Investigation of the possibility for using ZrO2 and ZrSiO4 for Zr additions to liquid ferrosilicon

Abstract: Ferrosilicon containing 50-75% Si and 1.0-5.0% Zr is used as inoculant in the cast iron industry. Zr can be added to liquid ferrosilicon by use of Zr metal or zirconium ferroalloy (FeSiZr). Then the recovery of Zr, i.e. the fraction of Zr transferred from the additive to the ferrosilicon, as well as the hit rate on specification is high. The aim of this study was to investigate the recovery of Zr from zircon sand, ZrSiO4, and zirconia, ZrO2, in comparison to zirconium ferroalloy when added to liquid ferrosilicon with 75% Si at 1600⁰C.  Also the refining effect of the different additives on Al was investigated. The experiments were carried out by stirring samples of controlled amounts of ferrosilicon and Zr additive in a graphite crucible at 1600⁰C and under inert Ar atmosphere for certain amounts of time. The reaction between ferrosilicon and Zr additive was stopped by rapid cooling of the samples. ICP-OES provided the concentration of Zr and Al and LECO O/N the concentration of O. SEM-ESD was used to examine the microstructures of ferrosilicon and Zr additive after experiments. It was found that ZrO2 was reduced by Si at the particle surface to yield dissolved Zr and ZrSiO4. The ZrSiO4 additive decomposed via two simultaneous reactions, one yielding ZrO2, Si and O2 and the other Zr, Si and O2. The recovery of Zr from ZrO2 and ZrSiO4 was significantly lower than from FeSiZr. Of ZrO2 and ZrSiO4, ZrO2 yielded the highest Zr recovery; the difference was much bigger than predicted by thermodynamics. It was discussed if that could be due to a higher reaction rate of the ZrO2, caused by the smaller size (APS 1 µm compared to d50 91 µm) and larger surface area of this addition. It was also found that utilization of density differences to separate the ferrosilicon and Zr additive did not work for zirconia under the same conditions as it worked for zircon sand, although zirconia has a higher density than zircon sand. The reason was the smaller particle size of the ZrO2 powder. No refining of Al was observed.