This work is a further step to develop a finite element model to simulate localized corrosion of aluminum alloys driven by micro-galvanic effects. The focus herein is to explore the effect of density (porosity and tortuosity) of Al(OH)(3) precipitates generated both on the electrode surface and in the liquid phase. Two coupled processes are identified and discussed, both influencing the local pH: the Al3+ dissolution from the electrode surface, and the steric hindrance effects on mass transport of species between the bulk solution and the anolyte next to the corroding surface. With the densest precipitate investigated, Al3+ dissolution is more effectively blocked and the mass transport largely hindered of Al3+ ions leaving the electrode surface. With increasing porosity of the precipitate, Al3+ dissolution is enhanced, also the mass transport of species in the electrolyte. The most severe localized acidification inside the occluded volume occurs when the density, namely ascribed by porosity, of precipitate is at an intermediate level with epsilon(c )= 0.01. In qualitative agreement with experimental observations, this work highlights the importance of corrosion product density on the progress of localized corrosion.

The characterisation of passive oxide films on heterogeneous microstructures is needed to assess local degradation (corrosion, cracking) in aggressive environments. The Volta potential is a surface-sensitive parameter which can be used to assess the surface nobility and hence passive films. In this work, it is shown that the Volta potential, measured on super duplex stainless steel by scanning Kelvin probe force microscopy, correlates with the electrochemical properties of the passive film, measured by electrochemical impedance spectroscopy and potentiodynamic polarisation. Natural oxidation by ageing in ambient air as well as artificial oxidation by immersion in concentrated nitric acid improved the nobility, both reflected by increased Volta potentials and electrochemical parameters. Passivation was associated with vanishing of the inherent Volta potential difference between the ferrite and austenite, thereby reducing the galvanic coupling and hence improving the corrosion resistance of the material. Hydrogen-passive film interactions, triggered by cathodic polarisation, however, largely increased the Volta potential difference between the phases, resulting in loss of electrochemical nobility, with the ferrite being more affected than the austenite. A correlative approach of using the Volta potential in conjunction with electrochemical data has been introduced to characterise the nobility of passive films in global and local scale.

The copper patina colour has been systematically explored through a large set of short- and long-term exposed copper metal samples. The initial brown-black appearance is attributed to semiconducting properties of cuprite (Cu2O) and fully attained at thickness 0.8 +/- 0.2 mu m. The characteristic green-blue appearance is due to the colour forming Cu(II)-ion in the outer patina layer which needs to be 12 +/- 2 mu m to fully cover the inner cuprite layer. No significant influence of atmospheric environment on patina colour is discerned. The green-blue patina colour on historic copper was attained after shorter exposures than in modem copper due to more inhomogeneous microstructure.

The role of Sn on the atmospheric corrosion performance of binary Cu-Sn bronze alloys (4–6 wt.% Sn) compared with Cu metal used in outdoor architecture is elucidated in terms of microstructure, native surface oxide composition, patina evolution, corrosion rates, appearance and metal release. Results are presented for non-exposed surfaces and surfaces exposed at different urban and marine sites in Europe up to 5 years and based on multi-analytical findings from microscopic, spectroscopic, electrochemical and chemical investigations. Alloying influenced the corrosion, aesthetic appearance and patina evolution, differently for urban and marine sites, whereas no effects were observed on the release pattern.

The influence of surface adsorption of benzotriazole (BTAH) and of chloride ions (Cl-) on the kinetics of copper electrodeposition/dissolution in copper sulfate solutions and on copper deposit characteristics have been investigated using electrochemical quartz crystal microbalance (EQCM) combined with cyclic voltammetry (CV). The addition of BTAH alone increases the overpotential of copper deposition, whereas a Cu(I)BTA complex forms at potentials higher than 0.08 V (vs. SCE) accompanied with the occurrence of copper anodic dissolution. With simultaneous addition of BTAH and Cl-, surface adsorption of Cl- competes with that of BTAH during the initial stage of copper nucleation. Different cuprous reaction intermediates form in the examined potential range -0.4 to 0.3 V (vs. SCE), which partly eliminate the favorable effect of BTAH on the deposited copper. A BTAH-containing adsorbed layer formed on the matte side of electrodeposited copper film in the presence of BTAH with or without Cl-, exhibiting a barrier surface property and an improved corrosion resistance compared with the copper film electrodeposited in the electrolyte without addition of BTAH.

Accelerated NVDA (VDA 233-102) tests were performed on bare Zn and Al sheets, Galfan coating (Zn-5 wt-% Al) and Galvalume coating (Zn-55 wt-% Al) on steel. ZnO, Zn(OH)(2) and Zn-5(OH)(8)Cl-2 center dot H2O were the main corrosion products identified on both bare Zn sheet and Galfan. AlOOH and Al(OH)(3) were preferentially formed on bare Al sheet and Galvalume. In addition, Zn-Al-containing corrosion products, Zn6Al2(OH)(16)CO3 center dot 4H(2)O and/or Zn2Al(OH)(6)Cl center dot 2H(2)O were identified on both Galfan and Galvalume. Corrosion products of Zn6Al2(OH)(16)CO3 center dot 4H(2)O with a platelet morphology were preferentially formed in the zinc-rich interdendritic regions of the Galvalume surface. Galfan revealed a similar corrosion behaviour as bare Zn sheet, whereas Galvalume exhibited similar behaviour as bare Al sheet. Deposition of chlorides highly influenced the corrosion of both Galvalume and Al rather than Galfan and Zn due to the rapid local damage of the compact native thin film of Al2O3.

This paper presents an in-depth characterisation study of the patina formed on a copper tile taken from the roof of Queen Anne's Summer Palace in Prague after close to 400 years of exposure to the action of the atmosphere. A wide variety of techniques have been performed, including metallographic and chemical analysis (electrogravimetry, AAS, XRF) of the copper matrix, and spectroscopic and microscopic investigations (GIXRD, TEM/EDS and SEM/EDS) to determine the composition and structure of the patina. The major conclusions of the study are: (a) the base copper contains abundant inclusions mainly of rosiaite (PbSb2O6); (b) the patina is formed by an inner sublayer of cuprite (Cu2O) and an outer sublayer of brochantite [Cu4SO4(OH)6] and antlerite [Cu3SO4(OH)4] and traces of azurite [Cu3(CO3)2(OH)2]; and (c) the brochantite/antlerite crystals are randomly doped with Fe and C.

The morphology and elemental composition of cross sections of eight historic copper materials have been explored. The materials were taken from copper roofs installed in different middle and northern European environments from the 16th to the 19th century. All copper substrates contain inclusions of varying size, number and composition, reflecting different copper ores and production methods. The largest inclusions have a size of up to 40 μm, with most inclusions in the size ranging between 2 and 10 μm. The most common element in the inclusions is O, followed by Pb, Sb and As. Minor elements include Ni, Sn and Fe. All historic patinas exhibit quite fragmentized bilayer structures, with a thin inner layer of cuprite (Cu2O) and a thicker outer one consisting mainly of brochantite (Cu4SO4(OH)6). The extent of patina fragmentation seems to depend on the size of the inclusions, rather than on their number and elemental composition. The larger inclusions are electrochemically nobler than the surrounding copper matrix. This creates micro-galvanic effects resulting both in a profound influence on the homogeneity and morphology of historic copper patinas and in a significantly increased ratio of the thicknesses of the brochantite and cuprite layers. The results suggest that copper patinas formed during different centuries exhibit variations in uniformity and corrosion protection ability.