Microbial corrosion of galvanized steel in a simulated recirculating cooling tower system

In this study, mixed species biofilm formation including sulphate reducing bacteria (SRB) on the galvanized steel surfaces and also microbiologically influenced corrosion (MIC) of galvanized steel were observed in a model recirculating cooling water system during 10 months. A biofilm which had a heterogeneous structure formed on galvanized steel coupons. The results suggested that galvanized steel was corroded by microorganisms as well as SRB in the biofilm. Extracellular carbohydrate was degraded and quantities of carbohydrate were positively correlated with the weight loss. The concentrations of zinc in the biofilm showed significant correlations with weight loss, carbohydrate amount and SRB count.     

Corrosion behavior of steel under wet and dry cycles containing Cr ion

The corrosion behavior of mild steel has been investigated during the wet and dry cyclic transitions containing Cr³⁺ ion added as sulfate in order to gain a better understanding of the influence of Cr on the atmospheric corrosion of steels. The corrosion rate during drying is greatly suppressed by the existence of Cr³⁺ ion in the electrolyte covered with the surface. Lower corrosion rates are observed during drying even if the surface have been polarized to negative potentials below −200 mV_SHE during the wet corrosion conditions in which the surface-covered electrolyte contains Cr³⁺ ion. This corrosion behavior is identical to the case of Cr-containing steel for the wet and dry cyclic transitions without the addition of Cr³⁺ ion. The composition of rust layer after the wet and dry cyclic transitions is composed of α-FeOOH, γ-FeOOH and Fe_3−δO₄ for both cases of non-Cr³⁺ and Cr³⁺-containing condition, and no significant difference in the mass fraction of the above rust substances between two conditions is observed by means of Mössbauer spectroscopy. The only difference in the rust layer is that the rust formed under the wet and dry cyclic transitions containing Cr³⁺ ion contains a certain amount of Cr near the steel/rust interface. Those results suggest that the role of Cr during the wet and dry cyclic transitions is the inhibition of the rust reduction and the formation of Fe²⁺-state intermediate by the existence of Cr in the rust layer. This can lead to the inhibition of the oxygen reduction during drying.     

Study of iron benzoate as a novel steel corrosion inhibitor pigment for protective paint films

The aim of this work was to study the lab-synthesized iron benzoate as a novel steel corrosion inhibitor pigment to formulate anticorrosive paint films. The iron benzoate anticorrosive properties were studied by electrochemical and spectroscopic essays employing pigment suspensions. In a second stage, it was evaluated the performance of anticorrosive paint films containing iron benzoate by accelerated (salt spray and humidity chambers) and EIS tests. The protective layer nature grown under the paint films in the salt spray chamber was also assessed.Experimental results shown that ferric benzoate was adequate to formulate anticorrosive paint films with improved anticorrosive assessed.     

Atmospheric corrosion of Galfan coatings on steel in chloride-rich environments

Galfan coatings on steel in laboratory exposures with predeposited NaCl and cyclic wet/dry conditions exhibit nearly the same corrosion products as after 5 years of marine exposure. A general scenario for corrosion product evolution on Galfan in chloride-rich atmospheres is proposed. It includes the initial formation of ZnO, ZnAl₂O₄ and Al₂O₃ and subsequent formation of Zn₆Al₂(OH)₁₆CO₃⋅4H₂O, and Zn₂Al(OH)₆Cl⋅2H₂O and/or Zn₅Cl₂(OH)₈⋅H₂O. An important phase is Zn₆Al₂(OH)₁₆CO₃⋅4H₂O, which largely governs the reduced long-term zinc runoff from Galfan. A clear influence of microstructure could be observed on corrosion initiation in the slightly zinc-richer η-Zn phase adjacent to the β-Al phase.     

An electrochemical study of the delamination of polymer coatings on galvanized steel

The relationship between the rate of polymer delamination and the intensity of either anodic or cathodic current under the paint has been investigated for the zinc/surface treatment/polymer system by using a special electrochemical cell. Three types of surface treatment were investigated: simple alkaline degreasing, trication phosphating, and a chromate free conversion coating. Significant differences were observed for the three substrates. The alkaline resistance of the conversion coatings was determined using an ICP atomic emission spectroelectrochemical method. The results are interpreted in terms of the differing chemical stability of the conversion layers towards hydroxide generated by oxygen reduction.     

The effect of synthetic zinc corrosion products on corrosion of electrogalvanized steel. II. Zinc reactivity and galvanic coupling zinc/steel in presence of zinc corrosion products

The reactivity of zinc under synthetic zinc patinas and the galvanic coupling in steel/patina/Zn are studied. Zn₅(OH)₆(CO₃)₂ and Na₂Zn₃(CO₃)₄⋅3H₂O inhibit zinc anodic dissolution in NaCl, while Zn₅(OH)₈Cl₂ H₂O and Zn₄(OH)₆SO₄ nH₂O do not. The galvanic current in steel/patina/NaCl/Zn is smaller as compared to steel/NaCl/Zn. The inhibiting effect decreases with time for Na₂Zn₃(CO₃)₄⋅3H₂O or Zn₄(OH)₆SO₄ nH₂O due to the transformation into Zn(OH)₂. In NaHCO₃, the polarity between zinc and steel can reverse. The effect of confinement on the cathodic current is stronger than the initial effect of patina which is explained by the instability of the patinas under rapid pH-increase.     

Microbial corrosion resistance of galvanized coatings with 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one as a biocidal ingredient in electrolytes

Electrodeposition of galvanized coatings from electrolyte containing 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) can increase microbial corrosion resistance. Coatings were found to inhibit the growth and metabolism of sulphate-reducing bacteria (SRB). Open circuit potentials and corrosion rates of coupons revealed DCOIT effectively influences the coating property. Energy diffraction spectrum and infrared absorption spectra were used to detect DCOIT on the coating surface. Scanning electron microscopy and X-ray diffraction revealed morphological and structural modifications. Electrochemical impedance spectroscopy and polarization techniques determined the corrosion behaviour of coatings in SRB. Results showed coatings formed from electrolytes with DCOIT have improved microbial corrosion resistance and bactericidal action.     

Investigation on dual corrosion performance of magnesium-rich primer for aluminum alloys under salt spray test (ASTM B117) and natural exposure

Magnesium-rich primers perform very well on outdoor exposure and actual test conditions, yet fail rapidly in accelerated corrosion testing (salt spray test - ASTM B117). To investigate the behavioral dichotomy, Mg-rich primers exposed to salt spray testing and natural weathering were characterized at periodic intervals. The results revealed the presence of a thin and porous magnesium hydroxide layer in primers exposed to salt spray, and in natural exposure, a thicker, protective magnesium carbonate layer was detected and characterized. Samples exposed to atmospheric carbon dioxide exhibit excellent corrosion resistance but salt spray conditions are not conducive to facilitate magnesium carbonate formation.     

Rust formed on cannons of XVIII century under two environment conditions

The corrosion products of two ancient cannons exposed to atmospheric corrosion were analysed by X-ray powder diffraction, transmission Mössbauer spectroscopy and scanning electron microscopy (SEM). After almost three centuries exposed in marine environment one of them was moved to a rural region and was maintained in this environment for approximately 30 years. The inland region has an altitude of 1000 m above sea level and consequently low aggressiveness. The studied rusts were obtained from external and internal surfaces of the cannon barrels. This investigation, using three different techniques, was done to check if the relatively short time (ca. 30 years) in rural area was sufficient to change the characteristics of the thick rust formed during long time exposure (ca. 300 years) in marine atmosphere. The time-environment effects change the physical nature of rust, mainly observed by Mössbauer spectroscopy results.     

Effect of surface condition on the initial corrosion of galvanized reinforcing steel embedded in concrete

The present work was aimed at determining the effect of coating surface condition on the initial corrosion of hot-dip galvanized reinforcing steel bar (HDG rebar) in ordinary Portland cement (OPC) concrete. During zinc corrosion in OPC concrete, calcium hydroxyzincate (CHZ) formed on untreated HDG steel provided sufficient protection against corrosion. Therefore, it is concluded that treating HDG rebar with dilute chromic acid is unnecessary as a method of passivating zinc. A layer of zinc oxide and zinc carbonate formed, through weathering, on HDG bars increased the initial corrosion rate and passivation time compared with the non-weathered rebar exposed to concrete. HDG steel with an alloyed coating, i.e. containing only of Fe-Zn intermetallic phases, required a longer time to passivate than those with a pure zinc surface layer. The lower zinc content of the surface limited the rate of CHZ formation; hence, delayed passivation. Regardless of the surface condition, the coating depth loss after two days of embedment in ordinary Portland cement concrete was insignificant.     

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.     

Effect of cations on corrosion of zinc and carbon steel covered with chloride deposits under atmospheric conditions

The effect of sodium, calcium, and magnesium chlorides deposited on zinc and carbon steel surfaces was studied under atmospheric conditions. The cations strongly affected the corrosion rate of zinc, whereas they had a significantly lower impact on the corrosion of carbon steel. The corrosivity of cations of chloride salts for zinc increased in order of Mg²⁺ < Ca²⁺ < Na⁺. The higher corrosion resistance of zinc treated with calcium and magnesium chlorides was connected to prevention of formation of hydrozincite during zinc exposure in wet air. It was observed that zinc weight loss and the carbonate to simonkolleite ratio in corrosion products were correlating. The principal protective effect of bivalent cations can be seen in the decrease of pH of the surface electrolyte, which was caused by hydrolysis of such cations and subsequent formation of simonkolleite that blocked the cathodic sites.     

Carbon steel corrosion in clay-rich environment

We investigated the carbon steel corrosion in carbon dioxide clay-rich environment to understand its behavior under geological conditions. The results show the formation of magnetite as the main corrosion product in the first step of the corrosion process, followed by the formation of different corrosion products with complex mixtures of iron-oxide, hydroxycarbonate, hydroxychloride and sulfide phases. These results strongly contrast with similar experiments conducted under H₂ atmosphere where the major corrosion products consisted of iron sulfides. It appears then important to consider all the geochemical parameters including gas composition to better study corrosion of steel buried in geological formations.     

Carbonation of Mg powder to enhance the corrosion resistance of Mg-rich primers

This paper is a continuation of our investigation into the characteristic dichotomy of Mg-rich primers between accelerated salt-fog testing and natural weathering. Our earlier study suggested that magnesium powder reacted with atmospheric CO₂ to form a protective carbonate layer on its surface. In this study, magnesium powder was treated with aqueous carbonic acid to accelerate magnesium carbonate development. The treated magnesium powder was formulated into a Mg-rich primer and evaluated for its corrosion resistance. The Mg-rich primer formulated with the treated Mg powder performed better in the salt-fog test than the control primer based on untreated Mg powder.     

Chemistry of corrosion products on Zn-Al-Mg alloy coated steel

Zn-Al-Mg alloy (ZM) coating provides a decisively enhanced corrosion resistance in a salt spray test according to DIN EN ISO 9227 (NSS) compared to conventional hot-dip galvanised zinc (Z) coating because of its ability to form a very stable, well adherent protecting layer of zinc aluminium carbonate hydroxide, Zn₆Al₂(CO₃)(OH)₁₆·4H₂O on the steel substrate. This protecting layer is the main reason for the enhanced corrosion resistance of the ZM coating. Surface corrosion products on ZM coated steel consist mainly of Zn₅(OH)₆(CO₃)₂, ZnCO₃ and Zn(OH)₂ with additions of Zn₅(OH)₈Cl₂ · H₂O and a carbonate-containing magnesium species.     

Initial NaCl-particle induced atmospheric corrosion of zinc—Effect of CO2 and SO2

Initial corrosion and secondary spreading effects during NaCl particle induced corrosion on zinc was explored using in situ and ex situ FTIR microspectroscopy, optical microscopy, and SEM/EDAX. The secondary spreading effect which occurs upon introduction of humid air on NaCl deposited zinc surfaces was strongly dependent on the CO₂ and SO₂ content of the introduced air. Ambient level of CO₂ (350 ppm) resulted in a relatively low spreading effect, whereas the lower level of CO₂ (<5 ppm) caused a much faster spreading over a larger area. In the presence of SO₂, the secondary spreading effect was absent which could limit the cathodic process in this case. At <5 ppm CO₂, the corrosion is more localized, with the formation of simonkolleite (Zn₅(OH)₈Cl₂ · H₂O), zincite (ZnO) and sodium carbonate (Na₂CO₃), and a larger effective cathodic area. At 350 ppm CO₂, the corrosion is more general and formation of simonkolleite, hydrozincite (Zn₅(OH)₆(CO₃)₂) and sodium carbonate was observed. Sodium carbonate was mainly formed in more alkaline areas, in the inner edge of the electrolyte droplet and in the secondary spreading area. Oxidation of sulphur and concomitant sulphate formation was enhanced in the presence of NaCl particles, due to the formation of a droplet, the separation of the anodic and cathodic areas and the accompanying differences in chemical composition and pH in the surface electrolyte.     

Corrosion and corrosion test methods of zinc coated steel sheets on automobiles

The effect of zinc and zinc alloy coated steel sheets on perforation corrosion in actual automobiles and the relevant accelerated corrosion test methods were studied. The main factor affecting corrosion in the crevice of lapped panels was the coating weights of zinc and zinc alloys rather than the type of coating. Perforation corrosion process of galvanized steel in the crevice of lapped portion in automobiles was divided in four stages. Based on the analysis of corrosion in actual automobiles, a Perforation Corrosion Index, PCI for lapped steel panels was proposed. Assuming PCI for various accelerated corrosion test methods, the corrosion resistance of various types of coated steel sheets in actual environments was evaluated.     

Morphology and phase composition of corrosion products formed at the zinc-iron interface of a galvanized steel

The corrosion products formed on the inner wall of pipes made of galvanized low carbon steel, exposed for ∼2 years to water flowing in a large household heating system, were analysed using X-ray diffraction, Mössbauer and Raman spectroscopic techniques, as well as metallographic techniques. Products grew in the form of large-sized tubercles that gradually developed causing base metal losses up to perforation of the steel pipe. Considerable differences in the phase composition were found between the products formed in contact with the steel and those constituting the outer part of tubercles. The former were mainly made of FeCO₃ (siderite), with small amounts of Zn₅(CO₃)₂(OH)₆ (hydrozincite), ZnCO₃ (smithsonite), (Fe,Zn)CO₃ mixed carbonate and CaCO₃ (calcite), the latter mainly by Fe(III) oxyhydroxide goethite. Both parts of the tubercles also contained small amounts of other ferric oxyhydroxides, γ-FeOOH (lepidocrocite) and β-FeOOH (akaganeite), and very small amounts of hematite. The procedures used proved effective for an adequate identification of both the iron-containing and iron-free compounds in the corrosion products as well as for suggesting a corrosion mechanism.     

Long-term trends in the corrosion state and surface properties of the stainless steel tubes of steam generators decontaminated chemically in VVER-type nuclear reactors

At some VVER-type pressurized water nuclear reactors (Russian-type PWR) different versions of the so-called AP-CITROX method have been widely used for the chemical decontamination of the heat exchanger tubes of steam generators. In the period of 2000–2007, within the frame of a joint-project dealing with the comprehensive investigation of the corrosion state of the steam generators of the Paks Nuclear Power Plant, Hungary, effects of the AP-CITROX chemical decontamination procedure on the corrosion and surface characteristics of the heat exchanger tubes have been studied. These studies provide evidences that some adverse features (formation of a “hybrid” layer with accelerated corrosion rate and great mobility) can be detected after 1–3 years of applying the AP-CITROX procedure. The present work is a continuation of the above program and focused on the long-term trends in the corrosion state and structure of protective oxide-layer grown on the decontaminated surfaces. The results of electrochemical (voltammetric), surface analytical (SEM–EDX, CEMS) and mobility (ICP–OES) studies have revealed that (1) some beneficial changes in the corrosion characteristics, mobility and chemical composition of the inner surfaces of decontaminated heat exchanger tubes can be observed in the long run, and (2) the passivity of the oxide-layers formed on decontaminated surfaces of steel tubes exhibits favorable tendency after 4–7 years under normal operation conditions.     

Understanding corrosion via corrosion product characterization: II. Role of alloying elements in improving the corrosion resistance of Zn–Al–Mg coatings on steel

Corrosion products are identified on Zn, ZnMg and ZnAlMg coatings in cyclic corrosion tests with NaCl or Na₂SO₄ containing atmospheres. For Mg-containing alloys the improved corrosion resistance is achieved by stabilization of protective simonkolleite and zinc hydroxysulfate. At later stages, the formation of layered double hydroxides (LDH) is observed for ZnAlMg. According to thermodynamic modeling, Mg²⁺ ions bind the excess of carbonate or sulfate anions preventing the formation of soluble or less-protective products. A preferential dissolution of Zn and Mg at initial stages of corrosion is confirmed by in situ dissolution measurement. The physicochemical properties of different corrosion products are compared.