CN1388089A - 压电陶瓷组合物、压电陶瓷元件及压电陶瓷组合物的制造方法 - Google Patents

压电陶瓷组合物、压电陶瓷元件及压电陶瓷组合物的制造方法 Download PDF

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CN1388089A
CN1388089A CN02122046A CN02122046A CN1388089A CN 1388089 A CN1388089 A CN 1388089A CN 02122046 A CN02122046 A CN 02122046A CN 02122046 A CN02122046 A CN 02122046A CN 1388089 A CN1388089 A CN 1388089A
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piezoelectric ceramic
ceramic composition
temperature
piezoelectric
room temperature
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CN1226232C (zh
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木村雅彦
安藤阳
小川智之
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Murata Manufacturing Co Ltd
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Abstract

本发明提供了以式(Na1－xLix)NbO3表示的具有主要由Na、Li、Nb及O元素构成的钙钛矿结构的化合物为主成分、且机械品质因数Qm有所提高的压电陶瓷组合物。其主成分的结晶系与原来在室温下稳定的结晶系不同,原来在比室温高的温度区稳定的结晶系在室温下为准稳定状态。

Description

压电陶瓷组合物、压电陶瓷元件及 压电陶瓷组合物的制造方法
技术领域
本发明涉及压电陶瓷组合物、压电陶瓷元件及压电陶瓷组合物的制造方法，特别涉及适合用作压电陶瓷滤波器、压电陶瓷振荡器及压电陶瓷振子等压电陶瓷元件等的材料的压电陶瓷组合物及使用了该压电陶瓷组合物的压电陶瓷材料等。
背景技术
压电陶瓷滤波器、压电陶瓷振荡器及压电陶瓷振子等压电陶瓷元件所用的压电陶瓷组合物，以往广泛采用以锆钛酸铅(Pb(TixZr1-x)O3)或钛酸铅(PbTiO3)为主成分的压电陶瓷组合物。但是，以锆钛酸铅或钛酸铅为主成分的压电陶瓷组合物，由于其组成中含有大量的铅，因此存在的问题是，在制造过程中，由于铅氧化物的蒸发，导致产品的均匀性下降。为了防止因制造过程中铅化物蒸发而引起产品均匀性下降，最好采用组成中完全不含铅或仅含少量铅的压电陶瓷组合物。
与上不同的是，对于用式(Na1-xLix)NbO3表示的一系列的化合物为主成分的压电陶瓷组合物，由于在其组成中不含铅氧化物，因此不产生上述问题。
然而，对于以式(Na1-xLix)NbO3表示的一系列的化合物为主成分的压电陶瓷组合物，其机械品质因数Qm较小。这样的压电陶瓷组合物存在的问题是，不适用于像压电陶瓷滤波器等对机械品质因数Qm有较高要求的元件。
另外，对于以式(Na1-xLix)NbO3表示的一系列的化合物为主成分的压电陶瓷组合物以比较低的温度从室温中的稳定结晶系变为比室温高的温度区中稳定的结晶系，结果存在的问题是，在相变温度其共振频率发生较大变化。
因此，本发明的主要目的在于提供以式(Na1-xLix)NbO3表示的具有主要由Na、Li、Nb及O元素构成的钙钛矿结构的化合物为主成分、且机械品质因数Qm可得到提高的压电陶瓷组合物。
本发明的另一目的在于提供使用了前述压电陶瓷组合物的压电陶瓷元件，所述压电陶瓷组合物以式(Na1-xLix)NbO3表示的具有主要由Na、Li、Nb及O元素构成的钙钛矿结构的化合物为主成分，且机械品质因数Qm可得到提高。
本发明的目的之三在于提供前述压电陶瓷组合物的制造方法，所述压电陶瓷组合物以式(Na1-xLix)NbO3表示的具有主要由Na、Li、Nb及O元素构成的钙钛矿结构的化合物为主成分，且机械品质因数Qm可得到提高。
发明内容
本发明的压电陶瓷组合物是以具有主要由Na、Li、Nb及O元素构成的钙钛矿结构的化合物为主成分的压电陶瓷组合物，该组合物的特征是，主成分的结晶系与原来在室温下稳定的结晶系不同，原来在比室温高的温度区稳定的结晶系在室温下处于准稳定状态。
例如，本发明的压电陶瓷组合物中，原来在室温下稳定的结晶系是菱形晶系，原来在比室温高的温度区稳定的结晶系是单斜晶系。
本发明的压电陶瓷组合物中，构成主成分的化合物用式(Na1-xLix)NbO3(式中，0.02≤X≤0.30)表示。
另外，本发明的压电陶瓷组合物中，构成主成分的化合物用式(Na1-xLix)NbO3(式中，0.08≤X≤0.18)表示。
另外，本发明的压电陶瓷组合物中，构成主成分的化合物用式(1-n)[(Na1-xLix)1-yKy](Nb1-zTaz)O3-nM1M2O3(式中，0.02≤x≤0.30，0≤y≤0.2，0≤z≤0.2，0≤n≤0.1，M1为2价金属元素，M2为4价金属元素)表示。在这种情况下，M1为选自Mg、Ca、Sr及Ba的至少一种，M2为选自Ti、Zr、Sn及Hf的至少一种。
另外，本发明的压电陶瓷元件是包含本发明的压电陶瓷组合物形成的压电陶瓷及形成于压电陶瓷的电极的压电陶瓷元件。
本发明的压电陶瓷组合物的制造方法的特征是，对压电陶瓷组合物进行极化处理后，在结晶系处于稳定状态的温度或高于该温度、但低于构成主成分的化合物失去强介电性的温度的温度下，对压电陶瓷组合物进行加热。
本发明的压电陶瓷组合物的制造方法中，对压电陶瓷组合物进行加热的温度在250℃～400℃的范围内。
在本发明的以具有主要由Na、Li、Nb及O元素构成的钙钛矿结构的化合物为主成分的压电陶瓷组合物中，主成分的结晶系与原来在室温下稳定的结晶系不同，原来在比室温高的温度区稳定的结晶系在室温下处于准稳定状态。这里的所谓准稳定状态是指在某一物质的温度不断变化时，在相变点不向原来应该是稳定的结晶相转变，而原来的结晶相处于非常长的不平衡状态并持续保持不变的状态。例如，钛酸钡(BaTiO3)通常在室温下为稳定的正方晶系，通过1460℃以上的高温下的急冷，能够得到室温下的六方晶系。这里所说的准稳定状态是指与室温下的六方晶系的钛酸钡相同的状态。另外，该准稳定状态不是随着从低温到高温的温度变化产生的，而是随着从高温到低温的温度变化产生，即是指在低温显示在更高温度下原来应该是稳定的结晶相的情况。
这样，就圆片状压电陶瓷振子沿厚度方向纵向振动的机械品质因数Qm而言，则以具有主要由Na、Li、Nb及O元素构成的钙钛矿结构的化合物为主成分的压电陶瓷组合物的机械品质因数Qm可从500左右或小于500提高至1000以上。
另外，本发明的压电陶瓷组合物，由于原来在比室温高的温度区稳定的结晶系在室温下处于准稳定状态，因此即使达到原来的相变温度，也不产生相变，共振频率没有大的变化。
本发明的压电陶瓷组合物的主成分是具有主要由Na、Li、Nb及O元素构成的钙钛矿结构的化合物，该化合物以式(Na1-xLix)NbO3(式中，0.02≤x≤0.30)表示，在这种情况下本发明的效果显著，是比较理想的。另外，在0.08≤x≤0.18时，本发明的效果特别显著，是最理想的。另外，本发明的以式(1-n)[(Na1-xLix)1-yKy](Nb1-zTaz)O3-nM1M2O3(式中，0.02≤x≤0.30，0≤y≤0.2，0≤z≤0.2，0≤n≤0.1，M1为2价金属元素，M2为4价金属元素)表示的化合物为主成分的压电陶瓷组合物也有效果。在这种情况下，最好M1为选自Mg、Ca、Sr及Ba的至少一种，M2为选自Ti、Zr、Sn及Hf的至少一种。
本发明的压电陶瓷组合物用式(Na1-xLix)NbO3表示时，只要近似(Na1-xLix)NbO3的式即可，Na、Li、Nb或O的比例相对于化学计量组成即使偏离5％左右也没有特别关系。另外，本发明的压电陶瓷组合物中即使混入极少量的Al、Mn、Fe、Si、Co、Pb等也没有问题。
本发明的压电陶瓷组合物的制造方法是在对压电陶瓷组合物进行极化处理后，在结晶系处于稳定状态的温度或高于该温度、但低于构成主成分的化合物失去强介电性的温度的温度下，对压电陶瓷组合物进行加热。此时，对压电陶瓷组合物进行加热的温度在250℃～400℃的范围内。
本发明的上述目的、特征及优点通过以下参照附图而进行的对发明实施方式的详细说明将得到更进一步的阐明。
附图说明
图1为以式(Na0.87Li0.13)NbO3表示的试样的X射线衍射图。
图2所示为使用了以式(Na0.87Li0.13)NbO3表示的试样No.6的热处理前后的压电陶瓷振子的宽度振动共振频率温度变化曲线图。
图3所示为本发明的压电陶瓷振子的立体图。
图4为图3所示的压电陶瓷振子的剖面示意图。
符号说明
10  压电陶瓷振子
12  压电陶瓷
12a、12b  压电陶瓷层
14a、14b、14c  振动电极
16a、16b、16c  引出电极
18a、18b  引线
20a、20b  外部端子
具体实施方式
首先，准备Na2CO3、LiCO3、K2CO3、Nb2O5、Ta2O5、CaCO3、BaCO3、TiO2及ZrO2作为初始原料，秤取这些原料，使它们形成式(1-n)[(Na1-xLix)1-yKy](Nb1-zTaz)O3-nM1M2O3(式中，0.01≤x≤0.35，0≤y≤0.25，0≤z≤0.25，0≤n≤0.2，M1为Ca或Ba，M2为Ti或Zr)表示的组合物，然后用球磨机进行约16小时的湿法混合，得到混合物。将得到的混合物干燥后，以700～900℃进行预烧结，得到预烧结物。然后，将该预烧结物进行粗粉碎后，适量加入有机粘合剂，用球磨机进行16小时湿法粉碎，通过40目的筛子进行粒度调节。然后，将它以1500kg/cm2的压力成型，形成直径为12mm、厚度为0.6mm的圆片，将它在大气中以1000～1300℃进行烧结，得到圆片状陶瓷。利用常规方法在该陶瓷的表面(两个主面)涂布银糊，进行烧结，形成银电极，然后在100～250℃的绝缘油中施加3～10KV/mm的直流电压30～60分钟，进行极化处理，得到压电陶瓷(试样)。然后，将这些试样加热至150～500℃(热处理)。
图1(a)所示为试样No.7等以式(Na0.87Li0.13)NbO3表示的圆片状试样在形成电极之前(未极化)经粉碎得到的粉末试样在室温下的X射线衍射图。另外，图1(b)所示为与上述组成相同的圆片状试样在形成电极、进行极化之后去掉电极经粉碎得到的粉末试样在室温下的X射线衍线图。图1(a)所示的图与图1(b)所示的图可以认为是几乎相同的图。根据发明者们进行分析的结果认为，图1(a)所示的图及图1(b)所示的图表示菱形晶系。然后，将与上述组成相同的圆片状试样在形成电极、进行极化后再加热至350℃，再使温度降至室温，去掉电极，经粉碎得到粉末试样，这样得到的粉末试样在室温下的X射线衍射图示于图1(c)。图1(c)所示的图与图1(a)所示的图及图1(b)所示的图有明显不同。特别是在2θ为35～45°左右时可看出这些图有很大差异。根据发明者们进行分析的结果可以认为，图1(c)所示的图是单斜晶系的图。将与上述组成相同的圆片状试样在形成电极之前(未极化)粉碎得到粉末试样，在温度发生变化时对该试样进行X射线衍射，结果表明从图1(c)看到的图与200～350℃附近的高温区稳定的结晶相的图一致，在刚刚极化处理后，室温下显示为菱形晶系晶体结构的试样在350℃的温度下进行热处理后在室温下显示为单斜晶系晶体结构。这就表明在极化后通过进行加热处理，原来在高温下稳定的结晶相在室温下处于准稳定状态。将极化后进行过热处理的试样放置2个月，再进行同样的X射线衍射分析能得到同样的结果。
同样，对以式(1-n)[(Na1-xLix)1-yKy](Nb1-zTaz)O3-nM1M2O3(式中，M1为2价金属元素，M2为4价金属元素)表示的本发明范围的其它试样的热处理前后结晶系进行研究，其结果是，无论哪一种试样都显现出同样的关系。另外，本发明的提高Qm的效果仅仅在结晶相显现出准稳定状态的情况下出现。
以下，对热处理前后的上述圆片状压电陶瓷振子沿厚度方向纵向振动基波的机电耦合系数Kt及机械品质因数Qm进行测定。将这些结果示于表1及表2中。
                                                              表1
                                                                                                         *表示该试样在本发明的范围之外
试样No. M1  M2   x     y     z     n     热处理温度(℃)              热处理前                 热处理后
结晶系  kt(％)     Qm     结晶系   kt(％)     Qm
    1 - -   0.01     0     0     0     350 菱形晶系     23     110     单斜晶系     18  1000
    2 - -   0.02     0     0     0     350 菱形晶系     25     190     单斜晶系     18  1210
    3 - -   0.05     0     0     0     350 菱形晶系     31     185     单斜晶系     25  1280
    4 - -   0.08     0     0     0     350 菱形晶系     36     320     单斜晶系     27  1950
    5* - -   0.13     0     0     0     500 菱形晶系     46     350     单斜晶系     不可测
    6 - -   0.13     0     0     0     400 菱形晶系     46     350     单斜晶系     30  2060
    7 - -   0.13     0     0     0     350 菱形晶系     46     350     单斜晶系     31  2100
    8 - -   0.13     0     0     0     300 菱形晶系     46     350     单斜晶系     40  1850
    9* - -   0.13     0     0     0     150 菱形晶系     46     350     菱形品系     46  350
    10 - -   0.18     0     0     0     350 菱形晶系     39     385     单斜晶系     32  1920
    11 - -   0.3     0     0     0     350 菱形晶系     28     270     单斜晶系     20  1230
    12 - -   O.35     0     0     0     350 菱形晶系     18     190     单斜晶系     15  1010
    13 - -   0.13   0.1     0     0     350 菱形晶系     48     245     单斜晶系     33  1710
    14 - -   0.13   0.2     0     0     350 菱形晶系     36     225     单斜晶系     26  1580
    15 - -   0.13   0.25     0     0     350 菱形晶系     25     185     单斜晶系     23  1210
                                                                      表2
试样No. M1  M2   x     y     Z   n   热处理温度(℃)             热处理前                 热处理后
结晶系   kt(％)     Qm     结晶系   kt(％)  Qm
    16  -  -   0.13     0     0.1   0     350 菱形晶系     42     310     单斜晶系     37  1810
    17  -  -   0.13     0     0.2   0     350 菱形晶系     38     250     单斜晶系     34  1660
    18  -  -   0.13     0     0.25   0     350 菱形晶系     33     190     单斜晶系     25  1380
    19  Ca  Ti   0.13     0     0   0.05     350 菱形晶系     45     320     单斜晶系     33  1850
    20  Ca  Ti   0.13     0     0   0.1     350 菱形晶系     41     260     单斜晶系     25  1530
    21  Ca  Ti   0.13     0     0   0.2     350 菱形晶系     30     180     单斜晶系     19  1020
    22  Ba  Ti   0.13     0     0   0.05     350 菱形晶系     40     300     单斜晶系     30  1770
    23  Ba  Ti   0.13     0     0   0.1     350 菱形晶系     38     265     单斜晶系     26  1430
    24  Ba  Ti   0.13     0     0   0.2     350 菱形晶系     30     190     单斜晶系     19  1000
    25  Ca  Zr   0.13     0     0   0.05     350 菱形晶系     39     300     单斜晶系     30  1720
    26  Ca  Zr   0.13     0     0   0.1     350 菱形晶系     36     240     单斜晶系     24  1300
    27  Ca  Zr   0.13     0     0   0.2     350 菱形晶系     25     180     单斜晶系     16  1040
    28  -  -   0.13     0     0   0     250 菱形晶系     46     350     单斜晶系     36  1980
表1及表2所示的值是在相同组成的试样得到最大机械品质因数Qm的条件(预烧结温度、烧结温度、极化时的绝缘油的温度、直流电压)下的值。
另外，表1中的试样No.5，由于热处理温度过高，因此失去强介电性及压电性，在本发明的范围外。另外，表1中的试样No.9，由于热处理温度过低，即由于未达到高温结晶相稳定的温度，因此结晶形未变化，也在本发明的范围外。
与上述不同的是，如表1及表2所示可知，在本发明范围内的试样，其机械品质因素Qm都大幅度提高，是特别适合用作压电陶瓷滤波器、压电陶瓷振荡器、压电陶瓷振子等压电陶瓷元件等的材料的压电陶瓷组合物。
另外，对于试样No.1～28的各试样，在热处理前及热处理后，用阻抗分析仪测定温度在-40℃～400℃之间变化时的宽度振动共振频率，观察共振频率是否有大幅度变化(发生相变)。将这些结果示于表3中。另外，特别将使用了试样No.6的压电陶瓷振子的热处理前后的温度与宽度振动共振频率的关系画成曲线示于图2中。
           表3
          *表示该试样在本发明的范围之外
    试样No.     共振大幅度变化(相变发生)
    热处理前     热处理后
    1     确认     未确认
    2     确认     未确认
    3     确认     未确认
    4     确认     未确认
    5*     不可测
    6     确认     未确认
    7     确认     未确认
    8     确认     未确认
    9*     确认     确认
    10     确认     未确认
    11     确认     未确认
    12     确认     未确认
    13     确认     未确认
    14     确认     未确认
    15     确认     未确认
    16     确认     未确认
    17     确认     未确认
    18     确认     未确认
    19     确认     未确认
    20     确认     未确认
    21     确认     未确认
    22     确认     未确认
    23     确认     未确认
    24     确认     未确认
    25     确认     未确认
    26     确认     未确认
    27     确认     未确认
    28     确认     未确认
由表3及图2所示的结果可知，在热处理前，全部试样都出现大幅度的共振频率变化(相变发生)，而大热处理后，试样No.5由于去极化而不可测，试样No.9出现大幅度的共振频率变化(相变发生)。
与上述不同的是，本发明范围内的试样都未出现大幅度的共振频率变化(相变发生)。
例如，由图2所示曲线可知，热处理前的试样No.6的共振频率随温度变化是非线性的，热处理后的试样No.6的共振频率随温度变化是线性的。在压电陶瓷滤波器、压电陶瓷振荡器及压电陶瓷振子等中，常常要求共振频率的温度变化率要小。在这样的情况下，若共振频率的温度变化是线性关系，则比较容易通过校正将变化率控制在较小范围内。与此相反，在共振频率的温度变化是非线性的情况下，很难通过校正控制变化率。另外，对于热处理前的试样No.6，共振频率的温度变化在升温时及降温时是不同的，随升降温的速度而变化。即共振频率的温度变化具有迟滞。而在热处理后的试样No.6中，在常规温度-40～125℃的范围内几乎未发现迟滞。
本发明的压电陶瓷组合物并不仅限定于上述实施例的组成，只要在本发明的技术要点范围内都有效。
另外，上述实施例中所示的机械品质因数Qm是关于圆片状压电陶瓷振子的厚度纵向振动的例子，但本发明的效果不限定于圆片状压电陶瓷振子的厚度纵向振动，对于宽度振动、厚度切变振动或厚度纵向振动高次共振波等，用作其它压电陶瓷元件、特别是压电陶瓷振荡器等的其它振动模式，也与厚度纵向振动的情况同样有效。
另外，上述实施例中所示的频率的温度变化是圆片状压电陶瓷振子的宽度振动的例子，但本发明的效果不限定于圆片状压电陶瓷振子的宽度振动，其它的压电陶瓷元件的厚度纵向振动或厚度切变振动等也同样有效。
图3所示为本发明的压电陶瓷振子的立体图，图4为其剖面示意图。图3及图4所示的压电陶瓷振子10包含长方体形的压电陶瓷12。压电陶瓷12包含2片压电陶瓷层12a及12b。这些压电陶瓷12a及12b由上述本发明的压电陶瓷组合物形成，层叠后形成一体。另外，这些压电陶瓷层12a及12b如图4箭头形成，在相同的厚度方向极化。
在压电陶瓷层12a与12b之间，在其中央形成圆形振动电极14a，由该振动电极14a至压电陶瓷12的一端面形成T字形的引出电极16a。另外，在压电陶瓷12a的表面的中央形成圆形振动电极14b，由该振动电极14b至压电陶瓷12的另一端面形成T字形的引出电极16b。在压电陶瓷层12b的表面的中央形成圆形振动电极14c，由该振动电极14c至压电陶瓷12的另一端面形成T字形的引出电极16c。
然后，一外部端子20a通过引线18a与引出电极16a连接，另一外部端子20b通过另外的引线18b与引出电极16b及16c连接。
另外，本发明也适用于除上述压电陶瓷振子10以外的压电陶瓷振子、压电陶瓷滤波器及压电陶瓷振荡器等其它的压电陶瓷元件。
本发明能够得到适合用作压电陶瓷滤波器、压电陶瓷振荡器及压电陶瓷振子等压电陶瓷元件等的材料的压电陶瓷组合物及使用了该压电陶瓷组合物的压电陶瓷元件，所述压电陶瓷组合物以式(Na1-xLix)NbO3表示的具有主要由Na、Li、Nb及O元素构成的钙钛矿结构的化合物为主成分，其机械品质因数Qm有所提高，而且完全不含或仅含少量的铅或铅化合物。
另外，由于本发明的压电陶瓷组合物的原来在比室温高的温度区稳定的结晶系在室温处于准稳定状态，因此达到原来的相变温度也不产生相变，共振频率没有大的变化。

Claims (9)

1.压电陶瓷组合物，以具有主要由Na、Li、Nb及O元素构成的钙钛矿结构的化合物为主成分，其特征在于，所述主成分的结晶系与原来在室温下稳定的结晶系不同，原来在比室温高的温度区稳定的结晶系在室温下处于准稳定状态。
2.如权利要求1所述的压电陶瓷组合物，其特征还在于，所述原来在室温下稳定的结晶系为菱形晶系，所述原来在比室温高的温度区稳定的结晶系为单斜晶系。
3.如权利要求1所述的压电陶瓷组合物，其特征还在于，所述构成主成分的化合物由(Na1-xLix)NbO3表示，式中0.02≤x≤0.30。
4.如权利要求3所述的压电陶瓷组合物，其特征还在于，所述构成主成分的化合物由(Na1-xLix)NbO3表示，式中0.08≤x≤0.18。
5.如权利要求1所述的压电陶瓷组合物，其特征还在于，所述构成主成分的化合物由式(1-n)[(Na1-xLix)1-yKy](Nb1-zTaz)O3-nM1M2O3表示，式中，0.02≤x≤0.30，0≤y≤0.2，0≤z≤0.2，0≤n≤0.1，M1为2价金属元素，M2为4价金属元素。
6.如权利要求5所述的压电陶瓷组合物，其特征还在于，所述M1为选自Mg、Ca、Sr及Ba的至少一种，所述M2为选自Ti、Zr、Sn及Hf的至少一种。
7.压电陶瓷元件，其特征在于，包含权利要求1所述的压电陶瓷组合物形成的压电陶瓷和形成于所述压电陶瓷的电极。
8.权利要求1所述的压电陶瓷组合物的制造方法，其特征在于，在对所述压电陶瓷组合物进行极化处理后，在所述结晶系处于稳定状态的温度或高于该温度、但低于构成所述主成分的化合物失去强介电性的温度的温度下，对所述压电陶瓷组合物进行加热。
9.如权利要求8所述的压电陶瓷组合物的制造方法，其特征还在于，对所述压电陶瓷组合物进行加热的温度在250℃～400℃的范围内。
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