Outdoor-indoor corrosion of metals in tropical coastal atmospheres

Results of indoor and outdoor atmospheric corrosion tests conducted during a long period of time at Cuba and Campeche (Mexico) indicated very high corrosion rates at both sites which have humid-tropical marine climate. We found that the outdoor corrosivity ranges from C3 to >C5 according to ISO 9223 nevertheless metals exposed to sheltered conditions presented higher corrosion rates compared to outdoors, whereas in closed (indoor) environments the corrosion rate significantly decreased. It is recommended to define an additional level of corrosivity for tropical coastal atmospheres in outdoor and sheltered conditions as corrosion depends on the geographical position and exposure conditions.     

Tracing correlations of corrosion products and microclimate data on outdoor bronze monuments by Principal Component Analysis

Although the corrosion of outdoor bronzes has been extensively studied for the last decades, there is no quantitative correlation of corrosion products to microclimatic factors. The present work aims to demonstrate how Principal Component Analysis (PCA) can serve this purpose. Thirty corrosion product samples were collected from the bronze monument of Theodoros Kolokotronis (Nafplio, Greece) and analysed using X-Ray Diffractometry (XRD). The quantitative XRD data together with data on surface orientation and exposure to rain or wind were treated by PCA and three distinct groups were found. Each group includes samples of similar composition and microclimate characteristics showing that PCA may give useful information on corrosion mechanisms.     

Organic films for protection of copper and bronze against acid rain corrosion

In this paper, the anticorrosive effects of surface films formed on copper and bronzes by different organic inhibitors (mainly benzotriazole derivatives) are evaluated. Several alloys, nominally similar in composition to ancient artistic bronzes, were studied in comparison with copper. The protective efficiency of the organic coatings was tested by electrochemical ac and dc measurements performed both in acid and neutral rain. The experimental data show that benzotriazole derivatives with a long aliphatic chain form thin and very protective films on copper. The presence of the alloying elements (e.g. Sn, Zn, Pb) and multiphasic structures decrease the organic film performances. Nevertheless, among the compounds used, the most efficient, 5-octyl-1,2,3-benzotriazole (C8), seems to be a promising coating in the bronze conservation field.     

Effect of Fe-Zn alloy layer on the corrosion resistance of galvanized steel in chloride containing environments

In this study, the effect of Fe-Zn alloy layer that is formed during galvanizing process on the corrosion behavior of galvanized steel has been investigated. The galvanostatic dissolution of galvanized steel was carried out in 0.5 M NaCl solution to obtain the Fe-Zn alloy layer on the base steel. The alloy layer was characterized to be composed of FeZn₁₃, FeZn₇ and Fe₃Zn₁₀ intermetallic phases, which constitute the zeta, delta1 and gamma layers of galvanized steel, respectively. It was observed that the alloy layer has similar cathodic polarization behavior but different anodic polarization behavior compared to galvanized steel. The anodic current plateau of alloy layer was up to 100 times lower than that of galvanized coating. Corrosion test performed in wet-dry cyclic condition has shown that the alloy layer has lower corrosion rate as compared to galvanized steel. From the results of corrosion test of alloy layer and base steel, it was concluded that Zn²⁺ has positive effect on the protectiveness of the zinc corrosion products. The measurement of surface potential over the alloy/steel galvanic couple has confirmed the galvanic ability of alloy layer to protect both the alloy layer itself and the base iron during initial stage of atmospheric corrosion.     

The role of rusts in corrosion and corrosion protection of iron and steel

The processes of atmospheric corrosion of iron and steel and the properties of corrosion products (rusts) are modeled based on a quantitative evaluation of the chemical reactions pertaining to corrosion to elucidate the conditions with which corrosion-protective rust films form. Based on the model, it is suggested that in the initial stage of corrosion, in the rusts, the pH of the aquatic system is maintained at 9.31 owing to an equilibrium with iron(II) hydroxide and the rate of air-oxidation at this pH is very fast, and that dense, self-repairing rust films form, protecting the underlying iron and steel. However, after corrosion stops, the rust film deteriorates due to the dissolution and shrinkage by aging, and the deteriorated rust film separates the anode and cathode reaction products (Fe²⁺ and OH⁻ ions) to cause crevice corrosion. The air-oxidation of iron(II) in anode channels without the presence of OH⁻ ions results in strongly acidic solutions (pH 1.41), causing acid-corrosion. It is proposed that good catalysts (e.g. copper(II) and phosphate ions) accelerate the air-oxidation at low pH, delaying the crevice- and acid-corrosion stages. Further, it is argued that iron compounds with negative charges due to the non-stoichiometric proportions of the lattice oxide ions and metal ions (solid oxoanions of iron) exhibit stable cation-selective permeability even with a drop in pH. Rust films including such compounds would stop the passage of aggressive anions and act to protect iron and steel.     

A mechanistic study of initial atmospheric corrosion kinetics using electrical resistance sensors

This paper describes a novel experimental approach to the study of atmospheric corrosion of iron and zinc, utilising electrical resistance sensors that are sensitive to corrosion losses of the order of one atomic monolayer. Using such devices, a mechanistic study of the initial stages in the atmospheric corrosion of iron and zinc was performed in a rectangular flow cell using controlled relative humidity (RH), temperature and gas flow rate. Additionally, the effects of SO₂ contamination in the gas phase and prior NaCl contamination of the metal surface were studied. It was found that the initial corrosion kinetics of iron and zinc are, not unexpectedly, dominated by the development of surface corrosion product films, but that the growth kinetics vary with metal, humidity, etc. Specifically, in the presence of gas-phase SO₂, activation energies and kinetic and chemical rate orders were consistent with control of the atmospheric corrosion process by solution-phase oxidation of sulphite–sulphate ion. For iron, this implies that the well-known sulphate-nest theory is inoperative at least during the early stages of atmospheric corrosion. In contrast, for chloride–contaminated zinc, the data were consistent with a rate-controlled diffusion of a species, probably water vapour or oxygen, through a thickening corrosion product film. Finally, the kinetic and chemical rate orders for corrosion of chloride–contaminated iron precluded a diffusion-controlled mechanism, but were consistent with a rate-controlling process involving some regeneration of chloride: e.g. as in metal–ion hydrolysis in a pit or similar localised corrosion events.     

Effect of direct current electric field on atmospheric corrosion behavior of copper under thin electrolyte layer

A thin layer electrochemical cell was successfully developed to study the atmospheric corrosion behavior of copper film in printed circuit board (PCB-Cu) under thin electrolyte layer (TEL) and direct current electric field (DCEF) by electrochemical impedance and electrochemical noise analysis. The electrochemical measurements and SEM morphologies after corrosion test indicate that DCEF decreases the corrosion of PCB-Cu under TEL. The corrosion rate and probability of pitting corrosion of PCB-Cu under DCEF decrease due to the electric migration of aggressive Cl⁻ ion out of working electrode surface.     

The effect of oxygen partial pressure on the filiform corrosion of organic coated iron

An in-situ time-lapse optical microscopy study, using a novel dual-compartment cell is used to gain mechanistic understanding of filiform corrosion (FFC) affecting an organic-coated iron surface. The apparatus allows independent control of environments surrounding the filament head and tail regions. When oxygen-containing environments surround the filament head, an anterior cathodic arc is formed, constraining the filament head electrolyte. When oxygen is removed from the vicinity of the head, FFC propagation rates remain unchanged, although the constraining arc is not present. Maximum propagation is observed when oxygen is available for transport through the filament tail to the rear of the head.     

Differences between corrosion products formed on copper exposed in Tokyo in summer and winter

We analyzed the copper corrosion products that formed during a month in summer and a month in winter at three sites in Tokyo using several analytical techniques. The X-ray diffraction patterns revealed that cuprite Cu₂O and posnjakite Cu₄SO₄(OH)₆·H₂O formed on copper exposed in summer. By contrast, only cuprite was found in winter exposed copper. The X-ray fluorescence results indicated that the amounts of sulfur and chlorine on the copper plates exposed in summer were much greater than those in winter. This could be explained by the change in particulate sulfate and sea salt concentrations. Depth profiling analysis by Auger electron spectroscopy revealed that the oxide layer formed in summer was thicker than that in winter. This difference in oxide layer thickness could have been due to the differences in temperature, relative humidity, and the amount of sulfur and chlorine on the copper plate.     

Multianalytical in situ investigation of the initial atmospheric corrosion of bronze

Atomic force microscopy (AFM) and infrared reflection absorption spectroscopy (IRAS) were used for in situ investigations of the initial atmospheric corrosion of bronze. In addition ex situ XPS investigations were carried out on the samples before and after the exposure, as well as on the sputtered bronze sample. Investigations were carried out in synthetic air with 80% relative humidity (RH) and synthetic air with 80% RH with 250 ppb SO₂. At 80% RH, small features covering the surface were observed with AFM, whereas IRAS detected that more water is adsorbed on the bronze sample surface compared to pure copper. Large features on top of smaller features were observed with AFM on the bronze surface exposed to SO₂-containing humidified air. These large features were identified as copper sulfite. Furthermore, cuprous oxide was detected approximately 500 min after the introduction of SO₂. This fact and the XPS results indicate the formation of a protective lead oxide layer already during the preparation of the sample, which is destroyed by the SO₂-containing environment and leads to the formation of cuprous oxide and copper sulfite.     

Application of GC-MS metabolic profiling to ‘blue-green water’ from microbial influenced corrosion in copper pipes

This paper presents a novel application of fluorescence spectroscopy and gas chromatography-mass spectrometry (GC-MS) to water samples exposed to copper piping which had undergone some degree of microbial influenced corrosion. Using 3D fluorescence spectroscopy we were able to observe the ‘protein-like’ fluorophore associated with presence of bacteria, and cross reference this with derivatized fatty acid metabolites determined via GC-MS analyses of the same sample. This methodology can be used as a simple screening tool to establish the presence or otherwise of microbial processes in waters, and correlation of specific metabolite profiles with different microbes will further enhance the utility of this tool.     

A new corrosion inhibitor for copper protection

Methyl 3-((2-mercaptophenyl)imino)butanoate (MMPB) was synthesized as inhibitor compound for copper protection. The molecule was designed with azole, thiol functional groups and carboxylate tail group. The inhibition efficiency was examined in acidic chloride media, by means of various electrochemical and spectroscopy techniques. Electrochemical study results showed that high efficiency of MMPB was mainly related with its capability of complex formation with Cu(I) at the surface. The thiol group also improves the adsorptive interaction with the surface, as the carboxylate groups provide extra intermolecular attraction.     

Thermodynamic studies on corrosion inhibition of aqueous solutions of amino/carboxylic acids toward copper by EMF measurement

Electromotive force (E) measurements were made on an electrochemical cell [Cu_xHg|CuCl₂(m) in a solvent S|AgCl-Ag] (where S is a dilute aqueous solution (0.01 m) of amino acid (glycine, alanine, methionine and glutamic acid) or aliphatic carboxylic acid (formic acid, acetic acid, n-butyric acid and glutaric acid)) at 30 °C. These measured E values were used to compute the dissociation constants (K₁ and K₂) and the degree of dissociation (α₁ and α₂) by iterative procedures. The standard cell potential (E°) and the mean activity coefficient (γ_±) of CuCl₂ were also determined. The E° data were next used to evaluate the Gibbs energy of transfer of CuCl₂ from water to dilute aqueous solutions of the amino/carboxylic acids. The negative values suggested that these acids act as potential corrosion inhibitors. The magnitudes of values show that the amino acids act as better corrosion inhibitors towards copper than the aliphatic carboxylic acids.     

Comparative investigation into the corrosion of different bronze alloys suitable for outdoor sculptures

Several bronze alloys, suitable for production of outdoor sculptures, were developed in the frame of the European project “Eurocare-Bronzart”. The elemental composition of the alloys was searched to fulfil specific criteria such as: reduction of lead content, good resistance toward corrosion and aesthetic characteristics conformable to artistic purposes. After metallurgical characterization, the resistance toward corrosion was evaluated in artificial environments. Ageing experiments were performed in a salt spray cabinet and in a climatic chamber in the presence of a controlled concentration of SO₂. The Thin Layer Activation (TLA) method was applied to calculate the thickness loss of activated specimens exposed to artificial corrosive atmospheres. After artificial ageing experiments the surface of the materials was investigated by SEM-EDS techniques.The bronze alloys containing different percentage of nickel showed the best properties of resistance toward corrosion.     

Indoor atmospheric corrosion in Cuba. A report about indoor localized corrosion

Indoor weight loss of steel, chloride, sulphur compounds and dust deposition rate were determined in six storehouses having different characteristics. Relative humidity and temperature were determined in three storehouses. A model for indoor corrosion of steel depending on time of exposure and deposition of dust, sulphur compounds and chlorides is proposed. Dust deposition plays an important role indoors. The position of the sample has also a significant influence on corrosion. Indoor corrosion aggressivity in Cuban storehouses ranges in classification IC3 and IC4 according to the new ISO proposal of indoor aggressivity.A report about the presence of localized corrosion indoors (filiform like) using a special designed sample is made.     

Corrosion behaviour of aluminium in copper containing environment

Corrosion behaviour of pure aluminium galvanically connected to metallic copper or in the presence of Cu²⁺ ions was investigated by electrochemical measurements in Na₂SO₄ and Na₂SO₄ + NaCl test solutions. It has been found that in aerated Cl⁻ ion containing solutions pitting corrosion of aluminium emerged immediately, while in the absence of oxygen this process was less violent. Effect of passivating pre-treatment of aluminium surface on corrosion behaviour Cu-Al bimetallic system is also demonstrated.     

Multianalytical in-situ investigations of the early stages of corrosion of copper, zinc and binary copper/zinc alloys

A new experimental infrared reflection absorption spectroscopy (IRRAS) set-up for in-situ investigation of corrosion phenomena occurring in the metal–atmosphere interface was developed. It was applied in combination with in-situ tapping-mode atomic force microscopy (TM-AFM) and phase detection imaging (PDI) to study the early stages of corrosion of pure copper and pure zinc as well as to determine the influence of increasing zinc contents in brass. Additionally, ex-situ secondary ion mass spectrometry (SIMS) investigations were carried out on the samples after exposure.The investigations were accomplished in synthetic air with 80% relative humidity (RH) and synthetic air with 80% RH and 250 ppb SO₂. The experiments showed that an increase of the zinc content in the brass alloy yields to an increase of the dimension of the corrosion features formed on the metal surface during weathering. Large features on top of smaller features were observed with TM-AFM on the surfaces exposed to SO₂-containing humidified air, which could be identified by IRRAS as metal sulphur compounds. Furthermore, an increased amount of physisorbed water on the metal surfaces was determined with IRRAS in dependence of the increasing zinc content in the brass samples.     

Hydrogen ion reduction in the process of iron rusting

Since the acceptance of the electrochemical rusting mechanism, oxygen reduction has been considered the main cathodic process, while H⁺ reduction has been overlooked for the past four decades because oxygen can be readily renewed due to the thin layer of solution film formed during atmospheric corrosion. This study shows that measurable hydrogen can be detected at the surface opposite to the corroding side of the specimen during wet-dry cycles, and a clear correlation exists between the quantities of hydrogen permeated through iron sheet and weight loss. Results suggest the intrinsic importance of H⁺ reduction that merits further investigation.     

Laboratory scale investigation into the corrosion of copper in a sulphur-containing environment

The effect of temperature and gas composition on the corrosion rate and corrosion by-product of copper foil was studied by exposing it to sulphur (S₂), S₂ + hydrochloric acid (HCl) and hydrogen sulphide. The temperature was varied from 80 to 140 °C. Copper foil reacted with S₂ to form CuS, Cu₉S₈ and Cu_1.8S. Corrosion rates ranged from 9.6 μm/h at 110 °C to 0.5 μm/h at 140 °C. The presence of HCl caused pitting and enhanced the corrosion rate above 112 °C. Cu₂S formed when copper was exposed to hydrogen sulphide gas. Sulphide scale that formed was friable and non-adherent.