0000000000230651
AUTHOR
Ralf Stannarius
Strain‐induced compression of smectic layers in free‐standing liquid crystalline elastomer films
The deformation of oriented smectic liquid crystal elastomer films with smectic layers parallel to the film surface was studied using optical reflectometry and small angle X‐ray diffraction. Reflectometry data show that in the chosen material, in‐plane strain causes a change in the optical thickness of the free‐standing films. Small angle X‐ray scattering was used to explore the molecular origin of this effect. The X‐ray scattering data confirm that the change in optical thickness originates from the compression of the individual smectic layers. The measured Poisson ratio in the smectic A and C* phases is close to ½, in contrast to the smectic elastomers investigated earlier by Nishikawa et…
Structure and elastic properties of smectic liquid crystalline elastomer films
Mechanical measurements, x-ray investigations, and optical microscopy are employed to characterize the interplay of chemical composition, network topology, and elastic response of smectic liquid crystalline elastomers (LCEs) in various mesophases. Macroscopically ordered elastomer films of submicrometer thicknesses were prepared by cross linking freely suspended smectic polymer films. The cross-linked material preserves the mesomorphism and phase transitions of the precursor polymer. The elastic response of the smectic LCE is entropic, and the corresponding elastic moduli are of the order of MPa. In the tilted ferroelectric smectic-C* phase, the network structure plays an important role. Du…
Free-standing smectic LC elastomer films
ABSTRACTWe probe the mesophase transitions and layer structures in thin ordered smectic liquid crystalline elastomer films by means of x-ray diffraction and optical microscopy. Oriented elastomer films of submicrometer thickness are produced by crosslinking freely suspended smectic polymer films. After crosslinking, the mesomorphism is similar to that of the precursor polymer. Smectic layers align parallel to the film plane. The layer spacing increases with temperature in the SmC* phase while it decays above the SmC*-SmA transition.
Preparation of actuating fibres of oriented main-chain liquid crystalline elastomers by a wetspinning process
We present a versatile method to prepare oriented fibres with a defined thickness from main-chain liquid crystalline elastomers. A microfluidic setup is utilized to inject a solution of a photocrosslinkable smectic A main-chain polymer into a co-flowing stream of silicone oil. Diffusion of the solvent into the oil yields solid polymer filaments that are crosslinked in a continuous way by UV-irradiation. The obtained fibres are highly oriented and show a reversible and significant contraction during the liquid crystal's phase transition.
Gelation of smectic liquid crystal phases with photosensitive gel forming agents.
This paper studies the potential of 3 newly synthesized low molecular weight gelling agents (2 of them with azo groups) with the semicarbazide group as a H-bonding motif to gel the smectic phase of a commercial chiral smectic C material. To detect gelation two methods were used: the stabilization of the director pattern, which measures the interaction of the physical gel network with the LC-director, and the suppression of the onset of electrohydrodynamic instabilities, which measures the increase of viscosity. Special emphasis was put on the influence of the photochemical - isomerization of the gelling agents on gelation.From the stabilization of the director pattern an elastic component c…
De Vries smectic A phase formed by a liquid crystal side chain copolymer? A13C NMR study
We study the orientation and order parameter of a liquid crystalline random side chain copolymer by 13C NMR. Evidence has previously been presented that this material forms a de Vries smectic A phase. The NMR data show that the molecular tilt angle in the smectic A phase is very small or zero and the smectic A–smectic C* transition is attributed predominantly to a change of the molecular tilt rather than azimuthal ordering. We discuss the NMR results in the context of earlier X‐ray and elastic characterizations of structurally similar materials.
Mechanical manipulation of molecular lattice parameters in smectic elastomers.
Smectic liquid crystalline elastomers (SLCE) represent unique materials that combine a 1-D molecular lattice arrangement and orientational order with rubber-elasticity mediated by a polymer network. Such materials may exhibit large thermo-mechanical, opto-mechanical and electro-mechanical effects, due to the coupling of macroscopic sample geometry and microscopic structural features. It is shown that the molecular layer dimensions in the smectic phases can be influenced reversibly by macroscopic strain of the material. We present a microscopic model on the basis of experimental results obtained by mechanical dilatation measurements, optical interferometry, X-ray scattering, (13)C NMR, FTIR …
Mechanical and optical properties of continuously spun fibres of a main-chain smectic A elastomer
Oriented smectic liquid crystal elastomer fibres are prepared with a special wet-spinning technique. The continuous spinning process in principle allows the preparation of fibres with arbitrary length. In comparison to ordinary rubbers, they have unique mechanical properties that qualify them as potential candidates for mechanical actuator applications. We demonstrate that these fibres show a remarkable contraction and extension at the transition from the ordered smectic to the disordered isotropic phase. We characterise their most relevant physical properties, viz. the thermally driven shape changes, stress–strain relations and optical birefringence, by optical and mechanical measurements.
Hydrogen bonded ferroelectric liquid crystal gels in freely suspended film geometry
We study freely suspended films of smectic C* liquid crystalline gels by means of polarizing microscopy. The gel point of the system is determined from the suppression of flow in the films. The network of hydrogen bonds is mechanically fragile but stabilizes orientation patterns of the sample, in particular it stores the texture present during gelation. Electro-optical experiments are performed to study the dynamics of the sample reorientation under the influence of in-plane electric fields. Mesogen orientation and optical properties can be switched in electric fields of a few kV m−1. After removal of electric fields, the network restores the ‘frozen-in’ texture. This texture can be erased …
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…
Differences between smectic homo‐ and co‐polysiloxanes as a consequence of microphase separation
This paper compares smectic phases formed from LC‐homo‐ and LC‐co‐polysiloxanes. In the homopolysiloxane, each repeating unit of the polymer chain is substituted with a mesogen, whereas in the copolysiloxanes mesogenic repeating units are separated by dimethylsiloxane units. Despite a rather similiar phase sequence of the homo‐ and co‐polysiloxanes—higher ordered smectic, smectic C* (SmC*), smectic A (SmA) and isotropic—the nature of their phases differs strongly. For the copolymers the phase transition SmC* to SmA is second order and of the ‘de Vries’ type with a very small thickness change of the smectic layers. Inside the SmA phase, however, the smectic thickness decreases strongly on ap…
Study of smectic elastomer films under uniaxial stress
We study the mechanical properties of free-standing films of smectic liquid crystalline elastomers. Macroscopically ordered elastomer films of submicrometer thickness are prepared from freely suspended smectic A polymer films by photo crosslinking. The deformation characteristics depend criticically on the sample composition, in particular on the density of mesogenic side chains at the siloxane backbone. In materials where the siloxane backbone is only partially substituted (dilute systems), a uniaxial stretching of the films in the layer plane is accompanied by a shrinkage of the smectic layers. This layer shrinkage is to only a minor extent achieved by the induction of a molecular tilt. W…
Elastic Properties of Liquid Crystal Elastomer Balloons
We introduce a method to measure elastic properties of smectic liquid crystalline elastomers. Freely suspended smectic polymer films containing photoreactive groups are inflated to spherical bubbles and crosslinked by UV light irradiation. After crosslinking, the balloon volume is varied and elastic properties of the material are determined from the relation between radius and inner excess pressure. The influence of the network topology on the elastic behaviour is discussed.