The painter, Vincent van Gogh, and some of his contemporaries frequently made use of the pigment chrome yellow that is known to show a tendency toward darkening. This pigment may correspond to various chemical compounds such as PbCrO(4) and PbCr(1-x)S(x)O(4), that may each be present in various crystallographic forms with different tendencies toward degradation. Investigations by X-ray diffraction (XRD), mid-Fourier Transform infrared (FTIR), and Raman instruments (benchtop and portable) and synchrotron radiation-based micro-XRD and X-ray absorption near edge structure spectroscopy performed on oil-paint models, prepared with in-house synthesized PbCrO(4) and PbCr(1-x)S(x)O(4), permitted us to characterize the spectroscopic features of the various forms. On the basis of these results, an extended study has been carried out on historic paint tubes and on embedded paint microsamples taken from yellow-orange/pale yellow areas of 12 Van Gogh paintings, demonstrating that Van Gogh effectively made use of different chrome yellow types. This conclusion was also confirmed by in situ mid-FTIR investigations on Van Gogh's Portrait of Gauguin (Van Gogh Museum, Amsterdam).

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The darkening of the original yellow areas painted with the chrome yellow pigment (PbCrO(4), PbCrO(4)·xPbSO(4), or PbCrO(4)·xPbO) is a phenomenon widely observed on several paintings by Vincent van Gogh, such as the famous different versions of Sunflowers. During our previous investigations on artificially aged model samples of lead chromate, we established for the first time that darkening of chrome yellow is caused by reduction of PbCrO(4) to Cr(2)O(3)·2H(2)O (viridian green), likely accompanied by the presence of another Cr(III) compound, such as either Cr(2)(SO(4))(3)·H(2)O or (CH(3)CO(2))(7)Cr(3)(OH)(2) [chromium(III) acetate hydroxide]. In the second part of this work, in order to demonstrate that this reduction phenomenon effectively takes place in real paintings, we study original paint samples from two paintings of V. van Gogh. As with the model samples, in view of the thin superficial alteration layers that are present, high lateral resolution spectroscopic methods that make use of synchrotron radiation (SR), such as microscopic X-ray absorption near edge (μ-XANES) and X-ray fluorescence spectrometry (μ-XRF) were employed. Additionally, μ-Raman and mid-FTIR analyses were carried out to completely characterize the samples. On both paint microsamples, the local presence of reduced Cr was demonstrated by means of μ-XANES point measurements. The presence of Cr(III) was revealed in specific areas, in some cases correlated to the presence of Ba(sulfate) and/or to that of aluminum silicate compounds.

Chrome yellows, a class of pigments frequently used by painters of the Impressionism and Post‐impressionism period, are known for their different chemical stability; the latter depends on the chemical composition (PbCrO4, PbCr1−xSxO4) and crystalline structure (monoclinic or orthorhombic) of the material. The possibility to distinguish among different forms of this pigment is therefore relevant in order to extend knowledge on the corresponding degradation process that is observed on several original paintings. For this purpose, three paintings conserved at the Van Gogh Museum (Amsterdam) were analyzed using noninvasive Raman spectroscopy, while equivalent investigations employing bench‐top instrumentation were performed to obtain information from micro‐samples originating from these works of art. In each painting, the chrome yellow was identified either as monoclinic PbCrO4 or in the form of monoclinic PbCr1−xSxO4 (x < 0.25) or S‐rich orthorhombic PbCr1−xSxO4 (x ~ 0.5). Our ability to make this fairly subtle distinction is based on a Raman study of several oil paint model samples made up of monoclinic and/or orthorhombic crystalline forms of PbCrO4 and PbCr1−xSxO4 (0.1 ≤ × ≤ 0.8). These paints were studied using several excitation wavelengths (namely 785.0, 532.0, 514.5, and 488 nm). Because of the absence of the resonance Raman effect, which strongly enhances the chromate symmetric stretching band, and the absence of any laser‐induced photodecomposition, it is advantageous to acquire data at 785.0 nm. The band‐shape and the position of the chromate bending modes proved to be more sensitive to the solid solution composition and crystalline structure than the stretching modes and can be used as distinctive spectral markers to discriminate among the different chrome yellow forms that are present. Copyright © 2014 John Wiley & Sons, Ltd.

Abstract-To recognize speech, handwriting, or sign language, many hybrid approaches have been proposed that combine Dynamic Time Warping (DTW) or Hidden Markov Models (HMMs) with discriminative classifiers. However, all methods rely directly on the likelihood models of DTW/HMM. We hypothesize that time warping and classification should be separated because of conflicting likelihood modeling demands. To overcome these restrictions, we propose using Statistical DTW (SDTW) only for time warping, while classifying the warped features with a different method. Two novel statistical classifiers are proposed-Combined Discriminative Feature Detectors (CDFDs) and Quadratic Classification on DF Fisher Mapping (Q-DFFM)-both using a selection of discriminative features (DFs), and are shown to outperform HMM and SDTW. However, we have found that combining likelihoods of multiple models in a second classification stage degrades performance of the proposed classifiers, while improving performance with HMM and SDTW. A proof-of-concept experiment, combining DFFM mappings of multiple SDTW models with SDTW likelihoods, shows that, also for model-combining, hybrid classification can provide significant improvement over SDTW. Although recognition is mainly based on 3D hand motion features, these results can be expected to generalize to recognition with more detailed measurements such as hand/body pose and facial expression.