Due to the refractory nature of α-spodumene (LiAlSi₂O₆) and petalite (LiAlSi₄O₁₀), two major lithium minerals, conventional lithium recovery processes involve a high-temperature pre-treatment (>1000 °C) to induce a phase transition to tetragonal β-spodumene, an open structure allowing easier access to lithium through ion exchange. Considering that these high temperatures are not dictated by thermodynamics but rather sluggish kinetics, the study investigates the mechanisms enhancing the rate of transformation to β-spodumene at lower temperatures while minimizing the growth of metastable hexagonal β-quartz typically observed at the onset of the conversion. The heat treatment of natural α-spodumene revealed that rapid growth of β-spodumene veinlets is achieved at ≤600 °C by activation of alkali-rich fluid inclusions, through a dissolution–recrystallization process. For petalite, the mechanism of the phase transition, initiated at ≈750 °C is a solid-state transformation keeping crystallographic coincidence with the mineral host. Synthetic growth experiments along the LiAlSi₂O₆-LiAlSi₄O₁₀ join indicate a compositional dependence on the resulting β-phase structure, where minor sodium doping strongly favors β-spodumene, as the tetrahedral framework of β-quartz does not allow the extent of deformation to accommodate the larger alkali. These findings open opportunities for energy-efficient lithium recovery pathways where the phase transition and ion exchange can be achieved simultaneously without a high-temperature pre-treatment.

After the high-temperature pretreatment of α-spodumene to induce a phase transition to β-spodumene, a derivative of the silica polymorph keatite, often coexisting with metastable Li-stuffed β-quartz (γ-spodumene)_, the conventional approach to access lithium is through ion exchange with hydrogen using concentrated sulfuric acid, which presents drawbacks associated with the production of low-value leaching residues. As sodium and magnesium can produce more interesting aluminosilicate byproducts, this study investigates Na⁺ ↔ Li⁺ and Mg²⁺ ↔ 2 Li⁺ substitution efficiencies in β-spodumene and β-quartz. Thermal annealing at 850 °C of the LiAlSi₂O₆ silica derivatives mixed with an equimolar proportion of Na endmember glass of equivalent stoichiometry (NaAlSi₂O₆) indicates that sodium incorporation in β-quartz is limited, whereas the main constraint for not attaining complete growth to a Na_0.5Li_0.5AlSi₂O₆ β-spodumene solid solution is co-crystallization of minor nepheline. For similar experiments in the equimolar LiAlSi₂O₆-Mg_0.5AlSi₂O₆ system, the efficient substitution of Mg for Li is observed in both β-spodumene and β-quartz, consistent with the alkaline earth having an ionic radius closer to lithium than sodium. Ion exchange at lower temperatures was also evaluated by exposing coexisting β-spodumene and β-quartz to molten salts. In NaNO₃ at 320 °C, sodium for lithium exchange reaches ≈90% in β-spodumene but less than ≈2% in β-quartz, suggesting that to be an efficient lithium recovery route, the formation of β-quartz during the conversion of α-spodumene needs to be minimized. At 525 °C in a molten MgCl₂/KCl medium, although full LiAlSi₂O₆-Mg_0.5AlSi₂O₆ solid solution is observed in β-quartz, structural constraints restrict the incorporation of magnesium in β-spodumene to a Li_0.2Mg_0.4AlSi₂O₆ stoichiometry, limiting lithium recovery to 80%.

The decomposition of silicates in sulfuric acid to extract rare earth elements (REE) is typically characterized by the formation of an amorphous silica layer surrounding the receding crystal that may act as a passivation barrier limiting the rate of mineral dissolution. In this context, sulfuric acid treatment experiments coupled with detailed characterization of the evolution of the decomposition reaction were performed on natural allanite (CaREEAl₂Fe²⁺Si₃O₁₁O[OH]), as well as synthetic neodymium disilicate (Nd₂Si₂O₇), orthosilicate (Ca₂Nd₈(SiO₄)₆O₂), and orthophosphate (NdPO₄) phases in order to investigate if there are key factors, operating on a wide range of silicates, that negatively impact REE recovery. While, as expected, the acid strength is the driver in promoting the decomposition of the orthophosphate, for the silicates investigated, no matter their crystalline structure and chemical resistance, there is a severe passivation mechanism at play in concentrated H₂SO₄. However, in all cases, this effect can be minimized by water dilution, which strongly enhances sulfate-forming cation transfer across the produced amorphous silica layer. Taking into consideration this distinct characteristic of the mode of decomposition of silicates in sulfuric acid should help in defining optimal extraction strategies.