A preliminary evaluation of chemical interaction between sanitizing products and silk.

The ongoing Coronavirus crisis involved almost all sectors as well as museums, collections, and historical sites all over the world. Even though artworks do not have the ability to spread the virus, the pandemic officially introduced in cultural sites alcohol-based products (even by visitors for personal use) as these products were indicated to be able to inactivate the virus and were imposed by many local authorities. In this context, the need to conciliate the safety of the visitors and the protection of artworks represents a challenging task. The possibility that accumulation of vapour coming from the sanitizing solutions or from accidental spills, potentially caused also by visitors, should be considered. The study focuses specifically on the possible interactions between sanitizing alcohol-based products and silk, since this material is present in many cultural sites all over the world on upholsteries and tapestries. The recommended sanitising solution (75% ethanol, 20% water, 5% benzalkonium chloride) selected by the Italian Ministry for Cultural Heritage (MIBACT) was considered. Pure distilled water, absolute ethanol and water/ethanol blends in different concentrations were also tested. Chemical and morphological variations on the silk have been evaluated with Scanning Electron Microscopy - SEM, Atomic Force Microscopy - AFM and portable instruments (contact microscope, colorimeter, Infrared and Raman spectroscopy). IR and Raman analyses did not detect significant chemical changes in silk. However, Raman spectra showed, after immersion treatments, minor variations in the intensity of peaks attributed to dyes. Residues of benzalkonium chloride after immersion tests in sanitising solution are present, confirmed also by SEM and AFM analyses. Even if chemical spectroscopic changes were not relevant, the colour of few samples seemed to consistently fade after immersion treatments, thus affecting the visual appearance of textiles.

Exploring the Porosity in Ceramics at the nm Scale: From Understanding Historical Ceramics to Innovative Materials Design.

Ceramics are complex objects and a rich source of information: they constitute a large part of the staple memory of past and present human activities. A deep understanding of traditional ceramics is an essential key to designing new ceramic materials. The demanding synthesis of ceramics with fine-tuned properties, such as enhanced mechanical, electrical, optical or magnetic characteristics, must be associated with cutting-edge analysis procedures in order to improve the engineering process. In this context, we describe a neutron-based non-destructive approach to investigating the nanoporosity of an historical pottery matrix as an effective investigation technique for exploring both traditional and advanced ceramic materials.

Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology.

Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of "non-traditional" isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic separation using TRU-Spec resin. Tin isotopic analysis was performed relying on Sb as an internal standard used for mass bias correction. The reproducibility over a period of 1 month (n = 42) for the mass bias-corrected Sn isotope ratios is in the range of 0.06-0.16 per mil (2 s), for all the ratios monitored.

Unraveling the optoelectronic properties of CoSbx intrinsic selective solar absorber towards high-temperature surfaces.

The combination of the ability to absorb most of the solar radiation and simultaneously suppress infrared re-radiation allows selective solar absorbers (SSAs) to maximize solar energy to heat conversion, which is critical to several advanced applications. The intrinsic spectral selective materials are rare in nature and only a few demonstrated complete solar absorption. Typically, intrinsic materials exhibit high performances when integrated into complex multilayered solar absorber systems due to their limited spectral selectivity and solar absorption. In this study, we propose CoSbx (2 < x < 3) as a new exceptionally efficient SSA. Here we demonstrate that the low bandgap nature of CoSbx endows broadband solar absorption (0.96) over the solar spectral range and simultaneous low emissivity (0.18) in the mid-infrared region, resulting in a remarkable intrinsic spectral solar selectivity of 5.3. Under 1 sun illumination, the heat concentrates on the surface of the CoSbx thin film, and an impressive temperature of 101.7 °C is reached, demonstrating the highest value among reported intrinsic SSAs. Furthermore, the CoSbx was tested for solar water evaporation achieving an evaporation rate of 1.4 kg m-2 h-1. This study could expand the use of narrow bandgap semiconductors as efficient intrinsic SSAs with high surface temperatures in solar applications.

How perfluoroalkyl substances modify fluorinated self-assembled monolayer architectures: An electrochemical and computational study.

There is an urgent need for sensing strategies to screen perfluoroalkyl substances (PFAS) in aqueous matrices. These strategies must be applicable in large-scale monitoring plans to face the ubiquitous use of PFAS, their wide global spread, and their fast evolution towards short-chain, branched molecules. To this aim, the changes in fluorinated self-assembled monolayers (SAM) with different architectures (pinholes/defects-free and with randomized pinholes/defects) were studied upon exposure to both long and short-chain PFAS. The applicability of fluorinated SAM in PFAS sensing was evaluated. Changes in the SAM structures were characterised combining electrochemical impedance spectroscopy and voltammetric techniques. The experimental data interpretation was supported by molecular dynamics simulations to gain a more in-depth understanding of the interaction mechanisms involved. Pinhole/defect-free fluorinated SAM were found to be applicable to long-chain PFAS screening within switch-on sensing strategy, while a switch-off sensing strategy was reported for screening of both short/long-chain PFAS. These strategies confirmed the possibility to play on fluorophilic interactions when designing PFAS screening methods.

Accelerated Ageing Procedures to Assess the Stability of an Unconventional Acrylic-Wax Polymeric Emulsion for Contemporary Art.

This research evaluates the stability of an aqueous emulsion of acrylic copolymers and waxes. Edelwachs, generally applied on wood, has been recently used as an unconventional medium in contemporary painting. Through Pyrolysis-Gas Chromatography-Mass Spectrometry (Py-GC-MS) and Fourier Transformed Infrared Attenuated Total Reflectance (FT-IR-ATR) analyses, the composition of Edelwachs was defined as a mixture of acrylic polymers (MA, MMA, nBA, nBMA), Carnauba and microcrystalline waxes and additives. Mock-ups-obtained mixing Edelwachs with titanium white, zinc white and ultramarine blue were subjected to UV, high temperatures, and high relative humidity accelerated ageing. The effect of the ageing procedures was evaluated through optical microscopy, colourimetric measurements, FT-IR-ATR, Thermogravimetry and Differential Scanning Calorimetry (TG-DSC) and wettability measures. FT-IR-ATR spectra do not show significant variations in terms of chemical stability, indicating a fair stability of Edelwachs as a painting binder. UV and high temperature treatments show the most relevant effects in terms of colorimetric changes (increasing of b*) and thermal stability. The TG-DSC highlights the influence of the pigments (specifically zinc white) mainly on the thermal behaviour of the acrylates. The unexpected decrease of wettability of the paint films, registered after ageing, may indicate a possible phase separation among acrylates and waxes.

Scanning Microscopy Techniques as an Assessment Tool of Materials and Interventions for the Protection of Built Cultural Heritage.

Scanning microscopy techniques have emerged as powerful scientific tools for analysing materials of architectural or archaeological interest, since the commercialization of the first scanning electron microscopy instrumentation in the early 60s. This study is aimed at reviewing and highlighting the significance of several scanning microscopy techniques employed in the protection of built heritage. The diffusion of scanning electron microscopy with energy-dispersive X-ray spectroscopy analysis (SEM-EDX) is proven to be the widest among the available scanning microscopy techniques, while transmission electron microscopy (TEM) applications are steadily present in the field of built heritage protection. The building material characterization, the weathering mechanism investigation, and the development of compatible and performing conservation materials are some major research areas where the application of the aforementioned techniques is discussed. The range of techniques, along with aspects of instrumentation and sample preparation are, also, considered.