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.

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.

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 > 300 years of exposure to the action of the atmosphere. A wide variety of techniques have been used, including metallographic and chemical analysis (electrogravimetry, AAS, XRF) of the copper matrix, and spectroscopic and microscopic investigations (GIXRD, FTIR, 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 [Cu-3(CO3)(2)(OH)(2)]; and (c) the brochantite/antlerite crystals are randomly doped with Fe and C.

The initial steps of Cu₂O sulphidation to Cu₂S have been studied using plane-wave density functional theory at the PBE-D3+U level of sophistication. Surface adsorption and dissociation of H₂S and H₂O, as well as the replacement reaction of lattice oxygen with sulphur, have been investigated for the most stable (111) and (100) surface facets under oxygen-lean conditions. We find that the (100) surface is more susceptible to sulphidation than the (111) surface, promoting both H₂S adsorption, dissociation and the continued oxygen–sulphur replacement. The results presented in this proceeding bridge previous results from high-vacuum experiments on ideal surface to more realistic corrosion conditions and set the grounds for future mechanistic studies. Potential implications on the long-term final disposal of spent nuclear fuel are discussed.

The influence of the composition of stainless steels on atmospheric corrosion resistance in a marine environment in Dubai was investigated after 2 y and 4 y of exposure. Different stainless steel grades with different surface finishes were included in the investigation: three ferritic stainless steels, five austenitic stainless steels, and four duplex stainless steels. The alloying elements chromium (Cr) and molybdenum (Mo) both had a beneficial influence on the corrosion resistance. The pitting resistance equivalent number (PREN =%Cr + 3.3%Mo + 16%N) and the (%Cr + 3.3%Mo) content in the surface film correlated well to the atmospheric corrosion resistance. An increased Cr content both in the bulk material and in the passive film improved the atmospheric corrosion resistance and the additional presence of Mo was effective in preventing red rust and also reduced the depth of pits. The depth of the pitting attack and the degree of aesthetic degradation were both influenced by alloying level, surface finish, and exposure conditions (open and sheltered). In the severe marine environment in Dubai, it is necessary to use Mo-bearing high-Cr stainless steel for adequate atmospheric corrosion resistance. The most resistant stainless steel grades were the high alloyed grades which ranked in the order UNS S31254 similar to UNS S3750 < UNS S34565 < UNS S32654. The duplex stainless steel grade S32205 may be considered for construction and architectural materials in Dubai but is likely to require more maintenance.

A finite element model for simulating the propagation of intermetallic particle driven micro-galvanic corrosion in an Al-matrix model system is presented. The model revealed dynamic changes related to localized corrosion, including the moving dissolution boundary, the deposition of reaction products (Al(OH)(3)), and their blocking effect. Modelling was focused on the effects of key geometric parameters, including the radius of cathodic particle (range 0.5 to 4 mu m) and the width of an assumed anodic ring surrounding the particle (range 0.1 to 2 mu m). Simulations revealed the dynamic flow of molecular and ionic species, along with influence of geometrical constraints. For ring widths below 0.5 mu m, deposition of Al(OH)(3) inside the dissolving volume was inhibited due to limited transport of OH- and O-2 into a constrained volume - resulting in local acidification. An increase in cathodic particle radius at given ring width resulted in a greater dissolution by providing a larger cathodic area for O-2 reduction, quantifying the effect of cathode/anode ratio. The model was also developed to include two cathodic particles to explore any interaction. The present study reveals a physicochemical model that contributes toward a framework for multi-process localized corrosion systems, which can be further adapted to commercial alloy systems.

Based on exposures in chloride-rich field and laboratory atmospheres, a mechanism of rust exfoliation of carbon steel is proposed. Key ingredients are structural transformations between main rust phases (goethite, lepidocrocite, spinel oxides and akageneite) during varying exposure conditions and their large difference in molar volume with a factor of five between the most compact and least compact rust phase. Akaganeite transformed to spinel results in volume contraction, lepidocrocite to spinel in volume expansion and in both cases stresses are introduced in the rust multilayer. At sufficiently high chloride deposition rates (similar to 300 mg/m(2).d), the rust multilayer eventually detaches resulting in rust exfoliation.

A finite element method model has been elaborated aiming at a deeper insight into the influence of microstructure on micro-galvanic corrosion of Al alloys. The model considers a dynamic corroding surface and takes into account kinetic data from local electrochemical reactions, transport of O-2 and ionic species (e.g., Al3+, H+, Cl-), homogeneous reactions in the electrolyte, deposition of reaction products and its influence on both anodic and cathodic reactions. As a first step, an Al matrix with a micrometer-sized cathodic intermetallic particle exposed in 0.1 M NaCl has been considered. The simulation predicts the dynamic changes of the corroding surface, and the flow and distribution of ionic species and of O-2 in space and time. The calculated pH of the electrolyte inside and nearby the occluded corroding volume suggests the formation of insoluble Al(OH)(3) on both the cathodic and anodic areas. This results in blocking effects of anodic and cathodic reactions and in eventual termination of the micro-galvanic corrosion. The predicted deposition of corrosion product is in good agreement with in-situ atomic force microscopy measurements.

In this article results from earlier studies have been compiled in order to compare the protection efficiency of self-assembled monolayers (SAM) of alkanethiols for copper, zinc, and copper-zinc alloys exposed to accelerated indoor atmospheric corrosion conditions. The results are based on a combination of surface spectroscopy and microscopy techniques. The protection efficiency of investigated SAMs increases with chain length which is attributed to transport hindrance of the corrosion stimulators in the atmospheric environment, water, oxygen and formic acid, towards the copper surface. The transport hindrance is selective and results in different corrosion products on bare and on protected copper. Initially the molecular structure of SAMs on copper is well ordered, but the ordering is reduced with exposure time. Octadecanethiol (ODT), the longest alkanethiol investigated, protects copper significantly better than zinc, which may be attributed to the higher bond strength of Cu-S than of Zn-S. Despite these differences, the corrosion protection efficiency of ODT for the single phase Cu20Zn brass alloy is equally efficient as for copper, but significantly less for the heterogeneous double phase Cu40Zn brass alloy.

Presents a comprehensive look at atmospheric corrosion, combining expertise in corrosion science and atmospheric chemistry Is an invaluable resource for corrosion scientists, corrosion engineers, and anyone interested in the theory and application of Atmospheric Corrosion Updates and expands topics covered to include, international exposure programs and the environmental effects of atmospheric corrosion Covers basic principles and theory of atmospheric corrosion chemistry as well as corrosion mechanisms in controlled and uncontrolled environments Details degradation of materials in architectural and structural applications, electronic devices, and cultural artifacts Includes appendices with data on specific materials, experimental techniques, atmospheric species.