Synthesis of ZSM‐5 Films and Monoliths with Bimodal Micro/Mesoscopic Structures

A route to synthesize ZSM‐5 crystals with a bimodal micro/mesoscopic pore system has been developed in this study; the successful incorporation of the mesopores within the ZSM‐5 structure was performed using tetrapropylammonium hydroxide (TPAOH)‐impregnated mesoporous materials containing carbon nanotubes in the pores, which were encapsulated in the ZSM‐5 crystals during a solid rearrangement process within the framework. Such mesoporous ZSM‐5 zeolites can be readily obtained as powders, thin films, or monoliths.     

Inside Front Cover: The Elastic Properties and Plastic Behavior of Two‐Dimensional Polymer Structures Fabricated by Laser Interference Lithography (Adv. Funct. Mater. 10/2006)

The probing of the micromechanical properties within a two‐dimensional polymer structure with sixfold symmetry fabricated via interference lithography reveals a nonuniform spatial distribution in the elastic modulus “imprinted” with an interference pattern in work reported by Tsukruk, Thomas, and co‐workers on p. 1324. The image prepared by M. Lemieux and T. Gorishnyy shows how the interference pattern is formed by three laser beams and is transferred to the solid polymer structure. The elastic and plastic properties within a two‐dimensional polymer (SU8) structure with sixfold symmetry fabricated via interference lithography are presented. There is a nonuniform spatial distribution in the elastic modulus, with a higher elastic modulus obtained for nodes (brightest regions in the laser interference pattern) and a lower elastic modulus for beams (darkest regions in the laser interference pattern) of the photopatterned films. We suggest that such a nonuniformity and unusual plastic behavior are related to the variable material properties “imprinted” by the interference pattern.     

Phosphorus‐containing polyaryloxydiphenylsilanes with high flame retardance arising from a phosphorus–silicon synergistic effect

Polyaryloxydiphenylsilanes were prepared from phosphorus‐containing diols and diphenydichlorolsilane through solution polymerization. With a stoichiometric imbalance in feed monomers, the resulting polymers exhibited moderate melting points and good processing properties. The polymers prepared showed initial decomposition temperatures above 340 °C, excellent thermal stability, high char yields at 850 °C and very high limited oxygen index values of 56–59. The polymers' char yields and their (P + Si) contents showed linear relationships. © 2003 Society of Chemical Industry     

Enhanced Photoelectrochemistry in CdS/Au Nanoparticle Bilayers

Three different configurations of Au‐nanoparticle/CdS‐nanoparticle arrays are organized on Au/quartz electrodes for enhanced photocurrent generation. In one configuration, Au‐nanoparticles are covalently linked to the electrode and the CdS‐nanoparticles are covalently linked to the bare Au‐nanoparticle assembly. The resulting photocurrent, φ = 7.5 %, is ca. 9‐fold higher than the photocurrent originating from a CdS‐nanoparticle layer that lacks the Au‐nanoparticles, φ = 0.8 %. The enhanced photocurrent in the Au/CdS nanoparticle array is attributed to effective charge separation of the electron–hole pair by the injection of conduction‐band electrons from the CdS‐ to the Au‐nanoparticles. Two other configurations involving electrostatically stabilized bipyridinium‐crosslinked Au/CdS or CdS/Au nanoparticle arrays were assembled on the Au/quartz crystal. The photocurrent quantum yields in the two systems are φ = 10 % and φ = 5 %, respectively. The photocurrents in control systems that include electrostatically bridged Au/CdS or CdS/Au nanoparticles by oligocationic units that lack electron‐acceptor units are substantially lower than the values observed in the analogous bipyridinium‐bridged systems. The enhanced photocurrents in the bipyridinium‐crosslinked systems is attributed to the stepwise electron transfer of conduction‐band electrons to the Au‐nanoparticles by the bipyridinium relay bridge, a process that stabilizes the electron–hole pair against recombination and leads to effective charge separation.     

Development of a Continuous Segmented Flow Tubular Reactor and the “Scale‐out” Concept – In Search of Perfect Powders

The synthesis of powders with controlled shape and narrow particle size distributions is still a major challenge for many industries. A continuous Segmented Flow Tubular Reactor (SFTR) has been developed to overcome homogeneity and scale‐up problems encountered when using batch reactors. Supersaturation is created by mixing the co‐reactants in a micromixer inducing precipitation; the suspension is then segmented into identical micro‐volumes by a non‐miscible fluid and sent through a tube. These micro‐volumes are more homogeneous when compared to large batch reactors leading to narrower size distributions, better particle morphology, polymorph selectivity and stoichiometry. All these features have been demonstrated on single tube SFTR for different chemical systems. To increase productivity for commercial application the SFTR is being “scaled‐out” by multiplying the number of tubes running in parallel instead of scaling‐up by increasing their size. The versatility of the multi‐tube unit will allow changes in type of precipitate with a minimum of new investment as new chemistry can be researched, developed and optimised in a single tube SFTR and then transferred to the multi‐tube unit for powder production.     

Panchromatic Chromophore Mixtures in an AlPO4‐5 Molecular Sieve: Spatial Separation Effects and Energy Transfer Cascades

Dye‐loaded AlPO₄‐5 single crystals were prepared by microwave‐assisted hydrothermal synthesis from a batch, containing a mixture of three chromophores (Coumarin 40, Rhodamine BE50, and Oxazine 1) differing in their absorption range, molecular dimensions, and solubilities. Confocal fluorescence images reveal a spatial separation effect of the dye molecules, where the slimmer, more‐soluble dye molecule (Coumarin 40) is uniformly distributed in the body of the single crystal, and the bulky and/or less‐soluble ones (Rhodamine BE50, Oxazine 1) are situated in distinct domains. Visible spectra show good panchromatic absorption of visible light. Fluorescence lifetime measurements indicate the presence of an energy transfer cascade of the entirely fixed dye molecules from Coumarin 40 to Oxazine 1. The transfer mechanism is predominantly radiative.     

The polymerisation of 2-furyl vinyl ketone

Summary 2-Furyl vinyl ketone was polymerised using anionic, cationic and free-radical initiators. Yields and molecular weights varied with the type of activation. Whereas radical polymerisation gave a product possessing a regular vinylic structure, other kinds of units were detected in the polymers prepared with anionic and cationic catalysts.     

NO emission characteristics in counterflow diffusion flame of blended fuel of H2/CO2/Ar

Flame structure and NO emission characteristics in counterflow diffusion flame of blended fuel of H₂/CO₂/Ar have been numerically simulated with detailed chemistry. The combination of H₂, CO₂ and Ar as fuel is selected to clearly display the contribution of hydrocarbon products to flame structure and NO emission characteristics due to the breakdown of CO₂. A radiative heat loss term is involved to correctly describe the flame dynamics especially at low strain rates. The detailed chemistry adopts the reaction mechanism of GRI 2.11, which consists of 49 species and 279 elementary reactions. All mechanisms including thermal, NO₂, N₂O and Fenimore are taken into account to separately evaluate the effects of CO₂ addition on NO emission characteristics. The increase of added CO₂ quantity causes flame temperature to fall since at high strain rates a diluent effect is prevailing and at low strain rates the breakdown of CO₂ produces relatively populous hydrocarbon products and thus the existence of hydrocarbon products inhibits chain branching. It is also found that the contribution of NO production by N₂O and NO₂ mechanisms are negligible and that thermal mechanism is concentrated on only the reaction zone. As strain rate and CO₂ quantity increase, NO production is remarkably augmented. Copyright © 2002 John Wiley & Sons, Ltd.     

Ranking Pages by Topology and Popularity within Web Sites

We compare two link analysis ranking methods of web pages in a site. The first, called Site Rank, is an adaptation of PageRank to the granularity of a web site and the second, called Popularity Rank, is based on the frequencies of user clicks on the outlinks in a page that are captured by navigation sessions of users through the web site. We ran experiments on artificially created web sites of different sizes and on two real data sets, employing the relative entropy to compare the distributions of the two ranking methods. For the real data sets we also employ a nonparametric measure, called Spearman's footrule, which we use to compare the top-ten web pages ranked by the two methods. Our main result is that the distributions of the Popularity Rank and Site Rank are surprisingly close to each other, implying that the topology of a web site is very instrumental in guiding users through the site. Thus, in practice, the Site Rank provides a reasonable first order approximation of the aggregate behaviour of users within a web site given by the Popularity Rank.