Four compounds from 3FmHPhF homologous series of chiral smectogenic fluorinated compounds (m = 2, 4, 5, 6) were studied by frequency domain dielectric spectroscopy, electro-optic measurements, X-ray diffraction and differential scanning calorimetry. Values of the relaxation time and dielectric increment of relaxation processes versus temperature and bias field were determined. The temperature-dependent tilt angles, spontaneous polarisations, switching times, rotational viscosities, and average intermolecular distances and correlation lengths within smectic layers were obtained. Experimental results were supplemented by density functional theory calculations of isolated 3FmHPhF molecular geometries, and the relationship between the molecular structures and the transverse component of their dipole moments was studied for the mesogens with m = 2, 4, 5, 6, 7. The results are discussed in terms of the length of the CmH2m flexible carbon chain of the homologues.
Four new synthesised liquid crystalline compounds belonging to the homologous series of fluorinated biphenyl benzoate esters have been studied to compare their dielectric and electrooptic properties. Three of the studied compounds exhibited ferro- and antiferroelectric phases while one of them exhibited only one liquid crystalline phase – ferroelectric SmC*. No paraelectric phase was detected and straight transition between isotropic liquid and ferroelectric phases was observed for all studied compounds. Tilt angle for all of the studied compounds was equal to ca. 45ᵒ in the liquid crystalline phases, except temperature range close to the isotropic liquid–ferroelectric smectic phase transition. Temperature dependences of helical pitch, spontaneous polarisation and switching time have been determined. Based on XRD results, temperature dependence of the layer thickness has also been found. Only one relaxation process has been revealed in the ferroelectric as well as antiferroelectric phases, even the bias field up to 8 V/µm was applied. The dielectric and electrooptic data are discussed based on the mean-field theory predictions.
Physical properties of the partially fluorinated compound 3F5FPhF, with hockey stick-like molecules, were studied by complementary methods. Apart from the already reported paraelectric SmA*, ferroelectric SmC* and antiferroelectric SmC*A phases, the presence of the smectic C*α subphase in the phase sequence was proved by differential scanning calorimetry, polarising optical microscopy, electro-optic and dielectric spectroscopy methods. The temperature dependence of the smectic layer thickness and correlation length of the lateral short-range order was determined by X-ray diffraction. Based on dielectric measurements three relaxation processes were revealed in the antiferroelectric SmC*A phase (two collective: PL, PH and one molecular: s-process), two collective ones (Goldstone and soft modes) were found both in the ferroelectric SmC* phase and SmC*α subphase while one relaxation process (soft mode) in the paraelectric SmA* phase. The results were compared with that obtained for other structurally similar compounds, and it was shown that even addition of one methylene group to the side chain influences much on the physical properties.
The main goal of this paper was to study the dielectric properties of hybrid binary and ternary composites based on biodegradable polymer Ecoflex®, single walled carbon nanotubes (SWCN), and liquid crystalline 4′-pentyl-4-biphenylcarbonitrile (5CB) compound. The obtained results were compared with other created analogically to Ecoflex®, hybrid layers based on biodegradable polymers such as L,D-polylactide (L,D-PLA) and polycaprolactone (PCL). Frequency domain dielectric spectroscopy (FDDS) results were analyzed taking into consideration the amount of SWCN, frequency, and temperature. For pure Ecoflex®, two relaxation processes (α and β) were identified. It was shown that the SWCN admixture (in the weight ratio 10:0.01) did not change the properties of the Ecoflex® layer, while in the case of PCL and L,D-PLA, the layers became conductive. The dielectric constant increased with an increase in the content of SWCN in the Ecoflex® matrix and the conductive behavior was not visible, even for the greatest concentration (10:0.06 weight ratio). In the case of the Ecoflex® polymer matrix, the conduction relaxation process at a frequency ca. several kilohertz appeared and became stronger with an increase in the SWCN admixture in the matrix. Addition of oleic acid to the polymer matrix had a smaller effect on the increase in the dielectric response than the addition of liquid crystal 5CB. Fourier transform infrared (FTIR) results revealed that the molecular structure and chemical character of the Ecoflex® and PCL matrixes remained unchanged upon the addition of SWCN or 5CB in a weight ratio of 10:0.01 and 10:1, respectively, while molecular interactions appeared between L,D-PLA and 5CB. Moreover, adding oleic acid to pure Ecoflex® as well as the binary and ternary hybrid layers with SWCN and/or 5CB in a weight ratio of Ecoflex®:oleic acid equal to 10:0.3 did not have an influence on the chemical bonding of these materials.
The effect of the presence of titanium dioxide in two new imines, (E,E)-(butane-1,4-diyl)bis(oxybutane-4,1-diyl) bis(4-{[(benzo[d][1,3]thiazol-2-yl)methylidene]amino}benzoate) (SP1) and (E)-N-[(benzo[d][1,3]thiazol-2-yl)methylidene]-4-dodecylaniline (SP2), on the properties and stability of imine:TiO2 composites for organic device applications were examined. The investigated titanium dioxide (in anatase form, obtained via the sol–gel method) exhibited a surface area of 59.5 m2/g according to Brunauer–Emmett–Teller theory, and its structure is a combination of both meso- and microporous. The average pore diameter calculated by the Barrett–Joyner–Halenda method was 6.2 nm and the cumulative volume of pores was 0.117 m3/g. The imine SP1 exhibited columnar organization (Col), while SP2 revealed a hexagonal columnar crystalline phase (Colhk). The imine:TiO2 mixtures in various weight ratio (3:0, 3:1, 3:2, 3:3) showed a lower energy gap and HOMO–LUMO energy levels compared to pure TiO2. This implies that TiO2 provides not only a larger surface area for sensitizer adsorption and good electron collection, but also causes a shift of the imine energy levels resulting from intermolecular interaction. Also the temperature of the phase transition was slightly affected with the increase of TiO2 concentration in imine-based composites. The changes observed in the Fourier transform middle-infrared absorption (FT-MIR) spectra confirmed the significant influence of TiO2 on structural properties of both investigated imines. Similar interactions of oxygen vacancies existing on the TiO2 surface with SP1 and SP2 were observed. The imine:TiO2 mixtures showed good air stability and reusability, which demonstrates its potential for organic device applications.