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.     

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     

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.     

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.     

Controlled release matrices and micro/nanoparticles of chitosan with antimicrobial potential: development of new strategies for microbial control in agriculture

The control of micro‐organisms responsible for pre‐ and postharvest diseases of agricultural products, mainly viruses and fungi, is a problem that remains unresolved, together with the environmental impact of the excessive use of chemicals to tackle this problem. Current efforts are focused on the search for efficient alternatives for microbial control that will not result in damage to the environment or an imbalance in the existing biota. One alternative is the use of natural antimicrobial compounds such as chitosan, a linear cationic biopolymer, which is biodegradable, biocompatible and non‐toxic, has filmogenic properties and is capable of forming matrices for the transport of active substances. The study of chitosan has attracted great interest owing to its ability to form complexes or matrices for the controlled release of active compounds such as micro‐ and nanoparticles, which, together with the biological properties of chitosan, has allowed a major breakthrough in the pharmaceutical and biomedical industries. Another important field of study is the development of chitosan‐based matrices for the controlled release of active compounds in areas such as agriculture and food for the control of viruses, bacteria and fungi, which is one of the least exploited areas and holds much promise for future research. © 2013 Society of Chemical Industry     

Intrinsically Formed Trivalent Titanium Ions in Sol–Gel Titania

Electron paramagnetic resonance (EPR) room-temperature observation of trivalent titanium in sol–gel titania has been reported. This unprecedented detection of stable paramagnetic signals in this titania, which was treated at 200°–800°C, occurred regardless of whether the atmosphere was reducing, inert, or oxidating. The possibility that the paramagnetic signals may originate from an metal impurity other than titanium was completely excluded by analyzing the samples using three different ion-beam-analysis techniques: Rutherford backscattering spectroscopy, particle-induced X-ray emission resonance, and energy-recoil detection analysis. The paramagnetic signals appeared at precisely the temperature range of the sample dehydroxylation, which suggests a mechanism for explaining these Ti³⁺ EPR spectra.     

Muscle tissue structural changes and texture development in sea bream, Sparus aurata L., during post-mortem storage

Sea bream, Sparus aurata L., specimens were studied in pre-rigor (3 h) and during the following post-mortem days: 1, 5, 10, 15 and 22. Muscle and textural parameters were evaluated on 6 specimens/stage. Structural results showed scarce fibre-to-fibre detachment on pre-rigor, which increased during the post-mortem degradation. Ultrastructural changes revealed rapid muscle degradation. In pre-rigor myofibrils were detached to both sarcolemma and endomysium. Intermyofibrillar spaces increased and some mitochondriae and sarcoplasmic reticulum were swollen. After 1 day, the sarcolemma appeared occasionally disrupted and the interfibrillar spaces increased. From 5 to 10 days, the I-band and Z line presented some alterations, although these were more severe at 15-22 days. Thus, in these two last stages, loss of I-band, Z line and actin filaments was observed, that coincides with the alteration of the hexagonal arrangement in these advanced stages. Also, the fragmentation of myofibrils increased from 5 to 10 days on. Sarcolemma and endomysium were gradually disrupted throughout the post-mortem stages with total loss at 22 days. Consequently, the interfibrillar spaces increased at last stages. Autophagic mechanisms increased from 5 days on, with an intense destruction of all the intracytoplasmic organelles. Textural parameters decreased from pre-rigor until 5-10 days, mainly associated to detachment of myofibers to sarcolemma-endomysium.