CN108558391B - 一种具有巨压电响应的无铅压电陶瓷及其制备方法 - Google Patents

一种具有巨压电响应的无铅压电陶瓷及其制备方法 Download PDF

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CN108558391B
CN108558391B CN201810668020.4A CN201810668020A CN108558391B CN 108558391 B CN108558391 B CN 108558391B CN 201810668020 A CN201810668020 A CN 201810668020A CN 108558391 B CN108558391 B CN 108558391B
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周昌荣
曾卫东
许积文
黎清宁
杨玲
袁昌来
陈国华
饶光辉
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Guilin University of Electronic Technology
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Abstract

本发明公开了一种具有巨压电响应的无铅压电陶瓷材料及其制备方法，材料组成为：Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3+0.05wt%Co+0.05wt%Cu。其中Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3通过固相合成法，Co与Cu分别以沉淀的形式在表面二次包覆形成，通过烧结技术产生特殊的分级次梯度结构，产生巨压电效应，这些性能目前超过了所有报道的无铅压电陶瓷。产品经实验测量，具有非常优异的压电性能，准静态压电常数d 33=1820pC/N，压电应变常数
Figure DEST_PATH_IMAGE001
=2032pm/V，性能稳定，成本低廉，适合大规模工业生产。

Description

一种具有巨压电响应的无铅压电陶瓷及其制备方法
技术领域
本发明涉及无铅压电陶瓷材料，具体是一种具有巨压电响应的无铅压电陶瓷材料及其制备方法。
背景技术
压电材料是一种智能材料，能够实现机械信号与电信号的转换，以及产生电驱动的声波发射和功率输出，广泛应用于制备换能器、微位移器、传感器、谐振器及滤波器等一系列电子元件，是一种不可或缺的高技术新材料之一。传统压电陶瓷主要是以含铅的锆钛酸铅(PZT)系材料为主，其主要成分是氧化铅( 60~ 70% 以上) 。氧化铅是一种易挥发的有毒物质，在生产、使用及废弃后的处理过程中，都会给人类和生态环境造成损害。PbO 的挥发也会造成陶瓷中的化学计量比的偏离，使产品的一致性和重复性降低，需要密封烧结，使成本提高。随着环境保护意识的增强，寻找可替代传统铅基陶瓷材料的高性能无铅压电陶瓷成为紧迫的市场需求。
目前开发的无铅压电陶瓷中钛酸钡(BT)基及铌酸钠钾基陶瓷[(K，Na)NbO3，KNN]，由于其较高的压电系数，显现出它巨大的应用潜力。通过调节陶瓷组分来构筑相界，被广泛应用来提高陶瓷的压电系数，但无铅压电陶瓷压电系数止步于600 ~ 700 pC/N，很难再进一步提高。因而，通过原料组成和工艺结合，从而提高压电陶瓷的性能显得非常有必要，这也为无铅压电陶瓷的应用开辟了一条新路。
发明内容
本发明的目的是提供一种ABO3型钙钛矿结构，具有巨压电响应的钛酸钡(BT)基无铅压电陶瓷材料及其制备方法，该陶瓷材料具有环境友好、稳定性好、压电常数可达d 33=1820pC/N，压电应变常数为
Figure 129788DEST_PATH_IMAGE002
=2032pm/V。
本发明一种具有巨压电响应的钛酸钡(BT)基无铅压电陶瓷材料，其组成为：
Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3+0.05wt%Co+0.05wt%Cu；
其中Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3通过固相合成法，Co与Cu分别以沉淀的形式在表面二次包覆形成，通过烧结技术产生特殊的分级次梯度结构，产生巨压电效应，这些性能目前超过了所有报道的无铅压电陶瓷。
上述具有巨压电响应的无铅压电陶瓷材料的制备方法，采用固相合成法，结合包覆和微波烧结形成特殊的梯度结构，具体包括如下步骤：
（1）配料、混合均匀；
按照Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3的化学计量分别称取分析纯原料CaCO3、BaCO3、SrCO3、Cr2O3、SnO2和TiO2，装入球磨罐中，以氧化锆为磨球、无水乙醇为球磨介质，充分混合球磨24小时，分离磨球，将原料在60℃烘干；
（2）预烧
将烘干后的粉料压制成大块坯体，放入高铝坩埚加盖，于1200℃保温2小时合成固溶体；
（3）Co包覆粉体
将预合成的Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3在玛瑙研钵中研磨1小时，放入烧杯中，按照Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3+0.05wt%Co化学计量加入Co(NO3)2溶液，一边搅拌，一边超声分散，混合均匀后，滴入2wt%氨水，在颗粒表面形成Co的沉淀，抽滤洗净；
（4）Cu二次包覆
抽滤洗净后的粉体干燥后，再在高铝坩埚中于1050℃保温2小时预合Co分级梯度结构，然后将合成的Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3+0.05wt%Co在玛瑙研钵中研磨1小时，放入烧杯中，按照Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3+0.05wt%Co+0.05wt%Cu化学计量加入Cu(NO3)2溶液，一边搅拌，一边超声分散，混合均匀后，滴入2wt%氨水，在颗粒表面形成Cu的沉淀，抽滤洗净；
（5）成型
将步骤（4）抽滤洗净的粉体在100℃干燥后，在100Mpa冷等静压成型；
（6）微波烧结
将步骤（5）成型的原料采用微波快速烧结，在1300℃保温15分钟，烧结成瓷；烧结后的样品加工成两面光滑、厚度约0.5mm的薄片，两面镀银电极制备成具有巨压电响应的无铅压电陶瓷材料。
目前，无铅压电陶瓷压电系数为600 ~ 700 pC/N，本发明制备的无铅压电陶瓷材料，经实验测量，准静态压电常数d 33=1820pC/N，压电应变常数
Figure 984611DEST_PATH_IMAGE002
=2032pm/V，具有巨压电响应和非常优异的压电性能，性能稳定，成本低廉，绿色环保，制备方法简单，适合大规模工业生产。
附图说明
图1为本发明无铅压电陶瓷的压电应变常数曲线图。
具体实施方式
下面结合实施例和附图对本发明内容作进一步的说明，但不是对本发明的限定。
实施例
一种具有巨压电响应的无铅压电陶瓷材料，组成为：
Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12 Cr0.01O3+0.05wt%Co+0.05wt%Cu。
上述陶瓷材料的制备方法，具体步骤如下：
（1）配料、混合均匀；
按照Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3的化学计量分别称取分析纯原料CaCO3、BaCO3、SrCO3、Cr2O3、SnO2和TiO2，装入球磨罐中，以氧化锆为磨球、无水乙醇为球磨介质，充分混合球磨24小时，分离磨球，将原料在60℃烘干；
（2）预烧
将烘干后的粉料压制成大块坯体，放入高铝坩埚加盖，于1200℃保温2小时合成固溶体；
（3）Co包覆粉体
将步骤（2）预合成的Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3在玛瑙研钵中研磨1小时，放入烧杯中，按照Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3+0.05wt%Co化学计量加入Co(NO3)¬2溶液，一边搅拌，一边超声分散，混合均匀后，滴入2wt%氨水，在颗粒表面形成Co的沉淀，抽滤洗净；
（4）Cu二次包覆
抽滤洗净的粉体干燥后再在高铝坩埚中于1050℃保温2小时预合Co分级梯度结构，然后将合成的Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3+0.05wt%Co粉体在玛瑙研钵中研磨1小时，放入烧杯中，按照Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3+0.05wt%Co+0.05wt% Cu化学计量加入Cu(NO3)2溶液，一边搅拌，一边超声分散，混合均匀后，滴入2wt%氨水，在颗粒表面形成Cu的沉淀，抽滤洗净；
（5）成型
将步骤（4）抽滤洗净的粉体在100℃干燥后，在100Mpa冷等静压成型；
（6）微波烧结
将步骤（5）成型的原料采用微波快速烧结，在1300℃保温15分钟烧结成瓷；烧结后的样品加工成两面光滑、厚度约0.5mm的薄片，两面镀银电极制备成具有巨压电响应的无铅压电陶瓷材料。
将实施例制备的陶瓷材料，在硅油中极化，极化电场5000V/mm，温度35℃，时间10分钟。所得样品放置24小时后按IRE标准对制成的压电陶瓷进行压电性能测量；性能测量结果如下：
Figure DEST_PATH_IMAGE004
压电应变常数曲线如图1所示。

Claims (2)

1.一种具有巨压电响应的无铅压电陶瓷材料，其特征在于：该陶瓷材料组成为：Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3+0.05wt%Co+0.05wt%Cu；
其中Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3通过固相合成法，Co与Cu分别以沉淀的形式在表面二次包覆形成，通过烧结技术产生特殊的分级次梯度结构，产生巨压电效应。
2.根据权利要求1所述的无铅压电陶瓷材料的制备方法，其特征在于，包括如下步骤：
（ 1 ） 配料、混合均匀；
按照Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3的化学计量分别称取分析纯原料CaCO3、BaCO3、SrCO3、Cr2O3、SnO2和TiO2，装入球磨罐中，以氧化锆为磨球、无水乙醇为球磨介质，充分混合球磨24小时，分离磨球，将原料在60℃烘干；
（ 2 ） 预烧
将烘干后的粉料压制成大块坯体，放入高铝坩埚中加盖，于1200℃保温2小时合成固溶体；
（3）Co包覆粉体
将步骤（2）预合成的Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3在玛瑙研钵中研磨1小时，放入烧杯中，按照Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3+0.05wt%Co化学计量加入Co(NO3)2溶液，一边搅拌，一边超声分散，混合均匀后，滴入2wt%氨水，在颗粒表面形成Co的沉淀，抽滤洗净；
（4）Cu二次包覆
抽滤洗净的粉体干燥后，再在高铝坩埚中于1050℃保温2小时预合Co分级梯度结构，然后将合成的Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3+0.05wt%Co粉体在玛瑙研钵中研磨1小时，放入烧杯中，按照Ba0.975Sr0.005Ca0.02Ti0.87Sn0.12Cr0.01O3+0.05wt%Co+0.05wt% Cu化学计量加入Cu(NO3)2溶液，一边搅拌，一边超声分散，混合均匀后，滴入2wt%氨水，在颗粒表面形成Cu的沉淀，抽滤洗净；
（5）成型
将步骤（4）抽滤洗净的粉体在100℃干燥后，在100Mpa冷等静压成型；
（6）微波烧结
将步骤（5）成型的原料采用微波快速烧结，在1300℃保温15分钟，烧结成瓷；烧结后的样品加工成两面光滑的薄片，两面镀银电极制备成具有巨压电响应的无铅压电陶瓷材料。
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