Rare earth elements (REEs) are a group of 17 metallic elements, including 15 lanthanides, scandium and yttrium, which have remarkably similar chemical and physical properties. Nowadays, rare earth metals are widely used in such fields as electronics, petroleum, and metallurgy. Rare earth elements are considered as vitamin to modern industry and critical resources to many countries. Neodymium is a light lanthanide, and its demand has been substantially boosted due to the broad application of NdFeB permanent magnets in electronics and new energy industries. Oxide-fluoride electrolysis is the main commercial method to produce rare earth metals and their alloys, especially light lanthanides, in both primary and secondary production. The oxide-fluoride electrolysis process involves first the dissolution of rare earth oxide(s) (REO(s)) in a molten fluoride, which serves as both a solvent and an electrolyte. During an electrochemical process, rare earth cations are reduced at the cathode and the respective metal is formed. Even though this method was adopted from laboratory to industrial production about 50 years ago, the exact mechanism of the process is not fully clarified. A deeper understanding of the process from both physicochemical and electrochemical points of view is crucial for process optimization, improving its current efficiency and power consumption. Maintaining enough REOs in the electrolyte and having a fast dissolution are crucial factors for good industrial practice. Identifying the electrochemical reactions involved during the electrolysis is vitally important for promoting target reactions and restricting side reactions, which are linked directly to the economic indicators of the process. Therefore, this thesis focuses on the solubility of REOs in molten fluorides, developing a semi-empirical model for the estimation of REO solubility, dissolution behavior of Nd2O3 in molten fluoride, and electrochemical behavior of Nd(III) in fluoride melt.@en

The dissolution of rare earth oxides in molten fluorides is a critical step in the preparation of the corresponding rare earth metals by oxide-fluoride electrolysis. However, quantitatively understanding the nature of dissolution, especially in the case of molten salts, is usually difficult to be achieved by postmortem characterization. In this paper, the dissolution behavior of Nd₂O₃ particles in molten fluorides was studied via in situ observation with confocal scanning laser microscopy. Combining direct observation with thermodynamic analyses on the oxide dissolution, the rate-limiting step(s) and the effects of parameters like temperature, salt type, and composition on the dissolution rate are identified. This study provides a methodology to estimate the dissolution kinetics of rare earth oxides in molten fluorides during their primary and secondary processing.

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The analytical and numerical description of the effective dissolution kinetics of spherical particles into a solvent is often difficult in chemical and metallurgical engineering. The crucial first step is to identify the dissolution mechanisms, and subsequently, relevant kinetics parameters can be calculated. In this article, three frequently used approximations, i.e., the invariant-field (IF) (Laplace), reverse-growth (RG), and invariant-size (IS) (stationary-interface) approximations, are systematically discussed and compared with numerical simulation results. The relative errors of the dissolution curves and total dissolution time of the three approximations to the numerical simulations are calculated. The results reveal the appropriate application ranges of the approximations for given precision levels. With further experimental validation, this research provides a methodology to properly assess dissolution kinetics and adequately estimate effective diffusion coefficients and activation energy under the experimental uncertainties.

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