A two-step reaction mechanism of oxygen release from Pd/CeO2: mathematical modelling based on step gas concentration experiments

Topics in Catalysis - A mathematical model has been developed to study the transient release of oxygen from a 1 wt% Pd/CeO2 catalyst in the 450–550 °C range based on alternate...     

Design and analysis of single-factor experiments: Analysis of variance of the effect of rice husk ash and commercial fillers in NR compounds

Summary White rice husk ash (WRHA) and black rice husk ash (BRHA) were incorporated into natural rubber (NR) using a laboratory-sized two-roll mill. A conventional vulcanization system was used for curing and physical tests of the NR vulcanized involved determining of tensile and tear resistances. For comparison purposes, precipitated silica (Zeosil-175) and carbon black (N774) were used too. Using the analysis of variance of single-factor experiments, it can be concluded that: BRHA is non-reinforcing filler and its use is limited to 20 phr; WRHA is semi-reinforcing filler and the variation of filler loading (0 up to 50 phr) causes the maximum variation upon tensile strength of NR compounds; and, that although carbon black and silica are reinforcing fillers, a real reinforcement is reached up to 20 phr for tensile strength.     

Rice husk ash filled natural rubber. I. Overall rate constant determination for the vulcanization process from rheometric data

Black rice husk ash (BRHA) and white rice husk ash (WRHA) were incorporated into natural rubber (NR) using a laboratory‐size two‐roll mill. A conventional vulcanization system (CV) was chosen and cure studies were carried out on a TI‐100 Curometer. The torque curves were obtained at 150, 160, 170, and 180°C. The overall rate and the apparent activation energy for the vulcanization process were calculated for each compound assuming that vulcanization follows first‐order kinetics. For comparison purposes, two commercial fillers, precipitated silica (Zeosil‐175) and carbon black (N762), were also used. It was observed that addition of WRHA to NR compounds increased the cross‐linking rate and lowered the apparent activation energy more markedly than the other fillers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1194–1203, 2003     

Nanocomposites based on polyethylene and Mg-Al layered double hydroxide. I. Synthesis and characterization

Low density polyethylene (LDPE)/Mg-Al layered double hydroxide (LDH) nanocomposites have been synthesized with different compositions by melt-mixing technique using maleic anhydride grafted polyethylene as compatibilizer. LDH has been modified by sodium dodecylbenzene sulfonate using reconstruction method and characterized by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. The nanocomposites are characterized by different techniques such as, transmission electron microscopy (TEM), XRD and rheology. The TEM analysis shows a complex nature of particle dispersion in the polymer matrix with wide distribution of particles sizes and shapes. The rheological analysis showed significant changes in linear viscoelastic responses of the composites, even at very low concentration (2 phr) of LDH materials, in comparison to the pure polymer in low frequency regime in dynamic frequency sweep experiments. These changes are related to the LDHs-polymer chains interactions resulting in network-like structure.     

Electrodeposition of polypyrrole on aluminium in aqueous tartaric solution

The electrosynthesis of polypyrrole (PPy) has been achieved on aluminium in aqueous medium of tartaric acid by means of cyclic voltammetry, potentiostatic and galvanostatic techniques. Scanning electron microscopy (SEM) and X-ray microanalysis by energy spectroscopy dispersion (EDS) applying on surfaces show that the PPy coating is developed from the metal surface through the cracks of the initial Al₂O₃ layer.A mechanism involving the participation of the supporting electrolyte and the pyrrole (Py) in distinct active sites was proposed based on the linear sweep voltammetry. It is observed for all applied electrochemical techniques that the pyrrole concentration has to be higher than 0.1 M to allow the polypyrrole electrodeposition in acid medium.Scanning electron microscopy, secondary electrons (SE) and backscattering electrons (BE), shows that the PPy coating obtained in galvanostatic and potentiostatic modes starts with small islands at weak applied potentials or current densities. Moreover, EDS reveals a good homogeneity and compactness of the film achieved in galvanostatic method. The corrosion results in 3% NaCl medium show that the PPy coating decreases the corrosion behaviour of the aluminium. The bilayer Al₂O₃/PPy shows a capacitor with future applications.     

Thioglycolate-elicited rat macrophages exhibit alterations in incroporation and oxidation of fatty acids

Incorporation and oxidation of fatty acids (FA) were investigated in resident and thioglycolate-clicited (TG-elicited) rat macrophages (Mϕ). Both cell types presented a time-dependent incorporation of [¹⁴C]-labeled palmitic acid (PA), oleic acid (OA), linoleic acid (LA), and arachidonic acid (AA) up to 6h. The total amount of [¹⁴C]-FA incorporated by resident Mϕ after 6 h was: AA>PA=LA>OA. TG-elicited cells presented a 50% reduction in the incorporation of LA, PA, and AA, whereas that of OA remained unchanged as compared to resident Mϕ. The FA were oxidized by resident Mϕ as follows: LA>OA>PA>AA. TG elicitation promoted a reduction of 42% in LA oxidation and a marked increase in AA oxidation (280%). The increased oxidation of AA in TG-elicited cells may account for the lower production of prostaglandins in Mϕ under these conditions. The full significance of these findings for Mϕ function, however, remains to be examined.     

Prediction of mean square radius of gyration of tree-like polymers by a general kinetic approach

This paper describes a kinetic method to predict the z-average molecular mean square radius of gyration of tree-like polymers formed by irreversible reactions, assuming Gaussian chains. It is based on the population balance equations for the two-sided molecular distributions of pendant chains associated with every chemically distinguishable kind of bonds. An automated method for the solution of those equations is valid both before as well as after gelation for complex kinetic schemes. Examples of its use are presented with polycondensation systems leading to hyperbranched polymers, the anionic polymerization of mono- and divinyl monomers and a radical polymerization with terminal branching and transfer to polymer.     

The CH4/NO/O2 “Lean-deNOx” Reaction on Mesoporous Mn-Based Mixed Oxides

High surface area Mn-based porous oxides (MANPO) containing additives like Ce, Sr and La were found to be very active and selective materials under 0.67% CH₄/0.2% NO/5% O₂ lean-deNO _x conditions in the 200–300°C low-temperature range. These materials perform also impressively in the presence of 4% H₂O in the feed stream, where a N₂ selectivity of 98% and an excellent stability over 24 h on stream have been observed. The MANPO materials can be considered serious competitors of noble metals for low-temperature lean-deNO _x applications.     

Catkin liked nano-Co3O4 catalyst built-in organic microreactor by PEMOCVD method for trace CO oxidation at room temperature

In this paper, tricobalt tetraoxide (Co₃O₄) catalyst was coated on the polydimethylsiloxane microchannel by the plasma-enhanced metal-organic chemical vapor deposition technology. The obtained Co₃O₄ film was characterized by SEM, XRD, XPS, and TEM, and the results show that the as-deposited Co₃O₄ film was initially composed of many cauliflowers-shaped microclusters. Also, the microcauliflower was transformed from an amorphous phase to a crystal phase when the Co₃O₄ film was treated by Ar and O₂ plasma for more than 20 min, and the crystal lattice line occurred on the surface of nano-sized-Co₃O₄ particles. Meanwhile, the interface of Co₃O₄ particles with diameter between 3 and 12 nm became obvious and some nano-catkin structures were also formed on the Co₃O₄ film. The ratio of Co³⁺/Co²⁺ in the spinel-type Co₃O₄ was nearly 2, and the nano-particles predominantly expose their {311}, {111}, and {220} planes. These morphologies and structure characteristics were found to be ideal for increasing the catalytic activity efficiency of Co₃O₄ for CO oxidation, and the catalytic stability of Co₃O₄ coated on the organic microreactor lasted nearly 85 h for trace CO oxidation at room temperature.     

Comparative study of homogeneous and heterogeneous styrene polymerizations with Ni(acac)2/MAO catalytic system

Styrene polymerization was carried out with Ni(acac)₂/MAO and Ni(acac)₂/SiO₂/MAO. The influence of reaction parameters (Al/Ni mole ratio, catalyst concentration, temperature and time polymerization) on styrene polymerization was evaluated. It was observed that both catalytic systems were affected by reaction parameters and that the heterogeneous catalyst presented higher activity than the homogeneous one. Polystyrenes with different molecular weight, stereoregularity and polydispersity were obtained. These results suggest that different active catalyst species could have been present. In addition, two types of methylaluminoxane (MAO) with different molecular weights were also evaluated as cocatalyst. As a result, the catalyst activity and stereospecificity were strongly affected by the MAO type.