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<p>The detailed reaction pathway for the aluminothermic reduction of TiO<sub>2</sub> has remained elusive due to its characteristically ultra-fast, combustion-like nature. This study systematically elucidates the reaction pathway of the CaO- and CaCl<sub>2</sub>-assisted aluminothermic reduction of TiO<sub>2</sub> for the precise fabrication of Ti<sub>2</sub>O, employing TG-DSC, high-temperature <i>in-situ</i> XRD, and SEM-EDS. The process involves multiple titanium-bearing intermediates, such as Ti<sub>2</sub>O<sub>3</sub>, TiO, CaTiO<sub>3</sub>, CaTi<sub>2</sub>O<sub>4</sub>, and TiAl<sub>3</sub>. The transient formation of TiAl<sub>3</sub> during the initial rapid-reaction stage deviates from the thermodynamically predicted pathway, attributed to localized over-reduction caused by non-uniform Al distribution and intense exothermic heat. The overall process evolves through three distinct temperature-dependent stages (&lt;&#xa0;660&#xa0;°C, 660&#xa0;°C to 772&#xa0;°C, &gt;&#xa0;772&#xa0;°C). The synergistic roles of CaO and CaCl<sub>2</sub> are essential. CaO acts as a thermodynamic coupling agent to enhance the driving force, while CaCl<sub>2</sub> serves as a kinetic accelerator to facilitate mass transfer, collectively enabling the precise fabrication of Ti<sub>2</sub>O.</p>

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Reaction Pathway of the CaO- and CaCl2-Assisted Aluminothermic Reduction of TiO2 for the Precise Fabrication of Ti2O

  • 期刊论文

  • 发表日期：

    2026年1月7日

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  • Taotao Cai,
  • Ying Zhang,
  • Shili Zheng,
  • Yi Zhang

摘要

The detailed reaction pathway for the aluminothermic reduction of TiO2 has remained elusive due to its characteristically ultra-fast, combustion-like nature. This study systematically elucidates the reaction pathway of the CaO- and CaCl2-assisted aluminothermic reduction of TiO2 for the precise fabrication of Ti2O, employing TG-DSC, high-temperature in-situ XRD, and SEM-EDS. The process involves multiple titanium-bearing intermediates, such as Ti2O3, TiO, CaTiO3, CaTi2O4, and TiAl3. The transient formation of TiAl3 during the initial rapid-reaction stage deviates from the thermodynamically predicted pathway, attributed to localized over-reduction caused by non-uniform Al distribution and intense exothermic heat. The overall process evolves through three distinct temperature-dependent stages (< 660 °C, 660 °C to 772 °C, > 772 °C). The synergistic roles of CaO and CaCl2 are essential. CaO acts as a thermodynamic coupling agent to enhance the driving force, while CaCl2 serves as a kinetic accelerator to facilitate mass transfer, collectively enabling the precise fabrication of Ti2O.