López D O, Robles-Hernández B, Salud J, de la Fuente M R, Sebastián N, Diez-Berart S, Jaen X, Dunmur D A, Luckhurst G R
Grup de Propietats Físiques dels Materials (GRPFM-GCMM), Departament de Física, E.T.S.E.I.B, Universitat Politècnica de Catalunya, Diagonal, 647 08028 Barcelona, Spain.
Departamento de Física Aplicada II, Facultad de Ciencia y Tecnología, Universidad del País Vasco, Apartado 644, E-48080 Bilbao, Spain.
Phys Chem Chem Phys. 2016 Feb 14;18(6):4394-404. doi: 10.1039/c5cp07605f.
We report a calorimetric study of a series of mixtures of two twist-bend liquid crystal dimers, the 1'',7''-bis(4-cyanobiphenyl)-4'-yl heptane (CB7CB) and 1''-(2',4-difluorobiphenyl-4'-yloxy)-9''-(4-cyanobiphenyl-4'-yloxy) nonane (FFO9OCB), the molecules of which have different effective molecular curvatures. High-resolution heat capacity measurements in the vicinity of the NTB-N phase transition for a selected number of binary mixtures clearly indicate a first order NTB-N phase transition for all the investigated mixtures, the strength of which decreases when the nematic range increases. Published theories predict a second order NTB-N phase transition, but we have developed a self-consistent mean field Landau model using two key order parameters: a symmetric and traceless tensor for the orientational order and a short-range vector field which is orthogonal to the helix axis and rotates around of the heliconical structure with an extremely short periodicity. The theory, in its simplified form, depends on two effective elastic constants and explains satisfactorily our heat capacity measurements and also predicts a first-order NTB-N phase transition. In addition, as a complementary source of experimental measurements, the splay (K1) and bend (K3) elastic constants in the conventional nematic phase for the pure compounds and some selected mixtures have been determined.
我们报道了对两种扭曲弯曲液晶二聚体混合物的量热研究,这两种二聚体分别是1'',7''-双(4-氰基联苯)-4'-基庚烷(CB7CB)和1''-(2',4-二氟联苯-4'-氧基)-9''-(4-氰基联苯-4'-氧基)壬烷(FFO9OCB),它们的分子具有不同的有效分子曲率。对选定数量的二元混合物在NTB-N相变附近进行的高分辨率热容测量清楚地表明,所有研究的混合物都发生了一级NTB-N相变,当向列相范围增加时,相变强度会降低。已发表的理论预测NTB-N相变是二级相变,但我们使用两个关键序参量开发了一个自洽平均场朗道模型:一个用于取向序的对称且无迹张量,以及一个与螺旋轴正交并以极短周期围绕螺旋结构旋转的短程矢量场。该理论的简化形式取决于两个有效弹性常数,令人满意地解释了我们的热容测量结果,并且还预测了一级NTB-N相变。此外,作为实验测量的补充来源,还测定了纯化合物和一些选定混合物在常规向列相中的展曲(K1)和弯曲(K3)弹性常数。