CN115073159B - 一种具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷及其低温含氧热压烧结制备方法 - Google Patents

一种具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷及其低温含氧热压烧结制备方法 Download PDF

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CN115073159B
CN115073159B CN202210912495.XA CN202210912495A CN115073159B CN 115073159 B CN115073159 B CN 115073159B CN 202210912495 A CN202210912495 A CN 202210912495A CN 115073159 B CN115073159 B CN 115073159B
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陈巧红
杨心怡
杨华斌
关士博
王雪婷
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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居里温度及高压电性能的铁酸铋‑钛酸钡陶瓷及其低温含氧热压烧结制备方法，所述陶瓷的组成通式为：(1‑u)BiFeO3‑uBaTiO3+1.0mol%MnCO3+xmol%(Bi0.5Na0.25Li0.25)TiO3+ymol%Ba(W1/2Cu1/2)O3+zmol%B2O3，其中u、x、y和z表示摩尔分数，(Bi0.5Na0.25Li0.25)TiO3、Ba(W0.5Cu0.5)O3及B2O3为低温烧结助剂，且0.20≤u≤0.45，0＜x≤2.0，0≤y≤5.0，0≤z≤5.0。本方法通过添加烧结助剂，可在820℃‑920℃及25Mpa压力、在含氧气氛下条件下热压烧结成瓷。本发明降低了铁酸铋‑钛酸钡陶瓷的烧结温度、减少了Bi元素的挥发、提高了陶瓷的致密度和降低了陶瓷的介电损耗，获得了高压电性能、高居里温度及低介电损耗的无铅压电陶瓷。

Description

一种具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷及 其低温含氧热压烧结制备方法
技术领域
本发明涉及无铅压电陶瓷及低温热压烧结制备技术，涉及铁酸铋-钛酸钡陶瓷，尤其是一种具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷及其低温含氧热压烧结制备方法。
背景技术
压电陶瓷在航空航天、核电、石油化工、地质勘探、冶金、汽车燃油监控、3D打印、高温超声波应用等高技术领域具有广泛应用。目前在该领域内的应用主要以锆钛酸铅(PZT)及其改性的压电陶瓷体系为主，为了节约能源和降低生产成本，通过采用各种烧结助剂来降低陶瓷的烧结温度，同时多层压电陶瓷为了降低内电极成本，也希望获得更低的烧结温度。目前锆钛酸铅体系的烧结温度已经降到了950℃左右，但是在此温度下烧结制备多层压电陶瓷仍存在铅挥发问题，严重污染环境，因此压电陶瓷的无铅化具有重要的社会意义。
BiFeO3-BaTiO3陶瓷具有居里温度高、烧结温度低、无毒、钙钛矿结构的优异特性，然而在烧结过程中，由于BiFeO3与BaTiO3的烧结成瓷温度差太大，分别为830℃和1400℃，烧结温度过低则成瓷不充分，无法极化。烧结温度过高则Bi元素挥发严重。为了平衡化合价，Bi元素挥发会导致陶瓷中产生大量氧空位和晶格缺陷以及孔洞，使得该体系的介电损耗很高而无法极化，添加Mn元素掺杂改性后，有效的提高了该体系电阻率，降低了介电损耗，但介电损耗仍然偏高(≥5％)，因此降低BiFeO3-BaTiO3陶瓷的介电损耗可以从降低烧结温和提高陶瓷致密度方面来开展工作。
公开号为CN102584195A的专利公开了一种铋基钙钛矿型无铅压电陶瓷及其低温制备方法，采用通过添加低温烧结助剂的固相合成烧结方法，成功将烧结温度降至900℃左右，但是铋元素的挥发和介电损耗偏高的问题仍然未得到解决。
热压烧结是一种常用的陶瓷制备方法，然而由于需要耐高温的热压模具，因此热压烧结需要在无氧保护气氛下烧结。在BiFeO3-BaTiO3体系陶瓷的制备过程中，由于该体系极易在烧结过程中产生氧空位，因此无法在无氧气氛下烧结。
发明内容
针对上述现有技术存在的问题，本发明提供一种具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷及其低温含氧热压烧结制备方法，以降低BiFeO3-BaTiO3体系陶瓷的烧结温度，减少Bi元素的挥发、提高该体系陶瓷的居里温度和高温温度稳定性，获得具有高压电性能、高居里温度、低介电损耗的BiFeO3-BaTiO3无铅压电陶瓷。
实现本发明目的的技术方案是：
一种具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷，所述陶瓷的组成通式为：
(1-u)BiFeO3-uBaTiO3+1.0mol％MnCO3+xmol％(Bi0.5Na0.25Li0.25)TiO3+ymol％Ba(W1/2Cu1/2)O3+zmol％B2O3，其中u、x、y和z表示摩尔分数，(Bi0.5Na0.25Li0.25)TiO3、Ba(W0.5Cu0.5)O3及B2O3为低温烧结助剂，且0.20≤u≤0.45，0＜x≤2.0，0≤y≤5.0，0≤z≤5.0。
所述具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷的低温含氧热压烧结制备方法，包括如下步骤：
1)以分析纯Fe2O3、Bi2O3、Li2CO3、Na2CO3、TiO2和纳米BaTiO3粉末为原料，按照(1-u)BiFeO3-uBaTiO3+xmol％(Bi0.5Na0.25Li0.25)TiO3进行配料，其中0.20≤u≤0.45，0＜x≤2.0，以无水乙醇为介质球磨24h，取出后在100℃烘干12h、200-250目过筛，放入高铝坩埚中压紧、加盖，以250℃/h的升温速率升温至750℃保温6h合成备用；
2)以分析纯BaCO3、WO3和CuO为原料，按照Ba(Cu1/2W1/2)O3化学式的比例配料，混合球磨24h，取出后烘干、200-250目过筛，放入高铝坩埚中压紧加盖，以250℃/h的升温速率升至850℃保温6h合成备用；
3)将步骤1)合成的(1-u)BiFeO3-uBaTiO3+xmol％(Bi0.5Na0.25Li0.25)TiO3及步骤2)合成的Ba(Cu1/2W1/2)O3粉末与B2O3及MnCO3按照(1-u)BiFeO3-uBaTiO3+1.0mol％MnCO3+xmol％(Bi0.5Na0.25Li0.25)TiO3+ymol％Ba(Cu1/2W1/2)O3+zmol％B2O3配料，其中0.20≤u≤0.45，0＜x≤2.0，0≤y≤5.0，0≤z≤5.0，并以无水乙醇为介质，球磨24h后取出烘干、200-250目过筛备用；
4)将步骤3)合成的粉末放入热压烧结机中，采用氧化铝刚玉模具，直接在空气或纯氧气氛条件下，以5℃/min的速率升温至100℃，保温15min排除粉末中的水蒸气，再以20℃/min的升温速率快速升温至820℃-920℃的烧结温度后保持温度不变，并开始加压至25Mpa，保温保压30min后，断电、开水冷，快速冷却至室温；
5)将烧结后的样品根据需求切割成大小不同的陶瓷片，并打磨加工成两面光滑、厚度为0.5-1.0mm的薄片，披银电极；
6)将所烧制的压电陶瓷片在硅油中极化，极化电场6000V/mm，温度120℃，保温时间30min，保持电场并冷却至室温。
本发明采用氧化铝刚玉模具，同时在BiFeO3-BaTiO3粉末中添加烧结助剂Ba(W1/ 2Cu1/2)O3、(Bi0.5Na0.25Li0.25)TiO3、B2O3降低烧结温度，将该体系在纯氧气氛或含氧气氛条件下热压烧结，最低热压烧结温度降到了820℃，同时还利用(Bi0.5Na0.25Li0.25)TiO3的低容忍因子特性提高该体系的居里温度和高温温度稳定性，最终获得了具有高压电性能、高居里温度、低介电损耗的BiFeO3-BaTiO3无铅压电陶瓷。
本发明产生的积极效果是：
(1)本技术方案充分利用了Ba(Cu1/2W1/2)O3与(Bi0.5Na0.25Li0.25)TiO3的钙钛矿结构和低熔点的特性，与(1-u)BiFeO3-uBaTiO3形成良好的固溶体，同时通过添加低熔点的B2O3，在烧结过程中形成低温液相，大幅降低该体系的热压烧结温度至820℃，促进晶界移动和晶粒长大，获得晶粒生长均匀的压电陶瓷；另一方面，充分利用(Bi0.5Na0.25Li0.25)TiO3的低容忍因子的特性，提高了该体系的居里温度和高温稳定性；
(2)热压烧结为在一密闭的空间进行，可以有效的防止Bi元素的挥发，也会减少孔洞和氧空位的产生，同时热压提高了陶瓷的致密度，减少了晶格缺陷，有利于降低陶瓷的介电损耗；
(3)本热压烧结是在含氧气氛条件下完成，可以有效地避免BiFeO3-BaTiO3陶瓷在热压烧接过程中氧空位的产生，并且在降温时采用水冷强制快速降温，减少了降温阶段的时间，有利于减少中间相的产生。
本发明通过添加烧结助剂和热压工艺，成功地将(1-u)BiFeO3-uBaTiO3+1.0mol％MnCO3陶瓷的烧结温度从960℃降低至820℃-920℃，并在降低烧结温度的同时，将该体系的相对致密度从95％提高到了99％，获得了具有高居里温度、高压电性能及低介电损耗的压电陶瓷样品，其具有优异的压电性能和高温稳定性。实施例1制备的样品原位动态退极化测试结果表明，见附图1，本发明技术制备的压电陶瓷，使用温度范围可达到300℃以上，在最高温度点315℃时，其压电性能达到了498pC/N，与现有公开的技术对比，在如此高的温度下，尚未有压电性能超越300pC/N的压电陶瓷材料，因此本发明所制备的陶瓷，具有重大的突破性和创新性。
附图说明
图1为本发明实施例1制备的陶瓷的原位动态退极化曲线图。
具体实施方式
下面通过实施例和附图对本发明内容作进一步的阐述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1：
一种具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷，所述陶瓷的化学式为：0.68BiFeO3-0.32BaTiO3+1.0mol％MnCO3+1.0mol％(Bi0.5Na0.25Li0.25)TiO3+2.5mol％B2O3+
3.0mol％Ba(Cu1/2W1/2)O3，
所述陶瓷的低温含氧热压烧结制备方法包括如下步骤：
(1)以分析纯Fe2O3、Bi2O3、Li2CO3、Na2CO3、TiO2和纳米BaTiO3粉末为原料，按照0.68BiFeO3-0.32BaTiO3+1.0mol％(Bi0.5Na0.25Li0.25)TiO3进行配料，以无水乙醇为介质球磨24h，取出后在100℃烘干12h、200目过筛，放入高铝坩埚中压紧、加盖，以250℃/h的升温速率升温至750℃保温6h合成备用；
(2)以分析纯BaCO3、WO3和CuO为原料，按照Ba(Cu1/2W1/2)O3化学式的比例配料，混合球磨24小时，取出后烘干、200目过筛，放入高铝坩埚中压紧加盖，以250℃/h的升温速率升至850℃保温6h合成备用；
(3)将步骤(1)合成的0.68BiFeO3-0.32BaTiO3+1.0mol％(Bi0.5Na0.25Li0.25)TiO3及步骤(2)合成的Ba(Cu1/2W1/2)O3粉末与B2O3及MnCO3按照0.68BiFeO3-0.32BaTiO3+1.0mol％MnCO3+1.0mol％(Bi0.5Na0.25Li0.25)TiO3+3.0mol％Ba(Cu1/2W1/2)O3+2.5mol％B2O3配料，并以无水乙醇为介质，球磨24h后取出烘干、200目过筛备用；
(4)将步骤(3)合成的粉末放入热压烧结机中，采用氧化铝刚玉模具，直接在空气或纯氧气氛条件下，以5℃/min的升温速率升温至100℃，保温15min排除粉末中的水蒸气，再以20℃/min的升温速率升温至880℃的烧结温度后保温，同时逐渐加压至25Mpa，保温保压30min后，断电、开水冷，快速冷却至室温；
(5)将烧结后的样品根据需求切割成大小不同的陶瓷片，并打磨加工成两面光滑、厚度为1.0mm的薄片，薄片呈硬币形状或长方体形，披银电极；
(6)将所烧制的压电陶瓷片在硅油中极化，极化电场6000V/mm，温度120℃，保温时间30min，保持电场并冷却至室温。
性能测量结果如下：
d33(pC/N) Qm kp εr Tanδ(％) Tc(℃) Td(℃)
498 74 0.32 665 1.53 523 490
实施例1制备的样品原位动态退极化测试结果表明，见附图1，本发明技术制备的压电陶瓷，使用温度范围可达到300℃以上，在最高温度点315℃时，其压电性能达到了498pC/N。
实施例2：
一种具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷，所述陶瓷的化学式为：
0.70BiFeO3-0.30BaTiO3+1.0mol％MnCO3+2.0mol％Ba(Cu1/2W1/2)O3+2.5mol％B2O3+
1.5mol％(Bi0.5Na0.25Li0.25)TiO3，
所述陶瓷的低温含氧热压烧结制备方法同实施例1，不同的是步骤(4)的烧结温度为870℃。
性能测量结果如下：
d33(pC/N) Qm kp εr Tanδ(％) Tc(℃) Td(℃)
466 68 0.34 647 1.38 556 525
实施例3：
一种具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷，所述陶瓷的化学式为：
0.65BiFeO3-0.35BaTiO3+1.0mol％MnCO3+1.0mol％Ba(Cu1/2W1/2)O3+2.5mol％B2O3+
1.0mol％(Bi0.5Na0.25Li0.25)TiO3；
所述陶瓷的低温含氧热压烧结制备方法同实施例1，不同的是步骤(4)的烧结温度920℃。性能测量结果如下：
d33(pC/N) Qm kp εr Tanδ(％) Tc(℃) Td(℃)
418 50 0.28 781 1.95 473 445
实施例4：
一种具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷，所述陶瓷的化学式为：
0.75BiFeO3-0.25BaTiO3+1.0mol％MnCO3+2.0mol％Ba(Cu1/2W1/2)O3+1.0mol％B2O3+
1.0mol％(Bi0.5Na0.25Li0.25)TiO3；
所述陶瓷的低温含氧热压烧结制备方法同实施例1，不同的是步骤(4)的烧结温度为820℃。
性能测量结果如下：
d33(pC/N) Qm kp εr Tanδ(％) Tc(℃) Td(℃)
407 39 0.31 583 0.96 590 545
上述实施例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。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的保护范围由所附权利要求及其等同物限定。

Claims (7)

1.一种具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷，其特征在于，所述陶瓷的组成通式为：
(1-u)BiFeO3-uBaTiO3+1.0mol％MnCO3+xmol％(Bi0.5Na0.25Li0.25)TiO3+ymol％Ba(W1/ 2Cu1/2)O3+zmol％B2O3，其中u、x、y和z表示摩尔分数，(Bi0.5Na0.25Li0.25)TiO3、Ba(W0.5Cu0.5)O3及B2O3为低温烧结助剂，且0.20≤u≤0.45，0＜x≤2.0，0＜y≤5.0，0＜z≤5.0。
2.权利要求1所述的具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷的低温含氧热压烧结制备方法，其特征在于，包括如下步骤：
1)以分析纯Fe2O3、Bi2O3、Li2CO3、Na2CO3、TiO2和纳米BaTiO3粉末为原料，按照(1-u)BiFeO3-uBaTiO3+xmol％(Bi0.5Na0.25Li0.25)TiO3进行配料，其中0.20≤u≤0.45，0＜x≤2.0，以无水乙醇为介质球磨24h，取出后在100℃烘干12h、200-250目过筛，放入高铝坩埚中压紧、加盖，以250℃/h的升温速率升温至750℃保温6h合成备用；
2)以分析纯BaCO3、WO3和CuO为原料，按照Ba(Cu1/2W1/2)O3化学式的比例配料，混合球磨24h，取出后烘干、200-250目过筛，放入高铝坩埚中压紧加盖，以250℃/h的升温速率升至850℃保温6h合成备用；
3)将步骤1)合成的(1-u)BiFeO3-uBaTiO3+xmol％(Bi0.5Na0.25Li0.25)TiO3及步骤2)合成的Ba(Cu1/2W1/2)O3粉末与B2O3及MnCO3按照(1-u)BiFeO3-uBaTiO3+1.0mol％MnCO3+xmol％(Bi0.5Na0.25Li0.25)TiO3+ymol％Ba(Cu1/2W1/2)O3+zmol％B2O3配料，其中0.20≤u≤0.45，0＜x≤2.0，0＜y≤5.0，0＜z≤5.0，并以无水乙醇为介质，球磨24h后取出烘干、200-250目过筛备用；
4)将步骤3)合成的粉末放入热压烧结机中，采用氧化铝刚玉模具，直接在空气或纯氧气氛条件下，以5℃/min的速率升温至100℃，保温15min排除粉末中的水蒸气，再以20℃/min的升温速率快速升温至820℃-920℃的烧结温度后保持温度不变，并开始加压至25Mpa，保温保压30min后，断电、开水冷，快速冷却至室温；
5)将烧结后的样品根据需求切割成大小不同的陶瓷片，并打磨加工成两面光滑、厚度为0.5-1.0mm的薄片，披银电极；
6)将所烧制的压电陶瓷片在硅油中极化，极化电场6000V/mm，温度120℃，保温时间30min，保持电场并冷却至室温。
3.根据权利要求1所述的具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷，其特征在于，所述陶瓷的化学式为：
0.68BiFeO3-0.32BaTiO3+1.0mol％MnCO3+1.0mol％(Bi0.5Na0.25Li0.25)TiO3+2.5mol％B2O3+3.0mol％Ba(Cu1/2W1/2)O3。
4.权利要求3所述的具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷的低温含氧热压烧结制备方法，其特征在于，包括如下步骤：
(1)以分析纯Fe2O3、Bi2O3、Li2CO3、Na2CO3、TiO2和纳米BaTiO3粉末为原料，按照0.68BiFeO3-0.32BaTiO3+1.0mol％(Bi0.5Na0.25Li0.25)TiO3进行配料，以无水乙醇为介质球磨24h，取出后在100℃烘干12h、200目过筛，放入高铝坩埚中压紧、加盖，以250℃/h的升温速率升温至750℃保温6h合成备用；
(2)以分析纯BaCO3、WO3和CuO为原料，按照Ba(Cu1/2W1/2)O3化学式的比例配料，混合球磨24小时，取出后烘干、200目过筛，放入高铝坩埚中压紧加盖，以250℃/h的升温速率升至850℃保温6h合成备用；
(3)将步骤(1)合成的0.68BiFeO3-0.32BaTiO3+1.0mol％(Bi0.5Na0.25Li0.25)TiO3及步骤(2)合成的Ba(Cu1/2W1/2)O3粉末与B2O3及MnCO3按照0.68BiFeO3-0.32BaTiO3+1.0mol％MnCO3+1.0mol％(Bi0.5Na0.25Li0.25)TiO3+3.0mol％Ba(Cu1/2W1/2)O3+2.5mol％B2O3配料，并以无水乙醇为介质，球磨24h后取出烘干、200目过筛备用；
(4)将步骤(3)合成的粉末放入热压烧结机中，采用氧化铝刚玉模具，直接在空气或纯氧气氛条件下，以5℃/min的升温速率升温至100℃，保温15min排除粉末中的水蒸气，再以20℃/min的升温速率升温至880℃的烧结温度后保温，同时逐渐加压至25Mpa，保温保压30min后，断电、开水冷，快速冷却至室温；
(5)将烧结后的样品根据需求切割成大小不同的陶瓷片，并打磨加工成两面光滑、厚度为1.0mm的薄片，薄片呈硬币形状或长方体形，披银电极；
(6)将所烧制的压电陶瓷片在硅油中极化，极化电场6000V/mm，温度120℃，保温时间30min，保持电场并冷却至室温。
5.根据权利要求1所述的具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷，其特征在于，所述陶瓷的化学式为：
0.70BiFeO3-0.30BaTiO3+1.0mol％MnCO3+2.0mol％Ba(Cu1/2W1/2)O3+2.5mol％B2O3+1.5mol％(Bi0.5Na0.25Li0.25)TiO3。
6.根据权利要求1所述的具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷，其特征在于，所述陶瓷的化学式为：
0.65BiFeO3-0.35BaTiO3+1.0mol％MnCO3+1.0mol％Ba(Cu1/2W1/2)O3+2.5mol％B2O3+1.0mol％(Bi0.5Na0.25Li0.25)TiO3。
7.根据权利要求1所述的具有高居里温度及高压电性能的铁酸铋-钛酸钡陶瓷，其特征在于，所述陶瓷的化学式为：
0.75BiFeO3-0.25BaTiO3+1.0mol％MnCO3+2.0mol％Ba(Cu1/2W1/2)O3+1.0mol％B2O3+1.0mol％(Bi0.5Na0.25Li0.25)TiO3。
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