和相应的电流-电场回线(I-V curves)。
图3为实施例1、2、3、4所制备的不同铷掺杂量的无铅压电陶瓷在3.5kV/mm电场极化20min后，测得的室温压电常数d33的值。
具体实施方式
下面结合具体实施方式对比本发明的权利要求做进一步的详细说明。
实施例1：制备BNT-BKT-BT无铅压电陶瓷。
按照0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.5TiO3-0.04BaTiO3的摩尔化学计量比称取原料Bi2O3,Na2CO3,K2CO3,BaCO3和TiO2混合均匀，将配好的料放入以无水乙醇为介质、氧化锆球为磨球的尼龙罐中球磨，在400r/min的转速下球磨12h。再将球磨后的浆料于80℃烘干。烘干后的粉料过200目筛后置于氧化铝坩埚中，在800℃下预烧3h，得到预烧粉。再将预烧粉在400r/min的转速下球磨24h，再于80℃烘干。将上述粉末过筛后，加入预烧粉总质量1％加入聚乙烯醇缩丁醛(PVA)，充分研磨至粉料呈粒状，得到颗粒均匀的粉料，并在20Mpa的压强下保压5min压制成直径为10mm，厚度为1.2mm左右的圆柱生坯。将上述生坯置于氧化铝坩埚中，利用同等组分的预烧粉埋烧，首先以2℃/min的升温速率至600℃保温1h排胶，然后以5℃/min的升温速率至1165℃保温2h烧结，随炉自然冷却，制得无铅压电陶瓷。对烧结好的陶瓷块体进行打磨和抛光，在两面涂覆中温银浆，在550℃下保温30min烧成银电极。上述被银后的无铅压电陶瓷块体在硅油浴中在3.5kV/mm的条件下极化20min，即得到0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.5TiO3-0.04BaTiO3无铅压电陶瓷元件。
实施例2：制备BNT-BKT-BT-Rb0.05无铅压电陶瓷。
按照0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.45Rb0.05TiO3-0.04BaTiO3的化学计量比称取原料Bi2O3,Na2CO3,K2CO3,BaCO3,Rb2CO3和TiO2粉，将配好的料放入以无水乙醇为介质、氧化锆球为磨球的尼龙罐中球磨，在400r/min的转速下球磨12h。再将球磨后的浆料于75℃烘干。烘干后的粉料过200目筛后置于氧化铝坩埚中，在850℃下预烧3h，得到预烧粉。再将预烧粉在400r/min的转速下球磨24h，再于80℃烘干。将上述粉末过筛后，加入预烧粉总质量0.8％加入聚乙烯醇缩丁醛(PVA)，充分研磨至粉料呈粒状，得到颗粒均匀的粉料，并在20Mpa的压强下保压5min压制成直径为10mm，厚度为1.2mm左右的圆柱生坯。将上述生坯置于氧化铝坩埚中，利用同等组分的预烧粉埋烧，首先以2℃/min的升温速率至550℃保温1h排胶，然后以5℃/min的升温速率至1160℃保温2h烧结，随炉自然冷却，制得无铅压电陶瓷。对烧结好的陶瓷块体进行打磨和抛光，在两面涂覆中温银浆，在500℃下保温25min烧成银电极。上述被银后的无铅压电陶瓷块体在硅油浴中在3.5kV/mm的条件下极化20min，即得到0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.5TiO3-0.04BaTiO3无铅压电陶瓷元件。
实施例3：制备BNT-BKT-BT-Rb0.10无铅压电陶瓷。
按照0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.40Rb0.10TiO3-0.04BaTiO3的化学计量比称取原料Bi2O3,Na2CO3,K2CO3,BaCO3,Rb2CO3和TiO2粉，将配好的料放入以无水乙醇为介质、氧化锆球为磨球的尼龙罐中球磨，在400r/min的转速下球磨12h。再将球磨后的浆料于85℃烘干。烘干后的粉料过200目筛后置于氧化铝坩埚中，在850℃下预烧3h，得到预烧粉。再将预烧粉在400r/min的转速下球磨24h，再于85℃烘干。将上述粉末过筛后，加入预烧粉总质量1％加入聚乙烯醇缩丁醛(PVA)，充分研磨至粉料呈粒状，得到颗粒均匀的粉料，并在20Mpa的压强下保压5min压制成直径为10mm，厚度为1.2mm左右的圆柱生坯。将上述生坯置于氧化铝坩埚中，利用同等组分的预烧粉埋烧，首先以2℃/min的升温速率至650℃保温1h排胶，然后以5℃/min的升温速率至1180℃保温2h烧结，随炉自然冷却，制得无铅压电陶瓷。对烧结好的陶瓷块体进行打磨和抛光，在两面涂覆中温银浆，在600℃下保温35min烧成银电极。上述被银后的无铅压电陶瓷块体在硅油浴中在3.5kV/mm的条件下极化20min，即得到0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.5TiO3-0.04BaTiO3无铅压电陶瓷元件。
实施例4：制备BNT-BKT-BT-Rb0.20无铅压电陶瓷。
按照0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.30Rb0.20TiO3-0.04BaTiO3的化学计量比称取原料Bi2O3,Na2CO3,K2CO3,BaCO3,Rb2CO3和TiO2粉，将配好的料放入以无水乙醇为介质、氧化锆球为磨球的尼龙罐中球磨，在400r/min的转速下球磨12h。再将球磨后的浆料于80℃烘干。烘干后的粉料过200目筛后置于氧化铝坩埚中，在800℃下预烧3h，得到预烧粉。再将预烧粉在400r/min的转速下球磨24h，再于80℃烘干。将上述粉末过筛后，加入预烧粉总质量1％加入聚乙烯醇缩丁醛(PVA)，充分研磨至粉料呈粒状，得到颗粒均匀的粉料，并在20Mpa的压强下保压5min压制成直径为10mm，厚度为1.2mm左右的圆柱生坯。将上述生坯置于氧化铝坩埚中，利用同等组分的预烧粉埋烧，首先以2℃/min的升温速率至600℃保温1h排胶，然后以5℃/min的升温速率至1165℃保温2h烧结，随炉自然冷却，制得无铅压电陶瓷。对烧结好的陶瓷块体进行打磨和抛光，在两面涂覆中温银浆，在550℃下保温30min烧成银电极。上述被银后的无铅压电陶瓷块体在硅油浴中在3.5kV/mm的条件下极化20min，即得到0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.5TiO3-0.04BaTiO3无铅压电陶瓷元件。
为了证明本发明提供的技术方案的效果，下面给出本申请制备的无铅压电陶瓷结果结果，具体如下：
图1是实施例1、2、3、4所制备的不同铷掺杂量的无铅压电陶瓷的XRD检测结果，可以看出所有制备的产物均为纯相，不含有任何的杂质。所制备的BNT-BKT-BT-Rbx(x＝0,0.05,0.10,0.20)均形成了均匀的固溶体，从46.5°左右的分峰看来，所有组分均是三方相和四方相共存的结构，但随着铷掺杂量的增多，四方相含量逐渐减少。
图2是实施例1、2、3、4所述制备的不同铷掺杂量的无铅压电陶瓷的铁电电滞回线(P-E loops)和相应的电流-电场回线(I-V curves)，从结果可以看出铷掺杂量x为0和0.05时，压电陶瓷体现出饱和丰满的电滞回线，并且电流-电场回线具有双峰，说明是典型铁电体。而当铷掺杂量x增加到0.10和0.20时，电滞回线明显收缩，,电流-电场回线具有四峰，说明产生了铁电相到弛豫相的转变。随着铷掺杂量的增多，压电陶瓷的矫顽场单调减小。
图3是实施例1、2、3、4所述制备的不同铷掺杂量的无铅压电陶瓷在3.5kV/mm电场极化20min后，测得的室温压电常数d33的值，可以看出少量的进行铷掺杂，可以提高压电陶瓷的压电性能，最高d33在x＝0.05时获得，为210pC/mm。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (7)

1.一种高压电系数钛酸铋钠基无铅压电陶瓷，其特征在于，其组分原料及其摩尔百分比含量为0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.45Rb0.05TiO3-0.04BaTiO3；
所述的高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，依次包括下述步骤：
步骤一：配料合成
根据0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.45Rb0.05TiO3-0.04BaTiO3的化学计量比称取原料Bi2O3，Na2CO3，K2CO3，BaCO3，Rb2CO3和TiO2进行配料，将配好的料放入以无水乙醇为介质、氧化锆球为磨球的尼龙罐中球磨，再将球磨后的浆料于75-85℃烘干；
步骤二：预烧
烘干后的粉料过筛后置于氧化铝坩埚中，在750-850℃下预烧2-4h，得到预烧粉，再将预烧粉置于球磨机中进行二次球磨，再于75-85℃烘干；
步骤三：造粒
将步骤二的粉末过筛后，按照预烧粉质量百分比0.8-1.2%加入聚乙烯醇缩丁醛，充分研磨至粉料呈粒状，得到颗粒均匀的粉料；步骤四：压制成型
将步骤三中的粉料压制成直径为8-12mm，厚度为1.0-1.4mm的圆柱生坯；
步骤五：排胶烧结
将上述生坯置于氧化铝坩埚中，利用同等组分的预烧粉埋烧，首先以2℃/min的升温速率至550-650℃保温1h排胶，然后以5℃/min的升温速率至1160-1180℃保温2h烧结，随炉自然冷却，制得无铅压电陶瓷；
步骤六：被银
对烧结好的陶瓷块体进行打磨和抛光，在两面涂覆中温银浆，在500-600℃下保温25-35min烧成银电极；
步骤七：极化
将述被银后的无铅压电陶瓷块体在硅油浴中极化处理，即得到0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.45Rb0.05TiO3-0.04BaTiO3 无铅压电陶瓷元件。
2.权利要求1所述的一种高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，其特征在于，依次包括下述步骤：
步骤一：配料合成
根据0.85Bi0.5Na0.5TiO3-0.11Bi0.5K0.45Rb0.05TiO3-0.04BaTiO3的化学计量比称取原料Bi2O3，Na2CO3，K2CO3，BaCO3，Rb2CO3和TiO2进行配料，将配好的料放入以无水乙醇为介质、氧化锆球为磨球的尼龙罐中球磨，再将球磨后的浆料于75-85℃烘干；
步骤二：预烧
烘干后的粉料过筛后置于氧化铝坩埚中，在750-850℃下预烧2-4h，得到预烧粉，再将预烧粉置于球磨机中进行二次球磨，再于75-85℃烘干；
步骤三：造粒
将步骤二的粉末过筛后，按照预烧粉质量百分比0.8-1.2%加入聚乙烯醇缩丁醛，充分研磨至粉料呈粒状，得到颗粒均匀的粉料；
步骤四：压制成型
将步骤三中的粉料压制成直径为8-12mm，厚度为1.0-1.4mm的圆柱生坯；
步骤五：排胶烧结
将上述生坯置于氧化铝坩埚中，利用同等组分的预烧粉埋烧，首先以2℃/min的升温速率至550-650℃保温1h排胶，然后以5℃/min的升温速率至1160-1180℃保温2h烧结，随炉自然冷却，制得无铅压电陶瓷；
步骤六：被银
对烧结好的陶瓷块体进行打磨和抛光，在两面涂覆中温银浆，在500-600℃下保温25-35min烧成银电极；
步骤七：极化
将述被银后的无铅压电陶瓷块体在硅油浴中极化处理，即得到0.85Bi0.5Na0.5TiO3-0.11Bi0.5 K0.45Rb0.05TiO3-0.04BaTiO3 无铅压电陶瓷元件。
3.根据权利要求2所述的一种高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，其特征在于，步骤一中所述的配料、磨球和无水乙醇的质量比为4:2:1。
4.根据权利要求2所述的一种高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，其特征在于，步骤一和步骤二中的球磨机的转速均为400r/min，步骤一球磨时间为12h，步骤二球磨时间为24h。
5.根据权利要求2所述的一种高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，其特征在于，步骤二中预烧粉的预烧时间为3h。
6.根据权利要求2所述的一种高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，其特征在于，步骤四中压制生坯时的压制压强为20Mpa，保压时间为5min。
7.根据权利要求2所述的一种高压电系数钛酸铋钠基无铅压电陶瓷的制备方法，其特征在于，步骤七中的极化时间为10-30min，极化电场为2-4kV/mm。
CN201810124947.1A 2018-02-07 2018-02-07 一种高压电系数钛酸铋钠基无铅压电陶瓷及其制备方法 Active CN108147813B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810124947.1A CN108147813B (zh) 2018-02-07 2018-02-07 一种高压电系数钛酸铋钠基无铅压电陶瓷及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810124947.1A CN108147813B (zh) 2018-02-07 2018-02-07 一种高压电系数钛酸铋钠基无铅压电陶瓷及其制备方法

Publications (2)

Publication Number Publication Date
CN108147813A CN108147813A (zh) 2018-06-12
CN108147813B true CN108147813B (zh) 2021-03-16

Family

ID=62459897

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810124947.1A Active CN108147813B (zh) 2018-02-07 2018-02-07 一种高压电系数钛酸铋钠基无铅压电陶瓷及其制备方法

Country Status (1)

Country Link
CN (1) CN108147813B (zh)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109206135B (zh) * 2018-09-28 2020-05-19 华中科技大学 一种具有高温度系数的热敏陶瓷材料及其制备方法
CN110015894B (zh) * 2019-05-06 2020-04-07 广州光鼎科技集团有限公司 一种高温下介电稳定的钛酸铋钠基陶瓷及其制备方法和应用
CN111018518A (zh) * 2019-12-17 2020-04-17 上海交通大学 致密强荧光高压电性能的nbt-kbt-bt基多功能陶瓷材料及制备方法
CN112062555A (zh) * 2020-09-17 2020-12-11 广西大学 一种利用功能团掺杂诱导bnt-bt基无铅负电卡材料的制备方法
CN113061025A (zh) * 2021-05-21 2021-07-02 安徽大学 一种无铅钛酸铋钠基x9r型陶瓷电容器材料及其制备方法
CN113964266B (zh) * 2021-10-13 2023-09-19 中国科学院光电技术研究所 一种制备高性能铋基无铅压电驱动器的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3598243B2 (ja) * 1999-09-30 2004-12-08 株式会社東芝 圧電単結晶組成物およびその圧電単結晶ウェハー
CN101381231A (zh) * 2008-10-10 2009-03-11 北京工业大学 一种三元系钛酸铋钠基无铅压电陶瓷材料及其制备方法
CN103482973A (zh) * 2013-09-10 2014-01-01 天津大学 无铅四元体系电致应变压电陶瓷材料及制备方法和产品
CN103613382B (zh) * 2013-12-04 2015-04-22 天津大学 钛酸铋钠-钛酸钡-钛酸铋钾无铅压电织构陶瓷及其制备方法
JP6365126B2 (ja) * 2014-08-29 2018-08-01 Tdk株式会社 圧電組成物および圧電素子

Also Published As

Publication number Publication date
CN108147813A (zh) 2018-06-12

Similar Documents

Publication Publication Date Title
CN108147813B (zh) 一种高压电系数钛酸铋钠基无铅压电陶瓷及其制备方法
CN111302797B (zh) 一种铌酸钾钠基无铅压电陶瓷及其制备方法
KR100821542B1 (ko) 압전 자기 및 그 제조방법
EP2610233B1 (en) Piezoelectric ceramic and piezoelectric device
CN110981468B (zh) 一种钛酸铋钠基压电陶瓷的制备方法
EP3000795A1 (en) Piezoelectric composition, piezoelectric element and sputtering target
CN106064942B (zh) 高居里温度无铅snkbt压电陶瓷及其制备方法
CN110357624B (zh) 高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料及其制备方法
CN107903055B (zh) 一种梯度掺杂钛酸铋钠基多层无铅压电陶瓷
CN106977196B (zh) 一种非化学计量比钛酸铋钠基陶瓷及其制备方法和应用
CN113880576A (zh) 低烧结温度和各向异性的铌酸锶钡钠钨青铜型压铁电陶瓷材料及其制备方法
CN113582692A (zh) 低温烧结的铌酸钾钠基无铅压电陶瓷材料及其制备方法
CN111018519B (zh) 一种铌酸钠掺杂钛酸铋钠-铝酸铋陶瓷的制备方法
CN105130419B (zh) 一种高电致应变无铅压电陶瓷材料及其制备方法与应用
CN107162585A (zh) 一种钛酸铋钠基电致伸缩陶瓷及其制备方法和应用
CN114292102B (zh) 一种铁酸铋-钛酸钡基无铅压电陶瓷材料及其制备方法
CN110550953A (zh) 一种钛酸铋钠基无铅压电陶瓷及其制备方法
CN108129145B (zh) 一种x7r陶瓷电容器介质材料及其制备方法
KR101866845B1 (ko) 전계유기 변형 특성이 우수한 무연 압전 세라믹 조성물 및 이의 제조방법
CN106986629B (zh) 一种钛酸铋基铋层状结构铁电陶瓷靶材的制备方法
CN111606707B (zh) 一种容温稳定性压电陶瓷材料以及制备方法
CN107056281B (zh) 一种高应变钛酸铋钠基陶瓷及其制备方法
KR20180003277A (ko) 전계유기 변형특성이 우수한 무연 압전 세라믹스의 제조방법
KR101806207B1 (ko) 변형율이 높고 저온소성이 가능한 삼성분계 무연 압전 세라믹스 및 이의 제조방법
KR101352607B1 (ko) 유전체 자기 조성물, 유전체 자기 조성물의 제조 방법 및 전자 부품

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