西安交大《JMST》:新的強韌化機制!晶界沉淀誘發晶界非等原子比高熵相相變
第一作者:齊永良
通訊作者:江 峰、劉 峰、孫 軍
通訊單位:西安交通大學金屬材料強度國家重點實驗室;西北工業大學分析測試中心
DOI:https://doi.org/10.1016/j.jmst.2021.01.061
通常,晶界沉淀顆粒的析出會對合金塑性產生顯著的不利影響,在拉伸載荷作用下容易發生晶間斷裂,導致合金塑性大幅下降。為此,我們提出了一種全新的策略,利用晶界沉淀顆粒引起的局部應力集中作為驅動力來觸發晶界處預設的非等原子比高熵相的相變。這種在晶界處的原位應力誘導相變引入了相變誘發塑性(TRIP)效應,使得沉淀強化型(FeCoNiCr)90Ti5Al5高熵合金能夠兼具高強度和高塑性(抗拉強度高于1.5 GPa,斷后延伸率高于38%)。這種“局部應力集中誘發晶界亞穩相相變”的策略可以充分利用晶界沉淀顆粒的生成(而不是避免)同時提高高熵合金的強度和塑性。
金屬材料晶界上的沉淀顆粒可以通過多種效應的疊加,在提高合金強度方面發揮重要作用,如晶界上的沉淀顆粒可以通過促進晶粒的形核和阻礙晶粒的長大來細化晶粒,同時在變形過程中可以作為物理障礙,阻礙位錯運動。然而,這些晶界沉淀顆粒在大幅增加金屬材料強度的同時,通常也會導致金屬材料塑性的顯著損失。在加載條件下,由于晶界沉淀顆粒與基體之間彈塑性變形的高度不相容性,會在晶界沉淀顆粒和基體界面處產生較高的局部應力集中。如果持續拉伸含有大量晶界沉淀顆粒的合金,會導致合金晶界局部應力水平迅速增加,從而會很快產生界面微裂紋、沉淀顆粒脫粘和最終的晶間斷裂。
由于晶界沉淀顆粒誘發的晶間脆化是安全關鍵應用中需要重點關注的問題,因此研究者們一直致力于克服由晶界沉淀引起的負面影響。研究者經常采用的一種策略是抑制晶界沉淀顆粒的析出,同時促進晶粒內部沉淀顆粒的析出。然而,這種策略在很大程度上限制了合金的成分和力學性能。另一個流行的策略是盡可能減小晶界沉淀顆粒的尺寸,同時盡可能使其在合金中均勻分布,以分散局部應力集中。然而,以上這些方法顯然不能根本性地解決問題。解決這一長期困擾材料科學家和工程師問題的關鍵,在于探索如何創新地利用晶界顆粒和基體界面的局部應力集中作為驅動力來觸發有利于提高合金塑性的強化機制,如相變誘發韌性和相變誘發塑性機制等。也就是說,如何能夠實現利用晶界沉淀顆粒細化晶粒、阻礙位錯運動大幅度提高合金強度的同時,還能夠大幅度提高合金的塑性。
從這一設想出發,本文提出了一種利用晶界沉淀顆粒引發的局部應力集中來激發預置在晶界上的機械亞穩相相變的新策略:在合金拉伸變形前,通過采用特定的壓力加工或熱處理工藝手段,在晶界析出顆粒周圍預置機械亞穩相,作為預置相變區。當外加應力引起的局部應力集中達到臨界相變應力時,這些預置相變區將被迫發生相變,從而產生相變誘發塑性機制。
基于此,西安交通大學金屬材料強度國家重點實驗室孫軍教授、江峰教授和西北工業大學分析測試中心劉峰教授合作,通過采用大變形量冷軋變形(90%)和中溫時效工藝(650 ℃/24 h),在新設計的晶界沉淀強化型(FeCoNiCr)90Ti5Al5高熵合金的晶界上預置了非等原子比Cr51Fe25Co18Ni6機械亞穩相(Cr-rich相)。在室溫拉伸變形過程中Cr-rich相在晶界沉淀顆粒(Heusler相)引起的局部應力集中作用下發生了從體心立方向密排六方結構的相變,實現了晶界沉淀強化型(FeCoNiCr)90Ti5Al5高熵合金強度和塑性的同時提升。
Fig. 1. Schematic of the novel strategy of using local stress concentration-induced phase transformation at grain boundaries (GBs). (a) GB regions with precipitates are prone to initiating cracks due to the local stress concentration induced by GB precipitates. (b) The proposed strategy of using this local stress concentration to trigger a phase transformation of the second phase preseted at GBs, providing additional transformation-induced plasticity (TRIP).
Fig. 2. Exceptional combination of strength and ductility achieved by the CR-Ti5Al5 alloy at room temperature. (a) Engineering stress–engineering strain curves of the Ti5Al5 alloy samples (NCR-Ti5Al5, CR-Ti5Al5-1, and CR-Ti5Al5-2). The insert shows the corresponding true stress and work-hardening rate curves as a function of true strain. (b) Yield strength (YS) versus the product of strength and elongation of the designed Ti5Al5 HEA compared with those of other high-performing FeCoNiCr-based HEAs.
Fig. 3. Typical microscopic structure of the undeformed CR-Ti5Al5 HEA. (a) A STEM-HAADF image showing a unique four-phase structure: bcc Heusler precipitates and Cr-rich bcc phase in the GB region, and fcc matrix and fcc L12 nanoprecipitates in the grain interior. (b) STEM-EDS maps revealing the qualitatively elemental distribution among the four phases in the alloy, confirming the presence of the Cr-rich phase. (c-e) SAED patterns of c the Cr-depleted bcc Heusler precipitate, (d) the disordered Cr-rich bcc phase, and e the disordered fcc matrix containing Cr-depleted L12 nanoprecipitates. (f) High-resolution SEM image showing the morphology of the three phases: Heusler particles (blue arrows), L12 particles (red arrows), and Cr-rich phase (green arrows) in the alloys. (g-j) Atomic-scale analyses using atom probe tomography (APT). (g) Three-dimensional (3D) reconstruction of the 45 at.% Cr and 12 at.% Ni isoconcentration surfaces presenting the morphologies of the Cr-rich phase and its neigh boring matrix. (h) One-dimensional (1D) concentration profile quantitatively showing the chemical composition of the Cr-rich phase and its neigh boring matrix. (i) 3D reconstruction of the 35 at.% Ni isoconcentration surfaces revealing the morphology of the L12 nanoprecipitates in the matrix. The number density and average diameter of the L12 nanoprecipitates were 4.79 × 1023 m-3 and ~5.9 nm, respectively. (j) 1D concentration profile quantitatively showing the chemical composition of the L12 nanoprecipitates and the matrix.
Fig. 4. Tensile deformation mechanisms in the CR-Ti5Al5 HEA at room temperature. (a) Bright-field TEM images at a tensile strain of 5% showing interaction of the Cr-rich phase and Heusler particles. A considerable number of dislocations (white arrows) pile up at the interface between the Cr-rich phase and the Heusler particles, indicating a severe local stress concentration. (b-g) Representative TEM-EDS images after tensile fracture showing the Cr-rich phase undergoing a stress-induced phase transformation from the original bcc to hcp structure. (b) STEM-HAADF image showing a typical deformed microstructure containing Heusler particles, microvoids (red circles), the Cr-rich hcp phase, and stacking faults (SFs, yellow arrows). (c) Qualitative STEM-EDS showing the elemental distribution corresponding to (b). (d), (e) Microdiffraction patterns of the Heusler and Cr-rich hcp phases, respectively. (f) Interface between the L21 and Cr-rich hcp phases showing a clear dislocation wall (the region outlined by red dotted lines). (g) Interface (red dotted line) between the Cr-rich hcp phase and fcc matrix.
本文在晶界沉淀強化型(FeCoNiCr)90Ti5Al5高熵合金中引入了一個全新、可顯著增加合金加工硬化能力的變形機制:晶界應力集中誘發晶界第三相相變。這種新的變形機制,可以彌補傳統的沉淀強化型高熵合金單純依靠位錯滑移機制而導致加工硬化能力不足的缺點,通過相變誘發塑性效應顯著提高合金的加工硬化能力,使合金在具有高強度的同時兼具優異的塑性,呈現出更佳的強度和塑性組合。
作者簡介
本文的通訊作者為西安交通大學孫軍教授、江峰教授和西北工業大學劉峰教授,參與此項研究工作的還有西安交通大學丁向東教授、賀林教授、宗洪祥副教授、張華磊副教授、趙龍博士、孫遜博士、吳亞科博士,南京理工大學沙剛教授、靳慎豹博士。
本文第一作者為齊永良,西安交通大學博士研究生,已發表晶界沉淀強化型高熵合金SCI論文3篇,分別采用大冷變形/完全再結晶、痕量硼摻雜和利用晶界沉淀引起的局部應力集中誘發晶界非等原子比高熵相的相變等策略,來大幅提升沉淀強化型高熵合金的力學性能。
本文來自“JMST期刊”。
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