CN115286386B - 一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷及其制备方法 - Google Patents

一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷及其制备方法 Download PDF

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CN115286386B
CN115286386B CN202211035937.3A CN202211035937A CN115286386B CN 115286386 B CN115286386 B CN 115286386B CN 202211035937 A CN202211035937 A CN 202211035937A CN 115286386 B CN115286386 B CN 115286386B
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ceramic
potassium sodium
stoichiometric
sodium bismuth
powder
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CN115286386A (zh
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朱建国
李洪江
邢洁
谭智
谢李旭
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Sichuan University
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Sichuan University
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Abstract

本发明公开了一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷及其制备方法，采用传统的固相法制备了通式为(K0.45936Na0.51764Bi0.023)(Nb0.89958+0.957xTa0.05742Zr0.04Fe0.003)O3(‑0.01≤x≤0.04)的陶瓷粉体；再通过造粒压片、排胶、烧结和被银测试等传统的电子陶瓷制备工艺制备压电陶瓷，结果表明，过量的Nb5+占据B位，显著影响压电陶瓷的微观结构、介电和压电性能，此外，过量的Nb5+掺杂通过提供畴壁钉住效应提高了陶瓷的温度稳定性，其中在(K0.45936Na0.51764Bi0.023)(Nb0.90915Ta0.05742Zr0.04Fe0.003)O3陶瓷中可以同时获得居里温度TC＝300℃、介电损耗tanδ＝0.024、机电耦合系数kp＝0.516和压电常数d33＝450pC/N，介电常数εr＝1644，使铌钽锆铁酸钾钠铋陶瓷具有广泛的应用前景，包括传感器、执行器和其他电子设备。

Description

一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷及其制备方法
技术领域
本发明涉及无铅压电陶瓷材料技术领域，特别是涉及一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷及其制备方法。
背景技术
目前，锆钛酸铅(PZT)基陶瓷材料体系被广泛研究，用于各种应用领域，如传感器、驱动器和其他电子设备，但是铅基陶瓷的使用危害人体健康和环境。因此，在压电器件中使用环保型无铅陶瓷的要求越来越高。在众多无铅候选材料中，铌酸钾钠(KNN)基陶瓷材料体系因其巨大的压电系数(d33)、较高的居里温度(TC)和环境友好性而备受关注。为了获得能够替代铅基陶瓷的高性能KNN基陶瓷，人们对其压电性能、应变性能和温度稳定性进行了大量的研究。近年来，压电材料的研究取得了一些进展，并对其中的机制机理进行了探讨。然而，KNN基陶瓷的综合电性能问题仍然没有得到很好的解决，例如，具有高压电常数d33的KNN基陶瓷往往是在低TC条件下获得的，其温度稳定性较差，这些结果并不足以用于实际应用。因此，人们一直致力于提高 KNN基陶瓷的综合电学性能。
为了更好地理解掺杂机理，需要深入研究原子水平的局域结构，这对提高无铅压电陶瓷的功能性能至关重要。KNN基陶瓷的压电和介电性能受钙钛矿型结构(ABO3)中某些A或B阳离子的替换影响，从而影响多晶相变、晶粒结构、铁电畴结构和铁电性能。本发明发现B位非化学计量掺杂与多晶相变的行为、微观结构、铁电性、压电性和介电性能之间的关系几乎没有报道。适量或过量的B位非化学计量掺杂可以提高陶瓷的结晶度，这可以归因于在A 位上产生空位，从而在烧结过程中增强离子的扩散。
众所周知，具有多晶型相界结构的KNN基陶瓷的压电和介电性能对温度有很强的依赖性。因此，较高的d33和机电耦合因子(kp)值总是以降低陶瓷的TC为代价。如何克服大d33、kp与高TC的矛盾已经成为一个热点问题。本发明发现B位非化学计量掺杂KNN基陶瓷可以在保持居里温度TC较高的情况下获得较高的d33。此外，B位非化学计量的引入导致陶瓷中存在缺陷偶极子和畴壁钉住效应，这有助于提高d33的温度稳定性和介电损耗(tanδ)。因此，对B位非化学计量掺杂KNN基陶瓷的压电和介电性能进行更具体的研究是值得的。
发明内容
本发明的目的是提供一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷及其制备方法，以解决现有技术中KNN基陶瓷的综合电学性能较差的问题，本发明利用在KNN基陶瓷的B位非化学计量掺入Nb5+的方法提供一种综合电性能优良的铌钽锆铁酸钾钠铋陶瓷。
为实现上述目的，本发明提供了一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷，该陶瓷材料的通式如下：
(K0.45936Na0.51764Bi0.023)(Nb0.89958+0.957xTa0.05742Zr0.04Fe0.003)O3，
其中，-0.01≤x≤0.04。
优选的，该陶瓷材料的压电性能：压电系数d33为300-450pC/N、居里温度TC为300-305℃、机电耦合因子kp为0.385-0.516、介电常数εr为 1400-1644、介电损耗tanδ为0.024-0.038。
优选的，x为0.01。
优选的，该陶瓷材料的压电性能：压电系数d33为450pC/N、居里温度TC为300℃、机电耦合因子kp为0.516、介电常数εr为1644和介电损耗tanδ为0.024。
一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷的制备方法，包括以下步骤：
(1)固相法制备铌钽锆铁酸钾钠铋陶瓷粉体
将原料分别按通式进行称量、配料，之后放于聚氨酯球磨罐中并加入分散介质，然后放入行星球磨机中球磨直至混合均匀，将混合均匀的浆料盛装在不锈钢盆中，在烘灯下烘烤得到干燥好的粉料，把干燥好的粉料装入坩埚中，在程序控温箱式炉中升温至850℃～950℃下预烧6小时，得到预烧粉体；
(2)二次球磨
将步骤(1)制备的预烧粉体放于聚氨酯球磨罐中再次加入分散介质，之后放入行星球磨机中进行二次球磨，然后在烘灯下烘烤得到干燥好的陶瓷粉体；
(3)造粒压片
将步骤(2)中干燥好的陶瓷粉体与5～10wt％聚乙烯醇粘结剂充分混合后进行造粒，形成分布均匀的颗粒，然后在单轴压强力10～15MPa下压成直径 10mm、厚度1mm的预制陶瓷圆片；
(4)排胶烧结
将步骤(3)中的预制陶瓷圆片在温度500℃～550℃排胶，然后在温度 1090℃～1120℃烧结3～5小时制成烧结陶瓷圆片；
(5)被银极化
将烧结陶瓷圆片刷上浓度为5～15wt％的银浆，然后在温度700℃～800℃继续烧结10～15分钟制成样品，在室温～120℃之间的油浴中进行极化制成压电陶瓷。
优选的，步骤(1)中各种掺杂元素的原料为其氧化物或碳酸盐。
优选的，步骤(1)和步骤(2)中球磨时，粉料：锆球为1：2～3，粉料：分散介质为1：2～3，分散介质为无水乙醇，球磨时间为15-20小时，转速为 250～320r/mi n，烘烤时间为2-3小时。
优选的，步骤(1)中球磨后的粒径分布为D50＝0.7～0.8μm， D90＝1.7～1.8μm，D97＝2.2～2.4μm。
优选的，步骤(2)中球磨后的粒径分布为D50＝0.3～0.4μm， D90＝0.7～0.8μm，D97＝1.2～1.5μm。
优选的，步骤(5)极化过程中极化电压从小逐步增加到预定极化电压，极化场强为3～4kV/mm，保压时间为10～15分钟。
一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷的应用，此陶瓷材料作为无铅压电陶瓷应用。
因此，本发明采用上述结构的一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷及其制备方法，具有以下有益效果：
1、利用非化学计量Nb5+优化铌钽锆铁酸钾钠铋陶瓷的综合电性能，其中当x为0.01，该陶瓷材料的压电性能：压电系数d33为450pC/N、居里温度TC为300℃、机电耦合因子kp为0.516、介电常数εr为1644和介电损耗tanδ为0.024；
2、过量Nb5+的引入导致缺陷偶极子和畴壁钉住效应，有利于提高铌钽锆铁酸钾钠铋陶瓷压电性能的温度稳定性，在保持居里温度不变的情况下，提高了陶瓷材料的压电系数、机电耦合因子、介电常数，降低了介电损耗，进而提高了陶瓷材料的综合电学性能。
下面通过附图和实施例，对本发明的技术方案做进一步的详细描述。
附图说明
图1为具有不同含量的Nb5+的铌钽锆铁酸钾钠铋陶瓷材料的X射线衍射图谱；
图2为图1的放大图；
图3为不同含量的Nb5+的铌钽锆铁酸钾钠铋陶瓷的扫描电镜照片(SEM)；
图4为不同含量的Nb5+的铌钽锆铁酸钾钠铋陶瓷的的PFM图像，扫描区域为4×4μm；
图5为具有不同含量的Nb5+的铌钽锆铁酸钾钠铋陶瓷材料的d33和TC；
图6为具有不同含量的Nb5+的铌钽锆铁酸钾钠铋陶瓷材料的kp和tanδ；
图7为具有不同含量的Nb5+的铌钽锆铁酸钾钠铋陶瓷材料的高温介温曲线；
图8为具有不同含量的Nb5+的铌钽锆铁酸钾钠铋陶瓷材料的低温介温曲线；
图9为具有不同含量的Nb5+的铌钽锆铁酸钾钠铋陶瓷材料的电滞回线图；
图10为具有不同含量的Nb5+的铌钽锆铁酸钾钠铋陶瓷材料的原位d33温度稳定性，插图为Δd33/d33RT与温度的关系图。
具体实施方式
以下将对本发明进行进一步的描述，需要说明的是，本实施例以本技术方案为前提，给出了详细的实施方式和具体的操作过程，但本发明并不限于本实施例。
实施例1
一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷的制备方法，包括以下步骤：
(1)固相法制备铌钽锆铁酸钾钠铋陶瓷粉体
将原料分别按通式：(K0.45936Na0.51764Bi0.023)(Nb0.89001Ta0.05742Zr0.04Fe0.003)O3(x＝-0.01，编号1#)，(K0.45936Na0.51764Bi0.023)(Nb0.89958Ta0.05742Zr0.04Fe0.003)O3(x＝0.00，编号2#)，(K0.45936Na0.51764Bi0.023)(Nb0.90915Ta0.05742Zr0.04Fe0.003)O3(x＝0.01，编号3#)，(K0.45936Na0.51764Bi0.023)(Nb0.91872Ta0.05742Zr0.04Fe0.003)O3(x＝0.02，编号4#)，(K0.45936Na0.51764Bi0.023)(Nb0.92829Ta0.05742Zr0.04Fe0.003)O3(x＝0.03，编号5#)，(K0.45936Na0.51764Bi0.023)(Nb0.93786Ta0.05742Zr0.04Fe0.003)O3(x＝0.04，编号6#)进行称量、配料，放于聚氨酯球磨罐中(粉料：锆球＝1：2～3)，以无水乙醇为分散介质 (粉料：无水乙醇＝1：2～3)，放入行星球磨机中球磨15到20小时(转速为 250～320r/mi n)，将混合均匀的浆料盛装在不锈钢盆中，在烘灯下烘烤2到3 小时，把干燥好的粉料装入坩埚中，然后在程序控温箱式炉中升温至900℃下预烧6小时，得到1#、2#、3#、4#、5#、 6#(K0.45936Na0.51764Bi0.023)(Nb0.89958+0.957xTa0.05742Zr0.04Fe0.003)O3预制粉体。
(2)二次球磨
将制备的1#、2#、3#、4#、5#、6#(K0.45936Na0.51764Bi0.023)(Nb0.89958+ 0.957xTa0.05742Zr0.04Fe0.003)O3预制粉料放于聚氨酯球磨罐中进行二次球磨(粉料：锆球＝1：2～3)，以无水乙醇为分散介质(粉料：溶剂＝1：2～3)，放入行星球磨机中球磨15到20小时(转速为250～320r/mi n)，在烘灯下烘烤2到3小时得到陶瓷粉体，通过激光粒度仪测试球磨后粒径分布为：D50＝0.3～0.4μm；D90＝0.7～0.8μm；D97＝1.2～1.5μm。
(3)造粒压片
在上述烘干的陶瓷粉体与8wt％聚乙烯醇粘结剂充分混合后进行造粒，形成分布均匀的颗粒，然后在单轴压强力10～15MPa下压成直径10mm、厚度 1mm的1#、2#、3#、4#、5#、6#(K0.45936Na0.51764Bi0.023)(Nb0.89958+0.957xTa0.05742Zr0.04Fe0.003)O3预制陶瓷圆片。
(4)排胶烧结
将上述1#、2#、3#、4#、5#、6#(K0.45936Na0.51764Bi0.023)(Nb0.89958+ 0.957xTa0.05742Zr0.04Fe0.003)O3预制陶瓷圆片在温度520℃排胶，然后在温度1100℃烧结4小时制成1#、2#、3#、4#、5#、 6#(K0.45936Na0.51764Bi0.023)(Nb0.89958+0.957xTa0.05742Zr0.04Fe0.003)O3烧结陶瓷圆片。
(5)被银极化
将上述烧结后获得的1#、2#、3#、4#、5#、6#(K0.45936Na0.51764Bi0.023)(Nb0.89958+ 0.957xTa0.05742Zr0.04Fe0.003)O3烧结陶瓷圆片刷上浓度为 10wt％的银浆，然后在温度750℃烧结12分钟制成样品。烧银后在烤炉上340℃左右烘烤30分钟左右，准备极化。在100℃之间的油浴中，进行极化。极化电压从小逐步增加到预定极化电压，极化场强为3kV/mm，保压时间为12分钟，制成1#、2#、3#、4#、5#、6#(K0.45936Na0.51764Bi0.023)(Nb0.89958+ 0.957xTa0.05742Zr0.04Fe0.003)O3压电陶瓷。
实施例2
对实施例1中制成的1#、2#、3#、4#、5#、 6#(K0.45936Na0.51764Bi0.023)(Nb0.89958+ 0.957xTa0.05742Zr0.04Fe0.003)O3压电陶瓷进行电学性能测试和表征。
在室温25℃、湿度45～65％RH的环境中静置24h后，使用相关仪器测量样品的各项电学参数(kp,d33,εr,tanδ等)，其中介电常数与损耗的测试频率为1kHz。需要说明的是上述测试方法均为本领域常规使用的方法，在此不再赘述。
(1)XRD表征
图1描述了六种(K0.45936Na0.51764Bi0.023)(Nb0.89958+0.957xTa0.05742Zr0.04Fe0.003)O3陶瓷的相结构和相纯度，其XRD图谱显示合成的KNN基陶瓷为单一钙钛矿结构，过量Nb5+能够进入KNN晶格中，形成固溶体。如图2所示，为了进一步表征陶瓷随Nb5+含量增加的相结构演变，分裂峰随着Nb5+含量的增加而变化。
(2)SEM表征
图3显示了抛光和热蚀刻(K0.45936Na0.51764Bi0.023)(Nb0.89958+ 0.957xTa0.05742Zr0.04Fe0.003)O3陶瓷材料的SEM显微照片，显示了密集堆积的立方体状晶粒的随机取向。陶瓷的表面形貌表明小晶粒围绕着大晶粒，这是异常生长的结果，从而导致较高的体积密度。适当非化学计量Nb5+含量可以大大提高(K0.45936Na0.51764Bi0.023)(Nb0.89958+ 0.957xTa0.05742Zr0.04Fe0.003)O3陶瓷的致密化和晶粒长大，而过量的Nb5+不利于致密组织的形成。
(3)PFM表征
图4展示与化学计量的(K0.45936Na0.51764Bi0.023)(Nb0.89958Ta0.05742Zr0.04Fe0.003)O3陶瓷(x＝0)相比，非化学计量的(K0.45936Na0.51764Bi0.023)(Nb0.90915Ta0.05742Zr0.04Fe0.003)O3陶瓷(x＝0.01)的纳米畴和片层结构分布更为致密和均匀，这些结果表明适当的Nb5+含量占据B位可以细化极性纳米区域的尺寸，增加陶瓷材料的致密性。
(4)电学性能表征
图5显示了(K0.45936Na0.51764Bi0.023)(Nb0.89958+0.957xTa0.05742Zr0.04Fe0.003)O3陶瓷在不同 x含量下的d33和TC。d33先增大后逐渐减小，在x＝0.01时达到最大值450pC/N。而Nb5+的加入量为化学计量的量时，d33值为380pC/N。虽然在KNN基陶瓷中通常能够实现450pC/N的d33值，但很少报道在高TC下实现如此大的d33值，说明本发明制备的陶瓷材料在较高的温度下，稳定性较高。
图6展示了kp也表现出与d33相似的演化趋势，在x＝0.01处达到峰值 0.516。tanδ值先减小后逐渐增大，在x＝0.01时达到最小值0.024。
图7显示了εr值随(K0.45936Na0.51764Bi0.023)(Nb0.89958+0.957xTa0.05742Zr0.04Fe0.003)O3陶瓷从室温到500℃温度的变化。随着测量温度的升高，样品在TC处表现出显著的铁电四方到顺电立方相变。加入Nb5+后TC值基本保持不变。
考虑到在～60℃观察到的相对介电常数峰与R-T相变有关，该峰观察到的温度变化表明了Nb5+加入后的铌钽锆铁酸钾钠铋陶瓷结构转变。图8描述了陶瓷的TR-T值与Nb5+含量的关系。当x<0.01时，TR-T随着Nb5+含量的增加而降低，这可归因于容差因子值的降低。然而，当x>0.01时，随着x的进一步增加， TR-T呈现相反的趋势，这与缺陷偶极子的形成有关。
图9展示了(K0.45936Na0.51764Bi0.023)(Nb0.89958+0.957xTa0.05742Zr0.04Fe0.003)O3陶瓷具有典型的P-E环，这表明所有样品都是铁电体。随着Nb5+浓度从-0.01增加到0.02，陶瓷的剩余极化(Pr)值先增大后减小。而 (K0.45936Na0.51764Bi0.023)(Nb0.89958+0.957xTa0.05742Zr0.04Fe0.003)O3(x＝0.03和0.04)陶瓷的 Pr值异常增大，可归因于泄漏电流的增大。(K0.45936Na0.51764Bi0.023)(Nb0.89958+0.957xTa0.05742Zr0.04Fe0.003)O3(x＝0.03和0.04)陶瓷的泄漏电流可能是由非化学计量学诱导的移动带电缺陷引起的。
图10表明非化学计量Nb5+的引入导致晶格中存在缺陷偶极子，从而控制畴壁钉住效应。稳定畴结构和降低畴壁迁移率也可能有助于d33值的温度稳定性。
因此，本发明采用上述结构的一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷及其制备方法，过量的Nb5+占据B位，显著影响压电陶瓷的微观结构、介电、铁电和压电性能，此外，过量的Nb5+掺杂通过提供畴壁钉住效应提高了陶瓷的温度稳定性，其中在(K0.45936Na0.51764Bi0.023)(Nb0.90915Ta0.05742Zr0.04Fe0.003)O3陶瓷中可以同时获得居里温度TC＝300℃、介电损耗tanδ＝0.024、机电耦合系数kp＝0.516 和压电常数d33＝450pC/N，介电常数εr＝1644，使铌钽锆铁酸钾钠铋陶瓷具有广泛的应用前景，包括传感器、执行器和其他电子设备。
最后应说明的是：以上实施例仅用以说明本发明的技术方案而非对其进行限制，尽管参照较佳实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对本发明的技术方案进行修改或者等同替换，而这些修改或者等同替换亦不能使修改后的技术方案脱离本发明技术方案的精神和范围。

Claims (8)

1.一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷，其特征在于：该陶瓷材料的通式如下：
(K0.45936Na0.51764Bi0.023)(Nb0.89958+0.957xTa0.05742Zr0.04Fe0.003)O3，
其中，x为0.01。
2.根据权利要求1所述的一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷，其特征在于：该陶瓷材料的压电性能：压电系数d33为450pC/N、居里温度TC为300℃、机电耦合因子kp为0.516、介电常数εr为1644和介电损耗tanδ为0.024。
3.根据权利要求1-2任一项所述的一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷的制备方法，其特征在于：包括以下步骤：
(1)固相法制备铌钽锆铁酸钾钠铋陶瓷粉体
将原料分别按通式进行称量、配料，之后放于聚氨酯球磨罐中并加入分散介质，然后放入行星球磨机中球磨直至混合均匀，将混合均匀的浆料盛装在不锈钢盆中，在烘灯下烘烤得到干燥好的粉料，把干燥好的粉料装入坩埚中，在程序控温箱式炉中升温至850℃～950℃下预烧6小时，得到预烧粉体；
(2)二次球磨
将步骤(1)制备的预烧粉体放于聚氨酯球磨罐中再次加入分散介质，之后放入行星球磨机中进行二次球磨，然后在烘灯下烘烤得到干燥好的陶瓷粉体；
(3)造粒压片
将步骤(2)中干燥好的陶瓷粉体与5～10wt％聚乙烯醇粘结剂充分混合后进行造粒，形成分布均匀的颗粒，然后在单轴压强力10～15MPa下压成直径10mm、厚度1mm的预制陶瓷圆片；
(4)排胶烧结
将步骤(3)中的预制陶瓷圆片在温度500℃～550℃排胶，然后在温度1090℃～1120℃烧结3～5小时制成烧结陶瓷圆片；
(5)被银极化
将烧结陶瓷圆片刷上浓度为5～15wt％的银浆，然后在温度700℃～800℃继续烧结10～15分钟制成样品，在室温～120℃之间的油浴中进行极化制成压电陶瓷。
4.根据权利要求3所述的一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷的制备方法，其特征在于：步骤(1)中各种掺杂元素的原料为其氧化物或碳酸盐。
5.根据权利要求3所述的一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷的制备方法，其特征在于：步骤(1)和步骤(2)中球磨时，粉料：锆球为1：2～3，粉料：分散介质为1：2～3，分散介质为无水乙醇，球磨时间为15-20小时，转速为250～320r/min，烘烤时间为2-3小时。
6.根据权利要求3所述的一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷的制备方法，其特征在于：步骤(1)中球磨后的粒径分布为D50＝0.7～0.8μm，D90＝1.7～1.8μm，D97＝2.2～2.4μm。
7.根据权利要求3所述的一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷的制备方法，其特征在于：步骤(2)中球磨后的粒径分布为D50＝0.3～0.4μm，D90＝0.7～0.8μm，D97＝1.2～1.5μm。
8.根据权利要求3所述的一种非化学计量Nb5+的铌钽锆铁酸钾钠铋陶瓷的制备方法，其特征在于：步骤(5)极化过程中极化电压从小逐步增加到预定极化电压，极化场强为3～4kV/mm，保压时间为10～15分钟。
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