Egg Yolk Binders Research Articles

Mechanical and moisture-related properties of selected dried tempera paints

Mechanical properties—modulus of elasticity and strain at break, water vapour sorption, and hygroscopic expansion of selected egg tempera and distemper paints were determined as a function of relative humidity (RH) filling in this way a critical gap in the knowledge required for the analysis of fracturing processes in paintings. The experimental work was made possible by the preparation of several tempera paints, mimicking the historical materials, in the form of large specimens. Lead white, azurite, and yellow ochre were selected as pigments, and egg yolk and rabbit skin glue as binding media. The water vapour sorption and the moisture-related swelling of the paints were dominated by the proteinaceous components of the binders. The linear hygroscopic expansion coefficient of the dried egg yolk binder was approximately 1 × 10−4 per 1% RH, several times less than the coefficient of the collagen glue (4 × 10−4 per 1% RH). The moduli of elasticity of egg tempera paints at the RH mid-range were comparable to the moduli of aged oil paints, whilst the modulus of elasticity of the distemper paint was close to values measured for animal glue-based grounds. The paints experienced the transition from brittle to ductile states on increasing RH. The egg tempera paints were found to be more brittle than the distemper paint, gessoes, and, generally, aged oil paints. The observations modify a frequently used laminar model of panel paintings in which the mismatch in the response of glue-based ground layer and wood substrate to variations in RH has been identified as the worst-case condition for the fracturing of the entire pictorial layer. This study demonstrated that tempera could be more brittle than the ground layer and in consequence more vulnerable to cracking.

SO2-Induced Aging of Hematite- and Cinnabar-Based Tempera Paint Mock-Ups: Influence of Binder Type/Pigment Size and Composition

Hematite- and cinnabar-based paint mock-ups prepared with either rabbit glue or egg yolk binder were artificially aged in an SO2-rich atmosphere, as a model system for investigating the deterioration of tempera paints exposed to an industrial atmosphere. The overall research aim was to identify the type of degradation occurring in tempera paints and the different alteration mechanisms related to the physical, mineralogical and chemical characteristics of the paint. Tempera mock-ups were prepared by mixing binder (egg yolk or rabbit glue) and pigment (cinnabar of different particle sizes or hematite) and were then exposed to SO2 for 2 months in accelerated aging tests. The colour, gloss, reflectance, roughness and micro-texture of the surfaces of the mock-ups were determined before and after the tests. In addition, chemical and mineralogical changes were determined by X-ray Powder Diffraction (XRPD), Attenuated Total Reflection-Fourier Transform Infrared spectroscopy (ATR-FTIR) and Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (SEM-EDS) analysis. Colorimetric changes were confirmed, mainly in the cinnabar-based paints containing egg yolk, and in the hematite-based paints containing rabbit glue. Neoformed mineral phases have not been detected by XRPD, but precipitation of gypsum on the exposed surfaces has been confirmed by SEM. For cinnabar-based paints, the amount of sulfate-rich deposits was higher on egg yolk mock-ups than on rabbit glue samples, though the opposite was observed for the hematite-based paints. This confirmed the influence of the binder composition and pigment-binder tandem in the susceptibility to SO2 deposition. Pigment particle size did not have a clear influence on the physical and chemical changes in the tempera mock-ups during the ageing tests.

Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 1: Accelerated Aging of Smalt and Lapis Lazuli-Based Paints

The behavior of historic tempera paints exposed to pollutant gases is an important issue when developing conservation strategies. In this work, binary tempera paint mock-ups that were made with either smalt or lapis lazuli pigments mixed with either rabbit glue or egg yolk binders were exposed to an SO2 accelerated aging test in order to find out more about the forms and mechanisms of alteration resulting from pigment-binder interaction. To this end, spectrophotometry, hyperspectral image analysis, and profilometry were used to study macro-scale, physical changes taking place on the surface of the paints, affecting color, gloss, reflectance, and roughness. Likewise, chemical and mineralogical changes were evaluated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (ATR-FTIR), polarized light microscopy (PLM), and scanning electron microscopy with micro-analysis (SEM-EDS), which was also used to visualize micro-texture changes in the paints. The smalt-based tempera showed a higher degree of deterioration than the lapis lazuli-based tempera, in particular a notable whitening related to the precipitation of sulfate-rich salts and to binder and pigment chemical alterations. Moreover, whereas aged egg yolk-based paints showed visible color change due to damage to the oily binder and the pigments, the most evident change in rabbit glue-based paints was binder loss. The alteration suffered by the pigments varied in line with their composition; thus, smalt (blue cobalt-containing glass) grains were more sensitive to SO2 exposure than lapis lazuli-(Na,Ca)8[(S,Cl,SO4,OH)2|(Al6Si6O24)]-crystals. In the smalt grains, the SO2 test caused K+ leaching from the glass matrix, which was detected by means of K/Co ratios, but the lazurite crystals (main component of lapis lazuli) were unaffected (regardless of the binder used in the tempera). The most likely source of the crystallized sulfate rich salts were the impurities that were detected in association with the natural lapis lazuli pigment, i.e., calcite and diopside. Indeed, the precipitation of efflorescences is the main cause of the optical changes found in the smalt- and lapis lazuli-based tempera, in addition to the physical-chemical damage to the binders. The information reported here would be useful for preventive conservation, as well as for art restorers, who are planning work on paintings in which paints of this kind were used.

Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 2: Accelerated Aging of Azurite- and Malachite-Based Paints

In order to improve our knowledge of the weathering response of tempera paints exposed to an industrial atmosphere, azurite- and malachite-based paint mock-ups prepared with either rabbit glue or egg yolk binders were artificially aged in an SO2 rich atmosphere. The aim was to identify the different alteration mechanisms and forms of degradation in the paints by observing their physical (color, gloss, reflectance, and roughness), mineralogical, chemical, and micro-textural characteristics. Superficial physical changes were evaluated by stereomicroscopy, spectrophotometry, gloss measurement, hyperspectral imaging, and roughness measurements. Chemical and mineralogical changes were evaluated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy with microanalysis (SEM-EDS), which was also used to evaluate the micro-texture of the paints. The differences between the fresh temperas were due mainly to the binder (egg yolk or rabbit glue) used in the paint mixture, which also played a crucial role in the different deterioration patterns in the artificially aged paint mock-ups. Thus, the egg yolk-based paints remained physically quite intact after SO2 exposure, although they suffered more significant chemical degradation, above all in the form of copious precipitation of Cu and Ca-rich sulfate salts and the subsequent yellowing of the egg yolk binder. The SO2 aged rabbit glue-based mock-ups showed microscopically important crack formation and binder loss and fewer sulfated salts precipitated on the surface of the paints.

Saponification in egg yolk-based tempera paintings with lead-tin yellow type I

Saponification occurring in paint layers of artworks represents a serious degradation process affecting the appearance and stability of paintings. Formation of metal soaps is mostly reported as a consequence of the interaction of lead white or zinc white with oil binder. We found the distinct symptoms of saponification in paint layers consisting of lead-tin yellow type I and egg yolk binder in a panel painting from the 15th century. This scarce finding induced the study of interactions between lead-tin yellow type I with three different binders: (i) egg yolk tempera, (ii) emulsion of egg yolk and oil, and (iii) oil. The interactions were studied in long-term model experiments using infrared spectroscopy (FTIR) and powder X-ray diffraction (XRD). Based on the results, a set of mixed lead carboxylates of the series Pb(C16)2-x(C18)x, where x = 0; 0.25; 0.5; 0,75; 1; 1.5 and 2, was synthesised as reference materials suitable as a basis for proper identification of neo-formed lead soaps by FTIR and XRD. The formation of lead soaps was detected already within 1 month of reaction in egg yolk containing binders, whereas no soap was formed during 6 months of the experiment in the oil mixture. The neo-formed soaps are various mixed lead carboxylates containing both palmitate (C16) and stearate (C18) in one crystal structure and the proportion of carboxylate anions is affected by the type of the binder. We found the C16:C18 ratio in mixed lead carboxylates is higher in egg yolk tempera samples in accordance with the more abundant palmitic acid in egg yolk fat. On the other hand, the lower C16:C18 ratio in emulsion binder correlates with increased content of stearic acid, suggesting contribution of both binders, i.e. egg yolk and oil, to the soap formation.

Analysis of heritage stones and model wall paintings by pulsed laser excitation of Raman, laser-induced fluorescence and laser-induced breakdown spectroscopy signals with a hybrid system

Abstract Analysis of heritage stone samples, alabaster, gypsum, limestone and marble, and model wall paintings was carried out with a laboratory, hybrid system based on the pulsed laser excitation of Raman, laser-induced fluorescence and laser-induced breakdown spectroscopy signals. The system is based on a nanosecond Q-switched Nd:YAG laser operating at its second (532 nm), third (355 nm) and fourth (266 nm) harmonics and a spectrograph coupled to a time-gated intensified charge coupled device for spectral analysis allowing detection with temporal resolution. For the stone samples, Raman spectra display the characteristic vibration modes of SO42− of calcium sulfate, in alabaster and gypsum, and of free CO32− of calcium carbonate, in limestone and marble. Simultaneously acquired laser-induced fluorescence spectra reveal characteristic bands that help to distinguish between heritage stone types. The elemental composition of stone samples is obtained by laser-induced breakdown spectroscopy upon excitation at 355 nm. Spectra of all stone samples reveal their elemental composition that includes Ca, Na, Mn and Sr and the presence of molecular species, such as CN, C2 and CaO. Additional emission lines, ascribed to Mg, Si, Al and K, appear with different intensities according to the nature of the stone material. Model wall paintings, based on a red pigment, prepared as fresco or mixed with two different binders, were also studied. The complementary information provided by the three spectroscopic modes allows the identification of the pigment as red vermillion and of the different preparations based on the pigment alone or in mixtures with linseed oil and egg yolk binders.

X-ray and ion irradiation effects on azurite, malachite and alizarin pictorial models

The analysis by intense radiation sources of painting materials used in artworks gives valuable information about their composition and state of conservation, but it can also induce undesired modifications on the studied substrates. Here we use X-ray photoelectron spectroscopy (XPS) to follow the surface chemical changes that prolonged irradiation with soft X-rays (with maximum doses ranging from ~1.2×1017 to ~3.4×1017photonscm−2) produce on azurite, malachite and alizarin pigments and on two egg-yolk temperas containing azurite or alizarin. The effects following exposure to Argon ion irradiation have been also studied for malachite and azurite tempera. XPS spectra of the samples show that both types of radiation induce similar superficial alterations, although, at the selected experimental conditions, the modification rate is slower for exposure to soft X-rays. The highest radiation stability is shown for alizarin and, on the contrary, azurite and malachite experience a progressive chemical reduction of Cu2+ to Cu+. The reduction of copper takes also place in the azurite tempera, while the proteins and lipids of the egg-yolk binder of azurite and alizarin temperas are subjected to degradation by irradiation with photons and ions. By employing XPS, the cleavage of CN, CO(H) and CO bonds has been identified in the egg-yolk temperas.

An evaluation of the impact of urban air pollution on paint dosimeters by tracking changes in the lipid MALDI-TOF mass spectra profile

We evaluated the impact of urban air pollution on egg yolk tempera paint dosimeters (binary mixture samples made with historic artist´s blue, red and white pigments) by tracking changes over time in their lipid matrix-assisted laser desorption ionization time-of-flight mass spectra (MALDI-TOF-MS) profiles. We studied triacylglycerols (TGs), phospholipids (PLs) and their oxidation by-products from paint dosimeters that had been exposed outdoors for six months to the polluted atmosphere in the city center of Granada (Spain). Four types of chickens’ eggs were also analyzed to find out whether their lipid mass spectra (lipid fingerprints) varied significantly. The ultimate goal of this research is to provide a precise analytical protocol to show whether the changes in the egg yolk identified in paint dosimeters are due to pigment-binder interactions. The Bligh-Dyer (BD) method was optimized for the extraction of the lipids. This innovative procedure included a washing-step prior to the mass spectrometric analysis, which proved crucial for obtaining higher quality lipid fingerprints. A novel interpretation of the results is proposed by applying the BD method, which suggests that transesterification processes occurred in the lipid fractions that were catalyzed by the pigments in the paint dosimeters. In blank dosimeters specific ions produced by oxidative cleavage of PLs and/or TGs may be used as markers of the presence of egg yolk binders. The composition and structure of the specific lipid compounds are also tentatively proposed. In aged dosimeters the intact content of the TGs and PLs decreased; however, we propose that short-chain oxidative products arising from TGs and PLs are present in all the samples, except for the white lead based dosimeter. We end with a new explanation as to why this dosimeter behaves differently from the others.

Egg yolk identification and aging in mixed paint binding media by NMR spectroscopy.

NMR spectroscopy is a powerful analytical tool for the identification and quantitative analysis of organic materials in a cultural heritage context. In this report, we present an analytical NMR protocol for the identification and semiquantification of egg yolk binders and mixed binding media that also contain a drying oil, namely linseed oil. The samples studied have been artificially and/or naturally aged in order to simulate the composition of organic materials in paintings. Analysis of the 1D and 2D NMR spectra showed that egg yolk can be identified even in binding media of considerable age via signals originating from cholesterol and/or cholesterol oxidation products present in the aged binding medium. Based on cholesterol-related and other lipid signals in the NMR spectra of egg yolk binders, a molecular marker (R/F) that suggests the presence of egg yolk in paint binders is proposed. Via this marker, the presence of egg yolk in the organic material obtained from an early 18th century Greek icon is confirmed, and this is further verified by 2D NMR spectroscopy. It is demonstrated that NMR molecular markers developed to estimate the hydrolysis/oxidation state of oil paintings are also suitable for the analysis of egg yolk and mixed medium (egg yolk-linseed oil) binders, indicating the generality of the NMR methodological approach in the analysis of organic materials in a cultural heritage context.

Screening and quantification of proteinaceous binders in medieval paints based on μ-Fourier transform infrared spectroscopy and multivariate curve resolution alternating least squares

This work aims at screening the presence and predicting the quantity of the binding media used to produce red and blue medieval paints based on the combined use of μ-Fourier-transform infrared (μ-FTIR) spectroscopy and multivariate curve resolution alternating least squares (MCR-ALS). Using different modes of application, MCR-ALS is proposed with a dual objective: 1) classical MCR-ALS is used for a first qualitative analysis of the presence/absence of certain binders in historical samples; 2) correlation constrained MCR-ALS is applied for quantitative analysis of binding media used to produce red and blue medieval paints and to provide structural spectral information about all compounds in the sample.Correlation constrained MCR-ALS introduces a constraint to establish internal calibration models for quantitative analysis in the resolution algorithm. This approach has been first applied to synthetic binder mixtures in order to check for the possibility of designing an appropriate calibration model to validate the quantitative analysis of the three binders that were potentially used in the medieval paints under study: parchment glue, egg white and egg yolk. Finally, classical and correlation constrained MCR-ALS were applied in a set of historical medieval manuscripts (illuminations) of three Portuguese Monasteries to provide qualitative and quantitative information about their binding media. Parchment glue and egg white have been often found separately or in mixtures of different proportions, whereas the egg yolk binder seems to be generally absent in all samples (or in very minor amounts in a few of them). Correlation constrained MCR-ALS resolution has provided reliable results with less rotational ambiguity than classical MCR-ALS with softer constraints. Quantitative values in historical samples should be interpreted only as current values, since there is no available knowledge about the effects of aging processes on the binders of these paints.

Assessment of Raman microscopy coupled with principal component analysis to examine egg yolk–pigment interaction based on the protein CH stretching region (3100–2800 cm−1)

This work seeks to identify the slight changes in the characteristic CH stretching region (3100–2800 cm−1) of a protein‐based binder and fatty acid esters from egg yolk, which may occur in complex paint samples due to the presence of particular pigments. To date, this protein region—where historic pigments do not show characteristic Raman bands—has not been used to identify possible interactions between painting materials, in spite of its potential due to the mentioned feature. This study is based on the investigation of pure egg yolk model samples and tempera model samples prepared by mixing this binder with some historic pigments (cinnabar, raw Sienna, lead white, gypsum, calcite, azurite, lapis lazuli and smalt) as binary samples. All samples were analyzed in this region by Raman microscopy (RM) coupled with principal component analysis (PCA) for three color groups (red, white and blue) separately. The results show relevant spectral changes in the CH stretching region of amino acids and polyunsaturated fatty acids esters of the egg yolk binder, particularly in the azurite, lead white and gypsum‐based tempera samples. Lesser interactions were discerned in the tempera samples made with smalt, as well as shift in the region of polyunsaturated fatty acid esters of the egg yolk binder in the cinnabar and raw Sienna‐based tempera paintings. No interactions were recognized between the egg yolk and the pigments calcite and lapis lazuli. The effectiveness of applying RM combined with PCA for identifying interaction processes between binders and pigments is demonstrated. Copyright © 2011 John Wiley & Sons, Ltd.