A thermodynamic analysis of the synthesis of face-centred cubic (fcc) and body-centred cubic (bcc) solid solutions of Ti-based alloys produced by mechanical alloying was performed. Four Ti-based alloys were analysed: (i) Ti-13Ta-3Sn (at.%), (ii) Ti-30Nb-13Ta (at.%), (iii) Ti-20Nb-30Ta (wt. %) and (iv) Ti-33Nb-4Mn (at.%). The milled powders were characterized by X-ray diffraction, and the crystallite size and microstrain were determined using the Rietveld and Williamson–Hall methods. The Gibbs free energy of mixing for the formation of a solid solution of the three ternary systems (Ti-Ta-Sn, Ti-Nb-Ta and Ti-Nb-Mn) was calculated using an extended Miedema’s model, applying the Materials Analysis Applying Thermodynamics (MAAT) software. The values of the activity of each component were determined by MAAT. It was found that increasing the density of crystalline defects, such as dislocations and crystallite boundaries, changed the solubility limit in these ternary systems. Therefore, at longer milling times, the Gibbs free energy increases, so there is a driving force to form solid solutions from elemental powders. Finally, there is agreement between experimental and thermodynamic data confirming the formation of solid solutions.
Acidithiobacillus ferrooxidans has been shown to be a good depressant of pyrite in freshwater and seawater flotation. However, the effect of these bacteria over copper-activated pyrite has not been studied. At the industrial scale, the activation of pyrite with copper is a common process that occurs because ions, released from other minerals, react with pyrite. This is a problem because ions facilitate the reaction of pyrite with the xanthate collectors, becoming hydrophobic and reaching the froth. In this study, microflotation experiments in a Hallimond tube were conducted to evaluate the depressant effect of A. ferrooxidans over non-activated and Cu-activated pyrite in freshwater and seawater flotation. The experiments were carried out at pH 4, 6, 8, 10 and 12 and pyrite was mixed with CuSO4 at and M in order to activate its surface. Considering the results obtained in the microflotation tests, it is possible to conclude that Acidithiobacillus ferrooxidans is able to depress non-activated and Cu-activated pyrite at the entire pH range studied (4–12) in freshwater. On the other hand, the use of bacteria in flotation with seawater proved to be effective to depress non-activated and Cu-activated pyrite at pH 8 and 10 with better results achieved at pH 10. At this pH, the non-activated pyrite recovery dropped from 96% to 15%, and the recovery of Cu-activated pyrite dropped from 95% to 32% when the activation was carried out at M, and from 87% to 50% when the activation was conducted at M of CuSO4. The XPS analysis showed that chalcopyrite and copper (II) hydroxide were formed on the pyrite surface when it is contacted with CuSO4.
In the present work, the streaming potential of A. ferrooxidans and pyrite was measured in two environments: fresh and saline water (water with 35 g/L of NaCl) at different pH values. Also, attachment kinetics of A. ferrooxidans to pyrite was studied in fresh and saline water at pH 4. The results show that A. ferrooxidans and pyrite had lower streaming potentials (comparing absolute values) in saline water than in fresh water, indicating the compression in the electrical double layer caused by Cl− and Na+ ions. It was also determined that the bacteria had a higher level of attachment to pyrite in fresh water than in saline water. The high ionic strength of saline water reduced the attractive force between A. ferrooxidans and pyrite, which in turn reduced bacterial attachment. Electrostatic interactions were determined to be mainly repulsive, since the bacteria and mineral had the same charge at pH 4. Despite this, the bacteria adhered to pyrite, indicating that hydrophobic attraction forces and Lifshitz–van der Waals interactions were stronger than electrostatic interactions, which caused the adhesion of A. ferrooxidans to pyrite.