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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.
A non-invasive methodological approach has been carried out to identify the pigments and classify the binding media of the reverse painting on glass Kreuzabnahme (1914/15) by Carlo Mense.
Mense was a member of the group Rhenish Expressionists around August Macke and got interested in the technique of painting on the reverse side of a glass panel. The studied painting indicates a remarkably painted reverse and front side, which creates a unique visual appearance of the glass. The applied noninvasive, spectroscopic approach includes X-ray fluorescence, VIS spectroscopy, Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy. The measurements revealed inorganic Pigments mixed with drying oil as binder. Together with common pigments, such as lead white, barium sulphate, bone black, cinnabar, chrome yellow, ochre, and viridian, an unusual additional material was found, Strontium white.
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.
This thesis addresses the development of a methodological approach for the non-invasive identification of colourants and for the classification of binding media in reverse glass paintings from the early 20th century. For this purpose, mobile and miniaturized devices were used to measure the paintings in situ. The methodology includes X-ray fluorescence (XRF), VIS spectroscopy (VIS), Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). In a first step the capabilities of DRIFTS for binding media classification and pigment identification were tested.
DRIFTS enables, besides Raman spectroscopy, the collection of molecular information of a substance that can be used as characteristic fingerprint spectrum. However, the simultaneous collection of both specular (surface) and diffuse (volume) reflection leads to complicated mixed DRIFT spectra, that can vary strongly for one substance depending on the dominant fraction of reflected light. Specular reflection causes several spectral distortions like inverted bands, band shifts and derivative-like features whereas pure diffuse reflections leads to an intensity enhancement of combination bands and overtones. Both specular and diffuse reflection cannot be optically separated, and their proportion depends on material properties like the absorption coefficient and the refractive index as well as on Parameters like surface roughness, porosity, grain size and angle of incidence and detection. A direct comparison of DRIFT spectra with IR spectra of other methods (e.g. transmission, ATR) is not possible, hence the creation of DRIFTS databases was needed. The next step was the complimentary utilization of Raman spectroscopy and DRIFTS for the dentification of synthetic organic colourants. Such colourants are in the further chapters called synthetic organic pigments (SOP) even when it’s not always entirely clear if they are soluble dyes or pigments that are practically insoluble in the medium in which they are incorporated. Raman spectroscopy is generally the method of choice when dealing with SOP, but fluorescence can hamper the Raman spectrum severely, inhibiting the proper identification of the pigment.
DRIFTS was successfully applied and several SOP like synthetic alizarin (PR83), the yellow azo pigments (e.g. PY1) or the red and orange β-naphthol pigments (e.g. PR3) could be identified in the paintings solely by means of DRIFTS. The holistic methodological sequence was defined after the successful establishment of DRIFTS as serious analytical alternative. As the time is always the most limiting factor for in situ measurement campaigns in museums, the 9
sequence needs to be time saving but also efficient. The methodology starts with quick measurements by XRF and VIS to get a first idea of the pigment composition, followed by the validation of the results with the vibrational spectroscopies for selected points.
Measurements of reverse glass paintings by Carlo Mense and Wassily Kandinsky were conducted to test the entire procedure. A high number of pigments could be identified, including several rare ones like strontium white (SrSO4), PR60 and PB52. The binding media were classified using the previously recorded references. The results were set in the art historian context and were discussed in a multidisciplinary way. The influence of Asian art, especially of Chinese reverse glass paintings as source of inspiration for artists of the “Blauer Reiter” collective (e.g. Wassily Kandinsky, Gabriele Münter, Franz Marc und Heinrich Campendonk) is shown. Non-invasive measurements of two Chinese reverse glass paintings from the late 19th and early 20th century were conducted, enabling a comparison of the palettes of Chinese and European painters. The Chinese palette includes heavy use of red lead and orpiment, pigments that were hardly sed in Europe anymore. More modern pigments like zinc white, cadmium yellow, viridian, chromates, cobalt blues or SOP were not found at all in the Chinese paintings.
Scientific analysis based on spectroscopic methods provide essential information on the composition of colourants and binders in paintings. These results can be set in a historical context and help to confirm art historical interpretations. Proofs of certain pigments can be used for dating purposes and may reveal if the artist used not only local but also imported materials. A pilot study of two Chinese reverse glass paintings from the late 19th (Yingying and Hongniang) and early 20th centuries (The Archer) was performed using a multi-analytical approach including X-ray fluorescence (XRF), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and Raman spectroscopy. This approach allowed the identification of the pigments and the classification of 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.
Mit der Bezeichnung Hinterglasmalerei wird allgemein der Begriff der Glasmalerei assoziiert. Auch wenn in beiden Fällen Glas das Trägermaterial ist, bezeichnet Hinterglasmalerei jedoch eine völlig andere Technik. Während bei der Glasmalerei die Farben auf den Bildträger eingebrannt werden, handelt es sich bei der Hinterglasmalerei um eine Kaltmalerei. Selbsttrocknende Farben werden auf die Rückseite der Glastafel aufgetragen, zuweilen wird die Malweise durch aufwendige Veredelungstechniken ergänzt. Mehr und mehr rückt diese Technik, die materialtechnologisch zwischen Tafelmalerei und Glasmalerei zu verorten ist, in den Blickwinkel einer interessierten Öffentlichkeit, wie dies eine zunehmende Anzahl verschiedener Ausstellungen zur Hinterglasmalerei belegen. Die vorliegende Publikation beschäftigt sich in erster Linie mit kunsttechnologischen und materialanalytischen Aspekten der Hinterglasmalerei und ermöglicht tiefe Einblicke in die künstlerische Arbeitsweise und in die Verwendung unterschiedlichster Materialien.