CN110818432B - 一种超细高熵硼化物纳米粉体及其制备方法 - Google Patents

一种超细高熵硼化物纳米粉体及其制备方法 Download PDF

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CN110818432B
CN110818432B CN201911133527.0A CN201911133527A CN110818432B CN 110818432 B CN110818432 B CN 110818432B CN 201911133527 A CN201911133527 A CN 201911133527A CN 110818432 B CN110818432 B CN 110818432B
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CN110818432A (zh
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褚衍辉
叶贝琳
刘红华
韩杨洁
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South China University of Technology SCUT
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Abstract

本发明公开了一种超细高熵硼化物纳米粉体及其制备方法。该制备方法包括以下步骤：（1）将HfO2粉、ZrO2粉、Ta2O5粉、Nb2O5粉、TiO2粉、Cr2O3粉、MoO3粉或WO3粉中的任意四种或四种以上的粉体采用湿法球磨均匀混合，将得到的浆料旋转蒸干，将所得干燥粉体与B2O3粉、Mg粉和MgCl2混合研磨；（2）将步骤（1）中研磨后的粉体加热进行镁热还原反应，然后冷却至室温，整个过程中通入Ar气保护；（3）将步骤（2）中反应后的物质洗涤、过滤和干燥，最终得到的粉体即为所述超细高熵硼化物纳米粉体。本发明方法合成的高熵纳米粉体成分均匀、粒径细小，这些优点使得该方法具有发展成大规模工业生产的潜力。

Description

一种超细高熵硼化物纳米粉体及其制备方法
技术领域
本发明属于高熵化合物技术领域，具体涉及一种超细高熵硼化物纳米粉体及其制备方法。
背景技术
高熵陶瓷材料因具有巨大的组分空间、独特的微观结构以及可调控的性能而引起国内外研究者的广泛关注。目前，高熵陶瓷材料的研究主要集中在高熵氧化物、硼化物以及碳化物陶瓷材料的研究。其中，高熵硼化物陶瓷因其具有极高的熔点、较低的热导率、优异的力学性能以及良好的高温抗腐蚀能力而受到国内外学者的广泛研究。然而，目前在制备的高熵硼化物块体陶瓷材料中普遍存在晶粒粗大、孔隙率高、部分金属元素偏析及含有氧化物杂质相等诸多问题。因此，高纯超细高熵硼化物粉体的合成对于解决上述问题起到至关重要的作用。目前，国内外关于高纯超细高熵硼化物粉体的合成方法报道较少。
文献:“Feng L,Fahrenholtz WG,Hilmas GE.Two-step synthesis process forhigh-entropy diboride powders.Journal of the American Ceramic Society,2019；00:1～7.”介绍了一种以TiO2粉、ZrO2粉、HfO2粉、Nb2O5粉和Ta2O5粉作为金属源，以B4C粉作为硼源，以C粉作为还原剂、采用碳/硼热还原技术与固溶技术相结合的两步法最终在2000℃的高温下合成出(Hf,Ta,Ti,Zr,Nb)B2高熵硼化物粉体。该方法不仅合成工艺复杂、制备温度高、设备要求高，而且合成的高熵硼化物粉体粒径粗大(亚微米级)，这些缺点严重限制了该方法的推广和应用。
发明内容
为了克服现有技术的缺点与不足，本发明的目的在于提供一种超细高熵硼化物纳米粉体及其制备方法。该方法以HfO2粉、ZrO2粉、Ta2O5粉、Nb2O5粉、TiO2粉、Cr2O3粉、MoO3粉或WO3粉中的任意四种或四种以上的粉体作为金属源，以B2O3粉作为硼源，以Mg粉作为还原剂，以MgCl2作为熔盐，在低温下通过原料在熔盐中发生镁热还原直接一步合成出成分均匀的超细高熵硼化物纳米粉体，该方法不仅合成工艺简单、合成原料价格低廉、合成温度低(900～1200℃)、设备要求低，而且制备的高熵纳米粉体成分均匀、粒径细小(平均粒径约为40～50nm)。
本发明的目的至少通过如下之一的技术方案实现。
一种超细高熵硼化物纳米粉体的制备方法，包括如下步骤：
(1)将HfO2粉、ZrO2粉、Ta2O5粉、Nb2O5粉、TiO2粉、Cr2O3粉、MoO3粉或WO3粉中的任意四种或四种以上的粉体采用湿法球磨均匀混合，将得到的浆料旋转蒸干，将所得干燥粉体与B2O3粉、Mg粉和MgCl2盐混合研磨；
(2)将步骤(1)中研磨后的粉体加热进行镁热还原反应，然后冷却至室温，整个过程中通入Ar气保护；
(3)将步骤(2)中反应后的物质洗涤、过滤和干燥，最终得到的粉体即为所述超细高熵硼化物纳米粉体。
进一步的，所述步骤(1)中，ZrO2粉、TiO2粉、MoO3粉及WO3粉的纯度≥99％，粒径为50～200nm；HfO2粉、Nb2O5粉、Ta2O5粉及Cr2O3粉的纯度≥99％，粒径为1～3μm；B2O3粉的纯度≥99％，粒径为1～10μm；Mg粉的纯度≥99.9％，粒径为40～50μm；所述MgCl2盐纯度为分析纯。
进一步的，步骤(1)中，HfO2粉、ZrO2粉、Ta2O5粉、Nb2O5粉、TiO2粉、Cr2O3粉、MoO3粉及WO3粉中的任意四种或四种以上的粉体按金属元素等摩尔比均匀混合。
进一步的，步骤(1)中，金属氧化物粉体的总量与B2O3粉的摩尔比为1:2～1:7；金属氧化物粉体的总量与Mg粉的摩尔比为1:15～1:30；MgCl2盐总的质量为各金属氧化物粉体、B2O3粉及Mg粉总质量的3～20倍。
进一步的，步骤(1)中，湿法行星球磨的磨球材质为ZrO2，转速为400～500r/min，球磨时间为8～24h，旋转蒸干时间为1～5h。
进一步的，步骤(1)中，手动研磨时间为30～60min。
进一步的，步骤(2)中，加热时升温速率为5～10℃/min，反应温度为900～1200℃，反应时间为1～3h，通入Ar气的流量为100～300sccm。
进一步的，步骤(3)中，洗涤是分别用去离子水和稀盐酸对步骤(2)反应后的物质进行清洗，且盐酸的浓度为20～40vol％；干燥温度为40～80℃，干燥时间为2～5h。
进一步的，步骤(3)中，所述去离子水的温度为80～100℃，盐酸的温度为室温。
上述制备方法制得的超细高熵硼化物纳米粉体。
与现有技术相比，本发明具有如下优点和有益效果：
(1)本发明所述制备方法所采用的原料价格低廉、合成温度低、合成工艺简单、设备要求低、生产成本低，有利于大规模工业化生产；
(2)本发明所述制备方法合成的超细高熵硼化物纳米粉体粒径细小(平均粒径约为40～50nm)、成分均匀。
附图说明
图1为实施例1中合成的超细(Zr,Ta,Nb,Ti)B2高熵纳米粉体的XRD图谱；
图2为实施例1中合成的超细(Zr,Ta,Nb,Ti)B2高熵纳米粉体的SEM图及EDS能谱图。
具体实施方式
以下结合具体实施例及附图对本发明技术方案作进一步详细描述，但本发明的保护范围及实施方式不限于此。
本发明具体实施例中，采用的ZrO2粉、TiO2粉、MoO3粉及WO3粉的纯度≥99％，粒径为50～200nm；HfO2粉、Nb2O5粉、Ta2O5粉及Cr2O3粉的纯度≥99％，粒径为1～3μm；B2O3粉的纯度≥99％，粒径为1～10μm；Mg粉的纯度≥99.9％，粒径为40～50μm；所述MgCl2盐纯度为分析纯；所述盐酸的浓度为20～40vol％，湿法球磨的磨球材质为ZrO2。
实施例1
(1)分别称取0.62g的ZrO2粉体、1.10g的Ta2O5粉体、0.66g的Nb2O5粉体、0.40g的TiO2粉体，将上述粉体采用湿法球磨技术以400r/min的转速混合8h后旋转蒸干1h，所得干燥粉体与2.09g的B2O3粉、5.47g的Mg粉及31.02g的MgCl2盐置于玛瑙研钵中并手动研磨30min使粉体混合均匀，将上述混合粉体转移至于刚玉方舟中；
(2)将方舟放入管式炉中，对管式炉进行抽真空处理，抽真空10min后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，说明系统密封完好，此过程重复三次。通入Ar气至常压，之后以5℃/min的升温速率将炉温从室温升至900℃，保温1h；随后关闭电源自然冷却至室温，整个过程中通Ar气保护，Ar气的流量保持在100sccm；
(3)将得到的混合物在80℃的去离子水中以及室温下20vol％稀盐酸中洗涤过滤后放入40℃的烘箱中干燥2h得到目标产物。
图1为本实施例制备的粉体的XRD图谱，该图谱表明，所合成的粉体为(Zr0.25Ta0.25Nb0.25Ti0.25)B2相，未含有其他杂质相。图2为本实施例合成的高熵硼化物纳米粉体的SEM图及EDS元素分布图，由图2中的b-e可知，合成的粉体中Zr、Ta、Nb、Ti四种金属元素均匀分布。由图可知，本实施例合成的高熵硼化物纳米粉体的平均粒径约为40nm。
实施例2
(1)分别称取1.05g的HfO2粉体、0.62g的ZrO2粉体、0.66g的Nb2O5粉体、1.10g的Ta2O5粉体，将上述粉体采用湿法球磨技术以450r/min的转速混合16h后旋转蒸干3h，所得干燥粉体与7.31g的B2O3粉、10.94g的Mg粉和433.6g的MgCl2盐置于玛瑙研钵中并手动研磨45min使粉体混合均匀，将上述粉体转移至刚玉方舟中；
(2)将方舟放入管式炉中，对管式炉进行抽真空处理，抽真空10min后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，说明系统密封完好，此过程重复三次。通入Ar气至常压，之后以8℃/min的升温速率将炉温从室温升至1050℃，保温2h；随后关闭电源自然冷却至室温，整个过程中通Ar气保护，Ar气的流量保持在200sccm；
(3)将得到的混合物在90℃的去离子水及30vol％稀盐酸中洗涤后过滤并放入60℃的烘箱中干燥3.5h得到目标产物。
该条件下合成的高熵硼化物纳米粉体为纯相，平均粒径约为45nm，参见实施例1的图。
实施例3
(1)分别称取0.66g的Nb2O5粉体、1.10g的Ta2O5粉体、0.40g的TiO2粉体、1.16g的WO3粉体，将上述粉体采用湿法球磨技术以500r/min的转速混合24h后旋转蒸干5h，所得干燥粉体与4.70g的B2O3粉、8.20g的Mg粉和243.3g的MgCl2盐置于玛瑙研钵中并手动研磨60min使粉体混合均匀，将上述粉体转移至刚玉方舟中；
(2)将方舟放入管式炉中，对管式炉进行抽真空处理，抽真空10min后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，说明系统密封完好，此过程重复三次。通入Ar气至常压，之后以10℃/min的升温速率将炉温从室温升至1200℃，保温3h；随后关闭电源自然冷却至室温，整个过程中通Ar气保护，Ar气的流量保持在300sccm；
(3)将得到的混合物在100℃的去离子水及40vol％稀盐酸中洗涤后过滤并放入80℃的烘箱中干燥5h得到目标产物。
该条件下合成的高熵硼化物纳米粉体为纯相，平均粒径约为50nm，参见实施例1的图。
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，其它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 (7)

1.一种超细高熵硼化物纳米粉体的制备方法，其特征在于，包括如下步骤：
(1)将HfO2粉、ZrO2粉、Ta2O5粉、Nb2O5粉、TiO2粉、Cr2O3粉、MoO3粉或WO3粉中的任意四种或四种以上的粉体采用湿法球磨均匀混合，将得到的浆料旋转蒸干，将所得干燥粉体与B2O3粉、Mg粉和MgCl2盐混合研磨；金属氧化物粉体的总量与B2O3粉的摩尔比为1:2～1:7；金属氧化物粉体的总量与Mg粉的摩尔比为1:15～1:30；MgCl2盐总质量为各金属氧化物粉体、B2O3粉及Mg粉总质量的3～20倍；
(2)将步骤(1)中研磨后的粉体加热进行镁热还原反应，然后冷却至室温，整个过程中通入Ar气保护；
(3)将步骤(2)中反应后的物质洗涤、过滤和干燥，最终得到的粉体即为所述超细高熵硼化物纳米粉体；所述超细高熵硼化物纳米粉体为纯相；
所述步骤(2)中，加热时升温速率为5～10℃/min，反应温度为900～1200℃，反应时间为1～3h；
所述步骤(1)中，HfO2粉、ZrO2粉、Ta2O5粉、Nb2O5粉、TiO2粉、Cr2O3粉、MoO3粉及WO3粉中的任意四种或四种以上的粉体按照金属元素等摩尔比均匀混合。
2.根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中，所述ZrO2粉、TiO2粉、MoO3粉及WO3粉的纯度≥99％，粒径为50～200nm；HfO2粉、Nb2O5粉、Ta2O5粉及Cr2O3粉的纯度≥99％，粒径为1～3μm；B2O3粉的纯度≥99％，粒径为1～10μm；Mg粉的纯度≥99.9％，粒径为40～50μm；所述MgCl2盐纯度为分析纯。
3.根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中，湿法球磨的磨球材质为ZrO2，转速为400～500r/min，球磨时间为8～24h，旋转蒸干时间为1～5h，混合研磨时间为30～60min。
4.根据权利要求1所述的制备方法，其特征在于，所述步骤(2)中，通入Ar气的流量为100～300sccm。
5.根据权利要求1所述的制备方法，其特征在于，所述步骤(3)中，洗涤是分别用去离子水和稀盐酸对步骤(2)反应后的物质进行清洗，且盐酸的浓度为20～40vol％；干燥温度为40～80℃，干燥时间为2～5h。
6.根据权利要求5所述的制备方法，其特征在于，所述去离子水的温度为80～100℃，盐酸的温度为室温。
7.权利要求1-6任一项所述制备方法制得的超细高熵硼化物纳米粉体。
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