Stradivari's Varnish Revisited: Feature Improvements Using Chemical Modification.

The most widespread varnish formulations used by master violin-makers of the "Italian Golden Age", including Antonio Stradivari, were based on mixtures of siccative oils (e.g., linseed oil) and natural resins (e.g., colophony). Similar formulations are still used for the finish of contemporary instruments. Although most precious violins made by Stradivari and other Cremonese Masters are kept in museums, several instruments are still played and their finish may undergo deterioration due to contact with the players. Moreover, the decay of the traditional varnish may occur due to mechanical stress and natural aging caused by environmental agents (e.g., exposure to uncontrolled light, humidity, and temperature changes). The main aim of this research work is to investigate the possible improvement of varnish resistance to the decay induced by different aging processes. For this purpose, the traditional varnish (linseed oil/colophony 3:1 w/w) was recreated in the laboratory following an ancient recipe and then it was functionalized with a cross-linking agent (3-Glycidyloxypropyltrimethoxysilane, GLYMO). Plain and functionalized varnishes underwent artificial aging (UV light, temperature, and humidity variations), and their properties were comparatively studied using different techniques. All the results suggest that the functionalized varnish displays improved resistance to the aging process and particularly enhanced photostability and increased hardness (resistance to scratches).

New Insight on Archaeological Metal Finds, Nails and Lead Sheathings of the Punic Ship from Battle of the Egadi Islands.

The wreck of the Punic ship exhibited at the Archaeological Park of Lilybaeum (Marsala, Italy) is a unique example in the world. In this paper, the investigation of some metal finds (30 nails and 3 fragments of sheathings) belonging to the wreck of the Punic ship is reported. Portable X-ray fluorescence and Raman spectroscopy allowed us to identify the elements and compounds constituting them and make some deductions about their composition. X-ray diffractometry, polarised optical microscopy and scanning electron microscopy of the collected micro-samples allowed us to explain the degradation that occurred in the underwater environment.

Improved chemometric approach for XRF data treatment: application to the reverse glass paintings from the Lipari collection.

The Aeolian cultural heritage preserves hundreds of testimonies of the past that have passed through six millennia of history. Among these, the Archeological Park of the Aeolian Islands with the Museum Luigi Bernabò Brea (Italy) preserves a valuable set of artworks, which are related to a little-known 'popular' figurative heritage. It is an assemblage of small glass foils decorated using the technique of reverse painting, datable to between the end of the 17th century and the end of the 18th century, and actually under investigation by historians. Here, an X-ray fluorescence (XRF) spectroscopy study (performed with portable equipment) is combined with a multivariate approach that allows us to define the best way to process the data to detect compositional differences and similarities among the glass supports. The Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) were applied both on normalized spectra and on normalized peak areas in order to establish the chemometric approach with the highest grouping ability. Results showed that the analysis of the normalized area provides the most reliable grouping based on the different elemental compositions, without problems coming from the background or peak-shape distortions. The obtained results can be used by researchers involved in the analysis of XRF data as a guideline to perform chemometrics. Furthermore, regarding the reverse glass, they can be divided into different typologies based on composition differences, providing a further discrimination criterion for historians involved in the study of the collection to determine the provenance and dating of the items.

Urea Glass Route as a Way to Optimize YAGG:Ce3+,Cr3+,Pr3+ Nanocrystals for Persistent Luminescence Applications.

A new approach for the synthesis of Y3Al2Ga3O12 (YAGG) nanophosphors allowing the preparation of crystallites with sizes starting from 45 nm is presented. The controllability of the energy and trap density of the resulting material samples by annealing temperature was confirmed by thermoluminescence (TL) measurements. It has been shown that the annealing of samples at temperatures up to 1300 °C does not cause any substantial growth of crystallites, still remaining below 100 nm, but leads to changes in the activation energy of the persistent luminescence (PersL) process. On the other hand, annealing above 1400 °C results in grain growth on the submicron scale, which was confirmed by X-ray powder diffraction (XRPD) and electron transmission microscopy (TEM) measurements. In addition, with an increase in the molar ratio of urea to the total amount of metals used (R), qualitative changes are observed in the PersL process occurring from the excited states of Cr3+ and Pr3+ ions. This proves the influence of the synthesis process, in particular of the metal complexation at its initial stage, on the final structure ordering in the annealed materials. These observations are linked to previously reported defects in the YAGG structure, leading to PersL.

Archaeometric study of execution techniques of white Attic vases: the case of the Perseus crater in Agrigento.

The white ground crater by the Phiale Painter (450-440 BC) exhibited in the "Pietro Griffo" Archaeological Museum in Agrigento (Italy) depicts two scenes from Perseus myth. The vase is of utmost importance to archaeologists because the figures are drawn on a white background with remarkable daintiness and attention to detail. Notwithstanding the white ground ceramics being well documented from an archaeological and historical point of view, doubts concerning the compositions of pigments and binders and the production technique are still unsolved. This kind of vase is a valuable rarity, the use of which is documented in elitist funeral rituals. The study aims to investigate the constituent materials and the execution technique of this magnificent crater. The investigation was carried out using non-destructive and non-invasive techniques in situ. Portable X-ray fluorescence and Fourier-transform total reflection infrared spectroscopy complemented the use of visible and ultraviolet light photography to get an overview and specific information on the vase. The XRF data were used to produce false colour maps showing the location of the various elements detected, using the program SmART_scan. The use of gypsum as the material for the white ground is an important result that deserves to be further investigated in similar vases.

Conservation state of two paintings in the Santa Margherita cliff cave: role of the environment and of the microbial community.

The conservation of ancient paintings sited in humid environments is an actual challenge for restorers, because it needs the knowledge of the materials the paintings are made up and of their interaction with a peculiar surrounding environment; thus, tailored procedures and strategies aimed at restoring and preserving paintings are necessary. Santa Margherita's cave in Castellammare del Golfo (Trapani, Italy) is a natural cave, containing the remains of paintings, in a poor state of conservation, belonging to an ancient church dated back to the Middle Age. The present manuscript reports the monitoring of environmental conditions (i.e., temperature and humidity) in a full year, as well as a study on the materials constituting the stone support and the paintings together with a survey of the microbial community. The findings allow us to define the causes that mainly involve the degradation of the paintings. In detail, the degradation of the east and the west walls occurred differently because of the exposure to the sea aerosol, which influenced the salt composition, also contributing to diversifying the bacterial community. Some specific actions to plan the conservation and restoration of paintings and to preserve the site are suggested.

Sicilian Byzantine Icons through the Use of Non-Invasive Imaging Techniques and Optical Spectroscopy: The Case of the Madonna dell'Elemosina.

The iconographic heritage is one of the treasures of Byzantine art that have enriched the south of Italy, and Sicily in particular, since the early 16th century. In this work, the investigations of a Sicilian Icon of Greek-Byzantine origin, the Madonna dell'Elemosina, is reported for the first time. The study was carried out using mainly non-invasive imaging techniques (photography in reflectance and grazing visible light, UV fluorescence, infrared reflectography, radiography, and computed tomography) and spectroscopic techniques (X-ray fluorescence and infrared spectroscopy). The identification of the constituent materials provides a decisive contribution to the correct historical and artistic placement of the Icon, a treasure of the Eastern European historical community in Sicily. Some hidden details have also been highlighted. Most importantly, the information obtained enables us to define its conservation state, the presence of foreign materials, and to direct its protection and restoration.

Microstructure and phase composition of bronze Montefortino helmets discovered Mediterranean seabed to explain an unusual corrosion.

Two Monterfortino helmets, recovered in the Mediterranean seabed, show unusual features with respect to the more common helmets of the same period and found in underwater environments. Hence, they were investigated by a multi-analytical approach, which allowed us to identify the compounds constituting the helmets and to make some considerations about their metallurgy, although all the metal was converted to degradation products. The helmets, originally made in bronze, have maintained their original shape because of copper sulphides formation. The observed differences in composition between the two helmets were attributed to the position modification, of one of them, into the seabed along centuries. For the first time, a microstructural investigation permits to reconstruct the history of the aging processes involved in the total oxidation of roman bronze helmet metal.

Graphene Coating Obtained in a Cold-Wall CVD Process on the Co-Cr Alloy (L-605) for Medical Applications.

Graphene coating on the cobalt-chromium alloy was optimized and successfully carried out by a cold-wall chemical vapor deposition (CW-CVD) method. A uniform layer of graphene for a large area of the Co-Cr alloy (discs of 10 mm diameter) was confirmed by Raman mapping coated area and analyzing specific G and 2D bands; in particular, the intensity ratio and the number of layers were calculated. The effect of the CW-CVD process on the microstructure and the morphology of the Co-Cr surface was investigated by scanning X-ray photoelectron microscope (SPEM), atomic force microscopy (AFM), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). Nanoindentation and scratch tests were performed to determine mechanical properties of Co-Cr disks. The results of microbiological tests indicate that the studied Co-Cr alloys covered with a graphene layer did not show a pro-coagulant effect. The obtained results confirm the possibility of using the developed coating method in medical applications, in particular in the field of cardiovascular diseases.

Particle size-related limitations of persistent phosphors based on the doped Y3Al2Ga3O12 system.

Co-doped Ce3+, Cr3+ and Pr3+ yttrium-aluminium-gallium garnet powders of various sizes were obtained by co-precipitation method. The microstructure and morphology were investigated by XRPD, TEM and gas porosimetry. The luminescence properties were studied by excitation and emission spectra, quantum yield and decay times. Thermoluminescence measurements were performed to evaluate the activation energy, traps redistribution and frequency factor. Limitation in the energy transfer between dopant ions in the small particles, traps depth and surface defects were considered and investigated as responsible for the quenching of persistent luminescence. The phosphors annealed at 1100 °C show the optimal persistent luminescence and nano-particle size.

Chemometric Tools to Point Out Benchmarks and Chromophores in Pigments through Spectroscopic Data Analyses.

Spectral preprocessing data and chemometric tools are analytical methods widely applied in several scientific contexts i.e., in archaeometric applications. A systematic classification of natural powdered pigments of organic and inorganic nature through Principal Component Analysis with a multi-instruments spectroscopic study is presented here. The methodology allows the access to elementary and molecular unique benchmarks to guide and speed up the identification of an unknown pigment and its recipe. This study is conducted on a set of 48 powdered pigments and tested on a real-case sample from the wall painting in S. Maria Delle Palate di Tusa (Messina, Italy). Four spectroscopic techniques (X-ray Fluorescence, Raman, Attenuated Total Reflectance and Total Reflectance Infrared Spectroscopies) and six different spectrometers are tested to evaluate the impact of different setups. The novelty of the work is to use a systematic approach on this initial dataset using the entire spectroscopic energy range without any windows selection to solve problems linked with the manipulation of large analytes/materials to find an indistinct property of one or more spectral bands opening new frontiers in the dataset spectroscopic analyses.

Formulation of Mesoporous Silica Nanoparticles for Controlled Release of Antimicrobials for Stone Preventive Conservation.

The biotic deterioration of artifacts of archaeological and artistic interest mostly relies on the action of microorganisms capable of thriving under the most disparate environmental conditions. Thus, to attenuate biodeterioration phenomena, biocides can be used by the restorers to prevent or slow down the microbial growth. However, several factors such as biocide half-life, its wash-out because of environmental conditions, and its limited time of action make necessary its application repeatedly, leading to negative economic implications. Sound and successful treatments are represented by controlled release systems (CRSs) based on porous materials. Here, we report on the design and development of a CRS system based on mesoporous silica nanoparticles (MSNs), as a carrier, and loaded with a biocide. MSNs, with a diameter of 55 nm and cylindrical pores of ca. 3-8 nm arranged as parallel arrays concerning the NP diameter, and with 422 m2/g of specific surface area were synthesized by the sol-gel method assisted by oil in water emulsion. Biocide loading and release were carried out in water and monitored by UV-Vis Spectroscopy; in addition, microbiological assay was performed using as control the MCM-41 mesoporous silica loaded with the same biocide. The role of specific supramolecular interaction in regulating the release is discussed. Further, we demonstrated that this innovative formulation was useful in inhibiting the in vitro growth of Kocuria rhizophila, an environmental Gram-positive bacterial strain. Besides, the CRS here prepared reduced the bacterial biomass contaminating a real case study (i.e., stone derived from the Santa Margherita cave located in Sicily, Italy), after several months of treatment thus opening for innovative treatments of deteriorated stone artifacts.

Graphene Oxide Carboxymethylcellulose Nanocomposite for Dressing Materials.

Sore, infected wounds are a major clinical issue, and there is thus an urgent need for novel biomaterials as multifunctional constituents for dressings. A set of biocomposites was prepared by solvent casting using different concentrations of carboxymethylcellulose (CMC) and exfoliated graphene oxide (Exf-GO) as a filler. Exf-GO was first obtained by the strong oxidation and exfoliation of graphite. The structural, morphological and mechanical properties of the composites (CMCx/Exf-GO) were evaluated, and the obtained composites were homogenous, transparent and brownish in color. The results confirmed that Exf-GO may be homogeneously dispersed in CMC. It was found that the composite has an inhibitory activity against the Gram-positive Staphylococcus aureus, but not against Gram-negative Pseudomonas aeruginosa. At the same time, it does not exhibit any cytotoxic effect on normal fibroblasts.

Multimetallic Oxynitrides Nanoparticles for a New Generation of Photocatalysts.

A versatile synthetic strategy for the preparation of multimetallic oxynitrides has been designed and here exemplarily discussed considering the preparation of nanoscaled zinc-gallium oxynitrides and zinc-gallium-indium oxynitrides, two important photocatalysts of new generation, which proved to be active in key energy related processes from pollutant decomposition to overall water splitting. The synthesis presented here allows the preparation of small nanoparticles (less than 20 nm in average diameter), well-defined in size and shape, yet highly crystalline and with the highest surface area reported so far (up to 80 m2 g-1 ). X-ray diffraction studies show that the final material is not a mixture of single oxides but a distinctive compound. The photocatalytic properties of the oxynitrides have been tested towards the decomposition of an organic dye (as a model reaction for the decomposition of air pollutants), showing better photocatalytic performances than the corresponding pure phases (reaction constant 0.22 h-1 ), whereas almost no reaction was observed in absence of catalyst or in the dark. The photocatalysts have been also tested for H2 evolution (semi-reaction of the water splitting process) with results comparable to the best literature values but leaving room for further improvement.

Non-conventional Ce:YAG nanostructures via urea complexes.

Ce:YAG nanostructures (Ce:YAG = Cerium in Yttrium Aluminium Garnet), easy to control and shape, have been prepared via templating approach using natural and synthetic materials (i.e. paper, cotton wool and glass wool) previously soaked with a gel-like metals precursor and then thermally treated to achieve the wished morphology. The final material, otherwise difficult to process, can be easily moulded, it is lightweight, portable and forms, at the nanoscale, homogeneous layers of interconnected but not agglomerated nanoparticles (15 ± 5 nm). Using the same synthetic route, called Urea-Glass-Route, but in absence of a template, extremely pure Ce:YAG nanoparticle (45 ± 5 nm) can be also prepared, highly crystalline and well-defined in size and shape. Both structural and optical properties of the final materials were investigated, showing high optical quality. The support allows the production of a multifunctional material with mouldable shape and potential lighting application for large structures combining the strength, chemical durability, fire resistance, and translucency of glass fibres. Last, but not least, the synthetic path also allows an easy scaling up of the process: the first, key step for practical application of nanosized rare-earth doped YAG on large scale.

Synthesis and antibacterial activity of iron-hexacyanocobaltate nanoparticles.

This paper deals with the synthesis and characterization of iron-hexacyanocobaltate (FeHCC) and its antibacterial properties. The nanoparticles were prepared by a facile co-precipitation technique. Crystal structure, particle morphology, and elemental composition were determined using X-ray Powder Diffraction, X-ray fluorescence spectroscopy, Transmission Electron Microscopy (TEM), and Infrared Spectroscopy (IR). The antibacterial activity of the FeHCC nanoparticles was tested against Escherichia coli and Staphylococcus aureus as models for Gram-negative and Gram-positive bacteria, respectively, by bacterial counting method and microscopic visualization (TEM, FEG-SEM, and fluorescence microscopy). The results showed that the FeHCC nanoparticles bind to the bacterial cells, inhibit bacterial growth in a dose- and time-dependent manner, inducing a loss of the membrane potential, the production of reactive oxygen species and the release of macromolecules (nucleic acids and proteins) in the extracellular environment. To the best of our knowledge, this is the first study reporting the antimicrobial effects of metal-hexacyanometallates suggesting practical uses of these materials in different areas, such as self-cleaning surfaces or food packaging.

Chromium liquid waste inertization in an inorganic alkali activated matrix: leaching and NMR multinuclear approach.

A class of inorganic binders, also known as geopolymers, can be obtained by alkali activation of aluminosilicate powders at room temperature. The process is affected by many parameters (curing time, curing temperature, relative humidity etc.) and leads to a resistant matrix usable for inertization of hazardous waste. In this study an industrial liquid waste containing a high amount of chromium (≈ 2.3 wt%) in the form of metalorganic salts is inertized into a metakaolin based geopolymer matrix. One of the innovative aspects is the exploitation of the water contained in the waste for the geopolymerization process. This avoided any drying treatment, a common step in the management of liquid hazardous waste. The evolution of the process--from the precursor dissolution to the final geopolymer matrix hardening--of different geopolymers containing a waste amount ranging from 3 to 20%wt and their capability to inertize chromium cations were studied by: i) the leaching tests, according to the EN 12,457 regulation, at different curing times (15, 28, 90 and 540 days) monitoring releases of chromium ions (Cr(III) and Cr(VI)) and the cations constituting the aluminosilicate matrix (Na, Si, Al); ii) the humidity variation for different curing times (15 and 540 days); iii) SEM characterization at different curing times (28 and 540 days); iv) the trend of the solution conductivity and pH during the leaching test; v) the characterization of the short-range ordering in terms of TOT bonds (where T is Al or Si) by (29)Si and (27)Al solid state magic-angle spinning nuclear magnetic resonance (ss MAS NMR) for geopolymers containing high amounts of waste (10-20%wt). The results show the formation of a stable matrix after only 15 days independently on the waste amount introduced; the longer curing times increase the matrices stabilities and their ability to immobilize chromium cations. The maximum amount of waste that can be inertized is around 10 wt% after a curing time of 28 days.

Mechanical treatment of TiO2 and ZrO2 oxide mixtures.

The mixed ZrO2-TiO2 system (5-50 wt% of ZrO2) has been studied to investigate the influence of the mechanical treatment on its physicochemical properties depending on the composition, time of milling (5, 10 and 20 min, r.p.m. 82) and temperature (400, 550 and 700 degrees C). Samples were characterized by Raman spectroscopy, X-ray powder diffraction, Scanning Electron Microscopy coupled with Energy Dispersion X-ray analyzer, High Resolution-Transmission Electron Microscopy and nitrogen adsorption porosimetry. Results show that srilankite (TiZrO4) phase has been produced. No influence of the milling time and temperature on the phase composition is observed. The presence of zirconia increases the thermal stability of anatase phase up to 700 degrees C hindering the anatase rutile phase transformation.

Ce:YAG nanoparticles embedded in a PMMA matrix: preparation and characterization.

A Ce:YAG-poly(methyl methacrylate) composite was prepared using in situ polymerization by embedding the Ce:YAG nanopowder in a blend of methyl methacrylate (MMA) and 2-methacrylic acid (MAA) monomers and activating the photopolymerization using a radical initiator. The obtained nanocomposite was yellow and transparent. Its characterization was performed using transmission electron microscopy, small angle X-ray scattering, (13)C cross-polarization magic-angle spinning nuclear magnetic resonance, and photoluminescence spectroscopy. Results showed that Ce:YAG nanoparticles are well dispersed in the polymeric matrix whose structure is organized in a lamellar shape. The luminescence properties of the nanocomposite do not show quenching or a significant spectral shift, indicating that the nanocomposite can be useful for advanced applications such as white LED construction.

Effects of solvent-free microwave extraction on the chemical composition of essential oil of Calamintha nepeta (L.) Savi compared with the conventional production method.

The essential oil of Calamintha nepeta has been obtained by solvent-free microwave extraction (SFME) and by classical hydrodistillation (HD). A comparative qualitative-quantitative study on the composition of the oils was carried out. A total of 38 compounds, constituting 97.6% of the oil, were identified in the oil obtained by SFME, whereas 46 compounds, representing 95.4% of the oil, were characterized in the HD oil. SFME-distilled oil is richer in lightly oxygenated monoterpenes (LOM) than HD oil. It also has a higher amount of sesquiterpenes and a lower quantity of hydrocarbon monoterpenes. HD oil seems to be affected by chemical changes more than SFME oil.