Properties of poly(ethylene terephthalate)–poly(ethylene naphthalene 2,6‐dicarboxylate) blends with montmorillonite clay

The production and properties of blends of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) with three modified clays are reported. Octadecylammonium chloride and maleic anhydride (MAH) are used to modify the surface of the montmorillonite–Na⁺ clay particles (clay–Na⁺) to produce clay–C18 and clay–MAH, respectively, before they are mixed with the PET/PEN system. The transesterification degree, hydrophobicity and the effect of the clays on the mechanical, rheological and thermal properties are analysed. The PET–PEN/clay–C18 system does not show any improvements in the mechanical properties, which is attributed to poor exfoliation. On the other hand, in the PET–PEN/clay–MAH blends, the modified clay restricts crystallization of the matrix, as evidenced in the low value of the crystallization enthalpy. The process‐induced PET–PEN transesterification reaction is affected by the clay particles. Clay–C18 induces the largest proportion of naphthalate–ethylene–terephthalate (NET) blocks, as opposed to clay–Na⁺ which renders the lowest proportion. The clay readily incorporates in the bulk polymer, but receding contact‐angle measurements reveal a small influence of the particles on the surface properties of the sample. The clay–Na⁺ blend shows a predominant solid‐like behaviour, as evidenced by the magnitude of the storage modulus in the low‐frequency range, which reflects a high entanglement density and a substantial degree of polymer–particle interactions. Copyright © 2005 Society of Chemical Industry     

Effect of medium-chain fatty acid positional distribution in dietary triacylglycerol on lymphatic lipid transport and chylomicron composition in rats

The present study was carried out to examine if the positional distribution of medium-chain fatty acid (MCF) in dietary synthetic fat influences lymphatic transport of dietary fat and the chemical composition of chylomicrons in rats with permanent cannulation of thoracic duct. Four types of synthetic triacylglycerol were prepared: (i) sn-1(3) MCF-sn 2 linoleic acid, (ii) interesterified sn-1(3) MCF-sn 2 linoleic acid, (iii) sn-2 MCF-sn-1(3) linoleic acid, and (iv) interesterified sn-2 MCF-sn-1(3) linoleic acid. A purified diet composed of equal amounts of the synthetic fat and cocoa butter was given to rats with permanent lymph duct cannulation. The positional distribution of MCF in the dietary fat had no significant effect on the lymph flow, triacylglycerol output, phospholipid output, lipid composition of chylomicrons, or the particle size. The positional distribution of MCF in the synthetic triacylglycerol was maintained in the chylomicron triacylglycerol. These results showed that MCF in the dietary triacylglycerol is transported into lymphatics and the positional distribution is well preserved in chylomicron triacylglycerol.     

Model for small superconducting variable-thickness bridge constrictions

We present a simple model to simulate small three-dimensional superconducting constrictions of variable thickness (VTBs) for which the cross-sectional dimensions are of the same order as the length, and both are less than (T). We study the behavior of the modulus of the order parameterf and the supercurrent densityJ _s as a function of the various dimensions. We find that the extent to whichf is depressed in the banks depends on the ratio of width to length of the constriction. We show that even for very abrupt geometries,J _s is not zero andf does not reach its equilibrium value immediately outside the constriction. On the basis of our results, we propose a more general expression for the effective length valid also when all dimensions are of the same order. The calculated values ofdI _c /dT are consistent with experimental data from well-characterized VTBs. We suggest that the discrepancy between the calculated and experimental values ofI _c R _n may be due to the nonuniformity of the normal current density in the constriction.     

The phase behavior of n-alkane systems

Normal alkanes show very complicated phase transition kinetics and macroscopic phase equilibrium behavior. This paper focuses on the phase stability and equilibrium of complicated mixtures like n-alkanes and on the enabling global optimization technologies needed to gather problem knowledge. The new ideas contained in this paper include:

(1) novel level set methods for gathering encoded knowledge;

(2) the differential geometry for uncovering pathways to more subtle knowledge;

(3) all supporting non-linearly constrained optimization techniques;

(4) all data handling needed to unravel complex solution structure.

These new ideas are incorporated within the integral path methodology or terrain methods recently developed by Lucia, A., & Yang, F. (2003) [Lucia, A., & Yang F. (2003). Multivariable terrain methods. AIChE Journal 49, 2553] and Lucia, DiMaggio, and Depa (2004) [Lucia, A., DiMaggio, P.A., & Depa, P. (2004). A geometric terrain methodology for global optimization. Journal of Global Optimization 29, 297]. This framework provides global knowledge for understanding solution structure, like the complex solution structure of n-alkanes. In particular, it is shown that knowledge of the Newton and tangent vector fields, Gauss curvature, integral path bifurcation points, and non-differentiable manifolds provides a deterministic way of finding additional solutions, saddle points, and other information that might otherwise go undetected.It is shown that the optimization tools developed in this work provide all knowledge of interest on the appropriate hypothetical single-phase or composite surface (i.e., minima, saddle points, singular points, and integral paths) in phase stability applications. This knowledge can be obtained by solving the phase stability problem exactly once, in a pre-processing step, and used to reliably initialize any multi-phase equilibrium calculation for any feed. This removes the need to repeatedly solve the phase stability problem as the feed composition changes and greatly increases computational efficiency. Numerical examples and geometric illustrations are used to elucidate key ideas and to show how the proposed approach can be used to unravel the complicated phase behavior of n-alkane mixtures.     

Photocatalytic treatment of water-soluble pesticides by photo-Fenton and TiO2 using solar energy

The technical feasibility and performance of photocatalytic degradation of four water-soluble pesticides (diuron, imidacloprid, formetanate and methomyl) have been studied at pilot scale in two well-defined systems of special interest because natural-solar UV light can be used: heterogeneous photocatalysis with titanium dioxide and homogeneous photocatalysis by photo-Fenton. The pilot plant is made up of compound parabolic collectors (CPCs) specially designed for solar photocatalytic applications. Experimental conditions allowed disappearance of pesticide and degree of mineralisation achieved in the two photocatalytic systems to be compared. In order to assure that the photocatalytic results are consistent, hydrolysis and photolysis tests have been performed with the four pesticides. The initial concentration tested with imidacloprid, formetanate and methomyl was 50 and 30 mg/l with diuron, and the catalyst concentrations were 200 mg/l and 0.05 mM with TiO₂ and iron, respectively. Total disappearance of the parent compounds and 90% mineralisation have been attained with all pesticides tested, methomyl being the most difficult to be degraded with both treatments. First-order rate constants, initial rate, time necessary for mineralising 90% of the initial TOC and hydrogen peroxide consumption were calculated in all cases, enabling comparison both of treatments and of the selected pesticide reactivity.     

Optimal performance assessment for a photo‐Fenton degradation pilot plant driven by solar energy using artificial neural networks

Artificial neural networks (ANN) were proposed as a multivariate experimental design tool for monitoring a photo‐Fenton treatment of wastewaters containing a synthetic mixture of pesticides. ANN and Nelder‐Mead simplex methods were used to find out the optimum operating parameters of a photo‐Fenton pilot plant. ANN was developed to predict the most important operating parameters (e.g., the total organic carbon and the initial mineralization kinetic rate constants of the reactions), which determine the photo‐catalytic degradation efficiency in photo‐Fenton processes. Experimental measurements of temperature, pH, hydrogen peroxide (H₂O₂) consumption, initial concentration of Fe²⁺, and the AE were used as input data for the ANN learning. A feed‐forward with one hidden layer, a Levenberg–Marquardt learning algorithm, a hyperbolic tangent sigmoidal transfer function and a linear transfer function were used to develop the ANN model. The best fitting of the training database was obtained with an ANN architecture constituted by seven neurons in the hidden layer. The simulated results were validated with experimental measurements, showing an acceptable agreement (R² > 0.99). The ANN was subsequently coupled with a Nelder–Mead simplex method to obtain the optimum operating parameters of the photo‐Fenton pilot plant. The H₂O₂ consumption was used as key variable for evaluating the optimization procedure. Errors less than 1% between simulated and experimental data were found. The obtained results showed that the use of ANN provides an excellent predictive performance tool with the additional capability to assess the influence of each operating parameter on the removal process of water pollutants. Copyright © 2011 John Wiley & Sons, Ltd.     

Conversion efficiency of glucose/xylose mixtures for ethanol production using Saccharomyces cerevisiae ITV01 and Pichia stipitis NRRL Y‐7124

BACKGROUND: Efficient conversion of glucose/xylose mixtures from lignocellulose is necessary for commercially viable ethanol production. Oxygen and carbon sources are of paramount importance for ethanol yield. The aim of this work was to evaluate different glucose/xylose mixtures for ethanol production using S. cerevisiae ITV‐01 (wild type yeast) and P. stipitis NRRL Y‐7124 and the effect of supplying oxygen in separate and co‐culture processes. RESULTS: The complete conversion of a glucose/xylose mixture (75/30 g L^?1) was obtained using P. stipitis NRRL Y‐7124 under aerobic conditions (0.6 vvm), the highest yield production being Y_p/s = 0.46 g g^?1, volumetric ethanol productivity Q_pmax = 0.24 g L^?1 h^?1 and maximum ethanol concentration P_max = 34.5 g L^?1. In the co‐culture process and under aerobic conditions, incomplete conversion of glucose/xylose mixture was observed (20.4% residual xylose), with a maximum ethanol production of 30.3 g L^?1, ethanol yield of 0.4 g g^?1 and Q_pmax = 1.26 g L^?1 h^?1. CONCLUSIONS: The oxygen present in the glucose/xylose mixture promotes complete sugar consumption by P. stipitis NRRL Y‐7124 resulting in ethanol production. However, in co‐culture with S. cerevisiae ITV‐01 under aerobic conditions, incomplete fermentation occurs that could be caused by oxygen limitation and ethanol inhibition by P. stipitis NRRL Y‐7124; nevertheless the volumetric ethanol productivity increases fivefold compared with separate culture. Copyright © 2011 Society of Chemical Industry     

Mechanosynthesis of the multiferroic cubic spinel Co2MnO4: Influence of the calcination temperature

Multiferroic materials showing magnetoelectric coupling are required in various technological applications. Many synthetical approaches can be used to improve the magnetic and/or electrical properties, in particular when the materials exhibit cationic valence fluctuations, as in the Co₂MnO₄ cubic spinel. In this compound, Co and Mn ions are in competition at the tetrahedral and octahedral positions, depending on their various oxidation states. The Co₂MnO₄ was prepared following two techniques: by a soft chemical route based on a modified polymer precursor method, and by a mechanoactivation route. Both approaches yield polycrystalline powders, but their crystallites sizes and particles morphologies differ as a function of the calcination conditions. The magnetic characterization (ZFC/FC cycles, ordering temperatures, ferromagnetic coercive fields and saturation magnetizations) showed that the synthesis procedure influenced the physical properties of Co₂MnO₄ mainly through the size of the magnetic domains, which play an important role on the magnetic interactions between the Co/Mn cations.     

Sodium phthalamates as corrosion inhibitors for carbon steel in aqueous hydrochloric acid solution

Three compounds of N-alkyl-sodium phthalamates were synthesized and tested as corrosion inhibitors for carbon steel in 0.5 M aqueous hydrochloric acid. Tests showed that inhibitor efficiencies were related to aliphatic chain length and dependent on concentration. N-1-n-tetradecyl-sodium phthalamate displayed moderate efficiency against uniform corrosion, 42–86% at 25 °C and 25–60% at 40 °C. Tests indicated that compounds behave as mixed type inhibitors where molecular adsorption on steel followed Langmuir isotherm, whereas thermodynamic suggested that a physisorption process occurred. XPS analysis confirmed film formation on surface, where Fe⁺² complexes and Fe⁺² chelates with phthalamates prevented steel from further corrosion.