https://orbilu.uni.lu/bitstream/10993/20503/1/Lagerwall%20%26%20Scalia%202012.pdf

A new era for liquid crystal research: Applications of liquid crystals in soft matter nano-, bio- and microtechnology

We review the research on carbon nanotube (CNT) dispersion in liquid crystals (LCs), focusing mainly on the approaches where the aim is to align CNTs along the LC director field, but also covering briefly the proposed possibility to enhance thermotropic LCs by CNT doping All relevant LC types are considered: thermotropic LC hosts allowing dynamic CNT realignment, lyotropic LC hosts allowing very high concentration of CNTs uniformly aligned over macroscopic areas and consequent removal of the LC, and LC phases formed by CNTs themselves, used in spinning high-quality carbon nanotube fibres We also discuss the issue of CNT dispersion in some detail, since successful nanotube separation is imperative for success in this field regardless of the type of LC that is considered We end by defining a few major challenges for the development of the field over the next few years, critical for reaching the stage where industrially viable protocols for LC-based CNT alignment can be defined

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Carbon nanotubes in liquid crystals

The production of strings (disclination lines and loops) has been observed by means of the Kibble mechanism of domain (bubble) formation in the isotropic-nematic phase transition of the uniaxial nematic liquid crystal 4-cyano-4'-n-pentylbiphenyl. The number of strings formed per bubble is about 0.6. This value is in reasonable agreement with a numerical simulation of the experiment in which the Kibble mechanism is used for the order parameter space of a uniaxial nematic liquid crystal.

The Cosmological Kibble Mechanism in the Laboratory: String Formation in Liquid Crystals

This paper presents an overview of liquid crystal (LC) models of phase diagrams, phase transitions, self-assembly, interfaces, defects, and rheology and their integrated applications to biological mesophase materials and processes. Biological liquid crystals, classified into analogues (helicoidal plywoods), biopolymer solutions (in vitro DNA, polypeptides, collagen solutions) and in vivo LCs (membranes, silk, DNA), are discussed in terms of molecular characteristics and the symmetry of the thermodynamic phases. The thermodynamics and self-assembly of biological liquid crystals (BLCs) are discussed in terms of the Doi–Maier–Saupe lyotropic model and its extensions to chiral phases, showing the role of excluded volume and chirality. The defect physics of BLCs is described using the Landau–de Gennes model of chiral and achiral nematostatics to identify (i) thermodynamic phases, and (ii) observed textures and defect lattices under confinement and flow. The rheology and flow properties of BLCs are described using the Leslie–Ericksen and the Landau–de Gennes models of nematodynamics. The applications of integrated thermodynamic/defect/rheology modeling to the experimental characterization of several BLCs, including collagen and DNA solutions, are shown to provide organizing principles and quantitative tools to establish the properties of these natural materials. The phase transitions, tactoidal spherulites, flow-birefringence in dilute solutions, and banded textures in sheared concentrated solutions of collagen show how the principles of LC physics operate in BLC materials. Drying and spreading drops of DNA solutions leading to the formation of nematic monodomain aligned along the contact line are shown to follow self-assembly structuring under the action of interfacial, bulk, and contact line torques. Finally modeling of spider and silkworm LC spinning is presented as an example of biological polymer processing, where a high performance fiber material is produced through a lyotropic LC protein solution. The concerted structuring action of capillary confinement, strong anchoring, and nematic flow leads to predictions in agreement with the reported textural transitions in the duct of spiders and silkworms. The quantitative description of BLC materials and processes using mesoscopic models provides another tool to develop the science and future biomimetic applications of these ubiquitous natural anisotropic soft materials.

Liquid crystal models of biological materials and processes

Combinations of liquid crystals and materials with unique features as well as properties at the nanoscale are reviewed. Particular attention is paid to recent developments, i.e., since 2007, in areas ranging from liquid crystal-nanoparticle dispersions to nanomaterials forming liquid crystalline phases after surface modification with mesogenic or promesogenic moieties. Experimental and synthetic approaches are summarized, design strategies compared, and potential as well as existing applications discussed. Finally, a critical outlook into the future of this fascinating field of liquid crystal research is provided.

Nanoparticles in liquid crystals and liquid crystalline nanoparticles.

The self-organizing properties of nematic liquid crystals can be used to align carbon nanotubes dispersed in them. Because the nanotubes are so much thinner than the elastic penetration length, the alignment is caused by the coupling of the unperturbed director field to the anisotropic interfacial tension of the nanotubes in the nematic host fluid. In order to relate the degree of alignment of the nanotubes to the properties of the nematic liquid crystal, we treat the two components on the same footing and combine Landau-de Gennes free energies for the thermotropic ordering of the liquid crystal and for the lyotropic nematic ordering of carbon nanotubes caused by their mutually excluded volumes. The phase ordering of the binary mixture is analyzed as a function of the volume fraction of the carbon nanotubes, the strength of the coupling and the temperature. We find that the degree of ordering of the nanorods is enslaved by the properties of the host liquid and that it can be tuned by raising or lowering the temperature or by increasing or decreasing their concentration. By comparing the theory to recent experiments, we find the anchoring energy of multiwalled carbon nanotubes to be in the range from 10 -10 to 10 -7 Nm -1 .

Alignment of carbon nanotubes in nematic liquid crystals.

The self-organizing properties of nematic liquid crystals (LCs) can be used to align carbon nanotubes (CNTs) dispersed in them. In the previous paper [P. van der Schoot, V. Popa-Nita, and S. Kralj, J. Phys. Chem. B 112, 4512 (2008)], we have considered the weak anchoring limit of the nematic LC molecules at the nanotube's surface, where the CNT alignment is caused by the anisotropic interfacial tension of the nanotubes in the nematic host fluid. In this paper, we present the theoretical results obtained for strong enough anchoring at the CNT-LC interface for which the nematic ordering around nanotube is apparently distorted. Consequently, relatively strong long-range and anisotropic interactions can emerge within the system. In order to get insight into the impact of LC ordering on the alignment of nanotubes we treat the two mixture components on the same footing and combine Landau-de Gennes free energy for the thermotropic ordering of the liquid crystal and Doi free energy for lyotropic nematic ordering of carbon nanotubes caused by their mutually excluded volume. The phase ordering of the binary mixture is analyzed as a function of the volume fraction of the carbon nanotubes, the strength of coupling, and the temperature. We find that the degree of ordering of the nanorods can be tuned by raising or lowering the temperature or by increasing or decreasing their concentration.

Liquid crystal-carbon nanotubes mixtures

We use the Landau-de Gennes theory of a nematic liquid crystal to investigate anew aspects of the properties of the interface between the isotropic and nematic liquid crystal phases of the same fluid. The equations of the static interface have been solved, both numerically and using asymptotic analysis, with an emphasis on the effect of inclusion of the order parameter biaxiality on the physical properties. We have compared the results of the exact solutions to the commonly used de Gennes ansatz, which assumes positive and uniform unixiality through the interface. Although the de Gennes ansatz in general gives good results, when bend and splay elastic constants dominate over the twist constants, it can lead to errors of up to 10% in the surface energy. The asymptotic analysis also shows that, by contrast with the de Gennes ansatz, the order parameter wings in the isotropic phase exhibit negative order parameter, with principal axis perpendicular to the surface. For moving interfaces, using an approximation which at this stage does not yet include hydrodynamic coupling, we have compared our results with the analogue of the de Gennes ansatz used by the present authors in an earlier paper. We find that including biaxiality leads to larger effects in the dynamic than in the static properties, and that whereas this is essentially a perturbation to the energy, the velocity of the moving interface can be significantly slowed down. The slowing down effects are strongly correlated with surface biaxiality, but both effects seem to be diminished when the isotropic phase is advancing.

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Statics and Kinetics at the Nematic-Isotropic Interface: Effects of Biaxiality

We study the influence of nanoparticles (NPs) on liquid crystal (LC) ordering. As regards the structural ordering we consider NPs as a source of a quenched random field. Roughly such a situation is encountered in mixtures of LCs and aerosil NPs (aerosil NPs are spherular ones). Using the semi-microscopic lattice model and Brownian molecular simulation we show that after a quench from the isotropic phase a quasi-stable domain pattern forms. The characteristic size of an average domain is inversely proportional to the concentration of NPs, and domain patterns exhibit memory effects. In the study of the phase behaviour we limit consideration to NPs resembling LC molecules. A Landau-type free energy expression is derived for the mixture, originating from the Maier‐Saupe molecular approach. We show that the resulting phase behaviour exhibits the slave–master behaviour as the temperature or pressure is varied.

The influence of nanoparticles on the phase and structural ordering for nematic liquid crystals

We extend the random anisotropy nematic spin model to study nematic-isotropic transitions in porous media. A complete phase diagram is obtained. In the limit of relative low randomness the existence of a triple point is predicted. For relatively large randomness we have found a depression in temperature at the transition, together with a first order transition which ends at a tricritical point, beyond which the transition becomes continuous. We use this model to investigate the motion of the nematic-isotropic interface. We assume the system to be isothermal and initially quenched into the metastable regime of the isotropic phase. Using an appropriate form of the free energy density we obtain the domain wall solutions of the time-dependent Ginzburg-Landau equation. We find that including a random field leads to smaller velocity of the interface and to larger interface width.

V. Popa-Nita

Papers

Alignment of carbon nanotubes in nematic liquid crystals.

Liquid crystal-carbon nanotubes mixtures

Statics and Kinetics at the Nematic-Isotropic Interface: Effects of Biaxiality

The influence of nanoparticles on the phase and structural ordering for nematic liquid crystals

Statics and kinetics at the nematic-isotropic interface in porous media