The surface diffusion of gold atoms on gold electrodes in acid solution and its dependence on the presence of foreign adsorbates

The surface diffusion coefficient (Ds) of Au atoms in 0.5 M H2SO4 at 298 K has been determined from the time dependence of the surface roughness factor of electrodispersed Au electrodes in 0.5 M H2SO4. The value of Ds for 0.5 M H2SO4 is 5 × 10−14 cm2 s−1, a figure which depends considerably on the presence of adsorbable species in solution. Thus, the adsorption of pyridine produces a remarkable decrease of Ds, whereas the adsorption of Cl− ion results in the opposite effect. The corresponding values of Ds are 1.2 × 10−14 cm2 s−1 for 0.5 M H2SO4 + 0.1 M pyridine, and 2.5 × 10−13 cm2 s−1 for 0.5 M H2SO4 + 5 × 10−4 M KCl. These results are interpreted through the influence of the adsorbate on the Au surface atom diffusion mechanism.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA)Facultad de Ciencias Exacta

The surface diffusion of gold atoms on gold electrodes in acid solution and its dependence on the presence of foreign adsorbates

The surface diffusion coefficient (Ds) of Au atoms in 0.5 M H2SO4 at 298 K has been determined from the time dependence of the surface roughness factor of electrodispersed Au electrodes in 0.5 M H2SO4. The value of Ds for 0.5 M H2SO4 is 5 × 10−14 cm2 s−1, a figure which depends considerably on the presence of adsorbable species in solution. Thus, the adsorption of pyridine produces a remarkable decrease of Ds, whereas the adsorption of Cl− ion results in the opposite effect. The corresponding values of Ds are 1.2 × 10−14 cm2 s−1 for 0.5 M H2SO4 + 0.1 M pyridine, and 2.5 × 10−13 cm2 s−1 for 0.5 M H2SO4 + 5 × 10−4 M KCl. These results are interpreted through the influence of the adsorbate on the Au surface atom diffusion mechanism.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA)Facultad de Ciencias Exacta

The mechanism of silver(I) oxide formation on polycrystalline silver in alkaline solution. Determination of nucleation and growth rates

The nucleation and growth of Ag(I) oxide layers on polycrystalline Ag electrodes is studied by potentiodynamic and potentiostatic current transients in 0.1 M NaOH. A model involving the diffusion controlled growth of a basal layer followed by the nucleation and growth of a secondary layer is proposed. Various nucleation parameters are estimated by comparing experimental data with simulated transients, and the results are discussed in terms of the atomistic theory of electrochemical phase formation. The influence of the nucleation parameters on the shape of the current transients is analysed and some controversial results in the literature are explained.Instituto de Investigaciones Fisicoquímicas Teóricas y AplicadasFacultad de Ciencias Exacta

The mechanism of silver(I) oxide formation on polycrystalline silver in alkaline solution. Determination of nucleation and growth rates

The nucleation and growth of Ag(I) oxide layers on polycrystalline Ag electrodes is studied by potentiodynamic and potentiostatic current transients in 0.1 M NaOH. A model involving the diffusion controlled growth of a basal layer followed by the nucleation and growth of a secondary layer is proposed. Various nucleation parameters are estimated by comparing experimental data with simulated transients, and the results are discussed in terms of the atomistic theory of electrochemical phase formation. The influence of the nucleation parameters on the shape of the current transients is analysed and some controversial results in the literature are explained.Instituto de Investigaciones Fisicoquímicas Teóricas y AplicadasFacultad de Ciencias Exacta

Kinetics of copper passivation and pitting corrosion in Na2SO4 containing dilute NaOH aqueous solution

The electrochemical behaviour of Cu in alkaline solutions containing Na2SO4 was studied using potentiodynamic and potentiostatic techniques complemented by scanning electron microscopy. The presence of Na2SO4 enhances Cu electrodissolution through the passive layer and decreases the breakdown potential. There is a critical OH-/sulphate concentration ratio for the onset of localized corrosion. The competitive interaction between OH- and sulphate ions at the passive layer can explain the experimental data. Pit initiation fits the point defect model for passivity breakdown. Pit growth involves a number of current contributions which can be distinguished through the analysis of current transients at constant potential by using nucleation and growth models.Instituto de Investigaciones Fisicoquímicas Teóricas y AplicadasFacultad de Ciencias Exacta

Electrochemical behaviour of copper in aqueous moderate alkaline media, containing sodium carbonate and bicarbonate, and sodium perchlorate

The voltammetric polarization of Cu specimens in Na2CO3, NaHCO3 and NaClO4 solutions (8-12pH range) has been investigated. Voltammetry data were complemented with SEM and electron microprobe analysis. Results are found to be in agreement with the passivation model developed for Cu in plain NaOH solutions. For the latter the process can be described in terms of two steps, namely, at low potentials the initial formation of a Cu2O thin layer followed by the growth of a massive Cu2O layer, and at higher potentials the appearance of a CuO-Cu(OH)2 layer. These processes are accompanied by the formation of soluble Cu species. Beyond a certain potential which increases with the solution pH, copper pitting takes place. This model can be extended to Cu in carbonate/bicarbonate containing solutions by considering that Cu carbonates precipitate as long as soluble ionic Cu species are produced, without interfering appreciably with the formation of Cu oxides. The appearance of copper carbonate species is enhanced when pitting corrosion sets in. The precipitation of Cu carbonates occurs principally around pits. Cu pitting, although it is observed for all solutions, becomes more noticeable at the lowest pH values. At a constant pH, the density of pits increases in the order NaClO4 > NaHCO3 > Na2CO3. The influence of the electrolyte composition on Cu pitting is closely related to the blockage capability for pit nucleation and growth of the corresponding copper salts. Passivation in the Cu2O-Cu(OH)2 region hinders pitting corrosion.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA)Facultad de Ciencias Exacta

Electrochemical behaviour of copper in aqueous moderate alkaline media, containing sodium carbonate and bicarbonate, and sodium perchlorate

The voltammetric polarization of Cu specimens in Na2CO3, NaHCO3 and NaClO4 solutions (8-12pH range) has been investigated. Voltammetry data were complemented with SEM and electron microprobe analysis. Results are found to be in agreement with the passivation model developed for Cu in plain NaOH solutions. For the latter the process can be described in terms of two steps, namely, at low potentials the initial formation of a Cu2O thin layer followed by the growth of a massive Cu2O layer, and at higher potentials the appearance of a CuO-Cu(OH)2 layer. These processes are accompanied by the formation of soluble Cu species. Beyond a certain potential which increases with the solution pH, copper pitting takes place. This model can be extended to Cu in carbonate/bicarbonate containing solutions by considering that Cu carbonates precipitate as long as soluble ionic Cu species are produced, without interfering appreciably with the formation of Cu oxides. The appearance of copper carbonate species is enhanced when pitting corrosion sets in. The precipitation of Cu carbonates occurs principally around pits. Cu pitting, although it is observed for all solutions, becomes more noticeable at the lowest pH values. At a constant pH, the density of pits increases in the order NaClO4 > NaHCO3 > Na2CO3. The influence of the electrolyte composition on Cu pitting is closely related to the blockage capability for pit nucleation and growth of the corresponding copper salts. Passivation in the Cu2O-Cu(OH)2 region hinders pitting corrosion.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA)Facultad de Ciencias Exacta

Fractal characterisation of electrodispersed gold electrodes

The fractal dimension of the surface, Ds, of thin columnar gold electrodeposits (surface roughness factor 50–100) grown on gold wire cathodes by electroreducing hydrous gold oxide layers has been determined by measuring the diffusion controlled current of the Fe(CN)4−6/Fe(CN)3−6 reaction. The diffusion current (I) vs. time (t) relationships obeyed a Iαt−α dependence with Ds = 2α + 1. The initial Ds, value is 2.5 ± 0.1, and decreases to 2.3 ± 0.1 by keeping the deposit in contact with the electrolyte solution at 298 K due to the smoothing of the rough metal surface by surface diffusion.Instituto de Investigaciones Fisicoquímicas Teóricas y AplicadasFacultad de Ciencias Exacta

Fractal surfaces of gold and platinum electrodeposits. Dimensionality determination by scanning tunneling microscopy

The structure of gold and platinum deposits grown on gold and platinum wire cathodes, respectively, by electroreduction of the corresponding oxide layers has been analyzed in terms of surface fractals by measuring the perimeter L and area A of intergranular voids. Perimeter and area were determined from scanning tunneling microscopy (STM) topographic images of the deposit surfaces. Fractal behavior, L ∞ AD'/2 with D'= 1.5 ± 0.1, is found for both platinum and gold deposits. From these measurements, the fractal dimension of the surfaces was 2.5. The D' value of the gold deposits decreases by aging in the electrolyte at 325 K as a consequence of surface diffusion processes.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA)Facultad de Ciencias Exacta

Roughening kinetics of chemical vapor deposited copper films on Si(100)

3 pages, 3 figures.The roughening kinetics of copper films synthesized by low pressure chemical vapor deposition (LPCVD) on Si(100) substrates was investigated by scanning tunneling microscopy (STM). By applying the dynamic scaling theory to the STM images, a steady growth roughness exponent (alfa)=0.81 ± 0.05 and a dynamic growth roughness exponent (beta)=0.62 ± 0.09 were determined. The value of (alfa) is consistent with growth model predictions incorporating surface diffusion. The value of (beta), while higher than expected from these models, can be related to LPCVD processing conditions favoring growth instabilities.This work was partially supported by the CSICCONICET cooperation program and by a grant from the NASA New Jersey Space Grant Consortium.Peer reviewe