Structural and phenomenological characterization of the thermoreversible sol-gel transition of a zirconyl aqueous precursor modified by sulfuric acid

The thermoreversible sol-gel transition is well-known in biological and organic polymeric systems but has not been reported for inorganic systems. In this paper we put in evidence a thermoreversible sol-gel transition for zirconyl chloride aqueous solutions modified by sulfuric acid in the ratio 3:1 Zr:SO4. The synthesis conditions are detailed and a variety of experimental techniques (turbidimetry, dynamic rheology, and EXAFS) have been employed for investigating the thermal reversibility and the chemical structure of this new material. Turbidimetric measurements performed for solutions containing different concentrations of precursor have evidenced that the sol-gel transformation temperature increases from 50 to 80 degrees C as the concentration of zirconyl chloride decreases from 0.22 to 0.018 mol L-1. A more detailed study has been done for the sample with [Zr] = 0.156 mol L-1, in which the sol-gel-sol transformation has been repeated several times by a cyclic variation of the temperature. The mechanical properties of this sample, evaluated by measuring the storage and the loss moduli, show a change from liquid like to viscoelastic to elastic behavior during the sol-gel transition and vice versa during the gel-sol one. In situ EXAFS measurements performed at the Zr K-edge show that no change of the local order around Zr occurs during the sol-gel-sol transition, in agreement with the concept of physical gel formation. We have proposed for the structure of the precursor an inner core made of hydroxyl and oxo groups bridging together zirconium atoms surrounded in surface by complexing sulfate ligands, the sulfate groups act as a protective layer, playing a key role in the linking propagation among primary particles during sol-gel-sol transition.

Rheology and fluid dynamics properties of sugarcane juice

The sugarcane juice is a relatively low-cost agricultural resource, abundant in South Asia, Central America and Brazil, with vast applications in producing ethanol biofuel. In that way, a good knowledge of the rheological properties of this raw material is of crucial importance when designing and optimizing unit operations involved in its processing. In this work, the rheological behavior of untreated (USCJ, 17.9 °Brix), clarified (CSCJ, 18.2 °Brix) and mixed (MSCJ, 18.0 °Brix) sugarcane juices was studied at the temperature range from 277K to 373K, using a cone-and-plate viscometer. These fluids were found to present a Newtonian behavior and their flow curves were well-fitted by the viscosity Newtonian model. Viscosity values lied within the range 5.0×10 -3Pas to 0.04×10 -3Pas in the considered temperature interval. The dependence of the viscosity on the temperature was also successfully modeled through an Arrhenius-type equation. In addition to the dynamic viscosity, experimental values of pressure loss in tube flow were used to calculate friction factors. The good agreement between predicted and measured values confirmed the reliability of the proposed equations for describing the flow behavior of the clarified and untreated sugarcane juices. © 2010 Elsevier B.V.