CN110204341A - 一种(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体及其制备方法 - Google Patents

一种(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体及其制备方法 Download PDF

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CN110204341A
CN110204341A CN201910458660.7A CN201910458660A CN110204341A CN 110204341 A CN110204341 A CN 110204341A CN 201910458660 A CN201910458660 A CN 201910458660A CN 110204341 A CN110204341 A CN 110204341A
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褚衍辉
刘达
叶贝琳
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South China University of Technology SCUT
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Abstract

本发明公开了一种(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体及其制备方法，该制备方法包括：（1）称取HfO2粉、TiO2粉、Nb2O5粉、Ta2O5粉、B4C粉以及C粉混合作为原料，通过研磨得到混合粉末；（2）将步骤（1）得到的混合粉末进行烧结，烧结过程中通惰性气体，烧结完成后进行冷却，最终得到所述(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体。本发明所述方法不仅工艺简单、生产成本低，而且合成的粉体晶粒细小、分布均匀、纯度高，且氧含量低于0.53wt%。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(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体及其制备方法
技术领域
本发明涉及属于高熵材料制备技术领域，具体涉及一种(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体及其制备方法。
背景技术
20世纪90年代末，中国台湾清华大学叶均蔚教授提出了高熵合金的概念。与传统合金相比，高熵合金具有更高的比强度、抗断裂能力、抗拉强度、抗腐蚀及抗氧化特性。受高熵合金概念的启发，高熵陶瓷作为一种新的陶瓷材料因具有潜在的优异性能在近年来受到广泛关注。目前研究的高熵陶瓷主要包含高熵氧化物，碳化物，氮化物以及硼化物。其中，高熵硼化物因具有高的硬度和熔点以及良好的耐蚀性、生物相容性和电化学性能，在超高温、生物医学和能源等领域具有广阔的发展潜力。高熵硼化物陶瓷粉体的合成对于高熵硼化物陶瓷的制备和应用至关重要。然而，目前国内外对于高熵硼化物陶瓷粉体的合成方法报道较少。
文献：“Liu D,Wen T,Ye B,Chu Y.Synthesis of superfine high-entropymetal diboride powders.Scripta Mater.2019；167:110-114.”介绍了一种高熵硼化物陶瓷粉体的制备方法。该方法将HfO2、ZrO2、TiO2、Nb2O5和Ta2O5五种氧化物粉体与B粉均匀混合后在1700℃反应得到(Hf,Zr,Ta,Nb,Ti,)B2高熵陶瓷粉体。该方法不仅制备的高熵陶瓷粉体晶粒尺寸较大(310nm)且分布不均匀(200-450nm)，而且经测试所合成的高熵硼化物含氧量高(2.06wt.％)，纯度较低，因此该方法合成的粉体烧结活性低，较难得到致密度高纯度高的高熵陶瓷。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不足，本发明的目的在于提供一种(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体及其制备方法，该方法以HfO2粉、TiO2粉、Nb2O5粉、Ta2O5粉、B4C粉和C粉为原料，在较低温度下通过硼/碳热还原反应直接成功制备出成分均匀且晶粒细小的(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体。该方法不仅工艺简单，而且制备的(Hf,Ta,Nb,Ti,)B2高熵陶瓷粉体晶粒细小且分布均匀，纯度高，氧含量低。
本发明的目的至少通过如下技术方案之一实现。
一种(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体的制备方法，该方法包括步骤：
(1)称取TiO2粉、HfO2粉、Nb2O5粉、Ta2O5粉、B4C和C粉混合作为原料，通过研磨得到混合粉末；
(2)将步骤(1)得到的混合粉末进行烧结，烧结过程中通Ar气保护，烧结完成后进行冷却最终得到所述(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体。
进一步地，步骤(1)中，Hf、Nb、Ta、Ti的摩尔比为1:1:1:1，该四种氧化物总的量与C粉的摩尔比为1:2.33，与B4C的摩尔比为1:0.8～1:0.93。
进一步地，步骤(1)中，HfO2粉、Nb2O5粉、Ta2O5粉和TiO2粉的纯度均≥99％，TiO2粉的粒径为50～200nm；HfO2粉、Nb2O5粉和Ta2O5粉的粒径均为1～3μm；B4C粉的纯度≥99.9％，粒径为3～5μm；C粉的纯度≥99.9％，粒径为0.7～0.9μm。
进一步地，所述步骤(1)中的研磨是将原料置于聚四氟乙烯球磨灌中，并加入ZrO2球磨珠研磨成混合粉末。
进一步地，步骤(1)中，研磨中所用的球磨珠与原料的质量比为5:1～20:1。
进一步地，球磨机的转速为300-500r/min；球磨时间为5～20h。
进一步地，步骤(2)中，烧结过程中升温速率为5～10℃/min，烧结温度为1750～1850℃，达到烧结温度后保温1～3h。
进一步地，步骤(2)中，所述惰性气体为Ar气。
由上述方法制备得到的所述(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体。
本发明是通过HfO2、Ta2O5、Nb2O5、TiO2与B4C和C发生硼/碳热还原反应直接合成(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体。与硼热还原反应相比，硼/碳热还原反应的产物除了目标产物外为CO气体，没有难去除的B2O3氧化物生成，因此合成的产物氧含量低，纯度高。
与现有技术相比，本发明具有如下优点和有益效果：
(1)本发明中的制备方法工艺简单，合成的粉体晶粒小且晶粒分布均匀。
(2)本发明中的制备方法合成的高熵陶瓷粉体氧含量低于0.53wt％，纯度高，使得该方法具有发展成大规模工业生产的潜力。
附图说明
图1为实施例1中合成的(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体的XRD图谱；
图2为实施例1中合成的(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体的SEM图及EDS能谱元素分布图。
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。
本发明实施例1-3中，采用的TiO2粉体的纯度≥99％，粒径为50～200nm；HfO2粉体的纯度≥99％，粒径为1～3μm；Nb2O5粉体的纯度≥99％，粒径为1～3μm；Ta2O5粉的纯度≥99％，粒径为1～3μm；B4C粉的纯度≥99.9％，粒径为3～5μm；C粉的纯度≥99.9％，粒径为0.7～0.9μm。
实施例1
一种(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体的制备，包括如下步骤：
(1)分别称取1.05g的HfO2粉体、0.40g的TiO2粉体、1.10g的Ta2O5粉体、0.66g的Nb2O5粉体、0.42g的C粉和0.72g的B4C粉体置于容量为150ml的聚四氟乙烯球磨罐中并加入56.00g ZrO2球磨子(原料中Hf、Ti、Nb和Ta的摩尔比为1:1:1:1，且原料中TiO2粉、HfO2粉、Nb2O5粉和Ta2O5粉的总量与C粉的摩尔比为1:2.33，TiO2粉、HfO2粉、Nb2O5粉和Ta2O5粉的总量与B4C粉的摩尔比为1:0.87，球磨珠与原料的质量比为12.9:1)。将该球磨罐置于球磨机中以400r/min的转速球磨13h得到混合粉体；
(2)将步骤(1)中得到的混合粉体放入带盖的石墨坩埚中并盖紧，将该石墨坩埚放入真空气氛炉中并对气氛炉进行抽真空处理，抽真空10min后使真空示数数值达到10-2MPa，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1800℃，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，得到(Hf0.25Ta0.25Nb0.25Ti0.25)B2高熵陶瓷粉体。
图1为本实施例制备的(Hf0.25Ta0.25Nb0.25Ti0.25)B2高熵陶瓷粉体的XRD图谱，该图谱表明，所制备的(Hf0.25Ta0.25Nb0.25Ti0.25)B2高熵陶瓷粉体为纯相，未含有其他杂质相。图2为本实施例制备(Hf0.25Ta0.25Nb0.25Ti0.25)B2高熵陶瓷粉体的SEM图以及元素分布图，由图2中(a)可知，该条件下合成的(Hf0.25Ta0.25Nb0.25Ti0.25)B2高熵陶瓷粉体晶粒大小较均匀，晶粒尺寸在200-300nm之间，由图2中的(b)-(e)可知，Hf、Ta、Nb和Ti四种组成元素均匀分布，经氮氧分析仪测定，粉体中的氧含量为0.49wt.％。
实施例2
一种(Hf,Ta,Nb,Ti,)B2高熵陶瓷粉体的制备，包括如下步骤：
分别称取1.05g的HfO2粉体、0.40g的TiO2粉体、1.10g Ta2O5粉体、0.66g Nb2O5粉体、0.42g的C粉和0.66g的B4C粉置于容量为150ml的聚四氟乙烯球磨罐中并加入21.45gZrO2球磨子(原料中Hf、Ti、Nb和Ta的摩尔比为1:1:1:1，且原料中TiO2粉、HfO2粉、Nb2O5粉和Ta2O5粉的总量与C粉的摩尔比为1:2.33，TiO2粉、HfO2粉、Nb2O5粉和Ta2O5粉的总量与B4C粉的摩尔比为1:0.8，球磨珠与原料的质量比为5:1)。将该球磨罐置于球磨机中以300r/min的转速球磨5h得到混合粉体；
将步骤(1)中得到的混合粉体放入带盖的石墨坩埚中并盖紧，将该石墨坩埚放入真空气氛炉中并对气氛炉进行抽真空处理，抽真空10min后使真空示数数值达到10-2MPa，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1750℃，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。该条件下合成的(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体为纯相，平均晶粒尺寸为200-300nm之间(参照实施例1的图1-2)，且粉体中的氧含量为0.51wt.％。
实施例3
一种(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体的制备，包括如下步骤：
分别称取1.05g的HfO2粉体、0.40g的TiO2粉体、1.10g Ta2O5粉体、0.66g Nb2O5粉体、0.42g的C粉和0.77g的B4C粉置于容量为150ml的聚四氟乙烯球磨罐中并加入88.00gZrO2球磨子(原料中Hf、Ti、Nb和Ta的摩尔比为1:1:1:1，且原料中TiO2粉、HfO2粉、Nb2O5粉和Ta2O5粉的总量与C粉的摩尔比为1:2.33，TiO2粉、HfO2粉、Nb2O5粉和Ta2O5粉的总量与B4C粉的摩尔比为1:0.93，球磨珠与原料的质量比为19.3:1)。将该球磨罐置于球磨机中以500r/min的转速球磨20h得到混合粉体；
将步骤(1)中得到的混合粉体放入带盖的石墨坩埚中并盖紧，将该石墨坩埚放入真空气氛炉中并对气氛炉进行抽真空处理，抽真空10min后使真空示数数值达到10-2MPa，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1850℃，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，该条件下合成的(Hf,Ta,Nb,Ti)B2高熵陶瓷粉体为纯相，平均晶粒尺寸在200-350nm之间(参照实施例1的图1-2)，粉体中的氧含量为0.53wt.％。
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 (9)

1.一种(Hf, Ta, Nb, Ti)B2高熵陶瓷粉体的制备方法，其特征在于，包括如下步骤：
（1）称取HfO2粉、TiO2粉、Nb2O5粉、Ta2O5粉、B4C粉以及C粉混合作为原料，通过研磨得到混合粉末；
（2）将步骤（1）得到的混合粉末进行烧结，烧结过程中通惰性气体，烧结完成后进行冷却，最终得到所述(Hf, Ta, Nb, Ti)B2高熵陶瓷粉体。
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，HfO2粉、TiO2粉、Nb2O5粉和Ta2O5粉的纯度均≥99%，TiO2粉的粒径为50~200 nm； HfO2粉、Nb2O5粉和Ta2O5粉的粒径均为1~3 μm；B4C粉的纯度≥99.9%，粒径为3~5 μm；C粉的纯度≥99.9%，粒径为0.7~0.9 μm。
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，原料中Hf、Ti、Nb和Ta的摩尔比为1:1:1:1，且原料中TiO2粉、HfO2粉、Nb2O5粉和Ta2O5粉的总量与C粉的摩尔比为1:2.33，与B4C的摩尔比为1:0.8~1:0.93。
4.根据权利要求1所述的制备方法，其特征在于，所述步骤（1）中的研磨是将原料置于聚四氟乙烯球磨灌中，并加入ZrO2球磨珠研磨成混合粉末。
5.根据权利要求4所述的制备方法，其特征在于，所述研磨中所用的球磨珠与原料的质量比为5:1~20:1。
6.根据权利要求4所述的制备方法，其特征在于，所述球磨机的转速为300-500 r/min，球磨时间为5~20 h。
7.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，烧结过程中升温速率为5~10℃/min，烧结温度为1750~1850℃，达到烧结温度后保温1~3 h。
8.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，惰性气体为Ar气。
9.权利要求1~8任一项所述制备方法制得的(Hf, Ta,Nb, Ti)B2高熵陶瓷粉体。
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