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The phase behavior and molecular ordering of hexakishexyloxy triphenylene (HAT6) DLC under cylindrical nanoconfinement is studied utilizing differential scanning calorimetry (DSC) and dielectric spectroscopy (DS), where cylindrical nanoconfinement is established through embedding HAT6 into the nanopores of anodic aluminum oxide membranes (AAO), and a silica membrane with pore diameters ranging from 161 nm down to 12 nm. Both unmodified and modified pore walls were considered, and in the latter case the pore walls of AAO membranes were chemical treated with n octadecylphosphonic acid (ODPA) resulting in the formation of a 2.2 nm thick layer of grafted alkyl chains. Phase transition enthalpies decrease with decreasing pore size, indicating that a large proportion of the HAT6 molecules within the pores has a disordered structure, which increases with decreasing pore size for both pore walls. In the case of the ODPA modification the amount of ordered HAT6 is increased compared to the unmodified case. The pore size dependencies of the phase transition temperatures were approximated using the Gibbs Thomson equation, where the estimated surface tension is dependent on the molecular ordering of HAT6 molecules within the pores and upon their surface. DS was employed to investigate the molecular ordering of HAT6 within the nanopores. These investigations revealed that with a pore size of around 38 nm, for the samples with the unmodified pore walls, the molecular ordering changes from planar axial to homeotropic radial. However, the planar axial configuration, which is suitable for electronic applications, can be successfully preserved through ODPA modification for most of the pore sizes.
Surface layers have already been observed by broadband dielectric spectroscopy for Composite systems formed by adsorption of rod-like cyanophenyl derivates as probe molecules on the surface of oxide particles. In this work, features of the surface layer are reported; samples with different amounts of the probe molecules adsorbed onto oxide (nano) particles were prepared in order to study their interactions with the surface. Thermogravimetric analysis (TGA) was applied to analyze the amount of loaded probe molecules.
The density of the surface species ns was introduced and its values were estimated from quantitative Fourier transform infrared spectroscopy (FTIR) coupled with TGA. This parameter allows discriminating the composites into several groups assuming a similar interaction of the probe molecules with the hosts of a given group. An influence factor H is further proposed as the ratio of the number of molecules in the surface layer showing a glassy dynamics and the number of molecules adsorbed tightly on the surface of the support: It was found for aerosil composites and used for calculating the maximum filling degree of partially filled silica MCM-41 composites showing only one dielectric process characteristic for glass-forming liquids and a bulk behavior for higher filling degrees.