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Title: Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses

Abstract

An anomaly in differential scanning calorimetry has been reported in a number of metallic glass materials in which a broad exothermal peak was observed between the glass and crystallization temperatures. The mystery surrounding this calorimetric anomaly is epitomized by four decades long studies of Pd-Ni-P metallic glasses, arguably the best glass-forming alloys. Here we show, using a suite of in-situ experimental techniques, that Pd-Ni-P alloys have a hidden amorphous phase in the supercooled liquid region. The anomalous exothermal peak is the consequence of a polyamorphous phase transition between two supercooled liquids, involving a change in the packing of atomic clusters over medium-range length scales as large as 18 Å. With further temperature increase, the alloy reenters the supercooled liquid phase which forms the room-temperature glass phase upon quenching. Finally, the outcome of this study raises a possibility to manipulate the structure and hence the stability of metallic glasses through heat-treatment.

Authors:
 [1];  [2];  [3];  [3];  [4];  [5];  [5];  [5];  [6]
  1. Nanjing Univ. of Science and Technology, Nanjing (China); City Univ. of Hong Kong, Hong Kong (China)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. City Univ. of Hong Kong, Hong Kong (China)
  4. Australian Nuclear Science and Technology Organization (ANSTO), Kirrawee, NSW (Australia)
  5. Hokkaido Univ., Sapporo (Japan)
  6. City Univ. of Hong Kong, Hong Kong (China); City Univ. of Hong Kong Shenzhen Research Institute, Shenzhen (China)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division; National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1372661
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; glasses; phase transitions and critical phenomena

Citation Formats

Lan, S., Ren, Y., Wei, X. Y., Wang, B., Gilbert, E. P., Shibayama, T., Watanabe, S., Ohnuma, M., and Wang, X. -L.. Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses. United States: N. p., 2017. Web. doi:10.1038/ncomms14679.
Lan, S., Ren, Y., Wei, X. Y., Wang, B., Gilbert, E. P., Shibayama, T., Watanabe, S., Ohnuma, M., & Wang, X. -L.. Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses. United States. doi:10.1038/ncomms14679.
Lan, S., Ren, Y., Wei, X. Y., Wang, B., Gilbert, E. P., Shibayama, T., Watanabe, S., Ohnuma, M., and Wang, X. -L.. Fri . "Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses". United States. doi:10.1038/ncomms14679. https://www.osti.gov/servlets/purl/1372661.
@article{osti_1372661,
title = {Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses},
author = {Lan, S. and Ren, Y. and Wei, X. Y. and Wang, B. and Gilbert, E. P. and Shibayama, T. and Watanabe, S. and Ohnuma, M. and Wang, X. -L.},
abstractNote = {An anomaly in differential scanning calorimetry has been reported in a number of metallic glass materials in which a broad exothermal peak was observed between the glass and crystallization temperatures. The mystery surrounding this calorimetric anomaly is epitomized by four decades long studies of Pd-Ni-P metallic glasses, arguably the best glass-forming alloys. Here we show, using a suite of in-situ experimental techniques, that Pd-Ni-P alloys have a hidden amorphous phase in the supercooled liquid region. The anomalous exothermal peak is the consequence of a polyamorphous phase transition between two supercooled liquids, involving a change in the packing of atomic clusters over medium-range length scales as large as 18 Å. With further temperature increase, the alloy reenters the supercooled liquid phase which forms the room-temperature glass phase upon quenching. Finally, the outcome of this study raises a possibility to manipulate the structure and hence the stability of metallic glasses through heat-treatment.},
doi = {10.1038/ncomms14679},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {Fri Mar 17 00:00:00 EDT 2017},
month = {Fri Mar 17 00:00:00 EDT 2017}
}

Journal Article:
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Cited by: 6works
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  • Results of calorimetric, differential thermal analysis, and structural measurements are presented for a series of bulk metallic glass forming compositions in the Zr[endash]Ti[endash]Cu[endash]Ni[endash]Be alloy system. The calorimetric data for five alloys, prepared along the tie line between phase separating and nonphase separating compositions, show that the transition from phase separating to nonphase separating behavior is smooth. The bulk glasses near the center of the tie line exhibit large supercooled liquid regions: [Delta]T[approx]135 K, the largest known for a bulk metallic glass. [copyright] [ital 1999 American Institute of Physics.]
  • Results of calorimetric, differential thermal analysis, and structural measurements are presented for a series of bulk metallic glass forming compositions in the Zr{endash}Ti{endash}Cu{endash}Ni{endash}Be alloy system. The calorimetric data for five alloys, prepared along the tie line between phase separating and nonphase separating compositions, show that the transition from phase separating to nonphase separating behavior is smooth. The bulk glasses near the center of the tie line exhibit large supercooled liquid regions: {Delta}T{approx}135 K, the largest known for a bulk metallic glass. {copyright} {ital 1999 American Institute of Physics.}
  • Due to their scientific significance and potential engineering applications, bulk metallic glasses are among the most intensively studied advanced materials. Understanding the glass-forming ability (GFA) of these metallic alloys is a long-standing subject. While a large number of empirical factors have been proposed to correlate with GFA of the alloys, a full understanding of GFA remains a goal to achieve. Since glass formation is a competing process against crystallization, we have performed a systematic analysis on the crystallization kinetics of two known best metallic glass-formers Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} (in at. %) and Zr{sub 41.2}Ti{sub 13.8}Cu{sub 12.5}Ni{sub 10}Be{sub 22.5}more » based on classical nucleation and growth theory. Our results show that there is a dramatic difference between the two alloys in their nucleation behavior although they possess comparable GFA. Particularly, an extremely sharp nucleation peak ({approx}10{sup 18}/m{sup 3} s) is found for Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} around 632 K with a very small half maximum width of 42 K, implying that this alloy is an excellent candidate for nanocrystallization studies. Moreover, we have also found that the GFA of these alloys can be calculated to a high accuracy and precision based on the classical theory, suggesting that the classical theory may be sufficient to account for glass formation mechanism in these metallic alloys.« less
  • Despite its importance, a thermodynamic approach to determining the glass-forming ability (GFA) of bulk metallic glass (BMG) remains a goal to be achieved. We examined the GFA of water-quenched Pd-P-based and Pt{sub 60}Ni{sub 15}P{sub 25} BMG's in which their molten alloys were sufficiently treated with a dehydrated B{sub 2}O{sub 3} flux prior to and during quenching to room temperature. This allowed us to envisage the applicability of the classical steady-state homogeneous nucleation theory because the suppression of heterogeneous nucleation worked effectively. GFA was examined by comparing the critical cooling rate R{sub c}{sup h} for glass formation with the maximum diametermore » d{sub max} of glass. To calculate R{sub c}{sup h}, the homogeneous nucleation rate I{sub ss}(T), and the growth rate u{sub c}(T) were estimated as functions of the undercooling temperature of molten alloys. Then, the free energy difference {Delta}G{sub L-x}(T) between the liquid and crystalline phases, and the viscosity {eta}(T) of the liquid were experimentally determined while the surface energy {sigma}{sub sL}(T) at the liquid-nucleus interface was estimated by calculation. The d{sub max} of rod BMG's correlated strongly to R{sub c}{sup h} through the relation R{sub c}{sup h} {approx_equal}d{sub max}{sup -3}/10 mm{sup 3} Ks{sup -1}.« less