Electrically induced anchoring transition in cholesteric liquid crystal cells with different confinement ratios

Reorientation of cholesteric liquid crystal induced by the electrically controlled ionic modification of surface anchoring within the cell with confinement ratio exceeding 1 has been studied. The change of homeotropic surface anchoring to the planar one on the electrode-anode substrate under the action of DC voltage causes the formation of the modulated hybrid-aligned cholesteric layer in the cell. Optical texture of the liquid crystal layer with such an orientation structure is the linear periodic stripes. Homogeneity of emerging optical texture depending on the confinement ratio as well as on the prehistory of voltage application has been considered. It has been found that the ionic modification of surface anchoring results in total transformation of the diffraction pattern observed after the laser beam passing through the sample.     

Electrically induced anchoring transition in nematics with small or zero dielectric anisotropy

The orientational transitions induced by electrically controlled ionic modification of surface anchoring in liquid crystal cells based on the nematics with small or zero dielectric anisotropy Δε are considered. The type of director reorientation is shown to be independent of the sign of dielectric anisotropy and can be the same for the nematics with both negative and positive Δε. Besides, the orientational transition and corresponding switchable optical states do not depend on the Δε value and can be effectively realised even for the nematics with zero dielectric anisotropy.     

Cholesteric gratings induced by electric field in mixtures of liquid crystal and novel chiral ionic liquid

Formation of gratings upon alternating electric field in compositions of highly birefringent liquid crystal (LC) with novel chiral ionic liquid (CIL) enclosed in 10-µm-thick cells is studied. The compatibility of two organic components of the mixture is investigated. The grating is formed in 1–5% CIL mixtures and causes significant changes of the transmission of polarised light through the cells. Transmission of polarised λ = 633 nm light through the 5% CIL sample is studied with respect to frequency (1 Hz–3 MHz) and amplitude (up to 10 V) of alternating voltage and the results are used for sketch a voltage–frequency phase diagram. Two possible ways of formation of the gratings with perpendicular orientation to that formed from initial state are presented. Two twisting axes in the molecular alignments of the cholesteric LC gratings with perpendicular directions are proposed. Optical switch based on four different states of LC including two gratings with perpendicular directions is proposed. Moreover, behaviour of the rotation of a grating induced by AC field in hybrid planar-homeotropic cell is studied in two frequency regimes and rotation by more than 90° upon change of the AC field amplitude is observed.     

Nano-scale modification of ionic surfaces induced by electronic transitions

This paper presents a review of recent experimental and theoretical work on surface modification of alkali halides due to electronic excitations caused by electron and photon irradiation. In particular, several examples of free exciton and hot electron–hole pair formation in ionic materials are given. It is demonstrated that evolution of these primary excitations with subsequent defect formation and diffusion from the bulk to the surface, leads to dynamic surface modification and sputtering, often periodically varying with the irradiation dose. In turn, modification of the surface topography could affect and modulate periodically, the diffusion processes driving the defects from the bulk of the material towards its surface. Spectacular examples of such oscillatory yield dependencies, and corresponding surface nano-structure formation and evolution, are shown for electron- and photon-irradiated NaCl, KBr and KCl(0 0 1) surfaces of bulk crystals and thin epitaxial films. Important applications of these findings for quantitative characterisation of insulator surfaces and mass spectrometry are presented.     

Tuning the glass transition of siloxane-based poly(ionic liquid)s towards high ion conductivity

Herein, we report a simple and versatile synthetic approach towards siloxane-based poly(ionic liquid)s (PILs) with unusually low glass transition temperatures (T_g) down to −73°C, and thus “liquid-like” behavior at room temperature. We designed a polydimethylsiloxane-derived copolymer carrying dialkylimidazolium moieties, and by careful selection of the side-chain length and the type of anions we were able to manipulate its T_g over a wide range and reach high ionic conductivities (σ_DC) up to 4.8 × 10⁻⁵ S/cm at 300 K. The ionized species make up only a minor fraction (<25 mol%) of the overall repeating units and are supposedly randomly distributed: Yet our results indicate dramatic effects on the thermal properties due to repulsive interactions between ionic and non-ionic segments.     

Phase transition of layer structure of poly(p-benzenedithiol-co-p-diethynylbenzene) by heat or photon mode

Phase transition of the layer structure of poly(p-benzenedithiol-co-p-diethylbenzene) obtained in solid state polymerization was studied by a thermal treatment or UV irradiation under a nitrogen atmosphere. The peak intensities in the X-ray diffraction diagram of polymers gradually decreased with the thermal treatment time above 55°C. Below 50°C the layer structure of polymers hardly changed. The apparent activation energy for the phase transition was about 15 Kcal/mol [63 KJ/mol] at the initial stage and gradually decreased to a few Kcal/mol [ca. 2 KJ/mol]. UV light from a high-pressure mercury lamp also gradually induced the phase transition from the layer structure to an amorphous one. The pristine polymer possesses phase transition points at 75, 95 and 130°C. The exothermic transition at 75°C can be understood as the thermal destruction of the semistable layer structure. The exothermic transition at 95°C may be correspond to the cis → trans thermal isomerization of the C?°C bond in the polymer main chain. The diffuse reflectance spectrum of the pristine polymer differed from that of the amorphous polymer obtained by the thermal treatment of the pristine polymer. SEM photographs of the pristine polymer showed a particular surface structure, i.e. entangled fibrous material. TEM photographs of the pristine polymer exhibited a bright valley-and-hill structure, whereas that of the amorphous polymer obtained by thermal treatment exhibited a plain surface.     

Phase transition of layer structure of poly(1,4-benzenedithiol-co-1,4-diethynylbenzene) by photon mode

The effect of light wavelength on the phase transition of the layer structure of poly(1,4-benzenedithiol-co-1,4-diethynylbenzene) was studied under an air atmosphere at 18–22°C. The thin layer polymer crystals were prepared by solid state polymerization, and the amount of the layer structure was evaluated by an X-ray diagram. A monochromatic light with a wavelength in the region of ca. 500–600 nm was used as a light source. The amount of the layer structure was found to be altered by light. There were three characteristic wavelengths at 545.6, 567.8 and 590.1 nm, inducing pronounced peak intensities in the X-ray diagram. On the other hand, at 501.1, 539.6, 571.8 and 588.1 nm the light made the peak intensity decrease steeply. The phase transition was induced by a photon mode, but not by a heat mode. The amount of the layer structure was altered linearly with increasing irradiation time up to 60 min. However, over 60 min the change became dull. The total energy given to the polymers during the irradiation was about 24 X 10^?3 J/cm². Accordingly, the phase transition occurs with a high sensitivity to the light. The polymers were irradiated alternately by the light of 545.6 nm and 571.8 nm at intervals of 60 min, respectively. The amount of the layer structure was controlled reversibly by the light.     

利用双水相分离回收离子液体的研究进展

研究离子液体的分离与回收对于减少离子液体对环境的影响、提高离子液体的利用效率、降低离子液体的应用成本、促进离子液体的工业应用具有重要的意义.本文重点综述了利用无机盐-离子液体双水相、糖-离子液体双水相、聚合物-离子液体双水相和CO2诱导的离子液体双水相技术分离回收离子液体的研究进展,分析了影响离子液体分离回收的关键因素,评价了不同离子液体双水相体系的优缺点,展望了该领域的发展方向及面临的挑战.     

Effect of imidazolium-based ionic liquids on the aggregation behavior of twin-tailed cationic gemini surfactant in aqueous solution

Micellization behavior of the twin-tailed surfactants can be modulated by the addition of various modifiers. Ionic liquids (ILs) are one of them and are documented here. The beauty of these environmentally benign neoteric molecules lies in their structural versatility. Here, we have investigated the effect of three ILs: 1-butyl-3-methylimidazolium bromide ([C₄mim][Br]), 1-hexyl-3-methylimidazolium bromide ([C₆mim][Br]), and 1-octyl-3-methylimidazolium bromide ([C₈mim][Br]) on the aggregation and surface adsorption behavior of cationic gemini surfactant, bis(hexadecyldimethyl ammonium)propane dibromide (16-3-16) through experimentally measured electrical conductivities, surface tensions, and by spectral methods (UV-vis absorbance and fluorescence measurements). The main focus of the study is to observe the effect of added ILs on the critical micelle concentration (cmc), various surface parameters, aggregation number, and size of the aggregates of gemini surfactant. The results show that the more hydrophobic ILs, that is, [C₆mim][Br] and [C₈mim][Br] behave as electrolyte at lower concentration and cosurfactant at higher concentration, whereas moderately hydrophobic IL [C₄mim][Br] acts as an electrolyte at all concentration ranges studied. The modulating effects of ILs were also compared with conventional electrolyte (NaBr) at similar conditions.     

Orientational instability of nematic liquid crystal in a homeotropic cell with boundary conditions controlled by an electric field

We study the orientational instability of the director in a homeotropic nematic liquid crystal (NLC) cell in a DC electric field. The electric field is applied along or perpendicular to a cell surface depending on whether anisotropy of dielectric permittivity of NLC is positive or negative. The easy axis on one of the cell polymer substrates is allowed to deviate in perpendicular to the substrate plane due to the influence of the NLC and the electric field. It was established that the orientational instability of the director can have a threshold as well as be thresholdless which depends on the character of the coupling of the easy axis with the electric field. The temporal behaviour of a director and the easy axis during transition to the stationary state after turning on electric field and returning to the initial homogeneous state after turning off the field was investigated. In the case of the negative anisotropy of the static permittivity, the comparison of experimental and calculated time dependences of the easy axis reorientation angle let us to estimate values of the mobile easy axis viscosity coefficient and coupling parameter describing the coupling between the easy axis and the electric field.     

普鲁洛尼克型非离子表面活性剂的结构分析及其同系物分子量分布的测定

以ＦＡＢＭＳ、ＥＩＭＳ、ＦＴＩＲ等手段鉴定了从工业产品中分离得到的一种未知表面活性剂的化学结构为聚氧丙烯／聚氧乙烯共聚物，其商品名称为普鲁洛尼克（Ｐｌｕｒｏｎｉｃ）型非离子表面活性剂．用ＦＡＢＭＳ谱观察到该表面活性剂同系物的各种准分子离子峰呈近似的高斯分布，根据各种准分子离子峰的相对强度得出该表面活性剂同系物的分子量分布及平均分子量．     

Sphere-to-rod transition of short-chain PEO-b-PDMS-b-PEO in aqueous solution induced by copolymer concentration

A short-chain triblock copolymer EO9-DMS7-EO9 was synthesized by coupling reaction of allyl-terminated poly（ethylene oxide） and Si-H-terminated poly（dimethylsiloxane）. The structure and purity of synthesized copolymer was carefully characterized. Self-assembly behavior of EO9-DMST-EO9 triblock copolymer in water was investigated. And it was found that along with the increase of copolymer concentration, morphology of self-assembled aggregates transits from sphere to rod. A plausible understanding of the morphology transition for the investigated triblock copolymer was proposed.     

Effects of surfactants on the phase transition of poly(N-isopropylacrylamide) in water

The effects of both anionic (sodium dodecyl sulfate, SDS) and cationic (dodecylpyridine bromide, DPB) surfactants on the phase transition of narrowly distributed poly(N-isopropylacrylamide) (PNIPAM) microgel particles were investigated by laser light scattering. The addition of SDS swells the particles and increases the phase transition temperature, while DPB has a much smaller effect. This difference cannot be due to an association between the surfactant hydrophobic tail and PNIPAM because DPB and SDS have an identical hydrophobic tail. The amide groups in PNIPAM are slightly protonized in deionized water (pH ∼ 5.5). Our results contradict a previous prediction that oppositely charged surfactants will collapse a polyelectrolyte gel. After adding SDS, a two-step phase transition of the PNIPAM gel is observed. This suggests that SDS forms micelles inside the microgel with the help of the immobilized counter ions on the gel network. The SDS micelles are broken into individual SDS molecules in the first step of phase transition, while in the second step individual SDS molecules are gradually expelled. Surfactant effects on the microgel particles are compared with those of individual PNIPAM chains. © 1996 John Wiley & Sons, Inc.     

Gas–liquid mass transfer in the presence of ionic surfactant: effect of counter‐ions and interfacial turbulence

This work investigated the effect of counter‐ions and interfacial turbulence on oxygen transfer from gas to liquid phase containing ionic surfactant, and experiments were performed in a mechanically stirred reactor with flat gas–liquid interface. Counter‐ions in terms of hydration ability and polarizability influence the interfacial coverage of ionic surfactants (i.e. cetytrimethylammonium bromide (CTAB) and cetytrimethylammonium chloride) with the same hydrocarbon chain length, producing hindrance but in different extent on oxygen transfer. The addition of electrolyte (NH₄Br) substantially reduced the interfacial tension and surface charge of micelles (zeta potential) in CTAB system, and this salt effect greatly compressed interfacial double layer leading to gas transfer inhibition. The surface charge, aggregation number as well as stability of micelles formed above the critical micelle concentration could also alter interfacial configuration of surfactant layer reflected by gas absorption rate. Liquid turbulence was analyzed to decide the role of surfactant present in water on gas–liquid mass transfer, since Marangoni instability effect playing positive role should be taken into consideration under moderate liquid flow, while in turbulent system, contribution of Marangoni effect became overshadowed and consequently surfactant pose ‘barrier’ effect on gas transfer due to its surface active nature. Copyright © 2013 John Wiley & Sons, Ltd.     

An analysis of the swelling equilibrium of an ionic polymer network in a binary liquid mixture

An equation which represents the swelling equilibrium of an ionic polymer network in a binary liquid mixture is introduced and evaluated numerically. Discontinuous volume changes are obtained with pertinent values of the parameters. From two types of dependence of the degree of ionic dissociation on the composition of a liquid mixture, two types of volume transitions of an ionic gel are illustrated. One is the transition typically seen in acrylamide gels, and the other is a re-entrant transition typical of isopropylacrylamide gels. The selective dissolution factor of two liquids into a swollen polymer network also becomes discontinuous in accordance with the discontinuous volume change. Transition points and the spinodal line are calculated from a generalized form of the free energy change of the swollen gel system. © 1994 John Wiley & Sons, Inc.