CN115093212B - 一种使用温度超过300℃的高性能铁酸铋-钛酸钡陶瓷及其低温液相烧结制备方法 - Google Patents
一种使用温度超过300℃的高性能铁酸铋-钛酸钡陶瓷及其低温液相烧结制备方法 Download PDFInfo
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Abstract
本发明公开了一种使用温度超过300℃的高性能铁酸铋‑钛酸钡陶瓷及其低温液相烧结制备方法，其组成通式为：(1‑u)BiFeO3‑uBaTiO3+1.0mol％MnCO3+x[Bi0.5(NatLi0.5‑t)]TiO3+yB2O3，其中u、x、y和t表示摩尔分数，[Bi0.5(NatLi0.5‑t)]TiO3及B2O3为烧结助剂，且0.25≤u≤0.40，0＜x≤0.01，0＜y≤0.05，0≤t≤0.5。本发明利用具有低容忍因子的[Bi0.5(NatLi1‑t)]TiO3，在降低(1‑u)BiFeO3‑uBaTiO3陶瓷烧结温度的同时，又提高了该陶瓷的高温压电性能和高温稳定性，获得了在高温下具有优异压电性能的无铅压电陶瓷，使用温度超过300℃，在T＞300℃时，其压电性能可达400pC/N以上，最高原位退极化温度点达到360℃，相比于现有压电陶瓷，高温压电性能得到了大幅提升。
Description
技术领域
本发明涉及无铅压电陶瓷及其低温液相烧结技术，尤其是一种使用温度超过300℃的高性能铁酸铋-钛酸钡陶瓷及其低温液相烧结制备方法。
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。
文献[Serhiy O，J Am Ceram Soc,2009,92(12):2957-2961]报导了具有高居里温度与良好压电性能的BiFeO3–BaTiO3基无铅压电陶瓷，烧结温度在950-975℃，该体系具有很好的高温稳定性，居里温度高达400-600℃，而退极化温度也高达400℃以上；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，采用低温烧结助剂加固相合成烧结的方法，成功将烧结温度降至900℃左右。
压电陶瓷的发展趋势是无铅化、多层片式化、微型化等，而多层压电陶瓷制备的关键在于实现低温内电极材料的共烧，但是目前多层压电陶瓷在与低温电极材料共烧时仍然成本较高，其主要原因是烧结温度较高(≥950℃)，为了提高内电极材料的稳定性，需要在电极材料中添加一定比例的贵金属如钯、铂等。由于钯、铂等价格昂贵，因此内电极材料的成本占到了整个多层压电陶瓷生产成本的80％以上，导致成本高昂无法下降。因此，研究与发展更低温度下烧结的压电陶瓷材料对于降低企业生产成本，具有重大意义。
发明内容
本发明的目的是针对上述现有技术，提供一种使用温度超过300℃的高性能铁酸铋-钛酸钡陶瓷及其低温液相烧结制备方法，可以在高于300℃以上温度使用，并且具有优异的高温压电性能，同时[Bi0.5(NatLi0.5-t)]TiO3还可以降低陶瓷的烧结温度，减少Bi元素的挥发和氧空位的产生，降低陶瓷的介电损耗。
实现本发明目的的技术方案是：
一种使用温度超过300℃的高性能铁酸铋-钛酸钡陶瓷，其组成通式为：
(1-u)BiFeO3-uBaTiO3+1.0mol％MnCO3+x[Bi0.5(NatLi0.5-t)]TiO3+yB2O3，其中u、x、y和t表示摩尔分数，[Bi0.5(NatLi0.5-t)]TiO3及B2O3为烧结助剂，且0.25≤u≤0.40，0＜x≤0.01，0＜y ≤0.05，0≤t≤0.5。
所述使用温度超过300℃的高性能铁酸铋-钛酸钡陶瓷的低温液相烧结制备方法，包括如下步骤：
1)以分析纯Fe2O3、Bi2O3、BaCO3、TiO2、Li2CO3、Na2CO3和B2O3为原料，按照 (1-u)BiFeO3-uBaTiO3+x[Bi0.5(NatLi0.5-t)]TiO3+yB2O3进行配料，其中0.25≤u≤0.40，0＜x≤0.01， 0＜y≤0.05、0≤t≤0.5，以无水乙醇为介质球磨24h，取出后在100℃烘干12h、过筛，过筛目数为200-250目，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)将步骤1)预烧合成的(1-u)BiFeO3-uBaTiO3+x[Bi0.5(NatLi1-t)]TiO3+yB2O3粉末与MnCO3按照(1-u)BiFeO3-uBaTiO3+1.0mol％MnCO3+x[Bi0.5(NatLi0.5-t)]TiO3+yB2O3配料，并以无水乙醇为介质，球磨24h后取出烘干、过筛，过筛目数为200-250目；
3)将过筛后的粉末加入5％PVA溶液造粒，在钢模中于100MPa下压制成呈硬币形状、直径1.0cm的素片；
4)成型的素片以5℃/h的升温速率缓慢升温至600℃，保温6h排胶，再以20℃/min的升温速率到830℃-950℃的烧结温度后保温4-8h，随炉冷却到室温，烧结后的样品加工成两面光滑、厚度1.0mm的薄片，披银电极；
5)将所制的压电陶瓷片在硅油中极化，极化电场6000V/mm，温度100℃，时间30min，保持电场并冷却至室温。
本发明通过在BiFeO3-BaTiO3固溶体陶瓷中添加钙钛矿结构的[Bi0.5(NatLi1-t)]TiO3及氧化物B2O3，在降低烧结温度的同时，又可以提高BiFeO3-BaTiO3陶瓷的压电性能和居里温度，进而使BiFeO3-BaTiO3陶瓷介电损耗大幅下降。
本发明的积极效果是：
(1)充分利用了[Bi0.5(NatLi0.5-t)]TiO3的钙钛矿结构，能与(1-u)BiFeO3-uBaTiO3+1.0mol％MnCO3形成固溶体，避免了以Li2CO3添加时Li1+以间隙原子或占位原子的形式存在，减少了陶瓷的晶格常数畸变、避免引起化合价的不平衡进而导致氧空位的产生，降低了陶瓷的介电损耗；
(2)[Bi0.5(NatLi0.5-t)]TiO3具有很低的容忍因子(取t＝0时)：
其中RLi为Li离子的半径，RBi为Bi离子的半径，RTi为Ti离子的半径，Ro为O离子的半径，因此，根据容忍因子与居里温度的关系，其应该具有较高的居里温度，通过将 [Bi0.5(NatLi1-t)]TiO3与(1-u)BiFeO3-uBaTiO3+1.0mol％MnCO3形成固溶体，可以有效地提高该体系的居里温度和温度稳定性；
(3)本发明所制备的陶瓷，具有优异的高温压电性能d33＞400pC/N和超过300℃的使用温度，且不含有毒元素Pb及贵金属Sc等；
(4)本发明采用钙钛矿结构的[Bi0.5(NatLi0.5-t)]TiO3及氧化物B2O3复合烧结助剂大幅降低BiFeO3-BaTiO3陶瓷烧结温度，成功地将(1-u)BiFeO3-uBaTiO3+1.0mol％MnCO3陶瓷的烧结温度从960℃降低到了830℃，有效地减少了Bi元素的挥发和氧空位的产生，降低了陶瓷的介电损耗，因此从技术上看，具有重大突破和技术上的创新。
附图说明
图1为本发明陶瓷的介电温谱曲线图；
图2为本发明实施例1所制备陶瓷样品的原位动态退极化曲线图。
具体实施方式
下面通过实施例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：
一种使用温度超过300℃的高性能铁酸铋-钛酸钡陶瓷，其化学式为：
0.67BiFeO3-0.33BaTiO3+1.0mol％MnCO3+0.24mol％[Bi0.5(Na0.25Li0.25)]TiO3+2.5mol％B2O3，其低温液相烧结制备方法包括如下步骤：
(1)以分析纯Fe2O3、Bi2O3、BaCO3、TiO2、Na2CO3、Li2CO3和B2O3为原料，按照0.67BiFeO3-0.33BaTiO3+0.24mol％[Bi0.5(Na0.25Li0.25)]TiO3+2.5mol％B2O3进行配料，以无水乙醇为介质球磨24h，在100℃烘干12h、过筛，过筛目数为200目，放入高铝坩埚中压紧、加盖，并以250℃/h的升温速率升温至750℃，保温6h合成备用；
(2)将步骤(1)预烧合成的0.67BiFeO3-0.33BaTiO3+2.5mol％B2O3+ 0.24mol％[Bi0.5(Na0.25Li0.25)]TiO3粉末与MnCO3按照0.67BiFeO3-0.33BaTiO3+1.0mol％MnCO3+2.5mol％B2O3+0.24mol％[Bi0.5(Na0.25Li0.25)]TiO3配料，并以无水乙醇为介质，球磨24h后取出烘干、过筛，过筛目数为200目；
(3)将过筛后的粉末加入5％PVA溶液造粒，在钢模中于100MPa下压制成呈硬币形状、直径1.0cm的素片；
(4)成型的素片以5℃/h的升温速率升温在至600℃，保温6h排胶，再以20℃/min的速率快速升温到920℃的烧结温度后保温6h，断电后随炉冷却到室温，烧结后的样品加工成两面光滑、厚度1.0mm的薄片，披银电极，650℃烧银，保温30min；
(5)将所制备的压电陶瓷片在硅油中极化，极化电场6000V/mm，温度100℃，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(℃) |
| 403 | 36 | 0.28 | 587 | 2.1 | 470 | 430 |
实施例2：
一种使用温度超过300℃的高性能铁酸铋-钛酸钡陶瓷，其化学式为：
0.75BiFeO3-0.25BaTiO3+1.0mol％MnCO3+0.48mol％[Bi0.5(Na0.25Li0.25)]TiO3+5.0mol％B2O3，制备方法同实施例1，不同的是，步骤(4)中烧结温度为830℃，保温时间为6h。
性能测量结果如下：
| d33(pC/N) | Qm | kp | εr | tanδ(％) | Tc(℃) | Td(℃) |
| 337 | 43 | 0.26 | 483 | 1.80 | 510 | 480 |
实施例3：
一种使用温度超过300℃的高性能铁酸铋-钛酸钡陶瓷，其化学式为：0.65BiFeO3-0.35BaTiO3+1.0mol％MnCO3+0.96mol％[Bi0.5(Na0.1Li0.4)]TiO3+2.5mol％B2O3，制备方法同实施例1，不同的是，步骤(4)中烧结温度840℃，保温时间为6h。
性能测量结果如下：
| d33(pC/N) | Qm | kp | εr | tanδ(％) | Tc(℃) | Td(℃) |
| 364 | 45 | 0.276 | 543 | 2.46 | 450 | 405 |
实施例4：
一种使用温度超过300℃的高性能铁酸铋-钛酸钡陶瓷，其化学式为：0.70BiFeO3-0.30BaTiO3+1.0mol％MnCO3+0.36mol％(Bi0.5Li0.5)TiO3+2.50mol％B2O3，制备方法同实施例1。
性能测量结果如下：
| d33(pC/N) | Qm | kp | εr | tanδ(％) | Tc(℃) | Td(℃) |
| 369 | 39 | 0.31 | 543 | 2.25 | 489 | 460 |
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。
高温压电陶瓷用于汽车燃油监控、核电、军工、石油勘探以及航天航空等领域，通常压电性能和使用温度之间为一对立关系，也就是说使用温度越高，则压电性能越底，对于在300℃以上温度范围使用的压电陶瓷，其压电性能常低于100pC/N，本发明制备的陶瓷其居里温度在450-510℃之间，见图1，由于在室温至居里温度之间没有其他相变，原位动态退极化测试曲线表明本发明所制备陶瓷的实际使用温度可达到300℃以上，见图2，实施例1制备的样品在实际使用过程中的最高使用温度和性能随温度变化情况，相比于现有技术，本发明陶瓷在性能上具有重大突破。
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 (2)
1.一种使用温度超过300℃的高性能铁酸铋-钛酸钡陶瓷，其特征在于，其组成通式为：
(1-u)BiFeO3-uBaTiO3+1.0mol%MnCO3+x[Bi0.5(Na t Li0.5-t )]TiO3+yB2O3，其中u、x、y和t表示摩尔分数，[Bi0.5(Na t Li0.5-t )]TiO3及B2O3为烧结助剂，且0.25≤u≤0.40，0＜x≤0.01，0＜y≤0.05，0＜t＜0.5。
2.权利要求1所述的使用温度超过300℃的高性能铁酸铋-钛酸钡陶瓷的低温液相烧结制备方法，其特征在于，包括如下步骤：
1）以分析纯Fe2O3、Bi2O3、BaCO3、TiO2、Li2CO3、Na2CO3和B2O3为原料，按照(1-u)BiFeO3-uBaTiO3+x[Bi0.5(Na t Li0.5-t )]TiO3+yB2O3进行配料，其中0.25≤u≤0.40，0＜x≤0.01，0＜y≤0.05、0＜t＜0.5，以无水乙醇为介质球磨24h，取出后在100℃烘干12h、过筛，过筛目数为200-250目，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）将步骤1）预烧合成的(1-u)BiFeO3-uBaTiO3+x[Bi0.5(Na t Li0.5-t )]TiO3+yB2O3粉末与MnCO3按照(1-u)BiFeO3-uBaTiO3+1.0mol%MnCO3+x[Bi0.5(Na t Li0.5-t )]TiO3+yB2O3配料，并以无水乙醇为介质，球磨24h后取出烘干、过筛，过筛目数为200-250目；
3）将过筛后的粉末加入5%PVA溶液造粒，在钢模中于100MPa下压制成呈硬币形状、直径1.0cm的素片；
4）成型的素片以5℃/h的升温速率缓慢升温至600℃，保温6h排胶，再以20℃/min的升温速率到830℃-950℃的烧结温度后保温4-8h，随炉冷却到室温，烧结后的样品加工成两面光滑、厚度1.0mm的薄片，披银电极；
5）将所制的压电陶瓷片在硅油中极化，极化电场6000V/mm，温度100℃，时间30min，保持电场并冷却至室温。
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Application publication date: 20220923 Assignee: Guilin Xianjingkuangbao Technology Development Co.,Ltd. Assignor: GUILIN University OF ELECTRONIC TECHNOLOGY Contract record no.: X2023980046674 Denomination of invention: A high-performance bismuth ferrite barium titanate ceramic with a usage temperature exceeding 300 degC and its low-temperature liquid phase sintering preparation method Granted publication date: 20230922 License type: Common License Record date: 20231109 Application publication date: 20220923 Assignee: Guilin Sensing Material Technology Co.,Ltd. Assignor: GUILIN University OF ELECTRONIC TECHNOLOGY Contract record no.: X2023980046110 Denomination of invention: A high-performance bismuth ferrite barium titanate ceramic with a usage temperature exceeding 300 degC and its low-temperature liquid phase sintering preparation method Granted publication date: 20230922 License type: Common License Record date: 20231107 |