CN113754443B - 一种高熵六硼化物纳米晶陶瓷及其制备方法和应用 - Google Patents

一种高熵六硼化物纳米晶陶瓷及其制备方法和应用 Download PDF

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CN113754443B
CN113754443B CN202110965886.3A CN202110965886A CN113754443B CN 113754443 B CN113754443 B CN 113754443B CN 202110965886 A CN202110965886 A CN 202110965886A CN 113754443 B CN113754443 B CN 113754443B
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hexaboride
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褚衍辉
马梦冬
韩杨洁
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South China University of Technology SCUT
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Abstract

本发明公开了一种高熵六硼化物纳米晶陶瓷及其制备方法和应用。本发明的高熵六硼化物纳米晶陶瓷的制备方法包括有以下步骤：1)将NaBH4、La2O3、CeO2、Nd2O3和Eu2O3混合进行研磨，再压制成片，得到混合粉体压片；2)将混合粉体压片置于保护气氛中进行煅烧，再进行酸洗和水洗，得到高熵六硼化物纳米粉体；3)将高熵六硼化物纳米粉体预压成坯体，再进行加压烧结，即得高熵六硼化物纳米晶陶瓷。本发明的高熵六硼化物纳米晶陶瓷的晶粒细小、硬度高，且其制备过程简单、制备温度低、原材料价格低廉、对设备要求低，适合进行大规模工业生产。

Description

一种高熵六硼化物纳米晶陶瓷及其制备方法和应用
技术领域
本发明涉及高熵陶瓷技术领域，具体涉及一种高熵六硼化物纳米晶陶瓷及其制备方法和应用。
背景技术
“高熵”设计理念是近些年来国际上的研究热点，该设计理念最早应用在合金材料领域。高熵合金材料经过十几年来的发展，在力学、电磁学、耐高温、抗腐蚀等方面表现出传统合金材料无法比拟的优异性能，成为未来最有发展潜力的新型材料之一。
高熵陶瓷材料具有巨大的组成调控空间、独特的微观结构、可调控的性能以及各种潜在的应用等特点，引起了国内外研究人员的极大关注。截止今日，各类高熵氧化物、高熵硼化物、高熵碳化物等高熵陶瓷材料相继被报道，而高熵硼化物陶瓷(例如：高熵一硼化物陶瓷、高熵二硼化物陶瓷、高熵六硼化物陶瓷等)是目前研究最为广泛、体系发展最为丰富的一类高熵陶瓷材料。
高熵六硼化物陶瓷具有功函数低、导电性好、熔点高等优点，在热电子发射阴极材料领域展现出诱人的应用前景。然而，目前关于高熵六硼化物陶瓷的研究尚处于起步阶段，相关报道很少。“Qin M,Yan Q,Liu Y,et al.Bulk high-entropy hexaborides.Journalof the European Ceramic Society,2021,41:5775～5781.”公开了一种以金属粉体及硼粉为原料，采用放电等离子烧结(SPS)在1700℃下保温10min来制备高熵六硼化物陶瓷的方法，该方法不仅存在原料价格昂贵、制备温度高等问题，而且合成的高熵六硼化物陶瓷存在晶粒尺寸粗大(3.48μm～5.05μm)、硬度低(16GPa～18GPa)等问题，严重限制了高熵六硼化物陶瓷的推广和应用。
发明内容
本发明的目的在于提供一种高熵六硼化物纳米晶陶瓷及其制备方法和应用。
本发明所采取的技术方案是：
一种高熵六硼化物纳米晶陶瓷的制备方法，包括有以下步骤：
1)将NaBH4、La2O3、CeO2、Nd2O3和Eu2O3混合进行研磨，再压制成片，得到混合粉体压片；
2)将混合粉体压片置于保护气氛中进行煅烧，再进行酸洗和水洗，得到高熵六硼化物纳米粉体；
3)将高熵六硼化物纳米粉体预压成坯体，再进行加压烧结，即得高熵六硼化物纳米晶陶瓷。
优选的，一种高熵六硼化物纳米晶陶瓷的制备方法，包括有以下步骤：
1)将NaBH4、La2O3、CeO2、Nd2O3和Eu2O3混合进行研磨，再压制成片，得到混合粉体压片；
2)将混合粉体压片置于保护气氛中进行煅烧，再进行酸洗、水洗、过滤和干燥，得到高熵六硼化物纳米粉体；
3)将高熵六硼化物纳米粉体注入模具，进行加压烧结，即得高熵六硼化物纳米晶陶瓷。
优选的，步骤1)所述NaBH4的物质的量与La2O3、CeO2、Nd2O3和Eu2O3中金属元素的总物质的量的比为6:1～8:1。
优选的，步骤1)所述La2O3、CeO2、Nd2O3、Eu2O3的摩尔比为1:2:1:1。
优选的，步骤1)所述La2O3、CeO2、Nd2O3和Eu2O3均呈粉末状，纯度均≥99.9％，粒径均为5μm～10μm。
优选的，步骤1)所述研磨的时间为30min～60min。
优选的，步骤1)所述压制的压力为10MPa～30MPa。
优选的，步骤2)所述煅烧的具体操作为：以8℃/min～12℃/min的升温速率升温至1100℃～1300℃，保温1h～3h。
优选的，步骤2)所述煅烧在氩气气氛中进行。
优选的，步骤2)所述酸洗采用的酸为浓度1mol/L～3mol/L的盐酸。
优选的，步骤2)所述水洗在80℃～100℃下进行。
优选的，步骤2)所述干燥温度在40℃～80℃下进行，干燥时间为3h～5h。
优选的，步骤3)所述加压烧结在压力4GPa～8GPa、温度1300℃～1500℃的条件下进行，烧结时间为10min～30min。
本发明的有益效果是：本发明的高熵六硼化物纳米晶陶瓷的晶粒细小、硬度高，且其制备过程简单、制备温度低、原材料价格低廉、对设备要求低，适合进行大规模工业生产。
具体来说：
1)本发明的高熵六硼化物纳米晶陶瓷的晶粒尺寸仅80nm～100nm，远小于现有的高熵六硼化物纳米晶陶瓷的3.48μm～5.05μm，且通过调整制备温度、保温时间和烧结压力等参数还可以对制备的高熵六硼化物纳米晶陶瓷的晶粒尺寸进行灵活控制；
2)本发明的高熵六硼化物纳米晶陶瓷的硬度可达18.4GPa～24.2GPa，高于现有的高熵六硼化物纳米晶陶瓷的16GPa～18GPa，力学性能更加优异；
3)本发明的高熵六硼化物纳米晶陶瓷的制备过程简单，烧结温度由现有工艺的1700℃降至1100℃～1500℃，且原材料价格低廉、对设备的要求低，适合进行大规模工业生产。
附图说明
图1为实施例2中的高熵六硼化物纳米粉体的XRD图谱。
图2为实施例2中的高熵六硼化物纳米晶陶瓷表面的SEM图和EDS能谱元素分布图。
图3为实施例2中的高熵六硼化物纳米晶陶瓷断面的SEM图。
具体实施方式
下面结合具体实施例对本发明作进一步的解释和说明。
实施例1～3中的La2O3粉、CeO2粉、Nd2O3粉和Eu2O3粉的粒径均为5μm～10μm，纯度均高于99％，NaBH4的纯度为分析纯。
实施例1：
一种高熵六硼化物纳米晶陶瓷，其制备方法包括有以下步骤：
1)将4.53g的NaBH4、3.25g的La2O3粉、3.44g的CeO2粉、3.36g的Nd2O3粉和3.52g的Eu2O3粉加入玛瑙研钵，手动研磨30min，再加入不锈钢模具内，在10MPa的压力下压制成片，得到混合粉体压片；
2)将混合粉体压片装入刚玉方舟后放入管式炉中，对管式炉进行抽真空处理使真空压力表数值达到-0.1MPa，保真空10min，观察真空表指示是否变化，如无变化则说明系统密封完好，此过程重复3次，再通入氩气至常压，再以10℃/min的升温速率将炉温从室温升至1100℃，保温3h，随后自然冷却至室温，再将得到的产物用浓度1mol/L的盐酸洗涤，过滤，滤得的固体用80℃的去离子水洗涤，过滤，将滤得的固体置于干燥箱中40℃干燥5h，得到高熵六硼化物纳米粉体；
3)将高熵六硼化物纳米粉体预压成圆柱形坯体，再放入氮化硼坩埚内，再将氮化硼坩埚放入高压组装件中，高压组装件由石墨加热体、氮化硼隔层、氧化锆保温层、导电钢帽和传压介质叶腊石构成，再将高压组装件放入六面顶压机中，压力升至8GPa，以100℃/min的升温速率升温至1300℃，保温10min，再以100℃/min的降温速率降至室温，缓慢泄压，即得高熵六硼化物纳米晶陶瓷。
经测试，本实施例的高熵六硼化物纳米晶陶瓷的晶粒尺寸约80nm，维氏硬度为20.1GPa～22.5GPa。
实施例2：
一种高熵六硼化物纳米晶陶瓷，其制备方法包括有以下步骤：
1)将5.292g的NaBH4、3.25g的La2O3粉、3.44g的CeO2粉、3.36g的Nd2O3粉和3.52g的Eu2O3粉加入玛瑙研钵，手动研磨45min，再加入不锈钢模具内，在20MPa的压力下压制成片，得到混合粉体压片；
2)将混合粉体压片装入刚玉方舟后放入管式炉中，对管式炉进行抽真空处理使真空压力表数值达到-0.1MPa，保真空10min，观察真空表指示是否变化，如无变化则说明系统密封完好，此过程重复3次，再通入氩气至常压，再以10℃/min的升温速率将炉温从室温升至1200℃，保温2h，随后自然冷却至室温，再将得到的产物用浓度2mol/L的盐酸洗涤，过滤，滤得的固体用90℃的去离子水洗涤，过滤，将滤得的固体置于干燥箱中60℃干燥4h，得到高熵六硼化物纳米粉体；
3)将高熵六硼化物纳米粉体预压成圆柱形坯体，再放入氮化硼坩埚内，再将氮化硼坩埚放入高压组装件中，高压组装件由石墨加热体、氮化硼隔层、氧化锆保温层、导电钢帽和传压介质叶腊石构成，再将高压组装件放入六面顶压机中，压力升至6GPa，以100℃/min的升温速率升温至1400℃，保温20min，再以100℃/min的降温速率降至室温，缓慢泄压，即得高熵六硼化物纳米晶陶瓷。
性能测试：
1)本实施例步骤2)中的高熵六硼化物纳米粉体的X射线衍射(XRD)谱图如图1所示。
由图1可知：步骤2)中的高熵六硼化物纳米粉体为(La,Ce,Nd,Eu)B6相，不含其他杂质相，表明原料粉末在加热反应的过程中通过扩散形成了高熵固溶体相。
2)本实施例的高熵六硼化物纳米晶陶瓷表面的扫描电镜(SEM)图和EDS能谱元素分布图如图2所示(图2中的a为SEM，b为EDS能谱元素分布图)。
由图2中的a可知：本实施例的高熵六硼化物纳米晶陶瓷烧结致密，无明显孔洞。
由图2中的b可知：本实施例的高熵六硼化物纳米晶陶瓷元素分布均匀。
3)本实施例的高熵六硼化物纳米晶陶瓷断面的SEM图如图3所示。
由图3可知：本实施例的高熵六硼化物纳米晶陶瓷的晶粒尺寸约90nm。
另外，经测试，本实施例的高熵六硼化物纳米晶陶瓷的维氏硬度为22.1GPa～24.2GPa。
实施例3：
一种高熵六硼化物纳米晶陶瓷，其制备方法包括有以下步骤：
1)将6.048g的NaBH4、3.25g的La2O3粉、3.44g的CeO2粉、3.36g的Nd2O3粉和3.52g的Eu2O3粉加入玛瑙研钵，手动研磨60min，再加入不锈钢模具内，在30MPa的压力下压制成片，得到混合粉体压片；
2)将混合粉体压片装入刚玉方舟后放入管式炉中，对管式炉进行抽真空处理使真空压力表数值达到-0.1MPa，保真空10min，观察真空表指示是否变化，如无变化则说明系统密封完好，此过程重复3次，再通入氩气至常压，再以10℃/min的升温速率将炉温从室温升至1300℃，保温1h，随后自然冷却至室温，再将得到的产物用浓度3mol/L的盐酸洗涤，过滤，滤得的固体用100℃的去离子水洗涤，过滤，将滤得的固体置于干燥箱中80℃干燥3h，得到高熵六硼化物纳米粉体；
3)将高熵六硼化物纳米粉体预压成圆柱形坯体，再放入氮化硼坩埚内，再将氮化硼坩埚放入高压组装件中，高压组装件由石墨加热体、氮化硼隔层、氧化锆保温层、导电钢帽和传压介质叶腊石构成，再将高压组装件放入六面顶压机中，压力升至4GPa，以100℃/min的升温速率升温至1500℃，保温30min，再以100℃/min的降温速率降至室温，缓慢泄压，即得高熵六硼化物纳米晶陶瓷。
经测试，本实施例的高熵六硼化物纳米晶陶瓷的晶粒尺寸约100nm，维氏硬度为18.4GPa～21.8GPa。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (6)

1.一种高熵六硼化物纳米晶陶瓷的制备方法，其特征在于，包括有以下步骤：
1)将NaBH4、La2O3、CeO2、Nd2O3和Eu2O3混合进行研磨，再压制成片，得到混合粉体压片；
2)将混合粉体压片置于保护气氛中进行煅烧，再进行酸洗和水洗，得到高熵六硼化物纳米粉体；
3)将高熵六硼化物纳米粉体预压成坯体，再进行加压烧结，即得高熵六硼化物纳米晶陶瓷；
步骤1)所述NaBH4的物质的量与La2O3、CeO2、Nd2O3和Eu2O3中金属元素的总物质的量的比为6:1～8:1；
步骤1)所述La2O3、CeO2、Nd2O3、Eu2O3的摩尔比为1:2:1:1；
步骤2)所述煅烧的具体操作为：以8℃/min～12℃/min的升温速率升温至1100℃～1300℃，保温1h～3h；
步骤3)所述加压烧结在压力4GPa～8GPa、温度1300℃～1500℃的条件下进行，烧结时间为10min～30min。
2.根据权利要求1所述的高熵六硼化物纳米晶陶瓷的制备方法，其特征在于：步骤1)所述La2O3、CeO2、Nd2O3和Eu2O3均呈粉末状，纯度均≥99.9％，粒径均为5μm～10μm。
3.根据权利要求1所述的高熵六硼化物纳米晶陶瓷的制备方法，其特征在于：步骤1)所述压制的压力为10MPa～30MPa。
4.根据权利要求1所述的高熵六硼化物纳米晶陶瓷的制备方法，其特征在于：步骤2)所述酸洗采用的酸为浓度1mol/L～3mol/L的盐酸。
5.一种高熵六硼化物纳米晶陶瓷，其特征在于，其由权利要求1～4中任意一项所述的方法制备得到。
6.权利要求5所述的高熵六硼化物纳米晶陶瓷在制备热电子发射阴极材料中的应用。
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