The effect of magnesium additions on the microstructure and cut edge corrosion resistance of zinc aluminium alloy galvanised steel

The magnesium levels in 20 μm thick 4.5% Al/Zn galvanising coatings applied to 0.7 mm gauge steel under continuous galvanising conditions were altered from 0.0% to 0.05%. The additions result in an increase in the zinc dendrites (volume fraction from 6% to 22% and number from 150 to 325 mm⁻²) since magnesium depresses the eutectic temperature increasing the freezing range. The microstructural modification results in increasing cut edge corrosion determined using a scanning vibrating electrode technique for 24 h exposure to 5% NaCl. The Mg additions result in an increase in zinc loss (from 80 to 185 μg), an increase in active anode numbers (from 600 to 1700 m⁻¹ cut edge) and an increase in the number of long lived anodes.     

The corrosion of Fe3Al alloy in liquid zinc

A systematic study of the isothermal corrosion testing and microscopic examination of Fe₃Al alloy in liquid zinc containing small amounts of aluminum (less than 0.2 wt.%) at 450 °C was carried out in this work. The results showed the corrosion of Fe₃Al alloy in molten zinc was controlled by the dissolution mechanism. The alloy exhibited a regular corrosion layer, constituted of small metallic particles (diameter: 2-5 μm) separated by channels filled with liquid zinc, which represented a porosity of about 29%. The XRD result of the corrosion layer formed at the interface confirmed the presence of Zn and FeZn_6.67. The corrosion rate of Fe₃Al alloy in molten zinc was calculated to be approximately 1.5 × 10⁻⁷ g cm⁻² s⁻¹. Three steps could occur in the whole process: the superficial dissolution of metallic Cr in the corrosion layer, the new phase formation of FeZn_6.67 and the diffusion of the dissolved species in the channels of the corrosion layer.     

Corrosion protection of magnesium alloy AZ31 sheets by spin coating process with poly(ether imide) [PEI]

In the present study, the potential of poly(ether imide) as corrosion protective coating for magnesium alloys was evaluated using the spin coating technique. The influence of different parameters on the coating properties was evaluated and the corrosion behaviour of the coatings was investigated using electrochemical impedance spectroscopy. The best corrosion protection was obtained preparing the coatings under N₂ atmosphere, using 15 wt.% solution in N′N′-dimethylacetamide (DMAc) which resulted in a coating of approximately 2 μm thickness, with an initial impedance of 10⁹ Ω cm² and of 10⁵ Ω cm² after 240 h of exposure to a 3.5% NaCl solution.     

Corrosion behaviour of magnetron sputtered α- and β-Ta coatings on AISI 4340 steel as a function of coating thickness

The corrosion behaviour of magnetron sputtered α- and β-Ta coated AISI 4340 steels was studied with potentiodynamic polarization and electrochemical impedance spectroscopy. The coating porosity was observed to decrease with increasing coating thickness. For coatings less than 10 μm thick (α- or β-Ta), porosity was significant and open pores resulted in severe localized corrosion of the steel substrate, coating delamination, and overall coating failure. Additionally, the β-Ta coatings were more susceptible than the α-phase to delamination. As for the 50 and 100 μm thick α-Ta coatings, the electrochemical impedance behaviour was comparable to that of Ta foil, demonstrating the coating viability and corrosion resistance.     

High rate deposition of thick CrN and Cr2N coatings using modulated pulse power (MPP) magnetron sputtering

As a variation of high power pulsed magnetron sputtering technique, modulated pulse power (MPP) magnetron sputtering can achieve a high deposition rate while at the same time achieving a high degree of ionization of the sputtered material with low ion energies. These advantages of the MPP technique can be utilized to obtain dense coatings with a small incorporation of the residual stress and defect density for the thick coating growth. In this study, the MPP technique has been utilized to reactively deposit thick Cr₂N and CrN coatings (up to 55 μm) on AISI 440C steel and cemented carbide substrates in a closed field unbalanced magnetron sputtering system. High deposition rates of 15 and 10 μm per hour have been measured for the Cr₂N and CrN coating depositions, respectively, using a 3 kW average target power (16.7 W/cm² average target power density), a 50 mm substrate to target distance and an Ar/N₂ gas flow ratio of 3:1 and 1:1. The CrN coatings showed a denser microstructure than the Cr₂N coatings, whereas the Cr₂N coatings exhibited a smaller grain size and surface roughness than those of the CrN coatings for the same coating thickness. The compressive residual stresses in the CrN and Cr₂N coatings increased as the coating thickness increased to 30 μm and 20 μm, respectively, but for thicker coatings, the stress gradually decreased as the coating thickness increased. The CrN coatings exhibited an increase in the scratch test critical load as the thickness was increased. Both CrN and Cr₂N coatings showed a decrease in the hardness and an increase in the sliding coefficient of friction as the coating thickness increased from 2.5 to 55 μm. However, the wear rate of the CrN coatings decreased significantly as the coating thickness was increased to 10 μm or higher. The 10-55 μm CrN coating exhibited low wear rates in the range of 3.5-5 × 10⁻⁷ mm³ N⁻¹ m⁻¹. To the contrary, the Cr₂N coating exhibited relatively low wear resistance in that high wear rates in the range of 3.5 to 7.5 × 10⁻⁶ mm³ N⁻¹ m⁻¹ were observed for different thicknesses.     

Scratch-resistant anticorrosion sol-gel coating for the protection of AZ31 magnesium alloy via a low temperature sol-gel route

A novel hybrid sol-gel/polyaniline coating has been developed for application onto an AZ31 magnesium alloy for corrosion protection. Electrochemical Impedance Spectroscopy in 3.5 wt% NaCl and diluted Harrison’s solutions, along with salt spray tests showed that the coating possesses excellent corrosion resistance. The hybrid coating was modified by doping with silica nanoparticles (for scratch resistance) and cured at a low temperature of 75 °C. Whilst conventional sol-gel methods tend to limit the coating thickness values up to 10 μm, the new hybrid sol-gel/polyaniline system presented here allows thick coatings to be deposited, in this case, around 50-60 μm.     

Microstructural changes in zinc aluminium alloy galvanising as a function of processing parameters and their influence on corrosion

The effect of cooling rate and substrate gauge upon the microstructure and corrosion resistance of Galfan (Zn-4.5 wt.%Al) coated steels is presented. The coatings, applied to steel of gauges 0.47 mm (light gauge) and 0.67 mm (heavy gauge) on a coil coating line, were subjected to three different cooling rates by increasing output from 55% to 100% of the total power from a high powered cooling rig. The increase in cooling rate did not significantly alter the volume fraction of the primary zinc, this remaining at ∼20%. However, the size and number of the primary zinc dendrites were altered. The fast cooled samples contained small but numerous (∼3000 mm⁻² in the heavy gauge and ∼2850 mm⁻² in the light gauge) dendrites as opposed to the slow cooled samples where there were fewer (∼1850 mm⁻² for the heavy gauge and ∼1500 mm⁻² in the light gauge) dendrites of greater size. Characterisation of the surface revealed a reduction in eutectic cell size (∼1.8 mm to ∼0.8 mm on the heavy gauge and ∼2.1 mm to ∼1.2 mm on the light gauge) with increasing cooling rate. This leads to an increased unit length of depressed boundary between the eutectic cells. The eutectic microstructure is also finer (with reduced inter-lamella spacing) in the fast cooled samples again reflecting the more rapid nucleation of the coating.The scanning vibrating electrode technique (SVET) has been used to quantify the effects of these microstructural changes upon the surface and cut edge corrosion performance. There is an increase in corrosion activity on the surface of the fast cooled samples (metal loss 150 μg to 260 μg on the heavy gauge and 50 μg to 80 μg on the light gauge) primarily due to the increased length of depressed boundaries. Applying the same analysis to the cut edge, a decrease in corrosion occurs upon the faster cooled specimens. Metal loss calculations show a decrease (140 μg to 75 μg on the heavy gauge and 190 μg to 115 μg on the light gauge) as the cooling rate is increased. The higher intensity long lived anodes at the cut edge in the slower cooling rate samples are directly related to the increase in zinc dendrite size within the coating as nucleation rates are reduced.     

Metal release from various grades of stainless steel exposed to synthetic body fluids

Release rates of individual alloy constituents have been determined from seven grades of stainless steels exposed to two synthetic body fluids, used as surrogates for different areas of potential exposure in the lung: “Gamble’s solution”, (pH 7.4) that represents the interstitial fluid of the deep lung, and artificial lysosomal fluid (ALF) that represents the more acidic (pH 4.5-5) milieu of particles following their phagocytosis by macrophages. Total metal release rates from all grades of stainless steel investigated were low (<5 μg cm⁻² week⁻¹). The more acidic environment of ALF resulted in significantly higher total metal release rates (0.3-4.6 μg cm⁻² week⁻¹) compared to Gamble’s solution (<0.1 μg cm⁻² week⁻¹).     

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).     

Improvement in the corrosion resistance of TiB2/A356 composite by molten-salt electrodeposition and anodization

This study reported a novel treatment to improve the corrosion resistance of TiB₂/A356 composites. The method was employed in combination of the molten-salt electrodeposition and subsequent electrochemical anodization technique. By means of molten-salt electrodeposition, the Al coatings were deposited on the surface of TiB₂/A356 composites. It was found that the morphology of the Al coatings is closely related to the current density. Thus, under the suitable condition, a dense and uniform Al coating can be obtained, with the crystal size in the range of 0.5–2 μm and the coating thickness of ~ 9 μm. This continuous Al layer can eliminate the adverse corrosion contribution of TiB₂ particles in Al matrix. The following step of anodization was designed to convert the Al film to an anodized Al oxide film for further corrosion protection. The electrochemical corrosion behavior was evaluated by potentiodynamic polarization curves and electrochemical impedance spectroscopy. These results showed the corrosion resistance was greatly enhanced in TiB₂/A356 composites with an anodized Al-coating than that of the anodized composites. It is evident that the new treatment of metal electrodeposition in molten salts and following anodization is an effective method of anti-corrosion in composites.     

Long-term atmospheric corrosion properties of thermally sprayed Zn,Al and Zn–Al coatings exposed in a coastal area

The long-term atmospheric corrosion properties of thermally sprayed Zn, Al and Zn–Al coatings have been evaluated using an electrochemical impedance measurement and several analytical techniques. All the thermal-sprayed specimens with 100 μm coating thickness have protected the steel substrates. In case of the Zn–Al coating, the red rust was not observed regardless of the coating thickness. The corrosion products were identified by the XRD analysis. Preferential dissolution of zinc was observed on the Zn–Al coating by EPMA analysis. The electrochemical impedance results provided an insight about the surface structures of each thermally sprayed coating.     

Corrosion evaluation of microarc oxidation coatings formed on 2024 aluminium alloy

Dense alumina ceramic coatings of 7 μm thickness were fabricated on 2024 aluminium alloy by microarc oxidation (MAO). The corrosion behaviour of the MAO coated alloys was evaluated using potentiodynamic polarisation and EIS measurements. The results show that the corrosion process of the coated alloy can be divided into three stages: (1) the initial stage (the first 2-6 h of immersion): penetration of corrosion medium into the aluminium alloy was inhibited by coating; (2) the second stage (after 24 h of immersion), corrosion medium penetrated to attack the interface between the substrate and the coating; (3) the final stage (after about 96 h): corrosion process was controlled by the diffusion of corrosion products.     

Electrochemical characterisation of the porosity and corrosion resistance of electrochemically deposited metal coatings

Electrochemical techniques for the assessment of porosity in electrodeposited metal coatings are reviewed. The determination of porosity and corrosion, resistance is illustrated by electrochemical data from three coating/substrate systems namely: electroless nickel on aluminium and steel and immersed gold coatings on an electroless copper-plated ABS polymer. Nickel coatings were up to 24 μm thick while gold deposits had thickness between 75 and 190 nm. Tafel extrapolation and linear polarisation resistance methods were used to determine the corrosion rate of the coated substrates. The aluminium samples were tested in 5% w/v (0.85 mol dm^− 3) NaCl, while coated steel and ABS samples were immersed in 0.125 mol dm^− 3 H₂SO₄ and 0.1 mol dm^− 3 NaBH₄, respectively, at 295 K. Current vs. time curves and anodic polarisation behaviour have also been considered.     

Zinc modified polypyrrole coating on mild steel

Polypyrrole (PPy) films (∼ 1.7 μm thick) have been electrodeposited on mild steel (MS) substrates from 0.1 M pyrrole containing aqueous oxalic acid solution, by using cyclic voltammetry technique. Then, the polymer coatings were modified with deposition of zinc particles (∼ 1 mg/cm²), at a constant potential value of − 1.20 V in 0.2 M ZnSO₄ solution. The corrosion performance of zinc modified PPy coating has been investigated in 3.5% NaCl solution, by using electrochemical impedance spectroscopy and anodic polarisation curves. Also, the corrosion behaviours of zinc modified PPy coated platinum and single PPy coated MS samples have been investigated, for comparison. It was shown that zinc modified coating exhibited very low permeability and provided important cathodic protection to MS for considerably long immersion period. The voluminous zinc corrosion products are formed during exposure time in aggressive solution, giving rise to a blocking effect on the porous structure and led to effective barrier behaviour of zinc modified PPy coating, even after 96 h of exposure time to corrosive solution.     

The atmospheric corrosion of copper at two sites in Portugal: a comparative study

This paper presents a comparative study on the atmospheric corrosion of copper, at two sites, in Portugal, with exposures started in two different seasons (summer and winter). Particular attention is devoted to the initial stages of the corrosion process.The levels of pollutants, namely of SO₂ and chlorides, in both atmospheres, have been measured, over the periods from August 1999 to July 2000 and from November 2000 until July 2001. Climatic data for both sites and both periods has been collected and analysed.Kinetics of the corrosion process (weight losses) have shown to be described by: Δm=kt^0.6 and Δm=kt^0.4, with k equal to 3.4 (g m⁻² month^−0.6) and 17 (g m⁻² month^−0.4), for the one year exposures, started in summer, at the urban and maritime atmospheres, respectively. Exposures started in winter, at the urban atmosphere, have lead to kinetics described by Δm=kt^0.7 with k=5.0 (g m⁻² month^−0.7).The chemical composition and the morphology of the copper patinas, corresponding to exposures of 2 and 12 months, at the two sites, are compared as well as the morphology of the corroded surfaces.     

Corrosion behaviour of zinc deposits obtained under pulse current electrodeposition: Effects of coumarin as additive

The corrosion behaviour of zinc deposits obtained under pulsed current electrodeposition from an acidic chloride bath in the presence and absence of coumarin has been investigated. The effects of pulse peak current density (J_p) on the morphology of zinc deposits were studied by scanning electron microscopy. An increase in J_p from 40 to 280 A dm⁻² yields deposits with a finer grain size. The refinement of the grain size was more considerable in the presence of coumarin (J_p = 280 A dm⁻²). The preferred orientation of zinc deposits was studied by X-ray diffraction. At J_p = 40 A dm⁻², the preferred orientation of zinc deposits was (1 0 3) and changed to (0 0 2) at J_p = 80 A dm⁻². An increase in J_p to 280 A dm⁻² did not change the preferred crystallographic orientations except for an increase in the peak intensity of the (0 0 2) plane. In the presence of coumarin, the preferred crystallographic orientations changed at J_p = 280 A dm⁻² from the (0 0 2) plane to the (1 0 3) plane. The corrosion behaviour was investigated in an aerated 3.5% NaCl solution; the anodic polarization and electrochemical impedance spectroscopy curves were performed. The corrosion resistance of zinc deposits was improved by increasing the pulse peak current density (J_p); whereas, the presence of coumarin did not improve the corrosion resistance.     

Corrosion and metal release rates of Ni substrates under a porous gold coating

Noble metal coatings intended to protect devices from corrosion may have small porosity that allows corrosive fluid to attack the substrate alloy. A technique combining electrochemical tests and chemical analysis is described that measures low levels of porosity and low corrosion product release rates from the substrate. The technique has been applied to an electrodeposited gold coating on a nickel substrate. The results yielded a porosity of 1.8 × 10⁻³, defined as the area of substrate exposed to corrosion/area of the coating. Galvanic coupling between gold and nickel was found to increase the rate of nickel corrosion by about a factor of 10. A simplified model showed that if the substrate alloy does not passivate, the corrosion product release rate is expected to increase with exposure time.     

Pitting corrosion mechanism of Type 304 stainless steel under a droplet of chloride solutions

Pitting corrosion of Type 304 stainless steel under drops of MgCl₂ solution has been investigated to clarify the rusting mechanism in marine atmospheres. A pitting corrosion test was performed under the droplets with various combinations of the diameter and thickness (height) by exposure to a constant relative humidity. Probability of occurrence of pitting corrosion decreased with decreasing the diameter and thickness. Pitting corrosion progressed only when the [Cl⁻] exceeded 6 M (RH < 65%). In almost cases, there was a small hole (∼10 μm diameter) in the center of a single pit, which may be the trace of an inclusion particle like MnS dissolved out. The pitting corrosion mechanism of Type 304 under droplets containing chloride ions has been proposed.     

Effect of plasma surface treatment and heat treatment ambience on mechanical and corrosion protection properties of hybrid sol-gel coatings on aluminum

Hybrid sol-gel coatings derived from a base catalyzed hydrolysis of tetraethylorthosilicate and methyltriethoxysilane were deposited on aluminum substrates by a dip coating technique. Some of the coatings were deposited on substrates whose surfaces were pre-treated using atmospheric-air plasma prior to coating in order to study the effect of surface activation by plasma pre-treatment. The coated substrates were heat treated in different ambiences like air, flowing N₂ and vacuum to see the effect of heat treatment ambience on the properties of the coatings. Characterization of the coatings after heat treatment was carried out with respect to coating thickness, pencil scratch hardness, adhesion, water contact angle and their microstructure. Corrosion testing for all the coatings was carried out by electrochemical polarization measurements as well as electrochemical impedance spectroscopy in 3.5% NaCl solution for 1 h exposure time to investigate on their corrosion resistance. Coating thicknesses ranging from 1 μm-5 μm were obtained by varying the withdrawal speeds. Heat treatment in a controlled atmosphere with low oxygen content was seen to improve the hydrophobicity of coated surface, as measured by water contact angles (20^o — air; 71^o — N₂; 95^o — vacuum), thereby improving the corrosion resistance. Surface pre-treatment using open-air plasma was seen to improve the adhesion of the sol-gel coatings thus making it possible to obtain adherent and thick coatings in a single dip coating process. Both the methods of processing the coatings reduced the corrosion rate of aluminum from 1.95 mpy to 0.004 mpy in case of coatings densified in nitrogen and to 0.00068 mpy for coatings deposited on a plasma treated substrate and densified in air.     

Modelling the relationship between microstructure of Galfan-type coated steel and cut-edge corrosion resistance incorporating diffusion of multiple species

This paper describes a considerable extension to a previously documented [S.G.R. Brown, N.C. Barnard, 3D computer simulation of the influence of microstructure on the cut edge corrosion behaviour of a zinc aluminium alloy galvanized steel, Corrosion Science 48 (2006) 2291-2303], first-order model used to simulate the localized degradation experienced in Zn-4.5 wt% Al steel coatings exposed to 5% NaCl aqueous solution. The temporal localization and intensity of discrete corrosion effects are predicted using established relationships and, in contrast to earlier models, the evolution of multiple concentration fields is included and calculated using straight-forward finite difference techniques. Changes in composition are included in the quantification of both anodic and cathodic processes involved in the corrosion of steel coatings in contact with aerated saline solutions. Reported [J. Elvins, J.A. Spittle, D.A. Worsley, Microstructural changes in zinc aluminium alloy galvanising as a function of processing parameters and their influence on corrosion, Corrosion Science 47 (2005) 2740-2759] and modelled performances of typical Galfan composition coated steels are evaluated for different coating microstructures undergoing so-called cut-edge corrosion. In summary, this latest model successfully matches measured rates of metal loss during localized corrosion. Additionally, the inclusion of multiple species diffusion functionality has greatly improved the simulation of the cathodic reaction in particular and the overall form of the current density distribution near the corroding surface.