CN107266072A - 一种低温烧结pzt95‑5压电陶瓷的制备方法 - Google Patents

一种低温烧结pzt95‑5压电陶瓷的制备方法 Download PDF

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CN107266072A
CN107266072A CN201710119134.9A CN201710119134A CN107266072A CN 107266072 A CN107266072 A CN 107266072A CN 201710119134 A CN201710119134 A CN 201710119134A CN 107266072 A CN107266072 A CN 107266072A
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pzt95
ferroelectric ceramic
ferroelectric
ceramic material
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曹剑武
邢文芳
周雅伟
李志鹏
王志强
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No 52 Institute of China North Industries Group Corp Yantai Branch
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Abstract

本发明涉及一种高抗电强度、高剩余极化强度、低损耗且烧结温度低的铁电陶瓷材料，以及其制备方法，与其制得的压电元件。本发明的铁电陶瓷材料的成分为Pb1‑xCdx(Zr0.965Ti0.035)O3(x＝0‑0.03)+1wt％Nb2O5+bwt％Li2CO3(PCZT95/5)。本发明通过添加氧化镉(CdO和Li2CO3)，调整合适的Zr/Ti比，在降低烧结温度(从1350℃降低到1050℃)的情况下，制备出具有高抗电强度、高剩余极化强度和低损耗的致密PCZT95/5铁电陶瓷材料，该铁电陶瓷材料适用于多层PZT95/5厚膜器件，将解决目前将单片PZT95/5粘接后机械强度和抗电击穿强度不高的难题，同时对于器件的可靠性和小型化都有很大的帮助，在爆炸铁电体电源的工业和国防领域等方面具有良好的应用前景。

Description

一种低温烧结PZT95-5压电陶瓷的制备方法
技术领域
本发明涉陶瓷材料低温技术，特别涉及低温烧结PZT95-5压电陶瓷，其制备方法，以及所制得的压电元件。
背景技术
锆钛摩尔比为95/5的锆钛酸铅压电陶瓷体系简称PZT95/5，因具有体积小，储能密度高的优点而一直是PZT系压电陶瓷研究的重点。尤其是在爆电电源及军事上要求高稳定性元器件方面具有重要的应用价值，例如可以用于中子产生器的电源上。由于含锆较高，PZT95 /5陶瓷一般要求高温(1300℃)烧结，高温下体系中的铅挥发严重，造成化学计量比不准确，最终制品性能恶化，也对环境造成了危害。
20世纪90年代以来，压电陶瓷元器件为了适应集成电路表面组装技术(SurfaceMount Technology)的发展需要，正在向小型化、整机一体化、高性能化、多功能化和集成化的方向发展。SMT中采用低温共烧陶瓷技术一方面可以提高组装密度、缩小体积、减轻体重，另一方面可以提高可靠性和性能，进而缩短组装周期。而叠层陶瓷是其中的研究热点之一。目前，实现叠层结构主要有两种方法，一种是先单片烧成，再粘结成叠层结构，但这种方法容易造成器件之间有空隙，容易被电压击穿，组装不便，同时降低了器件的整体性能。另一种是多层一次烧成，目前采用Pt、Pd等贵金属作为内电极，此方法的成本昂贵，但如果能用导电性良好，价格较低的Ag浆作为内电极将会大大降低成本。由于Ag的熔点比较低，为 961℃，过高的烧结温度会造成银离子向陶瓷内部扩散，使得陶瓷的绝缘电阻率降低，恶化压电材料的电学性能。同时另一方面，高烧结温度下的PZT95/5与内电极热膨胀系数差异会被放大，影响烧成后的效果。综上所述，低温烧结PZT95/5压电陶瓷的开发对于发展高可靠性、高电学性能、低成本叠层压电陶瓷具有重要意义。
发明内容
本发明的目的是为了解决现有PZT95/5铁电陶瓷烧结温度过高及低烧结温度下性能偏低等问题，而在此基础上提出的掺杂氧化镉(CdO)及碳酸锂(Li2CO3)结合混料和烧结工艺的改进优点制备烧结温度为1050℃的PZT95/5铁电陶瓷。同时本发明提供的PZT95/5铁电陶瓷材料的制备方法制备工艺简单、配方可调，可适用于规模生产。
本发明完整的技术方案包括：
一种低温烧结PZT95/5铁电陶瓷材料，其特征在于，所述的PZT95/5铁电陶瓷材料以掺杂铌改性的锆钛酸铅陶瓷为基体，并含有Cd和Li2CO3。
优选的，所述PZT95/5铁电陶瓷材料的组分包括：以通式(Pb1-xCdx)(Zr0.965Ti0.035)O3表示的第一组分，以及第二组分：a％wt的Nb2O5；和第三组分：b％wt的Li2CO3，其中，0.005≤x≤0.015， 0.8≤a≤1.2，0.05≤b≤0.15，其中，所述第二组分和第三组分的质量百分含量是相对于所述 PZT95/5铁电陶瓷材料整体而言。
所述的PZT95/5铁电陶瓷材料制备方法，其特征在于，包括如下工序：
(1)将所述PZT95/5铁电陶瓷材料所需元素的金属氧化物按照化学反应计量比配比磨至所需粒度并混合，得到混合料；
(2)将经工序(1)后的所述混合料于一定温度范围下保温一定时间，合成得到铌掺杂改性并含有Cd和Li2CO3的PZT95/5铁电陶瓷原料；
(3)将工序(2)所述铌掺杂改性并含有Cd和Li2CO3的PZT95/5铁电陶瓷原料制成粉体，压制成型获得素坯；
(4)将所述素坯在1050℃～1100℃温度下烧结获得所述PZT95/5铁电陶瓷材料。
优选的，所述工序(3)和工序(4)之间还包括将所述素坯排除有机物的工序。
优选的，在所述工序(2)中，合成温度范围为760℃～850℃，保温2～4h。
优选的，在所述工序(2)中，采用无水乙醇和氧化锆球作为球磨介质，将原料、氧化锆球和无水乙醇按照1∶1.2∶0.85的比例混合湿法球磨至所需粒度。
优选的，在所述工序(3)中，细磨采用去离子水和氧化锆球作为介质，将所述粉体、氧化锆球和去离子水按照质量比为1∶1.5∶1的比例混合湿法球磨至所需粒度。
优选的，在所述工序(4)中，使素坯在600℃～700℃温度范围内保温2～3小时以排除所述有机物。
优选的，所述金属氧化物分别为Pb3O4、ZrO2、TiO2、Nb2O5、CdO、Li2CO3。
所述的由PZT95/5铁电陶瓷材料制备的压电元件，所述压电元件的压电系数d33＞65pC/N，剩余极化强度Pr＞35μC/cm2。
本发明相对于现有技术的优点在于：通过选择适当的制备工艺，合适的Zr/Ti比，适量的氧化镉、碳酸锂掺杂量，以及适量的烧结助剂，在降低烧结温度的情况下，制备出具有高抗电强度、高剩余极化强度和低损耗的致密压电陶瓷材料及压电元件，该压电陶瓷材料在爆炸铁电体电源的工业和国防领域等方面具有良好的应用前景。
附图说明
图1是本发明实施例1的PZT95/5铁电陶瓷的显微形貌；
图2是本发明实施例2的PZT95/5铁电陶瓷的显微形貌；
图3是本发明实施例1的PZT95/5铁电陶瓷的电滞回线；
图4是本发明实施例2的PZT95/5铁电陶瓷的电滞回线；
图5是本发明实施例1和2的PZT95/5铁电陶瓷的XRD衍射图谱。
具体实施方式
下面结合附图和具体实施方式对本发明做进一步说明。
参照说明书附图，并结合下述实施方式进一步说明本发明，应理解本说明书及下述实施方式仅用于说明本发明，而非限制本发明。
本发明的PZT95/5铁电陶瓷的成分以掺杂铌改性的锆钛酸铅陶瓷为基体，并含有CdO、 Li2CO3，可以用以下通式表示：(Pb1-xCdx)(Zr0.965Ti0.035)O3+a％wtNb2O5+b％wtLi2CO3，其中， 0.005≤x≤0.015，0.8≤a≤1.2，0.05≤b≤0.15。
关于本发明的上述PZT95/5铁电陶瓷材料的制备，首先，将Pb3O4(工业纯)、ZrO2(工业纯)、TiO2(工业纯)、Nb2O5(化学纯)、CdO(分析纯)、Li2CO3(分析纯)按化学计量比称量，具体配比按照通式(Pb1-xCdx)(Zr0.965Ti0.035)O3+a％wtNb2O5+b％wtLi2CO3(0.005≤x≤0.015，0.8≤a≤1.2，0.05≤b≤0.15)来计算。以上原料采用市售产品或按照常规方法实验室制备的化合物。
可以通过湿法球磨是原料混合均匀并达到所需要的细度。在本发明中，球磨介质优选采用氧化锆球，但并不限定于此，也可使用其他如玛瑙球等介质。在实施例中，采用料、氧化锆球、无水乙醇为1∶2∶0.85的比例。在球磨机中球磨6～10小时。
球磨达到一定细度的原料经过烘干、压块，然后于高温下合成，优选地，合成温度范围为760℃～850℃保温2～4h。
将上述合成得到的铌掺杂改性的并含有CdO的PZT95/5铁电陶瓷块体研磨成粉体，湿法细磨15-40h后，出料烘干，添加5～10wt％PVA造粒成型，在100～200MPa的压强下将粉体压制成型获得素坯。优选的地，细磨采用去离子水和氧化锆球作为介质，将所述粉体、氧化锆球和去离子水按照质量比为1∶1.5∶1的比例混合湿法球磨至所需粒度。
在烧结之前通常还需要对压制成型的素坯在适当的温度下进行排塑。可以将成型好的样品放入箱式电阻炉等加热装置中进行排塑，排塑温度优选为600℃～700℃，时间优选为保温 1～2个小时。排胶升温速率不超过3℃/min。烧结温度优选为1050～1100℃，烧结时间优选为 2～5h。
为了测试本发明制得的PZT95/5铁电陶瓷材料的性能，将烧结好的样品根据规格要求进行机械加工；将加工好的样品进行超声清洗，烘干后上银电极，放入箱式电阻炉烧银；然后将有电极的样品放在硅油内，在一定的温度下，加高压电场，进行极化。经测试，本发明的方法制备的材料标准片的压电系数d33＞65pC/N，剩余极化强度Pr＞35μC/cm2。
本发明采用ZJ-3AN型准静态d33测量仪测试压电元件的压电系数。
下面更具体的说明本发明的PZT95/5铁电陶瓷的制备。应理解，以下步骤中的某个也可以省略或者使用能够达到同等效果的其他代替步骤，且每个步骤中的每个特征也不是必须或固定地而不可替换，而只是示例地说明。
本发明PZT95/5铁电陶瓷材料的制备方法可以包括：
(1)混合原料：以粉末状的Pb3O4、ZrO2、TiO2、Nb2O5、CdO和Li2CO3为原料，按化学计量比配比，采用无水乙醇，氧化锆球做介质，按照混合原料：氧化锆球：去离子水质量比为1∶2∶0.85的比例混合，湿法球磨6～10h；
(2)合成铌掺杂改性的并含有CdO、Li2CO3的PZT95/5铁电陶瓷粉体：将步骤(1)得到的原料倒入容器放进烘箱烘干后压块，并进行合成合成温度范围为760℃～850℃保温2～4h。并将合成好的块体研磨粉碎得到铌掺杂改性的并含有CdO、Li2CO3的 PZT95/5铁电陶瓷粉体；
(3)粉体的压制成型：将(2)所述粉体，采用去离子水，氧化锆球作介质，按照料∶氧化锆球∶去离子水质量比为1∶1.5∶1的比例湿法球磨15～40h后，出料烘干，添加 5～10wt％PVA造粒成型，在100～200MPa的压强下将分体压制成型；
(4)素坯排塑：在600～700℃温度范围内，保温1～2个小时，排除素坯中的有机物质，排塑速率不超过3℃/min。
(5)样品烧结：将排塑后的样品放入氧化铝坩埚里密闭烧结，最终在1050～1100℃温度范围内烧结，保温2～5h。
(6)将烧结好的样品根据规格要求进行机械加工；将加工好的样品进行超声清洗，烘干后上银电极，放入箱式电阻炉烧银；烧银条件是600～700℃，保温30min。然后将覆有电极的样品放入硅油高压极化，极化条件是：温度为120℃，电场为3～5kV/mm，时间为15～20min。
下面进一步列举实施例以详细说明本发明的示例制备工艺。应理解，下述实施例是为了更好地说明本发明，而非限制本发明。
实施例1
以Pb3O4、ZrO2、TiO2、Nb2O5、CdO和Li2CO3为原料，按 (Pb99.5Cd0.005)(Zr0.965Ti0.035)O3+1％wtNb2O5+0.1％wt Li2CO3的化学计量比配比，采用无水乙醇，氧化锆球做介质，按照混合原料∶氧化锆球∶去离子水＝1∶2∶0.85的比例混合，湿法球磨8h；将混好的原料倒入容器放进烘箱烘干后压块，并进行合成，合成温度范围为850℃保温2～4h。并将合成好的块体研磨粉碎得到铌掺杂改性的并含有CdO、Li2CO3的PZT95/5铁电陶瓷粉体；将所得粉体采用去离子水，氧化锆球作介质，按照料∶氧化锆球∶去离子水质量比为1∶1.5∶1 的比例湿法球磨24h后，出料烘干，添加6.75wt％PVA造粒成型，在150MPa的压强下将分体压制成型；将成型好的样品放入箱式电子炉进行排塑，排塑工艺为600℃保温1个小时；将排塑后的样品放入氧化铝坩埚里密闭烧结，烧成工艺为1050℃保温3.5h；将烧结好的样品根据规格要求进行机械加工；将加工好的样品进行超声清洗，烘干后上银电极，放入箱式电阻炉烧银；烧银条件是600～700℃，保温30min。然后将覆有电极的样品放入硅油高压极化，极化条件是：温度为120℃，电场为3～5kV/mm，时间为15～20min。材料标准片的主要性能是：d33＝70pC/N，Pr＝39μC/cm2。图1给出了本实施例所述材料的显微形貌，图3给出了本实施例所述材料的电滞回线，图5给出了本实施例所述材料的XRD衍射图谱。
实施例2
按照(Pb99Cd0.01)(Zr0.965Ti0.035)O3+1％wtNb2O5+0.15％wt Li2CO3配比，具体制备工艺如实施例1，所得标准片的主要性能是：d33＝67pC/N，Pr＝46μC/cm2。图2给出了本实施例所述材料的显微形貌，图4给出了本实施例所述材料的电滞回线，图5给出了本实施例所述材料的 XRD衍射图谱。
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制，凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效结构变化，均仍属于本发明技术方案的保护范围内。

Claims (10)

1.一种低温烧结PZT95/5铁电陶瓷材料，其特征在于，所述的PZT95/5铁电陶瓷材料以掺杂铌改性的锆钛酸铅陶瓷为基体，并含有Cd和Li2CO3。
2.如权利要求1所述的低温烧结PZT95/5铁电陶瓷材料，其特征在于，所述PZT95/5铁电陶瓷材料的组分包括：以通式(Pb1-xCdx)(Zr0.965Ti0.035)O3表示的第一组分，以及第二组分：a％wt的Nb2O5；和第三组分：b％wt的Li2CO3，其中，0.005≤x≤0.015，0.8≤a≤1.2，0.05≤b≤0.15，其中，所述第二组分和第三组分的质量百分含量是相对于所述PZT95/5铁电陶瓷材料整体而言。
3.如权利要求1或2所述的PZT95/5铁电陶瓷材料制备方法，其特征在于，包括如下工序：
(1)将所述PZT95/5铁电陶瓷材料所需元素的金属氧化物按照化学反应计量比配比磨至所需粒度并混合，得到混合料；
(2)将经工序(1)后的所述混合料于一定温度范围下保温一定时间，合成得到铌掺杂改性并含有Cd和Li2CO3的PZT95/5铁电陶瓷原料；
(3)将工序(2)所述铌掺杂改性并含有Cd和Li2CO3的PZT95/5铁电陶瓷原料制成粉体，压制成型获得素坯；
(4)将所述素坯在1050℃～1100℃温度下烧结获得所述PZT95/5铁电陶瓷材料。
4.权利要求3所述的PZT95/5铁电陶瓷材料制备方法，其特征在于，所述工序(3)和工序(4)之间还包括将所述素坯排除有机物的工序。
5.权利要求3或4所述的PZT95/5铁电陶瓷材料制备方法，其特征在于，在所述工序(2)中，合成温度范围为760℃～850℃，保温2～4h。
6.权利要求3或4所述的PZT95/5铁电陶瓷材料制备方法，其特征在于，在所述工序(2)中，采用无水乙醇和氧化锆球作为球磨介质，将原料、氧化锆球和无水乙醇按照1∶1.2∶0.85的比例混合湿法球磨至所需粒度。
7.权利要求3或4所述的PZT95/5铁电陶瓷材料制备方法，其特征在于，在所述工序(3)中，细磨采用去离子水和氧化锆球作为介质，将所述粉体、氧化锆球和去离子水按照质量比为1∶1.5∶1的比例混合湿法球磨至所需粒度。
8.权利要求3或4所述的PZT95/5铁电陶瓷材料制备方法，其特征在于，在所述工序(4)中，使素坯在600℃～700℃温度范围内保温2～3小时以排除所述有机物。
9.权利要求3或4所述的PZT95/5铁电陶瓷材料制备方法，其特征在于，所述金属氧化物分别为Pb3O4、ZrO2、TiO2、Nb2O5、CdO、Li2CO3。
10.一种由权利要求1或2任一项所述的由PZT95/5铁电陶瓷材料制备的压电元件，或由权利3至9中任意一项所述的制备方法获得的PZT95/5铁电陶瓷材料所制备的压电元件，其特征在于，所述压电元件的压电系数d33＞65pC/N，剩余极化强度Pr＞35μC/cm2。
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