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Phys Chem Chem Phys ; 20(39): 25268-25274, 2018 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-30276414


A modulated and conventional DSC study of the transitions between the twist-bend nematic (Ntb), regular nematic (N) and isotropic liquid (Iso) phases was performed on a series of difluoroterphenyl-based dimers with (CH2)n spacers; n = 5, 7, 9, 11. The enthalpy of Ntb-N transition decreases steeply with increasing n, while that of the N-Iso transition increases with n; hence, the greatest effect of increasing n is a lowering N phase enthalpy. Based on past and present X-ray scattering experiments, we estimate the average molecular conformation in the Ntb phase and perform torsion energy calculations on the spacer. From this, the lowering enthalpy of the N phase is attributed to the decreasing torsional energy cost of bringing the two terphenyls from an inclined twisted conformation in the Ntb phase, to almost parallel in the N phase. With increasing n the C-C bonds of the spacers twist less away from their trans conformation, thereby reducing the overall torsion energy of the N phase. It is speculated that the nearly continuous nature of the Ntb-N transition in n = 11 dimer is associated with the divergence of the helical pitch toward infinity which is intercepted by a final jump at the very weak (0.01 J g-1) first-order transition. Small-angle X-ray scattering results suggest similar local cybotactic layering in both nematic phases, with four sublayers, i.e. tails, mesogens, spacers, mesogens.

Soft Matter ; 14(16): 3003-3011, 2018 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-29485649


The main-chain liquid crystal (LC) copolyethers in which the nematic-nematic phase transition was first experimentally observed were revisited and re-characterised. Grazing incidence X-ray scattering revealed that the low-T nematic (Ntb) phase could be highly aligned by shearing, more so than in previously studied bent LC dimers. This was evidenced by a four-point wide-angle X-ray scattering pattern, which originates from convolution of two tilt distributions. Through intensity simulation the orientational order parameter associated with each of the distributions, as well as the conical angle of the Ntb phase, was calculated. Information regarding the polymer chain conformation was obtained using polarised infrared spectroscopy. The findings suggest the average conformation of the chains is a helix, and that the bend angle between mesogenic units is inversely related to temperature. All experimental evidence, including a jump in birefringence at the Ntb-nematic (N) phase transition, shows that copolyether samples mirror the behaviour of bent LC dimers over the transition. This confirms that the low-T nematic phase in copolyethers is indeed the same as that in LC dimers, now known to be the Ntb. The unusual broadening of transition peaks in complex heat capacity, obtained by modulated DSC experiments, is discussed.