Low temperature adsorption of ethylene and butadiene on platinum and palladium surfaces: A theoretical study of the diσ/π competition

The different low temperature coordination modes of ethylene and butadiene on a platinum (111) face, (110) face and on a palladium (111) face are compared on the basis of extended Hückel calculations. The nature of the chemical interaction between the olefin and the surface is detailed and the electronic factors that govern the coordination mode of the hydrocarbon are underlined. The different surfaces are modelled by a 49 or a 44 atoms cluster. A correction is applied in the calculation in order to minimize the artefact introduced by this cluster representation of an extended surface. For the adsorption, the respective importance of two electrons interactions and four electrons repulsions is the key point for the determination of the preferred mode. The di- coordination is more stable on platinum (111) but on the platinum (110) face the coordination yields the same adsorption energy than the di- one. This is roughly the same result for the palladium (111) face. The mode is there favored by a decrease of the four electrons repulsions caused either by a smaller number of metal neighbours for the surface atom (Pt(110)) or by a reduced radial expansion of the metal orbitals (Pd(111)). This coordination is associated with a smaller hybridization of the ethylene molecule. The results are extended to the adsorption of butadiene and this allows a qualitative explanation of the better selectivity for butadiene partial hydrogenation on palladium compared with platinum.     

Model-based intelligent user interface adaptation: challenges and future directions

Software and Systems Modeling - Adapting the user interface of a software system to the requirements of the context of use continues to be a major challenge, particularly when users become more...     

Mass transfer in 3D-printed electrolyzers: The importance of inlet effects

This article investigates the effect of inlet shape, entrance length, and turbulence promoters on mass transfer by using 3D-printed electrolyzers. Our results show that the inlet design can promote turbulence and lead to an earlier transition to turbulent flow. The Reynolds number at which the transition occurs can be predicted by the ratio of the cross-sectional area of the inlet to the cross-sectional area of the electrolyzer channel. A longer entrance length results in more laminar behavior and a later transition to turbulent flow. With an entrance length of 550 mm, the inlet design did no longer affect the mass transfer performance significantly. The addition of gyroid type turbulence promoters resulted in a factor of 2 to 4 increase in mass transfer depending on inlet design, entrance length, and the type of promoter. From one configuration to another, there was a minimal variation in pressure drop (<1600 Pa).     

Air impingement and intermittent drying: Application to apple and to mango

An original drying process combining air impingement and intermittent drying was studied on apple slices and mango cubes. The influence of four operating parameters (air velocity, drying/tempering periods, upper height, and air temperature) on the drying time and on the drying rate was evaluated. Continuous and intermittent drying were compared. The intermittency α = 1/7 (τ_on = 10 seconds and τ_off = 60 seconds) gave the best results. A time savings of 54% for apple and 67% for mango was reached. In continuous drying, a time savings of 4620 seconds was observed by increasing the air velocity from 6 to 40 m s^?1 for apple. Air temperatures of 328 K for apple and of 328 K or 338 K for mango were determined as optimum to prevent case‐hardening. Experimental results were fitted with the analytical solution of Fick's second law and the modified Page equation (average values R² = 0.985 and 0.961, for apple and mango, respectively). For both products, the apparent moisture diffusivity D_app, the drying constant k, the drying coefficient n, and the activation energy E_a, were identified. Activation energies calculated from the analytical solution were 30.3 and 36.8 kJ mol^?1 and were 25.4 and 30.0 kJ mol^?1 using the modified Page equation for apple and mango, respectively. Mango has an increased temperature sensitivity and thus will need less energy for drying than apple.     

Melt processing of nanocomposites of cellulose nanocrystals with biobased thermoplastic polyurethane

Nanocomposites of thermoplastic polyurethane (TPU) with cellulose nanocrystals (CNC) without and with surface treatment are obtained by melt processing. Nanocomposites are obtained with nanofiller weight content near of the theoretical percolation threshold (3.9 wt%). Visual observation of CNC agglomerates is sufficient to prove the inefficiency of the mixing in systems with untreated CNC. The crystallization kinetics of the TPU changes with the addition of CNC and this is confirmed by differential scanning calorimetry analysis. Thermogravimetric analysis prove that the addition of CNC increases the thermal stability of the TPU. From the rheological analysis it is possible to verify the absence of percolation and an intermediate state of sol–gel transition in the nanocomposites. CNC/TPU nanocomposites with 5 wt% of treated CNC present better mechanical performance than de neat TPU and the other processed nanocomposites and display around 130% increase in Young's modulus while retaining significant values of toughness, tensile strength and elongation at break.     

When a Tritrophic Interaction Goes Wrong to the Third Level: Xanthoxylin From Trees Causes the Honeybee Larval Mortality in Colonies Affected by the River Disease

The “River Disease” (RD), a disorder impacting honeybee colonies located close to waterways with abundant riparian vegetation (including Sebastiania schottiana, Euphorbiaceae), kills newly hatched larvae. Forager bees from RD-affected colonies collect honeydew excretions from Epormenis cestri (Hemiptera: Flatidae), a planthopper feeding on trees of S. schottiana. First-instar honeybee larvae fed with this honeydew died. Thus, we postulated that the nectars of RD-affected colonies had a natural toxin coming from either E. cestri or S. schottiana. An untargeted metabolomics characterization of fresh nectars extracts from colonies with and without RD allowed to pinpoint xanthoxylin as one of the chemicals present in higher amounts in nectar from RD-affected colonies than in nectars from healthy colonies. Besides, xanthoxylin was also found in the aerial parts of S. schottiana and the honeydew excreted by E. cestri feeding on this tree. A larva feeding assay where xanthoxylin-enriched diets were offered to 1^st instar larvae showed that larvae died in the same proportion as larvae did when offered enriched diets with nectars from RD-colonies. These findings demonstrate that a xenobiotic can mimic the RD syndrome in honeybee larvae and provide evidence of an interspecific flow of xanthoxylin among three trophic levels. Further, our results give information that can be considered when implementing measures to control this honeybee disease.

     

A finite volume–finite difference method with a stiff ordinary differential equation solver for advection–diffusion–reaction equation

A model for atmospheric pollutant transport is proposed considering an advection–diffusion–reaction equation. A splitting method is used to decouple the advection, diffusion and reaction parts. A scheme based on finite volume, finite difference and backward differentiation formula is used for solving an atmospheric transport-chemistry problem.     

Extracting Microfacet‐based BRDF Parameters from Arbitrary Materials with Power Iterations

We introduce a novel fitting procedure that takes as input an arbitrary material, possibly anisotropic, and automatically converts it to a microfacet BRDF. Our algorithm is based on the property that the distribution of microfacets may be retrieved by solving an eigenvector problem that is built solely from backscattering samples. We show that the eigenvector associated to the largest eigenvalue is always the only solution to this problem, and compute it using the power iteration method. This approach is straightforward to implement, much faster to compute, and considerably more robust than solutions based on nonlinear optimizations. In addition, we provide simple conversion procedures of our fits into both Beckmann and GGX roughness parameters, and discuss the advantages of microfacet slope space to make our fits editable. We apply our method to measured materials from two large databases that include anisotropic materials, and demonstrate the benefits of spatially varying roughness on texture mapped geometric models.     

Towards a smooth design process for static communicative node‐link diagrams

Node‐link infographics are visually very rich and can communicate messages effectively, but can be very difficult to create, often involving a painstaking and artisanal process. In this paper we present an investigation of node‐link visualizations for communication and how to better support their creation. We begin by breaking down these images into their basic elements and analyzing how they are created. We then present a set of techniques aimed at improving the creation workflow by bringing more flexibility and power to users, letting them manipulate all aspects of a node‐link diagram (layout, visual attributes, etc.) while taking into account the context in which it will appear. These techniques were implemented in a proof‐of‐concept prototype called GraphCoiffure, which was designed as an intermediary step between graph drawing/editing software and image authoring applications. We describe how GraphCoiffure improves the workflow and illustrate its benefits through practical examples.