The Effect of Pollutant Gases on Surfactant Migration in Acrylic Emulsion Films: A Comparative Study and Preliminary Evaluation of Surface Cleaning.

From their first employment in the 1950s, acrylic emulsions have remained widely used as art material today. Although under certain deteriorating conditions they are very stable, if exposed to high humidity and atmospheric pollutant gases, their structural and chemical conformation is strongly affected. Dealing with the resulting surfactant migration, various cleaning treatments were considered over the years. However, their choice remains difficult as they easily alter the acrylic component, especially if in contact with aqueous solutions. The present study focuses on investigating the stability of acrylic emulsion films exposed to accelerated aging by various pollutant gases. Firstly, a comparative analytical study was carried out in order to morphologically (by 3D optical and Atomic Force Microscopy) and chemically (by Raman and Infrared spectroscopy) characterize the reactions and degradation products. Subsequently, two water-based cleaning treatments were tested, and a preliminary evaluation of their cleaning effectiveness was performed. The results show that the reaction of atmospheric gas pollutants with water molecules in moisture leads to acidic reaction products that attack the acrylic matrix and favor the migration of the surfactant to the surface. The effectiveness of cleaning treatments depends on the aging conditions applied, which further lead to different surface morphological changes.

Combined LA-ICP-MS/LIBS: powerful analytical tools for the investigation of polymer alteration after treatment under corrosive conditions.

Polymers are used in a variety of different areas, including applications in food packaging, automotive and the semiconductor industry. Information about degradation of these materials during application, but also uptake of pollutants from the surrounding environment is therefore of great interest. Conventional techniques used for polymer characterization such as FT-IR or Raman spectroscopy, but also thermo-analytical techniques offer insights into degradation processes but lack the possibility to detect uptake of inorganic species. Moreover, these techniques do not allow the measurement of depth profiles, thus information about degradation or pollutant uptake with sample depth is not accessible. In this work, we propose LA-ICP-MS and LIBS as powerful analytical tools for polymer characterization, overcoming the limitations of conventional analytical techniques used for polymer analysis. Applicability of the developed procedures is demonstrated by the analysis of artificially weathered polyimides and modern art materials, indicating that the degradation of the polymer but also the uptake of corrosive gases is not limited to the sample surface. Finally, a tandem LA-ICP-MS/LIBS approach is employed, which combines the advantages of both laser-based procedures, enabling the simultaneous analysis of polymer degradation and cadmium uptake of polystyrene after exposure to UV radiation and treatment with artificial sea water.

Multivariate analysis and laser-induced breakdown spectroscopy (LIBS): a new approach for the spatially resolved classification of modern art materials.

The ever-increasing speed of exchange of ideas, information, and culture allows contemporary art to be in constant growth, especially concerning the choice of artistic materials. Their characterization is not only crucial for the study of artistic techniques but also for research into the stability of the material and, consequently, the best preservation practices. For this aim, an analytical method should have the advantages of not requiring sample preparation, performing superficial micro-analysis, and obtaining detailed spectral information. For this study, laser-induced breakdown spectroscopy (LIBS) was employed. It was used for the identification of modern paints composed of inorganic pigments and organic binders, such as acrylics, alkyds, and styrene-acrylics. Principal component analysis (PCA) was used to classify the different pure materials, above all, the polymeric binders. To distinguish the paint mixtures, whose LIBS spectral results were more complex due to the pigment/binder interaction, a statistical method recently employed in the cultural heritage field was chosen, namely, random decision forest (RDF). This methodology allows a reduction of the variance of the data, testing of different training data sets by cross-validation, an increase of the predictive power. Furthermore, for the first time, the distribution of different inorganic pigments and organic binder materials in an unknown sample was mapped and correctly classified using the developed RDF. This study represents the first approach for the classification of modern and contemporary materials using LIBS combined with two different multivariate analyses. Subsequent optimization of measurement parameters and data processing will be considered in order to extend its employment to other artistic materials and conservation treatments.

Pigment and Binder Concentrations in Modern Paint Samples Determined by IR and Raman Spectroscopy.

Knowledge of the techniques employed by artists, such as the composition of the paints, colour palette, and painting style, is of crucial importance not only to attribute works of art to the workshop or artist but also to develop strategies and measures for the conservation and restoration of the art. While much research has been devoted to investigating the composition of an artist's materials from a qualitative point of view, little effort has been made in terms of quantitative analyses. This study aims to quantify the relative concentrations of binders (acrylic and alkyd) and inorganic pigments in different paint samples by IR and Raman spectroscopies. To perform this quantitative evaluation, reference samples of known concentrations were prepared to obtain calibration plots. In a further step, the quantification method was verified by additional test samples and commercially available paint tubes. The results obtained confirm that the quantitative method developed for IR and Raman spectroscopy is able to efficiently determine different pigment and binder concentrations of paint samples with high accuracy.

Degradation of glass artifacts: application of modern surface analytical techniques.

A detailed understanding of the stability of glasses toward liquid or atmospheric attack is of considerable importance for preserving numerous objects of our cultural heritage. Glasses produced in the ancient periods (Egyptian, Greek, or Roman glasses), as well as modern glass, can be classified as soda-lime-silica glasses. In contrast, potash was used as a flux in medieval Northern Europe for the production of window panes for churches and cathedrals. The particular chemical composition of these potash-lime-silica glasses (low in silica and rich in alkali and alkaline earth components), in combination with increased levels of acidifying gases (such as SO(2), CO(2), NO(x), or O(3)) and airborne particulate matter in today's urban or industrial atmospheres, has resulted in severe degradation of important cultural relics, particularly over the last century. Rapid developments in the fields of microelectronics and computer sciences, however, have contributed to the development of a variety of nondestructive, surface analytical techniques for the scientific investigation and material characterization of these unique and valuable objects. These methods include scanning electron microscopy in combination with energy- or wavelength-dispersive spectrometry (SEM/EDX or SEM/WDX), secondary ion mass spectrometry (SIMS), and atomic force microscopy (AFM). In this Account, we address glass analysis and weathering mechanisms, exploring the possibilities (and limitations) of modern analytical techniques. Corrosion by liquid substances is well investigated in the glass literature. In a tremendous number of case studies, the basic reaction between aqueous solutions and the glass surfaces was identified as an ion-exchange reaction between hydrogen-bearing species of the attacking liquid and the alkali and alkaline earth ions in the glass, causing a depletion of the latter in the outermost surface layers. Although mechanistic analogies to liquid corrosion are obvious, atmospheric attack on glass ("weathering") is much more complex due to the multiphase system (atmosphere, water film, glass surface, and bulk glass) and added complexities (such as relative humidity and atmospheric pollutant concentration). Weathered medieval stained glass objects, as well as artifacts under controlled museum conditions, typically have less transparent or translucent surfaces, often with a thick weathering crust on top, consisting of sulfates of the glass constituents K, Ca, Na, or Mg. In this Account, we try to answer questions about glass analysis and weathering in three main categories. (i) Which chemical reactions are involved in the weathering of glass surfaces? (ii) Which internal factors (such as the glass composition or surface properties) play a dominant role for the weathering process? Can certain environmental or climatic factors be identified as more harmful for glasses than others? Is it possible to set up a quantitative relationship or at least an approximation between the degree of weathering and the factors described above? (iii) What are the consequences for the restoration and conservation strategies of endangered glass objects? How can a severe threat to precious glass objects be avoided, or at least minimized, to preserve these artifacts of our cultural heritage for future generations?