Synergic influence of a surfactant and ultrasonication on the preparation of soluble,conducting polydiphenylamine/silica‐nanoparticle composites

Conducting polydiphenylamine was used to encapsulate silica nanoparticles through the oxidative polymerization of diphenylamine in the presence of ultrasonic irradiation. The polymerization was performed in the presence of sodium lauryl sulfate as a surfactant. Experiments performed in the absence of ultrasound clearly demonstrated that the application of ultrasonication played multiple roles in the preparation of a composite of polydiphenylamine with silica nanoparticles. Ultrasonication dispersed the silica nanoparticles, converted sodium lauryl sulfate to lauryl alcohol, and augmented the dispersion of the silica‐nanoparticle/polydiphenylamine composite in an organic medium. Silica‐nanoparticle/polydiphenylamine composites were also prepared in the absence of ultrasound and/or sodium lauryl sulfate. The silica‐nanoparticle/polydiphenylamine composites were characterized with Fourier trans form infrared spectroscopy, ultraviolet–visible/near‐infrared spectroscopy, and thermogravimetric analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3912–3918, 2006     

Amelioration of mechanical brittleness in hyperbranched polymer. 1. Macroscopic evaluation by dynamic viscoelastic relaxation

Hyperbranched poly(ether ketone)-b-linear poly(ether ketone)-b-hyperbranched poly(ether ketone) (HLHPEK) triblock copolymers with two different block compositions were prepared as an approach to improve the mechanical brittleness of hyperbranched poly(ether ketone) (HPEK). From the time-temperature superposition of dynamic shear moduli, G′(ω) and G″(ω), of HPEK and two HLHPEKs, it was investigated that the junction points between G′(ω) and G″(ω) shifted to the higher frequencies and the rubbery plateau region spread wider over the reduced frequency axis as the linear blocks were introduced and their compositions were increased. Such changes in viscoelastic response were consequences of increase in the amount of chain entanglements additionally formed by the linear blocks. In order to verify the effect of the linear block incorporation on amelioration of the mechanical brittleness, the degree of brittleness and its improvement were evaluated from the temperature dependence of the shift factors, a_Ts, experimentally obtained during the superposition of the dynamic moduli and of the average viscoelastic relaxation times, τ_HNs, determined with empirical Havriliak-Negami distribution function. From the nonlinear curve fittings of the a_Ts and the τ_HNs by the Vogel-Tamman-Fulcher equation, the degree of brittleness for HPEK and HLHPEK triblock copolymers were quantified as values of the material parameter D, an indicative of deviation from the linear Arrhenius behavior and a measure of fragility of the given material. The tendency of increasing D values with the linear block compositions confirmed substantial improvement of the mechanical brittleness in the HLHPEK triblock copolymers compared to HPEK. Therefore, the approach to copolymerize HPEK with its chemically analogous linear counterpart was verified to be an effective strategy to impart molecular entanglements and hence ameliorate the mechanical brittleness on the basis of macroscopic rheological evaluation.     

On the modeling of electro-hydrodynamic flow in a wire-plate electrostatic precipitator

Modeling of the flow velocity fields for the electrohydrodynamic (EHD) flow in a wire-to-plate type electrostatic precipitator (ESP) was achieved. Solutions of the steady, two-dimensional Navier-Stokes equations have been computed. The equations were solved in the conservative finite-difference form on a fine uniform rectilinear grid of sufficient resolution to accurately capture the momentum boundary layers. The numerical procedure for differential equations was used by SIMPLEST [Michel, 2002], a derivative of Patankar’s SIMPLE algorithm, to bring rapid convergence. The Phoenics (Version 3.5.1) CFD code, coupled with Poisson’s and ion transport equations and electric body force in the momentum equation, developed in this study, was used for the numerical simulation. From calculations for the flow employing different flow models, the Chen-Kimk-ε turbulent model appeared to be the most appropriate choice to obtain a quantitative image of the resulting mean flow field and downstream wake flow of the rear wire, although this was obtained from a qualitative analysis due to the lack of experimental verification. The flow velocity field pattern showed a strong EHD secondary flow, which was clearly visible in the downstream regions of the corona wire despite the low Reynolds number for the electrode (Re_CW=12.4). Secondary flow vortices were also caused by the EHD with increases in the discharge current     

Preparation of Monodisperse ZrO2 by the Microwave Heating of Zirconyl Chloride Solutions

Based on the principle that the solubility of a salt decreases as the dielectric constant of the solvent decreases, zirconia powders were prepared by heating a zirconyl chloride solution with a 2-PrOH-water mixture as the solvent. The morphology, size, and size distribution of the resulting particles were highly sensitive to the heating method used on the starting solution. Particles formed under conventional heating methods were polydisperse, agglomerated spherical, or irregularly shaped because of inhomogeneous precipitation through the temperature gradient, the shear force induced by stirring, compositional nonuniformity, and the low heating rate. The present study demonstrated that microwaves provide an excellent means of heating uniformly and rapidly without stirring. The particles resulting from microwave treatment were monodisperse and spherical, with a mean diameter of 0.28 μm.     

Synthesis and characterization of new functional poly(urethane‐imide) crosslinked networks

To synthesize new functional poly(urethane‐imide) crosslinked networks, soluble polyimide from 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride, 4,4′‐oxydianiline, and maleic anhydride and polyurethane prepolymer from polycaprolactone diol, tolylene 2,4‐diisocyanate and hydroxyl ethyl acrylate were prepared. Poly(urethane‐imide) thin films were finally prepared by the reaction between maleimide end‐capped soluble polyimide (PI) and acrylate end‐capped polyurethane (PU). The effect of polyurethane content on dielectric constant, residual stress, morphology, thermal property, and mechanical property was studied by FTIR, prism coupler, Thin Film Stress Analyzer (TFSA), XRD, TGA, DMTA, and Nano‐indentation. Dielectric constant of poly(urethane‐imide) thin films (2.39–2.45) was lower than that of pure polyimide (2.46). Especially, poly(urethane‐imide) thin films with 50% of PU showed lower dielectric constant than other poly(urethane‐imide) thin films did. Lower residual stress and slope in cooling curve were achieved in higher PU content. Compared to typical polyurethane, poly(urethane‐imide) thin films exhibited better thermal stability due to the presence of the imide groups. The glass transition temperature, modulus, and hardness decreased with increase in the flexible PU content even though elongation and thermal expansion coefficient increased. Finally, poly(urethane‐imide) thin films with low residual stress and dielectric constant, which are strongly affected by the morphological structure, chain mobility, and modulus, can be suggested to apply for electronic devices by variation of PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 113–123, 2006     

Morphology and mechanical properties of liquid crystalline copolyester and poly(ethylene 2,6-naphthalate) blends

Blends of poly(ethylene 2,6-naphthalate) (PEN) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate), were prepared in a twin-screw extruder. Specimens for mechanical testing were prepared by injection molding. The morphology and mechanical properties were investigated by scanning electron microscopy (SEM) and an Instron tensile tester. SEM studies revealed that finely dispersed spherical domains of the liquid crystalline polymer (LCP) were formed in the PEN matrix, and the inclusions were deformed into fibrils from the spherical droplets with increasing LCP content. The morphology of the blends was found to be affected by their composition and a distinct skin-core morphology was found to develop in the injection molded samples of these blends. Mechanical properties were improved with increasing LCP content, and synergistic effects have been observed at 70 wt% LCP content whereas the elongation at break was found to be reduced drastically above 10 wt% of LCP content. This is a characteristic typical of chopped-fiber-filled composites. The improvement in mechanical properties is likely due to the reinforcement of the PEN matrix by the fibrous LCP phase as observed by scanning electron microscopy. The tensile and modulus mechanical behavior of the LCP/PEN blends was very similar to those of the polymeric composite, and the tensile strength and flexural modulus of the LCP/PEN 70/30 blend were two times the value of PEN homopolymer and exceeded those of pure LCP, suggesting LCP acts as a reinforcing agent in the blends.     

A numerical analysis of rate data for packed bed reactors in gas-solid reaction systems

A numerical solution of the pseudo-steady state governing equations on the basis of the Langmuir-Hinshelwood type rate equation was obtained by the approximate finite difference method in packed bed reactors for gas-solid reaction system. It was proved that the numerical method has good accuracy compared with the strict solution in the special case that the reaction rate can be represented by the first-order kinetics in terms of gaseous reactant and the effectiveness factor is unity druing the reaction. The numerical method is proposed to predict the transient of exit-gas compositions of a packed bed reactor used for gas-solid reaction systems. The exit-gas composition can be predicted from the conversion data of a single particle with varying reaction time. The present method can be easily applied to the systems involving adsorptive gaseous reactants and complex reaction behavior with structural changes of particles.     

Effect of adsorptive gaseous reactant on non-isothermal behavior for gas-solid reactions

The effect of adsorptive species on non-isothermal gas-solid reactions is studied on the basis of Langmuir-Hinshelwood kinetics. The concept of an effectiveness factor provides good information to ascertain the effect of adsorptive species and the transition of the rate controlling regime, in connection with the parameters, generally used in the analysis of non-isothermal behavior. For highly exothermic reactions, the effectiveness factor-Thiele modulus curves with multiple solutions are presented with respect to the modified adsorption equilibrium constant. The variations of the rate-controlling regime by the effect of adsorptive species are also discussed.     

A new characterization procedure for aqufous solutions with unknown composition

A new characterization procedure for aqueous solutions with unknown composition was proposed based on the binomial distribution of TOC (total organic carbon) fraction in terms of a characterizing variable, the Freundlich coefficient, k, so that the solution in question can be described by a finite number of pseudo.species identified with a certain k value. The validity and computational accuracy of this procedure has been demonstrated by characterizing three sets of experimental data chosen from different sources. Predictions based on this procedure yielded acceptable results that agreed closely with experimental data.     

Diffusional interference in liquid phase counter-adsorptions

A surface diffusion mocel with diffusional interference has been presented for the analysis of multicomponent adsorption of phenols by activated carbon. Surface diffusion coefficients for multicomponent adsorptions were estimated from the relationship between. the surface diffusion coefficient of each species and the surface coverage. The diffusional interference coefficients, W_ij, was determined from experimental counter-adsorption data. The numerical values of W_ij were in the range of 0.4–0.9, which show that the introduction of diffusional interference is necessary to analyze multicomponent counter-adsorptions properly. The proposed model successfully simulates the behaviour of phenols-activated carbon system in a batch adsorber.