A holistic approach using non-invasive multimodal imaging and spectroscopic techniques to study the materials (pigments, drawing materials and paper) and painting techniques of watercolour paintings is presented. The non-invasive imaging and spectroscopic techniques include VIS-NIR reflectance spectroscopy and multispectral imaging, micro-Raman spectroscopy, X-ray fluorescence spectroscopy (XRF) and optical coherence tomography (OCT). The three spectroscopic techniques complement each other in pigment identification. Multispectral imaging (near-infrared bands), OCT and microRaman complement each other in the visualisation and identification of the drawing material. OCT probes the micro-structure and light scattering properties of the substrate, while XRF detects the elemental composition that indicates the sizing methods and the filler content. The multiple techniques were applied in a study of forty-six nineteenth-century Chinese export watercolours from the Victoria and Albert Museum (V&A) and the Royal Horticultural Society (RHS) to examine to what extent the noninvasive analysis techniques employed complement each other and how much useful information about the paintings can be extracted to address art conservation and history questions. A micro-destructive technique of micro-fade spectrometry was used to assess the vulnerability of the paintings to light exposure. Most of the paint and paper substrates were found to be more stable than ISO Blue Wool 3. The palette was found to be composed of mostly traditional Chinese pigments. While the synthetic pigment, Prussian blue, made in Europe, was found on some of the paintings, none was found on the RHS paintings accurately recorded as being between 1817 and 1831 even though it is known that Prussian blue was imported to China during this period. The scale insect dyes, lac and cochineal, were detected on nearly every painting including those that fall within the identified date range. Cochineal is known to have been imported to China in the same period. While carbonbased ink was used for the drawings in the V&A paintings, graphite pencil was used in most of the RHS paintings. The majority of RHS paintings were on Western papers, but nearly all of the V&A paintings were on Chinese papers. Nearly all of the V&A painting substrates and hardly any of the RHS paintings were sized with alum. Elements such as Cu, Zn, Ti and Pb were detected on nearly all of the RHS papers regardless of whether they were Chinese or Western papers. These elements were largely absent from the V&A papers. The differences between the two collections reflect their discrete origins and intended purposes.
This paper examines for the first time the potential complementary imaging capabilities of Optical coherence tomography (OCT) and non-linear microscopy (NLM) for multi-modal 3D examination of paintings following the successful application of OCT to the in situ, non-invasive examination of varnish and paint stratigraphy of historic paintings and the promising initial studies of NLM of varnish samples. OCT provides image contrast through the optical scattering and absorption properties of materials, while NLM provides molecular information through multi-photon fluorescence and higher harmonics generation (second and third harmonic generation). OCT is well-established in the in situ non-invasive imaging of the stratigraphy of varnish and paint layers. While NLM examination of transparent samples such as fresh varnish and some transparent paints showed promising results, the ultimate use of NLM on paintings is limited owing to the laser degradation effects caused by the high peak intensity of the laser source necessary for the generation of nonlinear phenomena. The high intensity normally employed in NLM is found to be damaging to all non-transparent painting materials from slightly scattering degraded varnish to slightly absorbing paint at the wavelength of the laser excitation source. The results of this paper are potentially applicable to a wide range of materials given the diversity of the materials encountered in paintings (e.g. minerals, plants, insects, oil, egg, synthetic and natural varnish).
Self-organising map (SOM), an unsupervised machine learning algorithm based on neural networks, is applied to introduce a novel approach for the analysis of XRF spectral imaging data. This method automatically reduced hundreds of thousands of XRF spectra in a spectral image dataset to a handful of distinct clusters that share similar spectra. In this study, we show how clustering and the combination of spatial and spectral information can be used to aid materials identification and deduce the paint sequence. The efficiency and accuracy of the method is presented through the analysis of a Peruvian watercolour painting from the Getty Research Institute collection. Confirmation of the interpretation was provided by complementary non-invasive techniques, such as optical microscopy, reflectance and Raman spectroscopies.
Since the 'rediscovery' of the Selden map of China, an early seventeenth century map of Asia, in the Bodleian Library in Oxford, the importance of the map in our understanding of globalisation in the early seventeenth century has been recognised. One of the unresolved questions is the origin of the map. This paper addresses the question through material evidence provided by a holistic approach using a suite of complementary analytical techniques. The map was examined in situ and non-invasively by a remote spectral imaging instrument (PRISMS) modified for close range imaging, which was followed by a range of complementary techniques applied to a number of detached fragments, though most of the techniques are non-invasive and can be applied to the map directly in the future. The binding medium was found to be a gum, almost certainly gum Arabic, rather than the animal glue commonly used in Chinese paintings. Some of the pigments and their usage were found to be at odds with the common practice in paintings from China. The detection of gum Arabic, a binding medium used by the Europeans, South and West Asians and the use of a mixture of orpiment and indigo, commonly found in European, South and West Asian paintings gives further evidence on the unusual origins of this map. The likely detection of a basic copper chloride, such as atacamite, in the green areas suggests an influence from the South and West Asian rather than the European tradition. Detailed analysis of the various spectral bands of the spectral image cube along with visual inspection of the large scale colour image showed that the map was not fully planned at the beginning but rather painted in stages, at times by trial and error and that it was unfinished. A new hypothesis for the origin of the Selden map in Aceh Sumatra is proposed based on the new evidences.
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