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Probing Hidden Phase Transitions in Plastic Crystal Succinonitrile.

Hiroshi Abe1, Keiko Nishikawa2, Kozo Fujii2

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A hidden phase transition in succinonitrile (SN) plastic crystals (PCs) was discovered using slow heating. This transition, involving symmetry reduction, is only observable with ultralow-rate synchrotron X-ray scattering.

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Area of Science:

  • Materials Science
  • Crystallography
  • Phase Transitions

Background:

  • Succinonitrile (SN) exists as trans (0 D) and gauche (5.45 D) conformers.
  • Plastic crystals (PCs) are known for their unique orientational disorder.
  • Understanding phase transitions in molecular crystals is crucial for materials development.

Purpose of the Study:

  • To investigate the phase behavior of succinonitrile (SN) under slow heating conditions.
  • To characterize the structural changes associated with a potential hidden phase transition.
  • To determine the influence of heating rate on the observed phase transitions.

Main Methods:

  • Synchrotron small- and wide-angle X-ray scattering (SWAXS) was employed.
  • Measurements were conducted during slow heating (0.2 K/min) and conventional heating (∼5 K/min).
  • Analysis focused on Bragg reflection splitting and diffuse scattering patterns.

Main Results:

  • A previously hidden phase transition from a cubic plastic crystal (PC) phase to a lower-symmetry ferro-like ordered (fC) phase was observed.
  • The PC-fC transition involves a reduction in crystal symmetry.
  • This transition was exclusively detected at ultralow heating rates, with additional diffuse scattering observed.

Conclusions:

  • Succinonitrile exhibits a hidden phase transition that is highly sensitive to heating rate.
  • The ferro-like ordered (fC) phase is stable across thermal cycles.
  • Ultralow-rate synchrotron SWAXS is essential for revealing subtle phase transitions in plastic crystals.