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高熵合金

维基百科,自由的百科全书
面心立方结构CoCrFeMnNi原子结构[1]

高熵合金(英语:High-entropy alloysHEAs)简称HEA,通常是由五种或五种以上等量或相对比例金属形成的新型合金。名为“高熵合金”是因为当混合物中存在大量元素混合时的熵增加实质上更高,并且比例更接近相等。[2]

由于高熵合金可能具有许多理想的性质,因此在材料科学及工程上相当受到重视[3]。相对于以往的典型金属合金,合金主要的金属成分可能只有一至两种。例如会以铁为基础,再加入一些微量元素(等)来提升其特性,但因此所得的还是以铁为主的合金[3],其他元素比例实际相当低。过往的概念中,若合金中加的金属种类越多,会使其材质脆化,但高熵合金和以往的合金不同,有多种金属却不会脆化,是一种新的材料[1][3][4]

研究发现有些高熵合金的比强度比传统合金好很多,而且抗断裂能力抗拉强度、抗腐蚀及抗氧化特性都比传统的合金要好。高熵合金在2004年以前就已问世,但在2010年代才有许多相关的研究[3][5][6][7][8][9]

发展

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尽管早在1981年[10]、1996年[11]、以及整个1980年代就考究了理论上可以存在高熵合金。但制造出这些特殊合金,还要到2004年。

据说叶均蔚博士是在1995年驾车穿越新竹乡村时,想出了实际制造高熵合金方法。

高熵合金潜在应用包括用于潜艇、航天器、核武器、核反应堆[12]、喷气式飞机、远程高超音速导弹等等。[13][14]

叶均蔚博士的论文发表几个月后,布赖恩·康托尔英语Brian Cantor、I. T. H. Chang、P. Knight、A. J. B. Vincent提交了关于高熵合金的独立论文。

叶均蔚也是第一个提出“高熵合金”(英语:High-entropy alloys)一词的人,他将高构型熵归因于稳定固溶体相机制。[15]

尽管布赖恩·康托尔英语Brian Cantor直到2004年叶均蔚论文发表几个月后才发表论文,康托尔其实早在1970年代末1980年代初就完成了该领域的首项工作。康托尔英语Brian Cantor由于不知道叶均蔚的工作,康托尔英语Brian Cantor更喜欢称“高熵合金”为“多组分合金多元合金”(英语:multicomponent alloys)。康托尔英语Brian Cantor开发了高熵合金FeCrMnNiCo合金,类似的衍生物也被称为康托尔合金。[16]

在将高熵合金和多组分系统归类为单独一类材料之前,核科学家已经研究了一种现在可以归类为高熵合金的系统:在核燃料晶界和裂变气泡处的Mo-Pd-Rh-Ru-Tc粒子。[17]医疗行业对了解这些“五金属粒子”特别感兴趣,因为锝-99m是一种重要医学成像同位素。

定义

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没有普遍认可的HEA定义。最初将HEA定义为含有至少5种元素且原子百分比5到35的合金。[15]然而后来的研究表明,这个定义还可以扩展。建议只有形成没有金属间相的固溶体的合金才应该被认为是真正的高熵合金,因为有序相的形成会降低系统的熵。[18]一些作者将四组分合金也描述为高熵合金[19]也有建议只有2到4种元素合金满足HEA要求,也算高熵合金[20]理想气体常数1到1.5之间的混合熵也算[21]中熵合金[20]

合成

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使用现有技术截至2018年 (2018-Missing required parameter 1=month!)难以制造高熵合金,并且通常需要昂贵的材料和特殊的加工技术。[22]

高熵合金主要是使用依赖于金属相方法生产——如果金属在液态、固态、气态下合成。

增材制造(立体打印)[27][12]可产出具不同微观结构的合金,潜在地增加强度(1.3吉帕斯卡)、增加延展性[28]

其他技术包括热喷涂激光熔覆英语Cladding (metalworking)电镀[23][29]

例子

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高熵合金薄膜例子:

合金 相态 硬度(吉帕斯卡 相关模数(吉帕斯卡 参考
CoCrFeMnNi FCC 5.71 Er = 172.84 [30]
CoCrFeMnNiAl1.3 BCC 8.74 Er = 167.19 [30]
Al0.3CoCrFeNi FCC + BCC 11.09 E = 186.01 [31]
CrCoCuFeNi FCC + BCC 15 E = 181 [32]
CoCrFeMnNiTi0.2 FCC 8.61 Er = 157.81 [33]
CoCrFeMnNiTi0.8 无定形 8.99 Er = 151.42 [33]
CoCrFeMnNiV0.07 FCC 7.99 E = 206.4 [34]
CoCrFeMnNiV1.1 无定形 8.69 E = 144.6 [34]
(CoCrFeMnNi)99.5Mo0.5 FCC 4.62 Er = 157.76 [35]
(CoCrFeMnNi)85.4Mo14.6 无定形 8.77 Er = 169.17 [35]
(CoCrFeMnNi)92.8Nb7.2 无定形 8.1 Er ~105 [36]
TiZrNbHfTa FCC 5.4 [37]
FeCoNiCrCuAlMn FCC + BCC 4.2 [38]
FeCoNiCrCuAl0.5 FCC 4.4 [38]
AlCrMnMoNiZr 无定形 7.2 E = 172 [39]
AlCrMoTaTiZr 无定形 11.2 E = 193 [40]
AlCrTiTaZr 无定形 9.3 E = 140 [41]
AlCrMoNbZr BCC + 无定形 11.8 [42]
AlCrNbSiTiV 无定形 10.4 E = 177 [43]
AlCrSiTiZr 无定形 11.5 E ~206 [44]
CrNbSiTaZr 无定形 20.12 [45]
CrNbSiTiZr 无定形 9.6 E = 179.7 [46]
AlFeCrNiMo BCC 4.98 [47]
CuMoTaWV BCC 19 E = 259 [48]
TiVCrZrHf 无定形 8.3 E = 104.7 [49]
ZrTaNbTiW 无定形 4.7 E = 120 [50]
TiVCrAlZr 无定形 8.2 E = 128.9 [51]
FeCoNiCuVZrAl 无定形 8.6 E = 153 [52]
合金 RN (%) 相态 硬度(吉帕斯卡 相关模数(吉帕斯卡 参考
(FeCoNiCuVZrAl)N 30 无定形 12 E = 166 [52]
(TiZrNbHfTa)N 25 FCC 32.9 [37]
(TiVCrAlZr)N 50 FCC 11 E = 151 [51]
(AlCrTaTiZr)N 14 FCC 32 E = 368 [41]
(FeCoNiCrCuAl0.5)N 33.3 无定形 10.4 [38]
(FeCoNiCrCuAlMn)N 23.1 无定形 11.8 [38]
(AlCrMnMoNiZr)N 50 FCC 11.9 E = 202 [39]
(TiVCrZrHf)N 3.85 FCC 23.8 E = 267.3 [49]
(NbTiAlSiW)N 16.67 无定形 13.6 E = 154.4 [53]
(NbTiAlSi)N 16.67 FCC 20.5 E = 206.8
(AlCrNbSiTiV)N 5 FCC 35 E ~ 337 [43]
28 FCC 41 E = 360
(AlCrTaTiZr)N 50 FCC 36 E = 360 [54]
(Al23.1Cr30.8Nb7.7Si7.7Ti30.7)N50 FCC 36.1 E ~ 430 [55]
(Al29.1Cr30.8Nb11.2Si7.7Ti21.2)N50 FCC 36.7 E ~ 380
(AlCrSiTiZr)N 5 无定形 17 E ~ 232 [44]
30 FCC 16 E ~ 232
(AlCrMoTaTiZr)N 40 FCC 40.2 E = 420 [40]
(AlCrTaTiZr)N 50 FCC 35 E = 350 [56]
(CrTaTiVZr)N 20 FCC 34.3 E ~ 268 [57]
(CrNbTiAlV)N 67.86 FCC 35.3 E = 353.7 [58]
(HfNbTiVZr)N 33.33 FCC 7.6 E = 270 [59]

参考

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