Long-term durability study of perfluoropolymer membranes in low humidification conditions

This paper reports a study on the understanding of the performance decrease mechanisms of polymer electrolyte fuel cells under critical operating conditions. In order to investigate the durability of perfluorosulfonate membranes at low humidification conditions, long-term fuel cell tests have been carried out. Results evidenced a strong effect of low relative humidity on the commercial polymer membrane lifetime. Prolonged dehydration of the membranes led to a decrease of the three-dimensional reaction zone due to the ionomer degradation in the catalytic layer and a continuous loss of material in the membrane evidenced by a thickness decrease. The last effect provoked a collapse of the electrode structure.     

Supramolecular architectures of metal–organic host–guest compounds

Metal?Corganic frameworks are a class of materials with new and interesting properties (Angew Chem Int Ed 43:2334, 2004; Coorg Chem Rev 38:1213, 2009; Adv Mater 23:249, 2011). In particular, porous metal organic systems are attracting considerable interest because of their potential use as sensors, catalysts and, in general, in host?Cguest chemistry (Acc Chem Res 43:1115, 2010). The so-called ??wheel and axle?? compounds play an important role in the developing of supramolecular chemistry and there are a lot of studies dealing with their inclusion properties and host?Cguest chemistry (Comprehensive supramolecular chemistry, 1996). Classical ??wheel and axle?? molecules have a long, thin, central part (the axle) with two bulky ends (the wheels). Here, new compounds with host properties are described, that we called ??wheel and axle metal?Corganic?? diols (WAMOD), that are decorated with OH groups in the wheel. In particular, their clathration properties are discussed in connection with their crystal structures. A modular strategy is applied to obtain WAMODs: coordination chemistry is used together with soft interactions (H-bond, ?ШC?? interaction), with the aim to realize a dynamic framework that is able to reversibly capture and release a guest. The coordination bond is robust and permits to obtain WAMODs with different arrangements of the axle; the hydrogen bonds and/or the other soft interactions are responsible for the thin adjustments in the crystal packing that allow reversible adsorption/desorption of the guest.     

Distance dependent quenching effect in nanoparticle dimers

In this paper, we investigate the emission characteristics of a molecule placed in the gap of a nanoparticle dimer configuration. The emission process is described in terms of a local field enhancement factor and the overall quantum yield of the system. The molecule is represented as a dipolar source, with fixed length and fed by a constant current. We first describe the coupled dimer-molecule system and compare these results to a single sphere-molecule system. Next, the effect of dimer size is investigated by changing the radius of the nanoparticles. We find that when the radius increases, a saturation effect occurs that trends towards the case of a radiating dipole between two flat interfaces, which we refer to as a parallel plate waveguide geometry. An analytical solution for the parallel plate waveguide geometry is presented and compared to the results for the spherical dimer configuration. We use this approximation as a reference solution, and also, it provides useful guidelines to understand the physical mechanism behind the energy transfer between the molecule and the dimer. We find that the emission intensity undergoes a quenching effect only when the inter-nanoparticle gap distance of the dimer is very small, meaning that strong coupling prevails over energy engaged in the heating process unless the molecule is extremely close to the metal surface.     

Thiocyanate-free cyclometalated ruthenium sensitizers for solar cells based on heteroaromatic-substituted 2-arylpyridines

The first examples of thiocyanate-free thiophene-substituted Ru(ii) cyclometalated complexes, based on thiophene-derived 2-(2,4-difluorophenyl)pyridine ligands, are presented and investigated as photosensitizers in DSCs. Upon thiophene substitution the complexes presented enhanced optical properties compared to the reference dye with no thiophene substitution. DSCs based on the dithienyl-derived dye showed power conversion efficiencies up to 5.7%, more than twice that containing the complex without the thiophene substitution.     

A phase-field model for quasi-incompressible solid–liquid transitions

According to a unified thermodynamic scheme, we derive the general kinetic equation ruling the phase-field evolution in a binary quasi-incompressible mixture for both transition and separation phenomena. When diffusion effects are negligible in comparison with source and production terms, a solid–liquid phase transition induced by temperature and pressure variations is obtained. In particular, we recover the explicit expression of the liquid–pressure curve separating the solid from the liquid stability regions in the pressure–temperature plane. Consistently with physical evidence, its slope is positive (negative) for substances which compress (expand) during the freezing process.     

Social Influence Maximization in Hypergraphs

This work deals with a generalization of the minimum Target Set Selection (TSS) problem, a key algorithmic question in information diffusion research due to its potential commercial value. Firstly proposed by Kempe et al., the TSS problem is based on a linear threshold diffusion model defined on an input graph with node thresholds, quantifying the hardness to influence each node. The goal is to find the smaller set of items that can influence the whole network according to the diffusion model defined. This study generalizes the TSS problem on networks characterized by many-to-many relationships modeled via hypergraphs. Specifically, we introduce a linear threshold diffusion process on such structures, which evolves as follows. Let H=(V,E) be a hypergraph. At the beginning of the process, the nodes in a given set S⊆V are influenced. Then, at each iteration, (i) the influenced hyperedges set is augmented by all edges having a sufficiently large number of influenced nodes; (ii) consequently, the set of influenced nodes is enlarged by all the nodes having a sufficiently large number of already influenced hyperedges. The process ends when no new nodes can be influenced. Exploiting this diffusion model, we define the minimum Target Set Selection problem on hypergraphs (TSSH). Being the problem NP-hard (as it generalizes the TSS problem), we introduce four heuristics and provide an extensive evaluation on real-world networks.     

A thermodynamically consistent Ginzburg–Landau model for superfluid transition in liquid helium

In this paper, we propose a thermodynamically consistent model for superfluid-normal phase transition in liquid helium, accounting for variations of temperature and density. The phase transition is described by means of an order parameter, according to the Ginzburg–Landau theory, emphasizing the analogies between superfluidity and superconductivity. The normal component of the velocity is assumed to be compressible, and the usual phase diagram of liquid helium is recovered. Moreover, the continuity equation leads to a dependence between density and temperature in agreement with the experimental data.     

Attractors for a class of semi-linear degenerate parabolic equations

We consider degenerate parabolic equations of the form $$\left. \begin{array}{ll}\,\,\, \partial_t u = \Delta_\lambda u + f(u) \\u|_{\partial\Omega} = 0, u|_{t=0} = u_0\end{array}\right.$$ in a bounded domain ${\Omega\subset\mathbb{R}^N}$ , where Δ_λ is a subelliptic operator of the type $$\quad \Delta_\lambda:= \sum_{i=1}^{N} \partial_{x_i}(\lambda_{i}^{2} \partial_{x_i}),\qquad \lambda = (\lambda_1,\ldots, \lambda_N).$$ We prove global existence of solutions and characterize their longtime behavior. In particular, we show the existence and finite fractal dimension of the global attractor of the generated semigroup and the convergence of solutions to an equilibrium solution when time tends to infinity.     

Enhancement of silicon solar cell performances due to light trapping by colloidal metal nanoparticles

Photovoltaics is the most promising technology for the future of green energy production. To fully realize the potential use of photovoltaic technology, low manufacturing cost and high working photoconversion efficiency must be obtained. Light trapping by metal nanoparticles is an attractive strategy in thin film as well as in bulk silicon solar cells aimed to confine light within the active layer to promote the photon absorption and therefore achieving higher efficiency. In this paper, we tested the deposition of silver and gold nanoparticles on bulk silicon solar cells by colloidal technique in order to enhance their photovoltaic conversion efficiency by means of Plasmonic Light Scattering by metal nanoparticles. The feasible Plasmonic Light Scattering related enhancement was examined using spectral response and I–V measurements. Relative increases of the total delivered power under simulated solar irradiation were observed for cells both with and without antireflection coating using silver and gold nanoparticles.     

Characterisation of historic plastics using terahertz time-domain spectroscopy and pulsed imaging

Terahertz (THz) time-domain spectroscopy and 3D THz pulsed imaging have been explored with regard to polymer materials, both commodity and historic polymers. A systematic spectroscopic study of a wide range of different polymer materials showed significant differences in their spectra. Polyolefins and polystyrenes generally exhibit lower absorption than other examined polymers, various cellulose derivates, poly(vinyl chloride), poly(methyl methacrylate), polyamide, hard rubber and phenol formaldehyde resin, the last of these exhibiting the most intense absorption over the entire range, 0.15–4.2 THz. It was also examined how the presence of plasticisers in poly(vinyl chloride), the presence of fillers in polypropylene, and the degree of branching in polyethylene and polystyrene affect the spectra; inorganic fillers in polypropylene affected the absorption most. With 3D THz pulsed imaging, features in polymer objects were explored, appearing either as integral parts of the material (coatings and pores in foams) or as a consequence of physical deterioration (cracks, delamination). All of these features of various complexities can be successfully imaged in 3D. Terahertz technology is thus shown to have significant potential for both chemical and structural characterisation of polymers, which will be of interest to heritage science, but also to the polymer industry and development of analytical technologies in general.