CN102942360B - 无铅的铁电/电致伸缩陶瓷材料 - Google Patents

无铅的铁电/电致伸缩陶瓷材料 Download PDF

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CN102942360B
CN102942360B CN201210336994.5A CN201210336994A CN102942360B CN 102942360 B CN102942360 B CN 102942360B CN 201210336994 A CN201210336994 A CN 201210336994A CN 102942360 B CN102942360 B CN 102942360B
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A·陈
Y·只
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Abstract

一种无铅的铁电/电致伸缩陶瓷材料。包含二元体系固溶液的陶瓷组合物，由式子：(1-x)(Sr1-yBiy)TiO3+x(Na0.5Bi0.5)TiO3和(1-x)(Sr1-15yBiy)TiO3+x(Na0.5Bi0.5)TiO3表示，其中0＜x＜l和0＜y≤0.2。

Description

无铅的铁电/电致伸缩陶瓷材料
本申请是分案申请，原申请的申请日为2005年11月18日、申请号为200580039752.8(PCT/US2005/041902)、发明名称为“无铅的铁电/电致伸缩陶瓷材料”。
发明背景
本发明涉及铁电和电致伸缩陶瓷材料，特别是那些无铅并表现出非常强的剩余极化强度和大量纯电致伸缩的材料，尤其是在(Sr,Bi,Na)TiO3固溶液中。本发明的组合物进一步涉及钛酸铋钠盐和钛酸铋锶的固态溶液。
铁电材料表现出材料的永久电偶极矩可以通过应用外部电场进行重新取向。压电效应可以以简单的方式描述：当应用机械压时电被产生。相反地，通过对压电元件施用电场，产生机械变形。这被称为反压电效应。反压电效应有时与在固体电介质发生的电致伸缩效应相混淆。两种效应在两个重要的方面不同。压电应变与电场强度成比例，并随之改变信号，而电致伸缩应变与场强的平方成比例并因此独立于其方向。此外，压电应变通常比电致伸缩应变大若干数量级数，并且电致伸缩效应与压电效应同时发生，但在许多情况下出于实践目的可以被忽略。
在一些材料中，电致伸缩效应显著并可用于实践应用。例如，Pb(Mn1/3Nb2/3)O3(PMN)及其固溶液Pb(Mn1/3Nb2/3)O3-PbTiO3(PMN-PT)表现出高的电致伸缩应变水平，为70kV/cm下~0.1%，电致伸缩系数Qn=~0.02m4C-2。通常，PMN被称为“电致伸缩陶瓷”。相比于压电效应，电致伸缩效应具有许多独特的优势，例如更少或没有高频的磁滞损耗、温度稳定性、以及表现出快速的响应时间。
目前，每年生产了成千吨含铅铁电/电致伸缩材料例如PbZrO3-PbTiO3(PZT)、Pb(Mg1/3Nb2/3)O3-PbTiO3(PMN-PT)和Pb(Zn1/3Nb2/3)O3-PbTiO3(PZN-PT)，用于广泛范围的应用。由于铅的毒性，出于环境的原因，可选的无铅材料是高度需要的。欧盟(EU)颁布的新环境立法将在2006年7月1日生效（欧洲议会和2003年1月27日的会议的指示2002/95/EC限制某些有害物质在电器和电子设备中的使用）。对有害物质的限制指令限制了铅、镉、汞、六价铬和两种溴化阻燃剂。期望的是，美国和日本在不远的将来也将有类似的限制。因此，含有毒铅材料的取代物对于电子工业是高度期望的。
在过去的二十年中，已经作出巨大的努力来寻找高性能无铅材料。例如，(Bi0.5Na0.5)TiO3基系、Bi4Ti3O12基系、SrBi2Ta2O9基系、和BaTiO3基系已经被广泛研究。然而，这些无铅材料的剩余极化强度和电致伸缩性能仍远低于目前使用的含铅材料。一些列出的例子是钛酸钡BaTiO3材料和钛酸铋钠(Bi0.5Na0.5)TiO3材料。
钛酸铋钠(Bi1/2Na1/2)TiO3(BNT)更类似于PZT，具有~230℃的Tc、和室温介电常数(ε=2500~6000)。一些改良的BNT陶瓷显示出合理的铁电/压电性质，其使得该材料有希望作为PZT的取代物。自从二十世纪八十年代后期，已经付出努力研究无铅BNT取代PZT的可能性。简单的钙钛矿化合物，例如BaTiO3、PbTiO3、SrTiO3等，被用于改良BNT的铁电/压电性能。例如，Nagata和Takenaka(“Effect of sub stitution onelectrical properties of(Bi1/2Na1/2TiOs-based lead-free ferroelectrics”;Proc.of 12th IEEE Int.Symp.on Applications of Ferroelectrics (ed.Streiffer,S.K.,Gibbons,BJ.and Trurumi,T.);vol.I,pp45-51;July 30-August 2,2000;Honolulu,Hawaii,USA.)，得到报道为(Bi0.5Na0.5)TiO3系的最高剩余极化强度Pr值33.7μC/cm2，这似乎是目前为止在BNT基系的文献中公布的最好结果之一。
在一系列铁电/压电/电致伸缩材料(单晶和陶瓷)中已经观察到非常高的应变(高达~1%)，例如，四方BaTiO3单晶、和(Bi1/2Na1/2)TiO3基材料。然而，应变对电场曲线在合理频率(例如，在1Hz下)下表现出大的磁滞，原因在于压电效应。该材料没有表现出纯电致伸缩效应。当驱动器的位移需要进行精确控制时，这成为关键的缺点。
许多专利和专利申请已经公开了建立非铅介质陶瓷组合物的尝试。例如，Takenaka的美国专利5,637,542教导了一种二元体系，表示为(1-x)BNT-xNN的固溶液，其中当构成固溶液时BNT是(Bi1/2Na1/2)TiO3和NN是NaNbO3。Takenaka等人的美国专利6,004,474教导了一种无铅压电材料，由式子x[Bi1/2NA1]TiO3-y[MeNbO3]-(z/2)[Bi2O3.Sc2O3]表示，其中Me是K或Na。其它使用BNT的无铅压电陶瓷组合物被教导在Nishida等人的美国专利6,514,427、Yamaguchi等人的美国专利6,531,070、Kimura等人的美国专利6,258,291、Sato等人的美国专利申请2004/0127344以及Takase等人的美国专利申请2003/0001131。在美国专利申请2002/0036282中Chiang等人教导了钙钛矿化合物，其作为一种机电活性材料起作用并可以具有电致伸缩或压电特征。该化合物是碱性铋钙钛矿组合物，其中铅可以是一部分。
发明概述
本发明是基于这样的发现的结果：无铅材料可以被制备并表现出意想不到的高铁电和电致伸缩性能、以及合理的压电性能。该组成可以变化其比例，以获得不同的性质和功能，例如非常强的剩余极化强度和具有非常高的电致伸缩系数的大量纯电致伸缩应变。这通过如下实现：改变固溶液“(1-x)(Sr1-1.5yBiy)TiO3+x(Na0.5Bi0.5)TiO3”和“(1-x)(Sr1-yBiy)TiO3+x(Na0.5Bi0.5)TiO3”——其中0<x<l和0<y≤0.2——的极化强度和应变行为，并任选在Na位具有取代的K和/或Li和/或在Ti位具有Sn、Hf、Nb和/或Ta；和/或使用MnO2、和/或作为掺杂剂的CuO。
附图简述
图1在1Hz下，样品“(1-x)(Sr1-1.5yBiy)TiO3+x(Na0.5Bi0.5)TiO3”，其中y=0.2和x=0.8、0.9和1，极化强度(P)对电场(E)。
图2在1Hz下，样品“(1-x)(Sr1-1.5yBiy)TiO3+x(Na0.5Bi0.5)TiO3”，其中y=0.2和x=0.5，单极应变(S)对电场(E)。
图3样品“(1-x)(Sr1-1.5yBiy)TiO3+x(Na0.5Bi0.5)TiO3”，其中y=0.2和x=0.5，应变对P2。
图4在1Hz下，样品“(1-x)(Sr1-1.5yBiy)TiO3+x(Na0.5Bi0.5)TiO3”，
其中y=0.2和x=0.65，双极应变(S)对电场(E)。
发明详述
本发明是由“弛豫型铁电体（a ferroelectric relaxor）”+“铁电体”组成的组合物并产生高性能的无铅铁电固溶液。无铅弛豫型铁电材料(Sr,Bi)TiO3可以和(Na0.5Bi0.5)TiO3结合使用。
该组合物用式子“(1-x)(Sr1-1.5yBiy)TiO3+x(Na0.5Bi0.5)TiO3”表示，其中在(Sr1-1.5yBiy)TiO3中的Sr空位（即，0.5y Sr空位）保持电荷平衡，或者用“(1-x)(Sr1-yBiy)TiO3+x(Na0.5Bi0.5)TiO3”表示，其中0<x<1和0<y<0.2。该组合物被使用时，可以在Na位具有或不具有取代的K和/或Li，和/或在Ti位具有或不具有取代的Sn、Hf、Nb和/或Ta；和/或，使用MnO2、和/或CuO作为掺杂剂。
通过如本领域中已知的固态反应法，制备固溶液。根据组成称量原材料SrCO3、TiO2、Bi2O3、Na2CO3，并经球磨，以碾碎和混合粉末。混合的粉末被干燥并在空气中煅烧至800-900℃ 2-4小时。然后，该粉末被再次球磨，并干燥，压成盘或杆，在空气中于1200-1300℃烧结2-4小时。制备银或金电极并附着到盘或杆的两面上。对于压电测量，需要一个极化过程，其在50-100kV/cm的dc偏压下于80-120℃进行15分钟。
在室温下，使用改良的Sawyer-Tower电路，以及锁定放大器以1Hz驱动的线性可变位移传感器（LVDT），分别进行磁滞回线和应变测量。X射线衍射分析表明所有的组分是单相的。使用d33计，测量准静态压电常数。在HP 4284ALCR仪上进行介电常数测量。
实施例1：高铁电剩余极化强度固溶液
在具有“(1-x)(Sr1-1.5yBiy)TiO3+x(Na0.5Bi0.5)TiO3”的组合物的材料中，当y=0.2，和0.65≤x≤0.95时，该材料表现出良好的铁电性能。在室温下测量铁电磁滞回线(极化强度P对电场E)。在图1中画出当x=0.8和0.9时1Hz下的P~E 回线，x=1的样品也被绘图，作为比较。对于x=0.8，Pr为~24μC/cm2。然后，对于x=0.9，获得非常高的剩余极化强度~51μC/cm2，矫顽场为~50kV/cm。然而，随着进一步增加x，Pr降低。对于x=1，Pr为~30μC/cm2。
对于x=0.65-0.9的样品，通过准静态法测量，压电常数d33为80-120pC/N。
实施例2：高电致伸缩固溶液
在具有“(1-x)(Sr1-1.5yBiy)TiO3+x(Na0.5Bi0.5)TiO3”的组合物的材料中，当y=0.2，和x=0.5时，该材料表现出极好的电致伸缩性能。在室温和1Hz下测量电场驱动应变(S)。对于x=0.5，应变水平在~80kV/cm下达到~0.1%，如图2所示。注意到，对于x=0.5，应变水平为0.1%的样品，应变对电场曲线无磁滞。
已知，从电致伸缩效应产生的应变遵循理论上得到的二次关系式：
S=QP2
其中Q是电致伸缩系数。x=0.5的样品的应变S对P2图被示于图3中。可以看出，在整个电场范围内，S~P2曲线非常好地拟合成直线。这表明具有无磁滞高应变水平的纯粹的电致伸缩效应被观察到。通过图3中的实验数据拟合，得到Q=0.02m4C-2，其与PMN-PT的Q值一样高。
应当注意到，所谓的电致伸缩材料PMN-PT的应变行为偏离线性的S对P2关系。这表明，PMN-PT不表现出纯电致伸缩行为，并且除了电致伸缩效应以外，一些额外的因素包括压电效应发生。然而，图3中该S对P2曲线表现出良好的线性关系，表明具有0.1%高应变水平的“纯的”电致伸缩效应。这种性质对于应用例如要求精确移动的应变/位移驱动器而言具有巨大的潜力。
在较高的Bi和Na浓度下，例如x=0.65，样品表现出0.28%的应变水平（图4），但观察到轻微的磁滞回线。
结果表明一系列极好的铁电和电致伸缩性质被获得，涵盖从在固溶液体系中极强剩余极化强度到高纯电致伸缩效应。具体而言，剩余极化强度高至~51μC/cm2（具有的矫顽场为~50kV/cm）和在80kV/cm下“纯”电致伸缩应变水平为~0.1%，其中电致伸缩系数Q=0.02m4C-2；其相当于或甚至高于含铅铁电陶瓷例如PZT、PMN-PT和PZN-PT。这有力地表明该系统有望用于无铅铁电和电致伸缩应用。通过准静态法测量，压电常数d33为80-120pC/N。
由此可见，本发明的陶瓷组合物可以被用作铁电器件、电致伸缩器件或压电器件。具体的应用将包括铁电随机存取存储器、非线性光学器件、电致伸缩驱动器、生产用定位器件、扫描探针显微镜、表面声波器件、和压电驱动器，尽管该清单并非排它性的并将包括其它相似或类似的应用。
为了举例说明和描述的目的，本发明的上述实施方式已经被呈现。这些描述和实施方式不意图是穷尽性的或将本发明限制于公开的精确形式，并且明显地，根据上述公开，许多改变和变化是可能的。选择和描述实施方式，以最好地解释本发明的原理和它的实际应用，从而使本领域其它技术人员能够最好地利用其各种实施方式中的发明以及具有适合具体预期用途的其它变化的发明。本发明意图由下面的权利要求限定。

Claims (11)

1.陶瓷组合物，其包含二元体系固溶液，由下式表示：
(1-x)(Sr1-1.5yBiy)TiO3+x(Na0.5Bi0.5)TiO3，
其中0.5≤x<l和y=0.2。
2.权利要求1所述陶瓷组合物，其中所述组合物是多晶材料、单晶材料、薄膜以及织构型晶体材料的形式。
3.权利要求1所述陶瓷组合物，其中y=0.2，和0.65≤x≤0.9。
4.权利要求3所述陶瓷组合物，其中所述陶瓷组合物具有~51μC/cm2的剩余极化强度，其中矫顽场为~50kV/cm。
5.权利要求1所述陶瓷组合物，其中y=0.2，0.5≤x<0.65，并且所述陶瓷组合物是电致伸缩陶瓷材料。
6.权利要求5所述陶瓷组合物，其中所述陶瓷组合物具有在80kV/cm下为~0.1%的应变水平和电致伸缩系数Q=0.02m4C-2。
7.权利要求3所述陶瓷组合物，其中所述陶瓷组合物具有：d33水平达到80-120pC/N。
8.权利要求1所述陶瓷组合物，其中所述陶瓷组合物，在室温下，具有2000以上的介电常数。
9.权利要求1所述陶瓷组合物，其中所述组合物是杆、纤维、带或片的形式。
10.权利要求1所述陶瓷组合物，其中所述陶瓷组合物任选包括以下的一种或多种：在Na位取代K或Li或其组合；在Ti位取代Nb、Ta、Sn或Hf或其任意组合；或使用MnO2、CuO或其组合作为掺杂剂。
11.通过权利要求1所述陶瓷组合物制备的器件，其中所述器件选自铁电随机存取存储器、非线性光学器件、电致伸缩驱动器、生产用定位器件、扫描探针显微镜、表面声波器件或压电驱动器。
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