Evolution of Short-to-Medium Range Orders During the Liquid-Liquid Phase Transition of a Pd-Si Metallic Glass
DONG Weixia1,2, YAO Zhongzheng1, LIU Sinan1, CHEN Guoxing1, WANG Xun-Li2, WU Zhenduo3,4(), LAN Si1()
1 Herbert Gleiter Institute of Nanoscience, School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094, China 2 Department of Physics, City University of Hong Kong, Hong Kong 999077, China 3 Center for Neutron Scattering and Applied Physics, City University of Hong Kong (Dongguan), Dongguan 523000, China 4 Neutron Scattering Research Center, City University of Hong Kong Shenzhen Research Institute, Shenzhen 518057, China
Cite this article:
DONG Weixia, YAO Zhongzheng, LIU Sinan, CHEN Guoxing, WANG Xun-Li, WU Zhenduo, LAN Si. Evolution of Short-to-Medium Range Orders During the Liquid-Liquid Phase Transition of a Pd-Si Metallic Glass. Acta Metall Sin, 2024, 60(8): 1119-1129.
Liquid-liquid phase transition (LLPT) is a universal phenomenon that occurs in different types of liquids. Understanding its mechanism can help solve the long-standing mystery of liquid and amorphous structures. In metallic liquids, LLPT has been widely reported to be observed in the supercooled liquid region in multicomponent alloy systems. However, few observations of LLPT were reported in binary metallic systems, mainly due to the poor thermal stability of these systems in the supercooled liquid region. Herein, the phase transition of Pd82Si18 metallic glass in its supercooled liquid region was studied by in situ synchrotron X-ray scattering and transmission electron microscopy (TEM). The in situ synchrotron diffraction data revealed the precipitation of fcc crystals after 200 s of annealing at 638 K. Before 200 s, the position of the first broad diffraction peak, Q1, shifted toward lower momentum transfer (Q) values and the peak broadened, indicating the occurrence of LLPT at the initial stage of annealing. The structural changes occurring during LLPT were analyzed based on the pair distribution function; the changes were characterized by a transition from short- to medium-range orders as per the reduced atomic pair distribution function curve G(r). The intensity of peaks up to the fourth nearest neighbor shell in the G(r)curve exhibited different variations trends during LLPT. The peaks were classified into two groups: those indicating an fcc structure and those indicating a six-membered tricapped trigonal prism (6M-TTP; a typical medium-range order observed recently in Pd-based metallic glasses) structure. The number of peaks associated with the 6M-TTP structure gradually decreased during annealing. In contrast, the number of peaks associated with the fcc structure gradually increased at medium-range scale and decreased at short-range scale before 200 s. An analysis of the G(r) peaks indicated that LLPT is characterized by a transition from the 6M-TTP-type atomic cluster to a new type of cluster. This new type of cluster shows an atomic correlation similar to that observed in the fcc structure in the medium-range scale; however, its short-range order deteriorates. Further, high-angle annular dark field scanning TEM images revealed nanoscale structural heterogeneities during LLPT. The SAED and HRTEM results confirmed that the sample annealed for a short duration (i.e., before 200 s) with a nanoscale heterogeneous structure is amorphous, thus demonstrating the coexistence of two liquid phases. Notably, one of the two liquid phases is prone to crystallization under ion milling, thereby forming a crystal-amorphous network structure. The crystals formed due to ion milling exhibit the fcc structure and have the same crystal orientation. This research provides new evidence to unravel the LLPT mechanism in supercooled metallic liquids. Further, it presents a new model for explaining the complex structure and phase transition in metallic liquids.
Fund: National Key Research and Development Program of China(2021YFB3802800);National Natural Science Foundation of China(52222104);National Natural Science Foundation of China(52201190);National Natural Science Foundation of China/Research Grants Council of Hong Kong Special Administrative Region Joint Research Scheme, Project(N_CityU173/22);National Natural Science Foundation International (Regional) Cooperation and Exchange Project(12261160364);Open Research Fund of Songshan Lake Materials Laboratory(2022SLABFN19);Guangdong-Hong Kong-Macao Joint Laboratory for Neutron Scattering Science and Technology
Corresponding Authors:
WU Zhenduo, professor, Tel: (0769)26622690, E-mail: zd.wu@cityu-dg.edu.cnLAN Si, professor, Tel: (025)84315765, E-mail: lansi@njust.edu.cn
Fig.1 Profiles of structure factor(S(Q)) (a) and the differential structure factor (ΔS(Q)) (b) during the isothermal annealing for Pd82Si18 metallic glass (Annealing time for each line shown in Fig.1b corresponds to that in Fig.1a. Q—momentum transfer modulus; ΔS(Q) obtained by subtracting the respective S(Q) profile at the beginning of isothermal annealing (3 s); Q1 and Q2—the 1st and 2nd diffraction peaks;Q12, Q21, Q22, and Q23—crystallization peaks developed after 200 s)
Fig.2 Analyses of the integrated intensity of crystalline peaks Q12 (a), Q21 (b), Q22 (c), and Q23 (d) in S(Q)during the isothermal annealing for Pd82Si18 metallic glass (Insets show the enlarged views of integrated intensity at the beginning of isothermal annealing. The arrow in inset of Fig.2a marks the time when crystallization begins. t—isothermal annealing time)
Fig.3 Evolution of peak position (a) and peak width (b) of the 1st diffraction peak Q1 during the isothermal annealing for Pd82Si18 metallic glass (Insets show the enlarged views of peak position and peak width at the beginning of isothermal annealing. Arrows show the trends of the peak position and peak width before crystallization)
Fig.4 Reduced pair distribution function G(r) (a) and differential profiles ΔG(r) (b) for Pd82Si18 metallic glass during isothermal annealing (The annealing time for each line corresponds to that in Fig.1a. r—the distance between two atoms; G(r)—reduced pair distribution function; ΔG(r) obtained by subtracting the respective G(r) profile at the beginning of isothermal annealing (3 s); r1—the first shell; r21, r31, r33, r34, r42—the crystalline peaks in G(r); r22, r23, r32, r41—the amorphous peaks in G(r); the dashed lines and solid lines represent atomic pairs in fcc and 6M-TTP (six-membered tricapped trigonal prism) structure, respectively)
Fig.5 Integrated intensity of atomic pairs in the original amorphous phase peaks of r1 (a), r22 (b), r23 (c), and r32 (d) (Insets show the enlarged views of integrated intensity of corresponding atomic pairs at the beginning of isothermal annealing. Arrows indicate the trends of integrated intensity before crystallization)
Fig.6 Integrated intensity of atomic pairs in the newly formed crystalline peaks of r21 (a), r31 (b), r33 (c), and r42 (d) (Insets show the enlarged views of integrated intensity of corresponding atomic pairs at the beginning of isothermal annealing. Arrows indicate the trend of integrated intensity before crystallization)
Peak
Position
nm
Cluster structure
t ≤ 200 s
t > 200 s
r1
0.278
F + T
↓
↑
r21
0.406
F + T
▁
↑
r22
0.486
F + T
↓
↑
r23
0.547
T
↓
↓
r31
0.638
F
↑
↓
r32
0.702
T
↓
↓
r33
0.742
F + T
▁
↑
r34
0.846
F
▁
↑
r41
0.938
T
↓
↓
r42
0.101
F
↑
↑
Table 1 Summary of atomic pairs for different peaks in reduced pair distribution function patterns
Fig.7 High-angle dark-field scanning transmission electron microscopy (HAADF-STEM) image of as-cast sample Pd82Si18 metallic glass (a); bright-field TEM image (b), HAADF-STEM image (c), and HRTEM image (d) of Pd82Si18 metallic glass annealed at 663 K for 60 s (Inset in Fig.7b shows the corresponding SAED pattern)
Fig.8 Gaussian fitting results for the first shell of T(r) and the second shell g(r) (T(r)—radial distribution function, g(r)—pair distribution function) (a, b) fitting results of the first shell (a) and the second shell (b) of the sample Pd82Si18 that annealed for 200 s (1-atom—vertex-shared mode, 2-atom—edge-shared mode, 3-atom—face-shared mode, 4-atom—intercross-shared mode) (c) percentage of the Pd-Si and Pd-Pd atomic pairs obtained from the first shell fitting result of the sample Pd82Si18 annealed at 3 s, 200 s, and 2373 s (d) percent of 1-4 atomic connection obtained from the second shell fitting result of sample annealed at 3 s, 200 s, and 2373 s
Fig.9 Dark-field TEM image (a) and SAED pattern (b) of the Pd82Si18 sample after ion milling, and SEM image (c) and the HAADF-STEM image (d) of the crystallized Pd82Si18 sample annealed at 663 K
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