Organic Binding Media Research Articles

Identification of organic binding media in ancient architectural decoration by THM–Py–GC/MS

Animal glue, pine resin, starch, and tung oil were commonly used as binding media in ancient architectural decoration in China. Gum benzoin was also recorded in ancient Chinese literature but has not been detected in Chinese architectural decoration yet. To obtain comprehensive information on ancient binding media, this study investigated two types of gum benzoin using pyrolysis–gas chromatography/mass spectrometry with thermal-assisted hydrolysis and methylation (THM–Py–GC/MS). Subsequently, organic binding media used in the architectural decoration of Shuxiang Temple, which is a Royal Manchu temple in the Qing dynasty, were analyzed. Heat-boiled tung oil was identified as the major binding medium in architectural decoration. In addition, animal glue, blood, starch, pine resin, and gum benzoin from Styrax benzoin Dryand and Qi (urushiol-based lacquer) were also determined. For the first time, gum benzoin was detected as a binding medium in architectural decoration in China. The identification of various organic binding media used in the architectural decoration can provide scientific support to the ongoing conservation project related to Shuxiang Temple.

A Study on Correggio Wall Paintings: Characterization of Technique and Materials of Abbey Church of S. Giovanni Evangelista in Parma, Italy

This study deals with the materials of the sub-arch painting of the Del Bono Chapel of the Abbey Church of S. Giovanni Evangelista in Parma, Italy, datable to around 1523. The artist is Antonio Allegri, known as Correggio (1489–1534), who is considered to be one of the greatest painters of the 16th century. Micro-Raman spectroscopy, micro-Fourier transform infrared spectroscopy and gas chromatography coupled with mass spectrometry were used as the main techniques to identify the pigments and binding media. The analysis enabled us to identify the pigments which were characteristic of the epoch. Correggio’s palette was composed by mineral pigments—sometimes expensive ones such as lapis lazuli, azurite and cinnabar—together with a wide range of earths, or by synthetic pigments like smalt blue. From the amino acid content determination, it was shown that, in the samples containing lazurite, smalt, hematite, green earth and goethite, the protein fraction was attributable to the presence of a mixture of egg and animal glue, from which the use of the a secco technique could be assumed, with pigments that did not need organic binding media on the wall. For the gilding sample, the study found that Au foil had been applied on a brown background (oil-based missione).

RETRACTED ARTICLE: A new light on the grounds, pigments and bindings used in ancient Egyptian cartonnages from Tell Al Sawa, Eastern Delta, Egypt

Six mummies and their and cartonnages found at Tell Al Sawa, Eastern Delta, Egypt, provided 20 fragments of cartonnage for analysis to determine if the initial attribution of their age to the late period was correct. The cartonnage fragments were examined using SEM–EDAXS and FT-IR spectroscopy, and the results revealed that they comprised linen supports over a preparatory layer either of calcite or gypsum alone or in admixture mixed with organic binding medium of animal glue. The paint layer was applied using either natural mineral oxide earths such as iron oxide and lead oxide, strontium carbonate or the synthetic pigment Egyptian blue. The binding medium was found to be gum arabic. The pigment characterization revealed the unusual presence of a zinc silicate, noted in Egyptian painting for the first time.

Unraveling the Composition of Rembrandt's Impasto through the Identification of Unusual Plumbonacrite by Multimodal X-ray Diffraction Analysis.

Rembrandt (1606-1669) is renowned for his impasto technique, involving his use of lead white paint with outstanding rheological properties. This paint was obtained by combining lead white pigment (a mixture of cerussite PbCO3 and hydrocerussite Pb3 (CO3 )2 (OH)2 ) with an organic binding medium, but the exact formulation used by Rembrandt remains a mystery. A powerful combination of high-angle and high-lateral resolution x-ray diffraction was used to investigate several microscopic paint samples from four Rembrandt masterpieces. A rare lead compound, plumbonacrite (Pb5 (CO3 )3 O(OH)2 ), was detected in areas of impasto. This can be considered a fingerprint of Rembrandt's recipe and is evidence of the use of an alkaline binding medium, which sheds a new light on Rembrandt's pictorial technique.

Unraveling the Composition of Rembrandt's Impasto through the Identification of Unusual Plumbonacrite by Multimodal X‐ray Diffraction Analysis

AbstractRembrandt (1606–1669) is renowned for his impasto technique, involving his use of lead white paint with outstanding rheological properties. This paint was obtained by combining lead white pigment (a mixture of cerussite PbCO3 and hydrocerussite Pb3(CO3)2(OH)2) with an organic binding medium, but the exact formulation used by Rembrandt remains a mystery. A powerful combination of high‐angle and high‐lateral resolution x‐ray diffraction was used to investigate several microscopic paint samples from four Rembrandt masterpieces. A rare lead compound, plumbonacrite (Pb5(CO3)3O(OH)2), was detected in areas of impasto. This can be considered a fingerprint of Rembrandt's recipe and is evidence of the use of an alkaline binding medium, which sheds a new light on Rembrandt's pictorial technique.

Evolved Gas Analysis‐Mass Spectrometry to Identify the Earliest Organic Binder in Aegean Style Wall Paintings

AbstractAn organic binder was identified in the painted fragments from the Canaanite palace of Tel Kabri, Israel. Recently dated to the late 18th century B.C.E. by 14C, Tel Kabri is the most ancient of the Eastern Mediterranean sites in which Aegean style paintings have been found. The application of pigments was suspected to be using an organic binding medium, particularly for the Egyptian Blue pigment. Samples of blue paint were examined using evolved gas analysis‐mass spectrometry (EGA‐MS) in order to overcome the analytical challenges imposed by highly degraded aged proteinaceous materials. Egg was identified as the binder based on the presence of hexadecanonitrile and octadecanonitrile, confirming the use of a secco painting technique. Lysozyme C from Gallus gallus was detected by proteomics analysis, confirming the presence of egg. To our knowledge, this is the earliest use of egg as a binder in Aegean style wall paintings.

Evolved Gas Analysis-Mass Spectrometry to Identify the Earliest Organic Binder in Aegean Style Wall Paintings.

An organic binder was identified in the painted fragments from the Canaanite palace of Tel Kabri, Israel. Recently dated to the late 18th century B.C.E. by 14 C, Tel Kabri is the most ancient of the Eastern Mediterranean sites in which Aegean style paintings have been found. The application of pigments was suspected to be using an organic binding medium, particularly for the Egyptian Blue pigment. Samples of blue paint were examined using evolved gas analysis-mass spectrometry (EGA-MS) in order to overcome the analytical challenges imposed by highly degraded aged proteinaceous materials. Egg was identified as the binder based on the presence of hexadecanonitrile and octadecanonitrile, confirming the use of a secco painting technique. Lysozyme C from Gallus gallus was detected by proteomics analysis, confirming the presence of egg. To our knowledge, this is the earliest use of egg as a binder in Aegean style wall paintings.

Scientific analysis of tie luo, a Qing Dynasty calligraphy artifact in the Palace Museum, Beijing, China

Tie luo (affixed hanging) was an expressive form of traditional Chinese calligraphy or paintings, and popular in the imperial palaces for interior decorations in Qing Dynasty (1644–1911 C.E.). A piece of calligraphic tie luo, written by an eminent calligrapher Gu Gao (1763–1832 C.E.), was restored recently in the Palace Museum, Beijing, China. The paper with pigment coating specially made for this calligraphic piece was named as fenjian. This article presented results from materials identification prior to the restoration. Multianalysis with scientific approaches revealed how tie luo was manufactured. It could be concluded that the investigated tie luo used a paper made from bast fibers of mulberry trees. And the decorative ground layer for the piece was also studied, which indicated that a type of organic red pigments were used for the masterpiece. White lead was considered as the main pigment, mixed with a red dye extracted from sappanwood. Meanwhile, animal glue, drying oils and beeswax were confirmed as the organic binding media. In dye analysis, protosappanin B and brazilin as well as brazilein were identified, which implied that sappanwood was used for the organic manufacture of pigments. In addition, both Nowik type A and C were found in the research, which were characteristic of sappanwood for identification.

Influence of ns-laser wavelength in laser-induced breakdown spectroscopy for discrimination of painting techniques

The influence of ns-laser wavelength to discriminate ancient painting techniques such as are fresco, casein, animal glue, egg yolk and oil was investigated in this work. This study was carried out with a single shot laser on samples covered by a layer made of a mixture of the cinnabar pigment and different binders. Three wavelengths based on Nd: YAG laser were investigated (1064, 532 and 266nm). The plasma is controlled at the same electron temperature after an adjustment of pulse energy for these three wavelengths on a fresco sample without organic binder. This approach allows to eliminate the effects of laser pulse energy and the material laser absorption. Afterwards, the emission spectra were compared to separate different techniques. The organic binding media has been separated based on the relative emission intensity of the present CN or C2 rovibrational emissions. In order to test the capability of separating or identifying, the chemometric approach (PCA) was applied to the different matrix. The different solutions in term of wavelength range to optimise the identification was investigated. We focused on the evaluation for the laser wavelength to insure a better separation. The different capacity was interpreted by differentiating the binders by the altered interaction mechanisms between the laser photon and the binders. Also, the electron temperature in the plasma was estimated, which provided the evidences to our findings.

Revealing the binding medium of a Roman Egyptian painted mummy shroud

Abstract Ancient Egyptian painted artworks are usually understudied from an analytical point of view, due to their extremely fragile nature. Attention typically focuses on pigments since identification is possible with non-invasive techniques, while limited information is available in the literature regarding the organic binding media. Here successful determination of the binder of a Roman Egyptian painted mummy shroud (2nd–3rd century A.D.) achieved through the application of enzymatic digestion followed by matrix-assisted laser desorption ionization mass spectrometry (MALDI MS) is reported. The high specificity and sensitivity of this analytical strategy not only allowed the identification of the binding medium as a mixture of two different plant gums but also allowed the discrimination of the different species sources, even though the organic material was present in very small amounts and subject to degradation. The results of this study represent the first analytical identification of the earliest use of locust bean gum as a paint binder material as well as the use of gum arabic from an Acacia species different from the well-known Acacia senegal . The precise identification of the organic binder is a great step forward in the understanding of the painting materials and techniques used in Roman Egypt, of which little is known. The result of this research opens new avenues of art historical and conservation investigation into the specific plant sources and types selected by artists and it has implications for future conservation treatment options.

Examination and Analysis of Etruscan Wall Paintings at Caere, Italy

In 1983, the excavation of the ancient city of Caere near Rome, which became a UNESCO World Heritage Site in 2004, led to the unearthing of an underground sanctuary dating from the early third century bc. Known as the ‘Hypogaeum of Clepsina’, it consists of an underground room decorated with frescoes, drawings and inscriptions. The initiation of a new excavation campaign at Caere in 2012 provided the opportunity to study this rare example of Etruscan wall paintings of a non‐sepulchral nature from the Hellenistic era. The paintings were documented, photographed and samples were removed for analysis using a combination of scientific techniques. The observation that at least some of the painting was done on wet plaster supports the conclusion that the frescos are contemporaneous to the plastering of the walls in the hypogaeum in approximately 273 bc. The plaster is lime‐based and aggregate materials include potassium feldspar, clinopyroxene, quartz, hematite and magnetite. No organic binding medium was identified in the paint, suggesting a lime water binder. Paint materials identified are Egyptian blue, red iron oxide (hematite), yellow iron oxide (goethite), charcoal black, quartz, silicates and calcite. All the paint samples show a mineral accretion layer at the upper surface, caused by recrystallization of salts.

Analysis of artist’s palette on a 16th century wood panel painting by portable and laboratory Raman instruments

Non-destructive analysis of the artist’s palette of ancient wooden panel paintings is a difficult task and studies are rare. Here we compare different methods of analysis of a wooden panel painting, dated to the early sixteenth century, mainly by Raman and infrared spectroscopies. Raman spectra were recorded on collected/sampled micrometric fragments using portable Raman instruments with laser excitation lines at 532 and 785nm and transportable Raman instruments at 532, 633 and 785nm; a fixed 1064nm Raman spectrometer was also used. Infrared analyses were performed in Attenuated Total Reflection (ATR-FTIR) mode. Using the portable instrument, the Raman spectra evidenced white lead, calcite and vermilion only. Raman spectra recorded by transportable and fixed instruments enabled the identification of most of the artist’s palette: (i) white lead, calcite, gypsum and cerussite for white colour; (ii) vermilion, red lead, litharge, haematite for red; (iii) azurite, indigo and lapis lazuli for blue. IR spectra gave information on the organic binding media. XRF analysis on a brown pigment suggested an heterogeneous mixture of a red pigment (such as haematite and/or minium) and a green one as malachite. GC-MS analysis allowed identifying terpenic resin in the composition of the outer protective layer.

An integrated approach to the study of a reworked painting “Madonna with child” attributed to Pietro Lorenzetti

Abstract The painting “ Madonna with Child ”, attributed to Pietro Lorenzetti (14th century) and reworked around the middle of the 16th century, was studied by several techniques in order to characterize the materials used in the original and in the repainted areas. FORS, light microscopy, ESEM-EDX, ToF-SIMS and GC-MS were used. Red ochre and raw sienna earth were identified by FORS in the original parts of the painting. On the repainted parts of the panel, cinnabar, ultramarine blue and lead white were found. By means of GC-MS and ToF-SIMS measurements it was possible to identify the organic binding media used in the preparatory and painted layers.

Terahertz time domain spectroscopy for the analysis of cultural heritage related materials

A powerful broadband femtosecond laser-driven terahertz source was built and used to analyze cultural heritage and art-related materials in the terahertz region of the electromagnetic spectrum. The high signal-to-noise ratio available in our system revealed details in the absorption spectra which are inaccessible with traditional FTIR spectrometers. Clear spectral signatures were recorded from organic binding media thus demonstrating the potential of the approach for applications in the monitoring and analysis of cultural heritage materials.

The Byzantine wall paintings from the Protaton Church on Mount Athos, Greece: tradition and science

The present work is a study of the wall painting complex in the Protaton Church (1295) on Mount Athos, Greece. These paintings, high in artistic value, are themselves a monument—representative of the Macedonian iconographic style. What follows is historic data set against the results of analytical investigations: the fruit of extensive research aimed at determining precise details about the applied painting techniques for the wall paintings. Hitherto it has been held that what was traditionally defined as “Byzantine fresco” was executed only on wet plaster with limewater as the sole binding medium. Now, however, through the application of instrumental analytical investigations, it is possible to demonstrate that a mixed technique involving both al fresco and al secco was employed. Furthermore, it was determined, on the basis of results from gas chromatography–mass spectrometry (GC/MS), that egg together with a modest amount of animal glue were the organic binding media used for the Protaton art work. It is certain that the scenes were initially begun on wet plaster. During or even after drying the painting was completed using the aforementioned protein binding media, thanks to which a more resistant cohesion to the painted layers was secured.

Analytical characterization of binding medium used in ancient Chinese artworks by pyrolysis–gas chromatography/mass spectrometry

In the present work, we attempted to characterize the natural organic binding medium mostly used in ancient Chinese artworks by using the pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) technique. Chinese lacquer, tung oil, deer glue, colophony and peach gum were broadly used as binding media in Chinese paintings or painted pottery, and have been selected as the study materials in this paper. Artificially aged samples have been analyzed by Py–GC/MS in order to establish a useful reference as convenient and rapid analyses of real samples. The method is based on the on-line derivatization in the presence of excess tetramethylammonium hydroxide (TMAH) (25% aqueous solution) as methylating agent. Analyses results revealed that this simultaneous pyrolysis with methylation derivation technique (SPM) is very useful to the characterization of Chinese lacquer, tung oil and colophony but no obvious improvement to deer glue and peach gum. The fingerprint ions of each studied binding medium were established.

Characterisation of 15 th century red and black pastes used for wall decoration in the Qijmas El-Eshaqi mosque (Cairo, Egypt)

The use of coloured pastes for inlaying marble and limestone wall panels is one of the ornamental techniques that were widely used during the Mamluk period in Egypt (1250–1516 AD). Red and black pastes from Qijmas El-Eshaqe mosque (1482 AD) in Cairo were studied to identify their main components. The study of the samples involved the identification of the pigments, additive materials and organic binding media. The study was performed using various analytical methods such as polarising microscopy (PLM), scanning electron microscopy equipped with energy dispersive X-ray analyser (SEM-EDX), inductively-coupled plasma (ICP-AES), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR). These complementary analytical techniques provide precise identification of inorganic and organic substances used in the pastes. The results indicated that the red pigment is mainly obtained from red ochre containing hematite, whereas amorphous carbon (bone black and charcoal) was used to obtain the black colour. Both samples contain calcium sulphate, which was used to give some hardness to the pastes. Beeswax was used as an organic medium in both pastes. The study provides the information required for the conservation of the coloured paste ornaments.

Use of analytical pyrolysis to characterize Egyptian painting layers

An Egyptian wooden sarcophagus and a cartonnage (664–525 B.C.) were subjected to pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS) and Fourier-transform infrared spectroscopy (FT-IR) in order to characterize pigments and organic binding media. The aim of these investigations is to acquire a better knowledge of the painting technique used in ancient Egypt. Results showed that PY-GC-MS offered a rapid tool to discriminate between wax-based- and animal protein-based binders and to recognize the use of mixtures of the two products. FT-IR corroborated the pyrolysis findings, but sometimes provided less unequivocal results than PY-GC-MS. As an additional benefit, PY-GC-MS allowed the identification of a yellow pigment as the arsenic sulphide orpiment by means of the volatile As4 among the pyrolysis fragments.

Electron and Optical Microscopy of Prehispanic Mural Paintings

AbstractIn 1984, archaeologists discovered an important group of mural paintings at the site of Cacaxtla, Mexico. Research has been undertaken to analyze the Prehispanic pigments and the painting techniques employed in these paintings. The present work is focused on the use of colors in these paintings by means of optical microscopy (OM) and transmission electron microscopy (TEM). The stratigraphic structure of painting layers support the presence of an organic binding media. In addition, Maya blue is for the first time described physically by TEM.

Chemie und Technik altkretischer Vasenmalerei vom Kamares-Typ, II

Fragments of the Kamares-type ware were investigated by means of the scanning electron microscope, energy-dispersive X-ray microanalysis, and the Debye-Scherrer process. The black “Firnis” or “Urfirnis” of the decoration proved to be a silicate-type glaze which had a high content of iron and contained potassium as a flux. The body was given a high calcium content, so that its coefficient of expansion was increased and approximated to that of the glaze. The white was produced by means of talc. Firing must have taken place at a temperature of at least about 1000 °C. The red painting contains as its pigment iron oxides or hydroxides and may have been applied with an organic binding medium after the firing operation.[/p][/ab]