Influence of Cylindrical Submicrometer Confinement on the Static and Dynamic Properties in Nonyloxycyanobiphenyl (9OCB)

Broadband dielectric spectroscopy (102−1.9 × 109 Hz) and specific heat measurements have been performed on nonyloxycyanobiphenyl (9OCB) in the isotropic (I), nematic (N), and smectic A (SmA) phases confined to 200 nm diameter parallel cylindrical pores of Anopore membranes. Untreated and HTBA-treated membranes have been found to obtain axial and radial confinements, respectively. However, structural or configurational transitions in untreated membranes have been reported to exist in the SmA-mesophase of 9OCB. Both confinements clearly affect the N−I and SmA−N phase transitions. In the axial confinement, the analysis of the specific heat and static dielectric permittivity data leads to a second order SmA−N phase transition, which is known to be weakly first order for bulk 9OCB. Dynamic dielectric measurements have accounted for the different molecular motions in both confinements. On both mesophases, either N or SmA, the relaxation processes in axial configuration are faster than in the bulk. However, in radial confinement, they are either equal or slower than in the bulk. Additionally, there are no differences in the energy barrier hindering the molecular motions between the axial and radial confinements and even in relation to bulk. Likewise, dielectric results suggest that the extension inside the pores of the surface pinned molecular layer (proved to be temperature-dependent) persists at high enough temperature as a residual-thin layer adjacent to the pore wall.