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Incorporation of chlorine in nuclear waste glasses using high-pressure vitrification: Solubility, speciation, and local environment of chlorine

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  • معلومة اضافية
    • Contributors:
      Laboratoire de physique subatomique et des technologies associées (SUBATECH); Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique (IMT Atlantique); Institut Mines-Télécom Paris (IMT)-Institut Mines-Télécom Paris (IMT)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST); Nantes Université - pôle Sciences et technologie; Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie; Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ); Laboratoire de Planétologie et Géosciences UMR_C 6112 (LPG); Le Mans Université (UM)-Université d'Angers (UA)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST); Institut des Matériaux de Nantes Jean Rouxel (IMN); Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST); Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - Ecole Polytechnique de l'Université de Nantes (Nantes Univ - EPUN); Synchrotron SOLEIL (SSOLEIL); Centre National de la Recherche Scientifique (CNRS)
    • بيانات النشر:
      HAL CCSD
      Mineralogical Society of America
    • الموضوع:
      2023
    • Collection:
      Archives ouvertes Hal IMT Atlantique
    • نبذة مختصرة :
      International audience ; The solubility, speciation, and local atomic environment of chlorine have been determined for aluminoborosilicate glasses equilibrated with various sources of chlorine (NaCl and PdCl2) at high pressure (0.5-1.5 GPa) and high temperature (1350-1400 ?). The Cl solubility reaches up to 11 mol% in borosilicate glass and appears to be strongly influenced by the concentration of network-modifying cations (Ca and Na) and increases with increasing CaO + Na2O content. The Cl solubility is enhanced in Ca-bearing rather than Na-bearing borosilicate glass, suggesting a higher affinity of chlorine for alkaline-earth cations. Cl K-edge XANES and Cl 2p XPS spectra reveal that chlorine dissolves in glasses only as chloride species (Cl-) and no evidence of oxidized species is observed. Using PdCl2 as a chlorine source leads to a pre-edge signal for PdCl2 in the XANES spectra. The EXAFS simulations show that the Cl- local environment is charge compensated by Na+ or Ca2+ at a distance to first neighbor on the order of 2.7 angstrom, which is comparable to the observed distances in crystalline chloride compounds. The coordination to charge compensating cation is lower in the case of Ca2+ (similar to 1.1) than Na+ (similar to 4.3).
    • Relation:
      hal-04158377; https://hal.science/hal-04158377; https://hal.science/hal-04158377/document; https://hal.science/hal-04158377/file/Jolivet%20et%20al%202023_Cl%20in%20aluminoborosilicate%20glasses.pdf; INSPIRE: 2675831
    • الرقم المعرف:
      10.2138/am-2022-8599
    • Rights:
      info:eu-repo/semantics/OpenAccess
    • الرقم المعرف:
      edsbas.35E2B6D0