skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Chain Breakage in the Supercooled Liquid - Liquid Transition and Re-entry of the λ-transition in Sulfur

Abstract

Amorphous sulfur was prepared by rapid compression of liquid sulfur at temperatures above the λ-transition for to preserve the high-temperature liquid structure. We conducted synchrotron highenergy X-ray diffraction and Raman spectroscopy to diagnose the structural evolution of amorphous sulfur from room temperature to post-λ-transition temperature. Discontinuous changes of the first and second peaks in atomic pair-distribution-function, g(r), were observed during the transition from amorphous to liquid sulfur. The average first-neighbor coordination numbers showed an abrupt drop from 1.92 to 1.81. The evolution of the chain length clearly shows that the transition was accompanied by polymeric chains breaking. Furthermore, a re-entry of the λ-transition structure was involved in the heating process. The amorphous sulfur, which inherits the post-λ-transition structure from its parent melts, transformed to the pre-λ-transition liquid structure at around 391 K. Upon further heating, the pre-λ-transition liquid transformed to a post-λ-transition structure through the wellknown λ-transition process. Furthermore, this discovery offers a new perspective on amorphous sulfur’s structural inheritance from its parent liquid and has implications for understanding the structure, evolution and properties of amorphous sulfur and its liquids.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [5];  [3];  [3];  [3];  [3];  [4]
  1. Southwest Jiaotong Univ., Chengdu (China); Center for High Pressure and Technology Advanced Research, Shanghai (China)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Southwest Jiaotong Univ., Chengdu (China)
  4. Center for High Pressure and Technology Advanced Research, Shanghai (China); Carnegie Inst. of Washington, Argonne, IL (United States); Florida Intl Univ., Miami, FL (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
National Science Foundation of China; Fundamental Research Funds for the Central Universities; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1461349
Alternate Identifier(s):
OSTI ID: 1483746
Report Number(s):
BNL-209509-2018-JAAM
Journal ID: ISSN 2045-2322; 142941
Grant/Contract Number:  
AC02-06CH11357; SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 36 MATERIALS SCIENCE

Citation Formats

Zhang, Linji, Ren, Yang, Liu, Xiuru, Han, Fei, Evans-Lutterodt, Kenneth, Wang, Hongyan, He, Yali, Wang, Junlong, Zhao, Yong, and Yang, Wenge. Chain Breakage in the Supercooled Liquid - Liquid Transition and Re-entry of the λ-transition in Sulfur. United States: N. p., 2018. Web. doi:10.1038/s41598-018-22775-y.
Zhang, Linji, Ren, Yang, Liu, Xiuru, Han, Fei, Evans-Lutterodt, Kenneth, Wang, Hongyan, He, Yali, Wang, Junlong, Zhao, Yong, & Yang, Wenge. Chain Breakage in the Supercooled Liquid - Liquid Transition and Re-entry of the λ-transition in Sulfur. United States. doi:10.1038/s41598-018-22775-y.
Zhang, Linji, Ren, Yang, Liu, Xiuru, Han, Fei, Evans-Lutterodt, Kenneth, Wang, Hongyan, He, Yali, Wang, Junlong, Zhao, Yong, and Yang, Wenge. Wed . "Chain Breakage in the Supercooled Liquid - Liquid Transition and Re-entry of the λ-transition in Sulfur". United States. doi:10.1038/s41598-018-22775-y. https://www.osti.gov/servlets/purl/1461349.
@article{osti_1461349,
title = {Chain Breakage in the Supercooled Liquid - Liquid Transition and Re-entry of the λ-transition in Sulfur},
author = {Zhang, Linji and Ren, Yang and Liu, Xiuru and Han, Fei and Evans-Lutterodt, Kenneth and Wang, Hongyan and He, Yali and Wang, Junlong and Zhao, Yong and Yang, Wenge},
abstractNote = {Amorphous sulfur was prepared by rapid compression of liquid sulfur at temperatures above the λ-transition for to preserve the high-temperature liquid structure. We conducted synchrotron highenergy X-ray diffraction and Raman spectroscopy to diagnose the structural evolution of amorphous sulfur from room temperature to post-λ-transition temperature. Discontinuous changes of the first and second peaks in atomic pair-distribution-function, g(r), were observed during the transition from amorphous to liquid sulfur. The average first-neighbor coordination numbers showed an abrupt drop from 1.92 to 1.81. The evolution of the chain length clearly shows that the transition was accompanied by polymeric chains breaking. Furthermore, a re-entry of the λ-transition structure was involved in the heating process. The amorphous sulfur, which inherits the post-λ-transition structure from its parent melts, transformed to the pre-λ-transition liquid structure at around 391 K. Upon further heating, the pre-λ-transition liquid transformed to a post-λ-transition structure through the wellknown λ-transition process. Furthermore, this discovery offers a new perspective on amorphous sulfur’s structural inheritance from its parent liquid and has implications for understanding the structure, evolution and properties of amorphous sulfur and its liquids.},
doi = {10.1038/s41598-018-22775-y},
journal = {Scientific Reports},
number = 1,
volume = 8,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

High pressure jump apparatus for measuring Grűneisen parameter of NaCl and studying metastable amorphous phase of poly (ethylene terephthalate)
journal, May 2005

  • Hong, S. M.; Chen, L. Y.; Liu, X. R.
  • Review of Scientific Instruments, Vol. 76, Issue 5
  • DOI: 10.1063/1.1899443

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Origin of the λ Transition in Liquid Sulfur
journal, July 2007


Polymer content of sulfur quenched rapidly from the melt
journal, November 1970

  • Klement, William; Koh, Jae Chun
  • The Journal of Physical Chemistry, Vol. 74, Issue 24
  • DOI: 10.1021/j100718a017

Elemental sulfur
journal, June 1976


Chain-ring transition during exothermic "melting" in amorphous sulfur
journal, December 2014

  • Xu, JiAn; He, Zhu; Zhang, DouDou
  • Chinese Science Bulletin, Vol. 59, Issue 35
  • DOI: 10.1360/N972014-00698

Pressure and Time Dependences of the Supercooled Liquid-to-Liquid Transition in Sulfur
journal, February 2016


Understanding exceptional thermodynamic and kinetic stability of amorphous sulfur obtained by rapid compression
journal, January 2009

  • Yu, P.; Wang, W. H.; Wang, R. J.
  • Applied Physics Letters, Vol. 94, Issue 1
  • DOI: 10.1063/1.3064125

Optical absorption spectra of liquid sulphur over a wide absorption range
journal, July 1994


The glassy and supercooled state of elemental sulfur: Vibrational modes, structure metastability, and polymer content
journal, September 2013

  • Andrikopoulos, K. S.; Kalampounias, A. G.; Falagara, O.
  • The Journal of Chemical Physics, Vol. 139, Issue 12
  • DOI: 10.1063/1.4821592

Raman spectroscopy of sulfur, sulfur-selenium, and sulfur-arsenic mixtures
journal, November 1968

  • Ward, Anthony T.
  • The Journal of Physical Chemistry, Vol. 72, Issue 12
  • DOI: 10.1021/j100858a031

Probing the sulfur polymerization transition in situ with Raman spectroscopy
journal, May 2003

  • Kalampounias, A. G.; Andrikopoulos, K. S.; Yannopoulos, S. N.
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1566938

Structure and dynamics of liquid sulphur
journal, January 1999


Structural Transition in Compressed Amorphous Sulfur
journal, February 2008


Deformation-Induced Linear Chain−Ring Transition and Crystallization of Living Polymer Sulfur
journal, December 2007

  • Shao, Chunguang; An, Haining; Wang, Xiao
  • Macromolecules, Vol. 40, Issue 26
  • DOI: 10.1021/ma071803a

The structural properties of liquid and quenched sulphur II
journal, May 1994


The Nature of the Glassy State and the Behavior of Liquids at Low Temperatures.
journal, October 1948


The Viscosity of Sulfur 1
journal, April 1943

  • Bacon, Raymond F.; Fanelli, Rocco
  • Journal of the American Chemical Society, Vol. 65, Issue 4
  • DOI: 10.1021/ja01244a043

Pressure-induced solidifications of liquid sulfur below and above λ-transition
journal, April 2016


The density of liquid sulfur near the polymerization temperature
journal, February 1992

  • Zheng, K. M.; Greer, S. C.
  • The Journal of Chemical Physics, Vol. 96, Issue 3
  • DOI: 10.1063/1.462069

The glass transition temperature of polymeric sulphur
journal, January 1963


PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data
journal, July 2004

  • Qiu, Xiangyun; Thompson, Jeroen W.; Billinge, Simon J. L.
  • Journal of Applied Crystallography, Vol. 37, Issue 4, p. 678-678
  • DOI: 10.1107/S0021889804011744

Vibrational dynamics and stability of the high-pressure chain and ring phases in S and Se
journal, February 2007

  • Degtyareva, Olga; Hernández, Eduardo R.; Serrano, Jorge
  • The Journal of Chemical Physics, Vol. 126, Issue 8
  • DOI: 10.1063/1.2433944

The structural properties of liquid and quenched sulfur
journal, December 1988


Liquid sulfur: Local-order evidence of a polymerization transition
journal, February 1990


Chain breakage in liquid sulfur at high pressures and high temperatures
journal, May 2014


X‐Ray Diffraction in Crystals, Imperfect Crystals, and Amorphous Bodies
journal, April 1964

  • Guinier, A.; Lorrain, Paul; Lorrain, Dorothée Sainte‐Marie
  • Physics Today, Vol. 17, Issue 4
  • DOI: 10.1063/1.3051547

Power-law scaling and fractal nature of medium-range order in metallic glasses
journal, December 2008

  • Ma, D.; Stoica, A. D.; Wang, X. -L.
  • Nature Materials, Vol. 8, Issue 1
  • DOI: 10.1038/nmat2340

Universal Fractional Noncubic Power Law for Density of Metallic Glasses
journal, May 2014


Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996

  • Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
  • High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
  • DOI: 10.1080/08957959608201408