CN115286380B - 一种具有高退极化温度的bnkt-bt基复合陶瓷材料及其制备方法 - Google Patents

一种具有高退极化温度的bnkt-bt基复合陶瓷材料及其制备方法 Download PDF

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CN115286380B
CN115286380B CN202210932514.5A CN202210932514A CN115286380B CN 115286380 B CN115286380 B CN 115286380B CN 202210932514 A CN202210932514 A CN 202210932514A CN 115286380 B CN115286380 B CN 115286380B
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bnkt
temperature
ceramic material
composite ceramic
based composite
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CN115286380A (zh
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盛立远
张兴儒
王巧莉
肖忆楠
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Peking University Shenzhen Graduate School
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Peking University Shenzhen Graduate School
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Abstract

本发明公开一种具有高退极化温度的BNKT‑BT基复合陶瓷材料及其制备方法，属于电子材料压电陶瓷技术领域。该BNKT‑BT基复合陶瓷材料的化学通式为：0.85(Bi0.5Na0.5)TiO3‑0.11(Bi0.5K0.5)TiO3‑0.04BaTiO3‑xZnO，其中，0.1≤x≤0.3。该复合陶瓷材料以BNKT‑BT陶瓷作为基体，单相ZnO嵌入基体中间形成0‑3型复合结构。该材料不仅具有较高的退极化温度和较好的压电性能，其漏电流效应也能得到很好的抑制。

Description

一种具有高退极化温度的BNKT-BT基复合陶瓷材料及其制备 方法
技术领域
本发明属于电子材料压电陶瓷技术领域，具体涉及一种具有高退极化温度的BNKT-BT基复合陶瓷材料及其制备方法。
背景技术
随着物联网等新应用的出现，以不同形式的能量作为载体的信息交互变得越来越频繁，而高性能功能材料是保证交互可靠的关键。压电陶瓷是一类特殊的功能材料，通过压电效应使电能和机械能相互转化，在振荡器、滤波器等多种器件中实现电-声耦合。在当前器件微型化的发展趋势下，通过压电陶瓷完成的微小位移精密控制技术成为微机电系统集成的基础。广阔的应用背景催生了庞大的压电陶瓷商业市场，其中含铅陶瓷由于优异的电学性能占据了该市场的绝大部分份额。虽然铅基陶瓷的广泛应用促进了技术的进步，但生产制造和废物处理过程中，毒性铅元素的排放严重污染了生态环境。随着全球主要国家和组织相继通过立法来限制铅基陶瓷的应用，新型无铅替代产品的开发已成为相关产业的当务之急。
在众多可选择的无铅替代材料中，钙钛矿型(Bi0.5Na0.5)TiO3(BNT)基陶瓷由于优异的机电耦合性能被认为是最具潜力的无铅体系之一。目前BNT基陶瓷在应用方面还存在一个严重不足，即升温过程中会出现退极化现象。退极化现象是指陶瓷在升温过程中不稳定电畴持续分解直至极化消失的现象，是陶瓷由铁电相向遍历弛豫相转化所引起的。退极化性能的优异程度可用退极化温度Td进行定量比较，该温度反映了陶瓷能保持微弱压电性的高温极限。大量研究表明，典型的BNT基陶瓷退极化温度多在100℃以下，因此，如何提升退极化温度成为了BNT基陶瓷压电实用化进程中急需突破的一个瓶颈问题。
如果确定BNT基陶瓷退极化现象的成因是无铅压电陶瓷领域的重要基础性问题，目前材料学界普遍认为退极化温度的出现与晶格扭曲导致的随机场有关。由于固溶、掺杂等改性手段通常会加剧晶格扭曲和局域随机电场的改变，所以这类传统改性方法往往无法提高退极化温度。
发明内容
鉴于传统掺杂、固溶改性方式无法有效提高BNT基陶瓷退极化温度的事实，本发明的目的在于提供一种具有高退极化温度的BNKT-BT基复合陶瓷材料及其制备方法。该复合陶瓷材料以BNKT-BT陶瓷作为基体，单相ZnO嵌入基体中间形成0-3型复合结构。该材料不仅具有较高的退极化温度和较好的压电性能，其漏电流效应也能得到很好的抑制。
为实现上述目的，本发明提出如下技术方案：
一种具有高退极化温度的BNKT-BT基复合陶瓷材料，该BNKT-BT基复合陶瓷材料的化学通式为：0.85(Bi0.5Na0.5)TiO3-0.11(Bi0.5K0.5)TiO3-0.04BaTiO3-xZnO，其中，0.1≤x≤0.3。
本发明首先在室温下将四方相BKT和BT与三方相BNT固溶形成BNKT-BT基体，然后与纳米ZnO颗粒混合烧结，形成0-3型复合结构。该复合陶瓷材料保留了三方-四方准同型相界，具有较好的压电性能。
本发明还提供一种具有高退极化温度的BNKT-BT基复合陶瓷材料的制备方法，包括以下步骤：
1)将铋源、钠源、钾源、钛源、钡源依照化学计量比混合，以有机溶剂为介质，采用湿法球磨的方式混合浆料，球磨完毕后取出浆料干燥，得到充分混合的原料粉体进行球磨，在压片机中干压成型，得到原料块体；
2)将原料块体置于氧气氛围中进行预烧，得到BNKT-BT预烧块；
3)将得到的BNKT-BT预烧块进行研磨，得到BNKT-BT预烧粉末，然后依照化学计量比将BNKT-BT预烧粉末与纳米ZnO颗粒混合并进行二次球磨，干燥，得到混合粉体，然后加入粘合剂，静置，压制成型；
4)对压制成型的样品进行研磨，过筛，得到的粉体再次压制成型，得到陶瓷坯体；
5)将陶瓷坯体依次经过加热处理、烧结、打磨抛光，得到ZnO复合BNKT-BT基陶瓷；
6)在ZnO复合BNKT-BT基陶瓷表面涂覆银浆，烧银处理，即得到具有高退极化温度的BNKT-BT基复合陶瓷材料。
进一步地，步骤1)中，所述干压成型时压强为400Mpa，时间为1-3min。
进一步地，步骤2)中，所述预烧温度为820-850℃，时间为3-4h。
进一步地，步骤3)中，所述纳米ZnO颗粒直径为50-80nm。
进一步地，步骤3)中，所述粘合剂为5wt％的聚乙烯醇粘合剂；所述静置时间为12-15h；所述压制成型时压强为600Mpa，时间为3-6min。
进一步地，步骤4)中，所述再次压制成型时压强为400Mpa，时间为1-3min。
进一步地，步骤5)中，所述加热处理温度为550℃，时间为2-3h；所述烧结温度为1030-1070℃，烧结时间为1-1.5h，升温速率为9℃/min。
进一步地，步骤6)中，所述烧银处理温度为550-600℃，时间为40-50min。
与现有技术相比，本发明的有益效果为：
本发明保持了BNKT-BT基体中存在的三方-四方相界，因而基体材料的压电性能得到较好的保持。
本发明利用ZnO富集区域附近晶粒边界应力场对电畴的钉扎效应改善电畴稳定性，基体退极化行为得到明显改善。ZnO复合陶瓷相比纯基体材料退极化温度约有60℃的提升。
本发明采用固相反应法制备，工艺流程易控制，可重复性好，杂相控制较好，产品符合电子陶瓷材料行业需求，具有广阔的市场应用前景。制备的复合陶瓷材料退极化温度高于120℃，压电性能在110℃以下能够保持较好的温度稳定性。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为实施例1-3、对比例1制备的复合陶瓷材料X射线衍射(XRD)图；
图2为实施例2中x＝0.3时制备的0.85(Bi0.5Na0.5)TiO3-0.11(Bi0.5K0.5)TiO3-0.04BaTiO3-0.3ZnO复合陶瓷材料的扫描电镜分析结果：(a)形貌相；(b)Ti元素分布；(c)Bi元素分布；(d)Zn元素分布；
图3为实施例1-3、对比例1制备的复合陶瓷材料在不同频率交流电加载下的介电温谱和损耗谱，其中出现第一个介电反常峰的温度对应于基体的退极化温度Td；
图4为实施例1-3、对比例1制备的复合陶瓷材料的压电常数d33随退火温度的变化图。
具体实施方式
现详细说明本发明的多种示例性实施方式，该详细说明不应认为是对本发明的限制，而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式，并非用于限制本发明。另外，对于本发明中的数值范围，应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明，否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料，但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入，用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时，以本说明书的内容为准。
在不背离本发明的范围或精神的情况下，可对本发明说明书的具体实施方式做多种改进和变化，这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见的。本申请说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等，均为开放性的用语，即意指包含但不限于。
一种具有高退极化温度的BNKT-BT基复合陶瓷材料，该BNKT-BT基复合陶瓷材料的化学通式为：0.85(Bi0.5Na0.5)TiO3-0.11(Bi0.5K0.5)TiO3-0.04BaTiO3-xZnO，其中，0.1≤x≤0.3。
本发明首先在室温下将四方相BKT和BT与三方相BNT固溶形成BNKT-BT基体，之后与纳米ZnO颗粒混合烧结，形成0-3型复合结构。该复合陶瓷材料保留了三方-四方准同型相界，具有较好的压电性能。
本发明还提供一种具有高退极化温度的BNKT-BT基复合陶瓷材料的制备方法，包括以下步骤：
1)将铋源、钠源、钾源、钛源、钡源依照化学计量比混合，以有机溶剂为介质，采用湿法球磨20-24h，球磨机转速为300-400转/min，球磨完毕后取出浆料倒入玻璃培养皿中烘干3h，干燥箱温度105℃，得到干燥的原料粉体；在压片机中将原料粉体压成圆片，圆片直径为30mm，厚度为10mm，压强为400MPa，保压时间1-3min，优选为1min，得到原料块体；
磨球选用玛瑙材质，大、中、小球直径分别为20mm、10mm、6mm，个数按1：20：60配比。
所述铋源为Bi2O3；所述钠源为Na2CO3；所述钾源为K2CO3；所述钛源为TiO2；所述钡源为BaCO3；所述有机溶剂为无水乙醇(加入量为粉末总体积的30-50％，优选为40％)。
2)将原料块体放入箱式低温反应炉中，以3℃/min的速率升温至820-850℃，保温3-4h进行预烧，优选3h，气氛为氧气气氛，得到BNKT-BT预烧块；
3)将得到的BNKT-BT预烧块进行研磨，得到BNKT-BT预烧粉末，然后依照化学计量比将BNKT-BT预烧粉末与纳米ZnO颗粒(平均直径为50-80nm，优选为50nm)混合并进行二次球磨，球磨时间为12h(磨球配比及球磨机参数设置同步骤1)，干燥，得到混合粉体；
按2-3滴/g的速度向混合粉体中添加5wt％的聚乙烯醇粘合剂，充分搅拌后静置12-15h，优选12h，之后用压片机将粉料压成圆片，圆片直径30mm，厚度10mm，压强为600MPa，时间为3-6min，优选5min；
4)对压制成型的样品进行研磨并过筛，滤筛满足GB/T6003.1-2012，只保留研磨粉中直径在75-106μm之间的部分，将得到的粉体压成圆片，圆片直径13mm，厚度1mm，压强为400Mpa，时间为1-3min，优选1min，缓慢减压退模得到陶瓷坯体；
5)将陶瓷坯体放于低温反应炉中，以不高于2℃/min的速率升温至550℃并保温2-3h，排出坯体中水汽及有机物，得到排塑后的陶瓷坯体；
将排塑后的陶瓷坯体放置于高温反应炉中高温烧结，以9℃的速率快速升温至1030-1070℃并保温1-1.5h，之后自然降温至室温，得到陶瓷片；
其中0.1≤x＜0.2时，温度为1050-1070℃；
0.2≤x≤0.3时，温度为1030-1050℃；
对陶瓷片表面进行打磨抛光，得到ZnO复合BNKT-BT基陶瓷；
6)在ZnO复合BNKT-BT基陶瓷表面涂覆高温银浆，在550-600℃(优选560℃)条件下烧银40-50min优选40min，即得到具有高退极化温度的BNKT-BT基复合陶瓷材料。
进一步地，步骤3)中，所述纳米ZnO颗粒直径为50nm。
本发明所用原料Bi2O3(Alfa Aesar，99.9％)，Na2CO3(Acros Organics，99％)，TiO2(Acros Organics，99％)，BaCO3(Alfa Aesar，99％)，K2CO3(Acros Organics 99.9％)，ZnO(Aladdin 99.9％50nm)和无水乙醇。
实施例1
合成0.85(Bi0.5Na0.5)TiO3-0.11(Bi0.5K0.5)TiO3-0.04BaTiO3-xZnO复合陶瓷材料，其中，x＝0.1，具体实施方法如下：
1)将Bi2O3、TiO2、Na2CO3、K2CO3、BaCO3为初始原料，依照化学计量比进行称量，以无水乙醇(加入量为粉末总体积的40％)为介质，湿法球磨20h，球磨机转速为300转/min，球磨完毕后取出浆料倒入玻璃培养皿中烘干3h，干燥箱温度为105℃，得到干燥的原料粉体；
磨球选用玛瑙材质，大、中、小球直径分别为20mm、10mm、6mm，个数按1：20：60配比；
2)在压片机中将原料粉体压成圆片，圆片直径为30mm，厚度为10mm，压强为400MPa，保压时间1min，得到原料块体；
3)将原料块体放入箱式低温反应炉中，以3℃/min的速率升温至820℃，保温3h进行预烧，气氛为氧气气氛，得到BNKT-BT预烧块；
4)将得到的BNKT-BT预烧块进行研磨，得到BNKT-BT预烧粉末，然后依照化学计量比将BNKT-BT预烧粉末与纳米ZnO颗粒(平均直径为50nm)混合并进行二次球磨，球磨时间为12h(磨球配比及球磨机参数设置同步骤1)，球磨完后将浆料放入干燥箱干燥，得到混合粉体；
5)按2滴/g的速度向混合粉体中添加5wt％的聚乙烯醇粘合剂，充分搅拌后静置12h，之后用压片机将粉料压成圆片，圆片直径30mm，厚度10mm，压强为600MPa，时间为5min；
6)对压制成型的样品进行研磨并过筛，滤筛满足GB/T6003.1-2012，只保留研磨粉中直径在75-106μm之间的部分，将得到的粉体压成圆片，圆片直径13mm，厚度1mm，压强为400Mpa，时间为1min，缓慢减压退模得到陶瓷坯体；
7)将陶瓷坯体放于低温反应炉中，以不高于2℃/min的速率升温至550℃并保温3h，排出坯体中水汽及有机物，得到排塑后的陶瓷坯体；
8)将排塑后的陶瓷坯体放置于高温反应炉中高温烧结，以9℃的速率快速升温至1055℃并保温1.2h，之后自然降温至室温，得到陶瓷片；对陶瓷片表面进行打磨抛光，得到ZnO复合BNKT-BT基陶瓷；
9)在ZnO复合BNKT-BT基陶瓷表面涂覆高温银浆，在560℃条件下烧银40min，即得到具有高退极化温度的BNKT-BT基复合陶瓷材料(压电陶瓷振子)。
实施例2
合成0.85(Bi0.5Na0.5)TiO3-0.11(Bi0.5K0.5)TiO3-0.04BaTiO3-xZnO复合陶瓷材料，区别在于，其中，x＝0.3，具体实施方法同实施例1，步骤8)中，温度为1050℃。
实施例3
同实施例2，区别在于，x＝0.2。
对比例1
合成0.85(Bi0.5Na0.5)TiO3-0.11(Bi0.5K0.5)TiO3-0.04BaTiO3复合陶瓷材料，区别在于，其中，x＝0，具体实施方法同实施例1，步骤8)中，温度为1160℃。
图1为实施例1-3、对比例1制备的复合陶瓷材料X射线衍射(XRD)图。
从图1中可以看出，衍射角2θ在40°左右分裂的(003)峰和(021)峰说明存在三方对称性，46°左右分裂的(002)峰和(200)峰说明存在四方对称性。XRD结果证明ZnO复合陶瓷很好的保持了三方—四方准同型相界。
当x＝0.1时，XRD中存在少量纤维锌矿结构的ZnO衍射峰，证明有单相ZnO存在。
当x＝0.2，0.3时，XRD中纤维锌矿结构的ZnO衍射峰明显，且有少量杂相产生。
当x＝0时，XRD中只有一套钙钛矿结构晶格的衍射峰，没有其他杂相出现。
图2为实施例2中x＝0.3时制备的0.85(Bi0.5Na0.5)TiO3-0.11(Bi0.5K0.5)TiO3-0.04BaTiO3-0.3ZnO复合陶瓷材料的扫描电镜分析结果：(a)形貌相；(b)Ti元素分布；(c)Bi元素分布；(d)Zn元素分布。
从图中可以看出，ZnO富集区域孤立的分布在BNKT-BT基体中，形成0-3复合结构(一种压电陶瓷特定的结构)。
图3为x＝0，0.1，0.2，0.3时复合陶瓷材料在不同频率交流电加载下的介电温谱和损耗谱，其中出现第一个介电反常峰的温度对应于基体的退极化温度Td。(a)x＝0；(b)x＝0.1；(c)x＝0.2；(d)x＝0.3(上部曲线为箭头所指的介电常数εr，下部曲线为箭头所指的损耗tanδ，Td为退极化温度)。
图4为x＝0，0.1，0.2，0.3时制备的复合陶瓷材料的压电常数d33随退火温度的变化图。
从图3-4中可以看出，本发明实施例1-2制备的复合陶瓷材料退极化温度可达到120℃以上。当x＝0.1时，室温压电常数d33为123pC/N，退极化温度为122℃；当x＝0.2时，室温压电常数d33为110pC/N，退极化温度为127℃；当x＝0.3时，室温压电常数d33有一定下降，只有100pC/N，但退极化温度少量升高，为134℃；与实施例1和实施例2相比，当x＝0时，室温压电常数d33较高，达到132pC/N，但退极化温度仅为68℃。
本发明实施例1-3制备的复合陶瓷材料退极化行为得到明显改善，d33在低于110℃时能够保持相对稳定。
对比例2
同实施例1，区别在于，将纳米ZnO颗粒替换成氧化铌。
结果发现，制备得到的复合陶瓷材料退极化温度仅为110℃，室温压电常数d33为98pC/N。
对比例3
同实施例1，区别在于，将步骤1)中的球磨方式改变为搅拌混合。
结果发现，制备得到的复合陶瓷材料退极化温度仅为53℃，室温压电常数d33为70pC/N。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (4)

1.一种具有高退极化温度的BNKT-BT基复合陶瓷材料，其特征在于，该BNKT-BT基复合陶瓷材料的化学通式为：0.85(Bi0.5Na0.5)TiO3-0.11(Bi0.5K0.5)TiO3-0.04BaTiO3-xZnO，其中，x=0.1，0.2；
所述具有高退极化温度的BNKT-BT基复合陶瓷材料退极化温度高于120℃，压电性能在110℃以下能够保持较好的温度稳定性；
所述具有高退极化温度的BNKT-BT基复合陶瓷材料的制备方法，包括以下步骤：
1）将铋源、钠源、钾源、钛源、钡源依照化学计量比混合，以有机溶剂为介质进行球磨，干燥，干压成型，得到原料块体；
2）将原料块体置于氧气氛围中进行预烧，得到BNKT-BT预烧块；所述预烧温度为820-850℃，时间为3-4h；
3）依照化学计量比将BNKT-BT预烧块与纳米ZnO颗粒混合并进行二次球磨，干燥，然后加入粘合剂，静置，压制成型；所述纳米ZnO颗粒直径为50-80nm；
4）对压制成型的样品进行研磨，过筛，得到的粉体再次压制成型，得到陶瓷坯体；
5）将陶瓷坯体依次经过加热处理、烧结、打磨抛光，得到ZnO复合BNKT-BT基陶瓷；所述加热处理温度为550℃，时间为2-3h；所述烧结温度为1030-1070℃，烧结时间为1-1.5h，升温速率为9℃/min；
6）在ZnO复合BNKT-BT基陶瓷表面涂覆银浆，烧银处理，即得到具有高退极化温度的BNKT-BT基复合陶瓷材料；所述烧银处理温度为550-600℃，时间为40-50min。
2.根据权利要求1所述的具有高退极化温度的BNKT-BT基复合陶瓷材料，其特征在于，步骤1）中，所述干压成型时压强为400MPa，时间为1-3min。
3.根据权利要求1所述的具有高退极化温度的BNKT-BT基复合陶瓷材料，其特征在于，步骤3）中，所述粘合剂为5wt%的聚乙烯醇粘合剂；所述静置时间为12-15h；所述压制成型时压强为600MPa，时间为3-6min。
4.根据权利要求1所述的具有高退极化温度的BNKT-BT基复合陶瓷材料，其特征在于，步骤4）中，所述再次压制成型时压强为400MPa，时间为1-3min。
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