The invention of blue and purple pigments in ancient times.

PubMed

Berke, Heinz

2007-01-01

This tutorial review examines manmade blue and purple pigments appearing in antiquity. They were obtained by chemical synthesis from mineral starting materials and refer to chemical compounds: Egyptian Blue (CaCuSi4O10), Han Blue (BaCuSi4O10) and Han Purple (BaCuSi2O6), Maya Blue (x.indigo.(Mg,Al)4Si8(O,OH,H2O)24) and Ultramarine Blue (Na,Ca)8(AlSiO12)(S, SO4,Cl). The Egyptian and Chinese copper-based pigments are assumed to have been developed independently and are presumably an outcome of the historical developments in glazing techniques. A technology transfer from Egypt into China cannot be fully excluded but, based on the facts acquired up to now, looks less probable.

Application of photoacoustic infrared spectroscopy in the forensic analysis of artists' inorganic pigments.

PubMed

von Aderkas, Eleanor L; Barsan, Mirela M; Gilson, Denis F R; Butler, Ian S

2010-12-01

Fourier-transform photoacoustic infrared (PAIR) spectroscopy has been used in the analysis of 12 inorganic pigments commonly in use by artists today, viz., cobalt blue, ultramarine blue, Prussian blue, azurite, malachite, chromium oxide, viridian, cadmium yellow, chrome yellow, iron oxide, yellow ochre and Mars orange. The authenticity of these 12 commercial pigments was first established by recording their Raman spectra. The subsequent PAIR spectra were highly reproducible and matched well in the mid-IR region with previously published data for these pigments. A number of additional overtone and combination bands were also detected that will prove useful in the identification of the pigments in the future. The PAIR technique is a promising and reliable method for the analysis of inorganic pigments, especially since it involves much simpler preparation than is required for conventional IR measurements. Copyright © 2010. Published by Elsevier B.V.

Finnish wallpaper pigments in the 18th-19th century: Presence of KFe3(CrO4)2(OH)6 and odd pigment mixtures

NASA Astrophysics Data System (ADS)

Castro, Kepa; Knuutinen, Ulla; Vallejuelo, Silvia Fdez-Ortiz de; Irazola, Mireia; Madariaga, Juan Manuel

2013-04-01

Several Finish wallpapers from the 18th and 19th century were analysed by using Raman spectroscopy assisted with EDXRF instrumentation, in an attempt of determine the pigments used in their manufacture process as well as of trying to date some of the samples through pigment composition. All pigments present in samples were determined and surprisingly the unusual and strange iron (III) chromate yellow pigment was found. Besides, unusual mixtures were found to obtain fashionable colours, especially in blue and green areas, where more than one blue pigments were mixed with green and yellow pigments. Blue verditer, ultramarine blue, Prussian blue, chrome yellow, calcite, lead white, red and yellow iron oxide, gypsum and carbon black were identified. The presence of the risky and poisonous emerald green must be highlighted. The results were compared with those found in other wallpapers from Spain and France.

Cleaning of Fire Damaged Watercolor and Textiles Using Atomic Oxygen

NASA Technical Reports Server (NTRS)

Rutledge, Sharon K.; Banks, Bruce A.; Chichernea, Virgil A.; Haytas, Christy A.

2000-01-01

A noncontact technique is described that uses atomic oxygen generated under low pressure in the presence of nitrogen to remove soot from the surface of a test watercolor panel and strips of cotton, wool and silk. The process, which involves surface oxidation, permits control of the amount of surface material removed. The effectiveness of soot removal from test panels of six basic watercolors (alizarin crimson, burnt sienna, lemon yellow, yellow ochre, cerulean blue and ultramarine blue) and strips of colored cotton, wool and silk was measured using reflectance spectroscopy. The atomic oxygen removed soot effectively from the treated areas and enabled partial recovery of charred watercolors. However, overexposure can result in removal of sizing, bleaching, and weakening of the structure. With the proper precautions, atomic oxygen treatment appears to have great potential to salvage heavily smoke damaged artworks which were previously considered unrestorable.

The characterization of canvas painting by the Serbian artist Milo Milunović using X-ray fluorescence, micro-Raman and FTIR spectroscopy

NASA Astrophysics Data System (ADS)

Damjanović, Lj.; Gajić-Kvaščev, M.; Đurđević, J.; Andrić, V.; Marić-Stojanović, M.; Lazić, T.; Nikolić, S.

2015-10-01

A canvas painting by Milo Milunović "The Inspiration of the poet" was studied by energy dispersive X-Ray fluorescence (EDXRF), micro-Raman and Fourier transform infrared (FTIR) spectroscopy in order to identify materials used by the artist and his painting technique. Study is perfomed combining in situ non-destructive method with the preparation and study of cross-section samples and raw fragments of the samples. Milo Milunović, an eminent painter from Balkan region, made a copy of the Nicolas Poussin's original painting in Louvre in 1926/27. Obtained results revealed following pigments on the investigated canvas painting: vermilion, minium, cobalt blue, ultramarine, lead white, zinc white, cadmium yellow, chrome-based green pigment and several earth pigments - red and yellow ocher, green earth and umber. Ground layer was made of lead white mixed with calcium carbonate.

Characterization of Sorolla's gouache pigments by means of spectroscopic techniques

NASA Astrophysics Data System (ADS)

Roldán, Clodoaldo; Juanes, David; Ferrazza, Livio; Carballo, Jorgelina

2016-02-01

This paper presents the characterization of the Joaquín Sorolla's gouache sketches for the oil on canvas series "Vision of Spain" commissioned by A. M. Huntington to decorate the library of the Hispanic Society of America in New York. The analyses were focused on the identification of the elemental composition of the gouache pigments by means of portable EDXRF spectrometry in a non-destructive mode. Additionally, SEM-EDX and FTIR analyses of a selected set of micro-samples were carried out to identify completely the pigments, the paint technique and the binding media. The obtained results have confirmed the identification of lead and zinc white, vermillion, earth pigments, ochre, zinc yellow, chrome yellow, ultramarine, Prussian blue, chromium based and copper-arsenic based green pigments, bone black and carbon based black pigments, and the use of gum arabic as binding media in the gouache pigments.

The use of a multi-method approach to identify the pigments in the 12th century manuscript Liber Floridus

NASA Astrophysics Data System (ADS)

Deneckere, A.; De Reu, M.; Martens, M. P. J.; De Coene, K.; Vekemans, B.; Vincze, L.; De Maeyer, Ph.; Vandenabeele, P.; Moens, L.

2011-10-01

A selection of illuminations of the 12th century manuscript Liber Floridus was analysed with Raman spectroscopy (in situ and laboratory measurements), X-ray fluorescence spectroscopy, UV-fluorescence photography and infrared reflectography (IRR). The aim of this study is to determine the pigments used, in order to search for anachronisms. Using a combination of Raman spectroscopy (molecular information) and X-ray fluorescence spectroscopy (elemental information) following pigments could be identified: ultramarine (Na 8-10Al 6Si 6O 24S 2-4), azurite (2CuCO 3·Cu(OH) 2), caput mortuum (Fe 2O 3), vermilion (HgS), orpiment (As 2S 3) and lead white (2PbCO 3·Pb(OH) 2). Moreover, two synthetic red pigments, PR4 and PR176, and a degradation product, gypsum (CaSO 4·2H 2O), were present in the manuscript. To establish the origin of the modern materials UV-fluorescence photography was used. Infrared reflectography (IRR) was applied to visualise the underdrawing of the investigated folios.

Elemental identification of blue paintings traces present in historic cemeteries in the São Martinho region, southern Brazil

NASA Astrophysics Data System (ADS)

Costa, Thiago G.; Richter, Fábio Andreas; Castro, Elisiana Trilha; Gonçalves, Samantha; Spudeit, Daniel A.; Micke, Gustavo A.

2018-03-01

Cemeteries are of great significance in many communities, often being considered of invaluable historical, artistic, architectural and cultural significance and thus they need to be preserved. In this regard, understanding the historical aspects and the construction techniques used is essential for their protection. The purpose of this paper is to describe historical aspects of the funerary heritage present in the region of São Martinho in southern Brazil, along with an analysis of the blue paint found in cemeteries of German colonies in the region studied. FTIR analysis suggests that the binder is composed mostly of a protein resin and a small amount of lipid. The morphology of the pigment was investigated by SEM and EDS and the spectra revealed that the major elements present in the blue pigment are Na, Al, Si and S, with an overlap in the elemental mapping, indicative of ultramarine pigments. The GC-MS results are consistent with the type of binder identified by FTIR and indicate a mixture of oils, probably from vegetal sources, and proteins.

Chemical curing in alkyd paints: An evaluation via FT-IR and NMR spectroscopies

NASA Astrophysics Data System (ADS)

Bartolozzi, G.; Marchiafava, V.; Mirabello, V.; Peruzzini, M.; Picollo, M.

2014-01-01

A study aimed at determining the time necessary for an alkyd paint to attain chemical curing is presented. In particular, the object of our investigation was an oil paint made by Winsor & Newton, namely French ultramarine (PB29) in the Griffin Alkyd “fast drying oil colour” series. Using this paint, we prepared several mock-ups on glass. These were left in the laboratory at room temperature in a piece of furniture with glass doors for a total of 70 days. Samples were taken at different times, and the changes in their composition were monitored by means of FT-IR and multinuclear NMR spectroscopic analyses. Since the cross-linking reactions involved in the formation of the pictorial film mainly affect the amount of carbon-carbon double bonds, we monitored the decrease in allyl, diallyl and vinyl protons and carbons. The data obtained from the use of both techniques led us to conclude that, in our particular experimental conditions, the chemical curing of the paint layer is reached within the first 70 days, thus establishing the beginning of the ageing phenomena.

Development of massive multilevel molecular dynamics simulation program, Platypus (PLATform for dYnamic Protein Unified Simulation), for the elucidation of protein functions.

PubMed

Takano, Yu; Nakata, Kazuto; Yonezawa, Yasushige; Nakamura, Haruki

2016-05-05

A massively parallel program for quantum mechanical-molecular mechanical (QM/MM) molecular dynamics simulation, called Platypus (PLATform for dYnamic Protein Unified Simulation), was developed to elucidate protein functions. The speedup and the parallelization ratio of Platypus in the QM and QM/MM calculations were assessed for a bacteriochlorophyll dimer in the photosynthetic reaction center (DIMER) on the K computer, a massively parallel computer achieving 10 PetaFLOPs with 705,024 cores. Platypus exhibited the increase in speedup up to 20,000 core processors at the HF/cc-pVDZ and B3LYP/cc-pVDZ, and up to 10,000 core processors by the CASCI(16,16)/6-31G** calculations. We also performed excited QM/MM-MD simulations on the chromophore of Sirius (SIRIUS) in water. Sirius is a pH-insensitive and photo-stable ultramarine fluorescent protein. Platypus accelerated on-the-fly excited-state QM/MM-MD simulations for SIRIUS in water, using over 4000 core processors. In addition, it also succeeded in 50-ps (200,000-step) on-the-fly excited-state QM/MM-MD simulations for the SIRIUS in water. © 2016 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.

Chemical curing in alkyd paints: an evaluation via FT-IR and NMR spectroscopies.

PubMed

Bartolozzi, G; Marchiafava, V; Mirabello, V; Peruzzini, M; Picollo, M

2014-01-24

A study aimed at determining the time necessary for an alkyd paint to attain chemical curing is presented. In particular, the object of our investigation was an oil paint made by Winsor & Newton, namely French ultramarine (PB29) in the Griffin Alkyd "fast drying oil colour" series. Using this paint, we prepared several mock-ups on glass. These were left in the laboratory at room temperature in a piece of furniture with glass doors for a total of 70 days. Samples were taken at different times, and the changes in their composition were monitored by means of FT-IR and multinuclear NMR spectroscopic analyses. Since the cross-linking reactions involved in the formation of the pictorial film mainly affect the amount of carbon-carbon double bonds, we monitored the decrease in allyl, diallyl and vinyl protons and carbons. The data obtained from the use of both techniques led us to conclude that, in our particular experimental conditions, the chemical curing of the paint layer is reached within the first 70 days, thus establishing the beginning of the ageing phenomena. Copyright © 2013 Elsevier B.V. All rights reserved.

Virtuous colours for Mary. Identification of lapis lazuli, smalt and cochineal in the Andean colonial image of Our Lady of Copacabana (Bolivia)

PubMed Central

Tomasini, Eugenia P.; Marte, Fernando; Careaga, Valeria P.; Landa, Carlos Rúa; Siracusano, Gabriela

2016-01-01

The image of Our Lady of Copacabana, a gilded polychrome sculpture carved in maguey wood in 1583, is one of the most important devotions in the Americas. In former research, we have identified the use of gypsum, Armenian bole, cerussite and atacamite in its polychromy. In this study, a red sample taken from the Virgin's tunic and a blue sample extracted from the cloak have been analysed with the aim to identify both pigments and offer insights into the painting technique. Analysis by micro-Raman spectroscopy complemented with scanning electron microscopy–energy dispersive spectroscopy and high-performance liquid chromatography allowed the identification of carmine lake in the red sample. Analysis by micro-Raman spectroscopy of the surface of the blue sample and its cross section showed the presence of smalt—the blue-glass pigment—over a cerussite layer, bathed by a very thin ultramarine layer—from a probable native origin—following a pictorial tradition that would last even until the eighteenth century. This is the first time that lapis lazuli has been scientifically identified in a Spanish American colonial painted layer. This article is part of the themed issue ‘Raman spectroscopy in art and archaeology’. PMID:27799431

Photoacoustic signal attenuation analysis for the assessment of thin layers thickness in paintings

NASA Astrophysics Data System (ADS)

Tserevelakis, George J.; Dal Fovo, Alice; Melessanaki, Krystalia; Fontana, Raffaella; Zacharakis, Giannis

2018-03-01

This study introduces a novel method for the thickness estimation of thin paint layers in works of art, based on photoacoustic signal attenuation analysis (PAcSAA). Ad hoc designed samples with acrylic paint layers (Primary Red Magenta, Cadmium Yellow, Ultramarine Blue) of various thicknesses on glass substrates were realized for the specific application. After characterization by Optical Coherence Tomography imaging, samples were irradiated at the back side using low energy nanosecond laser pulses of 532 nm wavelength. Photoacoustic waves undergo a frequency-dependent exponential attenuation through the paint layer, before being detected by a broadband ultrasonic transducer. Frequency analysis of the recorded time-domain signals allows for the estimation of the average transmitted frequency function, which shows an exponential decay with the layer thickness. Ultrasonic attenuation models were obtained for each pigment and used to fit the data acquired on an inhomogeneous painted mock-up simulating a real canvas painting. Thickness evaluation through PAcSAA resulted in excellent agreement with cross-section analysis with a conventional brightfield microscope. The results of the current study demonstrate the potential of the proposed PAcSAA method for the non-destructive stratigraphic analysis of painted artworks.

Virtuous colours for Mary. Identification of lapis lazuli, smalt and cochineal in the Andean colonial image of Our Lady of Copacabana (Bolivia)

NASA Astrophysics Data System (ADS)

Tomasini, Eugenia P.; Marte, Fernando; Careaga, Valeria P.; Landa, Carlos Rúa; Siracusano, Gabriela; Maier, Marta S.

2016-12-01

The image of Our Lady of Copacabana, a gilded polychrome sculpture carved in maguey wood in 1583, is one of the most important devotions in the Americas. In former research, we have identified the use of gypsum, Armenian bole, cerussite and atacamite in its polychromy. In this study, a red sample taken from the Virgin's tunic and a blue sample extracted from the cloak have been analysed with the aim to identify both pigments and offer insights into the painting technique. Analysis by micro-Raman spectroscopy complemented with scanning electron microscopy-energy dispersive spectroscopy and high-performance liquid chromatography allowed the identification of carmine lake in the red sample. Analysis by micro-Raman spectroscopy of the surface of the blue sample and its cross section showed the presence of smalt-the blue-glass pigment-over a cerussite layer, bathed by a very thin ultramarine layer-from a probable native origin-following a pictorial tradition that would last even until the eighteenth century. This is the first time that lapis lazuli has been scientifically identified in a Spanish American colonial painted layer. This article is part of the themed issue "Raman spectroscopy in art and archaeology".

Raman analysis of complex pigment mixtures in 20th century metal knight shields of the Order of the Elephant.

PubMed

Lauridsen, Clara Bratt; Sanyova, Jana; Simonsen, Kim Pilkjær

2015-11-05

The pigment composition of six painted metal knight shields of the Order of the Elephant dating from the second half of the 20th century belonging to the Danish royal collection were studied using Raman microscopy. By focusing a 785 nm laser with a 50× objective on particles in paint cross sections, it was possible to identify the following 20 compounds: hematite, goethite, chrome red/orange, chrome yellow, zinc chrome yellow, carbon black, toluidine red PR3, chlorinated para red PR4, dinitroaniline orange PO5, phthalocyanine blue PB15, indanthrone blue PB60, ultramarine, Prussian blue, lead white, anatase, rutile, calcium carbonate, barium sulphate, gypsum and dolomite. The components were frequently present in complex pigment mixtures. Additional information was obtained by elemental analysis with scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) to identify cobalt blue, zinc white and cadmium red, as well as to indicate the presence of zinc white in some pigment mixtures. The study allowed a comparison between the industrially applied preparation layers and the artistic paint layers applied by the heraldic painter. Differences in the choice of paint and pigment types were observed on the earliest knight shields, demonstrating a general delay of industrial materials into artist paints. Copyright © 2015 Elsevier B.V. All rights reserved.

Virtuous colours for Mary. Identification of lapis lazuli, smalt and cochineal in the Andean colonial image of Our Lady of Copacabana (Bolivia).

PubMed

Tomasini, Eugenia P; Marte, Fernando; Careaga, Valeria P; Landa, Carlos Rúa; Siracusano, Gabriela; Maier, Marta S

2016-12-13

The image of Our Lady of Copacabana, a gilded polychrome sculpture carved in maguey wood in 1583, is one of the most important devotions in the Americas. In former research, we have identified the use of gypsum, Armenian bole, cerussite and atacamite in its polychromy. In this study, a red sample taken from the Virgin's tunic and a blue sample extracted from the cloak have been analysed with the aim to identify both pigments and offer insights into the painting technique. Analysis by micro-Raman spectroscopy complemented with scanning electron microscopy-energy dispersive spectroscopy and high-performance liquid chromatography allowed the identification of carmine lake in the red sample. Analysis by micro-Raman spectroscopy of the surface of the blue sample and its cross section showed the presence of smalt-the blue-glass pigment-over a cerussite layer, bathed by a very thin ultramarine layer-from a probable native origin-following a pictorial tradition that would last even until the eighteenth century. This is the first time that lapis lazuli has been scientifically identified in a Spanish American colonial painted layer.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'. © 2016 The Author(s).

Compositional and quantitative microtextural characterization of historic paintings by micro-X-ray diffraction and Raman microscopy.

PubMed

Romero-Pastor, Julia; Duran, Adrian; Rodríguez-Navarro, Alejandro Basilio; Van Grieken, René; Cardell, Carolina

2011-11-15

This work shows the benefits of characterizing historic paintings via compositional and microtextural data from micro-X-ray diffraction (μ-XRD) combined with molecular information acquired with Raman microscopy (RM) along depth profiles in paint stratigraphies. The novel approach was applied to identify inorganic and organic components from paintings placed at the 14th century Islamic University-Madrasah Yusufiyya-in Granada (Spain), the only Islamic University still standing from the time of Al-Andalus (Islamic Spain). The use of μ-XRD to obtain quantitative microtextural information of crystalline phases provided by two-dimensional diffraction patterns to recognize pigments nature and manufacture, and decay processes in complex paint cross sections, has not been reported yet. A simple Nasrid (14th century) palette made of gypsum, vermilion, and azurite mixed with glue was identified in polychromed stuccos. Here also a Christian intervention was found via the use of smalt, barite, hematite, Brunswick green and gold; oil was the binding media employed. On mural paintings and wood ceilings, more complex palettes dated to the 19th century were found, made of gypsum, anhydrite, barite, dolomite, calcite, lead white, hematite, minium, synthetic ultramarine blue, and black carbon. The identified binders were glue, egg yolk, and oil.

Short-term observational spatial memory in Jackdaws (Corvus monedula) and Ravens (Corvus corax).

PubMed

Scheid, Christelle; Bugnyar, Thomas

2008-10-01

Observational spatial memory (OSM) refers to the ability of remembering food caches made by other individuals, enabling observers to find and pilfer the others' caches. Within birds, OSM has only been demonstrated in corvids, with more social species such as Mexican jays (Aphelocoma ultramarine) showing a higher accuracy of finding conspecific' caches than less social species such as Clark's nutcrackers (Nucifraga columbiana). However, socially dynamic corvids such as ravens (Corvus corax) are capable of sophisticated pilfering manoeuvres based on OSM. We here compared the performance of ravens and jackdaws (Corvus monedula) in a short-term OSM task. In contrast to ravens, jackdaws are socially cohesive but hardly cache and compete over food caches. Birds had to recover food pieces after watching a human experimenter hiding them in 2, 4 or 6 out of 10 possible locations. Results showed that for tests with two, four and six caches, ravens performed more accurately than expected by chance whereas jackdaws did not. Moreover, ravens made fewer re-visits to already inspected cache sites than jackdaws. These findings suggest that the development of observational spatial memory skills is linked with the species' reliance on food caches rather than with a social life style per se.

Colour measurements of surfaces to evaluate the restoration materials

NASA Astrophysics Data System (ADS)

Lo Monaco, Angela; Marabelli, Maurizio; Pelosi, Claudia; Picchio, Rodolfo

2011-06-01

In this paper two case studies on the application of colour measurements for the evaluation of some restoration materials are discussed. The materials related to the research are: watercolours employed in restoration of wall paintings and preservative/consolidants for wood artifacts. Commercial watercolours, supplied by Maimeri, Windsor&Newton and Talens factories have been tested. Colour measurements have been performed by means of a reflectance spectrophotometer (RS) before and after accelerated ageing of watercolours at 92% relative humidity (RH) and in a Solar Box chamber. The experimental results show that watercolours based on natural earths and artificial ultramarine undergo the main colour changes, expressed as L*, a* and b* variations and total colour difference (▵E*). In the other cases colour differences depend on both watercolour typology and suppliers. The other example concerns the evaluation of colour change due to surface treatment of Poplar (Populus sp.) and chestnut (Castanea sativa L.) wood samples. The wooden samples have been treated with a novel organic preservative/consolidant product that has been tested also in a real case as comparison. The treated samples have been artificially aged in Solar Box chamber equipped with a 280 nm UV filter. Colour has been measured before and after the artificial ageing by means of a RS. Colour changes have been determined also for the main door of an historical mansion in Viterbo, made of chestnut wood, and exposed outdoors.

Optical pump-probe microscopy for biomedicine and art conservation

NASA Astrophysics Data System (ADS)

Fischer, Martin

2013-03-01

Nonlinear optical microscopy can provide contrast in highly heterogeneous media and a wide range of applications has emerged, primarily in biology, medicine, and materials science. Compared to linear microscopy methods, the localized nature of nonlinear interactions leads to high spatial resolution, optical sectioning, and larger possible imaging depth in scattering media. However, nonlinear contrast (other than fluorescence, harmonic generation or CARS) is generally difficult to measure because it is overwhelmed by the large background of detected illumination light. This background can be suppressed by using femtosecond pulse or pulse train shaping to encode nonlinear interactions in background-free regions of the frequency spectrum. We have developed this shaping technology to study novel intrinsic structural and molecular contrast in biological tissue, generally using less power than a laser pointer. For example we have recently been able to sensitively measure detailed transient absorption dynamics of melanin sub-types in a variety of skin lesions, showing clinically relevant differences of melanin type and distribution between cancerous and benign tissue.[1] Recently we have also applied this technology to paint samples and to historic artwork in order to provide detailed, depth-resolved pigment identification. Initial studies in different inorganic and organic pigments have shown a rich and pigment-specific nonlinear absorption signature.[2] Some pigments, for example lapis lazuli (natural ultramarine), even show marked differences in signal depending on its geographic origin and on age, demonstrating the potential of this technique to determine authenticity, provenance, technology of manufacture, or state of preservation of historic works of art.

Analysis of Wilhelm Ostwald's "Colour Organ" with Raman microspectroscopy

NASA Astrophysics Data System (ADS)

Bridarolli, Alexandra; Atak, Sefkan; Herm, Christoph

2016-11-01

The "Scientific Colour Organ" is a collection of 680 pigment powders, created by the chemist Wilhelm Ostwald in 1925 as a means to represent his colour system. Today, it remains a leading part of colour theory. Analysis of these materials was undertaken to understand how the colour system was realised and to gain indications for preservation of the collection to which it belongs. Dispersive Raman microspectroscopy was applied directly to the powders, as well as using alternative techniques to suppress fluorescence. Barium sulphate was detected in all of the samples with one exception. Portable X-ray fluorescence revealed that this compound was a constituent of lithopone pigment. Raman spectroscopy furthermore revealed synthetic ultramarine (C.I. PB 29) as well as six different synthetic organic pigments and dyes (C.I. PY3; C.I. PO5; C.I. PR81:1; C.I. PV2 and two different triarylmethane dyes). Thin-layer chromatography was applied to determine the exact combination of dyes causing the gradual change in colour of each powder compared to the adjacent samples. With the exception of triarylmethane, the synthetic organic dyes could be identified with Raman spectroscopy directly on the chromatographic plate. The efficiency of thin-layer chromatography combined with Raman spectroscopy for identification of organic pigments could thus be shown. X-ray fluorescence indicated the presence of tungsten-molybdenum lakes in some samples. Comparison of the analytical results to information published by Oswald in 1917 showed that he switched to more light-stable synthetic organic pigments used for his "Scientific Colour Organ".

Analytical investigation of Mudéjar polychrome on the carpentry in the Casa de Pilatos palace in Seville using non-destructive XRF and complementary techniques.

PubMed

Garrote, M A; Robador, M D; Perez-Rodriguez, J L

2017-02-15

The pigments, execution technique and repainting used on the polychrome wood ceilings and doors in the Casa de Pilatos (Seville, Spain) were studied using portable X-ray fluorescence equipment. Cross-sections of small samples were also analysed by optical microscopy, SEM with EDX analysis, micro-Raman and micro-infrared spectroscopy and X-ray diffraction. These carpentry works are magnificent examples of the Mudéjar art made in Spain in the early 16th century. Portable X-ray fluorescence gave good information on the different components of the polychrome. The SEM-EDX study of the surfaces of small samples gave information on their components and also characterized the compounds that had been deposited or formed by environmental contamination or by the alteration of some pigments. The SEM-EDX study of cross-sections facilitated the characterization of all layers and pigments from the support to the most external layer. The following pigments were characterized: red (cinnabar/vermillion, lead oxide, iron oxides and orpiment/realgar), black (carbon black), white (white lead and titanium barium white), yellow-orange-red-brown (orpiment/realgar and iron oxides), green (chromium oxide), blue (indigo blue and ultramarine blue), and gilding (gold leaf on bole). False gold, bronze and brass were also found. The pigments were applied with the oil painting technique over a support layer that had been primed with animal glue. This support layer was gypsum in some cases and white lead in others. This study is essential to the polychrome conservation of the studied artwork, and it will help clarify uncertainties in the history and painting of Mudéjar art. Copyright © 2016 Elsevier B.V. All rights reserved.

An investigation of multispectral imaging for the mapping of pigments in paintings

NASA Astrophysics Data System (ADS)

Zhao, Yonghui; Berns, Roy S.; Taplin, Lawrence A.; Coddington, James

2008-02-01

Compared with colorimetric imaging, multispectral imaging has the advantage of retrieving spectral reflectance factor of each pixel of a painting. Using this spectral information, pigment mapping is concerned with decomposing the spectrum into its constituent pigments and their relative contributions. The output of pigment mapping is a series of spatial concentration maps of the pigments comprising the painting. This approach was used to study Vincent van Gogh's The Starry Night. The artist's palette was approximated using ten oil pigments, selected from a large database of pigments used in oil paintings and a priori analytical research on one of his self portraits, executed during the same time period. The pigment mapping was based on single-constant Kubelka-Munk theory. It was found that the region of blue sky where the stars were located contained, predominantly, ultramarine blue while the swirling sky and region surrounding the moon contained, predominantly, cobalt blue. Emerald green, used in light bluish-green brushstrokes surrounding the moon, was not used to create the dark green in the cypresses. A measurement of lead white from Georges Seurat's La Grande Jatte was used as the white when mapping The Starry Night. The absorption and scattering properties of this white were replaced with a modern dispersion of lead white in linseed oil and used to simulate the painting's appearance before the natural darkening and yellowing of lead white oil paint. Pigment mapping based on spectral imaging was found to be a viable and practical approach for analyzing pigment composition, providing new insight into an artist's working method, the possibility for aiding in restorative inpainting, and lighting design.

Analytical investigation of Mudéjar polychrome on the carpentry in the Casa de Pilatos palace in Seville using non-destructive XRF and complementary techniques

NASA Astrophysics Data System (ADS)

Garrote, M. A.; Robador, M. D.; Perez-Rodriguez, J. L.

2017-02-01

The pigments, execution technique and repainting used on the polychrome wood ceilings and doors in the Casa de Pilatos (Seville, Spain) were studied using portable X-ray fluorescence equipment. Cross-sections of small samples were also analysed by optical microscopy, SEM with EDX analysis, micro-Raman and micro-infrared spectroscopy and X-ray diffraction. These carpentry works are magnificent examples of the Mudéjar art made in Spain in the early 16th century. Portable X-ray fluorescence gave good information on the different components of the polychrome. The SEM-EDX study of the surfaces of small samples gave information on their components and also characterized the compounds that had been deposited or formed by environmental contamination or by the alteration of some pigments. The SEM-EDX study of cross-sections facilitated the characterization of all layers and pigments from the support to the most external layer. The following pigments were characterized: red (cinnabar/vermillion, lead oxide, iron oxides and orpiment/realgar), black (carbon black), white (white lead and titanium barium white), yellow-orange-red-brown (orpiment/realgar and iron oxides), green (chromium oxide), blue (indigo blue and ultramarine blue), and gilding (gold leaf on bole). False gold, bronze and brass were also found. The pigments were applied with the oil painting technique over a support layer that had been primed with animal glue. This support layer was gypsum in some cases and white lead in others. This study is essential to the polychrome conservation of the studied artwork, and it will help clarify uncertainties in the history and painting of Mudéjar art.

Evaluation of MidIR fibre optic reflectance: Detection limit, reproducibility and binary mixture discrimination

NASA Astrophysics Data System (ADS)

Sessa, Clarimma; Bagán, Héctor; García, José Francisco

2013-11-01

MidIR fibre optic reflectance (MidIR-FORS) is a promising analytical technique in the field of science conservation, especially because it is non-destructive. Another advantage of MidIR-FORS is that the obtained information is representative, as a large amount of spectral data can be collected. Although the technique has a high potential and is almost routinely applied, its quality parameters have not been thoroughly studied in the specific application of analysis of artistic materials. The objective of this study is to evaluate the instrumental capabilities of MidIR-FORS for the analysis of artwork materials in terms of detection limit, reproducibility, and mixture characterisation. The study has been focused on oil easel painting and several paints of known composition have been analysed. Paint layers include blue pigments not only because of their important role along art history, but also because their physical and spectroscopic characteristics allow a better evaluation of the MidIR-FORS capabilities. The results of the analysis indicate that MidIR-FORS supplies a signal affected by different factors, such as the optical, morphological and physical properties of the surface, in addition to the composition of materials analysed. Consequently, the detection limits established are relatively high for artistic objects (Prussian blue - PB 2.1-6.5%; Phthalocyanine blue - Pht 6.3-10.2%; synthetic Ultramarine blue - UM 12.1%) and may therefore lead to an incomplete description of the artwork. Reproducibility of the technique over time and across surface has been determined. The results show that the major sources of dispersion are the heterogeneity of the pigments distribution, physical features, and band shape distortions. The total dispersion is around 4% for the most intense bands (oil) and increases up to 26% when weak or overlapped bands are considered (PB, Pht, UM). The application of different pre-treatments (cutoff of fibres absorption, Savizky-Golay smoothing