Search Results (16)

Ferroelectric and antiferroelectric smectic liquid crystalline (LC) phases are still at the center of investigations and interests for both their fundamental properties and variety of technological applications. This review aims to report the main contributions based on different nuclear magnetic resonance (NMR) techniques to the study of chiral liquid crystalline calamitic mesogens forming smectic phases, such as the SmA, the SmC* (ferroelectric), and the SmC*_A (antiferroelectric) phases. ²H NMR and ¹³C NMR techniques and their combination were of help in clarifying the local orientational properties (i.e., the molecular and fragments’ main orientational order parameters) at the transition between the SmA and the SmC* phases, and in the particular case of de Vries liquid crystals, NMR studies gave important clues regarding the actual models describing the molecular arrangement in these two phases formed by de Vries LCs. Moreover, this review describes how the combination of ²H NMR relaxation times’ analysis, ¹H NMR relaxometry, and ¹H NMR diffusometry was successfully applied to the study of chiral smectogens forming the SmC* and SmC*_A phases, with the determination of relevant parameters describing both rotational molecular and internal motions, collective dynamics, and translational self-diffusion motions. Several cases will be reported concerning NMR investigations of chiral ferroelectric and antiferroelectric phases, underlining the great potential of combined NMR approaches to the study of supramolecular, conformational, and dynamic properties of liquid crystals. Full article

Viscosity, elasticity, and viscoelastic properties are one of the most fundamental properties of liquid crystalline materials; the main problem in determining these properties is the multitude of physical parameters needed to determine the values of elasticity and viscosity constants. In this paper, a number of different measurement methods for the complete characterization of viscoelastic properties for smectic liquid crystalline materials and their mixtures are analyzed, both theoretically and experimentally. The way in which viscoelastic material constants are determined depends mainly on the application/purpose of the materials under study. The subject of this work was to review the methods used to determine viscoelastic effects in ferroelectric and antiferroelectric chiral liquid crystals, their mixtures, composite materials, and even in dielectric systems, which would bear the hallmark of a universal method allowing the application of sufficiently low electric fields. In the case of chiral liquid crystals with ferroelectric and antiferroelectric phases and their subphases, the following assumption applies: fulfilment of Hooke’s law (in the case of elastic coefficients) and preservation of laminar flow (in the case of viscosity coefficients). Full article

The dielectric properties of synclinic (ferroelectric SmC*) and anticlinic (antiferroelectric SmC_A*) smectic liquid crystals composed of molecules of one chiral version (S) are presented and compared with properties of racemic mixture (R, S), showing SmC and SmC_A phases. The racemic mixture completely loses its ferroelectric and antiferroelectric properties. Surprisingly, only one dielectric mode observed in the antiferroelectric SmC_A* phase disappeared in the dielectric response of the racemic SmC_A phase. Additionally, we observed that in the SmC phase, seen in the racemic mixture, the weak dielectric mode (named the X mode) is detected, which seems to be the continuation of the P_L mode existing in the racemic SmC_A. Moreover, this mode in the racemic SmC has nothing to do with the Goldstone mode, typical for the SmC* phase. This paper describes in detail the real and imaginary parts of dielectric permittivity in smectic phases for the enantiomer and racemate with and without a DC field, compares the properties of the X and P_L modes, and discusses the full scheme of dielectric modes in enantiomer and racemate. Full article

Orthoconic antiferroelectric liquid crystals (OAFLCs) represent unique self-organized materials with significant potential for applications in photonic devices due to their sub-microsecond switching times and high optical contrast in electro-optical effects. However, almost all known OALFCs suffer from low chemical stability and short helical pitch values. This paper presents the synthesis and study results of two chiral AFLCs, featuring a four-ring structure in the rigid core and high chemical stability. The mesomorphic properties of these compounds were investigated using polarizing optical microscopy and differential scanning calorimetry. Spectrometry and electro-optical studies were employed to estimate the helical pitch, tilt angle, and spontaneous polarization of the synthesized compounds and the prepared mixtures. All studied compounds exhibit enantiotropic chiral smectic mesophases including the SmA*, the SmC*, and a very broad temperature range of the SmC_A* phase. Doping top-modern antiferroelectric mixture with synthesized compounds offers benefits such as increased helical pitch and tilt angle values without significantly influencing spontaneous polarization. This allows the prepared mixture to be regarded as an OAFLC with high optical contrast, characterized by an almost perfect dark state. These valuable physicochemical and optical properties suggest significant potential of studied materials for practical applications. Full article

Since the discovery of the first ferroelectric liquid crystal (FLC) in the chiral smectic C (SmC*) phase, ferroelectricity in liquid crystals has attracted much attention due to not only the fundamental interest but also the applications. This review focuses on the evolution of the design concept for ferroelectric smectic liquid crystals. It progresses from considering macroscopic phase symmetry to designing intermolecular interactions. For the purpose of understanding the molecular organization in smectic phases, we propose a dynamic model of constituent molecules in the smectic A (SmA) and SmC* phases based on ¹³C NMR studies. Then, we follow the structure–property relationship in ferroelectric SmC* liquid crystals for FLC displays. We reconsider de Vries-like materials that can provide defect-free alignment. We pay attention to the electro-optical switching in the chiral de Vries smectic A phase. Finally, we show several liquid crystals exhibiting polar smectic A phases and discuss how the polar order occurs in the highest symmetric smectic A phase. Full article

Polymer-stabilized liquid crystals (PSLCs) are multi-functional materials consisting of polymer networks in a continuous phase of liquid crystals (LCs), of which polymer networks provide anchoring energy to align the LCs. A number of improvements are detailed, including polymer-stabilized nematic liquid crystals (PSNLCs), polymer-stabilized cholesteric liquid crystals (PSCLCs), polymer-stabilized blue phase liquid crystals (PSBPLCs), polymer-stabilized smectic liquid crystals (PSSLCs), polymer-stabilized ferroelectric liquid crystals (PSFLCs), and polymer-stabilized antiferroelectric liquid crystals (PSAFLCs) in this review. Polymer stabilization has achieved multiple functionalities for LCs; in smart windows, a sufficiently strong electric field allows the LCs to reorient and enables switching from a scattering (transparent) state to a transparent (scattering) state. For broadband reflectors, the reflection bandwidth of LCs is manually tuned by electric fields, light, magnetic fields, or temperature. PSBPLCs open a new way for next-generation displays, spatial light modulators, sensors, lasers, lenses, and photonics applications. Polymer networks in PSFLCs or PSAFLCs enhance their grayscale memories utilized in flexible displays and energy-saving smart cards. At the end, the remaining challenges and research opportunities of PSLCs are discussed. Full article

Viscoelastic properties are one of the most fundamental properties of chiral liquid crystals. In general, their determination is not a straightforward task. The main problem is the multitude of physical parameters needed to determine the value of the elasticity and viscosity constants. It is also necessary to consider the character of a respective phase. This problem is particularly important in the case of chiral phases such as ferroelectric and antiferroelectric phases or in the blue phases. There are several experimental methods to measure viscosity and elasticity constants in chiral phases. These methods use various phenomena to detect deformation, e.g., light transmission, polarization current, light modulation, dielectric constant and helix deformation or helix unwinding. Commonly, an external electric field is used to induce deformation, the homogeneity of which inside the cell is essential. This study is focused on the analysis of the effect of laser photobleaching on the electro-optic properties of the antiferroelectric liquid crystal and on the homogeneity of the electric field. The results obtained by confocal microscopy as a function of the cell depth are presented. The influence of the stabilization procedure of the isolated region performed by controlled laser photobleaching on the electro-optic properties has been studied. The observation was conducted using a polarizing microscope, and numerical analysis of two-dimensional colored textures was performed. The obtained results suggest that laser photobleaching can produce an anchoring effect, which has a positive effect on the electro-optic properties of antiferroelectric liquid crystal. Full article

The vitrification of the antiferroelectric hexatic smectic X_A* 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. Full article

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 (SmC_A* 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 SmX_A* phase is observed. In the case of the liquid crystal with the longest carbon chain (‘m’ = 7), the vitrification from the less ordered SmC_A* 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. Full article

Comparative study of chiral liquid crystalline (S)-(1)-4’-(1-methylheptylcarbonyl) biphenyl-4-yl 4-[4-(2,2,3,3,4,4,4-heptafluorobutoxy)butyl-1-oxy] benzoate (4HH) and (S)-4’-(1-methylheptyloxycarbonyl)biphenyl-4-yl 4-[4-(2,2,3,3,4,4,4-heptafluorobutoxy) butyl-1-oxy]-2,3-difluorobenzoate (4FF) is performed by complementary methods. For 4HH melting of the low-temperature crystal phase and subsequent cold crystallization (from antiferroelectric smectic ${\mathrm{C}}_{\mathrm{A}}^{*}$ phase to the high-temperature crystal phase) are reported, crystallization kinetics is examined and a monotropic hexatic ${\mathrm{SmX}}_{\mathrm{A}}^{*}$ phase is observed on cooling. For 4FF rich polymorphism in the solid state is investigated mainly by simultaneous X-ray diffraction and differential scanning calorimetry measurements. Influence of fluorosubstitution on structural, electro-optic and dielectric properties of the smectic phases is reported. Unit cell parameters of crystal phases of 4HH and 4FF are determined. The reported results show that the double fluorosubstitution slows down the Goldstone mode and P_H phason in the smectic phases and facilitates crystallization. Full article

The 1980s saw the development of ferroelectric chiral smectic C (SmC*) liquid crystals (FLCs) with a clear focus on their application in fast electro-optic devices. However, as the only known fluid ferroelectric materials, they also have potential in other applications, one of which is in heat-exchange devices based on the electrocaloric effect. In particular, ferroelectric liquid crystals can be both the electrocaloric material and the heat exchanging fluid in an electrocaloric device, significantly simplifying some of the design constraints associated with solid dielectrics. In this paper, we consider the electrocaloric potential of three SmC* ferroelectric liquid crystal systems, two of which are pure materials that exhibit ferroelectric, antiferroelectric, and intermediate phases and one that was developed as a room-temperature SmC* material for electro-optic applications. We report the field-induced temperature changes of these selected materials, measured indirectly using the Maxwell method. The maximum induced temperature change determined, 0.37 K, is currently record-breaking for an FLC and is sufficiently large to make these materials interesting candidates for the development for electrocaloric applications. Using the electrocaloric temperature change normalised as a function of electric field strength, as a function of merit, the performances of FLCs are compared with ferroelectric ceramics and polymers. Full article

Modification of the physical properties of the (S)-MHPOBC antiferroelectric liquid crystal (AFLC) by doping with low concentrations of gold nanoparticles is presented for the first time. We used several complementary experimental methods to determine the effect of Au nanoparticles on AFLC in the metal–organic composites. It was found that the dopant inhibits the matrix crystallization process and modifies the phase transitions temperatures and switching time, as well as increases the helical pitch and spontaneous polarization, while the tilt angle slightly changes. We also showed that both the LC matrix and Au nanoparticles show strong fluorescence in the green light range, and the contact angle depends on the temperature and dopant concentration. Full article

The behavior of two newly formulated bi-component orthoconic antiferroelectric liquid crystalline (OAFLC) systems, i.e., the Compound A + Compound B mixture system and Compound C + Compound B mixture system has been discussed in light of temperature and concentration dependencies of helical pitch length, spontaneous polarization, relaxation time, bulk viscosity, and the anchoring energy strength coefficient, together with static dielectric permittivity (ε) and dielectric anisotropy. Compound A + Compound B mixtures possess spontaneous polarization between 190–340 nC.cm⁻² and fast relaxation times between 190–320 µs in the smectic antiferroelectric SmC_A* phase at room temperature. Compound C + Compound B mixtures also have a spontaneous polarization in the range of 190–280 nC.cm⁻² and relaxation times in the range of 190–230 µs at room temperature. Most of the mixtures have a helical pitch below one micrometer in the SmC_A* phase. These advanced mixtures show a broad temperature range of the antiferroelectric SmC_A* phase, fast switching of molecules under an applied electric field, negative dielectric anisotropy and a short helical pitch, confirming the advantage of designing new polymer-stabilized OAFLC that is targeted for novel application in sensing devices, utilizing the fast responsive electro-optical modulation elements. Full article

The study of chiral symmetry breaking in liquid crystals and the consequent emergence of ferroelectric and antiferroelectric phases is described. Furthermore, we show that the frustration between two phases induces a variety of structural phases called subphases and that resonant X-ray scattering is a powerful tool for the structural analysis of these complicated subphases. Finally, we discuss the future prospects for clarifying the origin of such successive phase transition. Full article

We present small-angle X-ray scattering, polarized optical microscopy and electric current measurements of a sulfur-containing bent-core liquid crystal material for characterization of the layer and director structures, thermally and electrically driven transitions between antiferroelectric and ferroelectric structures and switching properties. It was found that the material has polarization-modulated homochiral synclinic ferroelectric (SmC_sP_Fmod), homochiral anticlinic antiferroelectric (SmC_aP_A) and racemic synclininc antiferroelectric (SmC_sP_A) structures that can be reversibly switched between each other either thermally and/or electrically. High switching polarization combined with softness of the liquid crystalline structure makes this compound a good candidate for applications in high-power capacitors and electrocaloric devices. Full article