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Synthèse et hydratation des hydroxydes lamellaires doubles : études des takovites

Abstract : Layered Double Hydroxide (LDH) are positively charged lamellar materials with a general formula written as [Ni2+1-xAI3+x(OH)2], [AZ-x/z, yH2O], where A is a compensating interlayer anion. These materials are easy to synthesize with adjustable structural parameters. The first part of this work focuses on the mechanisms operating upon synthesis of these compounds. The experimental approach combines analyses at the local scale by EXAFS with analyses at the semi-local scale by X Ray Scattering and Transmission Electron Microscopy. The hydrolytic behavior of pure nickel chloride and mixed nickel-gallium solutions was investigated. Nickel salts hydrolysis proceeds through the initial formation of long fibers that are then dissolved to form nickel hydroxide platelets. Upon hydrolysis of a mixed nickel -gallium solution, gallium oxyhydroxide like colloids form first whereas nickel ions do not react. Upon pH increase, gallium colloids are progressively replaced by LDH platelets through dissolution/reprecipitation. When synthesis is carried out by co-precipitation at constant pH, in the initial steps, aIl gallium atoms are incorporated jn a LDH phase whose stoichiometry differs from that corresponding to the initial conditions. SAXS experiments reveal the formation of fibrous colloids similar to those observed when nickel al one is hydrolyzed. Such fibrous species then dissolve which somehow adjusts the stoichiometry of the formed LDH.. AIl along the synthesis, part of nickel ions do not react and remain as monomers in the supematants. The second part deals with the hydration behavior of vriable charge Nil Al-sulfate LDHs that was investigated by combining i) water adsorption gravimetry measurements, ii) X-ray and neutron diffraction experiments under controlled water pressure and iii) Raman and infrared under controlled water pressure. The main " engine " for hydration is the ,interlayer anion whose interactions with the solid layer control the observed changes. For the high charge sample, anions, in a C3v, symmetry are linked to the layer through their apical oxygen atom. When water molecules are added, they move away from the layer to reach an situation of outer- sphere complex, that results in significant swelling of the structure. ln less charged LDHs, anions are linked more strongly to the layer. Vibrational spectroscopy results reveal that in these cases, the anions never reach an outer-sphere complex. Consequently, swelling is retarded or even nearly suppressed.
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Guillaume Defontaine. Synthèse et hydratation des hydroxydes lamellaires doubles : études des takovites. Sciences de la Terre. Institut National Polytechnique de Lorraine, 2004. Français. ⟨NNT : 2004INPL049N⟩. ⟨tel-01749822⟩

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