CN111875389A - 一种无铅压电陶瓷性能调控的方法 - Google Patents

一种无铅压电陶瓷性能调控的方法 Download PDF

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CN111875389A
CN111875389A CN202010810251.1A CN202010810251A CN111875389A CN 111875389 A CN111875389 A CN 111875389A CN 202010810251 A CN202010810251 A CN 202010810251A CN 111875389 A CN111875389 A CN 111875389A
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刘佳
马翠英
康乐
杜慧玲
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Xian University of Science and Technology
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Abstract

本发明涉及新型功能材料开发技术领域，具体涉及一种无铅压电陶瓷性能调控的方法，该方法在传统无铅压电陶瓷的基础上通过构筑高熵陶瓷并以其为主晶相，在其与第二相（或更多相）的准同型相界处，通过调整第二相（或更多相）含量对其综合性能进行优化。具体为：采用离子半径差优选高熵元素制备高熵陶瓷，第二相（或更多相）的含量可选取未高熵化无铅压电陶瓷与其准同型相界的±0.5处，经过球磨混合均匀后在1000oC~1500oC烧结范围内烧结2~6小时，获得综合性能优异的无铅压电陶瓷。本发明为无铅压电陶瓷提供了一种全新的性能调控方法，利用高熵陶瓷优异的介电性能，实现了高熵陶瓷在压电陶瓷领域中对其综合性能调控的应用。

Description

一种无铅压电陶瓷性能调控的方法
技术领域
本发明涉及新型功能材料开发技术领域，具体涉及一种无铅压电陶瓷性能调控的方法。
背景技术
铅基压电陶瓷由于其优异的压电、介电和铁电性能而广泛应用于震荡器、谐振器、换能器和储能器等领域。但是其主要成分为氧化铅（60~70%），从而对人类和生态环境造成了严重的损害。因此，研究开发高性能的无铅压电陶瓷具有非常重要的科学意义和紧迫的市场需求。目前，对无铅压电陶瓷的研究主要集中在铋层状压电陶瓷、钨青铜型无铅压电陶瓷和钙钛矿型无铅压电陶瓷等方面。但是与铅基压电陶瓷相比，无铅压电陶瓷无论在压电、介电还是铁电性能等方面都相差较远。因此，在实际应用中对无铅压电陶瓷性能的改善主要是将其于其他相关材料混合制备固溶体以提高其综合性能。目前，主要的研究方法有两种：一种是采用元素掺杂；另一种是引入第二相材料，通过寻找其与引入材料的准同型相界（MPB）对其综合性能进行调控。
高熵陶瓷是由高熵合金发展而来的一种新型陶瓷，可定义为由五种或五种以上组元等摩尔比或近等摩尔比混合后在高温下所获得的单相陶瓷，其构型熵大于1.61R（R为气体常数）。由于高熵陶瓷固有的原子序、组成的复杂性和明显的晶格畸变性，使其在材料硬度、导热率和耐蚀性等方面表现出独特的性能。特别是近年来对高熵功能材料的深入研究发现，高熵陶瓷呈现出特有的巨介电效应，从而为新型功能陶瓷的开发指明了方向。
目前传统采用元素掺杂改性或寻找准同型相界的方法来提高压电陶瓷的综合性能已经遇到瓶颈，如何进一步获得高性能压电陶瓷是目前的研究热点。因此，从高熵陶瓷的角度出发研究一种新型体系压电陶瓷性能的调控方法对高性能压电陶瓷的应用具有重要的科学意义。
发明内容
为解决上述问题，本发明提供了一种无铅压电陶瓷性能调控的方法，通过优选高熵组元，制备具有优异性能的高熵陶瓷并在其与其他相（第二相或更多相）的准同型相界附近调控其综合性能，从而实现高性能压电陶瓷的可控制备。
为实现上述目的，本发明采取的技术方案为：
一种无铅压电陶瓷性能调控的方法，包括如下步骤：
S1、高熵陶瓷原始粉体的配制：
采用离子尺寸差对所设计的高熵陶瓷进行高熵组元元素优选，将所选取的高熵组元前驱材料置于烘箱内，70oC~120oC干燥处理4~6 h，去除所含水分；
然后按照所设计的高熵陶瓷化学式计算高熵组元前驱材料的精确用量，并采用精度为0.01mg的分析天平分别称取所述前驱材料；
S2、将所称取的前驱材料置于球磨机内，球磨混合24h，烘干，得粉体材料；
S3、将所得的粉体材料800oC~950oC热处理2~6 h后，进行二次球磨，得高熵陶瓷粉；
S4、基于准同型相界实现性能调控：以所得的高熵陶瓷粉为主晶相，引入其他相，通过寻找准同型相界对其进行性能调控；
S5、将引入的其他相烘干后，采用精度为0.01mg的分析天平称取其他相，与所得的高熵陶瓷在其准同型相界附近进行混合，得混合料；
S6、将所得的混合料置于球磨机中，球磨混合24h后，烘干，造粒，压片成型，得高熵陶瓷预烧结坯体；
S7、采用箱式炉对高熵陶瓷预烧坯体进行烧结，具体烧结工艺参数为：从室温以5oC/min升温至目标温度1000oC~1500oC并保温2~6 h，再以2oC/min~10oC/min的降温速率，降温至室温，即得综合性能优异的压电陶瓷。
进一步地，所述无铅压电陶瓷为铋层状压电陶瓷、钨青铜型无铅压电陶瓷或钙钛矿型无铅压电陶瓷。
进一步地，所述其他相为碳酸钡、钛酸钡、碳酸锶、钛酸锶、铌酸钾、铌酸钠钾或钛酸铋钠中的一种或多种。
进一步地，所述步骤S2中，采用行星式球磨机、振摆球磨机或简易的滚筒球磨机实现球磨。
本发明通过采用离子尺寸差构筑高熵压电陶瓷，并在其与第二相（或更多相）的准同型相界附控制第二相（或更多相）的引入量，使得：（1）采用离子尺寸差对高熵元素进行优选，确保单相高熵陶瓷的形成；（2）高熵陶瓷热力学上的高熵效应促进了多组元在等摩尔比混合的情况下形成了单相结构陶瓷；（3）高熵陶瓷动力学上的迟滞扩散效应促进了单相高熵陶瓷在室温下的稳定性；（4）高熵陶瓷晶格上的畸变性使陶瓷晶胞正负电荷中心发生偏移，使其具有独有自发极化机制；（5）高熵陶瓷性能上的鸡尾酒效应使其性能具有极大的可设计性；（6）在高熵陶瓷与第二相（或更多相）的准同型相界附近因为电畴极化方向多，在电场力的作用下沿电场方向容易定向，使极化变化更容易，从而具有优异的综合性能。
本发明为无铅压电陶瓷提供了一种全新的性能调控方法，利用高熵陶瓷优异的介电性能，实现了高熵陶瓷在压电陶瓷领域中对其综合性能调控的应用。高熵陶瓷独特的鸡尾酒效应可完成对特殊性能要求的材料进行设计；所使用的前驱材料均为无铅材料，对环境无危害；实施过程简单易行，对设备没有特殊要求。
附图说明
图1为 0.94BNSCMT-0.06BT高熵陶瓷的显微形貌。
图2 为0.94BNSCMT-0.06BT高熵陶瓷的元素分布图。
图3 为0.94BNSCMT-0.06BT高熵陶瓷的XRD图谱。
图4为 0.94BNSCMT-0.06BT高熵陶瓷的介电温谱：(a) 相对介电常数；(b) 介电损耗。
图5为 0.94BNSCMT-0.06BT高熵陶瓷的电滞回线。
图6为 0.89BNSCMT-0.06BT-0.05KN高熵陶瓷的显微形貌。
图7为 0.89BNSCMT-0.06BT-0.05KN高熵陶瓷的元素分布图。
图8 为0.89BNSCMT-0.06BT-0.05KN高熵陶瓷的电滞回线。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
S1、以钛酸铋钠（Bi0.5Na0.5TiO3，BNT）基无铅压电陶瓷为主晶相，针对BNT结构（ABO3）中的A位进行高熵化处理，采用离子尺寸差δ(R A )可进行相关元素优选，离子尺寸差计算公式如式（1）所示：
Figure DEST_PATH_IMAGE001
式（1）
其中， R Ai 是高熵陶瓷A位阳离子离子半径，c i 是高熵陶瓷A位阳离子离子浓度。当δ(R A )＜～6.5%，可形成单相高熵陶瓷。本案例经计算可选择Bi、Na、Sr、Ca、Mg为A位高熵组元，其δ (R A )=6.2%；
S2、分别选取Bi2O3、Na2CO3、SrCO3、CaCO3、MgCO3和TiO2作为前驱材料，置于烘箱内，70oC~120oC烘干处理4~6h，去除所含水分，按照化学式Bi0.2Na0.2Sr0.2Ca0.2Mg0.2TiO3（BNSCMT）计算所需前驱材料用量，并采用精度为0.01mg的分析天平精确称量前驱材料；
S3、将称得前驱材料置于玛瑙球磨罐中，以玛瑙球为研磨球，无水乙醇为球磨介质，球、料和酒精比：6:1:1.2，球磨参数：300 转/分钟，采用行星式球磨机球磨24h后烘干，得粉体材料；
S4、将所得的粉体材料置于坩埚中，采用箱式炉， 800oC热处理4h后，进行二次球磨，获得BNSCMT高熵粉体；
S5、将钛酸钡烘干后，采用精度为0.01mg的分析天平精确称量钛酸钡用
量，在BNT与钛酸钡（BaTiO3，BT）的准同型相界处制备0.94BNSCMT-0.06BT
高熵陶瓷；
S7、将高熵粉体与钛酸钡混合料置于玛瑙球磨罐中，以玛瑙球有研磨球，无水乙醇为球磨介质，球、料和酒精比：6:1:1.2，球磨参数：300 转/分钟，采用行星式球磨机球磨24h后，采用冷冻干燥法烘干物料；
S8、采用聚乙烯醇（PVB）作为造粒剂，对所得干燥的混合料造粒过筛后，采用冷等静压成型，得预烧坯体尺寸为：φ10 × 0.2 mm；
S9、采用箱式炉对高熵陶瓷预烧坯体进行烧结，具体烧结工艺参数为：从室温以5oC/min升温至1250oC）并保温2h，再以10oC/min的降温速率，降温至室温，即得综合性能优异的压电陶瓷。
采用扫描电镜（SEM）结合能谱（EDS）对所获得0.94BNSCMT-0.06BT高熵陶瓷的微观形貌和元素分布进行分析可知，烧结后陶瓷晶粒尺寸大约为2微米左右，从元素的能谱面分布图可见，所有高熵元素均匀分布于陶瓷内部，无元素偏析现象；
采用X-射线衍射仪（XRD）对所获得0.94BNSCMT-0.06BT高熵陶瓷的物相结构进行分析可知，所制备的高熵陶瓷为单相立方钙钛矿结构，并且与标准立方钙钛矿结构卡片（PDF#31-0174）对比，其衍射峰均向高角度发生了偏移，说明其晶格结构缩小。
从0.94BNSCMT-0.06BT高熵陶瓷的介电温谱可以看到，通过对BNT陶瓷进行高熵化处理其相对介电常数得到了明显提高，介电损耗较小。
从0.94BNSCMT-0.06BT高熵陶瓷的电滞回线可以看出其呈典型的瘦长状，也证明了其损耗较小，经计算可得其储能密度为0.792 J/cm3，储能效率高达91%。
实施例2
在实施例1的基础上于BNT、BT和铌酸钾（KNbO3，KN）的准同型相界处设计三元高熵陶瓷体系，得到0.89BNSCMT-0.06BT-0.05KN高熵陶瓷，其制备工艺流程与实施例1相同，其烧结温度为1100oC，保温2h。
从0.89BNSCMT-0.06BT-0.05KN高熵陶瓷的微观形貌上可见，其晶粒尺寸大约为2微米左右，且尺寸分布均匀。
从0.89BNSCMT-0.06BT-0.05KN高熵陶瓷的元素分布图上可见，所选取的高熵元素均匀分散在陶瓷内部，无偏析现象出现。
从0.89BNSCMT-0.06BT-0.05KN高熵陶瓷的电滞回线上可见，其储能密度为0.684J/cm3，储能效率为90.5%。。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变化或修改，这并不影响本发明的实质内容。在不冲突的情况下，本申请的实施例和实施例中的特征可以任意相互组合。

Claims (4)

1.一种无铅压电陶瓷性能调控的方法，其特征在于：包括如下步骤：
S1、高熵陶瓷原始粉体的配制：
采用离子尺寸差对所设计的高熵陶瓷进行高熵组元元素优选，将所选取的高熵组元前驱材料置于烘箱内，70oC~120oC干燥处理4~6 h，去除所含水分；
然后按照所设计的高熵陶瓷化学式计算高熵组元前驱材料的精确用量，并采用精度为0.01mg的分析天平分别称取所述前驱材料；
S2、将所称取的前驱材料置于球磨机内，球磨混合24h，烘干，得粉体材料；
S3、将所得的粉体材料800oC~950oC热处理2~6 h后，进行二次球磨，得高熵陶瓷粉；
S4、基于准同型相界实现性能调控：以所得的高熵陶瓷粉为主晶相，引入其他相，通过寻找准同型相界对其进行性能调控；
S5、将引入的其他相烘干后，采用精度为0.01mg的分析天平称取其他相，与所得的高熵陶瓷在其准同型相界附近进行混合，得混合料；
S6、将所得的混合料置于球磨机中，球磨混合24h后，烘干，造粒，压片成型，得高熵陶瓷预烧结坯体；
S7、采用箱式炉对高熵陶瓷预烧坯体进行烧结，具体烧结工艺参数为：从室温以5oC/min升温至目标温度1000oC~1500oC并保温2~6 h，再以2oC/min~10oC/min的降温速率，降温至室温，即得综合性能优异的压电陶瓷。
2.如权利要求1所述的一种无铅压电陶瓷性能调控的方法，其特征在于：所述无铅压电陶瓷为铋层状压电陶瓷、钨青铜型无铅压电陶瓷或钙钛矿型无铅压电陶瓷。
3.权利要求1所述的一种无铅压电陶瓷性能调控的方法，其特征在于：所述其他相为碳酸钡、钛酸钡、碳酸锶、钛酸锶、铌酸钾、铌酸钠钾或钛酸铋钠中的一种或多种。
4.根据权利要求1所述的一种无铅压电陶瓷性能调控的方法，其特征在于：所述步骤S2中，采用行星式球磨机、振摆球磨机或简易的滚筒球磨机实现球磨。
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