Nonuniformity of phase structure in immiscible polymer blends

This article is focused on the phase structure development in immiscible polymer blends during melt mixing. Nonuniformity of the phase structure, i.e., the coexistence of areas containing particles with markedly different size distribution, was detected in quenched and compression molded samples of a number of various blends prepared by long and intensive mixing in the chamber of a Plasticorder. The same effect was found also for polystyrene/polyamide blends prepared in a twin‐screw extruder. It was shown that neglecting nonuniformity of the phase structure can lead to considerable error in evaluation of the effect of system parameters on the blend morphology. The reasons for the effect were discussed and it was found that inhomogeneous flow field in mixers is a plausible explanation of the nonuniform phase structure. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Synthesis and characterization of functional gradient copolymers of glycidyl methacrylate and butyl acrylate

Epoxy-functional spontaneous gradient copolymers of glycidyl methacrylate (G) and n-butyl acrylate (B) were synthesized via atom transfer radical polymerization (ATRP). The copolymerization reactions were carried out in toluene solution at 70 °C, using methyl 2-bromopropionate (MBrP) as initiator and copper chloride with N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) as the catalyst system. The kinetic behaviour of the statistical copolymerizations was studied in a wide composition interval with molar fractions of G ranging from 0.10 to 0.75. The synthesized copolymers were characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. ¹H NMR was employed to determine the copolymer composition, demonstrating the gradient character of the copolymers along the main chain in the whole monomer conversion interval. Apart from this, the sequence distribution and stereoregularity were analyzed. These microstructural experimental data agreed well with those calculated from Mayo-Lewis terminal model (MLTM) and a Bernoullian statistic with an isotacticity parameter of σ_G = 0.28 and a coisotacticity parameter of σ = 0.30.     

Molecular weight effect on the obtainment of parallel and perpendicular orientation in thermotropic poly(diethylene glycol <Emphasis Type="Italic">p,p′</Emphasis>-bibenzoate)

Summary The effect of molecular weight on the uniaxial orientation process has been analyzed in two samples of thermotropic poly(diethylene glycol p,p′-bibenzoate), evaluating the influence of that parameter on the type of orientation obtained. Several strain rates and deformation temperatures have been tested in order to map out the conditions for obtaining the two different kinds of orientation. The results show that in the lower molecular weight PDEB sample (M_w=31200) it is rather easy to get exclusively perpendicular “anomalous” orientation, with the molecular axes aligned transversely to the stretching direction. However, it is extremely difficult to obtain 100% parallel “normal” orientation. On the contrary, either type of orientation or a mixture of them can be easily developed for the higher molecular weight PDEB sample (M_w=102900).     

Simultaneous sulfide and acetate oxidation under denitrifying conditions using an inverse fluidized bed reactor

BACKGROUND: Simultaneous removal of sulfur, nitrogen and carbon compounds from wastewaters is a commercially important biological process. The objective was to evaluate the influence of the CH₃COO^?/NO₃^? molar ratio on the sulfide oxidation process using an inverse fluidized bed reactor (IFBR). RESULTS: Three molar ratios of CH₃COO^?/NO₃^? (0.85, 0.72 and 0.62) with a constant S^2?/NO₃^? molar ratio of 0.13 were evaluated. At a CH₃COO^?/NO₃^? molar ratio of 0.85, the nitrate, acetate and sulfide removal efficiencies were approximately 100%. The N₂ yield (g N₂ g^?1 NO₃^?‐N consumed) was 0.81. Acetate was mineralized, resulting in a yield of 0.65 g inorganic‐C g^?1 CH₃COO^?‐C consumed. Sulfide was partially oxidized to S⁰, and 71% of the S^2? consumed was recovered as elemental sulfur by a settler installed in the IFBR. At a CH₃COO^?/NO₃^? molar ratio of 0.72, the efficiencies of nitrate, acetate and sulfide consumption were of 100%, with N₂ and inorganic‐C yields of 0.84 and 0.69, respectively. The sulfide was recovered as sulfate instead of S⁰, with a yield of 0.92 g SO₄^2?‐S g^?1 S^2? consumed. CONCLUSIONS: The CH₃COO^?/NO₃^? molar ratio was shown to be an important parameter that can be used to control the fate of sulfide oxidation to either S⁰ or sulfate. In this study, the potential of denitrification for the simultaneous removal of organic matter, sulfide and nitrate from wastewaters was demonstrated, obtaining CO₂, S⁰ and N₂ as the major end products. Copyright © 2008 Society of Chemical Industry     

Assessing continuous bivariate effects among different groups through nonparametric regression models: An application to breast cancer detection

In many applications, the joint effect of two continuous covariates on the target binary response may vary across groups defined by levels of a given factor. A testing procedure that would enable this type of surface-by-factor interactions to be detected has been designed. To accomplish this goal, a logistic generalized additive model (GAM) with bivariate continuous interactions varying across groups defined by levels of a factor is considered. A local scoring algorithm based on local linear kernel smoothers was implemented to estimate the proposed logistic GAM. Bootstrap resampling techniques were used for the purpose of testing for factor-by-surface interactions. Given the high computational cost involved, binning techniques were used to speed up computation in the estimation and testing processes. The adequacy of the bootstrap-based test was assessed by means of a simulation study. If a factor-by-surface interaction is detected in the model, it is then established that the use of the odds-ratio curves is very useful in obtaining a direct interpretation of the fitted model. The benefits of using this methodology when analyzing real data are illustrated by applying the technique to the outputs produced by a computerized system dedicated to the early detection of breast cancer.     

Grouped Approach for the Design of H.264/AVC Motion Estimation Architectures

This letter presents a novel approach for organizing computational resources into groups within H.264/AVC motion estimation architectures, leading to reductions of up to 75% in the equivalent gate count with respect to state‐of‐the‐art designs.     

Use of recycled copper slag for blended cements

Copper slag is a by‐product generated during smelting to extract copper metal from the ore. The copper slag obtained may exhibit pozzolanic activity and may therefore be used in the manufacture of addition‐containing cements. In this paper the effect of the incorporation of the copper slag in cement is measured. Blends of copper slag with Portland cement generally possess properties equivalent to Portland cement containing fly ash, but very different to the silica fume incorporation. Copper slag and fly ash reduce the heat of hydration more effectively than silica fume in mortars. The replacement of 30% cement by copper slag reduces the flexural and compressive strength in a similar way to fly ash; however, after 28 days, the reduction is less than the percentage of substitution. Hydrated calcium aluminate phases were analysed using scanning electron microscopy (SEM) and X‐ray diffraction (XRD) techniques. The pozzolanic activity of copper slag is similar to that of fly ash and higher than silica fume. In the presence of low water/cement ratios, certain pozzolanic materials produce a very compact cement paste that limits the space available for hydration products, a determining factor in the formation of hydrated calcium aluminates. SEM was found to be a useful analytical technique when aluminates are formed and can be clearly detected by XRD. Copyright © 2008 Society of Chemical Industry     

Time Decay of the Activity of the Reduction Reaction of NO by CO on a Pd/Al2O3 Catalyst

An experimental study is made of the time decay of activity of the CO–NO reaction on a Pd/Al₂O₃ looking at the effect on reaction order and apparent activation energy. The optimum kinetics parameters fitting the steady state data at moderate pressures are determined. The time decay curves are analyzed through various catalyst deactivation models.     

Manifold mapping: a two-level optimization technique

In this paper, we analyze in some detail the manifold-mapping optimization technique introduced recently [Echeverría and Hemker in space mapping and defect correction. Comput Methods Appl Math 5(2): 107—136, 2005]. Manifold mapping aims at accelerating optimal design procedures that otherwise require many evaluations of time-expensive cost functions. We give a proof of convergence for the manifold-mapping iteration. By means of two simple optimization problems we illustrate the convergence results derived. Finally, the performances of several variants of the method are compared for some design problems from electromagnetics.     

Application of autoregressive spectral analysis to missing data problems

Time series solutions for spectral analysis in missing data problems use reconstruction of the missing data, or a maximum likelihood approach that analyzes only the available measured data. Maximum likelihood estimation yields the most accurate spectra. An approximate maximum likelihood algorithm is presented that uses only previous observations falling in a finite interval to compute the likelihood, instead of all previous observations. The resulting nonlinear estimation algorithm requires no user-provided initial solution, is suited for order selection, and can give very accurate spectra even if less than 10% of the data remains.