Calciothermic method

The calciothermic process is used for all the rare-earth metals except the four with high vapour pressures—i.e., low boiling points. The rare-earth oxide is converted to the fluoride by heating it with anhydrous hydrogen fluoride (HF) gas to form RF₃. The fluoride can also be made by first dissolving the oxide in aqueous HCl acid and then adding aqueous HF acid to precipitate the RF₃ compound from the solution. The fluoride powder is mixed with calcium metal, placed in a tantalum crucible, and heated to 1,450 °C (2,642 °F) or higher, depending upon the melting point of R. The calcium reacts with the RF₃ to form calcium fluoride (CaF₂) and R. Because those two products do not mix with one another, the CaF₂ floats on top of the metal. When cooled to room temperature, the CaF₂ is readily separated from R. The metal is then heated in a high vacuum in a tantalum crucible to above its melting point to evaporate the excess calcium. At that point R may be further purified by sublimation or distillation. This procedure is used to prepare all the rare earths except samarium, europium, thulium, and ytterbium.

In China, calciothermic reduction on a commercial scale is commonly performed in graphite crucibles. This leads to a severe contamination of the produced metals with carbon, which readily dissolves in the molten rare-earth metals. Common oxide crucibles, such as aluminum oxide (Al₂O₃) or zirconia (ZrO₂), are unsuitable for calciothermic reduction of the rare-earth metals because molten rare earths quickly reduce aluminum or zirconium, respectively, from their oxides, forming the corresponding rare-earth oxide.

Electrolytic method

The low-melting metals (lanthanum, cerium, praseodymium, and neodymium) may be prepared from the oxide by one of two electrolytic methods. The first method is to convert the oxide to the chloride (or fluoride) and then reduce the halide in an electrolytic cell. An electric current at a current density of about 10 A/cm² is passed through the cell to reduce the RCl₃ (RF₃) to Cl₂ (F₂) gas at the carbon anode and liquid R metal at the molybdenum or tungsten cathode. The electrolyte is a molten salt composed of RCl₃ (RF₃) and NaCl (NaF). The lanthanides prepared electrolytically are not as pure as those made by the calciothermic process.

The second electrolytic process reduces the oxide directly in an RF₃-LiF-CaF₂ molten salt. The main problem with this process is that the oxide solubility is quite low, and it is difficult to control the oxygen solubility in the liquid salt solution.

The electrolytic process is limited to the rare-earth metals that melt below 1,050 °C (1,922 °F), because those that melt much higher react with the electrolytic cell and electrodes. As a result, the electrolytic cell and electrodes must be replaced quite often, and the produced rare-earth metals are highly contaminated.

Large commercial applications use the individual metals lanthanum for nickel–metal hydride batteries, neodymium for Nd₂Fe₁₄B permanent magnets, and misch metal for alloying agents and lighter flints. Misch metal is a mixture of the rare-earth elements that has been reduced from a rare-earth concentrate in which the rare-earth content is the same as in the mined ores (i.e., generally about 50 percent cerium, 25 percent lanthanum, 18 percent neodymium, and 7 percent praseodymium). The lanthanum and neodymium metals are prepared for the most part by the direct electrolytic reduction of the oxides. Misch metal is generally prepared by the electrolysis of the mixed RCl₃.

Preparation of samarium, europium, thulium, and ytterbium: lanthanothermic process

The divalent metals europium and ytterbium have high vapour pressures—or lower boiling points than the other rare-earth elements, as can be seen when they are plotted versus atomic number—which makes it difficult to prepare them by the metallothermic or electrolytic methods. Samarium and thulium also have low boiling points, compared with the other lanthanide metals and also scandium and yttrium. The four metals with high vapour pressures are prepared by mixing R₂O₃ (R = samarium, europium, thulium, and ytterbium) with fine chips of lanthanum metal and placing the mixture in the bottom of a tall tantalum crucible. The mixture is heated to 1,400–1,600 °C (2,552–2,912 °F), depending on R. The lanthanum metal reacts with R₂O₃ to form lanthanum oxide (La₂O₃), and R evaporates and collects on a condenser at the top of the crucible that is about 500 °C (900 °F) colder than the reaction mixture at the bottom of the crucible. The four metals can be further purified by resubliming the metal.