Studying phosphate corrosion inhibition at the cut edge of coil coated galvanized steel using the SVET and EIS

The work deals with the effect of sodium phosphate on the corrosion at the cut edge of electrogalvanized steel, studied by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and the scanning vibrating electrode technique (SVET). Mapping of the ionic currents revealed that in non-inhibiting solution, the cathode shifts away from the anode as zinc corrosion products precipitate along concentric whitish lines that result from the location of the peak cathodic current. Sodium phosphate inhibits corrosion at the cut edge by precipitation of gel-like zinc phosphate clusters with barrier properties. Breakdown and repassivation of this layer can occur under certain conditions.     

Modification of zinc powder to improve the corrosion resistance of weldable primers

This paper reports the modification of zinc powder to improve the corrosion resistance of weldable primers. These primers are thin zinc rich organic coatings applied by roll coating at the steel manufacturer. The automotive industry uses them to protect areas in the car body that become inaccessible after joining processes. In this work, with the objective of increasing the corrosion resistance of these systems, the zinc particles were chemically treated or simply replaced by powder of 55AlZn alloy. The rest of the formulation remained intact. The performance of the commercial and modified formulations was compared by SEM, SVET and EIS. The best results were obtained when the zinc powder was replaced by powder of the aluminium zinc alloy.     

Corrosion inhibition at galvanized steel cut edges by phosphate pigments

The corrosion mechanisms and the inhibiting effect of sodium phosphate at cut edges on galvanized steel was studied by potentiodynamic polarization, EIS and monitoring of local ionic currents made by means of the scanning vibrating electrode technique (SVET). Assessment of zinc and of iron single electrodes was also made for comparison.In the absence of phosphate, corrosion of electrogalvanized steel at the cut edge is cathodically inhibited by the precipitation of zinc corrosion products over the steel surface. Mapping of the ionic currents revealed that the cathodic area becomes laterally shifted away from the anode as zinc corrosion products precipitate along parallel lines that are dictated by the location of the maximum cathodic currents. Sodium phosphate revealed inhibiting properties on the cut edge by precipitation of zinc phosphate, in the form of gel-like zinc phosphate clusters. Estimated inhibiting efficiencies for the cut edge were slightly above 80%.     

Challenges of chromate inhibitor pigments replacement in organic coatings

General considerations concerning pigment grade corrosion inhibitors are presented and new characteristic functional parameters proposed. The chemistry, contemporarily practiced for corrosion inhibitor pigment synthesis, as well as known mechanistic considerations relevant to the corrosion inhibitor species available in pigment grades, are reviewed. Inherent limits of chemistry are outlined regarding the feasibility of developing equally effective and versatile non-toxic alternatives for chromates.

Fundamental aspects of corrosion inhibitor pigment behavior are discussed in the context of organic coatings degradation mechanisms. Disclosed experimental data demonstrate that correlation exists between solubility of corrosion inhibitor pigments, leaching from, and osmotic blistering of organic coatings. A mathematical expression is proposed and empirically proven to adequately describe the leaching rate of corrosion inhibitor pigments from organic coatings.

The barrier function of some high performance organic coatings, such as aircraft or coil, is negligible and requires the contribution of an effective corrosion inhibitor pigment, which, typically, is strontium chromate. In this context, the feasibility of replacing chromate inhibitor pigments is assessed and the “gap” observable between the inhibitor performance of chromates and traditional non-chromate pigments is noted.

Experimental data are displayed regarding the corrosion inhibitor performance of a novel, organic–inorganic, hybrid type corrosion inhibitor pigment in typical aircraft primer application on aluminum and plated steel. The presented data demonstrate the feasibility of chromate replacement in this specific case.     

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.     

Electrochemical and DFT studies of β-amino-alcohols as corrosion inhibitors for brass

The electrochemical performance of 1-diethylamino-propan-2-ol (EAP) and 1,3-bis-diethylamino-propan-2-ol (DEAP) for brass in simulated atmospheric water is evaluated by potentiodynamic curves and electrochemical impedance spectroscopy (EIS). The experimental results show that the investigated compounds, which can effectively retard the anodic dissolution of brass, are anodic inhibitors. Furthermore, the inhibition efficiency of DEAP is higher than that of EAP at the same concentration. This observation is supported by density functional theoretical (DFT) parameters such as the highest occupied molecule energy level (E_HOMO), the lowest unoccupied molecule energy level (E_LUMO), the energy difference (ΔE) between E_HOMO and E_LUMO, Mulliken charges and the HOMO orbital.     

Electrochemical assessing corrosion inhibiting effects of zinc aluminum polyphosphate (ZAPP) as a modified zinc phosphate pigment

Undesirable anti-corrosion performance of zinc phosphate pigment, the classical chromate replacement, has led researchers to take modification into account. Polyphosphate-based anti-corrosion pigments as a result of modification of zinc orthophosphate have been found to function much more efficiently. This study aimed to evaluate performance of steel samples immersed in 3.5% NaCl aqueous solution-containing zinc aluminum polyphosphate (ZAPP) pigment extract compared to those involving conventional zinc phosphate (ZP) pigment extract and also no pigment (blank) using electrochemical tests such as electrochemical impedance spectroscopy (EIS) and linear polarization (LP) as well as surface analysis. Impedance spectra and polarization curves revealed two different trends, showing the superiority of ZAPP pigment. Based on the results of scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX), presence of a precipitated layer on the surface was confirmed when steel sample was immersed into the solution-containing ZAPP.     

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.     

Evaluation of the corrosion resistance of phosphate coatings obtained by anodic electrochemical treatment

The corrosion resistance of phosphate coating obtained by anodic electrochemical treatment at 4–6 mA/cm² is addressed in this paper. The corrosion performance of these coatings is also compared with the coatings obtained by chemical treatment. The regenerated phosphoric acid under the influence of anodic current causes a large variation in morphological features of the coatings. Immersion and salt spray tests indicate the ability of these coatings to act as a barrier film on mild steel. Polarization and electrochemical impedance spectroscopic (EIS) studies indicate that the corrosion resistance of phosphate coatings obtained by anodic treatment decreases with increase in current density employed for deposition. In spite of their higher coating weight, the corrosion resistance of phosphate coatings obtained by anodic treatment is inferior to those obtained by chemical treatment. The porosity or discontinuities created due to the dissolution of the coating under the influence of anodic current are considered responsible for the inferior corrosion resistance of these coatings. The study concludes that anodic treatment has only a limited scope for preparing phosphate coatings with improved corrosion resistance.     

The role of chromate in filiform corrosion inhibition

This paper is part of a study on filiform corrosion (FFC) on aluminum alloy 2024-T3 and focuses on the surface characterization of corroded samples. Untreated samples were used as well as samples which had undergone pretreatments including polishing, surface etching and chromated conversion coatings (CCC). These samples were coated with both pigmented and non-pigmented epoxy-based coatings. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS) analysis was used to investigate the nature of the surface as well as optical images to gauge the rate of FFC advancement. FFC corrosion rates decreased on samples which had received a surface etching pretreatment and a chromate conversion coating. Pigmented coatings reduced the rate of FFC further and led to two different types of corrosion surface morphology. On pretreated samples, the corrosion appeared deeper and pit-like, possibly due to an enhanced polymer-substrate bond. On untreated samples, widespread FFC developed. SEM and EDX analysis of various intermetallic particles (IMPs) on all samples, inside and outside of corroded regions, revealed that Cr from pigments was found deposited on Cu-containing intermetallics in corroded areas while Fe/Mn-containing particles were free from all pigment traces. These results suggest that the Cr deposition on Cu particles hinders the cathodic reduction of oxygen necessary for FFC advancement. For this reason, the coating pigments proved, under FFC conditions, to be a more effective inhibitor than the Cr originating from a chromate conversion coating.     

Zinc hypophosphite: a suitable additive for anticorrosive paints to promote pigments synergism

In this investigation, the synergism promoted by zinc hypophosphite in an anticorrosive pigment mixture is reported. This paper describes the anticorrosive behavior of a commercial pigment mixture containing zinc hypophosphite, reduced levels of zinc phosphate, and zinc oxide. The anticorrosive performance of the pigment mixture was assessed by electrochemical techniques (corrosion potential and linear polarization measurements) employing pigment suspensions. The behavior of each separate component of the mixture was also studied in the same way. The nature of the protective layer was investigated by scanning electron microscopy (SEM). In a second stage, the anticorrosive properties of the pigment were assessed by incorporating it into alkyd and epoxy paints that were evaluated by accelerated (salt spray and humidity tests) and electrochemical measurements. Experimental results showed that improved anticorrosion protection is achieved in paints with reduced zinc phosphate contents as a consequence of the synergistic interaction between zinc hypophosphite and the other components of the pigment mixture.     

Corrosion electrochemical behavior of epoxy anticorrosive paints based on zinc molybdenum phosphate and zinc oxide

Electrochemical impedance spectroscopy (EIS) was applied as a principal tool to describe the efficiency of anticorrosive epoxy paints (primers) based on zinc molybdenum phosphate (ZMP) pigment. Steel-coated samples were exposed to a 0.5 M NaCl solution. During the study the corrosion potential (E_oc) and R_p values also were monitored every 24 h. It is discussed the incorporation of micronized ZnO (1 μm) pigment to the base mixture and its positive, reinforcement effect on the protective properties of ZMP primer. The explanation is related to the izoelectric point (IEP) of ZnO particles (pH < 9), which determines their positive surface charge and electrostatic attraction with the molybdate anion. In this case the charge of the formed double layer capacitor is very high. Moreover, the mentioned attraction inhibits and saves ZnO particles from their rapid dissolution to hydroxide.     

A SVET investigation on the modification of zinc dust reactivity

Weldable primers are thin zinc-rich organic coatings that are weldable due to the electrical conductivity provided by the zinc dust. They are used in the automotive industry to provide corrosion protection in regions of difficult access. The zinc particles are highly susceptible to corrosion attack and, due to the small thickness, the protection conferred by these systems is limited.     

Effect of the surface modification of zinc powders with organosilanes on the corrosion resistance of a zinc pigmented organic coating

The surface modification of zinc particles using aqueous organosilane (OS) solutions was conducted to improve the anti-corrosion performance of zinc pigmented organic coatings (ZPC). The surfaces of modified zinc particles were characterized by scanning electron microscopy (SEM), the electrochemical polarization method and glow discharge spectrometry (GDS).     

Sodium zinc phosphate as a corrosion inhibitive pigment

A sodium zinc phosphate pigment synthesized using a co-precipitation method and characterized by X-ray diffraction was investigated for its corrosion inhibition activity in comparison with the commercial zinc phosphate using EIS in a 3.5% NaCl solution. A mild steel surface analysis after exposure to the test solutions was conducted using scanning electron microscope-energy dispersive X-ray and infrared spectroscopies. The results indicate that the corrosion inhibitive performance of the synthesized pigment is higher than that of the commercial zinc phosphate. This can be the result of the synthesized pigment's relatively high solubility, which affects the precipitation of a phosphate layer onto the mild steel surface and the modification of the crystalline structure of the corrosion products in the presence of the inhibitive pigment. The salt spray and wet pull-off tensile strength results revealed an improved corrosion protection of the coatings formulated with SZP.     

Electrosynthesis of polyaniline–molybdate coating on steel and its corrosion protection performance

Electrosynthesis of polyaniline–molybdate (PANI–MoO₄²⁻) on mild steel was achieved in oxalic acid medium using cyclic voltammetry technique. Adherent and homogeneous PANI–MoO₄²⁻ coating was obtained. The corrosion behavior of steel with PANI–MoO₄²⁻ coatings in 1% NaCl solutions was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy techniques. The coating was characterized by SEM, XPS, EDAX and FTIR. The self-healing ability of PANI–MoO₄²⁻ coating was confirmed by SVET technique. It has been found that the PANI–MoO₄²⁻ coating is able to offer higher corrosion protection in comparison to that of pure PANI coating due to inhibitive nature of molybdate ions.     

Electrochemistry and surface analysis of the effect of benzotriazole on the cut edge corrosion of galvanized steel

The effect of benzotriazole (BTAH) in high concentration on the cut edge corrosion of galvanized steel in sodium chloride solution was studied, using electrochemical polarization, EIS, SVET and XPS. It was observed that there is the formation of a BTAH surface film on both steel and zinc, which polarizes anodically both metals, greatly reducing their electrochemical activity and changing the rate control from diffusion at the cathode to mixed control. The protective film undergoes numerous events of local activation and repassivation. The XPS data revealed that the BTAH becomes differently bound to zinc depending on the metal being under self-corrosion or coupled to steel. Although the BTAH reduces the electrochemical activity of both materials, there is significant reduction of the cathodic protection effect of zinc.     

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%.     

Anticorrosive behaviour of alkyd paints formulated with ion-exchange pigments

Hexavalent chromium compounds (chromates) have been widely used as inhibitive pigments in the formulation of anticorrosive paints. However, their high toxicity and carcinogenic effects are forcing the development of effective chromate-free organic coatings. One such alternative, which is very attractive from a scientific point of view, is the use of ion-exchangeable pigments (IEPs).

The few studies conducted with this type of pigment are not conclusive about their anticorrosive efficiency and controversy surrounds their functioning mechanisms, interchange capacity and anticorrosive performance.

In the present research, which focuses on the anticorrosive protection of this type of pigment, alkyd paint coatings formulated with vanadate-hydrotalcite (HT/V) (anionic) and calcium/silica (Ca/Si) (cationic) IEPs have been applied on low carbon steel specimens. A traditional zinc chromate pigment has also been used for comparative purposes.

The effect of these non-toxic pigments on the protective properties of coatings has been tested by means of natural and accelerated corrosion tests (humidity, salt spray and Kesternich, 0.2 l SO₂) and electrochemical impedance spectroscopy (EIS).

None of the IEPs equalled the anticorrosive behaviour of the zinc chromate in the different tests. The anionic pigment (HT/V) seems to present good behaviour in chloride environments (salt spray, NaCl solutions, etc.) while the cationic pigment (Ca/Si) performs well in the humidity condensation and SO₂ tests.     

Some environmentally friendly formulations as inhibitors for mild steel corrosion in sulfuric acid solution

The corrosion resistance of mild steel in 1 M H₂SO₄ solution was evaluated after addition of Sn²⁺ and Zn²⁺, N-acetylcystein (ACC) and S-benzylcystein (BzC) as a function of concentration (5–1000 μM) and solution temperature (35–50°C). Eight blends were also investigated. Both polarization resistance (R _p) and electrochemical impedance spectroscopy (EIS) were employed. For single additives, Zn²⁺ ions acted as accelerator for mild steel corrosion while the other additives showed good performance. The most effective additive was Sn²⁺. Adsorption of Sn²⁺, ACC and BzC obeyed the Temkin adsorption isotherm and had a very high negative value of free energy of adsorption (−ΔG°_ads). All blends provided good inhibition which increased with rise in temperature. Corrosion kinetic parameters such as activation energy (E _a) and the pre-exponential factor (λ) were calculated and discussed. EIS revealed that the interface of the uninhibited and inhibited systems can be represented by the simple equivalent circuit R _e(R _ct Q _dl).