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Title: Structures of glasses created by multiple kinetic arrests

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/5.0080846 · OSTI ID:1909345

X-ray scattering has been used to characterize glassy itraconazole (ITZ) prepared by cooling at different rates. Faster cooling produces ITZ glasses with lower (or zero) smectic order with more sinusoidal density modulation, larger molecular spacing, and shorter lateral correlation between the rod-like molecules. We find that each glass is characterized by not one, but two fictive temperatures Tf (the temperature at which a chosen order parameter is frozen in the equilibrium liquid). The higher Tf is associated with the regularity of smectic layers and lateral packing, while the lower Tf with the molecular spacings between and within smectic layers. This indicates that different structural features are frozen on different timescales. The two timescales for ITZ correspond to its two relaxation modes observed by dielectric spectroscopy: the slower δ mode (end-over-end rotation) is associated with the freezing of the regularity of molecular packing and the faster α mode (rotation about the long axis) with the freezing of the spacing between molecules. Finally, our finding suggests a way to selectively control the structural features of glasses.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE; National Science Foundation (NSF)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1909345
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 156; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (28)

On the Dielectric Behavior of Unaligned Samples of 4-n-Octyl-4′-cyanobiphenyl (8CB) journal December 1999
Effect of composition on the width of the calorimetric glass transition in polymer-solvent and solvent-solvent mixtures journal January 2004
Estimation of activation energies for structural relaxation and viscous flow from DTA and DSC experiments journal July 1996
Anisotropic organic glasses journal April 2018
Extended range X-ray pair distribution functions
  • Benmore, C. J.; Alderman, O. L. G.; Robinson, D.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 955 https://doi.org/10.1016/j.nima.2019.163318
journal March 2020
Structure and dynamics of monohydroxy alcohols—Milestones towards their microscopic understanding, 100 years after Debye journal December 2014
A SAXS-WAXS study of the endothermic transitions in amorphous or supercooled liquid itraconazole journal November 2016
Relation between freezing-in due to linear cooling and the dynamic glass transition temperature by temperature-modulated DSC journal August 1998
Volume and enthalpy recovery of polystyrene journal March 2001
Controlling the Columnar Order in a Discotic Liquid Crystal by Kinetic Arrest of Disc Tumbling journal June 2021
Controlling Structure and Properties of Vapor-Deposited Glasses of Organic Semiconductors: Recent Advances and Challenges journal July 2020
Discotic Liquid Crystals for Opto-Electronic Applications journal February 2011
Molecular orientation in small-molecule organic light-emitting diodes journal January 2011
Molecular dynamics of itraconazole at ambient and high pressure journal January 2013
Organic glasses with tunable liquid-crystalline order through kinetic arrest of end-over-end rotation: the case of saperconazole journal January 2020
The structure of smectic A phases of compounds with cyano end groups journal January 1979
Decay of Pair Correlations in Hard Sphere Fluids journal September 1972
Glass Transition in o ‐Terphenyl journal February 1967
An atomistic description of the nematic and smectic phases of 4-n-octyl-4′ cyanobiphenyl (8CB) journal May 2013
Studies on Some Smectogenic Compounds with Large Bilayer Spacings journal July 1983
X-ray study of the sharpness of the smectic A layer structure journal January 1989
A practical method for the deconvolution of experimental curves journal October 1967
Simple experimental assessment of smectic translational order parameters journal December 2008
Organic Glasses with Tunable Liquid-Crystalline Order journal February 2018
X-Ray Scattering from Liquid Crystals. I. Cholesteryl Nonanoate and Myristate journal September 1972
Higher smectic-layer order parameters in liquid crystals determined by x-ray diffraction and the effect of antiferroelectricity journal January 1995
Origin of glassy dynamics in a liquid crystal studied by broadband dielectric and specific heat spectroscopy journal June 2007
FIT2D : a multi-purpose data reduction, analysis and visualization program journal March 2016