Studying the corrosion protection properties of an epoxy coating containing different mixtures of strontium aluminum polyphosphate (SAPP) and zinc aluminum phosphate (ZPA) pigments

Epoxy/polyamide coatings were loaded with different mixtures of strontium aluminum polyphosphate (SAPP) and zinc aluminum phosphate (ZPA) pigments. Moreover, a coating containing zinc phosphate (ZP) was prepared as a reference sample. The coatings were applied on St-37 steel substrates and then were exposed to 3.5 wt% NaCl solution up to 35 days. The corrosion inhibition properties of the pigments extracts were studied on bare steel samples by a potentiodynamic polarization technique after 24 h immersion. The morphological properties and corrosion resistance of the coatings were investigated by scanning electron microscope (SEM), optical microscope, electrochemical impedance spectroscopy (EIS) and salt spray tests.     

Comparison of the efficiency of inorganic nonmetal pigments with zinc powder in anticorrosion paints

This paper deals with the study of properties of anticorrosion pigments of varying chemical composition in epoxyester paints. Two type lines of paints were prepared. The first line comprised an anticorrosion pigment with a PVC concentration of 10% while the other line comprised an anticorrosion pigment with a PVC concentration = CPVC. The following nontoxic anticorrosion pigments were observed: zinc phosphate, zinc phosphomolybdate, calcium hydrogen phosphate, zinc phosphate modified with an organic corrosion inhibitor, strontium–aluminum polyphosphosilicate, zinc–aluminum polyphosphate, calcium metaborate, calcium ferrite, calcium borosolicate, and strontium chromate. The epoxyester primers were observed for the effect of the type of pigment on the anticorrosion properties. Anticorrosion efficiency was derived from tests in a condenser chamber and in a salt spray cabinet as well as from a test of chemical resistance of pigmented coatings. The evaluation of anticorrosion efficiency of inorganic nonmetal pigments was carried out by means of comparison with anticorrosion efficiency of metal dust.     

Studies of iron corrosion inhibition using chemical, electrochemical and computer simulation techniques

The inhibitive action of some benzimidazole derivatives namely 2-(2-furanyl)-1H-benzimidazole (FB), 2-(2-pyridyl) benzimidazole (PB) and 2-(4-thiazolyl) benzimidazole (TB), against the corrosion of iron in solutions of nitric acid has been studied using density function theory calculations (DFT), weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The calculated electronic parameters involved in the activity of the benzimidazole derivatives confirmed that the position of the side chain in the benzimidazole moiety affects the pattern of activity. The effectiveness of the benzimidazole derivatives is following the order TB > PB > FB. The same order is supported by the experimental chemical and electrochemical measurements. The relationships between inhibition efficiency of iron in 1.0 M HNO₃ and the molecular orbitals of the studied molecules as well as number of electrons transferred ΔN from the inhibitor molecules to the iron surface were calculated by DFT method. The inhibition efficiency increased with the increase in E_HOMO and decrease in E_LUMO-E_HOMO. TB had the highest inhibition efficiency because it had the highest HOMO energy and ΔN values, and it was most capable of offering electrons. Molecular modeling was used to evaluate the structural, electronic and reactivity parameters of the selected benzimidazole derivatives in relation to their effectiveness as corrosion inhibitors. Results obtained from weight loss, dc polarization and ac impedance measurements are in reasonably good agreement and show increased inhibitor efficiency with increasing inhibitor concentration.Data obtained from EIS were analyzed to model the corrosion inhibition process through equivalent circuit.     

The effects of zinc aluminum phosphate (ZPA) and zinc aluminum polyphosphate (ZAPP) mixtures on corrosion inhibition performance of epoxy/polyamide coating

The epoxy/polyamide coating was loaded with different pigment mixtures of the zinc phosphate (ZP), zinc aluminum phosphate (ZPA) and zinc aluminum polyphosphate (ZAPP) pigments. The electrochemical impedance spectroscopy (EIS) and salt spray test were used to investigate corrosion inhibition performance of the coatings. The adhesion strengths of the coatings were measured by a pull-off test. Results revealed lower coating pull-off strength loss when the ZPA and ZAPP pigments were used. A significant decrease in number of blisters together with low pull-off strength loss and best corrosion inhibition properties were observed when the mixture of 80:20 of ZAPP:ZPA was used.     

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.     

Electrochemical polymerization and initial corrosion properties of polyaniline-benzoate film on aluminum

Electrochemical synthesis of polyaniline (PANI) on aluminum electrode from aqueous solution of 0.25 mol dm⁻³ aniline and 0.2 mol dm⁻³ sodium benzoate has been investigated under potentiodynamic and galvanostatic conditions. Initial corrosion behavior of aluminum and PANI coated aluminum electrode exposed to 3% NaCl has been investigated using electrochemical potentiodynamic and impedance spectroscopy technique (EIS). It was shown that PANI coating initially provide corrosion protection of aluminum, decreasing the corrosion current density at least 15 times.     

Investigation of the anodic behavior of Al current collector in room temperature ionic liquid electrolytes

We have investigated the anodic behaviors of aluminum as a cathodic current collector for lithium ion batteries in several kinds of room temperature ionic liquids (RTILs) and EC + DMC solutions containing LiN(CF₃SO₂)₂ by cyclic voltammetry (CV), chronoamperometry (CA), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry and chronoamperometry data showed that the current density for aluminum foil with the RTIL electrolytes was less than that of aluminum foil in the EC + DMC solutions. Besides, much corrosion pits appeared on the aluminum foil surface after the electrochemical measurement in the EC + DMC solutions, while they were not observed on the aluminum foil with the RTIL electrolytes, suggesting that aluminum current collector was stable in the RTIL electrolytes. Further research by EDX and XPS analysis revealed that a good passivating film composed mainly of the products from the oxidation between aluminum and the anions of the RTIL electrolytes on the aluminum foil surface after the anodic polarization which suppressed the aluminum corrosion.     

Effect of ball milling on the corrosion resistance of magnesium in aqueous media

The influence of the high-energy ball milling on the corrosion behavior of magnesium in aqueous media has been investigated through electrochemical experiments complemented by morphological, structural, chemical and surface analyses. The milling duration was varied from 0 to 40 h. Polarization curves show that the milling procedure improves the magnesium corrosion resistance in passive conditions (KOH solution) and in more active corrosion conditions (borate solution). This is illustrated by the corrosion potential which becomes nobler with milling. The variation of the polarization resistance and related corrosion current with milling time is also an indication of the improvement of the Mg corrosion resistance due to the milling. Moreover, the passive current is significantly lower for milled Mg. The Mg crystallite size is reduced from >100 to 34 nm after 10 h of milling and does not decrease significantly with further milling. The iron contamination of the Mg powder due to the erosion of the milling tools is very low (0.09 wt.% after 40 h of milling). In contrast, a significant oxygen contamination occurs during milling (2.6 wt.% after 40 h of milling). XPS and AES data indicate MgO enrichment in the bulk of the milled Mg without significant MgO increase at the powder surface. The corrosion improvement was attributed to the increase through the milling process of the density of surface defects and grain boundaries susceptible to increase the number of nucleation sites for Mg hydroxylation in aqueous media, leading to the rapid formation of a dense and protective Mg(OH)₂ layer.     

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%.     

EIS and ENM as tools to evaluate inhibitive performance of second generation of phosphate-based anticorrosion pigments

The anticorrosion performance of zinc aluminum phosphate pigment was evaluated using electrochemical impedance spectroscopy, the electrochemical noise method and DC polarization. The results of the electrochemical tests revealed the superiority of zinc aluminum phosphate in comparison with zinc phosphate in terms of inhibitive characteristics. The trend and magnitude of resistances and current density plus the appearance of the impedance spectra and the power spectral density of the current noise indicated deposition of a layer on the surface of samples exposed to ZPA extract. SEM/EDX analysis confirmed the precipitation.     

Electrochemical study of protective behavior of organic coating pigmented with zinc aluminum polyphosphate as a modified zinc phosphate at different pigment volume concentrations

Electrochemical impedance spectroscopy was employed to evaluate protective performance of the solvent-borne epoxy coatings pigmented with zinc aluminum polyphosphate as a representative of phosphate-based anticorrosion compounds at different Lambda values. Furthermore, the effective ratio of the pigment volume concentration (PVC) to the critical pigment volume concentration (CPVC) was determined. To compare the function of zinc aluminum polyphosphate and zinc phosphate incorporated into coatings, electrochemical noise method as well as electrochemical impedance spectroscopy was taken into consideration. The trend and magnitude of charge transfer, coating and noise resistances plus the amplitude of the current noise fluctuation indicated superiority of the modified pigment. In order to provide an insight into the mechanism by which anticorrosion pigments improve protective behavior of coating, performance of bare metals exposed to pigment extracts was assessed through taking advantage of electrochemical impedance spectroscopy and electrochemical noise method as well.     

Insights into protection mechanisms of organic coatings from thermal testing with EIS

The proposition that corrosion rate is limited by the ionic resistance of an organic coating has been tested. Mild steel panels coated with an epoxy-phenolic paint were exposed to 3% sodium chloride solution at 50 °C for different periods and characterized by electrochemical impedance spectroscopy (EIS) across a range of temperatures (25–50 °C). Changes in the film resistance and charge-transfer resistance with temperature were analysed to deduce activation energies for the processes involved. It was found that the calculated activation energy from coating resistance is significantly lower than the activation energy for the charge transfer resistance. This suggests that the ionic resistance of the coating, as apparent in an AC measurement, cannot be controlling the corrosion rate. Coating resistances for free films of the same coating show even higher activation energy values, so that the resistance of un-degraded areas of the coating within the current path could be controlling the current flow. Potentiostatic pulse tests on coated metal have enabled iR-corrected polarization curves to be plotted at different temperatures that gave high activation energies from the estimated corrosion currents. This provides two possible explanations that can account for the results.     

Evaluation of an environmentally friendly anticorrosive pigment for alkyd primer

An alkyd formulation containing zinc phosphate (10 wt.%) was prepared and subsequently modified replacing the latter anticorrosive additive by a very low concentration of conducting polymer. Specifically, three modified paints, which contain polyaniline emeraldine base (undoped form), polyaniline emeraldine salt (doped form) and an eco-friendly polythiophene derivative (partially oxidized), were formulated. The properties and corrosion resistance of the four alkyd coatings have been characterized. Among the three modified paints, the one containing polythiophene shows the best adherence and the highest corrosion resistance. This has been attributed to the fact that the miscibility of the polythiophene derivative with the alkyd formulation is better than that of polyaniline. Furthermore, accelerated corrosion assays and electrochemical impedance spectroscopy measurements revealed that the corrosion resistance of the paint with polythiophene is several orders of magnitude higher than that with zinc phosphate. The polythiophene derivative has been found to induce the formation of a passivating and well-adhered layer between the coating and the surface, preventing the access of chloride anions and oxygen to the substrate.     

Electrochemical and surface analytical studies of the self-assembled monolayer of 5-methoxy-2-(octadecylthio)benzimidazole in corrosion protection of copper

5-Methoxy-2-(octadecylthio)benzimidazole (MOTBI) monolayer was self-assembled on fresh copper surface obtained after etching with nitric acid at ambient temperature. The optimum conditions for formation of self-assembled monolayer (SAM) were established using impedance studies. The optimum conditions are methanol as solvent, 10 mM concentration of the organic molecule and an immersion period of 24 h. The MOTBI SAM on copper surface was characterized by contact angle measurements, X-ray photoelectron spectroscopy and reflection absorption FTIR spectroscopy and it is inferred that chemisorption of MOTBI on copper surface is through nitrogen. Corrosion protection ability of MOTBI SAM was evaluated in aqueous NaCl solution using impedance, electrochemical quartz crystal nanobalance, potentiodynamic polarization and weight-loss studies. While bare copper showed a charge-transfer resistance (R_ct) value of 1.89 kΩ cm² in 0.20 M NaCl aqueous environment, the R_ct value for SAM covered copper surface is 123.4 kΩ cm². The MOTBI SAM on copper afforded corrosion inhibition efficiency of 98-99% in NaCl solution in the concentration range and in the temperature range studied. The SAM functions as a cathodic inhibitor. Quantum chemical calculations showed that MOTBI has relatively small ΔE between HOMO and LUMO and large negative charge in its benzimidazole ring, which facilitate formation of a polymeric [Cu⁺-MOTBI] complex on copper surface.     

A novel approach to heal the sol-gel coating system on magnesium alloy for corrosion protection

Sol-gel-based coatings exhibit high potentiality to be as an alternative to toxic chromate coatings for surface pre-treatment of metals and alloys. However, as soon as even small defects appear in the coating, the coating cannot stop the development of corrosion process. Present work demonstrates the possibility to use zinc nitrate as healing agent to repair the organic silane coatings in NaCl solution. The zinc nitrate was added to the 0.005 M NaCl solution where AZ91D magnesium alloy coated with organic silane coating was immersed. The healing process and the healing mechanism were investigated by electrochemical measurements and scanning electron microcopy coupled with energy dispersive spectroscopy. The results demonstrated the introduction of zinc nitrate to the electrolyte could stop the development of corrosion process of the coating system and a remarkable recovery on corrosion resistance could be obtained. This effect may be attributed to the formation of zinc oxide/hydroxide on the defective areas, hindering the corrosion activities.     

The impact of pigment volume concentration on the protective performance of polyurethane coating with second generation of phosphate based anticorrosion pigment

In this study the effect of conventional zinc phosphate and zinc aluminum phosphate, which represents second generation of phosphate based anticorrosion pigments, on the performance of a polyurethane coating was studied. While zinc phosphate modification was proved to be effective on the corrosion resistance, EIS data facilitated the determination of the optimum pigment volume concentration in which the coating offered the most efficient protection. The superiority of zinc aluminum polyphosphate was attributed to the release of more inhibiting species, leading to the formation of a protective layer at the coating/substrate interface. In addition to the assessment of the impact of pigment content on the resistance of polyurethane primer to cathodic disbonding, the dependency of adhesion strength on the pigment type was also studied using pull-off test.     

The effect of benzimidazole and zinc acetylacetonate mixture on cathodic disbonding of epoxy coated mild steel

Electrochemical behavior of mild steel in the presence of zinc acetylacetonate (Zn(acac)₂) and benzimidazole (BIMIDA) was evaluated by electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution and compared to zinc phosphate (ZP) pigment and zinc potassium chromate (ZPC) pigment extracts. Results showed superior performance of Zn(acac)₂ and BIMIDA mixture (ZBM) compared to ZP pigment, while it introduced inferior inhibitive action compared to ZPC pigment. The epoxy coatings were formulated with ZBM as anticorrosive additive, ZP and ZPC pigments. The disbonding rate of coated steel follows the order: Blank > ZP > ZBM > ZPC. EIS results showed a complex film could be formed at the hole area for the coatings formulated with ZP, ZBM and ZPC. It is concluded that the stronger the complex film on the surface, the lesser the cathodic disbonding rate would be.     

Corrosion resistance of plasma-anodized AZ91D magnesium alloy by electrochemical methods

Anodic coatings formed on magnesium alloys by plasma anodization process are mainly used as protective coatings against corrosion. The effects of KOH concentration, anodization time and current density on properties of anodic layers formed on AZ91D magnesium alloy were investigated to obtain coatings with improved corrosion behaviour. The coatings were characterized by scanning electron microscopy (SEM), electron dispersion X-ray spectroscopy (EDX), X-ray diffraction (XRD) and micro-Raman spectroscopy. The film is porous and cracked, mainly composed of magnesium oxide (MgO), but contains all the elements present in the electrolyte and alloy. The corrosion behaviour of anodized Mg alloy was examined by using stationary and dynamic electrochemical techniques in corrosive water. The best corrosion resistance measured by electrochemical methods is obtained in the more concentrated electrolyte 3 M KOH + 0.5 M KF + 0.25 M Na₃PO₄·12 H₂O, with a long anodization time and a low current density. A double electrochemical effects of the anodized layer on the magnesium corrosion is observed: a large inhibition of the cathodic process and a stabilization of a large passivation plateau.     

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.     

In vitro studies of hydrogen peroxide treated titanium for biomedical applications

Pure titanium substrate was subjected to chemical treatment with different concentrations of hydrogen peroxide and subsequently heat treated to produce a titania gel layer with anatase nature. The surface modified substrates were then immersed in simulated body fluid for the formation of calcium phosphate layer over the surface. Titanium treated with 15 wt.% of hydrogen peroxide produced a uniform porous layer, which was found to induce the calcium phosphate formation more easily. However, titanium treated with 5 wt.% and 25 wt.% of hydrogen peroxide exhibited inhomogeneous surface for the growth of calcium phosphate layer. Further, the corrosion behaviour of the untreated and hydrogen peroxide treated specimens in simulated body fluid was evaluated using potentiodynamic polarization and electrochemical impedance spectroscopy. The results have shown that the surface modified titanium using 15 wt.% of hydrogen peroxide exhibited higher corrosion resistance compared to specimens treated with other concentrations of hydrogen peroxide.