Unclonable human-invisible machine vision markers leveraging the omnidirectional chiral Bragg diffraction of cholesteric spherical reflectors

in Light: Science and Applications (2022), 11(309), 10103841377-022-01002-4

The seemingly simple step of molding a cholesteric liquid crystal into spherical shape, yielding a Cholesteric Spherical Reflector (CSR), has profound optical consequences that open a range of ... [more ▼]

The seemingly simple step of molding a cholesteric liquid crystal into spherical shape, yielding a Cholesteric Spherical Reflector (CSR), has profound optical consequences that open a range of opportunities for potentially transformative technologies. The chiral Bragg diffraction resulting from the helical self-assembly of cholesterics becomes omnidirectional in CSRs. This turns them into selective retroreflectors that are exceptionally easy to distinguish— regardless of background—by simple and low-cost machine vision, while at the same time they can be made largely imperceptible to human vision. This allows them to be distributed in human-populated environments, laid out in the form of QR-code-like markers that help robots and Augmented Reality (AR) devices to operate reliably, and to identify items in their surroundings. At the scale of individual CSRs, unpredictable features within each marker turn them into Physical Unclonable Functions (PUFs), of great value for secure authentication. Via the machines reading them, CSR markers can thus act as trustworthy yet unobtrusive links between the physical world (buildings, vehicles, packaging,...) and its digital twin computer representation. This opens opportunities to address pressing challenges in logistics and supply chain management, recycling and the circular economy, sustainable construction of the built environment, and many other fields of individual, societal and commercial importance. [less ▲]

Robust cholesteric liquid crystal elastomer fibres for mechanochromic textiles

in Nature Materials (2022), 21(12), 14411447

Mechanically responsive textiles have transformative potential in many areas from fashion to healthcare. Cholesteric liquid crystal elastomers have strong mechanochromic responses that offer attractive ... [more ▼]

Mechanically responsive textiles have transformative potential in many areas from fashion to healthcare. Cholesteric liquid crystal elastomers have strong mechanochromic responses that offer attractive opportunities for such applications. Nonetheless, making liquid crystalline elastomer fibres suitable for textiles is challenging since the Plateau–Rayleigh instability tends to break up precursor solutions into droplets. Here, we report a simple approach that balances the viscoelastic properties of the precursor solution to avoid this outcome and achieve long and mechanically robust cholesteric liquid crystal elastomer filaments. These filaments have fast, progressive and reversible mechanochromic responses, from red to blue (wavelength shift of 155 nm), when stretched up to 200%. Moreover, the fibres can be sewed into garments and withstand repeated stretching and regular machine washing. This approach and resulting fibres may be useful for applications in wearable technology and other areas benefiting from autonomous strain sensing or detection of critically strong deformations. [less ▲]

Lipid islands on liquid crystal shells

in Physical Review Research (2022), 4

By inducing phase separation in lipid monolayers on liquid crystal (LC) shells—thin hollow spheres of LC with water inside and outside—we reveal a rich set of coupled two- and three-dimensional (2D and 3D ... [more ▼]

By inducing phase separation in lipid monolayers on liquid crystal (LC) shells—thin hollow spheres of LC with water inside and outside—we reveal a rich set of coupled two- and three-dimensional (2D and 3D) self- organization phenomena enabled by the dual closely spaced internal and external spherical LC-water interfaces. Spindle-shaped 2D islands of condensed lipid monolayer first form at the primary interface where lipids are deposited, later also at the initially unexposed secondary interface, because lipids transfer through the LC. The LCs’ elastic response to the 3D deformation caused by islands moves them from thin to thick regions on the shell and creates an attraction between opposite-side islands, topologically separated by the LCs, until they stack in a sandwich-like manner. We propose that the phase separation may be used for studying liposome adsorption on soft hydrophobic substrates, and to create unconventional colloidal particles with programmed interactions. [less ▲]

Combining responsiveness and durability in liquid crystal-functionalised electrospun fibres with crosslinked sheath

in Liquid Crystals (2021)

Responsive functional composite fibre mats that are mechanically stable and impervious to water exposure are produced by coaxial electrospinning of thermotropic liquid crystal (LC) core inside a water ... [more ▼]

Responsive functional composite fibre mats that are mechanically stable and impervious to water exposure are produced by coaxial electrospinning of thermotropic liquid crystal (LC) core inside a water-based solution of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) forming the sheath. Because thermotropic LCs usually cannot be spun inside water-based solutions due to excessive interfacial tension γ, a n enabling step is the addition of ethanol or dioxane to the LC as a co-solvent compatible with both core and sheath fluids. This reduces γ sufficiently that coaxial jet spinning is possible. After spinning, thermal cross-linking of the PVA+PAA sheath yields LC-functionalised fibres that can be manipulated by hand and remain intact even upon full immersion in water. The LC core retains its behaviour, nematics showing well-aligned birefringence and transitioning to isotropic upon heating above the clearing point, and cholesterics showing selective reflection which is even enhanced upon water immersion due to the removal of sheath scattering. Our results pave the way to producing LC-functionalised responsive fibre mats using durable polymer sheaths, thereby enabling numerous innovative applications in wearable technology, and they also open new opportunities to study LCs in confinement, without visible impact of the container walls. [less ▲]

Stable Electrospinning of Core-Functionalized Coaxial Fibers Enabled by the Minimum-Energy Interface Given by Partial Core− Sheath Miscibility

in Langmuir (2021), 37(45), 1326513277

Core−sheath electrospinning is a powerful tool for producing composite fibers with one or multiple encapsulated functional materials, but many material combinations are difficult or even impossible to ... [more ▼]

Core−sheath electrospinning is a powerful tool for producing composite fibers with one or multiple encapsulated functional materials, but many material combinations are difficult or even impossible to spin together. We show that the key to success is to ensure a well-defined core−sheath interface while also maintaining a constant and minimal interfacial energy across this interface. Using a thermotropic liquid crystal as a model functional core and polyacrylic acid or styrene-butadiene-styrene block copolymer as a sheath polymer, we study the effects of using water, ethanol, or tetrahydrofuran as polymer solvent. We find that the ideal core and sheath materials are partially miscible, with their phase diagram exhibiting an inner miscibility gap. Complete immiscibility yields a relatively high interfacial tension that causes core breakup, even preventing the core from entering the fiber- producing jet, whereas the lack of a well-defined interface in the case of complete miscibility eliminates the core−sheath morphology, and it turns the core into a coagulation bath for the sheath solution, causing premature gelation in the Taylor cone. Moreover, to minimize Marangoni flows in the Taylor cone due to local interfacial tension variations, a small amount of the sheath solvent should be added to the core prior to spinning. Our findings resolve a long-standing confusion regarding guidelines for selecting core and sheath fluids in core−sheath electrospinning. These discoveries can be applied to many other material combinations than those studied here, enabling new functional composites of large interest and application potential. [less ▲]

Measuring the Anisotropy in Interfacial Tension of Nematic Liquid Crystals

in Crystals (2021), 11(6), 687

<jats:p>Liquid crystal (LC) phases typically show anisotropic alignment-dependent properties, such as viscosity and dielectric permittivity, so it stands to reason that LCs also have anisotropic ... [more ▼]

<jats:p>Liquid crystal (LC) phases typically show anisotropic alignment-dependent properties, such as viscosity and dielectric permittivity, so it stands to reason that LCs also have anisotropic interfacial tensions. Measuring the interfacial tension ? of an LC with conventional methods, such as pendant drops, can be challenging, however, especially when we need to know ? for different LC aligning conditions, as is the case when we seek ??, the interfacial tension anisotropy. Here, we present measurements of ?? of the common synthetic nematic LC compound 5CB against water using a microfluidic droplet aspiration technique. To ensure tangential and normal alignment, respectively, we add poly(vinyl alcohol) (PVA) and sodium dodecylsulfate (SDS), respectively, as a stabilizer and measure ? for different concentrations of stabilizer. By fitting the Szyszkowski equation to the data, we can extrapolate to zero-stabilizer concentration, obtaining the ? of 5CB to pure water for each alignment. For normal alignment, we find ??=31.9?0.8 mN?m-1, on the order of 1 mN?m-1 greater than ?$_$=30.8?5 mN?m-1 for tangential alignment. This resonates with the empirical knowledge that 5CB aligns tangentially to an interface with pure water. The main uncertainty arises from the use of polymeric PVA as tangential-promoting stabilizer. Future improvements in accuracy may be expected if PVA can be replaced by a low molar mass stabilizer that ensures tangential alignment.</jats:p [less ▲]

Liquid crystal elastomer shells with topological defect-defined actuation: Complex shape morphing, opening/closing, and unidirectional rotation

in Journal of Applied Physics (2021), 129(17), 174701

We produce hollow sphere liquid crystal elastomer (LCE) actuators from a nematic precursor mixture, brought into the shape of a self-closing shell with tangential anchoring of the director field n(r ... [more ▼]

We produce hollow sphere liquid crystal elastomer (LCE) actuators from a nematic precursor mixture, brought into the shape of a self-closing shell with tangential anchoring of the director field n(r), using a solvent-assisted microfluidic technique. By separating the shell production from the polymerization and cross-linking, the precursor is allowed to approach its equilibrium n(r) configuration in the shell, spontaneously forming topological defects of total strength +2. However, the photopolymerization into an LCE induces a brief but strong distortion of the overall n(r) and the defect configuration, even changing the ground state shape in the case of thick shells. The resulting LCE shells show a rich capacity for reversible shape morphing upon heating and cooling, the exact actuation mode defined by n(r), and the final defect configuration stabilized at the end of polymerization. In regions with a single +1 defect, a reversal of curvature from concave to convex is found, punctured shells exhibit a strong shape change between a nearly closed sphere at low temperature and an open-ended spherocylinder at high temperature, and all shells rotate upon actuation when suspended in a fluid. As the rotation is stronger during relaxation than during actuation, thus breaking the symmetry, the net rotation is unidirectional. [less ▲]

Embedding Intelligence in Materials for Responsive Built Environment using Liquid Crystal Elastomer Actuators and Sensors

E-print/Working paper (2021)

Liquid Crystal Elastomers (LCEs) are an exciting category of material that has tremendous application potential across a variety of fields, owing to their unique properties that enable both sensing and ... [more ▼]

Liquid Crystal Elastomers (LCEs) are an exciting category of material that has tremendous application potential across a variety of fields, owing to their unique properties that enable both sensing and actuation. To some, LCEs are simply another type of Shape Memory Polymer, while to others they are an interesting on-going scientific experiment. In this visionary article, we bring an interdisciplinary discussion around creative and impactful ways that LCEs can be applied in the Built Environment to support kinematic and kinetic buildings and situational awareness. We focus particularly on the autonomy made possible by using LCEs, potentially removing needs for motors, wiring and tubing, and even enabling fully independent operation in response to natural environment variations, requiring no power sources. To illustrate the potential, we propose a number of concrete application scenarios where LCEs could offer innovative solutions to problems of great societal importance, such as autonomous active ventilation, heliotropic solar panels systems which can also remove snow or sand autonomously, and invisible coatings with strain mapping functionality, alerting residents in case of dangerous (static or dynamic) loads on roofs or windows, as well as assisting building safety inspection teams after earthquakes. [less ▲]

From Equilibrium Liquid Crystal Formation and Kinetic Arrest to Photonic Bandgap Films Using Suspensions of Cellulose Nanocrystals

in Crystals (2020), 10(3), 199

The lyotropic cholesteric liquid crystal phase developed by suspensions of cellulose nanocrystals (CNCs) has come increasingly into focus from numerous directions over the last few years. In part, this is ... [more ▼]

The lyotropic cholesteric liquid crystal phase developed by suspensions of cellulose nanocrystals (CNCs) has come increasingly into focus from numerous directions over the last few years. In part, this is because CNC suspensions are sustainably produced aqueous suspensions of a fully bio-derived nanomaterial with attractive properties. Equally important is the interesting and useful behavior exhibited by solid CNC films, created by drying a cholesteric-forming suspension. However, the pathway along which these films are realized, starting from a CNC suspension that may have low enough concentration to be fully isotropic, is more complex than often appreciated, leading to reproducibility problems and confusion. Addressing a broad audience of physicists, chemists, materials scientists and engineers, this Review focuses primarily on the physics and physical chemistry of CNC suspensions and the process of drying them. The ambition is to explain rather than to repeat, hence we spend more time than usual on the meanings and relevance of the key colloid and liquid crystal science concepts that must be mastered in order to understand the behavior of CNC suspensions, and we present some interesting analyses, arguments and data for the first time. We go through the development of cholesteric nuclei (tactoids) from the isotropic phase and their potential impact on the final dry films; the spontaneous CNC fractionation that takes place in the phase coexistence window; the kinetic arrest that sets in when the CNC mass fraction reaches ~10 wt.\%, preserving the cholesteric helical order until the film has dried; the 'coffee-ring effect' active prior to kinetic arrest, often ruining the uniformity in the produced films; and the compression of the helix during the final water evaporation, giving rise to visible structural color in the films. [less ▲]

Dynamic tuning of the director field in liquid crystal shells using block copolymers

in Physical Review Research (2020), 2(3), 033160

When an orientationally ordered system, like a nematic liquid crystal (LC), is confined on a self-closing spherical shell, topological constraints arise with intriguing consequences that depend critically ... [more ▼]

When an orientationally ordered system, like a nematic liquid crystal (LC), is confined on a self-closing spherical shell, topological constraints arise with intriguing consequences that depend critically on how the LC is aligned in the shell. We demonstrate reversible dynamic tuning of the alignment, and thereby the topology, of nematic LC shells stabilized by the nonionic amphiphilic block copolymer Pluronic F127. Deep in the nematic phase, the director (the average molecule orientation) is tangential to the interface, but upon approaching the temperature TNI of the nematic-isotropic transition, the director realigns to normal. We link this to a delicate interplay between an interfacial tension that is nearly independent of director orientation, and the configuration-dependent elastic deformation energy of an LC confined in a shell. The process is primarily triggered by the heating-induced reduction of the nematic order parameter, hence realignment temperatures differ by several tens of degrees between LCs with high and low TNI, respectively. The temperature of realignment is always lower on the positive-curved shell outside than at the negative-curved inside, yielding a complex topological reconfiguration on heating. Complementing experimental investigations with mathematical modeling and computer simulations, we identify and investigate three different trajectories, distinguished by their configurations of topological defects in the initial tangential-aligned shell. Our results uncover a new aspect of the complex response of LCs to curved confinement, demonstrating that the order of the LC itself can influence the alignment and thereby the topology of the system. They also reveal the potential of amphiphilic block copolymer stabilizers for enabling continuous tunability of LC shell configuration, opening doors for in-depth studies of topological dynamics as well as novel applications in, e.g., sensing and programed soft actuators. [less ▲]