Failure mechanism of thin Al2O3 coatings grown by atomic layer deposition for corrosion protection of carbon steel

Combined analysis by electrochemical impedance spectroscopy (EIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and field emission scanning electron microscopy (FESEM) of the corrosion protection provided to carbon steel by thin (50 nm) Al₂O₃ coatings grown by atomic layer deposition (ALD) and its failure mechanism is reported. In spite of excellent sealing properties, the results show an average dissolution rate of the alumina coating of ∼7 nm h⁻¹ in neutral 0.2 M NaCl and increasing porosity of the remaining layers with increasing immersion time. Alumina dissolution is triggered by the penetration of the solution via cracks/pinholes through the coating to the substrate surface where oxygen reduction takes place, raising the pH. At defective substrate surface sites of high aspect ratio and concentrated residual mechanical stress (along scratches) presumably exposing a higher steel surface fraction, localized dissolution of the coating is promoted by a more facile access of the solution to the substrate surface enhancing oxygen reduction. De-adhesion of the coating is also promoted in these sites by the ingress of the anodic dissolution trenching the steel surface. Localized corrosion of the alloy (i.e. pitting) is triggered prior to complete dissolution of the alumina film on the elsewhere still coated surface matrix.     

Electrical capacitance tomography as a monitoring tool for high-shear mixing and granulation

Electrical capacitance tomography (ECT) was utilized for monitoring of high-shear mixing and high-shear granulation processes. A finite element method (FEM)-based reconstruction algorithm was utilized to take into account the specific geometrical characteristics of the experimental set-up. Two-dimensional ECT tomograms, mixing index curves and permittivity fractions were computed based on the measurements, and their suitability in the analysis of the processes was assessed. It was found that the different mixing processes and the different granulation processes could be analyzed based on these quantities.     

Effect of processing procedures and conditions on structural,morphological, and rheological properties of polyethylene/polyamide/nanoclay blends

The article deals with the effect of processing procedures and conditions on structural, morphological, and rheological properties of ternary blends composed of polyethylene (PE), polyamide (PA)‐12, and organically modified montmorillonite nanoclay with selective affinity. Samples were prepared from PE/PA and PA/PE blends, either by simultaneous mixing or from a polymer/clay masterbatch, using two processing conditions. The results have shown the existence of a weight fraction threshold, above which no significant processing effect was observed. Below this weight fraction threshold, the results tend to underline the significant role of two parameters that depend on processing procedures and/or conditions: the contact time between PE and PA phases and the contact time between clay and PA. Clay structure, blend morphology, and rheological properties were all shown to depend on these two parameters, and also on the nature of the matrix (PE or PA), because of the selective affinity of clay toward polymer phases. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

ANN modeling applied to NO x reduction with octane in a new microreactor

A silver/alumina catalyst was tested for its NO _x reduction activity during oxygen-rich conditions and during variation in the input parameters (nitric oxide, octane and oxygen). The experimental data using the microreactor was investigated by means of artificial neural networks (ANN).     

Effects of Electrospinning Parameters on Gelatin/Poly(ϵ‐Caprolactone) Nanofiber Diameter

An electrospinning procedure was carried out to fabricate gelatin/poly(?‐caprolactone) (Gt/PCL) nanofibers. Response surface methodology based on a three‐level, four‐variable Box‐Behnken design technique was used to model the resultant diameter of the as‐spun nanofibers. A second‐order model was obtained to describe the relationship between the fiber diameter and the electrospinning parameters, namely Gt concentration, PCL concentration, content of acetic acid in the overall solvent, and content of Gt solution in the blend solution. The individual and the interactive effects of these parameters on the fiber diameter were determined. Validation experiments verified the accuracy of the model which provided a simple and effective method for fabricating nanofibers with a controllable and predictable fiber diameter.     

Hydrogenation of l-Arabinose and d-Galactose Mixtures Over a Heterogeneous Ru/C Catalyst

Complete hydrogenation of d-galactose and l-arabinose mixtures on a Ru/C catalyst was achieved with excellent selectivities exceeding 95?%. No unexpected effects of temperature and pressure were observed. A detailed kinetic model was derived to describe the simultaneous hydrogenation of the monomeric sugars.     

Preparation and characterisation of α-methylstyrene–butadiene latexes for paper coating applications

The purpose of this work is to demonstrate how α-methylstyrene (AMS) can replace styrene in preparing styrene–butadiene (SB) type latexes and to compare the properties of the paper coating of the prepared α-methylstyrene–butadiene emulsion with the commercial styrene–butadiene latex reference sample. A lot of work is nowadays being conducted on different biorefinery concepts replacing fossil oil with biomass based raw materials due to the expected rise of the fossil oil cost. Aromatics can in principle be produced from renewable raw materials, such as lignin, sugars and terpenes for example. The potential methods include thermochemical conversions, catalytic fast pyrolysis, metabolic engineering, catalytic aromatisation and dehydrogenation among others. Terpenes, such as α-limonene and pinene, are possible sources of aromatics, and they can indeed be catalytically converted to p-cymene. Industrial hydrodealkylation and disproportionation processes developed by major petrochemical companies can further convert p-cymene to BTX aromatics or simultaneously dehydrogenate the alkyl chain of p-cymene to styrenic monomers such as α-methylstyrene. Based on the measured paper properties for uncalendered and calendered coated samples, AMS proved to be adequate to replace the oil based styrene in commercial reference SB latexes. Even though the emulsion polymerisation for the α-methylstyrene–butadiene latex was not optimised, almost all tested properties were at least equally good as in the commercial reference sample. α-Methylstyrene containing coating colours had slightly higher viscosity than the other coating colours. Coating colours containing α-methylstyrene seems to have an improved water retention compared to the commercial reference styrene–butadiene latex coating colour and the laboratory prepared styrene–butadiene coating colour. The paper coated with the commercial reference latex containing coating colour was less porous than the other coated papers. Despite of that, both dry and wet surface strength were at least equally good as in the case of the commercial reference latex. The results are promising when thinking of the future development of the bio-based latexes.     

Structural and rheological investigation of interphase in polyethylene/polyamide/nanoclay ternary blends

This study aims at investigating and characterizing the interphase in Polyethylene (PE)/Polyamide (PA) blends with nodular morphology, filled with organically modified Montmorillonite (C30B), using structural and rheological experimental techniques. PE/PA/C30B blends have been prepared by simultaneous mixing at a dispersed phase fraction (PE or PA) of 20% and a clay fraction ranging from 1 to 6%. Structural properties of the interphase have been investigated using XRD combined with TEM micrographs. The presence of numerous interphase defects is evidenced, and the effect of interphase disorder is discussed. Linear viscoelastic properties show the contribution of the interphase in PE matrix ternary blends at all clay fractions, whereas interphase effects are masked by the contribution of dispersed nanoclay particles in PA matrix ternary blends.     

Serendipitous Identification of a Covalent Activator of Liver Pyruvate Kinase

Enzymes are effective biological catalysts that accelerate almost all metabolic reactions in living organisms. Synthetic modulators of enzymes are useful tools for the study of enzymatic reactions and can provide starting points for the design of new drugs. Here, we report on the discovery of a class of biologically active compounds that covalently modifies lysine residues in human liver pyruvate kinase (PKL), leading to allosteric activation of the enzyme (EC₅₀=0.29 μM). Surprisingly, the allosteric activation control point resides on the lysine residue K282 present in the catalytic site of PKL. These findings were confirmed by structural data, MS/MS experiments, and molecular modelling studies. Altogether, our study provides a molecular basis for the activation mechanism and establishes a framework for further development of human liver pyruvate kinase covalent activators.     

Analysis of lipid classes by solid-phase extraction and high-performance size-exclusion chromatography

An improved method to analyze lipid classes of edible oils and fats by solid-phase extraction (SPE) and high-performance size-exclusion chromatography (HPSEC) is presented. A mixture of lipid standards was fractionated by the solid-phase extraction procedure (NH₂ phase) into polar and nonpolar fractions; these were then submitted to analysis by HPSEC. The size-exclusion chromatographic columns were three styrene/divinylbenzene columns with pore sizes of 100 Å and 50 Å. Light-scattering was used for the detection system, and the parameters of the detector were optimized to minimize the difference between the responses of the compounds studied. With this procedure it was possible to separate the following lipid classes: triacylglycerols, diacylglycerols, monoacylglycerols and free fatty acids, sterols, sterol esters, tocopherols and carotenoids. Quantitative analysis was studied for a light-scattering detector with several lipid standards of different molecular weights and unsaturation levels.