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Coexistence of Transient Liquid Droplets and Amorphous Solid Particles in Nonclassical Crystallization of Cerium Oxalate

Authors :
Maxime Durelle
Sophie Charton
Frédéric Gobeaux
Corinne Chevallard
Luc Belloni
Fabienne Testard
Sylvain Trépout
David Carriere
Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS)
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)
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)
Multimodal Imaging Center (Centre d'Imagerie Multimodale) (MIC)
Institut Curie [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)
Source :
Journal of Physical Chemistry Letters, Journal of Physical Chemistry Letters, 2022, 13, pp.8502-8508. ⟨10.1021/acs.jpclett.2c01829⟩
Publication Year :
2022
Publisher :
HAL CCSD, 2022.

Abstract

International audience; Crystallization from solution often occurs via “nonclassical” routes; that is, it involves transient, non-crystalline states like reactant-rich liquid droplets and amorphous particles. However, in mineral crystals, the well-defined thermodynamic character of liquid droplets and whether they convert─or not─into amorphous phases have remained unassessed. Here, by combining cryo-transmission electron microscopy and X-ray scattering down to a 250 ms reaction time, we unveil that crystallization of cerium oxalate involves a metastable chemical equilibrium between transient liquid droplets and solid amorphous particles: contrary to the usual expectation, reactant-rich droplets do not evolve into amorphous solids. Instead, at concentrations above 2.5 to 10 mmol L–1, both amorphous and reactant-rich liquid phases coexist for several tens of seconds and their molar fractions remain constant and follow the lever rule in a multicomponent phase diagram. Such a metastable chemical equilibrium between solid and liquid precursors has been so far overlooked in multistep nucleation theories and highlights the interest of rationalizing phase transformations using multicomponent phase diagrams not only when designing and recycling rare earths materials but also more generally when describing nonclassical crystallization.

Details

Language :
English
ISSN :
19487185
Database :
OpenAIRE
Journal :
Journal of Physical Chemistry Letters, Journal of Physical Chemistry Letters, 2022, 13, pp.8502-8508. ⟨10.1021/acs.jpclett.2c01829⟩
Accession number :
edsair.doi.dedup.....3cdf677dd3a1fc62c5f42074714fa668
Full Text :
https://doi.org/10.1021/acs.jpclett.2c01829⟩