CN113234983B - 一种NbTaTiZr双相等原子比高熵合金及其制备方法 - Google Patents
一种NbTaTiZr双相等原子比高熵合金及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种NbTaTiZr双相等原子比高熵合金及其制备方法,该制备方法包括如下步骤:步骤S1,将Ti、ZrH2、Nb、Ta金属原粉按等原子比加入到球磨罐中进行球磨合金化,制备出具有纳米级晶粒尺寸的NbTaTiZr合金粉末;步骤S2,在烧结压力为20‑40 MPa、700‑1100℃的条件下进行放电等离子体烧结。采用本发明的技术方案,显著提高材料的力学性能,为后续杨氏模量的调控降低难度,具有良好生物相容性,且能满足医用金属材料的要求。
Description
技术领域
本发明属于生物医用材料技术领域,尤其涉及一种NbTaTiZr双相等原子比高熵合金及其制备方法。
背景技术
生物医用材料是应用于疾病的诊断、治疗、康复和预防,以及替换生物体组织、器官、增进或恢复其功能的材料。生物材料的特征包括生物功能性和生物相容性。生物医用材料是保障人类健康的必需品,直接关乎人类的健康和生命安全。随着经济的快速发展,生活水平的不断提高,以及人口老龄化、新技术的注入,全球生物医用材料产业发展迅猛,产业规模不断提高。2016年,全球生物医用材料市场规模为1709亿美元,2020年突破3000亿美元,2016-2020年复合增长率约为16%。据此保守估计,至2025年全球生物医用材料产业规模将突破6000亿美元,正成为世界经济的支柱性产业。生物医用材料的发展不仅是社会、经济发展的迫切需求,也对国防事业以及国家安全具有重要意义。
按照材料的组成和结构,生物医用材料可以分为医用金属材料、医用无机非金属材料(生物陶瓷)、医用高分子材料、医用复合材料和生物衍生材料等。生物医用金属材料具有高强韧性、耐疲劳、易加工成形性等优良的综合性能。目前临床上应用的生物医用金属材料主要有不锈钢、钛及钛合金、钴基合金以及生物可降解镁合金。但是这些材料在应用中存在如下缺点:(1) 生物相容性差。金属材料中含有的Ni、V等对人体有害金属由于点腐蚀造成金属离子释放,引起细胞毒性和过敏,不宜在人体内长期使用;(2) 比重大、弹性模量高。与人体自然骨的杨氏模量(10-30 GPa)相比,金属材料的弹性模量高约为110-170 GPa,远远高于人体自然骨的杨氏模量,植入后容易引起人体骨骼的“应力屏蔽效应 (Stressshielding effect)”,从而诱发植入体周边正常组织脆弱化;(3) 植入成本高。传统的金属材料熔点高,加工困难,价格高昂,最终造成植入费用高。因此开发出一种满足力学性能要求、生物相容性良好、优良的抗生理腐蚀性以及易于加工成本低廉的医用金属材料非常必要。
目前钛及钛合金、不锈钢、钴基合金以及生物可降解镁合金等在临床上已取得广泛应用。同时,新型生物金属材料也在不断涌现,例如高熵合金、粉末冶金合金、非晶合金以及低模量钛合金等。其目的是制备出满足力学性能要求,同时又具备良好的生物相容性的植入材料。在众多元素之中,满足生物相容性的元素有Ti、Zr、Hf、Nb、Ta、Cr、Mo等,他们均属于难熔金属。
自2004年叶均蔚教授提出高熵的概念以来,高熵合金便作为一种极具研究前景的新型金属材料而受到广泛的研究。这是由于高熵合金具有一些传统合金无法比拟的优异性能,如高强度、高硬度、耐磨损耐腐蚀、抗氧化等。正因如此,将高熵的概念引入生物医用金属材料的设计制备中,以制备出具有良好生物相容性和高强度的生物医用金属材料。但是,在制备工艺上很多研究者采用的是真空电弧熔炼的方式去制备。而生物相容性良好的金属材料的熔点高,真空电弧熔炼存在明显的不足之处即往往导致材料晶粒粗化和成分不均匀,最终导致力学性能下降,为后续的杨氏模量的调控增加了难度。
发明内容
针对以上技术问题,本发明公开了一种NbTaTiZr双相等原子比高熵合金及其制备方法,显著地增强了材料的力学性能。
对此,本发明采用的技术方案为:
一种NbTaTiZr双相等原子比高熵合金的制备方法,其包括如下步骤:
步骤S1,将Ti、ZrH2、Nb、Ta金属原粉按等原子比加入到球磨罐中进行球磨合金化,制备出具有纳米级晶粒尺寸的NbTaTiZr合金粉末;
步骤S2,在烧结压力为20-40 MPa、700 - 1100℃的条件下进行放电等离子体烧结。
此技术方案从材料的设计出发,Ti、ZrH2、Nb、Ta均为生物相容性良好以及对人体无毒害作用的金属,从TiZr以及NbTa的二元相图可知,TiZr和NbTa的二元相图均为匀晶相图,两种元素间可以无限互熔,但由于固溶相之间存在互熔性差异进而导致形成两相。根据双元素体系的混合焓可知,Ti-Nb (+2 KJ/mol)、Ti-Ta (+1 KJ/mol)、Nb-Zr (+4 KJ/mol)、Ta-Zr (+3 KJ/mol)双元素对的混合焓值为正,也表明固溶相会分离。不仅如此,NbTaTiZr合金体系中还引入了H原子,H原子的存在会导致产生大量的空穴,空穴将促使元素的迁移,从而促使相的分离。从工艺的选择出发,由于生物相容性良好的金属元素同时也具有较高的熔点属于难熔金属,故而本发明技术方案采用机械合金化法制备合金粉末,该机械合金化法在合金的制备过程中能够有效降低合金化温度以及无其他热源输入,有效降低能耗,节约成本。经机械合金化过程,成功制备出纳米级晶粒尺寸的NbTaTiZr高熵合金粉末,进一步采用放电等离子体烧结技术制备出不同烧结温度条件下的NbTaTiZr大块高熵合金样品,所有的大块合金样品的微观结构均表现为双相且具有超细晶粒尺寸。根据Hall-Petch公式可知,超细的晶粒尺寸能有效的增强合金样品的屈服强度。原粉中的Zr源,采用的是更为安全的ZrH2,同时由于H原子作为间隙原子引入,进一步增强晶格畸变,具有间隙固溶强化效果,从而强化合金的力学性能。结果表明,在固溶强化、细晶强化以及间隙固溶强化三种强化机制的共同作用下,机械合金化与放电等离子体烧结技术的结合显著提高材料的力学性能。
作为本发明的进一步改进,步骤S2中,烧结压力为30 MPa。
作为本发明的进一步改进,步骤S2中,烧结温度为1000℃。
作为本发明的进一步改进,步骤S1中,球磨中,散粉时间间隔为1-5 h。
作为本发明的进一步改进,步骤S1中,球磨中,散粉时间间隔为1 h。
作为本发明的进一步改进,步骤S1球磨中,球料比为10~20:1。
作为本发明的进一步改进,步骤S1球磨中,球料比为15:1。
作为本发明的进一步改进,步骤S1球磨中,小不锈钢球的质量占磨球总质量为40~65%。其中,所述小不锈钢球为现有技术球磨中的小不锈钢球。
作为本发明的进一步改进,步骤S1球磨中,小不锈钢球的质量占磨球总质量为64%。
作为本发明的进一步改进,步骤S1中,得到的NbTaTiZr合金粉末的粒径分布在1-400μm,进一步优选的,平均粒径为57 μm。
作为本发明的进一步改进,步骤S2烧结后得到的NbTaTiZr双相等原子比高熵合金的晶粒尺寸为100~500 nm。本发明还公开了一种NbTaTiZr双相等原子比高熵合金,其采用如上任意一项所述的NbTaTiZr双相等原子比高熵合金的制备方法制备得到。
与现有技术相比,本发明的有益效果为:
本发明的技术方案,选用生物相容性良好的Ti、ZrH2、Nb、Ta金属为原料,采用机械合金化制备出具有纳米级晶粒尺寸的NbTaTiZr高熵合金粉末,利用放电等离子体能够快速固溶的特点得到同时具备良好生物相容性和生物安全性、具有超高强度和优异的耐腐蚀性以及具有超细晶粒尺寸的NbTaTiZr大块高熵合金样品,该方案将合金设计为双相合金体系,可调控两相的比例实现对不同性能的要求,且显著提高材料的力学性能,为后续杨氏模量的调控降低难度,具有良好生物相容性,且能满足医用金属材料的要求。
附图说明
图1是本发明实施例在不同烧结温度下得到的NbTaTiZr大块高熵合金样品的背散射图。其中,(a)为700℃烧结温度条件下的低倍背散射图,(b)~(f)分别为700℃、800℃、900℃、1000℃、1100℃烧结条件下的高倍背散射图。
图2是本发明实施例不同烧结温度条件下得到的NbTaTiZr大块高熵合金样品的性能图,其中(a)为硬度,(b)为应力-应变曲线。
图3是本发明实施例不同烧结温度条件下得到的NbTaTiZr大块高熵合金样品浸入Hanks’溶液后的极化曲线。
图4是本发明实施例不同工艺条件得到的样品的力学性能图,其中(a)为不同散粉时间间隔得到的样品的应力-应变曲线图,(b)为不同球料比得到的样品的应力-应变曲线图,(c)为不同小球质量占总质量百分数得到的样品的应力-应变曲线图,(d)~(f)为(a)~(c)所对应的屈服强度柱状对比图。
具体实施方式
下面对本发明的较优的实施例作进一步的详细说明。
实施例1
本实施例选用生物相容性良好的Ti, ZrH2, Nb, Ta金属为原料,采用机械合金化制备出具有纳米级晶粒尺寸的NbTaTiZr高熵合金粉末为前驱体,利用放电等离子体烧结工艺能够快速固溶的特点得到同时具备良好生物相容性和生物安全性、具有超高强度和优异的耐腐蚀性以及具有超细晶粒尺寸的NbTaTiZr大块高熵合金医用金属材料。具体包括如下步骤:
将Ti、ZrH2、Nb、Ta金属原粉按等原子比加入到不锈钢球磨罐中进行合金化,制备出具有纳米级晶粒尺寸、成分均匀且粒径分布广的NbTaTiZr合金粉末,粉末的粒径分布在1-400 μm,平均粒径为57 μm。为确保无其他杂质引入,未添加任何过程控制剂。具体的球磨工艺为:
散粉时间间隔为1-5 h,球料比为10~20:1。球磨中,小不锈钢球的质量占磨球总质量为40~65%。其中,所述小不锈钢球为现有技术球磨中的小不锈钢球。
进一步优选的,散粉时间间隔为1 h,球料比为15:1。球磨中,小不锈钢球的质量占磨球总质量为64%。
在烧结压力为30 MPa, 700 - 1100℃的条件下采用放电等离子体烧结工艺进行烧结(SPS)。步骤S2烧结后得到的NbTaTiZr双相等原子比高熵合金的晶粒尺寸为100~500nm。
本实施例采用粉末冶金工艺,还进行了不同烧结温度的实验。不同烧结温度得到的NbTaTiZr大块高熵合金样品的背散射图如图1所示。不同烧结温度条件下得到的NbTaTiZr大块高熵合金样品的硬度如图2(a)所示,应力-应变曲线如图2(b)所示。不同烧结温度条件下NbTaTiZr大块高熵合金样品浸入Hanks’ 溶液后的极化曲线如图3所示。当烧结温度为1000℃时,制备得到的大块NbTaTiZr高熵合金样品的屈服强度是采用电弧熔炼技术制备样品(有文献报道采用电弧熔炼技术制备的样品的屈服强度为1100 ±90 MPa)的2倍,且烧结温度为1000℃的大块样品未发生点蚀现象,并且与其他样品的自腐蚀电位以及电流密度对比发现,其展现出更优异的耐腐蚀性。
另外,针对球磨工艺,选用了散粉时间间隔为1 h、5 h、10 h的实验例,得到的样品的应力-应变曲线图和所对应的屈服强度柱状对比图如图4(a)和4(d)所示,可见不同的散粉时间间隔对力学性能影响也较大,散粉时间间隔为1 h的样品的屈服强度分别高于时间间隔5 h (28.6 %) 和10 h (11.0 %)。
本实施例还选用了球料比为10:1、15:1、20:1的实验例,得到的样品的应力-应变曲线图和所对应的屈服强度柱状对比图如图4(b)和4(e)所示,通过实验发现不同的球料比对力学性能的影响相对较小,球料比为15:1样品的屈服强度最高,相较于球料比10:1和20:1样品的屈服强度分别高出12.5 %和12.4 %。
本实施例还选用了小不锈钢球的质量占磨球总质量为64%、40%的实验例,得到的样品的应力-应变曲线图和所对应的屈服强度柱状对比图如图4(c)和4(f)所示,可见小不锈钢球的质量占磨球总质量的64 %的屈服强度比40 %的屈服强度仅高出7.4 %。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干简单推演或替换,都应当视为属于本发明的保护范围。
Claims (7)
1.一种NbTaTiZr双相等原子比高熵合金的制备方法,其特征在于,其包括如下步骤:
步骤S1,将Ti、ZrH2、Nb、Ta金属原粉按等原子比加入到球磨罐中进行球磨合金化,制备出具有纳米级晶粒尺寸的NbTaTiZr合金粉末,得到的NbTaTiZr合金粉末的粒径分布在1-400μm;
步骤S2,在烧结压力为20-40 MPa、700 - 1100℃的条件下进行放电等离子体烧结;
步骤S1中,球磨中,散粉时间间隔为1-5 h;
步骤S1球磨中,球料比为10~20:1;
步骤S1球磨中,小不锈钢球的质量占磨球总质量为40~65%。
2. 根据权利要求1所述的NbTaTiZr双相等原子比高熵合金的制备方法,其特征在于:步骤S2中,烧结压力为30 MPa,烧结温度为1000℃。
3. 根据权利要求2所述的NbTaTiZr双相等原子比高熵合金的制备方法,其特征在于:步骤S1中,球磨中,散粉时间间隔为1 h。
4.根据权利要求3所述的NbTaTiZr双相等原子比高熵合金的制备方法,其特征在于:步骤S1球磨中,球料比为15:1。
5.根据权利要求4所述的NbTaTiZr双相等原子比高熵合金的制备方法,其特征在于:步骤S1球磨中,小不锈钢球的质量占磨球总质量为64%。
6.根据权利要求1~5任意一项所述的NbTaTiZr双相等原子比高熵合金的制备方法,其特征在于:步骤S2烧结后得到的NbTaTiZr双相等原子比高熵合金的晶粒尺寸为100~500nm。
7.一种NbTaTiZr双相等原子比高熵合金,其特征在于:其采用如权利要求1~6任意一项所述的NbTaTiZr双相等原子比高熵合金的制备方法制备得到。
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