CN110128127B - 一种具有高压电性能及高温稳定性的铁酸铋-钛酸钡基无铅压电陶瓷及其制备方法 - Google Patents

一种具有高压电性能及高温稳定性的铁酸铋-钛酸钡基无铅压电陶瓷及其制备方法 Download PDF

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CN110128127B
CN110128127B CN201910582275.3A CN201910582275A CN110128127B CN 110128127 B CN110128127 B CN 110128127B CN 201910582275 A CN201910582275 A CN 201910582275A CN 110128127 B CN110128127 B CN 110128127B
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孙媛媛
杨华斌
黄蔚然
陈巧红
江民红
刘笑
张秀云
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Hefei Jinglong Environmental Protection Technology Co ltd
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Guilin University of Electronic Technology
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Abstract

本发明公开了一种具有高压电性能及高温稳定性的铁酸铋‑钛酸钡基无铅压电陶瓷及其制备方法，其组成通式为：xBiFeO3‑yBaTiO3+uBi(Ti0.5Zn0.5)O3+mP+tMnCO2，其中P为Ba(W0.5Cu0.5)O3、Ba(Cu1/3Nb2/3)O3、B2O3、Li2CO3、V2O5中的一种或多种烧结助剂的组合；x、y、u、m、t表示摩尔分数，且0.65≤x≤0.85,0.15≤y≤0.35,0.05<u≤0.25,0<m≤0.1,0<t≤0.1。其制备方法包括按组成通式配料，球磨，成型素片，排胶，烧结等工序，以及采用高温高压条件合成Bi(Ti0.5Zn0.5)O3，低温烧结助剂、快速升温以及高温淬火等工艺，制备出了最高压电常数可达到187pC/N，在530℃退极化温度时压电常数d33依然可以保持在145pC/N以上的高温无铅压电陶瓷。

Description

一种具有高压电性能及高温稳定性的铁酸铋-钛酸钡基无铅 压电陶瓷及其制备方法
技术领域
本发明涉及一种可在高温领域应用的铁酸铋-钛酸钡基高温无铅压电陶瓷的配方组成及其制备方法，具体是一种具有高压电性能及高温稳定性的铁酸铋-钛酸钡基无铅压电陶瓷及其制备方法。
背景技术
高温压电陶瓷是高温压电振动传感器中的核心元件，在航天航空、核能、石油勘探、汽车等领域具有重大需求，其突出特点是使用条件苛刻，工作温度高，使用寿命长，因此，高温领域的应用对压电振动传感器的核心敏感材料—压电陶瓷也提出了很高的要求：如高压电性能、高电阻率和高温稳定性等。目前国际上高温压电振动传感器主要包括260℃、482℃、649℃和760℃等不同温度系列产品。研究人员一直致力于获得同时具有高压电性能及高温稳定性的压电陶瓷，但高温压电陶瓷材料存在居里温度越高，则压电性能越低的问题，且一直未能突破这一研究瓶颈。
在高温压电陶瓷领域，钨青铜结构压电陶瓷和铋层状结构压电陶瓷由于受本身结构特点的影响，其压电性能无法得到进一步得提升，BiFeO3具有很高的居里温度(Tc＝830℃)其与BaTiO3形成固溶体，可获得高达600℃的居里温度和较高压电性能的BiFeO3-BaTiO3的固溶体，但是BiFeO3-BaTiO3体系的整体温度稳定性不高，退极化温度Td<500℃，YongquanGuo等报道的BiFeO3-BaTiO3-NdCoO3是目前文献报道的最高退极化温度Td＝525℃，但是在退极化温度点525℃时，其d33只有80pC/N左右，且介电损耗非常高，tgδ＞5％。Bi(Ti0.5Zn0.5)O3是一种具有高居里温度的四方相钙钛矿结构化合物，其与BiFeO3可形成固溶体。根据c/a比及容忍因子等理论计算，两者的固溶体在单斜相0.6BiFeO3-0.4Bi(Ti0.5Zn0.5)O3成分处的TC可以达到1227℃。为了进一步提高该体系的温度稳定性，本发明采用高温高压条件先单独合成Bi(Ti0.5Zn0.5)O3，同时采用烧结助剂，将其与BiFeO3-BaTiO3复合，获得了致密、具有高压电性能和高温稳定性的压电陶瓷。
发明内容
为了解决上述现有技术存在的问题，本发明的目的在于提供一种具有高压电性能及高温稳定性的铁酸铋-钛酸钡基无铅压电陶瓷及其制备方法。
为了进一步提高BiFeO3-BaTiO3体系的温度稳定性及压电性能，通过添加烧结助剂，将BiFeO3-BaTiO3与Bi(Zn0.5Ti0.5)O3进行复合，获得致密的BiFeO3-BaTiO3-Bi(Zn0.5Ti0.5)O3压电陶瓷。采用本发明技术制备的压电陶瓷，居里温度可达到Tc＝558℃，退极化温度达到Td＝530℃，且压电常数达到187pC/N，在530℃退极化温度时压电常数d33依然可以保持在145pC/N以上，该体系陶瓷有望应用在高温领域。
实现本发明的技术方案是：
一种具有高压电性能及高温稳定性的铁酸铋-钛酸钡基无铅压电陶瓷，其组成通式为：xBiFeO3-yBaTiO3+uBi(Ti0.5Zn0.5)O3+mP+tMnCO3，其中P为Ba(W0.5Cu0.5)O3、Ba(Cu1/ 3Nb2/3)O3、B2O3、Li2CO3、V2O5中的一种或多种烧结助剂的组合；x、y、u、m、t表示摩尔分数，且0.65≤x≤0.85,0.15≤y≤0.35,0.05<u≤0.25,0<m≤0.1,0<t≤0.1。
上述具有高压电性能及高温稳定性的铁酸铋-钛酸钡基无铅压电陶瓷的制备方法，包括如下步骤：
(1)以分析纯Fe2O3、Bi2O3、BaCO3、TiO2、MnCO3为原料，按照xBiFeO3-yBaTiO3+tMnCO3进行配料，将混合粉末以无水乙醇为介质球磨24小时，100℃/12小时在烘箱中烘干、过200目筛，然后放入高铝坩埚中压实加盖，再放入马弗炉中以250℃/h的升温速率到800℃预烧，保温6小时合成，并降温冷却至200℃以下后取出；
(2)以分析纯BaCO3、W2O3、CuO、Nb2O5为原料，按照Ba(W0.5Cu0.5)O3、Ba(Cu1/3Nb2/3)O3分别进行配料，将混合粉末以无水乙醇为介质球磨24小时，100℃/12小时在烘箱中烘干、过200目筛，放入高铝坩埚中压实加盖，再放入马弗炉中以250℃/h的升温速率到800-850℃预烧，保温6小时合成，并降温冷却至200℃以下后取出备用；
(3)将Bi2O3、TiO2、ZnO按照Bi(Ti0.5Zn0.5)O3的配比配料，其中Bi元素过量5％摩尔，以无水乙醇为介质球磨24小时，100℃/12小时在烘箱中烘干、过200目筛，放入高铝坩埚中压实加盖，再放入高压管式炉中以250℃/h的升温速率升温至900℃/6Gpa、保温4小时合成，降压、并降温冷却至200℃以下后取出备用；
(4)将步骤(1)预烧合成的xBiFeO3-yBaTiO3+tMnO2粉末和步骤(2)合成的烧结助剂粉末Ba(W0.5Cu0.5)O3、Ba(Cu1/3Nb2/3)O3或者B2O3、Li2CO3、V2O5等烧结助剂中的一种或多种，以及步骤(3)预烧合成的Bi(Ti0.5Zn0.5)O3粉末按照xBiFeO3-yBaTiO3+uBi(Ti0.5Zn0.5)O3+mP+tMnO2混合，其中0.65≤x≤0.85,0.15≤y≤0.35,0.05<u≤0.25,0<m≤0.1,0<t≤0.1，以无水乙醇为介质进行二次球磨24小时，取出干燥，过200目筛；
(5)将过筛后的粉末加入质量百分比浓度为的5％PVA溶液造粒，在钢模中于100MPa下压制成型，模具内直径为1cm；
(6)成型的素片放入管式炉中通纯氧以30℃/h的升温速率缓慢升温至600℃，保温24小时排胶；然后以20℃/min的升温速率快速升温到960-1000℃，保温120分钟，再以20℃/min快速降温至800℃保温60min，然后直接取出至空气中淬火；
(7)将烧结后样品抛光成两面光滑、厚度1mm的薄片，披银电极，650℃/30分钟烧银后备用；
(8)将披银电极后的压电陶瓷片在硅油中极化，极化电场6000V/mm，极化温度150℃，时间30分钟，保持电场冷却至室温。
本发明的积极效果是：
本发明为了获得更高的居里温度和压电性能，采用两步合成法，先单独合成xBiFeO3-yBaTiO3，再在高温高压条件下合成Bi(Ti0.5Zn0.5)O3，然后再添加烧结助剂将两者进行复合的方法，采用此技术可以防止直接合成Bi(Ti0.5Zn0.5)O3的困难，可以在xBiFeO3-yBaTiO3中添加更多的Bi(Ti0.5Zn0.5)O3，同时通过添加烧结助剂，进一步促进xBiFeO3-yBaTiO3与Bi(Ti0.5Zn0.5)O3的烧结并形成致密的固溶体，有利于获得更高温度稳定性的陶瓷。采用此技术制备的xBiFeO3-yBaTiO3+uBi(Ti0.5Zn0.5)O3+mP+tMnO2，具有超过558℃的居里温度和超过530℃的退极化温度，且保持较高的压电性能，这一性能远超目前有关于xBiFeO3-yBaTiO3+uBi(Ti0.5Zn0.5)O3体系压电陶瓷的公开文献报道和相关专利报道，这对于BiFeO3-BaTiO3体系压电陶瓷而言，从技术上看，具有重大突破和技术上的创新，并具有实用性。
具体实施方式
本发明的优选实施例详述如下：
实施例1：
成分：0.70BiFeO3-0.225BaTiO3+0.075Bi(Ti0.5Zn0.5)O3+0.025Ba(Cu1/3Nb2/3)O3+0.01MnCO3，制备方法包括如下步骤：
(1)以分析纯Fe2O3、Bi2O3、BaCO3、TiO2、MnCO3为原料，按照0.70BiFeO3-0.225BaTiO3+0.01MnCO3进行配料，将混合粉末以无水乙醇为介质球磨24小时，100℃/12小时在烘箱中烘干、过筛，放入高铝坩埚中压实加盖，再放入马弗炉中以250℃/h的升温速率到800℃预烧，保温6小时合成，并降温冷却至200℃以下后取出；
(2)以分析纯BaCO3、CuO、Nb2O5为原料，按照Ba(Cu1/3Nb2/3)O3进行配料，将混合粉末以无水乙醇为介质球磨24小时，100℃/12小时在烘箱中烘干、过筛，放入高铝坩埚中压实加盖，再放入马弗炉中以250℃/h的升温速率到850℃预烧，保温6小时合成，并降温冷却至200℃以下后取出备用；
(3)将Bi2O3、TiO2、ZnO按照Bi(Ti0.5Zn0.5)O3的配比配料，其中Bi元素过量5％摩尔，以无水乙醇为介质球磨24小时，100℃/12小时在烘箱中烘干、过筛，放入高铝坩埚中压实加盖，再放入高压管式炉中以250℃/h的升温速率升温至900℃/6Gpa、保温4小时合成，降压、并降温冷却至200℃以下后取出备用；
(4)将步骤(1)合成的0.70BiFeO3-0.225BaTiO3+0.01MnCO3粉末和步骤(2)合成的烧结助剂Ba(Cu1/3Nb2/3)O3烧结助剂，以及步骤(3)合成的Bi(Ti0.5Zn0.5)O3粉末，按照配方0.70BiFeO3-0.225BaTiO3+0.075Bi(Ti0.5Zn0.5)O3+0.025Ba(Cu1/3Nb2/3)O3+0.01MnCO3混合，以无水乙醇为介质进行二次球磨24小时后取出干燥，过筛；
(5)将过筛后的粉末加入质量百分比浓度为5％PVA的溶液造粒，在钢模中于100MPa下压制成型，模具内直径为1cm；
(6)成型的素片放入管式炉中通纯氧，并以30℃/h的升温速率缓慢升温至600℃，保温24小时排胶；然后以20℃/min的升温速率快速升温到980℃，保温120分钟，再以20℃/min快速降温至800℃保温60min，然后直接取出至空气中淬火；
(7)将烧结后样品抛光成两面光滑、厚度1mm的薄片，披银电极，650℃/30分钟烧银后备用；
(8)将披银电极后的压电陶瓷片在硅油中极化，极化电场6000V/mm，极化温度150℃，时间30分钟，保持电场冷却至室温。
性能测量结果如下：
d<sub>33</sub>(pC/N) Q<sub>m</sub> k<sub>p</sub>(％) ε<sub>r</sub> Tc(℃) T<sub>d</sub>(℃) tgδ(％)
167 147 0.29 106 532 505 3.13
实施例2：
成分：0.76BiFeO3-0.24BaTiO3+0.10Bi(Ti0.5Zn0.5)O3+0.025Ba(Cu0.5W0.5)O3+0.01MnCO3，制备方法同实施例1。
性能测量结果如下：
d<sub>33</sub>(pC/N) Q<sub>m</sub> k<sub>p</sub>(％) ε<sub>r</sub> Tc(℃) T<sub>d</sub>(℃) tgδ(％)
172 127 0.30 99 553 525 3.15
实施例3：
成分：0.75BiFeO3-0.25BaTiO3+0.10Bi(Ti0.5Zn0.5)O3+0.02Li2CO3+0.01MnCO3，制备方法同实施例1，不同的是烧结温度为970℃。
性能测量结果如下：
d<sub>33</sub>(pC/N) Q<sub>m</sub> k<sub>p</sub>(％) ε<sub>r</sub> Tc(℃) T<sub>d</sub>(℃) tgδ(％)
187 117.4 0.31 108 558 530 2.99
实施例4：
成分：0.75BiFeO3-0.20BaTiO3+0.125Bi(Ti0.5Zn0.5)O3+0.02Ba(W0.5Cu0.5)O3+0.0025B2O3+0.01MnCO3，制备方法同实施例1，不同的是烧结温度为960℃。
性能测量结果如下：
d<sub>33</sub>(pC/N) Q<sub>m</sub> k<sub>p</sub>(％) ε<sub>r</sub> Tc(℃) T<sub>d</sub>(℃) tgδ(％)
137 179.4 0.26 111 546 520 3.01
本发明所列举的成分的上下限、区间取值以及工艺参数的上下限、区间取值都能实现本发明，在此不一一列举实施。

Claims (1)

1.一种具有高压电性能及高温稳定性的铁酸铋-钛酸钡基无铅压电陶瓷，其特征在于：其组成通式为xBiFeO3-yBaTiO3+uBi (Ti0.5Zn0.5)O3+mP+tMnCO3，其中x、y、u、m、t表示摩尔分数，且 0.65≤x≤0.85，0.15≤y≤0.35，0.05<u≤0.25，0<m≤0.1，0<t≤0.1，P为Ba(W0.5Cu0.5)O3、Ba(Cu1/3Nb2/3)O3、B2O3、V2O5中的一种或多种烧结助剂的组合；
所述的具有高压电性能及高温稳定性的铁酸铋-钛酸钡基无铅压电陶瓷的制备方法，包含如下步骤：
（1）以分析纯Fe2O3、Bi2O3、BaCO3、TiO2、MnCO3为原料，按照xBiFeO3-yBaTiO3+tMnO2进行配料，其中0.65≤x≤0.85，0.15≤y≤0.35，0<m≤0.1，0<t≤0.1，将混合粉末以无水乙醇为介质球磨24小时，100℃/12小时在烘箱中烘干、过筛，放入高铝坩埚中压实加盖，再放入马弗炉中以250℃/h的升温速率到800℃预烧，保温6小时合成，并降温冷却至200℃以下后取出；
（2）以分析纯BaCO3、W2O3、CuO、Nb2O5为原料，按照Ba(W0.5Cu0.5)O3、Ba(Cu1/3Nb2/3)O3进行配料，将混合粉末以无水乙醇为介质球磨24小时，100℃/12小时在烘箱中烘干、过筛，放入高铝坩埚中压实加盖，再放入马弗炉中以250℃/h的升温速率到850℃预烧，保温6小时合成，并降温冷却至200℃以下后取出备用；
（3）将Bi2O3、TiO2、ZnO按照Bi (Ti0.5Zn0.5)O3的配比配料，以无水乙醇为介质球磨24小时，100℃/12小时在烘箱中烘干、过筛，放入高铝坩埚中压实加盖，再放入高压管式炉中以250℃/h的升温速率升温至900℃/6Gpa、保温4小时合成，降压、并降温冷却至200℃以下后取出备用；
（4）将步骤（1）、步骤（2）和步骤（3）合成的xBiFeO3-yBaTiO3+tMnO2预烧粉末和Bi(Ti0.5Zn0.5)O3预烧粉末，以及Ba(W0.5Cu0.5)O3、Ba(Cu1/3Nb2/3)O3或者B2O3、V2O5中的一种或多种烧结助剂的组合，按照xBiFeO3- yBaTiO3+uBi(Ti0.5Zn0.5)O3+mP+tMnO2混合，其中0.65≤x≤0.85，0.15≤y≤0.35，0.05<u≤0.25，0<m≤0.1，0<t≤0.1，以无水乙醇为介质进行二次球磨24小时，取出干燥，过筛；
（5）将过筛后的粉末加入质量百分比浓度为的5%PVA溶液造粒，在钢模中于100MPa下压制成型，模具内直径为1cm；
（6）成型的素片放入管式炉中通纯氧以30℃/h的升温速率缓慢升温至600℃，保温24小时排胶；然后以20℃/min的升温速率快速升温到960-1000℃，保温120分钟，再以20℃/min快速降温至800℃保温60min，然后直接取出至空气中淬火；
（7）将烧结后样品抛光成两面光滑、厚度1mm的薄片，披银电极，650℃/30分钟烧银后备用；
（8）将披银电极后的压电陶瓷片在硅油中极化，极化电场6000V/mm，极化温度150℃，时间30分钟，保持电场冷却至室温。
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