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Synthetic rutile was prepared from titanium slag melt with low energy consumption and a small amount of additive (B₂O₃) in our previous work. The modification mechanism of titanium slag was not clear enough. The migration and enrichment behaviors of Ca and Mg elements during cooling and crystallization of boron-bearing titanium slag melt were characterized by XRF, FESEM, EMPA, and XPS. Results show that when additive (B₂O₃) is added, Ti elements are migrated and enriched in the area to generate rutile, while Ca, Mg, and B elements are migrated and enriched in another area to generate borate. With the additive (B₂O₃) amount increased, Ca and Mg element migration is complete and more thorough. Additive (B₂O₃) promotes rutile formation and inhibits the formation of anosovite during cooling and crystallization of titanium slag melt. With the additive (B₂O₃) amount increasing from 0% to 6%, the proportion of Ti³⁺ in the modified titanium slag reduces from 9.15% to 0%, and the proportion of Ti⁴⁺ increases from 90.85% to 100% under the same cooling and crystallization condition. The result will lay the foundation for the efficient preparation of synthetic rutile by adding B₂O₃ to the titanium slag melt.