La restauración del Retrato Trivulzio de Antonello da Messina

El artículo presenta la intervención llevada a cabo en 2006 sobre el Retrato de hombre de Antonello da Messina, que pertenece a las colecciones del Museo Cívico de Arte Antiguo del Palacio Madame. The article presents the intervention carried out in 2006 about the Portrait of a man of Antonello da Messina, which belongs to the collections of the Civic Museum of Ancient Art of the Madame Palace.El artículo presenta la intervención llevada a cabo en 2006 sobre el Retrato de hombre de Antonello da Messina, que pertenece a las colecciones del Museo Cívico de Arte Antiguo del Palacio Madame.&nbsp

Basic features of Ne*–HX (X = Cl, Br) chemi-ionization reactions

Total and partial ionization cross sections for Ne*(3P2,0)–HX (X ¼ Cl, Br) are presented in a comparative way as a function of the collision energy between 0.02–0.5 eV. New mass spectrometric data on Ne*–HBr chemi-ionization are discussed and analyzed with already published data on Ne*–HCl, highlighting similarities and differences of the collisional stereodynamics of the two systems. Basic features of the interaction potentials, driving reactive collisions, suggest that reaction channels, leading to the formation of parent HX+ ions in the ground and excited electronic state and to the formation of associated NeHX+ ions as well as of NeH+ proton transfer species, are selectively opened within angular cones exhibiting different orientation and acceptance

Chromium speciation methods and infrared spectroscopy for studying the chemical reactivity of lead chromate-based pigments in oil medium

Environmental factors, such as light, humidity and temperature are triggering agents for the alteration of organic and/or inorganic constituents of oil paintings. The oxidation of the organic material is favored by increasing of relative humidity and temperature, whereas processes involving changes of the oxidation states of a number of inorganic pigments (e.g., vermilion, cadmium yellows, zinc yellows, chrome yellows) are mainly activated by light-exposure. In view of the optimization of the long-term conservation and restoration strategies of paintings it is of relevant interest to establish the consequences of thermal parameters (temperature and relative humidity) on the chemical/photochemical-reactivity and the nature of the alteration products of light sensitive-pigments in oil medium.To this aim here we propose a multi-method analytical approach based on the combination of diffuse reflectance UV–Vis, FTIR, synchrotron radiation (SR)-based micro X-ray fluorescence (μ-XRF)/micro-X-ray absorption near edge structure (XANES) and electron paramagnetic resonance (EPR) spectroscopies for studying the effects of different relative humidity conditions before and after light exposure on the reactivity of a series of lead chromate-based pigments [such as PbCrO$_4$∙ PbO (monoclinic), PbCrO$_4$ (monoclinic) and PbCr$_{0.2}$S$_{0.8}$O$_4$ (orthorhombic)] in an oil medium. The investigation of paint models was also compared to that of a late 19th century historical orthorhombic PbCr$_{0.4}$S$_{0.6}$O$_4$ oil paint.Diffuse reflectance UV–Vis and FTIR spectroscopies were used to obtain information associated with chromatic changes and the formation of organo-metal degradation products at the paint surface. SR-based Cr K-edge μ-XANES/μ-XRF mapping analysis and EPR spectroscopy were employed in a complementary fashion to determine the amount, nature and distribution of Cr(III) and Cr(V)-based alteration compounds within the paints with micrometric spatial resolution.Under the employed thermal aging conditions, lead(II)-carboxylates and reduced Cr-compounds (in abundance of up to about 35% at the surface) have been identified in the lead chromate-based paints. The tendency of chromates to become reduced increased with increasing moisture levels and was favored for the orthorhombic PbCr$_{0.2}$S$_{0.8}$O$_4$ compounds. The redox process gave rise to the formation of Cr(V)-species in relative amount much higher than that was formed in the equivalent paint which was exposed only to light. After light-exposure of the thermally aged paints, compounds ascribable to the oxidation of the organic binder were detected for all the types of pigments. Nevertheless, the previous thermal treatment increased the tendency toward photo-reduction of only the PbCr$_{0.2}$S$_{0.8}$O$_4$ pigment. For this light-sensitive compound, the thickness variation of the reduced Cr-rich (ca. 70%) photo-alteration layer with moisture levels could be ascribed to a surface passivation phenomenon that had already occurred before photochemical aging

Synchrotron-based X-ray spectromicroscopy and electron paramagnetic resonance spectroscopy to investigate the redox properties of lead chromate pigments under the effect of visible light

Correction for 'Synchrotron-based X-ray spectromicroscopy and electron paramagnetic resonance spectroscopy to investigate the redox properties of lead chromate pigments under the effect of visible light' by Letizia Monico et al., J. Anal. At. Spectrom., 2015, 30, 1500–1510

Evidence for Degradation of the Chrome Yellows in Van Gogh’s Sunflowers : A Study Using Noninvasive In Situ Methods and Synchrotron-Radiation-Based X-ray Techniques

This paper presents firm evidence for the chemicalalteration of chrome yellow pigments in Van Goghs Sunflowers (Van Gogh Museum, Amsterdam). Noninvasive in situ spectroscopic analysis at several spots on the painting, combined with synchrotron-radiation-based X-ray investigationsof two micro-samples, revealed the presence of different types of chrome yellow used by Van Gogh, including the lightfast PbCrO$_{4}$ and the sulfur-rich PbCr$_{1-x}$SxO$_{4}$ (x~0.5) variety that is known for its high propensity to undergo photoinduced reduction. The products of this degradation process, i.e., CrIII compounds, were found at the interface between the paint and the varnish. Selected locations of the painting with the highest risk of color modification by chemical deterioration of chrome yellow are identified, thus calling for careful monitoring in the future

Characterization and Removal of a Disfiguring Oxalate Crust on a Large Altarpiece by Hans Memling

During the conservation treatment of Memling’s Christ with Singing and Music-making Angels, three panel paintings that are among the most monumental works in early Netherlandish art, the conservators came across insoluble surface layers containing calcium oxalates. A very thin and irregular layer of this type, hardly visible to the naked eye, was spread across the surface of all three panels. A much thicker layer forming an opaque and highly disfiguring crust that obscured the composition (Figs. 15.1 and 15.7) was locally present on areas of dark copper-containing paint, where multiple layers of old discolored coatings and accretions remained in place before the most recent cleaning

Full spectral XANES imaging using the Maia detector array as a new tool for the study of the alteration process of chrome yellow pigments in paintings by Vincent van Gogh

A combination of synchrotron radiation (SR) micro X-ray fluorescence ($\mu$-XRF) and XRF mode X-ray absorption near edge structure (XANES) measurements at the Cr K-edge already allowed us to establish that the photo-reduction of chromates to Cr(III) compounds is the cause of darkening of chrome yellow pigments $(PbCr_{1}−_{x}S_{x}O_{4}, 0 ≤ x ≤ 0.8)$ in a number of paintings by Vincent van Gogh and in corresponding artificially aged paint models. A silicon drift detector (SDD) was employed to record the Cr-K XRF radiation in these X-ray micro beam-based measurements. However, in view of the limited count rate capabilities and collection solid angle of a single device, $\mu$-XRF and $\mu$-XANES employing single element SDDs (or similar) are primarily suited for collection of spectral data from individual points. Additionally, collection of XRF maps via point-by-point scanning with relatively long dwell times per point is possible but is usually confined to small areas. The development of the 384 silicon-diode array Maia XRF detector has provided valuable solutions in terms of data acquisition rate, allowing for full spectral (FS) XANES imaging in XRF mode, i.e., where spectroscopic information is available at each pixel in the scanned map. In this paper, the possibilities of SR Cr K-edge FS-XANES imaging in XRF mode using the Maia detector are examined as a new data collection strategy to study the speciation and distribution of alteration products of lead chromate-based pigments in painting materials. The results collected from two micro-samples taken from two Van Gogh paintings and an aged paint model show the possibility to perform FS-XANES imaging in practical time frames (from several minutes to a few hours) by scanning regions of sample sizes of the same order (more than 500 $\mu$m). The sensitivity and capabilities of FS-XANES imaging in providing representative chemical speciation information at the microscale (spatial resolution from ~ 2 to 0.6 $\mu$m) over the entire scanned area are demonstrated by the identification of $Cr(OH)_{3}$, Cr(III) sulfates and/or Cr(III) organometallic compounds in the corresponding phase maps, as alteration products. Comparable Cr-speciation results were obtained by performing equivalent higher spatial resolution SR $\mu$-XRF/single-point $\mu$-XANES analysis using a more conventional SDD from smaller regions of interest of each sample. Thus, large-area XRF mode FS-XANES imaging (Maia detector) is here proposed as a valuable and complementary data collection strategy in relation to “zoomed-in” high-resolution μ-XRF mapping and single-point $\mu$-XANES analysis (SDD)