Heterogeneous equilibria and the kinetics of isotropic liquid-nematic phase transition in a multicomponent mixture 4-alkyl-4′-cyanobiphenyls

The isotropic liquid-nematic phase transition and the kinetics of growth of nematic phase drops during this phase transition were studied by polarization optical microscopy and IR spectroscopy for a four-component system during cooling. The statistical drop size distribution was described in terms of the equilibrium thermodynamics of irreversible processes. An analysis of the time dependences of the mean diameter of drops showed the presence of two kinetic stages of nematic phase growth and allowed them to be described by the universal law of cluster growth. In conformity with the Gibbs phase rule, nematic phases with different compositions can coexist at equilibrium.     

Kinetics of formation of polymer dispersed liquid crystals in a liquid-crystalline polymer matrix

With the use of optical polarization microscopy, the kinetics of phase separation during cooling of molten mixtures of a nematic low-molecular-mass liquid crystal and a liquid crystalline polymer is studied to produce polymer dispersed liquid crystals. The statistical drop-size distribution of a low-molecular-mass liquid crystal is described in the terms of equilibrium thermodynamics of irreversible processes. For a nematic polymer component of a mixture, the analysis of time dependences of the average diameter of drops of a low-molecular-mass liquid crystal makes it possible to reveal two stages in the kinetics of their growth and to describe this process according to the universal law of cluster growth. For a smectic polymer component, the Avrami equation is used to quantitatively describe the kinetics of growth of low-molecular-mass liquid-crystal drops.     

A statistical study of the kinetics of phase separation for a liquid crystalline mixture

The kinetics of cholesteric phase growth during the phase separation of an isotropic liquid crystalline mixture was studied by polarizing optical microscopy within the framework of the thermodynamics of irreversible processes. The rules governing time-dependent changes in the parameters of the statistical droplet size distribution of the cholesteric phase were determined. The influence of the thickness of the liquid crystalline mixture layer on the size of the droplets formed was studied.     

KINETICSOF TRANSITION FROM ISOTROPIC TO CHOLESTERIC PHASE FOR A THERMOTROPIC CELLULOSE DERIVATIVE

The kinetics of mesophase formation of a thermotropic hydroxyethyl cellulose acetatefrom isotropic phase to cholesteric mesophase has been studied by means of depolariz-ing transmittance method. Avrami type analysis of the data gives an exponent n close to1, which suggests the nucleation followed by rod-like growth. It means that the kineticbehavior of phase transition from isotropic to cholesteric mesophase is very similar to thatof the mesophase formation from isotropic to nematic mesophase.     

The kinetics of nematic phase size growth during the phase transition in an isotropic melt of liquid crystalline azomethine dimer

Polarizing microscopy was used to study the kinetics of formation and droplet size growth of the ordered (nematic) phase during the phase separation of an azomethine dimer melt at various rates of cooling. The statistical droplet size distribution of the nematic phase during phase separation was described by a model derived in terms of the thermodynamics of irreversible processes. Two kinetic phase separation stages were observed and described by the universal scaling function.     

Synthesis and properties of cholesteric liquid crystalline elastomers

The synthesis of new side-chain cholesteric liquid crystalline elastomers, containing the flexible non-mesogenic crosslinking agent M-1 and the cholesteric monomer M-2, is described by a one-step hydrosilication reaction. The chemical structures of the monomers and network polymers obtained were confirmed by FT-IR spectroscopy. Their mesogenic properties and phase behavior were investigated by differential scanning calorimetry, polarizing optical microscopy, and x-ray diffraction measurements. The influence of the crosslinking units on the phase behavior is discussed. The network polymers showed elasticity, reversible phase transitions, and cholesteric Grandjean texture. The experimental results demonstrated that the glass transition temperatures and isotropization temperatures of network elastomers decreased as the concentration of crosslinking units was increased, but the cholesteric phase was not disturbed.     

Synthesis and properties of polysiloxane side chain cholesteric elastomers

The synthesis of new side chain cholesteric liquid crystalline elastomers containing the flexible non-mesomorphic crosslinking agent M-1 and the cholesteric monomer M-2 by a one-step hydrosilylation reaction is described. The chemical structures of the obtained monomers and network polymers were confirmed by ¹H NMR and FTIR spectroscopy. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. The glass transition temperatures and isotropic temperatures of the mesomorphic elastomers decreased as the concentration of crosslinking units increased; in the mesomorphic region the liquid crystalline elastomers showed elasticity, reversible phase transitions and Grandjean texture. The flexible crosslinking agent did not disturb the cholesteric structure; moreover, it was beneficial for adjusting the helix of the cholesteric liquid crystalline polymers, and cholesteric elastomers P-6, P-7, show reversible selective reflection of visible light.     

Growth dynamics of a liquid crystal at the three- to two-dimensional crossover in a hele-shaw cell

The radial growth of a cholesteric liquid crystal phase was studied experimentally in a thick Hele-Shaw cell. In the experiments, nucleation and growth of the cholesteric phase occurs after a temperature quench from the isotropic liquid. The growth process changes from three- to two-dimensional when the growing phase touches the substrates of the Hele-Shaw cell. It was found that the growth rate generally increases at the dimensional crossover. Also, this increase in growth rate is approximately constant, independent of the depth of the temperature quench. Possible causes for the observed experimental behavior are discussed.     

A Combination of Selective Light Reflection and Fluorescence Modulation in a Cholesteric Polymer Matrix

Summary: The phase behavior and optical properties of a cholesteric ternary copolymer, containing nematogenic phenylbenzoate, cholesteric, and photochromic diarylethene side groups, and its mixture with 2 wt.‐% fluorescent dopant were studied. The investigation of the kinetics of a photochemical opening‐cycle process of the photochromic groups in the cholesteric mixture proved the energy transfer from the fluorescent dopant to the photochromic diarylethene groups. It was shown that the fluorescence intensity of the fluorescent dopant could be controlled by the portion of the “closed” form of the diarylethene groups. During the photocyclization of the photochromic groups a “degeneration” of the selective light reflection of the cholesteric matrix is observed.

Fluorescence‐resonance energy transfer makes possible the process of photosensitization of the back ring‐opening photoreaction of the photochromic diarylethene groups in the cholesteric polymer matrix.     

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.     

Blue-phase drops on a glass interface and their decoration at the cholesteric transition

Free-surface drops of blue phase attached to a glass slide present topologically concentric lines, which we first believed to be steps at the air interface, as this was often observed in smectic drops or in other liquid crystals. Actually these contours lie at the glass interface, or in its close vicinity, but do not really form steps. While the existence of steps at the air interface cannot be excluded, we did not observe them in this study. Reproducible decorations were observed at the transition from the blue phase to the cholesteric liquid crystal, and showed a geometry close to that found in certain biological structures, which may be considered as stabilized analogues of blue phases.     

Fixation of a cholesteric helical structure by the photopolymerization of a cholesteryl derived monomer

A cholesteryl derived monomer was synthesized according to a conventional synthetic route; it exhibits a cholesteric phase above 129°C, and shows a red colour due to selective reflection in the cholesteric phase. Photopolymerization of the monomer was carried out at 135°C in the cholesteric phase. The helical structure of the cholesteric phase of the monomer was frozen by photopolymerization. A peak based on the selective reflection of the cholesteric phase was detected at 615 nm in the transmittance UV-Vis spectrum. Mixtures of the monomer with a binaphthyl derivative were prepared to control the selective reflection wavelength; they all also exhibited a cholesteric phase. The selective reflection wavelength of the mixture was dependent upon the ratio of the binaphthyl derivative in the mixture. This wavelength became shorter with increasing ratio of the binaphthyl derivative. The polymer films obtained by photopolymerization displayed almost the same selective reflection wavelength as the corresponding mixtures before photopolymerization. The selective reflection wavelength of the polymer films did not change up to about 250°C.     

Photo-optical properties of photopolymerizable cholesteric compositions

Compositions consisting of nematogenic diacrylate monomer and chiral dopants capable of forming the cholesteric mesophase and of photopolymerizing were obtained and studied. For the first time, the change of optical properties and cholesteric helix pitch during photocrosslinking of diacrylate under UV irradiation (365 nm) was investigated. The kinetics of photopolymerization was studied and several stages of this process were observed. Cholesteric photopolymerizable blends containing chiral photosensitive dopant capable of E–Z isomerizing under UV irradiation (313 nm) were studied. The decrease of the helix twisting power of the dopant during photoisomerization was observed resulting in untwisting of the helix and shift of the selective light reflection peak into the long-wavelength region of the spectrum. The possibility of the photoregulation of optical properties of such blends with following fixation of structure and of these properties by means of photopolymerization under UV irradiation (365 nm) was demonstrated.     

Fixation of a cholesteric helical structure by the photopolymerization of a cholesteryl derived monomer

A cholesteryl derived monomer was synthesized according to a conventional synthetic route; it exhibits a cholesteric phase above 129°C, and shows a red colour due to selective reflection in the cholesteric phase. Photopolymerization of the monomer was carried out at 135°C in the cholesteric phase. The helical structure of the cholesteric phase of the monomer was frozen by photopolymerization. A peak based on the selective reflection of the cholesteric phase was detected at 615 nm in the transmittance UV-Vis spectrum. Mixtures of the monomer with a binaphthyl derivative were prepared to control the selective reflection wavelength; they all also exhibited a cholesteric phase. The selective reflection wavelength of the mixture was dependent upon the ratio of the binaphthyl derivative in the mixture. This wavelength became shorter with increasing ratio of the binaphthyl derivative. The polymer films obtained by photopolymerization displayed almost the same selective reflection wavelength as the corresponding mixtures before photopolymerization. The selective reflection wavelength of the polymer films did not change up to about 250°C.     

Photosensitive cholesteric polymers with azobenzene-containing chiral groups and mixtures of cholesteric copolymer with chiral-photochromic dopants

New chiral photochromic cholesteric comb-shaped acrylic copolymers and low molecular mass dopants containing azobenzene photosensitive fragments and chiral groups based on menthol and menthone were synthesized. For the copolymers and their mixtures with low molecular mass dopants, the phase behaviour and optical properties were studied. Under irradiation with UV and visible light, the untwisting of cholesteric helix takes place, and the selective light reflection maximum is shifted to the long wavelength spectral region. This shift is related to the E-Z isomerization of the azobenzene chiral groups. For the copolymers and mixtures of the cholesteric polymer with the menthyl-containing dopant, this process is thermally reversible. The specific features of the kinetics of the forward and the reverse thermal processes were characterized. It was demonstrated, that the copolymers and mixtures of the cholesteric copolymer with the menthyl-containing dopant may be used for coloured reversible recording of optical information. For such materials, their resistance with respect to the repeated 'recording-erasing' cycles was tested, and the fatigue resistance was shown to be rather high.     

Morphological Features of the First Growth Steps of Polymeric Coatings from the Active Gas Phase on the Activated Surface

Morphological features of the first growth stages of polytetrafluoroethylene films from the active gas phase on the silicon surface treated by various methods were studied. The influence of the surface energy of the support on the distribution of polymer microparticles in these stages, on the distribution kinetics was determined.     

Phase behaviour of copolymers containing cholesterol and 4-methoxybiphenyl as mesogenic groups

Liquid crystalline side group copolymers containing cholesterol and methoxybiphenyl were synthesized and investigated by size exclusion chromatography, ¹H NMR, polarization microscopy, X-ray diffraction, differential scanning calorimetry and additionally by measuring the birefringence and the optical reflection of the cholesteric phase. This cholesteric phase could be obtained by copolymerization of two monomers whose homopolymers exhibit only smectic phases. The cholesteric phase exists over a broad range of copolymer composition. For the cholesterol containing homopolymer an S_A2 bilayer phase was observed, whereas the methoxybiphenyl homopolymer shows a highly ordered E phase below an S_A1 monolayer phase. The layer periods of the S_A phases of the copolymers depend on the composition. By measuring the birefringence the order parameter in the cholesteric phase could be determined.     

Photosensitive cholesteric polymers with azobenzene-containing chiral groups and mixtures of cholesteric copolymer with chiral-photochromic dopants

New chiral photochromic cholesteric comb-shaped acrylic copolymers and low molecular mass dopants containing azobenzene photosensitive fragments and chiral groups based on menthol and menthone were synthesized. For the copolymers and their mixtures with low molecular mass dopants, the phase behaviour and optical properties were studied. Under irradiation with UV and visible light, the untwisting of cholesteric helix takes place, and the selective light reflection maximum is shifted to the long wavelength spectral region. This shift is related to the E-Z isomerization of the azobenzene chiral groups. For the copolymers and mixtures of the cholesteric polymer with the menthyl-containing dopant, this process is thermally reversible. The specific features of the kinetics of the forward and the reverse thermal processes were characterized. It was demonstrated, that the copolymers and mixtures of the cholesteric copolymer with the menthyl-containing dopant may be used for coloured reversible recording of optical information. For such materials, their resistance with respect to the repeated 'recording-erasing' cycles was tested, and the fatigue resistance was shown to be rather high.