1. Introduction
Gilding is an ornamental decoration in paintings which consists of applying a very thin layer of gold (the gold leaf) using different techniques. Gilding was a very widespread technique in medieval art, especially in the Byzantine and Renaissance periods, where the gold leaf was used in paintings on wooden panels to enhance the visual effect of the saints’ halos. Moreover, in the middle ages, many paintings were executed using the gold leaf as a background (gold ground). Usually, the gold in gildings was used pure but gold alloys as well as alloys simulating the colour of gold have been also found. In this respect, the “oro di metà” (halfway) gilding was used mainly in Italy from the thirteenth to the fifteenth centuries but its structure and composition still remain unclear.
In the painting of the fifteenth century by the Master of St. Ivo depicting S. Peter between St. Anthony Abbot and St. Mary Magdalene, the “
oro di metà” gilding represents a rare example of its excellent state of preservation, which makes it one of the few cases that has come to us so intact. Moreover, this gilding was applied according to both the most common execution techniques at that time: “
a guazzo” (water gilding) on the background and “
a missione” (gilding with mordant) on the borders of the garments. Briefly, in the water gilding, the gold foil is laid onto an adhesive layer consisting mainly of earth pigments mixed with a protein binder (as egg-white and rabbit glue) and with some water commonly known as “
bole”, over gypsum ground. The bole gives a warm color to the gold as well being a cushion for successive treatments as for example burnishing and punching [
1]. On the contrary, in the gilding with mordant, the gold foil is laid on an oil-based mordant usually made of linseed oil mixed with pigments as driers. This technique is particularly suitable for decorations and small details [
1].
The term “
oro di metà” or “
oro mezzo” was explicitly used by Cennini [
2] describing different gilding techniques and warning against the tarnishing of silver which is a constituent of this type of gilding. Actually, the use of “
oro di metà” foils was very widespread in Tuscany since the end of the thirteenth century, so much so that in the years 1315–1316 when the painters were admitted to the guild of the “Arte dei Medici e degli Speziali” (the guild of doctors and pharmacists) of Florence, in the statute is mentioned the “
aurum di metà” regarding the penalties for those who were using it instead of fine gold without declaring it [
3]. Throughout the fourteenth century until the end of the fifteenth century, the “
oro di metà” is observed in the gilding of some paintings by Jacopo del Casentino, Pacino di Buonaguida, Bernardo Daddi, and Puccio di Simone [
4]; Neri di Bicci as well in his “Ricordanze” [
5] certifies the use of “
oro mezzo” on many “anticha” altar plates reporting even the price, which is about half of that of the fine gold [
6]. As prescribed by the Florentine Statutes of 1396 and 1403 [
7,
8,
9], the “
oro di metà” foil results to have the same dimensions as that of silver; therefore, analyzing the costs [
10], with the price of 100 pieces of fine gold, approximately 200 pieces of “
oro mezzo” could be obtained with a size ranging from 8.3 to 7.3 cm
2.
Despite the existence of these very important historical documents which would suggest the use of two different foils (one of silver and one of gold) cast as a “sandwich”, in the nineteenth century, Merrifield and Eastlake [
8] translated the “
oro di metà” as “gold that is much alloyed” similar to other translators that used the expression “gold alloy”. Similarly, Milanesi in 1859 introduced the meaning “
oro falso battuto” (fake beaten gold) along with other translators that referred to “
oro di metà” as a gold leaf that is “false” or “
only half genuine” without giving neither any specifications nor the right importance to this artistic executional technique.
An overview of all the definitions, meanings and assumptions ascribed to the expression “
oro di metà”, over the centuries, is precisely described by Skaug [
8]. However, we would like to give particular emphasis to the metal leaf commonly used in the European middle ages and known in French as “
or parti”, in dutch as “
partijtgoud” and in german “
gedeelt Gold” which share with “
oro di metà” an etymological allusion to a real divided structure.
In this work, the observation carried out by means of both a polarized light optical microscope (OM) and an Ultra-High Resolution Scanning Electron Microscope (UHR-SEM) have confirmed, as far as we know for the first time, the presence of two distinct very thin metal foils with different thicknesses in the “oro di metà” gilding. Moreover, Energy Dispersive X-Ray (EDX) analysis has allowed for characterizing the composition of the gold and silver layers which have been found out to be separated and overlapped as well as identifying the degradation products of the silver layer responsible for the blackening process. Finally, complementary vibrational spectroscopic techniques such as micro-ATR-FTIR and micro-Raman spectroscopy were used in order to characterize the molecular composition of the “bole” as well as the preparation layers.
History of the Painting
Fragmentary and incomplete is the information regarding the painting of the Master of St. Ivo. However, Bernacchioni and Tartuferi [
11,
12] have been able to find out some important information to trace its origin and history.
In 1895, the painting was at the collection of the Banca Popolare di Genova and it was auctioned at the Sangiorgi Gallery in Rome. This is the oldest piece of information on the provenance of this painting. Then, it was divided into three pieces.
However, the inscription on the base of the S. Peter throne says that the wood panel painting was commissioned by Piero di Giovanni Ringli in 1438 when he was the castellan assigned by the Sforza as captain of the garrison to defend and control the Fortress of Avenza, a small village in Lunigiana (Tuscany, Italy), from Genova’s power. In support of this, the presence of the coat of arms of the diocese of Luni with the horns of the moon pointing upwards, refers to Lunigiana. The historical and political context of that period suggests the church of Avenza as a possible place of provenance of the painting. In particular, from 1437 to 1441, before returning to Genoa’s control, Avenza was under the control of the Republic of Florence, thus explaining the presence of a painting made by the Florentine painter the Master of St. Ivo in that region.
The painting underwent only one restoration intervention in the early twentieth century, consisting of the separation of the triptych into three separated panels, their framing as well as the pictorial recovery of the draperies. Moreover, the painting was in a private American collection from the early twentieth century until 1993 and subsequently was put up for auction twice without undergoing further restorations.
Thus, this painting represents a very exceptional case in terms of conservation because it is devoid of previous interventions of cleaning so much that the original varnish is still present on the surface.
2. Sampling, Samples Preparation and Methodology
Eleven samples were taken from the painting by using a scalpel in order to gather information on many issues about the technical execution and composition of gildings, painting layers, and the ground (preparation layer). The fragments were cast in epoxy-resin, dried and finely polished for the cross-sections preparation. In particular, polishing was carefully carried out using discs at different mesh (800-1000-1200-4000) in order to perform the process very delicately. The stratigraphies were then observed by reflected polarized light OM and by an UHR-SEM. The elemental composition of different layers was provided by means of EDX spectroscopy; whereas, the molecular composition was provided by using micro-ATR-FTIR and micro-Raman spectroscopy.
Figure 1 shows a panoramic view of the entire painting along with the sampling points. The cross-section described in this work was taken from sampling area highlighted in blue colour. After microscopic observation, this sample was considered crucial for the interpretation and the assessment of the gilding technical execution with respect to other samples where gildings were either in a bad conservation state or completely gone.
Optical microscopy observation was carried out using the polarised light microscope Eclipse 150 by Nikon provided with five different magnification objectives (5×, 10×, 20×, 50× and 100×).
SEM-EDX observation and measurements were carried out at the Center of Electronic Microscopies “Laura Bonzi” (Ce.M.E-CNR) by using an UHR-SEM Gaia 3 FIB/SEM by Tescan which represents a step forward in the field of advanced electron microscopy. The electronic beam of this microscope enables the possibility of imaging at the “nano” scale level (up to 0.7 nm at 15 keV), even with samples sensitive to electron beams such as the majority of cultural heritage materials. The limit of detection of the EDX semi-quantitative analysis falls into the range of 0.2–1 w% depending on the specific elements.
FT-IR spectra of the red sample were collected with a FT-IR spectrometer Agilent Technologies Cary 660 coupled with Cary 620 Microscope, equipped with a MCT detector. The spectra were acquired in ATR mode with Germanium crystal, collecting 64 scans, with a resolution of 4 cm−1 in the 4000–400 cm−1 range. Spectra were processed using Agilent Resolutions Pro software.
Raman measurements were performed under an XPlora Horiba micro-Raman instrumentation equipped with three laser excitation sources. In particular, spectra of the ground layer were carried out using a 785 nm laser wavelength, a 100× objective, and diffraction grating of 1200 g/mm. The spectra were collected using an accumulation time of 20 s.
4. Conclusions
In this work, the divided structure of gold and silver layers in the “oro di metà” gilding of the fifteenth-century was scientifically demonstrated for the first time. The use of last-generation SEM-EDX instrumentation was crucial for this approach allowing the imaging and analysis of very thin (under micron) layers separately. Elemental colour mapping of the gilding was also performed confirming the divided structure of the metal layers. Moreover, from BSE-SEM images, an estimation of the different thickness of gold and silver was provided along with the confirmation, for the first time, of their hypothetical use in relation 1/3.
The advantage of overlapping two separated layers of gold and silver with respect to an alloy was essentially aesthetic. As soon as it was made, this gilding used to be so bright that it could have been mistaken for pure gold. On the contrary, the gold/silver alloy, used since ancient times (in minting for example), did not have the same effect but a cold color instead.
Besides, in this work, considerations regarding the tarnishing and degradation mechanism of the silver layer were made. The transformation of silver in silver–sulphide as a corrosion product was also demonstrated. Finally, the use of vibrational spectroscopies at the micro level such as Raman and ATR-FTIR allowed the molecular identification of the mineral phases constituting the “bole” as well as the ground layer.