Soft mode and related behaviour in the SmA and SmC* phases of a ferroelectric liquid crystalline polymer by dielectric spectroscopy

Anomalous dielectric relaxation behaviour is observed in the ferroelectric liquid crystalline polymer (viz. ferroelectric copolysiloxane (R)-COPS 11-10) around the ferroelectric SmC* to paraelectric SmA phase transition. Measurements have been performed on sample of thickness ～10 μm in indium-tin-oxide coated cell in the frequency range 10 Hz to 13 MHz. With increase of temperature, a gradual shift of the soft mode frequency towards the higher frequency side was observed, while a decrease in the relaxation strength was seen with the corresponding increase in temperature. The shifts of the soft modes in the SmC* and SmA phase are considered to be due to change in the viscosity of the polymer, as an increase in viscosity increases fluctuations of the coupling between the dipoles in the network even far from the paraelectric-ferroelectric phase transition. Application of a bias field causes a shift of the critical frequency towards the higher frequency side, while the dielectric strength (δε) decreases under the bias field. The Cole-Cole fitting parameters obtained from the best fit of the dielectric constant data are found to be consistent with other similar materials. Another relaxation mode (molecular mode) was also observed which comes into play in both the smectic phases (SmC% and SmA) and contributes to the dielectric permittivity.     

Critical behaviour of the order parameters at the SmC* to SmA phase transition in a ferroelectric liquid crystal mixture

Critical behaviour of the order parameters has been investigated in the ferroelectric liquid crystal mixture ZLI‐3654 in a 7.5 µm thick planar cell. The temperature dependence of the primary (tilt angle) and secondary (spontaneous polarisation) order parameters is considered. The critical exponent (β) has been evaluated from the fitting of the temperature dependence of the experimental data for both tilt angle and spontaneous polarisation. Experimental results are compared with the predictions of the de Gennes and Landau models.     

Broadband dielectric spectroscopy on a discotic liquid crystalline polymer

Broadband dielectric spectroscopy is employed for the first time to study the molecular dynamics in discotic liquid crystalline polymers. One dielectric relaxation process is found which is strongly broadened and asymmetric. It is assigned a local hindered rotation of the ester groups attaching the spacer to the discotic mesogen. This assignment is supported by NMR measurements on the identical substance.Dedicated to Prof. E. W. Fischer on the occasion of his 60th birthday.     

Broad band dielectric relaxation spectroscopy of molecular reorientation in smectic liquid crystalline phases (SmA, SmB, and CrE)

Broad band dielectric measurements reveal that the reorientation of non-chiral rod-shaped low molecular mass liquid crystals is active around their molecular long axis and a short axis, in the smectic A and hexatic smectic B phase, respectively, as well as in the soft crystalline E phase of two isomeric stilbene compounds possessing an equal molecular length of their all-trans -conformations. One ('generalized') Arrhenius equation describes the temperature dependence of the reorientation around a molecular short axis for each of these phases of both compounds. A change of the activation energy related to the reorientation around a molecular short axis is accompanied by a slowing down of the reorientation around the molecular long axis in the soft crystalline E phase in one of these compounds, compelling evidence for a coupling of both reorientations. This result is discussed with respect to the biaxiality of the soft crystalline E phase.     

A dielectric study of three chiral liquid crystals presenting SmC*FI phases

We have performed a detailed dielectric study of three compounds presenting ferrielectric phases over large temperature intervals. The relaxation processes detected in the SmC*_FI phases are highly polidispersive. We have repeatedly observed the surface layer mode described by Bourny et al. [1] and a weak ferrielectric mode, whose relaxation frequency is always higher on heating than on cooling runs. The temperature interval where SmC*_FI phases occur is apparently independent of cooling/heating rates and of the history of the sample.     

Synthesis and SmC* properties of chiral liquid crystalline terephthalates

Chiral ester derivatives of terephthalic acid containing one, three, or five phenyl rings were prepared by using (S)-2-methylbutanol or (R)-2-chloropropanol as starting materials. The one-ring terephthalates did not exhibit any liquid crystalline phases, but one of them was used as a chiral dopant in ferroelectric mixtures. Elongation of the aromatic core structure to three and five phenyl rings stabilized the SmA phase, whereas a (monotropic) SmC* phase was detected in some three-ring and five-ring derivatives. In ferroelectric mixtures based on the terephthalates, spontaneous polarizations up to 340 nC cm2 were measured.     

Structural and conformational investigations in SmA and different SmC phases of new hockey stick-shaped compounds

New meta -substituted homologous three-ring mesogens, the 4-(3-n-decyloxyphenyliminomethyl) phenyl 4-n-alkyloxybenzoates, have been synthesized, which are non-linear due only to the attachment of one of the alkyloxy groups in a meta -position. The mesophases were studied by optical microscopy, differential scanning calorimetry, NMR spectroscopy, X-ray diffraction, and electro-optical and dielectric measurements. Unusual phase behaviour was observed on varying the length of the terminal chain. The most interesting finding is the occurrence of two polymorphic tilted smectic phases designated as SmC₁ and SmC₂. The existence of these phases was revealed by calorimetric studies and also from the pronounced difference in optical textures. It was shown from NMR measurements that the molecular orientation changes from a synclinic to an anticlinic arrangement in the SmC₁ to SmC₂ phase transition. It has also been shown, using NMR, that the SmC₁ → SmC₂ phase transition in these compounds is accompanied by a conformational change in the molecular fragment containing the aromatic ring with the meta-substituted terminal alkyloxy chain. This conformational change is linked to a change in the shape of the molecules and leads to a different packing of the molecules within the layers of the SmC₂ phase. From dielectric measurements an increase by a factor of two was detected in the molecular mobility at the transition into the low temperature SmC₂ phase. This finding supports a change in the packing as result of conformational changes.     

Structural and conformational investigations in SmA and different SmC phases of new hockey stick-shaped compounds

New meta -substituted homologous three-ring mesogens, the 4-(3- n -decyloxyphenyliminomethyl) phenyl 4- n -alkyloxybenzoates, have been synthesized, which are non-linear due only to the attachment of one of the alkyloxy groups in a meta -position. The mesophases were studied by optical microscopy, differential scanning calorimetry, NMR spectroscopy, X-ray diffraction, and electro-optical and dielectric measurements. Unusual phase behaviour was observed on varying the length of the terminal chain. The most interesting finding is the occurrence of two polymorphic tilted smectic phases designated as SmC 1 and SmC 2 . The existence of these phases was revealed by calorimetric studies and also from the pronounced difference in optical textures. It was shown from NMR measurements that the molecular orientation changes from a synclinic to an anticlinic arrangement in the SmC 1 to SmC 2 phase transition. It has also been shown, using NMR, that the SmC 1 →SmC 2 phase transition in these compounds is accompanied by a conformational change in the molecular fragment containing the aromatic ring with the meta -substituted terminal alkyloxy chain. This conformational change is linked to a change in the shape of the molecules and leads to a different packing of the molecules within the layers of the SmC 2 phase. From dielectric measurements an increase by a factor of two was detected in the molecular mobility at the transition into the low temperature SmC 2 phase. This finding supports a change in the packing as result of conformational changes.     

The characteristic dielectric behaviour in ferroelectric liquid crystals at a phase transition and the contribution of the soft mode

The characteristic dielectric behaviour of ferroelectric liquid crystals with a large spontaneous polarization has been studied as functions of the D.C. bias field, frequency, cell thickness and applied pressure. Under the condition in which the contribution of the Goldstone mode is suppressed, a sharp peak in the temperature dependence of the dielectric constant is clearly observed at the transition between S_A and S*_C phases T _{S C *s A}. The relaxation of the soft mode is observed both in the S_A and S*_C phases by eliminating the contribution of the Goldstone mode under a D.C. bias field. Another relaxation is also observed in the S*_C phase around several kHz in addition to that of the soft mode and the Goldstone mode. The pressure effect on the soft mode was also studied.     

The characteristic dielectric behaviour in ferroelectric liquid crystals at a phase transition and the contribution of the soft mode

The characteristic dielectric behaviour of ferroelectric liquid crystals with a large spontaneous polarization has been studied as functions of the D.C. bias field, frequency, cell thickness and applied pressure. Under the condition in which the contribution of the Goldstone mode is suppressed, a sharp peak in the temperature dependence of the dielectric constant is clearly observed at the transition between S_A and S*_C phases T_SC*sA. The relaxation of the soft mode is observed both in the S_A and S*_C phases by eliminating the contribution of the Goldstone mode under a D.C. bias field. Another relaxation is also observed in the S*_C phase around several kHz in addition to that of the soft mode and the Goldstone mode. The pressure effect on the soft mode was also studied.     

Molecular and collective modes in ferroelectric liquid crystals studied by dielectric spectroscopy

The complex dielectric permittivity has been measured for a ferroelectric liquid crystal in the range 102-109Hz. Six different relaxations have been obtained and characterized: soft mode (SmA* and SmC* phases), Goldstone mode (SmC* phase), rotation around molecular long axis, rotation around molecular short axis, ferroelectric domain mode (SmC* phase) and an internal motion associated with a polar group. Strengths and frequencies of these modes have been obtained for the different phases for different bias fields. Using these results together with spontaneous polarization and molecular tilt measurements we have also obtained the rotational viscosities associated with the soft mode and the Goldstone mode. We explain the results in the light of the so-called Landau extended model, concluding that the biquadratic coupling between polarization and tilt is quite important with regard to the bilinear coupling. This fact has been used to explain the noticeable increase of the activation energy of the frequency of the mode related to the rotation around the molecular long axis at the SmA*-SmC* phase transition.     

Fourier-transform infrared study of the switching process in a ferroelectric liquid crystalline polymer

The implementation of the step-scan technique on our FT-IR spectrometer enabled us to follow the electric-field induced reorientation dynamics of different molecular segments of a ferroelectric liquid crystalline polymer on a sub-millisecond time scale. It was detected that not only the mesogen but also the spacer and at least part of the backbone take part in the reorientation process.     

Interfacial tension between a liquid crystalline polyesteramide and polypropylene obtained by dielectric spectroscopy

Dielectric spectroscopy is an unexplored technique in the elucidation of the morphology of polymer blends. Especially the appearance of interfacial polarization can reveal important information about the microstructure of a polymer blend. A model system of liquid crystalline polymer fibers lined up in a thermoplastic matrix was investigated. After heating above the melting temperature of both phases, the fibers developed distortions which grew with time. Dielectric spectroscopy was used to follow the change in shape of the distorted fibers. The use of only two frequencies made it possible to increase the number of relevant data points in the initial stages of the fiber breakup process. From these measurements it was possible to calculate the growth rate and hence the interfacial tension between the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 815–825, 1998     

Spacer length dependence of TGBC* and SmA phases in cholesteryl and dihydrocholesteryl-containing trimer liquid crystals

Two series of trimer liquid crystals were investigated that contain a biphenylyl central group and two cholesteryl or dihydrocholesteryl terminal mesogenic groups. Only compounds with even spacers were investigated. The dihydrocholesteryl-containing trimers show a triply intercalated smectic A (SmA) phase when the spacer lengths are greater than 8, whereas the cholesteryl-containing trimers exhibit this triply intercalated SmA phase when the spacer lengths are more than 6. With shorter spacers, a twist grain boundary C* (TGBC*) phase was found. This is revealed by the formation of a typical dotted square grid pattern upon cooling from the chiral nematic (N*) phase in the planar texture. The dots are spaced by a distance of about 1.5-1.8 µm. Upon cooling from the N* phase in the focal conic texture a striped pattern is observed with the same spacing. X-ray diffraction revealed a repeat distance for the TGBC* phase that corresponds with a monolayer ordering. The results show that the weaker interaction between the dihydrocholesteryl groups compared with cholesteryl groups or longer spacers destabilize the monolayer TGBC* phase.     

Horizontal chevron domain formation and smectic layer reorientation in SmC* liquid crystals stabilized by polymer networks

The influence of a polymer network, stabilizing an initial texture of horizontal chevron geometry, on the in-plane smectic C* layer reorientation process is studied for different applied electric field conditions. As expected, the reorientation of smectic layers is strongly slowed down and eventually suppressed by the network, even at rather low monomer concentrations. Polymer network formation in a uniformly reoriented smectic layer state reveals that the network acts in two ways: first it gives a biased elastic torque counteracting a field of such symmetry as to cause a change from the templated layer direction; second it introduces an increased effective viscosity counteracting the reorientation in both directions. The behaviour of samples stabilized by two different kinds of polymer networks, created in between the smectic layers (intra-layer) and across them (inter-layer), is then investigated and discussed.     

Phase behaviour and electro-optic characteristics of a polymer stabilized ferroelectric liquid crystal

The effects of adding a diacrylate monomer or its polymerized network to a ferroelectric liquid crystal have been characterized. The monomer lowers the temperatures of transition to the more ordered phases, whereas the polymer network phase separates into polymer rich and LC rich phases and has little effect on the LC phase behaviour. Ferroelectric polarization decreases comparably in both monomer and networked systems. As the network concentration increases, the size of LC domains decreases considerably. With low concentrations of polymer and, thus large LC domains, optical response and tilt angle remain fairly independent of polymer concentration, but as the polymer concentration increases, switching speed and tilt angle decrease dramatically. Polymerization rate maxima increase with monomer concentration until saturation of monomer in the liquid crystal is reached. The rate maxima then decrease as monomer must diffuse from monomer rich droplets. Double bond conversion during the polymerization is comparable for all monomer concentrations below 50 per cent.     

Polarization and viscosity measurements of ferroelectric liquid crystalline monomer polymer mixtures

Measurements of spontaneous polarization, tilt angle and response time on mixtures of a ferroelectric side chain polyacrylate with a low molecular mass liquid crystal of a very similar structure are reported. From the obtained values the rotational viscosity for the ferroelectric switching process is calculated. All mixtures exhibit an Arrhenius-like temperature dependence of the rotational viscosity, the values for the polymer being three orders of magnitude higher than for the low molecular mass compound.     

Horizontal chevron domain formation and smectic layer reorientation in SmC* liquid crystals stabilized by polymer networks

The influence of a polymer network, stabilizing an initial texture of horizontal chevron geometry, on the in-plane smectic C* layer reorientation process is studied for different applied electric field conditions. As expected, the reorientation of smectic layers is strongly slowed down and eventually suppressed by the network, even at rather low monomer concentrations. Polymer network formation in a uniformly reoriented smectic layer state reveals that the network acts in two ways: first it gives a biased elastic torque counteracting a field of such symmetry as to cause a change from the templated layer direction; second it introduces an increased effective viscosity counteracting the reorientation in both directions. The behaviour of samples stabilized by two different kinds of polymer networks, created in between the smectic layers (intra-layer) and across them (inter-layer), is then investigated and discussed.     

A microscopic model considering the effect of molecular biaxiality on ferroelectric ordering of liquid crystalline smectic C* phases

On the basis of a mean-field approach, a microscopic model is presented to explain some ferroelectric properties of induced smectic C* phases of chiral dipolar guest molecules in an achiral smectic C host phase. The molecular biaxiality of the chiral dopants has been taken into account, resulting in a polar and quadrupolar ordering of the molecular short axes in the rotational distribution function of the guest molecules. This model explains the dependence of the magnitude and sign of the spontaneous polarization on the molecular structure of a series of cyclo-hexanone derivatives used as chiral dopants, as well as the effect of a local field at higher dopant concentrations.     

Electro-optic and dielectric properties of new binary ferroelectric and antiferroelectric liquid crystalline mixtures

Several new binary liquid crystalline mixtures have been designed and their properties were studied by complementary methods. It has been shown that even both pure components used for the mixture design possess the ferroelectric behaviour; the induced antiferroelectric smectic phase has been detected for one of the prepared mixtures. The phase diagram has been constructed and the existence of the antiferroelectric phase was confirmed by switching time and dielectric spectroscopy measurements. Some of the resulted mixtures possess very high values of the tilt angle that reaches close below 45° degrees at saturation. Values of spontaneous polarisation were found within 50–200 nC/cm² in dependence of the mixture’s composition. Due to specific properties, the obtained mixtures might be interesting for further design of multicomponent mixtures and formulation of the advanced nanocomposite systems.