Search

We consider an approach to mathematical modeling of photodegradation of polymer nanocomposites with photoactive additives using the Monte Carlo methods. We principally pay attention to the strength decrease of these materials under solar light action. We propose a new term, "photocatalytic fatigue", which we apply to the particular case when the mechanical strength decreases only owing to the presence of photocatalytically active components in polymeric nanocomposite material. The propriety of the term is based on a relative similarity of photostimulated mechanical destructive processes in nanocomposites with photoactive additives and mechanical destructive processes typical for metal high-cycle fatigue. Formation of the stress concentrations is one of the major causes of fatigue cracks generation in metals. Photocatalytic active nanoparticles of semiconductors initiate a generation of the stress concentrations under sunlight irradiation. The proposed mathematical model is a Wöhler curve analog for the metal high-cycle fatigue. We assume that equations for high-cycle fatigue curves of samples with stress concentrations could be used in mathematical modeling of polymer nanocomposites photodegradation. In this way, we replace the number of loading cycles with the exposition time in the equations. In the case of polypropylene and polyester samples with photoactive titanium dioxide, the experimental parameters of phenomenological equations for "photocatalytic fatigue" are calculated using one of the Monte Carlo methods based on the random search algorithm. The calculating scheme includes a solution of the extreme task of finding of the minimum of nonnegative transcendent multivariable function, which is a relative average quadratic deviation of calculated values of polymeric nanocomposite stress in comparison with corresponding experimental values. The applicability of the "photocatalytic fatigue" model for polymer nanocomposites with photoactive nanoparticles is confirmed by the example of polypropylene and polyester samples. The approximation error of the experimental strength values for them did not exceed 2%. [ABSTRACT FROM AUTHOR]

This paper aims to consider approximation-estimation tests for decision-making by machine-learning methods, and integral-estimation tests are defined, which is a generalization for the continuous case. Approximation-estimation tests are measurable sampling functions (statistics) that estimate the approximation error of monotonically increasing number sequences in different classes of functions. These tests make it possible to determine the Markov moments of a qualitative change in the increase in such sequences, from linear to nonlinear type. If these sequences are trajectories of discrete quasi-deterministic random processes, then moments of change in the nature of their growth and qualitative change in the process match up. For example, in cluster analysis, approximation-estimation tests are a formal generalization of the "elbow method" heuristic. In solid mechanics, they can be used to determine the proportionality limit for the stress strain curve (boundaries of application of Hooke's law). In molecular biology methods, approximation-estimation tests make it possible to determine the beginning of the exponential phase and the transition to the plateau phase for the curves of fluorescence accumulation of the real-time polymerase chain reaction, etc. [ABSTRACT FROM AUTHOR]

Graphitic carbon nitride (gCN) is a promising n-type semiconductor widely investigated for photo-assisted water splitting, but less studied for the (photo)electrochemical degradation of aqueous organic pollutants. In these fields, attractive perspectives for advancements are offered by a proper engineering of the material properties, e.g., by depositing gCN onto conductive and porous scaffolds, tailoring its nanoscale morphology, and functionalizing it with suitable cocatalysts. The present study reports on a simple and easily controllable synthesis of gCN flakes on Ni foam substrates by electrophoretic deposition (EPD), and on their eventual decoration with Co-based cocatalysts [CoO, CoFe2O4, cobalt phosphate (CoPi)] via radio frequency (RF)-sputtering or electrodeposition. After examining the influence of processing conditions on the material characteristics, the developed systems are comparatively investigated as (photo)anodes for water splitting and photoelectrocatalysts for the degradation of a recalcitrant water pollutant [potassium hydrogen phthalate (KHP)]. The obtained results highlight that while gCN decoration with Co-based cocatalysts boosts water splitting performances, bare gCN as such is more efficient in KHP abatement, due to the occurrence of a different reaction mechanism. The related insights, provided by a multi-technique characterization, may provide valuable guidelines for the implementation of active nanomaterials in environmental remediation and sustainable solar-to-chemical energy conversion. [ABSTRACT FROM AUTHOR]