CN114605154B - 一种基于金属预合金化的高熵陶瓷材料及其制备方法 - Google Patents

一种基于金属预合金化的高熵陶瓷材料及其制备方法 Download PDF

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CN114605154B
CN114605154B CN202210336920.5A CN202210336920A CN114605154B CN 114605154 B CN114605154 B CN 114605154B CN 202210336920 A CN202210336920 A CN 202210336920A CN 114605154 B CN114605154 B CN 114605154B
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祖宇飞
田洪亮
王梓
刘应军
李丹丹
代吉祥
沙建军
陈国清
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Dalian University of Technology
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Abstract

本发明属于高熵陶瓷制备方法领域，具体涉及一种基于金属预合金化的高熵陶瓷材料及其制备方法。以第IV副族、第V副族或第VI副族的金属作为高熵陶瓷材料的金属元素，先通过球磨法将金属元素进行合金化形成单一BCC结构的多主元固溶体，再向多主元固溶体中添加非金属元素，利用热压烧结或放电等离子烧结使非金属元素与多主元固溶体发生反应生成高熵陶瓷材料。利用该方法可以实现在较低的温度与压力下制备高熵陶瓷材料，且所得陶瓷组元稳定、成分均匀、无偏析、无氧化物残留等缺陷，在材料性能的提升与产品制备的成本控制方面均有益处。

Description

一种基于金属预合金化的高熵陶瓷材料及其制备方法
技术领域
本发明涉及高熵陶瓷制备方法领域，更具体的是，本发明涉及一种通过金属预合金化制备高熵陶瓷制备方法。
背景技术
高熵材料是一类由多种元素以等/近等摩尔比组成的多主元材料，打破了传统的材料设计理念。高熵材料的多主元特征可以引起较大的混合熵，形成熵稳定多主元固溶体结构，表现出优于传统材料性能的特征，是目前材料科学领域的前沿和热点。高熵材料概念的提出，最早可追溯至2004年中国台湾学者叶均蔚等人提出的高熵合金，经近20年的快速发展，正逐渐步入工程化应用。随着研究的不断深入，高熵材料设计理念已于2015年拓展至陶瓷领域。其中，高熵陶瓷是由五种或五种以上结构相似的陶瓷组成的单相固溶体，具有诸多优异的性能：极高的熔点、优良的室温及高温力学性能、以及优异的抗氧化、抗烧蚀、耐蚀性、生物相容性和电化学性能等，在航空航天、生物医学等诸多领域具有更大的发展潜力。
近几年，研究者们已开发出多种适用于高熵陶瓷的制备方法，如：热压烧结法、放电等离子烧结法、高温自蔓延法、氧化物热还原法等。然而，由于陶瓷材料存在物质扩散慢的本征问题，多种成分的陶瓷在烧结制备过程中难以形成单相固溶体，这就需要极高的烧结温度和较长的保温时间来实现多主元的高度固溶。这势必会增大生产成本，并对生产设备提出更高的要求。例如，目前热压烧结法和放电等离子烧结法可获得致密度较高且固溶度较好的高熵陶瓷，但其存在制备温度过高的问题(通常高达2000℃)；如果降低制备温度(<1800℃)，则难以实现高熵陶瓷材料的高致密和/或高度固溶。此外，通过氧化物热还原反应烧结法可一定程度降低制备温度，但存在氧化物易残留影响其高温性能的问题。总之，高熵陶瓷制备目前仍面临着制备温度过高、工艺流程复杂、氧化物残留、多主元难以完全固溶、成分偏析等问题，严重限制了其推广与应用。因此，如何在较低温度下制备高纯、高度固溶且无偏析的高熵陶瓷，是其走向工程应用的关键之一。
发明内容
本发明的目的在于提供一种基于金属预合金化的高熵陶瓷材料的低温制备方法，解决传统制备方法的制备温度过高、工艺流程复杂、氧化物残留、多主元难以完全固溶、成分偏析等问题。本发明首次采用金属预合金化的思路在较低的温度下成功制备高纯高度固溶的高熵陶瓷材料。首先，将高熵陶瓷所需的金属元素进行机械合金化形成预合金化金属粉体，再根据高熵陶瓷具体物相比例来设计非金属元素与金属固溶体比例，在热压或放电等离子烧结过程中利用金属固溶体与非金属的反应同步实现高熵陶瓷的合成与致密化。该方法制备工艺简单、所需温度较低，所得高熵陶瓷具有成分均匀、多主元高度固溶、缺陷少、致密度高、无氧化物残留、晶粒尺寸小等优点。
本发明的技术方案：
一种基于金属预合金化的高熵陶瓷材料制备方法，以第IV副族、第V副族或第VI副族的金属作为高熵陶瓷材料的金属元素，先通过球磨法将金属元素进行合金化形成单一BCC结构的多主元固溶体，再向多主元固溶体中添加非金属元素，利用热压烧结或放电等离子烧结使非金属元素与多主元固溶体发生反应生成高熵陶瓷材料。
进一步的，所述的金属元素为Ti、V、Cr、Zr、Nb、Mo、Hf、Ta、W中的 5种以上混合；非金属元素为B、C、Si中的一种或多种以上混合。
进一步的，一种基于金属预合金化的高熵陶瓷材料制备方法，具体步骤如下：
1)球磨制备合金化金属粉体：取等摩尔比的各金属元素的粉体放入球磨罐中，加入磨球介质，充入惰性气体，以200～400r/min的转速进行球磨24～72h，使金属粉体完全合金化形成单一BCC结构的固溶体；所述磨球介质与金属元素粉体的质量比为5～20:1；
2)合金化金属粉体与非金属粉体混合：将非金属元素的粉体放入步骤1) 的球磨罐中，与单一BCC结构的固溶体混合，加入无水乙醇，进行湿式球磨，球料配比为5～20:1，以球磨转速为200～400r/min球磨12～24h得到混合浆料；
3)反应烧结制备高熵陶瓷：对步骤2)得到的混合浆料进行烘干研磨得到干燥粉体，将干燥粉体施加5-100MPa的压力冷压成坯体；然后置于真空或氩气环境下，施加15～40MPa的压力，在以10～50℃/min的升温速率加热到1600～1900℃烧结1-60min；最后，以5～15℃/min的降温速率降至1000℃，然后随炉自然冷却至室温，得到高熵陶瓷材料。
进一步的，金属元素总的摩尔比与非金属元素的摩尔比添加量关系如下：
1)当所述的金属原料为Ti、V、Cr、Zr、Nb、Mo、Hf、Ta、W中的5种以上混合(Me)，且非金属原料为单质碳时，金属元素总的摩尔比与单质碳的摩尔比为：nMe:nC＝1:1-1.1；
2)当所述的金属元素为Ti、V、Cr、Zr、Nb、Mo、Hf、Ta、W中的5种以上混合(Me)，且非金属原料为单质硼时，金属元素总的摩尔比与单质硼的摩尔比为：nMe:nB＝1:1-2.2；
3)当所述的金属元素为Ti、V、Cr、Zr、Nb、Mo、Hf、Ta、W中的5种以上混合(Me)，且非金属原料为碳化硼、单质碳和单质硅的混合物时，金属元素总的摩尔比与非金属元素总的摩尔比为：nMe:nB4C:nC:nSi＝2:1-1.1:0.5-3:1.5-4；
进一步的，所述的磨球介质为玛瑙球、碳化钨球或氧化锆，所述的金属元素的粉体纯度≥99％，粒径为0.5～100μm；磨球介质包括大球和小球，大球直径为8～14mm，小球直径为3～5mm，大球与小球个数比为3-9:1。
进一步的，烘干温度为30℃，真空度＜100Pa。
与现有技术相比，本发明的优点在于：
(1)本发明为已知报道中首次采用金属粉体预合金化形成单相固溶体再与非金属粉体反应来实现低温制备高度固溶的高熵陶瓷。本方法利用金属扩散能力远高于陶瓷的特点，利用高能球磨首先实现金属元素的高度固溶，再根据高熵陶瓷目标成分设计高熵合金粉体与非金属粉体的比例，最后根据反应特点设计特定的烧结温度和保温时间，确保在反应合成过程中不会出现高熵材料偏析甚至脱溶现象。以该方法制得的高熵陶瓷不但组元稳定、成分均匀、无偏析、无氧化物残留等缺陷，且烧结温度较目前已报道的方法更低，工艺简单节约成本。
(2)本发明制备高熵陶瓷过程中，加入过量的非金属粉体能够消耗原始粉体中的氧元素，能够改善材料的可烧结性和纯度。
(3)本发明可实现性和推广性高，不但可制备硼化物基高熵陶瓷，还可采用此方法制备高熵碳化物陶瓷等。
附图说明
图1金属固溶体粉末xrd检测图。
具体实施方式
下面进一步通过实施例以详细说明本发明。但应注意，以下所述是对本发明的解释而并非限定。
实施例1
(1)以等摩尔比的Ti、Zr、Nb、W和Mo五种商业金属粉为原料，以使用碳化钨磨球与碳化物球磨罐，在行星式球磨机中以350r/min的转速进行球磨60h，得到具有BCC结构的固溶体的金属粉体；碳化钨磨球与金属元素粉体的质量比为10:1。(附图1)
(2)按照金属元素总的摩尔比与非金属原料总的摩尔比为：nMe:nB4C:nC:nSi＝2:1.1:3:4的比例称取碳化硼粉、石墨粉和单质硅粉与15ml的无水乙醇溶剂混合，以球磨转速为250r/min湿式球磨24h得到均匀的混合浆料，球料配比为10:1。
(3)将混合浆料置于真空干燥箱中在真空环境下以30℃恒温干燥8h，随后将其研磨过筛，得到混合均匀的粉体。
(4)将混合粉体置于直径20mm的石墨模具中，将坯体与模具置于真空热压烧结炉中，在真空的条件下以10℃/min的升温速率升温至1600℃并保持 30MPa的恒压。在1600℃保温10min，以5℃/min降温速率降至1000℃随后自然冷却至室温，得到高熵硼化物陶瓷复合材料(Ti0.2Zr0.2Nb0.2W0.2Mo0.2)B2-SiC。
实施例2
于实施例1中的步骤类似，所不同的是，金属粉元素选取为等摩尔比Ti、 Zr、Nb、Ta、Hf五种金属元素，按照金属元素总的摩尔比与非金属原料总的摩尔比为：nMe:nB4C:nC:nSi＝2:1.1:0.5:1.5的比例称取碳化硼粉、石墨粉和单质硅粉，按照此方法可制备出SiC含量不同与实施例1的高熵硼化物陶瓷复合材料 (Ti0.2Zr0.2Nb0.2Ta0.2Hf0.2)B2-SiC。
实施例3
于实施例1中的步骤类似，所不同的是，金属粉元素选取为等摩尔比V、 Cr、Nb、Ta、Hf五种金属元素，按照金属元素总的摩尔比与非金属原料总的摩尔比为：nMe:nB＝1:2.2称取无定型硼粉，按照此方法可制备出高熵硼化物陶瓷 (V0.2Cr0.2Nb0.2Ta0.2Hf0.2)B2。
实施例4
于实施例1中的步骤类似，所不同的是，金属粉元素选取为等摩尔比V、 Zr、Nb、Ta、W五种金属元素，按照金属元素总的摩尔比与非金属原料总的摩尔比为：nMe:nB＝1:1.1称取无定型硼粉，按照此方法可制备出高熵硼化物陶瓷 (V0.2Zr0.2Nb0.2Ta0.2W0.2)B。
实施例5
于实施例1中的步骤类似，所不同的是，金属粉元素选取为等摩尔比V、 Cr、Zr、Ta、Hf五种金属元素，按照金属元素总的摩尔比与非金属原料总的摩尔比为：nMe:nB＝1:1.1称取石墨粉，按照此方法可制备出高熵碳化物陶瓷 (V0.2Cr0.2Zr0.2Ta0.2Hf0.2)C。
实施例6
于实施例1中的步骤类似，所不同的是，金属粉元素选取为等摩尔比Ti、V、 Cr、Ta、Hf五种金属元素，按照金属元素总的摩尔比与非金属原料总的摩尔比为：nMe:nB＝1:1.1称取石墨粉，按照此方法可制备出高熵碳化物陶瓷(Ti0.2V0.2Cr0.2 Ta0.2Hf0.2)C。
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式，并且很显然，根据上述教导，可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及其实际应用，从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。

Claims (4)

1.一种基于金属预合金化的高熵陶瓷材料制备方法，其特征在于，以第IV副族、第V副族或第VI副族的金属作为高熵陶瓷材料的金属元素，先通过球磨法将金属元素进行合金化形成单一BCC结构的多主元固溶体，再向多主元固溶体中添加非金属元素，利用热压烧结或放电等离子烧结使非金属元素与多主元固溶体发生反应生成高熵陶瓷材料；
所述的金属元素为Ti、V、Cr、Zr、Nb、Mo、Hf、Ta、W中的5种以上混合；非金属元素为B、Si中的一种，或B、C、Si中的多种以上混合；
具体步骤如下：
1）球磨制备合金化金属粉体：取等摩尔比的各金属元素的粉体放入球磨罐中，加入磨球介质，充入惰性气体，以200~400 r/min的转速进行球磨24~72 h，使金属粉体完全合金化形成单一BCC结构的固溶体；所述磨球介质与金属元素粉体的质量比为5~20:1；
2）合金化金属粉体与非金属粉体混合：将非金属元素的粉体放入步骤1）的球磨罐中，与单一BCC结构的固溶体混合，加入无水乙醇，进行湿式球磨，球料配比为5~20:1，以球磨转速为200~400 r/min球磨12~24 h得到混合浆料；
3）反应烧结制备高熵陶瓷：对步骤2）得到的混合浆料进行烘干研磨得到干燥粉体，将干燥粉体施加5-100MPa的压力冷压成坯体；然后置于真空或氩气环境下，施加15~40 MPa的压力，在以10~50℃/min的升温速率加热到1600~1900℃烧结1-60 min；最后，以5~15℃/min的降温速率降至1000℃，然后随炉自然冷却至室温，得到高熵陶瓷材料；
金属元素总的摩尔比与非金属元素的摩尔比添加量关系如下：
1）当所述的金属元素为Ti、V、Cr、Zr、Nb、Mo、Hf、Ta、W中的5种以上混合，且非金属元素为单质硼时，金属元素总的摩尔比与单质硼的摩尔比为：nMe:nB=1:1-2.2；
2）当所述的金属元素为Ti、V、Cr、Zr、Nb、Mo、Hf、Ta、W中的5种以上混合，且非金属元素为碳化硼、单质碳和单质硅的混合物时，金属元素总的摩尔比与非金属元素总的摩尔比为：nMe:nB4C:nC:nSi =2:1-1.1:0.5-3:1.5-4。
2.根据权利要求1所述的一种基于金属预合金化的高熵陶瓷材料制备方法，其特征在于，所述的磨球介质为玛瑙球、碳化钨球或氧化锆，所述的金属元素的粉体纯度≥99%，粒径为0.5～100μm；磨球介质包括大球和小球，大球直径为8~14 mm，小球直径为3~5 mm，大球与小球个数比为3-9:1。
3.根据权利要求1所述的一种基于金属预合金化的高熵陶瓷材料制备方法，其特征在于，烘干温度为30℃，真空度＜100Pa。
4.一种基于金属预合金化的高熵陶瓷材料，其特征在于，所述的高熵陶瓷材料是由权利要求1-3任一所述的制备方法制得的。
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