Uncovering modern paint forgeries by radiocarbon dating.

Art forgeries have existed since antiquity, but with the recent rapidly expanding commercialization of art, the approach to art authentication has demanded increasingly sophisticated detection schemes. So far, the most conclusive criterion in the field of counterfeit detection is the scientific proof of material anachronisms. The establishment of the earliest possible date of realization of a painting, called the terminus post quem, is based on the comparison of materials present in an artwork with information on their earliest date of discovery or production. This approach provides relative age information only and thus may fail in proving a forgery. Radiocarbon (14C) dating is an attractive alternative, as it delivers absolute ages with a definite time frame for the materials used. The method, however, is invasive and in its early days required sampling tens of grams of material. With the advent of accelerator mass spectrometry (AMS) and further development of gas ion sources (GIS), a reduction of sample size down to microgram amounts of carbon became possible, opening the possibility to date individual paint layers in artworks. Here we discuss two microsamples taken from an artwork carrying the date of 1866: a canvas fiber and a paint chip (<200 µg), each delivering a different radiocarbon response. This discrepancy uncovers the specific strategy of the forger: Dating of the organic binder delivers clear evidence of a post-1950 creation on reused canvas. This microscale 14C analysis technique is a powerful method to reveal technically complex forgery cases with hard facts at a minimal sampling impact.

The Ins and Outs of 14C Dating Lead White Paint for Artworks Application.

Lead white is known as one of the oldest pigments in art and can be used as a dating material. Upon production following the Stack process, the 14C isotope of atmospheric carbon dioxide is fixed in the carbonate, and its radiocarbon dating can be used as a proxy for the age of a painting. The previously reported carbonate hydrolysis protocol reaches its limitation when confronted with samples presenting a mixture of carbonates, such as lead carbonate (cerussite or hydrocerussite), calcium carbonate (calcite), and/or calcium magnesium carbonate (dolomite). Thermogravimetric analyses indicate that decomposition of lead carbonate can be achieved at 350 °C in TGA diagrams, as other mineral carbonates only decompose to carbon dioxide at temperatures above 700 °C. Thus, a thermal approach is proposed to separate the various carbonates and isolate the specific 14C signature to the lead carbonate. In practice, however, discrepancies between the measured radiocarbon ages and expected ages were observed. FTIR analyses pointed to the formation of metal carboxylates, an indicator that the organic binder is not inert and plays a role in the dating strategy. Upon drying, oxidation and hydrolysis take place leading to the formation of free fatty acids, which in turn interact with the different carbonates upon heating. Their removal was achieved by introduction of a solvent extraction step prior to the thermal treatment, which was confirmed by GC-MS analyses, and thus, the collected carbon dioxide at 350 °C results can be assigned correctly to the decomposition of the lead white pigment. The proposed procedure was furthermore verified on mixed carbonate-bearing paint samples collected from a Baroque oil painting.

Material Characterization of Silicones for Additive Manufacturing.

Three-dimensional printing is ideally suited to produce unique and complex shapes. In this study, the material properties of polysiloxanes, commonly named silicones, produced additively by two different methods, namely, multi-jet fusion (MJF) and material extrusion (ME) with liquid printing heads, are investigated. The chemical composition was compared via Fourier-transform infrared spectroscopy, evolved gas analysis mass spectrometry, pyrolysis gas chromatography coupled to mass spectrometry, and thermogravimetry (TGA). Density and low-temperature flexibility, mechanical properties and crosslink distance via freezing point depression were measured before and after post-treatment at elevated temperatures. The results show significant differences in the chemical composition, material properties, as well as surface quality of the tested products produced by the two manufacturing routes. Chemical analysis indicates that the investigated MJF materials contain acrylate moieties, possibly isobornyl acrylate linking branches. The hardness of the MJF samples is associated with crosslinking density. In the ashes after TGA, traces of phosphorus were found, which could originate from initiators or catalysts of the curing process. The ME materials contain fillers, most probably silica, that differ in their amount. It is possible that silica also plays a role in the processing to stabilize the extrusion strand. For the harder material, a higher crosslink density was found, which was supported also by the other tested properties. The MJF samples have smooth surfaces, while the ME samples show grooved surface structures typical for the material extrusion process. Post-treatment did not improve the material properties. In the MJF samples, significant color changes were observed.

The natural constituents of historical textile dyes.

The sources and structures of dyes used to colour Western historical textiles are described in this tutorial review. Most blue and purple colours were derived from indigo--obtained either from woad or from the indigo plant--though some other sources (e.g. shellfish and lichens) were used. Reds were often anthraquinone derivatives obtained from plants or insects. Yellows were almost always flavonoid derivatives obtained from a variety of plant species. Most other colours were produced by over-dyeing--e.g. greens were obtained by over-dyeing a blue with a yellow dye. Direct analysis of dyes isolated from artefacts allows comparison with the historical record.