Discretely Blended Martensen Interpolation

Martensen interpolation has been investigated in Dahmen et?al. (Numer Math 52:564–639, 1988), Delvos (2003), Martensen (Numer Math 21:70–80, 1973), Siewer (BIT Numer Math 46:127–140, 2006). In this paper we investigate bivariate constructions using Boolean methods (Delvos and Schempp, Boolean methods in interpolation and approximations. Pitman research notes in mathematical series. Wiley, New York, 1989).     

On the direct connection of rheological elements in nonlinear continuum mechanics

The structure of complicated phenomenological material models at finite strains is often exemplified with the help of rheological elements. Thereby, simple material behaviour, i.e. elasticity or viscous and plastic flow, are composes by components. In our approach, we directly apply this concept to obtain material models at finite strains. Towards this end, the thermodynamically consistent material behaviour of single elements is defined first. Subsequently, the elements are connected by evaluation of stress equilibria equations formulated on interconnecting configurations. The basic equations of this concept are presented using the example of nonlinear viscoelasticity of Maxwell type. The model results from a series connection of an elastic and a viscous element, whereas both are formulated in a thermodynamically consistent way within the framework on nonlinear continuum mechanics. Furthermore, an approach of numerical implementation using the stress equilibria is suggested. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Exploring between the extremes: conversion-dependent kinetics of phosphite-modified hydroformylation catalysis

The kinetics of the hydroformylation of 3,3-dimethyl-1-butene with a rhodium monophosphite catalyst has been studied in detail. Time-dependent concentration profiles covering the entire olefin conversion range were derived from in situ high-pressure FTIR spectroscopic data for both, pure organic components and catalytic intermediates. These profiles fit to Michaelis-Menten-type kinetics with competitive and uncompetitive side reactions involved. The characteristics found for the influence of the hydrogen concentration verify that the pre-equilibrium towards the catalyst substrate complex is not established. It has been proven experimentally that the hydrogenolysis of the intermediate acyl complex remains rate limiting even at high conversions when the rhodium hydride is the predominant resting state and the reaction is nearly of first order with respect to the olefin. Results from in situ FTIR and high-pressure (HP) NMR spectroscopy and from DFT calculations support the coordination of only one phosphite ligand in the dominating intermediates and a preferred axial position of the phosphite in the electronically saturated, trigonal bipyramidal (tbp)-structured acyl rhodium complex.     

Temperature analysis of laser heated polymers on microsecond time scales

To investigate the temperature profiles on laser heated polymer films, we track the thermal radiation with 1 μs time and 1 μm spatial resolution. The resulting two-dimensional temperature graphs are compared to finite element simulations in order to understand the heat conversion and flow. The temperature measurement setup consists of a NIR laser and an optical detection system, which includes high performance optics and a microsecond gated camera, equipped with several interference filters. In this way the thermal radiation is detected in the visible range with spectral resolution. Fitting the spectrum with Planck’s law, two-dimensional micrographs of the temperature distribution are obtained. For polystyrene surfaces we were able to analyze the heating and the ablation behavior. Good agreement was found between experimental results and finite element simulations, when ablation is limited to a few tens of nanometers of the film thickness. Ablation of polystyrene starts at 150°C, 50 K above the glass transition temperature. We suggest a photomechanical ablation mechanism at that threshold fluence. For ablation at higher fluence and peak temperature, experiments indicate a thermal decomposition reaction. The temperature range of spinodal decomposition is not reached and can in our case be ruled out as ablation mechanism.     

Microscale investigation of surface contaminations during silicon epitaxial growth

Microchimica Acta - Epitaxial (epi) stacking faults on silicon wafers with <100>- and <111>-orientation were induced by intentional contamination with substances...     

Tuning Single‐Molecule Dynamics in Functionalized Mesoporous Silica

Diffusion of single molecules of a substituted terrylene diimide dye in functionalized mesoporous silica films was monitored by single‐molecule fluorescence microscopy. By varying the chemical nature and density of the functional groups, the diffusion dynamics of the dye molecules can be controlled precisely. The picture shows a sketch of a dye molecule in a pore, diffusion data for different phenyl functionalization densities, and the trajectory of one molecule in a cyanopropyl‐functionalized film.

     

Electronic Structure and Absorption Spectra of Biferrocenyl and Bisfulvalenide Diiron Radical Cations: Detection and Assignment of New Low‐Energy Transitions

New transitions : Low‐energy electronic transitions have been detected spectroscopically in the Fe^II–Fe^III mixed‐valent biferrocenyl radical cation, but are absent in the spectra of the neutral analogue. They have been assigned by time‐dependent DFT calculations (squares in figure). Analogous investigations were performed for the bisfulvalenide Fe^II–Fe^III radical cation.