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1. Oxidation Behavior of the Skutterudite Material Yb0.2Co4Sb12

Author

Judith Monnier, Philippe Masschelein, Lionel Aranda, Patrice Berthod, Anne Dauscher, Nicolas David, Christophe Candolfi, Bertrand Lenoir, M. Benyahia, Richard Drevet, Driss Kenfaui, Eric Alleno, Institut Jean Lamour (IJL), Université de Lorraine (UL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ytterbium, Materials science, Oxide, chemistry.chemical_element, 02 engineering and technology, engineering.material, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 01 natural sciences, Redox, chemistry.chemical_compound, 0103 physical sciences, Thermoelectric effect, Oxidizing agent, Skutterudite, ComputingMilieux_MISCELLANEOUS, 010302 applied physics, Spinel, Metallurgy, Metals and Alloys, 021001 nanoscience & nanotechnology, Condensed Matter Physics, chemistry, Chemical engineering, 13. Climate action, Mechanics of Materials, engineering, Degradation (geology), 0210 nano-technology
Abstract

The skutterudite materials belonging to the CoSb3 family are widely studied for thermoelectric applications. They are typically used under vacuum, but applications under oxidizing environments are increasingly considered. The addition of ytterbium is known to enhance the thermoelectric properties of CoSb3, but the corresponding impact on the oxidation behavior of the skutterudite material is barely explored. For that purpose, the present research describes the oxidation behavior of Yb0.2Co4Sb12 under a flow of air at 800 K for 15, 50, 100, and 1000 hours. The oxidation treatment induces the growth of a surface layer made of three oxides in various amounts as a function of the oxidation time. The spinel oxide CoSb2O4/CoO·Sb2O3 and CoSb2O6 are observed from 15 hours of oxidation, whereas Sb2O4 is formed only from 100 hours of treatment. To assess the impact of ytterbium, the oxidation behavior of Yb0.2Co4Sb12 is compared to that of CoSb3 oxidized in the same experimental conditions. The results show that the low amount of ytterbium promotes the oxidation reactions of the skutterudite material. Nonetheless, the impact on the degradation of the material remains acceptable to use Yb0.2Co4Sb12 for thermoelectric applications under oxidizing environments.

Published
2021
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2. Site Occupancy Determination in Th 2 Zn 17 - and TbCu 7 -types Sm 2 Fe 17– x Co x Compounds using Synchrotron Resonant Diffraction

Author

Erik Elkaim, Karine Provost, Jean-Marc Joubert, Thomas Bartoli, Valérie Paul-Boncour, Jacques Moscovici, Lotfi Bessais, Judith Monnier, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), and Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
inorganic chemicals, Diffraction, [PHYS]Physics [physics], 010405 organic chemistry, Rietveld refinement, chemistry.chemical_element, Thermal treatment, 010402 general chemistry, 01 natural sciences, Synchrotron, 0104 chemical sciences, law.invention, Inorganic Chemistry, Crystallography, Transition metal, chemistry, law, Mössbauer spectroscopy, Physical and Theoretical Chemistry, Cobalt, Earth (classical element), ComputingMilieux_MISCELLANEOUS
Abstract

Sm2Fe17 compounds are high-performance permanent magnets. Cobalt substitution allows us to further improve their magnetic properties. Depending on the thermal treatment, cobalt-substituted compounds can be synthesized either in the TbCu7 (disordered) or in the Th2Zn17 (ordered) structure type. Rietveld refinement of the number of transition metal dumbbells replacing rare-earth atoms from synchrotron powder diffraction data shows that the TbCu7 disordered structure has the same composition as the ordered one (a transition metal-to-rare earth ratio of 8.5). Then, cobalt site occupancies have been determined in both structures using synchrotron resonant (anomalous) diffraction. Cobalt is found to be absent from the dumbbell sites. The diffraction results are confirmed by Mossbauer spectroscopy.

Published
2021
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3. Improvement of reversible H storage capacity by fine tuning of the composition in the pseudo-binary systems A2-xLaxNi7 (A = Gd, Sm, Y, Mg)

Author

Judith Monnier, Véronique Charbonnier, Michel Latroche, Junxian Zhang, Nicolas Madern, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), and National Institute of Advanced Industrial Science and Technology (AIST)

Subjects
crystal structure, Materials science, Hydrogen, chemistry.chemical_element, FOS: Physical sciences, 02 engineering and technology, Crystal structure, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Hydrogen storage, Transition metal, Materials Chemistry, Alkaline earth metal, Condensed Matter - Materials Science, Rietveld refinement, Mechanical Engineering, Metals and Alloys, Materials Science (cond-mat.mtrl-sci), Sorption, Yttrium, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, thermodynamic tuning, Mechanics of Materials, Physical chemistry, 0210 nano-technology
Abstract

International audience; A2B7 compounds (A = rare earth or Mg, B = transition metal) are widely studied as active materials for negative electrode in Ni-MH batteries. By playing on the substitution rate of both A and B elements, it is possible to prepare various compositions. This strategy will help to improve the properties, for example get a higher reversible hydrogen capacity and a well-adapted hydrogen sorption pressure. Indeed, A can be almost all light rare earths (La to Gd), yttrium and alkaline earth metals (Mg or Ca), whereas B can contain various late transition metals (Mn to Ni). To understand the effects of composition on the physicochemical properties of La2Ni7-based compound, various pseudo-binary systems have been investigated: Gd2-xLaxNi7 (x = 0, 0.6, 1, 1.5), Sm2-xLaxNi7 (x = 0, 0.5, 1, 1.5), Y2-xLaxNi7 (x = 0, 0.4, 0.5, 0.6, 0.8, 1, 1.5, 1.75) and A0.5La1.1Mg0.4Ni7 (A = Sm, Gd and Y). To determine their crystallographic properties, X-ray diffraction analysis was performed followed by Rietveld refinement. Thermodynamic properties regarding reversible hydrogen sorption were investigated at room temperature. Quaternary compounds present drastically improved sorption properties in the frame of practical energy storage applications with reversible capacity equivalent to 400 mAh/g for the compound La1.1Sm0.5Mg0.4Ni7.

Published
2021
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4. Investigation of H Sorption and Corrosion Properties of Sm2MnxNi7−x (0 ≤ x < 0.5) Intermetallic Compounds Forming Reversible Hydrides

Author

Valérie Paul-Boncour, Nicolas Madern, Junxian Zhang, Michel Latroche, Véronique Charbonnier, Judith Monnier, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), and National Institute of Advanced Industrial Science and Technology (AIST)

Subjects
Control and Optimization, Materials science, Galvanic anode, Inorganic chemistry, Intermetallic, metallic hydrides, Energy Engineering and Power Technology, chemistry.chemical_element, Binary compound, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, lcsh:Technology, Corrosion, chemistry.chemical_compound, Hydrogen storage, magnetic measurements, Electrical and Electronic Engineering, Engineering (miscellaneous), Condensed Matter - Materials Science, rare earths, corrosion, Renewable Energy, Sustainability and the Environment, Nanoporous, lcsh:T, Ni-MH batteries, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Nickel, chemistry, Hydroxide, 0210 nano-technology, Energy (miscellaneous)
Abstract

Intermetallic compounds are key materials for energy transition as they form reversible hydrides that can be used for solid state hydrogen storage or as anodes in batteries. ABy compounds (A = Rare Earth (RE); B = transition metal; 2 < y < 5) are good candidates to fulfill the required properties for practical applications. They can be described as stacking of AB5 and AB2 sub-units along the c crystallographic axis. The latter sub-unit brings a larger capacity, while the former one provides a better cycling stability. However, ABy binaries do not show good enough properties for applications. Upon hydrogenation, they exhibit multiplateau behavior and poor reversibility, attributed to H induced amorphization. These drawbacks can be overcome by chemical substitutions on the A and/or the B sites leading to stabilized reversible hydrides. The present work focuses on the pseudo-binary Sm2MnxNi7-x system (0 0.3 leading to larger and flatter isotherm curves, allowing for reversible capacity >1.4 wt %. Regarding corrosion, the binary compound corrodes in alkaline medium to form rare earth hydroxide and nanoporous nickel. As for the Mn-substituted compounds, a new corrosion product is formed in addition to those above mentioned, as manganese initiates a sacrificial anode mechanism taking place at the early corrosion stage., Comment: Special Issue : Hydrogen Storage Properties of Materials

Published
2020
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5. Characterization of refractory steel oxidation at high temperature

Author

Jean-Marc Joubert, Rita Baddour-Hadjean, Antonin Steckmeyer, Judith Monnier, Nicolas Madern, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Chimie métallurgique des terres rares (CMTR), Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, General Chemical Engineering, Oxide, chemistry.chemical_element, 02 engineering and technology, Manganese, engineering.material, 01 natural sciences, [SPI.MAT]Engineering Sciences [physics]/Materials, Corrosion, chemistry.chemical_compound, 0103 physical sciences, [CHIM]Chemical Sciences, General Materials Science, ComputingMilieux_MISCELLANEOUS, 010302 applied physics, Austenite, Spinel, technology, industry, and agriculture, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Microstructure, Chromia, chemistry, Chemical engineering, engineering, Chromite, 0210 nano-technology
Abstract

The high temperature oxidation behavior of two highly alloyed refractory austenitic steels is studied at 1000 °C under air. Both short-term oxidation kinetics and long-term oxidation products are investigated. Structural, elemental and morphological analyses are coupled to characterize the oxide phases’ formation. Chromia and spinel are the main phases for both samples although they suffer important descaling after 4 weeks oxidation, but alloying elements are responsible for the formation of many other oxides. Microstructures are compared and discussed. New Raman spectra are reported for manganese chromite spinels. Their assignments are provided and discussed at the light of the proposed cationic distribution.

Published
2018
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6. Anisotropic Nanoporous Nickel Obtained through the Chemical Dealloying of Y 2 Ni 7 for the Comprehension of Anode Surface Chemistry of Ni‐ M H Batteries

Author

Christine Cachet-Vivier, Valérie Paul-Boncour, Judith Monnier, Junxian Zhang, Nicolas Madern, Stéphane Bastide, Michel Latroche, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), and Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chemistry, Nanoporous, Intermetallic, chemistry.chemical_element, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Corrosion, Anode, Nickel, Chemical engineering, 0210 nano-technology, Anisotropy, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2019
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7. Fast and scalable preparation of tetrahedrite for thermoelectrics via glass crystallization

Author

Annie Pradel, Gaëlle Delaizir, Julie Bourgon, C. Godart, Elsa B. Lopes, Bertrand Lenoir, Andrea Piarristeguy, Jean-Baptiste Vaney, Manuel F. C. Pereira, António Pereira Gonçalves, Eric Alleno, Judith Monnier, Instituto Superior Técnico Universidade de Lisboa (C2TN), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Axe 3 : organisation structurale multiéchelle des matériaux (SPCTS-AXE3), Science des Procédés Céramiques et de Traitements de Surface (SPCTS), Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM), Centro de Recursos Naturais e Ambiente (CERENA), Instituto Superior Técnico, Universidade Técnica de Lisboa (IST), Projet ANR, ANR-11-PRGE-0010,VTG,Verres et vitrocéramiques de chalcogénures en tant que matériaux thermoélectriques pour des applications autour de l'ambiante(2011), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), and Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Glass ceramics, Analytical chemistry, chemistry.chemical_element, 02 engineering and technology, engineering.material, 010402 general chemistry, 01 natural sciences, law.invention, Bismuth, Antimony, Thermoelectric manufacturing, law, Seebeck coefficient, Materials Chemistry, Crystallization, Waste heat recovery, Mechanical Engineering, Tetrahedrite, Metallurgy, Metals and Alloys, Low-cost thermoelectric materials, 021001 nanoscience & nanotechnology, Thermoelectric materials, Copper, Tetrahedrites, 0104 chemical sciences, chemistry, Mechanics of Materials, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], engineering, Melt spinning, 0210 nano-technology
Abstract

A Cu 12 Sb 3.6 Bi 0.4 S 10 Se 3 glass was prepared by melt spinning and crystallized by heat treatments at selected temperatures, the total preparation procedure taking less than one day. The sample characterization by powder X-ray diffraction, scanning and transmission electron microscopy complemented with EDS indicate the formation of compact materials, with a tetrahedrite relative weight fraction higher than 90% when treated at temperatures close to the crystallization peaks (∼200° C). Selenium enters the tetrahedrite structure, while bismuth precipitates in submicron and nanosized spherical shape phases depleted in copper and enriched in antimony, sulfur and selenium (when compared with the matrix composition). The characterization of electrical transport properties (electrical resistivity and Seebeck coefficient) indicate a behavior similar to that obtained by other methods on Cu 12 Sb 4 S 13 , with a maximum power factor of ∼400 μW/K 2 m at room temperature.

Published
2016
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8. Nanoscale investigation by TEM and STEM-EELS of the laser induced yellowing

Author

Marie Godet, Mandana Saheb, Nicolas Gauquelin, Judith Monnier, Eric Leroy, Julie Bourgon, Véronique Vergès-Belmin, Christine Andraud, Johan Verbeeck, Laboratoire de recherche des monuments historiques (LRMH), Centre de Recherche sur la Conservation (CRC ), Muséum national d'Histoire naturelle (MNHN)-Ministère de la Culture et de la Communication (MCC)-Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)-Ministère de la Culture et de la Communication (MCC)-Centre National de la Recherche Scientifique (CNRS), Centre de Recherche pour la Conservation des Collections (CRCC), Electron Microscopy for Materials Science - EMAT (Antwerp, Belgium), Universiteit Antwerpen [Antwerpen], Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Universiteit Antwerpen = University of Antwerpen [Antwerpen], Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)-Ministère de la Culture et de la Communication (MCC)-Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)-Ministère de la Culture et de la Communication (MCC), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), and Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Nanostructure, General Physics and Astronomy, 02 engineering and technology, Substrate (electronics), 01 natural sciences, law.invention, chemistry.chemical_compound, Crystallinity, Structural Biology, law, 0103 physical sciences, [CHIM]Chemical Sciences, General Materials Science, Irradiation, Magnetite, 010302 applied physics, Physics, Cell Biology, Hematite, 021001 nanoscience & nanotechnology, Laser, Chemistry, Chemical engineering, chemistry, Transmission electron microscopy, visual_art, visual_art.visual_art_medium, 0210 nano-technology
Abstract

International audience; Nd-YAG QS laser cleaning of soiled stone at 1064 nm can sometimes result in a more yellow appearance compared to other cleaning techniques. Especially in France, this yellowing effect is still considered as a major aesthetic issue by the architects and conservators. One explanation states that the yellowing is linked to the formation of iron-rich nanophase(s) through the laser beam interaction with black crusts that would re-deposit on the cleaned substrate after irradiation. To characterize these nanophases, a model crust containing hematite was elaborated and laser irradiated using a Nd-YAG QS laser. The color of the sample shifted instantaneously from red to a bright yellow and numerous particles were ablated in a visible smoke. Transmission electron microscopy (TEM) was used to examine the morphology and the crystallinity of the neo-formed compounds, both on the surface of the samples and in the ablated materials. In addition, an investigation of the chemical and structural properties of the nanophases was conducted by X-ray dispersive energy (EDX) and electron energy loss (EELS) spectroscopies. It was found that both the surface of the sample and the ablated materials are covered by crystallized nano-spheres and nano-residues, all containing iron and oxygen, sometimes along with calcium and sulfur. In particular an interfacial area containing the four elements was evidenced between some nanostructures and the substrate. Magnetite Fe3O4 was also identified at the nanoscale. This study demonstrates that the laser yellowing of a model crust is linked to the presence of iron-rich nanophases including CaxFeySzOδ nanostructures and magnetite Fe3O4 at the surface after irradiation.

Published
2018
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9. Effect of Ni, Bi and Se on the tetrahedrite formation

Author

Elsa B. Lopes, Benjamin Villeroy, António Pereira Gonçalves, Bertrand Lenoir, C. Godart, and Judith Monnier

Subjects
Materials science, Scanning electron microscope, General Chemical Engineering, Tetrahedrite, Analytical chemistry, chemistry.chemical_element, 02 engineering and technology, General Chemistry, engineering.material, 010402 general chemistry, 021001 nanoscience & nanotechnology, Microstructure, 01 natural sciences, 0104 chemical sciences, Crystallography, Differential scanning calorimetry, Antimony, chemistry, Phase (matter), Thermoelectric effect, engineering, 0210 nano-technology, Spectroscopy
Abstract

Materials based on Cu12Sb4S13 tetrahedrites have been seen in recent years as promising materials for thermoelectric applications. However, the effect of small amounts of additional elements (used to tune the electrical transport properties) on the formation of the phases was not investigated. In this work we present such study, by means of powder X-ray diffraction, scanning electron microscopy complemented with energy-dispersive spectroscopy, and differential scanning calorimetry, using the Taguchi method to design the experiments. The effect of Ni, Bi and Se (i) in the volume percentage of tetrahedrite, (ii) in the temperature at which the Class III (tetrahedrite + chalcostibite + antimony → skinnerite) reaction occurs and (iii) in the final melting temperature of Cu12−xNixSb4−yBiyS13−zSez materials rapidly cooled from 950 °C was investigated. Se was observed to have a strong positive influence on the formation of tetrahedrite, while Ni and Bi were seen to promote the decrease of its volume percentage. A decrease of the Class III reaction and final melting temperatures was also observed after the introduction of Se, with Ni inducing the increase of the reaction and the decrease of the melting temperatures and Bi having only minor effects. The analysis of the microstructures indicate that high Ni concentrations lead to the first solidification of the NiS phase, while in the other compositions the (tetrahedrite/skinnerite) phase or mixtures of phases is first formed.

Published
2016
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10. Stabilization of Metastable Thermoelectric Crystalline Phases by Tuning the Glass Composition in the Cu–As–Te System

Author

Gabriel J. Cuello, Christophe Candolfi, Gaëlle Delaizir, Julie Cornette, Jean-Baptiste Vaney, Judith Monnier, Andrea Piarristeguy, Vivian Nassif, Annie Pradel, António Pereira Gonçalves, Romain Viennois, Eric Alleno, Bertrand Lenoir, Elsa B. Lopes, Cédric Morin, Julie Carreaud, Maggy Colas, Mickaël Bigot, Institut Jean Lamour (IJL), Université de Lorraine (UL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), IRCER - Axe 3 : organisation structurale multiéchelle des matériaux (IRCER-AXE3), Institut de Recherche sur les CERamiques (IRCER), Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Instituto Superior Técnico, Universidade Técnica de Lisboa (IST), Institut Laue-Langevin (ILL), ILL, CRG et Grands Instruments (CRG ), Institut Néel (NEEL), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chemistry, Scanning electron microscope, Analytical chemistry, Recrystallization (metallurgy), 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Microstructure, 01 natural sciences, 0104 chemical sciences, Amorphous solid, Inorganic Chemistry, symbols.namesake, Condensed Matter::Materials Science, visual_art, Thermoelectric effect, symbols, visual_art.visual_art_medium, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Ceramic, Physical and Theoretical Chemistry, 0210 nano-technology, Ternary operation, Raman scattering
Abstract

International audience; Recrystallization of amorphous compounds can lead to the stabilization of metastable crystalline phases, which offers an interesting way to unveil novel binary or ternary compounds and control the transport properties of the obtained glass ceramics. Here, we report on a systematic study of the Cu–As–Te glassy system and show that under specific synthesis conditions using the spark-plasma-sintering technique, the α-As2Te3 and β-As2Te3 binary phases and the previously unreported AsTe3 phase can be selectively crystallized within an amorphous matrix. The microstructures and transport properties of three different glass ceramics, each of them containing one of these phases with roughly the same crystalline fraction (∼30% in volume), were investigated in detail by means of X-ray diffraction, scanning electron microscopy, neutron thermodiffraction, Raman scattering (experimental and lattice-dynamics calculations), and transport-property measurements. The physical properties of the glass ceramics are compared with those of both the parent glasses and the pure crystalline phases that could be successfully synthesized. SEM images coupled with Raman spectroscopy evidence a “coast-to-island” or dendriticlike microstructure with microsized crystallites. The presence of the crystallized phase results in a significant decrease in the electrical resistivity while maintaining the thermal conductivity to low values. This study demonstrates that new compounds with interesting transport properties can be obtained by recrystallization, which in turn provides a tuning parameter for the transport properties of the parent glasses.

Published
2018
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11. Spark plasma sintering and hydrogen pre-annealing of copper nanopowder

Author

Benjamin Villeroy, Yannick Champion, C. Godart, Loïc Perrière, and Judith Monnier

Subjects
Materials science, Annealing (metallurgy), Scanning electron microscope, Mechanical Engineering, Metallurgy, Oxide, Sintering, chemistry.chemical_element, Spark plasma sintering, Condensed Matter Physics, Microstructure, Copper, Grain growth, chemistry.chemical_compound, chemistry, Mechanics of Materials, General Materials Science
Abstract

Copper nanopowders were sintered using Spark Plasma Sintering (SPS). Special attention was paid to the presence of natural surface oxide and reductive thermal treatments under H 2 atmosphere were carried out to remove it. The sintering mechanisms were investigated by the means of disrupted experiments at various temperatures to reach different shrinkage rates. Optimized experiments were also carried out to reach a maximum densification. The samples were characterized and compared using density measurement, X-ray diffraction, mechanical tests (tension and compression) and analysis of the fracture surfaces with scanning electron microscope. On the one hand, it results that during the SPS treatment, the raw powder undergoes a series of oxide transformations from CuO to Cu 2 O. On the other hand, reductive treatment drastically decreases the sintering temperature, from 650 °C to 260 °C, to reach 90% density without grain growth. Higher mechanical strength, up to 750 MPa, also shows better consolidation.

Published
2015
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12. Thermoelectric properties and stability of glasses in the Cu-As-Te system

Author

Christophe Candolfi, Raphaël Escalier, Maggy Colas, Gaëlle Delaizir, Julie Carreaud, Bertrand Lenoir, António Pereira Gonçalves, Annie Pradel, Rozenn Le Parc, Michel Ribes, Judith Monnier, Jean-Baptiste Vaney, Andrea Piarristeguy, Cédric Morin, Eric Alleno, Julie Cornette, Elsa B. Lopes, Institut Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Science des Procédés Céramiques et de Traitements de Surface (SPCTS), Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Instituto Superior Técnico Universidade de Lisboa (C2TN), ANR-11-PRGE-0010,VTG,Verres et vitrocéramiques de chalcogénures en tant que matériaux thermoélectriques pour des applications autour de l'ambiante(2011), Université de Lorraine (UL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM), and Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Chalcogenide, Spark plasma sintering, 02 engineering and technology, 01 natural sciences, law.invention, symbols.namesake, chemistry.chemical_compound, Differential scanning calorimetry, Thermal conductivity, law, 0103 physical sciences, Thermoelectric effect, Materials Chemistry, Crystallization, glass, 010302 applied physics, 021001 nanoscience & nanotechnology, Thermoelectric materials, thermoelectric properties, chemistry, Chemical physics, Ceramics and Composites, symbols, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], chalcogenides, 0210 nano-technology, Raman spectroscopy
Abstract

International audience; Chalcogenide glasses and more importantly their glass-ceramics counterparts have been an interesting but very peculiar class of thermoelectric materials, with inherently low thermal conductivity (

Published
2017
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13. Effect of Air Annealing on the Structural and Magnetic Properties of LaMnO3 Perovskite Produced by Reactive Spark Plasma Sintering Route

Author

Y. Regaieg, Mohamed Koubaa, A. Cheikhrouhou, Judith Monnier, G. Delaizir, Benjamin Villeroy, C. Godart, L. Sicard, Frédéric Herbst, and S. Ammar-Merah

Subjects
Materials science, Rietveld refinement, Analytical chemistry, Spark plasma sintering, Condensed Matter Physics, Electronic, Optical and Magnetic Materials, Magnetization, chemistry.chemical_compound, Lanthanum manganite, chemistry, Antiferromagnetism, Néel temperature, Powder diffraction, Perovskite (structure)
Abstract

Perovskite-type lanthanum manganite (LaMnO3) was synthesized from Mn2O3 and La2O3 precursor powders using the Spark Plasma Sintering technique (SPS). The in situ reaction proceeds in a few minutes at 1000 °C under 50 MPa with a very high heating rate of 100 °C/min. The Rietveld refinement of the X-ray powder diffraction shows that LaMnO3 sample crystallizes in a perovskite structure of O′-type orthorhombic symmetry with Pbnm space group. After annealing at 1000 °C in air for 10 hrs, the symmetry changes to rhombohedral with R-3c space group. For the as prepared sample, two critical temperature points in the temperature dependence of the ZFC and FC magnetization occurring at 125 K and 145 K are observed. They are suggested to be related to A-type antiferromagnetic Neel temperature and ferromagnetic short range order, respectively. The ferromagnetic component in the annealed sample increases indicating the expected variation in the concentration of Mn3+ and Mn4+ ions, which was attributed to the oxygen stoichiometry effects.

Published
2013
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14. Relationship between H2 sorption properties and aqueous corrosion mechanisms in A2Ni7 hydride forming alloys (A = Y, Gd or Sm)

Author

Lionel Goubault, Suzanne Joiret, Valérie Paul-Boncour, Judith Monnier, B. Puga, Junxian Zhang, Véronique Charbonnier, Patrick Bernard, Michel Latroche, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interfaces et Systèmes Electrochimiques (LISE), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), SAFT [Bordeaux], Société des accumulateurs fixes et de traction (SAFT), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)

Subjects
Magnetic Measurements, Materials science, Hydrogen, Intermetallic, Energy Engineering and Power Technology, chemistry.chemical_element, Raman Micro-spectroscopy, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 7. Clean energy, 01 natural sciences, Corrosion, Metal, Crystallinity, [CHIM]Chemical Sciences, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, Renewable Energy, Sustainability and the Environment, Hydride, Metallurgy, Ni-MH batteries, 021001 nanoscience & nanotechnology, Metallic hydrides, 0104 chemical sciences, Chemical engineering, Electron diffraction, chemistry, 13. Climate action, visual_art, visual_art.visual_art_medium, TEM, 0210 nano-technology, [CHIM.OTHE]Chemical Sciences/Other
Abstract

International audience; Intermetallic compounds A 2 B 7 (A = rare earth, B = transition metal) are of interest for Ni‐MH batteries. Indeed they are able to absorb hydrogen reversibly and exhibit good specific capacity in electrochemical route. To understand the effect of rare earth on properties of interest such as thermodynamic, cycling stability and corrosion, we synthesized and studied three compounds: Y 2 Ni 7 , Gd 2 Ni 7 and Sm 2 Ni 7. Using Sieverts' method, we plot pc‐isotherms up to 10 MPa and study hydride stability upon solid‐gas cycling. Electrochemical cycling was also performed, as well as calendar and cycling corrosion study. Corrosion products were characterized by means of X‐ray diffraction, electron diffraction, Raman micro‐spectroscopy and scanning and transmission electron microscopies. Magnetic measurements were also performed to calculate corrosion rates. A corrosion mechanism, based on the nature of corrosion products, is proposed. By combining results from solid‐ gas cycling, electrochemical cycling and corrosion study, we attribute the loss in capacity either to corrosion or loss of crystallinity.

Published
2016
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15. Investigation of the Mechanisms Involved in the Sintering of Chalcogenide Glasses and the Preparation of Glass-Ceramics by Spark Plasma Sintering

Author

Mathieu Hubert, Gaëlle Delaizir, Xianghua Zhang, Yann Gueguen, Laurent Calvez, C. Godart, Judith Monnier, Axe 3 : organisation structurale multiéchelle des matériaux (SPCTS-AXE3), Science des Procédés Céramiques et de Traitements de Surface (SPCTS), Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM), LAboratoire de Recherche en Mécanique Appliquée (LARMAUR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Chalcogenide, Sintering, Spark plasma sintering, Chalcogenide glass, Space, 02 engineering and technology, Porous glass, 01 natural sciences, chemistry.chemical_compound, 0103 physical sciences, Materials Chemistry, [CHIM]Chemical Sciences, Ceramic, 010302 applied physics, Metallurgy, Optics, 021001 nanoscience & nanotechnology, Amorphous solid, Devitrification, chemistry, Transparent, visual_art, Transition, Ceramics and Composites, visual_art.visual_art_medium, Crystallization, 0210 nano-technology
Abstract

International audience; The sintering of the 80GeSe2-20Ga2Se3 chalcogenide glass composition as well as the preparation of the corresponding glass-ceramics has been investigated using pulsed current electrical sintering also known as spark plasma sintering. Amorphous powder has been synthesized by mechanical alloying. Due to the electrical insulating property of this glass composition, powder is heated mostly through the heating of the graphite die. It was found that densification of glass powder occurs through a viscous flow mechanism prior to devitrification. A model has been successfully applied to determine the viscosity and activation energy of the glass. This model has been confirmed by ball penetration technique to determine the glass sample viscosity.

Published
2012
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16. Localisation of oxygen reduction sites in the case of iron long term atmospheric corrosion

Author

Ivan Guillot, Philippe Dillmann, Emilien Burger, Delphine Neff, Pascal Berger, and Judith Monnier

Subjects
Carbon steel, Chemistry, General Chemical Engineering, Metallurgy, General Chemistry, engineering.material, Chemical reaction, Oxygen reduction, Corrosion, Ferrous, Cathodic reaction, Atmospheric corrosion, Homogeneous, engineering, General Materials Science
Abstract

In different fields of civil engineering and cultural heritage, the corrosion behaviour of century old ferrous artefacts must be accurately evaluated, especially under uncontrolled conditions. This approach requires an understanding of the role played by the several hundred micrometre thick corrosion layers formed on ancient metals. Combining the study of historical mild steels and a new re-corroding experiment using isotopic tracers, we show here that mechanisms controlling corrosion kinetics differ according to the nature and the organisation of various microscopic phases, leading to a decoupling of anodic and cathodic reaction or to a homogeneous corrosion.

Published
2011
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17. Polymorphism in Thermoelectric As2Te3

Author

Judith Monnier, Bertrand Lenoir, Gabriel J. Cuello, Cédric Morin, Jean-Baptiste Vaney, Julie Carreaud, Eric Alleno, Annie Pradel, Serena Corallini, Gaëlle Delaizir, Elsa B. Lopes, Andrea Piarristeguy, Vivian Nassif, Christophe Candolfi, Jean-Claude Crivello, António Pereira Gonçalves, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Axe 3 : organisation structurale multiéchelle des matériaux (SPCTS-AXE3), Science des Procédés Céramiques et de Traitements de Surface (SPCTS), Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM), Institut Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Department of Quimica, ITN, ITN, Portugal, CRG et Grands Instruments (CRG), Institut Néel (NEEL), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF), Institut Laue-Langevin (ILL), ILL, ANR-11-PRGE-0010,VTG,Verres et vitrocéramiques de chalcogénures en tant que matériaux thermoélectriques pour des applications autour de l'ambiante(2011), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)

Subjects
Phase transition, Chemistry, Calorimetry, Crystal structure, Inorganic Chemistry, Crystallography, symbols.namesake, Polymorphism (materials science), Thermoelectric effect, symbols, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Physical and Theoretical Chemistry, van der Waals force, Isostructural, Monoclinic crystal system
Abstract

International audience; Metastable β-As2Te3 (R3̅m, a = 4.047 Å and c =29.492 Å at 300 K) is isostructural to layered Bi2Te3 and is known for similarly displaying good thermoelectric properties around 400 K. Crystallizing glassy-As2Te3 leads to multiphase samples, while β-As2Te3 could indeed be synthesized with good phase purity (97%) by melt quenching. As expected, β-As2Te3 reconstructively transforms into stable α-As2Te3 (C2/m, a = 14.337 Å, b = 4.015 Å, c = 9.887 Å, and β = 95.06°) at 480 K. This β → α transformation can be seen as the displacement of part of the As atoms from their As2Te3 layers into the van der Waals bonding interspace. Upon cooling, β-As2Te3 displacively transforms in two steps below TS1 = 205−210 K and TS2 = 193−197 K into a new β′ As2Te3 allotrope. These reversible and first-order phase transitions give rise to anomalies in the resistance and in the calorimetry measurements. The new monoclinic β′-As2Te3 crystal structure (P21/m, a = 6.982 Å, b = 16.187 Å, c = 10.232 Å, β = 103.46° at 20 K) was solved from Rietveld refinements of X-ray and neutron powder patterns collected at low temperatures. These analyses showed that the distortion undergone by β-As2Te3 is accompanied by a 4-fold modulation along its b axis. In agreement with our experimental results, electronic structure calculations indicate that all three structures are semiconducting with the α-phase being the most stable one and the β′-phase being more stable than the β-phase. These calculations also confirm the occurrence of a van der Waals interspace between covalently bonded As2Te3 layers in all three structures.

Published
2015
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18. Structural and Hydrogen Storage Properties of Y2Ni7 Deuterides Studied by Neutron Powder Diffraction

Author

Virginie Serin, César Magén, Judith Monnier, Junxian Zhang, Lionel Goubault, Véronique Charbonnier, Patrick Bernard, Michel Latroche, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), SAFT, Direction de la Recherche, Université de Bordeaux (UB), University of Zaragoza - Universidad de Zaragoza [Zaragoza], Centre d'élaboration de matériaux et d'études structurales (CEMES), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Institut National des Sciences Appliquées (INSA)-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées (INSA)-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Diffraction, Hydrogen capacities, Hydrogen, X ray diffraction, Absorption cycles, Neutron diffraction, Analytical chemistry, chemistry.chemical_element, 02 engineering and technology, Crystal structure, Hydrogen storage properties, 010402 general chemistry, 01 natural sciences, Hydrogen storage, Nickel, TheoryofComputation_ANALYSISOFALGORITHMSANDPROBLEMCOMPLEXITY, Plateau pressures, ComputingMethodologies_SYMBOLICANDALGEBRAICMANIPULATION, Dehydrogenation, Physical and Theoretical Chemistry, Deuterium compounds, Room temperature, Neutrons, [PHYS]Physics [physics], Structural properties, Cobalt, States of charges, Neutron powder diffraction, 021001 nanoscience & nanotechnology, Unit cell parameters, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, Hydrogenation properties, General Energy, chemistry, Deuterium, 0210 nano-technology, Powder diffraction, MathematicsofComputing_DISCRETEMATHEMATICS
Abstract

cited By 4; International audience; The crystal structure and hydrogenation properties of Gd2Co7-type Y2Ni7 were investigated by X-ray diffraction (XRD), Sievert's method, and neutron powder diffraction. Unlike Nd2Ni7 and La2Ni7, Y2Ni7 exhibits three plateau pressures and forms three hydrides at room temperature. The maximum hydrogen capacity reaches 8.9 H/fu at 10 MPa at the first absorption cycle. The compound can be cycled by a solid-gas route, and structural properties are fully recovered after dehydrogenation. For the first time, the structural properties of rhombohedral A2B7Dx deuterides were studied. They were investigated by neutron powder diffraction at three different states of charge (x = 2.1, 4.1, and 8.8). Deuterium positions as well as variation of unit cell parameters are given and discussed in this paper. (Figure Presented).

Published
2015
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19. Identification of a new pseudo-binary hydroxide during calendar corrosion of (La, Mg)2Ni7-type hydrogen storage alloys for Nickel-Metal Hydride batteries

Author

H. Chen, Michel Latroche, Julie Bourgon, Suzanne Joiret, Judith Monnier, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interfaces et Systèmes Electrochimiques (LISE), Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Inorganic chemistry, Energy Engineering and Power Technology, chemistry.chemical_element, Raman micro spectroscopy, Corrosion, Metal, Hydrogen storage, chemistry.chemical_compound, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, Electrode material, Renewable Energy, Sustainability and the Environment, Hydride, Nanoporous, Metallurgy, Ni-MH batteries, Combination of techniques, Nickel, chemistry, visual_art, visual_art.visual_art_medium, TEM, Hydroxide, [CHIM.OTHE]Chemical Sciences/Other
Abstract

International audience; To improve the performances of Nickel-Metal Hydride batteries, an important step is the understanding of the corrosion processes that take place in the electrode material. In particular, the present study focuses for the first time on the model (La, Mg)2Ni7 system. The calendar corrosion in 8.7 M KOH medium was investigated from 6 h to 16 weeks immersion. By a unique combination of structural and elemental characterisations, the corrosion products are evidenced in those systems. In particular, we demonstrate that Ni and Mg combine in a pseudo-binary hydroxide Mg1−xNix(OH)2 whereas La corrodes into nanoporous La(OH)3 needles with inner hollow nanochannels.

Published
2014
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20. XAS and XRD in situ characterisation of reduction and reoxidation processes of iron corrosion products involved in atmospheric corrosion

Author

Ivan Guillot, Eddy Foy, Mandana Saheb, Denis Testemale, Judith Monnier, Philippe Dillmann, Solenn Reguer, François Mirambet, Laboratoire Pierre Süe (LPS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre d'Etude de Saclay, Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Matériaux, Rayonnements, Structure (MRS), Institut Néel (NEEL), Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS), Centre de recherche et de restauration des musées de France (C2RMF), Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture et de la Communication (MCC), Laboratoire Archéomatériaux et Prévision de l'Altération (LAPA - UMR 3685), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de Recherches sur les Archéomatériaux (IRAMAT), Université de Technologie de Belfort-Montbeliard (UTBM)-Université d'Orléans (UO)-Université Bordeaux Montaigne-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Matériaux, Rayonnements, Structure (NEEL - MRS), Ministère de la Culture et de la Communication (MCC)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Technologie de Belfort-Montbeliard (UTBM)-Université d'Orléans (UO)-Université Bordeaux Montaigne (UBM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), and Université d'Orléans (UO)-Université de Technologie de Belfort-Montbeliard (UTBM)-Centre National de la Recherche Scientifique (CNRS)-Université Bordeaux Montaigne

Subjects
X-ray absorption spectroscopy, Materials science, 020209 energy, General Chemical Engineering, [SDE.MCG]Environmental Sciences/Global Changes, Inorganic chemistry, Maghemite, 02 engineering and technology, General Chemistry, engineering.material, 021001 nanoscience & nanotechnology, Corrosion, Electrochemical cell, Ferrihydrite, chemistry.chemical_compound, chemistry, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, 0202 electrical engineering, electronic engineering, information engineering, engineering, General Materials Science, Lepidocrocite, 0210 nano-technology, Iron(II) hydroxide, ComputingMilieux_MISCELLANEOUS, Magnetite
Abstract

An electrochemical cell has been used for performing in situ X-ray diffraction and absorption spectroscopy structural characterisation by transmission during electrochemical measurements. This cell has been used to reduce lepidocrocite and ferrihydrite, two iron oxides involved in low-carbon steel atmospheric corrosion mechanisms. The reduced phases have been identified in situ as magnetite and iron II hydroxide, two phases that can play a key role in corrosion mechanisms. The reoxidation of the reduced phases was also studied, and lead to the formation of magnetite/maghemite and to the formation of the initial reducible phases lepidocrocite and ferrihydrite.

Published
2014
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21. Thermal stability and thermoelectric properties of CuxAs40−xTe60−ySey semiconducting glasses

Author

António Pereira Gonçalves, Jean-Baptiste Vaney, Eric Alleno, Christophe Candolfi, Andrea Piarristeguy, Annie Pradel, Anne Dauscher, Michel Ribes, Gaëlle Delaizir, Claude Godart, Elsa B. Lopes, Judith Monnier, Bertrand Lenoir, Institut Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Instituto Tecnológico e Nuclear, Instituto Superior Técnico, Universidade Técnica de Lisboa (IST), Axe 3 : organisation structurale multiéchelle des matériaux (SPCTS-AXE3), Science des Procédés Céramiques et de Traitements de Surface (SPCTS), Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Chalcogenide, Analytical chemistry, Mineralogy, Chalcogenide glass, 02 engineering and technology, Thermoelectric Materials at room temperature, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, Thermal conductivity, Thermoelectric effect, Materials Chemistry, Thermal stability, Physical and Theoretical Chemistry, X-ray spectroscopy, Glassy semiconductors, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Thermoelectric materials, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, chemistry, 13. Climate action, Content (measure theory), Ceramics and Composites, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology
Abstract

We report on the thermal behavior and thermoelectric properties of bulk chalcogenide glasses in the systems Cu{sub x}As{sub 40−x}Te{sub 60} (20≤x≤32.5) and Cu{sub x}As{sub 40−x}Te{sub 60−y}Se{sub y}, (0≤y≤9) synthesized by conventional melt-quenching techniques. The thermal stability of these glasses was probed by differential scanning calorimetry to determine the characteristic T{sub g} and ΔT temperatures, both of which increasing noticeably with y. Thermoelectric properties were found to be mainly influenced by the Cu concentration with respect to the Se content. The thermal conductivity is practically composition-independent throughout the compositional range covered. A maximum ZT value of 0.02 at 300 K increasing to 0.06 at 375 K was achieved for the composition Cu{sub 30}As{sub 10}Te{sub 54}Se{sub 6}. - Graphical abstract: Effect of substitution of Te by Se and As by Cu on thermal stability and thermoelectric properties of Cu{sub x}As{sub 40−x}Te{sub 60−y}Se{sub y} semiconducting glasses. - Highlights: • We studied substitution of Te by Se in Cu–As–Te thermoelectric chalcogenide glasses. • Cu–As–Te–Se glasses were prepared by conventional melt-quenching method. • Se inclusion increases thermal stability in Cu–As–Te glasses. • Increasing copper concentration enhances thermoelectric properties. • ZT of 0.02 was achieved at 300 K and 0.06 at 375 K.

Published
2013
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22. Semiconducting glasses: A new class of thermoelectric materials?

Author

António Pereira Gonçalves, Annie Pradel, Andrea Piarristeguy, Bertrand Lenoir, Elsa B. Lopes, Claude Godart, Patrick Ochin, Judith Monnier, Jean-Baptiste Vaney, Gaëlle Delaizir, Instituto Tecnológico e Nuclear, Instituto Superior Técnico, Universidade Técnica de Lisboa (IST), Axe 3 : organisation structurale multiéchelle des matériaux (SPCTS-AXE3), Science des Procédés Céramiques et de Traitements de Surface (SPCTS), Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Chalcogenide, Mineralogy, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, Thermal conductivity, Electrical resistivity and conductivity, Thermal, Thermoelectric effect, Materials Chemistry, Physical and Theoretical Chemistry, High copper, Semiconducting glasses, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Thermoelectric materials, Engineering physics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, chemistry, Ceramics and Composites, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, Tellurium, Thermoelectric glasses
Abstract

International audience; The deeper understanding of the factors that affect the dimensionless figure of merit, ZT, and the use of new synthetic methods has recently led to the development of novel systems with improved thermoelectric performances. Albeit up to now with ZT values lower than the conventional bulk materials, semiconducting glasses have also emerged as a new family of potential thermoelectric materials. This paper reviews the latest advances on semiconducting glasses for thermoelectric applications. Key examples of tellurium-based glasses, with high Seebeck coefficients, very low thermal conductivities and tunable electrical conductivities, are presented. ZT values as high as 0.2 were obtained at room temperature for several tellurium-based glasses with high copper concentrations, confirming chalcogenide semiconducting glasses as good candidates for high-performance thermoelectric materials. However, the temperature stability and electrical conductivity of there ported glasses are still not good enough for practical applications and further studies are still needed to enhance them.

Published
2012
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23. An innovative approach to develop highly performant chalcogenide glasses and glass-ceramics transparent in the infrared range

Author

Gaëlle Delaizir, Judith Monnier, Xianghua Zhang, Hongli Ma, Laurent Calvez, Mathieu Hubert, Claude Godart, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Groupe d'Etudes des Matériaux Hétérogènes (GEMH), Université de Limoges (UNILIM)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Chalcogenide, Infrared, Mie scattering, Spark plasma sintering, Sintering, 02 engineering and technology, 7. Clean energy, 01 natural sciences, chemistry.chemical_compound, symbols.namesake, Optics, 0103 physical sciences, Ceramic, Rayleigh scattering, 010302 applied physics, business.industry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Atomic and Molecular Physics, and Optics, Amorphous solid, chemistry, visual_art, visual_art.visual_art_medium, symbols, Optoelectronics, 0210 nano-technology, business
Abstract

International audience; An innovative way to produce chalcogenide glasses and glass-ceramics for infrared devices is reported. This new method of synthesis at low temperature combining ball-milling and sintering by SPS (Spark Plasma Sintering) is a technological breakthrough to produce efficient infrared chalcogenide glasses and glass-ceramics. This technique will offer the possibility to strongly decrease the cost of infrared devices and to produce new chalcogenide glasses. It will also permit to increase the potential of some glass compositions by allowing their shaping at desired dimensions.

Published
2011
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24. Study of archaeological artefacts to refine the model of iron long-term indoor atmospheric corrosion

Author

Ludovic Bellot-Gurlet, Ivan Guillot, Delphine Neff, Eddy Foy, Ludovic Legrand, Solenn Reguer, Judith Monnier, François Mirambet, Stéphane Perrin, Emmanuel Rocca, Philippe Dillmann, Laboratoire Pierre Süe (LPS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement (LAMBE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Évry-Val-d'Essonne (UEVE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Dynamique Interactions et Réactivité (LADIR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie du solide minéral (LCSM), Université Paul Verlaine - Metz (UPVM)-Université Henri Poincaré - Nancy 1 (UHP)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherches sur les Archéomatériaux (IRAMAT), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Université Bordeaux Montaigne-Université de Technologie de Belfort-Montbeliard (UTBM), Laboratoire de recherche des monuments historiques (LRMH), Centre de Recherche sur la Conservation (CRC ), Muséum national d'Histoire naturelle (MNHN)-Ministère de la Culture et de la Communication (MCC)-Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)-Ministère de la Culture et de la Communication (MCC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Etude de la Corrosion Aqueuse (LECA), Service de la Corrosion et du Comportement des Matériaux dans leur Environnement (SCCME), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Département de Physico-Chimie (DPC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Université de Technologie de Belfort-Montbeliard (UTBM)-Université d'Orléans (UO)-Université Bordeaux Montaigne (UBM)-Centre National de la Recherche Scientifique (CNRS), and Université de Technologie de Belfort-Montbeliard (UTBM)-Université d'Orléans (UO)-Université Bordeaux Montaigne-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nuclear and High Energy Physics, Goethite, Akaganéite, XAS, 020209 energy, Iron, Mineralogy, 02 engineering and technology, engineering.material, Rust, Microscopic scale, Corrosion, Imaging, Synchrotron, [SPI.MAT]Engineering Sciences [physics]/Materials, Ferrihydrite, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, 0202 electrical engineering, electronic engineering, information engineering, General Materials Science, Lepidocrocite, Chemistry, Characterisation, X-ray absorption spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Archaeology, Term (time), Nuclear Energy and Engineering, visual_art, Raman spectroscopy, engineering, visual_art.visual_art_medium, 0210 nano-technology, Atmospheric corrosion
Abstract

International audience; The study of long-term indoor atmospheric corrosion is involved in the field of the interim storage of nuclear wastes. Indeed study of archaeological artefacts is one of the only mean to gather information on very long periods. Concerning ancient items, due to the complexity of the system, it is necessary to couple many analytical techniques from the macro to the microscopic scale. This enables to propose a description of the Amiens cathedral chain rust layers, made of a matrix of goethite, with lepidocrocite and akaganeite locally present and marbling of a poor crystallized phase associated to ferrihydrite. Electrochemical measurements permit to study the reduction capacity of the rust layer and to draw reduction mechanisms of the so-called active phases, by in situ experiments coupled with X-ray diffraction and X-ray absorption spectroscopy.

Published
2008
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25. X-ray absorption spectroscopy study of the various forms of phosphorus in ancient iron samples

Author

Delphine Vantelon, Philippe Dillmann, Judith Monnier, and Solenn Reguer

Subjects
X-ray absorption spectroscopy, Phosphorus, media_common.quotation_subject, Metallurgy, Inorganic chemistry, chemistry.chemical_element, Phosphate, XANES, Analytical Chemistry, Ferrous, Corrosion, chemistry.chemical_compound, Speciation, chemistry, Atmospheric corrosion, Spectroscopy, media_common
Abstract

Several ancient world heritage iron-based structures present quite good corrosion resistance that is generally related to the presence of phosphorus in their metallic substrate. However, the exact protection mechanisms have not yet been explained. In order to better understand the role of this element, in the conditions of atmospheric corrosion, both its distribution and speciation were investigated. To do so, a combination of microXRF and microXANES at the P K-edge was used, together with micro-Raman investigations. This methodology was applied on two types of ancient ferrous samples. For both types, two sources of phosphorus, global endogenous as well as localised exogenous were revealed. From these two sources, the phosphorus was seen to be heterogeneously distributed in the corrosion products. The shape of the XANES spectra demonstrated that the phosphorus is present as phosphate complexes with all the iron corrosion products present in the layers.

Published
2011
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