Oxide films mass transport

Chen Y-X, Heinen M, Jusys Z, Behm RJ. Dissociative adsorption and oxidation of formaldehyde on a Pt film electrode under controlled mass-transport conditions, an in-situ spectro-electrochemical flow-cell study. To he published. 

The effect of fluoride ions on the electrochemical behaviour of a metal zirconium electrode was studied by Pihlar and Cencic in order to develop a sensor for the determination of zirconium ion. Because elemental zirconium is always covered by an oxide layer, the anodic characteristics of a Zr/Zr02 electrode are closely related to the composition of the electrolyte in contact with it. These authors found the fluoride concentration and anodic current density to be proportional in hydrochloric and perchloric acid solutions only. In other electrolytes, the fluoride ion-induced dissolution of elemental zirconium led to an increase in the ZrOj film thickness and hindered mass transport of fluoride through the oxide layer as a result. The... 

In a typical spectroelectrochemical measurement, an optically transparent electrode (OTE) is used and the UV/vis absorption spectrum (or absorbance) of the substance participating in the reaction is measured. Various types of OTE exist, for example (i) a plate (glass, quartz or plastic) coated either with an optically transparent vapor-deposited metal (Pt or Au) film or with an optically transparent conductive tin oxide film (Fig. 5.26), and (ii) a fine micromesh (40-800 wires/cm) of electrically conductive material (Pt or Au). The electrochemical cell may be either a thin-layer cell with a solution-layer thickness of less than 0.2 mm (Fig. 9.2(a)) or a cell with a solution layer of conventional thickness ( 1 cm, Fig. 9.2(b)). The advantage of the thin-layer cell is that the electrolysis is complete within a short time ( 30 s). On the other hand, the cell with conventional solution thickness has the advantage that mass transport in the solution near the electrode surface can be treated mathematically by the theory of semi-infinite linear diffusion. 

The curve shown in Fig. 3 cannot proceed indefinitely in either direction. In the cathodic direction, the deposition of copper ions proceeds from solution until the rate at which the ions are supplied to the electrode becomes limited by mass-transfer processes. In the anodic direction, copper atoms are oxidized to form soluble copper ions. While the supply of copper atoms from the surface is essentially unlimited, the solubility of product salts is finite. Local mass-transport conditions control the supply rate so a current is reached at which the solution supersaturates, and an insulating salt-film barrier is created. At that point the current drops to a low level further increase in the potential does not significantly increase the current density. A plot of the current density as a function of the potential is shown in Fig. 5 for the zinc electrode in alkaline electrolyte. The sharp drop in potential is clearly observed at -0.9 V versus the standard hydrogen electrode (SHE). At more positive potentials the current density remains at a low level, and the electrode is said to be passivated. 

To obtain quantitative expressions for the corrosion current and the corrosion potential, one has to substitute the proper expression for the metal-dissolution- and electronation-current densities. If no oxide films form on the surface of the corroding metal and neither of the current densities is controlled by mass transport, i.e., there is no concentration overpotential, one can insert the Butler-Volmer expression for the deelectronation- and electronation-current densities. Thus,... 

Carpio and coworkers [4] supported this hypothesis via a potentiodynamic study of a set of HN03-containing slurries. The corrosion currents and potentials under both the static and the dynamic conditions were practically the same. This is consistent with the fact that there was no native copper oxide film formed because of the presence of these slurries. As a matter of fact, the corrosion currents decreased slightly upon abrasion of the copper surface. The contact between the metal surface and the abrasive pad may have limited the mass transport of chemicals to and from the copper surface. This was verified via an AC impedance measurement that showed the importance of the systems mass transport. It was also concluded that in a dissolution-controlled process, mechanical abrasion would not enhance the chemical corrosion rate or reduce the mass transport of reactants and/or products in the system. 

Another strategy to improve transport efficiency of the Ba(thd)2 and process reproducibility is to use NH, which is a simple amine adduct, as a carrier gas for the precursor. This idea was suggested by A. Baron in 1990 for the MOCVD of high T, superconducting oxide films containing Ba ions. J. S. Lee et al. recently reported in - situ mass spectroscopic analysis results of the MOCVD of SrTi03 thin... 

Because of the importance of microstructure on dielectric and ferroelectric properties, the transformation pathway associated with conversion of the amorphous film into the crystalline state has been studied extensively. The basic mechanism involved is one of nucleation and growth, although the formation of intermediate phases that can impact the thermodynamic driving forces associated with the transformation frequently occurs. " Another key aspect of CSD films is that crystallization occurs well below the melting point of the materials. Therefore, compared to standard mixed-oxide processing of bulk materials, the thermodynamic driving forces associated with the transformation are much greater and the kinetics of mass transport are much less. 

In situ STM studies of the oxidation of a Pd film in the SMSI state at elevated temperature show a thickening of the encapsulating film (Fig. 8.7a-c). The film prior to oxidation had a hexagonal pin-wheel structure on the raised triangular island on the Pd film. After oxidation (Fig. 8.7c), the island was decorated heavily with a thickened, rough layer of Ti implying the formation of an oxide film of higher stoichiometry (possibly TP+), or mass transport of Ti to the Pd surface from the Ti surface. 

At the current peak, the critical current at which the effect of mass transport reaches its maximum and the surface is covered with an oxide films, PS ceases to form. Although diffusion has a strong effect in the electropolishing region, the current is not fully limited by the diffusion process. ... 

Recently Perusich and Alkire [105] have proposed a mathematical model to determine the reaction and transport between liquid microjets and a reactive solid surface. Conditions were established under which oxide depassivation and repassivation occurs as a function of ultrasonic intensity, surface film thickness, and fluid microjet surface coverage. The model was based on the concept that cavitation induces sufficient momentum and mass transfer rates (water hammer pressures as described earlier) at a surface to create oxide film stresses leading to depassivation. The model was used to evaluate experimental data on the corrosion behavior of iron in sulfuric acid [106,107], Focused ultrasound was used to investigate processes that influence depassivation and repassivation phenomena on pure and cast iron in 2N H2S04 at two ultrasound frequencies and at power intensities of up to 7.8 kW/cm2. 

Secondary mass spectrometry (SIMS), XPS and Auger spectroscopy are suitable to study the thick oxide films, as the nature and composition of them are strongly dependent on the electrode potential and the current distribution of the corrosion process. Thus, the local chemical composition can define the mass transport (metal ions, anions, water, etc.) effects to corrosion and then, the dissolution rate too. 

---