CN113896526B - 一种压电性高、高温绝缘性好的压电材料及其制备方法 - Google Patents
一种压电性高、高温绝缘性好的压电材料及其制备方法 Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 54
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Abstract
本发明公开了一种压电性高、高温绝缘性好的压电材料及其制备方法，该压电材料，该压电材料通过在CaBi4Ti4O15(CBT)压电陶瓷的A、B位采用(Na0.5Bi0.5)2+、(Nb2/3Cu1/3)4+复合离子同时掺杂制得，获得的铋层状结构压电陶瓷材料具有较高的压电性(15～18pC/N)、居里温度(786～798℃)及良好的高温绝缘电阻(500℃下的电阻值为2.1～2.6MΩ)，是制作高温加速度传感器较为理想的压电元件材料。本发明提供的铋层状结构压电材料采用传统的固相反应法即可制备，制备工艺简单稳定，操作方便，适于大规模工业生产的推广，具有实际的应用价值和广泛的应用前景。
Description
技术领域
本发明属于压电陶瓷生产技术领域，具体涉及一种压电性高、高温绝缘性好的压电材料及其制备方法。
背景技术
压电效应是指机械能与电能之间相互转换的现象，即施加机械应力能引起电极化或施加电场能引起应变，这类具有压电效应的材料被称为压电材料。近年来压电传感器的应用环境逐渐向高温环境延伸，比如航空发动机、燃气轮机、地热能开发、地质勘探、核能反应堆等对高温压电传感器的需求量不断增加，则随之而来的就是对性能优异的高温压电材料的迫切需求。
在各类压电材料中，铋层状结构铁电压电材料(BLSFs，通式为(Bi2O2)2+(Am- 1BmO3m+1)2-，m为1～5的整数或小数)普遍具有较高的居里温度，某些材料体系甚至可以超过900℃，所以其最大可使用温度高于600℃，其还显示出良好的抗疲劳性、低老化率、高电阻率等优点。
但是BLSFs材料具有极化较困难，压电活性较差的缺点；同时其电阻率会随温度的升高急速下降，这极大的限制了BLSFs在高温压电传感器的实际应用。因此如何得到具有高压电性和良好的高温绝缘性的铋层状结构压电陶瓷材料成为本领域研究的热点。
发明内容
本发明的目的在于克服现有技术中存在的铋层状结构压电陶瓷材料难以同时具有高压电性和良好的高温绝缘性的技术问题，提供一种具有高压电性和良好的高温绝缘性的铋层状结构压电陶瓷材料及其制备方法。
本发明选取钛酸铋钙压电陶瓷材料作为改进基础，钛酸铋钙(CaBi4Ti4O15，简称CBT)是一种典型的铋层状结构铁电压电材料，其中铋层为(Bi2O2)2+，在(CaBi2Ti4O13)2-的类钙钛矿结构中A位由两种离子(CaBi2)占据，B位是Ti4。
CaBi4Ti4O15居里温度高达790℃，但由于其压电活性较低(压电常数仅为7pC/N左右)，严重限制了其在高温压电方面的应用。本发明通过在CaBi4Ti4O15(CBT)压电陶瓷的A、B位分别引入(Na0.5Bi0.5)2+、(Nb2/3Cu1/3)4+复合离子，极大的提高了其压电性和高温绝缘性，同时保证了其较高的居里温度。该材料在高温压电传感器领域具有实际的应用价值。
为了实现本发明的上述目的，本发明采用以下技术方案，
一种压电性高、高温绝缘性好的压电材料，该压电材料通过在CaBi4Ti4O15压电陶瓷材料的A、B位分别引入(Na0.5Bi0.5)2+、(Nb2/3Cu1/3)4+复合离子得到。
进一步地，所述压电材料的化学通式为:
Ca1-x(Na0.5Bi0.5)x Bi4Ti4-y(Nb2/3Cu1/3)yO15
式中x＝0.05，0＜y≤0.1，x、y均代表摩尔比例。
本发明还提供了上述压电性高、高温绝缘性好的压电材料的制备方法，其包括以下步骤：
S1、球磨：按化学组成为Ca1-x(Na0.5Bi0.5)x Bi4Ti4-y(Nb2/3Cu1/3)yO15的化学计量比称取原料，式中x＝0.05，0＜y≤0.1，x、y均代表摩尔比例，将称量好的原料倒入球磨罐中，以锆球为介质，无水乙醇为溶剂球磨12h；
S2、二次球磨：将球磨后的混合料在120℃下烘干，烘干后的粉料在坩埚中压实并盖上坩埚盖，预烧结获得所需压电陶瓷粉体，然后进行二次球磨，仍以锆球为介质，无水乙醇为溶剂，球磨时间为24h；
S3：成型：将二次球磨后的浆料在120℃下烘干，烘干后的粉体放入玛瑙钵中充分研磨后，加入粘合剂进行研磨造粒、过筛后压制成型，成型压力为1.5-2MPa，进行排胶处理后得到陶瓷胚体；
S4：烧结：将排胶后的陶瓷胚体置于密闭坩埚中烧结，得到陶瓷片；
S5、极化：将烧结完成的陶瓷片两面抛光并印刷上电极，电极材料为金或铂，升温后施加电压进行极化。
进一步地，步骤S1中，所述原料为：CaCO3、Bi2O3、TiO2、Nb2O5、CuO、Na2CO3。
进一步地，步骤S2中，所述预烧结的温度为750～900℃，升温速率为3～5℃/min，保温时间为2～4h。
进一步地，步骤S3中，所述研磨造粒时，粘合剂的用量为混合粉料总质量的5～8％；所述粘合剂优选为重量百分比为8％的聚乙烯醇水溶液。
进一步地，步骤S3中，排胶处理的升温速率为1℃/min，升温至650℃，保温时间优选2小时。
进一步地，步骤S4中，所述烧结温度为1050～1150℃，烧结的时间为2～4h。
进一步地，步骤S5中，电极材料为铂，在两面抛光的陶瓷片上被铂并且烧铂作为电极；烧铂温度为950℃，烧铂时间为10～20min。
进一步地，步骤S5中，极化的温度为160～180℃，极化的电场强度为10～12kv/mm，极化的时间为20～30分钟。
本技术方案与背景技术相比，至少具有如下优点：
本发明通过在CaBi4Ti4O15(CBT)压电陶瓷的A、B位采用(Na0.5Bi0.5)2+、(Nb2/3Cu1/3)4+复合离子同时掺杂，获得的铋层状结构压电陶瓷材料具有较高的压电性(15～18pC/N)、居里温度(786～798℃)及良好的高温绝缘电阻(500℃下的电阻值为2.1～2.6MΩ)，综合以上各性能，本发明提供的铋层状结构压电材料是制作高温加速度传感器较为理想的压电元件材料。
本发明提供的铋层状结构压电陶瓷材料采用传统的固相反应法即可制备，制备工艺简单稳定，操作方便，适于大规模工业生产的推广，具有实际的应用价值和广泛的应用前景。
附图说明
图1为本发明实施例1～实施例3提供的压电材料的压电性能退火实验图。
具体实施方式
现有技术中存在铋层状结构压电陶瓷材料难以同时具有高压电性和良好的高温绝缘性的技术问题。
为此，本发明提供一种压电性高、高温绝缘性好的压电材料及其制备方法，以解决上述技术问题。
为了使本发明的目的、特征和优点更加的清晰，以下结合更具体的实施例，对本发明的具体实施方式做出更为详细的说明，在下面的描述中，阐述了很多具体的细节以便于充分的理解本发明，但是本发明能够以很多不同于描述的其他方式来实施。因此，本发明不受以下公开的具体实施的限制。
实施例1
制备符合化学通式为：Ca1-x(Na0.5Bi0.5)x Bi4Ti4-y(Nb2/3Cu1/3)yO15，x＝0.05，y＝0.01的改性压电陶瓷。
各原料：CaCO3(纯度99.99％)、Bi2O3(纯度99.99％)、TiO2(纯度99.9％)、Nb2O5(纯度99.99％)、CuO(纯度99％)、Na2CO3(纯度99.8％)，按照以上计量比配料，所有原料放入球磨罐中混合球磨12h；球磨后的混合料在120℃下烘干，烘干后的粉料在坩埚中压实并盖上坩埚盖，置于高温烧结炉中在825℃下预烧结4h；将预烧结后的粉料二次球磨24h；取料烘干(120℃)后，加入浓度为8％的聚乙烯醇粘合剂，粘结剂用量为二次球磨后粉料总质量的5～8％，研磨均匀后过60目筛并压制成直径14mm的薄圆坯，成型压力为1.5-2MPa，在650℃下进行排胶处理；然后将陶瓷圆坯置于密闭坩埚中于1050℃下烧结3小时；烧结好的陶瓷样品两面抛光，被铂电极再烧铂，烧铂温度为950℃，烧铂时间为10分钟；在160℃硅油中施加12kV/mm的直流电场保持30分钟，参照图1所示，得到的陶瓷Ca0.95(Na0.5Bi0.5)0.05Bi4Ti3.99(Nb2/ 3Cu1/3)0.01O15的压电性能如下：d33＝15pC/N。介温图谱显示其居里温度TC＝786℃；测试刷铂电极的陶瓷在500℃下的电阻为2.4MΩ。
实施例2
制备符合化学组成Ca1-x(Na0.5Bi0.5)x Bi4Ti4-y(Nb2/3Cu1/3)yO15，x＝0.05，y＝0.03的改性压电陶瓷。
各原料：CaCO3(纯度99.99％)、Bi2O3(纯度99.99％)、TiO2(纯度99.9％)、Nb2O5(纯度99.99％)、CuO(纯度99％)、Na2CO3(纯度99.8％)按照以上计量比配料，放入球磨罐中混合球磨12h；球磨后的混合料在120℃下烘干，烘干后的粉料在坩埚中压实并盖上坩埚盖，置于高温烧结炉中在825℃下预烧结4h；将预烧结后的粉料二次球磨24h；取料烘干(120℃)后，加入浓度为8％的聚乙烯醇粘合剂，粘结剂用量为二次球磨后粉料总质量的5～8％，研磨均匀后过60目筛并压制成直径14mm的薄圆坯，成型压力为1.5-2MPa，在650℃下进行排胶处理；然后将陶瓷圆坯于1050℃下烧结3h；烧结好的陶瓷样品两面抛光，被铂电极再烧铂，烧铂温度为950℃，烧铂时间为10分钟。在160℃硅油中施加12kV/mm的直流电场保持30分钟，参照图1所示，得到的陶瓷Ca0.95(Na0.5Bi0.5)0.05Bi4Ti3.97(Nb2/3Cu1/3)0.03O15的压电性能如下：d33＝18pC/N。介温图谱显示其居里温度TC＝798℃；测试刷铂电极的陶瓷在500℃下的电阻为2.6MΩ。
实施例3
制备符合化学组成Ca1-x(Na0.5Bi0.5)x Bi4Ti4-y(Nb2/3Cu1/3)yO15，x＝0.05，y＝0.05的改性压电陶瓷。
各原料：CaCO3(纯度99.99％)、Bi2O3(纯度99.99％)、TiO2(纯度99.9％)、Nb2O5(纯度99.99％)、CuO(纯度99％)、Na2CO3(纯度99.8％)按照以上计量比配料，放入球磨罐中混合球磨12h；球磨后的混合料在120℃下烘干，烘干后的粉料在坩埚中压实并盖上坩埚盖，置于高温烧结炉中在825℃下预烧结4h；将预烧结后的粉料二次球磨24h；取料烘干(120℃)后，加入浓度为8％的聚乙烯醇粘合剂，粘结剂用量为二次球磨后粉料总质量的5～8％，研磨均匀后过60目筛并压制成直径14mm的薄圆坯，成型压力为1.5～2MPa，在650℃下进行排胶处理；然后将陶瓷圆坯于1050℃下烧结3小时；烧结好的陶瓷样品两面抛光，被铂电极再烧铂，烧铂温度为950℃，烧铂时间为10分钟。在160℃硅油中施加12kV/mm的直流电场保持30分钟，参照图1所示，得到的陶瓷Ca0.95(Na0.5Bi0.5)0.05Bi4Ti3.95(Nb2/3Cu1/3)0.05O15的压电性能如下：d33＝16pC/N。介温图谱显示其居里温度TC＝790℃；测试刷铂电极的陶瓷在500℃下的电阻为2.1MΩ。
下表1给出了本发明各实施例提供的CBT压电陶瓷在高温下的绝缘电阻。
表1各实施例陶瓷样品在不同温度下的高温绝缘电阻值
本发明各实施例提供的铋层状结构压电陶瓷材料具有较高的压电性(15～18pC/N)、居里温度(786～798℃)及良好的高温绝缘电阻(500℃下的电阻值为2.1～2.6MΩ)。同时根据本发明各实施例提供的CBT铋层状压电陶瓷材料的压电常数退火实验结果来看，如图1所示，在温度范围为室温～700℃时，该铋层状结构压电陶瓷的压电常数d33稳定性极好；但是温度＞700℃时，其d33值衰减比较快。说明该压电陶瓷在700℃范围内性能稳定，可用为高温压电传感器理想的压电陶瓷材料，适合于高温条件下使用。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (9)
1.一种压电性高、高温绝缘性好的压电材料，其特征在于：所述压电材料通过在CaBi4Ti4O15压电陶瓷材料的A、B位分别引入(Na0.5Bi0.5)2+、(Nb2/3Cu1/3)4+复合离子得到，所述压电材料的化学通式为:
Ca1-x(Na0.5Bi0.5)xBi4Ti4-y(Nb2/3Cu1/3)yO15
式中x＝0.05，0＜y≤0.1，x、y均代表摩尔比例。
2.一种权利要求1所述的压电性高、高温绝缘性好的压电材料的制备方法，其特征在于：包括以下步骤：
S1、球磨：按化学组成为Ca1-x(Na0.5Bi0.5)xBi4Ti4-y(Nb2/3Cu1/3)yO15，式中x＝0.05，0＜y≤0.1，x、y均代表摩尔比例；准备原料，放入球磨罐中球磨；
S2、二次球磨：将球磨后的混合料下烘干后预烧结获得所需压电陶瓷粉体，然后进行二次球磨；
S3：成型：将二次球磨后的浆料烘干，烘干后的粉体充分研磨后，加入粘合剂进行研磨造粒、过筛后压制成型，成型压力为1.5～2MPa，进行排胶处理后得到陶瓷胚体；
S4：烧结：将排胶后的陶瓷胚体置于密闭坩埚中烧结，得到陶瓷片；
S5、极化：将烧结完成的陶瓷片两面抛光并印刷上电极，电极材料为金或铂，升温后施加电压进行极化。
3.根据权利要求2所述的制备方法，其特征在于：步骤S1中，所述原料为：CaCO3、Bi2O3、TiO2、Nb2O5、CuO、Na2CO3。
4.根据权利要求2所述的制备方法，其特征在于：步骤S2中，所述预烧结的温度为750～900℃，升温速率为3～5℃/min，保温时间为2～4h。
5.根据权利要求2所述的制备方法，其特征在于：步骤S3中，所述研磨造粒时，粘合剂的用量为混合粉料总质量的5～8％；所述粘合剂为聚乙烯醇水溶液。
6.根据权利要求2所述的制备方法，其特征在于：步骤S3中，排胶处理的升温速率为1℃/min，升温至650℃，保温时间为2小时。
7.根据权利要求2所述的制备方法，其特征在于：步骤S4中，所述烧结温度为1050～1150℃，烧结的时间为2～4h。
8.根据权利要求2所述的制备方法，其特征在于：步骤S5中，电极材料为铂，在两面抛光的陶瓷片上被铂并且烧铂作为电极；烧铂温度为950℃，烧铂时间为10～20min。
9.根据权利要求2所述的制备方法，其特征在于：步骤S5中，极化的温度为160～180℃，极化的电场强度为10～12kV /mm，极化的时间为20～30分钟。
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