CN105555735A - 基于钛酸铋钠(bnt)的不含铅的压电陶瓷材料 - Google Patents

基于钛酸铋钠(bnt)的不含铅的压电陶瓷材料 Download PDF

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CN105555735A
CN105555735A CN201480050913.2A CN201480050913A CN105555735A CN 105555735 A CN105555735 A CN 105555735A CN 201480050913 A CN201480050913 A CN 201480050913A CN 105555735 A CN105555735 A CN 105555735A
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piezoceramic material
lead
ybatio
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E·亨尼希
A·基纳斯特
M·特普费尔
M·霍夫曼
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PI Ceramic GmbH Keramische Technologien und Bauelemente
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Priority to CN202110971968.9A priority patent/CN114085078A/zh
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Abstract

本发明涉及基于钛酸铋钠(BNT)并且具有以下基本组成的不含铅的压电陶瓷材料：x(Bi0.5Na0.5)TiO3-yBaTiO3-zSrTiO3，其中x+y+z＝1，并且0<x<1，0<y<1，0≤z≤0.07，或x(Bi0.5Na0.5)TiO3-yBaTiO3-zCaTiO3，其中x+y+z＝1，并且0<x<1，0<y<1，0<z≤0.05，或x(Bi0.5Na0.5)TiO3-y(Bi0.5K0.5)TiO3-zBaTiO3，其中x+y+z＝1，并且0<x<1，0<y<1，0≤z<1，其特征在于，加入一定量的含磷材料，使得压电陶瓷材料中的磷浓度为100至2000ppm。

Description

基于钛酸铋钠(BNT)的不含铅的压电陶瓷材料
本发明涉及根据权利要求1的前序部分的基于钛酸铋钠(BNT)并且具有一定基本组成的不含铅的压电陶瓷材料，并且特别涉及在RoHS指令(指令2011/65/EU)的含义内在均相材料中的铅含量<0.1重量％的不含铅的材料。
基于钛酸铅锆(PZT)的压电致动器、压电传感器和其它压电组件为目前的现有技术，其中越来越需要使压电陶瓷材料不含铅。
在现有技术的进一步发展中，尝试开发基于BNT(钛酸铋钠)的不含铅的压电陶瓷材料。
所述材料长期已知并且基本组成描述于JP62202576(BNT-BT和BNT-BKT)和DE19530592C2(BNT-BT-CT)。Takenaka(SensorandMaterials；3(1988)123-131)详细描述了使用例如钛酸锶对所述材料进行改性。
在这些基本研究的基础之上，现有技术中描述了其它实施方案。对此例如参见US2002/014196A1、EP1231192A1。
所有基于BNT的组成的基本问题是烧结时的极差压实并且出现所谓的巨晶生长连同高的导电性。具有非均相结构的压电陶瓷体不能很好地极化，使得不能达到希望的材料性能或者出现过大的材料性能变化。JP2004-075449中提出通过锰、铬、铁、钴或铌酸盐针对性地进行替代从而抑制巨晶生长。
本申请人的关于用锰和铜对BNT材料进行改性的研究虽然显示出烧结情况的部分改进，但是仍然显示出巨晶生长的连续倾向以及电数据的劣化。
因此要指出的是，经改性的BNT组成倾向于材料中不均匀分布的巨晶生长或粗晶结构的形成。在此，巨晶的出现不受控制并且高度取决于制备条件和烧结条件。晶粒生长虽然可以通过低烧结温度得以抑制，这却造成<5.6g/cm3的低烧结密度。不希望的巨晶生长或粗晶结构的结果是温度相关度极高的低比绝缘电阻，陶瓷体的较差极化性，和在兆赫范围内的厚度波动的扰乱的波动情况。
在申请人的研究中还发现，泄漏电流高度取决于结构和温度。
此外要指出的是，经改性的BNT组成通常具有小的烧结区间，这造成在技术上难以控制的问题。烧结区间被理解为由两个温度数据限定的范围，在所述范围内在材料燃烧时实现需要的陶瓷性能。小的烧结区间因此造成只有在燃烧中可以以极小的温度耐受性性操作时才能实现压电陶瓷材料的希望的性能，这在技术上是难以控制的。小的烧结区间因此造成经济上的缺点，因为相对大量的产品为次品。
基于上述内容，因此本发明的目的是提供基于BNT的不含铅的压电陶瓷材料，所述压电陶瓷材料具有均质细晶结构并且在150℃的温度下具有≥5*108Ω的比绝缘电阻。本发明的另一个目的在于，提供基于BNT的不含铅的压电陶瓷材料，所述压电陶瓷材料具有大的烧结区间，特别是≥40K的烧结区间。
通过权利要求1的特征组合，以及制备相应压电陶瓷材料的方法和通过基于根据本发明的材料制备的压电陶瓷体或多层致动器实现本发明的目的。
因此，出发点是基于钛酸铋钠的并且不含铅的压电陶瓷材料，所述压电陶瓷材料具有以下基本组成
x(Bi0.5Na0.5)TiO3-yBaTiO3-zSrTiO3，其中x+y+z＝1
并且0<x<1，0<y<1，0≤z≤0.07
优选0<x<1，0.1<y<0.25，0≤z≤0.07
更优选0<x<1，0.1≤y≤0.20，0≤z≤0.03
或
x(Bi0.5Na0.5)TiO3-yBaTiO3-zCaTiO3，其中x+y+z＝1
并且0<x<1，0<y<1，0<z≤0.05
优选0<x<1，0.1<y<0.25，0<z≤0.05
更优选0<x<1，0.1≤y≤0.20，0<z≤0.02
或
x(Bi0.5Na0.5)TiO3-y(Bi0.5K0.5)TiO3-zBaTiO3，其中x+y+z＝1
并且0<x<1，0<y<1，0≤z<1
优选0<x<1，0.1<y<0.3，0≤z≤0.15
更优选0<x<1，0.1≤y≤0.24，0≤z≤0.05。
通过加入一定量的含磷材料，使得在压电陶瓷材料中的磷浓度为100至2000ppm，从而获得根据本发明的压电陶瓷材料。
根据本发明，通过基于钛酸铋钠(BNT)的且不含铅的压电陶瓷材料实现所述目的，所述压电陶瓷材料具有以下组成
x(Bi0.5Na0.5)TiO3-yBaTiO3-zSrTiO3，其中x+y+z＝1
并且0<x<1，0<y<1，0≤z≤0.07
优选0<x<1，0.1<y<0.25，0≤z≤0.07
更优选0<x<1，0.1≤y≤0.20，0≤z≤0.03
或
x(Bi0.5Na0.5)TiO3-yBaTiO3-zCaTiO3，其中x+y+z＝1
并且0<x<1，0<y<1，0<z≤0.05
优选0<x<1，0.1<y<0.25，0<z≤0.05
更优选0<x<1，0.1≤y≤0.20，0<z≤0.02
或
x(Bi0.5Na0.5)TiO3-y(Bi0.5K0.5)TiO3-zBaTiO3，其中x+y+z＝1
并且0<x<1，0<y<1，0≤z<1
优选0<x<1，0.1<y<0.3，0≤z≤0.15
更优选0<x<1，0.1≤y≤0.24，0≤z≤0.05
其特征在于
加入一定量的含磷材料，使得压电陶瓷材料中的磷浓度为100至2000ppm。
术语ppm(百万分之)在此涉及以压电陶瓷组成的总质量计的磷质量。
在一个优选的实施方案中，根据本发明的压电陶瓷材料具有<0.1重量％的铅含量。
在一个优选的实施方案中，根据本发明的基于钛酸铋钠(BNT)的压电陶瓷材料被设计成具有以下基本组成
x(Bi0.5Na0.5)TiO3-yBaTiO3-zSrTiO3，其中y≥0.1并且x+y+z＝1，或
x(Bi0.5Na0.5)TiO3-yBaTiO3-zCaTiO3，其中y≥0.1并且x+y+z＝1，或
x(Bi0.5Na0.5)TiO3-y(Bi0.5K0.5)TiO3-zBaTiO3，其中y≥0.1并且x+y+z＝1
其中加入一定量的含磷材料，使得在压电陶瓷材料中的磷浓度为100至2000ppm。
在一个优选的实施方案中，不含铅的压电陶瓷材料被设计成含磷化合物为无机磷酸盐、磷酸氢盐或磷酸二氢盐。
在一个特别优选的实施方案中，不含铅的压电陶瓷材料被设计成含磷化合物选自KH2PO4(KDP)、(NH4)H2PO4(ADP)。
虽然在宽的用量范围内实现了根据本发明的加入含磷材料的效果，但是已经发现，当不含铅的压电陶瓷材料被设计成以一定量加入含磷材料使得不含铅的压电陶瓷材料中的磷浓度为100至2000ppm时，实现特别有利的性能。
已经发现，当在根据本发明的陶瓷材料中磷浓度超过2000ppm时，材料混合物至压电陶瓷材料的可加工性较差。当浓度小于100ppm时，不再以足够程度实现本发明所致力于的效果。
在一个优选的实施方案中，加入一定量的含磷材料，使得不含铅的压电陶瓷材料中的磷浓度为250至2000ppm，更优选270至1800ppm。
已经发现，当基本组成包含以氧化物或复合钙钛矿形式(Perowskite)的添加剂时，可以以特别有利的方式影响不含铅的压电陶瓷材料的性能。
出人意料地，通过根据本发明的不含铅的压电陶瓷材料可以将烧结区间调节至≥40K。
本发明还涉及制备各种不含铅的压电陶瓷材料的方法。根据本发明的方法有利地被设计成包括以下步骤：
-制备基本组成的原料混合物，
-制备基本组成的煅烧产物，
-精细研磨煅烧产物，
-特别通过喷雾造粒制备颗粒，或者制备用于多层过程或“共烧”过程的浇注浆料，
-以包括烧结的已知方式在正常大气条件下进行再加工。
在本发明的含义内，“共烧”过程被理解为特别创新的制备方法，其中首先浇注压电陶瓷材料的薄膜，然后在未处理(Gruezustand)状态下配置电极。由多个单独薄膜层压形成压电元件，然后在单个方法步骤中连同内部电极一起烧结，如例如DE10234787中所述。
可以在精细研磨时和/或在制备喷雾浆料或浇注浆料时加入磷或含磷材料。
根据本发明的方法被特别优选地设计成在制备喷雾浆料或浇注浆料时加入磷或含磷材料。所述方法的优点在于，首先可以大规模制备精细研磨的基本组成的粉末，并且加入磷的量和方式可以适应之后的方法步骤(喷雾浆料、浇注浆料)的要求。
在制备根据本发明的不含铅的压电陶瓷材料的特别优选的方法中，首先提供基本组成的煅烧产物。然后优选以单晶铁电性KDP或ADP的形式以270至1800ppm的浓度加入磷。可以在精细研磨时或者在制备喷雾浆料或浇注浆料时加入。这种材料的再加工(包括在正常大气条件下烧结)根据已知技术进行。
本发明还涉及基于上述压电陶瓷材料的压电陶瓷多层致动器。所述压电陶瓷多层致动器例如通过DE10234787或DE202012012009已知。
本发明还涉及基于上述压电陶瓷材料的压电结构元件，所述压电结构元件由至少一个具有至少两个电极的压电陶瓷体组成，本发明特别还涉及特别以其厚度波动操作的压电超声变换器。
所使用的含磷材料可以被理解为烧结助剂，其中磷组分在此具有决定性意义。通过在BNT基本组成中针对性地加入磷克服了如下业内偏见：磷虽然以积极方式抑制晶粒生长，但是却使相应压电陶瓷材料的压电性能劣化。
出人意料地发现，通过使用含磷材料不仅可以有效地抑制巨晶生长并且因此可以实现均质的细晶结构，而且同时也实现了压电陶瓷材料的≥40K的宽的烧结区间。这在技术上具有重要意义，因为宽的烧结区间是经济地制备材料、多层致动器或结构元件的前提。此外，根据本发明的压电陶瓷材料在150℃下具有≥5*108Ω的高比绝缘电阻，这对于在所述元件中的使用是非常有利的。
通过根据本发明的压电陶瓷材料，在1120℃至1240℃的温度范围内，在≥40K的宽烧结区域内得到均质的细晶结构。还有利的是，确定高温下绝缘电阻的升高和因此更好的极化情况。基于根据本发明的不含铅的压电陶瓷材料制备的致动器在宽的温度范围内具有高的绝缘电阻，同时根据本发明的超声变换器具有显著的厚度波动和高的耦合因子。
要指出的是，出人意料地，使用含磷添加剂造成对巨晶生长的抑制和均质的细晶结构，并且可以通过加入磷的方式和量在一定限度内影响退极化温度的位置。
可以在精细研磨时或者在喷雾造粒时加入含磷添加剂。但是也可以想到在制备浇注浆料时使用含磷分散剂和/或添加剂，或者在制备这种浆料时使用含磷粘合剂。
通过合适地选择含磷分散剂和/或添加剂带来的技术优点是，不会负面影响精细研磨浆料、浇注浆料或喷雾浆料的粘度。
此外，磷的引入可以远高于由常见原料污染和常见分散剂浓度引入的值，并且可以针对性地调节加入的磷量。
一个可能的替代形式是在原料混合时加入磷或者用含磷液体浸渍固体。但是也可以设想，以受体掺杂物的形式将磷引入基本组成(钛被磷部分替代)。
已经发现，可以以几乎任何含磷材料的形式将磷加入根据本发明的材料。虽然磷酸二氢钾或磷酸二氢铵是特别优选的含磷材料，但是也可以通过任何其它含磷材料加入磷。
本申请的发明人通过研究发现，通过加入含磷材料造成退极化温度的一定降低。在此，退极化温度降低的效果对于不同的含磷材料而不同。已经发现，相比于加入磷酸二氢钾的情况，例如加入磷酸二氢铵造成退极化温度的明显更剧烈的降低。所述预料之外的效果造成本发明具有其它优点：通过选择其它含磷材料，在压电陶瓷材料的其它性能保持不变的同时，可以在一定限度内控制退极化温度的降低。这因此具有重要意义，因为根据压电陶瓷材料的希望的使用目的寻求一定的退极化温度。虽然通常希望力争退极化温度的尽可能小的降低，但是对于一定的应用可能有用的是实现退极化温度的剧烈降低。这特别适合于压电陶瓷材料必须仅在极窄的温度区间内起作用的使用目的。对于所述应用可能有意义的是力争退极化温度的剧烈降低，因为在从下方接近退极化温度时压电陶瓷材料的希望的压电性能得以改进。
本发明还涉及含磷材料在基于钛酸铋钠(BNT)并且具有上述基本组成的压电陶瓷材料中用于减少巨晶生长并且用于实现均质的细晶结构的用途，其中以一定量使用含磷材料，使得在压电陶瓷材料中的磷浓度为100至2000ppm，特别是250至2000ppm，更优选270至1800ppm。下文借助于实施例和对比试验的描述更详细地解释本发明。
实施例
下文描述的测量结果涉及基本体系x(Bi0.5Na0.5)TiO3-yBaTiO3-zSrTiO3。
图1描述了样本制备的一般技术流程。“*”表示可以进行权利要求书中描述的加入含磷材料的技术步骤。
原料的混合和煅烧产物的精细研磨分别在搅拌球磨机中进行。
含磷材料的加入具体地在以下技术步骤中进行：
FM精细研磨
G在造粒时加入
VS在有机制浆从而制备薄膜时加入
根据如下等级进行结构表征：
0材料不可加工
1细晶的均质结构
2非均质结构，巨晶生长
3粗晶结构
在烧结的圆柱体上根据浮力法确定样本密度，对于给定的烧结温度以平均值的形式给出，对于在给定温度范围内具有可测量电值的最低烧结温度以“单位为g/cm3的密度>”的形式给出。
对于电测量，使用直径为12mm、绝缘边缘为0.5mm并且厚度为0.5mm的金属化样本。在80℃和5kV/mm下进行极化15分钟。
“S”表示具有测量值的强烈变化、共振曲线的干扰或在径向波动或厚度波动中的过低的最大相位角的样本。
kp或kt为径向波动或厚度波动的耦合因子。
退极化温度Td通常被定义为经极化样本的介电常数随温度变化的曲线中的拐点。
在50V下在极化的样本上将温度从室温升高至200℃从而确定比绝缘电阻ρis。
通过激光干涉仪在2kV/mm下确定机电应变S3。表中给出室温下的值和相关的样本电流I。
表2中显示了在所研究的温度范围内的特征值。
图表和光显微结构照片涉及表中通过各个样本序号定义的组成。
下文详细描述现有技术和需要消除的缺陷：
图2，表1中的样本1a至1f，显示了基本组成0.85(Bi0.5Na0.5)TiO3-0.12BaTiO3-0.03SrTiO3的烧结密度随烧结温度变化的曲线。特征在于低烧结温度下的低密度，窄的烧结区间和由样本分解(Bi、Na蒸发)造成的高烧结温度下的密度降低。
相应的光显微结构照片(图3)显示，在所研究的温度范围的中间，从压实程度不足的细晶材料转变成巨晶生长并且在更高的烧结温度下转变成粗晶结构。
不利之处在于绝缘电阻随着样本温度过度降低(图4：样本1a至1f)。结果是不足的或不明确的极化以及过低或剧烈变化的电值。
在样本电流的图表中在更高的电场强度和更高的温度下明显看到不可容忍的导电性(图5a：样本1a至1f，图5b：样本1d)。致动器的工作温度因此受到明显限制。
在不同温度下烧结的样本的阻抗和厚度波动相的曲线图(图6：样本1a至1f)公开了结构和共振情况之间的关系(分别显示了3个单独样本)。材料的特征在于
·曲线走向在各个烧结温度下的强烈变化
·曲线走向在烧结温度变化时的强烈变化
·在更高的烧结温度下受到强烈干扰的共振情况。
数据列于表1中。
因此发现，所使用的烧结温度无一造成足够良好且可再现的电值或机电值，并且现有的技术不适合大规模生产。
表2中列出的未落入权利要求范围的样本2a、5a、9a、10a、14和15显示出相当的情况。
如下实施例显示了根据本发明制备的组成的情况。
实施例1：
根据流程图(图1)加工基本组成0.85(Bi0.5Na0.5)TiO3-0.12BaTiO3-0.03SrTiO3，并且
·在精细研磨时加入含磷分散剂(PE169，生产商AkzoNobel)
·或者在造粒时通过加入粘合剂引入磷酸二氢钾。
具有2275ppmP(KDP)的样本2i或具有2695ppmP(ADP)的样本2m无法通过这种方式加工。
正如光显微结构照片(图7：样本2a至2h)显示，根据本发明加入>＝250ppm的磷造成均质的细晶结构。
图8(样本2a、2b、2c、2e和2g)显示在加入根据本发明的≥250ppm的量的磷时明显改进了压实。
此外，出人意料地发现在较高的温度下比绝缘电阻明显升高几个数量级(图9：样本2a至2h)。因此从250ppm的磷开始保证了足够良好并且可再现的样本极化。
图10a至10e清楚显示在根据本发明的≥250ppm的磷含量下，即使在较高的温度下仍然发现样本电流明显降低。因此即使在较高的操作温度下，致动器的操作也是可能的。
样本性能的变化明显减少。如果观察在不同温度下烧结的样本的特征共振曲线，发现在根据本发明的≥250ppm的磷含量下，在不同温度下烧结的样本之间的差别明显减少，因此烧结区间出人意料地增宽至技术上可用的容易实现的温度范围(表3a、3b，图11)。
表3a
表3b
出人意料地，通过选择含磷材料可以在宽范围内调节退极化温度。图12(样本2a、2c至2h、2j至2l)显示了不同磷源和磷含量的退极化温度Td。因此开启了针对应用来改变退极化温度的可能性。
实施例2：
根据表2的样本3、4、5b、6和2n为基本组成0.85(Bi0.5Na0.5)TiO3-0.12BaTiO3-0.03SrTiO3的根据本发明的可大规模使用的其它改性实施例。
明显的技术优点在于，在实施例3和5b中材料在精细研磨之前在无磷情况下加工，并且在制浆从而喷雾造粒时才加入磷。
在实施例4、6中在精细研磨时加入磷，在实施例2n中在有机制浆从而浇注薄膜时加入磷。
有利的是，在精细研磨之前可以独立于初级成形过程(压制或浇注薄膜)统一进行大规模的材料加工，因此加入磷的方式和量可以最佳地适应于各个成形过程。
然而还有利的是决定粘度的含磷分散剂或粘合剂和基本上“中性粘度的”添加剂(例如KDP或ADP)的可能的组合。
图13和14，样本3显示了根据本发明的组成在25至150℃的温度范围内的机电伸长和样本电流。
实施例3：
表2包括基本组成x(Bi0.5Na0.5)TiO3-yBaTiO3-zSrTiO3的关于BaTiO3含量和SrTiO3含量的变体作为根据本发明的其它实施例。
摘自表2
在y≥0.10的范围内，材料体系在磷改性方面的行为与基本组成0.85(Bi0.5Na0.5)TiO3-0.12BaTiO3-0.03SrTiO3相似。
在y<0.10的范围内，要求磷含量在上述要求保护的数值范围内。

Claims (14)

1.基于钛酸铋钠(BNT)的不含铅的压电陶瓷材料，其具有以下基本组成
x(Bi0.5Na0.5)TiO3-yBaTiO3-zSrTiO3，其中x+y+z＝1
并且0<x<1，0<y<1，0≤z≤0.07
或
x(Bi0.5Na0.5)TiO3-yBaTiO3-zCaTiO3，其中x+y+z＝1
并且0<x<1，0<y<1，0<z≤0.05
或
x(Bi0.5Na0.5)TiO3-y(Bi0.5K0.5)TiO3-zBaTiO3，其中x+y+z＝1，
并且0<x<1，0<y<1，0≤z<1
其特征在于
加入一定量的含磷材料，使得在压电陶瓷材料中的磷浓度为100至2000ppm。
2.根据权利要求1所述的基于钛酸铋钠(BNT)的不含铅的压电陶瓷材料，其中基本组成为
x(Bi0.5Na0.5)TiO3-yBaTiO3-zSrTiO3，其中y≥0.1并且x+y+z＝1，或
x(Bi0.5Na0.5)TiO3-yBaTiO3-zCaTiO3，其中y≥0.1并且x+y+z＝1，或
x(Bi0.5Na0.5)TiO3-y(Bi0.5K0.5)TiO3-zBaTiO3，其中y≥0.1并且x+y+z＝1。
3.根据权利要求1或2所述的不含铅的压电陶瓷材料，
其特征在于，
含磷化合物为无机磷酸盐、磷酸氢盐或磷酸二氢盐。
4.根据权利要求1至3任一项所述的不含铅的压电陶瓷材料，
其特征在于，
含磷化合物选自KH2PO4、(NH4)H2PO4。
5.根据权利要求1至4至少一项所述的不含铅的压电陶瓷材料，
其特征在于，
加入一定量的含磷材料，使得在不含铅的压电陶瓷材料中的磷浓度为250至2000ppm，特别是270至1800ppm。
6.根据权利要求1至5任一项所述的不含铅的压电陶瓷材料，
其特征在于，
基本组成包含以氧化物或复合钙钛矿形式的添加剂。
7.根据权利要求1至6任一项所述的不含铅的压电陶瓷材料，
其特征在于，
烧结区间≥40K。
8.制备根据前述权利要求1至7任一项所述的不含铅的压电陶瓷材料的方法，
其特征在于以下步骤：
-制备基本组成的原料混合物，
-制备基本组成的煅烧产物，
-精细研磨煅烧产物，
-特别通过喷雾造粒制备颗粒，或者制备用于多层过程或“共烧”过程的浇注浆料，
-以包括烧结的已知方式在正常大气条件下进行再加工。
9.基于根据权利要求1至7任一项所述的不含铅的压电陶瓷材料的压电陶瓷多层致动器。
10.基于根据权利要求1至7任一项所述的不含铅的压电陶瓷材料的压电陶瓷结构元件，优选包括至少一个具有至少两个电极的压电陶瓷体，更优选以压电超声变换器的形式。
11.含磷材料在基于钛酸铋钠(BNT)的压电陶瓷材料中用于减少巨晶生长的用途，所述压电陶瓷材料具有以下基本组成
x(Bi0.5Na0.5)TiO3-yBaTiO3-zSrTiO3，其中x+y+z＝1并且0<x<1，0<y<1，0≤z≤0.07，或
x(Bi0.5Na0.5)TiO3-yBaTiO3-zCaTiO3，其中x+y+z＝1并且0<x<1，0<y<1，0<z≤0.05，或
x(Bi0.5Na0.5)TiO3-y(Bi0.5K0.5)TiO3-zBaTiO3，其中x+y+z＝1并且0<x<1，0<y<1，0≤z<1
其中使用一定量的含磷材料，使得压电陶瓷材料中的磷浓度为100至2000ppm，特别是250至2000ppm，更优选270至1800ppm。
12.根据权利要求11所述的用途，其中基本组成为
x(Bi0.5Na0.5)TiO3-yBaTiO3-zSrTiO3，其中y≥0.1并且x+y+z＝1，或
x(Bi0.5Na0.5)TiO3-yBaTiO3-zCaTiO3，其中y≥0.1并且x+y+z＝1，或
x(Bi0.5Na0.5)TiO3-y(Bi0.5K0.5)TiO3-zBaTiO3，其中y≥0.1并且x+y+z＝1。
13.根据权利要求11或12所述的用途，
其特征在于，含磷化合物为无机磷酸盐、磷酸氢盐或磷酸二氢盐。
14.根据权利要求11至13任一项所述的用途，
其特征在于，含磷化合物选自KH2PO4、(NH4)H2PO4。
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