'PERMIT' ion migration test for measuring the chloride ion transport of concrete on site

The ingress of chlorides into concrete is predominantly by the mechanism of diffusion and the resistance of concrete to the transport of chlorides is generally represented by its coefficient of diffusion. The determination of this coefficient normally requires long test duration (many months). Therefore, rapid test methods based on the electrical migration of ions have widely been used. The current procedure of chloride ion migration tests involves placing a concrete disc between an ion source solution and a neutral solution and accelerating the transport of ions from the source solution to the neutral solution by the application of a potential difference across the concrete disc. This means that, in order to determine the chloride transport resistance of concrete cover, cores should be extracted from the structure and tested in laboratories. In an attempt to facilitate testing of the concrete cover on site, an in situ ion migration test (hereafter referred to as PERMIT ion migration test for the unique identification of the new test) was developed. The PERMIT ion migration test was validated in the lab by carrying out a comparative investigation and correlating the results with the migration coefficient from the one-dimensional chloride migration test, the effective diffusion coefficient from the normal diffusion test and the apparent diffusion coefficient determined from chloride profiles. A range of concrete mixes made with ordinary Portland cement was used for this purpose. In addition, the effects of preferential flow of ions close to the concrete surface and the proximity of reinforcement within the test area on the in situ migration coefficients were investigated. It was observed that the in situ migration index, found in one working day, correlated well with the chloride diffusion coefficients from other tests. The quality of the surface layer of the cover concrete and the location of the reinforcement within the test area were found to affect the flow of ions through the concrete during the test. Based on the data, a procedure to carry out the PERMIT ion migration test was standardised.

Relevance of heterometallic binding energy for metal underpotential deposition

We present first-principles calculations for a number of metals adsorbed on several different metallic substrates. Some of these systems are very relevant in electrochemistry, especially in the field of underpotential deposition phenomena. The present studies reveal the existence of a relationship between the excess binding energy and the surface energy difference between substrate and adsorbate. Comparisons with experimental underpotential shifts show that excess binding energies are systematically underestimated. By analyzing experimental information on different systems, we conclude that this discrepancy between our vacuum calculations and experiments carried out in an electrolytic solution is likely to be due to anion adsorption and/or solvent effects.

Tight-binding simulation of current-carrying nanostructures

The tight-binding (TB) approach to the modelling of electrical conduction in small structures is introduced. Different equivalent forms of the TB expression for the electrical current in a nanoscale junction are derived. The use of the formalism to calculate the current density and local potential is illustrated by model examples. A first-principles time-dependent TB formalism for calculating current-induced forces and the dynamical response of atoms is presented. An earlier expression for current-induced forces under steady-state conditions is generalized beyond local charge neutrality and beyond orthogonal TB. Future directions in the modelling of power dissipation and local heating in nanoscale conductors are discussed.

Time-dependent tight binding

Starting from a Lagrangian mean-field theory, a set of time-dependent tight-binding equations is derived to describe dynamically and self-consistently an interacting system of quantum electrons and classical nuclei. These equations conserve norm, total energy and total momentum. A comparison with other tight-binding models is made. A previous tight-binding result for forces on atoms in the presence of electrical current flow is generalized to the time-dependent domain and is taken beyond the limit of local charge neutrality.

Relative energetics and structural properties of zirconia using a self-consistent tight-binding model

We describe an empirical, self-consistent, orthogonal tight-binding model for zirconia, which allows for the polarizability of the anions at dipole and quadrupole levels and for crystal field splitting of the cation d orbitals, This is achieved by mixing the orbitals of different symmetry on a site with coupling coefficients driven by the Coulomb potentials up to octapole level. The additional forces on atoms due to the self-consistency and polarizabilities are exactly obtained by straightforward electrostatics, by analogy with the Hellmann-Feynman theorem as applied in first-principles calculations. The model correctly orders the zero temperature energies of all zirconia polymorphs. The Zr-O matrix elements of the Hamiltonian, which measure covalency, make a greater contribution than the polarizability to the energy differences between phases. Results for elastic constants of the cubic and tetragonal phases and phonon frequencies of the cubic phase are also presented and compared with some experimental data and first-principles calculations. We suggest that the model will be useful for studying finite temperature effects by means of molecular dynamics.

Interactions of 1-Methylimidazole with UO2(CH3CO2)2 and UO2(NO3)2: Structural, Spectroscopic and Theoretical Evidence for Imidazole Binding to the Uranyl Ion

The first definitive high-resolution single-crystal X-ray structure for the coordination of the 1-methylimidazole (Meimid) ligand to UO2(Ac)2 (Ac = CH3CO2) is reported. The crystal structure evidence is confirmed by IR, Raman, and UV-vis spectroscopic data. Direct participation of the nitrogen atom of the Meimid ligand in binding to the uranium center is confirmed. Structural analysis at the DFT (B3LYP) level of theory showed a conformational difference of the Meimid ligand in the free gas-phase complex versus the solid state due to small energetic differences and crystal packing effects. Energetic analysis at the MP2 level in the gas phase supported stronger Meimid binding over H2O binding to both UO2(Ac)2 and UO2(NO3)2. In addition, self-consistent reaction field COSMO calculations were used to assess the aqueous phase energetics of combination and displacement reactions involving H2O and Meimid ligands to UO2R2 (R = Ac, NO3). For both UO2(NO3)2 and UO2(Ac)2, the displacement of H2O by Meimid was predicted to be energetically favorable, consistent with experimental results that suggest Meimid may bind uranyl at physiological pH. Also, log(Knitrate/KAc) calculations supported experimental evidence that the binding stoichiometry of the Meimid ligand is dependent upon the nature of the reactant uranyl complex. These results clearly demonstrate that imidazole binds to uranyl and suggest that binding of histidine residues to uranyl could occur under normal biological conditions.