From cellulosic based liquid crystalline sheared solutions to 1D and 2D soft materials

Liquid crystalline cellulosic-based solutions described by distinctive properties are at the origin of different kinds of multifunctional materials with unique characteristics. These solutions can form chiral nematic phases at rest, with tuneable photonic behavior, and exhibit a complex behavior associated with the onset of a network of director field defects under shear. Techniques, such as Nuclear Magnetic Resonance (NMR), Rheology coupled with NMR (Rheo-NMR), rheology, optical methods, Magnetic Resonance Imaging (MRI), Wide Angle X-rays Scattering (WAXS), were extensively used to enlighten the liquid crystalline characteristics of these cellulosic solutions. Cellulosic films produced by shear casting and fibers by electrospinning, from these liquid crystalline solutions, have regained wider attention due to recognition of their innovative properties associated to their biocompatibility. Electrospun membranes composed by helical and spiral shape fibers allow the achievement of large surface areas, leading to the improvement of the performance of this kind of systems. The moisture response, light modulated, wettability and the capability of orienting protein and cellulose crystals, opened a wide range of new applications to the shear casted films. Characterization by NMR, X-rays, tensile tests, AFM, and optical methods allowed detailed characterization of those soft cellulosic materials. In this work, special attention will be given to recent developments, including, among others, a moisture driven cellulosic motor and electro-optical devices.

Lipid-Based Liquid Crystals As Carriers for Antimicrobial Peptides: Phase Behavior and Antimicrobial Effect

International audience

New discotic liquid crystals based on large polycyclic aromatic hydrocarbons as materials for molecular electronics

A series of new columnar discotic liquid crystalline materials based on the superphenalene (C96) core has been synthesized by oxidative cyclodehydrogenation with iron(III) chloride of suitable three-dimensional oligophenylene precursors. These compounds were investigated by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide angle X-ray scattering (WAXS), and showed highly ordered supramolecular arrays and mesophase behavior over a broad temperature range. Good solubility, through the introduction of long alkyl chains, and the fact that these new superphenalene derivatives were found to be liquid crystalline at room temperature enabled the formation of highly ordered films (using the zone-casting technique), a requirement for application in organic electronic devices. The one-dimensional, intracolumnar charge carrier mobilities of superphenalene derivatives were determined using the pulse-radiolysis time-resolved microwave conductivity technique (PR-TRMC). Electrical properties of different C96-C12 architectures on mica surfaces were examined by using Electrostatic Force Microscopy (EFM) and Kelvin Probe Force Microscopy (KPFM). Hexa-peri-hexabenzocoronene (C42) derivatives substituted at the periphery with six branched alkyl ether chains were also synthesized. It was found that the introduction of ether groups within the side chains enhances the affinity of the discotic molecules towards polar surfaces, resulting in homeotropic self-assembly (as shown by POM and 2D-WAXS) when the compounds are processed from the isotropic state between two surfaces. A new, insoluble, superphenalene building block bearing six reactive sites was prepared, and was further used for the preparation of dendronized superphenalenes with bulky dendritic substituents around the core. UV/Vis and fluorescence experiments suggest reduced π-π stacking of the superphenalene cores as a result of steric hindrance between the peripheral dendritic units. A new family of graphitic molecules with partial ”zig-zag” periphery has been established. The incorporation of ”zig-zag” edges was shown to have a strong influence on the electronic properties of the new molecules (as studied by solution and solid-state UV/Vis, and fluorescence spectroscopy), leading to a significant bathochromic shift with respect to the parent PAHs (C42 and C96). The reactivity of the additional double bonds was examined. The attachment of long alkyl chains to a ”zig-zag” superphenalene core afforded a new, processable, liquid crystalline material.

Nanomechanics of cellulose crystals and cellulose-based polymer composites

Cellulose-polymer composites have potential applications in aerospace and transportation areas where lightweight materials with high mechanical properties are needed. In addition, these economical and biodegradable composites have been shown to be useful as polymer electrolytes, packaging structures, optoelectronic devices, and medical implants such as wound dressing and bone scaffolds. In spite of the above mentioned advantages and potential applications, due to the difficulties associated with synthesis and processing techniques, application of cellulose crystals (micro and nano sized) for preparation of new composite systems is limited. Cellulose is hydrophilic and polar as opposed to most of common thermoplastics, which are non-polar. This results in complications in addition of cellulose crystals to polymer matrices, and as a result in achieving sufficient dispersion levels, which directly affects the mechanical properties of the composites. As in other composite materials, the properties of cellulose-polymer composites depend on the volume fraction and the properties of individual phases (the reinforcement and the polymer matrix), the dispersion quality of the reinforcement through the matrix and the interaction between CNCs themselves and CNC and the matrix (interphase). In order to develop economical cellulose-polymer composites with superior qualities, the properties of individual cellulose crystals, as well as the effect of dispersion of reinforcements and the interphase on the properties of the final composites should be understood. In this research, the mechanical properties of CNC polymer composites were characterized at the macro and nano scales. A direct correlation was made between: Dispersion quality and macro-mechanical properties Nanomechanical properties at the surface and tensile properties CNC diameter and interphase thickness Lastly, individual CNCs from different sources were characterized and for the first time size-scale effect on their nanomechanical properties were reported. Then the effect of CNC surface modification on the mechanical properties was studied and correlated to the crystalline structure of these materials.

Security devices based on liquid crystals doped with a colour dye

Liquid crystal properties make them useful for the development of security devices in applications of authentication and detection of fakes. Induced orientation of liquid crystal molecules and birefringence are the two main properties used in security devices. Employing liquid crystal and dichroic colorants, we have developed devices that show, with the aid of a polarizer, multiple images on each side of the device. Rubbed polyimide is used as alignment layer on each substrate of the LC cell. By rubbing the polyimide in different directions in each substrate it is possible to create any kind of symbols, drawings or motifs with a greyscale; the more complex the created device is, the more difficult is to fake it. To identify the motifs it is necessary to use polarized light. Depending on whether the polarizer is located in front of the LC cell or behind it, different motifs from one or the other substrate are shown. The effect arises from the dopant colour dye added to the liquid crystal, the induced orientation and the twist structure. In practice, a grazing reflection on a dielectric surface is polarized enough to see the effect. Any LC flat panel display can obviously be used as backlight as well.

Lenticular arrays based on liquid crystals

Lenticular array products have experienced a growing interest in the last decade due to the very wide range of applications they can cover. Indeed, this kind of lenses can create different effects on a viewing image such as 3D, flips, zoom, etc. In this sense, lenticular based on liquid crystals (LC) technology is being developed with the aim of tuning the lens profiles simply by controlling the birefringence electrically. In this work, a LC lenticular lens array has been proposed to mimic a GRIN lenticular lens array but adding the capability of tuning their lens profiles. Comb control electrodes have been designed as pattern masks for the ITO on the upper substrate. Suitable high resistivity layers have been chosen to be deposited on the control electrode generating an electric field gradient between teeth of the same electrode. Test measurements have allowed us to demonstrate that values of phase retardations and focal lengths, for an optimal driving waveform, are fairly in agreement. In addition, results of focusing power of tuneable lenses were compared to those of conventional lenses. The behaviour of both kinds of lenses has revealed to be mutually similar for focusing collimated light and for refracting images.

2D tunable graded index prism beam steering device based on nematic liquid crystals

Liquid crystal devices are being used in many non-display applications in order to construct small devices controlled by low voltage electronics without mechanical components. In this work, we present a novel liquid crystal device for laser beam steering. In this device the orientation of the liquid crystal molecules can be controlled. A change in the liquid crystal orientation results in a change of the refractive index. When a laser beam passes through the device, the beam will be deviated (Fig.1) and the device works a prism. The main difference between this device and a prism is that in the device the orientation profile of the liquid crystal molecules can be modified so that the laser beam can be deviated a required angle: the device is tuneable.

Photonic Logic Based on Molecular Reorientation of Nematic Liquid Crystals

A new type of photonic logic, based on the use of nematic liquid crystals is proposed. The system takes advantage of the refractive-index changes induced by laser beams. Examples of AND, OR and NOR functions are presented.

Wedged analog tunable beam steering device based on cholesteric liquid crystals

In this work we propose a novel cholesteric liquid crystal beam steering device based on the Kerr effect. The first version of the device consists of two ITO coated glass plates, with intentionally prepared electrodes, assembled together with a thickness gradient between both sides of the device. One side of the cell has two substrates at direct contact; the other side has separated substrates to form the wedge. The cell was filled with a cholesteric liquid crystal. The liquid crystal material is an innovative mixture called 1892E with extremely low viscosity doped with a ZLI chiral nematogen. The proposed beam steering device based on cholesteric liquid crystals has great potential for many photonic applications. Results describing the performance of the device and the properties of the selected liquid crystals are presented.

Design and demonstration of an electronically scanned reflectarray antenna at 100 GHz using multiresonant cells based on liquid crystals

The design, fabrication and measured results are presented for a reconfigurable reflectarray antenna based on liquid crystals (LC) which operates above 100 GHz. The antenna has been designed to provide beam scanning capabilities over a wide angular range, a large bandwidth and reduced Side-Lobe Level. Measured radiation patterns are in good agreement with simulations, and show that the antenna generates an electronically steerable beam in one plane over an angular range of 55º in the frequency band from 96 to 104 GHz. The Side Lobes Level is lower than -13 dB for all the scan angles and -18 dB is obtained over 16% of the scan range. The measured performance is significantly better than previously published results for this class of electronically tunable antenna, and moreover verifies the accuracy of the proposed procedure for LC modeling and antenna design.

Rheological behavior, zeta potential, and accelerated stability tests of Buriti oil (Mauritia flexuosa) emulsions containing lyotropic liquid crystals

Background: It is well known that the Amazon region presents a huge biodiversity; therefore, countless natural resources are being employed in the production of phytocosmetics and phytomedicines. Objective: The purpose of this work was to obtain emulsions produced with Buriti oil and nonionic surfactants. Methods: Two surfactant systems were employed (Steareth-2 associated to Ceteareth-5 and to Ceteareth-20) to produce the emulsions using phase diagram method. Emulsions were obtained by echo-planar imaging method at 75 degrees C. Rheological behavior and zeta potential were evaluated, and accelerated stability tests were performed. Results: All emulsions analyzed presented pseudoplastic behavior. Zeta potential values were obtained between -14.2 and -53.3 mV. The formulations did not show changes in either physical stability, pH, or rheological behavior after accelerated stability tests. Significant differences were observed only after temperature cycling test. Conclusion: Based on these results, the emulsions obtained could be considered as promising delivery systems.

Micro – and nanofibers and liquid crystals for ligth-scattering shutters: Simulation of electrp-optical properties

This work demonstrates the feasibility of using polymeric micro- and nanofiber-composed films and liquid crystals as electrically switchable scattering light shutters. We present a concept of electro-optic device based on an innovative combination of two mature technologies: optics of nematic liquid crystals and electrospinning of nanofibers. These devices have electric and optical characteristics far superior to other comparable methods. The simulation presented shows results that are highly consistent with those of experiments and that explain the working mechanism of the devices.

Dynamics of transient pattern formation in nematic liquid crystals

We analyze the dynamics of a transient pattern formation in the Fréedericksz transition corresponding to a twist geometry. We present a calculation of the time-dependent structure factor based on a dynamical model which incorporates consistently the coupling of the director field with the velocity flow and also the effect of fluctuations. The appearance and development of a characteristic periodicity is described in terms of the time dependence of the maximum of the structure factor. We find a well-defined time for the appearance of the pattern and a subsequent stage of pattern development in which the characteristic periodicity tends to an asymptotic value.

Open-cell photoacoustic investigation of the thermal effusivity of liquid crystals

We report the use of an open photoacoustic cell configuration for the evaluation of thermal effusivity of liquid crystals. Initially, the method is calibrated using water and glycerol as transparent liquid samples, and the role of thermal conductivity of these liquids on the photoacoustic signal amplitude is discussed. To demonstrate the application of the present method for the evaluation of thermal effusivity of liquid crystals, we have used certain multicomponent nematic liquid crystal mixtures, namely BL001, BL002, BL032, and BL035. Each of these liquid crystal mixtures contains four to nine components and are primarily based on the cyanobiphenyl structure. The measured values of thermal effusivity of BL001 and BL002 were found to be almost the same, but differ from those of BL032 and BL035, which implies a difference in composition of the latter two from the former two mixtures.

A numerical method for solving the dynamic three-dimensional Ericksen-Leslie equations for nematic liquid crystals subject to a strong magnetic field

A finite difference technique, based on a projection method, is developed for solving the dynamic three-dimensional Ericksen-Leslie equations for nematic liquid crystals subject to a strong magnetic field. The governing equations in this situation are derived using primitive variables and are solved using the ideas behind the GENSMAC methodology (Tome and McKee [32]; Tome et al. [34]). The resulting numerical technique is then validated by comparing the numerical solution against an analytic solution for steady three-dimensional flow between two-parallel plates subject to a strong magnetic field. The validated code is then employed to solve channel flow for which there is no analytic solution. (C) 2009 Elsevier B.V. All rights reserved.