Nonlinear dynamics and neo-piagetian theories in problem solving: perspectives on a new epistemology and theory development

In this study, an attempt is made to integrate Nonlinear Dynamical Systems theory and neo-Piagetian theories applied to creative mental processes, such as problem solving. A catastrophe theory model is proposed, which implements three neo-Piagetian constructs as controls: the functional M-capacity as asymmetry and logical thinking and the degree of field dependence independence as bifurcation. Data from achievement scores of students in tenth grade physics were analyzed using dynamic difference equations and statistical regression techniques. The cusp catastrophe model proved superior comparing to the pre-post linear counterpart and demonstrated nonlinearity at the behavioral level. The nonlinear phenomenology, such as hysteresis effects and bifurcation, is explained by an analysis, which provides a causal interpretation via the mathematical theory of self-organization and thus building bridges between NDS-theory concepts and neo-Piagetian theories. The contribution to theory building is made, by also addressing the emerging philosophical, - ontological and epistemological- questions about the processes of problem solving and creativity.     

A Smoluchowski model of crystallization dynamics of small colloidal clusters

We investigate the dynamics of colloidal crystallization in a 32-particle system at a fixed value of interparticle depletion attraction that produces coexisting fluid and solid phases. Free energy landscapes (FELs) and diffusivity landscapes (DLs) are obtained as coefficients of 1D Smoluchowski equations using as order parameters either the radius of gyration or the average crystallinity. FELs and DLs are estimated by fitting the Smoluchowski equations to Brownian dynamics (BD) simulations using either linear fits to locally initiated trajectories or global fits to unbiased trajectories using Bayesian inference. The resulting FELs are compared to Monte Carlo Umbrella Sampling results. The accuracy of the FELs and DLs for modeling colloidal crystallization dynamics is evaluated by comparing mean first-passage times from BD simulations with analytical predictions using the FEL and DL models. While the 1D models accurately capture dynamics near the free energy minimum fluid and crystal configurations, predictions near the transition region are not quantitatively accurate. A preliminary investigation of ensemble averaged 2D order parameter trajectories suggests that 2D models are required to capture crystallization dynamics in the transition region.     

Volatile Compounds Present in Carbon Blacks Produced by Thermal Plasmas

Carbon black nanopowders were produced using two thermal plasma processes based on DC, respectively ICP plasma torches. Although the produced particles were in the nanometer size range, the values obtained for the surface area of the particles using a Brunauer Emmett Teller technique were very small. This indicated the presence of contaminants in the experimental powders, as confirmed by Raman spectroscopy and Thermogravimetric Analysis. A thermal treatment process was developed in order to extract these volatile compounds, which were then identified using a Gas Chromatography—Mass Spectrometry method. The experimental powders were analyzed using Scanning and Transmission Electron Microscopy, X-Ray Diffraction and Raman Spectroscopy before and after the thermal treatment in order to determine the effect of the heat treatment on the powder structural properties.     

Theoretical analysis of the spin Hamiltonian parameters in Co(II)S4 complexes, using density functional theory and correlated ab initio methods

A systematic Density Functional Theory (DFT) and multiconfigurational ab initio computational analysis of the Spin Hamiltonian (SH) parameters of tetracoordinate S = 3/2 Co((II))S(4)-containing complexes has been performed. The complexes under study bear either arylthiolato, ArS(-), or dithioimidodiphosphinato, [R(2)P(S)NP(S)R'(2)](-) ligands. These complexes were chosen because accurate structural and spectroscopic data are available, including extensive Electron Paramagnetic Resonance (EPR)/Electron Nuclear Double Resonance (ENDOR) studies. For comparison purposes, the [Co(PPh(3))(2)Cl(2)] complex, which was thoroughly studied in the past by High-Field and Frequency EPR and Variable Temperature, Variable Field Magnetic Circular Dichroism (MCD) spectroscopies, was included in the studied set. The magnitude of the computed axial zero-field splitting parameter D (ZFS), of the Co((II))S(4) systems, was found to be within ~10% of the experimental values, provided that the property calculation is taken beyond the accuracy obtained with a second-order treatment of the spin-orbit coupling interaction. This is achieved by quasi degenerate perturbation theory (QDPT), in conjunction with complete active space configuration interaction (CAS-CI). The accuracy was increased upon recovering dynamic correlation with multiconfigurational ab initio methods. Specifically, spectroscopy oriented configuration interaction (SORCI), and difference dedicated configuration interaction (DDCI) were employed for the calculation of the D-tensor. The sign and magnitude of parameter D was analyzed in the framework of Ligand Field Theory, to reveal the differences in the electronic structures of the investigated Co((II))S(4) systems. For the axial complexes, accurate effective g'-tensors were obtained in the QDPT studies. These provide a diagnostic tool for the adopted ground state configuration (±3/2 or ±1/2) and are hence indicative of the sign of D. On the other hand, for the rhombic complexes, the determination of the sign of D required the SH parameters to be derived along suitably constructed symmetry interconversion pathways. This procedure, which introduces a dynamic perspective into the theoretical investigation, helped to shed some light on unresolved issues of the corresponding experimental studies. The metal hyperfine and ligand super-hyperfine A-tensors of the C(2) [Co{(SPPh(2))(SP(i)Pr(2))N}(2)] complex were estimated by DFT calculations. The theoretical data were shown to be in good agreement with the available experimental data. Decomposition of the metal A-tensor into individual contributions revealed that, despite the large ZFS, the observed significant anisotropy should be largely attributed to spin-dipolar contributions. The analysis of both, metal and ligand A-tensors, is consistent with a highly covalent character of the Co-S bonds.     

Detection,isolation and identification of multiple actuator and sensor faults in nonlinear dynamic systems: Application to a waste water treatment process

The goal in many fault detection and isolation schemes is to increase the isolation and identification speed. This paper, presents a new approach of a nonlinear model based adaptive observer method, for detection, isolation and identification of actuator and sensor faults. Firstly, we will design a new method for the actuator fault problem where, after the fault detection and before the fault isolation, we will try to estimate the output of the instrument. The method is based on the formation of nonlinear observer banks where each bank isolates each actuator fault. Secondly, for the sensor problem we will reformulate the system by introducing a new state variable, so that an augmented system can be constructed to treat sensor faults as actuator faults. A method based on the design of an adaptive observers’ bank will be used for the fault treatment. These approaches use the system model and the outputs of the adaptive observers to generate residues. Residuals are defined in such way to isolate the faulty instrument after detecting the fault occurrence. The advantages of these methods are that we can treat not only single actuator and sensor faults but also multiple faults, more over the isolation time has been decreased. In this study, we consider that only abrupt faults in the system can occur. The validity of the methods will be tested firstly in simulation by using a nonlinear model of waste water treatment process with and without measurement noise and secondly with the same nonlinear model but by using this time real data.     

Observation of abruptly autofocusing waves

We report on the experimental observation of abruptly autofocusing waves. This interesting family of wave packets has been realized by using a radially symmetric Airy intensity distribution. As demonstrated in our experiments, these waves can exhibit unusual features, such as the ability to autofocus by following a parabolic trajectory toward their focus.     

Tight-Binding study of Boron structures

We have performed Linearized Augmented Plane Wave (LAPW) calculations for five crystal structures (alpha, dhcp, sc, fcc, bcc) of Boron which we then fitted to a non-orthogonal tight-binding model following the Naval Research Laboratory Tight-Binding (NRL-TB) method. The predictions of the NRL-TB approach for complicated Boron structures such as R105 (or β-rhombohedral) and T190 are in agreement with recent first‐principles calculations. Fully utilizing the computational speed of the NRL-TB method we calculated the energy differences of various structures, including those containing vacancies using supercells with up to 5000 atoms.     

A Calcium Solid State Ion Selective Minisensor Based on Lipid Films on ZnO Nanorods

This article describes the development of a calcium solid minisensor based on lipid films on ZnO nanorods. The lipid film was composed from dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylcic acid (DPPA). The calibration graph was logarithmically related to the concentration of calcium ions in the range from 10^?6 to 10^?3 M. The response times of the electrode were less than 5 s. No memory effects were observed for this electrode. The reproducibility of the electrode was less than 5 %. The electrode has shown good stability for a period of 1 month. The influence of a wide range of metals and anions as potential interferences was checked. The method was applied to the rapid detection of calcium ions in mineral waters.     

Electrochemical Aptasensor Based on Polycarboxylic Macrocycle Modified with Neutral Red for Aflatoxin B1 Detection

Novel electrochemical aptasensors based on glassy carbon electrodes modified with electropolymerized Neutral red and polycarboxylated macrocyclic ligands onto which the DNA aptamers were covalently attached have been developed for detection of Aflatoxin B1 (AFB1). The interaction with an analyte resulted in the decrease of the cathodic peak current of the probe measured by CV and in the increase of the electron transfer resistance determined by EIS. The limit of detection was found to be 0.1 nM for CV and 0.05 nM for EIS methods, respectively. The aptasensor makes it possible to detect AFB1 in peanuts, cashew nuts, white wine and soy sauce with a recovery of 85–100 %.