Evolution of Short-to-Medium Range Orders During the Liquid-Liquid Phase Transition of a Pd-Si Metallic Glass

doi:10.11900/0412.1961.2024.00057

Acta Metall Sin

2024, Vol. 60

Issue (8): 1119-1129 DOI: 10.11900/0412.1961.2024.00057

Research paper

Current Issue | Archive | Adv Search

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.

Download:

HTML

PDF(3047KB)
Export: BibTeX | EndNote (RIS)

Abstract

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.

Key words: metallic glass supercooled liquid liquid-liquid phase transition crystallization synchrotron X-ray scattering transmission electron microscopy

Received: 29 February 2024

ZTFLH:

TG 111

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

	Service

	E-mail this article
	Add to citation manager
	E-mail Alert
	RSS
	（）
	Articles by authors
	DONG Weixia
	YAO Zhongzheng
	LIU Sinan
	CHEN Guoxing
	WANG Xun-Li
	WU Zhenduo
	LAN Si

URL:

https://www.ams.org.cn/EN/10.11900/0412.1961.2024.00057 OR https://www.ams.org.cn/EN/Y2024/V60/I8/1119

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 Pd₈₂Si₁₈metallic 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)

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

1	Tanaka H. General view of a liquid-liquid phase transition [J]. Phys. Rev., 2000, 62E: 6968
2	Harrington S, Zhang R, Poole P H, et al. Liquid-liquid phase transition: Evidence from simulations [J]. Phys. Rev. Lett., 1997, 78: 2409
3	Kurita R, Tanaka H. On the abundance and general nature of the liquid-liquid phase transition in molecular systems [J]. J. Phys. Condens. Matter, 2005, 17: L293
4	Zalden P, Quirin F, Schumacher M, et al. Femtosecond X-ray diffraction reveals a liquid-liquid phase transition in phase-change materials [J]. Science, 2019, 364: 1062 doi: 10.1126/science.aaw1773 pmid: 31197008
5	Lan S, Wu Z D, Wei X Y, et al. Structure origin of a transition of classic-to-avalanche nucleation in Zr-Cu-Al bulk metallic glasses [J]. Acta Mater., 2018, 149: 108
6	Gallo P, Bachler J, Bove L E, et al. Advances in the study of supercooled water [J]. Eur. Phys. J., 2021, 44E: 143
7	Wilding M C, Wilson M, McMillan P F. Structural studies and polymorphism in amorphous solids and liquids at high pressure [J]. Chem. Soc. Rev., 2006, 35: 964 pmid: 17003901
8	Boates B, Bonev S A. First-order liquid-liquid phase transition in compressed nitrogen [J]. Phys. Rev. Lett., 2009, 102: 015701
9	Mukherjee G D, Boehler R. High-pressure melting curve of nitrogen and the liquid-liquid phase transition [J]. Phys. Rev. Lett., 2007, 99: 225701
10	Mishima O, Calvert L D, Whalley E. An apparently first-order transition between two amorphous phases of ice induced by pressure [J]. Nature, 1985, 314: 76
11	Mishima O, Takemura K, Aoki K. Visual observations of the amorphous-amorphous transition in H₂O under pressure [J]. Science, 1991, 254: 406 pmid: 17742228
12	Brazhkin V V, Popova S V, Voloshin R N. High-pressure transformations in simple melts [J]. High Pressure Res., 1997, 15: 267
13	Tamblyn I, Bonev S A. Structure and phase boundaries of compressed liquid hydrogen [J]. Phys. Rev. Lett., 2010, 104: 065702
14	Kim K H, Amann-Winkel K, Giovambattista N, et al. Experimental observation of the liquid-liquid transition in bulk supercooled water under pressure [J]. Science, 2020, 370: 978 doi: 10.1126/science.abb9385 pmid: 33214280
15	Henry L, Mezouar M, Garbarino G, et al. Liquid-liquid transition and critical point in sulfur [J]. Nature, 2020, 584: 382
16	Yang Z Q, Xu J X, Zhao G, et al. Ab initio investigation of the first-order liquid-liquid phase transition in molten sulfur [J]. Phys. Rev., 2024, 109B: 014209
17	Yao B, Paluch M, Wojnarowska Z. Effect of bulky anions on the liquid-liquid phase transition in phosphonium ionic liquids: Ambient and high-pressure dielectric studies [J]. Sci. Rep., 2023, 13: 3040 doi: 10.1038/s41598-023-29518-8 pmid: 36810358
18	Yao B B, Paluch M, Dulski M, et al. Tailoring phosphonium ionic liquids for a liquid-liquid phase transition [J]. J. Phys. Chem. Lett., 2023, 14: 2958 doi: 10.1021/acs.jpclett.3c00099 pmid: 36939303
19	Zhou C, Hu L N, Sun Q J, et al. Indication of liquid-liquid phase transition in CuZr-based melts [J]. Appl. Phys. Lett., 2013, 103: 171904
20	Ge J C, He H Y, Zhou J, et al. In-situ scattering study of a liquid-liquid phase transition in Fe-B-Nb-Y supercooled liquids and its correlation with glass-forming ability [J]. J. Alloys Compd., 2019, 787: 831
21	Dong W X, Wu Z D, Ge J C, et al. In situ neutron scattering studies of a liquid-liquid phase transition in the supercooled liquid of a Zr-Cu-Al-Ag glass-forming alloy [J]. Appl. Phys. Lett., 2021, 118: 191901
22	Dong W X, Ge J C, Ke Y B, et al. In-situ observation of an unusual phase transformation pathway with Guinier-Preston zone-like precipitates in Zr-based bulk metallic glasses [J]. J. Alloys Compd., 2020, 819: 153049
23	Lan S, Ren Y, Wei X Y, et al. Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses [J]. Nat. Commun., 2017, 8: 14679 doi: 10.1038/ncomms14679 pmid: 28303882
24	Lan S, Blodgett M, Kelton K F, et al. Structural crossover in a supercooled metallic liquid and the link to a liquid-to-liquid phase transition [J]. Appl. Phys. Lett., 2016, 108: 211907
25	Küchemann S, Samwer K. Ultrafast heating of metallic glasses reveals disordering of the amorphous structure [J]. Acta Mater., 2016, 104: 119
26	Hammersley A P. FIT2D: A multi-purpose data reduction, analysis and visualization program [J]. J. Appl. Cryst., 2016, 49: 646
27	Qiu X, Thompson J W, Billinge S J L. PDFgetX2: A GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data [J]. J. Appl. Cryst., 2004, 37: 678
28	Koza M M, Schober H, Fischer H E, et al. Kinetics of the high- to low-density amorphous water transition [J]. J. Phys. Condens. Matter 2003, 15: 321
29	Price D L, Moss S C, Reijers R, et al. Intermediate-range order in glasses and liquids [J]. J. Phys. Condens. Matter 1989, 1: 1005
30	Sampath S, Benmore C J, Lantzky K M, et al. Intermediate-range order in permanently densified GeO₂ glass [J]. Phys. Rev. Lett., 2003, 90: 115502
31	Ge J C, Luo P, Wu Z D, et al. Correlations of multiscale structural evolution and homogeneous flows in metallic glass ribbons [J]. Mater. Res. Lett., 2023, 11: 547
32	Egami T, Billinge S J L. Underneath the Bragg Peaks: Structural Analysis of Complex Materials [M]. 2nd Ed., San Diego, the USA: Pergamon, 2012: 1
33	Klug H P, Alexander L E. X-Ray Diffraction Procedures: For Polycrystalline and Amorphous Materials [M]. 2nd Ed., Hoboken: Wiley, 1974: 1
34	Gaskell P H. Local and medium range structures in amorphous alloys [J]. J. Non-Cryst. Solids, 1985, 75: 329
35	Lan S, Zhu L, Wu Z D, et al. A medium-range structure motif linking amorphous and crystalline states [J]. Nat. Mater., 2021, 20: 1347 doi: 10.1038/s41563-021-01011-5 pmid: 34017117
36	Masumoto T, Maddin R. The mechanical properties of palladium 20 a/o silicon alloy quenched from the liquid state [J]. Acta Metall., 1971, 19: 725
37	Ma D, Stoica A D, Yang L, et al. Nearest-neighbor coordination and chemical ordering in multicomponent bulk metallic glasses [J]. Appl. Phys. Lett., 2007, 90: 211908
38	Ding J, Ma E, Asta M, et al. Second-nearest-neighbor correlations from connection of atomic packing motifs in metallic glasses and liquids [J]. Sci. Rep., 2015, 5: 17429 doi: 10.1038/srep17429 pmid: 26616762
39	Ohkubo T, Hirotsu Y. Electron diffraction and high-resolution electron microscopy study of an amorphous Pd₈₂Si₁₈ alloy with nanoscale phase separation [J]. Phys. Rev., 2003, 67B: 094201
40	Bussey J M, Weber M H, Smith-Gray N J, et al. Examining phase separation and crystallization in glasses with X-ray nano-computed tomography [J]. J. Non-Cryst. Solids, 2023, 600: 121987
41	Stoica M, Sarac B, Spieckermann F, et al. X-ray diffraction computed nanotomography applied to solve the structure of hierarchically phase-separated metallic glass [J]. ACS Nano, 2021, 15: 2386 doi: 10.1021/acsnano.0c04851 pmid: 33512138
42	Zhou Q, Han W C, Luo D W, et al. Mechanical and tribological properties of Zr-Cu-Ni-Al bulk metallic glasses with dual-phase structure [J]. Wear, 2021, 474-475: 203880
43	Kumar G, Nagahama D, Ohnuma M, et al. Structural evolution in the supercooled liquid of Zr₃₆Ti₂₄Be₄₀ metallic glass [J]. Scr. Mater., 2006, 54: 801
44	Zheng H J, Lv Y M, Sun Q J, et al. Thermodynamic evidence for cluster ordering in Cu₄₆Zr₄₂Al₇Y₅ ribbons during glass transition [J]. Sci. Bull., 2016, 61: 706
45	Marcus M A. Phase separation and crystallization in amorphous Pd-Si-Sb [J]. J. Non-Cryst. Solids, 1979, 30: 317
46	Liu S N, Wang L F, Ge J C, et al. Deformation-enhanced hierarchical multiscale structure heterogeneity in a Pd-Si bulk metallic glass [J]. Acta Mater., 2020, 200: 42
47	Kim D H, Kim W T, Park E S, et al. Phase separation in metallic glasses [J]. Prog. Mater. Sci., 2013, 58: 1103

[1]	LI Biao, ZHANG Long, YAN Tingyi, FU Huameng, YUAN Xudong, WEN Mingyue, ZHANG Hongwei, LI Hong, ZHANG Haifeng. Effects of Heat Treatment Processes and W Wire Properties on Residual Stress in W Wire Reinforced Zr-Based Metallic Glass Composites[J]. 金属学报, 2024, 60(8): 1055-1063.
[2]	YANG Ruize, ZHAI Ruzong, REN Shaofei, SUN Mingyue, XU Bin, QIAO Yanxin, YANG Lanlan. Evolution and Healing Mechanism of 1Cr22Mn16N High Nitrogen Austenitic Stainless Steel Interface Microstructure During Plastic Deformation Bonding[J]. 金属学报, 2024, 60(7): 915-925.
[3]	XIONG Yi, LUAN Zewei, MA Yunfei, LI Yong, ZHA Xiaoqin. Effect of Surface Nanocrystallization Induced by Supersonic Fine Particles Bombardment on Corrosion Fatigue Behavior of 300M Steel[J]. 金属学报, 2024, 60(5): 627-638.
[4]	JIANG Haowen, PENG Wei, FAN Zengwei, WANG Yangxin, LIU Tengshi, DONG Han. Effect of Ag on Microstructure and Mechanical Properties of Austenitic Stainless Steel[J]. 金属学报, 2024, 60(4): 434-442.
[5]	TIAN Teng, ZHA Min, YIN Haoliang, HUA Zhenming, JIA Hailong, WANG Huiyuan. Enhanced Mechanical Properties and Thermal Stability Mechanism of a High Solid Solution Al-Mg Alloy Processed by Cryogenic High-Reduction Hard-Plate Rolling[J]. 金属学报, 2024, 60(4): 473-484.
[6]	CHEN Shenghu, WANG Qiyu, JIANG Haichang, RONG Lijian. Effect of δ-Ferrite on Hot Deformation and Recrystallization of 316KD Austenitic Stainless Steel for Sodium-Cooled Fast Reactor Application[J]. 金属学报, 2024, 60(3): 367-376.
[7]	HU Baojia, ZHENG Qinyuan, LU Yi, JIA Chunni, LIANG Tian, ZHENG Chengwu, LI Dianzhong. Recrystallization Controlling in a Cold-Rolled Medium Mn Steel and Its Effect on Mechanical Properties[J]. 金属学报, 2024, 60(2): 189-200.
[8]	ZHAO Peng, XIE Guang, DUAN Huichao, ZHANG Jian, DU Kui. Recrystallization During Thermo-Mechanical Fatigue of Two High-Generation Ni-Based Single Crystal Superalloys[J]. 金属学报, 2023, 59(9): 1221-1229.
[9]	CHANG Songtao, ZHANG Fang, SHA Yuhui, ZUO Liang. Recrystallization Texture Competition Mediated by Segregation Element in Body-Centered Cubic Metals[J]. 金属学报, 2023, 59(8): 1065-1074.
[10]	LI Fulin, FU Rui, BAI Yunrui, MENG Lingchao, TAN Haibing, ZHONG Yan, TIAN Wei, DU Jinhui, TIAN Zhiling. Effects of Initial Grain Size and Strengthening Phase on Thermal Deformation and Recrystallization Behavior of GH4096 Superalloy[J]. 金属学报, 2023, 59(7): 855-870.
[11]	LOU Feng, LIU Ke, LIU Jinxue, DONG Hanwu, LI Shubo, DU Wenbo. Microstructures and Formability of the As-Rolled Mg- xZn-0.5Er Alloy Sheets at Room Temperature[J]. 金属学报, 2023, 59(11): 1439-1447.
[12]	WU Caihong, FENG Di, ZANG Qianhao, FAN Shichun, ZHANG Hao, LEE Yunsoo. Microstructure Evolution and Recrystallization Behavior During Hot Deformation of Spray Formed AlSiCuMg Alloy[J]. 金属学报, 2022, 58(7): 932-942.
[13]	GUO Lu, ZHU Qianke, CHEN Zhe, ZHANG Kewei, JIANG Yong. Non-Isothermal Crystallization Kinetics of Fe₇₆Ga₅Ge₅B₆P₇Cu₁ Alloy[J]. 金属学报, 2022, 58(6): 799-806.
[14]	LIU Shuaishuai, HOU Chaonan, WANG Engang, JIA Peng. Plastic Rheological Behaviors of Zr₆₁Cu₂₅Al₁₂Ti₂ and Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ Amorphous Alloys in the Supercooled Liquid Region[J]. 金属学报, 2022, 58(6): 807-815.
[15]	LI Jinfu, LI Wei. Structure and Glass-Forming Ability of Al-Based Amorphous Alloys[J]. 金属学报, 2022, 58(4): 457-472.

No Suggested Reading articles found!

Viewed

Full text

Abstract

Cited

Shared

Discussed