Ru-implanted titanium near-surface alloys were generated by ion implantation, characterized (Ru concentration/ depth profiles) by Rutherford backscattering, and subsequently anodically oxidized to form electrocatalytically active RuxTil_xOJTi electrodes. The electrochemical behavior of the metallic-like electrodes was investigated in acidic chloride, perchlorate, and sulfate media. A correlation between the rate of the C12 evolution reaction and the Ru-implant profiles established that the reaction is first order in the concentration of Ru(IV) in the oxide at the oxide/solution interface, and enabled an in situ evaluation of the latter quantity. The Tafel slope for the C12 evolution reaction is 40 mV, i.e., o E/O log i = 2.303 (2RT/3F). The reaction order with respect to chloride ion concentration, 0 log i/0 log [C1-], approaches 1.0 and 2.0 at high and low chloride Concentrations, respectively. A modified Volmer-Heyrovsky mechanism, one in which the role of adsorbed chloride ions is taken into account, is shown to be consistent with the aforementioned diagnostic parameters.ion implantation, a nonequilibrium doping technique, enables the controlled introduction of virtually any element into the near-surface region of any substrate, typically to a depth up to a few hundred nanometers. The concentration/depth profile of the implanted species (determined, for example, by Rutherford backscattering) *Electrochemical Society Active Member. may be tailored over a wide range by varying the energy of the incident ions and the number of ions (coulombs of charge) implanted at each energy. As a surface modification technique, ion implantation has found widespread application for improving the electronic, optical, tribological, and corrosion characteristics of materials (1-4). The rates of many technologically important electrochemical charge transfer reactions occurring at elec-) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 128.255.6.125 Downloaded on 2015-06-03 to IP

During charge or discharge of batteries with a binary molten salt mixture as t~he electrolyte, composition gradients are produced by the electrode reactions and the differences in mobilities of the electroactive and nonelectroactive ions. The effects of current density, electrode separatioa, and initial composition of the electrolyte are predicted by an analytical solution of the flux equations derived with transport properties similar to those of LiCI-KC1 mixtures. Numerical solution of the flux equations predicts the composition profiles in lithium sulfur battery analogs with LiC1-KCI mixtures of differing compositions. Either complete depletio,n of the electroactive constituent at one electrode, or precipitation of a solid phase at the electrodes, could result from the predicted composition gradients. Changes in electrolyte composition at the electrodes may also affect J-phase formation at the sulfur electrode during discharge. * Electrochemical Society Active Member. ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 169.230.243.252 Downloaded on 2015-02-18 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 169.230.243.252 Downloaded on 2015-02-18 to IP

Composition gradients, in molten AgNO3‐NaNO3 mixtures contained in silica frits, are produced by electrolysis between silver electrodes and analyzed by three methods: (i) in situ potentiometry, (ii) chemical analysis of sections of quenched electrolyte, and (iii) scanning electron microscopy with associated x‐ray fluorescence spectroscopy. The composition changes are calculated a priori from transport and thermodynamic properties independently measured in the free melt and corrected for the porosity of the frits. Since the ion flows in AgNO3‐NaNO3 are analogous to those in the normalLiCl‐normalKCl electrolyte of Li/S batteries, the former system serves as a convenient model system for the mixed electrolyte of the Li/S battery. The predicted gradients are compared to the experimental data from the three methods.

M(NMe(2))(4) (M = Ti, Zr, Hf) were found to react with H(2)SiR'Ph (R' = H, Me, Ph) to yield H(2), aminosilanes, and black solids. Unusual amide hydride complexes [(Me(2)N)(3)M(mu-H)(mu-NMe(2))(2)](2)M (M = Zr, 1; Hf, 2) were observed to be intermediates and characterized by single-crystal X-ray diffraction. [(Me(2)N)(3)M(mu-D)(mu-NMe(2))(2)](2)M (1-d(2), 2-d(2)) were prepared through reactions of M(NMe(2))(4) with D(2)SiPh(2). Reactions of (Me(2)N)(3)ZrSi(SiMe(3))(3) (5) with H(2)SiR'Ph were found to give aminosilanes and (Me(2)N)(2)Zr(H)Si(SiMe(3))(3) (6). These reactions are reversible through unusual equilibria such as (Me(2)N)(3)ZrSi(SiMe(3))(3) (5) + H(2)SiPh(2) right arrow over left arrow (Me(2)N)(2)Zr(H)Si(SiMe(3))(3) (6) + HSi(NMe(2))Ph(2). The deuteride ligand in (Me(2)N)(2)Zr(D)Si(SiMe(3))(3) (6-d(1)) undergoes H-D exchange with H(2)SiR'Ph (R' = Me, H) to give 6 and HDSiR'Ph. The reaction of Ti(NMe(2))(4) with SiH(4) in chemical vapor deposition at 450 degrees C yielded thin Ti-Si-N ternary films containing TiN and Si(3)N(4). Ti(NMe(2))(4) reacts with SiH(4) at 23 degrees C to give H(2), HSi(NMe(2))(3), and a black solid. HNMe(2) was not detected in this reaction. The reaction mixture, upon heating, gave TiN and Si(3)N(4) powders. Analyses and reactivities of the black solid revealed that it contained -H and unreacted -NMe(2) ligands but no silicon-containing ligand. Ab initio quantum chemical calculations of the reactions of Ti(NR(2))(4) (R = Me, H) with SiH(4) indicated that the formation of aminosilanes and HTi(NR(2))(3) was favored. These calculations also showed that HTi(NH(2))(3) (3b) reacted with SiH(4) or H(3)Si-NH(2) in the following step to give H(2)Ti(NH(2))(2) (4b) and aminosilanes. The results in the current studies indicated that the role of SiH(4) in its reaction with Ti(NMe(2))(4) was mainly to remove amide ligands as HSi(NMe(2))(3). The removal of amide ligands is incomplete, and the reaction thus yielded "=Ti(H)(NMe(2))" as the black solid. Subsequent heating of the black solid and HSi(NMe(2))(3) may then yield TiN and Si(3)N(4), respectively, as the Ti-Si-N materials.