Mattel's ©Barbie: Preventing Plasticizers Leakage in PVC Artworks and Design Objects through Film-Forming Solutions.

The main conservation problem of p-PVC artworks is phthalate-based plasticizer migration. Phthalate migration from the bulk to the surface of the materials leads to the formation of a glossy and oily film on the outer layers, ultimately reducing the flexibility of the material. This study aimed to develop a removable coating for the preservation of contemporary artworks and design objects made of plasticized polyvinyl chloride (p-PVC). Several coatings incorporating chitosan, collagen, and cellulose ethers were assessed as potential barriers to inhibiting plasticizer migration. Analytical techniques including optical microscopy (OM), ultraviolet/visible/near-infrared spectroscopy (UV/Vis/NIR), Fourier transform infrared spectroscopy with attenuated total reflection (FTIR-ATR), and scanning electron microscopy (SEM) were utilized to evaluate the optical and chemical stability of selected coating formulations applied to laboratory p-PVC sheet specimens. Subsequently, formulations were tested on a real tangible example of a design object, ©Barbie doll, characterized by the prevalent issue of plasticizer migration. Furthermore, the results obtained with the tested formulations were evaluated by a group of conservators using a tailored survey. Finally, a suitable coating formulation capable of safeguarding plastic substrates was suggested.

Analytical Investigations of XIX-XX Century Paints: The Study of Two Vehicles from the Museum for Communications of Frankfurt.

Over the centuries, humans have developed different systems to protect surfaces from the influence of environmental factors. Protective paints are the most used ones. They have undergone considerable development over the years, especially at the turn of the 19th and 20th centuries. Indeed, between the two centuries, new binders and pigments have been introduced in the constituent materials of paints. The years in which these compounds have been introduced and spread in the paint market allow them to be defined as markers for the dating of paints and painted artifacts. The present work is focused on the study of the paints of two vehicles of the Frankfurt Museum of Communication, i.e., a carriage and a cart, that was designed for the German Postal and Telecommunications Service roughly between 1880 and 1920. The characterization of the paints was performed through in situ non-invasive techniques, i.e., portable optical microscopy and multispectral imaging, and laboratory non-destructive techniques, i.e., FT-IR ATR spectroscopy and SEM-EDS. The analytical investigation and the comparison with the data reported in the literature allowed us to determine the historicity of the paints, which are all dated before the 1950s.

Natural based products for cleaning copper and copper alloys artefacts.

Copper alloys objects can deteriorate their conservation state through irreversible corrosion. Since in the cultural heritage field every artefact is unique and any loss irreplaceable, solutions for conservation are needed. Hence, there is the necessity to stop the corrosion process with a suitable cleaning and conservation process to avoid further degradation processes without changing its morphological aspect. Chelating solutions are commonly used in chemical cleaning, mainly sodium salts of ethylenediaminetetraacetic acid (EDTA). However, it is resistant to water purification procedures and is not biodegradable. The goal of this study was to see if applying an ecologically friendly chelating agent as an alternative to EDTA cleaning procedures for cultural heritage was suitable. In this study were chosen six natural-based chelators that could be a new green non-toxic alternative to EDTA in corrosion-inhibiting properties. They were tested for cleaning copper artefacts exposed to atmospheric environment in polluted areas. The study considered four amino acids, a glucoheptonate (CSA) and an industrial green chelator (GLDA). The effectiveness was tested on corrosion copper compounds and on laboratory corroded copper sheets. Finally, the cleaning efficacy was tested on four Roman coins and a modern copper painting. To define the cleaning efficacy, surface analytical investigations have been carried out by means ICP-OES, UV-VIS, µ-Raman, spectro-colorimetry, XRD and FTIR. Among the amino acids, alanine was the most effective, showing an unaltered noble patina and a good effective copper recovery from corrosion patinas.

Mattel's Barbie: Investigation of a Symbol-Analysis of Polymeric Matrices and Degradation Phenomena for Sixteen Dolls from 1959 to 1976.

Mattel's Barbie dolls are the most famous and iconic dolls since 1959. Today, they are being collected by individuals and often conserved in museum environments due to their cultural and historical significance reflecting everyday life and historical events. However, just like most museum objects made of plastics, both historical and more recent Barbies show evident degradation phenomena. Firstly, Barbies were made of plasticized polyvinyl chloride (PVC), affected by the migration of additives-mostly the plasticizers-from the bulk phase to the outermost layer, appearing as a tacky and glossy exudate. Over the years, Barbies' polymeric constituents were replaced with more stable ones, whose additives migration is limited compared to PVC, even though still occurring. Multispectral photography in visible (VIS) and ultraviolet (UV) light, microscopical observations in VIS and UV light, and Fourier Transform Infrared spectroscopy in the Attenuated Total Reflectance mode (FT-IR ATR) were performed to characterize the constituent materials of 15 Barbies produced between 1959 and 1976, bridging the information gap on their processing over the years. The micro-invasive multi-analytical approach also allowed for the characterization of the degradation products, permitting the reference of the exudated compound to the specific bulk polymer.

In Situ Application of Anti-Fouling Solutions on a Mosaic of the Archaeological Park of Ostia Antica.

Biodegradation is among the most common issues affecting Cultural Heritage stone materials in outdoor environments. In recent years, the application of chemical agents with biocidal activity has been the most usual practice when dealing with biofilm removal. In outdoor environments, the use of these biocides is not effective enough, since the materials are constantly exposed to environmental agents and atmospheric pollutants. Thus, it becomes necessary to protect the surface of Cultural Heritage works with antimicrobial coatings to either prevent or at least limit future colonization. In this study, innovative biocides-both natural and synthetic-were applied on a Roman mosaic located in the Archaeological Park of Ostia Antica to compare their effectiveness in removing the biological degradation affecting it. In addition, an antimicrobial coating called "SI-QUAT" was applied and analyzed in situ. SI-QUAT has recently entered the market for its prevention activity against biocolonization. The biocidal activity of these products was tested and monitored using different analytical portable instruments, such as the multispectral system, the spectrocolorimeter, and the bioluminometer. The analyses showed that promising results can be obtained using the combination of the biocide and the protective effect of Preventol® RI50 and SI-QUAT.

In-Situ Comparative Study of Eucalyptus, Basil, Cloves, Thyme, Pine Tree, and Tea Tree Essential Oil Biocide Efficacy.

Bio-colonization is a dynamic and multiphasic process headed by microorganisms. Conventional treatments to process affected stone materials include chemical biocides, whose formulations are mainly composed of quaternary ammonium salts(QAs), reported to be toxic for human health, dangerous for the environment, and not biodegradable. Accordingly, novel green and eco-friendly products are a promising alternative to treat stone materials deteriorated by microorganism colonization. In this study, the efficacy of pure essential oils (EOs) and a mix of EOs was assessed in situ and compared to a conventional biocide based on QAs, and two commercially green products based on EOs, which were taken as references, through application on a mosaic located at the Archaeological Park of Ostia Antica (Rome). The EO biocide efficacy was analyzed by ultraviolet induced luminescence, spectro-colorimetry and bio-luminometry analyses while the possibility of their permanence on simulated substrate was studied by FTIR spectroscopy. It was observed by FTIR analysis, that EOs considered volatile can leave a residue after the application; typical fingerprint bands at about 2926, 1510, and 1455 cm-1 were recorded in the EO spectra. Every tested oil was confirmed to have a biocide action although minimal in relation to the most conventional products based on QAs. The synergy of the essential oils revealed positive results, showing a stronger biocide efficacy. Further investigation should be carried out to develop the method of application and study of essential oils on cultural heritage.

Deep Eutectic Solvents (DESs): Preliminary Results for Their Use Such as Biocides in the Building Cultural Heritage.

Biodeterioration is an increasingly widespread process of degradation in the context of the conservation of cultural heritage, which involves a combination of physical and chemical damages together with an aesthetic alteration of materials. For biological damage on monuments caused by pathogens, macro- and microorganisms, chemical treatments are generally used, most of the time dangerous for the environment and for the operator. In this context, new eco-friendly products represent necessary tools for the treatment of biologically deteriorated stone surfaces and represent a new challenge in the field of restoration and conservation of materials of cultural interest. A relatively new class of unconventional green solvents are deep eutectic solvents (DESs), which have peculiar chemical-physical characteristics such as being non-toxic, ecological, biodegradable, non-flammable, and stable in the presence of water. Furthermore, many DESs known in the literature have also been shown to have a biocidal action. All these characteristics make DESs very advantageous and safe, and they could be used as biocidal agents for the treatment of biodegraded surfaces of cultural heritage, being non-toxic for the environment and for the operator. So far, they are used in various fields, but they still represent a novel frontier in the cultural heritage sector. The present research aims at testing five different DESs for the first time in cultural heritage. In particular, DESs are applied to a mosaic located in the Ostia Antica Archaeological Park (Rome), and their efficiency is compared with a biocide product currently used in the restoration field, namely, Preventol RI50, through luminescence, bio-luminometry, and spectrocolorimetry analysis. The preliminary results achieved show the different behaviors of each DESs, highlighting the possibility of employing them in the field of cultural heritage. Further studies have been planned, some of which are already underway, to investigate the properties of DESs and indicate any improvements to make them more effective, both as solvents and as biocides, and easy to apply to various types of materials. The results obtained from this first study are very promising for the use of DES as a new green strategy for cleaning and conservation treatments of materials in the field of cultural heritage.

Combined Use of Non-Invasive and Micro-Invasive Analytical Investigations to Understand the State of Conservation and the Causes of Degradation of I Tesori del Mare (1901) by Plinio Nomellini.

In this study, the investigation of the oil painting on canvas I Tesori del Mare made by Plinio Nomellini in 1901 is presented. The aim of the research was threefold: the examination of the state of conservation in view of the restoration treatment, together with the identification of the causes of degradation and the study of the artistic technique. During the years, the artwork underwent several cleaning and fixing interventions, resulting in a patchy appearance of the surface. Nevertheless, the presence of consistent liftings persists, while the protective coating shows uneven chromatic alteration, both requiring further analysis. Multispectral imaging allowed for better visualization of the figuration's structure and the restored areas. The combined use of Raman spectroscopy, Fourier Transform Infrared spectroscopy in the Attenuated Total Reflection mode (FT-IR ATR), and Scanning Electron Microscopy coupled with an Energy Dispersive Spectroscopy (SEM/EDS) enabled better understanding of the stratigraphy through the identification of some pigments, the binder, and the aged varnish layer on the top. SEM/EDS highlighted the presence of zinc in both the ground layer and the paint layers. Furthermore, FT-IR ATR spectroscopy showed peaks related to metal soaps such as zinc stearate, which are known to cause severe delamination of the paint layers, explaining the recurring lifting issues. Eventually, the varnish layer was found to be acrylic resin, presumably mixed with varnishes applied in past restoration treatments.

Protection of Urban Art Painting: A Laboratory Study.

Urban art is a form of artistic visual expression and communication that is created in the street and generally in the public dimension of urban spaces. Often these kinds of artworks are in outdoor environments, and they usually suffer from atmospheric weathering and anthropic vandalism. Recently, several strategies have been used to limit or remove the effects of such vandalism. Currently, the use of quartz paints is growing among artists; such paints after setting are more porous and rough on the surface with respect to regular paints. The aim of the study is to assess the performance of anti-graffiti coatings on quartz artworks paints. Two anti-graffiti products were chosen, and their behaviors were assessed in the laboratory by means of contact angle measurement, water capillary test, colorimetric analysis, and optical and electron microscopy. Results showed good water repellence efficacy of the tested products, demonstrating that they are suitable for the protection of urban art, but at least two applications on the surface are needed to achieve good performance.

Surface and volume non-invasive methods for the structural monitoring of the bass-relief 'Madonna con Bambino' (Gorizia, Northern Italy).

Structural analysis of marble statues, carried out by non-invasive and in situ methods, is crucial to define the state of conservation of the artworks and to identify the deterioration phenomena that can affect them. In this work, we combined in situ non-destructive techniques, ultrasonic tomography (US), ultraviolet-induced visible fluorescence (UV-IF) and X-ray fluorescence (XRF) to study the bass-relief 'Madonna con Bambino' (Gorizia, Italy). The US revealed the presence of some metallic pivots, associated with areas of high sound velocity; moreover, a more degraded area has been identified in the lower part of the bass-relief. The acquired UV-IF image confirmed the presence of surface degradation, allowing a preliminary evaluation of the extension of a fracture, from surface to bulk. In addition, the different materials (both original and/or integrations) that compose the studied surface have been identified. The XRF has contributed to define the nature of the inorganic materials applied during undocumented previous restoration works on the surface as filler for lacunae.

XPS characterization of (copper-based) coloured stains formed on limestone surfaces of outdoor Roman monuments.

Limestone basements holding bronzes or other copper alloys artefacts such as sculptures, decorations and dedicatory inscriptions are frequently met both in modern and ancient monuments. In outdoor conditions, such a combination implies the corrosion products of the copper based alloy, directly exposed to rainwater, will be drained off and migrate through the porous surfaces, forming stains of different colours and intensities, finally causing the limestone structures to deteriorate.In this work we have analysed samples from two modern limestone monuments in Rome, the Botticino surfaces of the 'Vittoriano' (by G.Sacconi, 1885-1911- Piazza Venezia) and the travertine basement of the 'Statua dello Studente' (by A.Cataldi, 1920- University city, La Sapienza), and focussed our investigation on the chemical composition of the copper-stained zones using XPS (X-ray Photoelectron Spectroscopy) as a surface-specific technique.Based on observations reporting on the structure and bonding at the calcite surfaces we have identified copper complexes and mixed calcium/copper carbonates associated with the stains, as well as the chemical state of other elements therein included, and related the compositional changes with differences in chromatic characteristics and sampling locations.