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).
Motivated by the need for greater understanding of systems that involve interfaces between a nematic liquid crystal, a solid substrate, and a passive gas that includes nematic--substrate--gas three-phase contact lines, we analyse a two-dimensional static ridge of nematic resting on a solid substrate in an atmosphere of passive gas. Specifically, we obtain the first complete theoretical description for this system, including nematic Young and Young--Laplace equations, and then, under the assumption that anchoring breaking occurs in regions adjacent to the contact lines, we use the nematic Young…
We investigate the tight packing of nematic polymers inside a confining hard sphere. We model the polymer {\sl via} the continuum Frank elastic free energy augmented by a simple density dependent part as well as by taking proper care of the connectivity of the polymer chains when compared with simple nematics. The free energy {\sl ansatz} is capable of describing an orientational ordering transition within the sample between an isotropic polymer solution and a polymer nematic phase. We solve the Euler-Lagrange equations numerically with the appropriate boundary conditions for the director and …
We investigate condensation of a long confined chiral nematic polymer inside a spherical enclosure, mimicking condensation of DNA inside a viral capsid. The Landau-de Gennes nematic free energy {\sl Ansatz} appropriate for nematic polymers allows us to study the condensation process in detail with different boundary conditions at the enclosing wall that simulate repulsive and attractive polymer-surface interactions. Increasing the chirality, we observe a transformation of the toroidal condensate into a closed surface with an increasing genus, akin to the ordered domain formation observed in cr…
We present a Monte Carlo simulation of a polymer nematic for varying volume fractions, concentrating on the structure function of the sample. We achieve nematic ordering with stiff polymers made of spherical monomers that would otherwise not form a nematic state. Our results are in good qualitative agreement with theoretical and experimental predictions, most notably the bowtie pattern in the static structure function.
Conformations of a single semiflexible polymer chain dissolved in a low molecular weight liquid crystalline solvents (nematogens) are examined by using a mean field theory. We takes into account a stiffness and partial orientational ordering of the polymer. As a result of an anisotropic coupling between the polymer and nematogen, we predict a discontinuous (or continuous) phase transition from a condensed-rodlike conformation to a swollen-one of the polymer chain, depending on the stiffness of the polymer. We also discuss the effects of the nematic interaction between polymer segments.
We present an experimental study of the isotropic-nematic phase transition in an aqueous mixture of charged semi-flexible rods (fd virus) and neutral polymer (Dextran). A complete phase diagram is measured as a function of ionic strength and polymer molecular weight. At high ionic strength we find that adding polymer widens the isotropic-nematic coexistence region with polymers preferentially partitioning into the isotropic phase, while at low ionic strength the added polymer has no effect on the phase transition. The nematic order parameter is determined from birefringence measurements and is…
The nematic ordering in semiflexible polymers with contour length $L$ exceeding their persistence length $\ell_p$ is described by a confinement of the polymers in a cylinder of radius $r_{eff}$ much larger than the radius $r_ρ$, expected from the respective concentration of the solution. Large scale Molecular Dynamics simulations combined with Density Functional Theory are used to locate the Isotropic-Nematic ($I-N$)-transition and to validate this cylindrical confinement. Anomalous fluctuations, due to chain deflections from neighboring chains in the nematic phase are proposed. Considering de…
We directly visualize single polymers with persistence lengths ranging from $\ell_p=0.05$ to 16 $μ$m, dissolved in the nematic phase of rod-like {\it fd} virus. Polymers with sufficiently large persistence length undergo a coil-rod transition at the isotropic-nematic transition of the background solvent. We quantitatively analyze the transverse fluctuations of semi-flexible polymers and show that at long wavelengths they are driven by the fluctuating nematic background. We extract both the Odijk deflection length and the elastic constant of the background nematic phase from the data.
Binary mixtures of semiflexible polymers with the same chain length but different persistence lengths separate into two coexisting different nematic phases when the osmotic pressure of the lyotropic solution is varied. Molecular Dynamics simulations and Density Functional Theory predict phase diagrams either with a triple point, where the isotropic phase coexists with two nematic phases, or a critical point of unmixing within the nematic mixture. The difference in locally preferred bond angles between the constituents drives this unmixing without any attractive interactions between monomers.
Most, but not all, liquid crystals tend to align when subject to shear flow, while most nematic polymeric liquid crystals undergo a tumbling instability, where the director rotate with the flow. The reasons of this instability remain elusive, as it is possible to find similar molecules exhibiting opposite behaviors. We propose a theory suitable for describing a wide range of material behaviors, ranging form nematic elastomers to nematic polymers and nematic liquid crystals, where the physical origins of tumbling emerge clearly. There are two possible ways to relax the internal stress in a nema…
The critical field of the Freedericksz transition and switching dynamics are investigated for polymer stabilized nematic liquid crystals as a function of polymer concentration. A simple phenomenological model is proposed to describe the observed critical field and dynamic response time behaviors as a function of concentration. In this model the polymer fibrils form director domains, which are bounded by virtual surfaces with a finite anchoring energy. The Freedericksz transition occurs independently within each of these domains.
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…
We derive the "conservation law" for nematic polymers in tensorial form valid for quadrupolar orientational order in contradistinction to the conservation law in the case of polar orientational order. Due to microscopic differences in the coupling between the orientational field deformations and the density variations for polar and quadrupolar order, we find that respective order parameters satisfy fundamentally distinct constraints. Being necessarily scalar in its form, the tensorial conservation law is obtained straightforwardly from the gradients of the polymer nematic tensor field and conn…
We provide experimental evidence that photoalignment at the nematic liquid crystal (NLC) - polymer interface can not be simply considered as a two-dimensional process. Moreover, our experiments clearly indicate that the photoaligning process does not depend on the individual properties of the NLC material and those of the interfacing polymer exclusively. According to our measurements, the polymer and the NLC layer "sense-each-other", i.e., the polymer-liquid crystal interface should be regarded as a coupled system, where the two components mutually influence each other. Furthermore, we show th…
The relation between elasticity and yielding is investigated in a model polymer solid by Molecular-Dynamics simulations. By changing the bending stiffness of the chain and the bond length, semicrystalline and disordered glassy polymers - both with bond disorder - as well as nematic glassy polymers with bond ordering are obtained. It is found that in systems with bond disorder the ratio Ty/G between the shear yield strength Ty and the shear modulus G is close to the universal value of the atomic metallic glasses. The increase of the local nematic order in glasses leads to the increase of the sh…
We 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 a \emph{complementarity} relation: one is maximum where the other is minimum. Moreover, we identify a \emph{bleaching} regime: for sufficiently large values of an activation parameter (which measures the mismatch between the degrees of order in polymer organization in the refe…
We explore the implications of the conservation law(s) and the corresponding "continuity equation(s)", resulting from the coupling between the positional and the orientational order in main-chain polymer nematics, by showing that the vectorial and tensorial forms of these equations are in general not equivalent and can not be reduced to one another, but neither are they disjoint alternatives. We analyze the relation between them and elucidate the fundamental role that the chain backfolding plays in the determination of their relative strength and importance. Finally, we show that the correct p…
The influence of the molecular structure of the nematic liquid crystal (NLC) on the photoalignment process at the NLC -- polymer interface has been investigated experimentally. NLCs having exclusively phenyl-, or cyclohexane rings in the rigid core, as well as NLCs containing both phenyl and cyclohexane groups have been considered. Substantial differences have been found in the photoalignment process depending on the molecular structure of the NLC, supporting the assumption that the polymer -- NLC interface should be regarded as a coupled system, where the two components mutually influence eac…
Using a geometry-based fundamental measure density functional theory, we calculate bulk fluid phase diagrams of colloidal mixtures of vanishingly thin hard circular platelets and hard spheres. We find isotropic-nematic phase separation with strong broadening of the biphasic region upon increasing the pressure. In mixtures with large size ratio of platelet and sphere diameter, there is also demixing between two nematic phases with differing platelet concentrations. We formulate a fundamental-measure density functional for mixtures of colloidal platelets and freely overlapping spheres, which rep…
Orientational dynamics in the isotropic phase of a comb-shaped nematic polymer with mesogenic and functional side groups was studied using the Kerr effect and dielectric spectroscopy. For the first time, it was found that in a mesogenic polymer, in contrast to low-molecular-weight mesogens, the relaxation of the electric birefringence of a melt above the temperature of the nematic-isotropic phase transition can be presented by a sum of several exponential processes, two of which play a decisive role. These main processes replace each other in a temperature range of about fifty degrees. Dielect…
We establish a macroscopic description of the splay--density coupling in semiflexible main-chain nematic polymers with hairpins, using a vectorial continuity constraint for the "recovered" polar order of the chain tangents and introducing chain backfolds (hairpins) as its new type of sources besides chain ends. We treat both types of sources on a unified basis as a mixture of two ideal gases with fixed composition. Performing detailed Monte Carlo simulations of nematic monodomain melts of "soft" worm-like chains with variable length and flexibility, we show via their structure factors that the…
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 $h^3$). NPN sheets bear a director field $\mathbf{m}$ 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 pla…
The optical polarimetry technique is used to explore molecular ordering of nematic liquid crystals 5FPFFPP3 embedded in parallel cylindrical channels of alumina membranes with pore walls covered by a SE-1211 polymer film enhancing normal anchoring. A chemical film deposition from organic solution apparently results in inhomogeneous coverage with local islands on the channels walls. Accordingly, a coexistence of differently ordered LC regions (nanodomains), characterized by positive and negative anisotropy, results in a weak effective (average) optical birefringence. Repeated polymer deposition…
We formulate the dynamical theory of nematic polymers, starting from a microscopic Poisson bracket approach. We find that the Poisson bracket between the nematic director and momentum depends on the (Maier-Saupe) order parameter of the nematic phase. We use this to derive reactive couplings of the nematic director to the strain rates. Additionally, we find that local dynamics breaks down as the polymers begin to overlap. We offer a physical picture for both results.
The elastic interactions between objects embedded in a nematic liquid crystal are usually caused by the average distorsion-rather than by the fluctuations-of the nematic orientational field. We argue that for sufficiently small particles, the nematic-mediated interaction originates purely from the fluctuations of the nematic director. This Casimir interaction decays as d^(-6), d being the distance between the particles, and it dominates van der Waals interactions close to the isotropic-to-nematic transition. Considering the nematic as a polymer solvent, we show that the onset of this Casimir i…
A spontaneous buckling transition in thin layers of monodomain nematic liquid crystalline gel was observed by polarized light microscopy. The coupling between the orientational ordering of liquid crystalline solvent and the translational ordering of crosslinked polymer backbones inside the nematic gel contributes to such buckling transition. As the nematic mesogens become more ordered when the gel is cooled down from a higher gelation temperature, the polymeric backbones tend to elongate along the direction parallel to the nematic director, which is perpendicular to the rigid glass surfaces in…
We investigate the pseudo-Casimir force in a slab of material composed of nematically ordered long polymers. We write the total mesoscopic energy together with the constraint connecting the local density and director fluctuations and evaluate the corresponding fluctuation free energy by standard methods. It leads to a pseudo-Casimir force of a different type than in the case of standard, short molecule nematic. We investigate its separation dependence and its magnitude and explicitly derive the relevant limiting cases.
We theoretically study the nematic ordering transition of rods that are able to elastically adjust their mutually excluded volumes. The model rods, which consist of a hard core surrounded by a deformable shell, mimic the structure of polymer-coated, rod-like fd virus particles that have recently been the object of experimental study [K.~Purdy et al., Phys. Rev. Lett. \textbf{94}, 057801 (2005)]. We find that fluids of such soft rods exhibit an isotropic-nematic phase transition at a density higher than that of the corresponding hard-rod system of identical diameter, and that at coexistence the…
We report on fast electro-optic switching (response time 0.1 ms) of a blue-phase-polymer templated nematic with a broad-temperature range of thermodynamic stability and hysteresis-free performance. The nematic fills a polymer template that imposes a periodic structure with cubic symmetry and submicron period. In the field-free state, the nematic in polymer template is optically isotropic. An applied electric field causes non-zero optical retardance. The approach thus combines beneficial structural and optical features of the blue phase (cubic structure with submicron periodicity) and superior …
This paper reviews the research work on the liquid crystalline (LC) polymer vesicles (polymersomes), where the thermotropic nematic and smectic phases are displayed in the lyotropic bilayer polymer membrane. LC polymersomes possess the properties of both liquid crystals and polymers, the two essential soft matters. LC polymersomes offer, on the one hand, novel examples of the interplay between orientational order and the curved geometry of a two dimensional membrane. Spherical, ellipsoidal and tetrahedral vesicles are discussed. On the other hand, LC polymersomes enable novel design of stimuli…
Linear polymers and other connected "line liquids" exhibit a coupling between density and equilibrium nematic order on the macroscopic level that gives rise to a Meyer-de Gennes vectorial conservation law. Nevertheless, isotropic linear polymer melts/solutions exhibit fluctuations of the density and of the nematic order that are not coupled by this vectorial constraint, just like for isotropic liquids composed of disconnected non-spherical particles. It takes the proper tensorial description of the nematic order in linear polymer liquids, leading to a tensorial conservation law connecting dens…
In the shear flow of liquid crystalline polymers (LCPs) the nematic director orientation can align with the flow direction for some materials, but continuously tumble in others. The nematic dumbbell (ND) model was originally developed to describe the rheology of flow-aligning semi-flexible LCPs, and flow-aligning LCPs are the focus in this paper. In the shear flow of monodomain LCPs it is usually assumed that the spatial distribution of the velocity is uniform. This is in contrast to polymer solutions, where highly non-uniform spatial velocity profiles have been observed in experiments. We ana…
We theoretically analyze the waveguide regime of light propagation in a cylindrical pore of a polymer matrix filled with liquid crystals assuming that the effective radial optical anisotropy is biaxial. From numerical analysis of the dispersion relations, the waveguide modes are found to be sensitive to the field-induced changes of the anisotropy. The electro-optic properties of the polymer porous polyethylene terephthalate (PET) films filled with the nematic liquid crystal 5CB are studied experimentally and the experimental results are compared with the results of the theoretical investigatio…
We studied the dynamics of isotropic-nematic transitions in liquid crystalline polymers by integrating time-dependent Ginzburg-Landau equations. In a concentrated solution of rodlike polymers, the rotational diffusion constant Dr of the polymer is severely suppressed by the geometrical constraints of the surrounding polymers, so that the rodlike molecules diffuse only along their rod directions. In the early stage of phase transition, the rodlike polymers with nearly parallel orientations assemble to form a nematic polydomain. This polydomain pattern with characteristic length l, grows with se…
We present and analyze correlation functions of a main-chain polymer nematic in a continuum worm-like chain description for two types of constraints formalized by the tensorial and vectorial conservation laws, both originating in the microscopic chain integrity, i.e., the conectivity of the polymer chains. In particular, our aim is to identify the features of the correlation functions that are most susceptible to the differences between the two constraints. Besides the density and director autocorrelations in both the tensorial and vectorial cases, we calculate also the density -- director cor…
Nematic polymeric 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 polymeric network is minimized, the intrinsic (Guassian) 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 approximat…
We study the possibility of the spinodal decomposition in the induction period of the polymer crystallization. This phenomenon was first reported in an X-ray scattering experiment, and has still been controversial due to various experiments and theories that support or deny the phenomenon. In this article, we explain the condition for the spinodal decomposition to occur in polymer melts by deriving a Ginzburg-Landau model of the free energy as a functional of the density and the orientation of the segments, where we introduce the excluded volume and the nematic interactions through a combinati…
Partially wetting nematic liquid crystal (NLC) films on substrates are unstable to dewetting-type instabilities due to destablizing solid/NLC interaction forces. These instabilities are modified by the nematic nature of the films, which influences the effective solid/NLC interaction. In this work, we focus on the influence of imposed substrate anchoring on the instability development. The analysis is carried out within a long-wave formulation based on the Leslie-Ericksen description of NLC films. Linear stability analysis of the resulting equations shows that some features of the instability, …
We study the effect of dielectric anisotropy of polymers on their equilibrium ordering within mean-field theory but with a formalism that takes into account the full n-body nature of van der Waals forces. Dielectric anisotropy within polymers is to be expected as the electronic properties of the polymer will typically be different along the polymer than across its cross section. It is therefore physically intuitive that larger charge fluctuations can be induced along the chain than perpendicular to it. We show that this dielectric anisotropy leads to n-body interactions which can induce an iso…
We consider the impact of the elastomer network on the structure and fluctuations in the isotropic-genesis nematic elastomer, via a phenomenological model that underscores the role of network compliance. The model contains a network-mediated nonlocal interaction as well as a new kind of random field, which reflects the memory of the nematic order present at cross-linking, and also encodes local anisotropy due to localized polymers. Thus, we predict a regime of short-ranged oscillatory spatial correlations (both thermal and glassy) in the nematic alignment trapped into the network.
We study theoretically the entropic elasticity of a semi-flexible polymer, such as DNA, confined to two dimensions. Using the worm-like-chain model we obtain an exact analytical expression for the partition function of the polymer pulled at one end with a constant force. The force-extension relation for the polymer is computed in the long chain limit in terms of Mathieu characteristic functions. We also present applications to the interaction between a semi-flexible polymer and a nematic field, and derive the nematic order parameter and average extension of the polymer in a strong field.
Inspired to understand the complex spectrum of space-filling organizations the dsDNA genome within the capsid of bacterial viruses, we study a minimal, coarse-grained model of single chains densely-packed into a finite spherical volume. We build the three basic elements of the model--i) the absence of chain ends ii) the tendency of parallel-strand alignment and iii) a preference of uniform areal density of chain segments--into a polymer nematic theory for confined chains. Given the geometric constraints of the problem, we show that axially symmetric packings fall into one of three topologies: …
The interplay of nematic order and phase separation in solutions of semiflexible polymers in solvents of variable quality is investigated by density functional theory (DFT) and molecular dynamics (MD) simulations. We studied coarse-grained models, with a bond-angle potential to control chain stiffness, for chain lengths comparable to the persistence length of the chains. We varied both the density of the monomeric units and the effective temperature that controls the quality of the implicit solvent. For very stiff chains only a single transition from an isotropic fluid to a nematic is found, w…
A paradigm for internally driven matter is the active nematic liquid crystal, whereby the equations of a conventional nematic are supplemented by a minimal active stress that violates time reversal symmetry. In practice, active fluids may have not only liquid crystalline but also viscoelastic polymer degrees of freedom. Here we explore the resulting interplay by coupling an active nematic to a minimal model of polymer rheology. We find that adding polymer can greatly increase the complexity of spontaneous flow, but can also have calming effects, thereby increasing the net throughput of spontan…
Polymer-dispersed liquid crystal (PDLC) composites have long been a focus of study for their unique electro-optical properties which have resulted in various applications such as switchable (transparent/translucent) windows. These composites are manufactured using desirable "bottom-up" techniques, such as phase separation of a liquid crystal/polymer mixture, which enable production of PDLC films at very large scales. LC domains within PDLCs are typically spheroidal, as opposed to rectangular for an LCD panel, and thus exhibit substantially different behaviour in the presence of an external fie…
We study the monodomain (single-crystal) nematic elastomer materials, all side-chain siloxane polymers with the same mesogenic groups and crosslinking density, but differing in the type of crosslinking. Increasing the proportion of long di-functional segments of main-chain nematic polymer, acting as network crosslinking, results in dramatic changes in the uniaxial equilibrium thermal expansion on cooling from isotropic phase. At higher concentration of main chains their behaviour dominates the elastomer properties. At low concentration of main-chain material, we detect two distinct transitions…
We discuss why it is physical to keep terms in the nematic rubber elastic free energy that reflect the order parameter dependence of the natural size of the network polymers. We address a point of difficulty in some mathematical approaches to this problem.
Considerable recent attention has been given to the study of shape formation using modern responsive materials that can be preprogrammed to undergo spatially inhomogeneous local deformations. In particular, nematic liquid crystal polymer networks offer exciting possibilities in this context. In this paper, we discuss the generation of Gaussian curvature in thin nematic sheets using smooth in-plane director fields patterned across the surface. We highlight specific patterns which encode constant Gaussian curvature of prescribed sign and magnitude and present experimental results which appear to…
Nematic elastomers are rubbery solids which have liquid crystals incorporated into their polymer chains. These materials display many unusual mechanical properties, one such being the ability to form fine-scale microstructure. In this work, we explore the response of taut and appreciably stressed sheets made of nematic elastomer. Such sheets feature two potential instabilities -- the formation of fine-scale material microstructure and the formation of fine-scale wrinkles. We develop a theoretical framework to study these sheets that accounts for both instabilities, and we implement this framew…
We describe a general implementation of the Fynewever-Yethiraj density functional theory (DFT) for the investigation of nematic and cholesteric self-assembly in arbitrary solutions of semi-flexible polymers. The basic assumptions of the theory are discussed in the context of other generalised Onsager descriptions for flexible polyatomic systems. The location of the isotropic-to-nematic phase transition is found to be in good agreement with molecular simulations for elongated chains up to relatively high polymer flexibilities, although the predictions of the theory in the nematic regime lead to…
Liquid crystals are synthetic and biological viscoelastic anisotropic soft matter materials that combine liquid fluidity with crystal anisotropy and find use in optical devices, sensor/actuators, lubrication, super-fibers. Frequently mesogens are mixed with colloidal and nanoparticles, other mesogens, isotropic solvents, thermoplastic polymers, cross-linkable monomers, among others. This comprehensive review present recent progress on meso and macro scale thermodynamic modelling, highlighting the (i) novelties in spinodal and binodal lines in the various phase diagrams, (ii) the growth laws un…
