A Study on the Thermodynamic Characteristics of Dimer Liquid Crystal(CBA-10) by Phase Transition

이량체액정(CBA-10)의 상전이에 따른 열역학적 특성에 관한 연구

The PVT and $^2H$-NMR characteristic of main-chain dimer liquid crystals having structures such as ${\alpha}$, ${\omega}$-bis[4,4'-cyanobiphenyl) oxy] alkane(CBA-10) were studied. In this work, V-T curves obtained from isobaris measurements on various pressures, volume changes were observed at the nematic-isotropic and nematic-crystal phase transition. The volume changes at the transition exhibit slight odd-even effect with respect to the number of methylene unit n. The values of the$({\Delta}S_{tr})_V$ obtained at the NI transition for CBA-10 was $12.6J/mol{\cdot}K$. The values of $({\Delta}S_{CN})_V$ for the CN transition was estimated on the basis of DSC data : $65.3J/mol{\cdot}K$. For both transition, it was found that the correction about the volume change is significant, ranging from 40 to 60% of the total transition entropy observed under constant pressure. The RIS analysis of the spectra was performed so as to elucidate the conformational characteristics of the spacer in the nematic phase. The conformational entropy changes at both CN and NI interphases were estimated on the basis of the nematic conformations taken from the conformation map as well as those derived from the simulation. The estimated conformational entropy change values were then compared with the corresponding constant-volume entropies obtained from PVT measurements. The correspondence between both entropy values was found to be quite good in consideration of the uncertainties involved in both experiment and calculations.

주쇄형고분자액정(CBA-10)의 PVT와 $^2H$-NMR측정으로 상전이에 따른 열역학적 특성을 고찰하였다. 부피 변화에 의한 NI 및 CN 상전이가 발생하였으며, 일정체적하의 상전이 엔트로피 $({\Delta}S_{NI})_V$와 $({\Delta}S_{CN})_V$값 12.6, $65.3J/mol{\cdot}K$를 각각 구하였으며, 체적변화에 따른 엔트로피는 일정압력하에 얻어진 전이엔트로피의 40~60%정도였다. $^2H$-NMR/RIS 해석으로 nematic conformation을 결정하였으며, NI 및 CN 상전이에 의한 conformation entropy를 구하여 PVT측정에서 구한 일정체적하의 엔트로피와 비교한 결과, 거의 대응하다는 것을 알 수 있었다. 이러한 결과로부터 주쇄형액정의 상전이에 있어서 spacer conformation 변화가 중요한 역할을 하고 있음을 밝혔다.