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Title: Pressure Induced Liquid-to-Liquid Transition in Zr-based Supercooled Melts and Pressure Quenched Glasses

Abstract

Through high-energy x-ray diffraction and atomic pair density function analysis we find that Zr-based metallic alloy, heated to the supercooled liquid state under hydrostatic pressure and then quenched to room temperature, exhibits a distinct glassy structure. The PDF indicates that the Zr-Zr distances in this glass are significantly reduced compared to those quenched without pressure. Annealing at the glass transition temperature at ambient pressure reverses structural changes and the initial glassy state is recovered. This result suggests that pressure causes a liquid-to-liquid phase transition in this metallic alloy supercooled melt. Such a pressure induced transition is known for covalent liquids, but has not been observed for metallic liquids. The High Pressure Quenched glasses are stable in ambient conditions after decompression.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1394136
DOE Contract Number:
AC05-00OR22725
Resource Type:
Journal Article
Resource Relation:
Journal Name: Scientific Reports; Journal Volume: 7; Journal Issue: 1
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Dmowski, W., Gierlotka, S., Wang, Z., Yokoyama, Y., Palosz, B., and Egami, T. Pressure Induced Liquid-to-Liquid Transition in Zr-based Supercooled Melts and Pressure Quenched Glasses. United States: N. p., 2017. Web. doi:10.1038/s41598-017-06890-w.
Dmowski, W., Gierlotka, S., Wang, Z., Yokoyama, Y., Palosz, B., & Egami, T. Pressure Induced Liquid-to-Liquid Transition in Zr-based Supercooled Melts and Pressure Quenched Glasses. United States. doi:10.1038/s41598-017-06890-w.
Dmowski, W., Gierlotka, S., Wang, Z., Yokoyama, Y., Palosz, B., and Egami, T. 2017. "Pressure Induced Liquid-to-Liquid Transition in Zr-based Supercooled Melts and Pressure Quenched Glasses". United States. doi:10.1038/s41598-017-06890-w.
@article{osti_1394136,
title = {Pressure Induced Liquid-to-Liquid Transition in Zr-based Supercooled Melts and Pressure Quenched Glasses},
author = {Dmowski, W. and Gierlotka, S. and Wang, Z. and Yokoyama, Y. and Palosz, B. and Egami, T.},
abstractNote = {Through high-energy x-ray diffraction and atomic pair density function analysis we find that Zr-based metallic alloy, heated to the supercooled liquid state under hydrostatic pressure and then quenched to room temperature, exhibits a distinct glassy structure. The PDF indicates that the Zr-Zr distances in this glass are significantly reduced compared to those quenched without pressure. Annealing at the glass transition temperature at ambient pressure reverses structural changes and the initial glassy state is recovered. This result suggests that pressure causes a liquid-to-liquid phase transition in this metallic alloy supercooled melt. Such a pressure induced transition is known for covalent liquids, but has not been observed for metallic liquids. The High Pressure Quenched glasses are stable in ambient conditions after decompression.},
doi = {10.1038/s41598-017-06890-w},
journal = {Scientific Reports},
number = 1,
volume = 7,
place = {United States},
year = 2017,
month = 7
}
  • Through high-energy x-ray diffraction and atomic pair density function analysis we find that Zr-based metallic alloy, heated to the supercooled liquid state under hydrostatic pressure and then quenched to room temperature, exhibits a distinct glassy structure. The PDF indicates that the Zr-Zr distances in this glass are significantly reduced compared to those quenched without pressure. Annealing at the glass transition temperature at ambient pressure reverses structural changes and the initial glassy state is recovered. This result suggests that pressure causes a liquid-to-liquid phase transition in this metallic alloy supercooled melt. Such a pressure induced transition is known for covalent liquids,more » but has not been observed for metallic liquids. The High Pressure Quenched glasses are stable in ambient conditions after decompression.« less
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  • The coordination environment of Ti (IV) in a number of Ti-silicate and Ti-aluminosilicate glasses has been determined by x-ray absorption fine structure (XAFS) spectroscopy at the Ti K-edge at ambient temperature and pressure. These glasses contain 2.7-30.5 wt% TiO{sub 2} and varying amounts of Na{sub 2}O, K{sub 2}O, or CaO (5.0-38.7 wt%) and Al{sub 2}O{sub 3} (0-11.9 wt%), and have NBO/T ratios ranging from 0.07 - 0.81. Quantitative analysis of the Ti XANES spectra, based on ab initio multiple-scattering calculations for a variety of Ti-containing clusters. and anharmonic analysis of the normalized XAFS oscillations suggest the presence of three typesmore » of atoms around Ti: O first neighbors, (Si, Ti)-second neighbors, and alkali third neighbors. Five-coordinated Ti, {sup [5]}Ti, is the dominant Ti species in the glasses most concentrated in Ti ( > 16 wt% TiO{sub 2}) and is located in distorted square pyramids (({sup [5]}TiO) O{sub 4}), with one short Ti=O titanyl distance ( 1.67- 1.70 {+-} 0.03 {Angstrom}) and four long Ti-O distances ( 1.94-1.95 {+-} 0.02 {Angstrom}). In addition, minor amounts of {sup [4]}Ti were detected, the proportion of {sup [4]}Ti increasing in the order: Na glasses < K glasses. {sup [4]}Ti is the dominant Ti species in the potassic glasses with the lowest TiO{sub 2} contents ({approx}3-6 wt%) and highest NBO/T ratio. The relative amount of {sup [4]}Ti increases in the order: Ca glass < K glass. Finally, {sup [6]}Ti is a minor species (<20%) when detected in these glasses. The presence of Ti-(Si, Ti) correlations near 3.2-3.4 {+-} 0.1 {Angstrom}, as in crystalline Na{sub 2}({sup [5]}TiO)SiO{sub 4}, is consistent with {sup [5]}TiO{sub 5} and SiO{sub 4}/TiO{sub 5} polyhedra sharing corners in these glasses, with Ti-O-(Si, Ti) angles of {approx}120{degrees}-130{degrees} {+-} 10{degrees}. These models also provide a structural basis for the study of glasses and melts at higher temperatures. 83 refs., 10 figs., 5 tabs.« less
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