CN109956748A - 一种锆钛酸铅-锰铋基钙钛矿-铅基复合钙钛矿多元低温烧结大功率压电陶瓷及其制备方法 - Google Patents

一种锆钛酸铅-锰铋基钙钛矿-铅基复合钙钛矿多元低温烧结大功率压电陶瓷及其制备方法 Download PDF

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CN109956748A
CN109956748A CN201910246316.1A CN201910246316A CN109956748A CN 109956748 A CN109956748 A CN 109956748A CN 201910246316 A CN201910246316 A CN 201910246316A CN 109956748 A CN109956748 A CN 109956748A
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lead
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manganese
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左如忠
黄廷伟
祁核
付健
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Hefei University of Technology
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Abstract

本发明涉及一种锆钛酸铅‑锰铋基钙钛矿‑铅基复合钙钛矿多元低温烧结大功率压电陶瓷及其制备方法，其特征在于，组成通式为：(1‑n)[(1‑u‑v)Pb(Zr1‑zTiz)O3+uBi(MnxDy)O3+vPb(EtFw)O3]+nM。本发明的陶瓷可采用常规陶瓷制备方法制备合成，具有菱形铁电相和四方铁电相的准同型相界，同时具有优异的压电性能和高的机械品质因数，以及高的居里温度，低的烧结温度，适合在大功率换能器领域应用。

Description

一种锆钛酸铅-锰铋基钙钛矿-铅基复合钙钛矿多元低温烧结 大功率压电陶瓷及其制备方法
技术领域
本发明涉及一种压电陶瓷及其制备方法，更准确地说是锆钛酸铅-锰铋基钙钛矿-铅基复合钙钛矿多元低温烧结大功率压电陶瓷及其制备方法。
背景技术
大功率压电陶瓷由于同时具有高压电系数(d33)，机电耦合系数(kp)和机械品质因数(Qm)，广泛应用于超声波电动机和陶瓷变压器等。常见大功率压电陶瓷材料主要有两类：以锆酸铅(PbZrO3，简称PZ)、钛酸铅(PbTiO3，简称PT)、和驰豫铁电组成如铌镁酸铅(Pb(Mg1/ 3Nb2/3)O3，简称PMN)、铌锌酸铅(Pb(Zn1/3Nb2/3)O3，简称PZN)等组成三元体系，位于三方(R)铁电相与四方(T)铁电相组成的准同型相界附近加入受主掺杂剂(如MnO2、SiO2和Fe2O3等)，以及具有两性特征的钙钛矿固溶体系如锆钛酸铅-铌锰酸铅(Pb(Zr,Ti)O3-Pb(Mn1/3Nb2/3)O3，简称PZT-PMnN)、锆钛酸铅-锑锰酸铅(Pb(Zr,Ti)O3-Pb(Mn1/3Sb2/3)O3，简称PZT-PMS)等。目前已报道的研究工作有Y.Yan,K.H.Cho,S.Priya，J.Am.Ceram.Soc.，94(11),3953-3959；Q.C.Wu,M.M.Hao,Z.Q.Zeng,X.C.Wang,W.Z.Lv,G.F.Fan,Ceram.Int.,43(14)10866-10872)。同时，近年来已有很多关于含铅材料的发明专利被申请授权(CN201010547255，CN201110141080，CN107573067A，CN105819854A)。遗憾的是，以上这些体系通常需要高于1250℃的烧结温度，这不利于生产成本的降低和多层压电陶瓷器件的开发。掺杂烧结助剂可有效降低烧结温度，但通常以压电和机电性能劣化为代价。铋基复合钙钛矿如钛锰酸铋(Bi(Mn1/2Ti1/2)O3，简称BMT)，已成功替代PZT形成三元固溶体，具有优异的铁电和压电性能、高居里温度(Tc)和相对较低的烧结温度。铅基复合弛豫铁电体如PZN、PMN等具有相对较低的烧结温度，可有效地促进PZT基陶瓷的致密化，优化提升电学性能，并通过在MPB附近少量掺杂金属氧化物来进一步改性。遗憾的是，现有文献中还未见有锆钛酸铅-锰铋基钙钛矿-铅基复合钙钛矿多元低温烧结大功率压电陶瓷的组成设计、电性能和制备工艺的研究报道。
发明内容
本发明是为避免上述现有技术所存在的不足之处，提供一种锆钛酸铅-锰铋基钙钛矿-铅基复合钙钛矿多元低温烧结大功率压电陶瓷及其制备方法。该体系具有良好的压电性能、高的机械品质因数、高的居里温度、低的烧结温度。本体系压电陶瓷组成具有菱形铁电相和四方铁电相的准同型相界。
为达到以上目的，本发明所采用的技术方案如下：
一种锆钛酸铅-锰铋基钙钛矿-铅基复合钙钛矿多元低温烧结大功率压电陶瓷，其特征在于本压电陶瓷的组成由以下通式表示：
(1-n)[(1-u-v)Pb(Zr1-zTiz)O3+uBi(MnxDy)O3+vPb(EtFw)O3]+nM；
所述的通式中n，u，v，x，y，z，t，w为各物质的摩尔分数，取值均小于1；
并且n≥0，u>0，v>0，x＞0，y＞0，z＞0，t＞0，w＞0，2x+ay＝3，bt+cw＝4，x+y＝1，t+w＝1，其中a，b，c分别为D、E和F的化合价数或者平均化合价数；
D选自Ti4+、Zr4+、Nb5+、Ta5+、Sb5+、W6+金属离子中的一种或者多种；
E、F分别选自Mg2+、Zn2+、Co2+、Ni2+、Cd2+、Sc3+、Yb3+、In3+、Fe3+、Nb5+、Ta5+、W6+金属离子中的一种或者多种；
M选自Na、K、Li、Ag、Cu、Fe、Mn、Nd、Sm、Nb、La的金属氧化物中的一种或多种,为多种时，其摩尔分数之和为1。
锆钛酸铅-锰铋基钙钛矿-铅基复合钙钛矿多元低温烧结大功率压电陶瓷的制备方法，主要包括湿球磨、预烧、坯料制作、烧结、被银和极化，其特征在于：所述湿球磨是将按通式(1-n)[(1-u-v)Pb(Zr1-zTiz)O3+uBi(MnxDy)O3+vPb(EtFw)O3]+nM所示化学组成的化学计量比称取的各原料混合，以去离子水为介质混合并球磨6-12小时得湿料；所述预烧是将所述湿料烘干后放置于氧化铝坩埚中于800-950℃煅烧合成，保温1-4小时，得预合成粉料；所述坯料制作是将所得预合成粉料经研碎以去离子水为介质并球磨6-12小时，干燥后过110-130目筛并在50-200MPa的压力下冷压成型为坯体；所述烧结是在空气中常压下采用埋粉法提供保护气氛，将所得坯体置于倒放的双坩埚中，于950-1150℃烧结1-4小时得瓷坯；所述被银是在经抛光的瓷坯两端面被银电极；所述极化是将带有电极的样品置于25-150℃硅油中加极化直流电压2-4kV/mm，保温5-30分钟。
与已有技术相比，本发明的特点以及有益效果体现在：
1、本发明多元复合低温烧结大功率压电陶瓷组成拥有类似于传统压电陶瓷组成的位于菱形铁电相和四方铁电相的准同型相界结构，具有优异的压电性能、机械品质因数和高居里温度。
2、本发明的压电陶瓷因自身含有氧化铋、氧化锌以及氧化铅等低熔点的氧化物，使得该组成体系的本征烧结温度较低，此外，少量的金属氧化物添加剂能够进一步优化电学性能的同时有效降低烧结温度，节约能耗和制备费用。
3、本发明多元复合系低温烧结大功率压电陶瓷采用传统压电陶瓷的制备技术和工业用原料获得，具有实用性。
附图说明
图1为实施例1中组成为：0.9Pb(Zr0.48Ti0.52)O3+0.04Bi(Mn2/3Sb1/3)O3+0.06Pb(Mg1/3Nb2/3)O3，样品在1120℃烧结2小时后介电-温度特性曲线。
图2为实施例2中组成为：0.8937Pb(Zr0.48Ti0.52)O3+0.03972Bi(Mn2/3Sb1/3)O3+0.05958Pb(Ni1/3Nb2/3)O3+0.007Sm2O3，样品在1020℃烧结2小时后样品的电滞回线。
图3为实施例3中组成为：0.8928Pb(Zr0.505Ti0.495)O3+0.03968Bi(Mn1/2Ti1/2)O3+0.05952Pb(Zn1/3Nb2/3)O3+0.004CuO+0.004Fe2O3，样品的断面的扫描电镜照片。
图4为实施例4中组成为：0.8964Pb(Zr0.505Ti0.495)O3+0.03984Bi(Mn2/3Nb1/3)O3+0.05976Pb(Zn1/3Nb2/3)O3+0.004CuO，样品X射线衍射图谱。
具体实施方式
一种锆钛酸铅-锰铋基钙钛矿-铅基复合钙钛矿多元低温烧结大功率压电陶瓷的制备方法，其特征在于：
a、按通式(1-n)[(1-u-v)Pb(Zr1-zTiz)O3+uBi(MnxDy)O3+vPb(EtFw)O3]+nM所示化学组成的化学计量比称量化学纯或分析纯的碳酸盐或金属氧化物进行配料；
b、配好的原料以去离子水为溶剂，经6-12小时的湿球磨得湿料，所得湿料干燥后在氧化铝坩埚中于800-950℃煅烧1-4小时，重复湿球磨和煅烧工艺一次，得到预合成粉料；
c、将所得预合成粉料经研碎以去离子水为介质并球磨6-12小时，干燥后过110-130目筛并在50-200MPa的压力下冷压成型为坯体；
d、在空气中常压下于950-1150℃烧结1-4小时得瓷坯，升温速率为3-6℃/min；
e、在经抛光的瓷坯两端面被银电极后置于25-150℃硅油中加极化直流电压2-4kV/mm，保温5-30分钟得到大功率压电陶瓷。
f、按照IRE的标准对压电陶瓷样品进行压电和机电耦合性能的测试。
实施例1
按上述实施方式依次进行各步骤，本实施例采用压电陶瓷的组成通式为：
0.9Pb(Zr0.48Ti0.52)O3+0.04Bi(Mn2/3Sb1/3)O3+0.06Pb(Mg1/3Nb2/3)O3。煅烧温度为850℃、时间为2小时。以去离子水为介质的湿球磨时间为10小时。经模压成型后，坯体烧结温度为1120℃，时间为2小时。在经抛光的瓷坯两端面被银电极后置于150℃硅油中加极化直流电压4kV/mm，保温15分钟得到大功率压电陶瓷。
本实施例制备的压电陶瓷的介电-温度特性曲线如图1所示，测得样品的其它物理性能：居里温度为296℃，介电常数为1420(1kHz)，压电常数为287pC/N，平面机电耦合系数为54％，机械品质因数为1420，介电损耗为0.77％(1kHz)。
实施例2
按上述实施方式依次进行各步骤，本实施例压电陶瓷的组成通式为：
0.8937Pb(Zr0.48Ti0.52)O3+0.03972Bi(Mn2/3Sb1/3)O3+0.05958Pb(Ni1/3Nb2/3)O3+0.007Sm2O3。煅烧温度为850℃、时间为2小时。以去离子水为介质的湿球磨时间为10小时。经模压成型后，坯体烧结温度为1020℃，时间为2小时。在经抛光的瓷坯两端面被银电极后置于150℃硅油中加极化直流电压4kV/mm，保温15分钟得到大功率压电陶瓷。
本实施例制备的压电陶瓷电滞回线如图2所示，其物理性能为：居里温度为302℃，介电常数为1620(1kHz)，压电常数为305pC/N，平面机电耦合系数为58％，机械品质因数为1650，介电损耗为0.67％(1kHz)。
实施例3
按上述实施方式依次进行各步骤，本实施例压电陶瓷的组成通式为：
0.8928Pb(Zr0.505Ti0.495)O3+0.03968Bi(Mn1/2Ti1/2)O3+0.05952Pb(Zn1/3Nb2/3)O3+0.004CuO+0.004Fe2O3。煅烧温度为850℃、时间为2小时。以去离子水为介质的湿球磨时间为10小时。经模压成型后，坯体烧结温度为1020℃，时间为2小时。在经抛光的瓷坯两端面被银电极后置于150℃硅油中加极化直流电压4kV/mm，保温15分钟得到大功率压电陶瓷。
本实施例制备的压电陶瓷断面的扫描电镜照片如图3所示，其物理性能为：居里温度为323℃，介电常数为1672(1kHz)，压电常数为365pC/N，平面机电耦合系数为61％，机械品质因数为1102，介电损耗为0.41％(1kHz)。
实施例4
按上述实施方式依次进行各步骤，本实施例压电陶瓷的组成通式为：
0.8964Pb(Zr0.505Ti0.495)O3+0.03984Bi(Mn2/3Nb1/3)O3+0.05976Pb(Zn1/3Nb2/3)O3+0.004CuO。煅烧温度为850℃、时间为2小时。以去离子水为介质的湿球磨时间为10小时。经模压成型后，坯体烧结温度为1100℃，时间为2小时。在经抛光的瓷坯两端面被银电极后置于150℃硅油中加极化直流电压4kV/mm，保温15分钟得到大功率压电陶瓷。
本实施例制备的压电陶瓷的X射线衍射图谱如图4所示，其物理性能为：居里温度为323℃，介电常数为1554(1kHz)，压电常数为330pC/N，平面机电耦合系数为59％，机械品质因数为1250，介电损耗为0.41％(1kHz)。

Claims (2)

1.一种锆钛酸铅-锰铋基钙钛矿-铅基复合钙钛矿多元低温烧结大功率压电陶瓷，其特征在于本压电陶瓷的组成由以下通式表示：
(1-n)[(1-u-v)Pb(Zr1-zTiz)O3+uBi(MnxDy)O3+vPb(EtFw)O3]+nM；
所述的通式中n，u，v，x，y，z，t，w为各物质的摩尔分数，取值均小于1；
并且n≥0，u>0，v>0，x＞0，y＞0，z＞0，t＞0，w＞0，2x+ay＝3，bt+cw＝4，x+y＝1，t+w＝1，其中a，b，c分别为D、E和F的化合价数或者平均化合价数；
D选自Ti4+、Zr4+、Nb5+、Ta5+、Sb5+、W6+金属离子中的一种或者多种；
E、F分别选自Mg2+、Zn2+、Co2+、Ni2+、Cd2+、Sc3+、Yb3+、In3+、Fe3+、Nb5+、Ta5+、W6+金属离子中的一种或者多种；
M选自Na、K、Li、Ag、Cu、Fe、Mn、Nd、Sm、Nb、La的金属氧化物中的一种或多种,为多种时，其摩尔分数之和为1。
2.锆钛酸铅-锰铋基钙钛矿-铅基复合钙钛矿多元低温烧结大功率压电陶瓷的制备方法，主要包括湿球磨、预烧、坯料制作、烧结、被银和极化，其特征在于：所述湿球磨是将按通式(1-n)[(1-u-v)Pb(Zr1-zTiz)O3+uBi(MnxDy)O3+vPb(EtFw)O3]+nM所示化学组成的化学计量比称取的各原料混合，以去离子水为介质混合并球磨6-12小时得湿料；所述预烧是将所述湿料烘干后放置于氧化铝坩埚中于800-950℃煅烧合成，保温1-4小时，得预合成粉料；所述坯料制作是将所得预合成粉料经研碎以去离子水为介质并球磨6-12小时，干燥后过110-130目筛并在50-200MPa的压力下冷压成型为坯体；所述烧结是在空气中常压下采用埋粉法提供保护气氛，将所得坯体置于倒放的双坩埚中，于950-1150℃烧结1-4小时得瓷坯；所述被银是在经抛光的瓷坯两端面被银电极；所述极化是将带有电极的样品置于25-150℃硅油中加极化直流电压2-4kV/mm，保温5-30分钟。
CN201910246316.1A 2019-03-29 2019-03-29 一种锆钛酸铅-锰铋基钙钛矿-铅基复合钙钛矿多元低温烧结大功率压电陶瓷及其制备方法 Pending CN109956748A (zh)

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Application publication date: 20190702