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).

A Nanofocused Light on Stradivari Violins: Infrared s-SNOM Reveals New Clues Behind Craftsmanship Mastery.

It is well-known that all the phases of the manufacturing influence the extraordinary aesthetic and acoustic features of Stradivari's instruments. However, these masterpieces still keep some of their secrets hidden by the lack of documentary evidence. In particular, there is not a general consensus on the use of a protein-based ground coating directly spread on the wood surface by the Cremonese Master. The present work demonstrates that infrared scattering-type scanning near-fields optical microscopy (s-SNOM) may provide unprecedented information on very complex cross-sectioned microsamples collected from two of Stradivari's violins, nanoresolved chemical sensitivity being the turning point for detecting minute traces of a specific compound, namely proteins, hidden by the matrix when macro or micro sampling approaches are exploited. This nanoresolved chemical-sensitive technique contributed new and robust evidence to the long-debated question about the use of proteinaceous materials by Stradivari.

Data from Multiple Portable XRF Units and Their Significance for Ancient Glass Studies.

X-ray fluorescence spectroscopy is a non-destructive technique employed for elemental analysis of a wide range of materials. Its advantages are especially valued in archaeometry, where portable instruments are available. Considering ancient glass, such instruments allow for the detection of some major, minor, and trace elements linked to the deliberate addition of specific components or to impurities in the raw materials of the glass batch. Besides some undoubted advantages, portable XRF (p-XRF) has some limitations that are addressed in this study. The performance assessment of four different p-XRF units and the reconciling of their output were conducted. The results show the limitations in cross-referencing the data obtained from each unit and suggest procedures to overcome the issues. The p-XRF units were tested on the set of Corning reference glasses and on a small set of archaeological glasses with known composition. The compatibility of the output was assessed using multivariate statistical tools. Such a workflow allows us to consider data from multiple sources in the same frame of reference.

The impact of alkaline treatments on elasticity in spruce tonewood.

It is commonly believed that violins sound differently when finished. However, if the role of varnishes on the vibrational properties of these musical instruments is well-established, how the first components of the complete wood finish impact on the final result is still unclear. According to tradition, the priming process consists of two distinct stages, called pre-treatment and sizing. The literature reports some recipes used by old Cremonese luthiers as primers, mainly based on alkaline aqueous solutions and protein-based glues. In this manuscript, we analyze the impact of these treatments on the mechanical properties of the material. The combination of two pre-treatments and three sizes is considered on nine different plates. We compare the vibrational properties before and after the application and assess the effects of the different primers, also supported by finite element modeling. The main outcome is that the combination of particular treatments on the violin surface before varnishing leads to changes not only to the wood appearance, but also to its vibrational properties. Indeed pre-treatments, often considered negligible in terms of vibrational changes, enhance the penetration of the size into the wood structure and strengthen the impact of the latter on the final rigidity of the material along the longitudinal and radial directions.

Preliminary Cleaning Approach with Alginate and Konjac Glucomannan Polysaccharide Gel for the Surfaces of East Asian and Western String Musical Instruments.

The cleaning of string musical instruments is challenging due to the traditional finishing treatments used by the makers. Multilayered coating systems were applied to Western musical instruments, while the Nakdong technique was applied in East Asia. Furthermore, by restorations and performance, dust and grime were overlapped together with polishes, adhesives, and varnishes. Gel cleaning is important in the field of conservation because of the ability to selectively remove chemical and biological degradation products from the surface, minimizing the interactions with the inner layers. In this study, hydrogels based on sodium alginate (SA) and konjac glucomannan (KG) polysaccharides were applied on laboratory mock-ups of East Asian and Western instruments to test their ability to remove synthetic soiling and sweat from the surface. In particular, SA cross-linked with calcium cations and KG cross-linked with borate gels were used. To control the exposure of the cleaning solvent on the surface of mock-ups, the moisture content of the gels was determined. The effectiveness of removing synthetic contaminants was investigated by noninvasive analytical methods. Stereomicroscopy and colorimetry, together with Fourier Transform Infrared (FTIR) spectroscopy in reflection mode and X-Ray Fluorescence (XRF), were used to evaluate the cleaning efficacy. Overall, polysaccharide hydrogels resulted in promising cleaning systems on both smooth and rough surfaces of wood.

Study of a surface coating present on a Renaissance Piety from the Museum of Ancient Art (Castello Sforzesco, Milan).

The surface coating present on a marble Piety dating to the Renaissance period and stored at the Castello Sforzesco-Museum of Ancient Art (Milan, Italy) was studied and chemically characterised. For this purpose, both portable non-invasive (XRF and colorimetric measurements) and micro-invasive techniques (FTIR-ATR and SEM-EDS), have been applied. The statue has been recently submitted to a restoration, since its surface appeared dark and yellowed, before an exhibition at the Louvre Museum and the original appearance of the marble surface recovered thanks to the surface coating removal. Through the analytical characterisation carried out before and after the marble cleaning, the presence of a degradation layer composed by gypsum was evidenced on the stone. The origin of this layer is ascribable to the exposure of the statue to outdoor environment and interaction with atmospheric pollution. The chemical nature of the coating applied at the end of nineteenth century also responsible for the surface alteration was hypothesized.

Biopolymer Gels as a Cleaning System for Differently Featured Wooden Surfaces.

The cleaning of some wooden artefacts can be challenging due to peculiar surface roughness and/or particular finishing treatments that favour the deposition of dirt and contaminants. The most common cleaning system used by conservators is agar gel, characterized by its rigidity and brittleness, which challenges the cleaning of rough and irregular surfaces typical of most wooden artefacts. In this work, alginate crosslinked with calcium (CA) and konjac glucomannan crosslinked with borax (KGB) gels were proposed to solve this issue. They were prepared and applied to smooth- and rough-surfaced mock-ups replicating wooden musical instruments' surfaces that had been subsequently covered by artificial soiling and sweat contaminants. The mechanical properties of CA and KGB gels, including their stability over a 60-day storage time, were evaluated by a texture analyzer, while cleaning efficacy was analytically evaluated by non-invasive X-ray fluorescence mapping and profilometric investigation. CA gel appeared to have a higher tensile strength and elongation at break. KGB gel was shown to be soft and resilient, indicating its suitability for cleaning rough surfaces. After repeating the cleaning application three times on the rough-surfaced mock-ups, both the CA and KGB gels were shown to have cleaning efficacy. The results obtained with CA and KGB were compared with those from the Agar application.

Reflection FTIR spectroscopy for the study of historical bowed string instruments: Invasive and non-invasive approaches.

A micro-sample detached from a historical bowed string instrument represents a valuable record of the materials used by the great Masters of violin-making art. It allows researchers to collect a wealth of information and to disclose - at least partially - their procedures for finishing and varnishing. In the present work, a set of four cross-sectioned micro-samples - collected from well-preserved bowed string instruments made by Antonio Stradivari and Lorenzo Storioni - are investigated by Synchrotron Radiation (SR) FTIR micro-spectroscopy in reflection mode. SR-FTIR spectra are discussed both as point analysis and as univariate and multivariate chemical maps. The same cross-sections are also investigated by optical microscopy under UV light and SEM-EDX. Moreover, data obtained directly from the musical instruments by a non-invasive approach employing a portable reflection FTIR spectrometer are also considered. FTIR investigation of the cross-sections is a challenging task for such brittle and complex layered micro-samples. Nevertheless, the high intensity of the analytical SR beam used in reflection geometry allowed us to obtain informative FTIR spectra and to fully preserve the integrity of the samples. Both the non-invasive and the micro-invasive reflection FTIR approaches can reveal the materials spread on the wood surface to finish the musical instruments. The fingerprint of Lorenzo Storioni's production around 1790 emerged from the study of the cross-sectioned samples, definitely different from the technique of Stradivari.

Spectroscopic Analysis to Characterize Finishing Treatments of Ancient Bowed String Instruments.

Historical bowed string instruments exhibit acoustic features and aesthetic appeal that are still considered inimitable. These characteristics seem to be in large part determined by the materials used in the ground and varnishing treatments after the assembly of the instrument. These finishing processes were kept secret by the violinmakers and the traditional methods were handed down orally from master craftsmen to apprentices. Today, the methods of the past can represent a secret to be revealed through scientific investigations. The "Cremonese" methods used in the 17th and 18th centuries were lost as the last Great Masters from the Amati, Guarneri, and Stradivari families passed away. In this study, we had the chance of combining noninvasive and microinvasive techniques on six fragments of historical musical instruments. The fragments were detached from different instruments during extraordinary maintenance and restoration treatments, which involved the substitution of severely damaged structural parts like top plates, back plates, or ribs. Therefore, the fragments can offer to the scientists a valuable overview on the materials and techniques used by the violinmakers. The results obtained by portable X-ray fluorescence, optical microscopy, scanning electron microscopy coupled with energy dispersive X-ray spectrometry, and Fourier transform infrared microscopy allowed us to: (1) determine the stratigraphy of six instruments; (2) obtain new information about the materials involved in the finishing processes employed in Cremona; and (3) elucidate the technological relationship among the procedures adopted in the violin making workshops during the considered period.