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Title: Thermal conductivity of Glycerol’s liquid, glass, and crystal states, glass-liquid-glass transition, and crystallization at high pressures

Abstract

To investigate the effects of local density fluctuations on phonon propagation in a hydrogen bonded structure, we studied the thermal conductivity κ of the crystal, liquid, and glassy states of pure glycerol as a function of the temperature, T, and the pressure, p. We find that the following: (i) κ{sub crystal} is 3.6-times the κ{sub liquid} value at 140 K at 0.1 MPa and 2.2-times at 290 K, and it varies with T according to 138 × T{sup −0.95}; (ii) the ratio κ{sub liquid} (p)/κ{sub liquid} (0.1 MPa) is 1.45 GPa{sup −1} at 280 K, which, unexpectedly, is about the same as κ{sub crystal} (p)/κ{sub crystal} (0.1 MPa) of 1.42 GPa{sup −1} at 298 K; (iii) κ{sub glass} is relatively insensitive to T but sensitive to the applied p (1.38 GPa{sup −1} at 150 K); (iv) κ{sub glass}-T plots show an enhanced, pressure-dependent peak-like feature, which is due to the glass to liquid transition on heating; (v) continuous heating cold-crystallizes ultraviscous glycerol under pressure, at a higher T when p is high; and (vi) glycerol formed by cooling at a high p and then measured at a low p has a significantly higher κ than the glass formed by coolingmore » at a low p. On heating at a fixed low p, its κ decreases before its glass-liquid transition range at that p is reached. We attribute this effect to thermally assisted loss of the configurational and vibrational instabilities of a glass formed at high p and recovered at low p, which is different from the usual glass-aging effect. While the heat capacity, entropy, and volume of glycerol crystal are less than those for its glass and liquid, κ{sub crystal} of glycerol, like its elastic modulus and refractive index, is higher. We discuss these findings in terms of the role of fluctuations in local density and structure, and the relations between κ and the thermodynamic quantities.« less

Authors:
 [1]
  1. Department of Physics, Umeå University, 901 87 Umeå (Sweden)
Publication Date:
OSTI Identifier:
22493736
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 6; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CRYSTALLIZATION; CRYSTALS; ENTROPY; FLUCTUATIONS; GLASS; GLYCEROL; HEATING; HYDROGEN; LIQUIDS; PHONONS; PRESSURE DEPENDENCE; REFRACTIVE INDEX; SPECIFIC HEAT; TEMPERATURE DEPENDENCE; THERMAL CONDUCTIVITY

Citation Formats

Andersson, Ove, and Johari, G. P., E-mail: joharig@mcmaster.ca. Thermal conductivity of Glycerol’s liquid, glass, and crystal states, glass-liquid-glass transition, and crystallization at high pressures. United States: N. p., 2016. Web. doi:10.1063/1.4941335.
Andersson, Ove, & Johari, G. P., E-mail: joharig@mcmaster.ca. Thermal conductivity of Glycerol’s liquid, glass, and crystal states, glass-liquid-glass transition, and crystallization at high pressures. United States. doi:10.1063/1.4941335.
Andersson, Ove, and Johari, G. P., E-mail: joharig@mcmaster.ca. Sun . "Thermal conductivity of Glycerol’s liquid, glass, and crystal states, glass-liquid-glass transition, and crystallization at high pressures". United States. doi:10.1063/1.4941335.
@article{osti_22493736,
title = {Thermal conductivity of Glycerol’s liquid, glass, and crystal states, glass-liquid-glass transition, and crystallization at high pressures},
author = {Andersson, Ove and Johari, G. P., E-mail: joharig@mcmaster.ca},
abstractNote = {To investigate the effects of local density fluctuations on phonon propagation in a hydrogen bonded structure, we studied the thermal conductivity κ of the crystal, liquid, and glassy states of pure glycerol as a function of the temperature, T, and the pressure, p. We find that the following: (i) κ{sub crystal} is 3.6-times the κ{sub liquid} value at 140 K at 0.1 MPa and 2.2-times at 290 K, and it varies with T according to 138 × T{sup −0.95}; (ii) the ratio κ{sub liquid} (p)/κ{sub liquid} (0.1 MPa) is 1.45 GPa{sup −1} at 280 K, which, unexpectedly, is about the same as κ{sub crystal} (p)/κ{sub crystal} (0.1 MPa) of 1.42 GPa{sup −1} at 298 K; (iii) κ{sub glass} is relatively insensitive to T but sensitive to the applied p (1.38 GPa{sup −1} at 150 K); (iv) κ{sub glass}-T plots show an enhanced, pressure-dependent peak-like feature, which is due to the glass to liquid transition on heating; (v) continuous heating cold-crystallizes ultraviscous glycerol under pressure, at a higher T when p is high; and (vi) glycerol formed by cooling at a high p and then measured at a low p has a significantly higher κ than the glass formed by cooling at a low p. On heating at a fixed low p, its κ decreases before its glass-liquid transition range at that p is reached. We attribute this effect to thermally assisted loss of the configurational and vibrational instabilities of a glass formed at high p and recovered at low p, which is different from the usual glass-aging effect. While the heat capacity, entropy, and volume of glycerol crystal are less than those for its glass and liquid, κ{sub crystal} of glycerol, like its elastic modulus and refractive index, is higher. We discuss these findings in terms of the role of fluctuations in local density and structure, and the relations between κ and the thermodynamic quantities.},
doi = {10.1063/1.4941335},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 6,
volume = 144,
place = {United States},
year = {2016},
month = {2}
}