Diamond-wire sawing silicon waste (DWSSW) as a reductant of the Pidgeon process is beneficial for alleviating the high energy consumption of primary magnesium production. However, the oxygen in DWSSW exists in the form of SiO2 coated on the Si surface, which is not conducive to the silicothermic reaction and thus affecting the yield of primary magnesium. In this study, we proposed a modified deoxidation method utilizing ammonium fluoride (NH4F) and hydrochloric acid (HCl) solutions to deoxidize the DWSSW. It was found that NH4F solution effectively reduced the oxygen content in DWSSW and the deoxidation efficiency increased with higher NH4F concentration. The addition of HCl further enhanced the deoxidation efficiency, leading to a minimum oxygen content of 1.31% in the deoxidized DWSSW. Transmission electron microscopy (TEM) images indicated a significant reduction in SiO2 layer thickness, which improves the chemical reactivity of the material. The deoxidized DWSSW was subsequently employed as the reductant in the Pidgeon process to produce primary magnesium. Consequently, the reduction conversion of the Pidgeon process increased by 6.7% compared to raw DWSSW. This work not only provided an effective solution to reduce the oxygen content in DWSSW, but also expanded its application in Pidgeon process, promoting primary magnesium industry towards energy conservation and cost reduction.
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Poor corrosion resistance is a critical barrier to the widespread application of magnesium alloys. Statistically, the literature reported that approximately 70% of as-cast AZ31 magnesium alloys exhibit corrosion rates exceeding 1 mm·y−1 in 3.5 wt.% NaCl solution, which is unacceptable for industrial use. Furthermore, there is a considerable discrepancy in the corrosion rates reported by different studies (as-cast alloys ranging from 0.4 to 215 mm·y−1). These phenomena may be attributed to the uncontrollable content of impurity elements in commercial magnesium alloys, which fluctuate widely between batches. In the present work, we prepared as-cast AZ31 magnesium alloys with different impurity contents using two different purities of raw magnesium (Mg-99.9% and Mg-99.99%). The impact of impurity contents on the corrosion resistance of AZ31 magnesium alloys was then analyzed. The AZ31 magnesium alloy prepared with 99.99% raw magnesium showed superior corrosion resistance compared with that prepared with 99.9% raw magnesium, with a reduction in corrosion rate by approximately 98% and a decrease in the fluctuation range of corrosion rate by 91%. Thus, enhancing the purity of raw magnesium is an effective method to improve both the corrosion resistance and consistency of magnesium alloys.
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It is practically difficult to find titanium sponges with low and stable aluminum impurities on the market even though it is the precondition to prepare high-purity titanium. Analysis indicates that almost all the aluminum impurities in the titanium sponge are inherited from the magnesium used to reduce titanium tetrachloride. However, it remains elusive for decades why magnesium produced through the silicothermic reduction method contains a high content of aluminum impurities with large fluctuations. By recourse to thermodynamic calculations and comparative experiments, we demonstrate that fluorite, a material used as a catalyst in the silicothermic reduction method to produce magnesium, is the chief culprit for the pest aluminum and propose a mechanism to rationalize the observed phenomena. Our findings indicate that one practical way to produce qualified magnesium for the production of high-purity titanium is to abandon fluorite during the production of magnesium with the silicothermic reduction method.
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