A comprehensive review is presented of the extractive metallurgy of rare earths. The topics covered are: world rare earth resources and production; ore processing and separation of individual rare earths; reduction, refining, and ultrapurification of rare earth elements; methods for rare earth materials analysis; and a selection of the numerous rare earth applications. World rare earth reserves are abundant and would last for well beyond the next century. However, all of the 16 naturally occurring rare earth elements are not equally distributed in the ore minerals. This, compounded with the problems specific to the isolation and recovery of each of the rare earths, sets the stage for an unequal rare earth availability. The close chemical similarity of rare earths looses its importance when divergent physical properties determine the processes for rare earth element reduction and refining. The rare earth metals, alloys, and compounds have been as pure as could be determined. Finally, the commercial...

Extractive Metallurgy of Rare Earths

Melt‐textured growth of polycrystalline YBa2Cu3O7−δ superconductor using directional solidification created an essentially 100% dense structure consisting of long, needle‐ or plate‐shaped crystals preferentially aligned parallel to the a‐b conduction plane. The new microstructure, which completely replaces the previous granular and random structure in the sintered precursor, exhibits dramatically improved transport Jc values at 77 K of ∼17 000 A/cm2 in zero field and ∼4000 A/cm2 at H=1 T (as compared to ∼500 and ∼1 A/cm2, respectively, for the as‐sintered structure), with the severe field dependence of Jc (‘‘weak‐link’’ problem) no longer evident in the new melt‐textured material. The improvement in Jc is attributed to the combined effects of densification, alignment of crystals, and formation of cleaner grain boundaries. Microstructure and distribution of various phases present in the melt‐textured material are discussed in relation to the superconducting properties.

High critical currents in Y‐Ba‐Cu‐O superconductors

A liquid phase processing method for the fabrication of bulk YBa2Cu3Ox superconductors with large current carrying capacity has been developed. Slow cooling through the peritectic transformation (1030–980 °C) has been shown to control the microstructure of these superconductors. A cooling rate of 1 °C/h in this temperature range has yielded a microstructure with long plate type, thick grains oriented over a wide area. Current density up to 18 500 A/cm2 has been obtained by continuous direct current measurements and in excess of 62 000 A/cm2 with pulse current of 10 ms duration and 75 000 A/cm2 using 1 ms pulse. The strong magnetic field dependence observed in sintered bulk 1‐2‐3 superconductors is also minimized to a large extent where a current density in excess of 37 000 A/cm2 is obtained in a field of 6000 G.

High current density in bulk YBa2Cu3Ox superconductor

A reduced oxygen atmosphere during melt processing turned out to be critical for the fabrication of NdBa2Cu3Oy (Nd123) superconductors possessing high superconducting transition temperature (Tc) with a sharp transition and large critical current density (Jc) at 77 K. In a dc magnetization measurement, Nd123 superconductors melt processed in flowing a mixture gas of 1% O2 in Ar exhibited the Tc of about 95 K and the transition width of 1.5 K with the applied field of 10 Oe. A four‐probe measurement showed the zero resistive transition Tc (R=0) of about 95 K. An anomalous peak effect in the magnetization hysteresis (M‐H) loops was commonly observed and lead to large magnetic Jc of 2×104 A/cm2 at 77 K and 2 T for the applied field H parallel to the c axis of a sample (H∥c). This achievement is attributable to a preferential formation of high Tc phase (x<0.1) among the Nd1+xBa2−xCu3Oy solid solutions in a reduced oxygen atmosphere.

Melt processing for obtaining NdBa2Cu3Oy superconductors with high Tc and large Jc

Unlike Y123 which forms only a stoichiometric compound, the light rare earth elements (LREs: La, Nd, Sm, Eu, Gd) form a solid solution . The presence of such solid solution caused a depression in the superconducting transition temperatures , particularly for La123, Nd123 and Sm123 when they are melt processed in air. Recently, we have found that the of these LRE123 superconductors can greatly be enhanced when they are melt processed in a reduced oxygen atmosphere. Furthermore, values of these superconductors were larger than that of a good quality Y123 superconductor in high magnetic fields at 77 K. In this article, on the basis of our study over the last several years, the melt processes for LRE - Ba - Cu - O are described, the microstructural and superconducting properties of the superconductors are reviewed and the flux pinning mechanism is also discussed.

https://iopscience.iop.org/article/10.1088/0953-2048/9/12/001/pdf

Melt-processed light rare earth element - Ba - Cu - O

The progress toward major applications of ${\mathrm{YBa}}_{2}$${\mathrm{Cu}}_{3}$${\mathrm{O}}_{7\mathrm{\ensuremath{-}}\mathrm{\ensuremath{\delta}}}$-type high-${T}_{c}$ superconductors has been hindered by low critical current densities (${J}_{c}$) and their significant deterioration in weak magnetic fields. The present work demonstrates that these problems can successfully be overcome through proper microstructural control using molten oxide processing. Melt-textured growth of ${\mathrm{YBa}}_{2}$${\mathrm{Cu}}_{3}$${\mathrm{O}}_{7\mathrm{\ensuremath{-}}\mathrm{\ensuremath{\delta}}}$ from a supercooled melt created an essentially 100% dense structure consisting of locally aligned, long, needle-shaped grains (typically 40--600 \ensuremath{\mu}m in length). The needles appear to have their long axes parallel to the conduction plane (basal plane) of the orthorhombic structure, with a low-angle orientation change between adjacent grains. This new microstructure, which completely replaces the previous granular and random structure of the sintered precursor, exhibits a dramatically higher transport ${J}_{c}$ (7400 A/${\mathrm{cm}}^{2}$ at 77 K) than the typical sintered materials (${J}_{c}$=150--600 A/${\mathrm{cm}}^{2}$). Even more significant is the much reduced field dependence of ${J}_{c}$(\ensuremath{\approxeq}1000 A/${\mathrm{cm}}^{2}$ at H=1 T as compared to \ensuremath{\approxeq}1 A/${\mathrm{cm}}^{2}$ in the sintered structure), indicating that the coupling between grains is much stronger in the new structure. The mechanism responsible for the suppressed weak-link behavior in the melt-textured material is inferred to be the combined effects of the densification, alignment of crystals, and formation of cleaner grain boundaries.

Melt-textured growth of polycrystalline YBa2Cu3O7- delta with high transport Jc at 77 K.

The Bi‐Sr‐Ca‐Cu‐O superconductors have been doped with various noble metals and their superconducting properties have been investigated. The resistivity and magnetic susceptibility measurements on sintered Bi4Sr3Ca2Cu4O16+x containing 20% by weight of Au, Ag, or Pt‐group metals indicate that Au and the Pt‐group metals significantly suppress or eliminate the superconducting transition in Bi‐Sr‐Ca‐Cu‐O. Only Ag is found to be benign, maintaining both the 115 and 85 K transitions in the compound. This nonpoisoning behavior of silver is of significant technical importance because of the need for a proper stabilizing normal metal for composite superconductor wire, nonreactive crucible materials for melt processing or crystal growth, and suitable nonpoisonous substrates or barriers for thin‐ or thick‐film superconducting devices.

Superconductivity in the Bi-Sr-Ca-Cu-O compounds with noble metal additions

Melt‐textured YBa2Cu3O7−δsuperconductor with a long and well‐aligned grain structure is shown to exhibit magnetic hysteresis at 77 K which is the largest ever reported for bulk polycrystalline Y‐Ba‐Cu‐O. The large ΔM resulted in a magnet‐like behavior as well as a strong suspension phenomenon. It is shown, contrary to the previous reports, that the suspension behavior observed in Y‐Ba‐Cu‐O is a generic consequence of large grain size, and not due to the presence of Ag oxide or Ag particles. There appears to be no substantial enhancement in flux pinning and J c by these particles. Comparisons of magnetization behavior in various YBa2Cu3O7−δ samples (polycrystals, silver‐oxide doped, melt‐textured, and single crystals) indicated that for applied fields substantially larger than H c 1 the current flow that gives rise to the observed magnetization is intragranular. The pinning force and hence the critical current is roughly the same [J c (magn)∼104 A/cm2] within a factor of ∼2 regardless of grain size, grain boundary configuration, presence of second phase particles, or increased dislocation and twin densities.

M. E. Davis

Papers

High critical currents in Y‐Ba‐Cu‐O superconductors

Melt-textured growth of polycrystalline YBa2Cu3O7- delta with high transport Jc at 77 K.

Superconductivity in the Bi-Sr-Ca-Cu-O compounds with noble metal additions

Large magnetic hysteresis in a melt‐textured Y‐Ba‐Cu‐O superconductor

Grain-growth enhancement in the YBa2Cu3O7−δ superconductor by silver-oxide doping