CN101023538B - 压电材料 - Google Patents

压电材料 Download PDF

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CN101023538B
CN101023538B CN2005800314154A CN200580031415A CN101023538B CN 101023538 B CN101023538 B CN 101023538B CN 2005800314154 A CN2005800314154 A CN 2005800314154A CN 200580031415 A CN200580031415 A CN 200580031415A CN 101023538 B CN101023538 B CN 101023538B
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nitrogen
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T·科米恩
A·J·贝尔
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Goodrich Control Systems
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Abstract

一种具有通式(BiFeO3)x-(PbTiO3)1-x的压电钙钛矿混合氧化物的混合物，该混合物含有最多5原子％的镧或其他稀土元素取代物，通式中x值为0.5-0.9。这样的混合物能够承受燃气轮机的工作温度，适合用在航天和其他应用领域的传感和致动功能上。

Description

压电材料 
本发明涉及压电材料，尤其但不排他地提供能够承受诸如在燃气涡轮发动机中的高温并能在这样的高温下运转的压电材料。 
压电材料在宽范围的各种应用中被广泛用作传感器和致动器。压电材料传统上是基于通常称为PZT的锆钛酸铅(Pb(TiZr)O3，尤其是钛酸铅与锆酸铅的比值为约50∶50的锆钛酸铅，因而这种材料具有四方晶系和菱形晶系对称体的混合物的变晶相界面。混合物暴露于过高矫顽电场的电场后，产生压电性能，导致称为畴的偶极子的基团旋转。则可以说材料被“极化”。压电效应只有在低于居里点的温度才明显，而在PZT情况，居里点在300℃区域，因此根据运转温度，限制了PZT的可能的应用范围。替代PZT的压电材料，虽然具有承受较高工作温度的能力，但在敏感性方面存在明显的缺陷，即对驱动信号的响应只表现为较小的物理变化。 
已知的替代PZT的压电材料包括如美国专利4977547公开的BiFeO3-PbTiO3(BFPT)，以及如美国专利4624796公开的掺杂锰的BFPT，这两种材料都能用于水下水诊器装置。虽然一直以来认为BFPT材料可以在较高温度下使用，尤其是该材料显示的压电效应，这种压电效应很大程度上与在允许的工作温度范围内的温度无关，但它们确实需要异常高的矫顽场，因而在没有使用薄片来使电介质击穿的风险降低到最小的情况，要发挥出它们全部的潜力是相当困难的。 
美国专利6685849阐述了具有通式(1-x)BiMeO3-xPbTiO3的钙钛矿固溶液，其中Me为至少一种选自以下的适当尺寸的阳离子：钪、铟、钇、镱、其他稀土金属以及它们的组合，x是约为0.5-0.9的摩尔分数。据称钙钛矿系统能够提供优于PZT组合物的高温性质。曾提出的其它可能的Me阳离子包括铁、镓、镁、镐和镍，混合物中可任选掺入其他元素，包括镧、铁、锰、铌、锡和钡，特别是根据居里点达到最佳性能。但是，在例举的Me阳离子中，Sc产生的最大居里点也只有450℃，该温度仍低于燃气轮机工作环境所需的温度，尽管铟和镱能保持了较高工作温度的前景。 
我们现在发现，另一组具有钙钛矿结构的混合物提供了能够承受燃气轮机运转温度的压电材料，该混合物同时在这样的高温下显示敏感性，因而这种混合物适合用于航天和其他应用领域的传感和致动功能。 
一方面，本发明提供一种具有通式(BiFeO3)x-(PbTiO3)1-x并含有多达5原子％的镧或其他稀土取代物的钙钛矿混合氧化物的混合物，通式中x值的范围为0.5-0.9。 
稀土元素为钪、钇和与镧系，铈至镥一起的镧。其中，优选钪、钇和镧，单独或组合作为本发明混合物的取代物。更优选，镧是稀土取代物，含量最多达3.5％，x的值为0.5-0.8，更优选0.5-0.75。镧的浓度在1.5-3.5原子％范围，例如2.5-3.0％。镧可以替代铋和/或铅组分，但优选替代铅。 
本发明的镧替代的铋化物的通式为Bi(x-y)LayFexPb1-xTi1-xO3，其中x为0.5-0.8，y为0.015-0.035，本发明的镧替代的铅化物的通式为BixFexPb(1-x-y)LayTi1-xO3，其中x为0.5-0.8，y为0.015-0.035。 
特别优选的是以上述范围上限的掺杂浓度用镧取代铅的混合物，因为它们能够在获得高压电系数的同时具有高电阻率。现有技术的混合物会在压电系数提高时发生电阻率值下降。 
助掺杂剂(co-dopant)可包含镧，特别是铟、锰、铌、钠和/或钾，含量优选最高为1.0原子％，以抑制电导率，而不会明显降低居里点，因此达到有效的最高工作温度。 
本发明混合物暴露于在超高矫顽场的电场中时显示压电性能，本发明的混合物可以采用常规混合氧化物合成方法以烧结丸粒的形式制备。已经发现丸粒的密度大于理论密度的95％，混合物的居里点超过620℃。X射线衍射(XRD)分析显示该混合物为多晶陶瓷，是纯钙钛矿相，伴有菱形晶相和四方晶相的混合物，在钙钛矿相与混合物之间存在变晶相界面，尤其是x为0.7±0.1的混合物。与未掺杂的材料相比，稀土元素掺杂剂使居里点略有降低，但随着场强度的增加产生较高的电介质击穿阈值。 
作为烧结丸粒的替代形式，本发明混合物可以以湿浆料或滑移料(slip)浇铸在活动带上，干燥后从该带上去下。然后，可以在浇铸带的表面上施加电极，将多个带层叠，进行烧结，形成多层或堆叠排列的带支承的多个电极，交替的电极电互连在一起，这在诸如柴油压电喷射器之类需要在12伏电源下运行的低压应用方面特别有用。然而，为了能使用银或诸如铜或镍之类的比铂族金属电极便宜的贱金属电极，烧结温度必须低于或等于1000℃，例如就银而言为 950℃。本发明混合物能够在这样的温度下烧结而不必使用玻璃状烧结助剂，而烧结助剂对PZT来说是必需的，否则，烧结温度必须在1200℃左右，而在熔融和促进烧结时仍对材料的压电性能造成损害。 
该方法的烧结步骤无论是在丸粒上还是在浇铸带上进行，都可以在空气或其他气氛中进行，以提高电阻率，并因此提高热极化能力和高温致动能力。可替代空气的气氛包括氧气、氮气、氢气与氮气的混合物以及氧气与氮气的混合物，尤其是在顺序使用的时候。 
本发明的实施方式将以例举的方式并参照附图来加以说明： 
图1所示为本发明的两种混合物((A)和(B))在1025℃下烧结2小时后的XRD谱图； 
图2所示为混合物(A)和(B)在100kHz频率下测得的相对介电常数对温度的曲线； 
图3所示为(A)和(B)的传导活化能的计算曲线。 
图4所示为混合物(A)的极化-场磁滞环； 
图5所示为混合物(A)在硅油中于6MV-1极化30分钟的d31对温度的曲线； 
图6所示为对各种镧取代铅的混合物的d33和电阻率的曲线。 
混合物的制备 
镧取代铋的混合物制备方法是：按适当比例称取前体粉末(Bi2O3，Fe2O3，La2O3，PbO和TiO2)，在丙醇中进行12小时球磨，干燥后，在高纯度氧化铝坩锅中于925℃下煅烧4小时。煅烧的粉末在丙酮中与1重量％粘合剂(Rohn andHass B7)再研磨12小时，干燥后压制成15mm的丸粒。烧除丸粒中的粘合剂，然后丸粒在1025℃焙烧2小时。烧结后丸粒的密度大于理论密度的95％；采用由X射线衍射测量值算出的菱形晶体积来确定密度时，以8.15g/cm3作为理论密度。 
制成的材料具有通式Bi0.68La0.02Fe0.70Pb0.30Ti0.30O3(A)和Bi0.63La0.02Fe0.65Pb0.35Ti0.35O3(B)。 
重叠的丸粒的X射线分析显示该材料为四方晶相和菱形晶相的混合物。显然不存在如Bi2O2.75这样的有害的非钙钛矿相(见图1)。就A和B中的四方晶相而言， 
Figure S05831415420070321D000031
；就菱形晶相而言， 
Figure S05831415420070321D000032
，斜角α＝89.635°。 
居里点是通过采用阻抗分析仪测定作为温度的函数的介电常数来确定的，在频率为100kHz的情况下，对A的测得值为623℃，对B的测得值为617℃(见图2)。数值略低于未掺杂的BFPT的对照物。 
电阻率的测定表明电阻率值与未掺杂BFPT的电阻率类似。根据这些数据可以计算出导电活化能(见图3)。在曲线的线性区域(忽略易导致高误差的低温和高温测定值)，记录A的活化能值为1.05eV，B的活化能值为1.12eV。在施加1MV m-1场下，A和B的室温电阻率均好于5×1011Ωm。 
图4所示为在100Hz下将电场强度提高到最大时A的PE环。为了提高断裂强度，将测试样品的厚度减小至80μm。对场强度为17MV m-1情况，环并不完全饱和(saturated)；当场强度大于该值时，发生电介质击穿。当场强度为17MV m-1时，测得极化强度为0.3Cm-2。 
组合物A的减薄和电极化(electroded)的样品(厚度为0.6mm)在75℃的硅油中于6MVm-1进行极化，得到室温下测得的压电系数，如表1所示。用Berlincourt计和阻抗分析法测定的d31之间获得良好的一致性。 
d31对温度的曲线(图5)显示，d31作为温度的函数，在25-250℃之间的变化较小(±8％)。此后d31大幅度增加，这在很大程度上归功于介电常数随温度的上升而增加。 
表1：对1025℃下烧结2小时，然后在75℃的硅油中于6MV m-1极化30分钟后的Bi0.68La0.02Fe0.70Pb0.30Ti0.30O3丸粒测定的压电性能 
  压电系数   数值   测定方法
  d33/pm V-1   90   Berlincourt计
  d31/pm V-1   25   Berlincourt计
  d31/pm V-1   23   阻抗分析法
  k31   0.141   阻抗分析法
  kP   0.237   阻抗分析法
  kt   0.2708   阻抗分析法
  σ   0.294   阻抗分析法
  sE 11/m2V-1   1.056×10-11   阻抗分析法
  εT33   285   阻抗分析法
制备了本发明的其他混合物，其中，镧取代了铅，镧的含量为2原子％和 3原子％。图6所示为对通式BixFexPb(1-x-y)LayTi1-xO3，其中x为0.5、0.55、0.6、0.65和0.7且y为0.02的混合物以及x为0.5和0.525且y为0.03的混合物的d33(平行于电场)压电系数和电阻率的测定结果。由图可以看到，通过提高镧浓度，压电系数和电阻率均得到提高。 
已对材料关于高场致动的特性进行表征。评价的性能是材料极化并因此显示压电性能所需的矫顽场；磁滞和线性度；疲劳；高电场d33和总应变性能。 
已经发现，对混合物Bi0.525Fe0.525Pb0.445La0.03Ti0.475O3，d33压电系数在低电场中为120pmV-1，在高电场中为160pmV-1，总应变为0.12％。这与未掺杂的PZT相似，但提供的工作温度在250℃以上。 

Claims (12)

1.一种通式为BixFexPb(1-x-y)LayTi1-xO3的钙钛矿混合氧化物混合物，通式中x值为0.5-0.8，y值为0.015-0.035。
2.如权利要求1所述的混合物，其特征在于，单独或组合使用钪或钇替换镧。
3.如权利要求1所述的混合物，其特征在于，镧的浓度为2.5-3.5原子％。
4.如前述权利要求中任一项所述的混合物，其特征在于，该混合物包含选自以下的助掺杂剂：铟、锰和/或铌。
5.如权利要求4所述的混合物，其特征在于，助掺杂剂的浓度最高为1.0原子％。
6.如权利要求1至4中如一项所述的混合物，该混合物为在载带上铸件的形式。
7.包含前述权利要求中任一项所述的混合物的丸粒，所述丸粒已进行烧结。
8.如权利要求7所述的丸粒，其特征在于，烧结步骤在除空气外的一种气氛中进行，该气氛包含氧气、氮气、氧气和氮气的混合物、或氢气和氮气的混合物。
9.一种多层压电器件，该器具包含权利要求6所述为在载带上铸件的形式的混合物的层叠排列，所述铸件的表面包括电极，交替的电极电互连在一起。
10.如权利要求9所述的器件，其特征在于，电极包含银或贱金属。
11.如权利要求9或10所述的器件，其特征在于，所述器件已进行了烧结。
12.如权利要求11所述的器件，其特征在于，烧结步骤在除空气外的一种气氛中进行，该气氛包含氧气、氮气、氧气和氮气的混合物、或氢气和氮气的混合物。
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