CN110914219A - 硬pzt陶瓷、压电多层部件和制造压电多层部件的方法 - Google Patents

硬pzt陶瓷、压电多层部件和制造压电多层部件的方法 Download PDF

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CN110914219A
CN110914219A CN201880049720.3A CN201880049720A CN110914219A CN 110914219 A CN110914219 A CN 110914219A CN 201880049720 A CN201880049720 A CN 201880049720A CN 110914219 A CN110914219 A CN 110914219A
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ceramic
multilayer component
pzt
piezoelectric
pzt ceramic
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CN110914219B (zh
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D.奥罗泽尔
M.普夫
B.德尔加斯特
A.格拉朱诺夫
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TDK Electronics AG
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Epcos AG
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Abstract

说明了一种硬锆钛酸铅（PZT）陶瓷，其具有ABO3结构，所述结构包括A位置和B位置，其中所述PZT陶瓷在所述B位置上掺杂了Mn和Nb，并且比例Nb/Mn<2。还说明了一种具有这种PZT陶瓷的压电多层部件以及一种用于制造压电多层部件的方法。

Description

硬PZT陶瓷、压电多层部件和制造压电多层部件的方法
技术领域
说明了一种硬锆钛酸铅（PZT）陶瓷、一种压电多层部件以及一种用于制造压电多层部件的方法。
背景技术
具有压电特性的PZT陶瓷可以承受高的电气和机械负荷。硬PZT陶瓷特别是可以用于共振应用，例如以压电变压器的形式。为了在压电变压器中使用PZT材料系统，重要的是在烧结期间保持材料特性并确保器件的几何形状。
发明内容
至少一个实施方式的任务是说明一种具有改善的特性的硬PZT陶瓷。其他任务是提供一种具有PZT陶瓷的压电多层部件以及一种用于制造压电多层部件的方法。这些任务通过根据独立权利要求的PZT陶瓷、压电多层部件以及方法加以解决。有利的配置是从属权利要求的主题。
说明一种硬锆钛酸铅（PZT）陶瓷，其具有ABO3结构，该结构包括A位置和B位置，其中所述PZT陶瓷在所述B位置上掺杂了Mn和Nb，并且比例Nb/Mn<2。
此处和下文中，PZT陶瓷应理解为基于
Figure 376141DEST_PATH_IMAGE001
系统的陶瓷。这种系统具有ABO3结构，其中对于纯锆钛酸铅来说Pb占据A位置，而
Figure 152336DEST_PATH_IMAGE002
占据B位置。如果所述陶瓷中还有其他元素，则称为掺杂，所述掺杂可能存在于所述A位置和/或所述B位置上。在此，式子ABO3描述了PZT陶瓷的晶体结构，其中在基本组成中A为2值，而B为4值。
如果基本组成
Figure 666494DEST_PATH_IMAGE003
被掺杂有受体，则称为“硬”PZT陶瓷。在这种情况下，受体是与A位置和B位置上的相应晶格原子相比化合价较低的正离子。硬PZT陶瓷的特征可以是低的机械损耗（Qm=1000至2000）或介电损耗（
Figure 61703DEST_PATH_IMAGE004
=0.3％至0.4％）。
可以获得在所述B位置上掺杂了Mn和Nb且比例Nb/Mn<2的PZT陶瓷，同时在其制造时在烧结期间硬压电特性没有明显下降。由此可以确保硬PZT陶瓷的材料特性以及包含所述PZT陶瓷的器件的几何形状得以保持。此外将实现的是，所述PZT陶瓷在大的配方范围内具有类似的硬压电特性，从而在制造用于制造所述PZT陶瓷的粉末状原始混合物时的工艺波动也几乎不会对包含所述PZT陶瓷的压电部件产生任何影响。
根据一个实施方式，1.4
Figure 610496DEST_PATH_IMAGE005
Nb/Mn
Figure 432958DEST_PATH_IMAGE006
2，特别是1.45
Figure 434413DEST_PATH_IMAGE005
Nb/Mn
Figure 633313DEST_PATH_IMAGE006
1.9。对于Nb与Mn的该比例来说，在烧结期间不会观察到所述硬压电特性的显著下降。
根据一个实施方式，所述PZT陶瓷具有通式
Figure 161246DEST_PATH_IMAGE007
。
在此，AxA包括掺杂元素AlxAl到AaxAa，其中a是在所述A位置上的掺杂元素的数量，并且
Figure 154610DEST_PATH_IMAGE008
。此外，BxB包括掺杂元素B1xB1到BbxBb，其中b是在所述B位置上的掺杂元素的数量，并且
Figure 643360DEST_PATH_IMAGE009
。这意味着，对于a=1来说，
Figure 380372DEST_PATH_IMAGE010
，或对于b=1来说，
Figure 638178DEST_PATH_IMAGE011
，因此分别在所述A位置上仅存在一种掺杂元素或在所述B位置上除了Mn和Nb之外还仅存在一种掺杂元素。对于a＞1或b＞1来说，在各自位置上存在掺杂元素A1、A2等直到Aa，或B1、B2等直到Bb。a例如可以为2，b同样例如可以为2。
A1至Aa彼此独立地选自包括Na、K、Nd、La、Ba、Sr、Ca、Bi和Ag的组。B1至Bb彼此独立地选自包括Fe、Zn、Ge、Sn、Al、Ga、Sb和Cu的组。例如，所述A位置可以掺杂有Na和/或K。所述B位置可以特别是掺杂有Cu。
上式中的“x”代表各自元素、即掺杂元素的份额。此外，
Figure 802443DEST_PATH_IMAGE012
1.2，0.4
Figure 44068DEST_PATH_IMAGE013
y
Figure 912667DEST_PATH_IMAGE013
0.6，对于A1到Aa中的每个0.0001
Figure 556138DEST_PATH_IMAGE013
xA
Figure 891305DEST_PATH_IMAGE013
0.05，对于B1到Bb的每个0.001
Figure 89068DEST_PATH_IMAGE013
xB
Figure 26937DEST_PATH_IMAGE013
0.05，以及0＜z
Figure 524914DEST_PATH_IMAGE013
0.25。xZr/xTi可以特别是等于1，y可以特别是等于0.5。
根据另一个实施方式，xMn＝（l+z）/3并且xNb＝（2-z）/3，并且以下适用：
Figure 30982DEST_PATH_IMAGE014
。
这意味着所有可能的B位置都被占用。
此外以下也适用：
Figure 981620DEST_PATH_IMAGE015
。
这意味着所有A位置和所有B位置都被占用。如果满足这些等式，即占用了所有可能的A位置和B位置，则所述PZT陶瓷或包含所述PZT陶瓷的部件具有特别好的硬压电特性和良好的可烧结性。
还说明了一种压电多层部件，其具有陶瓷层和布置在陶瓷层之间的至少两个电极的堆叠。所述陶瓷层包含根据以上陈述的硬PZT陶瓷。这意味着关于所述PZT陶瓷公开的所有特性也适用于所述多层部件，反之亦然。
所述压电多层部件可以是单片式实施的。所述陶瓷层上下叠加地布置。由于所述陶瓷层包含如上所述的PZT陶瓷，因此所述多层部件具有高的形状精度和均匀的偏转行为。
根据一个实施方式，所述至少两个电极包含元素铜。特别地，所述至少两个电极可以由元素铜组成。因此，它们也可以称为铜内电极。铜是廉价的电极材料，这可以有助于廉价地制造这种多层部件。
根据一个实施方式，所述压电多层部件是压电变压器。所述压电变压器特别可以是等离子发生器。
还说明了用于制造根据上述陈述的压电多层部件的方法。该方法包括步骤：以化学计量比制造粉末状原始混合物，所述原始混合物包含原始物质，所述原始物质包括Pb、Zr、Ti、Mn、Nb、来自Na、K、Nd、La、Ba、Sr、Ca、Bi和Ag的组中的至少一种以及来自Fe、Zn、Ge、Sn、Al、Ga、Sb和Cu的组中的至少一种的氧化物和/或碳酸盐；由所述原始混合物制造生坯薄膜；将生坯薄膜和电极层交替地堆叠以及烧结该堆叠。关于所述多层部件公开的所有特征也适用于该方法，反之亦然。
根据一个实施方式，所述原始物质以粉末形式存在，被混合并且研磨以制造所述原始混合物。通过制备粉末状的原始混合物并对其再次研磨和回火来制造生坯薄膜。这些生坯薄膜彼此上下堆叠，使得电极层布置在两个生坯薄膜之间。作为电极层，特别是可以使用铜电极。
根据一个实施方式，在选自900℃至1000℃（含1000℃）的范围、特别是选自950℃至1000℃的范围的温度下进行烧结。由此可以制造具有低介电损耗和高机电耦合效率的高密度PZT陶瓷。
根据一个实施方式，可以在惰性气体气氛中执行所述烧结。此外，还可以在还原条件下执行所述烧结。
由于所述PZT陶瓷的上述有利特性，利用该方法可以制造多层部件，该多层部件的几何形状在所述烧结期间得以保持并且该多层部件的压电材料特性在所述烧结期间得以保持。
附图说明
下面基于附图和实施例更详细地描述本发明。
图1示出了压电多层部件的示意性截面图。
在图中，相同或作用相同的部件均设有相同的附图标记。所显示的元件不应视为真实比例，而是可以夸大地显示各个元件以更好地理解。
具体实施方式
图1示出了压电多层部件的示意性截面图。该压电多层部件包含上下堆叠的陶瓷层10。在两个陶瓷层10之间存在电极20，例如铜内部电极，通过外部电极30接触电极20。所述多层部件是单片式多层部件。所述多层部件可以用作压电变压器。特别地，它可以是等离子发生器。
陶瓷层10包含具有ABO3结构并且在B位置上掺杂有Mn和Nb的硬PZT陶瓷。比例Nb/Mn<2。特别是，所述PZT陶瓷可以具有通式
Figure 598547DEST_PATH_IMAGE016
。在此，0<z
Figure 951030DEST_PATH_IMAGE005
0.25，由此比例Nb/Mn<2。A可以例如是Na，B可以例如是Cu。上面关于所述通式提及的A位置和B位置上的所有掺杂元素同样是可能的。有利地，所有A位置和所有B位置都被占用。
在下文中说明了用于PZT陶瓷的四个实施例M1至M4，这些实施例的根据净重针对比例Nb/Mn的额定值是1.79（M1），1.61（M2），1.45（M3）和1.9（M4）。在表1中说明了借助于RFA测量（RFA＝X射线频率分析）确定的粉末组成以及由此获得的Nb/Mn比例：
Figure 627999DEST_PATH_IMAGE017
表1。
在表2中说明了由上述粉末制造的片材样品（直径：12mm，高度：1mm）的这些实施例与具有比例Nb/Mn为2的比较样品（V）相比较的电测量数据。
Figure 65934DEST_PATH_IMAGE018
表2。
从表2中发现示例M1至M4的良好的硬压电特性。机械损耗Qm、相对介电常数
Figure 345606DEST_PATH_IMAGE019
、耦合系数kp和d33位于可接受范围内，以便在诸如压电变压器或等离子发生器的部件中使用。
本发明不受附图和实施例的限制。而是，本发明包括每个新特征和特征的每种组合，这特别是包括权利要求中的特征的每种组合，即使该特征或该组合本身在权利要求或实施例中未明确加以说明。
附图标记列表
10 陶瓷层
20 电极
30 外部电极。

Claims (11)

1.一种硬锆钛酸铅（PZT）陶瓷，具有ABO3结构，所述结构包括A位置和B位置，其中所述PZT陶瓷在所述B位置上掺杂了Mn和Nb，并且比例Nb/Mn<2。
2.根据权利要求1所述的PZT陶瓷，其中1.4
Figure DEST_PATH_IMAGE001
Nb/Mn
Figure 789944DEST_PATH_IMAGE002
2。
3.根据前述权利要求之一所述的PZT陶瓷，具有通式
Figure DEST_PATH_IMAGE003
，
其中AxA包括掺杂元素AlxAl到AaxAa，a是在所述A位置上的掺杂元素的数量，并且
Figure 441505DEST_PATH_IMAGE004
，
其中BxB包括掺杂元素B1xB1到BbxBb，b是在所述B位置上的掺杂元素的数量，并且
Figure DEST_PATH_IMAGE005
，
A1至Aa彼此独立地选自包括Na、K、Nd、La、Ba、Sr、Ca、Bi和Ag的组，
B1至Bb彼此独立地选自包括Fe、Zn、Ge、Sn、Al、Ga、Sb和Cu的组，
x是各自元素的份额，
Figure 955663DEST_PATH_IMAGE006
1.2，
0.4
Figure 944348DEST_PATH_IMAGE001
y
Figure 758720DEST_PATH_IMAGE001
0.6，
对于A1至Aa的每个，0.0001
Figure 581182DEST_PATH_IMAGE001
xA
Figure 582636DEST_PATH_IMAGE001
0.05，
对于B1到Bb的每个，0.001
Figure 781537DEST_PATH_IMAGE001
xB
Figure 184836DEST_PATH_IMAGE001
0.05，以及
0＜z
Figure 178200DEST_PATH_IMAGE001
0.25。
4.根据权利要求3所述的PZT陶瓷，其中xMn＝（l+z）/3和xNb＝（2-z）/3，并且以下适用：
Figure DEST_PATH_IMAGE007
，和
Figure 526005DEST_PATH_IMAGE008
。
5.一种压电多层部件，具有陶瓷层和布置在陶瓷层之间的至少两个电极的堆叠，其中所述陶瓷层包含根据前述权利要求之一所述的硬PZT陶瓷。
6.根据权利要求5所述的多层部件，其中，所述至少两个电极包含元素铜。
7.根据权利要求5或6之一所述的多层部件，其是压电变压器。
8.根据权利要求7所述的多层部件，其中，所述压电变压器是等离子发生器。
9.一种用于制造根据权利要求5至8之一所述的压电多层部件的方法，具有以下步骤：
-以化学计量比制造粉末状原始混合物，所述原始混合物包含原始物质，所述原始物质包括Pb、Zr、Ti、Mn、Nb、来自Na、K、Nd、La、Ba、Sr、Ca、Bi和Ag的组中的至少一种以及来自Fe、Zn、Ge、Sn、Al、Ga、Sb和Cu的组中的至少一种的氧化物和/或碳酸盐，
-由所述原始混合物制造生坯薄膜，
-将生坯薄膜和电极层交替地堆叠，以及
-烧结该堆叠。
10.根据权利要求9所述的方法，其中，在来自900℃至1000℃的范围的温度下进行烧结。
11.根据权利要求9或10之一所述的方法，其中在惰性气体气氛中进行烧结。
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