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This work addresses the identification of synthetic organic pigments (SOP) in ten modern reverse paintings on glass (1912-1946) by means of an in-situ multi-analytical approach. The combination of the complimentary properties of mobile Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) enabled the detection of sixteen SOP even in complex mixtures with inorganic compounds and binders. For the β-naphthol pigments, both Raman and DRIFTS yield appropriate results. DRIFTS was the preferred method for the detection of synthetic alizarin (PR83). Its diagnostic band pattern even allows its detection in complex mixtures with mineral pigments, binders and fillers. Raman spectroscopy yielded distinctive spectra for the triaryl carbonium pigments (PG1, PV2, PR81) and the two-yellow azo SOP (PY3, PY12), whereas DRIFT spectra were affected by extensive band overlapping. This may also occur in Raman spectra, but in less problematic amounts. Fluorescence is the major problem with Raman and it significantly hampers the SOP spectra even with the 785 nm laser. On the one hand the big spot size of DRIFTS (10 mm) limits the technique to rather large sampling areas, whereas the use of a 50× objective for in-situ Raman measurements permits a focus on small spots and aggregated SOP flakes. Moreover, “environmental” factors like temperature changes, artificial light, limited space and vibrations when people pass by need to be considered for in-situ measurements in museums.
Finally, the results show the experimental use of SOP in modern reverse glass paintings. Among several rare SOP (e.g. PB52, PR81), two of them (PG1, PV2) have never been reported before in any artwork.
This work addresses the identification of synthetic organic pigments (SOP) in eight modern reverse paintings on glass (1913–1946) by means of an in-situ multi-analytical approach. We combined the complementary properties of mobile Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to overcome the main disadvantages of each method: extensive band overlapping in DRIFT spectra and fluorescence problems in Raman spectra. A collection of DRIFTS reference spectra enables a precise pigment identification by DRIFTS and establishes this method as a serious non-destructive alternative for the identification of SOP. The group of β-naphthol pigments yielded valuable results for both methods, whereas synthetic alizarin (PR83) was preferentially detected by DRIFTS. Finally, uncommon triaryl carbonium pigments and two azo group-based yellows were identified in the paintings by means of Raman spectroscopy.
A non-invasivemethod has been carried out to show the capabilities and limitations of Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) for identifying of colourants and binders in modern reverse glass paintings. For this purpose, the reverse glass paintings “Zwei Frauen am Tisch” (1920–22), “Bäume” (1946) (both by Heinrich Campendonk), “Lofoten” (1933) (Edith Campendonk-van Leckwyck) and “Ohne Titel” (1954) (Marianne Uhlenhuth), were measured. In contrast to other techniques (e.g. panel and mural painting), the paint layers are applied in reverse succession. In multi-layered paint systems, the front paint layer may no longer be accessible. The work points out the different spectral appearance of a given substance (gypsum, basic lead white) in reverse glass paintings. However, inverted bands, band overlapping and derivative-shaped spectral features can be interpreted by comparing the spectra fromthe paintingswith spectra frompure powders and pigment/linseed oil mock-ups. Moreover, the work focuses on this method's capabilities in identifying synthetic organic pigments (SOP). Reference spectra of three common SOP (PG7, PY1, PR83) were obtained from powders and historical colour charts.We identified PR83 and PY1 in two reverse glass paintings, using the measured reference spectra. The recorded DRIFTS spectra of pure linseed oil, gum Arabic, mastic, polyvinyl acetate resin and bees wax can be used to classify the binding media of the measured paintings.
Development of a methodical approach for in-situ analysis of modern reverse paintings on glass
(2018)
The technique of painting on the reverse side of glass was rediscovered by artists in the early 20th century and gained great popularity, especially in Germany. In contrast to other paint techniques (e.g. panel and mural painting), the paint layers are applied in reverse succession starting with the foremost paint layer and ending with the primer (backmost layer). The paintings are viewed in reflected light, thus revealing an impressive gloss, luminosity and depth of colour.
Scientific investigation of the material provides important information for appropriate conservation concepts. Transport of the precious and fragile objects to the lab is often not feasible. Therefore, in-situ, non-invasive analysis is necessary to analyse colorants and binders. However, some analytical problems need to be considered: due to the reverse paint stratigraphy in reverse paintings on glass, the measured layer is always the backmost one. The analytical possibilities are extremely reduced, when the back is covered by a metal foil (or by paper, carton etc.). However, measurements through the glass (using Raman and VIS) can still yield information on the colourants of the front layer.
When the paint layer is accessible, we start our procedure using X-ray fluorescence (Tracer III-SD, Bruker AXS Microanalysis GmbH, 40 kV, 15 μA) and VIS reflectance spectroscopy (SPM 100, Gretag-Imaging AG). Both techniques provide first information on the inorganic colourants. Raman measurements (i-Raman®Plus, Bwtek inc., 785 nm, 50× objective, resolution 4 cm-1) are then carried out to clarify uncertain XRF measurements and to identify synthetic organic pigments (SOP). Diffuse Reflection-Infrared-Fourier-Transform Spectroscopy (DRIFTS; ExoScan, Agilent GmbH, 4000–650 cm-1, 500 scans, spectral resolution 4 cm-1) is used for the classification of the binders. Moreover, it may help to identify SOP, when fluorescence dominates the Raman signal. This analytical sequence yields the best results, when time is the limiting factor.
We present two in-situ studies of the paintings “Kreuzabnahme” (1914-15) by Carlo Mense and “Stadt am Morgen” (1921) by Walter Dexel. The painting “Kreuzabnahme” is an outstanding piece in Mense’s ɶuvre, because the glass plate was painted on both sides (Fig. 1). The results of the back-side show mainly inorganic pigments: basic lead white, talc, red and brown ochre, cinnabar, chrome yellow, viridian, ultramarine blue, Prussian blue and bone black. The classification of binding media using DRIFTS yields positive results for drying oil. Acrylic resin could be identified in two areas, resulting from a previous restauration treatment. For the front side painting, Mense used basic lead white, cinnabar, chrome yellow and umbra as pigments and oil as binder.
Measurements of the abstract painting “Stadt am Morgen” by Walter Dexel show zinc white, basic lead white, chalk, cinnabar, red lead, strontium yellow, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, brown ochre and bone black as pigments. Moreover, synthetic alizarin (PR83) was identified as dark red colorant. The results of DRIFTS classify oil as binding media.
We conclude that, the use of complementary spectroscopic methods yields the best results for in-situ analysis of reverse paintings on glass.
The technique of painting on the reverse side of a glass panel was rediscovered by German artists at the beginning of the 20th century. They appreciated the impressive gloss, luminosity, and depth of colours in this genre. Compared to stained glass, the distinctive properties of this technique are: (1) the paint is applied “cold”, hence, it doesn’t involve a firing step, (2) reverse paintings on glass are framed and always viewed in reflected light and (3) the reverse paint stratigraphy is different from canvas paintings, starting with the front most layer and ending with the backing layer. In 1908 several artists, including Gabriele Münter, Wassily Kandinsky, Heinrich Campendonk, August Macke and Franz Marc of the “Der Blaue Reiter” (the Blue Rider) collective took an interest in this technique and started to share their interest with other colleagues in Europe. Our pioneering project is tracing this transfer of knowledge by a multidisciplinary approach in terms of art history, paint technology and material science. More than 100 artists and >1000 reverse paintings on glass were identified during the project. This high number of objects clearly points out that this technique was by far more important for modern art than previously assumed. In-situ, non-invasive measurements (XRF, Raman, VIS, DRIFTS) on a well-considered selection of 67 paintings reveal the broad palette of colorants ranging from traditional to experimental. Special attention is paid to the impact of synthetic organic pigments (SOP) in artists palette. Demonstrative examples by W. Kandinsky, L. G. Buchheim and F. Jespers are used to discuss analytical challenges and highlights.
This work presents a spectroscopic study of metallic pigments and metal foils used in reverse glass paintings that were created between 1912 and 1954. Metallic pigments induce a notable sparkling effect by means of the lateral incidence of light, whereas metal foils enhance the gloss and create a glittering effect when the painting is viewed in reflected light. Both effects were desired features especially in modern reverse paintings on glass and applied by artists in manifold creative manner. The paper gives an overview on the composition of the metalfoils and metal pigments in 14 works as determined in situ by X-ray spectrometry. Metal foils made of tin, brass, aluminium and silver were found in nine paintings. Gold imitating Cu-Zn pigments in different hues and with various Cu/Zn net intensity ratios were recorded for six paintings. Silvery pigments were identified mainly as Al pigments, but also as Cu-Zn-Ni alloy in one case. Other uncommon metallic pigments were detected in Arlequin vindicatif (c. 1925) by Floris Jespers, who used not only Cu-Zn and Al pigments, but also brownish Cu and Cu-Zn-Sn pigments. Non-invasive diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) was used to classify the binding media of the metallic pigments. Drying oil and natural resin probably mixed with oil were the most common binding media. A polysaccharide-based binder was found in the silvery Cu-Zn-Ni pigment of Ohne Titel (1954) by Marianne Uhlenhuth.
First insights into Chinese reverse glass paintings gained by non invasive spectroscopic analysis
(2019)
A non-invasive methodological approach (X-ray fluorescence (XRF), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), Raman spectroscopy) has been carried out to identify the pigments and classify the binding media in two Chinese reverse glass paintings (The Archer, Yingying and Hongniang) from the late 19th and early 20th centuries. The results reveal a combined use of traditional Chinese and imported European materials. Several pigments like cinnabar, lead white, orpiment, carbon black and copper-arsenic green (probably emerald green) were found in both paintings; red lead, artificial ultramarine blue, Prussian blue and ochre appear in at least one of the paintings.
The presence of portlandite (Ca(OH)2) along calcite (CaCO3) in the fine-grained, white backing layer of Yingying and Hongniang indicates the presence of limewash. In Chinese tradition, limewash was produced from clamshells, and was then sold as clamshell white. In contrast to the Japanese pigment, Chinese clamshell white was made of finely grounded shells, which were heated over a low fire. The residue (CaO) forms portlandite (Ca(OH)2) when water is continuously added. This water-rich mixture is applied on the painting. Portlandite reacts with atmospheric CO2 during drying and forms fine-grained calcite (CaCO3) [1,2].
The identification of emerald green (The Archer) suggests an earliest manufacturing date in the 1830s [3] and promotes the sinological dating of the painting. Drying oil was classified as a binding media in most areas of both paintings. However, the orange background of The Archer yielded prominent bands of both proteinaceous and fatty binder.
This work presents a technical investigation of two Chinese reverse glass paintings from the late 19th and early 20th centuries. A multi-analytical, non-invasive approach (X-ray fluorescence (XRF), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), Raman spectroscopy) was used to identify the pigments and classify the binding media. The results reveal a combined use of traditional Chinese and imported European materials. Several pigments like cinnabar, lead white, orpiment, carbon black and copper-arsenic green (probably emerald green) were found in both paintings; red lead, artificial ultramarine blue, Prussian blue and ochre appear in at least one of the paintings. The proof of limewash (calcite and small amounts of portlandite) as a backing layer in Yingying and Hongniang indicates that clamshell white was also used for reverse glass paintings. Drying oil was classified as a binding media in most areas of both paintings. However, the orange background of The Archer yielded prominent bands of both proteinaceous and fatty binder.
The technique of painting on the reverse side of glass was rediscovered by artists in the early 20th century. The artist group “Der Blaue Reiter” around Wassily Kandinsky and Franz Marc got in touch with this technique in 1908 and 1909. In the following years it gained great popularity, especially in Germany. Nevertheless, the technique has not received its due appreciation in art history. It was considered as stained glass. However, the paint layers are applied cold, hence this artistic technique doesn’t involve a firing step.
Our multidisciplinary project investigates the art historic backgrounds, the painting techniques and materials of modern reverse paintings on glass. More than 1000 paintings from ~100 artists were discovered in the framework of our project. A selection of 60 paintings could be analyzed using non-invasive, in-situ methods such as Raman and VIS spectroscopy, Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS) and X-ray fluorescence (XRF). In this paper we want to point out the key role of Raman spectroscopy for our research. It offers the unique opportunity to measure paint layers from both sides. (front = through the glass; reverse = directly on the paint layer).
The technique of painting on the reverse side of a glass panel was rediscovered by German artists at the beginning of the 20th century. In contrast to other paint techniques (e.g. panel and mural painting), the paint layers are applied in reverse succession starting with the foremost paint layer and ending with the primer (backmost layer). The paintings are viewed in reflected light, thus revealing an impressive gloss, luminosity and depth of colour. The artist group “Der Blaue Reiter” (the Blue Rider) around W. Kandinsky and F. Marc got in touch with this technique in the summers of 1908 and 1909 and spread their knowledge in different regions. Our pioneering project is tracing this transfer of knowledge by a multidisciplinary approach in terms of art history, painting technology and material science. More than 100 artists and >1000 reverse paintings on glass (1905-1955) were identified during the project. This numbers clearly point out that this technique was by far more important for modern art than previously assumed. In-situ, non-invasive measurements (XRF, Raman, VIS, DRIFTS) on a well-considered selection of 67 paintings reveal the broad palette of colorants ranging from traditional to experimental materials. Special attention is paid on artists who are strongly connected to Berlin. Demonstrative examples by W. Dexel, G. Muche and L. Hildebrandt are used to discuss analytical challenges and highlights.