高熵合金
![](http://images.weserv.nl/?url=//upload.wikimedia.org/wikipedia/commons/thumb/b/bf/Atomic_structure_model_of_fcc_CoCrFeMnNi.png/220px-Atomic_structure_model_of_fcc_CoCrFeMnNi.png)
高熵合金(英語:High-entropy alloys、HEAs)簡稱HEA,通常是由五種或五種以上等量或相對比例金屬形成的新型合金。名為「高熵合金」是因為當混合物中存在大量元素混合時的熵增加實質上更高,並且比例更接近相等。[2]
由於高熵合金可能具有許多理想的性質,因此在材料科學及工程上相當受到重視[3]。相對於以往的典型金屬合金,合金主要的金屬成份可能只有一至兩種。例如會以鐵為基礎,再加入一些微量元素(碳、錳等)來提昇其特性,但因此所得的還是以鐵為主的合金[3],其他元素比例實際相當低。過往的概念中,若合金中加的金屬種類越多,會使其材質脆化,但高熵合金和以往的合金不同,有多種金屬卻不會脆化,是一種新的材料[1][3][4]。
研究發現有些高熵合金的比強度比傳統合金好很多,而且抗斷裂能力、抗拉強度、抗腐蝕及抗氧化特性都比傳統的合金要好。高熵合金在2004年以前就已問世,但在2010年代才有許多相關的研究[3][5][6][7][8][9]。
發展
儘管早在1981年[10]、1996年[11]、以及整個1980年代就考究了理論上可以存在高熵合金。但製造出這些特殊合金,還要到2004年。
據說葉均蔚博士是在1995年駕車穿越新竹鄉村時,想出了實際製造高熵合金方法。
高熵合金潛在應用包括用於潛艇、航天器、核武器、核反應堆[12]、噴氣式飛機、遠程高超音速導彈等等。[13][14]
在葉均蔚博士的論文發表幾個月後,布賴恩·康托爾、I. T. H. Chang、P. Knight、A. J. B. Vincent提交了關於高熵合金的獨立論文。
葉均蔚也是第一個提出「高熵合金」(英語:High-entropy alloys)一詞的人,他將高構型熵歸因於穩定固溶體相機制。[15]
儘管布賴恩·康托爾直到2004年葉均蔚論文發表幾個月後才發表論文,康托爾其實早在1970年代末1980年代初就完成了該領域的首項工作。康托爾由於不知道葉均蔚的工作,康托爾更喜歡稱「高熵合金」為「多組分合金、多元合金」(英語:multicomponent alloys)。康托爾開發了高熵合金FeCrMnNiCo合金,類似的衍生物也被稱為康托爾合金。[16]
在將高熵合金和多組分系統歸類為單獨一類材料之前,核科學家已經研究了一種現在可以歸類為高熵合金的系統:在核燃料晶界和裂變氣泡處的Mo-Pd-Rh-Ru-Tc粒子。[17]醫療行業對了解這些「五金屬粒子」特別感興趣,因為鍀-99m是一種重要醫學成像同位素。
定義
沒有普遍認可的HEA定義。最初將HEA定義為含有至少5種元素且原子百分比5到35的合金。[15]然而後來的研究表明,這個定義還可以擴展。建議只有形成沒有金屬間相的固溶體的合金才應該被認為是真正的高熵合金,因為有序相的形成會降低系統的熵。[18]一些作者將四組分合金也描述為高熵合金[19]也有建議只有2到4種元素合金滿足HEA要求,也算高熵合金[20]或理想氣體常數1到1.5之間的混合熵也算[21]「中熵合金」[20]
合成
使用現有技術截至2018年[update]難以製造高熵合金,並且通常需要昂貴的材料和特殊的加工技術。[22]
高熵合金主要是使用依賴於金屬相方法生產——如果金屬在液態、固態、氣態下合成。
- 大多數HEA已使用液相方法生產,包括電弧熔化(電弧爐)、感應熔化(感應爐)、布里奇曼-史托巴格法。
- 固態加工通常通過使用高能球磨機的機械合金化完成。這種方法生產的粉末可以使用傳統的粉末冶金方法或放電等離子燒結進行加工。這種方法可以生產出使用鑄造難以或不可能生產的合金,例如AlLiMgScTi。[23][24][25]
- 氣相處理包括濺鍍或 分子束外延等工藝,可用於仔細控制不同的元素組成以獲得高熵金屬[26]或陶瓷膜。[23]
增材製造(立體打印)[27][12]可產出具不同微觀結構的合金,潛在地增加強度(1.3吉帕斯卡)、增加延展性[28]
例子
高熵合金薄膜例子:
合金 | 相態 | 硬度(吉帕斯卡) | 相關模數(吉帕斯卡) | 參考 |
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 | 無定形 | 8.99 | Er = 151.42 | [33] |
CoCrFeMnNiV0.07 | FCC | 7.99 | E = 206.4 | [34] |
CoCrFeMnNiV1.1 | 無定形 | 8.69 | E = 144.6 | [34] |
(CoCrFeMnNi)99.5Mo0.5 | FCC | 4.62 | Er = 157.76 | [35] |
(CoCrFeMnNi)85.4Mo14.6 | 無定形 | 8.77 | Er = 169.17 | [35] |
(CoCrFeMnNi)92.8Nb7.2 | 無定形 | 8.1 | Er ~105 | [36] |
TiZrNbHfTa | FCC | 5.4 | — | [37] |
FeCoNiCrCuAlMn | FCC + BCC | 4.2 | — | [38] |
FeCoNiCrCuAl0.5 | FCC | 4.4 | — | [38] |
AlCrMnMoNiZr | 無定形 | 7.2 | E = 172 | [39] |
AlCrMoTaTiZr | 無定形 | 11.2 | E = 193 | [40] |
AlCrTiTaZr | 無定形 | 9.3 | E = 140 | [41] |
AlCrMoNbZr | BCC + 無定形 | 11.8 | — | [42] |
AlCrNbSiTiV | 無定形 | 10.4 | E = 177 | [43] |
AlCrSiTiZr | 無定形 | 11.5 | E ~206 | [44] |
CrNbSiTaZr | 無定形 | 20.12 | — | [45] |
CrNbSiTiZr | 無定形 | 9.6 | E = 179.7 | [46] |
AlFeCrNiMo | BCC | 4.98 | — | [47] |
CuMoTaWV | BCC | 19 | E = 259 | [48] |
TiVCrZrHf | 無定形 | 8.3 | E = 104.7 | [49] |
ZrTaNbTiW | 無定形 | 4.7 | E = 120 | [50] |
TiVCrAlZr | 無定形 | 8.2 | E = 128.9 | [51] |
FeCoNiCuVZrAl | 無定形 | 8.6 | E = 153 | [52] |
合金 | RN (%) | 相態 | 硬度(吉帕斯卡) | 相關模數(吉帕斯卡) | 參考 |
(FeCoNiCuVZrAl)N | 30 | 無定形 | 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 | 無定形 | 10.4 | — | [38] |
(FeCoNiCrCuAlMn)N | 23.1 | 無定形 | 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 | 無定形 | 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 | 無定形 | 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] |
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