Diffusion-controlled and "diffusionless" crystal growth near the glass transition temperature

Relation between liquid dynamics and growth kinetics of seven ROY polymorphs

Ye Sun, Hanmi Xi, M. D. Ediger, Ranko Richert, Lian Yu

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

The liquid dynamics of 5-methyl-2-[(2-nitrophenyl)amino]-3- thiophenecarbonitrile, named ROY for its red, orange, and yellow crystal polymorphs, was characterized by dielectric spectroscopy and differential scanning calorimetry. Four of these polymorphs show fast " diffusionless" crystal growth at low temperatures while three others do not. ROY was found to be a typical fragile organic liquid. Its α relaxation process has time-temperature superposition symmetry across the viscous range (τα =100 s-100 ns) with the width of the relaxation peak characterized by a constant ΒKWW of 0.73. No secondary relaxation peak was observed, even with glasses made by fast quenching. For the polymorphs not showing fast crystal growth in the glassy state, the growth rate has a power-law relation with τα, u α τα -xi, where xi ≈0.7. For the polymorphs showing fast crystal growth in the glassy state, the growth is so fast near and below the glass transition temperature Tg that thousands of molecular layers can be added to the crystalline phase during one structural relaxation time of the liquid. In the glassy state, this mode of growth slows slightly over time. This slowdown is not readily explained by the effect of physical aging on the thermodynamic driving force of crystallization, the glass vapor pressure, or the rate of structural relaxation. This study demonstrates that from the same liquid or glass, the growth of some polymorphs is accurately described as being limited by the rate of structural relaxation or bulk diffusion, whereas the growth of other polymorphs is too fast to be under such control.

Original languageEnglish (US)
Article number074506
JournalJournal of Chemical Physics
Volume131
Issue number7
DOIs
StatePublished - 2009

Fingerprint

Transition Temperature
Growth kinetics
Crystallization
Polymorphism
glass transition temperature
Glass
crystal growth
Structural relaxation
kinetics
Liquids
Growth
liquids
glass
Dielectric Spectroscopy
Vapor Pressure
Temperature
organic liquids
Differential Scanning Calorimetry
Dielectric spectroscopy
Thermodynamics

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry
  • Medicine(all)

Cite this

@article{5b9ef63d51cb41c9ae0f57e8278e477d,
title = "Diffusion-controlled and {"}diffusionless{"} crystal growth near the glass transition temperature: Relation between liquid dynamics and growth kinetics of seven ROY polymorphs",
abstract = "The liquid dynamics of 5-methyl-2-[(2-nitrophenyl)amino]-3- thiophenecarbonitrile, named ROY for its red, orange, and yellow crystal polymorphs, was characterized by dielectric spectroscopy and differential scanning calorimetry. Four of these polymorphs show fast {"} diffusionless{"} crystal growth at low temperatures while three others do not. ROY was found to be a typical fragile organic liquid. Its α relaxation process has time-temperature superposition symmetry across the viscous range (τα =100 s-100 ns) with the width of the relaxation peak characterized by a constant ΒKWW of 0.73. No secondary relaxation peak was observed, even with glasses made by fast quenching. For the polymorphs not showing fast crystal growth in the glassy state, the growth rate has a power-law relation with τα, u α τα -xi, where xi ≈0.7. For the polymorphs showing fast crystal growth in the glassy state, the growth is so fast near and below the glass transition temperature Tg that thousands of molecular layers can be added to the crystalline phase during one structural relaxation time of the liquid. In the glassy state, this mode of growth slows slightly over time. This slowdown is not readily explained by the effect of physical aging on the thermodynamic driving force of crystallization, the glass vapor pressure, or the rate of structural relaxation. This study demonstrates that from the same liquid or glass, the growth of some polymorphs is accurately described as being limited by the rate of structural relaxation or bulk diffusion, whereas the growth of other polymorphs is too fast to be under such control.",
author = "Ye Sun and Hanmi Xi and Ediger, {M. D.} and Ranko Richert and Lian Yu",
year = "2009",
doi = "10.1063/1.3200228",
language = "English (US)",
volume = "131",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "7",

}

TY - JOUR

T1 - Diffusion-controlled and "diffusionless" crystal growth near the glass transition temperature

T2 - Relation between liquid dynamics and growth kinetics of seven ROY polymorphs

AU - Sun, Ye

AU - Xi, Hanmi

AU - Ediger, M. D.

AU - Richert, Ranko

AU - Yu, Lian

PY - 2009

Y1 - 2009

N2 - The liquid dynamics of 5-methyl-2-[(2-nitrophenyl)amino]-3- thiophenecarbonitrile, named ROY for its red, orange, and yellow crystal polymorphs, was characterized by dielectric spectroscopy and differential scanning calorimetry. Four of these polymorphs show fast " diffusionless" crystal growth at low temperatures while three others do not. ROY was found to be a typical fragile organic liquid. Its α relaxation process has time-temperature superposition symmetry across the viscous range (τα =100 s-100 ns) with the width of the relaxation peak characterized by a constant ΒKWW of 0.73. No secondary relaxation peak was observed, even with glasses made by fast quenching. For the polymorphs not showing fast crystal growth in the glassy state, the growth rate has a power-law relation with τα, u α τα -xi, where xi ≈0.7. For the polymorphs showing fast crystal growth in the glassy state, the growth is so fast near and below the glass transition temperature Tg that thousands of molecular layers can be added to the crystalline phase during one structural relaxation time of the liquid. In the glassy state, this mode of growth slows slightly over time. This slowdown is not readily explained by the effect of physical aging on the thermodynamic driving force of crystallization, the glass vapor pressure, or the rate of structural relaxation. This study demonstrates that from the same liquid or glass, the growth of some polymorphs is accurately described as being limited by the rate of structural relaxation or bulk diffusion, whereas the growth of other polymorphs is too fast to be under such control.

AB - The liquid dynamics of 5-methyl-2-[(2-nitrophenyl)amino]-3- thiophenecarbonitrile, named ROY for its red, orange, and yellow crystal polymorphs, was characterized by dielectric spectroscopy and differential scanning calorimetry. Four of these polymorphs show fast " diffusionless" crystal growth at low temperatures while three others do not. ROY was found to be a typical fragile organic liquid. Its α relaxation process has time-temperature superposition symmetry across the viscous range (τα =100 s-100 ns) with the width of the relaxation peak characterized by a constant ΒKWW of 0.73. No secondary relaxation peak was observed, even with glasses made by fast quenching. For the polymorphs not showing fast crystal growth in the glassy state, the growth rate has a power-law relation with τα, u α τα -xi, where xi ≈0.7. For the polymorphs showing fast crystal growth in the glassy state, the growth is so fast near and below the glass transition temperature Tg that thousands of molecular layers can be added to the crystalline phase during one structural relaxation time of the liquid. In the glassy state, this mode of growth slows slightly over time. This slowdown is not readily explained by the effect of physical aging on the thermodynamic driving force of crystallization, the glass vapor pressure, or the rate of structural relaxation. This study demonstrates that from the same liquid or glass, the growth of some polymorphs is accurately described as being limited by the rate of structural relaxation or bulk diffusion, whereas the growth of other polymorphs is too fast to be under such control.

UR - http://www.scopus.com/inward/record.url?scp=69249171004&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=69249171004&partnerID=8YFLogxK

U2 - 10.1063/1.3200228

DO - 10.1063/1.3200228

M3 - Article

VL - 131

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 7

M1 - 074506

ER -