Morphology development in polyethylene/polystyrene blends: the influence of processing conditions and interfacial modification

The influence of processing conditions and interfacial modification on the morphology evolution and the composition range within which fully co‐continuous high density polyethylene/polystyrene blend structures can exist during blending in a single screw extruder was studied. Blends ranging from pure A to pure B component, with and without compatibilizer, were prepared under two different shear rates. It was found that high shear rates displaced the breakdown–coalescence balance of the dispersed nodules to the side of coalescence, narrowing the percolation domain and the critical composition for full co‐continuity decreased with increasing shear rates. The addition of a tri‐block compatibilizer induced the percolation threshold of the polystyrene phase to begin at lower percentages of polyethylene but the phase inversion point did not change. The experimental results are discussed in the light of various theoretical models. Copyright © 2005 Society of Chemical Industry     

Specimen preparation and image processing and analysis techniques for automated quantification of concrete microcracks and voids

Specimen preparation and image processing/analysis techniques were developed for use in automated quantitative microstructural investigation of concrete, focusing on concrete microcracks and voids. Different specimen preparation techniques were developed for use in fluorescent and scanning electron microscopy (SEM) of concrete; then techniques produce a sharp contrast between microcracks/voids and the body of concrete. The image processing/analysis techniques developed specifically for use with concrete address the following usages: automatic threshold; development of intersecting microcracks/voids and connected voids; distinction of microcracks form voids based on geometric attributes; and noise filtration.     

Determination of water activities and osmotic and activity coefficients of the system NaCl–BaCl2–H2O at 298.15 K

The water activities of the mixed aqueous electrolyte NaCl–BaCl₂(aq) are measured at total molalities from 0.25 mol kg⁻¹ to about saturation for different ionic strength fractions (y) of NaCl with y=0.33,0.50,0.67. The results allow the deduction of osmotic coefficients. The experimental results are compared with the predictions of the Zdanovskii, Stokes, and Robinson (ZSR), Kusik and Meissner (KM), Robinson and Stokes (RS), Lietzke and Stoughton (LSII), Reilly, Wood, and Robinson (RWR), and Pitzer models. From these measurements, the Pitzer mixing ionic parameters are determined and used to predict the solute activity coefficients in the mixture. The excess Gibbs energy is also determined.     

Comparative study of the electrical properties of diamond films grown by microwave plasma assisted and hot-filament chemical vapor deposition

Schottky diodes were built on different polycrystalline diamond films grown by Microwave Plasma and Hot Filament Chemical Vapor Deposition and their electrical properties were studied. The barrier height increased with the diamond film quality and the corresponding ideality factor decreased. Even though the lower-quality HFCVD film displayed poor rectifying properties, it was found to be much less sensitive to variations in the operating conditions (air vs. vacuum). The activation energies of the films depend on morphological parameters, as preferable grain size or orientation. The bulk conduction also depends on the quality of the deposited films, changing from ohmic to trap-free or shallow trap SCLC and SCLC with an exponential distribution of traps. The hypothesis of using the electrical measurements as an indicator for film quality has been discussed.     

Maghnite‐H+, a solid catalyst for the cationic polymerization of α‐methylstyrene

The polymerization of α‐methylstyrene (AMS) catalyzed by Maghnite‐H⁺ (Mag‐H) was investigated. Mag‐H is a montmorillonite sheet silicate clay, exchanged with protons. It was found that the cationic polymerization of AMS is initiated by Mag‐H at ambient temperature in bulk and in solution. The effect of the amount of Mag‐H, the temperature, and the solvent was studied. The polymerization rate increased with increase in the temperature and the proportion of catalyst, and it was larger in nonpolar solvents. These results indicated the cationic nature of the polymerization. It may be suggested that the polymerization is initiated by proton addition to monomer from Mag‐H. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Coincidence Doppler broadening spectroscopy in polyvinyl chloride after doping with Al2O3

Coincidence Doppler broadening of annihilation radiation (CDBAR) and Vickers hardness techniques were performed to study pure Al₂O₃, pure polyvinyl chloride (PVC), and doped PVC with different concentrations of Al₂O₃ (10–50%). The CDBAR ratio curves with respect to pure PVC were presented and reflect the momentum distribution of all the samples. The peak around 14.5 ×10^?3 m_oC in the CDBAR ratio curves suggests a large contribution of positron annihilation with the Al₂O₃. There is a linear correlation between the height of this peak and the Al₂O₃ concentration. The S‐ and W‐parameters were extracted from the CDBAR spectra and increase with increasing the Al₂O₃ concentration showing discontinuity at 30% of Al₂O₃ concentration on PVC. The present data confirmed that there is no positronium formation in pure Al₂O₃ as a result of smaller S‐parameter. The Vickers hardness increases with increasing the Al₂O₃ concentration in PVC showing a linear dependence with two different slopes depend on the Al₂O₃ concentration range. A correlation between the Vickers hardness (macroscopic data) and the W‐parameter (microscopic data) was observed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel thermally and mechanically stable hydrogel for enzyme immobilization of penicillin G acylase via covalent technique

κ‐Carrageenan hydrogel crosslinked with protonated polyethyleneimine (PEI⁺) and glutaraldehyde (GA) was prepared and evaluated as a novel biocatalytic support for covalent immobilization of penicillin G acylase (PGA). The method of modification of the carrageenan biopolymer is clearly illustrated using a schematic diagram and was verified by FTIR, elemental analysis, DSC, and INSTRON using the compression mode. Results showed that the gels' mechanical strength was greatly enhanced from 3.9 kg/cm² to 16.8 kg/cm² with an outstanding improvement in the gels thermal stability. It was proven that, the control gels were completely dissolved at 35°C, whereas the modified gels remained intact at 90°C. The DSC thermogram revealed a shift in the endothermic band of water from 62 to 93°C showing more gel‐crosslinking. FTIR revealed the presence of the new functionality, aldehydic carbonyl group, at 1710 cm^?1 for covalent PGA immobilization. PGA was successfully immobilized as a model industrial enzyme retaining 71% of its activity. The enzyme loading increased from 2.2 U/g (control gel) to 10 U/g using the covalent technique. The operational stability showed no loss of activity after 20 cycles. The present support could be a good candidate for the immobilization of industrial enzymes rich in amino groups, especially the thermophilic ones. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Free volume and permeabilities of O2 and H2 in Nafion membranes for polymer electrolyte fuel cells

The mechanism of gas permeation in Nafion membranes for polymer electrolyte fuel cells has been investigated from the viewpoint of free volume. Three different samples, a membrane with ionic exchange capacity (IEC) = 0.92 meq/g, and recast samples with IEC = 0.92 and 1.00 meq/g were used after drying. Free volume was quantified using the positron annihilation lifetime (PAL) technique and gas permeabilities were measured for O₂ and H₂ as functions of temperature and relative humidity. Good linear correlations between the logarithm of the permeabilities at different temperatures and reciprocal free volume indicate that gas permeation in dry Nafion is governed by the free volume. Nevertheless permeabilities are much smaller than the corresponding flexible chain polymer with a similar free volume size due to stiff chains of the perfluoroethylene backbone. In highly hydrated Nafion above 60% relative humidity, where the O₂ permeability varies oppositely to the free volume, gas permeation proved to be controlled by the gradual increase in overall flexibility of the Nafion–water system.     

Electrocopolymerization of aniline and ortho-phenylenediamine via facile negative shift of polyaniline redox peaks

Oxidative electropolymerization of aniline (Ani) in phosphoric acid (H₃PO₄) on composite 2B pencil graphite was accomplished using selected inorganic salts as supporting electrolytes. These salts determined the degree of conductivity of polyaniline (PAni) formed. The conductivity was in the order of CaCl₂ > KCl > ZnCl₂ > ZnSO₄ > Ca₃(PO₄)₂. The three pairs of redox peaks in the voltammogram of PAni formed in the presence of 0.06 M Ca₃(PO₄)₂ and 0.2 M ZnSO₄ have shifted 300 mV to the negative potential. The shifting of peaks is strongly influenced by type of anions' presence in the salts. However, the nature of the available cations had no significant effect. The negative shifts of redox peaks were exploited to facilitate the electrocopolymerization of Ani and ortho-phenylenediamine (oPD). The formation of the poly(Ani-co-oPD) was confirmed by the FTIR spectra.     

Optimal estimation of parameters of dynamical systems by neural network collocation method

In this paper we propose a new method to estimate parameters of a dynamical system from observation data on the basis of a neural network collocation method. We construct an object function consisting of squared residuals of dynamical model equations at collocation points and squared deviations of the observations from their corresponding computed values. The neural network is then trained by optimizing the object function.The proposed method is demonstrated by performing several numerical experiments for the optimal estimates of parameters for two different nonlinear systems. Firstly, we consider the weakly and highly nonlinear cases of the Lorenz model and apply the method to estimate the optimum values of parameters for the two cases under various conditions. Then we apply it to estimate the parameters of one-dimensional oscillator with nonlinear damping and restoring terms representing the nonlinear ship roll motion under various conditions. Satisfactory results have been obtained for both the problems.