Experimental and Numerical Investigations of Al/Mg Compounds

Al/Mg compounds produced by hydrostatic extrusion exhibit unique characteristics regarding high strength and low weight, which are required by safety part applications in lightweight constructions. Between the two materials an interface in form of a brittle intermetallic phase consisting of Al₂Mg₃ and Al₁₂Mg₁₇ arises during the production process. However, a certain plastic deformability of the semi-finished product is essential for further forming processes. Even under multi-axle load during a radial upsetting process, the interface maintains a full material joint although a fragmentation and a new secondary interface between the fragments can be observed. Due to the evaluations of light microscopy images and Eulerian Hencky strain values at the interface, which are obtained with the help of the Digital Image Correlation, a relation between the strain and the boundary layer's appearance seems reasonable. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

The difference one ligand atom makes – An altered oxygen transfer reaction mechanism caused by an exchange of selenium for sulfur

The influence of sulfur versus selenium coordination to molybdenum on the oxo transfer reaction mechanisms of functional models for oxidoreductases has been studied. The solution structure of the dimeric molybdenum compound with tridentate bis-anionic ligands containing a thioether function (⁻O(CH₂)₃S(CH₂)₃O⁻) has been determined using EXAFS spectroscopy to be able to compare a feature of its solution structure to that of its selenoether analogue. A significant difference is found for the solution structures of the two compounds. The thioether group remains coordinated in solution, whereas the selenoether does not. The influence of this difference on the catalytic oxo transfer has been investigated in detail by following the catalytic transition of PPh₃ to OPPh₃ with DMSO as oxygen donor with variation of both substrate concentrations.     

Molecular dynamics simulation of semirigid polymers

The chain rigidity of poly(p-hydroxybenzoate) was estimated through the theoretical evaluation of its persistence length (L_p). A non-Brownian molecular dynamics (MD) simulation of an isolated chain with 20 monomeric units was performed. The sampled conformational population was analyzed and the orientational correlation function between monomeric units along the chain was calculated. An algorithm based on the worm-like chain model was applied to evaluate the persistence length. The results were compared with those obtained from equilibrium models like the freely-rotating-chain and the rotational-matrix method with fluctuations. Equilibrium models give different results depending on the degree of accuracy used in describing the monomeric unit. The inclusion of thermal fluctuations is crucial to obtain realistic results. These coincide with those given by MD simulation when only nearest-neighbour orientational correlations are taken into account: inclusion of higher-order correlation terms leads to lower values of the persistence length. The origin of this discrepancy was investigated. The MD simulation results are characterized by an overrepresentation of conformations with a short end-to-end distance resulting from an anomalous energy concentration in the first bending mode of the chain. In analogy with previous simulation results from systems characterized by a week coupling amoung their degrees of freedom, failure in the energy equipartition is proposed as a likely explanation of the anomalous dynamical behaviour.     

Inexact inner–outer Golub–Kahan bidiagonalization method: A relaxation strategy

We study an inexact inner–outer generalized Golub–Kahan algorithm for the solution of saddle-point problems with a two-times-two block structure. In each outer iteration, an inner system has to be solved which in theory has to be done exactly. Whenever the system is getting large, an inner exact solver is, however, no longer efficient or even feasible and iterative methods must be used. We focus this article on a numerical study showing the influence of the accuracy of an inner iterative solution on the accuracy of the solution of the block system. Emphasis is further given on reducing the computational cost, which is defined as the total number of inner iterations. We develop relaxation techniques intended to dynamically change the inner tolerance for each outer iteration to further minimize the total number of inner iterations. We illustrate our findings on a Stokes problem and validate them on a mixed formulation of the Poisson problem.