Nonlinear numerical simulation of ferroelectric-ferromagnetic multifunctional composites

The theoretical background of nonlinear constitutive multifield behavior is presented. Nonlinear material models describing the ferroelectric or ferromagnetic behaviors are presented. Both physically and phenomenologically motivated constitutive models have been developed for the numerical calculation of the nonlinear magnetostrictive and ferroelectric behaviors. On this basis, the polarization in the ferroelectric and magnetization in the ferromagnetic respectively magnetostrictive phases are simulated and the resulting effects analyzed. The developed tools enable the prediction of the electromagnetomechanical properties of smart multiferroic composites and supply useful means for their optimization. Goals are to improve the efficiency of ME coupling and to reduce damage associated with the poling process. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Deterministic and stochastic behavior in ferroelectric particles

The response of a ferroelectric particle to an applied harmonic field is studied using the Fokker-Planck equation approach. The size effect in dielectric susceptibility is interpreted as the complementarity between stochastic resonance and response anomaly of the second-order phase transition. The borderline between stochastic and deterministic behavior is established. Two universal volume-independent ratios of the damping rates are predicted and may be verified in the relaxation experiments. The approach can be generalized also to other finite condensed systems.     

Comparison of numerical homogenization techniques in BT-CFO multiferroic particle composites

This work is restricted to linear material behavior, i.e. the structure is considered to be in a perfectly poled state. Different numerical homogenization methods are investigated and used to calculate effective properties of a 0-2 composite modelled in reprensentative volume elements. Bariumtitanate (BT) and cobaltferrite (CFO) are employed in the Finite Element model, where the roles of matrix and inclusion are mutable in principle. Mixed magnetoelectromechanical boundary conditions based on different homogenization theories are applied to the model. The calculated macroscopic behaviors described by the different approaches are compared and presented in the paper. The special focus is on the prediction of coefficients of magnetoelectric coupling with respect to an optimization of the structural arrangement of the composite. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Constitutive modeling of ferromagnetic and ferroelectric behaviors and application to multiferroic composites

In this paper, the constitutive modeling of nonlinear multifield behavior as well as the finite element implementation are presented. Nonlinear material models describing the magneto-ferroelectric or electro-ferromagnetic behaviors are presented. Both physically and phenomenologically motivated constitutive models have been developed for the numerical calculation of principally different nonlinear magnetostrictive behaviors. Further, the nonlinear ferroelectric behavior is based on a physically motivated constitutive model. On this basis, the polarization in the ferroelectric and magnetization in the ferromagnetic and magnetostrictive phases, respectively, are simulated and the resulting effects analyzed. Numerical simulations focus on the calculation of magnetoelectric coupling and on the prediction of local domain orientations going along with the poling process, thus supplying information on favorable electric-magnetic loading sequences. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mechanism of the living lactide polymerization mediated by robust zinc guanidine complexes

Zinc bis(chelate) guanidine complexes promote living lactide polymerization at elevated temperatures. By means of kinetic and spectroscopic analyses the mechanism has been elucidated for these special initiators that make use of neutral N-donor ligands. The neutral guanidine function initiates the polymerization by a nucleophilic ring-opening attack on the lactide molecule. DFT calculations on the first ring-opening step show that the guanidine is able to act as a nucleophile. Three transition states were located for ligand rearrangement, nucleophilic attack, and ring-opening. The second ring-opening step was modeled as a representation for the chain growth because here, the lactate alcoholate opens the second lactide molecule via two transition states (nucleophilic attack and ring-opening). Additionally, the resulting reaction profile proceeds overall exothermically, which is the driving force for the reaction. The experimental and calculated data are in good agreement and the presented mechanism explains why the polymerization proceeds without co-initiators.     

Ultrafast vibrational dynamics observed in higher electronic excited states of iodine using pump-UV DFWM spectroscopy

By using a combination of an initial pump pulse and a degenerate four-wave mixing process, we show that an interrogation of the vibrational dynamics occurring in different electronic states of molecules is possible. The technique is applied to iodine. The initial pump pulse is used to populate the B((3)Pi) state of molecular iodine in the gas phase. Now, by using an internal time delay in the DFWM process, which is resonant with the transition between the B state and a higher lying ion-pair state, the vibrational dynamics of the B state and the ion-pair state could be observed. States of even symmetry are investigated, which are accessed by a one photon transition from the B state. By a proper choice of the wavelengths used for the pump and DFWM beams, the dynamics of ion-pair states belonging to two different tiers are monitored.     

Influence of electronic resonances on mode selective excitation with tailored laser pulses

Femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) gives access to ultrafast molecular dynamics. However, the gain of the temporal resolution entails a poor spectral resolution due to the inherent spectral width of the femtosecond excitation pulses. Modifications of the phase shape of one of the exciting pulses results in dramatic changes of the mode distribution reflected in coherent anti-Stokes Raman spectra. A feedback-controlled optimization of specific modes making use of phase and/or amplitude modulation of the pump laser pulse is applied to selectively influence the anti-Stokes signal spectrum. The optimization experiments are performed under electronically nonresonant and resonant conditions. The results are compared and the role of electronic resonances is analyzed. It can be clearly demonstrated that these resonances are of importance for a selective excitation by means of phase and amplitude modulation. The mode selective excitation under nonresonant conditions is determined mainly by the variation of the spectral phase of the laser pulse. Here, the modulation of the spectral amplitudes only has little influence on the mode ratios. In contrast to this, the phase as well as amplitude modulation contributes considerably to the control process under resonant conditions. A careful analysis of the experimental results reveals information about the mechanisms of the mode control, which partially involve molecular dynamics in the electronic states.     

Lactide Polymerisation with Air‐Stable and Highly Active Zinc Complexes with Guanidine–Pyridine Hybrid Ligands

New class of air‐stable catalysts for lactide polymerisation: Guanidine–pyridine hybrid ligands (picture, left) were used to prepare a series of zinc complexes (e.g., depicted cation [ZnL₂(CF₃SO₃)]⁺, where L is the quinoline‐containing ligand with R¹=R²=R³=R⁴=Me), in which the ligand binds through two different N‐donor atoms. The zinc complexes show high activity in ring‐opening polymerisation of d,l ‐lactide (right), giving polylactide with molecular masses up to 176 000 g mol^?1 and in high yield.

     

Techniques for direct experimental evaluation of structure–transport relationships in disordered porous solids

Determining structure–transport relationships is critical to optimising the activity and selectivity performance of porous pellets acting as heterogeneous catalysts for diffusion-limited reactions. For amorphous porous systems determining the impact of particular aspects of the void space on mass transport often requires complex characterization and modelling steps to deconvolve the specific influence of the feature in question. These characterization and modelling steps often have limited accuracy and precision. It is the purpose of this work to present a case-study demonstrating the use of a more direct experimental evaluation of the impact of pore network features on mass transport. The case study evaluated the efficacy of the macropores of a bidisperse porous foam structure on improving mass transport over a purely mesoporous system. The method presented involved extending the novel integrated gas sorption and mercury porosimetry method to include uptake kinetics. Results for the new method were compared with those obtained by the alternative NMR cryodiffusometry technique, and found to lead to similar conclusions. It was found that the experimentally-determined degree of influence of the foam macropores was in line with expectations from a simple resistance model for a disconnected macropore network.