Aqueous Dispersions of Nanostructured Particles Hybridized with Mono- and Multifunctional POSS Methacrylates: Heterophase Polymerization and Material Properties of the Resulting Latex Films

The synthesis of aqueous dispersions of hybrid acrylic copolymer particles containing either a monofunctional or a multifunctional oligomeric silsesquioxane as a comonomer has been performed by heterophase free radical polymerization. The miniemulsion process allowed to produce stable latexes, as opposed to the less controlled emulsion route. The thermal, mechanical and surface properties of the nanocomposite latex films have been investigated

Confinement Effect in Diffusion-Controlled Stepwise Polymerization by Monte Carlo Simulation

Diffusion-controlled stepwise polymerization of a linear polymer confined in nanoscopic slits is simulated through a Monte Carlo approach. A noticeable influence of the confinement on the kinetics is found. The confinement modifies both the spatial pair distribution function and the diffusive properties of the polymers. As a consequence, the confined system can show either faster or slower reaction kinetics with respect to the bulk system, depending on the strength of intermolecular interactions. The predicted polydispersity of the polymer is in agreement with recent theories of diffusion-controlled stepwise polymerization, and can be slightly affected by the confinement.

Mutual Information in Molecular and Macromolecular Systems

The relaxation properties of viscous liquids close to their glass transition (GT) have been widely characterised by the statistical tool of time correlation functions. However, the strong influence of ubiquitous non-linearities calls for new, alternative tools of analysis. In this respect, information theory-based observables and, more specifically, mutual information (MI) are gaining increasing interest. Here, we report on novel, deeper insight provided by MI-based analysis of molecular dynamics simulations of molecular and macromolecular glass-formers on two distinct aspects of transport and relaxation close to GT, namely dynamical heterogeneity (DH) and secondary Johari–Goldstein (JG) relaxation processes. In a model molecular liquid with significant DH, MI reveals two populations of particles organised in clusters having either filamentous or compact globular structures that exhibit different mobility and relaxation properties. In a model polymer melt, MI provides clearer evidence of JG secondary relaxation and sharper insight into its DH. It is found that both DH and MI between the orientation and the displacement of the bonds reach (local) maxima at the time scales of the primary and JG secondary relaxation. This suggests that, in (macro)molecular systems, the mechanistic explanation of both DH and relaxation must involve rotation/translation coupling

Alkoxysilane functional acrylic latexes: influence of copolymer composition on self-curing behavior and film properties

Reactive latexes based on acrylic polymers with trimethoxysilyl groups in the side chain were prepared by semi-continuous emulsion copolymerization. The properties of the latex film related to the polymer network structure and their evolution upon thermal curing were studied as a function of the content of the reactive comonomer, trimethoxysilylpropyl methacrylate (TSPMA), ranging between 8 and 25 wt-%. In particular, the sensitivity to both organic solvent (chloroform) and water and the thermomechanical properties were investigated by swelling experiments and dynamic-mechanical analysis (DMA). The results are interpreted in terms of a transition from uniform to microheterogeneous crosslinking regime, possibly as the result of formation of polyorganosilsesquioxane-like (POSS) crosslinking domains at higher TSPMA content

Coincident Correlation between Vibrational Dynamics and Primary Relaxation of Polymers with Strong or Weak Johari-Goldstein Relaxation

The correlation between the vibrational dynamics, as sensed by the Debye-Waller factor, and the primary relaxation in the presence of secondary Johari-Goldstein (JG) relaxation, has been investigated through molecular dynamics simulations. Two melts of polymer chains with different bond length, resulting in rather different strength of the JG relaxation are studied. We focus on the bond-orientation correlation function, exhibiting higher JG sensitivity with respect to alternatives provided by torsional autocorrelation function and intermediate scattering function. We find that, even if changing the bond length alters both the strength and the relaxation time of the JG relaxation, it leaves unaffected the correlation between the vibrational dynamics and the primary relaxation. The finding is in harmony with previous studies reporting that numerical models not showing secondary relaxations exhibit striking agreement with experimental data of polymers also where the presence of JG relaxation is known

The harsh rule of the goals: Data-driven performance indicators for football teams

Sports analytics in general, and football (soccer in USA) analytics in particular, have evolved in recent years in an amazing way, thanks to automated or semi-automated sensing technologies that provide high-fidelity data streams extracted from every game. In this paper we propose a data-driven approach and show that there is a large potential to boost the understanding of football team performance. From observational data of football games we extract a set of pass-based performance indicators and summarize them in the H indicator. We observe a strong correlation among the proposed indicator and the success of a team, and therefore perform a simulation on the four major European championships (78 teams, almost 1500 games). The outcome of each game in the championship was replaced by a synthetic outcome (win, loss or draw) based on the performance indicators computed for each team. We found that the final rankings in the simulated championships are very close to the actual rankings in the real championships, and show that teams with high ranking error show extreme values of a defense/attack efficiency measure, the Pezzali score. Our results are surprising given the simplicity of the proposed indicators, suggesting that a complex systems' view on football data has the potential of revealing hidden patterns and behavior of superior quality