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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 behaviors 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−1 cooling rates (by differential scanning calorimetry). Microscopic observations enable estimation of the energy barrier for nucleation, which equals 409 kJ mol−1. 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−1 or 64 K min−1 for the linear and parabolic fits, 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 α-relaxation time could not be registered in a wide enough temperature range), is 244 K. [ABSTRACT FROM AUTHOR]

The aim of the study was to investigate the influence of the environment's pH on the degradation of the layers of the ternary composite l,d-PLA : 5CB : SWCN (10 : 1 : 0.5, w/w/w), where l,d-PLA (poly(lactic acid)) is a biodegradable polymer, 5CB is a well-known liquid crystal (4'-pentyl-4-biphenylcarbonitrile), and SWCN are single-walled carbon nanotubes. For this purpose, the samples were stored in air, distilled water, and solutions of 0.1 M NaOH and 0.1 M HCl, for up to 62 days. Using differential scanning calorimetry, atomic force microscopy, and infra-red spectroscopy methods it was observed that for both neat l,d-PLA and composite layers there was a poor degradation process after the storage under standard air conditions, distilled water, and 0.1 M HCl solution, while the erosion of the surface layer kept in 0.1 M NaOH solution was revealed just after 6 days. The longer storage in 0.1 M NaOH solution resulted in complete degradation of the l,d-PLA polymer layer, while the composite layer survived for up to 62 days. The solubilization of the polymeric l,d-PLA matrix in the composite after 62 days was so severe that it resulted in the vanishing of thermal effects on the DSC curve except for one that was probably connected with the glass transition of the residual quantity of the polymer that remained in the layer or the isotropisation of 5CB. As a result, we have shown that admixtures of 5CB and SWCN accelerate the degradation of l,d-PLA in the composite layer due to the hydrophilic/hydrophobic interface in the layer and act as plasticizers. The mechanism of the degradation process is also discussed., Competing Interests: The authors declare no conflicts of interest., (This journal is © The Royal Society of Chemistry.)