The structural properties of zinc ferrite nanoparticles with spinel structure dispersed in a highly porous SiO2 aerogel matrix were compared with a bulk zinc ferrite sample. In particular, the details of the cation distribution between the octahedral (B) and tetrahedral (A) sites of the spinel structure were determined using X-ray absorption spectroscopy. The analysis of both the X-ray absorption near edge structure and the extended X-ray absorption fine structure indicates that the degree of inversion of the zinc ferrite spinel structures varies with particle size. In particular, in the bulk microcrystalline sample, Zn2+ ions are at the tetrahedral sites and trivalent Fe3+ ions occupy octahedral sites (normal spinel). When particle size decreases, Zn2+ ions are transferred to octahedral sites and the degree of inversion is found to increase as the nanoparticle size decreases. This is the first time that a variation of the degree of inversion with particle size is observed in ferrite nanoparticles grown within an aerogel matrix.
The effect of microstructure and chemistry on the kinetics of passive layer growth and passivity breakdown of some Ti-based alloys, namely Ti-6Al-4V, Ti-6Al-7Nb and TC21 alloys, was studied. The rate of pitting corrosion was evaluated using cyclic polarization measurements. Chronoamperometry was applied to assess the passive layer growth kinetics and breakdown. Microstructure influence on the uniform corrosion rate of these alloys was also investigated employing dynamic electrochemical impedance spectroscopy (DEIS). Corrosion studies were performed in 0.9% NaCl solution at 37 °C, and the obtained results were compared with ultrapure Ti (99.99%). The different phases of the microstructure were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Chemical composition and chemistry of the corroded surfaces were studied using X-ray photoelectron spectroscopy (XPS) analysis. For all studied alloys, the microstructure consisted of α matrix, which was strengthened by β phase. The highest and the lowest values of the β phase’s volume fraction were recorded for TC21 and Ti-Al-Nb alloys, respectively. The susceptibility of the investigated alloys toward pitting corrosion was enhanced following the sequence: Ti-6Al-7Nb < Ti-6Al-4V << TC21. Ti-6Al-7Nb alloy recorded the lowest pitting corrosion resistance (Rpit) among studied alloys, approaching that of pure Ti. The obvious changes in the microstructure of these alloys, together with XPS findings, were adopted to interpret the pronounced variation in the corrosion behavior of these materials.