0000000000213255
AUTHOR
Friedrich Kremer
Molecular dynamics in low-molar and polymeric ferroelectric liquid crystals
Broadband dielectric spectroscopy covering the frequency range from 10−1 Hz to 109 Hz was employed to study the molecular dynamics in low-molar and polymeric ferrroelectric liquid crystals. At frequencies below 106 Hz the ferroelectric modes, soft and Goldstone mode are observed. In the frequency regime from 106 Hz to 109 Hz a fast relaxation process is found, which is assigned to the hindered rotation of the mesogens around their long molecular axis. It turns out that the molecular dynamics is not principally different between low-molar and polymeric systems.
Tagungsnachlese Berlin: Atome, Moleküle, Quantenoptik und Plasmen (AMOP), Chemische und Polymerphysik
Ordering and mobility of ferroelectric liquid crystal dimer as studied by FT-IR spectroscopy with 2D-IR correlation analysis
Both a conservative rapid-scan FT-IR technique and a novel step-scan FT-IR technique with 2D correlation analysis were used to study the orientation and the mobility ofa ferroelectric liquid crystal dimer during switching under an electric field. The detailed mutual arrangements of different molecular segments (mesogen, poly(methylene) chain, polysiloxane chain) in a smectic C* phase were derived from the static spectra. It was shown that the long mesogen axis, the average poly(methylene) and the average polysiloxane chain axes do not coincide with each other. The hindered rotation of the carbonyl group is confirmed. Time-resolved FT-IR technique was used to follow the segmental motion with…
Giant lateral electrostriction in ferroelectric liquid-crystalline elastomers
Mechanisms for converting electrical energy into mechanical energy are essential for the design of nanoscale transducers, sensors, actuators, motors, pumps, artificial muscles, and medical microrobots. Nanometre-scale actuation has to date been mainly achieved by using the (linear) piezoelectric effect in certain classes of crystals (for example, quartz), and 'smart' ceramics such as lead zirconate titanate. But the strains achievable in these materials are small--less than 0.1 per cent--so several alternative materials and approaches have been considered. These include grafted polyglutamates (which have a performance comparable to quartz), silicone elastomers (passive material--the constri…
The dielectric α -relaxation in polymer films: A comparison between experiments and atomistic simulations
The question of whether the glass transition temperature in thin polymer films depends on the film thickness or not has given rise to heated debate for almost two decades now. One of the most puzzling findings is the seemingly universal thickness independence of the dielectric α-relaxation observed for supported films. It is puzzling not only in view of the fact that other techniques or other geometries sometimes showed a significant shift of as a function of film thickness, but more so, because computer simulations for all types of polymer film models revealed changes in the structure and dynamics close to a hard surface or a free surface. Our results suggest to explain this apparent contr…
LC-Polymers with Axial Chirality
Abstract Liquid crystalline polymers with axial chirality are prepared. These polymers are chiral, not due to a single asymmetric carbon atom, but due to a larger molecular fragment, which is chiral as a whole. They exhibit cholesteric and chiral smectic C* phases. Dielectric spectroscopy proves strong ferroelectric properties in the chiral smectic C* phases of these polymers.
Optical suppression of ferroelectricity in polysiloxane copolymers with chiral and photochromic side groups
The ferroelectricity of surface-stabilized aligned films of polysiloxane copolymers containing chiral esters and photochromic azobenzene moieties within the side groups is suppressed on UV irradiation and is rebuilt on visible irradiation. The liquid crystalline polymer (Sc* 64 SA 80 i) shows ferroelectric behavior below 64°C. The photoinduced modification of supramolecular order and the corresponding changes in its dynamics are studied by polarized UV/vis spectroscopy and broad band dielectric spectroscopy (10−2–105 Hz). The dielectric measurements show that UV irradiation causes a loss of ferroelectricity within an interval of 10 K below the phase transition temperature. The photochemical…
Guided Optical Waves in a Ferroelectric Liquid Crystal Layer: A Birefringence Analysis of Molecular Orientation on the Switching Process
Abstract Guided optical waves are very sensitive to the alteration of optical properties of dielectric media. In this report, we demonstrate the use of guided waves for studying dynamic behavior of ferroelectric liquid crystals. Propagating light in the anisotropic medium suffers a birefringent effect, which causes coupling of p- and s-polarized light. Theoretical calculations, based on the Maxwell equations, successfully describe this phenomena, using a dielectric tensor diagonal in molecular coordinates, which is transformed to the laboratory coordinate system by three Euler angles. The waveguide measurements are able to probe the molecular orientation and movement of the liquid crystal m…
Time-Resolved Fourier-Transform Infrared Spectroscopy on the Inter- and Intramolecular Orientational Dynamics in Ferroelectric Liquid Crystalline Dimers
On a base of time-resolved step-scan IR-spectroscopy data, we present a detailed model of the segmental reorientation during the ferroelectric and electroclinic switching of a chiral liquid crystalline dimer. We detected that the magnitude of the motion of the molecular segments differ from each other: The tilt angle is maximal for the mesogens and minimal for the ``virtual polysiloxane backbone.'' In contrast to a recently published conjecture, we prove that in the \ensuremath{\mu}s scale the responses of different molecular segments are unambiguously synchronous with each other.
Relaxation and charge transport in mixtures of zwitterionic polymers and inorganic salts
Dielectric spectroscopy is employed to analyze the molecular dynamics and the charge transport in mixtures of zwitterionic polymers of the type poly(3-[N-(omega-methacryloyloxyalkyl)-N, N-dimethylammonio]propanesulfonate) with sodium iodide in the frequency range of 10(2) Hz-10(7) Hz and in the temperature range of 110 K-400 K. The amount of inorganic salt added varies from 0-200 mol-% relative to the number of zwitterionic groups present in the polymer, contributing strongly to the conductivity. One relaxation process is observed whose relaxation rate depends strongly on the length of the aliphatic spacer between the polymethacrylate main chain and the zwitterionic group. Exhibiting an Arr…
Molecular dynamics in liquid crystalline N-acylated oligoethylenimines as studied by broadband dielectric spectroscopy
The molecular dynamics and the charge transport in six liquid crystalline N-acylated oligoethylenimines were investigated by dielectric spectroscopy. The dielectric spectra in the temperature range from 125 K up to 400 K and in the frequency range between 10 -2 Hz and 10 7 Hz could be described by a conductivity contribution and three relaxation processes. The molecular assignment of the α-process is a relaxation of the rigid benzamide unit. Its mean relaxation time is influenced by the length of the alkoxy side chains, the spacer length (ethylene or propylene groups) and the neighboring repeating units. In the columnar mesophase this process is cooperative due to sterical hindrance. A norm…
The molecular dynamics of thermoreversible networks as studied by broadband dielectric spectroscopy
Polybutadienes modified by a small number of 4-phenyl-1,2,4-triazoline-3,5-dione form thermoreversible networks via hydrogen bonding between the polar stickers. The molecular dynamics of systems with different contents of polar stickers are investigated by broadband dielectric spectroscopy in the frequency regime of 10−1–109 Hz. Unmodified polybutadiene shows two relaxation processes, the α-relaxation which is correlated to the dynamic glass transition of the polybutadiene, and a β-relaxation corresponding to a local relaxation of polybutadiene segments. In the polar functionalized systems, besides these two relaxations, an additional relaxation process (called α*) is observed, which occurs…
FTIR spectroscopy of smectic elastomer films under lateral strain
Polarized Fourier transform infrared (FTIR) spectroscopy is used to study the strain‐induced compression of molecular layers in oriented smectic liquid crystal elastomer films. A reversible change of the smectic layer thickness in SmA and SmC* films in response to external strain was revealed earlier by optical reflectometry and X‐ray measurements. However, these methods cannot probe the mechanism of layer compression on a molecular level. Polarized FTIR spectra show that the induced mesogenic tilt, one of the possible mechanisms, is too small to provide the dominating contribution to the layer shrinkage. The FTIR absorbance spectra of stretched samples are also evidence that there are no s…
Induced roughness in thin films of smectic-C* elastomers
The surface topography of a thin homeotropically oriented film of ferroelectric smectic-C* elastomer is studied by atomic force microscopy. We find that when the film is mechanically stretched, its surface becomes increasingly rough, in proportion to the applied strain. The effect depends strongly on the nature of crosslinks forming the elastomer network. The r.m.s. roughness correlations show a consistent trend [h(x) − h(0)]21/2 ~ (x/ξ)0.5. We introduce a theoretical model assuming that random disorder in the smectic tilt angle is induced by deformations via the coupling of mesogens to the elastic network. The model describes the observed power law and gives a prediction for the correlatio…