CN113511892B - 一种高压电常数的压电陶瓷材料及其制备方法 - Google Patents

一种高压电常数的压电陶瓷材料及其制备方法 Download PDF

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CN113511892B
CN113511892B CN202110905959.XA CN202110905959A CN113511892B CN 113511892 B CN113511892 B CN 113511892B CN 202110905959 A CN202110905959 A CN 202110905959A CN 113511892 B CN113511892 B CN 113511892B
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方豪杰
贺亦文
张晓云
张斗
袁晰
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Hunan Meicheng Ceramic Technology Co ltd
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Abstract

本发明涉及电子陶瓷材料领域，具体为一种高压电常数的压电陶瓷材料及其制备方法，由以下化学式表示：PbxSr1‑x(SbyNb1‑y)a(Ti0.6SnzZr0.4‑z)bHf1‑a‑bO3‑cLnAlO3其中，x、y、z、a、b表示原子百分比，c代表LnAlO3占PbxSr1‑x(SbyNb1‑y)a(Ti0.6SnzZr0.4‑z)bHf1‑a‑bO3的质量百分比；其中，x为0.80‑0.86，y为0.5‑0.6，z为0.3‑0.35，a为0.18‑0.25，b为0.65‑0.73，c为0.02‑0.04；Ln为镧系元素，本发明所制备的压电陶瓷材料具有良好的压电、介电性能，在压电致动器、压电传感器等上有广阔的应用前景。

Description

一种高压电常数的压电陶瓷材料及其制备方法
技术领域
本发明涉及电子陶瓷材料领域，具体涉及一种高压电常数的压电陶瓷材料及其制备方法。
背景技术
压电陶瓷是能够将电能与机械能相互转换的功能型材料，如铌酸铅和锆钛酸铅压电陶瓷，由于具有良好的机械能与电能转换能力，被广泛应用于如超声传感器、压电致动器、压电变压器、压电电声器件等各个领域，随着电子器件向小型化、智能化的发展，对压电陶瓷的性能提出了越来越高的要求，如高压电常数、高介电常数和高机电耦合系数等，而开发高压电常数的压电陶瓷一直是本领域研究人员的研究重点。
发明内容
发明目的：针对现有技术的缺陷或改进需求，本发明提供了一种高压电常数的压电陶瓷材料及其制备方法。
本发明所采用的技术方案如下：
一种高压电常数的压电陶瓷材料，由以下化学式表示：
PbxSr1-x(SbyNb1-y)a(Ti0.6SnzZr0.4-z)bHf1-a-bO3-cLnAlO3
其中，x、y、z、a、b表示原子百分比，c代表LnAlO3占PbxSr1-x(SbyNb1-y)a(Ti0.6SnzZr0.4-z)bHf1-a-bO3的质量百分比；
其中，x为0.80-0.86，y为0.5-0.6，z为0.3-0.35，a为0.18-0.25，b为0.65-0.73，c为0.02-0.04；
Ln为镧系元素。
进一步地，x为0.82-0.85，y为0.53-0.55，z为0.31-0.33。
更进一步地，x为0.85，y为0.55，z为0.32。
进一步地，a为0.20-0.22，b为0.68-0.70，c为0.025-0.03。
更进一步地，a为0.20，b为0.70，c为0.03。
进一步地，La、Nd或Sm。
本发明还提供了一种高压电常数的压电陶瓷材料的制备方法，具体如下：
S1：按照化学式的计量比称取Pb3O4、SrCO3、Sb2O3、Nb2O5、TiO2、SnO2、ZrO2、HfO2、LnAlO3混合球磨10-15h后，升温至1200-1350℃预烧2-5h，恢复室温后继续球磨10-15h，得到预烧粉体；
S2：将预烧粉体加入无水乙醇中，超声分散后，加入硬脂酸，并以600-800r/min的速度搅拌3-5h后离心烘干，再与粘结剂混合均匀得到浆料，将浆料注射入模具中保压，得到坯体，将坯体加入脱胶液中，浸泡30-50min后取出烘干，再一段升温至600-650℃保温3-5h，再二段升温至1380-1450℃保温4-6h，得到压电陶瓷粗品。
S3：将压电陶瓷粗品表面抛光后被覆银电极，再置于硅油中加2-3kV/mm的直流电压极化5-15min即可。
进一步地，S2中粘结剂由聚乙烯醇缩丁醛与聚甲醛组成。
进一步地，S2中脱胶液为甲醇水溶液。
进一步地，S2中一段升温速度为10-20℃/min，二段升温速度为2-5℃/min。
本发明的有益效果：
目前国内的学者们对三元系Pb1-y-zSryBaz(Mg1/3Nb2/3)TimZrnO3+pwt.％La2O3、Pb1- mSrm(Mg1/3Nb2/3)TiyZrzO3+awt.％NiO+bwt.％SiO2+cwt.％La2O3+dwt.％Sm2O3等压电材料进行了研究，但其压电常数普遍不高，发明人采用Sn4+离子和Hf4+离子取代并引入LaAlO3进行复合，所制备的压电陶瓷材料致密度高，气孔少，在室温附近三方相和四方相共存，具有良好的压电、介电性能，其中压电常数≥833pC/N，介电常数≥7217，平面机电耦合系数≥0.78，介电损耗≤0.033％，在压电致动器、压电传感器等上有广阔的应用前景。
附图说明
图1为本发明实施例1所制备压电陶瓷材料室温下的显微结构图。
具体实施方式
实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例1：
一种高压电常数的压电陶瓷材料，由以下化学式表示：
Pb0.85Sr0.15(Sb0.55Nb0.45)0.20(Ti0.6Sn0.32Zr0.08)0.70Hf0.10O3-0.03LaAlO3
其制备方法如下：
按照化学式的计量比称取Pb3O4、SrCO3、Sb2O3、Nb2O5、TiO2、SnO2、ZrO2、HfO2、LnAlO3混合球磨15h后，升温至1300℃预烧5h，恢复室温后继续球磨12h，得到预烧粉体，将预烧粉体加入无水乙醇中，超声分散后，加入硬脂酸，并以800r/min的速度搅拌5h后离心烘干，再与聚乙烯醇缩丁醛与聚甲醛按质量比1:1组成的粘结剂混合均匀得到浆料，将浆料注射入模具中保压，注射压力为10MPa，保压压力为8.5MPa，保压时间为4s，得到坯体，将坯体加入浓度为15％的甲醇水溶液中，浸泡脱胶50min后取出烘干，以15℃/min的速度一段升温至600℃保温5h，再以5℃/min的速度二段升温至1450℃保温5h，得到压电陶瓷粗品，将压电陶瓷粗品表面抛光后被覆银电极，再置于硅油中加2.5kV/mm的直流电压极化10min即可。
实施例2：
一种高压电常数的压电陶瓷材料，由以下化学式表示：
Pb0.85Sr0.15(Sb0.55Nb0.45)0.20(Ti0.6Sn0.32Zr0.08)0.70Hf0.10O3-0.025LaAlO3
其制备方法如下：
按照化学式的计量比称取Pb3O4、SrCO3、Sb2O3、Nb2O5、TiO2、SnO2、ZrO2、HfO2、LnAlO3混合球磨10h后，升温至1250℃预烧5h，恢复室温后继续球磨10h，得到预烧粉体，将预烧粉体加入无水乙醇中，超声分散后，加入硬脂酸，并以800r/min的速度搅拌5h后离心烘干，再与聚乙烯醇缩丁醛与聚甲醛按质量比1:1组成的粘结剂混合均匀得到浆料，将浆料注射入模具中保压，注射压力为10MPa，保压压力为8.5MPa，保压时间为4s，得到坯体，将坯体加入浓度为15％的甲醇水溶液中，浸泡脱胶50min后取出烘干，以10℃/min的速度一段升温至600℃保温3h，再以3℃/min的速度二段升温至1380℃保温6h，得到压电陶瓷粗品，将压电陶瓷粗品表面抛光后被覆银电极，再置于硅油中加3kV/mm的直流电压极化15min即可。
实施例3：
一种高压电常数的压电陶瓷材料，由以下化学式表示：
Pb0.85Sr0.15(Sb0.55Nb0.45)0.20(Ti0.6Sn0.32Zr0.08)0.70Hf0.10O3-0.026LaAlO3
其制备方法如下：
按照化学式的计量比称取Pb3O4、SrCO3、Sb2O3、Nb2O5、TiO2、SnO2、ZrO2、HfO2、LnAlO3混合球磨10h后，升温至1200℃预烧2h，恢复室温后继续球磨10h，得到预烧粉体，将预烧粉体加入无水乙醇中，超声分散后，加入硬脂酸，并以600r/min的速度搅拌3h后离心烘干，再与聚乙烯醇缩丁醛与聚甲醛按质量比1:1组成的粘结剂混合均匀得到浆料，将浆料注射入模具中保压，注射压力为10MPa，保压压力为8.5MPa，保压时间为4s，得到坯体，将坯体加入浓度为15％的甲醇水溶液中，浸泡脱胶30min后取出烘干，以10℃/min的速度一段升温至600℃保温3h，再以2℃/min的速度二段升温至1380℃保温4h，得到压电陶瓷粗品，将压电陶瓷粗品表面抛光后被覆银电极，再置于硅油中加2kV/mm的直流电压极化5min即可。
实施例4：
一种高压电常数的压电陶瓷材料，由以下化学式表示：
Pb0.85Sr0.15(Sb0.55Nb0.45)0.20(Ti0.6Sn0.32Zr0.08)0.70Hf0.10O3-0.027LaAlO3
其制备方法如下：
按照化学式的计量比称取Pb3O4、SrCO3、Sb2O3、Nb2O5、TiO2、SnO2、ZrO2、HfO2、LnAlO3混合球磨15h后，升温至1350℃预烧5h，恢复室温后继续球磨15h，得到预烧粉体，将预烧粉体加入无水乙醇中，超声分散后，加入硬脂酸，并以800r/min的速度搅拌5h后离心烘干，再与聚乙烯醇缩丁醛与聚甲醛按质量比1:1组成的粘结剂混合均匀得到浆料，将浆料注射入模具中保压，注射压力为10MPa，保压压力为8.5MPa，保压时间为4s，得到坯体，将坯体加入浓度为15％的甲醇水溶液中，浸泡脱胶50min后取出烘干，以20℃/min的速度一段升温至650℃保温5h，再以5℃/min的速度二段升温至1450℃保温6h，得到压电陶瓷粗品，将压电陶瓷粗品表面抛光后被覆银电极，再置于硅油中加3kV/mm的直流电压极化15min即可。
实施例5：
一种高压电常数的压电陶瓷材料，由以下化学式表示：
Pb0.85Sr0.15(Sb0.55Nb0.45)0.20(Ti0.6Sn0.32Zr0.08)0.70Hf0.10O3-0.028LaAlO3
其制备方法如下：
按照化学式的计量比称取Pb3O4、SrCO3、Sb2O3、Nb2O5、TiO2、SnO2、ZrO2、HfO2、LnAlO3混合球磨10h后，升温至1350℃预烧2h，恢复室温后继续球磨15h，得到预烧粉体，将预烧粉体加入无水乙醇中，超声分散后，加入硬脂酸，并以600r/min的速度搅拌5h后离心烘干，再与聚乙烯醇缩丁醛与聚甲醛按质量比1:1组成的粘结剂混合均匀得到浆料，将浆料注射入模具中保压，注射压力为10MPa，保压压力为8.5MPa，保压时间为4s，得到坯体，将坯体加入浓度为15％的甲醇水溶液中，浸泡脱胶30min后取出烘干，以20℃/min的速度一段升温至600℃保温5h，再以2℃/min的速度二段升温至1450℃保温4h，得到压电陶瓷粗品，将压电陶瓷粗品表面抛光后被覆银电极，再置于硅油中加3kV/mm的直流电压极化5min即可。
对比例1
对比例1与实施例1基本相同，区别在于，不加入硬脂酸；
其制备方法如下：
按照化学式的计量比称取Pb3O4、SrCO3、Sb2O3、Nb2O5、TiO2、SnO2、ZrO2、HfO2、LnAlO3混合球磨15h后，升温至1300℃预烧5h，恢复室温后继续球磨12h，得到预烧粉体，将其与聚乙烯醇缩丁醛与聚甲醛按质量比1:1组成的粘结剂混合均匀得到浆料，将浆料注射入模具中保压，注射压力为10MPa，保压压力为8.5MPa，保压时间为4s，得到坯体，将坯体加入浓度为15％的甲醇水溶液中，浸泡脱胶50min后取出烘干，以15℃/min的速度一段升温至600℃保温5h，再以5℃/min的速度二段升温至1450℃保温5h，得到压电陶瓷粗品，将压电陶瓷粗品表面抛光后被覆银电极，再置于硅油中加2.5kV/mm的直流电压极化10min即可。
对比例2
对比例2与实施例1基本相同，区别在于，将粘结剂替换为聚乙烯醇。
对比例3
对比例3与实施例1基本相同，区别在于，不用甲醇水溶液浸泡处理。
其制备方法如下：
按照化学式的计量比称取Pb3O4、SrCO3、Sb2O3、Nb2O5、TiO2、SnO2、ZrO2、HfO2、LnAlO3混合球磨15h后，升温至1300℃预烧5h，恢复室温后继续球磨12h，得到预烧粉体，将预烧粉体加入无水乙醇中，超声分散后，加入硬脂酸，并以800r/min的速度搅拌5h后离心烘干，再与聚乙烯醇缩丁醛与聚甲醛按质量比1:1组成的粘结剂混合均匀得到浆料，将浆料注射入模具中保压，注射压力为10MPa，保压压力为8.5MPa，保压时间为4s，得到坯体，将坯体以15℃/min的速度一段升温至600℃保温5h，再以5℃/min的速度二段升温至1450℃保温5h，得到压电陶瓷粗品，将压电陶瓷粗品表面抛光后被覆银电极，再置于硅油中加2.5kV/mm的直流电压极化10min即可。
对比例4
对比例4与实施例1基本相同，区别在于，不加入LaAlO3。
性能测试：
压电常数是表征压电材料性能特有的一种参数，它反映压电体将机械能转换为电能(正压电效应)或将电能转换为机械能(逆压电效应)的转换能力。压电常数越大，表明材料将机械能与电能互相转换的能力越强，耦合效果越好，用ZJ-3型准静态d33测量仪测量样品的压电常数；
相对介电常数是表征介质材料的介电性质或极化性质的物理参数。其值等于以预测材料为介质与以真空为介质制成的同尺寸电容器电容量之比，该值也是材料贮电能力的表征，相对介电常数εr用如下方式测量：首先在两块极板之间为真空的时候测试电容器的电容C0，然后用同样的电容极板间距离但在极板间加入电介质后测得电容Cx，相对介电常数可以用下式计算：
εr＝Cx/C0
用阻抗分析仪测试室温下样品的谐振、反谐振频率，以及1kHz时的等效电阻、等效电容等参数，计算样品的平面机电耦合系数Kp、介电损耗tanδ。
对实施例1-5及对比例1-4所制备的压电陶瓷材料进行性能测试，测试结果如下表1所示：
表1
Figure BDA0003201557070000071
Figure BDA0003201557070000081
由上表1可知，本发明所制备的压电陶瓷材料具有良好的压电、介电性能，其中压电常数≥833pC/N，介电常数≥7217，平面机电耦合系数≥0.78，介电损耗≤0.033％，在压电致动器、压电传感器等上有广阔的应用前景。
以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (10)

1.一种高压电常数的压电陶瓷材料，其特征在于，由以下化学式表示：
PbxSr1-x(SbyNb1-y)a(Ti0.6SnzZr0.4-z)bHf1-a-bO3-cLnAlO3
其中，x、y、z、a、b表示原子百分比，c代表LnAlO3占PbxSr1-x(SbyNb1-y)a(Ti0.6SnzZr0.4-z)bHf1-a-bO3的质量百分比；
其中，x为0.80-0.86，y为0.5-0.6，z为0.3-0.35，a为0.18-0.25，b为0.65-0.73，c为0.02-0.04；
Ln为镧系元素。
2.如权利要求1所述的高压电常数的压电陶瓷材料，其特征在于，x为0.82-0.85，y为0.53-0.55，z为0.31-0.33。
3.如权利要求1所述的高压电常数的压电陶瓷材料，其特征在于，x为0.85，y为0.55，z为0.32。
4.如权利要求1所述的高压电常数的压电陶瓷材料，其特征在于，a为0.20-0.22，b为0.68-0.70，c为0.025-0.03。
5.如权利要求1所述的高压电常数的压电陶瓷材料，其特征在于，a为0.20，b为0.70，c为0.03。
6.如权利要求1所述的高压电常数的压电陶瓷材料，其特征在于，Ln为La、Nd或Sm。
7.一种如权利要求1-6中任一项所述的高压电常数的压电陶瓷材料的制备方法，其特征在于，具体如下：
S1：按照化学式的计量比称取Pb3O4、SrCO3、Sb2O3、Nb2O5、TiO2、SnO2、ZrO2、HfO2、LnAlO3混合球磨10-15h后，升温至1200-1350℃预烧2-5h，恢复室温后继续球磨10-15h，得到预烧粉体；
S2：将预烧粉体加入无水乙醇中，超声分散后，加入硬脂酸，并以600-800r/min的速度搅拌3-5h后离心烘干，再与粘结剂混合均匀得到浆料，将浆料注射入模具中保压，得到坯体，将坯体加入脱胶液中，浸泡30-50min 后取出烘干，再一段升温至600-650℃保温3-5h，再二段升温至1380-1450℃保温4-6h，得到压电陶瓷粗品;
S3：将压电陶瓷粗品表面抛光后被覆银电极，再置于硅油中加2-3kV/mm的直流电压极化5-15min即可。
8.如权利要求7所述的高压电常数的压电陶瓷材料的制备方法，其特征在于，S2中粘结剂由聚乙烯醇缩丁醛与聚甲醛组成。
9.如权利要求7所述的高压电常数的压电陶瓷材料的制备方法，其特征在于，S2中脱胶液为甲醇水溶液。
10.如权利要求7所述的高压电常数的压电陶瓷材料的制备方法，其特征在于，S2中一段升温速度为10-20℃/min，二段升温速度为2-5℃/min。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101265090A (zh) * 2008-04-21 2008-09-17 天津大学 锶、钡掺杂铌锑锆钛酸铅系压电陶瓷及制备方法
CN101445361A (zh) * 1999-03-29 2009-06-03 大森守 制备共晶陶瓷的方法
CN103145413A (zh) * 2013-03-21 2013-06-12 聊城大学 一种锡钛酸钡钙基无铅压电陶瓷及其制备工艺
CN103204679A (zh) * 2013-04-24 2013-07-17 淄博宇海电子陶瓷有限公司 一种低温烧结且老化率低的pzt压电陶瓷材料及其制备方法
CN105645957A (zh) * 2016-01-14 2016-06-08 广东捷成科创电子股份有限公司 一种高机电耦合性能锆钛酸铅细晶压电陶瓷及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101445361A (zh) * 1999-03-29 2009-06-03 大森守 制备共晶陶瓷的方法
CN101265090A (zh) * 2008-04-21 2008-09-17 天津大学 锶、钡掺杂铌锑锆钛酸铅系压电陶瓷及制备方法
CN103145413A (zh) * 2013-03-21 2013-06-12 聊城大学 一种锡钛酸钡钙基无铅压电陶瓷及其制备工艺
CN103204679A (zh) * 2013-04-24 2013-07-17 淄博宇海电子陶瓷有限公司 一种低温烧结且老化率低的pzt压电陶瓷材料及其制备方法
CN105645957A (zh) * 2016-01-14 2016-06-08 广东捷成科创电子股份有限公司 一种高机电耦合性能锆钛酸铅细晶压电陶瓷及其制备方法

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