Fabrication and characterization of nanocrystalline cellulose films prepared under vacuum conditions

When dried under ambient conditions, the self-assembled chiral nematic arrangement of nanocrystalline cellulose (NCC) in suspension can be preserved in NCC films that can reflect light at specific wavelengths, but the process is slow. Rapid preparation of NCC films was first proposed to cast under vacuum conditions to accelerate water evaporation rates and shorten the drying time. Vacuum preparation of NCC films has been found to not only retain the self-assembled structure but to also increase the chiral nematic pitch and red-shift the reflection wavelength of the films. This method provides a new path to prepare NCC iridescent films with tunable reflection wavelengths and reduced time in many areas.     

Study on selective reflection properties of chiral nematic liquid crystalline composites with a non‐uniform pitch distribution

The preparation is reported of particles of photopolymerisable monomer/chiral dopant composites with a crystalline (Cr)‐chiral nematic (N*) phase transition. By mixing particles with different pitches of the N* phase in the Cr phase and crosslinking the liquid crystal (LC) monomer molecules by photopolymerisation in the planarly oriented N* phase, an N*‐LC composite film with a non‐uniform pitch distribution was obtained. Experimental results show that the bandwidth of the reflection spectrum and the location of reflection band of the composite films can be controlled accurately by controlling the pitch lengths of the N* phase of the particles. Effects of polymerisation temperature and UV intensity on the non‐uniform pitch distribution of N*‐LC composite films were investigated.     

Dye induced great enhancement of broadband reflection from polymer stabilized cholesteric liquid crystals

A series of polymer stabilized cholesteric liquid crystals (PSCLCs) films were prepared from cholesteric liquid crystal (Ch‐LC) mixtures containing different components such as non‐reactive LC monomer, polymerizable monomer, chiral dopant, dye, and photoinitiator upon polymerization. The influence of the polymerizable monomer and dye of Ch‐LC mixtures on the reflection properties was investigated. The reflection bandwidth for all the samples can be increased by photo‐polymerization, and the network upon polymerization derived from two different polymerizable monomers with both one and two functional groups is more effective than that from one polymerizable monomer for broadening the reflection band. Especially, a dye‐doped Ch‐LC film can reflect incident light with the bandwidth over the wavelength range of 550–2350 nm, which is due to a greater pitch gradient formed inside of Ch‐LC film. The gradient pitch network structure was firstly demonstrated by scanning electron microscopy (SEM) with the film prepared from high diacrylate monomer concentration and subsequently proved by using a wash‐out/refill method. The nematic liquid crystals monomers was infiltrated into the polymer network that was prefabricated by removing the low molar weight LCs from the original PSCLCs film, and SEM exhibited the existence of a pitch gradient across the film thickness. The refilled nematic liquid crystals film showed broadband reflection after polymerzition, too. Copyright © 2011 John Wiley & Sons, Ltd.     

Cellulose Nanocrystal Elastomers with Reversible Visible Color

Responsive photonic crystals have potential applications in mechanical sensors and soft displays; however, new materials are constantly desired to provide new innovations and improve on existing technologies. To address this, we report stretchable chiral nematic cellulose nanocrystal (CNC) elastomer composites that exhibit reversible visible color upon the application of mechanical stress. When stretched (or compressed) the colorless materials maintain their chiral nematic structure but the helical pitch is reduced into the visible region, resulting in coloration of the CNC‐elastomer composite. By increasing the percentage elongation of the material (ca. 50–300 %), the structural color can be tuned from red to blue. The color of the materials was characterized by reflectance optical microscopy and reflectance circular dichroism to confirm the wavelength and polarization of the reflected light. We also probed the mechanism of the structural color using 2D‐X‐ray diffraction. Finally, by either water‐patterning the starting CNC film, or by forming a CNC film with gradient color, through masked evaporation, we were able to prepare encoded stretchable chiral nematic CNC‐elastomers.     

Coassembly of Nanorods and Nanospheres in Suspensions and in Stratified Films

The entropically driven coassembly of nanorods (cellulose nanocrystals, CNCs) and nanospheres (dye‐labeled spherical latex nanoparticles, NPs) was studied in aqueous suspensions and in solid films. In mixed CNC‐latex suspensions, phase separation into an isotropic latex‐NP‐rich and a chiral nematic CNC‐rich phase took place; the latter contained a significant amount of latex NPs. Drying the mixed suspension resulted in CNC‐latex films with planar disordered layers of latex NPs, which alternated with chiral nematic CNC‐rich regions. In addition, fluorescent latex NPs were embedded in the chiral nematic domains. The stratified morphology of the films, together with a random distribution of latex NPs in the anisotropic phase, led to the films having close‐to‐uniform fluorescence, birefringence, and circular dichroism properties.     

Induced Circular Dichroism of Chiral Nematic Cellulose Films

Colloidal chiral nematic suspensions of cellulose were prepared from dissolving grade wood pulp. On evaporation of the water, the suspension dries down to give iridescent cellulose films. The optical properties of the films may be characterized by incorporating dyes in the films, and following the ordering of the dye molecules by measurement of induced circular dichroism (ICD). Structural changes to the films, such as decreasing the chiral nematic pitch by increasing the salt content and increasing the chiral nematic order through magnetic alignment, can be monitored by measuring the changes in ICD.     

Lattice structure in liquid-crystal blue phase with various chiral concentrations

Lattice structures, including reflection lattice planes and lattice constant, of liquid-crystal blue phase I (BPI) are studied via the measurements on reflection spectrum and Kossel diagram as concentration of a chiral dopant is changed. Peaks of the reflection wavelength in BPI are mainly dominated by the lattice plane and the lattice constant, which are affected by the chiral concentration. In the chiral nematic state, as decreasing the chiral concentration the reflection peak will shift to a longer wavelength because the helical pitch linearly depends on the chiral concentration and becomes longer. However, this dependence of the chiral concentration and reflection wavelength is broken in the BPI. The reflection peak of BPI moves to a short wavelength when the chiral concentration is less due to the contraction of the lattice constant as well as helical pitch. Moreover, when the concentration of the chiral dopant increases over a certain value, a discontinuous shift in reflection peak occurs due to the production of the different lattice planes. It means that the relationship between the chiral concentration and the helical pitch in BPI is not the same as it in the chiral nematic phase and should be reconsidered.     

Chiral Nematic Cellulose Acetate Films; Reflectivity and Effect of Deacetylation

Cellulose acetate samples with a range of degrees of substitution (DS) were prepared by deacetylation of cellulose acetate (DS = 2.5). Chiral nematic solutions of the samples were prepared in formic acid. A handedness reversal from left to right was observed as the DS used to prepare the mesophase increased from 1.8 to 2.4. By selection of a suitably long-pitch mesophase, chiral nematic films cast from a CA (DS = 2.2)/formic acid solution showed a feint reflection of circularly polarized blue light. Deacetylation of this CA film gave a chiral nematic cellulose film with a more intense reflection band at the same wavelength. The improvement in intensity is attributed to the higher intrinsic birefringence of cellulose compared to cellulose acetate.     

Thermal tuning band gap in cholesteric liquid crystals

The phase of a liquid crystal (LC) changing from a nematic phase to a cholesteric (Ch) mesophase is achieved by adding different ratios of chiral dopants S811. By studying the transmission spectrum, we are able to measure the helical pitch in cholesteric phase. The pitch in the mixtures of nematic E7 and chiral dopants S811 as a function of the concentration of the dopant and temperature is investigated. The sensitivity of the selective reflection notch of the cholesteric phase to the thermal tuning depends strongly on the ratios of the chiral dopants. It reveals that the influence of temperature is more profound for those cholesteric liquid crystals (CLCs) which exhibit smectic A (SmA) at lower temperatures. When fitted using Keating's formula, the helical pitch calculated from our experimental results lies on the predicted curve. Optimised ratios of the mixture CLCs for the optimised reflection band with the specified wavelength ranging from 467 nm to 2123 nm are suggested.     

Structural Transition in Liquid Crystal Bubbles Generated from Fluidic Nanocellulose Colloids

The structural transition in micrometer‐sized liquid crystal bubbles (LCBs) derived from rod‐like cellulose nanocrystals (CNCs) was studied. The CNC‐based LCBs were suspended in nematic or chiral nematic liquid‐crystalline CNCs, which generated topological defects and distinct birefringent textures around them. The ordering and structure of the LCBs shifted from a nematic to chiral nematic arrangement as water evaporation progressed. These packed LCBs exhibited a specific photonic cross‐communication property that is due to a combination of Bragg reflection and bubble curvature and size.     

Polarization holographic grating recording in the cholesteric azobenzene‐containing films with the phototunable helix pitch

The recording of polarization gratings in films of a cholesteric liquid crystalline polymer with different helix pitch was studied in detail. For this purpose, the cholesteric mixture of the nematic azobenzene‐containing copolymer with a chiral‐photochromic dopant was prepared. The utilization of such mixture has made possible to realize dual optical photorecording in one system, first due to the phototuning of the helix pitch by UV light and second the polarization grating recording process by exposure with polarized visible light. The diffraction efficiency strongly depends on the cholesteric helix pitch and films thickness: the increase of the confinement ratio d/p (where d, film thickness; p, helix pitch) results in growth of the diffraction efficiency. Comparison of the induction of polarization gratings in cholesteric, nematic (copolymer without chiral dopant), and amorphous (nonannealed) cholesteric films revealed that only the cholesteric films were characterized by significant oscillations in the diffraction efficiency signal as well as by the presence of the maximum in the first‐order diffraction efficiency in the initial stage of the grating recording process. It was found that in addition to the polarization grating surface relief gratings (SRGs) were also formed in the studied systems, however, the amplitude of the SRG inscribed in the cholesteric films was lower (～20 nm) compared to the grating amplitude obtained in nematic films (～60 nm). Moreover, increasing helix pitch resulted in a decrease of the SRG amplitude. The obtained experimental data demonstrate the great potential of cholesteric LC mixtures of such type for different applications as photoactive materials for photonics. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 773–781     

Photoinduced polymer-stabilised chiral nematic liquid crystal films reflecting both right- and left-circularly polarised light

A phototunable polymer-stabilised liquid crystal film reflecting both right- and left-circularly polarised light has been successfully fabricated by a washout/refill method. The film was obtained by prefabricating the polymer network with a left-handed helical structure and then refilling a light-driven chiral nematic liquid crystal with a right-handed helical structure into the network. Interestingly, the reflection wavelength and the reflectivity properties can be precisely tuned by UV-light irradiation. A hyper-reflective notch, the reflectivity of which approaches 100%, was achieved in a layer when the pitch lengths of the two opposite helical structures are almost the same. Moreover, their original state can be properly returned by visible-light irradiation.     

3D nanomaterial silica aerogel via diffusion of chiral compound driven broadband reflection in chiral nematic liquid crystals

In the study, a novel method of broadening the bandwidth by fabricating the silica aerogel film composited with the chiral nematic liquid crystal (N*-LC) is proposed. Diffusion of chiral compound filled in the silica aerogel resulted in the non-uniform pitch distribution, which can be anchored by UV-radical polymerisation. The results strongly suggested that the reflection bandwidth could be broadened preferably by adjusting the silica aerogel condensation time, the content of UV polymerisable free radical monomer and the polymerisation temperature. The reflection bandwidth was broadened from 270 nm to 878 nm, and the centre wavelength was blue-shifted by 642 nm. A general correlation among the silica aerogel condensation time, the polymerisation condition, and the reflective region will be outlined.     

Photo-optical properties of polymer composites based on stretched porous polyethylene filled with photoactive cholesteric liquid crystal

A new type of polymer-liquid crystal composite with photovariable dichroism and birefringence is described. Porous stretched polyethylene films were used as polymer matrices. To induce a cholesteric phase in a commercial nematic host, a chiral photochromic dopant based on sorbide and cinnamic acid capable of E-Z isomerization under UV irradiation was used. A merocianine-type substance was selected as a dichroic dye. Introduction of a dye-doped cholesteric mixture with a helical pitch higher than ∼300 nm to polymer film led to an almost complete transition from a cholesteric to an oriented nematic phase, as well as to an increase in birefringence and the appearance of dichroism. Decrease of the helical pitch by increasing in the chiral dopant concentration in the liquid crystal-polymer composite results in a reduction of the dichroism values. UV irradiation of polymer composite leading to an isomerization of the chiral dopant and helix untwisting induces a noticeable gradual growth of dichroism and birefringence. These new composites can be considered as promising materials for optical applications.     

Photo‐optical properties of polymer composites based on stretched porous polyethylene filled with photoactive cholesteric liquid crystal

A new type of polymer–liquid crystal composite with photovariable dichroism and birefringence is described. Porous stretched polyethylene films were used as polymer matrices. To induce a cholesteric phase in a commercial nematic host, a chiral photochromic dopant based on sorbide and cinnamic acid capable of E–Z isomerization under UV irradiation was used. A merocianine‐type substance was selected as a dichroic dye. Introduction of a dye‐doped cholesteric mixture with a helical pitch higher than ～300 nm to polymer film led to an almost complete transition from a cholesteric to an oriented nematic phase, as well as to an increase in birefringence and the appearance of dichroism. Decrease of the helical pitch by increasing in the chiral dopant concentration in the liquid crystal–polymer composite results in a reduction of the dichroism values. UV irradiation of polymer composite leading to an isomerization of the chiral dopant and helix untwisting induces a noticeable gradual growth of dichroism and birefringence. These new composites can be considered as promising materials for optical applications.     

Hierarchically controlled helical graphite films prepared from iodine-doped helical polyacetylene films using morphology-retaining carbonization

One-handed helical graphite films with a hierarchically controlled morphology were prepared from iodine-doped helical polyacetylene (H-PA) films using the recently developed morphology-retaining carbonization method. Results from scanning electron microscopy indicate that the hierarchical helical morphology of the H-PA film remains unchanged even after carbonization at 800 °C. The weight loss of the film due to carbonization was very small; only 10-29% of the weight of the film before doping was lost. Furthermore, the graphite film prepared by subsequent heating at 2600 °C retained the same morphology as that of the original H-PA film and that of the helical carbon film prepared at 800 °C. The screwed direction, twisted degree, and vertical or horizontal alignment of the helical graphite film were well controlled by changing the helical sense, helical pitch, and orientation state of the chiral nematic liquid crystal (N*-LC) used as an asymmetric LC reaction field. X-ray diffraction and Raman scattering measurements showed that graphitic crystallization proceeds in the carbon film during heat treatment at 2600 °C. Transmission electron microscopy measurements indicate that ultrasonication of the helical graphite film in ethanol for several hours gives rise to a single helical graphite fibril. The profound potentiality of the present graphite films is exemplified in their electrical properties. The horizontally aligned helical graphite film exhibits an enhancement in electrical conductivity and an evolution of electrical anisotropy in which conductivity parallel to the helical axis of the fibril bundle is higher than that perpendicular to the axis.     

Copolyesters exhibiting a thermotropic cholesteric phase

Mesomorphic copolymers were synthesized by incorporating varying ratios of azelaic acid and (+)-3-methyl adipic acid into copolyesters based upon 4,4′-dihydroxybiphenyl. Introduction of the phenylene (+)-3-methyl adipate unit broadens the temperature range of the nematic phase of the azelate homopolymer and, at the same time, produces a chiral nematic (cholesteric) mesophase which exhibits various iridescent colors. Circular dichroism measurements were used to determine the pitch of the cholesteric liquid crystals. The pitch decreased gradually with increasing temperature, and the inverse pitch increased in direct proportion to the molar content of the units containing (+)-3-methyl adipate. The twisted cholesteric structure could be conserved by quenching to produce films with various colors at room temperature. Annealing these films at a temperature immediately below that of the crystal–mesophase transition improved the regularity of the cholesteric structure.     

Short wavelength light reflecting films from side‐chain liquid crystal homopolymers with chiral spacers

A series of acrylate monomers with alkoxy tails of varying lengths are synthesised and polymerised. The butoxy analogue had a stable enantiotropic cholesteric liquid crystalline phase which formed a grandjean texture when prepared as a thin film between glass slides. The polymer was mixed with a low molar mass nematic liquid crystal in various proportions and the pitch of the chiral nematic phases were determined using a cano‐wedge cell technique. The polymer prepared from (S)‐2‐(4‐butoxyphenyl‐4′‐benzoyloxy)‐1‐methyl ethyl acrylate had a pitch length of 113 nm which indicates that the polymer film could be employed in optical devices requiring selective reflection of light with short wavelengths in the region of 170 nm. Copyright © 2001 John Wiley & Sons, Ltd.     

The determination of cholesteric pitch from the diffusion profile A new experimental approach

The optical microscopic mass transport (OMMT) method was utilized to determine the cholesteric pitch values of the mixtures of mesogenic and non-mesogenic chiral species in nematic materials. The cholesteric pitch was determined by transient analysis of the diffusion profile established by allowing an initial cholestric composition (solute) to diffuse under semi-infinite linear boundary conditions into an oriented thin film of its corresponding nematic solvent. During the steady-state diffusion, where the initial concentration (pitch) remains constant, the transient analysis of the profile with a polarization microscope exhibits a maximum number of pitch discontinuity domains. The evaluation of the unknown pitch was carried out by extrapolation of the diffusion pitch gradient to the original diffusion source by using the exact relation between the pitch and the film thickness. The method is experimentally simple; at constant temperature and pressure, determination of the pitch depends only on the film thickness. There is a good agreement between the pitch values obtained with this method and those from conventional techniques.