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.     

Argentinean prehistoric pigments’ study by combined SEM/EDX and molecular spectroscopy

Composition of the prehistoric pigments’ (from Carriqueo rock shelter, Rio Negro province, Argentina) has been analysed by means of molecular spectroscopy (Fourier transform infrared (FTIR) and micro-Raman) and scanning electron microscopy (SEM) coupled to an energy-dispersive X-ray spectrometer (EDS). Red and yellow pigments were recognized as red and yellow ochre. The matrix of the pigments is composed of one or more substances. According to the matrix composition yellow and red pigments were also divided into two groups—i.e. those containing kaolinite or sulphates. Green pigment was detected as green earth, made up of celadonite as a chromophore.     

Investigation of roman age pigments found on pottery fragments

This work deals with the study of the physico-chemical characteristics of pigments found on pottery fragments from an excavation in Vicenza (Contrà Pedemuro S. Biagio). The examined pigments were: a blue colour on a terracotta fragment; an olive green on a black pot bottom; yellow traces on a red depurated terracotta; an olive green plate bottom with an amaranth “a fresco” test; a deep red on a depurated terracotta; a white trace, again on a depurated terracotta. The techniques used were optical microscopy, scanning electron microscopy (SEM), equipped with an energy dispresive (EDS) microanalysis detector, X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Most of those techniques were non-destructive and able to provide the required results. All the pigments belonged to the group of basic colours, we did not find “precious” pigments. They have many similarities to those discovered in other European sites in France and Switzerland, witnessing the active trading exchange in which X^a Regio, Venetia et Histria played an important role.     

Composition of prehistoric rock-painting pigments from Egypt (Gilf Kébir area)

The composition of rock-painting pigments from Egypt (Gilf Kebia area) has been analyzed by means of molecular spectroscopy such as Fourier transform infrared and micro-Raman spectroscopy and scanning electron microscopy coupled to an energy dispersive X-ray spectrometer and X-ray fluorescence analysis. Red and yellow pigments were recognized as red and yellow ochre with additional rutile.     

Use of Raman microspectroscopy to characterize wallpaintings in Cerro de las Cabezas and the Roman villa of Priego de Cordoba (Spain)

The analysis by Raman microscopy of several wallpainting fragments found at an archaeological site in Fuente Tojar and in the Roman villa of Priego de Cordoba, both in southern Spain, revealed that the most abundant colours in them were obtained from the usual pigments of the time. Thus, red corresponded to red ochre, which consisted of hematite mainly. Also, yellow came from yellow ochre (goethite), blue from Egyptian blue, and grey hues were obtained from mixtures of coal and calcite occasionally also containing gypsum. The components of some pigments were confirmed by X-ray diffraction spectroscopy. The two spectroscopic techniques were additionally used to examine the mortars and the preparatory layer present in the fragments.     

Microanalysis of blue pigments from the Ptolemaic temple of Hathor (Thebes), Upper Egypt: a case study

The aim of the present work was to characterize blue pigment samples collected from the Ptolemaic temple of Hathor (Thebes), the western bank of Luxor, Upper Egypt. The characterization of the examined pigments was carried out by means of optical microscopy, scanning electron microscopy equipped with an energy dispersive X‐ray detector, micro X‐ray fluorescence spectrometry and Fourier transform infrared spectroscopy. On the basis of the chemical composition and microstructure of the samples, the blue pigments were identified as Egyptian blue (cuprorivaite, CaCuSi₄O₁₀). Moreover, the micro X‐ray fluorescence analysis revealed significant quantities of lead in the glass phase suggesting that a leaded bronze scrap was used to produce the pigment. The optical examination of the paint layers showed that the pigments were applied on a thin layer consisting of gypsum (CaSO₄?2H₂O) and dolomite (CaMg(CO₃)₂). In addition, some pigment samples showed discoloration mainly in the form of green and black hues. The obtained results helped in improving our knowledge about some painting materials used during the Ptolemaic era of ancient Egypt. Copyright © 2012 John Wiley & Sons, Ltd.     

Romano-British wall-paintings II: Raman spectroscopic analysis of two villa sites at Nether Heyford, Northants

We report the analysis of 31 fragments of Roman wall-paintings from two adjacent villa sites near Northampton, which date from about 1800 years b.p. The specimens comprise pigments which are still attached to their substrate, affording an opportunity for the examination of interaction. The palette is rather restricted to a predominance of red (with shades varying from pink through to deep red), white and grey colours, with yellow, blue, brown and green being only rarely observed. This contrasts with Romano-British villa specimens from other sites where a more extensive palette has been recognised.     

Structural Characterization of a Novel Antioxidant Pigment Produced by a Photochromogenic <Emphasis Type="Italic">Microbacterium oxydans</Emphasis> Strain

The Microbacteriaceae family, such as Microbacterium, is well known for its ability to produce carotenoid-type pigments, but little has been published on the structure of such pigments. Here, we isolated the yellow pigment that is responsible for the yellowish color of a Microbacterium oxydans strain isolated from a decomposing stump of a resinous tree. The pigment, which is synthesized when the bacterium is grown under light, was purified and characterized using several spectroscopic analyses, such as ultraviolet-visible spectroscopy (UV–Vis), Fourier transform infrared spectroscopy (FTIR), ¹H and ¹³C nuclear magnetic resonance (¹H NMR, ¹³C NMR), and high-resolution mass spectrometry (HRMS). From these analysis, a molecular formula (C₂₇H₄₂O₂) and a chemical structure (8-hydroxymethyl-2,4,12-trimethyl-14-(2,6,6-trimethyl-cyclohex-2-enyl)-teradeca-3,7,9,11,13-pentan-2-ol) were deduced. The chemical properties of the pigment, such as aqueous stability at different pH, stability in different organic solvents, and antioxidant capacity, are also reported. Together, these data and previous studies have resulted in the identification of a new antioxidant pigment produced by M. oxydans. To the best of our knowledge, this is the first thorough investigation of this carotenoid-like pigment in the Microbacterium genera.     

Encapsulation of aluminum flakes with hybrid silica/poly(acrylic acid) nanolayers by combination of sol–gel and in situ polymerization methods: a corrosion behavior study

A combination of sol–gel method and in situ polymerization was used to form a hybrid silica/poly(acrylic acid) nanolayer for the corrosion protection of aluminum pigments. To this end, the pigment particles were first coated with a silica layer by sol–gel method. Tetraethylorthosilicate was used as a precursor and during a condensation reaction, an inorganic silica layer was formed. Then, 3-methacryloxypropyltrimethoxysilane was attached on the surface and in situ polymerization of acrylic acid (AA), as a hydrophile monomer, was performed. The obtained Al/Si/PAA flakes were characterized by different methods such as Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, and transmission electron microscopy (TEM). The attached PAA chains on the surface were deattached by HF aqueous solution and analyzed by gel permeation chromatography. Also, the surface energy of samples was measured using Owens and Wendt equation by means of contact angle data. As results, the characterizing tests approved the successful encapsulation of Al pigments and TEM image showed a 10–15 nm silica layer and a 20–25 nm PAA layer. Although the Al/Si pigments showed a quantity of evolved hydrogen, the hybrid coated pigments had excellent anticorrosive properties in acidic and alkaline solutions. Also, the surface free energy of Al/Si/PAA showed an increase compared to that of Al.     

Effect of inorganic cores on dye properties of inorganic-organic hybrid pigments yellow 12

Some inorganic-organic hybrid pigments were fabricated by depositing pigment yellow 12(P.Y.12) on the surface of three inorganic cores with different particle size (white carbon black,microsilica,palygorskite). Effect of inorganic cores on the morphology and structure of the hybrid pigments were systematically investigated by nanoparticle analyzer, Fourier transforms infrared spectroscopy, and X-ray diffraction. Results showed that all three inorganic cores were encapsulated by the organic pigment. The particle size of hybrid pigments was all smaller and had narrower diameter scatter than the original pigment. The water dispersion and flow ability of these fabricated pigments were slightly improved. Thermal and UV-Vis analyses showed that the hybrid pigments had better thermo- and photo-stabilities. Additionally, the properties of the hybrid pigments including color strength, lightness, and yellow hue index were also improved and the modified pigment with white carbon black had the best coloring performance and better heat resistance than original P.Y.12.     

Identification and Characterization of the Yellow Pigment Synthesized by Cupriavidus sp. USMAHM13

Microbial pigments are gaining intensive attention due to increasing awareness of the toxicity of synthetic colours. In this study, a novel polymer-producing bacterium designated as Cupriavidus sp. USMAHM13 was also found to produce yellow pigment when cultivated in nutrient broth. Various parameters such as temperature, pH and ratio of culture volume to flask volume were found to influence the yellow pigment production. UV-Visible, Fourier transform infrared and ¹³C-nuclear magnetic resonance analyses revealed that the crude yellow pigment might probably represent new bioactive compound in the carotenoid family. The crude yellow pigment also exhibited a wide spectrum of antimicrobial activity against Gram-negative and Gram-positive bacteria with their inhibition zones and minimal inhibitory concentrations ranged from 25 to 38 mm and from 0.63 to 2.5 mg/ml, respectively. To the best of our knowledge, this is the first report on the identification and characterization of yellow pigment produced by bacterium belonging to the genus Cupriavidus.     

A noninvasive complementary study of an Egyptian polychrome cartonnage pigments using SEM,EPMA, and Raman spectroscopy

Raman spectroscopy, optical microscopy, scanning electron microscopy (SEM), and electron probe microanalysis (EPMA) were used to study pigments on an Egyptian cartonnage from the Ptolemaic period (305–30 bc ). The surface morphology of each color region was examined using backscattering (BS) and secondary electron imaging. SEM X-ray energy dispersive spectrometry and EPMA wavelength dispersive spectroscopy provided semiquantitative chemical analysis of each pigment. Raman spectroscopy was used to identify the minerals associated with the pigments. This technique confirmed the presence of cinnabar (α-HgS) in the red part of the fragments. A mixture of orpiment (As₂S₃) and bonazziite (β-As₄S₄) and/or alacránite (As₈S₉) was detected in the yellow regions of the fragments. The orange pigment was confirmed to be a mixture of orpiment, uzonite (χ-As₄S₅), and pararealgar (As₄S₄). Egyptian blue (CaCuSi₄O₁₀) and Egyptian green ((Cu,Ca)SiO₃) pigments were detected from blue/green dark-colored regions of the fragments.     

Use of different spectroscopic techniques in the analysis of Roman age wall paintings

In this paper the analysis of samples of Roman age wall paintings coming from: Pordenone, Vicenza and Verona is carried out by using three different techniques: energy dispersive x-rays spectroscopy (EDS), x-rays fluorescence (XRF) and proton induced x-rays emission (PIXE). The features of the three spectroscopic techniques in the analysis of samples of archaeological interest are discussed. The studied pigments were: cinnabar, yellow ochre, green earth, Egyptian blue and carbon black.     

One-step synthesis of lamellar molybdate pillared hydrotalcite and its application for AZ31 Mg alloy protection

A novel anticorrosion pigment for AZ31 Mg alloy protection, molybdate pillared hydrotalcite (HT-MoO₄^2?), was successfully fabricated via a simple one-step process. The physicochemical properties of the samples were well characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), Raman spectra, and inductively coupled plasma (ICP) method, respectively. The results indicated that the material showed typical characteristics of molybdate intercalated hydrotalcite. Additionally, it was found that the sample exhibited nano-sized lamellar morphology with the particle size of 35–60 nm. Moreover, the coating on AZ31 Mg alloy containing HT-MoO₄^2? pigment showed obviously higher corrosion protection performance in comparison with the strontium chromate (SC) pigment by Electrochemical impedance spectroscopy (EIS) measurements. The mechanism of corrosion protection was proposed to be that the HT-MoO₄^2? pigment in the coating would cause the pigment to undergo amphoteric ion exchange with aggressive NaCl solution, leading to the release of molybdate and Zn²⁺ inhibitors.     

唐代彩绘陶俑中无机颜料的化学组成

采用X射线粉末衍射（XRD）、X射线荧光光谱（XRF）和扫描电子显微镜-能谱（SEM-EDS）等测试技术对西安西曹M16唐墓出土的2尊唐代彩绘陶俑颜料进行了化学组成分析。结果表明,陶俑中含有丰富的无机颜料,其中红色颜料的显色成分为铅丹（Pb₃O₄）;白色颜料的显色成分为铅白（PbCO₃）和石灰石（CaCO₃）;粉色颜料的主要显色成分为铅丹和铅白的混合物;青色颜料为铜绿（Cu₂（OH）₂CO₃）和青石（Cu₃（OH）₂（CO₃）₂）混合物。     

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.     

Integrated analytical techniques for the study of ancient Greek polychromy

The materials used in the decoration of three painted astragaloi (knucklebones) from the Koroneia cave (Greece) were investigated by means of sequential application of non-destructive and destructive techniques: optical microscopy, environmental scanning electron microscopy coupled with X-ray microanalysis (ESEM-EDX), Fourier transform infrared spectroscopy (FTIR) with micro-attenuated total reflection (μ-ATR) technique, high performance liquid chromatography (HPLC) coupled with UV-fluorescence and gas chromatography-mass spectrometry (GC-MS) were used.The main results highlighted that the three astragaloi were prepared with a ground of ochre or iron clay and painted with a proteinaceous matter such as binder egg tempera. Both FTIR and GC-MS agree in the detection of lipids that can be related to egg. Organic dyestuffs identified as madder lake and shellfish purple were used together with inorganic pigments.     

Studies of wall painting fragments from Kaiping Diaolou by SEM/EDX, micro Raman and FT-IR spectroscopy

The multi-technique analytical approach has proved to be a very effective tool for the analysis of artwork, as demonstrated by various studies. In this work, four micro-analysis methods were used to analyze the wall painting fragments in Kaiping Diaolou, a world cultural heritage enlisted in 2007. Field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray micro-analysis (EDX), combined with micro Raman and Fourier transform infrared (FT-IR) spectroscopy, provided a vast amount of information concerning the raw materials present in the pigments, organic binder, plasters and mortars of the wall painting. Four types of pigments (goethite, lazurite, chromium green and calcite) were identified on the surface layer of the wall paintings. The substrate under the pigment layer was found to be composed of cubic-like calcite (CaCO₃), micro-rod bundle-shaped syngenite (K₂Ca(SO₄)₂·H₂O), gypsum (CaSO₄·2H₂O) and silica (SiO₂). The organic binder can be attributed to animal glue (such as egg) and drying oil by micro FT-IR spectroscopy. These analysis results can provide important information for the conservation and restoration of the Kaiping Diaolou.     

Gold Gilding and Pigment Identification on a Post-Byzantine Icon from Kastoria,Northern Greece

The investigation of gilded gold, black and red pigments from the Byzantine icon of Panagia from the church of Agioi Anargyroi Gymnasiou in Kastoria, northern Greece is the aim of this study. Small fragments, having a gold leaf finish, were detached from the icon and were analyzed by Environmental Scanning Electron Microscopy coupled to Energy Dispersive System (ESEM-EDS) and Raman microscopy. The chemical (EDS) composition of the gilding material revealed a high gold content alloy (Au 81.34 wt%) with trace amounts of silver (Ag 1.66 wt%), copper (Cu 0.62 wt%) and iron (Fe 0.58 wt%). The Raman spectrum of the gold leaf showed characteristic bands at 236, 369, and 468 cm^?1. The red pigment on the surface comprises of Hg, S, and minor amounts of Pb and is attributed to the minerals cinnabar (HgS) and minium (Pb₃O₄). The black pigment has high carbon content, attributed to organic material (black carbon). The micro-Raman spectroscopy provided a more detailed determination of the composition of the red and black pigments. In particular, the vivid red color was attributed to cinnabar (bands at 253 and 342 cm^?1). Particles of black carbon (bands at 1345 and 1577 cm^?1) and oxalates (band at 861 cm^?1) were determined on the black pigments. Dark regions on the pigmented surface were assigned to a mixture of cinnabar [bands at 253 and 342 cm^?1] and minium [bands at 120, 142, 288, and 545 cm^?1]. The latter lead oxides might have been used either as a dryer or a burnish agent for the gold leaf. The micro-structural and chemical analysis of several distinct strata of the icon, as observed under ESEM, revealed a red-colored stratum beneath the gold leaf, with an iron aluminosilicate composition. This is the so-called bole (red clay) commonly used as sub-strata for gilding art objects. Multiple layers of white ground material, composed of gesso (gypsum) underlie the bole strata. Moreover, one thin organic binder (animal glue) was is observed within the gesso ground of the icon.