Optimization of deposition voltage of cataphoretic automotive primers assessed by EIS and AC/DC/AC

The dependence of the anticorrosive properties of a cataphoretic paint with the applied deposition voltage was studied by the so-called EIS tests; an accelerated cyclic test used in the automotive industry; and a rapid electrochemical test (AC/DC/AC) which combines EIS measurements with cathodic polarizations. DSC and TGA were employed for the coating characterisation. The traditional accelerated cyclic test was unable to distinguish the influence of the deposition voltage on the anticorrosive properties while electrochemical tests found an optimal range of deposition voltage between 270 and 320 V. The AC/DC/AC test obtained the same results as EIS tests but in only 24 h instead of months of evaluation. The technique AC/DC/AC is suggested as an accelerated technique able to determine the optimum range of deposition voltages to obtain the higher anticorrosive properties of an epoxy cataphoretic primer.     

Evaluation of cure temperature effects in cataphoretic automotive primers by electrochemical techniques

Companies producing organic coatings for the automotive industry frequently need to test newly formulated products or materials, habitually according to different production parameters, in order to determine their actual behaviour before large-scale production of the coating is implemented. Proper choice of the test for this characterisation and the method of evaluation are critical. On the one hand, the choice is important because it is often necessary to distinguish coatings with very similar performance. On the other hand, results must be obtained in relatively short times, for it is impracticable for the manufacturers to wait for the completion of outdoor exposure tests. To reduce lead times in the development process, the use of accelerated aging tests to predict durability of the coating is essential (the time needed to perform them, however, is usually at least 500 h). This article proposes the use of EIS and an electrochemical test, AC/DC/AC, which consists in a combination of impedance results and cathodic polarisations, in order to find out the performance of coatings with precision and in a very short time. These techniques have been used to determine the optimum range of curing temperatures of a primer in order to obtain the maximum anticorrosion properties. Results show very good degree of concordance between the two electrochemical tests, although the AC/DC/AC method is much faster.     

Application of electrochemical techniques to study the effect on the anticorrosive properties of the addition of ytterbium and erbium triflates as catalysts on a powder epoxy network

New low curing temperature epoxy powder coatings cured with o-tolylbiguanide and catalyzed by the use of erbium(III) and ytterbium(III) trifluoromethanesulfonates have been formulated. Their curing kinetics and anticorrosive properties have been studied and compared with a system commonly used in industry (o-tolylbiguanide/epoxy resin). Three different tests for measuring anticorrosive properties (EIS, AC/DC/AC, and salt fog spray) have been used together with an adherence test, in order to establish the ideal system. Results show that a system using 1 phr of ytterbium triflate presents good anticorrosive properties. The technique AC/DC/AC has shown its ability to evaluate properly and much faster than other techniques the anticorrosive properties of powder coatings with similar results.     

Composite Ni/Al2O3 coatings and their corrosion resistance

Composite coatings Ni/Al₂O₃ were electrochemically deposited from a Watts bath. Al₂O₃ powder with particle diameter below 1 μm was codeposited with the metal. The obtained Ni/Al₂O₃ coatings contained 5-6% by weight of corundum. The structure of the coatings was examined by scanning electron microscopy (SEM). It has been found that the codeposition of Al₂O₃ particles with nickel disturbs the nickel coating's regular surface structure, increasing its microcrystallinity and surface roughness. DC and AC electrochemical tests were carried out on such coatings in a 0.5 M solution of Na₂SO₄ in order to evaluate their corrosion resistance. The potentiodynamic tests showed that the corrosion resistance of composite coating Ni/Al₂O₃ is better than that of the standard nickel coating. After 14 days of exposure the nickel coating corrodes three times faster than the Ni/Al₂O₃ coating. The electrochemical behaviour of the coatings in the corrosive solution was investigated by electrochemical impedance spectroscopy (EIS). An equivalent circuit diagram consisting of two RC electric circuits: one for electrode, nickel corrosion processes and the other for processes causing coating surface blockage, were adopted for the analysis of the impedance spectra. The changes in the charge transfer resistance determined from the impedance measurements are comparable with the changes in corrosion resistance determined from potentiodynamic measurements.     

Anticorrosive properties of an epoxy-Meldrum acid cured system catalyzed by erbium III trifluromethanesulfonate

New low curing temperature powder epoxy coatings cured with Meldrum's acid and catalyzed by the use of erbium III trifluoromethanesulfonate have been formulated. Their curing kinetics and anticorrosive properties have been studied and compared with a system commonly used in industry (o-tolylbiguanide/epoxy resin) and with an epoxy powder coating homopolymerized by erbium III trifluoromethanesulfonate. Three different tests of anticorrosive properties (EIS, AC/DC/AC and salt fog spray) have been used together with an adherence test, in order to establish the best system. Results show that systems crosslinked with Meldrum's acid and catalyzed with erbium triflate present very fast curing kinetics and very good anticorrosive properties. The technique AC/DC/AC has shown its ability to evaluate properly and much faster than other techniques the anticorrosive properties of powder coatings.     

Evaluation of a high resistance paint coating with EIS measurements: Effect of high AC perturbations

Electrochemical impedance spectroscopy (EIS) was used to evaluate a high resistance paint coating immersed in 10% sodium chloride solution. Although this method was valuable in evaluating this type of coating there were many fluctuations in measured data at low AC perturbations. In this work the role of high AC perturbation to fit EIS data of high resistance coating with equivalent electrical circuit (EEC) was studied. EIS measurements showed that these fluctuations could be reduced by high AC perturbation. The impedance plots showed best fitting at 400 mV AC perturbation at the initial time of immersion and at 100 mV AC perturbation after 90 days of immersion. The coating resistance and coating capacitance were extracted from the Bode and Nyquist plots during the period of 90 days of immersion.     

Electrochemical corrosion behaviour of plasma electrolytic oxidation coatings on AM50 magnesium alloy formed in silicate and phosphate based electrolytes

PEO coatings were produced on AM50 magnesium alloy by plasma electrolytic oxidation process in silicate and phosphate based electrolytes using a pulsed DC power source. The microstructure and composition of the PEO coatings were analyzed by scanning electron microscopy (SEM) and X-ray Diffraction (XRD). The corrosion resistance of the PEO coatings was evaluated using open circuit potential (OCP) measurements, potentiodynamic polarisation tests and electrochemical impedance spectroscopy (EIS) in 0.1 M NaCl solution. It was found that the electrolyte composition has a significant effect on the coating evolution and on the resulting coating characteristics, such as microstructure, composition, coating thickness, roughness and thus on the corrosion behaviour. The corrosion resistance of the PEO coating formed in silicate electrolyte was found to be superior to that formed in phosphate electrolyte in both the short-term and long-term electrochemical corrosion tests.     

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 electrochemical behavior of CrN single-layer coating and Cr/CrN nanolayered coating produced by cathodic arc evaporation physical vapor deposition

The aim of the present work is to study the CrN single-layer coating and the Cr/CrN nanolayered coating by cathodic arc evaporation physical vapor deposition (CAE-PVD) on AISI 304 stainless steel and to assess the electrochemical behavior of the coatings. Field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) were utilized to study the morphology and microstructure of the coatings. The mechanical behavior of the coatings was studied by the nanoindentation technique. The electrochemical behavior of the formed coatings in 3.5 wt.% NaCl solution was investigated via electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP) tests. Based on the microscopic images, it was realized that both CrN and Cr/CrN coatings were formed having a dense structure on the substrate. The results of EIS measurements showed gradual changes in the polarization resistance of the Cr/CrN nanolayered coating during the immersion time. However, significant changes in the polarization resistance of the CrN single-layer coating were seen by increasing immersion time comparing with the Cr/CrN coating. The higher polarization resistance of the Cr/CrN coating can be attributed to the effects of the interface between the layers in comparison to the CrN coating.     

Poly(N-ethylaniline) coatings on 304 stainless steel for corrosion protection in aqueous HCl and NaCl solutions

Poly(N-ethylaniline) (PNEA) coatings were grown by potentiodynamic synthesis technique on 304 stainless steel (SS) alloy from 0.1 M of N-ethylaniline (NEA) in 0.3 M oxalic acid solution. Characterization of adhesive and electroactive PNEA coatings was carried out by cyclic voltammetry, FT-IR spectroscopy and scanning electron microscopy (SEM) techniques. The protective properties of PNEA coatings on SS were elucidated using linear anodic potentiodynamic polarization, Tafel and electrochemical impedance spectroscopy (EIS) test techniques, in highly aggressive 0.5 M HCl and 0.5 M NaCl solutions. Linear anodic potentiodynamic polarization test results proved that PNEA coating improved the degree of protection against pitting corrosion in HCl and NaCl solutions. Tafel test results showed that PNEA coating appears to enhancement protection for SS in 0.5 M NaCl and 0.5 M HCl solutions. However, according to long-term EIS results, PNEA coating is better for the protection of SS electrodes during the long immersion period in NaCl compared to that in HCl medium.     

Anticorrosive properties of an epoxy-Meldrum acid cured system catalyzed by erbium III trifluromethanesulfonate

New low curing temperature powder epoxy coatings cured with Meldrum's acid and catalyzed by the use of erbium III trifluoromethanesulfonate have been formulated. Their curing kinetics and anticorrosive properties have been studied and compared with a system commonly used in industry (o-tolylbiguanide/epoxy resin) and with an epoxy powder coating homopolymerized by erbium III trifluoromethanesulfonate. Three different tests of anticorrosive properties (EIS, AC/DC/AC and salt fog spray) have been used together with an adherence test, in order to establish the best system. Results show that systems crosslinked with Meldrum's acid and catalyzed with erbium triflate present very fast curing kinetics and very good anticorrosive properties. The technique AC/DC/AC has shown its ability to evaluate properly and much faster than other techniques the anticorrosive properties of powder coatings.     

Electrochemical study of the corrosion behaviour at the edges of electrocoated steel

Cathodic electrodeposition is currently used to protect the totality of the world automotive production against corrosion. Although this technology is highly competitive, some aspects, as the coverage of salient edges, could still be improved. Special paints containing flow modifiers have consequently been developed. Salt fog exposure on steel knife blades is the most frequently performed test to characterize the protection afforded by cataphoretic coatings against edge corrosion. In this study, a method based on electrochemical techniques, among which cathodic polarization and electrochemical impedance spectroscopy (EIS), is proposed for the special characterization of edge coverage in a faster and less restrictive way in comparison with salt fog spray. The combination of dc and ac measurements is also employed to accelerate the degradation process and to improve the fitting of EIS spectra. In order to validate these testing methods, different kinds of pretreatments and coatings were selected. The influence on edge corrosion of different parameters as the coating thickness and the amount of flow modifier were determined.     

High corrosion protection of a polyaniline/organophilic montmorillonite coating for magnesium alloys

Epoxy coatings containing polyaniline (PANI) and polyaniline/organophilic montmorillonite (PANI/OMMT) powders were prepared on the surface of AZ91D magnesium alloy. The corrosion performance of the coatings was evaluated by electrochemical impedance spectroscopy (EIS) and open-circuit potential analysis in 3.5% NaCl. The results indicate that the PANI/OMMT coating retained its high corrosion protection for AZ91D magnesium alloy after 6000 h of immersion. The protective mechanism conferred by the PANI/OMMT coating was also discussed. The effects of oxygen on the protective mechanism of PANI were evaluated by EIS measurements in a 3.5% deaerated NaCl solution.     

Acceleration and quantitative evaluation of degradation for corrosion protective coatings on buried pipeline: Part I. Development of electrochemical test methods

The electrochemical degradation of polyethylene coated onto SS400 was examined in synthetic groundwater. Electrochemical techniques (electrochemical impedance spectroscopy, potentiodynamic and potentiostatic polarization tests) and surface analysis (scanning electron microscopy) were used to accelerate and evaluate the coating degradation. The pulsed potentiostatic polarization test accelerating both the cathodic reduction and anodic oxidation reactions was applied to reproduce the coating degradation mechanisms of cathodic disbondment and oxide lifting. The applied potentials were determined to be ±300 mV_SCE versus open-circuit potential from the analysis of the anodic and cathodic polarization data. Results from the EIS confirmed that coating degradation is accelerated effectively by the pulsed potentiostatic polarization testing.     

Enhanced corrosion resistance of A3xx.x/SiCp composites in chloride media by La surface treatments

The influence of silicon carbide particles (SiCp) proportion and matrix composition of aluminium metal matrix composites (A3xx.x/SiCp) modified by lanthanum-based conversion or electrolysis coating was evaluated in 3.5 wt% NaCl aerated solution. The intermetallic compounds were preferentially covered by lanthanum-based conversion coatings obtained by immersion in 50 °C solution of La(III) salt, and the intermetallic compounds, SiCp and aluminium matrix were covered by lanthanum electrolysis treatment. The corrosion process was studied on the basis of gravimetric tests and electrochemical impedance spectroscopy (EIS) during immersion in 3.5 wt% NaCl aerated solution. The composition of both La coating and corrosion products was analyzed before and after accelerated testing, by scanning electron microscopy (SEM), atomic force microscopy (AFM), low-angle X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) to determine the influence of surface microstructural changes on corrosion behaviour during exposure to the corrosive environment. The corrosion process was more influenced by the concentration of alloy elements in the matrix than by the proportion of SiCp reinforcement. Both lanthanum treated surfaces presented better behaviour to chloride solution corrosion than original composite surfaces without treatment; however, electrolysis afforded a higher degree of protection than the conversion treatment because the coating was more extensive.     

Application of EIS and salt spray tests for investigation of the anticorrosion properties of polyurethane-based nanocomposites containing Cr2O3 nanoparticles modified with 3-amino propyl trimethoxy silane

The Cr₂O₃ nanoparticles were modified with 3-amino propyl trimethoxy silane in order to obtain proper dispersion and increment compatibility with the polyurethane coating matrix. The nanocomposites prepared were applied on the St-37 steel substrates. The existence of 3-amino propyl trimethoxy silane on the surface of the nanoparticles was investigated by Fourier transform infrared (FTIR) spectroscopy and thermal gravimetric analysis (TGA). Dispersion of the surface modified particles in the polyurethane coating matrix was studied by a field emission-scanning electron microscope (FE-SEM). The electrochemical impedance spectroscopy (EIS) and salt spray tests were employed in order to evaluate the corrosion resistance of the polyurethane coatings. Polarization test was done in order to investigate the corrosion inhibition properties of the Cr₂O₃ nanoparticle on the steel surface in 3.5 wt.% NaCl solution. The adhesion strengths of the coatings were evaluated by pull-off adhesion tester before and after 120 days immersion in 3.5 wt.% NaCl solution. FT-IR and TGA analyses revealed that surface modification of the nanoparticles with 0.43 silane/5 g pigment resulted in the greatest amount of silane grafting on the surface of particles. Results obtained from FE-SEM analysis showed that the surface modified nanoparticles dispersed in the coating matrix properly. Results obtained from EIS and salt spray analyses revealed that the surface modified particles enhanced the corrosion protection performance of the polyurethane coating considerably. The improvement was more pronounced for the coating reinforced with 0.43 g silane/5 g pigment. Moreover, the adhesion loss decreased in the presence of surface modified nanoparticles with 0.43 silane/5 g pigment.     

Evaluation of sub-micrometer parylene C films as an insulation layer using electrochemical impedance spectroscopy

We investigated the insulation performance of sub-micrometer parylene C films over time using electrochemical impedance spectroscopy (EIS). For this, interdigitated electrodes were fabricated and completely encapsulated with parylene C in thicknesses of 50, 100, 200, and 500 nm. The EIS was measured in phosphate buffered saline (PBS) solution under an accelerated aging condition at 90 °C over 45 days. To analyze the EIS data, the equivalent circuit models of coating at different stages of coating degradation were used and the lumped circuit parameters of the best fitted equivalent circuit model were extracted by curve fitting. The analysis of impedance using the equivalent circuit model and the FTIR measurements suggest that sub-micrometer parylene C coatings exhibited delamination resulting from water diffusion from the top surface as soon as being immersed in PBS solution, although the degree of delamination varied depending on the film thickness. The penetration of water through sub-micrometers thick parylene C films can occur as quickly as the film is in contact with solution, unlike for thicker coatings in several micrometers where water diffusion would be saturated before water reaches the bottom surface of the coating.     

Corrosion performance of waterborne coatings for structural steel

Among recently developed waterborne coatings, epoxy and acrylic based coatings have a special place. To study this kind of anticorrosive coatings, use is normally made of natural exposure and laboratory tests. The literature has recently reported that the salt spray test is not suitable for selecting/studying anticorrosive waterborne coatings. In this paper, the authors present the main results obtained in an experimental study involving laboratory tests and natural exposure in two atmospheric test sites of different corrosivity categories. The natural exposure and accelerated tests are complemented by other measurements in the laboratory, involving water uptake, adhesion and electrochemical measurements, to understand the anticorrosive performance of the paint systems under study. As accelerated tests, salt spray and prohesion were used. Indirect measurements of adhesion were made using cross-cut and pull-off tests. Electrochemical impedance spectroscopy (EIS) and noise (EN) were used for electrochemical characterization. The study concludes that the best anticorrosive behaviour was shown by epoxy-polyamide paint systems, including zinc-rich primers. The correlation between the results of salt spray and natural exposure in marine test sites was significantly better than that obtained using the prohesion test. The electrochemical results showed that it is very important to pay special attention when interpreting this kind of results.     

Development of a modified test cell for AC impedance testing of coated Al fins

An innovative test-cell arrangement is proposed and examined for electrochemical impedance spectroscopy (EIS) testing of coated thin sheet or foil samples. This arrangement uses a thin layer of medical cotton fabric as a medium containing and transporting 5% sodium chloride solution. This new EIS cell avoids the intervention of edge effect into EIS measurements of painted material. It also avoids the formation of crevice attack experienced at the edges of conventional sample holders or normally under the edge of the masking material. This arrangement is simple and flexible to suit different sizes and shapes of flat panel and foil samples. It can also be used effectively as specimen holders for other than thin sheets. The test cell is also suitable for any electrochemical tests other than impedance measurements. The accelerated results of the EIS present the viability of the EIS test cell to be used as an accelerated nondestructive, repetitive measurement of coated thin metal substrate.     

Influence of chloride ion concentration on the electrochemical corrosion behaviour of plasma electrolytic oxidation coated AM50 magnesium alloy

The electrochemical degradation of a silicate- and a phosphate-based plasma electrolytic oxidation (PEO) coated AM50 magnesium alloy obtained using a pulsed DC power supply was investigated using potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) in NaCl solutions of different chloride ion concentrations viz., 0.01 M, 0.1 M, 0.5 M and 1 M. The surface of the PEO coated specimens after 50 h of immersion/EIS testing was examined by optical microscopy and scanning electron microscopy. The results showed that the corrosion deterioration of PEO coated magnesium alloy in NaCl solutions was significantly influenced by chloride ion concentration. The silicate-based coating was found to offer a superior corrosion resistance to the magnesium substrate than the phosphate-based coatings in lower chloride ion concentration NaCl solutions (0.01 M and 0.1 M NaCl). On the other hand both these PEO coatings were found to be highly susceptible to localized damage, and could not provide an effective corrosion protection to Mg alloy substrate in solutions containing higher chloride concentrations (0.5 M and 1 M). The extent of localized damage was observed to be more with increase in chloride concentration in both the cases.