Influence of surface roughness on the electrochemical behavior of carbon steel

The effect of the surface roughness of carbon steel on corrosion properties was investigated using electrochemical tests, and surface and Kelvin probe force microscopy (KPFM) analyses. The results of electrochemical tests show that the corrosion rate of carbon steel is increased as the surface roughness increases. It was estimated using KPFM measurement that the difference in the Volta potential between the peak and the valley increased with increasing surface roughness. As the peak has a lower potential than that of the valley, the peak acts as an anode. The surface roughness affects the Volta potential, and the Volta potential difference is inversely proportional to electron work function (EWF). The larger difference in Volta potential between the peak and valley on the rougher surface and the smaller EWF accelerated the micro-galvanic corrosion between them. The surface analyses reveal that corrosion initiated along the peak lines. The results from this study suggest that an increase of surface roughness leads to a decrease of the corrosion resistance.     

Polyester-based powder coatings with montmorillonite nanoparticles applied on carbon steel

In nanotechnology and nanoscience the development of hybrid (organic-inorganic) nanocompounds has attracted particular attention due to the significant improvement in the properties and the wide diversity of applications compared to conventional composites. In this study, formulations of commercial powder coatings were investigated with 2 and 4% (w/w) of montmorillonite (MMT) in the polyester resin matrix. The coatings were applied by electrostatic spraying on AISI 1008 carbon steel panels. The samples were characterized by TGA, DSC, XRD and TEM. The corrosion performance was evaluated using the salt spray test. Transmission electron microscopy revealed the presence of MMT in the coatings in the exfoliated form. The formulations with MMT presented better performance in terms of the corrosion protection properties.     

Influence of silica nanoparticles added to an organosilane film on carbon steel electrochemical and tribological behaviour

The electrochemical behaviour and tribological properties of carbon steel coated with bis-[trimethoxysilylpropyl]amine (BTSPA) filled with SiO₂ were evaluated. The silane film filled with SiO₂ was prepared by adding different SiO₂ concentrations. The electrochemical behaviour of the coated steel was mainly evaluated by means of open-circuit potential (E_OC), electrochemical impedance spectroscopy (EIS) and polarization curves, in 0.1 mol L⁻¹ NaCl solution. Structural and morphological characterizations were made by optical, electron and atomic force microscopy (AFM). E_OC and EIS data showed that sample filled with 300 ppm SiO₂ presented the highest E_OC and total impedance value. AFM measurements showed a homogeneous particle distribution of SiO₂ particles. Nanohardness measurements showed SiO₂ promoted an increase of the hardness mean value (1.70 ± 0.11 GPa to non-filled BTSPA and 2.21 ± 0.05 GPa for sample filled with 300 ppm SiO₂). Silane films when filled with SiO₂ particles improved the corrosion resistance of the steel substrate. The optimum SiO₂ particles concentration in silane solution is 300 ppm SiO₂. Incorporation of an extra amount of silica into BTSPA film led to degradation of the corrosion protection of the film to the substrate.     

In situ electrochemical studies of forming-induced defects of organic coatings on galvanised steel

A new electrochemical setup is presented for in situ measurements during uniaxial forming of thin film coated metal substrates. This approach allows the formability analysis of a zinc pigmented organic coating on a galvanised steel substrate. The aim is to monitor the formation of defects during the forming process. The setup comprises an electrochemical microcapillary cell in a three-electrode arrangement and a miniaturised linear stretching device. The development of forming-induced defects is monitored in situ by applying electrochemical impedance spectroscopy (EIS) and also microscopically analysed by means of field emission scanning electron microscopy (FE-SEM). The studies were supported by GOM^® grid measurements and finite element simulations of model sample forming degrees. The established technique enables the evaluation of the correlation between forming degree and degradation of the barrier properties of organic coatings.Finally a phosphating process on the unformed and formed specimen is electrochemically and microscopically analysed to correlate the respective defect size with its local reactivity. The results show that stretching-induced defects occur at the interface between spherical Zn particles and the epoxy binder matrix. The defect size increases with increasing strain values. The phosphating process leads to the nucleation of phosphate crystals especially in the forming-induced defects and thereby reduces the free zinc in the defect area. The kinetic of the phosphating is accelerated with increasing size of the defect.     

Formation of polypyrrole coatings onto low carbon steel by electrochemical process

Thin polypyrrole coatings (∼ 10 μm thick) were formed on low carbon steel by an aqueous constant current electrochemical polymerization using oxalic acid as the electrolyte. The amount of polypyrrole coatings formed on steel increased with the applied current and monomer concentration. No significant change in the electropolymerization of pyrrole occurred as a result of increased electrolyte concentration. The induction time for electropolymerization decreased significantly with current density but was unaffected by the initial monomer and electrolyte concentration. The electropolymerization potential of pyrrole increased with increased current density (Cd), i.e., Ep = 0.62 + 0.41 [Cd], and decreased exponentially with increased monomer and electrolyte concentration, Ep = E₀ exp^-[M]. Scanning electron microscopy (SEM) showed that the microstructure of the polypyrrole coatings formed on steel was dependent on the current density to the extent that smoother and more uniform coatings are formed at low current density. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:417–424, 1997     

A study on the electrochemical inhomogeneity of organic coatings

The inhomogeneity of three organic coatings, phenolic resin, alkyd resin and poly(urethane) varnish, was studied using a wire beam electrode and a high resistance measurement technique by measuring the distribution of d.c. resistances on different surface areas of the coatings in a 3% NaCl solution. Two types of areas which showed a significant difference in their d.c. resistance were found to be a basic pattern of this inhomogeneity. Experimental findings in this work nicely proved the reality of ‘D' and ‘1' areas in organic coatings. The results are in good agreement with those of Mayne et al.. Results about the influence of the coating's thickness and layers on its inhomogeneity are also reported in this paper.     

Use of electrochemical methods to examine different surface preparation methods for organic coatings on steel

For preparation of steel surfaces before applying an organic coating, waterjetting is a modern, effective and environmentally friendly method. However there is a lack of data on its performance in terms of the subsequent protection afforded by the paint compared with more conventional methods. Hence previously exposed steel panels had their surfaces prepared in a variety of ways (abrasion, blasting with garnet entrained in water (10 K psi) and waterjetting without garnet at two velocities (20 K psi and 40 K psi)) prior to coating with two typical maintenance coatings. These were then exposed under immersion condition in the laboratory and monitored using the DC resistance method. Another set of samples were exposed in a salt spray test in accordance with ASTM B 117 for 500 h. At the end of both tests DC measurements were carried out and the samples were inspected visually in terms of blistering and rust. Results showed that both the immersion test and the salt spray test differentiated the surface preparations methods in the same order. Thus control panels performed the best. Nearly as good though were the two (20 K psi and 40 K psi) sets of waterjetted samples. The abraded samples were variable but overall provided less protection. The panels blasted with garnet entrained in water (10 K psi) samples proved to be the worst. Characterisation of the surfaces prior to coatings using the scanning electron microscope was also conducted. A tentative explanation for the differing protection afforded involving the integrity of the oxide film was suggested. Further work is needed to substantiate this. Overall, with samples in the immersion test, results using electrochemical methods proved themselves to be very effective in assessing and even predicting performance in a relatively short period of time. The results also correlated with the salt spray test. Also the work showed that waterjetting is a very effective way of preparing the surface prior to maintenance painting.     

Characterization of active pigments in damage of organic coatings on steel by means of electrochemical impedance spectroscopy

Active anticorrosive pigments are solid additives for primers which can give further protection for areas with coating damage in addition to their barrier effect. These pigments are expected to prevent corrosion of metal substrate in coating damage by build-up of permanently passive conditions at the metal surface (electrochemical protection) and/or by build-up of solid compounds which plug the coating damage (chemical protection). Electrochemical Impedance Spectroscopy (EIS) was applied to characterize the corrosion protection behaviour of alkyd primers containing different pigments. Impedance spectra were recorded in the frequency range 50 mHz f 50 kHz at the open-circuit potential as a function of the type of pigment and the exposure time in different corrosive media. In general, two different parts can be distinguished in the impedance diagrams. The higher frequency part is related to the insulating properties of the primer and the lower frequency part can be attributed to electrochemical processes taking place within the coating defects. The parameters derived from EIS results show that the low frequency data can be used for characterization of the protective properties of anticorrosive pigments in the presence of defects in organic coatings.     

碳钢试片实海电化学检测与腐蚀规律的相关性

引言 由于海水腐蚀的严重性和复杂性,材料在海洋环境中的腐蚀数据积累及试验研究一直受到各国的重视.美国ASTM曾委托LaQue腐蚀试验中心开展了全球14个海水腐蚀站点的材料腐蚀试验[1],为评价世界范围内海水的腐蚀性提供了依据.     

Ionic liquid enhanced electrochemical characterization of organic coatings

Our laboratory recently began work on the use of room temperature ionic liquids ((RTIL's) to enhance our capabilities for the electrochemical characterization of organic coatings [A.M. Simões, D. Tallman, G.P. Bierwagen, The use of ionic liquids for the electrochemical characterization of water transport in organic coatings, Electrochem. Solid-State Lett. 8 (2005) 60]. The RTIL's are electrically conductive liquids consisting of large molecules that can be used to investigate the electrochemical properties of coatings in a non-aqueous medium. The enhancement of coating characterization comes from the fact that RTIL's have sufficient conductivity to be an immersion medium for electrochemical measurements, but they do not directly penetrate and effect organic coatings as do aqueous electrolyte solutions. This allows the separate examination of the effects of water on coatings in immersion or cyclic exposure. Indeed, our initial studies showed that a hydrophilic RTIL could be used to electrochemically characterize the drying of a coating after immersion, a process which heretofore had not been followed electrochemically. Thus, electrochemical measurements of coatings based on aqueous electrolyte immersion can be enhanced by the use of RTIL's and the effects of water on the coatings under study isolated and analyzed separately, especially the diffusion of water out of coatings during drying processes. Recent papers from our group have introduced the methodology whereby RTIL's in conjunction with capacitance monitoring via electrochemical impedance spectroscopy (EIS) can be used to determine the diffusion coefficient of water out of a non-pigmented, additive free coating [A.M. Simões, D. Tallman, G.P. Bierwagen, The use of ionic liquids for the electrochemical characterization of water transport in organic coatings, Electrochem. Solid-State Lett. 8 (2005) 60; K. Allahar, B. Hinderliter, A. Simoes, D. Tallman, G. Bierwagen, S. Croll, Simulation of wet–dry cycling of organic coatings using ionic liquids, J. Electrochem. Soc. 154 (2007) 177–185; B. Hinderliter, K. Allahar, O. Stafford, S. Croll, Using Ionic Liquids to Measure Coating Properties via Electrochemical Impedance Spectroscopy, Presented the 2006 International Coatings Exposition, Federation of Societies for Coatings Technology, New Orleans, LA, 2006 Oct.; B.R. Hinderliter, K.N. Allahar, G.P. Bierwagen, D.E. Tallman, S.G. Croll, Thermal cycling of epoxy coatings using room temperature ionic liquids, J. Electrochem. Soc. 155 (3) (2008) 1]. The technique has been extended to several types of coatings as well as the study of the cyclic wetting and drying of coatings [K. Allahar, B. Hinderliter, A. Simoes, D. Tallman, G. Bierwagen, S. Croll, Simulation of wet–dry cycling of organic coatings using ionic liquids, J. Electrochem. Soc. 154 (2007) 177–185]. This latter set of processes is one of the key set of events in exterior exposure that causes the failure of exterior protective coatings. Recently, RTIL's have been used to simulate the alternate wetting and drying of a Zn-rich epoxy coating system. EIS experiments were conducted on the Zn-rich epoxy under constant immersion in 0.05 M NaCl and RTIL. The experimental results were analyzed to determine the dielectric response and changes due to Zn oxidation within the Zn-rich system.     

Protective properties of epoxy-based organic coatings on mild steel

The protective properties of epoxy-based organic coatings on mild steel substrates have been studied using the electrochemical impedance spectroscopy (EIS) technique. The effects of coating composition, film thickness and curing temperature on the lifetime of the epoxy coating were investigated. The results obtained indicate that the film composition dramatically affects the rate of corrosion of the metallic substrate. Coatings with low and high content of curing agent exhibit early failure when exposed to an air-saturated 0.5 M aqueous solution of NaCl. Extended lifetimes were observed for samples with a content of the curing agent equal to 8.5% by weight. An increase in lifetime was also observed on increasing the film thickness and the curing temperature. The failure mechanism seems to occur in two steps: the first step is related to water uptake in the film while the second step is related to Cl⁻ ion diffusion through the coating. The results have been interpreted in terms of a model in which the dielectric properties (capacitance and resistance) of the coating depend strongly on the coating composition and are affected by both the water and salt uptake into the film.     

Evaluation of the corrosion behavior of galvannealed steel in chloride aqueous solution and in tropical marine environment

An investigation was made into the corrosion behavior of commercial galvannealed steel in 10⁻² mol dm⁻³ NaCl aqueous solutions and in a tropical marine environment, using scanning electron microscopy (SEM), galvanostatic electrochemical stripping (GES), potentiodynamic linear polarization (PLP), and electrochemical impedance spectroscopy (EIS) techniques and open circuit measurements (E _oc). For purposes of comparison, a commercial galvanized steel was also subjected to similar corrosion tests. GES and SEM techniques allowed for the identification of ζ, δ and Γ intermetallic phases and revealed cracks in the galvannealed steel. The PLP, EIS and E _oc results indicated that the galvannealed coating was more corrosion resistant than galvanized coating in an aqueous medium, but that their corrosion behaviors were similar in the marine environment. The corrosion behavior of the galvannealed steel was affected by the evolution of the cracking process in the Zn–Fe layer due to the dissolution of zinc-rich phases, while the galvanized steel displayed generalized corrosion in the aqueous medium and localized corrosion in the marine environment.     

Layered double hydroxides as containers of inhibitors in organic coatings for corrosion protection of carbon steel

The present work focuses on the use of layered double hydroxides (LDH) as containers for corrosion inhibitors in an epoxy coating. 2-Benzothiazolylthio-succinic acid (BTSA), used as corrosion inhibitor, was intercalated by co-precipitation in magnesium–aluminum layered double hydroxides. The obtained LDH–BTSA was characterized by infrared spectroscopy, X-ray diffraction and scanning electron microscopy. BTSA release from LDH–BTSA in NaCl solutions was investigated by UV–vis spectroscopy. The inhibitive action of LDH–BTSA on carbon steel corrosion was characterized by electrochemical methods and the protective properties of an epoxy coating containing LDH–BTSA were evaluated by electrochemical impedance spectroscopy. It was shown that the BTSA was intercalated in the layered double hydroxide and its loading was about 33%. The BTSA release was dependent on the NaCl concentration in the electrolyte. The polarization curves obtained on the carbon steel sample showed that the LDH–BTSA is an anodic inhibitor. Its efficiency was about 90% at a concentration of 3 g/l. The impedance results showed that the incorporation of LDH–BTSA (3%) in the epoxy matrix improved the corrosion protection of the carbon steel.     

Characterisation of electrodeposited Co-W-P amorphous coatings on carbon steel

Electrochemistry and nucleation mechanism of induced co-deposition of cobalt, tungsten and phosphorus from a citrate bath was investigated using voltammetry and chronoamperometry techniques. It was found that the induced co-deposition of the species occurred under diffusion control and followed instantaneous nucleation mechanism. Co-W-P coatings were electrodeposited potentiostatically on plain carbon steels from a citrate bath containing CoSO₄, Na₂WO₄ and NaH₂PO₂. X-ray diffraction studies of the coatings revealed that the as-deposited Co₈₁W₁₀P₉ coatings had amorphous structure. The formation of some stoichiometric compounds like Co₃W, Co₂P and WP₂, however, was observed upon annealing at 600 °C. The hardness of the Co-W-P coatings increased with annealing temperature which was possibly due to the formation of these inter-elemental compounds. The corrosion resistance of the Co-W-P coatings increased with increase in annealing temperature which might also be due to the formation of the stoichiometric compounds at elevated temperatures. A comparison between coating characteristics of Co-W-P and chromium showed that the Co-W-P coatings exhibited nobler corrosion potential than chromium coatings.     

Protective properties of organic phosphate-pigmented coatings on phosphated steel substrates

Investigations have been carried out on properties of coatings, differing by their pigmentation and binder, and applied on different chemical pre-treatments of the steel surface. Paints based on alkyd and alkyd-melamine binders, pigmented with zinc phosphate and modified basic zinc phosphate were applied on amorphous and crystalline phosphated steel surface and, for the comparison purpose, on degreased steel surface. The effect of the binder, the pigment and the pre-treatment of the steel surface on the protective properties of the coatings were determined by measurements of adhesion, water absorption and water permeability and by results obtained in salt spray and Prohesion tests. Coatings based on alkyd binder show a lower damage degree and good retention of adhesion in corrosion conditions, in spite of a higher water absorption and water permeability and a lower initial adhesive strength. Protective properties of coatings have been found to be highly dependent upon the substrate pre-treatment. Chemical pre-treatment of the steel substrate increases the protective properties of the system, which is particularly evident in the case of crystalline phosphating and the coating pigmented with modified basic zinc phosphate. This phenomenon can be explained by the synergism between this phosphate pigment with crystalline phosphate layer.     

Corrosion behavior of carbon steel coated with magnesium electrodeposited from methyl magnesium chloride solution

Magnesium coating was electroplated on carbon steel to improve its corrosion protection. The analytical characterization of the magnesium coating was performed by scanning electron spectroscopy and energy dispersive X-ray spectroscopy. The electrochemical behavior of Mg-coated carbon steel was assessed by electrochemical impedance spectroscopy, open-circuit potential measurements and potentiodynamic polarization curves in 0.03% sodium chloride solution. The electrochemical results showed that the self-corrosion current density (i _corr) of magnesium-coated steel was 0.32 mA cm^?2 (about 1.8% of that of uncoated steel). Impedance results showed an increase of the total impedance when magnesium coating was applied on steel substrate. The corrosion protection was ensured by a two-step mechanism. The first step was cathodic polarization; the second step was the formation of a barrier due to magnesium oxides composed of MgO, Mg(OH₂) and Mg(OH₃)Cl.     

A one-step electrochemical synthesis of polyaniline-polypyrrole composite coatings on carbon fibers

Polyaniline-polypyrrole composite coatings were formed on carbon fibers by potentiostatic electrochemical polymerization. Electropolymerization was done by varying the applied potential and molar feed ratio of monomers. The dual nature of the composite coatings was deduced from the current-time (I-t) curves traced during polymerization. I-t curves were also used to predict the mechanism of the formation of composite coatings. UV-vis absorption spectroscopy was used to study the electronic structure of the composite coatings.     

Evolution of non-stoichiometric iron sulfide film formed by electrochemical oxidation of carbon steel in alkaline sour environment

Non-stoichiometric iron sulfide films (Fe_xS_y) were formed electrochemically on a 1018 carbon steel/1 M (NH₄)₂S, 500 ppm CN⁻ interface, using cyclic chronoamperometry for different time intervals. The films showed great stability in medium typical of the catalytic plants of PEMEX Mexico (0.1 M (NH₄)₂S, 10 ppm CN⁻ as NaCN, pH 8.8). Characterization of the films by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) show two different behaviors depending on the growth time. For films grown at times <15 min, oxidation of the film was continuous, while oxidation ability for the film formed at times >15 min was lower. Film characteristics were more clearly defined by EIS experiments, as the Nyquist diagrams show depressive loops with high, real impedance values (Zr>1 kΩ cm²) for films grown at longer times. Structural characterization by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM) correlated electrochemical behavior with topographical changes and chemical composition of the films formed. The abundance of sulfur and pyrrhotite is evident in the samples grown for increasing times, and is likely due to electrochemical/chemical oxidation of iron sulfides during film growth. The sulfur-rich layer is responsible for the passive character of these films. The equivalent electrical circuit describing the EIS spectra for films formed over longer times has fewer elements than that used to model EIS spectra for films grown at shorter times. In particular, diffusion of atomic hydrogen is not apparent in sulfur-enriched films, and the charge transfer is carried out at the metal/film interface with values that are insensitive to film thickness and chemical nature.     

Features of electrochemical noise generated during pitting of inhibited A516-70 carbon steel in chloride solutions

The features of electrochemical noise generated during pitting of A516-70 carbon steel in chloride solutions containing Na2CrO4 were investigated. Polarization curves showed that the threshold Cl– concentration in 0.01m Na2CrO4 solution to initiate pitting and the threshold CrO42– concentration in 0.1m NaCl solution to maintain passivation for A516-70 carbon steel were approximately 0.1m and 0.01m, respectively. Noise measurements indicated that above the critical Cl– concentration, the stochastic current fluctuations appeared after 5h of immersion, which was an indication of pit initiation. Increasing CrO42– concentration to 0.05m led to the production of symmetrical current spikes at the start of immersion. The noise pattern changed to frequent fluctuations with small amplitude during immersion. Noise analysis in the frequency domain showed that pitting initiation was characterized by the slope of the PSD plot approaching -2. Extending the immersion time decreased the pitting initiation rate, as indicated by the decreased PSD slope and increased PSD frequency.