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Condensed Matter > Soft Condensed Matter

Title: Crystallization kinetics of (S)-4'-(1-methylheptyloxycarbonyl)biphenyl-4-yl 4-[4-(2,2,3,3,4,4,4-heptafluorobutoxy)but-1-oxy]-2-fluorobenzoate

Abstract: Chiral liquid crystalline compounds belonging to the homologous series of (S)-4'-(1-methylheptyloxycarbonyl)biphenyl-4-yl 4-[m-(2,2,3,3,4,4,4-heptafluorobutoxy)alk-1-oxy]-2-fluorobenzoates show various behavior on cooling depending on the length of the CmH2m chain. The homologue with m = 2 crystallizes, while for m = 5, 6, 7, and presumably also for m = 3, the glass of the anticlinic smectic CA* phase is formed. The previous results for m = 4 suggest that this homologue may also be a glassformer. This paper presents the study of the crystallization kinetics for the compound with m = 4 in isothermal conditions (by polarizing optical microscopy) and for the 5-40 K/min cooling rates (by differential scanning calorimetry). Microscopic observations enable estimation of the energy barrier for nucleation, which equals 409 kJ/mol. The threshold cooling rate necessary for complete vitrification of the smectic CA* phase, obtained by extrapolating the enthalpy change during crystallization to zero, is equal to 81 K/min or 64 K/min for the linear and parabolic fit, respectively. The structural studies by X-ray diffraction show that crystal phases have lamellar structures both in the pristine sample and after crystallization from the melt but with different layer spacing. A weak relaxation process is detected in the sample after melt crystallization, revealing the presence of the conformational disorder. The dynamic glass transition temperature of the SmCA* phase, estimated from the relaxation time of the PH process (as the {\alpha}-relaxation time could not be registered in a wide enough temperature range), is 244 K.
Comments: 20 pages, 16 figures
Subjects: Soft Condensed Matter (cond-mat.soft); Materials Science (cond-mat.mtrl-sci); Chemical Physics (physics.chem-ph)
Journal reference: Physical Chemistry Chemical Physics 26 (2024) 10144-10155
DOI: 10.1039/D4CP00198B
Cite as: arXiv:2312.11082 [cond-mat.soft]
  (or arXiv:2312.11082v1 [cond-mat.soft] for this version)

Submission history

From: Aleksandra Deptuch [view email]
[v1] Mon, 18 Dec 2023 10:22:45 GMT (2279kb)

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