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The amount of counterions in layer-by-layer (LBL) films of poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS) has been determined with X-ray photoelectron spectroscopy (XPS) for films prepared from solutions with various NaCl concentrations. Sodium and chloride counterions are present in LBL films produced from salt solutions, which are located at the surface and in the bulk of the films. The percentage of bulk counterions increases with the ionic strength of the polyelectrolyte before reaching a constant value. The bulk sodium/sulfur percentage ratios tend to 0.8 for samples washed with pure water and for samples washed with NaCl aqueous solutions, while the bulk chlorine/nitrogen percentage ratios tend to 0.5 for the same samples. The ratio between the percentages of polyelectrolyte ionic groups lies close to unity for all samples, indicating that counterions do not contribute to charge compensation in the polyelectrolyte during the adsorption process. The presence of counterions in LBL films is explained by Manning condensation near the polyelectrolyte ionic groups, leading to inter-polyelectrolyte ionic bondings via ionic networks. It is believed that condensation leads to the formation of NaCl crystallites in these LBL films, which was confirmed by X-ray diffraction measurements.

a b s t r a c tMany aspects of bronze production during Late Bronze Age in Western Europe are so far unknown. In the present study selected artefact fragments and metallurgical debris, which include a slag fragment, from the emblematic Late Bronze Age habitat site of Castro da Senhora da Guia de Baiões (Viseu, Portugal) have been studied by optical microscopy, micro-EDXRF, SEM-EDS and XRD. Evidences were found for bronze production involving smelting and recycling. Compositional analysis showed that the artefacts are made of a bronze with 13 AE 3 wt.% Sn (average and one standard deviation) and a low impurity pattern, namely <0.1 wt.% Pb, being comparable with the composition of other bronzes from the same region (the Central Portuguese Beiras). This alloy is generally different from elsewhere Atlantic and Mediterranean bronzes, which show frequently slightly lower Sn contents and higher impurity patterns, namely Pb which is often present as an alloying element. The present study gives further support to early proposals suggesting the exploration of the Western Iberian tin resources during Late Bronze Age, and besides that, it indicates that metalworking and smelting could have been a commonplace activity requiring no specific facilities, being bronze produced at a domestic scale in this Western extreme of Europe.

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Novel bionanocomposite films of chitosan/montmorillonite (CS/MMT) activated with ginger essential oil (GEO) were produced and characterized in terms of their physical and morphological properties. The homogenization process led to a good interaction between the chitosan and the nanoparticles, however the exfoliation was diminished when GEO was incorporated. Film glass transition temperature did not statistically change with the incorporation of either MMT or GEO, however the value was slightly reduced, representing a relaxation in the polymer chain which corroborated with the mechanical and barrier properties results. Pristine chitosan films showed excellent barrier properties to oxygen with a permeability of 0.184 × 10−16 mol/m·s·Pa being reduced to half (0.098 × 10−16 mol/m·s·Pa) when MMT was incorporated. Although the incorporation of GEO increased the permeability values to 0.325 × 10−16 mol/m·s·Pa when 2% of GEO was integrated, this increment was smaller with both MMT and GEO (0.285 × 10−16 mol/m·s·Pa). Bionanocomposites also increased the UV light barrier. Thus, the produced bioplastics demonstrated their ability to retard oxidative processes due to their good barrier properties, corroborating previous results that have shown their potential in the preservation of foods with high unsaturated fat content.