We show terahertz reflection images of hidden paint layers in a painting on canvas and compare the results with X-ray Radiography and Infrared Reflectography. Our terahertz measurements show strong reflections from both the canvas/paint interface and from the raw umber/lead white interface, indicating sufficient refractive-index contrast. Our results show that X-rays cannot be used to image through the lead white pigment which effectively blocks the X-rays. Although Infrared Reflectography is capable of vaguely observing the hidden paint strokes from the canvas side, we show that only terahertz imaging is capable of providing information on the thickness of the hidden paint layers. Terahertz imaging is thus shown to be a powerful imaging method for art historians, conservators and conservation scientists.

Titanium white (TiO2) has been widely used as a pigment in the 20th century. However, its most photocatalytic form (anatase) can cause severe degradation of the oil paint in which it is contained. UV light initiates TiO2-photocatalyzed processes in the paint film, degrading the oil binder into volatile components resulting in chalking of the paint. This will eventually lead to severe changes in the appearance of a painting. To date, limited examples of degraded works of art containing titanium white are known due to the relatively short existence of the paintings in question and the slow progress of the degradation process. However, UV light will inevitably cause degradation of paint in works of art containing photocatalytic titanium white. In this work, a method to detect early warning signs of photocatalytic degradation of unvarnished oil paint is proposed, using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Consequently, a four-stage degradation model was developed through in-depth study of TiO2-containing paint films in various stages of degradation. The XPS surface analysis proved very valuable for detecting early warning signs of paint degradation, whereas the AFM results provide additional confirmation and are in good agreement with bulk gloss reduction.

The painting An Old Man in Military Costume in the J. Paul Getty Museum, by Rembrandt Harmensz van Rijn, was studied using two complementary, element-specific imaging techniques—neutron activation autoradiography (NAAR) and macro-X-ray fluorescence (MA-XRF) mapping—to reveal the second, hidden painting. NAAR provided a strong image of the face and cloak of the underlying figure, along with an indication of the chemical composition. The single-element distribution maps produced by MA-XRF mapping provided additional details into the shape of the underlying image and the composition of the pigments used. The underlying figure’s face is richer in mercury, indicative of the pigment vermilion, than the face of the figure on the surface. Likewise, the cloak of the underlying figure is richer in copper than the surface figure though the identity of the copper-containing pigment cannot be determined from these data. The use of iron earth pigments, specifically Si-rich umbers, is indicated through the complementary information provided by the NAAR and MA-XRF maps. These data are used to create a false color digital reconstruction, yielding the most detailed representation of the underlying painting to date.