Electrochemical and anticorrosion behavior of functionalized graphite nanoplatelets epoxy coating

Functionalized graphite nanoplatelets (FGNP) were used as efficient and compatible nano-particles to produce homogenous epoxy nano-coating with impressive anticorrosion behavior for carbon steel. The characterizations of the nano-particle and nano-coating were carried out by SEM, FT-IR, XRD, TEM and pull-off test. Fine distribution of nano-particles in the cured nano-coating with particle sizes of 20–40 nm was obtained. Electrochemical experiments, salt spray and X-ray fluorescence showed that the nano-coatings protect the metal substrate by formation of passive layer and physical barrier characteristics. Three samples (0.25%, 0.5% and 1%) of FGNP-epoxy coatings were prepared that 0.5% showed better anticorrosion properties.     

Mercapto functional azole compounds as organic corrosion inhibitors in a polyester-melamine coating

The corrosion inhibition of two mercapto functional azole compounds including 2-mercaptobenzimidazole (MBI) and 2-mercaptobenzoxazole (MBO) for mild steel in 1 M NaCl solution was studied by electrochemical impedance spectroscopy (EIS), then their impact on the protective performance of a polyester-melamine coating was evaluated using salt spray. EIS results revealed a higher corrosion inhibitive activity of MBI compared to that of MBO. Corrosion products were examined by SEM-EDX and FTIR. The results showed modification of the corrosion products in the presence of MBI and MBO. The salt spray results revealed an improved corrosion protection of the coatings formulated with MBI and MBO. There was almost no impact of MBI and MBO on adhesion strength and glass transition temperature of the coatings, meaning that their impact on the corrosion protection performance of the formulated coating could only be attributed to their effect on the corrosion products.     

Characterization of coating systems by scanning electrochemical microscopy: Surface topology and blistering

Operation of the scanning electrochemical microscope used in feedback mode over a coated metal allows changes in the state of the coating surface to be monitored during immersion in aqueous electrolytes. This paper reports changes in the coating induced by specific anions in the electrolyte in situ during immersion. Significant surface roughening is observed for immersion times shorter than 1 day when the electrolyte contains chloride ions. This effect is also observed when the oxygen dissolved in the electrolytic phase is employed as redox mediator for SECM imaging. The coated system exposed to chloride-free electrolytes containing sulphate or nitrate maintains a featureless topography within the same time scale. The observed features are due to the nucleation and growth of blisters at the metal/coating interface induced by chloride ions in the environment. The implication is that ionic migration occurs simultaneously with the absorption of water by the coating already from the beginning of exposure to the aqueous environment. The unique role of chloride ions compared with sulphate or nitrate ions towards coating performance has been established at a very early stage following immersion of the sample.     

Integrated electrochemical approach for the investigation of silane pre-treatments for painting copper

Copper surfaces are sometimes protected with an organic coating to improve the durability or the aesthetic properties. Examples of industrial applications are household appliances and heat exchanger components.     

Evaluation of electrochemical frequency modulation as a new technique for monitoring corrosion and corrosion inhibition of carbon steel in perchloric acid using hydrazine carbodithioic acid derivatives

Electrochemical frequency modulation, EFM is a new technique for corrosion rate measurements. With the EFM technique, the corrosion rate and corrosion kinetic parameters can be obtained instantaneously without prior knowledge of Tafel slopes, which makes this method an ideal technique for application as a corrosion monitoring tool. Results obtained with the EFM technique were shown to be in agreement with chemical (weight loss) and electrochemical methods (Tafel extrapolation and electrochemical impedance spectroscopy, EIS) for corrosion rate measurements. New synthesized hydrazine carbodithioic acid derivatives namely, N′-furan-2-yl-methylene-hydrazine carbodithioic acid (A), N′-(4-dimethylamino-benzylidene)-hydrazine carbodithioic acid (B) and N′-(3-nitro-benzylidene)-hydrazine carbodithioic acid (C) were examined as corrosion inhibitors for carbon steel in 1 M perchloric acid solution. The results obtained from both chemical and electrochemical measurements show that these compounds suppressed both anodic and cathodic processes of carbon steel corrosion in 1 M HClO₄ by adsorption on the electrode surface. The adsorption mode follows the Langmuir adsorption isotherm. The efficiency of the inhibitors increases in the order C > B > A.     

Adhesion characterization of protective organic coatings by electrochemical impedance spectroscopy

Adhesion is considered in many situations to be a very important property of organic coatings for corrosion protection and much scientific work is devoted both to the study of the mechanism involved in polymer-metal adhesion and to the ways of measuring this property. The large number of experimental methods in existence to obtain information on coating adhesion is an indication of both the scientific and the technological interests in this material science and engineering area, but it is also a consequence of the difficulty in measuring adhesion in a general sense. As a partial alternative to the traditional adhesion measurement approaches for organic coatings, the evaluation of adhesion by electrochemical techniques such as electrochemical impedance spectroscopy (EIS) is discussed for different examples. The influences on adhesion of different pretreatments or organic coatings are discussed, considering aluminium, galvanized steel, and stainless steel substrates, and we have shown that the information obtained by using an electrochemical approach can be used for adhesion evaluation, with particular attention to the monitoring of adhesion in an aqueous environment, which is the most detrimental for protective organic coatings.     

Resistance of metallic substrates protected by an organic coating containing glass flakes

The resistance against corrosion of an epoxy-polyamine-based coating immersed in a 3 wt.% sodium chloride solution was investigated by electrochemical impedance spectroscopy (EIS). The organic coating contained glass flakes as pigment in order to enhance its barrier characteristics. The data show that this coating is more strongly adhered and exhibits higher protection characteristics when applied onto carbon steel substrates than on galvanized steel. Though the capacitance of the coating (C_C) does not show any appreciable variation with immersion time, the resistance (R_PO) of the film is observed to increase with time upon immersion. The analysis of the data sustains that the organic film behaves as a porous, non-barrier coating. Two time constants are observed even at earlier exposures, and the improved corrosion resistance developed after the coating system was exposed to the test electrolyte is considered to originate from the precipitation of corrosion products within the pores in the film.     

Improvement of corrosion protective performance of organic coating on low carbon steel by PEO pretreatment

Employing pretreatment is a pressing need for preparing anticorrosive coatings on carbon steels. However, conventional pretreatments are usually based on Cr, P and some other toxic elements, which are harmful to human body. For this reason, green and environmental techniques attract more and more attention. In this paper, plasma electrolytic oxidation (PEO) process was used as a pretreatment to fabricate an underlayer for the organic coating on low carbon steel. The anticorrosive performance of the organic coated samples with and without PEO pretreatment was studied by potentiodynamic polarization, ac/dc/ac electrochemical impedance spectroscopy, salt spray and immersion tests, respectively. Results show that the PEO process produces an oxide layer with porous and rough surface structure on the low carbon steel substrate. The porous and rough PEO layer is beneficial for enhancing the adhesion strength and thickness of the organic topcoatings. The organic coated sample with PEO pretreatment exhibits improved corrosion resistance and longer service life in corrosive environment compared to that without PEO pretreatment.     

Electrochemical behavior and anticorrosion properties of modified polyaniline dispersed in polyvinylacetate coating on carbon steel

Conducting polyaniline (Pani) was prepared in the presence of methane sulfonic acid (MeSA) as dopant by chemical oxidative polymerization. The Pani-MeSA polymer was characterized by FT-IR, UV-vis, X-ray diffraction (XRD) and impedance spectroscopy. The polymer was dispersed in polyvinylacetate and coated on carbon steel samples by a dipping method. The electrochemical behavior and anticorrosion properties of the coating on carbon steel in 3% NaCl were investigated using open-circuit potential (OCP) versus time of exposure, and electrochemical techniques including electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and cyclic voltammetry (CV). During initial exposure, the OCP dropped about 0.35 V and the interfacial resistance increased several times, indicating a certain reduction of the polymer and oxidation of the steel surface. Later the OCP shifted to the noble direction and remained at a stable value during the exposure up to 60 days. The EIS monitoring also revealed the initial change and later stabilization of the coating. The stable high OCP and low coating impedance suggest that the conducting polymer maintains its oxidative state and provides corrosion protection for carbon steel throughout the investigated period. The polarization curves and CV show that the conducting polymer coating induces a passive-like behavior and greatly reduces the corrosion of carbon steel.     

电镀锌钝化处理耐蚀效果的电化学评估

采用线性极化电阻、开路电位及阳极极化曲线等电化学方法,评估了锌镀层经3种不同钝化液处理后在w=1%的NaCl溶液中的耐蚀性。结果表明,3种电化学方法测得的钝化膜耐蚀性与中性盐雾试验的结果相符,能够用于快速有效地评价电镀锌钝化处理的耐腐蚀效果。     

Corrosion of steel under the defected coating studied by localized electrochemical impedance spectroscopy

Corrosion of steel under the defected coating in near-neutral pH solution was investigated by localized electrochemical impedance spectroscopy (LEIS) measurements. The LEIS response is dependent on the size of the defect. For small defects, e.g., less than 200 μm in diameter, localized corrosion process and mechanism of steel, as indicated by the measured LEIS plots, change with time. The diffusion process dominates the interfacial corrosion reaction, which is due to the block effect of the deposited corrosion product combined with the geometrical factor of a large coating thickness/defect width ratio. In the presence of a big defect, e.g., up to 1000 μm, the LEIS responses measured at the defect are always featured by a coating impedance in the high-frequency range and an interfacial corrosion reaction in the low-frequency range. The block effect of corrosion product does not apply due to the relatively open geometry. Conventional EIS measurements on a macroscopic-coated electrode reflect the “averaged” impedance results from both coating and defect. The information of the localized electrochemical corrosion processes and mechanisms at the small defect is lost, and the coating impedance information is “averaged” out when a big defect is contained. LEIS measurement provides an essential technique to characterize microscopically the local electrochemical corrosion reaction of steel under the defected coating.     

The influence of ageing of epoxy coatings on adhesion of polyurethane topcoats and protective properties of coating systems

The dependence of adhesion and protective properties of coating systems on surface properties of epoxy intermediate coatings, aged and non-aged before an application of polyurethane topcoats, were examined. The intermediate coatings were aged 500 h in UV chamber. The surface free energy and polar groups were estimated after ageing. After applying polyurethane topcoats on aged and non-aged epoxy coatings, resistance to salt spray and thermal shocks were tested as well as internal stresses were measured before and after corrosion tests.The results showed that adhesion in coating systems with polyurethane topcoats applied on aged epoxy coatings depends strongly on the degradation degree of epoxy intermediate coatings and the value of generated internal stresses. Coatings with good adhesion retention in corrosion environments have good protective properties even when temporary blistering has occurred.     

The electrochemical behaviour of stainless steel AISI 304 in alkaline solutions with different pH in the presence of chlorides

Nowadays, stainless steel reinforcements appear as an effective solution to increase the durability of reinforced concrete structures exposed to very aggressive environments. AISI 304 is widely used for this purpose. Although the improved durability of reinforcing AISI 304, when compared to carbon steel, there is a high probability of pitting susceptibility in the presence of chlorides. Thus, the present work aims at studying the passivation and passivation breakdown of AISI 304 in alkaline solutions of different pH (pH from 13 to 9), simulating the interstitial concrete electrolyte. These solutions were contaminated with different concentrations of chloride ions (3% and 10%, as NaCl). The electrochemical behaviour was evaluated by d.c. potentiodynamic polarization and by electrochemical impedance spectroscopy (EIS).The morphological features and the changes observed in the surface composition were evaluated by Scanning Electron Microscopy (SEM) together with EDS chemical analysis.The results evidence that pH plays an important role in the evolution of the film resistance and charge transfer processes. Moreover, the effect is highly dependent upon the chloride content and immersion time.     

Effects of cathodic potential on the local electrochemical environment under a disbonded coating

A rectangular crevice assembly was used to investigate the effects of cathodic protection (CP) potential, bubbling CO₂ and surface condition on the crevice corrosion of X70 steel under a disbonded coating. The solution within the crevice becomes more alkaline due to the reduction of dissolved O₂. As a result, the potential of the steel reaches the protected potential range and thus the protection distance becomes longer when the applied CP potential is more negative. Potential drop (IR) mainly occurs in the vicinity of the opening. However, the introduction of CO₂ into the solution prevents the formation of an alkaline environment but gives rise to an environment with a nearly neutral pH and a uniform potential distribution in the crevice. In addition, it is found that the pre-corrosion product layer significantly decreases the polarization rate in the crevice.     

A comparative study of the available electrochemical methods for the investigation of epoxy and fluoropolymer coatings deterioration

The corrosion behaviour of phosphatized galvanized steel coated with both epoxy films of different thickness and fluoropolymer films has been studied by means of a.c. impedance spectroscopy (EIS), break-point frequency, potentiodynamic measurements and faradaic distortion methods as well as by the salt spray test. It was observed that the degradation of protective films appears after a long-lasting initial period but once the process starts, the area of defects increases with exposure time. The rate of degradation depends both on type of polymer and of film thickness for the same type of polymer. The same behaviour can be observed from the decrease in pore resistance and charge-transfer resistance (EIS) and increase in double-layer capacitance (a.c. impedance measurements) and corrosion current (potentiodynamic measurements and harmonic analysis).     

Surface and electrochemical characterization of pitting corrosion behaviour of 304 stainless steel in ground water media

The effectiveness of aminotrimethylidene phosphonic acid (ATMP) as a corrosion inhibitor in association with a bivalent cation like Zn²⁺ and non-ionic surfactant like polyoxyethylene sorbitan monooleate (Tween 80) were investigated by measuring corrosion losses using electrochemical techniques. The corrosion of 304 stainless steel in the ground water medium was inhibited by complexation of the inhibitor. A combined inhibition effect was achieved by adding both ATMP and Zn²⁺ along with Tween 80. The formulation functioned as a mixed type inhibitor. The synergistic effect of the inhibitor compound is calculated. Luminescence spectra, FTIR spectra, XRD, XPS and scanning electron microscopic studies were carried out to understand the mode of corrosion inhibition and also the morphological changes on the metal surface.     

Pyrrole-based silane primer for corrosion protection of commercial Al alloys. Part II. Corrosion performance in neutral NaCl solution

A chromate-free, direct-to-metal treatment using pyrrole-based silane (PySi) was developed for protection against corrosion of as-received commercial Al alloys, following the typical procedure for silane deposition. The protection performance of composite PPySi films, containing polysiloxane linkages and polypyrrole units, was evaluated in near neutral NaCl solution by simple corrosion tests such as single-cycle anodic polarization, corrosion potential monitoring and long-term immersion experiments. Control coatings of polymethylsiloxane (PMeSi) and electrochemically synthesized polypyrrole (Ppy) were also studied. The superior performance of PPySi with respect to PMeSi and Ppy was attributed to highly crosslinked, well-packed and adherent composite films of thickness of the order of microns, manifesting both barrier action and active protection. The use of pyrrole-based silane for corrosion protection of Al alloys constitutes a promising approach for effective replacement of chromium-based treatments in practical applications. Further investigation from the fundamental point of view is deserved.     

Resistance of metallic substrates protected by an organic coating containing aluminum powder

The corrosion behavior of an epoxy primer containing aluminum powder (10 vol.%) applied on carbon steel and on galvanized steel was examined by electrochemical impedance spectroscopy (EIS). The data show that this coating is more protective when applied onto carbon steel substrates, and that on galvanized steel thicker coatings allow to achieve similar protection levels as those obtained for carbon steel. These effects are probably due to aluminum pigments providing a cathodic protection of the substrate, and to the resulting products precipitating inside the pores of the polymeric coating. Three stages can be distinguished during exposure of the coated specimens. Upon immersion of the coated samples in the test solution, a pre-saturated stage is observed. After a certain period of immersion, which strongly depends on the thickness of the applied coating, a saturation stage is reached in which an effective protection of the metallic substrate against corrosion is achieved. Finally, at sufficiently long exposure times, swelling through the coating eventually leads to the detachment of the coating.     

Investigation of the chromate conversion coating on Alclad 2024 aluminium alloy: effect of the pH of the chromate bath

The parameters of the chromate bath, like temperature, pH, and fluoride content, strongly affect the morphology and chemical composition of the chromate conversion coating and as a consequence have a large influence on its corrosion performance. In this paper, electrochemical impedance spectroscopy (EIS) was used in combination with other techniques to investigate the role played by the pH of the chromate bath on the properties of the chromate film formed on Alclad 2024 aluminium alloy. Scanning electron microscopy (SEM), atomic force microscopy (AFM) and spectroscopic ellipsometry (SE) have shown the formation of a thicker and less dense chromate layer when the pH of the chromate bath is changed from 2.4 to 1.2. The analysis of the EIS spectra have highlighted that this change in pH leads to the formation of more protective and more resistant chromate corrosion products (CCP) inside the defects of the chromate film. When a thin, dense and protective layer of CCP is formed in the defects, the corrosion behaviour of the chromate conversion coating improves for two main reason: (a) further attack of the defects is avoided or delayed; (b) the change in volume caused by the formation of the CCP is limited resulting in a low level of stress in the film, which as a consequence is not detached from the aluminium substrate.