CN113248247A - 一种三元压电陶瓷及其制备方法和应用 - Google Patents

一种三元压电陶瓷及其制备方法和应用 Download PDF

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CN113248247A
CN113248247A CN202110698411.2A CN202110698411A CN113248247A CN 113248247 A CN113248247 A CN 113248247A CN 202110698411 A CN202110698411 A CN 202110698411A CN 113248247 A CN113248247 A CN 113248247A
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piezoelectric ceramic
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陈建国
沈昕
程晋荣
仝宾宾
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University of Shanghai for Science and Technology
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Abstract

本发明涉及压电陶瓷技术领域，尤其涉及一种三元压电陶瓷及其制备方法和应用。本发明提供的三元压电陶瓷的化学组成为：(1‑x‑y)BiFeO3‑xPbTiO3‑yBa(HfmTi1‑m)O3‑zMnO2。本发明通过引入Hf离子，可以大幅度提高三元压电陶瓷的压电性能，离子半径较大的Hf离子
Figure DDA0003129454790000011
取代了离子半径较小的钛离子

Description

一种三元压电陶瓷及其制备方法和应用
技术领域
本发明涉及压电陶瓷技术领域，尤其涉及一种三元压电陶瓷及其制备方法和应用。
背景技术
压电陶瓷广泛应用于汽车电子、航空航天和武器装备等领域。例如在高速发动机、内燃机以及相关重要部位的自检测，但上述工作环境的温度高达200～300℃。
其中，锆钛酸铅压电陶瓷以其优异的电性能和低廉的成本在工业上有着广泛的应用，其居里温度Tc和压电系数d33分别为386℃和370pC/N。同时，所述锆钛酸铅在200℃以上存在严重的退极化和热老化问题，不适合在极端高温环境下使用。因此，有必要寻找一种具有良好压电性能和温度稳定性的替代材料。
Bi(Me)O3-PbTiO3是一类高居里温度的材料。其中BiScO3-PbTiO3固溶体的居里温度虽然可达到632℃，具有优异的温度稳定性能。但是其具有较大的四方畸变度，矫顽场较大且高达100kV/cm，从而导致其难以被充分极化；同时，钪的价格昂贵，不适合大规模商业应用。
发明内容
本发明的目的在于提供一种三元压电陶瓷及其制备方法和应用。所述三元压电陶瓷具有优异的温度稳定性、更好的压电性能和较小的四方畸变。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种三元压电陶瓷，所述三元压电陶瓷的化学组成为：(1-x-y)BiFeO3-xPbTiO3-yBa(HfmTi1-m)O3-zMnO2；
其中，x，y，m和z为摩尔比，所述x，y，m和z的取值范围分别为：0<x≤0.3，0<y≤0.3，0<m≤1，0<z≤0.06。
优选的，所述m的取值范围为：0.08≤m≤0.12。
优选的，所述三元压电陶瓷的居里温度Tc为400～600℃，压电系数d33为150～400pC/N。
本发明还提供了上述技术方案所述的三元压电陶瓷的制备方法，包括以下步骤：
按照所述三元压电陶瓷的元素配比，将Bi2O3、Fe2O3、PbO、TiO2、BaCO3、MnO2和HfO2混合，依次进行球磨和煅烧，得到三元压电陶瓷粉体；
将所述三元压电陶瓷粉体和粘结剂混合后，依次进行造粒、压片和排胶，得到三元压电陶瓷素坯；
将所述三元压电陶瓷素坯进行烧结，得到所述三元压电陶瓷。
优选的，所述球磨的转速为200～300r/min，时间为4～10h；
所述煅烧的温度为700～850℃，时间为2～10h。
优选的，所述粘结剂为质量浓度为3％～8％的聚乙烯醇水溶液；
所述粘结剂与所述三元压电陶瓷粉体的质量比为1:20。
优选的，所述排胶的温度为600℃，时间为4h；
所述烧结的温度为900～1060℃，时间为1～4h。
本发明还提供了上述技术方案所述的三元压电陶瓷或上述技术方案所述的制备方法制备得到的三元压电陶瓷在汽车电子、航空航天、核电站和武器装备领域中的应用。
优选的，进行应用前，先将所述三元压电陶瓷依次进行镀银和极化处理。
优选的，所述极化的温度为100～140℃，电场为60～90kv/cm，时间为15～30min。
本发明提供了一种三元压电陶瓷，所述三元压电陶瓷的化学组成为：(1-x-y)BiFeO3-xPbTiO3-yBa(HfmTi1-m)O3-zMnO2；其中，x，y，m和z为摩尔比，所述x，y，m和z的取值范围分别为：0<x≤0.3，0<y≤0.3，0<m≤1，0<z≤0.06。本发明在所述三元压电陶瓷的材料中引入Hf离子，可以大幅度提高三元压电陶瓷的压电性能，主要在于(1-x-y)BiFeO3-xPbTiO3-yBaTiO3为纯钙钛矿结构(ABO3)，钛离子处于钙钛矿结构的B位，离子半径较大的Hf离子
Figure BDA0003129454780000021
取代了离子半径较小的钛离子
Figure BDA0003129454780000022
使得四方畸变度减小。氧化锰掺杂相较于现有技术的碳酸锰掺杂具有更高的体密度和电阻率，从而使的氧化锰掺杂的样品具有更高的压电性能。
具体实施方式
本发明提供了一种三元压电陶瓷，所述三元压电陶瓷的化学组成为：(1-x-y)BiFeO3-xPbTiO3-yBa(HfmTi1-m)O3-zMnO2；
其中，x，y，m和z为摩尔比，所述x，y，m和z的取值范围分别为：0<x≤0.3，0<y≤0.3，0<m≤1，0<z≤0.06。
在本发明中，所述m的取值范围优选为：0<m≤1。
在本发明中，所述三元压电陶瓷的居里温度Tc优选为400～600℃，压电系数d33优选为150～400pC/N。
本发明还提供了上述技术方案所述的三元压电陶瓷的制备方法，包括以下步骤：
按照所述三元压电陶瓷的元素配比，将Bi2O3、Fe2O3、PbO、TiO2、BaCO3、MnO2和HfO2混合，依次进行球磨和煅烧，得到三元压电陶瓷粉体；
将所述三元压电陶瓷粉体和粘结剂混合后，依次进行造粒、压片和排胶，得到三元压电陶瓷素坯；
将所述三元压电陶瓷素坯进行烧结，得到所述三元压电陶瓷。
在本发明中，若无特殊说明，所有制备原料均为本领域技术人员熟知的市售产品。
本发明按照所述三元压电陶瓷的元素配比，将Bi2O3，Fe2O3，PbO，TiO2，BaCO3，MnO2和HfO2混合，依次进行球磨和煅烧，得到三元压电陶瓷粉体。
在本发明中，所述球磨的转速优选为200～300r/min，更优选为220～280r/min，最优选为240～260r/min；时间优选为4～10h，更优选为5～8h。在本发明中，所述球磨优选为湿法球磨；所述湿法球磨的球磨介质优选为无水乙醇。
所述球磨完成后，本发明还优选包括将球磨后的物质进行干燥；本发明对所述干燥的过程没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。
在本发明中，所述煅烧的温度优选为700～850℃，更优选为740～800℃；时间优选为2～10h，更优选为3～7h。在本发明中，升温至所述煅烧的温度的升温速率优选为5℃/min。在本发明中，所述煅烧优选在氧化铝坩埚中进行。
所述煅烧完成后，本发明还优选包括冷却的过程，所述冷却的方式优选为随炉冷却，所述冷却后的温度优选为室温。
在本发明中，所述球磨和煅烧重复循环的次数优选≥1；作用是使得固相反应更为充分。
得到三元压电陶瓷粉体后，本发明将所述三元压电陶瓷粉体和粘结剂混合后，依次进行造粒、压片和排胶，得到三元压电陶瓷素坯。
在本发明中，所述粘结剂优选为质量浓度为3％～8％的聚乙烯醇水溶液，更优选为质量浓度为5％～6％的聚乙烯醇水溶液。
在本发明中，所述粘结剂与所述三元压电陶瓷粉体的质量比优选为1:20。
本发明对所述造粒的过程没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。
在本发明中，所述压片优选包括压制成型和冷等静压；所述压制成型的压力优选≤10MPa；本发明对所述压制成型的时间没有任何特殊的限定，采用本领域技术人员熟知的时间保证能够成型即可；所述冷等静压的压力优选为100～150MPa，更优选为120～130MPa；时间优选为5～15min，更优选为8～11min。
在本发明中，所述排胶的温度优选为600℃，时间优选为4h。升温至所述排胶温度的升温速率优选为0.2～0.9℃/min，更优选为0.5～0.7℃/min。
所述排胶完成后，本发明还优选包括冷却，所述冷却的方式优选为随炉冷却，所述冷却后的温度优选为室温。
得到三元压电陶瓷素坯后，本发明将所述三元压电陶瓷素坯进行烧结，得到所述三元压电陶瓷。
在本发明中，所述烧结的温度优选为900～1060℃，更优选为950～1050℃；时间优选为1～4h，更优选为1.5～3.5h。升温至所述烧结温度的升温速率优选为3～7℃/min，更优选为4～6℃/min。
本发明还提供了上述技术方案所述的三元压电陶瓷或上述技术方案所述的制备方法制备得到的三元压电陶瓷在汽车电子、航空航天、核电站和武器装备领域中的应用。
在本发明中，进行应用前，还优选先将所述三元压电陶瓷依次进行镀银和极化处理。
进行镀银前，本发明还优选包括将所述三元压电陶瓷进行打磨和抛光；本发明对所述打磨和抛光的过程没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。
本发明对所述镀银的过程没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。在本发明中，所述镀银后得到的银层的厚度优选为30～50μm，更优选为35～45μm，最优选为40μm。
在本发明中，所述极化的温度优选为100～140℃，更优选为105～135℃，最优选为110～130℃；电场优选为60～90kv/cm，更优选为65～75kv/cm；时间优选为15～30min，更优选为20～25min。
在本发明中，所述镀银的作用是作为电极，为之后的极化做准备，极化的作用是使得电畴取向一致化，以进一步的增大其压电性能。
所述镀银和极化完成后，本发明对所述应用的方法没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。
下面结合实施例对本发明提供的三元压电陶瓷及其制备方法和应用进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。
实施例1
三元压电陶瓷的化学组成为：0.65BiFeO3-0.19PbTiO3-0.16Ba(HfmTi1-m)O3-0.005MnO2(m＝0.08,0.1,0.12)；
按照所述三元压电陶瓷的元素配比，将Bi2O3，Fe2O3，PbO，TiO2，BaCO3，MnO2和HfO2混合后，放入球磨罐中，以无水乙醇作为球磨介质进行湿法球磨，所述球磨的转速为250r/min，时间为5h，烘干后装入氧化铝坩埚中，以5℃/min的升温速率升温至750℃，保温4h后，随炉冷却至室温，得到三元压电陶瓷粉体；
按照20:1的质量比，将所述三元压电陶瓷粉体和质量浓度为6％的聚乙烯醇水溶液混合均匀后，依次进行造粒、压制成型(10MPa)和冷等静压(130MPa，10min)后，以0.6℃/min的升温速率升温至600℃，保温4h后，随炉冷却至室温，得到三元压电陶瓷素坯；
将所述三元压电陶瓷素坯以5℃/min的升温速率升温至1040℃，保温2h后，随炉冷却至室温，得到三元压电陶瓷；
将所述三元压电陶瓷进行打磨和抛光后，镀银，得到厚度为40μm的银层后，在120℃的温度下于75kv/cm的电场下进行极化20min。
对比例1
参考实施例1，区别仅在于m＝0。
对比例2
参考实施例1，区别仅在于将二氧化锰替换为碳酸锰；制备过程中，将原料二氧化锰为替换碳酸锰。
测试例
采用传输线法，对实施例1和对比例1～2制备得到的三元压电陶瓷进行介电常数的测试；
采用准静态法，对实施例1和对比例1～2制备得到的三元压电陶瓷进行压电系数的测试；
采用传输线法，对实施例1和对比例1～2制备得到的三元压电陶瓷进行介电损耗的测试；
采用介电温谱法，对实施例1和对比例1～2制备得到的三元压电陶瓷进行居里温度的测试；
采用谐振法，对实施例1和对比例1～2制备得到的三元压电陶瓷进行机电耦合系数的测试；
采用阿基米德法，对实施例1和对比例1～2制备得到的三元压电陶瓷进行体密度的测试；
采用R-X阻抗测试法，对实施例1和对比例1～2制备得到的三元压电陶瓷进行电阻率的测试；
测试结果如表1和表2所示：
表1实施例1和对比例1制备得到的三元压电陶瓷的性能参数
Figure BDA0003129454780000061
Figure BDA0003129454780000071
表2实施例1中m＝0.08的三元压电陶瓷材料和对比例2制备得到的三元压电陶瓷材料的性能参数
Figure BDA0003129454780000072
由表1可知，三元压电陶瓷的体密度随着Hf离子的掺入量的增多而增大。体密度的增大使得压电系数d33从219提升到325，机电耦合系数kp从0.31提升到0.43。但是Hf的掺入会使得材料的居里温度有一定幅度的下降。实验结果表明，Hf离子的掺入可以大幅度提升BF-PT-BT压电陶瓷的压电性能；
由表2可知，掺杂MnO2的三元压电陶瓷与掺杂MnCO3的三元压电陶瓷相比具有更大的体密度和电阻率，所以掺杂MnO2的三元压电陶瓷具有更高的压电系数和机电耦合系数。
由上可知，Hf离子的引入和MnO2的掺杂可以改善三元压电陶瓷的压电性能。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

1.一种三元压电陶瓷，其特征在于，所述三元压电陶瓷的化学组成为：(1-x-y)BiFeO3-xPbTiO3-yBa(HfmTi1-m)O3-zMnO2；
其中，x，y，m和z为摩尔比，所述x，y，m和z的取值范围分别为：0<x≤0.3，0<y≤0.3，0<m≤1，0<z≤0.06。
2.如权利要求1所述的三元压电陶瓷，其特征在于，所述m的取值范围为：0.08≤m≤0.12。
3.如权利要求1或2所述的三元压电陶瓷，其特征在于，所述三元压电陶瓷的居里温度Tc为400～600℃，压电系数d33为150～400pC/N。
4.权利要求1～3任一项所述的三元压电陶瓷的制备方法，其特征在于，包括以下步骤：
按照所述三元压电陶瓷的元素配比，将Bi2O3、Fe2O3、PbO、TiO2、BaCO3、MnO2和HfO2混合，依次进行球磨和煅烧，得到三元压电陶瓷粉体；
将所述三元压电陶瓷粉体和粘结剂混合后，依次进行造粒、压片和排胶，得到三元压电陶瓷素坯；
将所述三元压电陶瓷素坯进行烧结，得到所述三元压电陶瓷。
5.如权利要求4所述的制备方法，其特征在于，所述球磨的转速为200～300r/min，时间为4～10h；
所述煅烧的温度为700～850℃，时间为2～10h。
6.如权利要求4所述的制备方法，其特征在于，所述粘结剂为质量浓度为3％～8％的聚乙烯醇水溶液；
所述粘结剂与所述三元压电陶瓷粉体的质量比为1:20。
7.如权利要求4所述的制备方法，其特征在于，所述排胶的温度为600℃，时间为4h；
所述烧结的温度为900～1060℃，时间为1～4h。
8.权利要求1～3任一项所述的三元压电陶瓷或权利要求4～7任一项所述的制备方法制备得到的三元压电陶瓷在汽车电子、航空航天、核电站和武器装备领域中的应用。
9.如权利要求8所述的应用，其特征在于，进行应用前，先将所述三元压电陶瓷依次进行镀电极和极化处理。
10.如权利要求8所述的应用，其特征在于，所述极化的温度为100～140℃，电场为60～90kv/cm，时间为15～30min。
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