Les oxydes de chrome dans les pigments et les décors de porcelaine

Chromium oxides are widely used in the ceramic industry because they are characterized by a large variety of colors. At the French porcelain manufacture of Sèvres, their coloring properties have been explored since the discovery of chromium at the end of the 18th century. The researches initiated by Brongniart lead to a group of 76 pigments for porcelain composed of chromium oxides, regularly synthesized at the laboratory of the manufacture. An exhaustive study was done on these pigments, which enables to propose a classification based on their mineralogical analysis and highlights the role of Cr3+ in the color of the pigments, without Cr6+. The mixture of one or two pigments and an uncolored frit is applied on the porcelain, and fired at high temperature to obtain a glaze, i.e. a partly glassy decorative layer on the top of the porcelain. Pigments composed of chromium are used to obtain green, pink, greenish-blue, brown and black glazes. This thesis focuses on a particular pigment, mainly composed of gahnite doped with chromium ZnAl2O4:Cr3+. This kind of pigment was identified in a collection of artefacts produced by the manufacture between the end of the 19th century and the beginning of the 20th century. This period corresponds to the artistic movement Art Nouveau. The solid solution ZnAl2-xCrxO4 was studied to get the structural environment of Cr, showing the role of the second neighbor Cr in the color variation. During firing of the glaze, a mechanism of gradual dissolution of the initial grains of pigments was determined, resulting of reactions with the uncolored frit. Our work shows the low solubility of Cr in glass and its preferential speciation in crystals, leading to crystalline phase changes or modifications of composition along solid solutions during the thermal treatment at high temperature. These modifications enable to understand the origin of color in porcelain glazes and the mechanism of glaze formation.Les oxydes de chrome permettent d’obtenir une large variété de couleurs, conduisant à leur utilisation répandue dans les arts céramiques. À la manufacture de Sèvres, leurs propriétés colorantes ont été explorées dès la découverte du chrome à la fin du 18ème siècle. Les travaux initiés par Brongniart ont conduit à une série de 76 pigments pour porcelaine composés d’oxydes de chrome, régulièrement synthétisés au laboratoire de la manufacture. Nous avons mené une étude exhaustive de ces pigments, permettant une classification basée sur leur analyse minéralogique et mettant en évidence le rôle du Cr3+ dans ces pigments, avec l’absence de Cr6+. Le mélange de ces pigments avec un composant incolore est appliqué sur la porcelaine, et porté à haute température afin d’obtenir un émail, c’est-à-dire une couche décorative partiellement vitreuse à la surface de la porcelaine. Les pigments composés de chrome se retrouvent dans les décors verts, roses, bleu-vert, marron et noirs. Après avoir caractérisé la spéciation et l’environnement du chrome dans l’ensemble de ces pigments, cette thèse s’est concentrée sur un pigment particulier, majoritairement composé de gahnite au chrome ZnAl2O4:Cr3+. Ce type de pigment a été identifié dans une série d’œuvres produites par la manufacture, entre la fin du 19ème et le début du 20ème siècle, correspondant à la période de l’art nouveau. La solution solide complète ZnAl2-xCrxO4 a été étudiée afin de préciser l’environnement structural du chrome, montrant l’importance des seconds voisins Cr dans les variations de couleur. Au cours de la cuisson de l’émail, un mécanisme de dissolution progressive des grains de pigments a été mis en évidence, résultant de l’interaction avec le composant incolore en cours de vitrification. Notre travail montre la faible solubilité du Cr dans le verre et sa spéciation préférentielle dans les cristaux, entrainant parfois des changements de phases ou des modifications de composition le long de solutions solides lors du traitement thermique à haute température. Ces modifications ont permis de mieux comprendre l’origine de la couleur dans les décors de porcelaine ainsi que les mécanismes de formation des émaux

Sodium electrochemical deintercalation and intercalation in O3-NaRhO2 and P2-NaxRhO2 layered oxides

International audienceSodium transition metal layered oxides are a class of materials which exhibits fascinating properties, such as high thermoelectric power. Whereas most of the work conducted so far focused on 3d transition metals, mainly cobalt, compounds with 4d metals could be excellent materials to obtain new strongly correlated electron systems. This work is focused on NaxRhO2 compounds, with O3- and P2-type structures. The P2-type structure was obtained by ion exchange from the potassium phase P2-K0.62RhO2. This type of synthesis was conducted here for the first time on layered oxides with 4d transition metals. The phase diagram of both structures was explored by sodium electrochemical deintercalation/intercalation in a battery. The existence of single phases was shown with presumably different physical properties. As an example, the O′3-Na1/2RhO2 compound electrochemically obtained for the first time exhibits a metallic behavior, whereas the O3-NaRhO2 phase is a semiconductor. The synthesis of each single phase existing in both the O3- and P2-type systems should lead to new insights into the structure-properties relationships of this class of materials

Chromium oxides in pigments and glazes for porcelain decoration

Les oxydes de chrome permettent d’obtenir une large variété de couleurs, conduisant à leur utilisation répandue dans les arts céramiques. À la manufacture de Sèvres, leurs propriétés colorantes ont été explorées dès la découverte du chrome à la fin du 18ème siècle. Les travaux initiés par Brongniart ont conduit à une série de 76 pigments pour porcelaine composés d’oxydes de chrome, régulièrement synthétisés au laboratoire de la manufacture. Nous avons mené une étude exhaustive de ces pigments, permettant une classification basée sur leur analyse minéralogique et mettant en évidence le rôle du Cr3+ dans ces pigments, avec l’absence de Cr6+. Le mélange de ces pigments avec un composant incolore est appliqué sur la porcelaine, et porté à haute température afin d’obtenir un émail, c’est-à-dire une couche décorative partiellement vitreuse à la surface de la porcelaine. Les pigments composés de chrome se retrouvent dans les décors verts, roses, bleu-vert, marron et noirs. Après avoir caractérisé la spéciation et l’environnement du chrome dans l’ensemble de ces pigments, cette thèse s’est concentrée sur un pigment particulier, majoritairement composé de gahnite au chrome ZnAl2O4:Cr3+. Ce type de pigment a été identifié dans une série d’œuvres produites par la manufacture, entre la fin du 19ème et le début du 20ème siècle, correspondant à la période de l’art nouveau. La solution solide complète ZnAl2-xCrxO4 a été étudiée afin de préciser l’environnement structural du chrome, montrant l’importance des seconds voisins Cr dans les variations de couleur. Au cours de la cuisson de l’émail, un mécanisme de dissolution progressive des grains de pigments a été mis en évidence, résultant de l’interaction avec le composant incolore en cours de vitrification. Notre travail montre la faible solubilité du Cr dans le verre et sa spéciation préférentielle dans les cristaux, entrainant parfois des changements de phases ou des modifications de composition le long de solutions solides lors du traitement thermique à haute température. Ces modifications ont permis de mieux comprendre l’origine de la couleur dans les décors de porcelaine ainsi que les mécanismes de formation des émaux.Chromium oxides are widely used in the ceramic industry because they are characterized by a large variety of colors. At the French porcelain manufacture of Sèvres, their coloring properties have been explored since the discovery of chromium at the end of the 18th century. The researches initiated by Brongniart lead to a group of 76 pigments for porcelain composed of chromium oxides, regularly synthesized at the laboratory of the manufacture. An exhaustive study was done on these pigments, which enables to propose a classification based on their mineralogical analysis and highlights the role of Cr3+ in the color of the pigments, without Cr6+. The mixture of one or two pigments and an uncolored frit is applied on the porcelain, and fired at high temperature to obtain a glaze, i.e. a partly glassy decorative layer on the top of the porcelain. Pigments composed of chromium are used to obtain green, pink, greenish-blue, brown and black glazes. This thesis focuses on a particular pigment, mainly composed of gahnite doped with chromium ZnAl2O4:Cr3+. This kind of pigment was identified in a collection of artefacts produced by the manufacture between the end of the 19th century and the beginning of the 20th century. This period corresponds to the artistic movement Art Nouveau. The solid solution ZnAl2-xCrxO4 was studied to get the structural environment of Cr, showing the role of the second neighbor Cr in the color variation. During firing of the glaze, a mechanism of gradual dissolution of the initial grains of pigments was determined, resulting of reactions with the uncolored frit. Our work shows the low solubility of Cr in glass and its preferential speciation in crystals, leading to crystalline phase changes or modifications of composition along solid solutions during the thermal treatment at high temperature. These modifications enable to understand the origin of color in porcelain glazes and the mechanism of glaze formation

Couleurs et émaux. Des décors de la Manufacture de Sèvres à la réactivité des pigments

International audienceUn décor de porcelaine est obtenu à l’aide de mélanges de pigments et de composants incolores qui, en se vitrifiant, fixent l’émail à la surface de l’objet et révèlent ainsi la couleu.Cet article s’intéresse à la stabilité d’un pigment de type spinelle au cours de la cuisson du décor. La caractérisation d’un grain de ce pigment par microscopie électronique, spectroscopie optique et absorption des rayons X, a permis de montrer que le changement de couleur parfois observé après cuisson résulte d’un enrichissement en chrome de la périphérie des grains de spinelle

La réactivité des pigments composés de chrome dans un décor de porcelaine

International audienceThis paper presents a comprehensive investigation at the microscopic scale of various pigments composed of chromium from the French ‘Manufacture de Sèvres’ to establish the origin of color in glazes. Electron microscopy coupled with X-ray diffraction allows the determination of the microstructure and composition of the crystalline phases after firing. X-ray absorption spectroscopy reveals subtle changes in the medium-range ordering around Cr with high spatial resolution, in the pigment grain or at the pigment/glass interface. Principal results indicate systematic and common changes whatever the pigment types: (i) Cr-enrichment for the final crystals, that controls the coloration of the glaze, (ii) migration of specific elements such as Al or Zn from the pigments to the amorphous part of the glaze, and (iii) crystallization of anorthite in the near proximity of the altered Cr-bearing crystalline pigments

Effect of Edge Charges on Stability and Aggregation of Ti₃C₂T_z MXene Colloidal Suspensions

International audienceHerein, the stabilities of aqueous Ti3C2Tz (MXene) colloidal suspensions were studied as a function of pH and sodium chloride concentrations using ς-potential and dynamic light scattering measurements. Complete sedimentation was observed when the pH was changed to 5 or 10. In the low pH regime, protons saturate the surface functional groups, rendering the ς-potential less negative that, in turn, leads to aggregation. In the high pH regime, the ς-potential remained constant up to a pH of almost 12. As the molarity of NaCl increases from 0 to 0.04, the ς-potential goes from −35 to −22.5 mV. At a molarity of 0.02, sedimentation was observed. When the pH or NaCl concentration is high, sedimentation occurred, presumably, because of a reduction in the double-layer thickness. In all cases, the sediment comprised crumpled Ti3C2Tz flakes. After adding charged nanoparticles to the colloidal suspension, at neutral pH, subsequent transmission electron microscope micrographs showed that the negative gold nanoparticles preferred the edges, whereas the positive ones preferred the surfaces. The charge differences between the edges and faces open opportunities for direct edge or face-specific organic functionalizations, similar to work done on other two-dimensional materials

Interaction between Cr-bearing pigments and transparent glaze: A transmission electron microscopy study

International audienceSpinel ZnAl2O4 and corundum Al2O3 doped with chromium are used as pink pigments in porcelain glazes. However, alteration of the color can occur during firing, and the resulting glaze appears brown and green respectively, instead of the expected pink. To investigate the mechanism of color change, electron transparent sections were prepared by Focused Ion Beam (FIB) at the interface between pigment and glaze. Observations under a transmission electron microscope (TEM) reveal a common mechanism for both systems. Al migration from the pigment toward the silicate melt results in alteration of the grain of pigments, and formation of a Cr enriched phase, with the same crystalline structure than the initial pigment. Furthermore, the formation of anorthite is reported, due to the increase of the local concentration of Al in the melt. The different morphologies of altered grains of pigment encountered in the glaze are discussed base on the TEM observations

Synthesis, properties and uses of chromium-based pigments from the Manufacture de Sèvres

International audienceChromium (Cr) is at the origin of a wide variety of coloration (green, pink and brown) in porcelain glazes from the French Manufacture de Sèvres. This element was introduced for the first time at the factory in 1804, just a few years after its discovery by Louis-Nicolas Vauquelin. Pigments for glazes were developed at the laboratory of the factory, leading to a palette of 76 references. While the synthesis protocol and the nature of the precursors of these pigments are kept in laboratory notebooks, the products have never been characterized. In this work, the pigments composed of Cr were characterized by X-ray diffraction (XRD), UV-visible spectroscopy and X-ray absorption near edge structure spectroscopy (XANES). The analyses reveal the presence of common crystalline phases, and open new perspectives for the synthesis of pigments containing chromium at the Manufacture de Sèvres

Mechanochemical synthesis and structural characterization of gallium sulfide Ga₂S₃

International audienceCrystalline gallium (III) sulfide Ga2S3 samples have been prepared by mechanical-alloying instead of usual heating process. A safe, energy-efficient, and fast process of only 4 h of mechanosynthesis led to the formation of polycrystalline Ga2S3 from pure Ga and S as raw materials. X-ray diffraction measurements and Rietveld refinements show that the as-prepared material is a mixture of mainly hexagonal wurtzite-type β-phase (68 ± 5 wt%; space group P63mc (No. 186)) along with some cubic sphalerite-type γ-phase (32 ± 5 wt%; space group F-43m (No. 216)). In situ high-temperature X-ray diffraction measurements show that the monoclinic phase (space group Cc (No. 9)) appears at 450 °C. Scanning electron microscopy analyses reveal that the morphology of the powder is characterized by aggregates of nanometric particles. Their sizes measured by laser diffraction show a median size around 170 nm after 4 h of ball-milling