Electrolytic production of metallic neodymium is carried out in fused neodymium fluoride salts containing neodymium oxide. Two major challenges pertaining to neodymium production in fluoride salts are a) low solubility of neodymium oxide in fluoride melt, b) possibility of anodic gas evolution (CO, CO ₂ , CF ₄ , C ₂ F ₆ ). In this study, iron is used as a reactive anode in the electrolysis process, promoting electrochemical dissolution of iron into the melt, preventing PFC (perfluorocarbon) gas evolution at the anode. Further, the rare earth oxide is converted to rare earth fluoride by the use of iron fluoride formed as the result of iron dissolution. Thus, the fluoridizing agent is constantly regenerated in-situ which enables the continuous conversion of neodymium oxide feed. The cathodic product is Nd–Fe alloy which can be used as a master alloy for the production of NdFeB magnets.

Electrolysis of molten fluorides is one of the promising methods for the recovery and recycling of rare earth metals from used magnets. Due to the dearth of phase equilibria data for molten fluoride systems, thermodynamic modelling of LiF-DyF₃-NdF₃ system using the CALPHAD approach was carried out. Gibbs energy modelling for LiF-NdF₃ and LiF-DyF₃ systems was performed using the constitutional data from literature. Ab initio calculations were used to obtain enthalpy of reaction of LiDyF₄, an intermediate phase that is found to exist in the LiF-DyF₃ system. Differential thermal analysis was carried out for selected compositions in the NdF₃-DyF₃ system, in order to determine liquidus and solidus temperatures. The Gibbs energy parameters for the limiting binaries determined in this work is used for modelling the Gibbs energy functions of equilibrium phases in the ternary system. Selected compositions of LiF-NdF₃-DyF₃ were subjected to DTA in order to validate the calculated phase temperatures involving melt.

In the present work, selective extraction of rare earth (RE) metals from NdFeB magnets is investigated by studying the effects of various fluxes, viz. AlF₃, ZnF₂, FeF₃ and Na₃AlF₆ in the LiF-NdFeB system. The aim is to convert RE from RE magnet into the fluoride salt melt. The results show the complete selective separation of neodymium (also dysprosium) from the magnet and formation of rare earth fluoride, leaving iron and boron unreacted. The formed rare earth fluoride can subsequently be processed in the same reactor through an electrolysis route so that RE can be deposited as a cathode product. The results of XRD and EPMA analysis of the reacted samples indicate that AlF3, ZnF2 and FeF3 can act as strong fluorinating agents for extraction of rare earth from NdFeB magnet, converting the RE to REF3. The results confirm the feasibility of the rare earth metals recovery from scrap NdFeB magnet as raw material. The fluoride conversion-electrolysis route suggested in the present work enables the extraction of rare earth metals in a single step using the above-mentioned fluxes.