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At least 109 records · Page 6

High Entropy Protected Sharp Magnetic Transitions in Highly Disordered Spinel Ferrites

How disorder affects magnetic ordering is always an intriguing question, and it becomes even more interesting in the recently rising high entropy oxides due to the extremely high disorder density. However, due to the lack of high-quality single crystal samples, the strong compositional disorder effect on magnetic transition has not been deeply investigated. In this work, we have successfully synthesized high-quality single crystalline high entropy spinel ferrites (Mg 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 ) x Fe 3-x O 4 . Our findings from high-temperature magnetization and neutron diffraction experiments showed ferrimagnetic transitions at 748, 694, and 674 K for x values of 1, 1.5, and 1.8, respectively. Notably, the magnetic transition almost showed no broadening for x values of 1 and 1.5, compared to Fe 3 O 4 . Extended X-ray absorption fine structure measurements provided insights into the elemental distribution among the octahedral and tetrahedral sites. The random distribution of elements across these sites reduced the formation of local clusters and short-range orders, enhancing sample homogeneity and preserving the sharpness of the magnetic transition, despite bond length variation. Here, our study not only marks the first successful synthesis of an HEO bulk single crystal exhibiting long-range magnetic order but also sheds light on the interaction between high configurational entropy and magnetic orderings. This opens new avenues for future research and applications of magnetic high entropy oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Framework Short-Range Order Observed in a Spinel-Type Li Superionic Conductor

Solid-state superionic conductors are characterized by rich structural disorders. Though structural complexities are central to their functionalities, they often give rise to short-range order that eludes detection by conventional diffraction-based techniques and is thus overlooked in establishing precise structure-property relationships. In this work, we synthesized single crystals of a recently discovered lithium (Li) superionic conductor Li16.2(1)In9.00(2)Sn1.10(1)O23.8 (LISO) for in-depth characterizations of structural subtleties. LISO exhibits an unusual spinel-like phase with significant Li overstoichiometry and a face-sharing Li network. Single-crystal neutron diffraction confirms significant Li disorder, as manifested in Li site splitting and partial occupancy. More importantly, synchrotron diffuse scattering combined with 3D-ΔPDF analysis and Monte Carlo simulations reveal short-range order in the nonalkali framework that might contribute to the phase stability and ionic conductivity. This work showcases an example in which subtle local energetics can be directly visualized in structurally disordered ionic conductors.

Chen, Yu↗

Local structural distortions drive magnetic molecular field in compositionally complex spinel oxide

Understanding how local distortions determine the functional properties of high entropy materials, containing five or more elements at the same crystallographic site, is an open challenge. We address this for a compositionally complex spinel oxide (Mn 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )Cr 2 O 4 (A 5 Cr 2 O 4 ). By comparatively examining extended X-ray absorption fine structure on A 5 Cr 2 O 4 and its parent counterparts, ACr 2 O 4 , along with density functional theory calculations for multiple configurations, we find that the element-specific distortions go beyond the first neighbor. Specifically, the strong Jahn-Teller distortion present in CuCr 2 O 4 is found to be completely suppressed in A 5 Cr 2 O 4 even locally. Instead, there is a broad distribution of Cu-O and Cu-Cr bond distances, while other A-O distances acquire certain specific values. This study demonstrates the additional flexibility of a cationic sublattice in maintaining a uniform long-range structure, in contrast to previous reports showing only the accommodative anionic sublattice. The mean-field magnetic interactions of A 5 Cr 2 O 4 exhibit a striking resemblance to those of NiCr 2 O 4 , despite the presence of multiple magnetic ions and variable bond lengths. This originates from the comparability of bond lengths around Cr in both materials. Our study paves the way for a deeper understanding of the impact of local structural distortions on the physical properties of compositionally complex quantum materials.

36 MATERIALS SCIENCE↗

High throughput screening of high entropy spinel electrolytes for multivalent batteries

High-entropy (HE) design emerged as a promising path for discovering multivalent superionic conductors. This work provides a computational exploration of the synthesizability of HE spinel-based electrolytes among the typical chemical space. Design principles have been established, while experimental synthesis has supported the stability rules predicted by computational data.

25 ENERGY STORAGE↗

Hund’s flat band in a frustrated spinel oxide

Electronic flat bands associated with quenched kinetic energy and heavy electron mass have attracted great interest for promoting strong electronic correlations and emergent phenomena such as high-temperature charge fractionalization and superconductivity. Intense experimental and theoretical research has been devoted to establishing the rich nontrivial metallic and heavy fermion phases intertwined with such localized electronic states. Here, in this study, we investigate the transition metal oxide spinel LiV 2 O 4 , an enigmatic heavy fermion compound lacking localized f orbital states. We use angle-resolved photoemission spectroscopy and dynamical mean-field theory to reveal a kind of correlation-induced flat band with suppressed interatomic electron hopping arising from intra-atomic Hund’s coupling. The appearance of heavy quasiparticles is ascribed to a proximate orbital-selective Mott state characterized by fluctuating local moments as evidenced by complementary magnetotransport measurements. The spectroscopic fingerprints of long-lived quasiparticles and their disappearance with increasing temperature further support the emergence of a high-temperature “bad” metal state observed in transport data. This work resolves a long-standing puzzle on the origin of heavy fermion behavior and unconventional transport in LiV 2 O 4 . Simultaneously, it opens a path to achieving flat bands through electronic interactions in d-orbital systems with geometrical frustration, potentially enabling the realization of exotic phases of matter such as the fractionalized Fermi liquids.

36 MATERIALS SCIENCE↗

Apollo 12 spinels as petrogenetic indicators

Lunar 12 spinel compositional variation and textures as petrogenetic indicators, showing magma differentiation by crystal settling after lunar surface extrusion

Reid, J. B., Jr.↗

Luna 16 - An opaque mineral study and a systematic examination of compositional variations of spinels from Mare Fecunditatis.

The opaque mineralogy of the Luna 16 soil sample is studied, with an emphasis on a detailed survey of the compositional variations of the Fe-Ti-Cr-Al-Mg spinels. Analytical data are also presented for ilmenite. Textural characteristics and shock-metamorphic effects on the opaque minerals are briefly described and comparisons are made throughout between the Luna 16 samples and published and unpublished data on the Apollo samples.

Haggerty, S. E.↗

X-ray structural study of chrome-aluminum lunar spinel from the Sea of Fertility

An X-ray structural study was made of a lunar spinel sample from the Sea of Fertility. The chemical composition and distribution of cations in the structure were characterized. Interpretation of the experimental data by the least squares method yielded the oxygen parameter u = 0.261 and the isotropic temperature factor 1.09 AU squared.

Nozik, Y. Z.↗

Solubility of Cr, Ti, and Al in co-existing olivine, spinel, and liquid at 1 atm

The partitioning of chromium between olivines, spinels and silicate liquids was studied as a function of temperature, oxygen fugacity, and cooling rate between 1175 and 1300 C and redox states near the Fe-FeO buffer. It is found that the weight ratio of Cr2O3 in olivine to that in the liquid increases slightly as oxygen fugacity decreases, but the effect is very small. The cooling experiments showed that the Cr2O3 content does not re-equilibrate with cooling.

Akella, J.↗