CN107867854A - 一种钛酸铋钠基陶瓷粉体及其制备方法 - Google Patents
一种钛酸铋钠基陶瓷粉体及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种钛酸铋钠（NBT）基陶瓷纳米粉体及其制备方法，以柠檬酸、乙二醇、钛酸丁酯、乙酸钡、硝酸铋、硝酸钠等为主要原料，按照通式(1−x)Na0.5Bi0.5TiO3–xBaTiO3称量与配料，通过控制体系温度和投料顺序以改性聚合物前驱体法制备粉体的过程。溶胶经焦化和煅烧等工艺制得组分均一、结晶性完整、平均粒径为47.5~53.8nm的NBT基陶瓷纳米粉体。促进了聚合物前驱体法在工业规模化生产NBT基纳米粉体方面的应用，具有非常高的应用价值和商业价值。
Description
技术领域
本发明涉及无铅压电陶瓷纳米粉体及其制备领域，具体为钛酸铋钠基陶瓷纳米粉体及利用改性聚合物前驱体法制备该粉体的方法。
背景技术
钛酸铋钠基压电陶瓷（称为NBT基陶瓷）材料具有较高的居里温度和室温附近优异的铁电性能等被人们所熟知，并被认为是最有可能成为替代含铅固溶体的一类材料。然而，NBT基陶瓷材料在传统高温烧结制备过程中会因为钠元素的挥发而导致结构中的组分不均一、性能波动大、缺陷种类多等缺点。为了改善NBT基陶瓷的烧结性并提高陶瓷的电学性能，通常通过优化陶瓷粉体的特性来实现。其中采用液相化学法制备高性纳米能粉体是一个非常有效的措施，主要集中于溶胶-凝胶法、水热合成法和乳液聚合法等。然而这些工艺方法往往存在设备费用投入高、工艺复杂和生产效率低等缺点，使得液相化学法制备NBT基陶瓷纳米粉体难于大规模生产。
近来，我国在材料产业中的投入不断加大，特别是对压电材料的投入和研发一直是关注的热点。所以，亟待优化液相化学法制备高质量NBT基陶瓷纳米粉体的问题，从而取代含铅材料在电子陶瓷元器件中的应用。NBT基陶瓷纳米粉体的研制必将促使NBT基陶瓷材料烧结性与电学性能的提升，带来NBT基陶瓷材料制备技术的发展与广泛应用，最终带来巨大经济和社会效益。
发明内容
为了克服传统液相法制备NBT基陶瓷纳米粉体工艺的复杂和难于连续化大规模生产等一系列不足问题，本发明提出一种利用改性聚合物前驱体法制备NBT基陶瓷纳米粉体及其制备方法。
本发明的目的是这样实现的：
一种钛酸铋钠基陶瓷粉体，通过对体系温度和投料顺序的控制，实现对聚合物前驱体法改性，达到利用溶液化学法制备高性能NBT基陶瓷纳米粉体的目的，其组成原料包括柠檬酸、乙二醇、钛酸丁酯、乙酸钡粉体、硝酸铋粉体和硝酸钠粉体；
所述钛酸丁酯：乙二醇：柠檬酸的摩尔质量比为1~2：13~16：4~6；
所述的一种钛酸铋钠基陶瓷纳米粉体，该粉体成分的组成可用化学式表示：(1−x)Na0.5Bi0.5TiO3–xBaTiO3，其中x=0.02~0.10；
所述的钛酸铋钠基陶瓷粉体的制备方法，包括以下步骤：
1）按照化学式中金属离子的摩尔比称取乙酸钡粉体、硝酸钠粉体并溶解在蒸馏水中，制得溶液；将按照化学式中金属离子的摩尔比称取的硝酸铋粉体溶解在质量分数为5%的稀硝酸水溶液中，得到硝酸铋溶液；
2）将原料柠檬酸、钛酸丁酯、乙二醇按照摩尔质量比称量后，均匀混合在乙醇中，在50~60℃下通过不断搅拌制得澄清溶液；
3）将步骤1）制备的乙酸钡溶液逐滴加入到步骤2）制备的澄清溶液中，搅拌1~2小时，并将溶液升高温度至70~80℃，不断搅拌制得均一溶液；
4）将步骤1）制备的硝酸铋溶液加入到步骤3）制备的均一溶液中，搅拌0.5~1小时，降温至50~60℃；而后逐滴加入步骤1）制备的硝酸钠溶液；搅拌0.5~1小时制得稳定的溶胶；
5）将步骤4）制备的溶胶在100~110℃的干燥箱中烘6~8小时制得凝胶；
6）将步骤5）制备的凝胶在400~500℃的高温炉中煅烧1~2小时，得到焦化多孔黑色团状物；
7）将步骤6）制备的团状物研磨后，在750~850℃的高温炉中煅烧1~2小时，制得NBT基纳米粉体。
积极有益效果：本发明通过对体系温度和投料顺序的控制对聚合物前驱体法改性，溶胶经过焦化和煅烧等工艺制得高性能NBT基陶瓷纳米粉体。解决了传统液相化学法具有的工艺过程复杂、连续化成产困难、费用高等一系列问题。制备的NBT基陶瓷纳米粉体组分均一、结晶性良好、粒径分布窄、平均粒径为47.3~53.8nm。促进了聚合物前驱体法在工业规模化生产NBT基纳米粉体方面的应用，具有非常高的应用价值和商业价值。
附图说明
图1为本发明中制备NBT基纳米粉体的透射电镜图；
图2为本发明中制备NBT基纳米粉体的高分辨透射电镜图。
具体实施方式
下面结合具体实施例，对本发明做进一步的说明：
一种钛酸铋钠基陶瓷粉体及其制备方法，通过对体系温度和投料顺序的控制，实现对聚合物前驱体法改性，达到利用溶液化学法制备高性能NBT基陶瓷纳米粉体的目的。主要原料包括柠檬酸、乙二醇、钛酸丁酯、乙酸钡粉体、硝酸铋粉体和硝酸钠粉体；通过制备溶胶、焦化和煅烧等工艺制得NBT基陶瓷纳米粉体；并通过现代分析测试技术探测粉体的性能，如图1、图2所示。
所述钛酸丁酯：乙二醇：柠檬酸的摩尔质量比为1~2：13~16：4~6；
所述的一种钛酸铋钠基陶瓷纳米粉体，该粉体成分的组成可用化学式表示：(1−x)Na0.5Bi0.5TiO3–xBaTiO3，其中x=0.02~0.10；
本发明采用改性聚合物前驱体法制备NBT基陶瓷纳米粉体，具体的实验技术方案如下：
1）按照化学式中金属离子的摩尔比称取乙酸钡粉体、硝酸钠粉体并溶解在蒸馏水中，制得溶液；将按照化学式中金属离子的摩尔比称取的硝酸铋粉体溶解在质量分数为5%的稀硝酸水溶液中，得到硝酸铋溶液；
2）将原料柠檬酸、钛酸丁酯、乙二醇按照摩尔质量比称量后，均匀混合在乙醇中，在50~60℃下通过不断搅拌制得澄清溶液；
3）将步骤1）制备的乙酸钡溶液逐滴加入到步骤2）制备的澄清溶液中，搅拌1~2小时，并将溶液升高温度至70~80℃，不断搅拌制得均一溶液；
4）将步骤1）制备的硝酸铋溶液加入到步骤3）制备的均一溶液中，搅拌0.5~1小时，降温至50~60℃；而后逐滴加入步骤1）制备的硝酸钠溶液；搅拌0.5~1小时制得稳定的溶胶；
5）将步骤4）制备的溶胶在100~110℃的干燥箱中烘6~8小时制得凝胶；
6）将步骤5）制备的凝胶在400~500℃的高温炉中煅烧1~2小时，得到焦化多孔黑色团状物；
7）将步骤6）制备的团状物研磨后，在750~850℃的高温炉中煅烧1~2小时，制得NBT基纳米粉体。
实施例1
制备0.98Na0.5Bi0.5TiO3–0.02BaTiO3纳米粉体：称取0.0511g乙酸钡粉体、0.4165g硝酸钠粉体分别溶解在蒸馏水中，制得溶液备用；称取2.3770g硝酸铋粉体溶解在15ml质量分数为5%的稀硝酸溶液中，制得溶液备用；称取6.3042g柠檬酸和7.4484g乙二醇溶解在8ml酒精中，搅拌均匀后将3.4036g钛酸丁酯逐滴加入到该酒精溶液中，并在55℃下不断搅拌制得澄清溶液；将乙酸钡溶液加入到上述溶液中，搅拌40分钟后，将温度提升到75℃，不断搅拌制得均一溶液；将硝酸铋溶液逐滴加入到上述均一溶液中，搅拌0.5小时，再降温至50℃后加入硝酸钠溶液，搅拌40分钟制得稳定的溶胶；将溶胶在105℃的高温炉中煅烧1小时，得到焦化多孔团状物；团状物经研磨后，在800℃的高温炉中煅烧2小时，制得0.98Na0.5Bi0.5TiO3–0.02BaTiO3纳米粉体。
0.98Na0.5Bi0.5TiO3–0.02BaTiO3纳米粉体的结晶性良好，平均粒径尺寸为47.5nm。
实施例2
制备0.96Na0.5Bi0.5TiO3–0.04BaTiO3纳米粉体：称取0.1022g乙酸钡粉体、0.4080g硝酸钠粉体分别溶解在蒸馏水中，制得溶液备用；称取2.3285g硝酸铋粉体溶解在14ml质量分数为5%的稀硝酸溶液中，制得溶液备用；称取6.3042g柠檬酸和7.4484g乙二醇溶解在8ml酒精中，搅拌均匀后将3.4036g钛酸丁酯逐滴加入到该酒精溶液中，并在55℃下不断搅拌制得澄清溶液；将乙酸钡溶液加入到上述溶液中，搅拌40分钟后，将温度提升到75℃，不断搅拌制得均一溶液；将硝酸铋溶液逐滴加入到上述均一溶液中，搅拌0.5小时，再降温至50℃后加入硝酸钠溶液，搅拌40分钟制得稳定的溶胶；将溶胶在105℃的高温炉中煅烧1小时，得到焦化多孔团状物；团状物经研磨后，在800℃的高温炉中煅烧2小时，制得0.96Na0.5Bi0.5TiO3–0.04BaTiO3纳米粉体。
0.96Na0.5Bi0.5TiO3–0.04BaTiO3纳米粉体的结晶性良好，平均粒径尺寸为49.1nm。
实施例3
制备0.94Na0.5Bi0.5TiO3–0.06BaTiO3纳米粉体：称取0.1533g乙酸钡粉体、0.3913g硝酸钠粉体分别溶解在蒸馏水中，制得溶液备用；称取2.2800g硝酸铋粉体溶解在13ml质量分数为5%的稀硝酸溶液中，制得溶液备用；称取6.3042g柠檬酸和7.4484g乙二醇溶解在8ml酒精中，搅拌均匀后将3.4036g钛酸丁酯逐滴加入到该酒精溶液中，并在55℃下不断搅拌制得澄清溶液；将乙酸钡溶液加入到上述溶液中，搅拌40分钟后，将温度提升到75℃，不断搅拌制得均一溶液；将硝酸铋溶液逐滴加入到上述均一溶液中，搅拌0.5小时，再降温至50℃后加入硝酸钠溶液，搅拌40分钟制得稳定的溶胶；将溶胶在105℃的高温炉中煅烧1小时，得到焦化多孔团状物；团状物经研磨后，在800℃的高温炉中煅烧2小时，制得0.94Na0.5Bi0.5TiO3–0.06BaTiO3纳米粉体。
0.94Na0.5Bi0.5TiO3–0.06BaTiO3纳米粉体的结晶性良好，平均粒径尺寸为51.9nm。
实施例4
制备0.92Na0.5Bi0.5TiO3–0.08BaTiO3纳米粉体：称取0.2044g乙酸钡粉体、0.3910g硝酸钠粉体分别溶解在蒸馏水中，制得溶液备用；称取2.2315g硝酸铋粉体溶解在12ml质量分数为5%的稀硝酸溶液中，制得溶液备用；称取6.3042g柠檬酸和7.4484g乙二醇溶解在8ml酒精中，搅拌均匀后将3.4036g钛酸丁酯逐滴加入到该酒精溶液中，并在55℃下不断搅拌制得澄清溶液；将乙酸钡溶液加入到上述溶液中，搅拌40分钟后，将温度提升到75℃，不断搅拌制得均一溶液；将硝酸铋溶液逐滴加入到上述均一溶液中，搅拌0.5小时，再降温至50℃后加入硝酸钠溶液，搅拌40分钟制得稳定的溶胶；将溶胶在105℃的高温炉中煅烧1小时，得到焦化多孔团状物；团状物经研磨后，在800℃的高温炉中煅烧2小时，制得0.92Na0.5Bi0.5TiO3–0.08BaTiO3纳米粉体。
0.92Na0.5Bi0.5TiO3–0.08BaTiO3纳米粉体的结晶性良好，平均粒径尺寸为52.5nm。
实施例5
制备0.90Na0.5Bi0.5TiO3–0.10BaTiO3纳米粉体：称取0.2555g乙酸钡粉体、0.3825g硝酸钠粉体分别溶解在蒸馏水中，制得溶液备用；称取2.1830g硝酸铋粉体溶解在11ml质量分数为5%的稀硝酸溶液中，制得溶液备用；称取6.3042g柠檬酸和7.4484g乙二醇溶解在8ml酒精中，搅拌均匀后将3.4036g钛酸丁酯逐滴加入到该酒精溶液中，并在55℃下不断搅拌制得澄清溶液；将乙酸钡溶液加入到上述溶液中，搅拌40分钟后，将温度提升到75℃，不断搅拌制得均一溶液；将硝酸铋溶液逐滴加入到上述均一溶液中，搅拌0.5小时，再降温至50℃后加入硝酸钠溶液，搅拌40分钟制得稳定的溶胶；将溶胶在105℃的高温炉中煅烧1小时，得到焦化多孔团状物；团状物经研磨后，在800℃的高温炉中煅烧2小时，制得0.90Na0.5Bi0.5TiO3–0.10BaTiO3纳米粉体。
0.90Na0.5Bi0.5TiO3–0.10BaTiO3纳米粉体的结晶性良好，平均粒径尺寸为53.8nm。
本发明通过对体系温度和投料顺序的控制对聚合物前驱体法改性，溶胶经过焦化和煅烧等工艺制得高性能NBT基陶瓷纳米粉体。解决了传统液相化学法具有的工艺过程复杂、连续化成产困难、费用高等一系列问题。制备的NBT基陶瓷纳米粉体组分均一、结晶性良好、粒径分布窄、平均粒径为47.3~53.8nm。促进了聚合物前驱体法在工业规模化生产NBT基纳米粉体方面的应用，具有非常高的应用价值和商业价值。
以上所述仅为本发明示意性的具体实施方式，并非用以限定本发明的范围，任何本领域的技术人员在不脱离本发明构思和原则的前提下所做出的等同变化与修改，均应属于本发明保护的范围。
Claims (4)
1.一种钛酸铋钠基陶瓷纳米粉体，其特征在于：主要制备原料包括柠檬酸、乙二醇、钛酸丁酯、乙酸钡粉体、硝酸铋粉体和硝酸钠粉体。
2.根据权利要求1所述的一种钛酸铋钠基陶瓷纳米粉体，其特征在于：该钛酸铋钠基陶瓷纳米粉体成分的组成可用化学式表示：(1−x)Na0.5Bi0.5TiO3–xBaTiO3，其中x=0.02~0.10。
3.根据权利要求1所述的一种钛酸铋钠基陶瓷纳米粉体，其特征在于：所述钛酸丁酯：乙二醇：柠檬酸的摩尔质量比为1~2：13~16：4~6。
4.如权利要求1所述的一种钛酸铋钠基陶瓷纳米粉体的制备方法，其特征在于：所述的NBT纳米粉体通过制备溶胶、焦化和煅烧等工艺制得，具体工艺步骤如下：
1）按照化学式中金属离子的摩尔比称取乙酸钡粉体、硝酸钠粉体并溶解在蒸馏水中，制得溶液；将按照化学式中金属离子的摩尔比称取的硝酸铋粉体溶解在质量分数为5%的稀硝酸水溶液中，得到硝酸铋溶液；
2）将原料钛酸丁酯：乙二醇：柠檬酸按照摩尔质量比为1~2：13~16：4~6称量后，均匀混合在乙醇中，在50~60℃下通过不断搅拌制得澄清溶液；
3）将步骤1）制备的乙酸钡溶液逐滴加入到步骤2）制备的澄清溶液中，搅拌1~2小时，并将溶液升高温度至70~80℃，不断搅拌制得均一溶液；
4）将步骤1）制备的硝酸铋溶液加入到步骤3）制备的均一溶液中，搅拌0.5~1小时，降温至50~60℃；而后逐滴加入步骤1）制备的硝酸钠溶液；搅拌0.5~1小时制得稳定的溶胶；
5）将步骤4）制备的溶胶在100~110℃的干燥箱中烘6~8小时制得凝胶；
6）将步骤5）制备的凝胶在400~500℃的高温炉中煅烧1~2小时，得到焦化多孔黑色团状物；
7）将步骤6）制备的团状物研磨后，在750~850℃的高温炉中煅烧1~2小时，制得NBT基纳米粉体。
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| CN102173785A (zh) * | 2011-01-21 | 2011-09-07 | 天津大学 | 一种宽工作温区热稳定型复合介质陶瓷的制备方法 |
| CN106995313A (zh) * | 2017-05-06 | 2017-08-01 | 信阳师范学院 | 一种铌酸钾钠基陶瓷粉体及其制备方法 |
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| CN102173785A (zh) * | 2011-01-21 | 2011-09-07 | 天津大学 | 一种宽工作温区热稳定型复合介质陶瓷的制备方法 |
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