Topological Imaging Methods for the Iterative Detection of Multiple Impedance Obstacles

Journal of Mathematical Imaging and Vision - In this paper, we investigate shape inversion algorithms based on the computation of iterated topological derivatives for the detection of multiple...     

Synthesis and spectroelectrochemistry of dithieno(3,2‐b:2′,3′‐d)pyrrole derivatives

New π‐conjugated polymers containing dithieno(3,2‐b:2′,3′‐d)pyrrole (DTP) were successfully synthesized via electropolymerization. The effect of structural differences on the electrochemical and optoelectronic properties of the 4‐[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl]aniline (DTP–aryl–NH₂), 10‐[4H‐dithiyeno(3,2‐b:2′,3′‐d)pirol‐4‐il]dekan‐1‐amine (DTP–alkyl–NH₂), and 1,10‐bis[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl] decane (DTP–alkyl–DTP) were investigated. The corresponding polymers were characterized by cyclic voltammetry, NMR (¹H‐NMR and ¹³C‐NMR), and ultraviolet–visible spectroscopy. Changes in the electronic nature of the functional groups led to variations in the electrochemical properties of the π‐conjugated systems. The electroactive polymer films revealed redox couples and exhibited electrochromic behavior. The replacement of the DTP–alkyl–DTP unit with DTP–aryl–NH₂ and DTP–alkyl–NH₂ resulted in a lower oxidation potential. Both the poly(10‐(4H‐Dithiyeno[3,2‐b:2′,3′‐d]pirol‐4‐il)dekan‐1‐amin) (poly(DTP–alkyl–NH₂)) and poly(1,10‐bis(4H‐dithieno[3,2‐b:2′,3′‐d]pyrrol‐4‐yl) decane) (poly(DTP–alkyl–DTP)) films showed multicolor electrochromism and also fast switching times (<1 s) in the visible and near infrared regions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40701.     

Structural evolution of poly(lactic acid)/poly(ethylene oxide)/unmodified clay upon ambient ageing

Poly(lactic acid) (PLA) and poly(ethylene oxide) (PEO)/unmodified clay masterbatches are compounded together in order to investigate the ambient ageing of the resulting PLA/PEO/clay ternary blends. Binary blends are miscible up to 20 wt PEO% and in ternary counterparts, clay is intercalated at a nanometric scale, similarly to the clay dispersion state in masterbatches. PEO/clay interactions are strong, as confirmed by the lower plasticization of ternary blends. Furthermore, structural modifications occurring over time are evidenced for all blends through the observation of changes in thermal responses. Over the 220‐day observation period, lower plasticized samples undergo physical ageing only whereas blends close to the miscibility limit know a rapid PLA/PEO phase separation without physical ageing. For blends with intermediate PEO concentrations, both phenomena are observed with slower PLA chain mobility transition. Remarkably clay appears to affect both phenomena, ternary blends having limited physical ageing and slower PLA/PEO segregation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40426.     

Blends of poly(3‐hydroxybutyrate) with poly(β‐alanine) and its derivatives

Nanofibers and films of poly(3‐hydroxybutyrate) (PHB)/nylon 3 [poly(β‐alanine) (N3)], PHB/poly(α‐methyl‐β‐alanine) (2mN3), and PHB/poly(β‐methyl‐β‐alanine) (3mN3) blends were prepared by electrospinning and film‐casting techniques, respectively. The miscibility of the blends was studied by Fourier transform infrared spectrometry, differential scanning calorimetry, thermogravimetric analysis, and X‐ray diffraction (XRD). The electrospinnability of the blends was studied by scanning electron microscopy. Some characteristic IR absorption bands of the components in the blends shifted gradually with changes in the compositions. The melting temperature and decomposition temperature of PHB decreased gradually with increasing fractions of N3, 2mN3, and 3mN3. The XRD spectra of all of the blends exhibited peaks with lower intensities compared to those of the neat species. The suppression of PHB crystallinity in the blends after blending was attributed to the disruption of its crystal lattice and the prevention of recrystallization of each component by means of other components and segmental interactions between the components in the amorphous phase. Thermal, spectroscopic, and optical analyses of the polymer blends revealed that the polymers were miscible with good compatibility, and this could have improved the scaffold properties of PHB. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40484.     

Investigation of current‐voltage characteristics and current conduction mechanisms in composites of polyvinyl alcohol and bismuth oxide

Temperature dependent current‐voltage (I–V) measurements of Au/Polyvinyl Alcohol + Bi₂O₃/n‐Si structure were conducted between 100 and 350 K for investigating the temperature dependence of I–V characteristics and current conduction mechanisms in the structure. Series resistance of the structure is calculated using Ohm's law and Cheungs' method. Ideality factor (n) and zero‐bias barrier height (Φ_Bo) were obtained considering thermionic emission theory. From 100 to 350 K, n changed from 32.1 to 3.54, and Φ_Bo changed from 0.27 to 0.99 eV. Obtained temperature dependent values of n and Φ_Bo suggested that thermionic emission is not the dominant current conduction mechanism. Therefore, Ln(I)–Ln(V) curves of the studied structure were plotted for investigating current conduction mechanisms in the structure and current flow is explained considering space charge limited current. Moreover, density of interface states (D_it) in the structure were calculated and its temperature dependence was investigated such that D_it values are reduced to the order of ～10¹³ eV^?1 cm^?2 from ～10¹⁴ eV^?1 cm^?2 with increasing temperature. POLYM. ENG. SCI., 54:1811–1816, 2014. © 2013 Society of Plastics Engineers     

Dispersive mixing efficiency of an elongational flow mixer on PP/EPDM blends: Morphological analysis and correlation with viscoelastic properties

Polypropylene and ethylene‐propylene‐diene terpolymer (PP/EPDM) blends were melt compounded in a new mixing device, designed in our laboratory under the trademark of RMX®, which predominantly generates elongational flows. Dispersion of the EPDM minor phase in PP was carried out in both RMX® and in an internal mixer (Haake Rheomix 600) at equivalent specific mixing energies and the resultant morphologies obtained by SEM were analyzed and compared. A better dispersive mixing efficiency of the RMX® mixer, i.e., lower D_n and D_v of the dispersed EPDM phase was observed. The impact of elongational flow was more pronounced for blends having a high viscosity ratio p, indicating an enhanced droplet break‐up mechanism, which was attributed to the combination of high shear rates inside the mixing element and important elongational flows in the convergent/divergent zones. The morphology of the blends was correlated with their linear viscoelastic properties by using the Palierne model. Very good agreement was found for the PP/EPDM 80/20 blends but for higher EPDM content, the Palierne model failed to describe the rheological behavior, which was attributed to percolation of the minor phase with increasing the concentration. Higher elasticity at low frequencies was observed for blends processed in the RMX®, which was attributed to a higher generated interfacial area. POLYM. ENG. SCI., 54:1444–1457, 2014. © 2013 Society of Plastics Engineers     

Kinetic modeling of hemicellulose hydrolysis in the presence of homogeneous and heterogeneous catalysts

Kinetic models were developed for the hydrolysis of O‐acetyl‐galactoglucomannan (GGM), a hemicellulose appearing in coniferous trees. Homogeneous and heterogeneous acid catalysts hydrolyze GGM at about 90°C to the monomeric sugars galactose, glucose, and mannose. In the presence of homogeneous catalysts, such as HCl, H₂SO₄, oxalic acid, and trifluoroacetic acid, the hydrolysis process shows a regular kinetic behavior, while a prominent autocatalytic effect was observed in the presence of heterogeneous cation‐exchange catalysts, Amberlyst 15 and Smopex 101. The kinetic models proposed were based on the reactivities of the nonhydrolyzed sugar units and the increase of the rate constant (for heterogeneous catalysts) as the reaction progresses and the degree of polymerization decreases. General kinetic models were derived and special cases of them were considered in detail, by deriving analytical solutions for product distributions. The kinetic parameters, describing the autocatalytic effect were determined by nonlinear regression analysis. The kinetic model described very well the overall kinetics, as well as the product distribution in the hydrolysis of water soluble GGM by homogeneous and heterogeneous catalysts. The modelling principles developed in the work can be in principle applied to hydrolysis of similar hemicelluloses as well as starch and cellulose. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1066–1077, 2014