In-Situ Analysis of Corrosion Products in Molten Salt: X-ray Absorption Reveals Both Ionic and Metallic Species.

Understanding and controlling the chemical processes between molten salts and alloys is vital for the safe operation of molten-salt nuclear reactors. Corrosion processes in molten salts are highly dependent on the redox potential of the solution that changes with the presence of fission and corrosion processes, and as such, reactor designers develop electrochemical methods to monitor the salt. However, electrochemical techniques rely on the deconvolution of broad peaks, a process that may be imprecise in the presence of multiple species that emerge during reactor operation. Here, we describe in situ measurements of the concentration and chemical state of corrosion products in molten FLiNaK (eutectic mixture of LiF-NaK-KF) by high-resolution X-ray absorption spectroscopy. We placed a NiCr foil in molten FLiNaK and found the presence of both Ni2+ ions and metallic Ni in the melt, which we attribute to the foil disintegration due to Cr dealloying.

Migration and Precipitation of Platinum in Anion-Exchange Membrane Fuel Cells.

Despite the recent progress in increasing the power generation of Anion-exchange membrane fuel cells (AEMFCs), their durability is still far lower than that of Proton exchange membrane fuel cells (PEMFCs). Using the complementary techniques of X-ray micro-computed tomography (CT), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) spectroscopy, we have identified Pt ion migration as an important factor to explain the decay in performance of AEMFCs. In alkaline media Pt+2 ions are easily formed which then either undergo dissolution into the carbon support or migrate to the membrane. In contrast to PEMFCs, where hydrogen cross over reduces the ions forming a vertical "Pt line" within the membrane, the ions in the AEM are trapped by charged groups within the membrane, leading to disintegration of the membrane and failure. Diffusion of the metal components is still observed when the Pt/C of the cathode is substituted with a FeCo-N-C catalyst, but in this case the Fe and Co ions are not trapped within the membrane, but rather migrate into the anode, thereby increasing the stability of the membrane.

Disorder in Ho2Ti2-x Zr x O7: pyrochlore to defect fluorite solid solution series.

Pyrochlore (A2B2O7) is an important, isometric structure-type because of its large variety of compositions and structural derivatives that are generally related to different disordering mechanisms at various spatial scales. The disordering is key to understanding variations in properties, such as magnetic behavior or ionic conduction. Neutron and X-ray total scattering methods were used to investigate the degree of structural disorder in the Ho2Ti2-x Zr x O7 (x = 0.0-2.0, Δx = 0.25) solid solution series as a function of the Zr-content, x. Ordered pyrochlores (Fd3̄m) disorder to defect fluorite (Fm3̄m) via cation and anion disordering. Total scattering experiments with sensitivity to the cation and anion sublattices provide unique insight into the underlying atomic processes. Using simultaneous Rietveld refinement (long-range structure) and small-box refinement PDF analysis (short-range structure), we show that the series undergoes a rapid transformation from pyrochlore to defect fluorite at x ≈ 1.2, while the short-range structure exhibits a linear increase in a local weberite-type phase, C2221, over the entire composition range. Enthalpies of formation from the oxides determined using high temperature oxide melt solution calorimetry support the structural data and provide insight into the effect of local ordering on the energetics of disorder. The measured enthalpies of mixing are negative and are fit by a regular solution parameter of W = -31.8 ± 3.7 kJ mol-1. However, the extensive short-range ordering determined from the structural analysis strongly suggests that the entropies of mixing must be far less positive than implied by the random mixing of a regular solution. We propose a local disordering scheme involving the pyrochlore 48f to 8a site oxygen Frenkel defect that creates 7-coordinated Zr sites contained within local weberite-type coherent nanodomains. Thus, the solid solution is best described as a mixture of two phases, with the weberite-type nanodomains triggering the long-range structural transformation to defect fluorite after accumulation above a critical concentration (50% Ti replaced by Zr).

Enhanced Magnetization of Cobalt Defect Clusters Embedded in TiO2-δ Films.

High magnetizations are desirable for spintronic devices that operate by manipulating electronic states using built-in magnetic fields. However, the magnetic moment in promising dilute magnetic oxide nanocomposites is very low, typically corresponding to only fractions of a Bohr magneton for each dopant atom. In this study, we report a large magnetization formed by ion implantation of Co into amorphous TiO2-δ films, producing an inhomogeneous magnetic moment, with certain regions producing over 2.5 µB per Co, depending on the local dopant concentration. Polarized neutron reflectometry was used to depth-profile the magnetization in the Co:TiO2-δ nanocomposites, thus confirming the pivotal role of the cobalt dopant profile inside the titania layer. X-ray photoemission spectra demonstrate the dominant electronic state of the implanted species is Co0, with a minor fraction of Co2+. The detected magnetizations have seldom been reported before and lie near the upper limit set by Hund's rules for Co0, which is unusual because the transition metal's magnetic moment is usually reduced in a symmetric 3D crystal-field environment. Low-energy positron annihilation lifetime spectroscopy indicates that defect structures within the titania layer are strongly modified by the implanted Co. We propose that a clustering motif is promoted by the affinity of the positively charged implanted species to occupy microvoids native to the amorphous host. This provides a seed for subsequent doping and nucleation of nanoclusters within an unusual local environment.

Ending aging in super glassy polymer membranes.

Aging in super glassy polymers such as poly(trimethylsilylpropyne) (PTMSP), poly(4-methyl-2-pentyne) (PMP), and polymers with intrinsic microporosity (PIM-1) reduces gas permeabilities and limits their application as gas-separation membranes. While super glassy polymers are initially very porous, and ultra-permeable, they quickly pack into a denser phase becoming less porous and permeable. This age-old problem has been solved by adding an ultraporous additive that maintains the low density, porous, initial stage of super glassy polymers through absorbing a portion of the polymer chains within its pores thereby holding the chains in their open position. This result is the first time that aging in super glassy polymers is inhibited whilst maintaining enhanced CO2 permeability for one year and improving CO2/N2 selectivity. This approach could allow super glassy polymers to be revisited for commercial application in gas separations.