PLS-DA and data fusion of visible Reflectance, XRF and FTIR spectroscopy in the classification of mixed historical pigments.

In this work samples of historical pigments of green hue were brushed on a canvas and studied by Visible Reflectance, X-Ray Fluorescence and Fourier Transform Infrared Spectroscopy. One hundred samples were investigated, all with green hue, these prepared from pigments themselves green, such as chromium oxide (Cr2O3) or from a mixture of pigments that result in green, for example, chrome yellow (PbCrO4) and Prussian blue (Fe4[Fe(CN)6]3). Because every sample investigated through the spectroscopic techniques were of green hue, the characterization of the pigments present in the mixtures through the visual inspection of spectra has become a complex task in some cases, also, due the large number of recorded spectra. In this work, classification models were developed using the multivariate statistical method Partial Least Squares Discriminant Analysis (PLS-DA) to automate the characterization of the pigments present in the mixtures. The models were developed to classify chromium oxide (Cr2O3), chrome yellow (PbCrO4), cerulean blue (CoO.nSnO2) and yellow ochre (Fe2O3·H2O + clay + silica). The models were developed from the fusion of data from the three spectroscopic techniques. However, before data fusion, pre-treatments of the spectral data were tested for their influence on the PLS-DA models. The models developed with data from the three techniques made it possible to classify the pigments of interest in the samples with up to 100% effectiveness. The results also indicate that fusion of the data from the three techniques allows to obtain fingerprints of the pigments of interest, which is not always possible using data from only one or two of the techniques applied in this work.

Investigating counterfeiting of an artwork by XRF, SEM-EDS, FTIR and synchrotron radiation induced MA-XRF at LNLS-BRAZIL.

In this work, a painting suspected of counterfeiting was analyzed using the synchrotron-based scanning macro X-ray fluorescence (MA-XRF) technique. The canvas has erasures including a signature erasure; however, some visible numbers indicate that the artwork may be from the 17th century. Through the studies' elemental maps, Cl-K and Ca-K were observed, which allowed us to reconstruct the signature present in the painting. Elemental maps of Ba-K, Ti-K, Fe-K, Zn-K, and Pb-K were also obtained from the painting, which made possible to visualize how the pigments based on these elements were used in the creative composition of the painting. In addition to the signature region, a region of the painting with dimensions of approximately 120 mm × 120 mm was investigated by synchrotron radiation induced MA-XRF, while keeping a high spatial resolution and elemental sensitivity. The measurements were carried out at the D09B micro-XRF beamline of the Brazilian Synchrotron Light Laboratory (LNLS), part of the Brazilian Center of Research in Energy and Materials, in Campinas Brazil. The painting was also investigated by SEM-EDS, and FTIR techniques. Those results, in addition to the supporting elemental maps, allowed additional information to be obtained, such as the binders used on the painting.

Analysis of silver coins from colonial Brazil by hand held XRF and micro-XRF.

In this work, 960 réis coins from the period when Brazil was a colony of Portugal were analyzed using the x-ray fluorescence (XRF) spectrometry. The history of these coins, dated between the end of the 17th century and the beginning of the 19th century, had a great influence on the immigration of the Portuguese Prince Regent D. João to Brazil, who arrived in 1808. Bearing in mind the need to expand the timid Brazilian monetary system, the Portuguese crown decided to collect Spanish silver pesos of 8 reales, recoined with a value of 960 réis. The recoinage procedure was carried out using a stamp; therefore, in many cases, it is possible to check the base currency. In this work, were investigated 17 samples of 960 réis coins by XRF, in which the base coin was 8 reales manufactured with raw materials from Mexican mines. In addition to characterizing the elemental composition of the coins, the XRF data were evaluated using multivariate statistical method of Robust Principal Component Analysis (ROBPCA), which was used to classify the coins based on their elemental composition. However, with XRF, elementary information is obtained for a depth of only a few micrometers. One of the essential issues in Ag-Cu metal alloys is the Ag enrichment, which can cause changes to the elemental composition of the surface. Therefore, initially, a study was carried out to verify whether the surface compositions of the coins were altered by the Ag enrichment.

Analysis of 19th century ceramic fragments excavated from Pirenópolis (Goiás, Brazil) using FT-IR, Raman, XRF and SEM.

This study used Raman, FT-IR and XRF spectroscopy and SEM to analyze ceramic fragments dating from the 19th century, excavated from an old farm in the municipality of Pirenópolis, Goiás, Brazil. The results show that the samples were produced in an open oven at a firing temperature below 500°C, using raw materials including kaolinite, hematite, magnetite, quartz, microcline, albite, anhydrite, calcite, illite, orthoclase and MnO2. Although the analyses showed similarities in the manufacturing process and the presence of many minerals was common in all samples, multivariate statistical methods (PCA) allowed a more detailed assessment of similarities and differences in the mineral composition of the samples. The results of the PCA showed that the samples excavated in one of the slave quarters (senzalas) group with those excavated at the farmhouse, where the landowner lived, which indicates a paternalistic attitude towards captives, including the sharing of ceramic materials of everyday use.

Analysis of clay smoking pipes from archeological sites in the region of the Guanabara Bay (Rio de Janeiro, Brazil) by FT-IR.

In this study, twenty samples of clay smoking pipes excavated in an 18km(2) area between the Macacu and Caceribu rivers, in the municipality of Itaboraí, Rio de Janeiro, Brazil were analyzed by FT-IR technique. The samples, excavated in different archeological sites of the region, are dated between the seventeenth and the nineteenth centuries and are part of the material culture left by Africans and African descendants that lived in the complex. FT-IR analyses and complementary SEM-EDS studies showed that the clay paste used in the manufacture of smoking pipes, mostly handcrafted, is composed of quartz, feldspar, phyllosilicates and iron oxides. Multivariate statistical tests (PCA) were applied to FT-IR data to assess the interactions between the archeological sites. The results indicated that one archeological site - Macacu IV - is greatly related to the other sites. The results obtained have helped archeologists and anthropologists in better understanding the manufacturing process employed in ancient ceramic artifacts produced during the period of colonial Brazil.

Analysis of a Brazilian baroque sculpture using Raman spectroscopy and FT-IR.

In this study, samples were taken from the sculpture of Our Lady of Sorrows and analyzed by Raman spectroscopy and FT-IR. This sculpture has been dated to the early eighteenth century. Samples were also examined using optical microscopy and Energy Dispersive Spectroscopy (EDS). Based on chemical analysis, the pigments vermilion [HgS], massicot [PbO] and azurite [Cu3(CO3)2(OH)2]were found in the sculpture polychrome. The results indicate that the green polychrome of the sculpture's mantle comes from the blending of massicot and azurite. Because the literature reports that the mantle of the Our Lady of Sorrows sculpture is blue, the mixing of these pigments results from a production error. The results also indicate the presence of Au in the sculpture, which indicates the originality of the piece. The results from this study helped restorers to choose the appropriate procedures for intervening in the sculpture and contributed to the knowledge about the manufacturing process of Brazilian baroque sculptures.