Coupling between SAXS and Raman spectroscopy applied to the gelation of colloidal zirconium oxy-hydroxide systems

Abstract

The colloidal sol–gel transition based on zirconyl nitrate solution systems is investigated in this work. The different steps occurring in the transition have been identified by coupling small angle X-ray scattering with Raman spectroscopy and rheology measurements. The effect of the experimental conditions, such as the zirconium precursor concentration and pH, on the transition is studied. The precise mechanisms involved during the transition are based on a detailed understanding of the nanostructure of these systems. In particular, the dissolution of the zirconium salt leads to the formation of cyclic tetramers that self-organize into a cylindrical shape. We clearly demonstrate that increasing the pH induces a strong attractive interaction between the cylinders, giving rise to a mass fractal dimension. For each system, two characteristic pH values have been determined via rheological measurements analysis, where gelation is notably slow below the first pH value and precipitation occurs above the second one. The complete description of the quaternary system (zirconyl nitrate + acetylacetone + ammonia + water) is an efficient formulation guide for the further combination with a templating route leading to structured Zr-based materials.