Multisensor hyperspectral imaging approach for the microchemical analysis of ultramarine blue pigments

This work presents a multisensor hyperspectral approach for the characterization of ultramarine blue, a valuable historical pigment, at the microscopic scale combining the information of four analytical techniques at the elemental and molecular levels. The hyperspectral images collected were combined in a single hypercube, where the pixels of the various spectral components are aligned on top of each other. Selected spectral descriptors have been defined to reduce data dimensionality before applying unsupervised chemometric data analysis approaches. Lazurite, responsible for the blue color of the pigment, was detected as the major mineral phase present in synthetic and good quality pigments. Impurities like pyrite were detected in lower quality samples, although the clear identification of other mineral phases with silicate basis was more difficult. There is no correlation between the spatial distribution of the bands arising in the Raman spectra of natural samples in the region 1200–1850 cm−1 and any of the transition metals or rare earth elements (REE). With this information, the previous hypothesis (based on bulk analysis) attributing these bands to luminescence emissions due to impurities of these elements must be revised. We propose the consideration of CO2 molecules trapped in the cages of the aluminosilicate structure of sodalite-type. Additionally, correlation between certain Raman features and the combined presence of Ca, P, and REE, in particular Nd, was detected for the lowest quality pigment. Our results highlight the usefulness of fusing chemical images obtained via different imaging techniques to obtain relevant information on chemical structure and properties.

Contemporary Methods for Production of Ultramarine

The article describes the features of ultramarine, its modifications, viz. ultramarine blue. The requirements for ultramarine blue grades are observed, the one-stage and two-stage technologies for the production of ultramarine blue are described, the advantages and disadvantages of both methods are listed, new recommendations for the production of ultramarine blue are offered.

Characterization of Two Historical Postage Stamps Made from Cotton Fibers and Their Restoration Trials Based on the Experimental Studies

Ancient stamps are suffering from the destructive effects of different kinds of inks that were prepared from different ingredients. Two Egyptian historical postage stamps printed in blue and red printing inks were evaluated and examined for their composition using a light microscope, SEM-EDS, FTIR, and Raman spectroscopic analyses. Mechanical, chemical, and deacidification treatments were done for the two stamps. Model stamps were made from the cotton pulp in the book house to simulate historical stamp paper with an average thickness of 11 microns. The unprinted and printed paper samples with printing inks that aged and unaged were treated with 0.7% Klucel G, 0.2% TiO2 NP, or a mixture of 0.7% Klucel G + 0.2% TiO2 NP, and the color change was measured and compared with the blank samples. The two stamps are suffering from high pH, where the margin color of the stamps changed to yellow-brown with weakness of the stamp paper. By SEM examination, stamps have suffered from fibers’ weakness and dryness resulting from the self-oxidation reactions. EDS elemental composition of the red stamp showed the presence of C, O, Na, Al, Si, Mg, S, Ca, Ba, and Fe, while in the blue stamp, it was C, O, Na, Al, Si, P, S, Cl, and Ca. Raman spectrometer wavelengths turn out that the blueprinting ink of the stamp was characterized with spectra of ultramarine blue (lazurite), while hematite was characterized by the red stamp. FTIR analysis for the printing inks identified that gum Arabic sample and linseed oil were the binding and color medium, respectively. From the model trials, it was observed that the treatment of a mixture of Klucel G and TiO2 NP had the best properties for the consolidation of stamps. The two historical stamps were documented through different spectroscopic analyses, and from the restoration trials, it was observed that the mixture of 7% Klucel G + 0.2% TiO2 NP appeared to be a new and effective method for recovering the historical postage stamps.

On the Two Working Palettes of Almada Negreiros at DN Building in Lisbon (1939–1940): First Analytical Approach and Insight on the Use of Cd Based Pigments

This paper reports the first analytical approach carried out on two working palettes by Portuguese modernist master Almada Negreiros, found in 1991 behind old wood cabinets at the DN building in Lisbon. This is the only known occasion Almada left behind the color experiments done before starting to paint in the nearby walls and as such, it is a unique opportunity to analyze the materials and painting techniques that were originally used. The analytical setup comprised in loco technical photography in Vis, UVF and NIR; p-OM, spectrophotometry in Vis and h-EDXRF, complemented by OM-Vis, µ-FT-IR and VP-SEM-EDS of painting micro-samples and pigments in powder form. Preliminary results suggested the use of fresco painting technique and revealed some technical details, such as the use of a coarse lime sand finishing mortar mixed with natural vegetable fibers, and the extensive use of cadmium-based pigments that were not commonly used (or even recommended) in an alkaline environment. The Cd pigments were used alone or in mixtures with Fe based pigments in the warm hues and with cobalt and ultramarine blue pigments in some green paint layers. No clear evidence of organic materials that could have been used as binders was detected.

Unexpected Findings in 16th Century Wall Paintings: Identification of Aragonite and Unusual Pigments

Sixteenth century wall paintings were analyzed from a church in an advanced state of decay in the Apennines of central Italy, now a remote area but once located along the salt routes from the Po Valley to the Ligurian Sea. Infrared spectroscopy (FTIR-ATR), X-ray diffraction (XRD) and scanning electron microscopy (SEM) with a microprobe were used to identify the painting materials, as input for possible future restoration. Together with the pigments traditionally used for wall painting, such as ochre, ultramarine blue, bianco di Sangiovanni, cinnabar/vermilion, azurite, some colors were also found to have only been used since the 18th century. This thus suggests that a series of decorative cycles occurred after the church was built, confirmed by the multilayer stratigraphy of the fragments. Some of these colors were also unusual, such as clinochlore, Brunswick green, and ultramarine yellow. The most notable result of the analytical campaign however, was the ubiquitous determination of aragonite, the mineralogical form of calcium carbonate, mainly of biogenic origin. Sources report its use in Roman times as an aggregate in mortars, and in the literature it has only been shown in Roman wall paintings. Its use in 16th century wall paintings is thus surprising.

Non-Destructive Analytical Investigation of Decorative Wallpapers Samples of the Nineteenth Century before Their Restoration

In this work, decorative wallpapers (19th century) from an historical palace located in Oiartzun (Basque Country, Spain) were analyzed before their restoration. Micro-energy dispersive X-ray fluorescence spectroscopy, Raman spectroscopy, and attenuated total reflectance infrared spectroscopy were used to investigate the elemental and molecular composition of pigments, the presence of binders, and the state of conservation of the paper support. The aim of the investigation was trying to understand the possible degradation pathways and identify the raw materials in order to choose the best restoration protocol according to the original aspect of wallpapers. As stated from both the elemental distribution and the identification of mineral phases by Raman spectroscopy, the most used pigment was lead chromate. It was mixed with other pigments such as ultramarine blue, zinc chromate, hematite, and atacamite among others to obtain different shades and they were applied mixed with an animal glue. Brass, identified thanks to elemental micro-EDXRF maps, was employed as a shiny decorative element. In addition, a partial degradation of cellulose was detected due to its natural ageing, the acidic nature of lignin, and to a phenomenon of humidity of the walls. Probably the deposition of black particulate matter was the cause of the darkening of the painting surfaces.

Non-Invasive Study on the Sinope Gospels

The 6th century Codex Sinopensis or Sinope Gospels (Paris, Bibliothèque nationale de France) is one of the most precious purple codices that survive from the Late Antique period. Together with the Vienna Genesis (Wien, Österreichische Nationalbibliothek) and the Rossano Gospels (Rossano Calabro, Museo Diocesano), it has an unusually rich decorative apparatus with scenes representing biblical episodes. It can be, therefore, considered one of the most important preserved artistic productions of the early medieval era. The manuscript has been subjected to a non-invasive diagnostic campaign to evaluate the quality of the colourants used in its decoration, to understand how the parchment was coloured, and to carry out a comparison with the Vienna Genesis and the Rossano Gospels. The techniques used were UV-visible diffuse reflectance spectrophotometry with optical fibres (FORS), X-ray fluorescence spectrometry (XRF), spectrofluorimetry, and optical microscopy. Analyses highlighted the presence of ultramarine blue, which, besides the use of pure gold for the ink and paint, certifies the high value of the manuscript. In addition, this must be seen as one of the earliest examples of its use in paintings. The purple colour of the parchment was identified as orchil, a dye extracted from lichens, similar to the results of analytical investigations carried out on other purple codices, and not the expected Tyrian purple dye.