Volume 90, Issue 3

The nature of the pigments or dyes used to dye the first Portuguese postage stamps has remained unknown until now. In this work, a study has been made of the inks used for red, rose, purple and orange colors in a selected number of Portuguese postage stamps from the period 1857 to 1909. This is based on analysis involving a variety of techniques (X-ray fluorescence, UV-Vis spectroscopy, HPLC-MS/HPLC-DAD, steady and time resolved fluorescence). It was found that the inks included, among others, the inorganic pigments cinnabar (HgS), lead oxide (Pb 3 O 4 ) and chromate (PbCrO 4 ), lead sulphide (PbS), and the organic compounds carminic acid and Eosin Y. The study demonstrated a non-destructive analysis method for identification of two molecules of color involving the UV-Vis (for carminic acid and Eosin Y) and fluorescence spectra, together with quantum yields and lifetimes (for Eosin Y).

The application of electrochemical techniques for obtaining analytical information of interest in the fields of archaeometry, conservation and restoration of cultural heritage goods is reviewed. Focused on voltammetry of immobilised particles and electrochemical impedance spectroscopy techniques, electrochemical measurements offer valuable information for identifying and quantifying components, tracing provenances and manufacturing techniques and provide new tools for authentication and dating.

As one of the most desired and expensive artists’ materials throughout history, there has long been interest in studying natural lapis lazuli. The traditional method of extracting the blue component, lazurite, from lapis lazuli, as outlined in Cennini’s Il Libro dell’Arte , involves a lengthy purification process: (1) finely grind the rock; (2) mix with pine rosin, gum mastic, and beeswax; (3) massage in water to collect the lazurite. Repeating the process produces several grades of the pigment, typically referred to as ultramarine blue. Here, we investigate the sulfur environment within the aluminosilicate framework of lazurite during its extraction from lapis lazuli. The sulfur XANES fingerprint from samples taken at the different stages in Cennini’s extraction method were examined. All spectra contain a strong absorption peak at 2483 eV, attributable to sulfate present in the lazurite structure. However, intensity variations appear in the broad envelope of peaks between 2470 and 2475 eV and the pre-peak at 2469.1 eV, indicating a variation in the content of trisulfur (S 3 − ˙) radicals. By studying the effect of each step of Cennini’s process, this study elucidates the changes occurring during the extraction and the variability within different grades of the precious coloring material. The increasing application of XANES to the study of artist’s materials and works of art motivated extending the research to assess the possibility of X-ray induced damage. Direct comparison of micro-focused and unfocused beam experiments suggests an increase of the S 3 − ˙ radicals with prolonged exposure. Analysis indicates that induced damage follows first-order kinetics, providing a first assessment on the acceptable amount of radiation exposure to define the optimal acquisition parameters to allow safe analyses of lapis lazuli and ultramarine pigments.

Lustering, a technique which involved the application of coloured translucent glazes over gilding and silvering was widely used to enrich and decorate altarpieces in the Baroque period. The decorations consist of a micrometric multilayered structure including several color glazes, metallic leaves and bole applied over a plaster ground. The collection of Baroque altarpieces, the oldest dating 1671 and the newest 1775 from the cathedral of Tortosa (Catalonia), is a perfect case of study of the materials used and the techniques employed throughout the period. Further information is obtained from the analysis of the reaction and aging compounds resulting from the interaction among the compounds present in the layers and between the different layers. A combination of sensitive analytical techniques, Synchrotron based μ-XRD and μ-IR and SEM-EDS which enabled the luster samples to undergo analysis without altering their original layered microstructure were selected. The nature of the compounds used to produce the yellow, green, red and blue glazes (pigments, pigment lakes and resins), metallic leaves and boles is presented. Relevant information from historical and conservation viewpoints about the origin and nature of the materials used, the making of the lusters and their reactivity and aging are also discussed.

Visible hyperspectral imaging (HSI) is a fast and non-invasive imaging method that has been adapted by the field of conservation science to study painted surfaces. By collecting reflectance spectra from a 2D surface, the resulting 3D hyperspectral data cube contains millions of recorded spectra. While processing such large amounts of spectra poses an analytical and computational challenge, it also opens new opportunities to apply powerful methods of multivariate analysis for data evaluation. With the intent of expanding current data treatment of hyperspectral datasets, an innovative approach for data reduction and visualization is presented in this article. It uses a statistical embedding method known as t-distributed stochastic neighbor embedding (t-SNE) to provide a non-linear representation of spectral features in a lower 2D space. The efficiency of the proposed method for painted surfaces from cultural heritage is established through the study of laboratory prepared paint mock-ups, and medieval French illuminated manuscript.

This paper presents an innovative poly(vinyl)alcohol-based film forming system, specifically devised for the controllable and selective cleaning of copper-based artifacts. Traditional cleaning procedures are commonly performed using mechanical and/or chemical methods. Unfortunately, both these methods present some limitations related to both the poor selectivity and invasiveness in case of the mechanical procedure, and to the scarce control over the involved reactions when dealing with a chemical approach. The innovative system proposed in this work allows combining the advantages of chemical and mechanical treatments thanks to the confinement of a complexing agent (EDTA) within a fluid, polymeric matrix, that is able to form a solid thin film upon drying. After treatment, the polymeric film can be completely removed from the artwork through a gentle peeling action. In this contribution, the film formation mechanism was investigated by means of thermal analysis and rheology; the role of plasticizers, volatile solvent fraction, and quantity of loaded EDTA is also discussed. Finally, the results of cleaning tests performed on artificially aged samples, and on a real case study, the “Fontana dei Mostri Marini” by Pietro Tacca in Florence, are presented.

Cultural heritage objects and structures are subjected to a range of weathering processes that result in their decay and destruction. To slow weathering rates and/or mitigate their effects, several protective and consolidant materials have been used during conservation interventions. Treatments based on organic polymers and alkoxysilanes, as well as some traditional inorganic treatments such as lime water, are in many cases either incompatible and/or show limited efficacy. In recent years nanolimes, that is, dispersions of Ca(OH) 2 nanoparticles in alcohol (as well as alcohol dispersions of other alkaline-earth metal hydroxide nanoparticles), have emerged as an effective and compatible conservation material. Here we review recent advances in the synthesis and application of nanolimes in the field of heritage conservation. First, we present an overview of lime-based conservation materials, with an emphasis on the earliest reports on the use of nanolimes. Subsequently, we present the different methods used to synthesize nanolimes. Afterwards, we describe their carbonation and its consolidation effects. Practical application of nanolimes in heritage conservation are summarized, including consolidation of stone, ceramics, lime mortars and mural painting, as well as deacidification of paper, canvas, and wood. The advantages and limitations of this novel nanotechnology for cultural heritage conservation are outlined. Finally, some conclusions and areas for future research are presented.

Water is the main vehicle of decay agents in Cultural Heritage building materials exposed to weathering. In this work, a simple method to produce superhydrophobic/oleophobic coatings building materials, including under outdoors conditions, has been developed. In addition, a study of the behavior of the developed coatings on different substrates (limestone, granite, concrete and wood) is reported. The addition of 40 nm-SiO 2 nanoparticles to a fluoroalkylsilane reduces surface energy and produces a Cassie-Baxter surface in all the materials evaluated. It promotes high static contact angle values of around 160°, and a contact angle hysteresis of around 3°, giving rise to repellence. The building surfaces also demonstrate an excellent self-cleaning performance. The coatings maintain the building materials esthetics as required in the Cultural Heritage field. Finally, the coating presents a long-lasting performance due to condensation reactions producing effective grafting to the four building materials evaluated.

This technical report reviews measurements of mass and volume, including a review of the SI for mass, length, and amount of substance; principles of mass measurement; calibration of masses and glassware; gravimetry; volumetry; and titrimetry. Measurement uncertainty, metrological traceability and aspects of quality assurance are also treated.