CN115073160B - 一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷的热压烧结制备方法 - Google Patents

一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷的热压烧结制备方法 Download PDF

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CN115073160B
CN115073160B CN202210912506.4A CN202210912506A CN115073160B CN 115073160 B CN115073160 B CN 115073160B CN 202210912506 A CN202210912506 A CN 202210912506A CN 115073160 B CN115073160 B CN 115073160B
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杨心怡
杨华斌
陈巧红
王雪婷
关士博
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Guilin University of Electronic Technology
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Abstract

一种具有微纳米电畴结构的铁酸铋‑钛酸钡陶瓷的热压烧结制备方法，其组成通式为：(1‑u)BiFe1‑x Ga x O3‑uBaTiO3+0.35mol%MnCO3+nCuO+pBi(Ti1/2Zn1/2)O3+mLi2CO3+yBi(Zn2/3Nb1/3)O3，其中u、x、n、p、m和y表示摩尔分数，Li2CO3和CuO为低温烧结助剂，且0.20≤u≤0.45，0≤x≤0.05，0≤n≤0.01，0＜p≤0.20，0＜m≤0.01，0≤y≤0.02。本发明利用烧结助剂和热压反复“捶打”工艺，降低了烧结温度，减少了Bi元素的挥发和降低了晶格缺陷浓度，提高了陶瓷的致密度，大幅降低了该体系的介电损耗。利用驰豫铁电材料Bi(Zn2/ 3Nb1/3)O3减小了陶瓷的电畴尺寸，提高了陶瓷的压电性能；利用Bi(Ti0.5Zn0.5)O3提高了陶瓷的居里温度，提高了陶瓷在高温下的温度稳定性，最高使用温度可达到350℃以上。

Description

一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷的热压烧结 制备方法
技术领域
本发明涉及无铅压电陶瓷的电畴结构调控及热压烧结制备技术领域，具体是一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷的热压烧结制备方法。
背景技术
压电陶瓷在航天航空、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)体系及其改性的压电陶瓷为主，在中高温领域则以PZT+BiScO3改性陶瓷以及PbNbO3(PN)体系为主，然而Sc元素价格昂贵，同时仍然含有毒元素Pb。而偏铌酸铅一方面压电性能偏低，另一方面也含有毒元素Pb，且使用温度范围受限(＜260℃)。从目前所有的压电陶瓷体系中，我们发现压电性能和陶瓷的居里温度成一种矛盾的对立关系，即压电性能越高，则其居里温度越低，使其使用温度范围受限；另一方面，若陶瓷的居里温度越高则压电性能越低，见附图1所示。因此如何突破这一限制，获得既具有高居里温度又具有高压电性能的无铅压电陶瓷，具有重要的研究意义。
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℃)，若烧结温度过低则成瓷不充分，无法极化，烧结温度过高则Bi元素挥发严重导致大量的氧空位、晶格缺陷以及孔洞的产生，使得该体系的介电损耗过高而无法极化。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度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，这种BiFeO3-BaTiO3基压电陶瓷低温烧结技术，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充分解决，且压电性能仍然偏低。
发明内容
本发明的目的是针对上述现有BF-BT陶瓷存在的问题，提供一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷的热压烧结制备方法，采用本发明技术制备的压电陶瓷具有致密度高、介电损耗低、压电性能高、使用温度范围宽的优点，可以满足样品在350℃范围内的高温下使用。
实现本发明的技术方案如下：
一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷，其组成通式为：
(1-u)BiFe1-xGaxO3-uBaTiO3+0.35mol％MnCO3+nCuO+pBi(Ti1/2Zn1/2)O3+mLi2CO3+
yBi(Zn2/3Nb1/3)O3，其中u、x、n、p、m和y表示摩尔分数，Li2CO3和CuO为低温烧结助剂，且0.20≤u≤0.45，0≤x≤0.05，0≤n≤0.01，0＜p≤0.20，0＜m≤0.01，0≤y≤0.02。
所述陶瓷的热压烧结制备方法包括如下步骤：
1)以分析纯Fe2O3、Bi2O3、Ga2O3、MnCO3、Li2CO3、TiO2、ZnO、Nb2O5、纳米BaTiO3粉末和CuO为原料，按照(1-u)BiFe1-xGaxO3-uBaTiO3+0.35mol％MnCO3+nCuO+pBi(Ti1/2Zn1/2)O3+mLi2CO3+yBi(Zn2/3Nb1/3)O3进行配料，其中0.20≤u≤0.45，0≤x≤0.05，0≤n≤0.01，0＜p≤0.20，0＜m≤0.01，0≤y≤0.02，以无水乙醇为介质球磨24h，取出后在100℃烘干12h、200-250目筛网过筛，放入高铝坩埚中压紧、加盖，以250℃/h的升温速率升温至760℃-800℃保温6h合成备用；
2)将步骤1)合成的(1-u)BiFe1-xGaxO3-uBaTiO3+0.35mol％MnCO3+nCuO+pBi(Ti1/ 2Zn1/2)O3+mLi2CO3+yBi(Zn2/3Nb1/3)O3粉末进行二次球磨24h后取出烘干、200-250目筛过筛备用；
3)将步骤2)合成的粉末放入热压烧结机中，在空气或纯氧气氛条件下，以10℃/min的速率升温至150℃，保温10min排除粉末中的水蒸气，再以20℃/min的升温速率快速升温至870℃-950℃的烧结温度后保持温度不变，同时逐渐加压至20MPa，保压5min后减压至5MPa，然后保压5min再次加压至20MPa，保压5min后再次减压至5MPa，保压5min，再次升压至40MPa，保压30min后断电、保持压强不变，并开水冷快速冷却至室温；
4)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0.50-1.0mm的薄片，披银电极；
5)将所烧制的压电陶瓷片在硅油中极化，极化电场5000V/mm，温度120℃，保持温度和电场不变，时间30min，保持电场并冷却至室温。
压电陶瓷的压电活性与陶瓷电畴结构有关，随着电畴尺寸的减小，即畴壁密度增加，压电性能增强。为了获得电畴结构均匀的纳米畴结构陶瓷，本发明在配方中引入驰豫铁电材料Bi(Zn2/3Nb1/3)O3打断陶瓷的长程有序结构，实现获得具有纳米畴结构的BF-BT(BiFeO3-BaTiO3)陶瓷。同时在前期的研究中，发明人发现BF-BT陶瓷固溶体的高温稳定性与该体系陶瓷引入的锌钛酸铋有关，锌钛酸铋含量越高，其高温稳定性越好，为了进一步提高该体系的温度稳定性，本发明通过引入具有高居里温度的Bi(Ti0.5Zn0.5)O3，以达到提高该体系温度稳定性的目的。
本发明通过添加烧结助剂后的热压烧结工艺，降低BiFeO3-BaTiO3陶瓷烧结温度的同时，可以有效地提高陶瓷的致密度和减少晶格缺陷，降低了陶瓷的介电损耗，热压烧结过程中通过反复“捶打”工艺，减少晶格缺陷增加陶瓷的均匀性；并通过引入Bi(Zn2/3Nb1/3)O3打断陶瓷的长程有序结构，实现对电畴结构的控制；通过引入四方相结构的Bi(Ti0.5Zn0.5)O3，获得四方性更高的BF-BT陶瓷，达到提高该体系温度稳定性的目的，获得了具有高压电性能及高温稳定性的无铅压电陶瓷，居里温度高达500℃-600℃，其压电性能最高可以达到500pC/N以上，工作温度范围可达到350℃以上，如图2所示，实施例1制备的样品压电陶瓷的原位动态退极化“温度-压电性能”曲线图，因此该制备方法在无铅压电陶瓷领域取得了突破性的进展，具有重要的里程碑意义。
本发明产生的积极效果是：
(1)通过添加Bi(Zn2/3Nb1/3)O3驰豫铁电成分，实现打断BF-BT陶瓷长程有序的晶体结构，获得纳米畴结构的BFBT陶瓷晶体，增加了陶瓷的电畴密度，提高了该体系的压电活性；
(2)充分利用热压烧结技术的优势，通过在烧结温度下的“加压-保压-减压-保压-加压”的反复“捶打”工艺，提高了BiFeO3-BaTiO3陶瓷的致密度，重新排列了陶瓷的组织结构，有利于减少陶瓷的晶格缺陷及孔洞、同时快速降温减少了中间相、抑制了氧空位的产生和Fe3+变价，降低了该体系的介电损耗，提高了该体系的压电性能；
(3)通过添加Bi(Ti0.5Zn0.5)O3进一步提高了该体系的居里温度，以实现提高该体系温度稳定性的目的，同时Bi(Ti0.5Zn0.5)O3的局域无序度较高，也有利于获得纳米畴结构的BiFeO3-BaTiO3陶瓷，提高该体系的压电性能。
附图说明
图1为压电陶瓷的晶体结构与居里温度之间的关系图；
图2为本发明实施例1所制备的压电陶瓷的原位动态退极化“温度-压电性能”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：
一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷，其化学式为：
0.68BiFe0.97Ga0.03O3-0.32BaTiO3+0.35mol％MnCO3+0.4mol％CuO+0.25mol％Li2CO3+
5.0mol％Bi(Ti0.5Zn0.5)O3+0.25mol％Bi(Zn2/3Nb1/3)O3。
所述陶瓷的热压烧结制备方法包括如下步骤：
(1)以分析纯Bi2O3、Fe2O3、Ga2O3、MnCO3、CuO、Li2CO3、TiO2、ZnO、Nb2O5和纳米BaTiO3粉末为原料，按照0.68BiFe0.97Ga0.03O3-0.32BaTiO3+0.35mol％MnCO3+0.4mol％CuO+0.25mol％Li2CO3+5.0mol％Bi(Ti0.5Zn0.5)O3+0.25mol％Bi(Zn2/3Nb1/3)O3进行配料，以无水乙醇为介质球磨24h，取出后在100℃烘干12h、250目筛网过筛，放入高铝坩埚中压紧、加盖，以250℃/h的升温速率升温至760℃保温6h合成备用；
(2)将步骤(1)合成的0.68BiFe0.97Ga0.03O3-0.32BaTiO3+0.35mol％MnCO3+0.25mol％Li2CO3+0.4mol％CuO+5.0mol％Bi(Ti0.5Zn0.5)O3+0.25mol％Bi(Zn2/3Nb1/3)O3粉末进行二次球磨24h后取出烘干、250目筛网过筛备用；
(3)将步骤(2)合成的粉末放入热压烧结机中，在空气或纯氧气氛条件下，以10℃/min的速率升温至150℃，保温10min排除粉末中的水蒸气，再以20℃/min的升温速率快速升温至930℃的烧结温度后保持温度不变，同时逐渐加压至20MPa，保压5min后减压至5MPa，保压5min再次加压至20MPa，保压5min后再次减压至5MPa，保压5min后再次升压至40MPa，保压30min后断电、保持压强不变，并开水冷快速冷却至室温；
(4)将烧结后的样品根据需求切割成大小不同、呈硬币形状或长方体形的陶瓷片，并打磨加工成两面光滑、厚度1.0mm的薄片，披银电极；
(5)将所烧制的压电陶瓷片在硅油中极化，极化电场5000V/mm，温度120℃，保持温度和电场不变，时间30min，保持电场并冷却至室温。
性能测量结果如下：
d33(pC/N)/350℃ Qm kp εr Tanδ(％) Tc(℃) Td(℃)
500.8 64 0.34 599 1.20 520 495
如图2所示，实施例1制备的样品，其压电性能最高可以达到500pC/N以上，工作温度范围可达到350℃以上。
实施例2：
一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷，其化学式为：
0.70BiFe0.99Ga0.01O3-0.30BaTiO3+0.35mol％MnCO3+0.5mol％CuO+0.4mol％Li2CO3+5.0mol％Bi(Ti0.5Zn0.5)O3+0.50mol％Bi(Zn2/3Nb1/3)O3。
所述陶瓷的热压烧结制备方法同实施例1，不同的是步骤(3)中烧结温度为900℃。
性能测量结果如下：
d33(pC/N)/350℃ Qm kp εr tanδ(％) Tc(℃) Td(℃)
468.6 58 0.32 573 1.42 590 565
实施例3：
一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷，其化学式为：
0.68BiFeO3-0.32BaTiO3+0.35mol％MnCO3+0.30mol％CuO+0.40mol％Li2CO3+5.0mol％Bi(Ti0.5Zn0.5)O3+0.25mol％Bi(Zn2/3Nb1/3)O3。
所述陶瓷的热压烧结制备方法同实施例1，不同的是步骤(3)中烧结温度为950℃。
性能测量结果如下：
d33(pC/N)/350℃ Qm kp εr tanδ(％) Tc(℃) Td(℃)
450 79 0.36 684 1.76 542 515
实施例4：
一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷，其化学式为：
0.72BiFe0.97Ga0.03O3-0.28BaTiO3+0.35mol％MnCO3+0.4mol％CuO+0.5mol％Li2CO3+2.5mol％Bi(Ti0.5Zn0.5)O3+0.75mol％Bi(Zn2/3Nb1/3)O3。
所述陶瓷的热压烧结制备方法同实施例1，不同的是步骤(3)中烧结温度为880℃。
性能测量结果如下：
d33(pC/N)/350℃ Qm kp εr tanδ(％) Tc(℃) Td(℃)
437 55 0.29 552 1.36 608 575
实施例5：
一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷，其化学式为：
0.76BiFe0.97Ga0.03O3-0.24BaTiO3+0.35mol％MnCO3+0.15mol％CuO+0.15mol％Li2CO3+5.0mol％Bi(Ti0.5Zn0.5)O3+0.25mol％Bi(Zn2/3Nb1/3)O3。
所述陶瓷的热压烧结制备方法同实施例1，不同的是步骤(3)中烧结温度为900℃。
d33(pC/N)/350℃ Qm kp εr tanδ(％) Tc(℃) Td(℃)
386 67 0.25 431 1.16 628 610
实施例6：
一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷，其化学式为：
0.60BiFe0.97Ga0.03O3-0.40BaTiO3+0.35mol％MnCO3+0.6mol％CuO+0.15mol％Li2CO3+3.0mol％Bi(Ti0.5Zn0.5)O3。
所述陶瓷的热压烧结制备方法同实施例1，不同的是步骤(3)中烧结温度为950℃。
d33(pC/N)/350℃ Qm kp εr tanδ(％) Tc(℃) Td(℃)
338 56 0.27 681 3.44 458 425
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。
本发明通过成分调整实现对陶瓷微观组织结构的调控，进而提高陶瓷的压电性能，并通过引入具有高居里温度的Bi(Ti0.5Zn0.5)O3，以提高体系陶瓷的居里温度。结合热压烧结的反复“捶打”技术，减少陶瓷的晶格缺陷，增加陶瓷的均匀性和致密度，并通过热压烧结的密闭环境，减少烧结过程中Bi元素的挥发，同时通过在含氧条件下热压烧结的快速升降温也有助于减少中间相的形成，减少氧空位的产生和Fe3+离子的变价，最终实现降低介电损耗的目的。采用本发明技术制备的压电陶瓷具有致密度高、介电损耗低、压电性能高、使用温度范围宽的优点，可以满足样品在350℃范围内的高温下使用，且最大的突破是样品在超过350℃时，其最高压电性能可达500pC/N，从目前所有公开的压电陶瓷体系开看，具有如此优异高温压电性能的压电陶瓷仍为首次获得，因此本发明具重大的突破性和创造性。
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 (1)

1.一种具有微纳米电畴结构的铁酸铋-钛酸钡陶瓷的热压烧结制备方法，包括如下步骤：
1)以分析纯Fe2O3、Bi2O3、Ga2O3、MnCO3、Li2CO3、TiO2、ZnO、Nb2O5、纳米BaTiO3粉末和CuO为原料，按照(1-u)BiFe1-xGaxO3-uBaTiO3+0.35mol％MnCO3+nCuO+pBi(Ti1/2Zn1/2)O3+mLi2CO3+yBi(Zn2/3Nb1/3)O3进行配料，其中0.20≤u≤0.45，0＜x≤0.05，0＜n≤0.005，0＜p≤0.05，0＜m≤0.005，0＜y≤0.0075，其中u、x、n、p、m和y表示摩尔分数，Li2CO3和CuO为低温烧结助剂，以无水乙醇为介质球磨24h，取出后在100℃烘干12h、200-250目筛网过筛，放入高铝坩埚中压紧、加盖，以250℃/h的升温速率升温至760℃-800℃保温6h合成备用；
2)将步骤1)合成的(1-u)BiFe1-xGaxO3-uBaTiO3+0.35mol％MnCO3+nCuO+pBi(Ti1/2Zn1/2)O3+mLi2CO3+yBi(Zn2/3Nb1/3)O3粉末进行二次球磨24h后取出烘干、200-250目筛过筛备用；
3)将步骤2)合成的粉末放入热压烧结机中，在空气或纯氧气氛条件下，以10℃/min的速率升温至150℃，保温10min排除粉末中的水蒸气，再以20℃/min的升温速率快速升温至870℃-950℃的烧结温度后保持温度不变，同时逐渐加压至20MPa，保压5min后减压至5MPa，然后保压5min再次加压至20MPa，保压5min后再次减压至5MPa，保压5min，再次升压至40MPa，保压30min后断电、保持压强不变，并开水冷快速冷却至室温；
4)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0.50-1.0mm的薄片，披银电极；
5)将所烧制的压电陶瓷片在硅油中极化，极化电场5000V/mm，温度120℃，保持温度和电场不变，时间30min，保持电场并冷却至室温。
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