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56 results on '"Nanomatériaux pour l'Energie et le Recyclage (LNER)"'

1. Behavior of mesoporous silica under 2 MeV electron beam irradiation

Author: Jun Lin, Yannick Guari, Cyrielle Rey, Clara Grygiel, Jérémy Causse, Xavier Deschanels, Sandrine Dourdain, Guillaume Toquer, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), 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), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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 Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), and ANR-18-CE05-0016,AUTOMACT,SEPARATION SUR SOLIDE ET AUTOCONDITIONNEMENT D'ACTINIDES PROVENANT D'EFFLUENTS CONTAMINES(2018)
Subjects: Work (thermodynamics), Materials science, 02 engineering and technology, General Chemistry, Mesoporous silica, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Electron beam irradiation, Volume (thermodynamics), Chemical engineering, Mechanics of Materials, Cathode ray, [CHIM]Chemical Sciences, General Materials Science, 0210 nano-technology, Porosity, Mesoporous material, Damage effects, ComputingMilieux_MISCELLANEOUS
Abstract: This work deals with the evolution of the mesoporous structure of two silicas MCM-41 and SBA-15 under a 2 MeV electron beam as a function of the dose (0–5 GGy). For a dose of 2 GGy, the pore volume of the two materials decreases significantly by 40–45%. The irradiation-induced porosity closure is significantly more effective on smaller pores, resulting in a loss of the mesoporous network concerning MCM-41 (pore diameter ∼ 3.8 nm) and the conservation of the SBA-15 one (pore diameter ∼ 7.0 nm). The mechanism of silica porosity closure/collapse has not been fully identified, but it might result from damage effects as “Knock-on” processes. From a technological point of view, this phenomenon could be exploited for RadioNuclides (RN) encapsulation in a self-evolving porous material.
Published: 2021
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2. Conversion of actinide nitrate surrogates into oxide using combustion synthesis process: A facile approach

Author: Cyrielle Rey, Xavier Deschanels, Julien Monnier, S. Chandra Mohan, Jérémy Causse, Eleonore Welcomme, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Exothermic reaction, Nuclear and High Energy Physics, Materials science, Oxide, Autoignition temperature, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Actinide, Atmospheric temperature range, 021001 nanoscience & nanotechnology, Combustion, 01 natural sciences, 7. Clean energy, 010305 fluids & plasmas, Adiabatic flame temperature, chemistry.chemical_compound, Nuclear Energy and Engineering, chemistry, Chemical engineering, 13. Climate action, 0103 physical sciences, General Materials Science, Reactivity (chemistry), 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: In recent years, the focus of research in the conversion routes for the actinide nitrates into oxides for the generation IV nuclear fuel cycle have attracted rapidly growing interest. One process is the self-sustained exothermic reaction of Solution Combustion Synthesis (SCS) methodology. It was applied here to the reaction of an actinide surrogate Gd(NO3)3,6H2O with glycine in air to produce ∼10−3 mol amounts of Gd2O3. The primary process parameters were the Gd/glycine ratio and heating rate, which affected the ignition temperature of the precursor mixture. An optimum ratio of one and a heating rate of 10 K min−1 resulted in nearly complete SCS conversion over the 483–573 K temperature range and ultrafine gadolinia powders. The 100- to 500-fold swelling of the reactant mixture plays a dynamic role in the reactivity of the system. Final products were characterized by X-Rays Diffraction (XRD), surface area analysis, carbon content, and Scanning Electron Microscopy (SEM). The structural characteristics of the final gadolinia phases have been interpreted by the adiabatic flame temperature calculation.
Published: 2019
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3. Impact of Silica Surface Nanoconfinement on the Microstructure of Alkoxysilane Layers Grafted by Supercritical Carbon Dioxide

Author: Vincent Larrey, Samuel Tardif, Susan Sananes Israel, Diane Rébiscoul, François Rieutord, André Ayral, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Nanostructures et Rayonnement Synchrotron (NRS ), Modélisation et Exploration des Matériaux (MEM), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Institut Européen des membranes (IEM), 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), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)
Subjects: Materials science, Supercritical carbon dioxide, Model system, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Microstructure, 01 natural sciences, Supercritical fluid, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, General Energy, Chemical engineering, 13. Climate action, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: The impact of nanoconfinement on the microstructure of alkoxysilane layers grafted by supercritical CO2 was determined using model system made of silica nanochannels, i.e., planar silica surface sp...
Published: 2019
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4. Characterization of the boron profile and coordination in altered glass layers by EEL spectroscopy

Author: H.P. Brau, Diane Rébiscoul, Martiane Cabié, Nicole Godon, Héléne Arena, Jaysen Nelayah, E. Garcés, Renaud Podor, C. Mansas, Département de recherche sur les technologies pour l'enrichissement, le démantèlement et les déchets (DE2D), 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), Etude de la Matière en Mode Environnemental (L2ME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire Matériaux et Phénomènes Quantiques (MPQ (UMR_7162)), Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Catalyse, Polymérisation, Procédés et Matériaux (CP2M), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Nanomatériaux pour l'Energie et le Recyclage (LNER), Département de recherche sur les Procédés et Matériaux pour les Environnements complexes (DPME), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), and Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, General Physics and Astronomy, chemistry.chemical_element, Spectroscopy, Electron Energy-Loss, 02 engineering and technology, Electron, 01 natural sciences, Structural Biology, Materials Testing, 0103 physical sciences, [CHIM]Chemical Sciences, General Materials Science, Sample preparation, Spectroscopy, Boron, ComputingMilieux_MISCELLANEOUS, 010302 applied physics, Minerals, Cell Biology, 021001 nanoscience & nanotechnology, Characterization (materials science), chemistry, Chemical engineering, Bonding strength, Nanometre, Glass, 0210 nano-technology, Layer (electronics)
Abstract: Electron energy-loss spectroscopy was used to characterize the boron profile and its coordination (BIII and BIV), along the complex alteration layer of glass samples altered for 511 days at 50 °C in solution containing FeCl2, MgCl2 and/or CaCl2. To reach this goal, the impact of both TEM operating conditions and sample preparation on the determination of the boron coordination was first studied using mineralogical and pristine glasses reference samples. Then, the boron concentration profiles were characterized in the glass alteration layer. These profiles were found to be S-shaped with a thickness around forty nanometers. The proportion of BIII was found to decrease with the boron total concentration (from the pristine glass to the gel layer), which suggests a higher bonding strength for BIV bonds than that of BIII bonds under the alteration conditions. These findings are of tremendous interest to advance further in the understanding of glass alteration mechanisms.
Published: 2021
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5. Extra-framework zirconium clusters in metal organic framework DUT-67 controlled by the choice of the metal precursor

Author: Philippe Trens, Thomas Cacciaguerra, Guillaume Toquer, Stefano Deabate, Ha Vu Le, Annalisa Martucci, Phuoc Hoang Ho, Luc Girard, Francesco Di Renzo, Nicola Precisvalle, Khoa D. Nguyen, 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 Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Ions aux Interfaces Actives (L2IA), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Nanomatériaux pour l'Energie et le Recyclage (LNER), Nanyang Technological University [Singapour], Department of Physics and Earth Sciences, University of Ferrara, 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), and Università degli Studi di Ferrara = University of Ferrara (UniFE)
Subjects: Diffraction, DUT-67, Materials science, Zirconium precursors, Scanning electron microscope, Formic acid, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, PE10_10, NO, Metal, Extra-framework clusters, Rietveld structure refinement, Zr-MOF, chemistry.chemical_compound, [CHIM]Chemical Sciences, General Materials Science, ComputingMilieux_MISCELLANEOUS, Zirconium, Condensation, Sorption, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Crystallography, chemistry, Mechanics of Materials, visual_art, visual_art.visual_art_medium, Metal-organic framework, 0210 nano-technology
Abstract: DUT-67 zirconium-thiophenedicarboxylate (TDC) MOFs have been synthesized in the presence of formic acid from different zirconium precursors. The materials formed have been characterized by X-ray diffraction, nitrogen sorption, scanning electron microscopy, and thermal gravimetry. Rietveld structure refinement has permitted to localize inside the microporosity zirconium and oxygen atoms of extraframework clusters (EFCs), whose conformation depended on the nature of the zirconium precursor. Dissolution-condensation processes of ZrCl4 and ZrOCl2 during the synthesis gave rise to Zr6 EFCs in one of every six cuboctahedral pores. Less numerous zirconia-like Zr12 oxo-clusters were formed from Zr isopropylate, whereas characteristic Zr8 nitro-clusters were formed from Zr oxonitrate. The distances between oxygen atoms of EFCs and framework were compatible with the presence of additional TDC linkers connected to the EFCs. The results have been interpreted in terms of competition between Zr species during the condensation of the MOF network.
Published: 2021
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6. Molecular dynamics simulation of ballistic effects in mesoporous silica

Author: Bertrand Siboulet, Jean-Marc Delaye, Xavier Deschanels, Yu Lou, Sandrine Dourdain, Mohamed Ruwaid Rafiuddin, Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), CEA- Saclay (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Nanomatériaux pour l'Energie et le Recyclage (LNER), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Modélisation Mésoscopique et Chimie Théorique (LMCT), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Laboratoire d'Etudes du Comportement à Long Terme des matériaux de conditionnement (LCLT), Département de recherche sur les Procédés et Matériaux pour les Environnements complexes (DPME), 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)-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: 010302 applied physics, Materials science, Sintering, 02 engineering and technology, Mesoporous silica, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, Electronic, Optical and Magnetic Materials, Ion, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Condensed Matter::Soft Condensed Matter, Molecular dynamics, Molecular geometry, Chemical engineering, 0103 physical sciences, Materials Chemistry, Ceramics and Composites, Radiation damage, [CHIM]Chemical Sciences, Irradiation, 0210 nano-technology, Displacement (fluid)
Abstract: International audience; Accumulation of ion displacement cascades in mesoporous silica material have been modeled using molecular dynamics (MD). For nuclear energies exceeding 30 keV/nm3, the volume and structural properties (Si-O-Si bond angle, coordination of O and Si) of the mesoporous silica material are modified thereby resulting in the complete collapse of the structure. Similar results were obtained from Au+ ion-irradiation (E = 0.5 MeV) experiments on mesoporous silica samples in which the density of the samples was shown to increase upon irradiation before saturating at deposited nuclear energies exceeding 30 keV/nm3. Both ion-irradiation experiments and MD simulations have shown that the ballistic effects are responsible for inducing densification of the mesoporous silica material. The mechanism underlying this densification is discussed in terms of irradiation induced sintering.
Published: 2020
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7. Colloidal sol of UO2 nanoparticles supported by multi-lamellar vesicles of carboxylate based surfactant

Author: Zijie Lu, Thomas Zemb, J. Lautru, Diane Rébiscoul, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Etude de la Matière en Mode Environnemental (L2ME), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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.chemical_classification, Carboxylic acid, technology, industry, and agriculture, chemistry.chemical_element, Nanoparticle, Ether, 02 engineering and technology, Uranium, 010402 general chemistry, 021001 nanoscience & nanotechnology, complex mixtures, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, chemistry.chemical_compound, Colloid, Colloid and Surface Chemistry, chemistry, Chemical engineering, Uranium oxide, [CHIM]Chemical Sciences, Carboxylate, 0210 nano-technology, Mesoporous material
Abstract: International audience; Producing compact monoliths of mesoporous uranium oxide that are free from surface active components and able to be wet by highly radioactive solutions is of great interest for future nuclear technologies. In this direction, metastable colloidal sols of UO2 using U(IV) as precursor and carboxylic surfactants (Polyoxyethylene(9) oleyl ether carboxylic acid C16/18:1E9COOH and Polyoxyethylene(10) lauryl ether carboxylic acid C12E10COOH) have been successfully prepared by indirect precipitation for 6 pH 8 with a molar ratio between uranium and surfactant U/S
Published: 2020
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8. In situ study of the synthesis of thorite (ThSiO 4 ) under environmental representative conditions

Author: Jérémy Causse, Nicolas Dacheux, Adel Mesbah, Eleonore Welcomme, Paul Estevenon, Philippe Moisy, Christophe Poinssot, Stéphanie Szenknect, Interfaces de Matériaux en Evolution (LIME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), 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), Nanomatériaux pour l'Energie et le Recyclage (LNER), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Materials science, Thorium, chemistry.chemical_element, Nanoparticle, 02 engineering and technology, Actinide, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Nanocrystalline material, Silicate, 0104 chemical sciences, Thorite, Inorganic Chemistry, chemistry.chemical_compound, Actinides in the environment, chemistry, Chemical engineering, 13. Climate action, [CHIM]Chemical Sciences, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Zircon
Abstract: Thorite, (ThSiO4) with a zircon type structure, is one of the most abundant natural sources of thorium on Earth. Generally, actinides are known to form nanoparticles in silicate medium, though no direct link between those colloids and the crystalline form of thorite was evidenced until now. Here we show the formation of thorite from colloids and nanocrystalline structures under experimental conditions close to environmental pH and temperature. Through in situ small and wide angle X-ray scattering (SWAXS) measurements, colloids with a few nanometers in size were first evidenced at a low reaction time. These colloids have elongated shapes and finally tend to aggregate after their size has reached 10 nm. Once aggregated, the system goes through a maturation step, ending with the emergence of nanocrystallites as thorite zircon structures. This maturation step is longer when the reaction temperature is decreased which highlights the kinetic considerations. These results have potential implications on the paragenesis of Th mineral deposits and also in the behaviour of Th and, by analogy, tetravalent actinides in the environment. The significant characteristics of this work are that Th-silicate colloids were demonstrated at low temperatures and a near neutral pH with long-term stability and a morphology in favor of high mobility in groundwater. If these species are formed in more diluted media, this could be problematic owing to the spreading of Th and, by analogy, other tetravalent actinides in the environment.
Published: 2020
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9. Linker-assisted structuration of tunable uranium-based hybrid lamellar nanomaterials

Author: Elisa Ré, Jérôme Maynadié, Xavier Le Goff, Daniel Meyer, Guillaume Toquer, Systèmes HYbrides pour la Séparation (LHyS), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Etude de la Matière en Mode Environnemental (L2ME), Nanomatériaux pour l'Energie et le Recyclage (LNER), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: Chemistry, Small-angle X-ray scattering, Nanoparticle, Nanotechnology, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, Nanomaterials, chemistry.chemical_compound, Studtite, Materials Chemistry, Uranium oxide, [CHIM]Chemical Sciences, Lamellar structure, 0210 nano-technology, Hybrid material, Nanoscopic scale
Abstract: International audience; Obtaining bulk materials ordered at the nanoscale using nanoparticles as building blocks is a new challenge for scientists and is of primary interest in some research areas. In this study, we developed a simple one-pot route towards nanostructured hybrid materials based on uranium oxide through a non-hydrolytic condensation process under mild solvothermal conditions (T = 160 °C) using ditopic organic linkers as structuring agents. The obtained materials present a sand rose morphology composed of agglomerated nanometric sheets with a lamellar substructure. Nanometric sheets are composed of inorganic fringes consisting of a studtite phase [(UO2)O2(H2O)2]·2H2O that alternates with organic fringes formed by the structuring organic linker. A multiparametric study based on SAXS experiments and TEM analyses has highlighted the control of structural parameters by varying some synthesis conditions. The interlamellar distances are tunable from 1.60 nm to 1.94 nm through the length of the structuring linker and the inter-sheet distance from 1.85 nm to 2.10 nm through synthesis temperature. This efficient one-pot route appears to be very promising for the production of tunable multiscale nanostructured hybrid materials and can be implemented in many research areas, paving the way for various applications.
Published: 2020
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10. Single-template periodic mesoporous organosilica with organized bimodal mesoporosity

Author: Wong Chi Man, M., Laird, M., Carcel, C., Oliviero, E., Toquer, Guillaume, Trens, P., Bartlett, J.R., Wong, M, Man, Chi, 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), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Western Sydney University, Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM), 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), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Materials science, Diffusion, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Micelle, PMOS logic, chemistry.chemical_compound, Dual porosity, [CHIM]Chemical Sciences, General Materials Science, Porosity, ComputingMilieux_MISCELLANEOUS, Condensation, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Poloxamer, Bimodal porosity, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Mesoporous organosilica, Chemical engineering, chemistry, Mechanics of Materials, Triethoxysilane, Periodic Mesoporous Organosilica, 0210 nano-technology
Abstract: Periodic mesoporous organosilicas (PMOs) are obtained by the hydrolysis-condensation of organobridged triethoxysilane precursors in the presence of surfactants as structure-directing agents (SDAs). After removal of the SDAs, the resulting materials usually exhibit monomodal, well-organized mesoporosity, with the size of the pores being controlled by the SDA. However, despite the potential technological applications of such materials with well-organized bimodal porosity, to the best of our knowledge, PMOs exhibiting two distinct types of ordered mesoporosity have barely been described. Herein, we describe a simple approach for modulating the dimensions of ordered monomodal 2D hexagonal and bimodal porosity in PMOs synthesized from 1,4-bis(triethoxysilyl)benzene (BTEB) and Pluronic P123 under acidic conditions, by varying the addition sequence of reactants. The approach employs a single SDA without degradation of the BTEB precursor. Reaction conditions leading to the formation of monomodal and bimodal porosity within the templated PMOs are identified. Our approach exploits the competition between the rates of (a) BTEB hydrolysis/condensation; and (b) diffusion, solubilization and partitioning of the unhydrolyzed and hydrolyzed precursor within the micelles. A mechanism describing the evolution of porosity within this system is proposed.
Published: 2020
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11. Surface Properties of Alkoxysilane Layers Grafted in Supercritical Carbon Dioxide

Author: Michael Odorico, André Ayral, Susan Sananes Israel, Valérie Flaud, Diane Rébiscoul, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Etude de la Matière en Mode Environnemental (L2ME), 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 Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), 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: Materials science, Supercritical carbon dioxide, Bilayer, technology, industry, and agriculture, Surfaces and Interfaces, Condensed Matter Physics, Grafting, Contact angle, chemistry.chemical_compound, chemistry, X-ray photoelectron spectroscopy, Chemical engineering, Triethoxysilane, Monolayer, Electrochemistry, [CHIM]Chemical Sciences, General Materials Science, Silicon oxide, Spectroscopy
Abstract: International audience; Silicon oxide surface properties can be easily modified by grafting alkoxysilane molecules. Here, we studied the structure and the morphology of ultrathin layers prepared by the grafting of alkoxysilanes having different head groups (thiol, amine, and iodo) in supercritical carbon dioxide (CO2) on model plane silicon oxide surfaces. Several characterization techniques (X-ray reflectivity, water contact angle, X-ray photoelectron spectroscopy, and atomic force microscopy (AFM)) were used to determine the physicochemical properties of the layers prepared at different temperatures. Moreover, for the first time, AFM peak force measurements were used to delve deeper into the determination of the structure of these ultrathin alkoxysilane layers. The results show that the grafting temperature and the nature of the head group strongly affect the morphology and structure of the grafted layers. Dense monolayers are obtained with 3-(mercaptopropyl)trimethoxysilane at 60 °C, polycondensed layers are always prepared with [3-(aminoethylamino)propyl]trimethoxysilane, and a dense bilayer is synthesized with 3-(iodopropyl)triethoxysilane at 120 °C.
Published: 2019
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12. Structural and Dynamical Properties of Water Confined in Highly Ordered Mesoporous Silica in the Presence of Electrolytes

Author: Fanni Juranyi, Diane Rébiscoul, Markus Baum, François Rieutord, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratory for Neutron Scattering and Imaging [Paul Scherrer Institute] (LNS), Paul Scherrer Institute (PSI), Nanostructures et Rayonnement Synchrotron (NRS ), Modélisation et Exploration des Matériaux (MEM), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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 Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: Kosmotropic, Properties of water, Materials science, Infrared spectroscopy, Sorption, 02 engineering and technology, Neutron scattering, Mesoporous silica, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Ion, chemistry.chemical_compound, General Energy, chemistry, 13. Climate action, Chemical physics, Molecule, Physical and Theoretical Chemistry, [CHIM.OTHE]Chemical Sciences/Other, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: The structural and dynamical properties of water confined in highly ordered mesoporous silica (SBA-15) in the presence of ions having various kosmotropic properties (XCl2 with X = Ba2+, Ca2+, and Mg2+) were characterized using thermogravimetric analysis, infrared spectroscopy, and quasi-elastic neutron scattering and were related to the surface density of ions obtained by sorption isotherms. The results highlight that the water network is perturbed by the confinement and that the dynamics of water molecules at a picosecond time scale is slowed by the presence of ions. These results are mainly explained by the presence of the interfacial layer where both the structure of the water network and the water dynamics are influenced by the surface ion excess and the kosmotropic properties of ions.
Published: 2018
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13. Structuring of di-alkyl-urethanesils

Author: E. Carbó-Argibay, José A. M. Catita, V. de Zea Bermudez, Rui F. P. Pereira, S. C. Nunes, Guillaume Toquer, M. C. Gonçalves, Paulo J. Ferreira, University of Trás-os-Montes and Alto Douro [Portugal] (UTAD), University of Minho [Braga], University of Texas at Austin [Austin], International Iberian Nanotechnology Laboratory, 4715-330 Braga, Portugal, International Iberian Nanotechnology Laboratory, Fernando Pessoa University, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), University of Beira Interior [Portugal] (UBI), Universidade de Trás-os-Montes e Alto Douro (UTAD), Universidade do Trás-os-Montes e Alto Douro, International Iberian Nanotechnology Laboratory (INL), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Materials science, Dodecane, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biomaterials, chemistry.chemical_compound, Acid catalysis, Amphiphile, Materials Chemistry, Lamellar structure, ComputingMilieux_MISCELLANEOUS, Alkyl, Tetrahydrofuran, chemistry.chemical_classification, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Silsesquioxane, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Crystallography, chemistry, Siloxane, Ceramics and Composites, 0210 nano-technology
Abstract: A novel organized di-urethane crossed-linked dodecyl/siloxane (di-alkyl-urethanesil) was synthesized by the sol–gel process and self-directed assembly, from the organosilane precursor (CH3CH2O)3-Si-(CH2)3-NHC( = O)O-(CH2)12-O(O = C)NH-(CH2)3-Si-(OCH2CH3)3, through a fine control of the reaction conditions (hyper-stoichiometric amount of water, minor amount of tetrahydrofuran, and acid catalysis; molar ratio Si:H2O:HCl:THF = 1:300:0.1:12.5). The new bridged silsesquioxane was identified by the notation d-Ut(CY)AC, where Y = 12 is the number of carbon atoms C of the bridging alkyl chains and AC represents acid catalysis. The d-Ut(C12)AC material exhibits a structured lamellar organization with medium long-range order, a texture composed of homogeneous lamellae immersed in a sponge-like matrix made of randomly distributed thin plates, and is thermally stable up to ca. 350 °C. Despite the hydrophobic nature of the dodecane chains, the weakness of the urethane–urethane hydrogen-bonded array formed led to the growth of moderately ordered assemblies of amphiphilic organo(bis-silanetriol) substructures comprising mainly all-trans conformers.
Published: 2018
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14. Why natural monazite never becomes amorphous: Experimental evidence for alpha self-healing

Author: Willlliamam John Weber, Xavier Deschanels, Sylvain Peuget, Cedric Baumier, Anne-Magalali Seydoux-Guillaume, Stefan Neumeier, Laboratoire Magmas et Volcans (LMV), Institut national des sciences de l'Univers (INSU - CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Recherche pour le Développement et la société-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS)-Observatoire de Physique du Globe de Clermont-Ferrand (OPGC), Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Institut national des sciences de l'Univers (INSU - CNRS), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centre de Sciences Nucléaires et de Sciences de la Matière (CSNSM), Université Paris-Sud - Paris 11 (UP11)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Service d'Etudes du Comportement des Matériaux de Conditionnement (SECM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut national des sciences de l'Univers (INSU - CNRS)-Université Jean Monnet - Saint-Étienne (UJM)-Institut de Recherche pour le Développement et la société-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS)-Observatoire de Physique du Globe de Clermont-Ferrand (OPGC), Institut national des sciences de l'Univers (INSU - CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Materials science, 010504 meteorology & atmospheric sciences, in situ TEM irradiation, geochronology, helium, 010502 geochemistry & geophysics, 01 natural sciences, 7. Clean energy, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, Geochemistry and Petrology, Monazite, Irradiation, 0105 earth and related environmental sciences, nuclear waste, Mineral, Continental crust, dual-ion beam irradiation, Actinide, thermochronology, Amorphous solid, Thermochronology, Geophysics, 13. Climate action, Chemical physics, Phosphate minerals, α self-healing
Abstract: International audience; Monazite, a common accessory rare-earth orthophosphate mineral in the continental crust widely used in U-Pb geochronology, holds promise for (U-Th)/He thermochronology and for the immobilization of Pu and minor actinides (MA) coming from spent nuclear fuel reprocessing. Previous results obtained on natural and plutonium-doped monazite have demonstrated the ability of this structure to maintain a crystalline state despite high radiation damage levels. However, the low critical temperature (180 °C), above which amorphization cannot be achieved in natural monazite under ion irradiation, does not explain this old and unsolved paradox: why do natural monazites, independent of their geological history, remain crystalline even when they did not experience any thermal event that could heal the defects? This is what the present study aims to address. Synthetic polycrystals of LaPO4-monazite were irradiated sequentially and simultaneously with α particles (He) and gold (Au) ions. Our results demonstrate experimentally for the first time in monazite, the existence of the defect recovery mechanism, called α-healing, acting in this structure due to electronic energy loss of α particles, which explains the absence of amorphization in natural monazite samples. This mechanism is critically important for monazite geo- and thermochronology and to design and predictively model the long-term behavior of ceramic matrices for nuclear waste conditioning.
Published: 2018
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15. Ion extraction applications of bilayer-structured hybrid silicas

Author: Romain Besnard, Robert Winkler, Stéphane Pellet-Rostaing, Guilhem Arrachart, Julien Cambedouzou, Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Nanomatériaux pour l'Energie et le Recyclage (LNER), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Thermogravimetric analysis, Materials science, Small-angle X-ray scattering, Bilayer, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Adsorption, Chemical engineering, Amphiphile, Materials Chemistry, [CHIM]Chemical Sciences, General Materials Science, Lamellar structure, Fourier transform infrared spectroscopy, 0210 nano-technology, Hybrid material, ComputingMilieux_MISCELLANEOUS
Abstract: The self-assembly behaviour of amino-undecyl-triethoxysilane, which can be considered as an amphiphilic organosilane, has been used for the preparation of nanostructured materials. Due to the possibilities offered by this approach, lamellar hybrid materials bearing amine groups can be achieved. In this study, the reactive amino groups at the surface of the hybrid silica were modified for introducing ligands. For this purpose, various glycolamic acid groups have been introduced at the interface between two bilayers on the hybrid material obtained after condensation of silylated amines. The availability of the amino groups and the efficiency of the chemical immobilization of amic acid ligands onto the materials were followed by FTIR, NMR and TGA analysis, and the structural modifications induced by grafting were evaluated by SAXS experiments. The resulting materials exhibit a large number of amic acid groups. The adsorption capacities for rare earth elements were also investigated.
Published: 2018
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16. Synthesis of geopolymer emulsions

Author: Angélique Barneoud-Chapelier, Jérémy Causse, Arnaud Poulesquen, Laboratoire d’étude des Ciments et Bitumes pour le Conditionnement (LCBC), Département de recherche sur les Procédés et Matériaux pour les Environnements complexes (DPME), 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)-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), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Département de recherche sur les technologies pour l'enrichissement, le démantèlement et les déchets (DE2D), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: Materials science, 02 engineering and technology, Hexadecane, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, DSC, chemistry.chemical_compound, Viscosity, Specific surface area, Geopolymer emulsions, General Materials Science, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], Porosity, Mechanical Engineering, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Geopolymer, Compressive strength, chemistry, Chemical engineering, Mechanics of Materials, Volume fraction, Emulsion, 0210 nano-technology
Abstract: International audience; The understanding of geopolymer emulsion synthesis is a major issue for several industrial applications such as the formation of hierarchically porous material for filtration, lightweight materials for civil engineering or even the conditioning of radioactive mineral oil. The aim of this paper is to study model emulsions (hexadecane dispersed in Na or K-metakaolin based geopolymer) with the highest volume fraction of C16 incorporated. The influence of the viscosity of the geopolymer paste controlled by the water content was studied and results show that emulsions are unstable for a viscosity ratio ηd/ηc lower than 0.01. Up to 70% in volume of C16 was incorporated within the K-geopolymer and hierarchical porous network was thus obtained. After oil removal by solvent extraction, a monolith with a compressive strength of around 0.5–0.6 MPa was characterized in terms of pore size distribution and specific surface area.
Published: 2020
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17. Effect of TiC incorporation on the optical properties and oxidation resistance of SiC ceramics

Author: Alexandre Maitre, Audrey Soum-Glaude, Guilhem Arrachart, Moustapha Coulibaly, Xavier Deschanels, Nicolas Pradeilles, Alban Jonchère, Hélène Aréna, Marion Vandenhende, Adel Mesbah, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Procédés, Matériaux et Energie Solaire (PROMES), Université de Perpignan Via Domitia (UPVD)-Centre National de la Recherche Scientifique (CNRS), Ions aux Interfaces Actives (L2IA), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Interfaces de Matériaux en Evolution (LIME), 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), ANR-16-CE08-0026,CARAPASS,NANOCOMPOSITES CARBURES ET CARBONITRURES COMME MATERIAUX SELECTIFS POUR LA CONVERSION PHOTOTHERMIQUE(2016), ANR-10-LABX-0022,SOLSTICE,Solar Energy, Science, Technology and Innovation for Energy Conversion(2010), ANR-10-EQPX-0049,SOCRATE,Solaire Concentré : Recherches Avancées et Technologies Energétiques(2010), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: optical properties, oxidation resistance, SiC, TiC, Materials science, reflectance, 02 engineering and technology, ceramics, 010402 general chemistry, 7. Clean energy, 01 natural sciences, high temperature, CSP, Air atmosphere, Thermal emittance, Ceramic, Oxidation resistance, Nanocomposite, Renewable Energy, Sustainability and the Environment, Nano composites, nano composite, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Chemical engineering, visual_art, visual_art.visual_art_medium, 0210 nano-technology, Selectivity, Layer (electronics)
Abstract: International audience; In concentrating solar power (CSP) technologies, the absorber material should be spectrally selective under severe operating conditions, i.e. ~1000°C under air atmosphere. SiC-TiC nanocomposites could be good candidates for this application due to their spectral selectivity at room temperature, but their behavior under CSP operating conditions is unknown. Therefore, the spectral selectivity and oxidation resistance of TiC-SiC composites were studied up to 500 °C, under air, for various compositions. During heating, the emittance increased with the temperature. After heating, the TiC grains at the surface were oxidized into TiO2, while SiC grains showed good behavior. However, despite little oxidation, the spectral selectivity of the nanocomposites remained interesting after heating. Specific oxidation tests up to 9 days at 1000°C under air showed an increase of the oxidation resistance with the amount of SiC. This result is the consequence of the formation of a protective layer of SiO2 preventing the oxidation of the TiC grains. The composition 30 at% TiC-70 at% SiC seems to be a good compromise between low oxidation and good selectivity.
Published: 2020
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18. Comparative effect of alkaline elements and calcium on alteration of International Simple Glass

Author: Emmanuelle Garcès, Nicole Godon, Hélène Aréna, Diane Rébiscoul, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire d'Etudes du Comportement à Long Terme des matériaux de conditionnement (LCLT), Département de recherche sur les technologies pour l'enrichissement, le démantèlement et les déchets (DE2D), 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)-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), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), This work was funded by CEA, ORANO, and EDF., Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Département de recherche sur les Procédés et Matériaux pour les Environnements complexes (DPME), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: [PHYS.NUCL]Physics [physics]/Nuclear Theory [nucl-th], Materials Science (miscellaneous), chemistry.chemical_element, 02 engineering and technology, Calcium, [PHYS.NEXP]Physics [physics]/Nuclear Experiment [nucl-ex], 01 natural sciences, chemistry.chemical_compound, 0103 physical sciences, Materials Chemistry, lcsh:TA401-492, 010302 applied physics, SIMPLE (dark matter experiment), Chemistry, Limiting, 021001 nanoscience & nanotechnology, Nanopore, Calcium carbonate, Chemical engineering, Chemistry (miscellaneous), Ceramics and Composites, lcsh:Materials of engineering and construction. Mechanics of materials, Charge compensation, 0210 nano-technology, Transport phenomena, Layer (electronics)
Abstract: In the concept of deep geological repository for High Level Wastes, the chemical elements present in the media are expected to impact the long-term behavior of the glass. The effects of Ca, K, and Cs on International Simple Glass glass alteration are compared through long-term experiments (180–500 days). These elements limit glass alteration by their incorporation into the gel layer. The limiting mechanisms driving glass alteration appear to be mainly diffusive, at least during the first six months. The three cations are not equally efficient in limiting glass alteration: the effects of Ca are stronger than those of Cs and K. Multi-element experiments show that the effects of these elements are additive and proportional to the quantity of each element incorporated. When they play the role of charge compensator in the gel network, their incorporation is competitive and follows the order Ca ≫ Cs > K. In addition, when Ca is added to the solution in excess, the quantity of elements incorporated into the gel layer is higher than the amount required for charge compensation. The incorporation of Ca in the gel nanopores as calcium carbonate could explain this phenomenon. These processes could slow the transport phenomena through the gel and enhance its protective properties.
Published: 2019
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19. Actinide and Lanthanide Adsorption onto Hierarchically Porous Carbons Beads: A High Surface Affinity for Pu

Author: Nicholas Scales, Erden Sizgek, Cyrielle Rey, Guilhem Arrachart, Glenna L. Drisko, Devlet Sizgek, Vittorio Luca, Zaynab Aly, Comisión Nacional de Energía Atómica [ARGENTINA] (CNEA), A CSIRO Materials Science and Engineering, Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Nanomatériaux pour l'Energie et le Recyclage (LNER), Australian Nuclear Science and Technology Organization, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This research received no external funding, being part of ANSTO’s scientific program., Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), and Australian Nuclear Science and Technology Organization (ANSTO)
Subjects: Lanthanide, actinide and lanthanide sorption, General Chemical Engineering, chemistry.chemical_element, Minor actinide, hierarchical pore structures, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Article, lcsh:Chemistry, chemistry.chemical_compound, Adsorption, polyacrylonitrile, General Materials Science, phenolic resin, Chemistry, carbon, Polyacrylonitrile, Actinide, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chemical engineering, lcsh:QD1-999, 13. Climate action, Ammonium persulfate, 0210 nano-technology, Mesoporous material, Carbon
Abstract: International audience; Structured carbon adsorbents were prepared by carbonizing macroporous polyacrylonitrile beads whose pores were lined with a mesoporous phenolic resin. After activation, the beads were tested for minor actinide (Np and Am), major actinide (Pu and U) and lanthanide (Gd) adsorption in varying acidic media. The activation of the carbon with ammonium persulfate increased the surface adsorption of the actinides, while decreasing lanthanide adsorption. These beads had a pH region where Pu could be selectively extracted. Pu is one of the longest lived, abundant and most radiotoxic components of spent nuclear fuel and thus, there is an urgent need to increase its security of storage. As carbon has a low neutron absorption cross-section, these beads present an affordable, efficient and safe means for Pu separation from nuclear waste.
Published: 2019
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20. Elaboration of microporous CeO2 thin layers having nanocrystallites network controlled by Pluronic P123: Impact of key experimental parameters

Author: Zijie Lu, Jérémy Causse, Xavier F. Le Goff, Diane Rébiscoul, Nicolas Mollard, Xavier Deschanels, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Etude de la Matière en Mode Environnemental (L2ME), Modélisation et Exploration des Matériaux (MEM), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])
Subjects: Materials science, Nanoparticle, 02 engineering and technology, Thermal treatment, 010402 general chemistry, 01 natural sciences, law.invention, Biomaterials, law, Materials Chemistry, [CHIM]Chemical Sciences, Thin film, Crystallization, Porosity, Thin layers, General Chemistry, Microporous material, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Chemical engineering, Ceramics and Composites, Crystallite, 0210 nano-technology
Abstract: International audience; Microporous ceria thin films having nanocrystallites network were synthesized by evaporation-induced self-assemblyprocess, using P123 amphiphilic copolymer as structure-directing agent. The impact of key experimental parameters,i.e., the sol ageing, the relative humidity (RH), the thermal treatment, on the thin layer elaboration were investigated.The results show that the organization of the nanoparticles is possible for a sol ageing time lower than 16 days and thatthe size of the mesophase within the thin layer increases with the relative humidity fixed during the film deposition.Finally, an increase of the thermal treatment temperature from 300 to 1000 °C leads to the formation of fluorite-likedioxide material coupled with a loss of nanocrystallites organization and porosity due to the increase of the size of thecrystallites. This loss of nanocrystallites organization is more drastic in the direction perpendicular to the surface andless pronounced along the surface. Thus, a compromise between the crystallization and the preservation of the porosityneeds to be found.
Published: 2019
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21. Dynamical and Structural Properties of Water in Silica Nanoconfinement – Impact of Pore Size, Ion Nature and Electrolyte Concentration

Author: Fanni Juranyi, Cyrielle Rey, Markus Baum, Diane Rébiscoul, François Rieutord, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Nanostructures et Rayonnement Synchrotron (NRS ), Modélisation et Exploration des Matériaux (MEM), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratory for Neutron Scattering and Imaging [Paul Scherrer Institute] (LNS), Paul Scherrer Institute (PSI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])
Subjects: Kosmotropic, Materials science, 02 engineering and technology, Electrolyte, Neutron scattering, 010402 general chemistry, 01 natural sciences, Ion, Electrochemistry, General Materials Science, Fourier transform infrared spectroscopy, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Aqueous solution, Sorption, Surfaces and Interfaces, [CHIM.MATE]Chemical Sciences/Material chemistry, Mesoporous silica, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Chemical engineering, 13. Climate action, [PHYS.COND.CM-GEN]Physics [physics]/Condensed Matter [cond-mat]/Other [cond-mat.other], [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, [CHIM.OTHE]Chemical Sciences/Other
Abstract: In this study, we characterized the structure and the dynamics at a picosecond scale of water molecules in aqueous solutions with cations having various kosmotropic properties (XCl2 where X = Ba2+, Ca2+, and Mg2+) confined in highly ordered mesoporous silica (MCM-41 and grafted MCM-41) by Fourier transform infrared spectroscopy and quasi-elastic neutron scattering. We pinpointed the critical pore size and the electrolyte concentration at which the influence of the ion nature becomes the main factor affecting the water properties. These results suggest that whatever the ions kosmotropic properties, for pore sizes ϕp < 2.6 nm and [XCl2] ≤ 1 M, the water dynamics is mainly slowed down by the size of the confinement. For pore sizes of 6.6 nm, the water dynamics depends on the concentration and kosmotropic properties of the ion more than on the confinement. The water properties within the interfacial layer were also assessed and related to the surface ion excesses obtained by sorption isotherms. We showed that, for pore sizes ϕp ≥ 2.6 nm, the surface ion excess at the pore surface is the main driver affecting the structural properties of water molecules and their dynamics within the interfacial layer.
Published: 2019
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22. Periodic Mesoporous Organosilicas from Polyion Complex Micelles - Effect of Organic Bridge on Nanostructure

Author: Nathalie Marcotte, Guillaume Toquer, Albane Birault, John R. Bartlett, Didier Cot, Philippe Trens, Emilie Molina, Michel Wong Chi Man, Corine Gérardin, Carole Carcel, 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), Institut Européen des membranes (IEM), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Western Sydney University, ANR-15-CE07-0005,MESOPIC,Ecoconception de matériaux mésoporeux multifonctionnels(2015), 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), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Montpellier (UM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM), University of the Sunshine Coast (USC), and Western Sydney University (UWS)
Subjects: Mesoporous hybrid organosilica, Micelles, Sol‐gel processes, Periodic mesoporous organosilica, Bridged silsesquioxanes, Nanostructure, Ethylene oxide, Periodic mesoporous organosilica, 010405 organic chemistry, Bridged silsesquioxanes, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, Micelle, 0104 chemical sciences, Inorganic Chemistry, Mesoporous hybrid organosilica, chemistry.chemical_compound, Mesoporous organosilica, Chemical engineering, chemistry, Phenylene, Copolymer, [CHIM]Chemical Sciences, Sol‐gel processes, Micelles, Acrylic acid, Antibacterial agent
Abstract: International audience; A new family of polyion complex (PIC)‐based periodic mesoporous organosilicas, PICPMOs, obtained by the hydrolysis‐condensation of organosilanes containing organic bridging units (phenylene, ethenylene and ethylene) in the presence of polyion complex (PIC) micelles as structure‐directing agents (SDAs), is described. The electrostatic interactions between the acrylic acid functions of a poly(ethylene oxide)‐b‐poly(acrylic acid) double‐hydrophilic block copolymer (DHBC) and the primary amine functions of a polyamine micellization agent control the formation of the core of the micellar complex, while the PEO chains of the micelle corona mediate the formation of the organic/inorganic interface that controls the evolution of the material. Herein, the micellization agent employed is an antibiotic drug, neomycin B. An important feature of this procedure is that the processing involves a “one‐pot” reaction, enabling the formation of the material and the direct encapsulation of the anti‐bacterial agent. This results in a reduction in the number and cost of processing steps, while offering the opportunity to easily tune the hybrid mesostructure. The PICPMO materials obtained are organized on different length scales, from long‐range‐ordered 2D hexagonal structuring in the case of the phenylene bridge to weakly organized wormlike structures in the case of the ethylene unit. The effect of organic bridge structure on the nanostructure and physical properties of the PICPMO is discussed.AbstractA new family of periodic mesoporous organosilicas, PICPMOs, is obtained, in the presence of polyion complex (PIC) micelles, by hydrolysis‐condensation of organosilanes containing various organic bridging units influencing the nanostructure and physical properties of the materials.
Published: 2019
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23. Amidophosphonate ligands as cerium extractants in supercritical CO$_2$

Author: Antoine Leybros, Guillaume Toquer, Antoine Leydier, Agnès Grandjean, Sofyane Bouali, Thomas Zemb, CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), This work was supported by funding from the CEA through the VADEN project, and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: General Chemical Engineering, chemistry.chemical_element, 02 engineering and technology, [PHYS.NEXP]Physics [physics]/Nuclear Experiment [nucl-ex], 010402 general chemistry, 01 natural sciences, Supercritical carbon dioxide, Molecule, Physical and Theoretical Chemistry, Solubility, Alkyl, chemistry.chemical_classification, Chemistry, solubility, Extraction (chemistry), 021001 nanoscience & nanotechnology, Condensed Matter Physics, extraction capacity, amidophosphonate, Supercritical fluid, 0104 chemical sciences, Cerium, cerium, Gravimetric analysis, Physical chemistry, 0210 nano-technology
Abstract: International audience; Industrial-scale rare earth extraction is typically performed by liquid-liquid extraction with large amounts of solvents, acids and organophosphorus ligands. An alternative is to use these extractants in supercritical CO$_2$ (SC-CO$_2$), where the crucial operating parameter is their solubility. Different molecules with amidophosphonate backbones have been synthesized and investigated in view of improving their solubility in SC-CO$_2$ and thereby their cerium extraction capacity. The CO$_2$-philicity of these extractants was adjusted by attaching branched or linear alkyl chains with four, six and eight carbons. Using a dynamic gravimetric setup, the solubility and cerium extraction capacity of these molecules were measured to vary from 1.56 to 2.47 mmol$_{ligand}$.mol$_{CO2}$$^{-1}$ and 0.25 to 0.46 mmol$_{Ce}$.mol$_{ligand}$$^{-1}$, respectively.The two properties were correlated and in both cases the highest values were obtained with a diisobutylamine chain. Solubility measurements between 313 and 331 K and between 13 and 28 MPa shows that optimal condition is (320 K ; 28 MPa).
Published: 2019
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24. Thin polymeric CuO film from EPD designed for low temperature photothermal absorbers

Author: Sanaa Shehayeb, Guillaume Toquer, Leila Ghannam, Michael Odorico, Xavier Deschanels, Iyad Karamé, J. Lautru, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Lebanese University [Beirut] (LU), Etude de la Matière en Mode Environnemental (L2ME), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Materials science, Scanning electron microscope, General Chemical Engineering, Nanoparticle, 02 engineering and technology, Electrophoretic deposition, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, PEI, Selective solar absorbers CuO, Chemical engineering, Selective tandem materials, Absorptance, Electrochemistry, Deposition (phase transition), Nanoparticles, [CHIM]Chemical Sciences, Wafer, Fourier transform infrared spectroscopy, 0210 nano-technology, Spectroscopy
Abstract: International audience; The creation of a tandem solar absorber based on highly UV–Vis–NIR absorbing nanofilm deposited onto a highly IR reflecting platinized silicon wafer is processed through electrophoretic deposition (EPD). The stabilization of a CuO colloidal aqueous suspension is first studied by adding polyethyleneimine (PEI) as cationic polymer acting both as charging agent and as electro-steric stabilizer. The colloidal stability as a function of the suspension pH is investigated prior to EPD, by Laser Doppler Velocimetry and atomic force microscopy. Tandem absorbers are obtained by varying different EPD parameters to control the thickness and the morphology of the film, in order to tune and optimize the final optical properties. The deposition thickness is then compared relative to the applied potential difference and the deposition time range. The morphology of the deposits and the thickness of the coatings are analysed by scanning electron microscopy (SEM). The density is obtained from energy-dispersive X-ray spectroscopy (EDX) using X-film software, total organic carbon (TOC) and Hamaker equation. CuO tandem absorbers are found to possess a high density with homogeneous and crack-free surfaces. Finally, absorptance (α) and emittance (ε) are calculated from the reflectance spectra of the UV–Vis–NIR and the Fourier Transform Infra-Red (FTIR) spectroscopy respectively. These latter values are combined to determine the efficiency (ƞ) of the tandem material.
Published: 2019
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25. SiC-TiC nanocomposite for bulk solar absorbers applications: Effect of density and surface roughness on the optical properties

Author: Audrey Soum-Glaude, Alexandre Maitre, Adel Mesbah, Alban Jonchère, Moustapha Coulibaly, Nicolas Pradeilles, Guilhem Arrachart, Marion Vandenhende, Hélène Aréna, Xavier Deschanels, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Procédés, Matériaux et Energie Solaire (PROMES), Université de Perpignan Via Domitia (UPVD)-Centre National de la Recherche Scientifique (CNRS), Ions aux Interfaces Actives (L2IA), Interfaces de Matériaux en Evolution (LIME), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), IRCER - Axe 4 : céramiques sous contraintes environnementales (IRCER-AXE4), 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), ANR-16-CE08-0026,CARAPASS,NANOCOMPOSITES CARBURES ET CARBONITRURES COMME MATERIAUX SELECTIFS POUR LA CONVERSION PHOTOTHERMIQUE(2016), ANR-10-EQPX-0049,SOCRATE,Solaire Concentré : Recherches Avancées et Technologies Energétiques(2010), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: SiC, TiC, Materials science, Scanning electron microscope, 02 engineering and technology, Surface finish, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Concentrated Solar Power, Surface roughness, Relative density, Thermal emittance, Composite material, Spectroscopy, roughness, density, Nanocomposite, Renewable Energy, Sustainability and the Environment, selectivity, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Absorptance, 0210 nano-technology
Abstract: International audience; In this study, the potential of SiC-TiC nano-composites as solar absorbers has been studied. For solar thermal applications, materials with high solar absorptance and low emittance are ideally sought for (spectral selectivity). A semi-molecular sol-gel synthesis route leading to nanometric homogenous composites was described. The resulting SiC-TiC nanocomposite powder was sintered at different temperatures to produce samples with various relative densities (from 57% to 96%). The samples morphology and composition were characterized by several techniques including Scanning Electron Microscopy (SEM), Energy-Dispersive X-Ray Spectroscopy (EDX), X-Ray Diffraction (XRD), carbon and oxygen elemental analyses. The link between the surface roughness and the relative density was precised and the effects on the optical properties (0.25–25 µm wavelength range) were studied. Comparisons were made with pure SiC and pure TiC samples with various relative densities.Overall, the sample emittance was found to strongly decrease with the increase in the relative density, leading to a great increase in the spectral selectivity, despite a little decrease in the solar absorptance. The TiC-SiC composite has an intermediate reflectance compared to the pure SiC and the pure TiC samples. With an absorptance of 0.76, an emittance of 0.44 and a selectivity of 1.74, the denser SiC-TiC could be a good candidate for bulk solar applications.
Published: 2019
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26. X-ray reflectivity analysis of SiO2 nanochannels filled with water and ions: A new method for the determination of the spatial distribution of ions inside confined media

Author: Samuel Tardif, Diane Rébiscoul, Niels Roelof Tas, François Rieutord, Markus Baum, Lionel Mercury, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Nanostructures et Rayonnement Synchrotron (NRS ), Modélisation et Exploration des Matériaux (MEM), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Transducers Science and Technology group, MESA+ Institute for Nanotechnology, University of Twente, Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Milieux Poreux - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), University of Twente [Netherlands], Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC)
Subjects: Surface (mathematics), Electron density, 010504 meteorology & atmospheric sciences, Chemistry, Analytical chemistry, Earth and Planetary Sciences(all), General Medicine, 010502 geochemistry & geophysics, Confined media, 01 natural sciences, Molecular physics, Ion, X-ray reflectivity, Adsorption, Planar, [SDU]Sciences of the Universe [physics], Perpendicular, Electric Double Layer, X-Ray Reflectivity, Layer (electronics), 0105 earth and related environmental sciences, adsorption kinetics
Abstract: International audience; Chemical reactions occurring at the material–aqueous solution interface are controlled by an interfacial layer of a few nm where conceptual models such as the Electrical Double or Triple Layer models can be applied. These models describing the spatial distribution of ions in term of perpendicular distance from the planar surface and ignoring topography or structure parallel to the surface are not validated in confined media. In order to investigate the critical dimensions of these models, our first approach was to use a model system consisting of two parallel plane surfaces of SiO 2 spaced of 5 nm (nanochannels) filled with salt solutions XCl 2 (X = Ca 2+ , Mg 2+ , Ba 2+). These filled nanochannels were characterized using hard X-Ray reflectivity for the determination of electron density profiles perpendicular to the surface. From these results, the surface densities of adsorbed ions at SiO 2 surface were calculated and the solution density inside the nanochannels was determined. This method opens new perspectives to a better understanding of water and ion distribution inside nanoconfined media.
Published: 2017
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27. Evolution of Silica Walls of Nanopores Filled with Water and Ions

Author: Julien Cambedouzou, Stephanie Szenknect, Markus Baum, M. Brossel, Diane Rébiscoul, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Physikalisches Institut [Köln], Universität zu Köln, Interfaces de Matériaux en Evolution (LIME), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), and Universität zu Köln = University of Cologne
Subjects: nanoporous silica, confined media, Earth and Planetary Sciences(all), dissolution, Mineralogy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Ion, Dissolution, Aqueous solution, Nanoporous, Small-angle X-ray scattering, water diffusion, SAXS, [CHIM.MATE]Chemical Sciences/Material chemistry, General Medicine, Microporous material, Mesoporous silica, 021001 nanoscience & nanotechnology, 6. Clean water, 0104 chemical sciences, Nanopore, Chemical engineering, Environmental science, aqueous solution, 0210 nano-technology
Abstract: International audience; The prediction of the evolution of nanoporous materials is of great interest in various fields particularly geology, environmental sciences, and nuclear waste management. Such prediction requires the use of modeling which is generally not adapted to confined media of few nanometers. In the present study, we have characterized the evolution of hexagonal mesoporous silica having 5 nm pore size (SBA15 type) at 50°C in water and in 0.2 M XCl 2 aqueous solutions, where X are different ions (X = Mg 2+ , Ca 2+ , Fe 2+ , Ba 2+), by in-situ Small Angle X-ray Scattering. The results allowed determination of the dissolution rates of the confining media, i.e. the silica, and water diffusion through the microporous silica wall as a function of the aqueous solution composition.
Published: 2017
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28. Study of self-association of gradient copolymers in supercritical CO 2 thanks to synchrotron and in-house small-angle X-rays scattering measurements

Author: Fabien Gasc, Bruno Corso, Jérémy Causse, Patrick Lacroix-Desmazes, 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), Etude de la Matière en Mode Environnemental (L2ME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), 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)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: chemistry.chemical_classification, Materials science, Small-angle X-ray scattering, Scattering, General Chemical Engineering, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, Supercritical fluid, 0104 chemical sciences, Styrene, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, Polymer chemistry, Copolymer, Molecule, Physical chemistry, Gradient copolymers, Physical and Theoretical Chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: Specific comblike gradient copolymers made of metal-complexing CO 2 -phobic units and fluorinated CO 2 -philic units were designed to study their self-association when solubilised in supercritical CO 2 (scCO 2 ). This paper shows that in-house SAXS measurements on scCO 2 systems are now possible thanks to both high-energy X-rays and specific high-pressure cell designed with beryllium windows. The copolymer system poly(1,1,2,2-tetrahydroperfluorodecylacrylate- co -4-(diphenylphosphino)styrene), poly(FDA- co -DPPS) was compared to homopolymer with thiol endgroup poly(FDA)-SH and more classical molecule, C 8 F 17 C 2 H 4 -SH (RfSH). The results show that the presence of the CO 2 -phobic part of the copolymer does not necessarily tend to favour self-association probably due to the polymer conformation. However, this CO 2 -phobicity favours inter-object correlation leading to aggregation.
Published: 2016
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29. Impact of Zn, Mg, Ni and Co elements on glass alteration: Additive effects

Author: J.-P. Mestre, Héléne Arena, Martiane Cabié, Nicole Godon, Diane Rébiscoul, E. Garcés, Renaud Podor, Laboratoire d'Etudes du Comportement à Long Terme des matériaux de conditionnement (LCLT), Département de recherche sur les technologies pour l'enrichissement, le démantèlement et les déchets (DE2D), 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)-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), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Etude de la Matière en Mode Environnemental (L2ME), Centre Pluridisciplinaire de Microscopie Electronique et de Microanalyse (AMU CP2M), Aix Marseille Université (AMU), Département de recherche sur les Procédés et Matériaux pour les Environnements complexes (DPME), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Nuclear and High Energy Physics, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, Zinc, 010501 environmental sciences, 01 natural sciences, Chloride, medicine, General Materials Science, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences, Aqueous solution, Precipitation (chemistry), Magnesium, Metallurgy, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 6. Clean water, Nickel, Nuclear Energy and Engineering, chemistry, 13. Climate action, 0210 nano-technology, Cobalt, Stoichiometry, medicine.drug
Abstract: The minor elements present in the nuclear glass composition or coming from the groundwater of the future repository may impact glass alteration. In this study, the effects of Zn, Mg, Ni and Co on the International Simple Glass (ISG) alteration were studied throughout 511 days of aqueous leaching experiments. The aim was to determine their additive or competitive effect on glass alteration and the nature of the alteration products. The four elements were introduced separately or altogether in solution as XCl 2 chloride salts (X = Zn, Mg, Ni or Co) with monthly additions to compensate for their consumption. The alteration kinetics were determined by leachate analyses (ICP-AES) and alteration products were characterized in terms of composition, morphology and microstructure (SEM, TEM-EDX, ToF-SIMS and XRD). Results indicate that when they are introduced separately, Zn, Mg, Ni and Co have the same qualitative and quantitative effect on glass alteration kinetics and on pH: they form secondary phases leading to a pH decrease and a significant increase in glass alteration. The secondary phases were identified as silicates of the added X element: trioctahedral smectites with a stoichiometry of[(Si (4-a) Al a ) (X (3-b) Al b ) O 10 (OH) 2 ] (a+b)− [X c Na d Ca e ] (2c+d+2e) + with a = 0.11 to 0.45, b = 0.00 to 0.29, c = 0, d = 0.19 to 0.74 and e = 0.10 to 0.14. . It was shown that as pH stabilizes at a minimum value, X-silicates no longer precipitate, thus leading to a significant drop in the glass alteration rate. This pH value depends on X and it has been identified as being 8 for Mg-silicates, probably around 7.3 for Ni and Co-silicates and less than 6.2 for Zn-silicates. When tested together, the effects of these four elements on glass alteration are additive and lead to the formation of a mix of X-silicates that precipitate as long as their constitutive elements are available and the pH is above their respective minimum value. This study brings new quantitative information about the effects of phyllosilicates precipitation on glass durability. These results are important since the precipitation of secondary phases could control, at least partially, the long-term behavior of nuclear glasses in geological repository conditions.
Published: 2016
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30. On the Operational Aspects of Measuring Nanoparticle Sizes

Author: Jean-Luc Pellequer, Christian Godon, Aurélie Habert, Louis Chantalat, Shu-wen W. Chen, Julien Cambedouzou, Johann Ravaux, Adèle Gerdil, Renaud Podor, Michael Odorico, Jean-Marie Teulon, Nathalie Herlin-Boime, Christine Moriscot, Institut de biologie structurale (IBS - UMR 5075 ), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Institut de Biosciences et Biotechnologies d'Aix-Marseille (ex-IBEB) (BIAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Signalisation de l'Adaptation des Végétaux à l'Environnement (SAVE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Etude de la Matière en Mode Environnemental (L2ME), Laboratoire Edifices Nanométriques (LEDNA), 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), Vinay, Laboratoire des Intéractions et Reconnaissances Moléculaires (LIRM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), European Project: AFM4NanoMed&Bio, Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Plant Environmental Physiology and Stress Signaling (PEPSS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), 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), and 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)
Subjects: Materials science, Scanning electron microscope, General Chemical Engineering, DLS, Nanoparticle, Nanotechnology, 02 engineering and technology, 010501 environmental sciences, 01 natural sciences, Article, lcsh:Chemistry, chemistry.chemical_compound, Dynamic light scattering, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Scanning transmission electron microscopy, General Materials Science, wet-STEM, 0105 earth and related environmental sciences, Small-angle X-ray scattering, Scattering, SAXS, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, metrology, lcsh:QD1-999, chemistry, Transmission electron microscopy, [SDV.TOX]Life Sciences [q-bio]/Toxicology, SEM, TEM, nanoparticles, Polystyrene, nanotoxicology, AFM, 0210 nano-technology
Abstract: International audience; Nanoparticles are defined as elementary particles with a size between 1 and 100 nm for at least 50% (in number). They can be made from natural materials, or manufactured. Due to their small sizes, novel toxicological issues are raised and thus determining the accurate size of these nanoparticles is a major challenge. In this study, we performed an intercomparison experiment with the goal to measure sizes of several nanoparticles, in a first step, calibrated beads and monodispersed SiO$_2$ Ludox®, and, in a second step, nanoparticles (NPs) of toxicological interest, such as Silver NM-300 K and PVP-coated Ag NPs, Titanium dioxide A12, P25(Degussa), and E171(A), using commonly available laboratory techniques such as transmission electron microscopy, scanning electron microscopy, small-angle X-ray scattering, dynamic light scattering, wet scanning transmission electron microscopy (and its dry state, STEM) and atomic force microscopy. With monomodal distributed NPs (polystyrene beads and SiO$_2$ Ludox®), all tested techniques provide a global size value amplitude within 25% from each other, whereas on multimodal distributed NPs (Ag and TiO$_2$) the inter-technique variation in size values reaches 300%. Our results highlight several pitfalls of NP size measurements such as operational aspects, which are unexpected consequences in the choice of experimental protocols. It reinforces the idea that averaging the NP size from different biophysical techniques (and experimental protocols) is more robust than focusing on repetitions of a single technique. Besides, when characterizing a heterogeneous NP in size, a size distribution is more informative than a simple average value. This work emphasizes the need for nanotoxicologists (and regulatory agencies) to test a large panel of different techniques before making a choice for the most appropriate technique(s)/protocol(s) to characterize a peculiar NP.
Published: 2019
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31. Synthesis of lamellar mesostructured phenylene-bridged periodic mesoporous organosilicas (PMO) templated by polyion complex (PIC) micelles

Author: Guillaume Toquer, Corine Gérardin, Nathalie Marcotte, Carole Carcel, John R. Bartlett, Albane Birault, Patrick Lacroix-Desmazes, Emilie Molina, Michel Wong Chi Man, 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), Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast, Maroochydore DC, QLD 4558, Australia, Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), 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), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), 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), University of the Sunshine Coast (USC), Nanomatériaux pour l'Energie et le Recyclage (LNER), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Micelle, Biomaterials, Polyion Complex Micelles, Phenylene, Materials Chemistry, Copolymer, [CHIM]Chemical Sciences, Lamellar structure, Hybrid material, Small-angle X-ray scattering, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, PMO, Polyelectrolyte, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Mesoporous organosilica, Chemical engineering, Ceramics and Composites, Hybrid materials, 0210 nano-technology
Abstract: International audience; Periodic mesoporous organosilicas (PMOs), obtained by the surfactant-mediated hydrolysis-condensation of bridged organosilanes, combine versatile organic functionalities with advantages of a stable inorganic framework. Here, we introduce a novel synthesis of lamellar mesostructured phenylene-bridged PMOs templated by polyion complex (PIC) micelles (PICPMOs). The micelles assemble by electrostatic interactions between oppositely charged polyelectrolytes, with one being part of a double hydrophilic block copolymer (DHBC), and the other being a polybase oligochitosan (OC). The PICPMO material was characterized by a range of techniques, including TEM, IR spectroscopy, SAXS, TGA and elemental analysis, which indicates that the material exhibits long-range ordering with an inter-lamellae distance of around 15nm. Advantages of the synthetic approach developed, together with potential applications of the PICPMOs, are discussed.
Published: 2019
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32. Molecular Dynamics Simulation of Mesoporous Silica under Ionic Ballistic Irradiations

Author: Lou, Yu, Siboulet, Bertrand, Dourdain, Sandrine, Deschanels, Xavier, Delaye, Jean-Marc, Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Nanomatériaux pour l'Energie et le Recyclage (LNER), Département de recherche sur les Procédés et Matériaux pour les Environnements complexes (DPME), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract: International audience; We performed simlulations of irradiation of silica mesoporous samples. We use DL_POLY 3 along with ZBL potentials. Irradiation results in a density modification which which trace versus the deposited energy. We alternate displacements cacsade with relaxation periods. We plot pressure variation and analyse the coordination.
Published: 2019

33. Confinement-Induced Electronic Excitation Limitation of Anthracene: The Restriction of Intramolecular Vibrations

Author: Dan A. Lerner, Guillaume Toquer, Philippe Trens, Altaf H. Basta, Lotfi Boudjema, 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), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), National Research Centre - NRC (EGYPT), 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), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Anthracene, Materials science, Absorption spectroscopy, Infrared, Nanoparticle, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, General Energy, chemistry, Absorption band, Intramolecular force, Imidazolate, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology, Excitation
Abstract: International audience; The spectroscopic behavior of anthracene encapsulated in porous zeolitic zinc imidazolate framework ZIF-8 was studied. Nanoparticles of ZIF-8 with high crystallinity and large specific surface areas were prepared in one-pot synthesis. Monitoring single anthracene encapsulation in a ZIF-8 cell was done by careful control of the synthesis of the hybrid. The molecular electronic spectra of anthracene adsorbed on the external surface of ZIF-8 were compared with those of encapsulated anthracene. It was demonstrated that the encapsulation of anthracene induced unexpected confinement effects including the restriction of intramolecular vibrations in its absorption spectrum. It was shown that vibronic components in the high-energy part of the S0 → S1 absorption band totally collapse upon encapsulation. Our study highlights the mechanism of confinement-induced electronic excitation limitation related to the restriction of intramolecular vibrations, which evidences the role of host–guest interaction in infrared absorption and fluorescence emission properties.
Published: 2018
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34. Impact of Fe, Mg and Ca elements on glass alteration: Interconnected processes

Author: J.-P. Mestre, Martiane Cabié, Diane Rébiscoul, Nicole Godon, E. Garcés, Héléne Arena, Renaud Podor, Etude de la Matière en Mode Environnemental (L2ME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire d'Etudes du Comportement à Long Terme des matériaux de conditionnement (LCLT), Département de recherche sur les technologies pour l'enrichissement, le démantèlement et les déchets (DE2D), 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)-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), Nanomatériaux pour l'Energie et le Recyclage (LNER), Centre Pluridisciplinaire de Microscopie Electronique et de Microanalyse (AMU CP2M), Aix Marseille Université (AMU), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), and Département de recherche sur les Procédés et Matériaux pour les Environnements complexes (DPME)
Subjects: Aqueous solution, Chemistry, Precipitation (chemistry), Magnesium, chemistry.chemical_element, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, Calcium, 010502 geochemistry & geophysics, 021001 nanoscience & nanotechnology, Microstructure, 01 natural sciences, Chloride, Chemical engineering, Geochemistry and Petrology, medicine, Leaching (metallurgy), Leachate, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences, medicine.drug
Abstract: In this study, the effects of Fe, Mg and Ca elements on the International Simple Glass (ISG) alteration were studied throughout 511 days of aqueous leaching experiments. The aim was to determine the processes involved and the additive or competitive nature of their effects on glass alteration. The three elements were introduced separately or together in solution as XCl2 chloride salts (X = Fe, Mg or Ca) with monthly additions to compensate for their consumption. Glass alteration was determined by leachate analyses (ICP-AES), and the alteration products were characterized in terms of composition, morphology and microstructure (SEM, TEM-EDX, ToF-SIMS and XRD). Two main processes were identified: (i) the precipitation of secondary phases integrating the added elements and (ii) the incorporation of the added elements into the gel layer. The first process enhances glass alteration and leads to a decrease in pH. The precipitation occurs in the presence of Fe and/or Mg. When these two elements are added simultaneously, their effects are additive. This phenomenon is self-limited; when a pH threshold value is reached (7.8 for Mg-silicates and 6.2 for Fe-silicates), the precipitation stops. The second process is mainly illustrated by the behavior of Ca. As this element is retained/incorporated into the gel layer, the gel layer becomes denser, and its protective properties increase. In lower proportions, Fe and Mg can also be incorporated into the gel layer. In the presence of each other, there is a competition between Ca, Fe and Mg to be incorporated into the gel layer. The quantity of element incorporated into the gel layer follows the order Ca ≫ Fe > Mg. These two processes are tightly linked to the evolution of the pH. As the secondary phases precipitate, the pH decreases, making Ca more soluble and less retained in the gel. When the precipitation stops, Fe and/or Mg can be incorporated into the gel in replacement for Ca. From these conclusions, an organogram was established that can be used to predict the effects of chemical elements on glass alteration depending on their behavior.
Published: 2018
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35. A new chemical route of nuclear fuel (U,Pu)O$_{2\pm \delta}$ by advanced thermal denitration in the presence of organic additive

Author: Leblanc, Martin, Leturcq, G., Welcomme, E., Deschanels, Xavier, Delahaye, T., CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), and CADARACHE, Bibliothèque
Subjects: [PHYS.NUCL] Physics [physics]/Nuclear Theory [nucl-th], [PHYS.NUCL]Physics [physics]/Nuclear Theory [nucl-th], [PHYS.NEXP] Physics [physics]/Nuclear Experiment [nucl-ex], [PHYS.NEXP]Physics [physics]/Nuclear Experiment [nucl-ex], ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2018

36. From colloidal precursors to metal carbides nanocomposites MC (M=Ti, Zr, Hf and Si): Synthesis, characterization and optical spectral selectivity studies

Author: Moustapha Coulibaly, Adel Mesbah, Guilhem Arrachart, Xavier Deschanels, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Interfaces de Matériaux en Evolution (LIME), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Nanocomposite, Materials science, Renewable Energy, Sustainability and the Environment, Composite number, Inorganic chemistry, Oxide, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Carbide, chemistry.chemical_compound, Chemical engineering, chemistry, Transition metal, Carbothermic reaction, Silicon carbide, [CHIM]Chemical Sciences, Carbon, ComputingMilieux_MISCELLANEOUS
Abstract: We investigate the possibility to combine silicon carbide with transition metal carbide (MC) in a nanocomposite type structure in order to enhance the optical properties of this material. Metal carbides have been prepared starting from colloidal oxide, with carbon introduced by sucrose followed by the complete conversion from oxide to carbide at 1550 °C through a carbothermal reduction under Ar atmosphere. The optical properties of individual metal carbides (SiC, TiC, ZrC and HfC) were first evaluated through their room temperature reflectance spectra measured from UV–visible to IR region. Emphasis was placed on the TiC compound as well as in the implementation of nanoscale SiC/TiC composite with respect to their intrinsic and spectral emittance properties.
Published: 2015
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37. Controlling the porosity of silicon carbide by templating molecular and polymeric precursors

Author: Nardin, T., Gouze, B., Cognet, M., Carboni, Michaël, Wong Chi Man, Michel, Diat, Olivier, Cambedouzou, Julien, Etude de la Matière en Mode Environnemental (L2ME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Systèmes HYbrides pour la Séparation (LHyS), Hétérochimie moléculaire et macromoléculaire (HMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS), Ions aux Interfaces Actives (L2IA), Nanomatériaux pour l'Energie et le Recyclage (LNER), PLANES, MELISSA, and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2018

38. Novel Highly Luminescent Amine-Functionalized Bridged Silsesquioxanes

Author: Luís D. Carlos, M. A. Cardoso, Guillaume Toquer, Verónica de Zea Bermudez, Rute A. S. Ferreira, Marta C. Ferro, Artur J.M. Valente, S. C. Nunes, Maria Manuela Silva, Rui F. P. Pereira, Departamento de Matemática e Aplicaçoes (DMA), Universidade do Minho, Universidade da Beira Interior, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Instituto Português de Oncologia de Lisboa, Francisco Gentil, Departemento de Fisica and CICECO, Universidade de Aveiro, Department of Chemistry and CQ-VR, University of Trás-os-Montes e Alto Douro, Universidade do Minho = University of Minho [Braga], University of Beira Interior [Portugal] (UBI), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Nanoparticle, Hydrochloric acid, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, lcsh:Chemistry, chemistry.chemical_compound, Polymer chemistry, morphology, luminescence, Tetrahydrofuran, Original Research, Science & Technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, sol-gel chemistry, 021001 nanoscience & nanotechnology, solvent-assisted structuring, 0104 chemical sciences, Chemistry, lcsh:QD1-999, chemistry, Sodium hydroxide, Siloxane, bis[(3-trimethoxysilyl)propyl]amine, bis[(3-trimethoxysilyl) propyl] amine, Amine gas treating, 0210 nano-technology, Luminescence, Stoichiometry
Abstract: Amine-functionalized bridged silsesquioxanes (BSs) were synthesized from bis[(3-trimethoxysilyl)propyl] amine via a solvent-mediated route. BS-1 and BS-2 were obtained at neutral pH with sub- and stoichiometric amounts of water, respectively, and high tetrahydrofuran content. BS-3 was prepared with hyperstoichiometric water concentration, high tetrahydrofuran content, and hydrochloric acid. BS-4 was synthesized with hyperstoichiometric water concentration, high ethanol content, and sodium hydroxide. BS-1 and BS-2 were produced as transparent films, whereas BS-3 and BS-4 formed white powders. Face-to-face stacking of flat or folded lamellae yielded quasi-hydrophobic platelets with emission quantum yields of 0.05 ± 0.01 (BS-1 and BS-2) or superhydrophilic onion-like nanoparticles with exciting emission quantum yields of 0.38 ± 0.03 (BS-3) and 0.33 ± 0.04 (BS-4), respectively. The latter two values are the largest ever reported for amine-functionalized siloxane-based hybrids lacking aromatic groups. Fast Grotthus proton hopping between = [Formula: see text]/ = NH groups (BS-3) and = N-/ = NH groups (BS-4), promoted by H+ and OH- ions, respectively, and aided by short amine-amine contacts provided by the onion-like morphology, account for this unique optical behavior., This work was supported by Fundacao para a Ciencia e a Tecnologia (FCT)/MEC and FEDER (contracts UID/QUI/00616/2013, POCI-01-0145-FEDER-007491, and UID/Multi/00709/2013) and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement, project UniRCell (Ref. SAICTPAC/0032/2015, POCI-01-0145-FEDER-016422), and project LUMECD (Ref. PTDC/CTM/NAN/0956/20149 and POCI-01-0145-FEDER-016884). RP and MC acknowledge FCT for grants SFRH/BPD/87759/2012 and SFRH/BD/118466/2016, respectively. SN also acknowledges FCT for grants SFRH/BPD/63152/2009 and Post-PhD Fellowship of LUMECD project. This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT-Ref. UID/CTM/50011/2013), financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement.
Published: 2018
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39. Strontium selectivity in sodium nonatitanate Na4Ti9O20·xH2O

Author: Arnaud Villard, Agnès Grandjean, Jean-François Dufrêche, Aurélie Merceille, Guillaume Toquer, Bertrand Siboulet, Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Nanomatériaux pour l'Energie et le Recyclage (LNER), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: inorganic chemicals, musculoskeletal diseases, Environmental Engineering, Health, Toxicology and Mutagenesis, Sodium, Inorganic chemistry, Regular solution, chemistry.chemical_element, symbols.namesake, Adsorption, Phase (matter), Physics::Atomic and Molecular Clusters, Environmental Chemistry, Strontium adsorption, Waste Management and Disposal, Decontamination, Strontium, Extraction (chemistry), Sodium nonatitanate, Free energy calculation, Pollution, Gibbs free energy, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, symbols, Selectivity
Abstract: International audience; We study the extraction of strontium by sodium nonatitanate powder from nitrate strontium and acetate sodium mixture. Experiments show that adsorption is quantitative. The excess Gibbs free energy has been modeled by various models (ideal, 2D Coulomb, regular solution model) for the solid phase. We find that the free energy of the solid phase is controlled by short-range interactions rather than long-ranged Coulombic forces. The selectivity is the consequence of a competition between the liquid and solid phases: both phases prefer strontium rather than sodium but the solid contribution is predominant.
Published: 2015
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40. Structure evolution of mesoporous silica under heavy ion irradiations of intermediate energies

Author: Nicolas Mollard, Yu Lou, Xavier Deschanels, Yves Serruys, David Simeone, Cyrielle Rey, Sandrine Dourdain, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), CEA- Saclay (CEA), Université Paris-Saclay, Service de recherches de métallurgie physique (SRMP), Département des Matériaux pour le Nucléaire (DMN), 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, Laboratoire Structures, Propriétés et Modélisation des solides (SPMS), Institut de Chimie du CNRS (INC)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Service des Recherches Métallurgiques Appliquées (SRMA), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: 010302 applied physics, [PHYS]Physics [physics], Materials science, Scanning electron microscope, Analytical chemistry, Nanotechnology, 02 engineering and technology, General Chemistry, Mesoporous silica, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, Fluence, Ion, Bond length, Mechanics of Materials, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, 0103 physical sciences, [CHIM]Chemical Sciences, General Materials Science, Irradiation, Thin film, 0210 nano-technology, Mesoporous material, ComputingMilieux_MISCELLANEOUS
Abstract: Mesoporous sol-gel silica thin films were irradiated with gold ions of medium energies from 0.5 MeV to 12 MeV. In all cases these porous materials are compacted as a result of mesopore collapse and deformation. X-ray reflectivity and SEM measurement show that the total compaction (densification) is achieved for a fluence of about 2 × 10 14 cm −2 (∼5 × 10 21 keV cm −3 ). The process of mesoporosity collapse seems different according to the irradiation regime (nuclear versus electronic). This effect results in a U-shaped evolution of the curve of the damage cross section as a function of the energy of ions Au. Infrared measurement of Au 0.5 MeV irradiated samples show a shift of TO 3 band towards lower wavenumber, related to Si-O-Si bond angle and Si-O bond length change. The sol-gel mesoporous and nonporous samples exhibit a delayed shift compared to thermal nonporous ones, which indicates that sol-gel materials are more radiation tolerant from this point of view. The sensitivity of these mesoporous structures to the damage caused by irradiation opens interesting prospects for obtaining self-conditioning materials.
Published: 2017
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41. Spectrally selective coatings obtained from electrophoretic deposition of CuO nanoparticles

Author: Leila Ghannam, Iyad Karamé, Sanaa Shehayeb, Guillaume Toquer, Xavier Deschanels, Lebanese University [Beirut] (LU), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: Materials science, Scanning electron microscope, Analytical chemistry, Nanoparticle, 02 engineering and technology, Surfaces and Interfaces, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, engineering.material, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electrophoretic deposition, Coating, Dynamic light scattering, Electric field, Materials Chemistry, engineering, Deposition (phase transition), Fourier transform infrared spectroscopy, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: Cathodic electrophoretic deposition (EPD) of CuO nanoparticles is investigated for the formation of CuO tandem photothermal absorber starting from CuO-isopropanol suspension. Prior to the deposition step, the stabilization of the suspension in request is achieved via the addition of Mg(NO 3 ) 2 acting as a stabilizer but, also as a binder for the final coating. The colloidal dispersion stability is studied as a function of the concentration of Mg(NO 3 ) 2 added to the suspension by dynamic light scattering coupled with laser doppler velocimetry in order to determine the size and the charge of particles respectively. EPD parameters, such as the electric field and deposition time, have been investigated in order to control the thickness and the morphology in order to select the most promising coatings. The evolution of the thickness, obtained from scanning electron microscopy images, as a function of deposition time for different applied electric field is in agreement with a linear Hamaker law type. This is also used here as a first attempt to extract the effective density of the coating. Finally, the conversion efficiency of the tandem material is calculated from the reflectance spectra of the UV–vis-NIR and the Fourier transform InfraRed spectroscopy in order to link the EPD parameters to the spectral selectivity. The optimal coating was formed with an applied electric field of 50 V·cm − 1 for a deposition time of 30 min yield the highest efficiency at 0.8.
Published: 2017
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42. Stable uranium sols as precursors for the elaboration of nanostructured nc-UO 2 materials

Author: Martin Leblanc, Zijie Lu, Jérémy Causse, Diane Rébiscoul, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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.chemical_classification, Materials science, Precipitation (chemistry), Diffusion, Inorganic chemistry, Nanoparticle, Infrared spectroscopy, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Micelle, 0104 chemical sciences, Colloid, Colloid and Surface Chemistry, Pulmonary surfactant, chemistry, 0210 nano-technology, Alkyl, ComputingMilieux_MISCELLANEOUS
Abstract: This study presents a colloidal sol-gel and templating method to elaborate sols as precursors for nanostructured and nanocrystallized nc-UO2 materials. Several parameters were controlled in order to obtain such sols and materials, such as nanoparticles size, sol stability, target pore size and pores organization. In this study, the nanoparticles formation was managed controlling the thermodynamics of the surfactant solution and the U(IV) species polycondensation kinetics The kinetics of the nanoparticles formation has been limited by the availability of the uranium species either by their complexation either by their diffusion limitation. To reach this goal, two types of surfactant at a concentration allowing to obtain micelles were used: a carboxylate surfactant with a non-ionic ployethoxylated part able to complex multicharged ions (AKYPO® RO 90 VG), and alkyl polyglucosides (Glucopon® 215) in sufficient concentration allowing the decrease of the uranium species diffusion. The surfactant solutions, the sols elaborated by indirect precipitation from U(IV) solution, the sols after freeze-drying and the final materials were characterized by Small and Wide Angle X-ray Scattering, Infrared Spectroscopy and microscopy at various scale. The results show that the complexation by AKYPO and the good degradation of these molecules allowed to obtain stable sols and a promising partially nanostructured nc-UO2 materials. With Glucopon, its high concentration in the sol, led to a carbon enriched material with few nc-UO2 zones.
Published: 2017
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43. Drivers of Water Transport in Glass: Chemical or Topological Effect of the Glass Network?

Author: Hélène Aréna, O. Bouty, Clémentine Mansas, Jean-Marc Delaye, Diane Rébiscoul, Florence Bruguier, Bruno Penelon, Thibault Charpentier, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Département de recherche sur les Procédés et Matériaux pour les Environnements complexes (DPME), 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), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), 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-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), CEA, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Département de recherche sur les technologies pour l'enrichissement, le démantèlement et les déchets (DE2D), 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), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: Materials science, chemistry.chemical_element, 02 engineering and technology, Topology, Condensed Matter::Disordered Systems and Neural Networks, 01 natural sciences, Molecular dynamics, symbols.namesake, Aluminosilicate, Interstitial defect, 0103 physical sciences, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Boron, Topology (chemistry), 010302 applied physics, Water transport, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Characterization (materials science), Condensed Matter::Soft Condensed Matter, General Energy, chemistry, symbols, 0210 nano-technology, Raman spectroscopy
Abstract: International audience; The relation existing between water transport in glass, topology, chemical elements (network former and charge compensator), and their structural role in glass were investigated through glass topology modeling, glass and water structure analyses, and water diffusion characterization. Two series of aluminosilicate glasses with and without boron and having various ratios of charge compensators CaO/Na 2 O were used. The glass structure was characterized using Raman spectroscopy and nuclear magnetic resonance. Their topologies, i.e., the density of bottlenecks and the interstitial sites, were obtained by molecular dynamics. For glasses without boron, the substitution of Na by Ca leads to the strengthening of the glass network. The results are similar for glasses with boron except if the amount of Na is not sufficient. In this case, a part of Ca is required as a charge compensator for AlO 4 and BO 4 units. This last result is important since it highlights that the presence of boron and the CaO/Na 2 O ratio drives the roles of Ca inside the glass structure. Moreover, glass topology is driven by boron presence and to a lesser extent by CaO/Na 2 O ratio. Water transport characterized by the duration of the predominance of the hydration/interdiffusion processes, the apparent water diffusion coefficient, and the water structure in the hydrated glass were studied and determined using X-ray reflectivity and attenuated total reflectance infrared spectroscopy. The results show that the duration of the predominance of the hydration/interdiffusion processes is driven by the ability of Si-OX bonds to be hydrolyzed as much as the fraction of free water clusters in hydrated glass. Moreover, for aluminosilicate glasses, we show that water transport is mainly driven by glass topology through the role of Ca and its amount in glass. Indeed, Ca strengthens the glass network by decreasing the density of the bottleneck allowing the diffusion of water molecules. When boron is added to the glass, water transport may be mainly driven by the chemical interactions between the water molecules, Ca, and the network former of glass matrix.
Published: 2017
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44. Adsorption and separation of hydrocarbons by the metal organic framework MIL-101(Cr)

Author: Guillaume Toquer, Céline Shepherd, Jong-San Chang, Naseem A. Ramsahye, Lotfi Boudjema, Hichem Belarbi, Philippe Trens, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), 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)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Dept Chem Engr, Univ. California, Santa Barbara, Dept Chem Engr, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Korean Research Institute of Chemical Technology (KRICT), Korean Research Institute of Chemical Technology, 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), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Sorbent, Chemistry, Elution, Inorganic chemistry, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Branching (polymer chemistry), 01 natural sciences, 0104 chemical sciences, Cyclic Hydrocarbons, Hexane, chemistry.chemical_compound, Colloid and Surface Chemistry, Adsorption, Metal-organic framework, Gas chromatography, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: The aim of this work is to study the adsorption of several hydrocarbons by MIL-101(Cr) in order to find trends in adsorption behavior and relate those to the physicochemical properties of the sorbates. The separation of saturated, unsaturated and cyclic hydrocarbons was investigated on MIL-101(Cr) by means of gas chromatography equipped with a filled column of the MOF. MIL-101(Cr), proved to be very efficient to separate mixtures of saturated, unsaturated or aromatic hydrocarbons. The influence of hydrocarbons branching is evaluated towards their separation. We found that linear hydrocarbons are eluted firstly in the case of the n -hexane isomers series. We also demonstrated that xylenes are partially separated by MIL-101: metaxylene and paraxylene being eluted together, before orthoxylene. MIL-101 behaves therefore as a shape selective material with respect to the isomers of n -hexane, or xylenes. This separation could be predicted by the Henry’s constants which are calculated from the adsorption isotherms of single components by MIL-101(Cr). It is then demonstrated that these Henry’s constants establish a new tool for predicting the separation efficiency of any sorbent.
Published: 2017
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45. Sorption pH dependance of strontium/calcium by sodium nonatitanate

Author: Jean-François Dufrêche, Agnès Grandjean, Philippe Trens, Guillaume Toquer, Bertrand Siboulet, Arnaud Villard, Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Nanomatériaux pour l'Energie et le Recyclage (LNER), 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), 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: Environmental Engineering, Base (chemistry), Health, Toxicology and Mutagenesis, Sodium, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, Calcium, Chemical Fractionation, 010402 general chemistry, 01 natural sciences, Adsorption, [CHIM]Chemical Sciences, Environmental Chemistry, Equilibrium constant, chemistry.chemical_classification, Strontium, Public Health, Environmental and Occupational Health, Aqueous two-phase system, Sorption, General Medicine, General Chemistry, Hydrogen-Ion Concentration, 021001 nanoscience & nanotechnology, Pollution, 0104 chemical sciences, Ion Exchange, chemistry, 0210 nano-technology
Abstract: International audience; Sodium nonatitanate powder is a layered material containing some potential exchangeable sodium ions between layers. In this work, sorption mechanism of this material has been studied and modeled at the solid-liquid interface. In particular, the ion-exchange mechanism is up to now not entirely known and especially the role of the pH on sorption properties. To investigate this latter, the solid is first equilibrated with inert acidic and base (nitric acid and triethylamine) for which the co-ions nitrate and triethylammonium do not penetrate the solid. The exchange between proton or divalent ions (strontium or calcium), and the sodium initially located in the sodium nonatitanate, is characterized through capillary ionic chromatography and conductivity experiments. To understand and explain the sorption properties, we modeled the equilibrium constant of different exchange reactions as a function of the solution pH. The equilibrium constants of the strontium/sodium and the calcium/sodium exchange have been obtained. We have shown the important role of the pH on the sorption rate of the strontium and moreover the hydrolysis rate of the sodium nonatitanate is calculated. We found that one eighth of sodium is spontaneously hydrolysed in aqueous phase whereas seven-eighths are exchanged by different divalent cations (strontium or calcium). Strontium and calcium exhibit similar exchange curves and competition with the proton adsorbed is modeled with global equilibrium constant. The prediction is in agreement with the conductivity experiments and the global extraction isotherms.
Published: 2017
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46. Effect of secondary phases on the evolution of glass alteration

Author: Gentaz, Lucile, Lombardo, T., Chabas, Anne, Loisel, C., Neff, Delphine, Rebiscoul, D., Palacin, Serge, 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), 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 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-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), IRAMAT - Laboratoire Métallurgies et Cultures (IRAMAT - LMC), Institut de Recherches sur les Archéomatériaux (IRAMAT), Université de Technologie de Belfort-Montbeliard (UTBM)-Université d'Orléans (UO)-Université Bordeaux Montaigne (UBM)-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), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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 Technologie de Belfort-Montbeliard (UTBM)-Université d'Orléans (UO)-Université Bordeaux Montaigne-Centre National de la Recherche Scientifique (CNRS)-Université de Technologie de Belfort-Montbeliard (UTBM)-Université d'Orléans (UO)-Université Bordeaux Montaigne-Centre National de la Recherche Scientifique (CNRS), Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture et de la Communication (MCC)-Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture et de la Communication (MCC), 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), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Université Bordeaux Montaigne-Université de Technologie de Belfort-Montbeliard (UTBM)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Université Bordeaux Montaigne-Université de Technologie de Belfort-Montbeliard (UTBM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), 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), 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), 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 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), Université de Technologie de Belfort-Montbeliard (UTBM)-Université d'Orléans (UO)-Université Bordeaux Montaigne-Centre National de la Recherche Scientifique (CNRS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.MATE] Chemical Sciences/Material chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry
Abstract: International audience; Whatever the environment (soils, water and atmosphere), glass of varying compositions undergo alteration process conditioned by exposure conditions and glass intrinsic chemical and physical properties. Modification varies from a simple loss of transparency to a severe material loss but always involve modifications of the structure and chemical composition at the interface between the glass and the environment (hydration, dealkalinisation, dissolution,…). In many cases, these alteration of the glass structure are associated to the conjointed precipitation of secondary phases outside of the glass network often in cracks and fractures or directly on the glass outer surface. On site and laboratory alteration were both carried out for two very different environent : atmospheric and burial conditions. In the case of atmospheric alteration analogues and original stained glasses were compared in order to study the early and long-term evolution of the glass weathering. The samples observed in the two types of site show comparable alteration patterns. The nature of the precipitates outlines the impact of specific environmental conditions but, in every exposure conditions, similarities can be drawn on the secondary phases retroactive impact on the glass alteration processes. Nano-scale chemical characterization of the various phases was carried out through SEM-EDX, TEM-EDX; mineralogical characterization through electron diffraction, and STXM (for the structural environment of Si and Fe). From those observation some comparison of the phases influence on the system evolution and glass alteration can be made. Often, the precipitations are located within cracks inside the glass object. In some cases the precipitates have a clogging effect and can even trap glass-borne elements released from further alteration, but more often than not, local dissolution/precipitation of these secondary minerals inside the network favours the widening of the fractures, which facilitate fluid circulation, hence triggering further glass dissolution (congruent and selective) and precipitation of other secondary phases.
Published: 2017

47. Copper hexacyanoferrate functionalized singlewalled carbon nanotubes for selective cesium extraction

Author: Julien Cambedouzou, Mohamed Ali Zaïbi, Meherzi Oueslati, Jérémy Causse, Jean-Louis Bantignies, H. Draouil, Laurent Alvarez, Valérie Flaud, Unité de nanomatériaux et photonique [Tunis], Faculté des Sciences Mathématiques, Physiques et Naturelles de Tunis (FST), Université de Tunis El Manar (UTM)-Université de Tunis El Manar (UTM), Université de Tunis, Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), 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), Etude de la Matière en Mode Environnemental (L2ME), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), 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: Thermogravimetric analysis, Chemistry, Inorganic chemistry, chemistry.chemical_element, Nanoparticle, Sorption, 02 engineering and technology, General Chemistry, Carbon nanotube, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Copper, Catalysis, 0104 chemical sciences, law.invention, [CHIM.GENI]Chemical Sciences/Chemical engineering, X-ray photoelectron spectroscopy, law, Caesium, Desorption, Materials Chemistry, 0210 nano-technology
Abstract: Single-walled carbon nanotubes (SWCNTs) are functionalized with copper hexacyanoferrate (CuHCF) nanoparticles and therefore constitutes promising solid substrates for the sorption of Cs+ ions from liquid effluents. The high mechanical resistance and large electrical conductivity of SWCNTs are associated to the ability of CuHCF nanoparticles to selectively complex Cs+ ions in order to achieve membrane-like buckypapers presenting high loading capacity of cesium. The materials are thoroughly characterized using electron microscopy, Raman scattering, X-ray photoelectron spectroscopy and thermogravimetric analyses. Cs sorption isotherms are plotted after liquid phase ionic chromatography of the Cs solutions before and after exposure to the materials. It is found that the total sorption capacity of the material reaches 230 mg.g-1, and that one third of the sorbed Cs (80 mg.g-1) is selectively complexed in the CuHCF nanoparticles grafted on SWCNTs. These high values open interesting perspectives in the integration of such materials in electrically driven devices for the controlled sorption and desorption of these ions.
Published: 2017
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48. Zirconium(IV)-Benzene Phosphonate Coordination Polymers: Lanthanide and Actinide Extraction and Thermal Properties

Author: Daniel Vega, Juan J. Tejada, Guilhem Arrachart, Cyrielle Rey, Vittorio Luca, Comisión Nacional de Energía Atómica [ARGENTINA] (CNEA), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Nanomatériaux pour l'Energie et le Recyclage (LNER), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Lanthanide, Zirconium, Aqueous solution, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Phosphonate, 0104 chemical sciences, law.invention, Amorphous solid, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, law, Hydrothermal synthesis, [CHIM]Chemical Sciences, Carboxylate, Physical and Theoretical Chemistry, Crystallization, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: Coordination polymers with different P/(Zr + P) molar ratios were prepared by combining aqueous solutions of Zr(IV) and benzenephosphonate derivatives. 1,3,5-Benzenetrisphosphonic acid (BTP) as well as phosphonocarboxylate derivatives in which carboxylate substitutes one or two of the phosphonate groups were chosen as the building blocks. The precipitates obtained on combining the two solutions were not X-ray amorphous but rather were indicative of poorly ordered materials. Hydrothermal treatment did not alter the structure of the materials produced but did result in improved crystalline order. The use of HF as a mineralizing agent during hydrothermal synthesis resulted in the crystallization of at least three relatively crystalline phases whose structure could not be determined owing to the complexity of the diffraction patterns. Gauging from the similarity of the diffraction patterns of all the phases, the poorly ordered precipitates and crystalline materials appeared to have similar underlying structures. The BTP-based zirconium phosphonates all showed a higher selectivity for lanthanides and thorium compared with cations such as Cs(+), Sr(2+), and Co(2+). Substitution of phosphonate groups by carboxylate groups did little to alter the pattern of selectivity implying that selectivity in the system was entirely determined by the -POH group with little influence from the -COOH groups. Samples with the highest phosphorus content showed the highest extraction efficiencies for lanthanide elements, especially the heavy lanthanides such as Dy(3+) and Ho(3+) with separation factors of around four with respect to La(3+). In highly acid solutions (4 M HNO3) there was a pronounced variation in extraction efficiency across the lanthanide series. In situ, nonambient diffraction was performed on ZrBTP-0.8 loaded with Th, Ce, and a complex mixture of lanthanides. In all cases the crystalline Zr2P2O7 pyrophosphate phase was formed at ∼800 °C demonstrating the versatility of this structure.
Published: 2016
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49. Monolithic zirconia foams synthesis from emulsion stabilized by colloidal clusters

Author: Agnès Grandjean, Alban Gossard, Guillaume Toquer, Jérémy Causse, Service des Procedés de Décontamination et d'Enrobage des Déchets (SPDE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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: Materials science, General Chemical Engineering, Nanoparticle, 02 engineering and technology, General Chemistry, Thermal treatment, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 6. Clean water, Industrial and Manufacturing Engineering, 0104 chemical sciences, Chemical engineering, Emulsion, Environmental Chemistry, Cubic zirconia, 0210 nano-technology, Porosity, Porous medium, ComputingMilieux_MISCELLANEOUS, Monoclinic crystal system, Sol-gel
Abstract: A novel procedure for the build-up of monolithic zirconia foams and macro-mesoporous zirconia powders has been developed. A Zr-based colloidal sol is used as emulsifier in an emulsion free of surfactant in molecular form and where stability is given by the presence of colloidal clusters at oil/water interface. The accurate control of the sol–gel transition of these clusters made of Zr-based nanoparticles leads to the elaboration of porous materials in a two-in-one step method. Different parameters have been studied to allow a good control of the porosity of the material. This latter, characterized by SEM and nitrogen adsorption–desorption, is easily tuned (from 15 nm to 20 μm) by varying the emulsion shearing rate and mode. In appropriate conditions, the emulsified system can either lead to the formation of macroporous zirconia monoliths or macro-mesoporous zirconia powders. The monoliths were identified by X-ray diffraction as two pure crystalline phases depending on the thermal treatment: tetragonal and monoclinic at 400 and 1000 °C, respectively. The mechanical properties of the monoliths as well as an example of using these materials for solid phase extraction process are finally discussed.
Published: 2016
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50. Effect of the chemical nature of different transition metal ferrocyanides to entrap Cs

Author: Agnès Grandjean, Yves Barré, Joulia Larionova, Jérémy Causse, Yannick Guari, Carole Delchet, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Laboratoire des Procédés Supercritiques et de Décontamination (LPSD), CEA, 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), Laboratoire des Procédés Supercritiques et de Décontamination, Commisariat de l'Energie Atomique, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and 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)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Health, Toxicology and Mutagenesis, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Analytical Chemistry, Metal, chemistry.chemical_compound, Transition metal, Oxidation state, Radiology, Nuclear Medicine and imaging, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Equilibrium time, Public Health, Environmental and Occupational Health, Sorption, 021001 nanoscience & nanotechnology, Pollution, Grain size, 0104 chemical sciences, Nuclear Energy and Engineering, chemistry, Caesium, visual_art, visual_art.visual_art_medium, Ferrocyanide, 0210 nano-technology
Abstract: Transition metal ferrocyanides are used since many years to selectively entrap radio-cesium from nuclear contaminated effluents. We investigate the cesium sorption properties on a series of ferrocyanides containing different transition metal ions (Ni2+, Co2+ and Cu2+) and outline the role of the chemical nature of the bivalent metal ion, the iron oxidation state, the presence of K+ in the structure and the grain size of the powders on the equilibrium time and efficiency of the Cs+ sorption.
Published: 2016
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