CN115504783B - 一种knn基无铅压电陶瓷及其制备方法 - Google Patents

一种knn基无铅压电陶瓷及其制备方法 Download PDF

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CN115504783B
CN115504783B CN202211309474.5A CN202211309474A CN115504783B CN 115504783 B CN115504783 B CN 115504783B CN 202211309474 A CN202211309474 A CN 202211309474A CN 115504783 B CN115504783 B CN 115504783B
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knn
piezoelectric ceramic
polarization
ball milling
based lead
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王宇东
刘曼丽
方映杰
马正阳
吴智
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Hunan Yizhong Electronic Ceramic Technology Co ltd
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Abstract

本发明涉及陶瓷材料领域，具体为一种KNN基无铅压电陶瓷及其制备方法，其化学结构式如下所示：(Na0.5K0.5)Nbx(TayZr1‑y)1‑xO3‑αLMnO3‑βMgAl2O4‑γ氧化物助剂，其中，x、y为摩尔比；α、β、γ为摩尔分数；x为0.85‑0.95，y为0.5‑0.67，α为0.2‑0.6％，β为0.5‑1％，γ为1‑5％；L为稀土元素，本发明所制备的KNN基无铅压电陶瓷具有较大的体积密度，各项性能优良，可以满足压电陶瓷器件应用的要求。

Description

一种KNN基无铅压电陶瓷及其制备方法
技术领域
本发明涉及陶瓷材料领域，具体涉及一种KNN基无铅压电陶瓷及其制备方法。
背景技术
压电陶瓷是一种能够将机械能和电能转换的具有压电效应的功能材料，广泛应用于电子、机械等各种领域，目前大规模使用的压电陶瓷材料体系主要是铅基压电陶瓷。铅基压电陶瓷具有优异的压电性能，并且可以通过掺杂取代来调节其性能以满足不同需求，但是这些陶瓷材料中含有大量对人体和环境有害的铅，目前环境保护问题日益引起人们的关注，压电陶瓷材料将最终实现无铅化，因而环境友好型无铅压电陶瓷成为研究的热点。
其中铌酸钾钠基无铅压电陶瓷以其相对优越的压电性能和较高的居里温度倍受关注，但是由于自身存在采用传统陶瓷工艺难烧结致密等问题。为了解决该缺陷、优化其性能、拓宽其应用范围，对其进行成分调控改性成为目前国内外科研工作者的研究热点。
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KNN基无铅压电陶瓷及其制备方法。
本发明所采用的技术方案如下：
一种KNN基无铅压电陶瓷，其化学结构式如下所示：
(Na0.5K0.5)Nbx(TayZr1-y)1-xO3-αLMnO3-βMgAl2O4-γ氧化物助剂
其中，x、y为摩尔比；
α、β、γ为摩尔分数；
x为0.85-0.95，y为0.5-0.67，α为0.2-0.6％，β为0.5-1％，γ为1-5％；
L为稀土元素。
进一步地，x为0.9-0.95，y为0.5-0.6。
进一步地，x为0.95，y为0.52。
进一步地，α为0.3-0.5％，β为0.8-1％，γ为2-3％。
进一步地，α为0.5％，β为0.8％，γ为2.5％
进一步地，L为La、Y、Er、Ho、Tm、Lu、Yb中的任意一种或多种。
进一步地，所述氧化物助剂为CuO、ZnO、MnO、CoO、Cr2O3、Li2O中的任意一种或多种。
本发明还提供了一种KNN基无铅压电陶瓷的制备方法：
按照化学结构式称量干燥后的碳酸钠、碳酸钾、五氧化二铌、氧化钽、氧化锆、LMnO3、MgAl2O4、氧化物助剂混合后球磨并烘干，得到混合物料，混合物料预烧后再次球磨并烘干，加入粘结剂造粒，采用模压法压制成坯，所得坯体在620-650℃保温排胶30-60min后，升温至1100-1150℃保温烧结1-2h，将烧结后的陶瓷两侧表面被银并高压极化。
进一步地，预烧温度为750-800℃，预烧时间为1-2h。
进一步地，高压极化在110-120℃的硅油中进行，极化电压为3-4kV/mm，极化时间为20-30min。
有益效果：
本发明提供了一种KNN基无铅压电陶瓷，KNN陶瓷中B位由Ta和Zr取代，在KNN基陶瓷中建立了类似PZT中的MPB，从而增强了陶瓷的性能，而且产生晶格畸变有利于晶胞自发极化转向，从而改善其极化特点，最终提高其压电活性，LMnO3和氧化物助剂在固相烧结中可与主晶相形成固溶体促进缺陷增加，促进颗粒重排，提高了晶界迁移率，使气孔充分排出，促进晶粒的发育，提高坯体的致密度，降低烧结温度并抑制Na和K在烧结过程中的挥发，近年来，研究者通过掺杂尖晶石第二相来改善钙钛矿结构陶瓷的介电性能，发明人尝试将尖晶石型MgAl2O4对KNN基陶瓷进行掺杂，第二相的钉扎作用影响了烧结时的传质过程和晶界迁移，抑制了大晶粒生长，使晶粒尺寸趋于均匀致密，获得较好的压电、介电性能，经测试，本发明所制备的KNN基无铅压电陶瓷具有较大的体积密度，各项性能优良，可以满足压电陶瓷器件应用的要求。
附图说明
图1为本发明实施例1所制备KNN基无铅压电陶瓷的表面SEM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KNN基无铅压电陶瓷，其化学结构式如下所示：
(Na0.5K0.5)Nb0.95(Ta0.52Zr0.48)0.05O3-0.5％LaMnO3-0.8％MgAl2O4-2.5％CuO
上述KNN基无铅压电陶瓷的制备方法如下：
按照化学结构式称量干燥后的碳酸钠、碳酸钾、五氧化二铌、氧化钽、氧化锆、LaMnO3、MgAl2O4、CuO混合后加入行星球磨机中，以无水乙醇为球磨介质，球磨16h，球磨转速为160r/min，球磨后50℃烘干，得到混合物料，混合物料780℃预烧1.5h后再次球磨8h并烘干，加入质量分数8％的聚乙烯醇溶液造粒，采用模压法压制成坯，压制压力为200MPa，所得坯体在650℃保温排胶50min后，升温至1135℃保温烧结1.5h，将烧结后的陶瓷两侧表面被银，在120℃的硅油中进行高压极化，极化电压为3kV/mm，极化时间为25min。
实施例2：
一种KNN基无铅压电陶瓷，其化学结构式如下所示：
(Na0.5K0.5)Nb0.95(Ta0.52Zr0.48)0.05O3-0.5％LaMnO3-0.8％MgAl2O4-2.5％CuO
上述KNN基无铅压电陶瓷的制备方法如下：
按照化学结构式称量干燥后的碳酸钠、碳酸钾、五氧化二铌、氧化钽、氧化锆、LaMnO3、MgAl2O4、CuO混合后加入行星球磨机中，以无水乙醇为球磨介质，球磨16h，球磨转速为160r/min，球磨后50℃烘干，得到混合物料，混合物料800℃预烧2h后再次球磨8h并烘干，加入质量分数8％的聚乙烯醇溶液造粒，采用模压法压制成坯，压制压力为200MPa，所得坯体在650℃保温排胶60min后，升温至1150℃保温烧结2h，将烧结后的陶瓷两侧表面被银，在120℃的硅油中进行高压极化，极化电压为4kV/mm，极化时间为30min。
实施例3：
一种KNN基无铅压电陶瓷，其化学结构式如下所示：
(Na0.5K0.5)Nb0.95(Ta0.52Zr0.48)0.05O3-0.5％LaMnO3-0.8％MgAl2O4-2.5％CuO
上述KNN基无铅压电陶瓷的制备方法如下：
按照化学结构式称量干燥后的碳酸钠、碳酸钾、五氧化二铌、氧化钽、氧化锆、LaMnO3、MgAl2O4、CuO混合后加入行星球磨机中，以无水乙醇为球磨介质，球磨16h，球磨转速为160r/min，球磨后50℃烘干，得到混合物料，混合物料750℃预烧1h后再次球磨8h并烘干，加入质量分数8％的聚乙烯醇溶液造粒，采用模压法压制成坯，压制压力为200MPa，所得坯体在620℃保温排胶30min后，升温至1100℃保温烧结1h，将烧结后的陶瓷两侧表面被银，在110℃的硅油中进行高压极化，极化电压为3kV/mm，极化时间为20min。
实施例4：
一种KNN基无铅压电陶瓷，其化学结构式如下所示：
(Na0.5K0.5)Nb0.95(Ta0.52Zr0.48)0.05O3-0.5％LaMnO3-0.8％MgAl2O4-2.5％CuO
上述KNN基无铅压电陶瓷的制备方法如下：
按照化学结构式称量干燥后的碳酸钠、碳酸钾、五氧化二铌、氧化钽、氧化锆、LaMnO3、MgAl2O4、CuO混合后加入行星球磨机中，以无水乙醇为球磨介质，球磨16h，球磨转速为160r/min，球磨后50℃烘干，得到混合物料，混合物料800℃预烧1h后再次球磨8h并烘干，加入质量分数8％的聚乙烯醇溶液造粒，采用模压法压制成坯，压制压力为200MPa，所得坯体在650℃保温排胶30min后，升温至1150℃保温烧结1h，将烧结后的陶瓷两侧表面被银，在120℃的硅油中进行高压极化，极化电压为3kV/mm，极化时间为30min。
实施例5：
一种KNN基无铅压电陶瓷，其化学结构式如下所示：
(Na0.5K0.5)Nb0.95(Ta0.52Zr0.48)0.05O3-0.5％LaMnO3-0.8％MgAl2O4-2.5％CuO
上述KNN基无铅压电陶瓷的制备方法如下：
按照化学结构式称量干燥后的碳酸钠、碳酸钾、五氧化二铌、氧化钽、氧化锆、LaMnO3、MgAl2O4、CuO混合后加入行星球磨机中，以无水乙醇为球磨介质，球磨16h，球磨转速为160r/min，球磨后50℃烘干，得到混合物料，混合物料750℃预烧2h后再次球磨8h并烘干，加入质量分数8％的聚乙烯醇溶液造粒，采用模压法压制成坯，压制压力为200MPa，所得坯体在620℃保温排胶60min后，升温至1150℃保温烧结2h，将烧结后的陶瓷两侧表面被银，在110℃的硅油中进行高压极化，极化电压为4kV/mm，极化时间为20min。
对比例1
与实施例1基本相同，区别在于，没有用Ta和Zr取代Nb，KNN基无铅压电陶瓷的化学结构式如下所示：
(Na0.5K0.5)NbO3-0.5％LaMnO3-0.8％MgAl2O4-2.5％CuO
对比例2
与实施例1基本相同，区别在于，不含LaMnO3。
对比例3
与实施例1基本相同，区别在于，不含MgAl2O4。
对比例4
与实施例1基本相同，区别在于，不含CuO。
性能测试：
以本发明实施例1-5及对比例1-4中所制备的KNN基无铅压电陶瓷作为样品进行性能测试；
根据阿基米德原理测试并计算得到的样品的体积密度；
采用ZJ-3AN型准静态d33测试仪测量样品的压电常数；
采用精密阻抗分析仪(Agilent HP4294A)分析试样的机电耦合系数kp及机械品质因数Qm，其中，压电应变常数d33越大表示压电性能越高，机械品质因数Qm越大表示压电陶瓷在共振振动时的损失越小；
机电耦合系数kp表示压电振子在振动过程中，将机械能转变为电能，或将电能转变为机械能的能效比例；
用Tonghui 2817测量陶瓷介电性能，测试温度为室温至400℃，测试频率1kHz。
测试结果如下表1所示：
表1：
Figure BDA0003906677450000061
Figure BDA0003906677450000071
由上表1可知，本发明所制备的KNN基无铅压电陶瓷具有较大的体积密度，各项性能优良，可以满足压电陶瓷器件应用的要求。
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 (2)

1.一种KNN基无铅压电陶瓷，其特征在于，其化学结构式如下所示：
(Na0.5K0.5)Nbx(TayZr1-y)1-xO3-α LaMnO3-β MgAl2O4-γ CuO
其中，x、y为摩尔比；
α、β、γ为摩尔分数；
x为0.95，y为0.52，α为0.5%，β为0.8%，γ为2.5%；
所述KNN基无铅压电陶瓷的制备方法如下：
按照化学结构式称量干燥后的碳酸钠、碳酸钾、五氧化二铌、氧化钽、氧化锆、LaMnO3、MgAl2O4、CuO混合后球磨并烘干，得到混合物料，混合物料预烧后再次球磨并烘干，所述混合物料的预烧温度为750-800℃，预烧时间为1-2h，再加入粘结剂造粒，采用模压法压制成坯，所得坯体在620-650℃保温排胶30-60min后，升温至1100-1150℃保温烧结1-2h，将烧结后的陶瓷两侧表面被银并高压极化。
2.如权利要求1所述的KNN基无铅压电陶瓷，其特征在于，高压极化在110-120℃的硅油中进行，极化电压为3-4kV/mm，极化时间为20-30min。
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