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


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 ▲]

Cellulose nanocrystal-based materials: from liquid crystal self-assembly and glass formation to multifunctional thin films

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 ▲]

Liquid crystal-functionalization of electrospun polymer fibers

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 ▲]

One-piece micropumps from liquid crystalline core-shell particles

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 ▲]

A New Era for Liquid Crystal Research: Applications of Liquid Crystals in Soft Matter Nano-, Bio- and Microtechnology

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 ▲]

Effects of chain branching and chirality on liquid crystalline phases of bent-core molecules: blue phases, de Vries transitions and switching of diastereomeric states

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 ▲]

Nematic-smectic transition under confinement in liquid crystalline colloidal shells

in Physical Review Letters (2011), 106(24), 247801

We carry out the first study of smectic liquid crystalline colloidal shells and investigate how their complex internal structure depends on the director configuration in the nematic phase, preceding the ... [more ▼]

We carry out the first study of smectic liquid crystalline colloidal shells and investigate how their complex internal structure depends on the director configuration in the nematic phase, preceding the smectic phase on cooling. Differences in the free energy cost of director bend and splay give an initial skewed distribution of topological defects in the nematic phase. In the smectic phase, the topological and geometrical constraints of the spherical shell imposed on the developing 1D quasi-long-range order create a conflict that triggers a series of buckling instabilities. Two different characteristic defect patterns arise, one driven by the curvature of the shell, the other by the strong nonuniformities in the director field in the vicinity of the topological defects. [less ▲]

Towards efficient dispersion of carbon nanotubes in thermotropic liquid crystals

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 ▲]

Self-assembled ordered structures in thin films of HAT5 discotic liquid crystal

in Beilstein Journal of Organic Chemistry (2010), 6(51), 103762651

Thin films of the discotic liquid crystal hexapentyloxytriphenylene (HAT5), prepared from solution via casting or spin-coating, were investigated by atomic force microscopy and polarizing optical ... [more ▼]

Thin films of the discotic liquid crystal hexapentyloxytriphenylene (HAT5), prepared from solution via casting or spin-coating, were investigated by atomic force microscopy and polarizing optical microscopy, revealing large-scale ordered structures substan- tially different from those typically observed in standard samples of the same material. Thin and very long fibrils of planar-aligned liquid crystal were found, possibly formed as a result of an intermediate lyotropic nematic state arising during the solvent evapor- ation process. Moreover, in sufficiently thin films the crystallization seems to be suppressed, extending the uniform order of the liquid crystal phase down to room temperature. This should be compared to the bulk situation, where the same material crystallizes into a polymorphic structure at 68 °C. [less ▲]

Electrospun Microfibres With Temperature Sensitive Iridescence From Encapsulated Cholesteric Liquid Crystal

in Journal of Materials Chemistry (2010), 20(33), 6866-6872

We apply coaxial electrospinning to produce core-sheath polymer composite fibres with encapsulated short-pitch cholesteric liquid crystal, giving the fibres iridescent colours due to selective reflection ... [more ▼]

We apply coaxial electrospinning to produce core-sheath polymer composite fibres with encapsulated short-pitch cholesteric liquid crystal, giving the fibres iridescent colours due to selective reflection within a narrow band of the visible wavelength spectrum. By modifying the feed rate of the liquid crystal during spinning we can tune the fibre diameter from the sub-micron range to about 7 mm, other ranges being accessible via further modifications of the spinning parameters. We demonstrate that the thinnest fibres display quantised colours, determined primarily by the core diameter, whereas the thicker fibres allow a quasi-continuous change in colour if the cholesteric helix pitch changes. Because of the strong response function of liquid crystals, phases as well as structures changing in response to small changes in the environment, the resulting non-woven fibre mats have potential for smart textiles, in particular in sensing applications. [less ▲]