Investigation of chiral smectic phases and conformationally disordered crystal phases of the liquid crystalline 3F5FPhH6 compound partially fluorinated at the terminal chain and rigid core

Complementary methods are applied to investigate the phase transitions and crystallization kinetics of the liquid crystalline compound denoted as 3F5FPhH6. Two crystal phases are confirmed, and one of them is the conformationally disordered (CONDIS) phase. Complexity of the melt crystallization process is revealed by the analysis with Friedman’s isoconversional method. The melt crystallization of 3F5FPhH6 shows different mechanisms depending on temperature, which is explained by the relation between the thermodynamic driving force and the thermal energy of translational degrees of freedom. The studied compound crystallizes even during fast cooling (30 K/min), unlike similar compounds with different fluorosubstitutions of the benzene ring, which form the smectic glass for moderate cooling rates. The tendency to vitrification of the smectic phase decreases apparently with the decreasing stability width of the $SmC_{A}$* phase and the increasing relaxation time of the collective relaxation process in this phase, at least for homologues differing from 3F5FPhH6 only by the type of fluorosubstitution

Challenges for education for security in the era of asymmetric conflicts

Education for Security is a school subject which has been taught in Polish middle schools since 2009 and in secondary schools since 2012. Although the security is one of the most important needs of every person, the subject is taught only on a basic level. To fulfil its primary purpose, Education for Security should evolve together with the development of the surrounding world, in which asymmetric conflicts are one of the main threats. However, in the curricula for every level of education, there is no direct reference to such conflicts. Therefore, it is necessary to start an educational fight with asymmetric threats. This creates the necessity of implementing new models of education, in which asymmetric threats will be defined, while in classes theory will be complemented with practical assignments. It should be remembered that the social potential of a nation is an important instrument in the fight with all threats, and an educated society will provide the best way of ensuring security in both personal and structural dimensions

Influence of alkyl chain length and fluorine atoms substitution on infrared spectra of chiral liquid crystalline esters

The infrared spectra were registered for series of three-ring liquid crystalline esters, differing in the structure of alkyl chain, in the substitution of benzene ring by fluorine atoms and in the type of helicoidal structure in the chiral smectic CA phase with antiferroelectric properties. The influence of molecular structure on the shift of signals coming from carbonyl group, located in the rigid core, was observed. Keywords: liquid crystals, helicoidal structure, chiral smectic CA phase, antiferroelectric crystalline phase, infrared spectroscop

Vibrational Dynamics of a Chiral Smectic Liquid Crystal Undergoing Vitrification and Cold Crystallization

Vibrational dynamics in the glass transition and the cold crystallization process of (S)-4′-(1-methyloctyloxycarbonyl) biphenyl-4-yl 4-[7-(2,2,3,3,4,4,4-heptafluorobutoxy) heptyl-1-oxy]-benzoate (3F7HPhH7) was studied by Fourier transform infrared spectroscopy (FTIR) during cooling/heating experimental runs. The measured spectra processing was supported by quantum chemical density functional theory (DFT) calculations (frequency assignments). The perturbation-correlation moving window two-dimensional analysis (PCMW2D) was performed to examine how the height of individual absorption bands change under with temperature. Two-dimensional correlation analysis (2D-COS) was used to detect freezing-in or activation of the stochastic movements during the vitrification and the cold crystallization processes. Upon cooling, the vitrification process involves freezing-in of the stochastic movements of ester groups. Upon heating, as the cold crystallization process begins, the first to respond are the vibrations of the C–O–C and C=O groups in the rigid core

Effect of Alkyl Chain Length on the Phase Situation of Glass-Forming Liquid Crystals

The phase behaviour of the latest synthesised compound belonging to a family of (S)-4′-(1-methyloctyloxycarbonyl) biphenyl-4-yl 4-[‘m’-(2,2,3,3,4,4,4-heptafluorobutoxy) ‘m’alkoxy]-benzoates (where ‘m’ means 3, 5 or 7 methylene groups) is described by polarizing optical microscopy, differential scanning calorimetry, X-ray diffraction and Fourier-transform infrared absorption spectroscopy. It has been shown that as the length of the alkyl chain increases, a given liquid crystal possesses a greater number of mesophases and at a higher temperature it goes into the isotropic liquid phase. All examined compounds form a chiral smectic phase with antiferroelectric properties (SmCA* phase), in which the temperature range of occurrence increases with the length of the molecule. The number of methylene groups also affects the glass transition. The compound with the shortest alkyl chain (‘m’ = 3) is vitrified from the conformationally disordered crystal phase. For the compound with five -CH2- groups (‘m’ = 5), a glass transition from the monotropic high-order hexatic smectic SmXA* phase is observed. In the case of the liquid crystal with the longest carbon chain (‘m’ = 7), the vitrification from the less ordered SmCA* phase is visible. Differences in the crystallization kinetics, e.g., the nucleation-controlled mechanism for the compound with the shortest carbon chain vs. the complex phenomenon for its longer homologs, are discussed

Molecular Dynamics and Kinetics of Isothermal Cold Crystallization in the Chiral Smectogenic 3F7FPhH6 Glassformer

An investigation of the glass transition of the antiferroelectric smectic CA* phase and cold crystallization of (S)-4′-(1-methylheptylcarbonyl)biphenyl-4-yl 4-[7-(2,2,3,3,4,4,4-heptafluoro- butoxy)heptyl-1-oxy]benzoate (denoted as 3F7FPhH6) by differential scanning calorimetry, polarizing optical microscopy and broadband dielectric spectroscopy is presented. The fragility index mf = 72, classifying 3F7FPhH6 as a glassformer with intermediate fragility, was obtained from the temperature dependence of the α-process relaxation time, measured upon cooling. Duplication of the α-process was observed exclusively upon heating, before the onset of cold crystallization, and is connected with the pre-transitional effect. The presence of two crystal phases likely influences the kinetics of cold crystallization; the idea stems from a comparison with previous results for the 3F7HPhF6 and 3F7HPhH7 compounds. Additionally, the presence of the smectic Cα* sub-phase in a narrow temperature range was proved based on the differential scanning calorimetry and broadband dielectric spectroscopy results, as well as the fractal dimension analysis of the textures obtained by polarizing optical microscopy

NMR spectra of chiral smectic liquid crystals differing in helical parameters

<p>Chiral liquid crystals with three-ring rigid core were examined. The method based on the selectively reflected light was used to determine the helical pitch. The helical twist sense was worked out using the polarimetry method. ¹H and ¹³C NMR measurements were performed. The influence of three molecular structure parameters: the type of chiral centre, the length of non-chiral chain and substitution of benzene ring by fluorine atoms, on helical pitch, handedness of helical structure and values of chemical shift in proton and carbon spectra was determined. The change of the length of non-chiral terminal chain has the most significant influence on the temperature dependence of helical pitch. All tested parameters have the biggest influence on the values of chemical shift of atoms in the chiral centre.</p

Phase Sequence, Kinetics of Crystallization and Molecular Dynamics of the Chiral Liquid Crystalline Compound Forming a Hexatic Smectic Glass

The vitrification of the antiferroelectric hexatic smectic XA* phase and cold crystallization are reported for (S)-4′-(1-methylheptylcarbonyl)biphenyl-4-yl 4-[5-(2,2,3,3,4,4,4-heptafluorobutoxy) heptyl-1-oxy]benzoate. The kinetics of isothermal cold crystallization and melt crystallization are investigated, revealing that both are controlled mainly by diffusion, as indicated by decrease in the characteristic crystallization time with increasing temperature of crystallization, with an activation energy of 114 kJ/mol. A weak relaxation process is detected in a crystal phase, with an activation energy of 38 kJ/mol, implying the conformationally disordered crystal phase. The estimated fragility parameter of the investigated glass former is equal to 94.5, which indicates rather high fragility