Atomic-resolution STEM-EDS studies of cation ordering in Ti-Nb oxide crystals

Ternary metal oxide compounds, such as Ti-Nb and Nb-W oxides, have renewed research interest in energy storage materials because these oxides contain multivalent metal ions that may be able to control the ion transport in solid lithium batteries. One of these oxides is Ti2Nb10O29, which is composed of metal–oxygen octahedra connected through corner-sharing and edge-sharing to form “block structures”. In the early 1970s Von Dreele and Cheetham proposed a metal-atoms ordering in this oxide crystal using Rietveld refined neutron powder diffraction method. Most recent studies on these oxides, however, have not considered cation ordering in evaluating the battery electrode materials. In this paper, by utilizing the latest scanning transmission electron microscopy combined with energy dispersive X-ray spectroscopy imaging technology, the cation chemical ordering in those oxide crystals was directly revealed at atomic resolution.

Alkali sulfates with aphthitalite-like structures from fumaroles of the Tolbachik volcano, Kamchatka, Russia. III. Solid solutions and exsolutions

ABSTRACT Six different exsolution types are found in crystals of aphthitalite-group alkali sulfates from exhalations of the active Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. The coexisting minerals in these exsolutions are metathénardite, ideally Na2SO4 (P63/mmc), and vanthoffite, Na6Mg(SO4)4 (P21/c) (Type I); metathénardite and belomarinaite, KNaSO4 (P3m1) (Type II); thénardite, Na2SO4 (Fddd), and aphthitalite, K3Na(SO4)2 (Pm1) (Type III); aphthitalite and arcanite, K2SO4 (Pnma) (Type IV); metathénardite and natroaphthitalite, KNa3(SO4)2 (Pm1) (Type V); and two chemical varieties of metathénardite (Type VI). The exsolution processes occur in crystals belonging to the high-temperature, hexagonal Na2SO4(I) (= metathénardite, P63/mmc) structure type with different K:Na ratios formed at temperatures higher than 500 °C. The similarity and hexagonal close-packed nature of the crystal structures of the coexisting phases, all representatives of aphthitalite-like structure types, cause the coherent conjugation of domains during diffusion and cation ordering in the parent phase. The breakdown of solid solution can be facilitated by the mosaic character of crystals of a parent phase (incoherent grain boundaries) and the presence of coherent twin boundaries. The heating of samples with exsolution Types II and V up to 700 °C over 24 h shows that diffusion of K and Na through the domain borders does not result in the complete disorder of these cations and the extinction of domains with different crystal structures.

A global study of dolomite stoichiometry and cation ordering through the Phanerozoic

ABSTRACT Various geochemical proxies are used to constrain the diagenetic origin and evolution of ancient dolomites. Dolomite stoichiometry (mole % MgCO3) and cation ordering, two mineralogical attributes that define dolomite, have also been shown to demonstrate utility in this regard. Observations from laboratory experiments and field studies suggest that these attributes broadly reflect the fluid chemistry and temperature of the dolomitizing environment. The degree to which these parameters reflect global conditions during dolomitization (e.g., seawater chemistry, eustasy, atmospheric pCO2) and long-term geological processes is poorly understood, however. Here, a large dataset consisting of mineralogical data from over 1,690 Phanerozoic dolomites from various geographic locations, stratigraphic ages, platform types, and depositional environments are queried to investigate the broader geological controls on dolomite stoichiometry and cation ordering in dolomites formed by early, near-surface dolomitization. A suite of statistical analyses performed on the global dataset indicate: 1) despite wide ranges at the eon, period, and epoch level, dolomite stoichiometry and cation ordering broadly increase with geologic age; 2) significant variations in dolomite stoichiometry and cation ordering throughout the Phanerozoic do not correlate with global parameters, such as seawater chemistry, eustasy, orogenic events, and ocean crust production; 3) dolomites associated with restricted depositional settings, such as restricted lagoons, and the intertidal and supratidal zones, are more stoichiometric than dolomites associated with open marine settings, such as the deep-subtidal and shallow-subtidal zones; and 4) dolomites from shallow ramps and epeiric carbonate platforms are generally more stoichiometric than dolomites from open shelves and isolated carbonate platforms. These observations permit a number of inferences to be drawn. First, the principal signal observed in the data is that local environmental conditions associated with platform type and depositional setting are the strongest control on dolomite mineralogy. The observation that more stoichiometric dolomites correlate with shallow and restricted depositional environments is consistent with laboratory experiments that show environmental factors, such as higher Mg:Ca, temperature, and salinity of the dolomitizing fluids yield more stoichiometric dolomite. Second, a weaker secondary signal is also observed such that dolomite stoichiometry and cation ordering both increase with geologic age, suggesting that progressive recrystallization driven by mineralogical stabilization during burial is also occurring. Collectively, these data suggest that spatial and temporal variations in stoichiometry and cation ordering reflect the interplay between local dolomitizing conditions near the surface and long-term mineralogical stabilization during burial.