Electrochemical characterization of 8-hydroxyquinoline-5-sulphonate/aluminium(III) aqueous solutions

8-Hydroxyquinoline-5-sulphonate/Al(III) aqueous solutions were studied both by potentiometric titrations and voltammetric measurements, in order to obtain the number, the stoichiometry and the stability constants of the complexes formed at equilibrium, and to evaluate the redox and (electro)kinetic properties of the free ligand and of the metal/ligand complexes. The complexes formed in 0.2 m (Na)Cl aqueous solution (stability log beta values ± standard deviation) are AlL⁺ (8.95 ± 0.05), AlL₂⁻ (17.43 ± 0.03) and AlL₃³⁻ (24.58 ± 0.05), where “L” denotes the free ligand in the completely deprotonated form (L²⁻, pK_a1 = 3.910 ± 0.008, pK_a2 = 8.319 ± 0.004). AlL₃³⁻ is the predominant Al(III) species in a very wide range of pH, metal and ligand concentrations and metal-to-ligand ratios. The free ligand shows an oxidation wave at 0.62 V versus SCE. The proposed oxidation mechanism includes a first reversible one-electron oxidation of the ligand, followed by a coupling reaction and by a second reversible one-electron oxidation, and finally by a decomposition reaction. The addition of Al(III) lowers the intensity of the oxidation wave due to the formation of the redox-inactive complex AlL₃³⁻. A residual low signal was attributed to the free ligand produced by the complex dissociation, AlL₃³⁻ = AlL₂⁻ + L²⁻. All the kinetic parameters involved in the ligand oxidation and in the complex disruption were calculated on the basis of the agreement between experimental and simulated linear sweep and cyclic voltammetries. Correctness of the mechanisms proposed was further confirmed “a posteriori” by the agreement between potentiometric and linear sweep voltammetric results. The low residual signal observed in the presence of fully formed complex was attributed to the free ligand produced by the complex dissociation, having a kinetic constant estimated 0.2 s⁻¹.     

Domain-specific discrete event modelling and simulation using graph transformation

Graph transformation is being increasingly used to express the semantics of domain-specific visual languages since its graphical nature makes rules intuitive. However, many application domains require an explicit handling of time to accurately represent the behaviour of a real system and to obtain useful simulation metrics to measure throughputs, utilization times and average delays. Inspired by the vast knowledge and experience accumulated by the discrete event simulation community, we propose a novel way of adding explicit time to graph transformation rules. In particular, we take the event scheduling discrete simulation world view and provide rules with the ability to schedule the occurrence of other rules in the future. Hence, our work combines standard, efficient techniques for discrete event simulation (based on the handling of a future event set) and the intuitive, visual nature of graph transformation. Moreover, we show how our formalism can be used to give semantics to other timed approaches and provide an implementation on top of the rewriting logic system Maude.     

Long-term cyclability of nanostructured LiFePO4

Amorphous LiFePO₄ was obtained by lithiation of FePO₄ synthesized by spontaneous precipitation from equimolar aqueous solutions of Fe(NH₄)₂(SO₄)₂·6H₂O and NH₄H₂PO₄, using hydrogen peroxide as oxidizing agent. Nano-crystalline LiFePO₄ was obtained by heating amorphous nano-sized LiFePO₄ for different periods of time. The materials were characterized by TG, DTA, X-ray powder diffraction, scanning electron microscopy (SEM) and BET. All materials showed very good electrochemical performance in terms of energy and power density. Upon cycling, a capacity fading affected the materials, thus reducing the electrochemical performance. Nevertheless, the fading decreased upon cycling and after the 200th cycle the cell was able to cycle for more than 500 cycles without further fading.     

Ceramic Microtubes from Preceramic Polymers

A novel process for the production of ceramic microtubes involving the microextrusion of preceramic polymers was studied. Microtubes with a wide range of inner and outer diameters and several centimeters long were produced from two silicone resins. A coextrusion approach was also used to extend the forming capability of the technique. The addition of carbon black resulted in electrically conductive silicon oxycarbide (SiOC) ceramic microtubes. SiOC microtubes possessed a high bending strength, ranging from ∼30–1100 MPa.     

Bi- and three-dimensional urban change detection using sentinel-1 SAR temporal series

GeoInformatica - Urban areas are subject to multiple and very different changes, in a two- and three-dimensional sense, mostly as a consequence of human activities, such as urbanization, but also...     

Statics Aware Grid Shells

We introduce a framework for the generation of polygonal gridshell architectural structures, whose topology is designed in order to excel in static performances. We start from the analysis of stress on the input surface and we use the resulting tensor field to induce an anisotropic nonEuclidean metric over it. This metric is derived by studying the relation between the stress tensor over a continuous shell and the optimal shape of polygons in a corresponding gridshell. Polygonal meshes with uniform density and isotropic cells under this metric exhibit variable density and anisotropy in Euclidean space, thus achieving a better distribution of the strain energy over their elements. Meshes are further optimized taking into account symmetry and regularity of cells to improve aesthetics. We experiment with quad meshes and hexdominant meshes, demonstrating that our gridshells achieve better static performances than stateoftheart gridshells.     

Endogenous games with goals: side-payments among goal-directed agents

Boolean games have been developed as a paradigm for modelling societies of goal-directed agents. In boolean games agents exercise control over propositional variables and strive to achieve a goal formula whose realization might require the opponents’ cooperation. The presence of agents that are goal-directed makes it difficult for an external authority to be able to remove undesirable properties that are inconsistent with agents’ goals, as shown by recent contributions in the multi-agent literature. What this paper does is to analyse the problem of regulation of goal-direct agents from within the system, i.e., what happens when agents themselves are given the chance to negotiate the strategies to be played with one another. Concretely, we introduce endogenous games with goals, obtained coupling a general model of goal-directed agents (strategic games with goals) with a general model of pre-play negotiations (endogenous games) coming from game theory. Strategic games with goals are shown to have a direct correspondence with strategic games (Proposition 1) but, when side-payments are allowed in the pre-play phase, display a striking imbalance (Proposition 4). The effect of side-payments can be fully simulated by taxation mechanisms studied in the literature (Proposition 7), yet we show sufficient conditions under which outcomes can be rationally sustained without external intervention (Proposition 5). Also, integrating taxation mechanisms and side-payments, we are able to transform our starting models in such a way that outcomes that are theoretically sustainable thanks to a pre-play phase can be actually sustained even with limited resources (Proposition 8). Finally, we show how an external authority incentivising a group of agents can be studied as a special agent of an appropriately extended endogenous game with goals (Proposition 11).     

Robust Adaptive Soft Landing Control of an Electromagnetic Valve Actuator for Camless Engines

This paper deals with a signal‐based robust adaptive approximation technique for a proportional derivative (PD) regulator which is applied to an electromagnetic valve actuator control for camless internal combustion engines. PD regulators generate very high spikes in the presence of unavoidable noise. These spikes cause high power dissipation and poor dynamic performance with a lack of precision. The presented method allows the reduction of the noise and not robust nonlinear uncertainties effects by using minimum variance analysis. The technique with which the PD regulator is approximated does not depend on the model of the controlled system. Hence, the technique is quite general and can be applied to any type of system. In addition, this paper describes a feasible real‐time self‐tuning of an approximated discrete PD regulator using a backward Euler technique. The main contribution of the paper is the presentation of an approximated PD controller using a minimum variance control strategy together with a weighted least squares method to adapt the parameters of this approximated controller. This control law realises a robust control technique with respect to the noise and nonlinear uncertainties. Moreover, a comparison with the approximate PD controller proposed in MATLAB by Mathworks is provided. The presented technique ensures a good dynamic performance, including low dissipation as well as accurate positioning and soft landing control.     

Pareto-based negotiation in distributed multidisciplinary design

The process of distributed engineering design calls for a methodology making use of the most recent advances in optimization-based design including multidisciplinary and multiobjective optimization. In distributed design, the participating teams do not have access to the design problems of other teams but may exchange limited information about their own current designs, making negotiation among themselves a key mechanism to reach a desired compromise which, nevertheless, is also a Pareto design to the original problem. A mathematical model of this distributed but decomposable design process is posed and solved using Lagrangian relaxation, while Pareto optimality is equivalently converted to single-objective optimality by means of multicriteria decision making strategies. The proposed coordination algorithm allows negotiation among the teams (subproblems) by sharing only limited information that is restricted to values of optimization quantities. The proposed modeling and solution scheme is applied to a numerical example representing the design of vehicle subsystems and components.