Dry powders reflectance model based on enhanced backscattering: case of hematiteα-Fe2O3.

By performing bidirectionnal reflectance distribution function (BRDF) measurements, we have identified backscattering as the main phenomenon involved in the appearance of dry nanocrystallized powders. We introduce an analytical and physically based BRDF model that relies on the enhanced backscattering theory to accurately reproduce BRDF measurements. These experimental data were performed on optically thick layers of dry powders with various grains' morphologies. Our results are significantly better than those obtained with previous models. Our model has been validated against the BRDF measurements of multiple synthesized nanocrystallized and monodisperse α-F e 2 O 3 hematite powders. Finally, we discuss the ability of our model to be extended to other materials or more complex powder morphologies.

Revealing the Nature of Black Pigments Used on Ancient Egyptian Papyri from Champollion Collection.

Although numerous papyri from ancient Egypt have been collected and preserved over the centuries, the recipe used to prepare black inks was only reported in manuscripts from the late Greco-Roman period. Black inks were mostly obtained after mixing carbon black with a binder agent and water. In previous studies performed on black inks apposed on papyri from ancient Egypt, additional chemical elements such as lead, iron, or copper were also identified, and the resulting chemical contrast with the papyrus support was used to virtually decrypt highly degraded or rolled papyri. Combining a series of synchrotron-based techniques with Raman spectroscopy and scanning electron microscopy, we investigated 10 papyri fragments from J.-F. Champollion's private collection. For each fragment, the carbon-black pigment found in the ink is identified as flame carbon (lampblack or soot). Using X-ray diffraction computed tomography, we show that the diffraction signal of the carbon-based pigment itself can be isolated. As a result, a contrast with the papyrus support is obtained, even in the absence of a specific chemical element in the ink. This is opening up new opportunities to decipher words written millennia ago, as part of our Cultural Heritage.

Neural networks for rapid phase quantification of cultural heritage X-ray powder diffraction data.

Recent developments in synchrotron radiation facilities have increased the amount of data generated during acquisitions considerably, requiring fast and efficient data processing techniques. Here, the application of dense neural networks (DNNs) to data treatment of X-ray diffraction computed tomography (XRD-CT) experiments is presented. Processing involves mapping the phases in a tomographic slice by predicting the phase fraction in each individual pixel. DNNs were trained on sets of calculated XRD patterns generated using a Python algorithm developed in-house. An initial Rietveld refinement of the tomographic slice sum pattern provides additional information (peak widths and integrated intensities for each phase) to improve the generation of simulated patterns and make them closer to real data. A grid search was used to optimize the network architecture and demonstrated that a single fully connected dense layer was sufficient to accurately determine phase proportions. This DNN was used on the XRD-CT acquisition of a mock-up and a historical sample of highly heterogeneous multi-layered decoration of a late medieval statue, called 'applied brocade'. The phase maps predicted by the DNN were in good agreement with other methods, such as non-negative matrix factorization and serial Rietveld refinements performed with TOPAS, and outperformed them in terms of speed and efficiency. The method was evaluated by regenerating experimental patterns from predictions and using the R-weighted profile as the agreement factor. This assessment allowed us to confirm the accuracy of the results.

Synthesis and fading of eighteenth-century Prussian blue pigments: a combined study by spectroscopic and diffractive techniques using laboratory and synchrotron radiation sources.

Prussian blue, a hydrated iron(III) hexacyanoferrate(II) complex, is a synthetic pigment discovered in Berlin in 1704. Because of both its highly intense color and its low cost, Prussian blue was widely used as a pigment in paintings until the 1970s. The early preparative methods were rapidly recognized as a contributory factor in the fading of the pigment, a fading already known by the mid-eighteenth century. Herein two typical eighteenth-century empirical recipes have been reproduced and the resulting pigment analyzed to better understand the reasons for this fading. X-ray absorption and Mössbauer spectroscopy indicated that the early syntheses lead to Prussian blue together with variable amounts of an undesirable iron(III) product. Pair distribution functional analysis confirmed the presence of nanocrystalline ferrihydrite, Fe10O14(OH)2, and also identified the presence of alumina hydrate, Al10O14(OH)2, with a particle size of ∼15 Å. Paint layers prepared from these pigments subjected to accelerated light exposure showed a tendency to turn green, a tendency that was often reported in eighteenth- and nineteenth-century books. The presence of particles of hydrous iron(III) oxides was also observed in a genuine eighteenth-century Prussian blue sample obtained from a polychrome sculpture.

Hidden mysteries in ancient Egyptian paintings from the Theban Necropolis observed by in-situ XRF mapping.

The material study of ancient Egyptian paintings began with the advent of Egyptology during the 19th century. By the 1930s, a lot had already been sampled and described. The limited palette for example has been analysed from actual painted surfaces but also from pigments and painting tools retrieved on site. However, most of these studies took place in museums while the painted surfaces, preserved in funerary chapels and temples, remained somewhat estranged from this primary physical understanding. The artistic process has been also reconstructed, mainly from the information presented by unfinished monuments, showing surfaces at different stages of completion. A lot of this modern and theoretical reconstruction is, however, based on the usual archaeological guessing game that aims at filling the remaining blanks. Our interdisciplinary project has decided to experiment on-site with state-of-the-art portable analysis tools, avoiding any physical sampling, to see if our knowledge of the work of the ancient Egyptian painters and draughtsmen could be taken at a further stage, while based on physical quantification that could be seen as a stronger and more reliable foundation for a redefined scientific hypothesis. The use of XRF mapping has, for instance, been applied to a known case of correction by surface repaint, something that is supposedly rare in the ancient Egyptian formal artistic process, while another fully unexpected one was discovered during the analytic exploration of a royal representation. In both cases, the precise and readable imaging of the physical composition of the painted surface offers a renewed visual approach based of chemistry, that can be shared through a multi- and interdisciplinary approach. However, this also leads to a more complex description of pigment mixtures that could have multiple meanings, where the practical often leads towards the symbolic, and from there hopefully to a renewed definition of the use of colours in complex sets of ancient Egyptian representations. At this stage, though the progress in this on-site material assessment of ancient works of art definitely means astonishing progress, one humbly has to face the fact that these ancient treasures shall still retain part of their defining mysteries.

Illustrating papyrus in Ancient Egypt.

Illustrated papyruses from Ancient Egypt have survived across millennia, depicting with vivid colors numerous stories and practices from a distant past. We have investigated a series of illustrated papyruses from Champollion's private collection showing scenes from the Book of the Dead, a document essential to prepare for the afterlife. The nature of the different pigments and their distribution are revealed by combining optical microscopy, Raman spectroscopy, and synchrotron X-ray powder diffraction and fluorescence. The standardized three-step process from the New Kingdom period was used, comprising a preparatory drawing made of red hematite, a coloring step using pigments from the Egyptian palette, and a final black contour drawn with a carbon-based ink. Interestingly, specific pigment mixes were deliberately chosen to obtain different shades. In some parts, the final contour significantly differs from the preliminary drawing, revealing the artist's creativity. These results enhance our knowledge of illustrative practices in Ancient Egypt.

Association of indigo with zeolites for improved color stabilization.

The durability of an organic color and its resistance against external chemical agents and exposure to light can be significantly enhanced by hybridizing the natural dye with a mineral. In search for stable natural pigments, the present work focuses on the association of indigo blue with several zeolitic matrices (LTA zeolite, mordenite, MFI zeolite). The manufacturing of the hybrid pigment is tested under varying oxidizing conditions, using Raman and ultraviolet-visible (UV-Vis) spectrometric techniques. Blending indigo with MFI is shown to yield the most stable composite in all of our artificial indigo pigments. In the absence of defects and substituted cations such as aluminum in the framework of the MFI zeolite matrix, we show that matching the pore size with the dimensions of the guest indigo molecule is the key factor. The evidence for the high color stability of indigo@MFI opens a new path for modeling the stability of indigo in various alumino-silicate substrates such as in the historical Maya Blue pigment.

Synthetic hydrocerussite, 2PbCO(3) x Pb(OH)(2), by X-ray powder diffraction.

Synthetic hydrocerussite [trilead dihydroxide dicarbonate, Pb(3)(CO(3))(2)(OH)(2)] can be easily obtained, as a white powder, by the action of carbon dioxide and water on either lead or litharge at pH 4-5. This compound is also found in lead corrosion technological products as a fine-grained phase. Ab initio crystal structure determination was carried out on X-ray powder diffraction data. The heavy-atom method and the Patterson function helped determine the crystallographic model and the atom locations. The Rietveld fitting procedure was used for the final refinement. The atomic arrangement is closely related to the structures of other lead hydroxide carbonates. The hydrocerussite structure can be viewed as a sequence of two types of layers stacked along [001]. Layer A is composed of Pb and CO(3), and layer B is composed of Pb and OH. The stacking sequence is ...BAABAA...