Colloid and Polymer Science

, Volume 293, Issue 1, pp 1–22 | Cite as

Recycling metals by controlled transfer of ionic species between complex fluids: en route to “ienaics”

  • Thomas ZembEmail author
  • Caroline Bauer
  • Pierre Bauduin
  • Luc Belloni
  • Christophe Déjugnat
  • Olivier Diat
  • Véronique Dubois
  • Jean-François Dufrêche
  • Sandrine Dourdain
  • Magali Duvail
  • Chantal Larpent
  • Fabienne Testard
  • Stéphane Pellet-Rostaing
Invited Review


Recycling chemistry of metals and oxides relies on three steps: dissolution, separation and material reformation. We review in this work the colloidal approach of the transfer of ions between two complex fluids, i.e. the mechanism at the basis of the liquid-liquid extraction technology. This approach allows for rationalizing in a unified model transformation such as accidently splitting from two to three phases, or uncontrolled viscosity variations, as linked to the transformation in the phase diagram due to ion transfer. Moreover, differences in free energies associated to ion transfer between phases that are the origin of the selectivity need to be considered at the meso-scale beyond parameterization of an arbitrary number of competing “complexes”. Entropy and electrostatics are taken into account in relation to solvent formulation. By analogy with electronics dealing about electrons transported in conductors and semi-conductors, this “ienaic” approach deals with ions transported between nanostructures present in colloidal fluids under the influence of chemical potential gradients between nanostructures coexisting in colloidal fluids. We show in this review how this colloidal approach generalizes the multiple chemical equilibrium models used in supra-molecular chemistry. Statistical thermodynamics applied to self-assembled fluids requires only a few measurable parameters to predict liquid-liquid extraction isotherms and selectivity in multi-phase chemical systems containing at least one concentrated emulsified water in oil (w/o) or oil in water (o/w) microemulsion.


Ieanics Liquid-liquid extraction Self-assembly Free energy of transfer Ion selectivity Adsoprtion isotherm 



The following PhD students and postdoctoral researchers have participated in solving experimental or theoretical difficulties in determining either structure or thermodynamics aspects of ienaics in solvents since 1986: Ian S Barnes and Paul-Joel Dérian for the percolation behaviour of w/o reverse aggregates, Corinne Erlinger-Verdier for the detection of micelles and the determination of three phase accident phase boundary limits, Sandrine Nave for the characterization of aggregates of TBP, Laurence Martinet for quantitative determination of europium extraction aspects, Sylvain Prévost and Hélène Coulombeau from the University of Versailles St Quentin for the solvent-free aspects of separation chemistry using thermo-sensitive extractants, Yannick Meridiano for measuring water co-extraction with acids allowing to quantify polar core volumes and Wolfram Müller for the aspects linked to liquid-solid extraction via non-classical precipitation. This work could not been done without permanent discussion and exchange of ideas with colleagues from industrial chemical engineering Departments at CEA initiated by Claude Musikas, Charles Madic and Bernard Boullis in the 1990s and still going on in 2013 with Laurence Berthon, Philippe Guilbaud and Jean Duhamet. Extremely fruitful discussions with Andreas Geist on breackdonw of “slope method”, Ken Nash on double complex fluid methods such as Talspeak and Ross Ellis including the electrochemistry term in the energy of transfer are acknowledged, together with ERC, within the “REE_-CYCLE” project 2013_2018.

This paper is the written version of the lecture given at the occasion of the Thomas Graham medal 2013 forwarded to Thomas Zemb by Walter Richtering on behalf of DKG on September 24th, 2013 in Paderborn. Facilitated access to the paper is brought by the DKG for which the help is acknowledged deeply.


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Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Thomas Zemb
    • 1
    Email author
  • Caroline Bauer
    • 1
  • Pierre Bauduin
    • 1
  • Luc Belloni
    • 2
  • Christophe Déjugnat
    • 1
  • Olivier Diat
    • 1
  • Véronique Dubois
    • 1
  • Jean-François Dufrêche
    • 1
  • Sandrine Dourdain
    • 1
  • Magali Duvail
    • 1
  • Chantal Larpent
    • 3
  • Fabienne Testard
    • 2
  • Stéphane Pellet-Rostaing
    • 1
  1. 1.Institut de Chimie Séparative de Marcoule (ICSM) UMR5257 CEA/CNRS/UM2/ENSCM, Site de MarcouleBagnols-sur-CèzeFrance
  2. 2.SIS2M, IRAMIS, CEA SaclayGif-sur-YvetteFrance
  3. 3.Institut Lavoisier de Versailles, UMR CNRS 8180Université de Versailles St Quentin-en-YvelinesVersaillesFrance

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