Nematic Networks Research Articles

Diverse Self-assembly Pathways in Nematic Compartment Network: Topological Percolation and Pathfinding.

The self-assembly of nematic molecules in microcompartments with unambiguously defined surface anchoring is well predictable and is likely to have a single stable topological structure. Here, in contrast, a confined nematic system comprising an array of microcompartments interconnected by channels is demonstrated, exhibiting diverse molecular assembly pathways leading to the formation of four types of topological structures and twelve different patterns randomly distributed. Intercompartment communication via channels plays a crucial role in the diversity of patterns and distributions. It determines the sizes and structures of domains separated by channel defects. The domain structure, which features a pathfinding algorithm and reverse tree structure, can be modelled by an isotropically directed bond percolation with additional restrictions. This system serves as a model for controlled randomness and restricted growth of networks, with potential applications in anticounterfeit protection as a physically unclonable function (PUF) with multiple-level communication protocols.

Stable graphene oxide-based lyotropic liquid crystals for interfacial lubrication

Lyotropic liquid crystals have lubricating properties due to their ordered assembly and fluidity, whose mesogens are often characterized by amphiphilic properties. Despite the attention that graphene oxide (GO) has been studied as a novel amphiphilic lyotropic mesogen this decade, and GO applied as a lubrication additive has been demonstrated in both oil and water-based systems, little research reveals the interfacial lubrication of GO liquid crystals yet. This work reports that GO aqueous dispersion can form lyotropic liquid crystals above a specific critical concentration of 5.00 mg/mL, providing a form of stable water-based lubricant, which can keep stable for several months and can reduce friction by 37.3% and wear by 25.24%. The liquid crystal phase was verified by polarizing microscope and synchrotron radiation small-angle X-ray scattering, and its rheological properties and viscoelasticity were studied by interfacial rheometer. The formation of lyotropic liquid crystals can enhance the stability of GO aqueous dispersions at high density, simultaneously ensuring friction decrease and anti-wear effect. It is attributed to the stable nematic network by the ordered GO sheets. The ordered assembly structure bears vertical shear force, therefore, reducing the wear. It is also assumed that the wide lateral size of graphene oxide promotes the nematic phase thus smoothes the graphene oxide film composed spontaneously under the coincidence of lamellar liquid crystal and 2D layered material. Through this work, the interlayer lubrication of GO was optimized, and the problem of GO dispersion sedimentation was solved by self-assembly. The range of interfacial lubrication of GO aqueous dispersion has been expanded and the synergistic effect is conducive to the environmentally friendly lubricants.

Collective transport and reconfigurable assembly of nematic colloids by light-driven cooperative molecular reorientations.

Nanomotors in nature have inspired scientists to design synthetic molecular motors to drive the motion of microscale objects by cooperative action. Light-driven molecular motors have been synthesized, but using their cooperative reorganization to control the collective transport of colloids and to realize the reconfiguration of colloidal assembly remains a challenge. In this work, topological vortices are imprinted in the monolayers of azobenzene molecules which further interface with nematic liquid crystals (LCs). The light-driven cooperative reorientations of the azobenzene molecules induce the collective motion of LC molecules and thus the spatiotemporal evolutions of the nematic disclination networks which are defined by the controlled patterns of vortices. Continuum simulations provide physical insight into the morphology change of the disclination networks. When microcolloids are dispersed in the LC medium, the colloidal assembly is not only transported and reconfigured by the collective change of the disclination lines but also controlled by the elastic energy landscape defined by the predesigned orientational patterns. The collective transport and reconfiguration of colloidal assemblies can also be programmed by manipulating the irradiated polarization. This work opens opportunities to design programmable colloidal machines and smart composite materials.

Dynamically Tunable Optical Cavities with Embedded Nematic Liquid Crystalline Networks.

Tunable metal-insulator-metal (MIM) Fabry-Pérot (FP) cavities that can dynamically control light enable novel sensing, imagingand display applications. However, the realization of dynamic cavities incorporating stimuli-responsive materials poses a significant engineering challenge. Current approaches rely on refractive index modulation and suffer from low dynamic tunability, high losses, and limited spectral ranges, and require liquid and hazardous materials for operation. To overcome these challenges, a new tuning mechanism employing reversible mechanical adaptations of a polymer network is proposed, and dynamic tuning of optical resonances is demonstrated. Solid-state temperature-responsive optical coatings are developed by preparing a monodomain nematic liquid crystalline network (LCN) and are incorporated between metallic mirrors to form active optical microcavities. LCN microcavities offer large, reversible and highly linear spectral tuning of FP resonances reaching wavelength-shifts up to 40nm via thermomechanical actuation while featuring outstanding repeatability and precision over more than 100 heating-cooling cycles. This degree of tunability allows for reversible switching between the reflective and the absorbing states of the device over the entire visible and near-infrared spectral regions, reaching large changes in reflectance with modulation efficiency ΔR=79%.

Effects of microtubule length and crowding on active microtubule network organization

Active filament networks can organize into various dynamic architectures driven by cross-linking motors. Densities and kinetic properties of motors and microtubules have been shown previously to determine active microtubule network self-organization, but the effects of other control parameters are less understood. Using computer simulations, we study here how microtubule lengths and crowding effects determine active network architecture and dynamics. We find that attractive interactions mimicking crowding effects or long microtubules both promote the formation of extensile nematic networks instead of asters. When microtubules are very long and the network is highly connected, a new isotropically motile network state resembling a "gliding mesh" is predicted. Using invitro reconstitutions, we confirm the existence of this gliding mesh experimentally. These results provide a better understanding of how active microtubule network organization can be controlled, with implications for cell biology and active materials in general.

Bending and Stretching in a Narrow Ribbon of Nematic Polymer Networks

AbstractWe study the spontaneous out-of-plane bending of a planar untwisted ribbon composed of nematic polymer networks activated by a change in temperature. Our theory accounts for both stretching and bending energies, which compete to establish equilibrium. We show that when equilibrium is attained these energy components obey acomplementarityrelation: one is maximum where the other is minimum. Moreover, we identify ableachingregime: for sufficiently large values of an activation parameter (which measures the mismatch between the degrees of order in polymer organization in the reference and current configurations), the ribbon’s deformation is essentially independent of its thickness.

A Ribbon Model for Nematic Polymer Networks

We present a theory of deformation of ribbons made of nematic polymer networks (NPNs). These materials exhibit properties of rubber and nematic liquid crystals, and can be activated by external stimuli of heat and light. A two-dimensional energy for a sheet of such a material has already been derived from the celebrated neo-classical energy of nematic elastomers in three space dimensions. Here, we use a dimension reduction method to obtain the appropriate energy for a ribbon from the aforementioned sheet energy. We also present an illustrative example of a rectangular NPN ribbon that undergoes in-plane serpentine deformations upon activation under an appropriate set of boundary conditions.

Active transformations of topological structures in light-driven nematic disclination networks

SignificanceTopological defects are marvels of nature. Understanding their structures is important for their applications in, for example, directed self-assembly, sensing, and photonic devices. There is recent interest in active motion and transformation of topological defects in active nematics. In these nonequilibrium systems, however, the motion and transformation of disclinations are difficult to control, thereby hindering their applications. Here, we propose a surface-patterned system engendering periodic three-dimensional disclinations, which can be excited by light irradiation and undergo a programmable transformation between different topological states. Continuum simulations recapitulating these topological structures characterize the bending, breaking, and relinking events of the disclinations during the nonequilibrium process. Our work provides an alternative dynamic system in which active transformation of topological defects can be engineered.

Ridge approximation for thin nematic polymer networks

Nematic polymer networks (NPNs) are nematic elastomers within which the nematic director is enslaved to the elastic deformation. The elastic free energy of a NPN sheet of thickness h has both stretching and bending components (the former scaling like h, the latter scaling like h3). NPN sheets bear a director field m imprinted in them (usually, uniformly throughout their thickness); they can be activated by changing the nematic order (e.g., by illumination or heating). This paper illustrates an attempt to compute the bending energy of a NPN sheet and to show which role it can play in determining the activated shape. Our approach is approximate: the activated surface consists of flat sectors connected by ridges, where the unit normal jumps and the bending energy is concentrated. By increasing the number of ridges, we should get closer to the real situation, where the activated surface is smooth and the bending energy is distributed on it. The method is applied to a disk with imprinted a spiraling planar hedgehog. It is shown that upon activation the disk, like a tiny hand, is able to grab a rigid lamina.

Multifunctional sensors based on liquid crystals scaffolded in nematic polymer networks.

Stimuli-responsive liquid crystal (LC) materials have attracted great attention due to their unique characteristics and anisotropic properties. They are not only important for fundamental studies, but also have many potential applications in the electro-optical and biochemical fields. Herein, the interference color obtained from a nematic polymer network-stabilized liquid crystal (PNLC) system is demonstrated to reflect the environmental conditions, including temperature and the presence of volatile organic vapors. The polymerization of LC monomers forms a stable network to template the LCs, while still maintaining the dynamic nature and thermal tunability of LCs. Via adjusting the concentration of LC monomer, a wide temperature sensing range can be achieved between 36 °C and 100 °C with visible color. The same sensor can be used to detect concentration profiles of toluene vapor in a microchannel with a limit of detection of 2300 ppm. This stimuli-responsive PNLC system is expected to be potentially useful for many other naked-eye sensing applications.

Ridge energy for thin nematic polymer networks

Minimizing the elastic free energy of a thin sheet of nematic polymer network among smooth isometric immersions is the strategy purported by the mainstream theory. In this paper, we broaden the class of admissible spontaneous deformations: we consider ridged isometric immersions, which can cause a sharp ridge in the immersed surfaces. We propose a model to compute the extra energy distributed along such ridges. This energy comes from bending; it is shown under what circumstances it scales quadratically with the sheet’s thickness, falling just in between stretching and bending energies. We put our theory to the test by studying the spontaneous deformation of a disk on which a radial hedgehog was imprinted at the time of crosslinking. We predict the number of folds that develop in terms of the degree of order induced in the material by external agents (such as heat and illumination).Graphic

Preferential Circularly Polarized Luminescence from a Nano-Segregated Liquid Crystalline Phase Using a Polymerized Twisted Nematic Platform.

In this study, a polymerized twisted nematic (TN) network was used as an extrinsic chiral platform to overcome the heterogeneity during spontaneous symmetry breaking in a mixed system comprising an achiral bent-core molecule and rod-like mesogen. The TN platform was prepared by photopolymerizing a reactive mesogen dispersed in a low molecular weight liquid crystal with TN orientation. The use of TN orientation to correct the degeneracy in bent-core molecular systems has been previously reported; however, to the best of our knowledge, this is the first study that uses an extrinsic chiral platform of a polymerized TN network. The heterogeneity in the nano-segregated phase of the achiral mixture was suppressed using the extrinsic TN platform with a twisted angle θ of ≥ |±30°|. When an achiral mixture doped with a luminescent guest molecule was refilled into the extrinsic chiral platform, preferential deracemization with one-handedness occurred, corresponding to the handedness of the TN platform. Therefore, circularly polarized luminescence with a preferential handedness can be achieved using this extrinsic chiral platform.

Irreversible Shear-Activated Gelation of a Liquid Crystalline Polyelectrolyte.

We report irreversible, shear-activated gelation in liquid crystalline solutions of a rigid polyelectrolyte that forms rodlike assemblies (rods) in salt-free solution. At rest, the liquid crystalline solutions are kinetically stable against gelation and exhibit low viscosities. Under steady shear at, or above, a critical shear rate, a physically cross-linked, nematic gel network forms due to linear growth and branching of the rods. Above a critical shear rate, the time scale of gelation can be tuned from hours to nearly instantaneously by varying the shear rate and solution concentration. The shear-activated gels are distinct in their structure and rheological properties from thermoreversible gels. At a fixed concentration, the induction time prior togelation decreases exponentially with the shear rate. This result indicates that shear-activated thermalization of the electrostatically stabilized rods overcomes the energy barrier for rod-rod contact, enabling rod fusion and subsequent irreversible network formation.

Mechanics of transiently cross-linked nematic networks

Polymeric networks are ubiquitous in biology and are vital components to some of the key functions of life. Composite networks of stiff and flexible polymers such as the actin-filamin network of the cytoskeleton posses novel mechanical properties that arise from physical interactions, geometry and topology of the network. Particularly, (a) the cross-linking chains in these networks dynamically break and reform in time that drive their rheological properties, and (b) stiff rod-like polymers have been found to show liquid crystalline phases including nematic alignment. Models of such transient nematic networks are either phenomenological or computational thereby lacking the simplicity of physics-based models in elucidating the key physical mechanisms. We present here a modelling framework using the statistically-based transient network theory to describe the rate-dependent mechanics of nematic networks. The model bridges continuum mechanics quantities to statistical measures of chain distribution in the network such as the conformation tensor. We show that the model degenerates to classical theories of anisotropic solids when the bonds are permanent and to anisotropic fluids when the bond exchange is rapid. The effect of the interplay between the bond dynamics and geometry of the network on its emergent mechanics is explored and illustrated using the example of a thin-walled tube under pressure. The generality of the framework and its potential to describe continuum level mechanics based on a variety of local physical interactions and network geometries is discussed.

A blend of stretching and bending in nematic polymer networks.

Nematic polymer networks are (heat and light) activable materials, which combine the features of rubber and nematic liquid crystals. When only the stretching energy of a thin sheet of nematic polymer network is minimized, the intrinsic (Gaussian) curvature of the shape it takes upon (thermal or optical) actuation is determined. This, unfortunately, produces a multitude of possible shapes, for which we need a selection criterion, which may only be provided by a correcting bending energy depending on the extrinsic curvatures of the deformed shape. The literature has so far offered approximate corrections depending on the mean curvature. In this paper, we derive the appropriate bending energy for a sheet of nematic polymer network from the celebrated neo-classical energy of nematic elastomers in three space dimensions. This task is performed via a dimension reduction based on a modified Kirchhoff-Love hypothesis, which withstands the criticism of more sophisticated analytical tools. The result is a surface elastic free-energy density where stretching and bending are blended together; they may or may not be length-separated, and should be minimized together. The extrinsic curvatures of the deformed shape not only feature in the bending energy through the mean curvature, but also through the relative orientation of the nematic director in the frame of the directions of principal curvatures.

A Mechanistic View of Collective Filament Motion in Active Nematic Networks

Protein filament networks are structures crucial for force generation and cell shape. A central open question is how collective filament dynamics emerges from interactions between individual network constituents. To address this question, we study a minimal but generic model for a nematic network in which filament sliding is driven by the action of motor proteins. Our theoretical analysis shows how the interplay between viscous drag on filaments and motor-induced forces governs force propagation through such interconnected filament networks. We find that the ratio between these antagonistic forces establishes the range of filament interaction, which determines how the local filament velocity depends on the polarity of the surrounding network. This force-propagation mechanism implies that the polarity-independent sliding observed in Xenopus egg extracts and in vitro experiments with purified components is a consequence of a large force-propagation length. We suggest how our predictions can be tested by tangible in vitro experiments whose feasibility is assessed with the help of simulations and an accompanying theoretical analysis.

Highly chromatic retardation via multi-twist liquid crystal films

Here we study birefringent films with highly customizable chromatic retardation spectra, using multi-twist liquid crystal (LC) films. These are made of two or more layers of chiral nematic LC polymer network materials, also known as reactive mesogens, which form a monolithic thin-film wherein the in-plane orientation of subsequent layers is automatically determined by the single alignment layer on the substrate. The multiple layer thicknesses and twists present many degrees of freedom to tailor the retardation. While prior work examined achromatic spectra, here we show how to use Mueller matrix analysis to create highly chromatic spectra. We experimentally demonstrate both a uniformly aligned retarder as a green/magenta color filter and a “hot” polarization grating (PG) that diffracts infrared while passing visible light. The three-twist color filter shows a contrast ratio in transmittance between polarizers as high as 10:1 between the half- and zero-wave retardation bands. The “hot” PG shows an average first-order efficiency of about 90% for 1000–2700 nm and an average zero-order efficiency of about 90% for 500–900 nm. The principles here can be extended to nearly any chromatic retardation spectra, including high/low/bandpass, and to nearly any LC orientation pattern, in general known as geometric-phase holograms.

Determinants of Polar versus Nematic Organization in Networks of Dynamic Microtubules and Mitotic Motors

SummaryDuring cell division, mitotic motors organize microtubules in the bipolar spindle into either polar arrays at the spindle poles or a “nematic” network of aligned microtubules at the spindle center. The reasons for the distinct self-organizing capacities of dynamic microtubules and different motors are not understood. Using in vitro reconstitution experiments and computer simulations, we show that the human mitotic motors kinesin-5 KIF11 and kinesin-14 HSET, despite opposite directionalities, can both organize dynamic microtubules into either polar or nematic networks. We show that in addition to the motor properties the natural asymmetry between microtubule plus- and minus-end growth critically contributes to the organizational potential of the motors. We identify two control parameters that capture system composition and kinetic properties and predict the outcome of microtubule network organization. These results elucidate a fundamental design principle of spindle bipolarity and establish general rules for active filament network organization.

Interfacial liquid crystalline mesophase domain on carbon nanofillers in aromatic thermosetting copolyester matrix

ABSTRACTThis work presents the formation process and thermophysical characteristics of preferentially oriented interfacial liquid crystalline (LC) mesophase domain emerging around graphene nanoplatelet (GNP) particles within an amorphous aromatic thermosetting copolyester (ATSP) matrix. Acetoxy‐ and carboxylic acid‐capped matched oligomers of ATSP interact with oxygen‐bearing functional groups on the GNPs during the thermal polymerization process which tethers the nanofillers to the crosslinked polymer backbone. Upon curing, a nematic phase LC network develops at the nanoparticle and matrix interface via the crystalline carbonaceous structure induced local ordering effects. The LC region exhibits a thermally reversible phase transition characteristic; attains an isotropic morphology through a heating cycle and reverses to the nematic form following a subsequent cooling cycle. Solid‐state nuclear magnetic resonance spectroscopy analysis reveals the presence of a robust interfacial attachment between the GNPs and ATSP backbone. The strong covalent conjugation induces a marked upshift in the glass transition temperature (Tg) in the ATSP‐GNP nanocomposites. Introduction of an LC interlayer region surrounding the nanofillers facilitated by a strong interfacial attachment mechanism could help to optimize the performance of polymer nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46584.

Anisotropic Dye Adsorption and Anhydrous Proton Conductivity in Smectic Liquid Crystal Networks: The Role of Cross-Link Density, Order, and Orientation.

In this work, the decisive role of rigidity, orientation, and order in the smectic liquid crystalline network on the anisotropic proton and adsorbent properties is reported. The rigidity in the hydrogen-bonded polymer network has been altered by changing the cross-link density, the order by using different mesophases (smectic, nematic, and isotropic phases), whereas the orientation of the mesogens was controlled by alignment layers. Adding more cross-linkers improved the integrity of the polymer films. For the proton conduction, an optimum was found in the amount of cross-linker and the smectic organization results in the highest anhydrous proton conduction. The polymer films show anisotropic proton conductivity with a 54 times higher conductivity in the direction perpendicular to the molecular director. After a base treatment of the smectic liquid crystalline network, a nanoporous polymer film is obtained that also shows anisotropic adsorption of dye molecules and again straight smectic pores are favored over disordered pores in nematic and isotropic networks. The highly cross-linked films show size-selective adsorption of dyes. Low cross-linked materials do not show this difference due to swelling, which decreases the order and creates openings in the two-dimensional polymer layers. The latter is, however, beneficial for fast adsorption kinetics.