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See detailOne-piece micropumps from liquid crystalline core-shell particles
Fleischmann, Eva-Kristina; Liang, Hsin-Ling; Kapernaum, Nadia et al

in Nature Communications (2012), 3

Responsive polymers are low-cost, light weight and flexible, and thus an attractive class of materials for the integration into micromechanical and lab-on-chip systems. Triggered by external stimuli ... [more ▼]

Responsive polymers are low-cost, light weight and flexible, and thus an attractive class of materials for the integration into micromechanical and lab-on-chip systems. Triggered by external stimuli, liquid crystalline elastomers are able to perform mechanical motion and can be utilized as microactuators. Here we present the fabrication of one-piece micropumps from liquid crystalline core-shell elastomer particles via a microfluidic double-emulsion process, the continuous nature of which enables a low-cost and rapid production. The liquid crystalline elastomer shell contains a liquid core, which is reversibly pumped into and out of the particle by actuation of the liquid crystalline shell in a jellyfish-like motion. The liquid crystalline elastomer shells have the potential to be integrated into a microfluidic system as micropumps that do not require additional components, except passive channel connectors and a trigger for actuation. This renders elaborate and high-cost micromachining techniques, which are otherwise required for obtaining microstructures with pump function, unnecessary. [less ▲]

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See detailTowards efficient dispersion of carbon nanotubes in thermotropic liquid crystals
Schymura, Stefan; Kühnast, Martin; Lutz, Vanessa et al

in Advanced Functional Materials (2010), 20(19), 3350-3357

Motivated by numerous recent reports indicating attractive properties of composite materials of carbon nanotubes (CNTs) and liquid crystals (LCs) and a lack of research aimed at optimizing such composites ... [more ▼]

Motivated by numerous recent reports indicating attractive properties of composite materials of carbon nanotubes (CNTs) and liquid crystals (LCs) and a lack of research aimed at optimizing such composites, the process of dispersing CNTs in thermotropic LCs is systematically studied. LC hosts can perform comparably or even better than the best known organic solvents for CNTs such as N-methyl pyrrolidone (NMP), provided that the dispersion process and choice of LC material are optimized. The chemical structure of the molecules in the LC is very important; variations in core as well as in terminal alkyl chain influence the result. Several observations moreover indicate that the anisotropic nematic phase, aligning the nanotubes in the matrix, per se stabilizes the dispersion compared to a host that is isotropic and thus yields random tube orientation. The chemical and physical phenomena governing the preparation of the dispersion and its stability are identified, taking into account enthalpic, entropic, as well as kinetic factors. This allows a guideline on how to best design and prepare CNT–LC composites to be sketched, following which tailored development of new LCs may take the advanced functional material that CNT–LC composites comprise to the stage of commercial application. [less ▲]

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See detailElectrolyte effects on the stability of nematic and lamellar lyotropic liquid crystal phases – colligative and ion-specific aspects
Dawin, Ute; Lagerwall, Jan UL; Giesselmann, Frank

in Journal of Physical Chemistry B (2009), 113(33), 11414-11420

We investigated the electrolyte effects on the stability of nematic and lamellar lyotropic liquid crystalline (LLC) phases formed by the simple anionic surfactant cesium pentadecafluorooctanoate (CsPFO ... [more ▼]

We investigated the electrolyte effects on the stability of nematic and lamellar lyotropic liquid crystalline (LLC) phases formed by the simple anionic surfactant cesium pentadecafluorooctanoate (CsPFO) in water. To the lyotropic guest phase, at the constant CsPFO-mass fraction of 0.55, the series of electrolytes LiCl, NaCl, KCl, CsCl, CsI, and Cs2SO4, respectively, was added at concentrations ranging from 0.5 to 2.5 mol %. With increasing electrolyte concentration two substantially different effects were observed. At low concentrations all added electrolytes caused an increase of the thermal stability of the LLC phases, favoring the lamellar phase over the nematic phase. This behavior is, at least qualitatively, understood within the packing parameter model. The extent of the stabilization clearly depends on the chemical nature of the added cation. For a given cation, however, the effect is colligative, i.e., independent of the chemical nature of the added anion. At higher salt concentrations a salting-out-like phase separation was induced. This effect is clearly ion-specific as the salting-out concentration varied for each cation following the order of the Hofmeister series for cations. [less ▲]

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See detailOn the balance between syn- and anticlinicity in smectic phases formed by achiral hockey-stick mesogens with and without chiral dopants
Enz, Eva; Findeisen-Tandel, Sonja; Dabrowski, Roman et al

in Journal of Materials Chemistry (2009), 19(19), 2950-2957

A series of achiral hockey-stick-shaped mesogens forming tilted smectic liquid crystal phases of synclinic SmC- as well as anticlinic SmCa-type was prepared and characterized. While all homologues exhibit ... [more ▼]

A series of achiral hockey-stick-shaped mesogens forming tilted smectic liquid crystal phases of synclinic SmC- as well as anticlinic SmCa-type was prepared and characterized. While all homologues exhibit both phases, the balance shifts from anticlinic to synclinic order upon elongation of the terminal chain at the meta-position, defining the hockey-stick shape. The elongation also leads to an increased kinetic hindrance of the transition between syn- and anticlinic phases and a decreased transition enthalpy. These observations indicate that a well-defined kink (short meta-substituted chain) promotes the anticlinic structure while a higher flexibility between kinked and rod-shape (long meta-substituted chain) promotes synclinic order. An intermediate chain-length homologue was selected as host material for doping with syn- and anticlinic rod-shaped chiral dopants, respectively, at varying concentrations. Opposite of what might be expected the balance between syn- and anticlinic order was not simply dictated by the choice of dopant. Instead, both types of tilting order prevailed with roughly the same strength as in the achiral host regardless of which chiral material was added, up to concentrations well beyond normal doping conditions. Thus, at least with hockey-stick-shaped achiral hosts, syn- as well as anticlinic chiral compounds can be used effectively as chiral dopants without necessarily having an important impact on the clinicity of the resulting mixture. The hockey-stick design concept should be useful in producing achiral anticlinic-forming mesogens for low-polarization, long-pitch antiferroelectric liquid crystal mixtures. Finally, we point out that a mixture study like the one carried out here yields a conclusive means of establishing the clinicity of achiral tilted smectics, an endeavour that can sometimes be far from trivial. [less ▲]

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See detailSpontaneous macroscopic carbon nanotube alignment via colloidal suspension in hexagonal columnar lyotropic liquid crystals
Scalia, Giusy; von Bühler, Clemens; Hägele, Constanze et al

in Soft Matter (2008), 4(3), 570-576

The self-assembly of amphiphilic molecules in aqueous solution into lyotropic liquid crystals (LCs), characterised by soft yet long-range ordered nanoscale structures, constitutes a fascinating phenomenon ... [more ▼]

The self-assembly of amphiphilic molecules in aqueous solution into lyotropic liquid crystals (LCs), characterised by soft yet long-range ordered nanoscale structures, constitutes a fascinating phenomenon at the heart of soft matter science which can be employed in a manifold of creative ways. Particularly interesting structures may arise as a result of functionalisation of the LC with appropriate guest molecules, adopting the order of their host. Here we combine cat- and anionic surfactants to form a liquid-crystalline colloidal suspension of carbon nanotubes (CNTs), which by virtue of the spontaneously formed hexagonal columnar LC structure are uniaxially aligned over macroscopic areas. The nanotube concentration can be so high, with sufficiently uniform alignment, that the mixture becomes a fluid linear polariser, the anisotropic optical properties of CNTs having been transferred to macroscopic scale by the LC. Moreover, thin and highly aligned filaments can be drawn and deposited in selected directions on arbitrary surfaces, after which the LC template can be rinsed away. Combined with recently developed methods for CNT fractionation according to chirality, the technique would yield an unprecedented degree of control in the practical realisation of carbon nanotube-based devices and materials. [less ▲]

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See detailNanotube alignment using lyotropic liquid crystals
Lagerwall, Jan UL; Scalia, G.; Haluska, Miroslav et al

in Advanced Materials (2007), 19(3), 359-364

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See detailMolecular model for de Vries type smectic-A–smectic-C phase transition in liquid crystals
Gorkunov, M. V.; Giesselmann, Frank; Lagerwall, Jan UL et al

in Physical Review. E : Statistical, Nonlinear, and Soft Matter Physics (2007), 75(6), 060701

We develop both phenomenological and molecular-statistical theory of smectic-A-smectic-C phase transition with anomalously weak smectic layer contraction. Using a general mean-field molecular model, we ... [more ▼]

We develop both phenomenological and molecular-statistical theory of smectic-A-smectic-C phase transition with anomalously weak smectic layer contraction. Using a general mean-field molecular model, we demonstrate that a relatively simple interaction potential suffices to describe the transition both in conventional and de Vries type smectics. The theoretical results are in excellent agreement with experimental data. The approach can be used to describe tilting transitions in other soft matter systems. [less ▲]

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See detailCarbon nanotubes in liquid crystals as versatile functional materials
Scalia, Giusy; Lagerwall, Jan UL; Schymura, Stefan et al

in Physica Status Solidi B. Basic Research (2007), 244(11), 4212-4217

Liquid crystals can be easily aligned in desired directions by treated surfaces or by external fields. The least ordered liquid crystal phase, the nematic, exhibits orientational order that can be easily ... [more ▼]

Liquid crystals can be easily aligned in desired directions by treated surfaces or by external fields. The least ordered liquid crystal phase, the nematic, exhibits orientational order that can be easily transferred onto carbon nanotubes dispersed in it. The alignment of the carbon nanotubes can be demonstrated by po- larized Raman spectroscopy. Carbon nanotubes not only well integrate in the matrix but also, even at very low concentration, have a detectable effect on the liquid crystal properties that can be very attractive for display applications. The presence of big aggregates of carbon nanotubes, on the other hand, interfere strongly with the switching behaviour of the liquid crystal, as we can show following the local switching of liquid crystal molecules with Raman spectroscopy. [less ▲]

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See detailEffect of phenyl rings in liquid crystal molecules on swcnts studied by raman spectroscopy
Scalia, G.; Lagerwall, Jan UL; Haluska, Miroslav et al

in Physica Status Solidi B. Basic Research (2006), 243(13), 3238-3241

Carbon nanotubes can be aligned by dispersing them in a liquid crystalline matrix. To control and opti- mize the obtained alignment it is important to understand the interactions between the molecules of ... [more ▼]

Carbon nanotubes can be aligned by dispersing them in a liquid crystalline matrix. To control and opti- mize the obtained alignment it is important to understand the interactions between the molecules of the liquid crystal host phase and the carbon nanotubes. To this end we have carried out resonant Raman spec- troscopy investigations of dispersions of single-wall carbon nanotubes (SWCNTs) in a liquid crystal com- pound comprising molecules with a biphenyl rigid core structure. We detect a distinct wavenumber shift of the radial breathing modes, confirming that the carbon nanotubes interact with the surrounding liquid crystal molecules, most likely through aromatic interactions (π-stacking). The interactions between liquid crystal host and nanotube guests are also evident from a polarizing microscopy study of the liquid crys- tal – isotropic phase transition in the proximity of bundles of nanotubes. The ordered liquid crystal phase is stable up to higher temperatures around the bundles than in areas without visible signs of CNTs. Con- versely, the transition from the disordered isotropic phase to the liquid crystal phase on cooling always nucleates at the carbon nanotube bundles. [less ▲]

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See detailCurrent topics in smectic liquid crystal research
Lagerwall, Jan UL; Giesselmann, Frank

in Chemphyschem : A European Journal of Chemical Physics and Physical Chemistry (2006), 7(1), 20-45

Interest in the smectic liquid-crystalline state of matter received a substantial boost with the discovery by Meyer in the mid-1970s that a chiral smectic C (SmC*) phase exhibits a spontaneous elec- tric ... [more ▼]

Interest in the smectic liquid-crystalline state of matter received a substantial boost with the discovery by Meyer in the mid-1970s that a chiral smectic C (SmC*) phase exhibits a spontaneous elec- tric polarization, and with the subsequent demonstration by Clark and Lagerwall of the surface-stabilized SmC* ferroelectric liquid crystal at the beginning of the 1980s. Since then, chiral smectic phases and their plethora of polar effects have dominat- ed the research in this field, which today has reached a mature state where the first commercial microdisplay applications are now shipping in millions-per-year quantities. In this Review we discuss some of the topics of highest interest in current smectic liquid crystal research, and address application-relevant research (de Vries-type tilting transitions without defect generation and high-tilt antiferroelectric liquid crystals with perfect dark state) as well as more curiosity-driven research (the nature and origin of the chiral smectic C subphases and their intermediate frustrated states between ferro- and antiferroelectricity). [less ▲]

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See detailOn the change in helix handedness at transitions between the sm-c* and sm-ca* phases in chiral smectic liquid crystals
Lagerwall, Jan UL; Giesselmann, Frank; Osipov, Mikhail A.

in Liquid Crystals (2006), 33(6), 625-633

Using a discrete model for the synclinic SmC* and the anticlinic SmC􏰀a phases we give a theoretical explanation for the fact that the helix twisting sense reverses at a transition between these phases ... [more ▼]

Using a discrete model for the synclinic SmC* and the anticlinic SmC􏰀a phases we give a theoretical explanation for the fact that the helix twisting sense reverses at a transition between these phases (direct transition or via the so-called chiral smectic C ‘subphases’) and we derive an explicit expression for the helical pitch in the SmC􏰀a phase. As the theory shows and as we also demonstrate experimentally, the reversal is of a different nature from helix inversions within a single phase, where the inversion is always coupled to a pitch divergence. At a clinicity change the common behaviour is instead pitch-shortening on approaching the phase transition and the associated helix twisting sense reversal. The phenomenon may be put to use in smart mixing in order to control the helix pitch, either for achieving long pitch for surface-stabilized ferroelectric and antiferroelectric liquid crystal displays; or a very short pitch, in the case of devices utilizing the deformed helix mode. [less ▲]

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See detailSimultaneous alignment and dispersion of carbon nanotubes with lyotropic liquid crystals
Lagerwall, Jan UL; Scalia, G.; Haluska, Miroslav et al

in Physica Status Solidi B. Basic Research (2006), 243(13), 3046-3049

We demonstrate that single-wall carbon nanotubes (SWCNTs) can be macroscopically aligned by means of templating in a lyotropic nematic liquid crystal (LC), a self-assembling anisotropic fluid with orienta ... [more ▼]

We demonstrate that single-wall carbon nanotubes (SWCNTs) can be macroscopically aligned by means of templating in a lyotropic nematic liquid crystal (LC), a self-assembling anisotropic fluid with orienta- tional but no translational order. The CNTs spontaneously adopt the alignment of the host, as we verify by means of resonant Raman spectroscopy. The aqueous LC host, based on the surfactant SDS, simultane- ously keeps the nanotubes well dispersed over time scales of months or longer. The LC can be loaded with CNTs to almost the same extent as the standard isotropic 1% surfactant solutions normally used for dispersing CNTs without any optically visible bundling occurring. [less ▲]

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See detailThe peculiar optic, dielectric and x-ray diffraction properties of a fluorinated de vries asymmetric-diffuse-cone-model ferroelectric liquid crystal
Lagerwall, Jan UL; Coleman, D.; Körblova, E. et al

in Liquid Crystals (2006), 33(1), 17-24

A new semi-fluorinated chiral smectic liquid crystal, W504, is investigated by electro-optic, dielectric and X-ray scattering experiments. It exhibits a huge dielectric soft mode response, strong ... [more ▼]

A new semi-fluorinated chiral smectic liquid crystal, W504, is investigated by electro-optic, dielectric and X-ray scattering experiments. It exhibits a huge dielectric soft mode response, strong electroclinic effect and a birefringence which increases considerably with the director tilt angle theta; typical characteristics of a SmA - SmC transition following the de Vries asymmetric diffuse cone (ADC) model in which the non-zero director tilt in SmC arises through an ordering of tilting directions rather than an actual increase in average molecule tilt <theta(mol)>. In W504 a small increase in <theta(mol)> of about 4 degrees is however detected in the SmC phase. Although the increase in molecule inclination is much less than the increase in director tilt h, saturating close to 30 degrees, it leads to a shrinkage of the smectic layers by about 1 angstrom, a result of the large initial molecule tilt in the SmA phase, <theta(mol)>(SmA) approximate to 30 degrees. The tilting transition in W504 is thus mainly an ADC model disorder - order transition, but it also has a component of a structural transition. The semi- fluorinated molecular structure of W504 leads to a very weak electron density modulation along the layer normal, giving a vanishing form factor in bulk samples which exhibit no (001) X-ray scattering peak. In thin films the (001) peak is however observed, indicating that the electron density modulation is enhanced by the breaking of the head - tail symmetry of the liquid crystal phase at the LC - air interface. [less ▲]

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See detailChiral smectic C subphases induced by mixing a bistereogenic antiferroelectric liquid crystal with a non-chiral liquid crystal
Lagerwall, Jan UL; Giesselmann, Frank; Rauch, Sebastian et al

in Ferroelectrics (2005), 315

By mixing a bistereogenic antiferroelectric liquid crystal (AFLC) compound, exhibiting only the SmQ and SmCa mesophases, with the achiral N-SmC liquid crystal HOAB we could induce all three AFLC SmC-type ... [more ▼]

By mixing a bistereogenic antiferroelectric liquid crystal (AFLC) compound, exhibiting only the SmQ and SmCa mesophases, with the achiral N-SmC liquid crystal HOAB we could induce all three AFLC SmC-type subphases, SmCalpha, SmCbeta and SmCgamma. This seems to be in contradiction with two recent postulations regarding the subphase stability, one of which suggests that the subphases appear as a result of strong chiral interactions, the other that these phases require high smectic order something one would generally not expect in mixtures. We have studied the helical pitch, optical tilt angle, spontaneous polarization and the x-ray diffraction due to the smectic layering, as a function of mixing ratio in order to better understand the relation between phase sequence and mixture composition. The smectic layer spacing shows a strongly non-linear behavior suggesting that the basic structure of the pure AFLC substance is retained up to a HOAB content of about 75\%. [less ▲]

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See detailElectrolyte effects on the nematic-isotropic phase transition in lyotropic liquid crystals
Mukherjee, Prabir K.; Lagerwall, Jan UL; Giesselmann, Frank

in Liquid Crystals (2005), 32(10), 1301-1306

A phenomenological approach to the description of the electrolyte effect on the nematic– isotropic phase transition in lyotropic liquid crystals is proposed. The influence of the electrolyte is discussed ... [more ▼]

A phenomenological approach to the description of the electrolyte effect on the nematic– isotropic phase transition in lyotropic liquid crystals is proposed. The influence of the electrolyte is discussed by varying the coupling between the concentration variables and the orientational order parameter. The analysis shows that the discontinuity in the first order nematic–isotropic phase transition as measured by TNI{T0 increases as a function of the NI weight fraction of the electrolyte. Here TNI is the first order nematic–isotropic phase transition temperature and TN0I is the extrapolated supercooling limit. The electrolyte dependence of the Cotton–Mouton coefficient and the non-linear dielectric effect in the isotropic phase above the nematic–isotropic phase transition are calculated. The theoretical predictions are found to be in good agreement with experimental results. [less ▲]

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See detailGeneration of frustrated liquid crystal phases by mixing an achiral n–smc mesogen with an antiferroelectric chiral smectic liquid crystal
Lagerwall, Jan UL; Giesselmann, Frank; Selbmann, Christine et al

in Journal of Chemical Physics (2005), 122(14), 144906

By mixing the achiral liquid crystal HOAB, exhibiting a nematic (N)-smectic-C (SmC) mesophase sequence, with the chiral antiferroelectric liquid crystal (AFLC) (S,S)-M7BBM7, forming the antiferroelectric ... [more ▼]

By mixing the achiral liquid crystal HOAB, exhibiting a nematic (N)-smectic-C (SmC) mesophase sequence, with the chiral antiferroelectric liquid crystal (AFLC) (S,S)-M7BBM7, forming the antiferroelectric SmCa phase, at least seven different mesophases have been induced which neither component forms on its own: a twist-grain-boundary (TGB) phase, two or three blue phases, the untilted SmA phase, as well as all three chiral smectic-C-type ``subphases,'' SmCalpha, SmCbeta, and SmCgamma. The nature of the induced phases and the transitions between them were determined by means of optical and electro-optical investigations, dielectric spectroscopy, and differential scanning calorimetry. The induced phases can to a large extent be understood as a result of frustration, TGB at the border between nematic and smectic, the subphases between syn and anticlinic tilted smectic organization. X ray scattering experiments reveal that the smectic layer spacing as well as the degree of smectic order is relatively constant in the whole mixture composition range in which AFLC behavior prevails, whereas both these parameters rapidly decrease as the amount of HOAB is increased to such an extent that no other smectic-C-type phase than SmC/SmC exists. By tailoring the composition we are able to produce liquid crystal mixtures exhibiting unusual phase sequences, e.g., with a direct isotropic-SmCa transition or a temperature range of the SmCbeta subphase of about 50 K. (C) 2005 American Institute of Physics. [less ▲]

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See detailDifferences between smectic homo- and copolysiloxanes as a consequence of microphase separation
Rössle, Martin; Braun, L.; Schollmeyer, D. et al

in Liquid Crystals (2005), 32(5), 533-538

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 ... [more ▼]

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 approaching the isotropic phase. For the homopolymer the phase transition SmC* to SmA is first order with a significant thickness change, indicating that this phase is not of the ‘de Vries’ type. This difference in the nature of the smectic phases is probably a consequence of microphase separation in the copolymer, which facilitates a loss of the tilt angle correlation between different smectic layers. This has consequences for the mechanical properties of LC- elastomers formed from homo- and co-polymers. For the elastomers from homopolymers the smectic layer compression seems to be rather high, while it seems to be rather small for the copolymers. [less ▲]

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See detailFrustration between syn- and anticlinicity in mixtures of chiral and non-chiral tilted smectic-c-type liquid crystals
Lagerwall, Jan UL; Heppke, Gerd; Giesselmann, Frank

in European Physical Journal E -- Soft Matter (2005), 18(1), 113-121

We study the effects of mixing ferroelectric and antiferroelectric liquid-crystal compounds (FLCs and AFLCs) when the former are strictly synclinic and the latter strictly anticlinic, i.e. one mixture ... [more ▼]

We study the effects of mixing ferroelectric and antiferroelectric liquid-crystal compounds (FLCs and AFLCs) when the former are strictly synclinic and the latter strictly anticlinic, i.e. one mixture component exhibits only SmC* and the other only SmCa* as tilted phase. Three different paths between syn- and anticlinicity were detected: transition directly between SmC* and SmCa*, transition via the SmCβ* and SmCγ* subphases, or by “escaping” the clinicity frustration by reducing the tilt to zero, i.e. the SmA* phase is extended downwards in temperature, separating SmC* from SmCa* in the phase diagram. The most common path is the one via the subphases, demonstrating that these phases appear as a result of frustration between syn- and anticlinic and, consequently, between syn- and antipolar order. For assessing the role of chirality, we also replaced the FLC with non-chiral synclinics. With one of the AFLCs, the route via supbhases was detected even in this case, suggesting that chirality —although necessary— does not have quite the importance that has previously been attributed to the appearance of the subphases. The path chosen in the mixture study seemed to be determined mainly by the synclinic component, the subphase induction occurring only when the SmA*-SmC* transition was second order. [less ▲]

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See detailFerroelectric polysiloxane liquid crystals with ‘de vries’-type smectic a* -smectic c* transitions
Rössle, Martin; Zentel, Rudolf; Lagerwall, Jan UL et al

in Liquid Crystals (2004), 31(6), 883-887

We report preliminary results of optical and small angle X-ray scattering (SAXS) experiments on the smectic A*2smectic C* transition in two ferroelectric liquid crystalline polysiloxanes. Although the ... [more ▼]

We report preliminary results of optical and small angle X-ray scattering (SAXS) experiments on the smectic A*2smectic C* transition in two ferroelectric liquid crystalline polysiloxanes. Although the optical tilt angle in the SmC* phases reaches values up to 30‡, temperature-dependent SAXS measurements clearly reveal that the smectic layer spacing is basically conserved during the A*–C* transition as well as in the subsequent C* phase. Connected with the A*–C* transition we further observed a significant increase in bire- fringence, hence reflecting an increase of orientational order. The practical absence of layer shrinkage and the enhanced orientational ordering are consistent with the de Vries diffuse cone model of smectic A2smectic C transitions. [less ▲]

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See detailOn the origin of high optical director tilt in a partially fluorinated orthoconic antiferroelectric liquid crystal
Lagerwall, Jan UL; Giesselmann, Frank; Saipa, Alexander et al

in Liquid Crystals (2004), 31(9), 1175-1184

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle ... [more ▼]

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle between the optic axis and the smectic layer normal in this material. The optical birefringence increases strongly below the transition to the tilted phases, showing that the onset of tilt is coupled with a considerable increase in orientational order. The layer spacing in the smectic A (SmA) phase is notably smaller than the extended length of the molecules constituting the mixture, and the shrinkage in smectic C (SmC) and smectic C-a (SmCa) is much less than the optical tilt angle would predict. These observations indicate that the tilting transition in W107 to a large extent follows the asymmetric de Vries diffuse cone model. The molecules are on average considerably tilted with respect to the layer normal already in the SmA phase but the tilting directions are there randomly distributed, giving the phase its uniaxial characteristics. At the transition to the SmC phase, the distribution is biased such that the molecular tilt already present in SmA now gives a contribution to the macroscopic tilt angle. In addition, there is a certain increase of the average tilt angle, leading to a slightly smaller layer thickness in the tilted phases. Analysis of the wide angle scattering data show that the molecular tilt in SmCa is about 20degrees larger than in SmA. The large optical tilt (45degrees) in the SmCa phase thus results from a combination of an increased average molecule tilt and a biasing of tilt direction fluctuations. [less ▲]

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