Analysis of organic colouring and binding components in colour layer of art works

Two methods of analysis of organic components of colour layers of art works have been tested: IR microspectroscopy of indigo, Cu-phthalocyanine, and Prussian blue, and MALDI-TOF-MS of proteinaceous binders and a protein-containing red dye. The IR spectra distortion common for smooth outer surfaces and polished cross sections of colour layer of art works is suppressed by reflectance measurement of microtome slices. The detection limit of the three blue pigments examined is ~0.3 wt% in reference colour layers in linseed oil binder with calcite as extender and lead white as a drying agent. The sensitivity has been sufficient to identify Prussian blue in repaints on a Gothic painting. MALDI-TOF-MS has been used to identify proteinaceous binders in two historical paintings, namely isinglass (fish glue) and rabbit glue. MALDI-TOF-MS has also been proposed for identification of an insect red dye, cochineal carmine, according to its specific protein component. The enzymatic cleavage with trypsin before MALDI-TOF-MS seems to be a very gentle and specific way of dissolution of the colour layers highly polymerised due to very long aging of old, e.g. medieval, samples.     

TG–DSC analysis applied to contemporary oil paints

Thermogravimetry coupled with differential scanning calorimetry (TG–DSC) has been commonly used in the field of conservation of Cultural Heritage for the study of art objects, especially for the characterisation of inorganic matrixes. In recent years, thermal analyses have been applied to the study of organic painting materials. The advantages of performing TG–DSC are linked to the fact that it is micro-destructive technique which does not require any treatment prior the analysis and provide useful information in relatively short time. The aim of this study is to describe the application of TG–DSC on the study of oil binders used in contemporary paints. Even if synthetic binders have become increasingly popular in the 20th century, many contemporary artists still prefer the more traditional media: drying oils. Although the wish of recalling traditional methods, much practical knowledge in paint preparation by mixing drying oil and pigments and in the behaviour of the mixture has been lost. This is mainly due to the different composition of contemporary materials in comparison with the traditional ones and may sometimes lead to different drying properties of the oil paint formulations and consequent problems in the art creation and conservation. For answer to this artistic need and in particular to the difficulties outlined by artists themselves in producing and employing oil paints, unpigmented and pigmented oil films were studied after a week, 1 and 2 years of natural drying under laboratory conditions. Thermal analyses were performed in air flow: the focus of this research was, in fact, to study the thermal and oxidative behaviours of young films for better understanding the very first processes leading to the formation of the film.     

Characterization of bile acids and fatty acids from ox bile in oil paintings by gas chromatography-mass spectrometry

Characterization of ox bile, traditionally used in painting, is of interest in the fields of archaeometry and conservation and restoration of works of art. Bile acids, fatty acids (F), and cholesterol found in ox bile have been identified using a derivatization method that combines the formation of ethyl esters from the carboxylic groups and the trimethylsilyl ethers from hydroxyl groups. This method of analysis is consistent with these others proposed by the authors to analyze drying oils, proteins, and diterpenic resins usually used as binders and varnishes by the painters. Bile acids from binary samples such as animal glue/ox bile, casein/ox bile and Arabic gum/ox bile have been successfully analyzed using the proposed method. Finally, a method of analysis of mixtures of drying oil and ox bile has been also proposed attempting to quantitatively characterize samples in which ox bile was added to the drying oil for increasing the surfactant properties.     

Gas chromatography/mass spectrometry of oils and oil binders in paintings

A GC/MS procedure has been developed, optimized, and applied to characterization of oil binders in paintings. The procedure involves hydrolysis of lipids to fatty acids (FAs) and derivatization of FAs to fatty acid methyl esters (FAMEs) by a solution of sodium methanolate in methanol at an elevated temperature. FAMEs are analyzed by temperature-programed GC followed by full-scan MS. Old and dried samples are subjected to extraction of nonpolymerized FAMEs into dichloromethane prior to hydrolysis. The method provides a good repeatability of results and has been applied to the characterization of common plant oils used in paintings, to commercial oil and tempera paints, to model painting samples, and to samples taken from real paintings. The fresh oils and binders can readily be identified and characterized. The ratio of the methyl esters of palmitic and stearic acids can be used to characterize oil binders in old works of art.     

Identification of drying oils in mixtures of natural binding media used for artistic and historic works by capillary electrophoresis

To characterise the technologies and to find the appropriate treatments, the identification of the binding media of artistic and historic objects is of high importance for the restorer and conservator. Often applied together with other binders, in the present paper, the applicability of a CZE method was ascertained for the identification of the constituents of drying oils in mixtures with animal glues and/or plant gums. The drying oils are identified after alkaline hydrolysis due to their content of long‐chain saturated and unsaturated fatty acids (palmitic, stearic, oleic, linoleic, linolenic) and shorter‐chain dicarboxylic acids (pimelic, suberic, azelaic, sebacic). The dicarboxylic acids occur as products of the unsaturated acids by oxidative degradation during the drying process. The possible interferences in CE caused by the other binders are amino acids and/or monosaccharides. Such interferences could be expected as indirect UV detection has to be used, which is highly unspecific. It was found that none of the constituents of the animal glues or plant gums migrate in the time window of the analytes, thus not obstructing the identification of the analytes in any of the oil mixtures with one binder, or with a combination of both. No interference is observed even in excess of the glues. The method was applied for the identification of a drying oil in a paint layer from a ceremonial mask originating from Papua New Guinea. There is evidence that the oil is most probably from candlenut tree (Aleurites moluccana).     

Stress development during drying of calcium carbonate suspensions containing carboxymethylcellulose and latex particles

Stress development during drying of coatings produced from aqueous dispersions of calcium carbonate particles in the presence and absence of organic binders was studied using a controlled-environment stress apparatus that simultaneously monitored drying stress, weight loss, and relative humidity. Specifically, the influence of two organic binders on drying stress evolution was investigated: (1) carboxymethylcellulose, a water-soluble viscosifying aid, and (2) a styrene-butadiene latex emulsion of varying glass transition temperature. The stress histories exhibited three distinct regions. First, a period of stress rise was observed, which reflected the capillary tension exerted by the liquid on the particle network. Second, a maximum stress was observed. Third, it was followed by a period of either stress decay or rise depending on the organic species present. Significant differences in stress histories were observed between coatings containing soluble and nonsoluble binders. Maximum drying stresses (sigmamax) of 0.2-0.5 MPa were observed for coatings produced from pure calcium carbonate or calcium carbonate-latex suspensions, whereas coatings with carboxymethylcellulose exhibited substantially higher sigmamax values of 1-2 MPa. Upon drying, these coatings were quite hygroscopic, such that cyclic variations in relative humidity induced large cyclic changes in residual stress.     

Stratigraphic Examination of a Korean Lacquered Wooden Coffin Sample by Pyrolysis/GC/MS

A lacquered wooden coffin decorated with gilded Sanskrit letters excavated in the Nongso ancient tomb site was constructed around the fourteenth century in Korea. Pyrolysis/gas chromatography/mass spectrometry was employed to identify the materials of the lacquered surface by analyzing the individual layers. The components of lacquer were detected in all four layers of wood substrate, black, brown, and gilded layers, indicating the coating material was Asian lacquer. The wood seems to be a kind of pine tree from the observation that pine resin-related components were detected in much of the wood substrate and decreasing in the upward direction. Markers of drying oil like azelaic acid and palmitic acid existed in large quantities in the black, brown, and gilded layers, indicating that drying oil was intentionally added to give a luster. In addition, compared with dried Asian lacquer from Korea, the lacquer used in the coffin was determined to be of the same type.     

Identification by GC-FID and GC-MS of amino acids, fatty and bile acids in binding media used in works of art

GC-FID was used as single methodology for the identification and differentiation of proteins, lipids and ox bile from binders used in artistic paintings. The samples were hydrolyzed by HCl. Subsequently, the simultaneous formation of volatile derivatives of the amino, fatty and bile acids with ethyl chloroformate was performed quickly and safely in an aqueous medium. The derivatives were separated by capillary GC and characterized by GC-MS. The ageing of drying oils was studied, identifying pelargonic acid among other degradation products. Proteinaceous and lipoid binding media were characterized by means of the quotients between the areas of the peaks for each amino or fatty acid with respect to the area of the peak for alanine or palmitic acid. Fatty acids from ox bile were easily identified by their retention times characteristic for eicosanoic, docosanoic and pentadecanoic acids. The suggested method was applied to the analysis of binders in baroque paintings by Palomino in Valencia (Spain). Animal gelatine and linseed oil were found.     

A study for the characterization of binding media from medieval polychrome sculptures by gas chromatography-mass spectrometry

Summary Binding media in samples taken from XIIth–XIIIth century polychrome sculptures in the Baptistery of Parma (Italy) were characterized by gas chromatography-mass spectrometry, after hydrolysis and derivatization procedures. The use of SE-52 capillary columns and the application of selected ion monitoring (SIM) allowed an increasing in the sensitivity and the ability to differentiate between animal glues, casein, egg and drying oils as components of the binders of paint and ground layers. Small amounts of material were enough for a satisfactory characterization.     

Identification by GC-FID and GC-MS of amino acids, fatty and bile acids in binding media used in works of art

GC-FID was used as single methodology for the identification and differentiation of proteins, lipids and ox bile from binders used in artistic paintings. The samples were hydrolyzed by HCl. Subsequently, the simultaneous formation of volatile derivatives of the amino, fatty and bile acids with ethyl chloroformate was performed quickly and safely in an aqueous medium. The derivatives were separated by capillary GC and characterized by GC-MS. The ageing of drying oils was studied, identifying pelargonic acid among other degradation products. Proteinaceous and lipoid binding media were characterized by means of the quotients between the areas of the peaks for each amino or fatty acid with respect to the area of the peak for alanine or palmitic acid. Fatty acids from ox bile were easily identified by their retention times characteristic for eicosanoic, docosanoic and pentadecanoic acids. The suggested method was applied to the analysis of binders in baroque paintings by Palomino in Valencia (Spain). Animal gelatine and linseed oil were found. Received: 27 September 2000 / Revised: 16 January 2001 / Accepted: 17 January 2001     

Capillary hydrodynamics of oligomer binders

In this work, we consider wetting and flow of oligomer binders for tissue fibers made of carbon and organic fibers. A correlation between the specific surface of fibers and strength of the boundary layers is established. The effect of fibers on structure formation of binders in the boundary layers is explained via the surface density of reticulation of fiber. The fibers with minimum surface reticulation exert a pronounced influence on the structure of binders, forming thicker and strong boundary layers.     

Thin surfactant layers at the solid interface

The formation of surfactant layers on solid surfaces is an important process in many industrial applications. The structure of these layers influences the properties of the solid in processing and use. We summarize the literature data on the structure of surfactant layers at the solid/liquid interface and our own results characterizing the interactions between solid surfaces and solutions or emulsions. Ideas are presented for the processes taking place at the solid surface during drying by heat treatment. An outlook is given of how to investigate surfactant layers on dry surfaces. Received: 11 July 1999/Accepted: 2 May 2000     

Direct chemolysis-gas chromatography-mass spectrometry for analysis of paint materials

A novel direct method using (m-trifluoromethylphenyl)trimethylammonium hydroxide (TFTMAH) has been developed for on-line (trans)esterification of lipidic materials (drying oils, egg) prior to GC-MS analysis. The method was first optimised by comparing three N-methylammonium hydroxide reagents (TMAH, PhTMAH, TFTMAH) and triolein as a lipid standard. Secondly, the procedure was tested on a series of fresh and naturally aged (up to 40 years) (un)pigmented drying oils and egg yolk reference film standards. Thirdly, the method was applied to the analysis of a sample from an altar painting "Resurrection of Christ" by Francesco Solimena (1723) from the Chapel of Upper Belvedere in Vienna. The relative proportions of the fatty acids from the translucent size layer confirm the presence of partially degraded oil, probably prepolymerised walnut oil.     

A Critical Review on the Analysis of Metal Soaps in Oil Paintings

Up to 70 % of the oil paintings conserved in collections present metal soaps, which result from the chemical reaction between metal ions present in the painted layers and free fatty acids from the lipidic binders. In recent decades, conservators and conservation scientists have been systematically identifying various and frequent conservation problems that can be linked to the formation of metal soaps. It is also increasingly recognized that metal soap formation may not compromise the integrity of paint so there is a need for careful assessment of the implications of metal soaps for conservation. This review aims to critically assess scientific literature related to commonly adopted analytical techniques for the analysis of metal soaps in oil paintings. A comparison of different analytical methods is provided, highlighting advantages associated with each, as well as limitations identified through the analysis of reference materials and applications to the analysis of samples from historical paintings.     

High performance liquid chromatography determination of fatty acids in drying oils following lipase action

This paper describes a quantitative analytical procedure to determine the fatty acid composition in drying oils like linseed, walnut and poppy seed. The procedure required the enzymatic hydrolysis of the oil triacylglycerol families by the action of Candida rugosa lipase. The fatty acids (FFAs) produced (linolenic, myristic, linoleic, palmitic, oleic and stearic) were extracted with n-heptane and derivatized with α-bromoacetophenone. Their separation and quantitative determination were performed by high-performance liquid chromatography employing a C18 column and an isocratic elution method coupled to ultraviolet detection. The analytical enzymatic procedure is sensitive for < 0.5 μg/mL of FFAs in a reduced sample of 0.1 mg of drying oil.     

Dehydration of aluminophosphate solutions in a microwave field

Dehydration of solutions of aluminophosphate binders in a microwave field to obtain aluminophosphate powders of various compositions is considered. The effect of drying conditions and of the chemical composition of aluminophosphate binders on the phase composition and solubility of the products obtained is analyzed.     

Thermoreversible gels of polymers in recycled motor oil

A study of the dynamic viscoelastic properties of gels of Ethylene Vinyl Acetate (EVA) and Styrene‐Butadiene‐Styrene (SBS) copolymers in recycled motor oil is presented. Both systems form gels with enhanced elastic moduli, with respect to SBS/aromatic oil gels which have been used to develop synthetic binders. Although the procedure described by Winter is conveniently applied to obtain gel‐sol transition of EVA/oil gels, it is not suitable for SBS/oil gels which do not give rise to a homogeneous liquid when they melt. For EVA/oil gels the relaxation exponent at the gel point is Δ=0.5, which according to Muthukumar's model corresponds to a fractal dimension d_f=2. The variation of the elastic modulus with polymer concentration follows the scaling law G_e‐cⁿ, with n=2.8 for EVA/oil and n=1.3 for SBS/oil. In the case of EVA/oil gels the validity of theoretical models relating fractal dimension to n exponent is discussed.     

Classification and identification of organic binding media in artworks by means of Fourier transform infrared spectroscopy and principal component analysis

Fourier transform infrared spectroscopy is a powerful analytical technique to study organic materials. However, in Cultural Heritage, since the sample under analysis is always a complicated matrix of several materials, data analysis performed through peak-by-peak comparisons of sample spectra with those of standard compounds is a tedious method that does not always provide good results. To overcome this problem, a chemometric model based on principal component analysis was developed to classify and identify organic binding media in artworks. The model allows the differentiation of five families of binders: drying oils, waxes, proteins, gums, and resins, taking into account the absorption bands in two characteristic spectral windows: C–H stretching and carbonyl band. This new methodology was applied in the characterization of binders in three kinds of artworks: papers of historical, archeological, and artistic value, easel paintings, and polychromed stone-based sculptures.     

Brønsted双核碱性离子液体的合成及其在制备生物柴油过程中的催化性能

以N-甲基吗啡啉和1,4-二溴丁烷为原料,通过两步法合成了新型Brønsted碱性双核离子液体.分别采用¹H-NMR、FT-IR和元素分析对合成的离子液体进行结构分析;采用TGA测试离子液体的热稳定性;同时测定了离子液体的溶解性和碱性.此外,考察了双核碱性离子液体在大豆油和甲醇酯交换反应中的催化活性.结果表明,当甲醇:大豆油=14:1(物质的量比)、离子液体用量为大豆油质量的5%、反应时间5 h、反应温度60 ℃时、生物柴油收率为 95.6%(质量分数),且离子液体经回收、真空干燥,重复使用6次后催化活性没有明显降低,仍能达到94%以上.     

Fingerprinting of egg and oil binders in painted artworks by matrix-assisted laser desorption ionization time-of-flight mass spectrometry analysis of lipid oxidation by-products

A matrix-assisted laser desorption ionization time-of-flight mass spectrometry-based approach was applied for the detection of various lipid classes, such as triacylglycerols (TAGs) and phospholipids (PLs), and their oxidation by-products in extracts of small (50–100 μg) samples obtained from painted artworks. Ageing of test specimens under various conditions, including the presence of different pigments, was preliminarily investigated. During ageing, the TAGs and PLs content decreased, whereas the amount of diglycerides, short-chain oxidative products arising from TAGs and PLs, and oxidized TAGs and PLs components increased. The examination of a series of model paint samples gave a clear indication that specific ions produced by oxidative cleavage of PLs and/or TAGs may be used as markers for egg and drying oil-based binders. Their elemental composition and hypothetical structure are also tentatively proposed. Moreover, the simultaneous presence of egg and oil binders can be easily and unambiguously ascertained through the simultaneous occurrence of the relevant specific markers. The potential of the proposed approach was demonstrated for the first time by the analysis of real samples from a polyptych of Bartolomeo Vivarini (fifteenth century) and a “French school” canvas painting (seventeenth century).