Natalia Osiecka

Signatures of glass transition in partially ordered phases

Features of glass transition in liquid crystalline nematic and smectic E, B and IA phases of selected materials observed by means of the polarising microscopy and Fourier transform infrared spectroscopy (FTIR) are reported. Evolution of cracking in the glass and a coincidence of its disappearance temperature with the glass transition temperature (Tg) on heating is shown and discussed in the context of processes that occur in the glass. The shape of temperature dependencies of absorption bands is shown as the signature of the glass transition.

Volumetric, dielectric, calorimetric and X-ray studies of smectogenic 10PBO8 at atmospheric and elevated pressures

The synthesis and pressure–volume–temperature (PVT), differential thermal analysis (DTA), dielectric and X-ray diffraction data of 2-(4-octylcarbonyloxyphenyl)-5-decylpyrimidine (10PBO8) are presented. The substance exhibits two crystalline and smectic C (SmC) phases on heating and a SmC–monotropic crystalline smectic B (SmBcr) SmBcr–crystal sequence of phase transitions on cooling. Above ca. 15 MPa, the SmBcr phase becomes enantiotropic (reversible polymorphism). The phase behaviour and molecular dynamics in the liquid crystalline phases are analysed and discussed, with the conformational component of the total entropy for the SmC–isotropic liquid transition estimated. We also calculate from the PVT results the potential parameter characterising the steepness of the interaction potential.

X-ray studies of the smectic B phase of the 4-bromobenzylidene-4′-alkoxyanilines

The results of X-ray studies of the nine members (4 ÷ 12) of the 4-bromobenzylidene-4′-alkyloxyaniline homologous series (nBBAA) in smectic B (SmB) and smectic A (SmA) phases are presented. Interestingly, no SmC phase was identified. The thickness of smectic layers in the SmA and SmB phases was estimated showing unexpectedly that in SmA it is bigger than in the SmB. For the SmB phase, orthorhombic unit cell parameters were determined as a function of temperature. The obtained data are discussed in relation to rotational dynamics.

Surface and liquid-crystalline properties of FmHnFm triblock semifluorinated n-alkanes.

A series of triblock semifluorinated n-alkanes of the general formula: F(CF2)m(CH2)n(CF2)mF, (in short FmHnFm), where m=10, 12, and n=6, 8, and 12 have been synthesized and employed for liquid crystalline studies and Langmuir monolayer characterization. Differential scanning calorimetry (DSC) measurements together with texture observation with polarizing microscope (POM) revealed the presence of liquid crystalline smectic phases for all the investigated homologs. The behavior of the studied molecules spread at the free water surface has also been investigated. Our results show for the first time that these unusual film-forming materials, which are completely hydrophobic in nature and do not possess any polar group in their structure, are surface active and form insoluble (Langmuir) monolayers at the air/water interface. Due to the fact that these molecules are chemically inert and, similar to the semifluorinated diblocks, are not toxic, they may be destined for biomedical uses as gas carriers and contrast agents, as well as in drug delivery systems.

Universal scaling of dielectric response of various liquid crystals and glass-forming liquids

Abstract We present a new generalized scaling relationship accounting both for the real and imaginary parts of the complex permittivity data. The generalized scaling procedure has been successfully used for various relaxation processes in liquid crystals (4-bromobenzylidene-4′-pentyloxyaniline, 4-bromobenzylidene-4′-hexyloxyaniline, 4′-butyl-4-(2-methylbutoxy)-azoxybenzene, 4-ethyl-4′-octylazoxybenzene), and in glass-forming liquids (glycerol, propylene carbonate, salol, cresolphthalein-dimethylether). As it is shown, one obtains common master-curve for liquid-like phases (isotropic liquid, cholesteric, nematic, smectic A), solid-like phases (smectic B, conformationally disorder crystal) and supercooled liquid phase.

Effect of flip-flop motion on dielectric spectra of highly ordered liquid crystals

This paper presents studies of dielectric response of chosen Schiff bases, which have similar molecular structures with different isomerizations of an azomethine bridging group, alkyloxy chain length with n=5 or n=6 carbon atoms, and a bromine or chlorine halogen terminal atom. Significant differences in the values of the maximum of dielectric absorption related to flip-flop molecular jumps in hexagonal smectic-B(Cry) phases have been found despite small differences of molecular dipole moments in these substances. This phenomenon is discussed in relation to the possibilities of the creation of dimers and to steric factors favoring motions.

Molecular Dynamic in Ethosuximide Glass Forming Pharmaceutical as Studied by Dielectric Relaxation Spectroscopy

Polymorphism and molecular dynamics of ethosuximide with molecules of left- and right-handed chirality have been studied in detail using dielectric spectroscopy. Density functional theory calculations of molecular conformations and dimer formation were performed to aid the interpretation of measurements. Moving window correlation analysis of the imaginary part of dielectric permittivity spectra allowed us to complete the monotropic system of phases found by the differential scanning calorimetry method. Extra transition connected with freezing-in/activation of slow molecular motions was identified in partially ordered crystal CrI phase. In high-temperature orientationally disordered CrIh and in low-temperature conformationally disordered CrIl phases, 2 relaxation processes were detected at frequency range below 105 Hz. In glass of CONDIS CrIl, β-relaxation was identified.