Towards the Understanding of the Aging Behavior of p-PVC in Close Contact with Minced Meat in the Artwork POEMETRIE by Dieter Roth.

This paper presents scientific investigations into the materiality and aging behavior of a copy of Dieter Roth's multiple POEMETRIE (1968), mainly made of p-PVC components and minced meat, with the aim of informing conservation-restoration strategies. The main issues were represented by plasticizer migration, fat diffusion, and leakage, which led to the formation of a sticky surface layer. Replicas of p-PVC without minced meat were prepared and artificially thermally aged, while several techniques were used to investigate both the artwork and the replicas in terms of materials and degradation state. These include UV/Vis imaging, pH measurements, FTIR-ATR, and Py-GC/MS. In addition to showing that p-PVC-based materials composed of slightly different plasticizers were affected by similar degradation pathways (i.e., plasticizer migration, yellowing, etc.), this study reports that fat components were also shown to be unstable, resulting in migration/leakage in different directions, where their degradation amplified that of the p-PVC bags. This work represents a first study of plasticizer migration and fat diffusion in the art and conservation context. Also, an ammine-wax type of lubricant was identified in the most recent p-PVC formulations as the replicas selected for this study, thus providing an important source of information in different polymer-based research areas.

Outside, Around, Inside. New Paths to Discover San Michele Castle (Cagliari, Sardinia).

In the framework of conservation and enhancement of cultural heritage, accessibility plays a crucial role. Architectural heritage peculiarities call for specific approaches: the same care must be adopted to improve accessibility to historic architecture, designing actions case by case. Starting from these considerations, the contribution is aimed to discuss the accessibility of fortified architecture, a not easily accessible heritage, to make it accessible both in a physical meaning as well as in cognitive, cultural and social. Particularly, the authors propose some reflections about alternative ways of usability for inaccessible architectures due to their typological configuration and as a consequence of previous conservation design. The case study is the medieval castle of San Michele in Cagliari (Sardinia), which was transformed several times during its life and restored at the end of the 20th century. The contribution analyses how a multidisciplinary approach is necessary for the formulation of effective accessibility solutions, especially in complex cases such as fortified architecture. This multidisciplinary approach must be accompanied by the widest possible consideration of the causes limiting accessibility, whether they are physical or related to motor, perceptive or cognitive disabilities.

Multi-Analytical Investigations of Andy Warhol's "Orange Car Crash": Polymeric Materials in Modern Paints.

This work presents strategic multi-analytical investigations performed on "Orange Car Crash" by Andy Warhol in order to make a well-informed conservation decision. For determining the type of binding medium used in the artwork, Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS) and Thermally Assisted Hydrolysis and Methylation of GC/MS (THM-GC/MS) were employed. The presence of a coating was investigated by Py-GC/MS. Moreover, the comprehension and elucidation of the paint stratigraphy were studied by examining cross-sections of samples taken from both canvases with Optical Microscopy (OM) under reflected visible (Vis) and ultraviolet light (UV) and by Scanning Electron Microscopy with Energy Dispersive X-ray spectroscopy (SEM-EDX). The investigation of possible synthetic organic pigments (SOPs) and extenders was performed by µ-Raman spectroscopy, while micro-Attenuated Total Reflection of Fourier-Transform Attenuated Total Reflection (µ-ATR-FTIR) allowed us to assign each component detected by Py-GC/MS or THM-GC/MS to a specific layer. The data collected from "Orange Car Crash" show mostly the application of acrylic-based paint as well as alkyd with rosin acids-based ink, thus providing fundamental information about the paint stratigraphy and chemical composition of each layer. In addition to the goal of informing an appropriate conservation-restoration strategy, this work represents a rare scientific study of a work by Andy Warhol.

A Multi-Analytical Approach for Studying the Effect of New LED Lighting Systems on Modern Paints: Chemical Stability Investigations.

This study aims to investigate the chemical stability of some modern paint samples exposed to a new Light Emitting Diode (LED)-lighting system and a halogen lamp by using micro-attenuated total reflectance of Fourier transform infrared spectroscopy (µ-ATR-FTIR), µ-Raman, pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and thermally assisted hydrolysis and methylation of GC/MS (THM-GC/MS). Those investigations were performed before and after the exposure of the samples to lightings for 1250, 2400, 3300, and 5000 h. The results obtained with µ-Raman spectroscopy show the high stability of the selected inorganic pigments after the exposure to the lighting systems; while similar to the UV/Vis/NIR results reported in a previous study, µ-ATR-FTIR and THM-GC/MS results evidence greater chemical changes occurring principally on the linseed oil binder-based mock-ups among the acrylic and alkyd-based samples. Moreover, principal component analyses (PCA) and hierarchical cluster analyses (HCA) of THM-GC/MS results highlight that those changes were mostly dependent on the exposure time and on the type of pigment, while being independent of the lighting system used. Finally, semi-quantitative µ-ATR-FTIR results show slight pigment enrichment at the paint surface due to the auto and photo-oxidative degradation of the linseed oil binder.

The effect of new LED lighting systems on the colour of modern paints.

This research focuses on the investigation of the effect of a new light emitting diode (LED)-lighting system which reproduces indoor museum conditions, on some self-made art paint colours (acrylic-, alkyd-, and linseed oil-based paints) often used in modern-contemporary art. A halogen lamp representing a traditional light source for museum lighting was also considered. Lighting-set-up and lighting optimization parameters were considered while Ultraviolet/Visible/Near Infrared (UV/Vis/NIR) spectrophotometry was used for investigating the colour change of the paint samples. Univariate analyses allowed determining the highest effect of the lighting systems on the linseed oil binder and ultramarine blue PB29 mixture upon ageing, according to the highest total colour change ΔE*ab. In a more specific and detailed way, variance analyses not only demonstrated the strong correlation between the type of binder and pigment used for the paint samples with the colour variation, but also showed that the short-wavelength blue LEDs influenced the change along the yellow-blue b* axis of the yellow and blue samples, whereas the halogen lamp mostly had an impact towards the red-green a* axis of mostly the green specimens.

What about Phenol Formaldehyde (PF) Foam in Modern-Contemporary Art? Insights into the Unaged and Naturally Aged Material by a Multi-Analytical Approach.

The ageing behavior of phenol formaldehyde (PF) foam, a material increasingly used in modern-contemporary art, was investigated by a multi-analytical approach. PF foams with open- and closed-cell structures were selected and analyzed in their unaged and naturally indoor-aged state by employing optical microscopy (OM) and fiber optical reflectance spectroscopy (FORS) for assessing their morphology and color alteration. Micro-Fourier transform infrared spectroscopy (µ-FTIR) was used for determining chemical changes and oxidation processes, and the acidity was monitored by pH measurements. The results clearly showed the extreme sensitivity of both open- and closed-cell PF foams to conditions typically found in indoor museums. OM indicated that the cells of the foams are prone to disrupt, and a tendency towards a red color shift was observed with FORS. µ-FTIR revealed the formation of quinone groups resulting from oxidation reactions. Finally, a slight decrease in the acidity was found by pH measurements.

Comprehensive Multi-Analytical Investigations on the Vietnamese lacquered Wall-Panel "The Return of the Hunters" by Jean Dunand.

This work presents a comprehensive, multi-analytical scientific approach for determining the type of lacquer and artistic materials used by Jean Dunand on his work "The Return of the Hunters" (1935). For this purpose, thermally assisted hydrolysis and methylation - gas chromatography/mass spectrometry (THM-GC/MS), optical microscopy (OM) in visible (Vis) and ultraviolet light (UV), and scanning electron microscopy - energy-dispersive X-ray spectroscopy (SEM-EDX) were selected. Furthermore, a novel application of micro attenuated total reflection Fourier transform infrared (µATR-FTIR) spectroscopic mapping by univariate and multivariate analysis was applied for studying the complex lacquer paint stratigraphy. The results show that Vietnamese lacquer was used as a binder, mixed together with linseed oil and pine resins as additives in combination with inorganic pigments, and that shellac was included on the top of the paint; they document an important step in the story of the transfer of Vietnamese lacquer painting techniques to Europe.

Optimization of sample treatment for the identification of anthraquinone dyes by surface-enhanced Raman spectroscopy.

The study and characterization of old artifacts such as pigments requires the use of techniques that need a small amount of sample to perform the analysis because of the high value of these samples. In recent years, organic molecules such as anthraquinone dyes have been identified by surface-enhanced Raman spectroscopy (SERS). However, different sample treatments must be applied to isolate the organic dye from the mordant, which produces great fluorescence in the Raman measurements. In this work, optimization of sample treatment for the SERS analysis of anthraquinone dyes was performed. Sample mass, the organic solvent, and its volume were optimized and different slide materials and excitation lasers were compared to choose the best conditions for the identification of the dyes. The optimization of sample treatment resulted in 5 mg of sample as the optimum amount. Further, two consecutive extractions with 0.5 mL of ethyl acetate was the best option for the extraction of the dye. A quartz slide was used instead of a glass slide to reduce background signal, and an excitation laser of 532 nm offers better results than one of 785 nm. The optimized method was applied to the characterization of the dyes used in Pompeian pink and purple lake pigments. Alizarin and purpurin anthraquinone dyes, obtained from madder lake, were identified as the organic colorants. The SERS results were confirmed by those obtained by means of UV-visible spectroscopy. Graphical Abstract ᅟ.

Photochemical degradation study of polyvinyl acetate paints used in artworks by Py-GC/MS.

Photochemical degradation of commercial polyvinyl acetate (PVAc) homopolymer and PVAc paints mixed with burnt umber, cobalt blue, cadmium red dark, nickel azo yellow and titanium white commonly used for artworks were studied by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR). Py-GC/MS with single-shot technique was used for the characterization of the thermal degradation of PVAc at different temperatures, while the double-shot technique of Py-GC/MS was used to reveal the differences in the specimens before and after UV ageing, including the changes of detectable amounts of deacetylation product - acetic acid and plasticizers such as diethyl phthalate (DEP). Furthermore, the relative concentration of the pyrolysis products of the paint samples could be measured and compared in the second step of the double-shot Py-GC/MS, which are highly dependent on the presence of pigments and the ageing status of PVAc paints.

UV ageing studies: evaluation of lightfastness declarations of commercial acrylic paints.

The lightfastness declarations of several different commercial acrylic paints and different quality series were tested by artificial UV ageing. To evaluate their lightfastness declarations, three acrylic colours (cadmium red, ultramarine blue and chromium oxide green) from six companies (Lascaux, Liquitex, Lukas, Rembrandt, Schmincke, and Winsor & Newton) were analysed before and after UV exposure. Characterisation and identification of these materials were carried out with Py-GC/MS, FTIR-ATR analyses, and colour measurements. Particular attention was focused on the Py-GC/MS measurements and on comparison of the single-shot method for pyrolysis of polymers and the double-shot mode which enables a unique combination of pyrolysis methods for analysis of polymers and thermal desorption for documentation of the volatile compounds. Depending on the particular company and the specific value of the lightfastness declaration, different binding media (i.e. poly(EA/MMA), poly(nBA/MMA), and poly(2-EHA/MMA)), and fillers (i.e. kaolinite, calcium carbonate, barite, and talc) were characterised and identified by Py-GC/MS and FTIR-ATR analyses. After UV exposure, several alteration processes with consequent formation of volatile compounds or new products were observed by both techniques, especially for the blue paints. In particular, the double-shot mode of Py-GC/MS enabled the detection of oxidation products, which could not be detected with the single-shot mode. Comparison of the lightfastness declarations for each of the blue, green, and red paints and the noted alterations broadly agreed for most of the paints.

Characterization and identification of acrylic binding media: influence of UV light on the ageing process.

This study characterizes and identifies two different acrylic binding media such as Plextol® D498 and Primal® AC33, which are widely used in modern and contemporary art. In order to investigate their fast photooxidative deterioration when exposed to ultraviolet (UV) light, ageing studies on these materials were carried out. For this purpose, pure synthetic materials but also mixed with different inorganic pigments were identified and characterized before and after UV exposure by means of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Particular attention was paid to the comparison of two different analytical methods: (1) single-shot method based on a pyrolysis for the analysis of polymers and (2) double-shot method, which allows a unique combination of thermal desorption for the analysis of volatile compounds and pyrolysis of the polymers themselves. These analyses have been complemented by Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) studies. The comparison of the results obtained from unaged samples and UV-aged clearly showed material alterations as well as the formation of new products, which were recorded by FTIR-ATR. Generally, these changes were more pronounced when the acrylic binding media were mixed with pigments. The double-shot technique of Py-GC/MS additionally allowed the detection of the phenolic antioxidant in unaged Plextol® D498, but no oxidation products could be identified by Py-GC/MS in all samples.