Iron oxidation state effect on the Mg-Al- Si-O glassy system

Mg-Al-Si-O glassy systems have a great importance in a wide range of industrial applications, specifically as an electrolyte for molten oxide electrolysis processes in steelmaking. Understanding how the iron oxidation state of the raw material (Fe2+/Fe3+) and its corresponding amount influence this glassy system's properties will be the aim of the current work. Iron oxides (as Fe2O3 or Fe3O4) were used to dope Mg-Al-Si-O system obtaining amorphous materials through an unconventional method: Laser Floating Zone (LFZ). Above 8% mol of Fe formation of magnetic phases or iron clusters, were observed in the glass matrix. Samples with Fe2O3 showed a higher crystal concentration, when compared with Fe3O4. The electron paramagnetic resonance measurements show a strong dependence on the iron source (Fe3O4 or Fe2O3). In addition, the magnetization decreases linearly with iron content, independently of iron oxidation state, except for samples with a higher concentration of Fe2O3(15% mol), due to sample crystallization. Moreover, with Fe3O4 as raw material there is an improvement (~250 times) of the electrical conductivity when compared with Fe2O3. The results show that the presence of Fe2+ on the glass influences the electrical conductivity, which could have impact in the efficiency of molten oxide electrolysis process.publishe

Tuning thermoelectric properties of Ca0.9Gd0.1MnO3 by laser processing

Donor-doped CaMnO3 is an n-type semiconductor with perovskite structure, being considered as a potential n-type leg in thermoelectric modules. This oxide presents stability at high temperatures and allows tuning the relevant electrical and thermal transport properties through doping. In this work, Ca0.9Gd0.1MnO3 precursors have been prepared to produce fibres through the laser floating zone technique using different pulling rates. However, as-grown fibres did not present thermoelectric properties due to the presence of high amounts of secondary phases, leading to very high electrical resistivity values. The results have highlighted the importance of annealing procedures to reduce electrical resistivity, due to the decrease of secondary phases amount, and producing promising thermoelectric performances. The annealed samples present higher ZT values when the growth rate is decreased, reaching around 0.22 for the lowest growth rate, which is very close to the best values reported in the literature for these materials. Moreover, this procedure possesses an additional advantage considering that these samples can be directly used as n-type legs in thermoelectric modules for high-temperature applications. However, further studies should be made to determine the optimal amount of dopant