Adsorption of the halogens on cerium dioxide

Summary CeO₂, alone or mixed with La₂O₃, is used as halogen adsorbent in the determination of carbon and hydrogen. Quantitative data are given on the adsorption of the single halogens on various samples of pure CeO₂ and La₂O₃. Retention of CO₂ and the influence of several parameters of special interest in the carbon and hydrogen determination, have been examined. It has been found that the conditions for optimum adsorption of the halogens are a large surface and relatively low adsorption temperature. Unfortunately these conditions cannot be applied in the determination of carbon and hydrogen.

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Zusammenfassung CeO₂ allein oder im Gemisch mit La₂O₃ wurde als Adsorbens für Halogen bei der CH-Bestimmung verwendet. Quantitative Angaben über die Adsorption der einzelnen Halogene an verschiedenen Mustern von reinem CeO₂ und La₂O₃ wurden gebracht. Die Retention von CO₂ und der Einfluß einzelner Parameter, die für die CH-Bestimmung von besonderem Interesse sind, wurden geprüft. Die besten Bedingungen für die Adsorption der Halogene sind große Oberfläche und relativ niedere Temperatur. Beide Bedingungen können leider bei der CH-Bestimmung nicht eingehalten werden.

     

The polymerization of propadiene by Ni(acac)2, C3H4, RnAlX3−n catalysts

Catalyst formation in the system Ni(acac)₂, C₃H₄, R_nAlX_3?n was studied. Polymerization experiments showed that, by replacing ionic groups such as acac^?, Br^?, Cl^? with alkyl or hydride groups, an active catalyst is obtained. Electrolysis of Ni(acac)₂ in tetrahydrofuran also gives an active catalyst. Lewis acids like (iBu)₃Al and Et₃Al increase the polymerization rate, while Lewis bases like pyridine and triphenylphosphine not only decrease the rate but also change selectivity. The selectivity is not changed if different transition metals (e.g. Co, Pd, Ni) are used. Kinetic measurements show a first order dependence on Ni. The dependence on (iBu)₃Al changes from first to zero order with increasing $\text{Al}\text{Ni}$ ratio. This can be explained by assuming that the very active catalyst is formed via an equilibrium between a nickel complex and (iBu)₃Al. A first order deactivation of the nickel catalyst is observed; it is faster during polymerization than during ageing of the catalyst.     

Formation of M2+(O2)(C3H8) species in alkaline-earth-exchanged Y zeolite during propane selective oxidation

The adsorption of oxygen and d2-propane (CH3CD2CH3) on a series of alkaline-earth-exchanged Y zeolite at room temperature was studied with in situ infrared spectroscopy. Surprisingly at room temperature, oxygen adsorption led to the formation of supercage M2+(O2) species. Further, at low propane coverage, propane was found to adsorb linearly on Mg2+ cations, but a ring-adsorption structure was observed for propane adsorbing on Ca2+, Sr2+, and Ba2+ cations. It is demonstrated that O2 and propane can simultaneously attach to one active center (M2+) to form a M2+(O2)(C3H8) species, which is proposed to be the precursor in thermal propane selective oxidation. Selectivity to acetone in the propane oxidation reaction decreases with increasing temperature and cation size due to the formation of 2-propanol and carboxylate ions. An extended reaction scheme for the selective oxidation of propane over alkaline earth exchanged Y zeolites is proposed.     

Time-series analysis of pressure fluctuations in gas–solid fluidized beds – A review

This work reviews methods for time-series analysis for characterization of the dynamics of gas–solid fluidized beds from in-bed pressure measurements for different fluidization regimes. The paper covers analysis in time domain, frequency domain, and in state space. It is a follow-up and an update of a similar review paper written a decade ago. We use the same pressure time-series as used by Johnsson et al. (2000). The paper updates the previous review and includes additional methods for time-series analysis, which have been proposed to investigate dynamics of gas–solid fluidized beds. Results and underlying assumptions of the methods are discussed.     

Buried oxide formation in Si by high-dose implantation of oxygen

The formation of a buried oxide film in Si by high-dose implantation of oxygen and subsequent annealing has been studied. It has been shown that this method can render good quality silicon-on-insulator with a dislocation density lower than 10⁵ cm^-2 and sharp interfaces. The microstructure after annealing was demonstrated to depend strongly on that in the as-implanted state. Silicon point defects have been argued to play an important role in the determination of the microstructure.     

Molecular weight determination for 1,2,1,2-polypropadiene

By using standard bromination conditions, the insoluble 1,2,1,2-polypropadiene (formed by Ni(acac)₂ or Co(acac)_{2 or 3}, C₃H₄, (iBu)₃Al catalysts) is transformed into a soluble bromopolypropadiene. Using this technique, determination of molecular weight becomes possible. It was found that the molecular weight increases with polymerization time until a steady value is reached. As the polymer yield continues to increase when a constant molecular weight has been reached, chain transfer must occur. The molecular weight of polybromopropadiene was independent of the concentrations of the catalyst components. From experiments with crosslinked polymers and from theoretical considerations, it was deduced that the low solubility of the original 1,2,1,2-polypropadiene is due to its high crystallinity.     

Fluidization of nanopowders: a review

Nanoparticles (NPs) are applied in a wide range of processes, and their use continues to increase. Fluidization is one of the best techniques available to disperse and process NPs. NPs cannot be fluidized individually; they fluidize as very porous agglomerates. The objective of this article is to review the developments in nanopowder fluidization. Often, it is needed to apply an assistance method, such as vibration or microjets, to obtain proper fluidization. These methods can greatly improve the fluidization characteristics, strongly increase the bed expansion, and lead to a better mixing of the bed material. Several approaches have been applied to model the behavior of fluidized nanopowders. The average size of fluidized NP agglomerates can be estimated using a force balance or by a modified Richardson and Zaki equation. Some first attempts have been made to apply computational fluid dynamics. Fluidization can also be used to provide individual NPs with a thin coating of another material and to mix two different species of nanopowder. The application of nanopowder fluidization in practice is still limited, but a wide range of potential applications is foreseen.     

Contact mechanics of highly porous oxide nanoparticle agglomerates

Efficient nanopowder processing requires knowledge of the powder’s mechanical properties. Due to the large surface area to volume ratio, nanoparticles experience relatively strong attractive interactions, leading to the formation of micron-size porous structures called agglomerates. Significant effort has been directed towards the development of models and experimental procedures to estimate the elasticity of porous objects such as nanoparticle agglomerates; however, none of the existing models has been validated for solid fractions below 0.1. Here, we measure the elasticity of titania (TiO\(_2\), 22 nm), alumina (Al\(_2\)O\(_3\), 8 nm), and silica (SiO\(_2\), 16 nm) nanopowder agglomerates by Atomic Force Microscopy, using a 3.75 \(\upmu\)m glass colloid for the stress–strain experiments. Three sample preparations with varying degree of powder manipulation are assessed. The measured Young’s moduli are in the same order of magnitude as those predicted by the model of Kendall et al., thus validating it for the estimation of the Young’s modulus of structures with porosity above 90 %.