Flexible Structures Based on a Short Pitch Cholesteric Liquid Crystals

We report on the realization and characterization of electro-responsive and pressure sensitive polydimethylsiloxane (PDMS) conductive photonic structures combined with the reconfigurable properties of short pitch cholesteric liquid crystals (aligned in Grandjean configuration). By combining ion-implantation process and surface chemistry functionalization, we have overcome the insulating properties of PDMS and induced long range organization of cholesteric liquid crystals, thus controlling both diffraction and selective Bragg reflection of light by means of external perturbations (electric field, pressure). We have characterized our devices in terms of morphological, optical and electro-optical properties.     

Dielectric and optical properties of polymer-liquid crystal composite

Dielectric properties of polymer-liquid crystal mixture, having constituent polymer, poly-butyl methacrylate (PBMA) and liquid crystal, cholesteryl nonanoate, are reported as a function of frequency and temperature. The measurement has been done in a temperature range of 300-375 K and frequency range of 100 Hz-10 MHz. The dielectric permittivity and dielectric loss shows significant changes with the addition of polymer molecules in liquid crystal. The significant feature of composite formation is that the pure liquid crystal and polymer do not show dielectric relaxation in the frequency range covered, while the composite shows relaxation peak at a particular frequency. The optical transmittance of pure liquid crystal and composite has also been measured and compared.     

Controlled structure and density of “living” polystyrene brushes on flat silica surfaces

Thin layers of polystyrene were grown from surface-grafted nitroxide initiators via controlled “living” free radical polymerization. The “reactive” Langmuir-Blodgett deposition method allowed an effective control of the initiator layer density leading to PS brushes with different and high grafting density and stretching. The influence of the grafting density on the layer structure was studied. Comparison with theoretical predictions for monodispersed brushes in bad solvent was discussed. The thickness was found to vary linearly with molecular weight and the density dependence was shown using wetting measurements. Special features of controlled radical nitroxide polymerization from a surface were discussed. A direct comparison of the molecular weight and polydispersity between surface and bulk polymers was made by de-grafting the brushes into a toluene/HF solution. Finally, some evidence of a “surface Fischer” effect was shown from re-initiated layers. Received 20 December 2001     

Continuous peeling extrusion of SEBS block copolymers

During continuous peeling, a central polymer rod free of visible defects was continuously extruded while being peeled at the die exit. Continuous peeling can occur at flow rates orders of magnitude higher than those at which initial surface cracking is observed. Thus, if continuous peeling can be controlled it may have potential industrial applications. The aim of this work was to study how different extrusion parameters (temperature, flow rate, die length and diameter) affect the presence of continuous peeling. The melt exiting the die has been filmed to link physical measurements and observations and to determine whether or not continuous peeling is present. Different criteria have been considered to represent the extrusion conditions under which continuous peeling may occur. Surface tension criteria can be used to try to predict the appearance and disappearance of continuous peeling. A correlation formula is also proposed for the rod diameter in terms of surface tension. Our results show that the ratio of the rod diameter to the die diameter is approximately 25% greater in the case of short-orifice dies (L/D ≈ 0) than for long capillaries (L/D ≈ 10). The correlations obtained allow analysis and discussion of flow regimes for possible applications.     

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.     

Zero-temperature properties of randomly self-interacting polymers

We study the zero-temperature behavior of several simple models for randomly self-interacting polymers in one and 1+1 dimensions. Results are based on exact enumeration and closed-form expressions.     

Analysis of the crystallization kinetics in poly(ethylene oxide) by calorimetric measurements

Summary Differential scanning calorimetric measurements in the early stage of isothermal crystal growth of polyethylene oxide are analysed in the light of irreversible thermodynamics. An accurate evaluation of the equilibrium melting temperature is done by fitting the thermograms obtained at different undercoolings and referring to the activation energy values already known from the literature. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Kinetic theories and mesoscopic models for solutions of nonhomogeneous liquid crystal polymers

We present a systematic derivation of hydrodynamic theories for nonhomogeneous nematic liquid crystal polymers (LCPs) by approximating the molecules as rigid ellipsoids, which can be either uniaxial molecules (spheroids) or biaxial ones. The short range interaction is assumed to be dominated by the excluded volume effect. Additional molecular properties with ellipsoidal molecules, e.g., a dipole–dipole interaction in extended nematics and chiral molecular structure in cholesterics, are accounted for through additional intermolecular potentials. Long-range molecular interaction is implemented through an averaged mean-field potential characterized by interaction functions. The extra elastic stress tensor is calculated using an extended virtual work principle consistent with conservation of angular momentum on the material volume, whereas the extra viscous stress is obtained by Batchelor’s volume averaging method. In the isothermal case, the theories are shown to satisfy the second law of thermodynamics, i.e., they admit positive production of entropy or energy dissipation. In the case of cholesterics, the kinetic theory reduces to the Leslie–Ericksen theory in the limit of weak translational diffusion, weak long range interaction, and weak flow.     

Syntheses and Crystal Structures of Two Coordination Polymers with Aromatic Dioxide as Bridge Ligands

Two coordination polymers, namely, two-dimensional complex 1 {[Cu(μ- L)1.5(ClO4)2(H2O)].(H2O)0.5}n (L = pyrazine-1,4-dioxide) and one-dimensional complex 2 [Co(μ-L)Br2(H2O)2]n, have been synthesized with pyrazine-1,4-dioxide as bridging ligands, and their crystal structures were determined by X-ray crystallography. Crystal data for complex 1: monoclinic system, space group C2/c, with a = 23.310(3), b = 12.2338(17), c = 10.6075(15) , β = 110.487(2)°, V = 2833.6(7) 3, Z = 8, C6H9Cl2CuN3O12.5, Mr = 457.60, Dc = 2.145 g/cm3, F(000) = 1832 and μ = 1.998 mm-1; and those for 2: monoclinic system, space group C2/c, with a = 11.012(3), b = 7.483(2), c = 11.451(3) , β = 101.654(4)°, V = 924.2(4) 3, Z = 4, C4H8Br2CoN2O4, Mr = 366.87, Dc = 2.637 g/cm3, F(000) = 700 and μ = 10.487 mm-1. 1 shows a two-dimensional sheet structure on the ac plane through the coordination of μ-L bridging ligands with Cu(II) ions, while 2 displays a zigzag one-dimensional chain along the c axis via the coordination of μ-L bridging ligand with Co(II) ions. Hydrogen bonds in 1 and 2 make the sheets (or chains) connect each other to form a three-dimensional structure.