Synthesis and characterization of white‐light‐emitting polyfluorenes containing orange phosphorescent moieties in the side chain

Two orange phosphorescent iridium complex monomers, 9‐hexyl‐9‐(iridium (III)bis(2‐(4′‐fluorophenyl)‐4‐phenylquinoline‐N,C^2′)(tetradecanedionate‐11,13))‐2,7‐dibromofluorene (Br‐PIr) and 9‐hexyl‐9‐(iridium(III)bis(2‐(4′‐fluorophenyl)‐4‐methylquinoline‐N,C^2′)(tetradecanedionate‐11,13))‐2,7‐dibromofluorene (Br‐MIr), were successfully synthesized. The Suzuki polycondensation of 2,7‐bis(trimethylene boronate)‐9,9‐dioctylfluorene with 2,7‐dibromo‐9,9‐dioctylfluorene and Br‐PIr or Br‐MIr afforded two series of copolymers, PIrPFs and MIrPFs, in good yields, in which the concentrations of the phosphorescent moieties were kept small (0.5–3 mol % feed ratio) to realize incomplete energy transfer. The photoluminescence (PL) of the copolymers showed blue‐ and orange‐emission peaks. A white‐light‐emitting diode with a configuration of indium tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/PIr05PF (0.5 mol % feed ratio of Br‐PIr)/Ca/Al exhibited a luminous efficiency of 4.49 cd/A and a power efficiency of 2.35 lm/W at 6.0 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.46, 0.33). The CIE coordinates were improved to (0.34, 0.33) when copolymer MIr10PF (1.0 mol % feed ratio of Br‐MIr) was employed as the white‐emissive layer. The strong orange emission in the electroluminescence spectra in comparison with PL for these kinds of polymers was attributed to the additional contribution of charge trapping in the phosphorescent dopants. © 2007 Wiley Periodicals, Inc. JPolym Sci Part A: Polym Chem 45: 1746–1757, 2007     

Deformation of styrene—divinylbenzene copolymers and hypercrosslinked polystyrenes during solvent adsorption and desorption

An automated procedure was developed for monitoring fast changes in the size of spherical samples of polymers during their contact with a solvent or drying. The kinetics of bulk deformation in these processes was studied for a series of cross-linked polymers, viz., gel-type and porous styrene—divinylbenzene copolymers and poly(divinylbenzenes), and hypercrosslinked polystyrenes. Gel, macroporous, and hypercrosslinked polystyrenes are substantially different in the rate, mechanism, and degree of swelling, which is associated with the principal differences in their physical structures. An unusual effect of a sharp decrease followed by a temporary increase in the volume of porous polystyrene and poly(divinylbenzene) materials were observed during desorption (evaporation) of organic solvents. Water desorption is accompanied by an excessive bulk compression of porous granules giving rise to negative deformations, which gradually relax to the state equilibrium for the dry polymer. The results of dynamic desorption porometry (for water desorption) are indicative of a bimodal size distribution of micropores in hypercrosslinked polystyrene. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 467–476, March, 2007.     

Effect of Deborah number and phase difference on peristaltic transport of a third-order fluid in an asymmetric channel

The effect of a third-order fluid on the peristaltic transport in an asymmetric channel is studied. The wavelength of the peristaltic waves is assumed to be large compared to the varying channel width, whereas the wave amplitudes need not be small compared to the varying channel width. The channel asymmetry is produced by choosing the peristaltic wave train on the walls to have different amplitudes and phase. The flow is investigated in a wave frame of reference moving with velocity of the wave. The effects of Deborah number, phase difference, varying channel width and wave amplitudes on the pumping characteristics, streamline pattern and trapping phenomena are investigated. It is observed that the trapping regions increase as the channel becomes more and more symmetric and the trapped bolus volume decreases for increasing Deborah number, phase difference and varying channel width whereas it increases for increasing flow rate and wave amplitudes. Furthermore, the obtained results could also have applications to a range of peristaltic flows for a variety of non-Newtonian fluids such as aqueous solutions of high-molecular weight polyethylene oxide and polyacrylamide.     

A molecular network model to describe the nonlinear viscoelastic behavior of polymers

A transient molecular network model is built to describe the nonlinear viscoelasticity of polymers by considering the effect of entanglement loss and regeneration on the relaxation of molecular strands. It is an extension of previous network theories. The experimental data on three thermoplastic polymers (ABS, PVC and PA6) obtained under various loading conditions are used to test the model. Agreement between the theoretical and experimental curves shows that the suggested model can describe successfully the relaxation behavior of the thermoplastic polymers under different loading rates by using relatively few relaxation modes. Thus the micromechanism responsible for strain-rate dependence of relaxation process and the origin of nonlinear viscoelasticity may be disclosed. The project supported by the National Natural Science Foundation of China and Doctorial Fund     

Heat transfer in lattice BGK modeled fluid

The thermal lattice BGK model is a recently suggested numerical tool aiming at solving problems of thermohydrodynamics. The quality of the lattice BGK simulation is checked in this paper by calculating temperature profiles in the Couette flow under different Eckert and Mach numbers. A revised lower order model is proposed to improve the accuracy and the higher order model is proved to be advantageous in this respect, especially in the flow regime with a higher Mach number.     

Current R & D activities at TRCRE in polymer processing by EB

The current status of the R & D activities is presented on electron beam processing of polymers being carried out at TRCRE. Topics included are sterilization of medical products, graft polymers for selective separation or absorbents and curing of liquid prepolymer-monomer systems.     

Complexes in polymers IV. FTIR microscopic characterization of thin organic polymer films containing embedded transition-metal carbonyl complexes

Thin films of polystyrene (PS), poly(methyl methacrylate) (PMMA) and polystyrene-polyacrylonitrile copolymer (PS-AN), containing various embedded transition-metal complexes, have been studied by FTIR microscopy. The spatial distributions of the transition-metal carbonyl complexes throughout the thin organic polymer films have been determined by a two-dimensional IR mapping procedure. The spectral variations observed in the distribution of the metal carbonyls throughout the different polymer films are discussed. The IR data show that the technique used to prepare the organometallic-embedded thin films (viz. freeze-drying of solutions followed by hot mechanical pressing of the residues) does in general lead to homogeneous films which may eventually find industrial application, e.g. as membrane sensors for small molecules.     

A simple formula for mean multiplexing delay for independent regenerative sources

Simple expressions are given for the mean delay, mean waiting time, and mean busy period length in a multiplexer. Data streams with active periods having a general distribution are permitted, and the data rate during the active periods can be random. Data can also arrive in batches. The key restrictions of the model are that the sources are independent, idle periods are exponentially distributed, and a source generates at least enough data during an active period to keep the server busy throughout the period. The exact formulas allow evaluation of the error in approximations such as a heavy traffic diffusion approximation.Both continuous and discrete time models are considered. The discrete-time model includes that studied by Viterbi and subsequently generalized by Neuts. The Pollaczek-Khinchine formula for the mean amount of work in anM/GI/1 queue is retrieved as a limiting case.Preliminary version presented at IEEE INFOCOM, San Francisco, April 1993.     

有机薄膜器件负电阻特性的影响因素

研究了影响有机染料掺杂聚合物薄膜器件负电阻特性的因素，为探索有机负电阻的机理提供实验依据。实验中制备了多种有机染料掺杂聚合物薄膜器件，研究了有机小分子染料、聚合物基体、薄膜组成及厚度、ITO和聚苯胺阳极等对有机染料掺杂聚合物薄膜器件负电阻特性的影响。在室温、大气环境下，所制备的多种有机染料掺杂聚合物器件在所加电压为3～4V时，观察到明显的负电阻特性，电流峰谷比最大约为8。负电阻现象及峰谷比的大小受膜厚和器件的结构、制备工艺等影响。提出用负电阻和二极管并联组成的等效电路模型解释影响负电阻特性的因素，认为负电阻特性与载流子的不平衡注入有关。在此基础上设计、合成了主链含唔二唑电子传输基团的可溶性聚对苯撑乙烯衍生物，该聚合物兼具空穴和电子传输功能，在空气中具有较稳定的N型负电阻特性。进一步控制相关材料和工艺条件，有可能得到易于控制的负阻效应，开发出新型的有机负电阻器件。