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.     

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.     

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.     

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.     

Influence of tensile stress on corrosion behaviour of high‐strength galvanized steel bridge wires in simulated acid rain

Corrosion behaviour of the high‐strength galvanized steel wires under tensile stress was researched by electrochemical polarization and salt spray test (SST) using simulated acid rain as electrolyte. Electrochemical polarization and SST results showed corrosion rate rose significantly with increasing tensile stress; white grains were observed by SEM after polarization, while cellular and dendritic crystals appeared on the rust layer after SST. XRD and TG‐DTA results revealed (Zn(OH)₂)₃ · ZnSO₄ · 5H₂O was the main corrosion product, and traces of Fe₂(SO₄)₂O · 7H₂O, Fe₂(SO₄)₃, Fe₂O₃ · H₂O were also detected. A three‐stage corrosion process for the galvanized steel wires during SST was proposed.     

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.     

Effects of NaCl and SO2 on the initial atmospheric corrosion of zinc

The influence of NaCl deposition on the corrosion of zinc in atmospheres with and without SO₂ was studied via quartz crystal microbalance. Regularity of the initial corrosion of zinc under these conditions was analyzed. The results show that NaCl can accelerate the corrosion of zinc. Mass gain of zinc increases with the exposure time, which can be correlated by using exponential decay function. The relationship between mass gain and amount of NaCl deposition is well linear at any time in air containing 1 ppm SO₂, but follows quadratic function in air without SO₂. More amount of NaCl deposition will slow down the corrosion to some extent after exposure for certain time in the presence of SO₂. The combined effect of NaCl and SO₂ on the corrosion of zinc is greater than that caused by each single component. Fourier transform infrared spectroscopy and X-ray diffraction were used to characterize the corrosion products of zinc. In the absence of SO₂, simonkolleite, Zn₅(OH)₈Cl₂·H₂O and zincite, ZnO are the dominant corrosion products, while zinc hydroxysulfate (Zn₄SO₄(OH)₆·3H₂O), zinc chloride sulfate hydroxide hydrate (Zn₁₂(SO₄)₃Cl₃·(OH)₁₅·5H₂O) and simonkolleite dominate in the presence of SO₂. Brief discussion on the mechanisms of atmospheric corrosion under these conditions was introduced.     

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.     

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.     

A study of the corrosion products of aluminum brass formed in sodium sulfate solution in the presence of chlorides

The surface film forming on Al brass specimens immersed in stagnant Na₂SO₄ solutions containing chlorides at pH values 3.0–7.25 was examined by using chemical, electrochemical and X-ray techniques. In the absence of chlorides the surface film consists of oxides (CuO, Cu₂O) and cupric basic sulfates Cu₃(SO₄)₂.4H₂O, stable in the whole range of pH; the surface film is quite homogeneous and no dezincification or localized corrosion occurs. In the presence of chlorides, the surface film consists also of cuprous chloride (CuCl) and of cupric [Cu(OH,Cl)₂.2H₂O] and aluminum oxychlorides [Al₄₅O₄₅(OH)₄₅Cl] and aluminum oxides (Al(OH)₃]. The weight of the corrosion products is a maximum in solutions containing 5 × 10⁻³ M NaCl at each pH value. In the most acidic solutions the surface film is physically and chemically extremely unhomogeneous, thus favouring the occurrence of dezincification or localized corrosion phenomena.     

AC corrosion - Part 1: Effects on overpotentials of anodic and cathodic processes

AC-induced corrosion is a controversial subject and many aspects of it need to be clarified, first and foremost, the mechanism and relationship between AC density and corrosion rate. This paper (Part 1) presents and discusses the effects of AC interference on kinetics parameters; the effects on corrosion rate and corrosion mechanism will be discussed in Part 2. Polarisation curves were obtained in different solutions (soil-simulating solution, 35 g L⁻¹ NaCl, 1 M FeSO₄, 1 M CuSO₄ and 1 M ZnSO₄) on different metallic materials (carbon steel, galvanised steel, zinc and copper) in the presence of AC interference (30-1000 A/m²).     

Influence of the corrosion products of copper on its atmospheric corrosion kinetics in tropical climate

In the present paper, the identification of the corrosion product phases formed on copper under different atmospheres of Cuban tropical climate is reported. Cuprite (Cu₂O), paratacamite (Cu₂Cl(OH)₃), posnjakite (Cu₄SO₄(OH)₆ · 2H₂O) and brochantite (Cu₄SO₄(OH)₆) were the main phases identified by X-ray diffraction (XRD) analysis and Fourier transform infrared spectroscopy (FTIR).Copper corrosion products are known to have a protective effect against corrosion. However, a different behaviour was obtained under sheltered coastal conditions. This can be due to the corrosion products morphology and degree of crystallisation, rather than their phase composition. A higher time of wetness and the accumulation of pollutants not washed away from the metal surface can also play an important role.     

Corrosion of copper and silver plates by volcanic gases

Corrosion products that had been formed on copper and silver plates exposed in Miyake Island, where suffered a volcanic eruption in 2000, were analyzed by X-ray techniques to get better understanding of copper and silver corrosion in harsh environment. The exposure experiment was carried out from September 2004 to April 2005. Many kinds of patina were found on copper such as cuprite (Cu₂O), posnjakite (Cu₄SO₄(OH)₆ · H₂O), brochantite (Cu₄SO₄(OH)₆), antlerite (Cu₃SO₄(OH)₄), and geerite (Cu₈S₅). For silver, silver chloride (AgCl) and silver sulfide (Ag₂S) were formed. Although the volcanic activity had greatly subsided, the atmospheric corrosion of copper and silver plates exposed on Miyake Island was mainly affected by volcanic gases, wet-dry cycles in the environment, and sea-salt aerosols.     

Laboratory studies of atmospheric corrosion—I. Weight loss and electrochemical measurements

Electrochemical studies have been performed with the atmospheric corrosion monitor (ACM) under thin layers of electrolyte which were drying out at R.H. < 100%. Galvanic couples (Cu/steel, Cu/zinc) and one-metal (steel, zinc) ACMs were used. Measurements were carried out as a function of R.H. and Na₂SO₄ concentration. In addition, weight loss data were collected under identical conditions in thin layer experiments for steel and zinc in 0.01N solutions of NaCl, Na₂SO₄, HCl, H₂SO₄ and distilled H₂O in air, air + 1 ppm SO₂, argon and argon + 1 ppm SO₂. The data obtained in air and air + SO₂ were compared to weight loss results in bulk solutions.The electrochemical technique makes it possible to follow the changes of corrosion rates with time. As observed in outdoor exposure, a large increase of corrosion rates occurs when the electrolyte layers become very thin, shortly before the surface dries out. These findings explain the results of the weight loss data which show for most environments a much larger corrosion rate than in the bulk electrolyte. An accelerating effect of SO₂ was observed for steel at higher R.H. values, while for zinc, no effect occurred in NaCl, Na₂SO₄ and H₂SO₄, but an inhibiting effect was measured in HCl and in distilled H₂O.Since weight loss and electrochemical data were recorded under identical conditions, it is possible to determine how accurately the ACM data reflect the true corrosion rate. It was found for Cu/steel ACMs that the electrochemical data follow the same trends as the weight loss data, but account for only about 20% of the corrosion rate. Due to larger scatter in the weight loss data, a similar efficiency factor could not be determined for Cu/zinc. For steel and zinc ACMs, the true Tafel slopes are not known, which makes a calculation of corrosion rates doubtful. The low cell efficiency is considered to be due to local corrosion of single cell plates and to i.r.-drop effects.Despite the fact that exact corrosion rates cannot, at present, be obtained from ACM data, the technique appears very valuable for following the changes of atmospheric corrosion behaviour and for time-of-wetness measurements.     

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.     

The characterization of patina components by X-ray diffraction and evolved gas analysis

Fourteen patinated copper specimens, seven each from the Statue of Liberty, New York Habor and from roofs at AT&T Bell Laboratories in Murray Hill, NJ, ranged in atmospheric exposure from 1 to 100 years. X-ray diffraction showed the presence of cuprite, Cu₂O, and brochantite, Cu₄(SO₄)(OH)₆, in all specimens and antlerite, Cu₃(SO₄)(OH)₄ (up to 0.7 times brochantite), atacamite, Cu₂Cl(OH)₃ (up to 1.6 times brochantite), and/or posnjakite, Cu₄(SO₄)(OH)₆ · 2H₂O (up to 5.2 times brochantite) in some. Posnjakite has been previously reported as a patina component only once during short term exposures in Eurasia. It appears to be an early corrosion product which subsequently converts to brochantite. Mass spectrographic examination of gases emitted from heated patinas provides further information on patina composition, in particular on the presence of both carbonate and oxalate in widely varying ratios.     

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.     

Optimization of deposition conditions for bright Zn-Fe coatings and its characterization

Sulfate bath having ZnSO₄ · 7H₂O, Fe₂(SO₄)₃ · H₂O and thiamine hydrochloride (THC) and citric acid (CA) in combination, represented as (THC + CA) was optimized for deposition of bright Zn-Fe alloy coating on mild steel. Bath constituents and operating parameters were optimized by standard Hull cell method, for peak performance of the coating against corrosion. The effect of current density (c.d.), pH and temperature on deposit characters, such as corrosion resistance, hardness and glossiness were studied and discussed. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) methods were used to assess the corrosion behaviors. Surface morphology, and composition of the coatings were examined using Scanning Electron Microscopy (SEM), interfaced with EDXA facility, respectively. The Zn-Fe alloy, with intense peaks corresponding to Zn(100) and Zn(101) phases, showed highest corrosion resistance, evidenced by X-ray diffraction (XRD) study. A new and cheap sulfate bath, for bright Zn-Fe alloy coating on mild steel has been proposed, and results are discussed.     

Examination of Aluminum Corrosion Products in Marine or Industrial Marine Atmosphere

A method has been developed to characterize the passivation film formed on aluminum in marine atmosphere, whether polluted or not by sulphur oxides and fluorides The information thus obtained was integrated by X-ray diffractometric analyses. The following corrosion products were found in the marine atmosphere: Al₂O₃· 3H₂O + Al (oxychoride) + Al (hydroxide) (The latter two compounds had not been revealed by X-ray analysis). The corrosion products found in the polluted atmosphere were: AlF₃; Al₂(SO₄)₃ · H₂SO₄; Al₁₁(OH)₃₀Cl₃; AlF_1.96(OH)_1.4; 16Al(OH,F)₃ · 6H₂O; AlF_1.65(OH)_1.35 · H₂O. Since the developed method provides useful quantitative information on the aluminum distribution between the various anions, it is deemed to be a useful tool to study the corrosion kineties and mechanism.     

Filter press plugging in zinc plant purification circuits

Mineralogical studies were carried out to identify the causes of filter press plugging in two zinc plant purification circuits. In the first circuit, Kraft paper covers were used over the filter cloths. An extensive layer of basic zinc sulfate, Zn₄(SO₄)(OH)₆.xH₂O or Zn₅(SO₄)₂)(OH)₆.xH₂O, precipitated on the surface of the Kraft paper and within the pores of the paper. In the second circuit, woven polypropylene cloth was used in the first-stage filter presses. The cloth was extensively covered by basic zinc sulfate, which also filled the relatively large pores in this type of material. An unwoven polypropylene cloth was used in the second-stage filter presses of this circuit. The significantly finer pores in this type of cloth appeared to be plugged by major amounts of zinc sulfate, ZnSO₄.xH₂O, that presumably crystallized because of the temperature-concentration conditions prevailing in that part of the circuit. For more information, contact T.T. Chen, CANMET, 555 Booth Street, Ottawa, Canada K1A 0G1: (613) 995-9490; fax (613) 996-9673; e-mail tchen@nrcan.gc.ca.