Tuning Self-Assembly in Liquid Crystal shells: from Interfacial- to Polymer-stabilization

Doctoral thesis (2018)

Liquid crystals form a subclass of soft materials which is easily influenced and deformed by a surface, an interface and the geometry. Of particular interest, in this thesis, is the confinement of liquid ... [more ▼]

Liquid crystals form a subclass of soft materials which is easily influenced and deformed by a surface, an interface and the geometry. Of particular interest, in this thesis, is the confinement of liquid crystals in shell geometry, imposing real or virtual defects that the liquid crystal cannot avoid. With the help of microfluidics, we prepare our research platform, liquid crystal shells, which contain and are surrounded by aqueous phases. In order to maintain such a shell structure in the aqueous phases, immiscible with the liquid crystal, appropriate stabilization is required. Here we explore two different pathways of interfacial stabilization and polymer stabilization and their impact on liquid crystal self-assembly. We primarily use either a polymeric or an ionic surfactant dissolving in water to stabilize shells and tune boundary conditions of shells. Depending on symmetrically or asymmetrically imposed boundary conditions, the nematic–isotropic phase transition appears as a single transi- tion or separated into two steps. We propose that the latter phenomenon can be understood as a result of an ordering-enhancing effect by surfactants. The nematic–smectic A phase transition is also investigated under varying boundary conditions. With a precise temperature control, we explore equilibrium smectic structures and introduce a new arrangement of focal conic arrays in shell geometry. Beyond stabilizing the shell from the shell exterior, but we also incorporate a photosensitive surface agent within the shell, enabling dynamic and reversible photoswitching of the liquid crystal alignment in real time. However, shells with interfacial stabilization cannot survive more than several weeks due to their intrinsic fluid interfaces. In particular, a liquid crystal shell can serve as a permeable mem- brane which lets the constituents of aqueous phases pass through, giving a significant influence on the liquid crystalline order. To tame liquid crystal self-assembly and make the shell struc- ture permanent, we use photopolymerization to stabilize the shells. With only 5% monomer, the entire configuration of each liquid crystal shell is locked and shell lifetime extends beyond several months. The liquid crystalline order is visualized on the nanoscale via the polymer network and we further demonstrate that the shell configurations can be a unique template for creating complex polymer networks. Finally a new experimental approach is introduced to making ultrathin shells and several issues on shell instability and alignment determination are addressed. [less ▲]

Elucidating the fine details of cholesteric liquid crystal shell reflection patterns

in Liquid Crystals (2017), 44(12-13),

Clusters of planar-aligned short-pitch cholesteric liquid crystal spheres generate dynamic colourful patterns due to multiple selective reflections from the radially oriented cholesteric helices in ... [more ▼]

Clusters of planar-aligned short-pitch cholesteric liquid crystal spheres generate dynamic colourful patterns due to multiple selective reflections from the radially oriented cholesteric helices in neighbour shells at varying distances. These photonic communication patterns were widely investigated for the cases of both droplets and shells, demonstrating not only intriguing optical phenomena but also potential for applications as new optical elements for photonics, sensing or security pattern generation. However, the optics of these clusters is truly complex and until now only the strongest and most fundamental reflections have been analysed and explained. In this report, we elucidate the origin of a number of more subtle reflections and we explain the extension in space of various spots as well as their internal colour variations. [less ▲]

Liquid crystals in micron-scale droplets, shells and fibers

in Journal of Physics : Condensed Matter (2017), 29

The extraordinary responsiveness and large diversity of self-assembled structures of liquid crystals are well documented and they have been extensively used in devices like displays. For long, this ... [more ▼]

The extraordinary responsiveness and large diversity of self-assembled structures of liquid crystals are well documented and they have been extensively used in devices like displays. For long, this application route strongly influenced academic research, which frequently focused on the performance of liquid crystals in display-like geometries, typically between flat, rigid substrates of glass or similar solids. Today a new trend is clearly visible, where liquid crystals confined within curved, often soft and flexible, interfaces are in focus. Innovation in microfluidic technology has opened for high-throughput production of liquid crystal droplets or shells with exquisite monodispersity, and modern characterization methods allow detailed analysis of complex director arrangements. The introduction of electrospinning in liquid crystal research has enabled encapsulation in optically transparent polymeric cylinders with very small radius, allowing studies of confinement effects that were not easily accessible before. It also opened the prospect of functionalizing textile fibers with liquid crystals in the core, triggering activities that target wearable devices with true textile form factor for seamless integration in clothing. Together, these developments have brought issues center stage that might previously have been considered esoteric, like the interaction of topological defects on spherical surfaces, saddle-splay curvature-induced spontaneous chiral symmetry breaking, or the non-trivial shape changes of curved liquid crystal elastomers with non-uniform director fields that undergo a phase transition to an isotropic state. The new research thrusts are motivated equally by the intriguing soft matter physics showcased by liquid crystals in these unconventional geometries, and by the many novel application opportunities that arise when we can reproducibly manufacture these systems on a commercial scale. This review attempts to summarize the current understanding of liquid crystals in spherical and cylindrical geometry, the state of the art of producing such samples, as well as the perspectives for innovative applications that have been put forward. [less ▲]

Correlation between structural properties and iridescent colors of cellulose nanocrystalline films

in Cellulose (2016)

We investigate the effect of shear flow applied during the drying of aqueous suspension of cellulose nanocrystals on optical reflective properties and structural characteristics of the resulting ... [more ▼]

We investigate the effect of shear flow applied during the drying of aqueous suspension of cellulose nanocrystals on optical reflective properties and structural characteristics of the resulting solidified films. Shear flow can significantly improve internal structural homogeneity of the films, while its effect on optical reflective properties is relatively minor. The measured width of the selective reflection peak is an order of magnitude larger than expected for an ideal helically modulated structure, which reflects a distribution of pitch values and possibly also of regimes of distorted helical modulation. We attribute these imperfections to the broad size distribution of the cellulose nanocrystals. [less ▲]

Transmission polarized optical microscopy of short-pitch cholesteric liquid crystal shells

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 ▲]

Dynamic and complex optical patterns from colloids of cholesteric liquid crystal droplets

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 ▲]

Tuneable Multicoloured Patterns From Photonic Cross Communication Between Cholesteric Liquid Crystal Droplets

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 ▲]

Tuning the defect configurations in nematic and smectic liquid crystalline shells.

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 ▲]