Moving from surfactant-stabilized aqueous rhodium (0) colloidal suspension to heterogeneous magnetite-supported rhodium nanocatalysts: Synthesis, characterization and catalytic performance in hydrogenation reactions

Wet impregnation of pre-synthesized surfactant-stabilized aqueous rhodium (0) colloidal suspension on silica was employed in order to prepare supported Rh-0 nanoparticles of well-defined composition, morphology and size. A magnetic core-shell support of silica (Fe(3)O4@SiO2) was used to increase the handling properties of the obtained nanoheterogeneous catalyst. The nanocomposite catalyst Fe3O4@SiO2-Rh-0 NPs was highly active in the solventless hydrogenation of model olefins and aromatic substrates under mild conditions with turnover frequencies up to 143,000 h(-1). The catalyst was characterized by various transmission electron microscopy techniques showing well-dispersed rhodium nanoparticles (similar to 3 nm) mainly located at the periphery of the silica coating. The heterogeneous magnetite-supported nanocatalyst was investigated in the hydrogenation of cyclohexene and compared to the previous surfactant-stabilized aqueous Rh-0 colloidal suspension and various silica-supported Rh-0 nanoparticles. Finally, the composite catalyst could be reused in several runs after magnetic separation. (C) 2011 Elsevier B. V. All rights reserved.

Analysis of energy dissipation in stirred suspension polymerisation reactors using computational fluid dynamics

This work evaluates the spatial distribution of normalised rates of droplet breakage and droplet coalescence in liquidliquid dispersions maintained in agitated tanks at operation conditions normally used to perform suspension polymerisation reactions. Particularly, simulations are performed with multiphase computational fluid dynamics (CFD) models to represent the flow field in liquidliquid styrene suspension polymerisation reactors for the first time. CFD tools are used first to compute the spatial distribution of the turbulent energy dissipation rates (e) inside the reaction vessel; afterwards, normalised rates of droplet breakage and particle coalescence are computed as functions of e. Surprisingly, multiphase simulations showed that the rates of energy dissipation can be very high near the free vortex surfaces, which has been completely neglected in previous works. The obtained results indicate the existence of extremely large energy dissipation gradients inside the vessel, so that particle breakage occurs primarily in very small regions that surround the impeller and the free vortex surface, while particle coalescence takes place in the liquid bulk. As a consequence, particle breakage should be regarded as an independent source term or a boundary phenomenon. Based on the obtained results, it can be very difficult to justify the use of isotropic assumptions to formulate particle population balances in similar systems, even when multiple compartment models are used to describe the fluid dynamic behaviour of the agitated vessel. (C) 2011 Canadian Society for Chemical Engineering

Keeping your balance while balancing a cylinder: interaction between postural and voluntary goals

The present study investigated whether postural responses are influenced by the stability constraint of a voluntary, manual task. We also examined how task constraint and first experience (the condition with which the participants started the experiment) influence the kinematic strategies used to simultaneously accomplish a postural response and a voluntary task. Twelve healthy, older adults were perturbed during standing, while holding a tray with a cylinder placed with the flat side down (low constraint, LC) or with the rolling, round side down (high constraint, HC). Central set changed according to the task constraint, as shown by a higher magnitude of both the gastrocnemius and tibialis anterior muscle activation bursts in the HC than in the LC condition. This increase in muscle activation was not reflected, however, in changes in the center of pressure or center of mass displacement. Task constraint influenced the peak shoulder flexion for the voluntary tray task but not the peak hip flexion for the postural task. In contrast, first experience influenced the peak hip flexion but not the peak shoulder flexion. These results suggest an interaction between two separate control mechanisms for automatic postural responses and voluntary stabilization tasks.

Application of the Z-scan technique to determine the optical Kerr coefficient and two-photon absorption coefficient of magnetite nanoparticles colloidal suspension

We investigate the occurrence of the optical Kerr effect and two-photon absorption when an oil-based magnetic Fe3O4 nanoparticles colloidal suspension is illuminated with high intensity femtosecond laser pulses. The frequency of the pulses is controlled and the Z-scan technique is employed in our measurements of the nonlinear optical Kerr coefficient (n(2)) and two-photon absorption coefficient (beta). From these values it was possible to calculate the real and imaginary parts of the third-order susceptibility. We observed that increasing the pulse frequency, additional physical processes take place, increasing artificially the absolute values of n(2) and beta. The experimental conditions are discussed to assure the obtention of reliable values of these nonlinear optical parameters, which may be useful in all-optical switching and optical power limiting applications. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4723829]