Distribution of pH during galvanic corrosion of a Zn/steel couple

The spatial distribution of pH during galvanic corrosion of a model Zn/steel couple immersed in 0.01 M NaCl was investigated using a scanning tungsten pH electrode. The couple consisted of a steel substrate with a 3 μm-thick layer of zinc electroplated at its center. During galvanic corrosion, marked changes in pH occurred, which were confined to a thin layer of solution ca. 1.5 mm over the couple surface. As the surface was approached, the pH over the zinc layer decreased slightly from ca. 5.6 in the original bulk solution, while the pH over the steel surface distant from the zinc layer increased to ca. 11.5. The area of low pH extended not only over the zinc layer, but also over the steel surface adjacent to the zinc. Zinc corrosion products precipitated in the region of high pH. The pH distribution arising from the galvanic corrosion of the couple is discussed in terms of the potential distribution and the morphology of the precipitated zinc corrosion products.     

Effect of Al on the galvanic ability of Zn-Al coating under thin layer of electrolyte

The effect of Al on the galvanic ability of Zn-Al coating has been studied under thin electrolyte layers by measuring surface potential and surface pH. The changes of surface potential and surface pH over Zn-Al/steel galvanic couple corroding in artificial sea water (ASW) were measured at 60% and 90% RH at 298 K. In the initial stage of corrosion, Zn-55Al coating has shown better galvanic protection ability than Zn-5Al coating in both 60% and 90% RH. However, Zn-5Al coating was better in long term corrosion. The better galvanic ability of Zn-55Al coating in the initial stage of corrosion was related to the observation of pH as low as low as 2 on its surface. The low pH value was due to hydrolysis of Zn²⁺ and Al³⁺ ions. The low pH value was further confirmed by observing evolution of gas due to H⁺ reduction on the Zn-55Al coating. With the progress of corrosion, the low pH region of coating layer extended towards the base steel. This helped expand the deposition of zinc corrosion products on the steel surface. The enhanced dissolution of zinc in Zn-55Al coating led to the formation of a barrier layer which limited the galvanic protection of remaining steel. This was not the case in Zn and Zn-5Al coating. The X-ray analyses of the corroded samples have shown the deposition of zinc corrosion products on the steel surface, which greatly depended on the RH value. The part of the steel surface covered with zinc corrosion products has shown relatively less noble potential than other part indicating that zinc corrosion products took a role to protect the base steel against corrosion. The results from surface potential and surface pH measurements were substantiated by the surface observation of the corroded sample during and after the corrosion test.     

Inhibition of corrosion-driven organic coating disbondment on galvanised steel by smart release group II and Zn(II)-exchanged bentonite pigments

Bentonite pigments exchanged with either zinc or group II cations are characterised as inhibitors of corrosion-driven cathodic disbondment of model polyvinylbutyral (PVB) coatings adherent to the intact zinc surface of hot dip galvanised steel. An in situ scanning Kelvin probe (SKP) technique is used to quantify rates of coating delamination as a function of pigment volume fraction (?_pt) and draw up a ranking order of inhibitor efficiency. Group II cation-exchanged bentonites show a moderate degree of inhibition, where rates of coating disbondment are reduced by up to 60-70% compared to the unpigmented case. In contrast, bentonite pigments containing exchangeable Zn²⁺ ions are markedly more effective, and no delamination is observed over periods of up to 24 h when ?_pt ≥ 0.1. The efficiency of in-coating Zn²⁺ is attributed to the ability to block underfilm cathodic oxygen reduction by reinforcing a pre-existing zinc (hydr)oxide layer.     

Surface potential distribution over a zinc/steel galvanic couple corroding under thin layer of electrolyte

In this study, surface potential and surface pH changes over a zinc/steel galvanic couple corroding in artificial seawater (ASW) at 60 and 90% RH have been investigated. The results from surface potential and surface pH measurements were substantiated by the surface observation of the corroded sample during and after the corrosion test. The potential difference over the zinc and steel surface in 90% RH was very low (less than 200 mV) showing that whole steel surface was under galvanic protection. On the other hand, in 60% RH, after several days of corrosion the potential difference between the zinc coating and the steel surface was very high (more than 500 mV) and hence the galvanic protection was limited to interface region. The X-ray analysis of the sample corroded in 60% RH has shown that the zinc corrosion products were deposited on the steel surface near the interface, the same region has shown a low pH compared to than in other part of the steel surface. This led to conclude that with the progress of corrosion, the coating surface of zinc coated steel acidifies by the hydrolysis reaction of the dissolved zinc ions, and the iron surface showed the alkalinity by the oxygen reduction reaction. Moreover, the parts of the steel surface covered with zinc corrosion products had developed relatively less noble potential than other parts indicating that zinc corrosion products took a role to protect the base steel against corrosion. It was assumed that this behavior was related to a combination of the water absorbing capability of zinc corrosion products and adsorption of zinc ion on the steel surface due to low pH.     

Polyaniline for corrosion prevention of mild steel coupled with copper

Polyaniline emeraldine base/epoxy resin (EB/ER) coating was investigated for corrosion protection of mild steel coupled with copper in 3.5% NaCl solution. EB/ER coating with 5-10 wt% EB had long-term corrosion resistance on both uncoupled steel and copper due to the passivation effect of EB on the metal surfaces. During the 150 immersion days, the impedance at 0.1 Hz for the coating increased in the first 1-40 days and subsequently remained constant above 10⁹ Ω cm², whereas that for pure ER coating fell below 10⁶ Ω cm² after only 30 or 40 days. Immersion tests on coated steel-copper galvanic couple showed that EB/ER coating offered 100 times more protection than ER coating against steel dissolution and coating delamination on copper, which was mainly attributed to the passive metal oxide films formed by EB blocking both the anodic and cathodic reactions. Salt spray tests showed that 100 μm EB/ER coating protected steel-copper couple for at least 2000 h.     

Multicomponent isotherms for biosorption of Ni and Zn

The capability of wheat straw to adsorb Ni²⁺ and Zn²⁺ was investigated using a batch system. The equilibrium removal of metal ions was obtained between 2.5 and 5 h for Ni²⁺ and about 3 h for Zn²⁺ over the initial concentration range from 5 to 150 ppm. Of the total amount of metal uptake by wheat straw, about 50% was adsorbed in the first 30 min. At a low initial concentration of 5 ppm, wheat straw was capable to reduce the metal concentration down to less than 1 ppm. For single-metal solutions, among the three models tested, namely the Langmuir, the Freundlich and the Temkin isotherms, the Freundlich model was suitable to describe the adsorption equilibrium for Ni²⁺ and Zn²⁺. For bimetal solutions, the IAST-Freundlich multicomponent isotherm best fitted the experimental data, among the four isotherm models investigated, the modified Langmuir multicomponent model, the Langmuir partially competitive model, the Freundlich multicomponent model and the IAST-Freundlich multicomponent model. The negative Gibbs free energy changes obtained at lower concentrations indicates that the adsorption was spontaneous. However, the spontaneity of the biosorption decreased with increases in the metal concentration from 5 to 50 ppm. For metal concentrations higher than 50 ppm, the adsorption became non-spontaneous. Scanning electron microscopic (SEM) images of wheat straw were also taken to exam the surface structure of the wheat straw along with the energy dispersive spectrum (EDS) analysis. The results obtained confirmed the adsorption of Ni²⁺ and Zn²⁺ on wheat straw, and showed that the inner surface of the wheat straw appeared to provide more adsorption sites for metal binding.     

The improvement of anticorrosion properties of zinc-rich organic coating by incorporating surface-modified zinc particle

The corrosion behaviors of zinc-rich coating with various zinc contents, ranging from 0 to 60 volume percent, in thin organic coatings (below 5 μm) were characterized by electrochemical impedance spectroscopy (EIS), free corrosion potential (E_corr) measurement and cycle corrosion test (CCT). It was verified that both coatings with 60 volume percent of zinc powder and without zinc powder showed good corrosion resistance mainly due to the cathodic protection and barrier effect, respectively. On the other hand, coatings with an intermediate concentration (10–40 vol.%) of zinc powder was not successful in protecting a steel substrate efficiently. To improve anticorrosion property of zinc-rich coating, the surface modification of zinc particle was carried out with derivatives of phosphoric and phosphonic acid in the aqueous solution. The effects of the surface modification of zinc particle on corrosion resistance of the coating were investigated with scanning vibrating electrode technique (SVET) and X-ray photoelectron spectroscopy (XPS). The best anti-corrosion performance was achieved when the incorporated zinc particle was treated with phosphoric acid 2-ethylhexyl ester and calcium ion simultaneously, which induced the formation of alkyl-phosphate-calcium complex layer of 190 nm in thickness on zinc particles. Corrosion resistance was improved by the decreased zinc activity and the increased compatibility between the formed complex layer on zinc surface and polymer binder matrix.     

Synergistic effect of tolutriazol and sodium carboxylates on zinc corrosion in atmospheric conditions

During the transport or the storage, galvanized steel products undergo the wet storage stain phenomenon, leading to the formation of unsightly and extensive white rust of zinc. In the context of development of temporary protection to replace mineral oils, the present study is focused on the combined action of sodium heptanoate (CH₃(CH₂)₅COONa, noted NaC₇) and 3-methyl benzotriazol (named tolutriazol, TTA) on zinc corrosion. Stationary and dynamic electrochemical measurements have shown that the association of NaC₇ and TTA provokes the formation of insoluble and hydrophobic passive layer, and lead to a positive synergy between the anodic and cathodic inhibiting actions of the two respective compounds. According to XPS and MEB analysis, the protective material is a layer containing zinc cation, heptanoate anion and TTA molecules, formed by a mechanism of precipitation on the zinc surface. In accordance with the coordination properties between Zn²⁺ and TTA determined by pH titration, the TTA molecules is trapped in a zinc soap, probably in a compound, Zn(TTA)₂(C₇)₂, which explains the efficiency of this formulation in the climatic chamber test.     

Investigation on the inhibition effect of aspartic acid and Zn2+ ions on carbon steel surface in aqueous solution

A protective film has been formed on the surface of carbon steel in aqueous environment using a synergistic mixture of an environment-friendly inhibitor, aspartic acid, and Zn²⁺. The synergistic effect of aspartic acid (AS) in controlling corrosion of carbon steel has been investigated by gravimetric studies in the presence of Zn²⁺. The formulation consisting of AS and Zn²⁺ has an excellent inhibition efficiency. The results of potentiodynamic polarization revealed that the formulations are of mixed-type inhibitor. Impedance studies of the metal/solution interface indicated that the surface film is highly protective against the corrosion of carbon steel in the aqueous environment. X-ray photoelectron spectroscopic analysis of the protective film showed the presence of the elements iron, nitrogen, oxygen, carbon, and zinc. The spectra of these elements in the surface film showed the presence of oxides/hydroxides of iron(III), Zn(OH)₂, and [Fe(III)/Fe(II)–Zn(II)-AS] complex. Further, surface characterization techniques such as Fourier transform infrared spectroscopy, scanning electron microscopy, and atomic force microscopy are used to ascertain the nature of the protective film formed on the carbon steel surface.     

Oxygen reduction reaction on electrodeposited zinc oxide electrodes in KCl solution at 70 °C

The reduction of oxygen was studied in 0.1 M KCl at 70 °C using the rotating disk electrode (RDE) technique on platinum and electrodeposited ZnO thin film electrodes deposited on platinum substrates. In the absence of Zn²⁺ ions in solution, a Tafel slope of 139 mV dec⁻¹ was obtained, a value close to that measured on bare platinum electrode (133 mV dec⁻¹) and ascribed to the limitation of the reaction rate by the first electron transfer. The main difference between the noble metal and the oxide electrode was a shift of the curves towards more negative potentials. In the presence of Zn²⁺ ions, the current density decreased significantly and the Tafel slope was measured at 282 mV dec⁻¹ showing that the electrode was partially blocked by zinc oxide formation reaction intermediates.     

Electrochemical studies on the alternating current corrosion of mild steel under cathodic protection condition in marine environments

Alternating current (AC) corrosion of mild steel in marine environments under cathodic protection (CP) condition was studied. Electrochemical studies at the two protection potentials namely −780 and −1100 mV versus SCE were examined by different techniques. DC polarization study was carried out for mild steel in natural seawater and 18.5 g/L NaCl solution to evolve corrosion current density. The corrosion rate determination, pH of the end experimental solution and surface morphology of the mild steel specimens under the influence of different AC current densities were studied. The amount of leaching of iron into the solution was estimated using inductively coupled plasma spectrometry. All these techniques revealed that AC influences the corrosion of mild steel in the presence of marine environments even though CP was given. Surface micrographs revealed that spreading of red rust products noticed on the mild steel surface. At −780 mV CP, red rusts are visually seen when the AC source was above 10 A/m² in both the media but red rusts are appeared after 20 A/m² in the case of −1100 mV CP. Weight loss measurements coupled with surface examination and solution analysis is a effective tool to characterize and quantify the AC corrosion of mild steel in marine environments.     

Protective mechanisms occurring on zinc coated steel cut-edges in immersion conditions

Electrochemical processes occurring on the cut-edge of a galvanized steel immersed in NaCl solutions were studied using numerical simulations, and in situ current and pH profiles measured over the cut-edge. These results clearly demonstrate that only the steel surface remote from the zinc coating is cathodically active, oxygen reduction being strongly inhibited in the vicinity of zinc. This trend was confirmed by local polarization curves recorded on these distinct areas. Ex-situ AES and SEM analysis and cathodic polarization curves in solutions containing Zn²⁺ ions led to conclude that this cathodic inhibition was related to the fast nucleation of a dense Zn(OH)₂ film on the steel surface. After a long term exposure, a new galvanic coupling takes place between the Zn(OH)₂ covered area, showing an anodic activity, and the remaining steel surface covered by bulky white zinc corrosion products.     

AISI 304 L stainless steel decontamination by a corrosion process using cerium IV regenerated by ozone Part I: Study of the accelerated corrosion process

This paper describes the study of a new decontamination process of AISI 304L stainless steel from dismantled nuclear power plants. A very thin active contaminated surface layer was stripped from the underlying metal by corrosion in a solution of nitric acid with the addition of cerium nitrate. The Ce⁴⁺/Ce³⁺ concentration ratio was initially equal to unity and ozone/oxygen bubbles were used to regenerate Ce³⁺ ions into Ce⁴⁺ ions. The study was performed in a laboratory cell prior to preliminary optimization in a three-litre reactor. The objective was to obtain a corrosion rate of about 10 micrometers per day. This target was reached in 10^–2 mol l^–1 of cerium nitrate with bubbling of a 1.56 g h^–1 ozone flow in a 60 l h^–1 total gas flow. The corrosion rate depended essentially on the Ce⁴⁺ concentration. The stainless steel exhibited intergranular corrosion. The corrosion rate was monitored by measuring the solution oxidizing potential using a precious metal electrode.     

The anodic dissolution of zinc and zinc alloys in alkaline solution. I. Oxide formation on electrogalvanized steel

The polarization behaviour of zinc in alkaline solution has been investigated using atomic emission spectroelectrochemistry. By independently measuring the oxidation rate of zinc (electrical current) and the rate of Zn²⁺ dissolution (partial elemental current) it is possible to calculate the amount of insoluble zinc cations produced at any instant. Assuming the insoluble cations are present as a zinc oxide film, the growth of this film as a function of potential and time was determined. On the basis of kinetic evidence, it was found that at least three forms of zinc based oxide/hydroxide films form during polarization experiments. Type I oxide formation occurs when the metal/electrolyte interface becomes locally saturated with Zn²⁺ ions. Type II oxide forms on the metal surface underneath the film of Type I oxide but has little inhibiting effect on zinc dissolution. Type III oxide is produced in much smaller quantity and results in a transition to the passive state. This may be due to a potential induced transition of Type II → Type III oxide.     

Diluted chemical bath deposition of CdZnS as prospective buffer layer in CIGS solar cell

In this study, dilute chemical bath deposition technique has been used to deposit CdZnS thin films on soda-lime glass substrates. The structural, morphological, optoelectronic properties of as-grown films have been investigated as a function of different Zn²⁺ precursor concentrations. The X-ray diffractogram of CdS thin-film reveals a peak corresponding to (002) plane with wurtzite structure, and the peak shift has been observed with the increase of the Zn²⁺ concentration upon formation of CdZnS thin film. From morphological studies, it has been revealed that the diluted chemical bath deposition technique provides homogeneous distribution of film on the substrate even at a lower concentration of Zn²⁺. Optical characterization has shown that the transparency of the film is influenced by Zn²⁺ concentration and when the Zn²⁺ concentration is varied from 0 M to 0.0256 M, bandgap values of resulting films range from 2.42 eV to 3.90 eV while. Furthermore, electrical properties have shown that with increasing zinc concentration the resistivity of the film increases. Finally, numerical simulation validates and suggests that CdZnS buffer layer with composition of 0.0032 M Zn²⁺ concentration would be a promising candidate in CIGS solar cell.     

Enhanced corrosion inhibition behavior of carbon steel in aqueous solution by Phosphoserine-Zn2+ system

The corrosion inhibition effect of carbon steel in aqueous solution was using a synergistic mixture of an environmentally friendly inhibitor system phosphoserine (PS) and Zn²⁺ using gravimetric studies, potentiodynamic polarization, and electrochemical impedance studies. Potentiodynamic polarization studies showed that the inhibitor system is a mixed type inhibitor. Electrochemical impedance studies of the metal/solution interface indicated that the surface film is highly protective against the corrosion of carbon steel in the aqueous solution. X-ray photoelectron spectroscopic analysis of the protective film exhibited the presence of the elements viz., iron, phosphorus, nitrogen, oxygen, carbon, and zinc. The chemical shifts in the binding energies of these elements inferred that the surface film is composed of oxides/hydroxides of iron, Zn(OH)₂, and [Fe(II)/(III)-Zn(II)-PS] complex. Further, the surface examination techniques viz., FTIR, SEM, and AFM studies confirm the formation of an adsorbed protective film on the carbon steel surface. Based on the results obtained, a suitable mechanism of corrosion inhibition is presented.     

Factorial experimental design for biosorption of iron and zinc using Typha domingensis phytomass

Typha domingensis phytomass was used as a biosorbent for metal ions removal from wastewater. A full 2³ factorial design of experiments was used to obtain the best conditions of biosorption of Fe³⁺ and Zn²⁺ from water solutions. The three factors considered were temperature, pH, and biosorbent dosage. Two levels for each factor were used; pH (2.5 and 6.0), temperature (25 and 45 °C), and phytomass loading weight (0.5 and 1 g/50 ml). Batch experiments were carried out using 50 ml solutions containing 10 mg/l Fe³⁺ and 4 mg/l Zn²⁺ simulating the concentration of those metals in a real wastewater effluent. The removal percentages of iron and zinc after 120 min of contact time were then evaluated. The results were analyzed statistically using the Minitab 15 statistical software to determine the most important factors affecting the metals removal efficiency. The pH was found to be the most significant factor for the two studied metal ions.     

Performance of zinc phosphate coatings obtained by cathodic electrochemical treatment in accelerated corrosion tests

The formation of zinc phosphate coating by cathodic electrochemical treatment and evaluation of its corrosion resistance is addressed. The corrosion behaviour of cathodically phosphated mild steel substrate in 3.5% sodium chloride solution exhibits the stability of these coatings, which lasts for a week's time with no red rust formation. Salt spray test convincingly proves the white rust formation in the scribed region on the painted substrates and in most part of the surface on unpainted surface. The protective ability of the zinc corrosion product formed on the surface of the coated steel is evidenced by the decrease in the loss in weight due to corrosion of the uncoated mild steel, when it is galvanically coupled with cathodically phosphated mild steel. Potentiodynamic polarization curves reveal that E_corr shifts towards higher cathodic values (in the range of −1000 to −1100 mV versus SCE) compared to that of uncoated mild steel and conventionally phosphated mild steel substrates. The i_corr value is also very high for these coatings. EIS studies reveal that zinc dissolution is the predominant reaction during the initial stages of immersion. Subsequently, the non-metallic nature of the coating is progressively increased due to the formation of zinc corrosion products, which in turn enables an increase in corrosion resistance with increase in immersion time. The zinc corrosion products formed may consist of zinc oxide and zinc hydroxychloride.     

A-type zeolite containing Ag/Zn as inorganic antifungal for waterborne coating formulations

The biocide cations Ag⁺ and Zn²⁺ were hosted in the cavities of an ordered aluminosiliceous framework. Starting from sodium A-type zeolite (NaA), LTA containing Ag⁺ (AgA), Zn²⁺ (ZnA) and Ag⁺/Zn (AgZnA) at different cation exchanged levels was obtained and its antifungal properties were evaluated. To determine the minimum inhibitory concentration (MIC) of the exchanged zeolites against Aspergillus niger, [Ag⁺] and [Zn²⁺] values ranging from 50 < [Ag⁺] < 1000 mg L⁻¹ to 650 < [Zn²⁺] < 2000 mg L⁻¹, respectively, were used for NaA, and for AgZnA: 30 < Ag⁺ < 250 mg L⁻¹. The zeolite sample having [Ag⁺] = 100 mg L⁻¹, [Zn²⁺] = 90 mg L⁻¹ produces a growth inhibition comparable to that achieved with 230 mg L⁻¹ of Ag⁺¹ (MIC value obtained for the single cation). The antifungal activity of these products after incorporation in waterborne coating formulations was also determined. Results indicate that Ag⁺ and Zn²⁺ supported on A-type zeolite could be a beneficial tool for the development of waterborne coatings with a longer protection against microbiological attack when compared to traditional organic biocides.     

Investigation on zinc phosphate effectiveness at different pigment volume concentrations via electrochemical impedance spectroscopy

This research is based on studying corrosion inhibitive effect of zinc phosphate at different pigment volume concentration (PVCs) in epoxy-polyamide system. EIS has been examined at open circuit potential (OCP) after 7 days of immersion in 3.5% NaCl solution to indicate electrochemical properties of epoxy coated mild steel at different levels of pigmentation. Coating capacitance, coating resistance, double layer capacitance and charge transfer resistance have been extracted from fitting of EIS results with an electrical circuit, while impedance magnitude at 100 mHz and phase angle (θ) at 10 kHz have been extracted directly from bode plots. Also OCP behavior was examined. Results showed best performance at PVC = 36.5%.