Steric control over molecular structure and supramolecular association exerted by tin- and ligand-bound groups in diorganotin carboxylates

Structural data (X-ray and solution and solid-state ^₁₁₉Sn NMR) show that skew-trapezoidal-bipyramidal diorganotin compounds of 2-quinaldate are invariably monomeric, owing to the steric bulk of the carboxylate ligand. In contrast, most of the analogous compounds of 2-picolinate (2-pic) can increase their coordination number by polymerization or the incorporation of solvent in their coordination sphere in the solid state. The exceptional compound is tBu₂Sn(2-pic)₂ (3), for which no increase in coordination number is apparent, a result that is correlated with the bulky tert-butyl groups. Thus, judicious choice of tin or ligand substituents can be exploited to dictate coordination number and/or the degree of supramolecular aggregation in the investigated systems.

Determination of lower-bound ductility for AZ31 magnesium alloy by use of the bulge specimens

Despite the high demand for industrial applications of magnesium, the forming technology for wrought magnesium alloys is not fully developed due to the limited ductility and high sensitivity to the processing parameters. The processing window for magnesium alloys could be significantly widened if the lower-bound ductility (LBD) for a range of stresses, temperature, and strain rates was known. LBD is the critical strain at the moment of fracture as a function of stress state and temperature. Measurements of LBD are normally performed by testing in a hyperbaric chamber, which is highly specialized, complex, and rare equipment. In this paper an alternative approach to determine LBD is demonstrated using wrought magnesium alloy AZ31 as an example. A series of compression tests of bulge specimens combined with finite element simulation of the tests were performed. The LBD diagram was then deduced by backward calculation.

ε-bounded state estimation for time-delay systems with bounded disturbances

A new problem on ε-bounded functional state estimation for time-delay systems with unknown bounded disturbances is studied in this paper. In the presence of unknown bounded disturbances, the common assumption regarding the observers matching condition is no longer required. In this regard, instead of achieving asymptotic convergence for the observer error, the error is now required to converge exponentially within a ball with a small radius ε > 0. This means that the estimate converges exponentially within an ε-bound of the true value. A general observer that utilises multiple-delayed output and input information is proposed. Sufficient conditions for the existence of the proposed observer are first given. We then employ an extended Lyapunov-Krasovskii functional which combines the delay-decomposition technique with a triple-integral term to study the ε-convergence problem of the observer error system. Moreover, the obtained results are shown to be more effective than the existing results for the cases with no disturbances and/or no time delay. Three numerical examples are given to illustrate the obtained results.

Linear functional state bounding for perturbed time-delay systems and its application

This paper considers time-delay systems with bounded disturbances. We study a new problem of finding an upper bound of an absolute value function of any given linear functional of the state vector starting from the origin of the system. Based on the Lyapunov-Krasovskii method combining with the recent Wirtinger-based integral inequality that has just been proposed by Seuret & Gouaisbaut (2013. Wirtinger-based integral inequality: application to time-delay systems. Automatica, 49, 2860-2866), sufficient conditions for the existence of an upper bound of the function are derived. The obtained results are shown to be more effective than those adapted from the existing works on reachable set bounding. Furthermore, the obtained results are applied to refine existing ellipsoidal bounds of the reachable sets. The effectiveness of the obtained results is illustrated by two numerical examples.

Sodium ion dynamics in a sulfonate based ionomer system studied by 23Na solid-state nuclear magnetic resonance and impedance spectroscopy

A poly(2-acrylamido-2-methyl-1-propane-sulphonate) (PAMPS) ionomer containing both sodium and quaternary ammonium cations functionalised with an ether group, has been characterised in terms of its thermal properties, ionic conductivity and sodium ion dynamics. The ether oxygen was incorporated to reduce the Na+ association with the anionic sulfonate groups tethered to the polymer backbone, thereby promoting ion dissociation and ultimately enhancing the ionic conductivity. This functionalised ammonium cation led to a significant reduction in the ionomer Tg compared to an analogue system without an ether group, resulting in an increase in ionic conductivity of approximately four orders of magnitude. The sodium ion dynamics were probed by 23Na solid-state NMR, which allowed the signals from the dissociated (mobile) and bound Na+ cations to be distinguished. This demonstrates the utility of 23Na solid-state NMR as a probe of sodium dynamics in ionomer systems.