Laser cleaning of works of art: evaluation of the thermal stress induced by Er:YAG laser

The Er:YAG laser has proven particularly efficient in cleaning procedures of works of art. The removal of the superficial deposits is achieved through melting, thermal decomposition and evaporation. However, the energy absorbed by vibrational modes is dissipated as heat, increasing the temperature of the surface coating that could cause damage on the object. The aim of this study was to evaluate the temperature increase induced by a Er:YAG MonaLaser (LLC., Orlando, FL, USA). To that purpose, we designed a dedicated device to perform the tests in an inert atmosphere or with a wetting agent, to measure the radiant energy per laser pulse. Tests were carried out both on graphite, which absorbs IR radiation and showed a very intense flash emission, and on different kind of samples representative of materials with different levels of conductivity and thermal diffusivity. Results obtained showed that the temperature increase in the irradiated surface depends on the substrate but never causes the damage of the organic and inorganic material. The use of a solvent as wetting agent has been also tested.     

A multi-analytical approach to studying binding media in oil paintings

This article presents a multi-analytical approach to investigating the drying, polymerisation and oxidative degradation of linseed oil, which had undergone various treatments known to be undertaken during the nineteenth century in preparation for painting. The oil was mechanically extracted from the same seed lot then processed by different methods: water washing, heat treatments, and the addition of driers, with and without heat. The oil was prepared in 1999 within the framework of the MOLART project. We compared thermogravimetric analysis (TG), which yields macromolecular information, with gas-chromatography mass-spectrometry (GC/MS) and direct exposure mass spectrometry (DE-MS), which provide molecular information. This comparison enabled us to elucidate the role of pre-treatment on the composition of the oil. TG and oxygen uptake curves registered at a constant temperature helped us to identify the different physical behaviour of the oil samples, thus highlighting the presence of hydrolysed, oxidised and crosslinked fractions, as a consequence of the different pre-treatments. GC/MS was used to characterise the soluble and non-polymeric fraction of the oil, to calculate the ratios of palmitic to stearic acid (P/S), and azelaic to palmitic acid (A/P), and to further evaluate the effects of oil pre-treatments. DE-MS using chemical ionisation with CH₄, enabled us to establish the chemical composition of the oil in different stages of ageing. DE-MS proved to be a useful tool for a simultaneous semi-quantitative characterisation of the free fatty acids, monoglycerids, diglycerides and triglycerides present in each sample. The combination of thermal analysis with GC/MS and DE-MS enabled a model to be developed, which unravelled how oil pre-treatments produce binders with different physical–chemical qualities.     

Loss of derivatives in evolution Cauchy problems

Abstract We study relations between modulus of continuity of the coefficients and loss of derivatives in the Cauchy problem for evolution operators with real characteristics in the Petrovsky sense. We also provide counterexamples to show that the obtained classification is sharp. Keywords: Cauchy problem, Evolution equations, Loss of regularity of the solution     

The effect of first-stage polymer Tg on the morphology and thermomechanical properties of structured polymer latex particles

A series of heterogeneous latexes having stage ratios of 40:60 between the first and second stage polymers were prepared by emulsion polymerization. The first-stage polymers were non-polar S-BuA with T_gs ranging from + 100 °C to + 20 °C and the second stage polymer was polar MMA–BuA–MAA having a T_g of 20 °C. The latex particle morphologies were studied using TEM and the thermomechanical properties of the resulting latex films were studied with DSC and DMA. Calculated diffusion rates for propagating species during the reactions were correlated to the observed morphologies and to the amount of interphase in the latex particles. To cite this article: O.J. Karlsson et al., C. R. Chimie 6 (2003).     

Characterisation of proteinaceous binders in artistic paintings by chromatographic techniques

This review discusses the application of chromatographic techniques (GC, HPLC and Py-GC) for the characterisation of proteinaceous materials in artistic paintings. The focus is on the various analytical steps that are needed to determine these natural materials in paint samples, from sampling and sample pre-treatment, including various methods of hydrolysis and derivatisation for GC and HPLC, to approaches for data evaluation.     

Analytical quality control for the determination of polychlorobiphenyls in environmental matrices

Analytical quality control procedures for ensuring reliable data in the determination of PCBs in environmental matrices are described. Several extraction procedures of PCBs from sediment samples are critically compared and recovery and reproducibility for PCBs determination in sediment and cod liver oil samples are evaluated. Extraction by 1:1n-hexane/acetone mixture in an ultrasonic bath and by supercritical fluids generally give a quantitative recovery and a coefficient of variation lower than 15%, while extraction by a Soxhlet system does not give such good results and requires much longer extraction times. Certified reference materials available from three international organizations, namely the Standards, Measurements and Testing programme of the European Union, the USA National Institute of Standards and Technology and the National Research Council of Canada were used. Finally, the on-going European Union QUASIMEME programme aimed at improving the analytical quality of marine pollution monitoring measurements of European laboratories is addressed.     

Analytical investigation of calcium oxalate films on marble monuments

This paper describes an analytical approach to investigate the origin of oxalate films on marble. Calcium oxalate films were collected on buildings of historical importance in Lucca and Pisa (Italy) and characterised by optical microscopy (OM), scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX), Fourier transform infrared (FTIR) spectroscopy (equipped with diamond cell), and gas chromatography-mass spectrometry (GC-MS). The morphology of the films was investigated by optical and electronic microscopy. FTIR analyses highlighted the presence of calcium oxalate (both as whewellite and weddellite), gypsum, calcite, nitrates, silicates and apatite, while EDX maps showed the distribution of elements. Several samples showed traces of organic compounds, identified by GC-MS as paraffin wax, lipids of animal origin and egg. The correlation between organic material and oxalate contents suggests the origin of the films from degradation processes of past surface treatment.     

Colorants and oils in Roman make-ups–an eye witness account

Archaeological cosmetics, as well as revealing ancient knowledge, contain a complex mixture of very different organic and inorganic components with diverse properties. Most information on the preparation of ancient cosmetics comes from classical texts. However, although analysis of products contained in archaeological objects has recently identified some ingredients, there is still little known about how the cosmetics were prepared.Using a multi-analytical approach, we studied the chemical composition of two Roman pink make-ups that were preserved on the surface of a Roman bronze cosmetic tool and in a glass unguentarium. The results revealed that both make-ups were colored by madder lake but prepared in two different ways and with two completely different matrices (i.e. scented oils in the first case and gypsum in the second) highlighting that the make-ups had been prepared thoroughly, the ingredients carefully selected and their properties and possibilities for good cosmetic use had been understood.     

TGMS analysis of archaeological bone from burials of the late Roman period

The use of thermogravimetric analysis–mass spectrometry (TGMS) to study the state of preservation of archaeological bones has been investigated. As part of a collaborative multi-analytical study, bones exhumed from graves of the late Roman period in France and Italy were examined. A decrease in organic matter for the archaeological bones compared to that for new bone was confirmed, demonstrating that diagenesis of aged bones can be detected using TGMS. Different amounts of collagen were determined for bones from different graves and could, for the majority of specimens, be correlated with the visually observed preservation states.