CN113582689B - 一种用于叠层致动器低温共烧压电陶瓷材料及其制备方法 - Google Patents

一种用于叠层致动器低温共烧压电陶瓷材料及其制备方法 Download PDF

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CN113582689B
CN113582689B CN202110994661.0A CN202110994661A CN113582689B CN 113582689 B CN113582689 B CN 113582689B CN 202110994661 A CN202110994661 A CN 202110994661A CN 113582689 B CN113582689 B CN 113582689B
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张博
阴伏星
李佳
蔡东
严伟
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Chengdu Huitong West Electronic Co ltd
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Abstract

本发明公开了一种用于叠层致动器低温共烧压电陶瓷材料及其制备方法，其化学通式为aPb(Mg1/3Nb2/3)‑bPb(Sb1/2Nb1/2)‑cPb(Zn1/ 3Nb2/3)‑dPb(Zr0.52Ti0.48)+x％LiF+y％MuOv+z％SrCO3，其中0.03≤a≤0.06；0.01≤b≤0.03；0.005≤c≤0.03；0.80≤d≤0.95，0<x≤0.2，0<y≤1，0<z≤0.2。通过调整陶瓷配方以及添加组合掺杂剂，可以将陶瓷的烧结温度从1200℃降至850～950℃，并能获得大的压电常数(d33≥500pC/N)、大的机电耦合系数(kp≥0.65)、以及较高居里点(Tc>250℃)及适中的介电常数(εr＝2000～4000)，可以满足叠层压电致动器共烧工艺对陶瓷材料的应用要求。

Description

一种用于叠层致动器低温共烧压电陶瓷材料及其制备方法
技术领域
本发明属于无机非金属电子材料技术领域，涉及一种压电陶瓷材料的制备方法，具体涉及一种用于叠层致动器低温共烧压电陶瓷材料及其制备方法。
背景技术
压电叠层致动器广泛应用于精密机械加工、微笑振动控制、微电子技术、光学校准等需要精确定位的高新技术领域。而这些应用领域需要压电陶瓷器件向小体积、低驱动、大位移、可集成等方向发展。压电叠层器件需要满足灵敏度高、静态输出力矩大、温度稳定性好等特点，而作为核心的压电驱动材料配方必须具备：高的压电常数以实现低电压驱动和大的输出力；高的机电耦合系数以便具有较宽的工作频率和较高的转换效率；较高的居里点从而改善器件的温度稳定性，才可以适应恶劣应用环境以及避免器件工作过程中产生的热量导致器件性能蜕化；适中的介电常数ε，避免交变电场下的发热和较高输入阻抗。
Pb(Mg1/3Nb2/3)-Pb(Zr0.52Ti0.48)(PMN-PZT)是一种典型的三元体系钙钛矿压电陶瓷材料，它具有高的压电常数、高的机电耦合系数以及较高的居里温度，是叠层致动器的关键材料。但该体系压电陶瓷烧结温度一般在1200℃以上，较高的烧结温度会导致材料中的铅挥发，污染环境的同时会导致陶瓷材料中化学计量比的偏离。这不仅会产生杂相，导致钙钛矿结构的变化，同时会恶化陶瓷的压电性能，还会影响产品批量生产的一致性。降低压电陶瓷烧结温度的方法有：1)改进制备工艺如化学方法制粉，提高粉体活性，降低陶瓷烧结温度，但该方法工艺复杂成本较高；2)添加玻璃粉或低熔点氧化物烧结助剂，在烧结过程中，玻璃或者低熔点氧化物形成液相，易于传质，有利于气孔的排除和陶瓷的致密化，降温效果非常明显，但陶瓷晶界容易聚集非铁电第二相，导致材料性能急剧恶化，不利于高性能水平的应用领域；
3)固溶或掺杂氧化物，形成过渡液相烧结，在烧结前期形成液相促进传质降低烧结温度，在烧结后期液相进入晶格，减少杂相的生成，避免了陶瓷性能的恶化。兼顾压电陶瓷的低温烧结以及高水平的压电性能是压电陶瓷低温烧结研究的难点。
电子科技大学的李元勋，研究了添加Sm2O3及玻璃助烧剂LBBS和LMZBS对于PZT烧结温度及压电性能的影响，烧结温度降低至850～900℃，但陶瓷的压电性能存在一定程度的下降，d33为260～330pC/N[郑阳.PZT基压电陶瓷的低温烧结及其应用[D].电子科技大学，2018.]。杭州应用声学研究所的胡望峰，研究了不同LiF助烧剂添加量对PZT压电陶瓷晶体结构、微观形貌、压电性能和烧结过程的影响，可以将陶瓷的烧结温度降低至1100℃，且能保持较好的压电性能(d33为416pC/N，Kp＝71％，εr＝1848)[赵世言,胡望峰.LiF/Li2CO3对PZT陶瓷低温烧结及压电性能的影响[J].压电与声光，2020，v.42；No.255(06)：82-87.]。压电陶瓷材料中提高材料的压电性能的同时，有可能会导致材料的居里温度降低(<300℃)，这对压电驱动器的应用不利。因此，进一步降低压电驱动材料烧结温度和改善其综合压电性能，满足纯银内电极的低温共烧，降低制作成本提高器件的成品率，是压电陶瓷低温烧结研究领域亟待解决的问题。Pb(Sb，Nb)O3及Pb(Zn，Nb)O3是俩种典型的PZT压电陶瓷软性改性添加体系，PMN-PZT中引入此俩种材料，通过改善多元材料组元的比例、控制PZT晶体结构中A、B位离子的空位比例，并采用微量元素掺杂的方法，从而达到降低烧结温度，获得一种低烧结温度、高压电常数、高居里温度及低介电损耗的高性能压电陶瓷材料。
发明内容
针对现有问题，本发明的目的在于提供一种用于叠层致动器低温共烧压电陶瓷材料及其制备方法。为了解决现有的压电陶瓷烧结温度过高导致的铅极易挥发，污染环境，以及现有低温配方压电性能下降，陶瓷居里温度低从而影响叠层致动器寿命可靠性的问题。
为实现本发明的目的，本发明提供如下技术方案：
为达到上述目的，本发明采用了以下技术方案。
1)化学通式为aPb(Mg1/3Nb2/3)-bPb(Sb1/2Nb1/2)-cPb(Zn1/3Nb2/3)-dPb(Zr0.52Ti0.48)+x％LiF+y％MuOv+z％SrCO3，简写为PMN-PSN-PZN-PZT，式中M为第一过渡系金属元素，其中0.03≤a≤0.06；0.01≤b≤0.03；0.005≤c≤0.03；0.80≤d≤0.95，0<x≤0.2，0<y≤1，0<z≤0.2。PMN-PSN-PZN-PZT为基体陶瓷粉体，LiF、MuOv、SrCO3为陶瓷材料配方中的辅料，x％、y％、z％分别表示对应的化合物占基体陶瓷粉体的质量百分比，u和v的数值取决于金属元素M的化合价，且u和v为整数，M为金属元素Fe、Co、Ni中的一种；
2)提供了一种用于叠层致动器的低温烧结压电陶瓷材料配方的制备方法，包括以下步骤：
步骤1：将Pb3O4、MgO、Nb2O5三种原料粉体混合预烧后得到Pb(Mg1/3Nb2/3)，简称PMN陶瓷先驱体粉体；将Pb3O4、Sb2O5、Nb2O5三种原料粉体混合预烧后得到Pb(Sb1/2Nb1/2)，简称PSN陶瓷先驱体粉体。
步骤2：根据1)中化学通式中的化学计量比计算称量步骤1中所述的PMN陶瓷先驱体粉体，以及Pb3O4、ZnO、Nb2O5、ZrO2、TiO2、等原料粉体，得到混合粉体A。将混合粉体A球磨均匀后预烧，预烧粉料按照质量百分比加入LiF、MuOv、SrCO3以及PSN陶瓷先驱体粉体等原料粉体，混合均匀后得到混合粉体B，混合粉体B经过球磨、烘干、等静压、烧结、切片等工艺获得所述的压电陶瓷材料。
所述步骤1中2种陶瓷先驱体粉体的预烧温度均为900～1000℃，保温时间为2～4h。
所述步骤2中混合粉体A的预烧温度为1000～1050℃，保温时间为1～2h。
所述步骤2中混合粉体A预烧后再按化学计量比加入PSN陶瓷先驱体粉体及辅料。
所述步骤2中混合粉体B不需要造粒，球磨烘干后，直接等静压成型为棒料，棒料在铅气氛中密封烧结，所述烧结温度为850～950℃，保温时间为2～3h。
所述步骤2中烧结、切片工艺后还包括陶瓷片被银以及极化工艺：在所述陶瓷片表面丝网印刷银浆，被银后的陶瓷片烧银后进行极化。
所述烧银温度为820～870℃，保温时间为20～30min；所述极化的条件包括：极化温度为100～140℃，极化电压为3～5kV/mm，极化时间为20～40min。
本发明的有益效果体现在：
1)本发明制备的低温烧结压电陶瓷材料配方在降低烧结温度的同时(850～950℃)，压电性能无明显下降(d33＝500pC/N)，且居里温度较高(Tc>250℃)，可以提升叠层致动器的可靠性及寿命，同时也降低对于环境的污染；
2)本发明制备的压电陶瓷材料配方及其制备方法，不需要对陶瓷进行造粒，简化工艺的同时也提升了陶瓷的致密度，有利于提升陶瓷的压电性能；
3)本发明制备工艺简单，操作方便，原料易得，制备成本较低。
附图说明
为了更清楚的说明本申请文件实施例或现有技术中的技术方案，下面将对实施例或现有技术的描述中所需要使用的附图作简单的介绍，显而易见地，下面描述中的附图仅是对本申请文件中一些实施例的参考，对于本领域技术人员来讲，在不付出创造性劳动的情况下，还可以根据这些附图得到其它的附图。
图1为本发明实施例1、2、3、4制备的压电陶瓷的XRD图谱；
图2为本发明实施例5制备的压电陶瓷断面SEM图谱；
图3为本发明实施例5制备的压电性能图；
图4为本发明实施例5制备的介电温谱图。
具体实施方式
下面结合实施例对本发明作进一步的描述，所描述的实施例仅仅是本发明一部分实施例，并不是全部的实施例。基于本发明中的实施例，本领域的普通技术人员在没有做出创造性劳动前提下所获得的其他所用实施例，都属于本发明的保护范围。
实施例1：
1)化学通式为0.06Pb(Mg1/3Nb2/3)-0.03Pb(Sb1/2Nb1/2)-0.01Pb(Zn1/3Nb2/3)-0.9Pb(Zr0.52Ti0.48)
，简写为0.06PMN-0.03PSN-0.01PZN-0.9PZT添加0.1％LiF+1％NiO+0.1％SrCO3；
2)按1)中的化学通式将Pb3O4、MgO、Nb2O5三种原料粉体混合在900℃预烧2h得到Pb(Mg1/3Nb2/3)，简称PMN陶瓷先驱体粉体；将Pb3O4、Sb2O5、Nb2O5三种原料粉体混合在950℃预烧2h后得到Pb(Sb1/2Nb1/2)，简称PSN陶瓷先驱体粉体；
3)根据1)中化学通式中的化学计量比计算称量步骤2)中所述的PMN陶瓷先驱体粉体，以及Pb3O4、ZnO、Nb2O5、ZrO2、TiO2、等原料粉体，得到混合粉体A。将混合粉体A球磨均匀后在1000℃预烧2h，预烧粉料按照质量百分比加入LiF、NiO、SrCO3以及PSN陶瓷先驱体粉体等原料粉体，混合均匀后得到混合粉体B。
4)混合粉体B经过球磨、烘干、等静压、在Pb气氛中850℃保温2h后，将烧结后的陶瓷切片得到压电陶瓷片，采用丝网印刷工艺在陶瓷片上制备Ag电极，将刷好Ag电极的陶瓷片置于烧银炉中烧银，烧银温度820℃，保温20min。
5)将烧银后的陶瓷片置于高温硅油中，按照100℃，3kV/mm，20min等工艺极化获得所述的压电陶瓷材料。
实施例2：
1)化学通式为0.05Pb(Mg1/3Nb2/3)-0.03Pb(Sb1/2Nb1/2)-0.02Pb(Zn1/3Nb2/3)-0.9Pb(Zr0.52Ti0.48)
，简写为0.05PMN-0.03PSN-0.02PZN-0.9PZT添加0.1％LiF+0.5％Fe2O3+0.1％SrCO3；
2)按1)中的化学通式将Pb3O4、MgO、Nb2O5三种原料粉体混合在900℃预烧4h得到Pb(Mg1/3Nb2/3)，简称PMN陶瓷先驱体粉体；将Pb3O4、Sb2O5、Nb2O5三种原料粉体混合在1000℃预烧4h后得到Pb(Sb1/2Nb1/2)，简称PSN陶瓷先驱体粉体；
3)根据1)中化学通式中的化学计量比计算称量步骤2)中所述的PMN陶瓷先驱体粉体，以及Pb3O4、ZnO、Nb2O5、ZrO2、TiO2、等原料粉体，得到混合粉体A。将混合粉体A球磨均匀后在1000℃预烧1h，预烧粉料按照质量百分比加入LiF、Fe2O3、SrCO3以及PSN陶瓷先驱体粉体等原料粉体，混合均匀后得到混合粉体B。
4)混合粉体B经过球磨、烘干、等静压、在Pb气氛中850℃保温3h后，将烧结后的陶瓷切片得到压电陶瓷片，采用丝网印刷工艺在陶瓷片上制备Ag电极，将刷好Ag电极的陶瓷片置于烧银炉中烧银，烧银温度830℃，保温20min。
5)将烧银后的陶瓷片置于高温硅油中，按照110℃，4kV/mm，20min等工艺极化获得所述的压电陶瓷材料。
实施例3：
1)化学通式为0.05Pb(Mg1/3Nb2/3)-0.02Pb(Sb1/2Nb1/2)-0.03Pb(Zn1/3Nb2/3)-0.9Pb(Zr0.52Ti0.48)
，简写为0.05PMN-0.02PSN-0.03PZN-0.9PZT添加0.1％LiF+1％NiO+0.2％SrCO3；
2)按1)中的化学通式将Pb3O4、MgO、Nb2O5三种原料粉体混合在1000℃预烧2h得到Pb(Mg1/3Nb2/3)，简称PMN陶瓷先驱体粉体；将Pb3O4、Sb2O5、Nb2O5三种原料粉体混合在950℃预烧2h后得到Pb(Sb1/2Nb1/2)，简称PSN陶瓷先驱体粉体；
3)根据1)中化学通式中的化学计量比计算称量步骤2)中所述的PMN陶瓷先驱体粉体，以及Pb3O4、ZnO、Nb2O5、ZrO2、TiO2、等原料粉体，得到混合粉体A。将混合粉体A球磨均匀后在1050℃预烧1h，预烧粉料按照质量百分比加入LiF、NiO、SrCO3以及PSN陶瓷先驱体粉体等原料粉体，混合均匀后得到混合粉体B。
4)混合粉体B经过球磨、烘干、等静压、在Pb气氛中900℃保温2h后，将烧结后的陶瓷切片得到压电陶瓷片，采用丝网印刷工艺在陶瓷片上制备Ag电极，将刷好Ag电极的陶瓷片置于烧银炉中烧银，烧银温度840℃，保温20min。
5)将烧银后的陶瓷片置于高温硅油中，按照120℃，3kV/mm，30min等工艺极化获得所述的压电陶瓷材料。
实施例4：
1)化学通式为0.06Pb(Mg1/3Nb2/3)-0.01Pb(Sb1/2Nb1/2)-0.03Pb(Zn1/3Nb2/3)-0.9Pb(Zr0.52Ti0.48)
，简写为0.06PMN-0.01PSN-0.03PZN-0.9PZT添加0.1％LiF+0.5％Co2O3+0.2％SrCO3；
2)按1)中的化学通式将Pb3O4、MgO、Nb2O5三种原料粉体混合在1000℃预烧2h得到Pb(Mg1/3Nb2/3)，简称PMN陶瓷先驱体粉体；将Pb3O4、Sb2O5、Nb2O5三种原料粉体混合在1000℃预烧2h后得到Pb(Sb1/2Nb1/2)，简称PSN陶瓷先驱体粉体；
3)根据1)中化学通式中的化学计量比计算称量步骤2)中所述的PMN陶瓷先驱体粉体，以及Pb3O4、ZnO、Nb2O5、ZrO2、TiO2、等原料粉体，得到混合粉体A。将混合粉体A球磨均匀后在1000℃预烧2h，预烧粉料按照质量百分比加入LiF、Co2O3、SrCO3以及PSN陶瓷先驱体粉体等原料粉体，混合均匀后得到混合粉体B。
4)混合粉体B经过球磨、烘干、等静压、在Pb气氛中950℃保温2h后，将烧结后的陶瓷切片得到压电陶瓷片，采用丝网印刷工艺在陶瓷片上制备Ag电极，将刷好Ag电极的陶瓷片置于烧银炉中烧银，烧银温度840℃，保温20min。
5)将烧银后的陶瓷片置于高温硅油中，按照130℃，4kV/mm，20min等工艺极化获得所述的压电陶瓷材料。
实施例5：
1)化学通式为0.04Pb(Mg1/3Nb2/3)-0.03Pb(Sb1/2Nb1/2)-0.03Pb(Zn1/3Nb2/3)-0.9Pb(Zr0.52Ti0.48)
，简写为0.04PMN-0.03PSN-0.03PZN-0.9PZT添加0.1％LiF+1％Co2O3+0.1％SrCO3；
2)按1)中的化学通式将Pb3O4、MgO、Nb2O5三种原料粉体混合在1000℃预烧4h得到Pb(Mg1/3Nb2/3)，简称PMN陶瓷先驱体粉体；将Pb3O4、Sb2O5、Nb2O5三种原料粉体混合在1000℃预烧4h后得到Pb(Sb1/2Nb1/2)，简称PSN陶瓷先驱体粉体；
3)根据1)中化学通式中的化学计量比计算称量步骤2)中所述的PMN陶瓷先驱体粉体，以及Pb3O4、ZnO、Nb2O5、ZrO2、TiO2、等原料粉体，得到混合粉体A。将混合粉体A球磨均匀后在1050℃预烧2h，预烧粉料按照质量百分比加入LiF、Co2O3、SrCO3以及PSN陶瓷先驱体粉体等原料粉体，混合均匀后得到混合粉体B。
4)混合粉体B经过球磨、烘干、等静压、在Pb气氛中950℃保温3h后，将烧结后的陶瓷切片得到压电陶瓷片，采用丝网印刷工艺在陶瓷片上制备Ag电极，将刷好Ag电极的陶瓷片置于烧银炉中烧银，烧银温度870℃，保温20min。
5)将烧银后的陶瓷片置于高温硅油中，按照140℃，5kV/mm，30min等工艺极化获得所述的压电陶瓷材料。
图1为本发明实施例5制备的压电陶瓷表面XRD图谱，由图1可以看出，压电陶瓷无杂相产生，为钙钛矿结构，且陶瓷结晶度较好。
图2为本发明实施例5制备的压电陶瓷断面SEM图谱，从图2可以看出，陶瓷晶粒尺寸在1～2μm，晶粒大小均匀，气孔少，陶瓷具有较高的致密度。
图3为本发明实施例5制备的压电陶瓷压电性能图，d33均>500pC/N，性能公差±10％。
图4为本发明实施例5制备的压电陶瓷居里温度图，Tc>250℃。
本发明的低温烧结压电陶瓷材料通过调整陶瓷配方以及添加组合掺杂剂，可以将陶瓷的烧结温度从1200℃降至850～950℃，并能获得大的压电常数(d33≥500pC/N)、大的机电耦合系数(kp≥0.65)、以及较高居里点(Tc>250℃)及适中的介电常数(εr＝2000～4000)，可以满足叠层压电致动器共烧工艺对陶瓷材料的应用要求。而压电陶瓷材料烧结温度的降低，有利于降低叠层压电驱动器件的制作成本，提高器件制作的成品率，有利于低温烧结压电陶瓷材料的工业化推广使用；同时可以降低叠层器件中Ag-Pd内电极中Pd的含量，从而降低器件制作成本，综上所述本发明具有重要意义。
尽管这里参照本发明的解释性实施例对本发明进行了描述，上述实施例仅为本发明较佳的实施方式，本发明的实施方式并不受上述实施例的限制，应该理解，本领域技术人员可以设计出很多其他的修改和实施方式，这些修改和实施方式将落在本申请公开的原则范围和精神之内。

Claims (7)

1.一种用于叠层致动器的低温共烧压电陶瓷材料，其特征在于：其化学通式为aPb(Mg1/3Nb2/3)-bPb(Sb1/2Nb1/2)-cPb(Zn1/3Nb2/3)-dPb(Zr0.52Ti0.48)+x％LiF+y％MuOv+z％SrCO3，式中M为第一过渡系金属元素，其中0.03≤a≤0.06；0.01≤b≤0.03；0.005≤c≤0.03；0.80≤d≤0.95，0<x≤0.2，0<y≤1，0<z≤0.2；PMN-PSN-PZN-PZT为基体陶瓷粉体，LiF、MuOv、SrCO3为陶瓷材料配方中的辅料，x％、y％、z％分别表示对应的化合物占基体陶瓷粉体的质量百分比，u和v的数值取决于金属元素M的化合价，且u和v为整数，M为金属元素Fe、Co、Ni中的一种；
所述的用于叠层致动器的低温共烧压电陶瓷材料的制备方法，包括以下步骤：
步骤1：将Pb3O4、MgO、Nb2O5三种原料粉体混合预烧后得到Pb(Mg1/3Nb2/3)，即PMN陶瓷先驱体粉体；将Pb3O4、Sb2O5、Nb2O5三种原料粉体混合预烧后得到Pb(Sb1/2Nb1/2)，即PSN陶瓷先驱体粉体，备用；
步骤2：按照化学通式，根据化学计量比计算称量步骤1中所述的PMN陶瓷先驱体粉体，以及Pb3O4、ZnO、Nb2O5、ZrO2、TiO2原料粉体，得到混合粉体A；将混合粉体A球磨均匀后预烧，预烧粉料按照质量百分比加入LiF、MuOv、SrCO3以及PSN陶瓷先驱体粉体等原料粉体，混合均匀后得到混合粉体B，混合粉体B经过球磨、烘干、等静压、烧结、切片工艺获得所述的压电陶瓷材料。
2.如权利要求1中所述的用于叠层致动器的低温共烧压电陶瓷材料，其特征在于，在步骤1中所述的PMN陶瓷先驱体粉体和PSN陶瓷先驱体粉体的预烧温度均为900～1000℃，保温时间为2～4h。
3.如权利要求1中所述的用于叠层致动器的低温共烧压电陶瓷材料，其特征在于，在步骤2中混合粉体A的预烧温度为1000～1050℃，保温时间为1～2h，且混合粉体A预烧后再按化学计量比加入PSN陶瓷先驱体粉体及辅料。
4.如权利要求1中所述的用于叠层致动器的低温共烧压电陶瓷材料，其特征在于，在步骤2中混合粉体B不需要造粒，球磨烘干后，直接等静压成型为棒料，棒料在铅气氛中密封烧结，所述烧结温度为850～950℃，保温时间为2～3h。
5.如权利要求1中所述的用于叠层致动器的低温共烧压电陶瓷材料，其特征在于，在步骤2中烧结、切片工艺后还包括陶瓷片被银以及极化工艺：在所述陶瓷片表面丝网印刷银浆，被银后的陶瓷片烧银后进行极化。
6.如权利要求5所述的用于叠层致动器的低温共烧压电陶瓷材料，其特征在于，所述烧银温度为820～870℃，保温时间为20～30min。
7.如权利要求5所述的用于叠层致动器的低温共烧压电陶瓷材料，其特征在于，所述极化的条件包括：极化温度为100～140℃，极化电压为3～5kV/mm，极化时间为20～40min。
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