Structure, Atomistic Simulations, and Phase Transition of Stoichiometric Yeelimite

ABSTRACT: Yeelimite, Ca4[Al6O12]SO4, is outstanding as an aluminate sodalite, being the framework of these type of materials flexible and dependent on ion sizes and anion ordering/disordering. On the other hand, yeelimite is also important from an applied perspective as it is the most important phase in calcium sulfoaluminate cements. However, its crystal structure is not well studied. Here, we characterize the room temperature crystal structure of stoichiometric yeelimite through joint Rietveld refinement using neutron and Xray powder diffraction data coupled with chemical soft-constraints. Our structural study shows that yeelimite has a lower symmetry than that of the previously reported tetragonal system, which we establish to likely be the acentric orthorhombic space group Pcc2, with a √2a × √2a × a superstructure based on the cubic sodalite structure. Final unit cell values were a = 13.0356(7) Å, b = 13.0350(7) Å, and c = 9.1677(2) Å. We determine several structures using density functional theory calculations, with the lowest energy structure being Pcc2 in agreement with our experimental result. Yeelimite undergoes a reversible phase transition to a higher-symmetry phase which has been characterized to occur at 470 °C by thermodiffractometry. The higher-symmetry phase is likely cubic or pseudocubic possessing an incommensurate superstructure, as suggested by our theoretical calculations which show a phase transition from an orthorhombic to a tetragonal structure. Our theoretical study also predicts a pressure-induced phase transition to a cubic structure of space group I43m. Finally, we show that our reported crystal structure of yeelimite enables better mineralogical phase analysis of commercial calcium sulfoaluminate cements, as shown by RF values for this phase, 6.9% and 4.8% for the previously published orthorhombic structure and for the one reported in this study, respectively.Universidad de Málaga. Campus de Excelencia Internacional. Andalucía Tech

The role of parent austenite grain size on the variant selection and intervariant boundary network in a lath martensitic steel

This study investigated the influence of parent austenite grain refinement on the intervariant boundary network (population and connectivity) in a lath martensitic steel. Parent austenite grain refinement revealed a progressive reduction in the fraction of the 60° misorientation boundaries in martensite, which was linked to a decrease in the 60° / [110] intervariant boundary population. The phenomenological theory of martensite crystallography demonstrated that the variant selection mechanism altered from the 3-variant clustering (V1V3V5) in the coarse parent austenite towards the 4-variant clustering (V1V2V3V4) in the fine parent austenite grain, due to the change in the lattice parameter of the parent and daughter phase in which the martensite transformation occurs, as measured using in situ neutron diffraction. The change in the variant clustering arrangement with the parent austenite grain refinement led to a progressive promotion of 60° / [111] and 10.5° / [011] intervariant boundaries at the expense of 60° / [110] martensite intervariant boundaries. Subsequently, the connectivity of low energy {110} tilt intervariant boundaries gradually increased through the refinement of parent austenite grain size, eventually reducing the high energy {110} twist boundary connectivity. This change improved the impact toughness of martensite produced from the fine-grained austenite as the weak connectivity of high energy boundaries delays the coalescence of voids, promoting ductile fracture.publishedVersio

In-situ synchrotron diffraction study of the phase evolution of the novel Na\u3csub\u3ex\u3c/sub\u3e(Fe\u3csub\u3e1/2\u3c/sub\u3eMn\u3csub\u3e1/2\u3c/sub\u3e)O\u3csub\u3e2\u3c/sub\u3e cathode for use in sodium-ion batteries

Abstract of a poster presentation at the 5th Australia-China Conference on Science, Technology and Eduction with the 5th Australia-China Symposium for Materials Science, at the University of Wollongong (UOW), Australia, on 21st - 23rd July 2014

Crystallographic origin of cycle decay of the high-voltage LiNi\u3csub\u3e0.5\u3c/sub\u3eMn\u3csub\u3e1.5\u3c/sub\u3eO\u3csub\u3e4\u3c/sub\u3e spinel lithium-ion battery electrode

High-voltage spinel LiNi0.5Mn1.5O4 (LNMO) is considered a potential high-power-density positive electrode for lithium-ion batteries, however, it suffers from capacity decay after extended charge-discharge cycling, severely hindering commercial application. Capacity fade is thought to occur through the significant volume change of the LNMO electrode occurring on cycling, and in this work we use operando neutron powder diffraction to compare the structural evolution of the LNMO electrode in an as-assembled 18650-type battery containing a Li4Ti5O12 negative electrode with that in an identical battery following 1000 cycles at high-current. We reveal that the capacity reduction in the battery post cycling is directly proportional to the reduction in the maximum change of the LNMO lattice parameter during its evolution. This is correlated to a corresponding reduction in the MnO6 octahedral distortion in the spinel structure in the cycled battery. Further, we find that the rate of lattice evolution, which reflects the rate of lithium insertion and removal, is ∼9 and ∼10% slower in the cycled than in the as-assembled battery during the Ni2+/Ni3+ and Ni3+/Ni4+ transitions, respectively

Gallium-Doped Li7La3Zr2O12 Garnet-Type Electrolytes with High Lithium-Ion Conductivity

Owing to their high conductivity, crystalline Li7–3xGaxLa3Zr2O12 garnets are promising electrolytes for all-solid-state lithium-ion batteries. Herein, the influence of Ga doping on the phase, lithium-ion distribution, and conductivity of Li7–3xGaxLa3Zr2O12 garnets is investigated, with the determined concentration and mobility of lithium ions shedding light on the origin of the high conductivity of Li7–3xGaxLa3Zr2O12. When the Ga concentration exceeds 0.20 Ga per formula unit, the garnet-type material is found to assume a cubic structure, but lower Ga concentrations result in the coexistence of cubic and tetragonal phases. Most lithium within Li7–3xGaxLa3Zr2O12 is found to reside at the octahedral 96h site, away from the central octahedral 48g site, while the remaining lithium resides at the tetrahedral 24d site. Such kind of lithium distribution leads to high lithium-ion mobility, which is the origin of the high conductivity; the highest lithium-ion conductivity of 1.46 mS/cm at 25 °C is found to be achieved for Li7–3xGaxLa3Zr2O12 at x = 0.25. Additionally, there are two lithium-ion migration pathways in the Li7–3xGaxLa3Zr2O12 garnets: 96h-96h and 24d-96h-24d, but the lithium ions transporting through the 96h-96h pathway determine the overall conductivity

Structural Insight into Layer Gliding and Lattice Distortion in Layered Manganese Oxide Electrodes for Potassium-Ion Batteries

Potassium-ion batteries (PIBs) are an emerging, affordable, and environmentally friendly alternative to lithium-ion batteries, with their further development driven by the need for suitably performing electrode materials capable of reversibly accommodating the relatively large K+. Layer-structured manganese oxides are attractive as electrodes for PIBs, but suffer from structural instability and sluggish kinetics of K+ insertion/extraction, leading to poor rate capability. Herein, cobalt is successfully introduced at the manganese site in the KxMnO2 layered oxide electrode material and it is shown that with only 5% Co, the reversible capacity increases by 30% at 22 mA g-1 and by 92% at 440 mA g-1. In operando synchrotron X-ray diffraction reveals that Co suppresses Jahn-Teller distortion, leading to more isotropic migration pathways for K+ in the interlayer, thus enhancing the ionic diffusion and consequently, rate capability. The detailed analysis reveals that additional phase transitions and larger volume change occur in the Co-doped material as a result of layer gliding, with these associated with faster capacity decay, despite the overall capacity remaining higher than the pristine material, even after 500 cycles. These results assert the importance of understanding the detailed structural evolution that underpins performance that will inform the strategic design of electrode materials for high-performance PIBs

High-resolution diffraction reveals magnetoelastic coupling and coherent phase separation in tetragonal CuMnAs

Tetragonal CuMnAs was the first antiferromagnet where reorientation of the N\'eel vector was reported to occur by an inverse spin galvanic effect. A complicating factor in the formation of phase-pure tetragonal CuMnAs is the formation of an orthorhombic phase with nearly the same stoichiometry. Pure-phase tetragonal CuMnAs has been reported to require an excess of Cu to maintain a single phase in traditional solid state synthesis reactions. Here we show that subtle differences in diffraction patterns signal pervasive inhomogeneity and phase separation, even in Cu-rich Cu$_{1.18}$Mn$_{0.82}$As. From calorimetry and magnetometry measurements, we identify two transitions corresponding to the N\'eel temperature (T$_N$) and an antiferromagnet to weak ferromagnet transition in Cu$_{1.18}$Mn$_{0.82}$As and CuMn$_{0.964}$As$_{1.036}$. These transitions have clear crystallographic signatures, directly observable in the lattice parameters upon in-situ heating and cooling. The immiscibility and phase separation could arise from a spinoidal decomposition that occurs at high temperatures, and the presence of a ferromagnetic transition near room temperature warrants further investigation of its effect on the electrical switching behavior.Comment: 10 pages, 9 figures, added author middle initia