Analysis of bulk and inorganic degradation products of stones,mortars and wall paintings by portable Raman microprobe spectroscopy

This work reports the use of a portable Raman microprobe spectrometer for the analysis of bulk and decaying compounds in carbonaceous materials such as stones, mortars and wall paintings. The analysed stones include limestone, dolomite and carbonaceous sandstone, gypsum and calcium oxalate, both mono- and dihydrated, being the main inorganic degradation products detected. Mortars include bulk phases with pure gypsum, calcite and mixtures of both or with sand, soluble salts being the most important degradation products. The pigments detected in several wall paintings include Prussian blue, iron oxide red, iron oxide yellow, vermilion, carbon black and lead white. Three different decaying processes have been characterised in the mortars of the wall paintings: (a) a massive absorption of nitrates that reacted with calcium carbonate and promoted the unbinding of pigment grains, (b) the formation of black crusts in the vault of the presbytery and (c) the thermodecomposition of pigments due to a fire.     

Analysis of pigments from Roman wall paintings found in Vicenza

The analysis of about 60 samples of wall paintings was carried out using different chemicophysical techniques: optical microscopy, scanning electron microscopy (SEM) equipped with an EDS microanalysis detector, X-ray powder diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The identified pigments were cinnabar, hematite, red ochre, celadonite, cuprorivaite (Egyptian blue), yellow ochre, goethite and carbon. Only in one case some lead white was found instead. In general, the mortar preparation did not correspond to the complex structure suggested by Vitruvius (De Architectura), but it generally showed a porous layer, with crushed grains under the pigment layer. In certain cases two superposed pigment layers were found: yellow superimposed on both red and pink, black on pink, green on black.     

Non-invasive and non-destructive micro-XRF and micro-Raman analysis of a decorative wallpaper from the beginning of the 19th century

Non-destructive and non-invasive micro-Raman fibre optic and micro-XRF analyses were performed to study a wallpaper from the beginning of the 19th century. The complementarity of these two non-destructive techniques is shown in this work. The analysed artwork is considered one of the most beautiful wallpapers ever manufactured according to the catalogues and books; it is known as Chasse de Compiègne, manufactured by Jacquemart, Paris, in 1812. During the analysis, an unexpected pigment was detected by both analytical techniques: lead-tin yellow type II. This pigment was used until ca. 1750, when other yellow pigments replaced it, thus it is very difficult to find it in paintings afterwards. Together with this pigment, red lead, Prussian blue, brochantite, yellow iron oxide, calcium carbonate, vermilion, carbon black of animal origin (bone black), lead white, and raw and burnt sienna were also determined by combining the analytical information provided by both techniques. A possible degradation of brochantite to antlerite is also discussed.     

Non-destructive in situ determination of pigments in 15th century wall paintings by Raman microscopy

Raman microscopy has been applied to the study of 15th century wall paintings in a chapel of St. Orso Priory palace (Aosta, Italy) in view of their restoration. The use of a transportable instrument has made it possible to work non-destructively in situ without sampling. The main inorganic pigments used by the unknown artist, namely mercury sulphide, azurite, white lead, red and yellow ochre, carbon black and lead tin yellow type I have been identified, and the presence of organic substances and of some decay products (calcium sulphate and oxalate) has been observed.     

Multianalytical approach to the analysis of English polychromed alabaster sculptures: μRaman, μEDXRF,and FTIR spectroscopies

A complete study of several English polychromed alabaster sculptures is presented. The support, pigment, and binders were characterised by combining μEDXRF, μRaman, and FTIR spectroscopies. Among the pigments, minium, vermilion, lead white, carbon black, red iron oxide, and a degraded green copper pigment were determined, together with gold leaf. The presence of the rare mineral moolooite (copper oxalate) was also found as a degradation product in the green areas, where weddellite (calcium oxalate dihydrate) was also determined. These facts, together with degradation of the green copper pigment, suggest microbiological degradation of the original materials. Remains of glue and a varnish were also determined by FTIR spectroscopy and principal-components analysis (PCA) of the spectra. Finally, PCA analysis was carried out to confirm whether the pieces came from the same quarry.     

Spectroscopic Characterization of the Architectural Painting from the Cizhong Catholic Church of Yunnan Province,China

The Cizhong Catholic Church, which incorporates local Chinese architectural styles and artistic motifs, witnessed the transmission of Catholicism in Yunnan Province in the late Qing Dynasty. The pigments of the paintings from the church were identified by micro-Raman Spectroscopy, micro X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The analyses indicated that chromogenic substances of the white pigment was calcite, that of the black pigment was carbon black, that of the red pigment was hematite, that of the blue pigment was artificial ultramarine, and that of the green pigment was emerald green. The study also revealed that artificial ultramarine and emerald green were probably imported or brought by French missionaries from Europe. In addition, emerald green was identified to have partially degraded into cornwallite.     

Transparent CoAl2O4 hybrid nano pigment by organic ligand-assisted supercritical water

Transparent types of inorganic pigments are important as they can be used in a variety of applications, such as metallic finishing, contrast enhancing luminescent pigments, high-end optical filters, and so on. Currently, the difficulty in producing monodisperse and stable binary metal oxide nano pigments at low temperature hampers the applicability and realization of transparent blue nano pigments. Here, for the first time, we report organic ligand capped CoAl2O4 hybrid transparent nano pigment, which has a particle size less than 8 nm with well-stabilized single nanocrystals, using organic ligand-assisted supercritical water as the reaction medium. The organic ligand capping could effectively inhibit the particle growth and also control the size of nanocrystals. This helps to diminish the scattering effect of the nano blue pigment, realizing a transparent cobalt blue nano pigment without any postheat treatment.     

A non-invasive XRF study supported by multivariate statistical analysis and reflectance FTIR to assess the composition of modern painting materials

The palette used in two paintings by Paul Cézanne, L'étang des soeurs dated c. 1875 and La route tournante, made in the last year of his life (1902), were analyzed using non-invasive spectroscopic methods. X-ray fluorescence combined with principal components analysis (PCA) and supported by reflectance near- and mid-FTIR was shown to be a powerful analytical tool to draw conclusions about the chemical identification of inorganic materials in paintings. Pigments and fillers such us Thénard's blue, Prussian blue, red ochre, kaolin, vermilion, lead white, zinc white and barium sulphate, were identified. Evidence for three different pigments, namely a copper arsenite pigment, chrome green (a mixture of chrome yellow and Prussian blue) and viridian has been obtained by the PCA analysis of elemental compositions of green hues.     

Analytical contributions to the evaluation of painting authenticity from Princely church of Curtea de Arges

The present study contains the analyses performed for pigment samples taken from the Princely church of Curtea de Arges, one of the oldest churches in Romania. The results of our investigations have shown the source of these samples, thus being identified the pigments: natural ultramarine, cinnabar, red earth, and calcium carbonate in the painting from the 14th century, the pigments: lead white, zinc white, and Prussian blue in the repainting from the 19th century and the pigments zinc white, titanium dioxide white, bone white, yellow ochre, red ochre, green earth, artificial ultramarine, and mars red in the interventions carried out in the 20th century. The analyses consisted of light microscopy (LM) and microchemical tests, as well as energy dispersive X-ray (EDX) analysis. This system of analyses allows one to precisely determine the authenticity of certain pigments, thus avoiding the dating errors for different interventions carried out on the original mural painting from the Saint Nicholas Princely church of Curtea de Arges.     

Characterization of slate ornaments from Teotihuacan by nuclear and conventional techniques

Several ornaments named tezcacuitlapilli (coccyx-mirrors) are described and chemical analyses of raw materials (slate and pigments) were carried out by neutron activation, X-ray diffraction, scanning electron microscopy and radiography. Elemental and statistical analyses revealed that three different kinds of slate were used in their manufacture. The white pigment contains gypsum while ochre, yellow and red pigments contain iron oxide. These ornaments were identified as coming from the Cave of the Sun Pyramid of Teotihuacan. An attempt was undertaken to reconstruct the contexts of their manufacture and symbolic interpretation.     

Analysis of Roman age wall paintings found in Pordenone, Trieste and Montegrotto

The aim of the present work is the study of many fragments of wall painting from archaeological excavations in three different Roman age sites dating back to the I Century before Common Era: Pordenone (località Torre); Trieste (Crosada) and Padova (Montegrotto). The techniques used were optical microscopy, scanning electron microscopy (SEM), equipped with a EDS microanalysis detector, X-rays powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Fourier transform Raman spectroscopy (FT-Raman) and electron paramagnetic resonance (EPR) spectroscopy. The identified pigments were: cinnabar, hematite, celadonite, glauconite, cuprorivaite (Egyptian blue), yellow and red ochre, calcite, limonite, coal black.In general, the mortar preparation did not correspond to the complex procedure suggested by Vitruvius (De Architectura), but generally showed a porous layer, with crushed grains under the pigment layer. In some cases, two superimposed pigment layers were found: yellow superimposed on both red and pink, black on pink, green on black.The slight differences we found in the use of the pigments in the three studied sites might show that the same technology, culture and taste spread all over the Roman Empire in North Eastern Italy (X^a Regio Venetia et Histria).     

Byzantine wall paintings from Mani (Greece): microanalytical investigation of pigments and plasters

The present case study concerns the technology of Byzantine wall paintings from the Mani Peninsula, Greece. An assemblage of 12 Byzantine churches, constructed in the tenth to fifteenth century, was included in an initial analytical survey. Two random samples of wall paintings were taken in each monument in order to study their micro stratigraphy and the composition of pigment and plaster layers. Polished sections were fabricated for examination with optical microscopy and scanning electron microscopy (SEM). Furthermore, selected samples were powdered and analysed with Fourier-transformed infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The analytical results achieved in this case study provided general conclusions concerning painting techniques for wall paintings in a rather provincial area of the Byzantine Empire. The palette comprised mainly earthen pigments like ochres and carbon black but occasionally also other pigments like cinnabar, minium and ultramarine. In view of future studies, a portable X-ray fluorescence analysis (XRF) set-up was tested.     

Triplet quenching and antioxidant effect of several carbon black grades in the photodegradation of LDPE doped with benzophenone as a photosensitiser

In a previous paper it was demonstrated for the first time, that carbon black pigments have the ability to operate as effective singlet and triplet quenchers. This work was undertaken directly in the polymer using the inherent long-lived luminescent species as triplet donor species. In order to ascertain the effectiveness of the quenching mechanism and its inter-relationship with carbon black parameters, a total of eight different carbon black pigments have been incorporated into low density polyethylene at different concentrations (0.1, 0.2, 0.4% w/w) and their effects determined on the quenching the triplet state of a known triplet photosensitiser, benzophenone (0.05% w/w). Using phosphorescence analysis at 77 K a large variability was observed in the benzophenone triplet lifetime quenching, the effect varying with the pigment type and the concentration of pigment. Photodegradation rates on the films were also performed in order to relate the quenching effect of the carbon black with films exposed to UVA light at 70°C. An unusual synergistic effect between the carbon black and the benzophenone sensitiser was observed compared with films containing only carbon black. The implications of carbon black pigments to operate as “super quenchers”, as well as antioxidants in this study and under practical concentration conditions is discussed. Although not consistent throughout, there is some indication that low surface area carbon black pigments can be the most effective quenchers of active excited states. However, the presence of surface containing oxygen groups can be related to the synergistic effect reported, using experimental design statistical analysis.     

A Comparative Study of Pigments from the Wall Paintings of Two Greek Byzantine Churches

The goal of this study was to characterize pigments used in the murals of two Byzantine churches, from Kastoria, northern Greece. The identification of the iconographer was also investigated by comparing the pigments applied in the wall paintings of the churches. Pigment microsamples of various colors were collected and analyzed by environmental scanning electron microscopy coupled with an energy dispersive system to characterize the elemental composition. Raman spectroscopy was employed to collect molecular spectra for characterization of mineralogical phases. Hematite, cinnabar, and minium were identified in red surfaces. Brown and yellow colors were assigned to mixtures of iron oxides, iron hydroxides, and calcite. Mixtures of iron, lead, and mercury compounds were used to produce different hues in the murals. Black tones were prepared primarily using charcoal and bone black. Grey colors were produced by a mixture of black carbon with calcite; blue hues, by a mixture of iron oxides, calcite, and black carbon. The minerals used were similar for both churches. However, the green color was prepared either by green earth or mixtures of iron oxides and calcite. A modern pigment, lithopone, was also determined, demonstrating restoration or overpainting and thus complicating possible correlations. Based on these preliminary results, the wall paintings could not be ascribed to a specific iconographer.     

Synthesis and study of mixed oxide inorganic pigment from Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZnO–CeO<Subscript>2</Subscript> system

Novel environment-friendly yellow mixed oxide inorganic pigment from Bi₂O₃–ZnO–CeO₂ system with the composition 23 mol% Bi₂O₃, 15 mol% ZnO and 62 mol% CeO₂ was successfully synthesized by a conventional solid-state reaction method. Comprehensive analyses were carried out to characterize the develop pigment powder including simultaneous TG–DTA thermal analysis, colour properties and particle size distribution. The results demonstrated that the optimum calcination for pigment synthesis was located at a range 800–950 °C. The colour of the studied mixed oxide pigment is connected with the calcination condition. The substitution of Zn²⁺ changes the colour from orange to yellow. The colour of the obtained samples was dependent on the calcination condition and the particle size distribution. The most saturated yellow hue was obtained at the calcination temperature of 950 °C for 2 h in a furnace of pure air and after its application into organic binder in mass tone. The value C of this sample was approx. 65. The mixed oxide pigments were also evaluated from the standpoint of their particle size distribution. Bi₂Ce₂O₇ is considered to be a non-toxic compound, and the other component (Zn²⁺ ions) is also the safe element. Therefore, the present mixed oxide could be an attractive candidate as a novel environment-friendly inorganic yellow pigment.     

Developments in the Field of Inorganic Pigments

The specific properties of inorganic pigments result from an interplay of solid-state properties, particle size, and particle shape. However, phenomena occurring at the pigment interfaces also have implications for the use of the pigment. The interrelations for individual classes of pigments are indicated, and two selected examples, namely transparent colored pigments and magnetic pigments, are subsequently discussed with particular attention being paid to industrial developments.     

Characterization of black pigment used in 30 BC fresco wall paint using instrumental methods and chemometry

Background and methods

Several standard powdered black pigments were characterized by means of thermogravimetry TG-DTG and allied techniques. These pigments were used to make standard plaster frescoes at this purpose prepared. The latter ones were subjected to Raman and reflectance analysis. The results obtained, together with TG data, were chemometrically processed and used to identify an analogous standard fresco fabricated by an unknown commercial black pigment, obtaining excellent results.

Results

The same colorimetric and reflectometric techniques, coupled with suitable chemometric techniques, were then successfully used to identify the type of black pigment present in an ancient roman fresco of the Imperial Age (30 B.C.).

Conclusion

TG-DTG resulted useful techniques to autenticate powdered black pigments.Colorimetry and Raman, but also the only colorimetry, were useful to identify an ancient black pigment in situ.

     

Raman spectroscopic study of a post-medieval wall painting in need of conservation

Raman spectroscopic studies of four specimens from an important angel wall painting in need of conservation work in a medieval church have provided some information about the pigments and pigment compositions which will influence possible future preservation and restoration strategies. Excitation of the Raman spectra at 1,064 nm in macroscopic mode and at 785 nm in microscopic mode revealed that the white pigment on the angel's wings was a mixture of barytes with calcite and lead white in minor composition. Although the specimens provided were not directly associated with coloured regions of the painting, yellow and blue microcrystals were found and they were identified as chrome yellow and lazurite, respectively. Red and brown particles were identified as cinnabar/vermilion and haematite. Several green particles were also found but could not be identified. The green and blue crystals could be related to neighbouring coloured regions of the artwork and the yellow colour could be identified as a background to the angel figure. Particles of carbon were found to be dispersed throughout the specimens and can be ascribed to soot from candles, heating stoves or oil lamps providing lighting in the church. No evidence for biological deterioration was found from the spectra. The unusual pigment palette is strongly suggestive of a later date of painting than was originally believed but there is a possibility that an earlier rendition exists underneath. Following a review of the spectroscopic data, a more extensive sampling protocol is recommended, from which some stratigraphic evidence could identify the underlying plaster and possible artwork.     

Raman analysis of ancient pigments on a tile from the Citadel of Algiers

A micro-Raman spectroscopy study of a multi-coloured (yellow, blue, white, redish-brown and brown-black) tile shard from the Citadel of Algiers was undertaken. XRD and EDX were used as complementary techniques. The study shows that the heterogeneous three-shade yellow pigment on the tile is composed largely of the ancient ternary (Pb-Sn-Sb) pyrochlore oxide with a dominant Pb-O vibration at 127 cm(-1) consistent with the Pb2SnSbO6.5 structure as verified by XRD. The literature assignment of this band at 132 cm(-1) probably comes from a mixture of pigments. The redish-brown and the brown-black pigments are found to be Naples yellow (Pb2Sb2O7) and lead(II) stannate (Pb2SnO4), respectively, while cobalt blue (CoAl2O4) gives the blue colour and cassiterite (SnO2) is the origin of the white colour. The bulk of the tile body is composed mainly of hematite (alpha-Fe2O3), maghemite (gamma-Fe2O3), magnetite (Fe3O4) and Quartz (alpha-SiO2) with traces of calcite (CaCO3) and amorphous carbon. Micro-Raman spectroscopy proved to be very useful in the characterization of pigments as well as the tile body. These results further establish Raman spectroscopy as a technique of choice for the analysis of pigments on archaeological artifacts. The results obtained here could be used in the restoration and preservation programme of the Citadel itself which stands today as a symbol of pre-colonial Algerian heritage.