Decomposition of nitric oxide over perovskite oxide catalysts: effect of CO2, H2O and CH4

Direct nitric oxide decomposition over perovskites is fairly slow and complex, its mechanism changing dramatically with temperature. Previous kinetic study for three representative compositions (La_0.87Sr_0.13Mn_0.2Ni_0.8O_3−δ, La_0.66Sr_0.34Ni_0.3Co_0.7O_3−δ and La_0.8Sr_0.2Cu_0.15Fe_0.85O_3−δ) has shown that depending on the temperature range, the inhibition effect of oxygen either increases or decreases with temperature. This paper deals with the effect of CO₂, H₂O and CH₄ on the nitric oxide decomposition over the same perovskites studied at a steady-state in a plug-flow reactor with 1 g catalyst and total flowrates of 50 or 100 ml/min of 2 or 5% NO. The effect of carbon dioxide (0.5–10%) was evaluated between 873 and 923 K, whereas that of H₂O vapor (1.6 or 2.5%) from 723 to 923 K. Both CO₂ and H₂O inhibit the NO decomposition, but inhibition by CO₂ is considerably stronger. For all three catalysts, these effects increase with temperature. Kinetic parameters for the inhibiting effects of CO₂ and H₂O over the three perovskites were determined. Addition of methane to the feed (NO/CH₄=4) increases conversion of NO to N₂ about two to four times, depending on the initial NO concentration and on temperature. This, however, is still much too low for practical applications. Furthermore, the rates of methane oxidation by nitric oxide over perovskites are substantially slower than those of methane oxidation by oxygen. Thus, perovskites do not seem to be suitable for catalytic selective NO reduction with methane.     

Effect of dynamic vulcanization on the microstructure and performance of polyethylene terephthalate/elastomer blends

Blends of polyethylene terephthalate (PET) and ethylene‐ethyl acrylate‐maleic anhydride terpolymer (E‐EA‐MAH) were dynamically crosslinked in a one‐step extrusion process. An amine‐terminated glycol reacting with MAH moieties was used as the crosslinking agent. The effect of blend composition and dynamic crosslinking on the microstructure and mechanical properties were investigated. Blend ratios ranging from 80:20 to 20:80 PET/E‐EA‐MAH were studied. The region of phase inversion was located for uncrosslinked and dynamically crosslinked blends. The rheological characterization was also carried out for these blends in comparison with the neat materials. After dynamic crosslinking, the phase inversion is shifted from the 30–40% range to the 70–80% range of elastomer content. This shift is induced by the increase of viscosity and elasticity of the network formed. Dynamically crosslinked blends show significant improvements in impact strength but also exhibit a decrease in elongation at break.     

Digital light processing stereolithography of hydroxyapatite scaffolds with bone-like architecture,permeability, and mechanical properties

This work deals with the additive manufacturing and characterization of hydroxyapatite scaffolds mimicking the trabecular architecture of cancellous bone. A novel approach was proposed relying on stereolithographic technology, which builds foam-like ceramic scaffolds by using three-dimensional (3D) micro-tomographic reconstructions of polymeric sponges as virtual templates for the manufacturing process. The layer-by-layer fabrication process involves the selective polymerization of a photocurable resin in which hydroxyapatite particles are homogeneously dispersed. Irradiation is performed by a dynamic mask that projects blue light onto the slurry. After sintering, highly-porous hydroxyapatite scaffolds (total porosity ~0.80, pore size 100-800 µm) replicating the 3D open-cell architecture of the polymeric template as well as spongy bone were obtained. Intrinsic permeability of scaffolds was determined by measuring laminar airflow alternating pressure wave drops and was found to be within 0.75-1.74 × 10⁻⁹ m², which is comparable to the range of human cancellous bone. Compressive tests were also carried out in order to determine the strength (~1.60 MPa), elastic modulus (~513 MPa) and Weibull modulus (m = 2.2) of the scaffolds. Overall, the fabrication strategy used to print hydroxyapatite scaffolds (tomographic imaging combined with digital mirror device [DMD]-based stereolithography) shows great promise for the development of porous bioceramics with bone-like architecture and mass transport properties.     

Proving linearizability with temporal logic

Linearizability is a global correctness criterion for concurrent systems. One technique to prove linearizability is applying a composition theorem which reduces the proof of a property of the overall system to sufficient rely-guarantee conditions for single processes. In this paper, we describe how the temporal logic framework implemented in the KIV interactive theorem prover can be used to model concurrent systems and to prove such a composition theorem. Finally, we show how this generic theorem can be instantiated to prove linearizability of two classic lock-free implementations: a Treiber-like stack and a slightly improved version of Michael and Scott’s queue.     

A density based segmentation method to determine the coordination number of a particulate system

The coordination number is an important parameter for understanding the particulate systems, especially when agglomerated particles are present. However, experimental determination of the coordination number is not trivial. In this study, we describe a 3D classification method, which is based on the revised DBSCAN (Density-Based Spatial Clustering of Applications with Noise) and its application to X-ray micro-tomographic (XMT) images to determine the coordination number distribution. Pellets of micro-crystalline cellulose were used as model particles. The validity of the segmentation was checked by comparing the particle size distribution (PSD) obtained by XMT-DBSCAN with PSD obtained by optical microscopy. The results were found to be in good agreement, demonstrating the suitability of the DBSCAN method. The means and standard deviations of coordination numbers were (8.2±1.7, n=994 particles), (8.1±1.5, n=904) and (6.2±1.2, n=159) for pellets with length based mean sizes of 157, 307 and 437 μm, respectively. The coordination number distribution was in line with previous finding in mono-sized acrylic beads.     

Composite droplets with core/shell morphologies prepared from HDPE/PS/PMMA ternary blends by twin‐screw extrusion

Ternary blends of PS and PMMA in a PE matrix were prepared by twin‐screw extrusion to investigate the core/shell encapsulation phenomenon in the composite droplet. The PS was found to encapsulate the PMMA to form composite droplets within the PE matrix as expected from the spreading coefficient theory. The effects of dispersed phase concentration, viscosity ratio, feeding sequence and twin‐screw operating conditions were investigated. The blend morphology was observed by scanning electron microscopy after selective extraction of either PS or PMMA, and average core and composite droplet diameters were determined by image analysis. Although it is known that the structure of composite droplet blends can be substantially altered through control of the volume fraction of the components in the dispersed phase, this study demonstrates that blends with a 1:1 composite droplet volume fraction are relatively stable to large variations in the minor phase viscosities and processing conditions. Twin‐screw extrusion thus provides a highly robust technique for the melt processing of blends possessing composite droplet morphologies. Polym. Eng. Sci. 44:749–759, 2004. © 2004 Society of Plastics Engineers.     

Mechanical Properties and Morphology of Ternary PP/EPDM/PE Blends

The ternary blends of high‐density polyethylene (PE), EPDM terpolymer and polypropylene (PP) have been used as a model low interfacial tension system to study encapsulation dynamics in ternary blends and their relation to the blends' mechanical properties. It was found that the modulus, tensile strength and impact resistance can be improved by PE addition if the PE is localized within the EPDM phase. A range of blend morphology was found depending on the PE viscosity and polymer incorporation sequence in the twin‐screw extruder. In the most favorable sequence, PE and EPDM were mixed together prior to their dispersion in the PP matrix. This practice resulted in a 50% increase in impact resistance when compared to mixing the three components in a single‐step.