A multi-surface model for ferroelectric ceramics - application to cyclic electric loading with changing maximum amplitude

Depending on the maximum amplitude of externally applied cyclic electric fields, ferroelectric ceramics show minor or major hysteresis. The materials also show asymmetric butterfly hysteresis in a prepoled material. Aiming at capturing these behaviour in a phenomenological constitutive model, a multi-surface modelling approach for ferroelectrics is introduced. In this paper, with the note on the motivation for a multi-surface model related to the results of new experimental investigations and also to experimental data reported in the literature, the constitutive relation for a rate dependent multi-surface ferroelectric model is developed. Following this, a brief graphical illustration shows how this model captures the objective phenomena. Consequently, the numerical implementation of the model to capture experimental results is demonstrated. Finally, the performance of this model to represent behaviour of decaying polarisation offset of electrically fatigued specimen is shown.     

Pd-catalyzed asymmetric allylic substitution reactions using P-chirogenic diaminophosphine oxides: DIAPHOXs

This paper describes the development of a new class of chiral phosphorus ligand: aspartic acid-derived P-chirogenic diaminophosphine oxides, DIAPHOXs, and their application to several Pd-catalyzed asymmetric allylic substitution reactions. Pd-catalyzed asymmetric allylic alkylation was initially examined in detail using diaminophosphine oxides 1a, resulting in the highly enantioselective construction of quaternary stereocenters. Mechanistic investigations revealed that 1a is activated by N,O-bis(trimethylsilyl)acetamide-induced tautomerization to afford a trivalent diamidophosphite species 12, which functions as the actual ligand. Furthermore, asymmetric allylic amination was examined using Pd-DIAPHOX catalyst systems, providing a variety of chiral allylic amines.