Protrusions, efflorescence, delamination, and opacity decreasing are severe degradation phenomena affecting oil paints with zinc oxide, one of the most common white pigments of the 20th century. Responsible for these dramatic alterations are the Zn carboxylates (also known as Zn soaps) originated by the interaction of the pigment and the fatty acids resulting from the hydrolysis of glycerides in the oil binding medium. Despite their widespread occurrence in paintings and the growing interest of the scientific community, the process of formation and evolution of Zn soaps is not yet fully understood. In this study micro-attenuated total reflection (ATR)-FT-IR spectroscopic imaging was required for the investigation at the microscale level of the nature and distribution of Zn soaps in the painting Alchemy by J. Pollock (1947, Peggy Guggenheim Collection, Venice) and for comparison with artificially aged model samples. For both actual samples and models, the role of AlSt(OH), a jellifying agent commonly added in 20th century paint tube formulations, proved decisive for the formation of zinc stearate-like (ZnSt) soaps. It was observed that ZnSt-like soaps first form around the added AlSt(OH) particles and then eventually grow within the whole painting stratigraphy as irregularly shaped particles. In some of the Alchemy samples, and diversely from the models, a peculiar distribution of ZnSt aggregates arranged as rounded and larger particles was also documented. Notably, in one of these samples, larger agglomerates of ZnSt expanding toward the support of the painting were observed and interpreted as the early stage of the formation of internal protrusions. Micro-ATR-FT-IR spectroscopic imaging, thanks to a very high chemical specificity combined with high spatial resolution, was proved to give valuable information for assessing the conservation state of irreplaceable 20th century oil paintings, revealing the chemical distribution of Zn soaps within the paint stratigraphy before their effect becomes disruptive.

The analytical study of historical collagen-based materials such as leather book covers is a complex task for conservation scientists. Historical leather presents a heterogeneous composition of both organic and inorganic materials that show an evident reactivity, particularly when exposed to specific environments. Its correct preservation in archival documents remains challenging as some aspects of its chemical composition, degradation, and effectiveness of conservation treatments are still not fully understood. Here, we describe a novel application of attenuated total reflection (ATR)–Fourier transform infrared spectroscopic imaging coupled with a macro ATR accessory to study historical leather book covers. This nondestructive and high spatial resolution approach has allowed the visualization of degradation phenomena affecting this fragile material, particularly the gelatinization of collagen and, for the first time, the detection of the formation of calcium stearate (metal carboxylates or soaps). In addition, the distribution of modified soybean oil used as a treatment to maintain properties such as elasticity and hydrophobicity of the leather was studied. The effect of anomalous dispersion on the strong IR bands obtained in the ATR mode and the resulting changes to the band positions are also discussed. This research addresses issues that are relevant to the conservation of archival materials of cultural heritage for future generations.

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Ancient bronze is subject to complex degradation which can lead, in cases where copper chlorides are present, to a cyclic and self-sustaining degradation process commonly referred to as “bronze disease”. If left untreated, bronze disease can eat away at a bronze object until it is entirely deteriorated. The presence of copper trihydroxychlorides is indicative that this process is underway and therefore the detection of these corrosion products is necessary in guiding conservation of ancient bronze artefacts. In this paper we present a high spatial/spectral resolution short wave infrared (SWIR) imaging solution for mapping copper trihydroxychlorides in ancient bronze, combining hyperspectral imaging with an in-house developed unsupervised machine learning algorithm for automated spectral clustering. For this work, verification was obtained through use of an in-house developed reference database of typical ancient bronze corrosion products from several archaeological sites, and from collections of the National Museum of China. This paper also explores the suitability, and limitations, of a visible to near-infrared (VNIR) hyperspectral imaging system as a more accessible solution for mapping copper trihydroxychlorides associated with bronze disease. We suggest that our hyperspectral imaging solution can provide a non-invasive, rapid, and high resolution material mapping within and across bronze objects, particularly beneficial for analysing large collections in a museum setting.