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At least 271 records · Page 15

Reversible Cl/Cl - redox in a spinel Mn 3 O 4 electrode

A unique prospect of using halides as charge carriers is the possibility of the halides undergoing anodic redox behaviors when serving as charge carriers for the charge-neutrality compensation of electrodes. However, the anodic conversion of halides to neutral halogen species has often been irreversible at room temperature due to the emergence of diatomic halogen gaseous products. Here, we report that chloride ions can be reversibly converted to near-neutral atomic chlorine species in the Mn 3 O 4 electrode at room temperature in a highly concentrated chloride-based aqueous electrolyte. Notably, the Zn 2+ cations inserted in the first discharge and trapped in the Mn 3 O 4 structure create an environment to stabilize the converted chlorine atoms within the structure. Characterization results suggest that the Cl/Cl - redox is responsible for the observed large capacity, as the oxidation state of Mn barely changes upon charging. Computation results corroborate that the converted chlorine species exist as polychloride monoanions, e.g., [Cl 3 ] - and [Cl 5 ] - , inside the Zn 2+ -trapped Mn 3 O 4 , and the presence of polychloride species is confirmed experimentally. Our results point to the halogen plating inside electrode lattices as a new charge-storage mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of iron in magnetic damping of Mg(Al,Fe) 2 O 4 spinel ferrite thin films

© 2020 Author(s). We have investigated magnesium aluminum ferrite thin films with a range of iron concentrations and identified the optimal iron content to obtain high crystalline quality thin films with the low magnetic damping required for spin current-based applications. Epitaxial MgAl 2-x FexO4 films with 0.8 < x < 2.0 were grown by pulsed laser deposition on single crystal MgAl2O4 substrates and were characterized structurally and magnetically. We find that the x = 1.5 composition minimizes the room-temperature magnetic damping with a typical Gilbert damping parameter of α eff = 1.8 × 10-3. This minimized damping is governed by a competition between the more robust magnetic ordering with increased iron content, x, and the more defective structure due to larger film-substrate lattice mismatch with increased iron content. The temperature-dependent magnetization curves indicate that Tc is suppressed below room temperature for iron content x ≤ 1.2 and eventually suppressed entirely for x = 0.8. X-ray magnetic circular dichroism results indicate that for all x the magnetic moment is dominated by Fe 3 + cations distributed in a 60:40 ratio on the octahedral and tetrahedral sites, with minimal contribution from Fe 2 + cations. Films with x = 1.4-1.6 exhibit very strong ferromagnetic resonance and low Gilbert damping with α eff = (1.8-6) × 10-3, making them ideal candidates for microwave and spintronic applications.

36 MATERIALS SCIENCE↗

Impact on aggregate/matrix bonding when a refractory contains zinc aluminate instead of spinel and magnesia‐chrome

The high hot strength of MgO–Cr 2 O 3 refractory is often ascribed to its intimate aggregate/matrix bonding. For a fundamental comparison with it, ~2 mm aggregates of MgO and Al 2 O 3 were separately embedded in ZnAl 2 O 4 and MgAl 2 O 4 matrices, sintered at 1600°C, and examined. It was found that similarity of thermal expansion coefficient (TEC) between the aggregate and the matrix is critical to achieve good bonding and this is more important than the extent of interdiffusion. The TEC mismatch of ≥ 5.7 × 10 -6 K -1 caused significant undesirable debonding in MgO aggregate/MgAl 2 O 4 matrix sample and MgO/ZnAl 2 O 4 despite >736 μm Zn 2+ diffusion depth in the latter. Direct bonding, as inferred from a thicker interfacial reaction layer and a greater shift of the aggregate/matrix interface before and after firing, was better in MgAl 2 O 4 /ZnAl 2 O 4 combination, followed by tabular Al 2 O 3 /ZnAl 2 O 4 and Al 2 O 3 /MgAl 2 O 4 . Powder X-ray diffraction indicated that the volatilization of ZnAl 2 O 4 at 1600°C in air was negligible compared to MgO–Cr 2 O 3 .

36 MATERIALS SCIENCE↗

Subsolidus reduction of lunar spinels.

Discussion of evidence that some lunar basalts must have exceeded the lower limit of crystallization oxygen fugacity (fO2) by several orders of magnitude. The evidence is based primarily on the decomposition of Cr-Al-ulvospinel, and is further supported in one case by the decomposition of olivine. The data suggest that some rocks have undergone intense nonequilibrium subsolidus reduction. The reduction phenomenon is widespread, and is considered to have developed either during initial deuteric cooling or as a result of a postcrystallization reduction event.

Haggerty, S. E.↗

Spinel-silicate co-crystallization relations in sample 15555

The results on the crystallization history of medium-grained mare basalt sample 15555,171, based on microprobe analyses (Dalton, 1973) of host and inclusion mineral pairs are summarized with emphasis placed on that part of the crystallization history during which chromite and ulvospinel were crystallizing. Compositional data on pyroxene olivine, chromite and ulvospinel in 15555,171 were collected using microprobe; data are based on corrected counts ratios for nine elements. It is concluded that systematic chemical relations between host and inclusion minerals suggest continuous in situ nucleation and growth of these minerals; that the data allow the possibility of some minerals, especially chromite, settling out of the melt during crystallization; and that the chromite to ulvospinel transition is correlated with a compositional change of the melt resulting from nucleation and growth of plagioclase.

Dalton, J.↗