Role of polarization and alignment in photoactuation of nematic elastomers

Changing the orientational order in liquid-crystal elastomers leads to internal stresses and changes of the sample shape. When this effect is induced by light, due to photoisomerization of constituent molecular moieties, the photomechanical actuation results. We investigate quantitatively how the intensity and the polarization of light affect photoactuation. By studying dissolved, as well as covalently bonded azo-dyes, we determine the changes in absorption and the response kinetics. For the first time we compare the response of aligned monodomain, and randomly disordered polydomain nematic elastomers, and demonstrate that both have a comparable photoresponse, strongly dependent on the polarization of light. Polarization-dependent photoactuation in polydomain elastomers gives an unambiguous proof of its mechanism since it is the only experiment that distinguishes from the associated thermal effects.     

Heat treatment effects on dielectric and physico-chemical properties of an epoxy polymer

Infrared (IR) spectroscopy, dielectric spectroscopy (DS), and thermally stimulated depolarization current (TSDC) have been used to study heat treatment effects on an epoxy-based polymer. Variations in physico-chemical and dielectric properties were examined for annealing temperatures between 55 and 170 °C. IR results have shown that heating causes both chain scission and thermal oxidation of the polymer, increasing thus the amount of trapped charges. The complex dielectric permittivity and the dielectric modulus have been analyzed, by means of DS, to highlight and separate charge relaxation phenomena from conduction contributions. Results indicate structural rearrangements, leading to a decrease of dipolar relaxation frequency (from 16 to 13.5 kHz) and an increase of the relaxation strength (around 20%). TSDC measurements have shown a current peak shift towards higher temperatures, and a significant intensity decrease, which is proportional to the quantity of released charges.     

Preparation of alkaline solid polymer electrolyte based on PVA-TiO2-KOH-H2O and its performance in Zn-Ni battery

A novel composite alkaline polymer electrolyte based on poly(vinyl alcohol) (PVA) polymer matrix, titanium dioxide (TiO₂) ceramic fillers, KOH, and H₂O was prepared by a solution casting method. The properties of PVA-TiO₂-KOH alkaline polymer electrolyte films were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and AC impedance techniques. DSC and XRD results showed that the domain of amorphous region in the PVA polymer matrix augmented when TiO₂ filler was added. The SEM result showed that TiO₂ particles dispersed into the PVA matrix although some TiO₂ aggregates of several micrometers were formed. The alkaline polymer electrolyte showed excellent electrochemical properties. The room temperature (20 °C) ionic conductivity values of typical samples were between 0.102 and 0.171 S cm⁻¹. The Zn-Ni secondary battery with the alkaline polymer electrolyte PVA-TiO₂-KOH had excellent electrochemical property at the low charge-discharge rate.     

Improvement of hydrophilic properties of electrospun polyamide-imide fibrous mats by atmospheric-pressure plasma treatment

Polyamide-imide (PAI) fibrous mats were fabricated through electrospinning and further treated with atmospheric-pressure plasma. The surface characteristics of the PAI fibrous mats were examined to determine the effect of plasma treatment on the hydrophilic properties. FT-IR, X-ray photoelectron spectroscopy, and contact-angle analysis indicated that the hydrophilicity of the PAI fibrous mats increased upon the introduction of hydrophilic groups by plasma treatment. The concentration of functional groups, including oxygen, and the surface roughness of the PAI fibrous mats increased with increasing treatment time. The optimum plasma treatment time for surface modification of the PAI fibrous mats under atmospheric pressure was 120 s.     

Electrical conductivity,optical properties and mechanical stability of 3, 4, 9, 10-perylenetetracarboxylic dianhidride based organic semiconductor

The 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) doped polymer films were prepared with Polypyrrole (PPy) and Polyvinyl alcohol (PVA) polymers by solution-casting. The change in structure and chemical composition of samples was identified by XRD and FTIR respectively. The UV–visible spectroscopy demonstrates the optical characteristics and band gap properties of sample. The homogeneous morphology of sample for higher wt% of PTCDA was examined by atomic force microscopy (AFM). The differential scanning calorimetry (DSC) results demonstrate the decrease in melting temperature (T_m) and degree of crystallinity (χ_c%) of polymeric organic semiconductor. The mechanical property demonstrates the high tensile strength and improved plasticity nature. Impedance spectroscopy was evaluated to determine the conductivity response of polymeric organic semiconductor. The highest DC conductivity (2.08×10⁻³ S/m) was obtained for 10 wt% of PTCDA at 140 °C. The decrease in activation energy (E_a) represents the non-Debye process and was evaluated from the slope of ln σ_dc vs. 10³/T plot.     

Theoretical and experimental approaches to kinetics at the collapse transition of a homopolymer

Summary We discuss some recent theoretical studies of the kinetics of the collapse transition in homopolymers. An isolated polymer is modelled using computer simulation, and a time-dependent mean-field theory. The mean-field theory is analysed analytically for early stages, and for short polymers the equations are studied numerically. The results of simulation and theory are compared yielding, we argue, a consistent physical picture. Quantitative comparisons are not yet given, but seem relatively promising. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4– 1994.     

Heterogeneous dynamics at the glass transition in van der Waals liquids, in the bulk and in thin films

It has been shown over the last few years that the dynamics close to the glass transition is strongly heterogeneous, both by measuring the diffusion coefficient of tagged particles or by NMR studies. Recent experiments have also demonstrated that the glass transition temperature of thin polymer films can be shifted as compared to the same polymer in the bulk. We propose here first a thermodynamical model for van der Waals liquids, which accounts for experimental results regarding the bulk modulus of polymer melts and the evolution of the density with temperature. This model allows us to describe the density fluctuations in such van der Waals liquids. Then, by considering the thermally induced density fluctuations in the bulk, we propose that the 3D glass transition is controlled by the percolation of small domains of slow dynamics, which allows to explain the heterogeneous dynamics close to T _g. We show then that these domains percolate at a lower temperature in the quasi-2D case of thin suspended polymer films and we calculate the corresponding glass transition temperature reduction, in quantitative agreement with experimental results of Jones and co-workers. In the case of strongly adsorbed films, we show that the strong adsorption amounts to enhance the slow domains percolation. This effect leads to 1) a broadening of the glass transition and 2) an increase of T _g in quantitative agreement with experimental results. For both strongly and weakly adsorbed films, the shift in T _g is given by a power law, the exponent being the inverse of that of the correlation length of 3D percolation. Received 21 March 2000 and Received in final form 4 December 2000     

Noise effects in two different biological systems

We investigate the role of the colored noise in two biological systems: (i) adults of Nezara viridula (L.) (Heteroptera: Pentatomidae), and (ii) polymer translocation. In the first system we analyze, by directionality tests, the response of N. viridula individuals to subthreshold signals plus noise in their mating behaviour. The percentage of insects that react to the subthreshold signal shows a nonmonotonic behaviour, characterized by the presence of a maximum, as a function of the noise intensity. This is the signature of the non-dynamical stochastic resonance phenomenon. By using a “soft” threshold model we find that the maximum of the input-output cross correlation occurs in the same range of noise intensity values for which the behavioural activation of the insects has a maximum. Moreover this maximum value is lowered and shifted towards higher noise intensities, compared to the case of white noise. In the second biological system the noise driven translocation of short polymers in crowded solutions is analyzed. An improved version of the Rouse model for a flexible polymer is adopted to mimic the molecular dynamics by taking into account both the interactions between adjacent monomers and the effects of a Lennard-Jones potential between all beads. The polymer dynamics is simulated in a two-dimensional domain by numerically solving the Langevin equations of motion in the presence of thermal fluctuations and a colored noise source. At low temperatures or for strong colored noise intensities the translocation process of the polymer chain is delayed. At low noise intensity, as the polymer length increases, we find a nonmonotonic behaviour for the mean first translocation time of the polymer centre of inertia. We show how colored noise influences the motion of short polymers, by inducing two different regimes of translocation in the dynamics of molecule transport.     

Thermal and non-thermal fluctuations in active polar gels

We discuss general features of noise and fluctuations in active polar gels close to and away from equilibrium. We use the single-component hydrodynamic theory of active polar gels built by Kruse and coworkers to describe the cytoskeleton in cells. Close to equilibrium, we calculate the response function of the gel to external fields and introduce Langevin forces in the constitutive equations with correlation functions respecting the fluctuation-dissipation theorem. We then discuss the breakage of the fluctuation-dissipation theorem due to an external field such as the activity of the motors. Active gels away from equilibrium are considered at the scaling level. As an example of application of the theory, we calculate the density correlation function (the dynamic structure factor) of a compressible active polar gel and discuss possible instabilities.