A pigment (CuS) identified by micro‐Raman spectroscopy on a Chinese funerary lacquer ware of West Han Dynasty

A blue pigment was identified by micro‐Raman spectroscopy, X‐ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM)/energy dispersive X‐ray (EDX) and X‐ray diffraction (XRD). The test sample, a funerary lacquer tray, belongs to West Han Dynasty (206 BC–AD 8) of China and was decorated with faint blue patterns. The result from Raman spectroscopy showed that the faint blue is covellite (CuS) due to the presence of a characteristic peak at 474.5 cm⁻¹, which further was confirmed by XRF, SEM–EDX and XRD. This research indicated that CuS had been used as a blue pigment to decorate lacquer wares from the West Han Dynasty in China. Copyright © 2009 John Wiley & Sons, Ltd.     

Micro‐Raman spectroscopy and VP‐SEM/EDS applied to the identification of mineral particles and fibres in histological sections

Histological sections of a patient affected by an important respiratory disease were analysed firstly by optical microscope(OM)—crossed polarisers—to identify the presence of incorporated inorganic particles, with particular attention to the fibrous ones. Then, the particles/fibres that were found were studied both with micro‐Raman spectroscopy and variable‐pressure scanning electron microscopy with energy‐dispersive spectroscopy (VP‐SEM/EDS). The two techniques allowed the in situ characterisation of the inorganic phases without disintegration of the organic matter. Micro‐Raman spectroscopy was able to identify the vibrating chemical groups of the mineral phase associated with the inorganic grain while the crystalline structure was preserved by the biological system. The VP‐SEM/EDS characterisation, defining the elemental chemical composition of the analysed particle/fibre, allowed confirmation of the mineral phase deducible from spectroscopic data or its identification with certainty when the spectroscopic data were not exhaustive. Copyright © 2009 John Wiley & Sons, Ltd.     

Analytical study of polychromy on exterior sculpted stone

A complete study on the remnants of the polychromy in the main entrance portal of Saint Paul's church (16th century, Úbeda, Spain) has been carried out using Raman microspectroscopy in combination with optical microscopy and scanning electron microscopy with energy dispersive X‐ray spectroscopy (SEM‐EDX). The polychromy in red areas showed the superposition of two well‐defined pictorial layers. The first one (probably original) was composed of cinnabar, red lead and hematite over a preparation coating containing calcite, gypsum and lead white. The second red pictorial layer was mainly constituted by cinnabar and was over a thicker preparation coating. Green samples showed a single pictorial layer over the weathered stone. The high fluorescence background made the examination of the latter samples extremely difficult by means of Raman microspectroscopy. SEM‐EDX detected abundance of copper and chlorine, and a detailed inspection of Raman spectra revealed the presence of a copper hydroxychloride, analogous to the naturally occurring mineral atacamite. Azurite remnants of the original polychromy were only found in the cracks of mortar joints. Alteration products like calcium and copper oxalates were also widely distributed in this layer. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman microscopy of prehistoric paintings in French megalithic monuments

Remains of pictorial decorations in a series of six representative megalithic monuments of Brittany (France) and two French stelae have been studied by micro‐Raman spectroscopy for the first time. Fungal colonies on the painted orthostats made it difficult to obtain in situ Raman spectra of the paint components. Nevertheless, paint micro‐specimens studied in the laboratory by micro‐Raman spectroscopy, X‐ray photoelectron spectroscopy and scanning electronic microscopy combined with energy dispersive X‐ray spectroscopy have made possible to characterise the materials present. The minerals α‐quartz, albite, microcline, muscovite, phlogopite, celadonite, beryl and anatase have been identified in the granitic rocks supporting the paintings, while dolomite and calcite are dominant in the calcareous rocky substrata. Haematite is the main component of the red pictographs, whereas amorphous carbon and manganese oxides/oxihydroxides have been used in the black ones. Calcite, gypsum and amorphous carbon have been detected as additional components of the paint in some cases. Contamination with modern tracing materials (polystyrene and ε‐copper‐phthalocyanine blue) has been detected in several cases. The presence of pigments as decorative elements in megalithic monuments of Western France and its possible relation with those of the Iberian Peninsula create interesting expectations for the knowledge of the European megalithic culture. Copyright © 2015 John Wiley & Sons, Ltd.     

Identification of pigments from the Shrine of Kaiping Diaolou by micro‐Raman spectroscopy

Shrines (or altars) are constructed in China for worshiping ancestors, Bodhisattva, and God of Wealth. In this work, pigments from the shrine of Kaiping Diaolou tower were analyzed by micro‐Raman spectroscopy, in conjunction with other analytical methods including scanning electron microscopy (SEM) with energy dispersive X‐ray spectroscopy (EDX) and X‐ray fluorescence (XRF). Paintings of the shrine were composed of 2–3 pigment layers and the total thickness was determined as about 200–300 µm by optical microscopy and SEM, indicating the fine painting skills applied in the construction of the shrine. The green pigments on the surface layer of the green fragment were identified as a mixture of lead phthalocyanine (PbPc) and cornwallite (Cu₅(AsO₄)₂(OH)₄) by XRF and micro‐Raman spectroscopy with two different excitation wavelengths (488 and 785 nm). Underneath the green layer, red and yellow ochre were found. The pigments on the surface layer of red and blue fragments were identified as hematite (Fe₂O₃) and lazurite or synthetic ultramarine [(Na₈(Al₆Si₆O₂₄)S₃)], respectively. Finally, the pigments under the two surface layers were identified by EDX and micro‐Raman spectroscopy as chromium oxide (Cr₂O₃), gypsum (CaSO₄·2H₂O) and calcite (CaCO₃). Copyright © 2011 John Wiley & Sons, Ltd.     

The daguerreotype surface as a SERS substrate: characterization of image deterioration in plates from the 19th century studio of Southworth & Hawes

Dramatic condition changes were noted in a group of daguerreotypes during a 10 month‐long exhibition featuring masterworks of the prominent Boston‐based studio of Southworth & Hawes. The changes took the form of a hazy, extended white surface layer and of white spots that partially obscured the images after between four weeks and 10 months of exhibition. Raman spectroscopy, complemented by in situ scanning electron microscopy–energy dispersive X‐ray spectrometry (SEM–EDS), was used to nondestructively characterize this form of image deterioration in eight representative daguerreotypes from the studio. Raman proved to be a sensitive technique to noninvasively identify the compounds on the plates due to the fact that their Ag surfaces behave as surface‐enhanced Raman scattering (SERS) substrates. A band at ca 242 cm⁻¹ assigned to the Ag Cl stretching mode was observed in the areas where a white surface layer or white spots are present. In some of the areas probed, substituted aromatic compounds were also detected. The presence of Ag Cl bonds on daguerreotype surfaces has profound implications for their exhibition and preservation due to the photosensitivity of silver chloride in the ultraviolet–visible range, which can generate metallic silver that would redeposit on the surfaces. The possible sources of the compounds detected on the surfaces of the plates are discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

X‐ray techniques applied to surface paintings of ceramic pottery pieces from Aguada Culture (Catamarca,Argentina)

X‐ray diffraction (XRD), energy dispersive spectrometry (EDS), x‐ray imaging (XRI) and scanning electron microscopy (SEM) techniques were applied to characterize and differentiate surface paintings of archeological pottery from the Aguada Ambato and Portezuelo styles (Catamarca, Argentina). Standard procedures are not always appropriate for such samples (paint layers are porous, nonplanar and discontinue). Image processing is necessary when chemical contrast is not discriminated. Soft x‐ray lines (e.g. Fe L) are more revealing because those detected come from shallower depths, clearly depicting the composition of the paint layer. These styles differ in mineralogy and chemistry suggesting that they are two distinctive entities not only on their designs but also on the materials chosen and the technology used. Aguada Portezuelo paints contain Ca (white), Fe? Mn (black), Fe? Mn? Ca (dark reddish) and Fe? Ca (reddish). The white ones correspond to gehlenite, a firing product (possible firing temperature ≥900–1000 °C); calcite and CaO occur in cases of firing temperatures <900 °C. Aguada Ambato presents difficulties for paint discrimination; only EDS spectra show slight differences. White paint from Tricolor Ambato contains mainly Pb‐phases (hatchite, anglesite, plumalsite), reddish paint resembles the paste (～Fe, hematite); reddish surfaces may have not been painted but polished. Black paint has scarce Mn–minerals. On Black Incised sherds no particular phase was identified suggesting possible organic pigments or resulting from the firing technique. The chemistry and mineralogy of the paste almost always overlap that of the paints; painted layer is irregular and partially worn by years of burial. Copyright © 2009 John Wiley & Sons, Ltd.     

Yellow pigments in painting: characterisation and UV laser‐induced modifications

Artistic yellow pigments, commonly employed from antiquity, were investigated by morphological, spectrophotometric and compositional analyses. Namely, scanning electron microscopy–energy dispersive X‐ray (SEM/EDX) characterisations and reflectance, attenuated total reflection–Fourier transform infrared spectroscopy (ATR‐FTIR) and Raman spectroscopy were carried out on egg yolk tempera models to discriminate the pigments. The models were irradiated with excimer KrF (248 nm) laser at different working conditions, and the effects induced on colour were related to chemical and physical modifications through the same analyses, as a function of laser parameters. It came out that the effects on the pictorial layers are always related to the modifications of the binding medium and, in addition, the laser radiation induces dehydration and transformation of iron oxides in natural earths. Copyright © 2009 John Wiley & Sons, Ltd.     

Characterization of colorants and opacifiers in roman glass mosaic tesserae through spectroscopic and spectrometric techniques

Several glass mosaic tesserae were recovered during the archeological excavation of the thermal baths at the ‘Villa dei Quintili’ in Rome and dated to the second century ad . This work reports the results of an archeometrical investigation performed, through a multi‐technique approach, on 19 colored opaque tesserae. The aims of the study were (1) the characterization of coloring and opacifying agents used for the production of the glass tesserae and (2) the definition of the technological processes involved. Colorimetric measurements allowed us to classify the tesserae in color groups, while the glassy matrix and the dispersed crystallites were characterized in detail through micro‐Raman spectroscopy, field emission scanning electron microscopy with energy dispersive X‐ray spectroscopy, laser ablation‐inductively coupled plasma‐mass spectrometry, and X‐ray powder diffraction analyses. Most of the glass shows the typical soda‐lime‐silicate composition (except for the orange and red tesserae). Raman results and elemental analysis prove the use of Sn–Pb antimonates to create yellow glass and of Ca‐antimonates for the white tesserae. A mixture of Sn–Pb antimonates and copper ions was used to obtain the emerald green color, while Ca‐antimonates were employed in both copper‐colored and cobalt‐colored blue glass to obtain different shades (blue‐green, dark, and light blue). X‐ray powder diffraction analyses reveal the presence of metallic copper (Cu⁰) and Cu₂O particles (cuprite) in red and orange tesserae, respectively. These results confirm the high technological level reached by the glassmakers of the Imperial Age. Copyright © 2014 John Wiley & Sons, Ltd.     

Pigment identification and decoration analysis of a 5th century Chinese lacquer painting screen: a micro‐Raman and FTIR study

To investigate the pigments and decoration applied to a wood‐based lacquer painting screen from the tomb of Si‐ma Jin‐long, Shanxi Province, central China, made by Chinese craftsmen in the 5th century, a combination of micro‐Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), wavelength dispersive X‐ray fluorescence (WDXRF), and microscopic examination was used. The obtained results are as follows: (1) the black, yellow, and red colors are identified as carbon black, orpiment and realgar, and cinnabar, respectively, by using micro‐Raman spectroscopy. The FTIR result shows that the white pigment filled in the leaves is not lead white, as assumed in the literature, but gypsum. Whether lead white was used at other locations remains unanswered and requires more samples for further work; (2) the thickness of each discernable pigment layer, as observed under the microscope, is approximately equal and the differences among them are small, suggesting a superfine painting skill; besides, a noticeable smooth interface between wood and the red grounding substance indicates that a polishing process might have been applied before the painting; (3) the red background was proved to contain cinnabar, but further FTIR analyses found no evidence for the presence of Chinese wood oil; and (4) the most interesting finding, rarely reported before, is that white grains of different sizes are found in both pigment layers and the grounding substance, which are perhaps an intentional addition. Further, in situ XRF and Raman analyses indicate that they are sourced from hydroxyapatite, coming probably from the intentional addition of animal bone ash to the lacquer. But how such a process could be finished and what purpose it served have not yet been answered. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of the provenance of medieval silver coins: potential and limitations of x‐ray analysis using photons,electrons or protons

One hundred and fifty seven ‘Tiroler Kreuzer’, a medieval currency from the county of Tyrol/Austria, were analysed in order to determine their place of mintage. The silver coins were produced during the 15th century in the mints of Merano (South Tyrol) and Hall (North Tyrol) but they have no marks or punches which would allow a clear distinction. Energy‐dispersive x‐ray fluorescence analysis (EDXRF) was applied without sampling in order to determine the silver contents and also minor (Cu, Pb, Bi) and trace elements (Fe, Au, Hg, Ni). Owing to corrosion processes, which changed the chemical composition of the surfaces of the coins, investigations of cross‐sections were necessary using energy‐dispersive x‐ray microanalysis in a scanning electron microscope (SEM/EDX) to determine the stage of corrosion and the Ag concentration of the core of the coins. The results showed differences of up to 50% between the composition of the core and the surface. Finally, proton‐induced x‐ray emission (PIXE) at an external proton beam was applied, in order to detect also Ni, an element which could not be measured by either EDXRF or SEM/EDX in the ppm range. The data show a clear difference in the Ni content between the coins from Merano (～0.1% Ni) and Hall (～0.01% Ni). Copyright © 2003 John Wiley & Sons, Ltd.     

Non‐invasive approach in the study of polychrome terracotta sculptures: employment of the portable XRF to investigate complex stratigraphy

In the field of conservation science, in situ non‐invasive analytical techniques are widely used to investigate polychrome surfaces as frescoes, mural or easel paintings. Indeed, these techniques allow achieving information on materials composition and they often reduce the micro‐sampling. In this work, in situ non‐invasive techniques have been used to study a complex system, terracotta polychrome sculptures. The presence of the priming, the numerous painted layers and the ground layer spread on a porous material substrate are the main features of these sculptures; therefore, their study requires a scientific approach based on results obtained by different analytical techniques. In order to evaluate potentialities and limitations of the non‐invasive approach to this complex case, the results of energy‐dispersive X‐ray fluorescence (EDXRF), spectrophotometry and optical microscopy have been compared with the data achieved by laboratory analytical investigation as optical and scanning electron microscopy, energy‐dispersive X‐ray microanalysis and Raman spectroscopy. In particular, XRF data collected on several polychrome terracotta are here re‐examined on the basis of the results obtained by laboratory techniques. Even if, in some cases, portable XRF may induce to a wrong interpretation of the stratigraphy, it can be considered a suitable instrument for a preliminary diagnostic campaign of terracotta polychrome sculptures. Copyright © 2011 John Wiley & Sons, Ltd.     

Insight into growth of Au–Pt bimetallic nanoparticles: an in situ XAS study

Au–Pt bimetallic nanoparticles have been synthesized through a one‐pot synthesis route from their respective chloride precursors using block copolymer as a stabilizer. Growth of the nanoparticles has been studied by simultaneous in situ measurement of X‐ray absorption spectroscopy (XAS) and UV–Vis spectroscopy at the energy‐dispersive EXAFS beamline (BL‐08) at Indus‐2 SRS at RRCAT, Indore, India. In situ XAS spectra, comprising both X‐ray near‐edge structure (XANES) and extended X‐ray absorption fine‐structure (EXAFS) parts, have been measured simultaneously at the Au and Pt L₃‐edges. While the XANES spectra of the precursors provide real‐time information on the reduction process, the EXAFS spectra reveal the structure of the clusters formed in the intermediate stages of growth. This insight into the formation process throws light on how the difference in the reduction potential of the two precursors could be used to obtain the core–shell‐type configuration of a bimetallic alloy in a one‐pot synthesis method. The core–shell‐type structure of the nanoparticles has also been confirmed by ex situ energy‐dispersive spectroscopy line‐scan and X‐ray photoelectron spectroscopy measurements with in situ ion etching on fully formed nanoparticles.     

Fluoropolymer‐based clear and white paint coatings composition analysis by X‐Ray fluorescence

A new method for the quantification of organic and inorganic phase fractions was developed for fluoropolymer/acrylic‐blend paints – clear and white paint coatings – on aluminum panels by using wavelength dispersive X‐ray fluorescence spectrometry (WDXRF). The method was developed for clear coat samples (only containing fluoropolymer and acrylic phases) as well as white paint samples by also measuring silica and titanium dioxide levels. Both WDXRF and X‐ray photoelectron spectroscopy (XPS), a surface technique, were investigated. For clear coat samples, we found that WDXRF provided far superior quantitative results to XPS, likely related to the extreme surface sensitivity of XPS, in this case a drawback more than a strength. For white paint samples, the X‐ray fluorescence spectrometry method achieved a relative accuracy typically better than 5% for the organic phases and better than 2% for the inorganic phases, for measurements on 8‐mm diameter samples. Copyright © 2013 John Wiley & Sons, Ltd.     

Microanalysis of clay‐based pigments in painted artworks by the means of Raman spectroscopy

FT Raman spectroscopy and micro‐Raman spectroscopy with lasers of three different wavelengths (1064 nm, 785 nm and 532 nm) were used for analysis of reference samples of natural clay pigments including white clay minerals (kaolinite, illite, montmorillonite), green earths (glauconite and celadonite) and red earths (natural mixtures of white clay minerals with hematite). In addition, eight micro‐samples obtained from historical paintings containing clay pigments in ground and colour layers have been examined. Powder X‐ray diffraction and micro‐diffraction were used as supplementary methods. It was found that laser operating at 1064 nm provided the best quality Raman spectra for distinguishing different white clay minerals, but the spectra of green and red earths were affected by strong fluorescence caused by the presence of iron. Green earth minerals could be easily distinguished by 532 or 785 nm excitation lasers, even in small concentrations in the paint layers. On the other hand, when anatase (TiO₂) or iron oxides (such as hematite) were present as admixtures (both are quite common, particularly in red earths), the collection of characteristic spectra of clay minerals which form the main component of the layer was hindered or even prevented. Another complicating factor was the fluorescence produced by organic binders when analysing the micro‐samples of artworks. In those cases, it is always necessary to use powder X‐ray micro‐diffraction to avoid misleading interpretations of the pigment's composition. Copyright © 2013 John Wiley & Sons, Ltd.     

Analysis of confiscated fireworks using Raman spectroscopy assisted with SEM‐EDS and FTIR

A forensic analysis of several samples of pyrotechnic artefacts was performed by Raman spectroscopy assisted by scanning electron microscopy/energy‐dispersive X‐ray spectroscopy (SEM‐EDS) and Fourier transform infrared (FTIR) analysis. Among the components, several nitrates, ammonium perchlorate, nitrocellulose, metallic titanium particles and shellac were detected. The combination of Raman spectroscopy and SEM‐EDS showed very useful performance. All components were detected by Raman spectroscopy except for shellac, kaolinite and titanium particles, which were not conclusive enough and had to be determined by FTIR and EDS. In contrast, many compounds were not detected by FTIR. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis,characterization, and electrochemical properties of imidazole derivatives functionalized single‐walled carbon nanotubes

The imidazole derivatives functionalized single‐walled carbon nanotubes (SWNTs) were synthesized by a diazonium‐based reaction. We have designed and synthesized two imidazole derivatives to modify SWNTs. The resulting products were characterized by Fourier transform infrared (FT‐IR) spectroscopy, Raman spectroscopy, ultraviolet visible (UV/Vis) spectroscopy, thermo gravimetric analysis (TGA), energy dispersive X‐ray spectroscopy (EDX), transmission electron microscopy (TEM), and atomic force microscopy (AFM). Electrochemical measurements via a cyclic voltammetry method revealed that the weak intramolecular electronic interactions presented between the attached imidazole derivatives groups and the nanotubes. Copyright © 2008 John Wiley & Sons, Ltd.     

Subsurface analysis of painted sculptures and plasters using micrometre‐scale spatially offset Raman spectroscopy (micro‐SORS)

A recently developed variant of spatially offset Raman spectroscopy (SORS) for the non‐invasive analysis of thin painted layers, micro‐SORS, has been applied, for the first time, to real objects of Cultural Heritage – namely painted sculptures and plasters. Thin layers of paint originating from multiple restoration processes often applied over many centuries have been analysed non‐destructively using micro‐SORS to depths inaccessible to, or unresolvable into separate layers, by conventional confocal Raman microscopy. The concept has been demonstrated on several artistic artefacts of historical significance originating from Italy and dating from the medieval to the 18th century. The technique extends the depth applicability of Raman spectroscopy and with its inherently high chemical specificity that expands the portfolio of existing non‐destructive analytical tools in Cultural Heritage permitting to avoid cross‐sectional analysis often necessitated with this type of samples with conventional Raman microscopy. Currently, the method is non‐invasive only for artworks that can be placed under Raman microscope although there is a prospect for its use in a mobile system with largely removed restrictions on sample dimensions. © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons Ltd.     

Characterization of pottery from Republic of Macedonia. III. A study of comparative mineralogical detection efficiency using micro‐Raman mapping and X‐ray diffraction

Point‐to‐point micro‐Raman and X‐ray diffraction (XRD) techniques were employed for characterization of minerals present in the pottery body of 27 glazed Byzantine and Ottoman pottery shreds, excavated at two different archaeological sites in the Republic of Macedonia: in Skopje (Skopsko Kale) and in Prilep (Markovi Kuli and Sv. Atanas Church). The Raman spectra of 18 Byzantine samples (dating from 12th−14th century) and nine Ottoman samples (dating from 17th−19th century) revealed 26 different minerals. XRD measurements were further performed on the same powder samples to validate the mineralogical assessment obtained by point‐to‐point micro‐Raman spectroscopy. Although only 13 different mineral phases were obtained by the XRD, the results obtained from the Raman and XRD spectra for the most abundant minerals in the investigated pottery bodies match quite well. However, the identification of the less abundant minerals in the clay matrixes from the XRD data was very difficult, if at all possible. The results emphasize the specifics of the applied techniques and their limits. Additionally, wavelength dispersive X‐ray fluorescence spectroscopy was used for the elemental analysis. Copyright © 2011 John Wiley & Sons, Ltd.