Influence of dielectric layers on estimates of diffusion coefficients and concentrations of ions from impedance spectroscopy.

We present the analysis of the impedance spectra for a binary electrolyte confined between blocking electrodes with dielectric layers. An expression for the impedance is derived from Poisson-Nernst-Planck equations in the linear approximation taking into account the voltage drop on the dielectric layer. The analysis shows that characteristic features of the frequency dependence of the impedance are determined by the ratio of the Debye length and the effective thickness of the dielectric layer. The impact of the dielectric layer is especially strong in the case of high concentrated electrolytes, where the Debye length is small and thus comparable to the effective thickness of the dielectric layer. To verify the model, measurements of the impedance spectra and transient currents in a liquid crystal 4-n-pentyl-4^{'}-cyanobiphenyl (5CB) confined between polymer-coated electrodes in cells of different thicknesses are performed. The estimates for the diffusion coefficient and ion concentration in 5CB obtained from the analysis of the impedance spectra and the transient currents are consistent and agree with previously reported data. We demonstrate that calculations of the ion parameters from the impedance spectra without taking into account the dielectric layer contribution lead in most cases to incorrect results. Application of the model to analyze violations of the low-frequency impedance scaling and contradictions in the estimates of the ion parameters recently found in some ionic electrolytes are discussed.

Gel formation in a mixture of a block copolymer and a nematic liquid crystal.

The viscoelastic properties of a binary mixture of a mesogenic side-chain block copolymer in a low molecular weight nematic liquid crystal are studied for mass concentrations ranging from the diluted regime up to a liquid crystalline gel state at about 3%. In the gel state, the system does not flow, exhibits a polydomain structure on a microscopic level, and strongly scatters light. Below the gelation point, the system is homogeneous and behaves like a usual nematic, so the continuum theory of liquid crystals can be applied for interpreting the experimental data. Using the dynamic Fréedericksz transition technique, the dependence of the splay elastic constant and the rotational viscosity on the polymer concentration have been obtained. Comparing the dynamic behavior of block copolymer solutions with the respective homopolymer solutions reveals that, above a mass concentration of 1%, self-assembling of the block copolymer chain segments in clusters occurred, resulting in a gel state at higher concentrations. The effective cluster size is estimated as a function of the concentration, and a scaling-law behavior near the sol-gel transition is confirmed. This technique may serve as an alternative method for determining the gelation point.

Diffusion model of photoaligning in azo-dye layers.

The model of the rotational diffusion of the azo-dye molecules under the action of polarized uv light was used to explain the formation of the photoinduced order in azo-dye layers. We consider both the approximations of negligible and strong molecular interaction during the process of the reorientation under the field of a polarized light. We constructed an experimental setup, based on a photoelastic modulator, that allows accurate in situ measurements of the phase retardation delta of thin film as a function of the exposure time t(exp) and exposure power W (W/ cm(2) ). A good agreement with experiment was observed. Fitting the experimental curves delta ( t(exp) ) for different power values W, we can estimate the coefficient of rotational diffusion D, azo-dye order parameter S ( t(exp) ), and other parameters of the rotational diffusion model.