References of "Lagerwall, Jan 50002154"
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See detailNanoparticles dispersed in liquid crystals: impact on conductivity, low-frequency relaxation and electro-optical performance
Urbanski, Martin UL; Lagerwall, Jan UL

in Journal of Materials Chemistry C (2016), 4(16), 3485-3491

We study the impact of functionalized gold nanoparticles on the impedance response of nematic nanoparticle/liquid crystal dispersions in the frequency range of 0.1 Hz–100 kHz. By fitting a suitable ... [more ▼]

We study the impact of functionalized gold nanoparticles on the impedance response of nematic nanoparticle/liquid crystal dispersions in the frequency range of 0.1 Hz–100 kHz. By fitting a suitable equivalent electric circuit model to the experimental data we show that nanoparticle doping does not affect the permittivity of the nematic host, but significantly increases its conductivity. This causes a Debye-type relaxation process in the Hz and low kHz regime, which originates from mobile charge carriers accumulating near the electrodes of the test cell. The effect of this electrode polarization on the electro-optical response of the nanocomposites is discussed with respect to threshold voltage and dielectric permittivity. We demonstrate that nanoparticle doping does not alter the electro-optic response at frequencies above the occurrence of electrode polarization, while it strongly deteriorates the performance in the low frequency regime. [less ▲]

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See detailHigh-fidelity spherical cholesteric liquid crystal Bragg reflectors generating unclonable patterns for secure authentication
Geng, Yong UL; Noh, Junghyun UL; Drevensek-Olenik, Irena et al

in Scientific Reports (2016), 6(26840), 1-8

Monodisperse cholesteric liquid crystal microspheres exhibit spherically symmetric Bragg reflection, generating, via photonic cross communication, dynamically tuneable multi-coloured patterns. These ... [more ▼]

Monodisperse cholesteric liquid crystal microspheres exhibit spherically symmetric Bragg reflection, generating, via photonic cross communication, dynamically tuneable multi-coloured patterns. These patterns, uniquely defined by the particular sphere arrangement, could render cholesteric microspheres very useful in countless security applications, as tags to identify and authenticate their carriers, mainly physical objects or persons. However, the optical quality of the cholesteric droplets studied so far is unsatisfactory, especially after polymerisation, a step required for obtaining durable samples that can be used for object identification. We show that a transition from droplets to shells solves all key problems, giving rise to sharp patterns and excellent optical quality even after polymerisation, the polymerised shells sustaining considerable mechanical deformation. Moreover, we demonstrate that, counter to prior expectation, cross communication takes place even between non-identical shells. This opens additional communication channels that add significantly to the complexity and unique character of the generated patterns. [less ▲]

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See detailTransmission polarized optical microscopy of short-pitch cholesteric liquid crystal shells
Geng, Yong UL; Noh, Junghyun UL; Lagerwall, Jan UL

in Proceedings of SPIE - The International Society for Optical Engineering (2016, March 07), 9769

We recently demonstrated that colloidal crystal arrangements of monodisperse droplets or shells of planar-aligned cholesteric liquid crystal exhibit intricate patterns of circularly polarized reflection ... [more ▼]

We recently demonstrated that colloidal crystal arrangements of monodisperse droplets or shells of planar-aligned cholesteric liquid crystal exhibit intricate patterns of circularly polarized reflection spots of different colors. The spots appear as a result of photonic cross communication between droplets, hence the patterns reflect the macroscopic arrangement of droplets or shells. Apart from being an interesting optical phenomenon, it offers attractive application opportunities in photonics and beyond, due to the unique characteristics of the patterns. It turns out that the optical quality of shells is much enhanced compared to that of droplets, hence we focus our attention primarily on shells, of varying thickness. Here we analyze and explain the intriguing textures arising when studying planar-aligned short-pitch cholesteric shells in transmission polarizing optical microscopy. In this case, the texture reflects the properties of each individual shell, without any sign of cross communication, yet also this pattern holds some fascinating mysteries. These can only be elucidated by considering all the peculiar optical properties of cholesterics together, as well as the unusual situation given by the spherical shell geometry. [less ▲]

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See detailRod packing in chiral nematic cellulose nanocrystal dispersions studied by small angle X-ray scattering and laser diffraction
Schütz, Christina; Agthe, Michael; Fall, Andreas et al

in Langmuir (2015), 31(23), 6507-6513

The packing of cellulose nanocrystals (CNC) in the anisotropic chiral nematic phase has been investigated over a wide concentration range by small angle X-ray scattering (SAXS) and laser diffraction. The ... [more ▼]

The packing of cellulose nanocrystals (CNC) in the anisotropic chiral nematic phase has been investigated over a wide concentration range by small angle X-ray scattering (SAXS) and laser diffraction. The average separation distance between the CNCs and the average pitch of the chiral nematic phase have been determined over the entire isotropic-anisotropic biphasic region. The average separation distances range from 51 nm, at the onset of the anisotropic phase formation, to 25 nm above 6 vol% (fully liquid crystalline phase) whereas the average pitch varies from 15.5 μm down to ≈2 μm as φ increases from 2.5 up to 6.5 vol%. Using the cholesteric order, we determine that the twist angle between neighboring CNCs increases from about 1 ° up to 4 ° as φ increases from 2.5 up to 6.5 vol%. The dependence of the twisting on the volume fraction was related to the increase in the magnitude of the repulsive interactions between the charged rods as the average separation distance decrease. [less ▲]

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See detailDynamic and complex optical patterns from colloids of cholesteric liquid crystal droplets
Noh, Junghyun UL; Drevensek-Olenik, Irena; Yamamoto, Jun et al

in Proceedings of the SPIE (2015), 9384

Drops or shells of a planar-aligned short-pitch cholesteric liquid crystal exhibit unique optical properties due to the combination of Bragg reflection in the cholesteric helix and a radial orientation of ... [more ▼]

Drops or shells of a planar-aligned short-pitch cholesteric liquid crystal exhibit unique optical properties due to the combination of Bragg reflection in the cholesteric helix and a radial orientation of the helix axis. If such a droplet is illuminated from above, light is reflected into a continuous set of cones, the opening angles of which depend on where on the droplet the light hits its surface. For the wavelength that fulfills the Bragg condition the reflection is dramatically enhanced, yielding the light cones colored. A photonic cross communication scheme arises for certain angles, reflecting light back to the observer from a different droplet than the one originally illuminated. This gives rise to an intricate pattern of colored and circularly polarized spots. A number of interesting applications may be developed based on this pattern, e.g. in identification and authentication devices. We have carried out a detailed spectrophotometric analysis of the patterns, localized to individual spot maxima. A quantitative comparison between the measured spectra and the reflection wavelength expected from a model for the pattern generation allows us to conclude that the droplets are in fact not spherical but slightly ellipsoidal. [less ▲]

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See detailUltra-long ordered nanowires from the concerted self-assembly of discotic liquid crystal and solvent molecules.
Park, J. H.; Kim, K. H.; Park, Y. W. et al

in Langmuir (2015), 31(34), 9432-9440

The realization of long and aligned molecular wires is a great challenge and different approaches have been proposed. Interestingly, hexapentyloxytriphenylene (HAT5) discotic liquid crystal molecules ... [more ▼]

The realization of long and aligned molecular wires is a great challenge and different approaches have been proposed. Interestingly, hexapentyloxytriphenylene (HAT5) discotic liquid crystal molecules, model system of molecules with flat and aromatic cores, can spontaneously form well aligned, micrometer long yet only tens of nanometers thick nanowires on solid surfaces. We have investigated the formation mechanism of these wires by using different solvents with selected characteristics like chemical structure, boiling point, vapor pressure and surface tension. When casting from toluene and benzene solutions, atomic force microscopy reveals that the discotics spontaneously form very long and thin wires, self-aligning along a common orientation. If instead dodecane or heptane are used, different and in general thicker structures are obtained. The chemical structure of the solvent appears to have a key role, coupling to the liquid crystal self-assembly by allowing solvent molecules to enter in the ordered structure if their design matches the core of HAT5 molecules, thereby guiding the assembly. However, also other aspects are relevant in the assembly, like the nature of the substrate or the rate of solvent evaporation, and these can favor or interfere with the self-assembly into long structures. The use of solvents with aromatic structure is advantageous not only because it affects the geometry of the assembly, promoting long wire formation, but it is also compatible with good quality of the intermolecular order, as suggested by a high anisotropy of the Raman spectra of the nanowires formed from these solvents. Finally, the electrical properties of ordered systems show a clearly higher electrical conductivity compared to the disorganized aggregates. [less ▲]

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See detailInfluence of interface stabilisers and surrounding aqueous phases on nematic liquid crystal shells
Noh, Junghyun UL; Reguengo De Sousa, Kevin; Lagerwall, Jan UL

in Soft Matter (2015), in press

We investigate the nematic–isotropic (N–I) transition in shells of the liquid crystal 5CB, surrounded by aqueous phases that conven- tionally are considered to be immiscible with 5CB. The aqueous phases ... [more ▼]

We investigate the nematic–isotropic (N–I) transition in shells of the liquid crystal 5CB, surrounded by aqueous phases that conven- tionally are considered to be immiscible with 5CB. The aqueous phases contain either sodium dodecyl sulfate (SDS) or polyvinyl alcohol (PVA) as stabiliser, the former additionally promoting homeotropic director alignment. For all shell configurations we find a depression of the clearing point compared to pure 5CB, indicating that a non-negligible fraction of the constituents of the surrounding phases enter the shell, predominantly water. In hybrid- aligned shells, with planar outer and homeotropic inner boundary (or vice versa), the N–I transition splits into two steps, with a consequent three-step textural transformation. We explain this as a result of the order-enhancing effect of a monolayer of radially aligned SDS molecules adsorbed at the homeotropic interface. [less ▲]

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See detailMultifunctional responsive fibers produced by dual liquid crystal core electrospinning
Kye, Yoomee; Kim, Changsoon; Lagerwall, Jan UL

in Journal of Materials Chemistry C (2015), 3

We demonstrate that coaxial electrospinning with more than one core channel, each containing a different type of liquid crystal, can be used to produce multifunctional fibers in a one-step process. They ... [more ▼]

We demonstrate that coaxial electrospinning with more than one core channel, each containing a different type of liquid crystal, can be used to produce multifunctional fibers in a one-step process. They respond to more than one stimulus or with multiple threshold values, and the individual cores may feature different physical properties such as iridescent reflection in one core and birefringence in another. In order to ensure good fiber morphology and intact, unmixed and well separated cores, two important precautions must be taken. First, the fibers should not be collected on a hydrophilic substrate, as this will lead to severe fiber deformation and core mixing after collection, as a result of capillary forces from the water that condenses on the fiber during spinning. Second, the addition of surfactants to the polymer solution should be avoided, although it may appear beneficial for the spinning process as it reduces surface tension and increases conductivity. This is because the surfactant enters the liquid crystal core, possibly together with water in the form of inverse micelles, seriously degrading the performance of the liquid crystal. [less ▲]

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See detailInfluence of Wetting on Morphology and Core Content in Electrospun Core-Sheath Fibers
Kim, Dae Kyom; Lagerwall, Jan UL

in ACS Applied Materials and Interfaces (2014), 6(18), 16441-16447

Coaxial electrospinning allows easy and cost-effective realization of composite fibers at the nano- and microscales. Different multifunctional materials can be incorporated with distinct localization to ... [more ▼]

Coaxial electrospinning allows easy and cost-effective realization of composite fibers at the nano- and microscales. Different multifunctional materials can be incorporated with distinct localization to specific regimes of the fiber cross section and extended internal interfaces. However, the final composite properties are affected by variations in internal structure, morphology, and material separation, and thus, nanoscale control is mandatory for high-performance application in devices. Here, we present an analysis with unprecedented detail of the cross section of liquid core-functionalized fibers, yielding information that is difficult to reveal. This is based on focused ion beam (FIB) lift-out and allowing HR-TEM imaging of the fibers together with nanoscale resolution chemical analysis using energy dispersive X-ray spectroscopy (EDS). Unexpectedly, core material escapes during spinning and ends up coating the fiber exterior and target substrate. For high core injection rate, a dramatic difference in fiber morphology is found, depending on whether the surface on which the fibers are deposited is hydrophobic or hydrophilic. The latter enhances postspinning extraction of core fluid, resulting in the loss of the functional material and collapsed fiber morphology. Finally, in situ produced TiO2 nanoparticles dispersed in the polymer appear strikingly different when the core fluid is present compared to when the polymer solution is spun on its own. [less ▲]

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See detailMacroscopic control of helix orientation in films dried from cholesteric liquid crystalline cellulose nanocrystal suspensions

Park, Ji Hyun; Noh, Junghyun UL; Schütz, Christina et al

in Chemphyschem : A European Journal of Chemical Physics and Physical Chemistry (2014), 15(7), 1477-1484

The intrinsic ability of cellulose nanocrystals (CNCs) to self-organize into films and bulk materials with helical order in a cholesteric liquid crystal is scientifically intriguing and potentially ... [more ▼]

The intrinsic ability of cellulose nanocrystals (CNCs) to self-organize into films and bulk materials with helical order in a cholesteric liquid crystal is scientifically intriguing and potentially important for the production of renewable multifunctional materials with attractive optical properties. A major obstacle, however, has been the lack of control of helix direction, which results in a defect-rich, mosaic-like domain structure. Herein, a method for guiding the helix during film formation is introduced, which yields dramatically improved uniformity, as confirmed by using polarizing optical and scanning electron microscopy. By raising the CNC concentration in the initial suspension to the fully liquid crystalline range, a vertical helix orientation is promoted, as directed by the macroscopic phase boundaries. Further control of the helix orientation is achieved by subjecting the suspension to a circular shear flow during drying. [less ▲]

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See detailTuneable Multicoloured Patterns From Photonic Cross Communication Between Cholesteric Liquid Crystal Droplets
Noh, Junghyun UL; Liang, Hsin-Ling; Drevensek-Olenik, Irena et al

in Journal of Materials Chemistry C (2014), 2(5), 806-810

Monodisperse droplets of planar-aligned cholesteric (N*) liquid crystal exhibit an intriguing capacity for photonic cross-communication, giving rise to colourful patterns that depend sensitively on the N ... [more ▼]

Monodisperse droplets of planar-aligned cholesteric (N*) liquid crystal exhibit an intriguing capacity for photonic cross-communication, giving rise to colourful patterns that depend sensitively on the N* pitch, droplet positions and illuminated area. The phenomenon results from a combination of omnidirectional selective reflection of N* droplets—which thus act as spherically symmetric self-assembled photonic crystals—and total internal reflection at the continuous phase surface. We outline how the unique optical properties can be employed in numerous applications. [less ▲]

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See detailCellulose nanocrystal-based materials: from liquid crystal self-assembly and glass formation to multifunctional thin films
Lagerwall, Jan UL; Schütz, Christina; Salajkova, Michaela et al

in NPG Asia Materials (2014), 6(1), 80

Cellulose nanocrystals (CNCs), produced by the acid hydrolysis of wood, cotton or other cellulose-rich sources, constitute a renewable nanosized raw material with a broad range of envisaged uses: for ... [more ▼]

Cellulose nanocrystals (CNCs), produced by the acid hydrolysis of wood, cotton or other cellulose-rich sources, constitute a renewable nanosized raw material with a broad range of envisaged uses: for example, in composites, cosmetics and medical devices. The intriguing ability of CNCs to self-organize into a chiral nematic (cholesteric) liquid crystal phase with a helical arrangement has attracted significant interest, resulting in much research effort, as this arrangement gives dried CNC films a photonic band gap. The films thus acquire attractive optical properties, creating possibilities for use in applications such as security papers and mirrorless lasing. In this critical review, we discuss the sensitive balance between glass formation and liquid crystal self-assembly that governs the formation of the desired helical structure. We show that several as yet unclarified observations—some constituting severe obstacles for applications of CNCs—may result from competition between the two phenomena. Moreover, by comparison with the corresponding self-assembly processes of other rod-like nanoparticles, for example, carbon nanotubes and fd virus particles, we outline how further liquid crystal ordering phenomena may be expected from CNCs if the suspension parameters can be better controlled. Alternative interpretations of some unexpected phenomena are provided, and topics for future research are identified, as are new potential application strategies. [less ▲]

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See detailLiquid crystal-functionalization of electrospun polymer fibers
Kim, Dae Kyom; Hwang, Minsik; Lagerwall, Jan UL

in Journal of Polymer Science. Part B, Polymer Physics (2013), 51(11), 855-867

A recently introduced new branch of applied polymer science is the production of highly functional and responsive fiber mats by means of electrospinning polymers that include liquid crystals. The liquid ... [more ▼]

A recently introduced new branch of applied polymer science is the production of highly functional and responsive fiber mats by means of electrospinning polymers that include liquid crystals. The liquid crystal, which provides the responsiveness, is most often contained inside fibers of core-sheath geometry, produced via coaxial electrospinning, but it may also be inherent to the polymer itself, for example, in case of liquid crystal elastomers. The first experiments served as proof of concept and to elucidate the basic behavior of the liquid crystal in the fibers, and the field is now ripe for more applied research targeting novel devices, in particular in the realm of wearable technology. In this perspective, we provide a bird’s eye view of the current state of the art of liquid crystal electrospinning, as well as of some relevant recent developments in the general electrospinning and liquid crystal research areas, allowing us to sketch a picture of where this young research field and its applications may be heading in the next few years. [less ▲]

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See detailTuning the defect configurations in nematic and smectic liquid crystalline shells.
Liang, H. L.; Noh, Junghyun UL; Zentel, R. et al

in Philosophical Transactions of the Royal Society of London. Series A : Mathematical and Physical Sciences (2013), 371(1988), 20120258

Thin liquid crystalline shells surrounding and surrounded by aqueous phases can be conveniently produced using a nested capillary microfluidic system, as was first demonstrated by Fernandez-Nieves et al ... [more ▼]

Thin liquid crystalline shells surrounding and surrounded by aqueous phases can be conveniently produced using a nested capillary microfluidic system, as was first demonstrated by Fernandez-Nieves et al. in 2007. By choosing particular combinations of stabilizers in the internal and external phases, different types of alignment, uniform or hybrid, can be ensured within the shell. Here, we investigate shells in the nematic and smectic phases under varying boundary conditions, focusing in particular on textural transformations during phase transitions, on the interaction between topological defects in the director field and inclusions in the liquid crystal (LC), and on the possibility to relocate defects within the shell by rotating the shell in the gravitational field. We demonstrate that inclusions in a shell can seed defects that cannot form in a pristine shell, adding a further means of tuning the defect configuration, and that shells in which the internal aqueous phase is not density matched with the LC will gently rearrange the internal structure upon a rotation that changes the influence of gravity. Because the defects can act as anchor points for added linker molecules, allowing self-assembly of adjacent shells, the various arrangements of defects developing in these shells and the possibility of tuning the result by modifying boundary conditions, LC phase, thickness and diameter of the shell or applying external forces make this new LC configuration very attractive. [less ▲]

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See detailMorphology and Core Continuity of Liquid-crystal-functionalized, Coaxially Electrospun Fiber Mats Tuned Via the Polymer Sheath Solution
Scalia, Giusy; Enz, Eva; Calò, Oronzo et al

in Macromolecular Materials and Engineering (2013), 298(5), 583-589

By electrospinning liquid crystals coaxially inside a polymer sheath, responsive fibers with application potential, e.g., in wearable sensors can be produced. We conduct a combined scanning electron ... [more ▼]

By electrospinning liquid crystals coaxially inside a polymer sheath, responsive fibers with application potential, e.g., in wearable sensors can be produced. We conduct a combined scanning electron/polarizing microscopy study of such fibers, concluding that a match between the properties of the sheath solution and that of the core fluid is vital for achieving well-formed and well-filled fibers. Problems that may otherwise arise are fibers that are continuously filled, but partially collapsed; or fibers in which the core breaks up into droplets due to a mismatch in elongational viscosity between inner and outer fluids. [less ▲]

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See detailUtilizing the Krafft phenomenon to generate ideal micelle-free surfactant-stabilized nanoparticle suspensions
Dölle, Sarah; Lechner, Bob-Dan; Park, Ji Hyun et al

in Angewandte Chemie International Edition (2012), 51(13), 3254-3257

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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 detailA New Era for Liquid Crystal Research: Applications of Liquid Crystals in Soft Matter Nano-, Bio- and Microtechnology
Lagerwall, Jan UL; Scalia, G.

in Current Applied Physics (2012), 12(6), 1387-1412

Liquid crystals constitute a fascinating class of soft condensed matter characterized by the counterin- tuitive combination of fluidity and long-range order. Today they are best known for their ... [more ▼]

Liquid crystals constitute a fascinating class of soft condensed matter characterized by the counterin- tuitive combination of fluidity and long-range order. Today they are best known for their exceptionally successful application in flat panel displays, but they actually exhibit a plethora of unique and attractive properties that offer tremendous potential for fundamental science as well as innovative applications well beyond the realm of displays. Today this full breadth of the liquid crystalline state of matter is becoming increasingly recognized and numerous new and exciting lines of research are being opened up. We review this exciting development, focusing primarily on the physics aspects of the new research thrusts, in which liquid crystals e thermotropic as well as lyotropic e often meet other types of soft matter, such as polymers and colloidal nano- or microparticle dispersions. Because the field is of large interest also for researchers without a liquid crystal background we begin with a concise introduction to the liquid crystalline state of matter and the key concepts of the research field. We then discuss a selection of promising new directions, starting with liquid crystals for organic electronics, followed by nanotemplating and nanoparticle organization using liquid crystals, liquid crystal colloids (where the liquid crystal can constitute either the continuous phase or the disperse phase, as droplets or shells) and their potential in e.g. photonics and metamaterials, liquid crystal-functionalized polymer fibers, liquid crystal elastomer actuators, ending with a brief overview of activities focusing on liquid crystals in biology, food science and pharmacology. [less ▲]

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See detailTowards tunable defect arrangements in smectic liquid crystal shells utilizing the nematic-smectic transition in hybrid-aligned geometries
Liang, Hsin-Ling; Zentel, Rudolf; Rudquist, Per et al

in Soft Matter (2012), 8(20), 5443-5450

We produce and investigate liquid crystal shells with hybrid alignment—planar at one boundary, homeotropic at the other—undergoing a transition between the nematic (N) and smectic-A (SmA) phases. The ... [more ▼]

We produce and investigate liquid crystal shells with hybrid alignment—planar at one boundary, homeotropic at the other—undergoing a transition between the nematic (N) and smectic-A (SmA) phases. The shells display a dynamic sequence of patterns, the details depending on the alignment agents and on the diameter and thickness of the shell. In shells of sufficient diameter we typically find a transient striped texture near the N–SmA transition, stabilising into a pattern of tiled, more or less regularly spaced focal conic domains in the SmA phase. The domain size and spacing decrease with reduced shell thickness. In case of strong homeotropic anchoring at one boundary and small shell size, however, the increased curvature favors homeotropic against planar alignment in the smectic phase, and the shell then tends to adapt to complete homeotropic alignment at the final stage of the transition. This is the first study of hybrid-aligned smectic shells and the results constitute a beautiful demonstration of the capacity for dynamic structure formation and reformation via self-assembly in soft matter. The new patterns extend the range of arrays of topological defects that can be realised with liquid crystals in spherical morphology and the correlation between the feature arrangements and the variable parameters of the shell and its environment opens a route towards tunability. However, the observed strong impact from increasing curvature, even for these rather large shells, indicates that the choice of alignment agents inducing planar or homeotropic alignment with varying strength will become critical when targeting the most attractive colloidal size scale of about a micron or smaller. [less ▲]

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See detailEffects of chain branching and chirality on liquid crystalline phases of bent-core molecules: blue phases, de Vries transitions and switching of diastereomeric states
Ocak, Hale; Bilgin-Eran, Belkiz; Prehm, Marko et al

in Soft Matter (2011), 7(18), 8266-8280

Bent-core molecules based on a resorcinol bisbenzoate core with a series of distinct substituents in different positions at the central resorcinol core have been synthesized and characterized. The focus ... [more ▼]

Bent-core molecules based on a resorcinol bisbenzoate core with a series of distinct substituents in different positions at the central resorcinol core have been synthesized and characterized. The focus is on the effect of branched terminal groups in the racemic and chiral forms on the mesomorphic properties. These were investigated by differential scanning calorimetry, optical polarizing microscopy, X-ray diffraction, electro-optic and dielectric methods. Only bent-core mesogens derived from 4- cyanoresorcinol exhibit liquid crystalline phases and the mesophases of these compounds are strongly influenced by the branching and enantiomeric composition of the terminal chains. Depending on the structure of the rod-like wings and the enantiomeric composition, cybotactic nematic phases (NcybC), BPIII-like isotropic mesophases (BPIIIcybC*) and various polar and apolar smectic phases (SmA, SmC, SmC*, SmCsPA, SmCsPA*) are formed. For one compound, a de Vries type smectic phase is observed and it appears that with decreasing temperature, order develops in two steps. First, at the SmA to SmC transition, the tilt direction becomes long range ordered and in a second step a long range ordering in bend direction takes place. Hence, for the optically active compound a transition from chirality induced polar switching to bend induced (shape induced) antiferroelectricity takes place. In this SmCsPA* phase a homogeneous layer chirality is induced under an applied electric field which interacts with the fixed molecular chirality leading to the energetically favoured diastereomeric state and giving rise to a field direction dependent uniform tilt director orientation. Field reversal induces a flipping of the layer chirality, which first leads to the less favorable diastereomeric state, and then this slowly relaxes to the more stable one by a spontaneous reversal of the tilt direction. [less ▲]

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