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1. Crystal growth and phase formation of high‐entropy rare‐earth monoclinic aluminates

   https://doi.org/10.1111/jace.19320  

   Pianassola, Matheus; Loveday, Madeline; Lalk, Rebecca; Pestovich, Kimberly; Melcher, Charles L.; Zhuravleva, Mariya (July 2023, Journal of the American Ceramic Society)

   Abstract For the first time, high‐entropy rare‐earth monoclinic aluminate crystals were grown via directional solidification using the micro‐pulling‐down method. Five high‐entropy compositions were formulated with a general formula RE₄Al₂O₉, where RE is an equiatomic mixture of five rare‐earth elements. The rare‐earth elements included were Lu, Yb, Er, Y, Ho, Dy, Tb, Gd, Eu, Sm, Nd, and La. High‐temperature powder X‐ray diffraction and Rietveld structure refinement indicated that all crystals were a single monoclinic phase and that rare‐earth average ionic radius did not affect phase purity. At room temperature, the refined lattice parameters increased consistently with increasing average ionic radii of the five compositions. One of the crystals had a typical high‐temperature phase transition of single‐RE RE₄Al₂O₉in the range of 1100–1150°C, which consisted of a lattice contraction upon heating. Differential scanning calorimetry indicated a thermal event corresponding to that phase transition. Electron probe microanalysis revealed Al‐rich inclusions on the surface of the crystals. Crystals containing Tb had dark surface features that became lighter after annealing in a reducing atmosphere, which indicated that Tb⁴⁺may be responsible for the dark features. 

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2. Thermal Analysis of High Entropy Rare Earth Oxides

   https://doi.org/10.3390/ma13143141  

   Ushakov, Sergey V.; Hayun, Shmuel; Gong, Weiping; Navrotsky, Alexandra (July 2020, Materials)

   null (Ed.)

   Phase transformations in multicomponent rare earth sesquioxides were studied by splat quenching from the melt, high temperature differential thermal analysis and synchrotron X-ray diffraction on laser-heated samples. Three compositions were prepared by the solution combustion method: (La,Sm,Dy,Er,RE)2O3, where all oxides are in equimolar ratios and RE is Nd or Gd or Y. After annealing at 800 °C, all powders contained mainly a phase of C-type bixbyite structure. After laser melting, all samples were quenched in a single-phase monoclinic B-type structure. Thermal analysis indicated three reversible phase transitions in the range 1900–2400 °C, assigned as transformations into A, H, and X rare earth sesquioxides structure types. Unit cell volumes and volume changes on C-B, B-A, and H-X transformations were measured by X-ray diffraction and consistent with the trend in pure rare earth sesquioxides. The formation of single-phase solid solutions was predicted by Calphad calculations. The melting point was determined for the (La,Sm,Dy,Er,Nd)2O3 sample as 2456 ± 12 °C, which is higher than for any of constituent oxides. An increase in melting temperature is probably related to nonideal mixing in the solid and/or the melt and prompts future investigation of the liquidus surface in Sm2O3-Dy2O3, Sm2O3-Er2O3, and Dy2O3-Er2O3 systems. 

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3. 21-Component compositionally complex ceramics: Discovery of ultrahigh-entropy weberite and fergusonite phases and a pyrochlore-weberite transition

   https://doi.org/10.1007/s40145-022-0575-5  

   Qin, Mingde; Vega, Heidy; Zhang, Dawei; Adapa, Sarath; Wright, Andrew J.; Chen, Renkun; Luo, Jian (April 2022, Journal of Advanced Ceramics)

   Abstract Two new high-entropy ceramics (HECs) in the weberite and fergusonite structures, along with the unexpected formation of ordered pyrochlore phases with ultrahigh-entropy compositions and an abrupt pyrochlore-weberite transition, are discovered in a 21-component oxide system. While the Gibbs phase rule allows 21 equilibrium phases, 9 out of the 13 compositions examined possess single HEC phases (with ultrahigh ideal configurational entropies: ∼2.7 k B per cation or higher on one sublattice in most cases). Notably, (15RE 1/15 )(Nb 1/2 Ta 1/2 )O 4 possess a single monoclinic fergusonite (C2/ c ) phase, and (15RE 1/15 ) 3 (Nb 1/2 Ta 1/2 ) 1 O 7 form a single orthorhombic (C222 1 ) weberite phase, where 15RE 1/15 represents Sc 1/15 Y 1/15 La 1/15 Pr 1/15 Nd 1/15 Sm 1/15 Eu 1/15 Gd 1/15 Tb 1/15 Dy 1/15 Ho 1/15 Er 1/15 Tm 1/15 Yb 1/15 Lu 1/15 . Moreover, a series of eight (15RE 1/15 ) 2+ x (Ti 1/4 Zr 1/4 Ce 1/4 H 1/4 ) 2−2 x (Nb 1/2 Ta 1/2 ) x O 7 specimens all exhibit single phases, where a pyrochlore-weberite transition occurs within 0.75 < x < 0.8125. This cubic-to-orthorhombic transition does not change the temperature-dependent thermal conductivity appreciably, as the amorphous limit may have already been achieved in the ultrahigh-entropy 21-component oxides. These discoveries expand the diversity and complexity of HECs, towards many-component compositionally complex ceramics (CCCs) and ultrahigh-entropy ceramics. 

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4. What we can learn in the kitchen sink: an example from garnet granulite

   Stowell, H.H. (January 2021, America Geophysical Union)

   Interpretation of geochronological and petrological data from partially-melted granulite is challenging. However, integration of multiple chronometers and mineral assemblage diagrams (MAD) can be used to estimate the nature and duration of processes. Excellent lower-crustal exposures of garnet granulite from the Malaspina Pluton, Fiordland New Zealand provide an ideal place to employ this kitchen sink approach. We use zircon U-Pb ages from LA-ICPMS, SHRIMP-RG, and CA-TIMS, garnet Lu-Hf and Sm-Nd ages, and MAD in order to evaluate local partial melting vs. melt injection, equilibrium volumes, P-T conditions, and the duration of lower crustal thermal events. Host diorite (H), garnet-clinopyroxene reaction zones (GRZ), coarse garnet selvages, and tonalite veins provide a record of intrusion and granulite facies partial melting. Zircon U-Pb ages range from 123 to 107 Ma (all); LA-ICPMS ages contain the entire range; CA-TIMS ages range from 118.30±0.13 to 115.7±0.18 Ma; and SHRIMP-RG ages range from 121.4±2 to 109.8±1.8 Ma. The latter two techniques are interpreted to indicate primary igneous crystallization from ~119 to ~116 Ma and the youngest ~110 Ma ages are interpreted as metamorphic zircon growth. Garnet ages for ~1 cm grains are ~113 Ma (Lu-Hf & Sm-Nd) and record metamorphic growth, and <0.3 mm grains with Sm-Nd ages from 113 to 104 Ma reflect high temperature intracrystalline diffusion and isotopic closure during cooling to amphibolite facies. Zircon trace-element compositions indicate 2 distinct crystallization trends reflecting evolution of primary magma batches. MAD indicate that garnet was not in equilibrium with sampled rock compositions. Instead, garnet shows apparent equilibrium with a modeled mixture of the GRZ and the H and grew in equilibrium with an effective bulk composition that shifted toward the leucosome. This would produce the observed increase in garnet grossular content. We conclude that: Malaspina rocks from Crooked Arm preserve evidence for 2 igneous layers which evolved as discrete magmas, igneous crystallization lasted 2 to 3 m.y., granulite metamorphism peaked ~ 3 m.y. after intrusion, metamorphism lasted ≥3 m.y., cooling occurred at ~20°C/m.y., and granulite minerals equilibrated with a mixture of solid phases and melt at ~14 kbar and 920°C (based on garnet compositions and MAD). 

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5. Evaluating electrochemical accessibility of 4f ⁿ 5d ¹ and 4f ⁿ⁺¹ Ln( ii ) ions in (C ₅ H ₄ SiMe ₃ ) ₃ Ln and (C ₅ Me ₄ H) ₃ Ln complexes

   https://doi.org/10.1039/D1DT02427B  

   Trinh, Michael T.; Wedal, Justin C.; Evans, William J. (October 2021, Dalton Transactions)

   The reduction potentials (reported vs. Fc + /Fc) for a series of Cp′ 3 Ln complexes (Cp′ = C 5 H 4 SiMe 3 , Ln = lanthanide) were determined via electrochemistry in THF with [ n Bu 4 N][BPh 4 ] as the supporting electrolyte. The Ln( iii )/Ln( ii ) reduction potentials for Ln = Eu, Yb, Sm, and Tm (−1.07 to −2.83 V) follow the expected trend for stability of 4f 7 , 4f 14 , 4f 6 , and 4f 13 Ln( ii ) ions, respectively. The reduction potentials for Ln = Pr, Nd, Gd, Tb, Dy, Ho, Er, and Lu, that form 4f n 5d 1 Ln( ii ) ions ( n = 2–14), fall in a narrow range of −2.95 V to −3.14 V. Only cathodic events were observed for La and Ce at −3.36 V and −3.43 V, respectively. The reduction potentials of the Ln( ii ) compounds [K(2.2.2-cryptand)][Cp′ 3 Ln] (Ln = Pr, Sm, Eu) match those of the Cp′ 3 Ln complexes. The reduction potentials of nine (C 5 Me 4 H) 3 Ln complexes were also studied and found to be 0.05–0.24 V more negative than those of the Cp′ 3 Ln compounds. 

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