CN1354155A - 压电陶瓷组合物 - Google Patents

压电陶瓷组合物 Download PDF

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CN1354155A
CN1354155A CN01134931A CN01134931A CN1354155A CN 1354155 A CN1354155 A CN 1354155A CN 01134931 A CN01134931 A CN 01134931A CN 01134931 A CN01134931 A CN 01134931A CN 1354155 A CN1354155 A CN 1354155A
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piezoelectric
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CN1142116C (zh
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高桥庆一
西田正光
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Panasonic Holdings Corp
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Abstract

本发明提供了一种压电陶瓷组合物,其不含铅,具有适合实际使用的压电性能。所述压电陶瓷组合物具有下述通式表示的复合钙钛矿结构:(1－x－y－z)BaTiO3－x(Bi1/2Na1/2)TiO3－yCaTiO3－zBa(Zn1/3Nb2/3)O3并包含比例满足下述通式中的x、y和z的条件的Ba、Ti、O、Bi、Na、Ca、Zn和Nb:0.0<x≤0.90,0.0≤y≤0.20,和0.0≤z≤0.05,y和z不同时为0。

Description

压电陶瓷组合物
发明领域
本发明涉及用于压电陶瓷元件的压电陶瓷组合物，尤其涉及用于压电晶体谐振器和压电振子，以及传感器、执行器、蜂鸣器等采用的压电元件的压电陶瓷组合物。
发明背景
包含作为主要组分的锆钛酸铅(PZT)或钛酸铅(PT)的陶瓷组合物广泛用作压电陶瓷组合物，所述压电陶瓷组合物应用在压电陶瓷振子、压电陶瓷滤波器、压电蜂鸣器、压电传感器和执行器的压电陶瓷元件中。为了改善上述组合物的陶瓷性能，可加入痕量的添加剂例如Mn等，或用Sr或复合氧化物例如Pb(Mg1/3Nb2/3)O3替代部分Pb以得到具有所需的压电性能的压电陶瓷。
另一方面，由于对于不含铅的压电陶瓷组合物来说，已知(Na，K)NbO3、Bi4Ti3O12等能够作为具有压电现象的铁电，但是，从实际使用效果看其并没有达到足够的性能，因此，实际上很难用于在高温条件下使用的传感器和执行器。
目前主要使用的典型压电陶瓷组合物如锆钛酸铅等含有大量的Pb，这对全球环境带来负面影响。目前公众的注意力已经被吸引到环境问题上来，而这些材料的废物的丢弃引起了严重的环境保护问题。在这些氛围下，迫切需要开发一种不含铅并具有适合实际应用的压电性能的材料。但是，目前，尚未有人提供压电性能高于PZT型陶瓷和PT型陶瓷(两者都含铅)的压电陶瓷组合物。特别是，含有作为主要组分的钛酸钡的陶瓷组合物已经被有限地应用于例如兰杰文型超声谐振器等。但是，这种类型的陶瓷组合物并不适合在通用传感器和执行器中实际应用。这是因为：当这种组合物用于上述传感器和执行器时，需要加热以结合并硬化咬合，还因为所述压电陶瓷组合物不能在高于居里温度(在该温度下铁电现象消失)的温度下加热。
发明概述
因此，本发明的目的是提供一种压电陶瓷组合物，该组合物不含铅，并且具有适于实际应用的压电性能，从而克服了上述问题。
根据本发明的压电陶瓷组合物具有下式表示的复合钙钛矿结构：
(1-x-y-z)BaTiO3-x(Bi1/2Na1/2)TiO3-yCaTiO3-zBa(Zn1/3Nb2/3)O3   (1)，所述组合物包含比例满足下式中的x、y和z的条件的Ba、Ti、O、Bi、Na、Ca、Zn和Nb：
        0.0＜x≤0.90，
        0.0≤y≤0.20，和    …(2)
        0.0≤z≤0.05，条件是y和z不同时为0(排除y＝z＝0的情况)。
上述本发明的压电陶瓷组合物不含铅，因此不会引起环境问题。此外，它具有相对大的机电耦合系数，因此适合用于压电陶瓷滤波器、压电陶瓷谐振器、压电传感器、压电执行器等的压电陶瓷元件。再者，由于上述压电陶瓷组合物具有耐热温度不低于约150℃的耐热性(热稳定性)，使得有可能采用固化温度为150℃的粘合剂构造压电元件。出于这种考虑，上述x的数值范围排除了0和1.0，因为单独使用公知样品BaTiO3或(Bi1/2Na1/2)TiO3难以提供具有足以实际使用的耐热性(热稳定性)的压电陶瓷组合物。当本发明压电陶瓷组合物由式(1)表示时，这种组合物不仅包括包含BaTiO3，(Bi1/2Na1/2)TiO3，CaTiO3和Ba(Zn1/3Nb2/3)O3的独立相，而且包括其中，至少，含有的各个原子Ba、Ti、O、Bi、Na、Ca、Zn和Nb的比例满足上述数值范围(2)的条件，并且这些原子构成由ABO3表示的钙钛矿结构的上式组合物。
所述压电陶瓷组合物优选含有0.01-1.0wt％的作为次要组分的MnO2。这是因为，除压电性能外，它尤其可以改善机械品质因数(在共振频率处的机械振动的锐度)。
此外，所述压电陶瓷组合物优选含有0.01-1.0wt％的作为次要组分的稀土氧化物例如Y2O3。这是因为，它可以降低电容依赖于时间的变化(随时间流逝的变化)，这使得压电性能随时间的稳定性得以提高。
次要组分即MnO2和稀土氧化物例如Y2O3的加入可以进一步有效地改善压电性能，这种次要组分的任一种的加入量应优选为不大于1.0wt％，因为如果这种次要组分的加入量不低于1.0wt％，就存在降低压电陶瓷的性能的危险。
附图的简要说明
图1是包含根据本发明的压电陶瓷组合物的执行器(10)的剖面图。
优选实施方案的详细描述
参照图1，执行器(10)包含具有在其两侧形成的电极(3a)和(3b)的压电陶瓷(1)，和具有在其两侧形成的电极(4a)和(4b)的压电陶瓷(2)。压电陶瓷(1)和(2)中的任意一个或两个是由根据本发明的压电陶瓷组合物制成的。在压电陶瓷(1)上形成的电极(3b)被用粘合剂固定到在压电陶瓷(2)上形成的电极(4a)上以构成用于制备执行器(10)的整体。本发明的压电陶瓷组合物描述如下。
本发明的压电陶瓷组合物具有基于BaTiO3的复合钙钛矿结构(ABO3)。本发明的压电陶瓷组合物由下式表示：
(1-x-y-z)BaTiO3-x(Bi1/2Na1/2)TiO3-yCaTiO3-zBa(Zn1/3Nb2/3)O3  (1)其中，x、y和z的值分别在下述范围内：
       0.0＜x≤0.90.
       0.0≤y≤0.20，和    …(2)
       0.0≤z≤0.05，(条件是y和z不同时为0(排除y＝z＝0的情况))。
在由通式ABO3表示的钙钛矿结构中，位置A是其中可以存在Ba，Bi，Na和Ca的位置，位置B是其中可以存在Ti，Zn和Nb的位置。上述本发明的压电陶瓷组合物不含铅，因此不存在引起环境问题的危险。
由于其加热温度范围窄，因此难以提高纯BaTiO3的加热温度。结果，得到的陶瓷不能具有足够的烧结密度，这导致一个问题，即当该陶瓷被极化处理以功能化为压电材料的时候，其产率往往会不利地降低。这是由于该陶瓷不能承受在极化处理过程中所施加的高电场。另一方面，通过用使性能降低较少的元件取代位置A或位置B制备的本发明的压电陶瓷组合物可以在较宽温度范围内加热，这使得有可能在提供最高烧结密度的温度下加热所述组合物。这样，所得的陶瓷可以具有较高的烧结密度。因此，使用本发明的压电陶瓷组合物可能达到高耐电压性能。因此，从其较宽的加热温度范围考虑，本发明的压电陶瓷组合物适合用作在传感器、执行器和振子中使用的压电晶体谐振器和压电振子的材料，并且通过采用本发明的压电陶瓷组合物可以容易地制造压电元件。
此外，常规的由BaTiO3组成的压电陶瓷组合物的居里温度(127℃)(该温度为材料失去压电现象的关键温度)相对较低，并且从这个角度看，所述组合物的耐热性(热稳定性)不足。另一方面，本发明的压电陶瓷组合物是通过将(Bi1/2Na1/2)TiO3加入到BaTiO3中制备的，因此可以具有较高的居里温度，并可以具有耐不低于150℃的高温的耐热性。因此，有可能使用固化温度为约150℃的粘合剂制造压电元件，即使在这种情况下，本发明的压电陶瓷组合物也不会变差。
当本发明的压电陶瓷组合物还含有CaTiO3时，可以形成更稳定的钙钛矿晶体结构。这是由于，如前所述，通过用Ca取代位置A降低了加热温度范围的下限，从而扩大了加热温度范围。此外，通过加入Ba(Zn1/3Nb2/3)O3，可以提高组合物的介电常数，这有助于压电元件的小型化。
由于本发明的由上式表示的压电陶瓷组合物具有相对大的机电耦合系数(给定的电输入转化为机械输出的速率的平方根，其代表了电-机转变能力)，本发明的压电陶瓷组合物可以实际用于压电陶瓷滤波器、压电陶瓷振子、压电传感器、压电执行器等。
此外，在上述压电陶瓷组合物含有0.01-1.0wt％的MnO2的情况下，尤其可以改善除压电性能外的机械品质因数，因此，这样的组合物能够提供作为用于传感器中的压电陶瓷的优异的压电性能。
此外，在上述压电陶瓷组合物含有0.01-1.0wt％的稀土氧化物例如Y2O3的情况下，可以降低电容随时间变化的速率，因此，这样的组合物能够改善压电性能随时间的稳定性。
具体实施方案
下面对本发明的实施例进行更详细的描述。但是，根据本发明的压电陶瓷组合物，并不限于下述实施例中描述的样品的配方，只要它们的配方在上述范围(2)内变化，就可以提供相似的效果。
实施例1
根据实施例1的压电陶瓷组合物制备如下。首先，称量作为原料的BaCO3，Bi2O3，NaCO3，CaCO3，TiO2和MnCO3，最终得到可能具有如表1所示的给定配制比例的压电陶瓷，将它们在球磨机中均匀混合。接着，在800-1,000℃温度下煅烧2小时以形成化合物。该化合物再次在球磨机中研磨，将聚乙烯醇加到该化合物颗粒中，并将混合物粒化。使粒化的粉末在70MPa的压力下单轴压缩模塑以形成直径为13mm的盘子，然后将其在1000-1400℃下加热2小时。
将盘状样品磨至厚0.3mm，在700℃下将Ag烤熔而凝结到样品盘上以在其上形成电极。此后，通过在80℃的硅油中向其上施加3-5KV/mm的电场30分钟对样品盘进行极化处理。按照相同的方法得到样品1-7和对比例1-4的那些样品的压电陶瓷。
测定1-7号样品和对比例1-4的压电陶瓷的具体的介电常数εr，tanδ，沿盘子半径方向平铺振动模式的耦合系数kp，沿盘子厚度方向垂直振动模式的耦合系数kt，机械品质因数QM和压电常数d31，并根据介电常数取决于温度的变化，通过找出介电常数变成最大值时的温度来测定压电陶瓷的压电现象消失时压电陶瓷的居里点。结果见表1和表2。在这方面，表示居里点Tc的那一栏上括号中的值给出了向AF相的转变点(抗铁电性)。由于压电现象在该转变点处消失，因此该转变点可以用作耐热性(热稳定性)以及居里点Tc的衡量标准。
为了进行对比，制备常规压电陶瓷组合物中使用的纯钛酸钡样品(对比例1)、纯铋钛酸钠样品(对比例2和3)，以及其中x为0的通式的组合物样品(对比例4)，其测定结果也列于表1和表2中。
                                     表1
    BaTiO31-x-y-z (Bi1/2Na1/2)TiO3x     CaTiO3y     MnO2(wt.％)
    样品1     0.05     0.90     0.05     0.5
    样品2     0.90     0.05     0.05     0.0
    样品3     0.85     0.10     0.05     0.0
    样品4     0.80     0.10     0.10     0.0
    样品5     0.70     0.10     0.20     0.0
    样品6     0.70     0.20     0.10     0.0
    样品7     0.60     0.20     0.20     0.0
  对比例1     1.00     0.00     0.00     0.0
  对比例2     0.00     1.00     0.00     0.0
  对比例3     0.00     1.00     0.00     0.5
  对比例4     0.95     0.00     0.05     0.0
表2
  εr   tanδ    kp    kt   QM     d31(E-11m/V)  Tc(℃)
  样品1   668   0.015   0.138  0.459   375     1.89 (180)
  样品2   481   0.027   0.217  0.451   124     3.22  154
  样品3   505   0.023   0.211  0.327   110     3.45  183
  样品4   512   0.021   0.205  0.343   132     3.24  181
  样品5   455   0.023   0.205  0.351   149     2.2  157
  样品6   442   0.025   0.188  0.357   137     1.69  165
  样品7   406   0.025   0.171  0.366   130     1.6  167
  对比例1   1190   0.026   0.201  0.321   112     3.18  127
  对比例2   402   0.022   0.185  0.441   113     2.08 (190)
  对比例3   335   0.02   0.130  0.438   816     1.4 (190)
  对比例4   1065   0.048   0.197  0.445   111     3.5  139
从表1和表2中可知，1-7号样品的压电陶瓷具有不低于150℃的作为耐热性(热稳定性)衡量标准的居里点，和足够大的机电耦合系数kp和kt。相反，对比例4的压电陶瓷的居里点低于150℃。因此，对比例4的压电陶瓷组合物在低于150℃的温度下失去压电现象，从而说明其耐热性(热稳定性)不足，纯钛酸钡样品(对比例1)同样存在该问题。
对比例1的压电陶瓷只有在1500°±15℃的加热温度范围内才能够具有96％的相对烧结密度。但是，例如，作为含另外一种元素的替代固体溶液的样品1的压电陶瓷在1330°±30℃的焙烧温度范围内具有不低于96.5％的相对烧结密度。
从上述事实可以理解，在较宽的加热温度范围内形成1-7号样品的压电陶瓷变得很容易，其中1-7号样品为(Bi1/2Na1/2)TiO3和CaTiO3于BaTiO3中的固体溶液，并且不含铅。此外，可知本实施例的样品1-7的压电陶瓷具有足够的耐热性(热稳定性)和机电耦合系数kp和kt。因此，如样品1-7的压电陶瓷中那样，式(1)的压电陶瓷组合物(其中x和y值分别为0.0＜x≤0.90和0.0≤y≤0.20)具有足够的耐热性(热稳定性)和足够的机电耦合系数kp和kt，因此可以适用作各种应用领域的压电元件。而且，含有MnO2的样品1的压电陶瓷具有表1和表2所示的增加的机械品质因数QM，因此尤其可适用于需要使用具有大机械品质因数QM的材料来制造的传感器和执行器。
实施例2
根据实施例2的压电陶瓷组合物制备如下。首先，称量作为原料的BaCO3，Bi2O3，NaCO3，CaCO3，TiO2，ZnO，Nb2O5和MnCO3，最终得到可具有如表3所示的给定配制比例的压电陶瓷，将它们在球磨机中均匀混合。接着，在800-1,000℃温度下煅烧2小时以形成化合物。该化合物再次在球磨机中研磨，将聚乙烯醇加到化合物颗粒中，并将混合物粒化。使粒化的粉末在70MPa的压力下单轴压缩模塑以形成直径为13mm的盘子，然后将其在1200-1400℃下加热2小时。将盘状样品磨至厚0.3mm，在700℃下将Ag烤熔而凝结到样品盘上以在其上形成电极。此后，通过在80℃的硅油中向其上施加3-5KV/mm的电场30分钟对样品盘进行极化处理。按照相同的方法得到样品8-14的压电陶瓷。
按照与实施例1相同的方法测定8-14号样品的压电陶瓷的具体的介电常数εr，tanδ，沿盘子半径方向平铺振动模式的耦合系数kp，沿盘子厚度方向垂直振动模式的耦合系数kt，机械品质因数QM和压电常数d31，和居里点Tc。测试结果见表4。
                                      表3
   BaTiO31-x-y-z (Bi1/2Na1/2)TiO3x    CaTiO3y  Ba(Zn1/3Nb2/3)O3z  MnO2(wt.％)
  样品8     0.84     0.10     0.05     0.01   0.0
  样品9     0.49     0.50     0.00     0.01   0.0
  样品10     0.14     0.80     0.05     0.01   0.0
  样品11     0.14     0.85     0.00     0.01   0.0
  样品12     0.14     0.85     0.00     0.01   1.0
  样品13     0.73     0.15     0.10     0.02   0.0
  样品14     0.78     0.20     0.00     0.02   0.0
  对比例5     0.98     0.00     0.00     0.02   0.0
  对比例6     0.93     0.00     0.05     0.02   0.0
  对比例7     0.78     0.00     0.20     0.02   0.0
  对比例8     0.60     0.20     0.15     0.05   0.0
                                  表4
  εr   tanδ      kp    kt     QM     d31(E-11m/V)   Tc(℃)
  样品8   468   0.023     0.176  0.345     117     2.14   150
  样品9   453   0.024     0.153  0.353     89     1.58   223
  样品10   793   0.025     0.195  0.428     83     2.42   238
  样品11   836   0.023     0.198  0.435     87     2.44   244
  样品12   634   0.013     0.126  0.442     376     1.82   245
  样品13   461   0.023     0.216  0.382     120     2.28   155
  样品14   436   0.024     0.207  0.321     132     2.03   166
  对比例5   2700   0.025      -    -      -      -   96
  对比例6   2414   0.024     0.165  0.238     189     4.6   102
  对比例7   1579   0.103     0.182  0.279     136     3.6   115
  对比例8   1075   0.033     0.188  0.329     134     3.27   123
从表3和表4中可知，与对比例5-8的压电陶瓷相比，8-14号样品的压电陶瓷具有不低于150℃的居里点和更高的耐热性(热稳定性)，还具有相对大的机电耦合系数kp和kt。对比例8{z[Ba(Zn1/3Nb2/3)O3的含量]设定为0.05}的压电陶瓷的居里点太低，因此，不适合使用。
从上述结果可以理解，8-14号样品的压电陶瓷(不含铅)具有足够的耐热性(热稳定性)和足够的机电耦合系数kp和kt，其中8-14号样品为(Bi1/2Na1/2)TiO3、CaTiO3和Ba(Zn1/3Nb2/3)O3于BaTiO3中的固体溶液。因此，本实施例样品8-14的压电陶瓷可以适用于各种压电元件，因为通式(1)的压电陶瓷组合物(其中x、y和z值分别为0.0＜x≤0.90和0.0≤y≤0.20和0.0≤z＜0.05)具有足够的耐热性(热稳定性)和足够的机电耦合系数kp和kt。
而且，含有1.0wt％的MnO2的样品12的压电陶瓷具有表4所示的增加的机械品质因数QM，因此尤其可适用于需要用具有大机械品质因数QM的材料制造的传感器和执行器。
实施例3
根据实施例3的压电陶瓷组合物制备如下。首先，称量作为原料的BaCO3，Bi2O3，NaCO3，CaCO3，TiO2，MnCO3，Y2O3，Dy2O3，Ho2O3和Yb2O3，最终得到可具有如表5所示的配制比例的压电陶瓷，将它们在球磨机中均匀混合。接着，在800-1,000℃温度下煅烧2小时以形成化合物。该化合物再次在球磨机中研磨，将聚乙烯醇加到化合物颗粒中，并将混合物粒化。使粒化的粉末在70MPa的压力下单轴压缩模塑以形成直径为13mm的盘子，然后将其在1200-1400℃下加热2小时。
将盘状样品磨至厚0.3mm，在700℃下将Ag烤熔而凝结到样品盘上以在其上形成电极。此后，通过在80℃的硅油中向其上施加3-5KV/mm的电场30分钟对样品盘进行极化处理。按照相同的方法得到样品15-20的压电陶瓷。
按照与实施例1相同的方法测定15-20号样品的压电陶瓷的具体的介电常数εr，tanδ，沿盘子半径方向平铺振动模式的耦合系数kp，沿盘子厚度方向垂直振动模式的耦合系数kt，机械品质因数QM和已经过1000小时后电容方面的变化速率。其测试结果如表6所示。
                                         表5
   BaTiO31-x-y-z (Bi1/2Na1/2)TiO3x    CaTiO3y  MnO2(wt.％)       稀土氧化物
  类型    含量(wt％)
    样品15     0.10     0.85     0.05   0.50     -     0.0
    样品16     0.10     0.85     0.05   0.50   Y2O3     0.5
    样品17     0.10     0.85     0.05   0.50   Y2O3     1.0
    样品18     0.10     0.85     0.05   0.50   Dy2O3     0.5
    样品19     0.10     0.85     0.05   0.50   HO2O3     0.5
    样品20     0.10     0.85     0.05   0.50   Yb2O3     0.5
   对比例9     0.10     0.85     0.05   0.50   Y2O3     1.5
                                  表6
  εr   tanδ    kp   kt    QM  1000h后电容变化速率(％)
  样品15   617   0.012   0.143  0.446   398     -0.98
  样品16   634   0.012   0.142  0.435   427     -0.53
  样品17   637   0.015   0.126  0.436   404     -0.48
  样品18   627   0.012   0.138  0.433   425     -0.50
  样品19   627   0.012   0.139  0.436   415     -0.53
  样品20   624   0.012   0.140  0.435   410     -0.50
  对比例9   654   0.045   0.050  0.165   40     -0.58
从表5和表6中可知，当就已经过1000小时后的电容变化速率将样品16-20的压电陶瓷与样品15的压电陶瓷对比时，稀土氧化物的加入有效地降低了电容随时间的变化速率，参见样品16-20的压电陶瓷。但是，如同在含有稀土氧化物的对比例9的压电陶瓷中看到的那样，如果稀土氧化物的含量为1.5wt％，所得的压电陶瓷具有降低的耦合系数kp和kt以及降低的机械品质因数QM。相反，由于样品16-20的压电陶瓷含有的稀土氧化物的量不大于1.0wt％，通过加入MnO2得以提高的机械品质因数QM并没有降低。在这方面，尽管没有列于表6中，样品15-20的压电陶瓷的居里点中的任意一个不低于150℃。
一些用在传感器中的电子元件需要具有大的机械品质因数QM，还需要具有抵抗随时间变化的稳定性。从这些需求的角度看，使用含有1.0wt％或更低的稀土氧化物和0.5wt％的MnO2的本实施例样品16-20的压电陶瓷可特别有效地提供实用的传感器和执行器。
如上所述，根据本发明的压电陶瓷组合物不含造成严重环境问题的铅，并且具有相对大的机电耦合系数和足够的耐热性(热稳定性)。因此，这些压电陶瓷组合物，例如，适合用作传感器、执行器、压电振子、滤波器等的压电元件用材料。

Claims (3)

1.一种压电陶瓷组合物，其具有下式表示的复合钙钛矿结构：(1-x-y-z)BaTiO3-x(Bi1/2Na1/2)TiO3-yCaTiO3-zBa(Zn1/3Nb2/3)O3，其中所述组合物包含比例满足x、y和z的下述条件的Ba、Ti、O、Bi、Na、Ca、Zn和Nb：
       0.0＜x≤0.90，
       0.0≤y≤0.20，和
       0.0≤z≤0.05，
条件是y和z不同时为0(排除y＝z＝0的情况)。
2.根据权利要求1的压电陶瓷组合物，其含有0.01wt％-1.0wt％的MnO2。
3.根据权利要求1或2的压电陶瓷组合物，其含有0.01wt％-1.0wt％的稀土氧化物。
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