Painting the Palace of Apries I: ancient binding media and coatings of the reliefs from the Palace of Apries, Lower Egypt

This study gives an account of the organic components (binders and coatings) found in the polychromy of some fragmented architectural reliefs from the Palace of Apries in Memphis, Egypt (26th Dynasty, ca. 589-568 BCE). A column capital and five relief fragments from the collections of the Ny Carlsberg Glyptotek in Copenhagen were chosen for examination, selected because of their well-preserved polychromy. Samples from the fragments were first investigated using Fourier transform infrared (FTIR) spectroscopy to screen for the presence of organic materials and to identify the chemical family to which these materials belong (proteinaceous, polysaccharides or lipid). Only the samples showing the potential presence of organic binder residues were further investigated using gas chromatography with mass spectrometry detection (GC-MS) targeting the analysis towards the detection and identification of compounds belonging to the chemical families identified by FTIR. The detection of polysaccharides in the paint layers on the capital and on two of the fragments indicates the use of plant gums as binding media. The interpretation of the sugar profiles was not straightforward so botanical classification was only possible for one fragment where the results of analysis seem to point to gum arabic. The sample from the same fragment was found to contain animal glue and a second protein material (possibly egg). While the presence of animal glue is probably ascribable to the binder used for the ground layer, the second protein indicates that either the paint layer was bound in a mixture of different binding materials or that the paint layer, bound in a plant gum, was then coated with a proteinaceous material. The surface of two of the investigated samples was partially covered by translucent waxy materials that were identified as a synthetic wax (applied during old conservation treatments) and as beeswax, respectively. It is possible that the beeswax is of ancient origin, selectively applied on yellow areas in order to create a certain glossiness or highlight specific elements

Violin varnishes: microstructure and nanomechanical analysis

The aim of the current work is twofold: to demonstrate the application of in situ non-invasive imaging by portable atomic force microscopy (AFM) on the surfaces of a violin and to integrate compositional and mechanical analysis at the nano scale level on model samples of varnished wood. These samples were prepared according to traditional recipes by an Italian lutemaker family well practised in the art. Samples of oil and spirit-based varnishes on maple wood, naturally and accelerated light aged, were studied. AFM was used to measure the nanomechanical properties of the model samples and established that the spirit-based varnish was stiffer than the oil-based. Synchrotron radiation micro- Fourier Transform Infra-red analysis of the layer structure revealed that stiffer spirit-based varnish showed less penetration into the wood than the oil-based. Further PeakForce Quantitative Nanomechanical Mapping (QNM) demonstrated a difference in adhesion values between the oil- and spirit-based sample

Ancient encaustic: An experimental exploration of technology, ageing behaviour and approaches to analytical investigation

The composition of the ancient wax-based painting technique known as encaustic has long been the subject of debate. Ancient sources provide few details of the technology, and modern understanding of the medium is restricted to theoretical interpretation and experimental observation. In this multi-analytical collaborative study, a number of analytical approaches were used to investigate the physical and molecular properties of a range of experimentally prepared encaustic paints before and after ageing. Analysis using gas chromatography mass spectrometry, Fourier transform infrared spectroscopy (invasive and non-invasive), X-ray diffraction and thermogravimetric analysis demonstrated how differences in the technology of production alter the properties and composition of the medium and showed how these are modified by the addition of pigment and the effects of ageing. Comparison of results from the different analytical techniques highlights the benefit of an integrated analytical approach to the analysis of ancient encaustic paints and the fundamental importance of insights from invasive study to evaluating the results of non-invasive analysis

An analytical approach based on X-ray diffraction, Fourier transform infrared spectroscopy and gas chromatography/mass spectrometry to characterize Egyptian embalming materials

An analytical approach based on X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Gas Chromatography-Mass Spectrometry (GC/MS) was used to characterize Egyptian embalming materials from the University of Florence’s (Italy) Natural History Museum. FTIR, was used as a fast fingerprinting tool due to its ability to characterise inorganic compounds and to highlight different classes of organic materials. GC/MS following alkaline hydrolysis, solvent extraction, and trimethylsilylation was used to determine the molecular nature of organic materials and their degradation products. The results show that the embalming materials consisted of complex mixtures of natural products as well as transformation products due both to natural ageing and human interventions. FTIR analyses, along with evidence of organic materials, enabled us to identify the presence of calcium oxalates, phosphates and carbonates while XRD patterns confirm the crystalline nature of both phosphates and oxalates. On the basis of the GC/MS identification of specific profiles of long-chain fatty acids, long-chain alcohols and alkanes, polycyclic terpene hydrocarbons and diterpenes, and triterpenes, we found that the balms of the mummies mainly consisted of beeswax, pine pitch and mastic resin. Ricinoleic acid suggests that castor oil was used as an ingredient in the mummification balm in three of the samples. The combination of results allowed the identification of the organic and inorganic composition of the residue of embalming material sampled from the skulls to be achieved and also permitted us to exclude the presence of possible products used during past restoration cure

Analysis of plant gums and saccharide materials in paint samples: Comparison of GC-MS analytical procedures and databases

Background: Saccharide materials have been used for centuries as binding media, to paint, to write and illuminate manuscripts and to apply metallic leaf decorations. Although the technical literature often reports on the use of plant gums as binders, actually several other saccharide materials can be encountered in paint samples, not only as major binders, but also as additives. In the literature, there are a variety of analytical procedures that utilize GC-MS to characterize saccharide materials in paint samples, however the chromatographic profiles are often extremely different and it is impossible to compare them and reliably identify the paint binder. Results: This paper presents a comparison between two different analytical procedures based on GC-MS for the analysis of saccharide materials in works-of-art. The research presented here evaluates the influence of the analytical procedure used, and how it impacts the sugar profiles obtained from the analysis of paint samples that contain saccharide materials. The procedures have been developed, optimised and systematically used to characterise plant gums at the Getty Conservation Institute in Los Angeles, USA (GCI) and the Department of Chemistry and Industrial Chemistry of the University of Pisa, Italy (DCCI). The main steps of the analytical procedures and their optimisation are discussed. Conclusions: The results presented highlight that the two methods give comparable sugar profiles, whether the samples analysed are simple raw materials, pigmented and unpigmented paint replicas, or paint samples collected from hundreds of centuries old polychrome art objects. A common database of sugar profiles of reference materials commonly found in paint samples was thus compiled. The database presents data also from those materials that only contain a minor saccharide fraction. This database highlights how many sources of saccharides can be found in a paint sample, representing an important step forward in the problem of identifying polysaccharide binders in paint samples

Organic materials in the wall paintings of the Vesuvian area

The main goal of the present paper is to add some data to the study of the painting techniques used by the Roman painters in the wall paintings of the Vesuvian Area. This study presents the results by using different analytical techniques on samples from several archaeological sites. The final purpose is to add analytical data to the already published literature on the topic of Roman painting such as the papers by Varone and Bearat on an excavation in Pompei along via dell’Abbondanza where the authors suggest that more than one painter worked together using contemporary fresco and tempera techniques. The authors indicate that some collected fragments could contain an organic substance, though there is no certainty about which type of substance

The issue of eosin fading: A combined spectroscopic and mass spectrometric approach applied to historical lakes

The huge number of complex formulations of synthetic dyes and pigments commercialized in the 19th century makes their comprehensive characterization both difficult and fundamental for their successful identifications in artworks. The description of the exact starting composition of a wide collection of reference materials is preliminary to the study of the challenging photo-degradation processes in which most of the early synthetic dyes and pigments are involved. In this paper, four eosin-based lakes, all containing eosin Y, and one also containing eosin B, but differing in the organic and inorganic materials used as fillers, were fully characterized. These formulations were reconstructed on the base of historical recipes from the extensive Wiesel's collection, dated to the 19th century and bought by Dr Kremer (Kremer Pigmente, Germany) in the 1990s. The composition of each formulation was characterized by Fourier transform infrared spectroscopy (FT-IR) and luminescence spectroscopy was used as a probe for their inert-distinction. Reference paint layers were then prepared by casting the lakes in linseed oil, and their ageing and impact on color change was monitored for one year by analyzing two sets of paint model systems by colorimetry. For each system, two sets were prepared and one was stored in the dark while the other exposed to natural light. The material distribution and homogeneity of the samples were tested by Synchrotron Radiation based micro infrared spectroscopy (SR-μ-FT-IR). Finally, an ultra-sensitive method based on Liquid Chromatography coupled with High Resolution Mass Spectrometry (LC-HRMS) allowed us to characterize eosin degradation products detected but never identified before, and to evaluate their kinetics of formation