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.     

Initial corrosion behavior of pure zinc in simulated tropical marine atmosphere

The initial corrosion behavior of pure zinc in a simulated tropical marine atmosphere was investigated using gravimetric method, scanning electron microscope combined with energy dispersive spectroscopy (SEM-EDS), X-ray diffractometry (XRD), Fourier transform infrared spectrometry (FTIR) and electrochemical impedance spectroscopy (EIS). The kinetics of corrosion process is a decelerating process following the empirical equation D=Atⁿ (n<1). The protectiveness of the corrosion product layer could be attributed to the formation of simonkolleite, Zn₅(OH)₈Cl₂·H₂O, which could inhibit the rate determining step, namely charge transfer step, of the electrochemical corrosion process. A model of the evolution process of the product layers formed on zinc was proposed. In addition, the regularity of the corrosion rate of zinc as a function of the NaCl deposition rate can be described by a power function.     

Corrosion product formation on Zn55Al coated steel upon exposure in a marine atmosphere

The formation of corrosion products on Zn55Al coated steel has been investigated upon field exposures in a marine environment. The corrosion products consisted mainly of zinc aluminium hydroxy carbonate, Zn_0.71Al_0.29(OH)₂(CO₃)_0.145·xH₂O, zinc chloro sulfate (NaZn₄(SO₄)Cl(OH)₆·6H₂O), zinc hydroxy chloride, Zn₅(OH)₈Cl₂·H₂O and zinc hydroxy carbonate, Zn₅(OH)₆(CO₃)₂ were the first three phases were formed initially while zinc hydroxy carbonate Zn₅(OH)₆(CO₃)₂ was formed after prolonged exposure in more corrosive conditions. The initial corrosion product formation was due to selective corrosion of the zinc rich interdendritic areas of the coating resulting in a mixture of zinc and zinc aluminium corrosion products.     

Corrosion resistance of zinc-magnesium coated steel

A significant body of work exists in the literature concerning the corrosion behaviour of zinc-magnesium coated steel (ZMG), describing its enhanced corrosion resistance when compared to conventional zinc-coated steel. This paper begins with a review of the literature and identifies key themes in the reported mechanisms for the attractive properties of this material. This is followed by an experimental programme where ZMG was subjected to an automotive laboratory corrosion test using acidified NaCl solution. A 3-fold increase in time to red rust compared to conventional zinc coatings was measured. X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy were used to characterize the corrosion products formed. The corrosion products detected on ZMG included simonkolleite (Zn₅Cl₂(OH)₈ · H₂O), possibly modified by magnesium uptake, magnesium hydroxide (Mg(OH)₂) and a hydroxy carbonate species. It is proposed that the oxygen reduction activity at the (zinc) cathodes is reduced by precipitation of alkali-resistant Mg(OH)₂, which is gradually converted to more soluble hydroxy carbonates by uptake of atmospheric carbon dioxide. This lowers the surface pH sufficiently to allow thermodynamically for general precipitation of insoluble simonkolleite over the corroding surface thereby retarding the overall corrosion reactions, leaving only small traces of magnesium corrosion products behind. Such a mechanism is consistent with the experimental findings reported in the literature.     

The temperature-dependence of the SO2-induced atmospheric corrosion of zinc; a laboratory study

The SO₂-induced atmospheric corrosion of zinc was studied at 4, 14, 22 and 30 °C and 95% RH. Each sample was exposed individually to synthetic atmospheres with careful control of SO₂ concentration (107 and 500 ppb), relative humidity and flow conditions. The initial reaction between SO₂ and zinc was studied in a time-resolved manner. Two-week exposures were performed to measure the corrosion rate and study the formation of corrosion products. Corrosion products were analysed by X-ray powder diffraction and ion chromatography. The corrosion rate was inversely dependent on temperature, the maximum rate being found at the lowest temperature. SO₂ deposition showed a similar trend with the highest deposition rate at 4 °C. At low temperature a thick film of ZnSO₄(aq) formed on the metal surface, whereas zinc hydroxysulphate (ZnSO₄ · 3Zn(OH)₂ · 4H₂O(s)) was the main corrosion product at 22 and 30 °C. The inverse temperature-dependence of the corrosion rate of zinc is proposed to be connected to the formation of sparingly soluble zinc hydroxy sulphate which slows down the deposition of SO₂ on the surface.     

Effects of NaCl and NH4Cl on the initial atmospheric corrosion of zinc

Effects of NaCl and NH₄Cl on the initial atmospheric corrosion of zinc were investigated via quartz crystal microbalance (QCM) in laboratory at 80% RH and 25 °C. The results show that both NaCl and NH₄Cl can accelerate the initial atmospheric corrosion of zinc. The combined effect of NaCl and NH₄Cl on the corrosion of zinc is greater than that caused by NH₄Cl and less than that caused by NaCl. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy and electron dispersion X-ray analysis (SEM/EDAX) were used to characterize the corrosion products of zinc. (NH₄)₂ZnCl₄, Zn₅(OH)₈Cl₂ · H₂O and ZnO present on zinc surface in the presence of NH₄Cl while Zn₅(OH)₈Cl₂ · H₂O and ZnO are the dominant corrosion products on NaCl-treated zinc surface. Probable mechanisms are presented to explain the experimental results.     

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.     

Comparison of corrosion behaviour of zinc in NaCl and in NaOH solutions. Part I: Corrosion layer characterization

The corrosion layer formed on zinc sample in 0.6 M NaCl and 0.5 M NaOH solution under ambient conditions has been investigated. The corrosion layer morphology was analyzed using scanning electron microscopy (SEM). X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the corrosion products of zinc. The thickness evolution of the corrosion layer was investigated by glow discharge optical emission spectroscopy (GDEOS). The corrosion layer formed in 0.5 M NaOH solution appeared more compact than that formed in 0.6 M NaCl solution. Zinc hydroxide chloride (Zn₅(OH)₈Cl₂·2H₂O) and zinc hydroxide carbonate (Zn₅(CO₃)₂(OH)₆) were formed on zinc surface in 0.6 M NaCl solution while in 0.5 M NaOH solution, zinc oxide (ZnO), zinc hydroxide (Zn(OH)₂) and zinc hydroxide carbonate (Zn₅(OH)₆(CO₃)₂·H₂O) were detected. Probable mechanisms of zinc corrosion products formation are presented.     

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.     

Corrosion behavior of carbon steel coated with a zinc-rich paint containing metallic compounds under wet and dry cyclic conditions

The corrosion behavior of carbon steel coated with a zinc-rich paint containing two metallic compounds, Al₂(SO₄)₃ and CaO, as anticorrosive additives was examined under wet and dry cyclic corrosion test conditions. The zinc-rich paint coating without the two metallic compounds formed a white corrosion product and red iron rust on the surface after the corrosion test, whereas the coating with the metallic compounds showed reduced surface corrosion products. The corrosion current density of the painted steel substrate decreased drastically due to the incorporation of metallic compounds in the paint. The zinc-rich paint coating modified with the metallic compounds contained dispersed simonkolleite (Zn₅(OH)₈Cl₂·H₂O) phase and possibly very fine CaSO₄ particles, which remarkably improved the protectiveness of the zinc-rich paint coating.     

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.     

Studies of galvanised steel atmospheric corrosion in Saudi Arabia

Abstract

This paper summarises the results obtained for galvanised steel specimens exposed in Saudi Arabia region for four years at four pure marine and five mixed marine (SO₂ polluted) sites. The atmospheres at these sites were characterised climatologically and in terms of their pollution level so that their corrosivity could be expressed in accordance with ISO standards. Chemical characterisation of the galvanised steel corrosion product layers was performed using X-ray diffraction. The main phases determined were zincite (ZnO), simonkolleite [Zn₅(OH)₈Cl₂.H₂O], smithsonite (ZnCO₃), magnetite (Fe₃O₄), gordaite [NaZn₄(SO₄)Cl(OH)₆Cl.6(H₂O)], hematite (Fe₂O₃), zinkosite (ZnSO₄), zinc chloride (ZnCl₂), zinc hydroxide sulphate hydrate [(Zn(OH)₂)₃(ZnSO₄)(H₂O)₃] and zinc sulphate hydroxide hydrate [ZnSO₄(OH)₂.5H₂O] was found on the specimens. The results obeyed well with the empirical kinetics equation of the form C?=?Ktⁿ, where K and C are the corrosion losses in mg cm^?2 after 1 and ‘t’ years of the exposure respectively, and ‘n’ is constant. Based on ‘n’ values, the corrosion mechanism of galvanised steel is predicted. The results obtained show that the corrosion rate of galvanised steel is a function of both the chloride, SO₂ pollution level and the humidity. Corrosion rate of galvanised steel specimens have been obtained by loss of weight after each year of exposure.     

Influence of anions on the formation and structure of artificial zinc rusts

To simulate the atmospheric corrosion of steels galvanized with Zn under different conditions, artificial zinc rusts of basic zinc salt (BZS) were prepared by hydrolyzing ZnO particles in aqueous solutions including ZnCl₂, ZnSO₄ and Zn(NO₃)₂. In ZnCl₂–ZnSO₄, ZnSO₄–Zn(NO₃)₂ and ZnCl₂–Zn(NO₃)₂–ZnSO₄ systems, zinc hydroxysulfate (Zn₄(OH)₆(SO₄)·nH₂O) was formed while zinc hydroxychloride (Zn₅(OH)₈Cl₂·H₂O) was generated in ZnCl₂–Zn(NO₃)₂ system. Zinc hydroxynitrate (Zn₅(OH)₈(NO₃)₂·2H₂O) was yielded in only Zn(NO₃)₂ system. All the formed artificial zinc rusts were hexagonal plate particles. These results suggest that SO_x is the most effective corrosive gas on the formation of BZS rusts on galvanized steel.     

Characterization of the corrosion products of electrodeposited Zn, Zn–Co and Zn–Mn alloys coatings

The morphology, composition, phase composition and corrosion products of coatings of pure Zn (obtained from two types of electrolytic bath: an acidic bath (Zn_acid) and a cyanide-free alkaline bath (Zn_alkaline)) and of Zn–Mn and Zn–Co alloys on steel substrates were studied. To achieve this, diverse techniques were used, including polarization curves, atomic force microscopy (AFM), scanning electron microscopy (SEM), glow discharge spectroscopy (GDS), X-ray diffraction (XRD), and the salt spray test. In the salt spray test, the exposure time required for the coatings to exhibit red corrosion (associated with the oxidation of steel) decreased in the following order: Zn–Mn_(432h) > Zn–Co_(429h) > Zn_{alkaline(298h)} > Zn_acid(216h). The shorter exposure times required for corrosion of the pure Zn coatings are related to the coating composition and the crystallographic structure. Analysis of the corrosion products disclosed that Zn₅(OH)₈Cl₂·H₂O was a corrosion product of all of the coatings tested. However, the formation of oxides of manganese (MnO, Mn_0.98O₂, Mn₅O₈) in the Zn–Mn coating, and the formation of the hydroxide Zn₂Co₃(OH)₁₀·2H₂O in the Zn–Co coating, produced more compact and stable passive layers, with lower dissolution rates.     

In situ infrared reflection spectroscopy studies of the initial atmospheric corrosion of Zn–Al–Mg coated steel

NaCl induced atmospheric corrosion of ZnAl2Mg2 coated, electrogalvanised (EG) and hot dipped galvanised (HDG) steel was studied using in situ infrared reflection absorption spectroscopy, XRD and SEM. Initial corrosion leads to the formation of Mg/Al and Zn/Al layered double hydroxides (LDHs) on ZnAl2Mg2, due to the anodic dissolution of Zn–MgZn2 phases and cathodic oxygen reduction on Zn–Al–MgZn2, Al-phases and on zinc dendrites. In contrast to EG and HDG, were no ZnO and Zn₅(OH)₈Cl₂⋅H₂O detected. This is explained by the buffering effect of Mg and Al which inhibit the ZnO formation, reduce the cathodic reaction and corrosion rate on ZnAl2Mg2.     

Characterization of black rust staining of unpassivated 55% Al–Zn alloy coatings. Effect of temperature, pH and wet storage

Wet storage staining is a phenomenon that occurs on both zinc coated and 55% Al–Zn coated steel sheets during shipment or storage in damp conditions. Whereas zinc coated sheets form white corrosion products, 55% Al–Zn coated steel sheets form black corrosion products. The effect of temperature, pH and wet storage on the occurrence of black rust staining of unpassivated Aluzink samples has been investigated in the laboratory in terms of corrosion product formation and composition. A characterization of corrosion products formed has been performed mainly based on scanning electron microscopy with X-ray microanalyses (SEM/EDS) for morphological and quantitative analyses and X-ray diffraction techniques (XRD) for crystalline phase identification. Black rust formation is strongly related to alkaline pH regions and is enhanced by the temperature. All black panels show the presence of Bayerite (Al(OH)₃), mainly formed on the aluminum rich dendrite branches and a basic zinc aluminum carbonate (Zn₆Al₂(OH)₁₆CO₃·4H₂O) formed in the zinc rich interdendritic alloy regions in contact with air. Blackening of Aluzink surfaces is connected to differences in optical properties of embedded metallic zinc and/or aluminum particles of different shape and size in the corrosion layer.     

Initial atmospheric corrosion of zinc in presence of Na2SO4 and （NH4）2S04

Initial atmospheric corrosion of zinc in the presence of Na₂SO₄ and (NH₄)₂SO₄ was investigated via quartz crystal microbalance(QCM) in laboratory at relative humidity(RH) of 80% and 25 °C. The results show that both Na₂SO₄ and (NH₄)₂SO₄ can accelerate the initial atmospheric corrosion of zinc. The combined effect of Na₂SO₄ and (NH₄)₂SO₄ on the corrosion of zinc is greater than that caused by (NH₄)₂SO₄ and less than that caused by Na₂SO₄. Fourier transform infrared spectroscopy(FTIR), X-ray diffractometry(XRD) and scanning electron microscopy(SEM) were used to characterize the corrosion products of zinc. (NH₄)₂Zn(SO₄)₂, Zn₄SO₄(OH)₆·5H₂O and ZnO present on zinc surface in the presence of (NH₄)₂SO₄ while Zn₄SO₄(OH)₆·5H₂O and ZnO are the dominant corrosion products on Na₂SO₄-treated zinc surface. Probable mechanisms are presented to explain the experimental results.     

Structure and properties of Ti(IV)-doped zinc hydroxychloride rusts formed at various temperatures

To simulate the atmospheric corrosion of steels galvanized with Ti–Zn alloys under different atmospheric temperatures, Ti(IV)-doped zinc hydroxychloride (Zn₅(OH)₈Cl₂·H₂O: ZHC) was prepared at various aging temperatures of 6–120 °C. Adding the Ti(IV) inhibited the crystallization and particle growth of ZHC, showing a minimum at 50 °C. Higher aging temperature promoted the formation of TiO₂ nano-particles. Elevating the aging temperature suppressed the adsorption of H₂O and CO₂ on Ti(IV)-doped ZHC. These results suggest that the alloying Ti in galvanized steel forms compact zinc rust layer at various atmospheric temperatures in marine environment, which would lead to the enhancement of corrosion resistance.     

Role of zinc compounds on the formation, morphology, and adsorption characteristics of β-FeOOH rusts

To simulate the corrosion of galvanized steel in marine zone, β-FeOOH was prepared by aging the FeCl₃ solutions containing ZnCl₂ and zinc rusts such as ZnO and zinc hydroxychloride (Zn₅(OH)₈Cl₂·H₂O:ZHC). Adding ZnCl₂, ZnO, and ZHC inhibited the crystallization and particle growth of β-FeOOH and the inhibitory effect was in order of ZHC ≈ ZnO > ZnCl₂. The adsorption of H₂O and CO₂ was suppressed by adding ZnCl₂, ZnO, and ZHC. These results imply that the rust formed on galvanized steel in marine environment is more compact, amorphous, and hydrophobic in nature which may lead to improve the corrosion resistance.     

Corrosion Behavior of Cu40Zn in Sulfide-Polluted 3.5% NaCl Solution

The corrosion behavior of a duplex-phase brass Cu40Zn in clean and sulfide-polluted 3.5% NaCl solutions was investigated by conducting electrochemical and gravimetric measurements. The corrosion product films were analyzed by scanning electron microscopy, energy-dispersive spectroscopy and x-ray diffraction. The presence of sulfide shifted the corrosion potential of Cu40Zn toward a more negative value by 100 mV and increased the mass loss rate by a factor of 1.257 compared with the result in the clean solution. The corrosion product film in the clean solution was thin and compact; it mainly consisted of oxides, such as ZnO and Cu₂O. By contrast, the film in the sulfide-polluted solution was thick and porous. It mainly contained sulfides and zinc hydroxide chloride (i.e., Zn₅(OH)₈Cl₂·H₂O). The presence of sulfide ions accelerated the corrosion damage of Cu40Zn by hindering the formation of protective oxides and promoting the formation of a defective film which consisted of sulfides and hydroxide chlorides.