Márcia Vilarigues

Characterisation of corrosion products in Cr implanted Mg surfaces

In this work we used medium and high fluence Cr implantation, 5×1016 and 5×1017/cm2 in an attempt to promote the formation of a Mg–Cr surface system with enhanced corrosion resistance, in particular under neutral and acid conditions. It is also the aim of this work to contribute to the study of the influence and role of the implanted ions in the corrosion progress and mechanisms. Unimplanted and Cr implanted magnesium surfaces were submitted to accelerated corrosion tests by the immersion technique. Concentration depth profiles of the implanted ions were obtained by use of Rutherford backscattering spectrometry (RBS). Information about the H and O contents and depth profiles were obtained by, respectively, elastic recoil detection and RBS, before and after immersion of the unimplanted and implanted surfaces in a 3 wt.% NaCl solution saturated with Mg(OH)2, for different periods of time. The elemental composition and surface distribution of the corroded surfaces were characterised by RBS and proton induced X-ray emission maps obtained with an ion microprobe, and complemented with electron microprobe analysis. Morphology of the affected surfaces was accessed by scanning electron microscopy.

Ochres and earths: matrix and chromophores characterization of 19th and 20th century artist materials.

The present paper describes the main results obtained from the characterization of a wide range of natural and synthetic ochre samples used in Portugal from the 19th to the 20th century, including powder and oil painting samples. The powder ochre samples came from several commercial distributors and from the collection of Joaquim Rodrigo (1912-1997), a leading Portuguese artist, particularly active during the sixties and seventies. The micro-samples of oil painting tubes came from the Museu Nacional de Arte Contemporânea-Museu do Chiado (National Museum of Contemporary Art-Chiado Museum) in Lisbon and were used by Columbano Bordalo Pinheiro (1857-1929), one of the most prominent naturalist Portuguese painters. These tubes were produced by the main 19th century colourmen: Winsor & Newton, Morin et Janet, Maison Merlin, and Lefranc. The samples have been studied using μ-Fourier Transform Infrared Spectroscopy (μ-FTIR), Raman microscopy, μ-Energy Dispersive X-ray fluorescence (μ-EDXRF), and X-ray diffraction (XRD). The analyzed ochres were found to be a mixture of several components: iron oxides and hydroxides in matrixes with kaolinite, gypsum and chalk. The results obtained allowed to identify and characterize the ochres according to their matrix and chromophores. The main chromophores where identified by Raman microscopy as being hematite, goethite and magnetite. The infrared analysis of the ochre samples allowed to divide them into groups, according to the composition of the matrix. It was possible to separate ochres containing kaolinite matrix and/or sulfate matrix from ochres where only iron oxides and/or hydroxides were detected. μ-EDXRF and Raman were the best techniques to identify umber, since the presence of elements such as manganese is characteristic of these pigments. μ-EDXRF also revealed the presence of significant amounts of arsenic in all Sienna tube paints.

Hydrogen plasma treatment of very thin p-type nanocrystalline Si films grown by RF-PECVD in the presence of B(CH3)3

Abstract We have characterized the structure and electrical properties of p-type nanocrystalline silicon films prepared by radio-frequency plasma-enhanced chemical vapor deposition and explored optimization methods of such layers for potential applications in thin-film solar cells. Particular attention was paid to the characterization of very thin (∼20 nm) films. The cross-sectional morphology of the layers was studied by fitting the ellipsometry spectra using a multilayer model. The results suggest that the crystallization process in a high-pressure growth regime is mostly realized through a subsurface mechanism in the absence of the incubation layer at the substrate-film interface. Hydrogen plasma treatment of a 22-nm-thick film improved its electrical properties (conductivity increased more than ten times) owing to hydrogen insertion and Si structure rearrangements throughout the entire thickness of the film.

Characterization of a Novel Intrinsic Luminescent Room‐Temperature Ionic Liquid Based on [P6,6,6,14][ANS]

Intrinsically luminescent room-temperature ionic liquids (RTILs) can be prepared by combining a luminescent anion (more common) or cation with appropriate counter ions, rendering new luminescent soft materials. These RTILs are still new, and many of their photochemical properties are not well known. A novel intrinsic luminescent RTIL based on the 8-anilinonaphthalene-1-sulfonate ([ANS]) anion combined with the trihexyltetradecylphosphonium ([P6,6,6,14 ]) cation was prepared and characterized by spectroscopic techniques. Detailed photophysical studies highlight the influence of the ionic liquid environment on the ANS fluorescence, which together with rheological and (1) H NMR experiments illustrate the effects of both the viscosity and electrostatic interactions between the ions. This material is liquid at room temperature and possesses a glass transition temperature (Tg ) of 230.4 K. The fluorescence is not highly sensitive to factors such as temperature, but owing to its high viscosity, dynamic Stokes shift measurements reveal very slow components for the IL relaxation.

Nineteenth century chrome yellow and chrome deep from Winsor & NewtonTM

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.

Statistics of colors in paintings and natural scenes

Painters reproduce some spatial statistical regularities of natural scenes. To what extent they replicate their color statistics is an open question. We investigated this question by analyzing the colors of 50 natural scenes of rural and urban environments and 44 paintings with abstract and figurative compositions. The analysis was carried out using hyperspectral imaging data from both sets and focused on the gamut and distribution of colors in the CIELAB space. The results showed that paintings, like natural scenes, have gamuts with elongated shapes in the yellow-blue direction but more tilted to the red direction. It was also found that the fraction of discernible colors, expressed as a function of the number of occurrences in the scene or painting, is well described by power laws. These have similar distribution of slopes in a log-log scale for paintings and natural scenes. These features are observed in both abstract and figurative compositions. These results suggest that the underlying chromatic structure of artistic compositions generally follows the main statistical features of the natural environment.

Features combination for art authentication studies: brushstroke and materials analysis of Amadeo de Souza-Cardoso

This work presents a tool to support authentication studies of paintings attributed to the modernist Portuguese artist Amadeo de Souza-Cardoso (1887-1918). The strategy adopted was to quantify and combine the information extracted from the analysis of the brushstroke with information on the pigments present in the paintings. The brushstroke analysis was performed combining Gabor filter and Scale Invariant Feature Transform. Hyperspectral imaging and elemental analysis were used to compare the materials in the painting with those present in a database of oil paint tubes used by the artist. The outputs of the tool are a quantitative indicator for authenticity, and a mapping image that indicates the areas where materials not coherent with Amadeo’s palette were detected, if any. This output is a simple and effective way of assessing the results of the system. The method was tested in twelve paintings obtaining promising results.

First archaeometric study on medieval glass found in Beja (Southern Portugal)

ABSTRACT During an archaeological intervention that took place in Beja (southern Portugal), at Avenida Miguel Fernandes, between August 2003 and March 2004, a set of 137 silos was discovered. The excavation yielded an assemblage of glass that can be dated between the fourteenth and the seventeenth centuries. For this investigation only the fragments from the medieval contexts were considered in order to provide an overview of the use of glass vessels in a Portuguese town in the fourteenth and fifteenth centuries. A group of eleven medieval glass fragments was chemically characterised by means of µ-PIXE (particle-induced X-ray emission) and UV-vis reflectance spectroscopy. Analysis by µ-PIXE enabled the determination of the chemical composition, and UV-vis reflectance spectroscopy was used as a complementary technique to identify the metallic elements responsible for different colours observed in the glasses. Results showed that the analysed objects are in the majority made of a soda-lime silica glass, indicating a connection with the Mediterranean tradition. Cobalt and copper were the colorants used to obtain the blue and turquoise glasses, respectively, whereas iron is responsible for the green and yellow colours.

Estimating the Colors of Paintings

Observers can adjust the spectrum of illumination on paintings for optimal viewing experience. But can they adjust the colors of paintings for the best visual impression? In an experiment carried out on a calibrated color monitor images of four abstract paintings obtained from hyperspectral data were shown to observers that were unfamiliar with the paintings. The color volume of the images could be manipulated by rotating the volume around the axis through the average (a*, b*) point for each painting in CIELAB color space. The task of the observers was to adjust the angle of rotation to produce the best subjective impression from the paintings. It was found that the distribution of angles selected for data pooled across paintings and observers could be described by a Gaussian function centered at 10o, i.e. very close to the original colors of the paintings. This result suggest that painters are able to predict well what compositions of colors observers prefer.

Swiss Stained-Glass Panels: An Analytical Study

The history and iconography of Swiss stained glass dating between the 16th and 18th centuries are well studied. However, the chemical and morphological characteristics of the glass and glass paints, particularly the nature of the raw materials, the provenance of the glass, and the technology used to produce it are less well understood. In this paper, we studied two sets of samples from stained-glass panels attributed to Switzerland, which date from the 16th to 17th centuries: the first set comes from Pena National Palace collection, the second from Vitrocentre Romont. The aims were to identify the materials used in the production of the glass, to find out more about their production origin and to characterize the glass paints. Both glass and the glass paints were analysed by particle-induced X-ray emission; the paints were additionally analysed by scanning electron microscopy-electron-dispersive X-ray spectroscopy (SEM-EDS). The results show that the glass from both sets was probably produced in the same region and that wood ash was used as a fluxing agent. Different recipes have been used to make the blue enamels. However, the cobalt ore used as a coloring agent in all of the blue enamels came from the mining district in Schneeberg, Germany.