Soft solution fluorine-free synthesis of anatase nanoparticles with tailored morphology

TiO₂ nanoparticles with tailored morphology have been synthesized under exceptionally soft conditions. The strategy is based on the use of a non-aqueous alcoholic reaction medium in which water traces, coming either from the air (atmospheric water) or from an ethanol–water azeotropic mixture (ethanol 96%), are incorporated in order to accelerate hydrolysis of the Ti–precursor. Moreover, organic surfactants have been used as capping agents so as to tailor crystal growth in certain preferential directions. Combinations of oleic acid and oleylamine, which lead to the formation of another surfactant, dioleamide, are employed instead of fluorine-based compounds, thus increasing the sustainability of the process. As a result, TiO₂ nanostructured hierarchical microspheres and individual nanoparticles with exposed high-energy facets can be obtained at atmospheric pressure and temperatures as low as 78 °C.     

Dense fine-grained biphasic calcium phosphate (BCP) bioceramics designed by two-step sintering

In this study, dense, fine-grained biphasic calcium phosphate bioceramics were designed via the two-step sintering method. The starting powder was nanosized calcium-deficient hydroxyapatite, whose phase composition, average particle size and morphology were characterized by XRD, FTIR, Raman spectroscopy, laser diffraction and FE-SEM. The phase transformations of the initial powder during heating up to 1200 °C were examined using TG/DSC. At first, conventional sintering was performed and the recorded shrinkage/densification data were used to find out the appropriate experimental conditions for two-step sintering. The obtained results show that two-step sintering yields BCP ceramics, consisting of hydroxyapatite and β-TCP, with full dense, homogeneous structure with average grain size of 375 nm. Furthermore, BCP ceramics obtained by the two-step sintering method exhibit improved mechanical properties, compared to conventionally sintered BCP.     

Phosphorus dynamics in permanent pastures: differential fertilizing and the animal effect

The general objective of this study was to evaluate the deviation between measured and estimated soil phosphorus (P) content, over 3 years, in a permanent bio-diverse pasture system in Southern Portugal with grazing sheep, and subjected to annual, differential P fertilization. The results can be a contribution to the development of practical and effective site-specific management strategies to minimize pasture yield variation. The soil and pasture samples were taken from a 6 ha field and were geo-referenced with RTK GPS. This procedure was carried out, each year, from March to May, according to the vegetative growth of the pasture. In October of each year the field was fertilized in a differential manner, as a function of soil P concentration measured at the end of the pasture growth cycle (May–June). Maps were developed in ARCGIS 9.3 considering: (1) the soil P concentration and pH; (2) the average P plant uptake; (3) the differential P application; and (4) the extractable P. The significant temporal variability of soil P concentration and pasture dry matter yield confirm the complexity of soil P dynamics in pastures involving two biological systems: plant and animal, under Mediterranean conditions and the consequent difficulties in implementing precision agriculture techniques. The results of this work indicate that 3 years of P variable-rate application rate were not sufficient to obtain homogeneous and adequate levels of P in the whole field for crop production. Despite differential P fertilization with the objective of obtaining homogenous values of soil P content in experimental field, the undulating topography of the experimental field associated with the presence of grazing animals adds a notable short-range spatial variation in nutrients that generally arises from heterogeneous excreta depositions. The small and positive final deviation between measured and estimated P levels suggests the irregular and gradual release of P by the fertilizer over years, contributing to an increase in soil P concentration. P input in fertilizer and removal in the crop greatly exceed all other inputs and outputs. However, the pH effect on extractable P, the estimation of amounts of export/import by livestock, atmospheric deposition or erosion/leaching losses are complex and justify more experiments to evaluate the confidence of long-term estimated P dynamic balance before sustained decision making is possible for differential pasture fertilization and site-specific management strategy implementation.     

In‐line optical techniques to characterize the polymer extrusion

In the past 15 years our research group has been creating new optical devices to characterize in real time the extrusion process. These detectors are made of a slit‐die fitted at the extruder exit from where the molten polymer flows, with a pair of transparent windows that allows a light beam to pass orthogonally through the molten flow. Following the reduction of the transmitted light intensity one is able to quantify the turbidity, which is a function of the type, concentration and particle size and shape of the second phase present in the flow. By evaluating the scattering pattern of a laser beam (LALLS) it is possible to get information upon the morphology of the molten polymeric system in real time during the extrusion. With the interposition of a pair of crossed polarizers in the optical beam, rheo‐polarimetry, it is possible to evaluate quantitatively the flow birefringence, which is a function of the degree of the polymer matrix orientation. POLYM. ENG. SCI., 54:386–395, 2014. © 2013 Society of Plastics Engineers     

Photocatalytic oxidation of oxalic acid in dilute aqueous solution,in a fully illuminated fluidized bed reactor

A comprehensive kinetic model for the photooxidation of oxalic acid (C₂O₄H₄) in a fluidized bed (FB) of a TiO₂/quartz sand composite, in a UV-fully illuminated photoreactor, was developed and correlated with experimental results. A proper solution for the mass balance of the reacting system was achieved by combining the complete radiation field profile and the most recent and updated pathway for the adsorption and photodecomposition of oxalic acid onto TiO₂ (Mendive et al., 2007), which was employed to determine the kinetic expression and model parameters.