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A novel immobilized Ca0.6Ho0.4MnO3 photocatalyst has been developed with high photocatalytic activity for Rhodamine 6G (Rh6G) photodegradation under visible light irradiation. The nanocrystalline Ca0.6Ho0.4MnO3 films were successfully deposited by RF-magnetron sputtering on unheated quartz glass substrates using Ca0.6Ho0.4MnO3 powder as sputtering target and its photocatalytic functionalities have been explored. The visible-light-responsive photocatalytic activity of Ca0.6Ho0.4MnO3 films was evaluated by the photodegradation of Rh6G aqueous solutions under visible light irradiation. The reusability of Ca0.6Ho0.4MnO3 films on fresh dye samples was studied, showing an efficient reuse, without decreasing the photocatalytic decolorization efficiency. Furthermore, X-ray diffraction of the reused films did not reveal additional phases indicating high photochemical stability of the films even after reusing them in successive runs. The photocatalytic efficiency of the nanocrystalline Ca0.6Ho0.4MnO3 films was further compared with TiO2 films also produced by sputtering and the results revealed a significant improvement in photocatalytic activity over TiO2 under visible light irradiation. Almost complete photodecolorization of a 5 ppm Rh6G solution was achieved in 4 h, while only 64% of dye degradation was observed in TiO2 photoassisted process. This work provides a feasible route to fabricate high-performance immobilized ABO3-based nanomaterials, and the finding opens up a new venue for designing visible light sensitive ternary compounds for photocatalytical applications. A novel immobilized Ca0.6Ho0.4MnO3 photocatalyst has been developed with high photocatalytic activity for Rhodamine 6G (Rh6G) photodegradation under visible light irradiation. The nanocrystalline Ca0.6Ho0.4MnO3 films were successfully deposited by RF-magnetron sputtering on unheated quartz glass substrates using Ca0.6Ho0.4MnO3 powder as sputtering target and its photocatalytic functionalities have been explored. The visible-light-responsive photocatalytic activity of Ca0.6Ho0.4MnO3 films was evaluated by the photodegradation of Rh6G aqueous solutions under visible light irradiation. The reusability of Ca0.6Ho0.4MnO3 films on fresh dye samples was studied, showing an efficient reuse, without decreasing the photocatalytic decolorization efficiency. Furthermore, X-ray diffraction of the reused films did not reveal additional phases indicating high photochemical stability of the films even after reusing them in successive runs. The photocatalytic efficiency of the nanocrystalline Ca0.6Ho0.4MnO3 films was further compared with TiO2 films also produced by sputtering and the results revealed a significant improvement in photocatalytic activity over TiO2 under visible light irradiation. Almost complete photodecolorization of a 5 ppm Rh6G solution was achieved in 4 h, while only 64% of dye degradation was observed in TiO2 photoassisted process. This work provides a feasible route to fabricate high-performance immobilized ABO3-based nanomaterials, and the finding opens up a new venue for designing visible light sensitive ternary compounds for photocatalytical applications.

The complex [Ph4P]2[Cu(bdt)2] (1(red)) was synthesized by the reaction of [Ph4P]2[S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1(red) is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound [Ph4P][Cu(bdt)2] (1(ox)). The interconversion between these two oxidation states can be switched by addition of O2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV-visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1(red) during its synthesis, since in its absence, 1(ox) is isolated. Both 1(red) and 1(ox) were structurally characterized by X-ray crystallography. EPR experiments showed that 1(red) is a Cu(II)-sulfur complex and revealed strong covalency on the copper-sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1(red) has a "thiyl radical character". Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1(red) is better described by the two isoelectronic structures [Cu(I)(bdt2, 4S(3-,)*)](2-) <--> [Cu(II)(bdt2, 4S(4-))](2-). On thermodynamic grounds, oxidation of 1(red) (doublet state) leads to 1(ox) singlet state, [Cu(III)(bdt2, 4S(4-))](1-).

Ca1-xSmxMnO3 (0≤x≤0.4) films were successfully fabricated on Indium Tin Oxide (ITO) coated quartz glass substrates by radio frequency magnetron sputtering technique (RF- magnetron sputtering) from compacted nanosized powder targets, and subsequent annealing at 800°C in air, for 6h. X-ray diffraction shows a pure typical perovskite phase for x≥0.1. Scanning electron microscopy and atomic force microscopy revealed that the film surface is dense, with low roughness, depending on the Sm content, even though a few cracks were observed. Crystallite size was found to decrease with the Sm content. The electrodes were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS).The oxide electrode's capacitance was estimated using both techniques and the corresponding roughness factors evaluated. The values obtained from the two methods show a good agreement. A comparison between the voltammetric data and those referred in the literature allowed finding out that the redox reaction occurring at the electrode surface involves the pair Mn4+/Mn3+. EIS measurements confirm the voltammetric data and they also give additional information about the film porosity and the charge transfer resistance. This last parameter is associated with the oxidation and reduction of the pair Mn3+/Mn4+and after normalized by the roughness factor shows an increase with samarium content.

We have measured the x-ray spectra from highly charged Si, S and Cl ions in collisions with thin foils using a high-resolution x-ray spectrometer. The observed lines have been assigned to various transitions in H-, He- and Li-like ions. For proper identification of line positions, the theoretical calculations have been carried out using a state-of-the-art MCDF code including QED effects, with which the experimental data is in excellent agreement. We have also observed, for the first time, x-rays arising out of the decay of long-lived resonant states in the He-like ions of each species. Details will be presented.

Systems externally reinforced by bonded fibre reinforced polymers (FRP) are widely used in the retrofitting and strengthening of reinforced concrete (RC) structures. A drawback of the usage of this technique lies on the uncertainty of the long term behaviour of those reinforcements. Researchers have paid heed to this aspect and a number of tests and alternative techniques have recently been described. An experimental programme developed to supplement work of the authors recently published and which focused on specimens not submitted to aggressive environments is described. The specimens used have the same geometry as in the previous paper, but they were exposed to salt fog cycles and dry/wet cycles with salt water for periods of 3000 h, 5000 h and 10,000 h. The interface of the glass fiber polymeric composite (GFRP)-to-concrete was characterized after the systems underwent such aggressive conditions. The GFRP wrap comprised of two layers and wet lay-up technique was used on its preparation and application. The cohesion and friction angle for GFRP-to-concrete interfaces were measured tat selected stages of ageing process and envelope failure laws were obtained based on the Mohr–Coulomb failure criterion. Changes of 27% in cohesion and 8% in the friction angle were found due to the attack of the interface and consequences of the changes are examined.

AbstractThe use of Fibre Reinforced Polymers (FRP) has recently become widespread in the construction industry. However, some drawbacks related to premature debonding of the FRP composites from the bonded substrates have been identified. One of the solutions proposed is the implementation of mechanical anchorage systems. Although some design guidelines have been developed, the actual knowledge continues to be rather limited. Thus, designers and researchers have not yet achieved any consensus on the efficiency of any particular anchor device in delaying or preventing the premature debonding failure mode that can occur in Externally Bonded Reinforcement (EBR) systems. This paper studies the debonding phenomenon of FRP anchoring systems with a linear variable width, with a numerical analysis based on the Distinct Element Method (DEM). Combined systems with constant and variable width are also discussed. The FRP-to-parent material interfaces are modelled with a rigid-linear softening bond–slip law. The numerical results showed that it is possible to attain the FRP rupture force with a variable width solution. This solution is particularly attractive when the bonded length is shorter than the effective bonded length because the strength of the interface can be highly incremented.

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Sustainable supply chain design is nowadays an important topic where not only economic and environmental aspects should be accounted for, but also social aspects are to be considered. A mathematical programming model was developed and a case-study was performed considering two different social indicators: one that prefers facility location in regions of lower GDP and the other in regions of higher unemployment rate. Results show that the outcome depends on the indicator used. However, for the case presented, minimum cost solution also corresponds to a good social solution regarding GDP, which could translate into economic incentives for the company.

The use of Fibre Reinforced Polymers (FRP) has recently become widespread in the construction industry. However, some drawbacks related to premature debonding of the FRP composites from the bonded substrates have been identified. One of the solutions proposed is the implementation of mechanical anchorage systems. Although some design guidelines have been developed, the actual knowledge continues to be rather limited. Thus, designers and researchers have not yet achieved any consensus on the efficiency of any particular anchor device in delaying or preventing the premature debonding failure mode that can occur in Externally Bonded Reinforcement (EBR) systems. This paper studies the debonding phenomenon of FRP anchoring systems with a linear variable width, with a numerical analysis based on the Distinct Element Method (DEM). Combined systems with constant and variable width are also discussed. The FRP-to-parent material interfaces are modelled with a rigid-linear softening bond–slip law. The numerical results showed that it is possible to attain the FRP rupture force with a variable width solution. This solution is particularly attractive when the bonded length is shorter than the effective bonded length because the strength of the interface can be highly incremented.

Apresentam-se neste artigo os resultados dos ensaios realizados à escala real de um conjunto de vigas de betão armado com secção em T, levados a cabo para avaliar o desempenho das armaduras de aço inoxidável no reforço à flexão de vigas de betão armado com armaduras pós-instaladas aplicadas com as técnicas de reforço EBR (Externally Bonded Reinforcement), NSM (Near Surface Mounted) e EBR com ancoragens metálicas nas extremidades. Os ensaios realizados demonstraram que as técnicas de reforço utilizadas permitem aumentar a rigidez à flexão em regime elástico. Porém, a viga reforçada através da técnica EBR teve uma rotura prematura antes de atingir o valor da carga de cedência da viga não reforçada. Já as vigas reforçadas com as técnicas NSM e EBR com ancoragens mecânicas superaram o valor da carga de cedência da viga de referência, e as ancoragens mecânicas proporcionaram bastante ductilidade à viga reforçada com esta técnica.