CN116410007B - 一种降低BaTiO3陶瓷块体中双孪晶密度的粉末机械预处理方法 - Google Patents
一种降低BaTiO3陶瓷块体中双孪晶密度的粉末机械预处理方法 Download PDFInfo
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Abstract
本发明公开了一种降低BaTiO3陶瓷块体中双孪晶密度的粉末机械预处理方法，该方法包括如下步骤：将无任何掺杂的纳米粒径(～50nm)BaTiO3纳米粉体用行星球磨机在低转速100r/min的转速下湿磨，将经过球磨处理的粉体烘干后放入放电等离子烧结炉中烧结至950℃保温>＝10min。本发明通过对初始粉体进行机械预处理，有效降低利用放电等离子烧结炉烧结后BaTiO3块体中双孪晶的密度。
Description
技术领域
本发明属于陶瓷材料粉末制备技术领域，尤其涉及一种降低BaTiO3陶瓷块体中双孪晶密度的粉末机械预处理方法。
背景技术
双孪晶(double twin)作为一种特殊的界面结构广泛的存在于各种材料中，其中在金属材料中非常常见，如Mg(Wang J,et al.Scripta materialia,2010,63(7):741-746.)，Ni合金(Wu B Y C,et al.Metallurgical and Materials Transactions A,2005,36:1927-1936.)等。通过外部施加载荷给材料，可以促使晶粒中形成双孪晶或者发生孪晶的迁移或合并。在金属材料中孪晶的形成被认为有利于提升材料的机械性能(Y.Gao,etal.Materials Science&Engineering A767(2019)138361)。
在钙钛矿陶瓷材料中双孪晶并不常见，但在BaTiO3陶瓷中双孪晶却经常被研究人员观察到。BaTiO3陶瓷作为一种重要的压电和铁电材料，为了获得优良的电学性能通常会考虑对BaTiO3进行掺杂来改变其化学组成，此外也可以通过改变其微结构如晶粒大小，取向等。有研究认为双孪晶的存在降低了晶粒生长的原子附着势垒(Kang M K,etal.Journal of the American Ceramic Society,2000,83(2):385-390.)，导致不均匀晶粒尺寸分布，而良好的电学性能通常与均匀的晶粒尺寸分布有关，所以避免烧结BaTiO3陶瓷块体的晶粒中出现双孪晶有重要的实际应用价值。
发明内容
发明目的：本发明的目的在于解决BaTiO3陶瓷烧结过程中出现双孪晶微结构的问题。提供了一种降低BaTiO3陶瓷块体中双孪晶密度的粉末机械预处理方法。该方法流程简单易重复，对指导工业化陶瓷生产具有参考价值。在不改变初始粉体形貌和尺寸的情况下降低SPS烧结之后样品中双孪晶的密度。
技术方案：为了解决上述技术问题，本发明提出一种降低BaTiO3陶瓷块体中双孪晶密度的粉末机械预处理方法，该方法包括以下步骤：
S1：将BaTiO3纳米粉体，研磨球，无水乙醇按照体积比1：10：11分别进行称取，研磨球选择第一直径的研磨球和第二直径的研磨球混合，并且第一直径大于第二直径；配级比例按照两个第二直径的研磨球配第一直径的研磨球；
S2：将称取好的研末球，BaTiO3纳米粉体，无水乙醇依次加入球磨罐中，球磨程序设置为100r/min，间隔20min，球磨24h，球磨结束后将浆料连同球磨罐一起放入鼓风干燥箱中烘干72h，将烘干的粉体块倒入研钵中研磨成粉体，然后将研磨后的粉体多次过筛，最终得到球磨处理后的粉体；
S3：将球磨处理后的BaTiO3纳米粉体倒入包裹有碳纸的石墨模具中，手动旋转压片机加压至10Mpa进行第一次预压，保压5-10min，将第一次预压完成的装有粉体压块的石墨模具放入放电等离子烧结炉中加压至70Mpa进行第二次预压，保压5-10min，预压完成后卸载压力至0Mpa；
S4：将预压完成装有粉体压块的石墨模具在放电等离子烧结炉中以20℃/min的升温速率加热至600℃，保温3-5min，以15℃/min的升温速率升温至950℃，并且保温>＝10min；升温过程中跟随温度升高，当温度到达600℃时，均匀加压至70Mpa，在600℃到950℃之间，以及保温过程中保持恒压70Mpa，加热完成后卸载压力至0Mpa并降温至室温；
S5：将使用放电等离子烧结炉烧结得到的块体放入管式炉中，通入氧气并按照1℃/min的加热速率缓慢加热至700℃，保温1-2h；该步骤为解决使用石墨模具引入的碳污染的问题，去除碳污染；
S6：将经过管式炉加热处理得到的陶瓷块体的断面利用离子刻蚀机进行刻蚀。
进一步的，所述的步骤S1中，磨球第一直径为5mm，磨球第二直径为3mm。
进一步的，所述的步骤S2中，球磨转速设置为100r/min。
进一步的，所述的步骤S5中，整个加热和降温过程中始终以相同流速通入氧气。
进一步的，步骤S6的磨样步骤工艺方法为：离子刻蚀机按照由高到底的电压，5kv刻蚀30min，4kv刻蚀30min，3kv刻蚀30min，2kv刻蚀1h，1kv刻蚀1h，对块体样品断面进行刻蚀抛光处理。
此外，本发明还提出一种降低BaTiO3陶瓷块体中双孪晶密度的机械预处理粉末烧结样品，该样品是通过上述方法烧结而成。
有益效果：与现有技术相比，本发明的技术方案具有以下有益效果：
1.本发明将未掺杂的BaTiO3纳米粉末利用行星球磨机球磨处理，接着将球磨后烘干的粉末在SPS中烧结成片，对样品进行扫描电子显微镜(SEM)观察，与现有SPS烧结未球磨BaTiO3纳米粉末技术相比，拥有明显更低的双孪晶密度。
2.本发明前期对粉体球磨处理参数进行摸索，将粉体，研磨球，无水乙醇按照体积比1：10：11分别进行称取，研磨球(氧化锆球)选择大小球混合，配级按照两个小球(3mm)配一个大球(5mm)，选择不同的研磨球配级可以使得粉体处理更充分。球磨机程序按照100r/min，间隔20min，球磨24h，保证了球磨处理不会进一步将初始粉体细化导致粒径发生改变；为比较球磨和未球磨粉体在SPS烧结后的微观结构的差异，两种粉体在SPS中的烧结程序要一致。
3.本发明对球磨和未球磨处理BaTiO3粉体用SPS烧结的样品进行SEM观察，首先对未球磨处理的粉体烧结的样品进行观察，发现样品中有大量的双孪晶，然后对球磨处理的粉体烧结的样品进行观察并未发现双孪晶，证实了球磨处理能有效降低样品中双孪晶的比例。本发明处理过程简单，可改进后用于工业化批量处理，能有效降低BaTiO3陶瓷中双孪晶缺陷密度，对调控材料微结构以及改进材料的性能具有实际指导意义。
附图说明
图1是本发明方法的流程图；
图2是未球磨和球磨处理后的粉体的颗粒尺寸分布图；
图3是未球磨处理粉体的SEM图；
图4是球磨处理粉体的SEM图；
图5是含双孪晶的晶粒的SEM图；
图6是不含双孪晶的晶粒的SEM图；
图7是未球磨处理粉体在放电等离子烧结炉中烧结至950℃保温10min的块体的断面SEM图；
图8是球磨处理粉体在放电等离子烧结炉中烧结至950℃保温10min的块体的断面SEM图；
图9是未球磨处理粉体在放电等离子烧结炉中烧结至950℃保温15min的块体的断面SEM图；
图10是球磨处理粉体在放电等离子烧结炉中烧结至950℃保温15min的块体的断面SEM图。
具体实施方式
为了使本发明的目的和技术方案更加清楚明白，以下结合实施例作详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。上述是发明技术方案的概述，以下结合附图和具体实施方式，对本发明做进一步说明。
如图1所示，本发明提供了一种降低BaTiO3陶瓷块体中双孪晶密度的粉末机械预处理方法，该方法步骤如下：
S1：将BaTiO3纳米粉体，研磨球，无水乙醇按照体积比1：10：11分别进行称取，研磨球选择第一直径的研磨球和第二直径的研磨球混合，并且第一直径大于第二直径；配级比例按照两个第二直径的研磨球配第一直径的研磨球；选择磨球第一直径为5mm，磨球第二直径为3mm；
S2：将称取好的研磨球，BaTiO3纳米粉体，无水乙醇依次加入球磨罐中，球磨程序设置为100r/min，间隔20min，球磨24h，球磨结束后将浆料连同球磨罐一起放入鼓风干燥箱中烘干72h，将烘干的粉体块倒入研钵中研磨成粉体，然后将研磨后的粉体多次过筛，最终得到球磨处理后的粉体；
S3：将球磨处理后的BaTiO3纳米粉体倒入包裹有碳纸的石墨模具中，手动旋转压片机加压至10Mpa进行第一次预压，保压5-10min，将第一次预压完成的装有粉体压块的石墨模具放入放电等离子烧结炉中加压至70Mpa进行第二次预压，保压5-10min，预压完成后卸载压力至0Mpa；
S4：将预压完成装有粉体压块的石墨模具在放电等离子烧结炉中以20℃/min的升温速率加热至600℃，保温3-5min，以15℃/min的升温速率升温至950℃，并且保温>＝10min；升温过程中跟随温度升高，当温度到达600℃时，均匀加压至70Mpa，在600℃到950℃之间以及保温过程中保持恒压70Mpa，加热完成后卸载压力至0Mpa并降温至室温；
S5：将使用放电等离子烧结炉烧结得到的块体放入管式炉中，通入氧气并按照1℃/min的加热速率加热至700℃，保温1-2h；该步骤为解决使用石墨模具引入的碳污染的问题，去除碳污染；
S6：将经过管式炉加热处理得到的陶瓷块体的断面利用离子刻蚀机进行刻蚀。
按上述条件处理粉体并烧结成BaTiO3陶瓷块体样品，用扫描电镜对BaTiO3块体样品的断面进行观察，注意晶粒中是否含双孪晶。图2显示球磨处理粉体和未球磨处理粉体保持几乎一样的颗粒尺寸分布。图3和图4显示的未球磨处理以及球磨处理粉体SEM图也证实球磨处理不仅没有改变颗粒大小也没有改变颗粒形状。图5展示了含有双孪晶的晶粒，图6展示了不含有双孪晶的晶粒。如图7所示，未处理粉体利用放电等离子烧结炉烧结至950℃保温10min的块体样品中包含的晶粒中基本都包含双孪晶。
如图8所示，球磨处理后的样品中包含的晶粒并未见到明显的双孪晶，表明双孪晶密度明显降低。如图9所示，当950℃保温至15min时，未球磨处理粉体烧结样品中晶粒尺寸相比于保温10min的大说明晶粒发生生长。未处理粉体样品中双孪晶始终存在，说明双孪晶不会随晶粒生长而消失。如图10所示，球磨处理后粉体950℃保温至15min时样品中晶粒生长后同样没有双孪晶出现，说明处理后粉体样品可以稳定的保持没有双孪晶状态。上述结果证实了对初始粉体进行球磨预处理可以有效降低BaTiO3陶瓷样品中双孪晶的数量。
根据上述说明书的揭示和教导，本发明所属领域的技术人员还可以对上述实施方式进行变更和修改。因此，本发明并不局限于上面揭示和描述的具体实施方式，对发明的一些修改和变更也应当落入本发明的权利要求的保护范围内。
Claims (4)
1.一种降低BaTiO3陶瓷块体中双孪晶密度的粉末机械预处理方法，其特征在于，该方法包括以下步骤：
S1：将BaTiO3纳米粉体，研磨球，无水乙醇按照体积比1：10：11分别进行称取，研磨球选择第一直径的研磨球和第二直径的研磨球混合，并且第一直径大于第二直径；配级比例按照两个第二直径的研磨球配第一直径的研磨球；
S2：将称取好的研磨球，BaTiO3纳米粉体，无水乙醇依次加入球磨罐中，球磨程序设置为100r/min，间隔20min，球磨24h，球磨结束后将浆料连同球磨罐一起放入鼓风干燥箱中烘干72h，将烘干的粉体块倒入研钵中研磨成粉体，然后将研磨后的粉体多次过筛，最终得到球磨处理后的粉体；
S3：将球磨处理后的BaTiO3纳米粉体倒入包裹有碳纸的石墨模具中，手动旋转压片机加压至10Mpa进行第一次预压，保压5-10min，将第一次预压完成的装有粉体压块的石墨模具放入放电等离子烧结炉中加压至70Mpa进行第二次预压，保压5-10min，预压完成后卸载压力至0Mpa；
S4：将预压完成装有粉体压块的石墨模具在放电等离子烧结炉中以20℃/min的升温速率加热至600℃，保温3-5min，以15℃/min的升温速率升温至950℃，并且保温大于等于10min；升温过程中跟随温度升高，当温度到达600℃时，均匀加压至70Mpa，在600℃到950℃之间以及保温过程中保持恒压70Mpa，加热完成后卸载压力至0Mpa并降温至室温；
S5：将使用放电等离子烧结炉烧结得到的块体放入管式炉中，通入氧气并按照1℃/min的加热速率加热至700℃，保温1-2h；
S6：将经过管式炉加热处理得到的陶瓷块体的断面利用离子刻蚀机进行刻蚀；
所述的步骤S1中，磨球第一直径为5mm，磨球第二直径为3mm。
2.根据权利要求1所述的一种降低BaTiO3陶瓷块体中双孪晶密度的粉末机械预处理方法，其特征在于，所述的步骤S5中，整个加热和降温过程中始终以相同流速通入氧气。
3.根据权利要求1所述的一种降低BaTiO3陶瓷块体中双孪晶密度的粉末机械预处理方法，其特征在于，步骤S6的磨样步骤工艺方法为：离子刻蚀机按照由高到低的电压，5kv刻蚀30min，4kv刻蚀30min，3kv刻蚀30min，2kv刻蚀1h，1kv刻蚀1h，对块体样品断面进行刻蚀抛光处理。
4.一种采用权利要求1-3任一项所述的降低BaTiO3陶瓷块体中双孪晶密度的粉末机械预处理方法制备得到的BaTiO3陶瓷块体。
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| CN113321506A (zh) * | 2021-07-08 | 2021-08-31 | 陕西科技大学 | 一种无铅弛豫铁电体陶瓷材料及制备方法 |
| CN113880570A (zh) * | 2021-11-11 | 2022-01-04 | 上海大学 | 一种降低BaTiO3陶瓷中双孪晶缺陷密度的粉末烧结方法 |
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| CN103360058A (zh) * | 2012-03-30 | 2013-10-23 | 太阳诱电株式会社 | 陶瓷粉末和层叠陶瓷电容器 |
| CN113321506A (zh) * | 2021-07-08 | 2021-08-31 | 陕西科技大学 | 一种无铅弛豫铁电体陶瓷材料及制备方法 |
| CN113880570A (zh) * | 2021-11-11 | 2022-01-04 | 上海大学 | 一种降低BaTiO3陶瓷中双孪晶缺陷密度的粉末烧结方法 |
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