RESUMO
Rare earth elements (REE) include the lanthanides (La-Lu), Y, and Sc which are critical elements for the green energy transition. The REE show a decrease in ionic radii with increased atomic numbers, which results in a so-called lanthanide contraction systematically affecting crystal structures and mineral properties. Here we present a compilation of reference Raman spectra of ten REE sesquioxides (A-, B- and C-type), five REE hydroxides, eight xenotime-structured REE phosphate endmembers and two solid solutions, seven monazite-structured REE phosphate endmembers and two solid solutions and seven rhabdophane endmembers with up to five Ce1-xLREEx rhabdophane solid solutions (LREE = La-Gd). Raman mode assignment is based on a detailed literature review summarizing existing analytical work and theoretical calculations and systematic trends observed in this study by analyzing different REE-bearing solids. The wavenumbers of the main REE-O Raman band systematically increase with decreasing ionic radii forming discrete linear trends within isostructural mineral groups, that can be used to estimate the REE-O mode in other solids with known REE-O coordination numbers. Photoluminescence using 266 nm, 532 nm and 633 nm excitation laser wavelengths for REE-bearing oxides, hydroxides, anhydrous and hydrous phosphates is also presented providing a new framework for identifying REE-phases in phosphate-bearing natural mineral deposits.
RESUMO
The heat capacity, C p, of synthetic hydroxyapatite [Ca5(PO4)3OH-OH-Ap], as well as of ten compositions along the OH-Ap-chlorapatite (Cl-Ap) join and 12 compositions along the OH-Ap-fluorapatite (F-Ap) join have been measured using relaxation calorimetry (heat capacity option of the Physical Properties Measurement System-PPMS) and differential scanning calorimetry (DSC) in the temperature range of 5-764 K. Apatites along the Cl-OH and F-OH joins were synthesized at 1100 °C and 300 MPa in an internally heated gas pressure vessel via an exchange process between synthetic fluorapatite or chlorapatite crystals (200-500 µm size) and a series of Ca(OH)2-H2O solutions with specific compositions and amounts relative to the starting apatite. The standard third-law entropy of OH-Ap, derived from the low-temperature heat capacity measurements, is S° = 386.3 ± 2.5 J mol-1 K-1, which is ~ 1% lower than that resulting from low-temperature adiabatic calorimetry data on OH-Ap from the 1950's. The heat capacity of OH-Ap above 298.15 K shows a hump-shaped anomaly centred around 442 K. Based on published structural and calorimetric work, this feature is interpreted to result from a monoclinic to hexagonal phase transition. Super ambient C p up to this transition can be represented by the polynomial: C p OH - Ap 298 K - 442 K J mol - 1 K - 1 = 1013.7 - 13735.5 T - 0.5 + 2.616718 10 7 T - 2 - 3.551381 10 9 T - 3 . . The DSC data above this transition were combined with heat capacities computed using density functional theory and can be given by the C p polynomial: C p OH - Ap > 442 K J mol - 1 K - 1 = 877.2 - 11393.7 T - 0.5 + 5.452030 10 7 T - 2 - 1.394125 10 10 T - 3 . Positive excess heat capacities of mixing, ∆C p ex, in the order of 1-2 J mol-1 K-1, occur in both solid solutions at around 70 K. They are significant at these conditions exceeding the 2σ-uncertainty of the data. This positive ∆C p ex is compensated by a negative ∆C p ex of the same order at around 250 K in both binaries. At higher temperatures (up to 1200 K), ∆C p ex is zero within error for all solid solution members. As a consequence, the calorimetric entropies, Scal, show no deviation from ideal mixing behaviour within a 2σ-uncertainty for both joins. Excess entropies of mixing, ∆Sex, are thus zero for the OH-Ap-F-Ap, as well as for the OH-Ap-Cl-Ap join. The C p-T behaviour of the OH-Ap endmember is discussed in relation to that of the F- and Cl-endmembers. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s00269-021-01167-1.