Sulphidation of an oxidic CoMo/Al2O3 catalyst under practical conditions: different kinds of sulphur species

The sulphidation of a CoMo/Al₂O₃ hydrotreating catalyst was studied under pressure and flow conditions close to industrial practice. The sulphiding mixture contained equal amounts of H₂S and CH₄ diluted in hydrogen under 3.9 MPa total pressure. The oxidic precursor was flushed by the reagent gas at 40°C for 10 h, then the temperature was raised to 400°C within 2 h. Mass variation was continuously recorded by means of a suspension magnetic balance, and the gas phase was analysed by mass spectrometry. Sulphur contents were also determined at intermediate temperatures by chemical analyses. Thus, mass variations due to the presence of adsorbed species or to the formation of CoMo sulphides could be distinguished. The rapid gain in mass noted at 40°C was mostly due to adsorption of H₂S over the oxidic solid, since it increased with H₂S partial pressure. At this stage, however, a small amount of the reactive oxygen was already exchanged for sulphur. Upon raising the temperature, the mass decreased due to a combination of desorption and sulphiding steps. Above 140°C, H₂S consumption was evidenced, together with water production, and the rate of sulphiding increased with the H₂S partial pressure. At 300°C, the mass variation was close to that expected for complete transformation into Co₉S₈ and MoS₂. Above 350°C, the mass further increased due to the replacement of adsorbed water by H₂S. At 400°C, an important excess mass was observed at all H₂S partial pressures. Thus, the adsorption sites on the metal sulphides are essentially saturated by H₂S species under practical conditions.     

The participation of crown ethers in the initiation of group-transfer polymerisation

Summary The use of crown ethers in conjunction with alkali metal salts, as catalysts in group-transfer polymerization, is discussed.     

Behavior of poly(ethylene‐co‐olefin) polymers as elastomeric materials

The properties of two new ethylene‐α‐olefin copolymers, namely, ethylene–1‐hexene copolymer (EHC) and ethylene–1‐octadecene copolymers (EOC), synthesized via metallocene catalysts were evaluated. The copolymerization was carried out in an autoclave reactor with Et(Indenyl)₂ZrCl₂/methylaluminoxane as a catalyst system. These single‐site catalysts (metallocene type) allow one to obtain very homogeneous copolymers with excellent control of the molecular weight distribution and proportion of comonomer incorporation. So, copolymers with 18 mol % comonomer in the case of EHC and 12 mol % for EOC were shaped, and activities around 100,000 kg of polymer mol^?1 of Zr bar^?1 h^?1 were reached. The properties of these copolymers were compared with other commercial elastomers, such as ethylene–propylene copolymers synthesized by Ziegler–Natta catalysts and an ethylene–octene copolymer obtained via metallocene catalysts. The results show that these new copolymers, in particular, EOC, had excellent elastomeric properties. Furthermore, they had a relatively low viscosity, which implied a good response during processing. Moreover, the effectiveness of these copolymers as impact modifiers for polyolefins was also studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3008–3015, 2004     

Effect of elastomer type and functionality on the behavior of toughened polyamide nanocomposites

The only shortcoming of PA6‐based nanocomposites is low toughness, which is the same as that of the matrix. This work is focused on optimization of toughening these nanocomposites by introduction of small amounts of finely dispersed elastomers. A comparison of reactively compatibilized and analogous nonreactive elastomer‐containing nanocomposites indicates the best‐balanced mechanical behavior for polar nonreactive elastomers such as NBR and E‐MA. This is explained by a significant compatibilizing effect of clay. Besides the elastomer particle size and its properties, the clay localization and its degree of ordering in the interfacial region also significantly influenced mechanical properties of the system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1571–1576, 2006     

Column Fractionation of Canola Oil Deodorizer Distillate Using Supercritical Carbon Dioxide

Semi-continuous column fractionation of canola oil deodorizer distillate using supercritical CO₂ (SCCO₂) was carried out to determine the feasibility of value-added processing of this feed material for the recovery of bioactive components such as sterols and tocopherols and to determine the effect of operating conditions [pressure (20, 25 MPa using a temperature gradient of 70–100 °C), temperature (70, 100 °C) and a linear temperature gradient (70–100 °C at 25 MPa)] on extract yield and separation efficiency. Total extract yield increased significantly (p ≤ 0.05) with pressure, whereas at isobaric conditions (25 MPa) the highest yield was obtained at the lowest temperature tested (70 °C). Fractionation efficiency was reflected in the composition of fractions and was affected by operating conditions. Residue composition was determined by extract yield in addition to selectivity. Use of the thermal gradient (70–100 °C) decreased the content of volatiles, free fatty acids and tocopherols while increasing sterol content significantly (p ≤ 0.05) to a level of 40% (GC area %) in the residue obtained at 25 MPa. The findings indicate the potential of canola oil deodorizer distillate as a source of sterols and warrant further research on the countercurrent column fractionation to improve the separation efficiency.     

Size and mechanical properties of craze zones at propagating crack tips in poly(methyl methacrylate) during fatigue loading

In specimens of high molecular weight poly(methyl methacrylate) the microregion at the crack tip has been investigated during fatigue crack propagation by applying the optical interference method in a specially constructed experimental set-up. Thus, in the frequency range of 0.4 to 50 Hz the size and contour of the craze zone were directly measured at upper and lower load of the cycles. In contrast to previous assumptions it is established that the maximum craze width at the crack tip and hence the maximum length of stretched fibrils increases strongly with crack propagation rate. The directly measured craze data and also the material parameters indirectly derived by the aid of the Dugdale model are related to those data which have been measured during continuous crack propagation under quasi-static tensile load. The spacings of the fatigue striations on the fracture surfaces are compared with the lengths of the craze zones.     

The effects of expanded perlite aggregate, silica fume and fly ash on the thermal conductivity of lightweight concrete

Thermal conductivity coefficients of concretes made up of mixtures of expanded perlite and pumice aggregates (PA) were measured. To determine the effect of silica fume (SF) and class C fly ash (FA) on the thermal conductivity of lightweight aggregate concrete (LWAC), SF and FA were added as replacement for cement by decreasing the cement weights in the ratios of 10%, 20% and 30% by weight.The highest thermal conductivity of 0.3178 W/mK was observed with the samples containing only PA and plain cement. It decreased with the increase of SF and FA as replacement for cement. The lowest value of thermal conductivity, which is 0.1472 W/mK, was obtained with the samples prepared with expanded perlite aggregate (EPA) replacement of PA and 70% cement+30% FA replacement of cement. Both SF and FA had a decreasing effect on thermal conductivity. EPA (used in place of PA) also induced a decrease of 43.5% in thermal conductivity of concrete.     

Compatibilization of PP/PBT and PP/PA6 blends with a new oxazoline-functionalized polypropylene

Summary Aim of this work was to study the effectiveness of a novel oxazoline-functionalized polypropylene as a compatibilizer for PP/PBT and PP/PA6 blends. This polypropylene-based compatibilizer mixes well with the polypropylene and is capable of reacting with the carboxylic and amine end groups of PBT and PA6. Significant improvements in blend toughness were achieved without reduction in strength and stiffness. These effects were related to stabilized morphology of finely dispersed minor phase well attached to the matrix. The enhanced interfacial interactions between the two phases, in particular at high PBT content were evidenced by increased melt viscosity.     

Influence of principal component analysis acceleration factor on velocity measurement in 2D and 4D PC-MRI

Objective

The objective of the study was to determine how to optimize 2D and 4D phase-contrast magnetic resonance imaging (PC-MRI) acquisitions to acquire flow velocities in millimetric vessels. In particular, we search for the best compromise between acquisition time and accuracy and assess the influence of the principal component analysis (PCA).

Materials and methods

2D and 4D PC-MRI measurements are conducted within two in vitro vessel phantoms: a Y-bifurcation phantom, the branches of which range from 2 to 5 mm in diameter, and a physiological subject-specific phantom of the carotid bifurcation. The same sequences are applied in vivo in carotid vasculature.

Results

For a vessel oriented in the axial direction, both 2D and axial 4D PC-MRI provided accuracy measurements regardless of the k-t PCA factor, while the acquisition time is reduced by a factor 6 for k-t PCA maximum value. The in vivo measurements show that the proposed sequences are adequate to acquire 2D and 4D velocity fields in millimetric vessels and with clinically realistic time durations.

Conclusion

The study shows the feasibility of conducting fast, high-resolution PC-MRI flow measurements in millimetric vessels and that it is worth maximizing the k-t PCA factor to reduce the acquisition time in the case of 2D and 4D axial acquisitions.

     

Structural Parameters of Membranes from Porous Glass in Aqueous Solutions of Electrolytes,Containing Singly-Charged (Na<Superscript>+</Superscript>, K<Superscript>+</Superscript>) and Triple-Charged (Fe<Superscript>3+</Superscript>) Cations

The structural parameters of micro- and macroporous glass-like membranes in the solutions containing sodium, potassium, and iron counterions were investigated. The dependences of the volumetric porosity of the membranes, structural resistance coefficients, filtration coefficients, specific surface, average pore radius on the conditions of obtaining porous glass, the composition of the electrolyte, and the contact time of the porous glass with the solution are analyzed.