Molecular mechanisms induced by phase modifiers used in hydrometallurgy: consequences on transfer efficiency and process safety

It is a matter of strategic independence for many countries to urgently find processes that take into account environmental and economic issues when recycling critical metals. Liquid–liquid (L/L) extraction is a promising method for recovering rare-earth elements from electrical and electronic waste. However, an optimized process on an industrial scale has not yet been established. One of the main reasons is the lack of fundamental knowledge. Therefore, designing a cost-effective and adaptive formulation is still beyond the scope of possibilities. This requires deciphering the molecular forces that control ion transfer beyond the classical supramolecular complexation and developing predictive models compatible with the design and control needs of recycling processes. In all liquid/liquid processes, the high loading of the organic solvent with metal salts/acids or extractant can sometimes lead to a third phase formation. Phase modifiers are often added to the solvent phase in order to prevent the formation of this third phase. However, the effect of these additives on the extraction efficiency as well as their mechanisms of action are still poorly understood. The phase modifiers used in industrial processes are mainly fatty alcohols, called “lipotropes”. In this paper, we study a new class of molecules opening new possibilities beyond the commonly used phase modifiers (i.e., n-octanol). These are the “hydrotropic” molecules. We first show the role of a model hydrotrope (PnP) in preventing the third phase formation for different extraction systems. We also show that the role of modifiers can be understood according to three molecular mechanisms: as co-solvent, as co-surfactant and by preferential solvation. The dominant molecular effect can be identified and quantified by combining surface tension and neutron scattering experiments. In the case of phase modifiers that are hydrotropes, the co-solvent or co-surfactant effect is dominant. In the case of “lipotropes”, the preferential solvation mechanism is emphasized. Finally, the consequences of these mechanisms on the extraction efficiency and selectivity are discussed

Caractérisation structurale, poreuse et mécanique de films minces de silice mésoporeuse.<br />Influence de la fonctionnalisation

This work dealt with the synthesis and characterization of mesoporous silica thin films. The synthesis uses the surfactant self-assembly route in order to template a silica gel. Hybrid thin films presenting a high degree of organization at the nanometer scale are obtained. Then the surfactant removal leads to materials of organized and tailored porosities and of large surface areas.Different synthesis parameters have been investigated. In situ measurements carried out by X ray Reflectivity (XR) and Grazing Incidence Small Angle X-ray Scattering (GISAXS) have evidenced the major role played by the relative humidity. Some surfactant removal methods by ethanol rinsing have also been tested, with the intent to empty the mesopores without collapsing the mesostructured films.Based on the complete analysis of the reflectivity curves, a new method to determine the porosity of thin films has been developed. In combination with GISAXS experiments the pore and wall sizes, the surface area of the films and their pore distortion were obtained.The mesopores have a perfect size to promote the capillary condensation of water at ambient relative humidity. As the electron density contrast decreases strongly when water infiltrates the mesopores, the XR and GISAXS techniques have permitted to monitor by different ways the adsorption and the desorption of water in the porous network. The pore size distribution and porosity were estimated from the analysis of isotherms. Looking at the direct film structure deformation during the humidity cycles, some mechanical properties have also been investigated yielding the quantitative determination of the Young Modulus.Finally, this thesis was concluded by the study of the mesoporous films functionalisation. Different kinds of chemical functions have been grafted at the surface of mesopore with the aim to modify their hydrophilicity or their chemical reactivity.Ce travail de thèse a porté sur la synthèse et la caractérisation de films minces de silice mésoporeuse. La synthèse de ces matériaux est basée sur l'auto-organisation de tensioactifs qui permettent de structurer à l'échelle nanométrique un squelette, constitué ici d'un gel de silice.Les paramètres pertinents influençant la structuration des films minces ont été appréhendés. En particulier, des études in situ par réflectivité des rayons X et par Diffusion en incidence rasante des rayons X (Grazing Incidence Small Angle X-ray Scattering, GISAXS), ont permis de mettre en évidence le rôle prédominant de l'humidité relative. Des protocoles d'extraction par rinçage à l'éthanol ont été établis pour dégager efficacement les structures mésoporeuses sans les écraser.Une méthode d'analyse de la porosité des films minces a ensuite été développée. Cette méthode est basée sur l'analyse quantitative des courbes de réflectivité par la méthode matricielle. Complémentée par l'analyse des clichés GISAXS, elle nous a permis de déterminer sur couche mince non seulement la porosité, la taille des pores et des murs mais aussi la surface spécifique et la distorsion des pores.Les pores de ces films mésoporeux ont une dimension idéale pour y parfaire l'étude de la condensation capillaire de l'eau. Quand l'eau pénètre dans les pores, le contraste de densité électronique décroît fortement. Ainsi, les techniques de diffusion des rayons X (réflectivité et GISAXS) permettent de suivre les isothermes de condensation et de désorption de l'eau dans les pores. La distribution de taille des pores peut alors être obtenue. Les isothermes d'adsorption d'eau ont permis également d'estimer la porosité, mais aussi d'appréhender par le biais de l'équation de Laplace, les propriétés mécaniques des films en accédant à leur module d'Young. Finalement nous avons conclu cette thèse par l'étude de la fonctionnalisation des films par divers groupements fonctionnels localisés à la surface des mésopores, dans l'optique de modifier leur hydrophilicité ou leur réactivité chimique

Caractérisation structurale, poreuse et mécanique de films minces de silice mésoporeuse (influence de la fonctionnalisation)

Ce travail de thèse a porté sur la synthèse et la caractérisation de films minces de silice mésoporeuse. La synthèse de ces matériaux est basée sur l auto-organisation de tensioactifs qui permettent de structurer à l'échelle nanométrique un squelette, constitué ici d un gel de silice. Les paramètres pertinents influençant la structuration des films minces ont été appréhendés. En particulier, des études in situ par réflectivité des rayons X et par Diffusion en incidence rasante des rayons X (Grazing Incidence Small Angle X-ray Scattering, GISAXS), ont permis de mettre en évidence le ro le prédominant de l humidité relative. Des protocoles d extraction par rinçage à l éthanol ont été établis pour dégager efficacement les structures mésoporeuses sans les écraser. Une méthode d'analyse de la porosité des films minces a ensuite été développée. Cette méthode est basée sur l analyse quantitative des courbes de réflectivité par la méthode matricielle. Complémentée par l'analyse des clichés GISAXS, elle nous a permis de déterminer sur couche mince non seulement la porosité, la taille des pores et des murs mais aussi la surface spécifique et la distorsion des pores. Les pores de ces films mésoporeux ont une dimension idéale pour y parfaire l'étude de la condensation capillaire de l eau. Quand l'eau pénètre dans les pores, le contraste de densité électronique décroît fortement. Ainsi, les techniques de diffusion des rayons X (réflectivité et GISAXS) permettent de suivre les isothermes de condensation et de désorption de l'eau dans les pores. La distribution de taille des pores peut alors être obtenue. Les isothermes d adsorption d eau ont permis également d'estimer la porosité, mais aussi d'appréhender par le biais de l'équation de Laplace, les propriétés mécaniques des films en accédant à leur module d Young. Finalement nous avons conclu cette thèse par l'étude de la fonctionnalisation des films par divers groupements fonctionnels localisés à la surface des mésopores, dans l'optique de modifier leur hydrophilicité ou leur réactivité chimique.This work dealt with the synthesis and characterization of mesoporous silica thin films. The synthesis uses the surfactant self-assembly route in order to template a silica gel. Hybrid thin films presenting a high degree of organization at the nanometer scale are obtained. Then the surfactant removal leads to materials of organized and tailored porosities and of large surface areas. Different synthesis parameters have been investigated. In situ measurements carried out by X ray Reflectivity (XR) and Grazing Incidence Small Angle X-ray Scattering (GISAXS) have evidenced the major role played by the relative humidity. Some surfactant removal methods by ethanol rinsing have also been tested, with the intent to empty the mesopores without collapsing the mesostructured films. Based on the complete analysis of the reflectivity curves, a new method to determine the porosity of thin films has been developed. In combination with GISAXS experiments the pore and wall sizes, the surface area of the films and their pore distortion were obtained. The mesopores have a perfect size to promote the capillary condensation of water at ambient relative humidity. As the electron density contrast decreases strongly when water infiltrates the mesopores, the XR and GISAXS techniques have permitted to monitor by different ways the adsorption and the desorption of water in the porous network. The pore size distribution and porosity were estimated from the analysis of isotherms. Looking at the direct film structure deformation during the humidity cycles, some mechanical properties have also been investigated yielding the quantitative determination of the Young Modulus. Finally, this thesis was concluded by the study of the mesoporous films functionalisation. Different kinds of chemical functions have been grafted at the surface of mesopore with the aim to modify their hydrophilicity or their chemical reactivity.LE MANS-BU Sciences (721812109) / SudocSudocFranceF

Analysis of water condensation in P123 templated 2D hexagonal mesoporous silica films by X-ray reflectivity

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Analysis of mesoporous thin films by X-ray reflectivity, optical reflectivity and grazing incidence small angle X-ray scattering

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Importance of weak interactions in the formulation of organic phases for efficient L/L extraction of metals

International audienceRecent experimental studies demonstrate the need to take into account weak interactions in the understanding of solvent extraction processes. This well-established industrial technology now beneficiates of a supramolecular approach, complementary to the traditional analysis based on coordination chemistry. In this article, we focus on the integration of a colloidal approach in the analysis of solvent extraction systems: organic phases employed are complex fluids, in which extracting molecules self-assemble into reverse aggregates. We detail the available analytical tools employed towards characterization of these organic phases, and emphasize the recent results in aggregation driven extraction. All experimental data is discussed in light of theoretical approaches which propose adequate thermodynamic models and shed light on the importance of entropy on the phenomena. Diluent effects or synergism have been successfully rationalized, efficient new formulations based on a physico-chemical analysis have been proposed, and the door is now open for further development at industrial scale

Extended Surfaces Nanopatterned with Functionalized Cavities for Positioning Nanoparticles

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In situ grazing incidence small-angle x-ray scattering real-time monitoring of the role of humidity during the structural formation of templated silica thin films

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