Joana Vaz Pinto

Thin films of titanium dioxide (TiO2) and titanium (Ti) were deposited onto glass and optical fiber supports through DC magnetron sputtering, and their transmission was characterized with regard to their use in optical fiber-based sensors. Deposition parameters such as oxygen partial pressure, working pressure, and sputtering power were optimized to attain films with a high reflectance. The films deposited on glass supports were characterized by UV-Vis spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Regarding the deposition parameters, all three parameters were tested simultaneously, changing the working pressure, the sputtering power, and the oxygen percentage. It was possible to conclude that a lower working pressure and higher applied power lead to films with a higher reflectance. Through the analysis of the as-sputtered thin films using X-ray diffraction, the deposition of both Ti and TiO2 films was confirmed. To study the applicability of TiO2 and Ti in fiber sensing, several thin films were deposited in single mode fibers (SMFs) using the sputtering conditions that revealed the most promising results in the glass supports. The sputtered TiO2 and Ti thin films were used as mirrors to increase the visibility of a low-finesse Fabry–Perot cavity and the possible sensing applications were studied.

The optimization of tungsten trioxide (WO3) nanoparticles produced via hydrothermal synthesis for application in electrochromic (EC) devices is reported. The structure and morphology of the nanoparticles are controlled by changing the acidity of the aqueous solvent added to the sol-gel precursor (peroxopolytungstic acid) during synthesis. Orthorhombic hydrated WO3 nanorods or monoclinic WO3 nanoslabs are obtained when HCl is added, while synthesis only in aqueous medium results in a mixture of both types of polymorphs. Dual-phase thin films are processed by inkjet printing deposition of the nanoparticles in flexible polyethylene terephthalate substrate with indium tin oxide coating (ITO PET) followed by the deposition of the precursor solution. When compared with purely amorphous tungsten oxide films, the dual phase ones present higher optical densities and improved capacity, and cyclability stability. The best results, obtained for orthorhombic hydrated nanoparticles (ortho-WO3·0.33H2O), are due to its high surface area and improved conductivity. Additionally, the ex situ X-ray diffraction (XRD) lithiation studies show evidence of a higher distortion of the monoclinic when compared with the orthorhombic crystallographic structure, which contribute to the inferior EC performance. These results validate the use of inkjet printing deposition with low processing temperatures for EC dual-phase thin films containing optimized nanoparticles which are compatible with low-cost substrates.

In this work we report the role of thickness on electrochromic behavior of nickel oxide (NiO) films deposited by e-beam evaporation at room temperature on ITO-coated glass. The structure and morphology of films with thicknesses between 100 and 500 nm were analyzed and then correlated with electrochemical response and transmittance modulation when immersed in 0.5 M LiClO4–PC electrolyte. The NiO exhibits an anodic coloration, reaching for the thickest film a transmittance modulation of 66% between colored and bleached state, at 630 nm, with a color efficiency of 55 cm2 C−1. Very fast switch between states was obtained, where coloration and bleaching times are 3.6 s cm−2 and 1.4 s cm−2, respectively.

© 2017 Elsevier Ltd. Graphical abstract: The electrochemical reduction of carbon dioxide dissolved in a solution of water and ionic liquid as electrolyte, at high-pressure and near room-temperature, is reported. This work describes an electro-deposition strategy for the preparation of copper substrate cathodes, coated with bimetallic zinc-copper films, obtained from deep-eutectic solvents plating baths. The prepared bimetallic cathodes showed electrochemical activity for syngas production in 1-butyl-3-methylimidazolium triflate, with yields of 85N$μ$L (normal microliter)cm−2C−1/170N$μ$Lcm−2h−1, high selectivities, tunable H2/CO ratio and low energetic requirements.

The Winsor & NewtonTM (W&N) nineteenth century archive database includes digitised images of hand- written instructions and workshop notes for the manufacture of their artists' materials. For the first time, all 183 production records for yellow lead chromate pigments were studied and evaluated. They revealed that W&N produced essentially three pigment types: lemon/pale based on mixed crystals of lead chromate and lead sulphate [Pb(Cr,S)O4]; middle on pure monoclinic lead chromate [PbCrO4]; and deep that contains the latter admixed with basic lead chromate [Pb2CrO5]; accounting for 53, 22, and 21% of the production, respectively. Production records for primrose (4%) were also included since the formulation results in mixed crystals with a high percentage of lead sulphate, which, according to the literature, leaves it more prone to degradation. Each pigment type is characterised by only one or two main synthetic pathways; process variations reveal a systematic and thorough search for a high-quality durable product. A comparison of the chemical composition of pigment reconstructions with early W&N oil paint tubes showed that their records entitled ‘pale' and ‘lemon' correlated with the pigment in their tube labelled chrome yellow and, ‘middle' and ‘deep' with the label chrome deep. Lemon and middle pigment formulations were made into oil paints to assess their relative photo-stability. The degradation process was followed by colorimetry and was studied by synchrotron radiation-based techniques. Based on the X-ray absorption spectroscopy data, the possibility for creating a stability index for chrome yellows is discussed. Keywords:

© 2017 The Author(s). This work focuses on the study of the 19th century yellow chromate pigments based on barium (BaCrO4), zinc (4ZnCrO4K2O3H2O) and strontium (SrCrO4). These pigments, which are reported to shift in hue and darken, have been found in 19th century artworks. A better understanding of their historic manufacture will contribute to the visual/chemical interpretation of change in these colours. Research was carried out on the Winsor & Newton (W&N) 19th century archive database providing a unique insight into their manufacturing processes. One hundred and three production records were found, 69% for barium, 25% for zinc and 6% for strontium chromates, mainly under the names Lemon, Citron and Strontian Yellow, respectively. Analysis of the records shows that each pigment is characterised by only one synthetic pathway. The low number of records found for the production of strontium chromate suggests W&N was not selling this pigment formulation on a large scale. Furthermore, contrary to what the authors have discovered for W&N chrome yellow pigments, extenders were not added to these pigment formulations, most probably due to their lower tinting strength (TS). The latter was calculated in comparison to pure chrome yellow (PbCrO4, 100% TS) resulting in 92% for barium, 65% for zinc potassium and 78% for strontium chromate pigments. This indicates that W&N was probably using extenders primarily to adjust pigment properties and not necessarily as a means to reduce their costs. Pigment reconstructions following the main methods of synthesis were characterised by complementary analytical techniques: Fibre optic reflectance spectroscopy, X-ray diffraction, micro-Raman and micro-Fourier transform infrared spectroscopies. These pigments can be clearly distinguished on the basis of their infrared CrO42-asymmetric stretching fingerprint profile (between 1000 and 700 cm-1) and of their Raman CrO42-stretching bands (850-950 cm-1). This enabled their identification in historic paint samples: a tube of late 19th century W&N Lemon Yellow oil paint and micro-samples from paintings by three Portuguese painters, António Silva Porto (1850-1893), João Marques de Oliveira (1853-1927) and Amadeo de Souza-Cardoso (1887-1918). The good correlation found between the reconstructions and historic samples validates their use as reference materials for future photochemical studies.

Titanium dioxide was synthesized on glass substrates from titanium (IV)isopropoxide and hydrochloride acid aqueous solutions through microwave irradiation using as seed layer either fluorine-doped crystalline tin oxide (SnO2:F) or amorphous tin oxide (a-SnOx). Three routes have been followed with distinct outcome: (i) equimolar hydrochloride acid/water proportions (1HCl:1water) resulted in nanorod arrays for both seed layers; (ii) higher water proportion (1HCl:3water) originated denser films with growth yield dependent on the seed layer employed; while (iii) higher acid proportion (3HCl:1water) hindered the formation of TiO2. X-ray diffraction (XRD) showed that the materials crystallized with the rutile structure, possibly with minute fractions of brookite and/or anatase. XRD peak inversions observed for the materials synthesized on crystalline seeds pointed to preferred crystallographic orientation. Electron diffraction showed that the especially strong XRD peak inversions observed for TiO2 grown from the 1HCl:3water solution on SnO2:F originated from a [001] fiber texture. Transmittance spectrophotometry showed that the materials with finer structure exhibited significantly higher optical band gaps. Photocatalytic activity was assessed from methylene blue degradation, with the 1HCl:3water SnO2:F material showing remarkable degradability performance, attributed to a higher exposure of (001) facets, together with stability and reusability.

The present work reports a simple and easy wet chemistry synthesis of cuprous oxide (Cu2O) nanospheres at room temperature without surfactants and using different precursors. Structural characterization was carried out by X-ray diffraction, transmission electron microscopy, and scanning electron microscopy coupled with focused ion beam and energy-dispersive X-ray spectroscopy. The optical band gaps were determined from diffuse reflectance spectroscopy. The photoluminescence behavior of the as-synthesized nanospheres showed significant differences depending on the precursors used. The Cu2O nanospheres were constituted by aggregates of nanocrystals, in which an on/off emission behavior of each individual nanocrystal was identified during transmission electron microscopy observations. The thermal behavior of the Cu2O nanospheres was investigated with in situ X-ray diffraction and differential scanning calorimetry experiments. Remarkable structural differences were observed for the nanospheres annealed in air, which turned into hollow spherical structures surrounded by outsized nanocrystals. FAU - Nunes, Daniela

The presentwork reports charging effects and surface potential variations in pure copper, cuprous oxide and cu- pric oxide nanowires observed by electrostatic force microscopy (EFM) and Kelvin probe force microscopy (KPFM). The copper nanowires were produced by wet synthesis, oxidation into cuprous oxide nanowires was achieved throughmicrowave irradiation and cupric oxide nanowireswere obtained via furnace annealing in at- mospheric conditions. Structural characterization of the nanowireswas carried out byX-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. During the EFM experiments the electrostatic field of the positive probe charged negatively the Cu-based nanowires, which in turn polarized the SiO2 dielectric substrate. Both the probe/nanowire capacitance as well as the sub- strate polarization increased with the applied bias. Cu2O and CuO nanowires behaved distinctively during the EFMmeasurements in accordancewith their band gap energies. Thework functions(WF) of the Cu-based nano- wires, obtained by KPFM measurements, yieldedWFCuO N WFCu N WFCu2O

© 2015 Elsevier B.V. Titanium dioxide was synthesized on glass substrates from titanium (IV)isopropoxide and hydrochloride acid aqueous solutions through microwave irradiation using as seed layer either fluorine-doped crystalline tin oxide (SnO2:F) or amorphous tin oxide (a-SnOx). Three routes have been followed with distinct outcome: (i) equimolar hydrochloride acid/water proportions (1HCl:1water) resulted in nanorod arrays for both seed layers; (ii) higher water proportion (1HCl:3water) originated denser films with growth yield dependent on the seed layer employed; while (iii) higher acid proportion (3HCl:1water) hindered the formation of TiO2. X-ray diffraction (XRD) showed that the materials crystallized with the rutile structure, possibly with minute fractions of brookite and/or anatase. XRD peak inversions observed for the materials synthesized on crystalline seeds pointed to preferred crystallographic orientation. Electron diffraction showed that the especially strong XRD peak inversions observed for TiO2 grown from the 1HCl:3water solution on SnO2:F originated from a [001] fiber texture. Transmittance spectrophotometry showed that the materials with finer structure exhibited significantly higher optical band gaps. Photocatalytic activity was assessed from methylene blue degradation, with the 1HCl:3water SnO2:F material showing remarkable degradability performance, attributed to a higher exposure of (001) facets, together with stability and reusability.