Comparisons of clear coating degradation in NaCl solution and pure water

Organic coating's degradation behavior is essential to its corrosion protective function and has been widely studied. A main function of anti-corrosive organic coatings is acting as barriers to water uptake and ion diffusion. It is of great fundamental importance to study the influence of different working fluids on the degradation of organic coatings. In this study, a 3.5 wt% NaCl solution and the pure water are adopted as the working fluids based on their distinct properties. The commercially available polyurethane and epoxy based clear coatings are chosen for evaluation. The coating degradation is monitored by electrochemical impedance spectroscopy (EIS) measurement. Equivalent circuit models are employed to interpret the EIS spectra. The time evolution of coating resistance, capacitance, and water volume fraction of the coating is analyzed. Besides the fact that the coating's barrier property is deteriorated by the percolating of both NaCl solution and pure water, we also discover that pure water leads to faster coating degradation, demonstrated by a more substantial decrease in coating resistance, a more prominent increase in coating capacitance, and a greater saturated water volume fraction.     

不同表面处理条件下复合涂层体系失效过程的EIS特征

研究了不同表面处理条件下环氧富锌/环氧云母氧化铁/氯化橡胶涂层体系的电化学阻抗谱特征。利用Bode图、涂层吸水率、涂层电阻及特征频率的变化评价了表面处理对涂层防护性能的影响。结果表明,基材表面状态不同的复合涂层体系吸水率相对稳定阶段所持续的时间长短顺序为：手工打磨>表面锈蚀>表面未处理,与涂层的防护寿命长短、涂层/基材间的黏附力大小顺序一致。此外,不论基材表面处理程度如何,当涂层体系的特征频率增加到1400 Hz左右时,涂层电阻均发生较快降低,吸水率发生较大增长,涂层失去防护作用。     

Evaluating water transport through high solid polyurethane coating using the EIS method

Buried pipelines are commonly coated with high solid polyurethane to prevent corrosion. The diffusion of water through the coating plays an essential role in the performance and endurance of the coating. This study focuses on the evaluation of water diffusion through polyurethane coatings. The effects of thickness and ambient temperature on water diffusion through polyurethane, which is coated on mild steel and immersed in 3.5% (weight fraction) NaCl solution, are evaluated using electrochemical impedance spectroscopy (EIS). Experimental observations clearly indicate that the water diffusion coefficient strongly depends on service temperature and the thickness of coating. Higher temperature (lower than T _g) increases water uptake of the polymer but no measurable changes were observed for the temperature change studied. EIS results show that the mechanism of corrosion does not change in the range of thicknesses and temperature investigated in this study.     

钛纳米聚合物涂料在NaCl溶液中的电化学阻抗谱

采用电化学阻抗谱方法对钛纳米聚合物涂料的防腐性能进行了研究,并通过与环氧树脂清漆、环氧玻璃鳞片涂料的对比,说明钛纳米聚合物涂料的防腐性能显著优于上述两种涂料的防腐性能。     

Studies of the impedance models and water transport behaviors of cathodically polarized coating

Cathodic protection (CP) is usually combined with organic coatings to protect metallic structures exposed to seawater. However, the application of CP would enhance coating failure, such as cathodic delamination. To date, there has been few works characterizing the impedance models and water transport behaviors of cathodically polarized coating. In the present article, the analyses of impedance models and water uptake processes of chlorinated rubber coating subjected to various levels of cathodic protection were studied during coatings aging process by electrochemical impedance spectroscopy (EIS).Four distinguished electrical equivalent circuits (EEC) were used to fit the EIS plots of coatings without CP, while only two were employed for samples with CP. Since no corrosion was expected to take place at the metal/coating interface for sample which was polarized cathodically. Coating capacitance was used to investigate the sorption characteristic of water in coating since the increase of C_c was associated with water penetration into the coating. Compared with the sample without CP, those coating systems under CP have a smaller water diffusion coefficient and a further water uptake process after the saturation period.     

Preliminary investigation of the impact of polymer composition on electrochemical properties of coatings as determined by electrochemical impedance spectroscopy

The influence of structural and systematic compositional variations in glycidyl carbamate (GC) functional polymers on the electrochemical properties of their coatings was studied. There are few reports which focus on the correlation of structural and compositional variations in polymer films with their electrochemical barrier properties, diffusion properties with regards to water and aqueous electrolytes, and corrosion performance. To begin to fill this knowledge gap, two sets of GC functional polymers were studied. The polymer compositions were designed to vary the extent of polar hydrophilic groups, non-polar hydrophobic groups, and reactive epoxy groups in the final coatings. Impedance responses of the coatings were found to be closely related to the structural and compositional variations of these GC polymer films. In addition, single frequency EIS experiments were used in an attempt to understand the water uptake behavior of these polymer films using NaCl solution and ionic liquid under immersed condition. The resulting transport property data of the films was correlated to their polymer structure and composition. Moreover, a novel attempt at ranking the stability of coating using capacitance measurement during a cyclic wetting–drying condition was also attempted. The information obtained from this work can potentially be used to optimize the polymer for the specific performance properties needed in the protective coating applications, saving significant time and effort in the research and development stage.     

Thermomechanical and corrosion inhibition properties of graphene/epoxy ester–siloxane–urea hybrid polymer nanocomposites

The effect of graphene on the corrosion inhibition properties of a hybrid epoxy–ester–siloxane–urea polymer was investigated. The weight fraction of graphene was varied from 1 to 2 wt%. Direct current polarization (DCP) and electrochemical impedance spectroscopic (EIS) techniques were used to measure the polarization and coating resistance of the coated aluminum alloy substrate. The grapheme/hybrid polymer composite coatings showed much higher corrosion inhibition property when compared to the neat hybrid polymer coating. An increase in glass transition temperature and rubbery region modulus was also observed for composites containing 1–2 wt.% of graphene. A direct correlation between the rubbery plateau modulus of free standing composite thin films and corrosion resistance of the composite coatings was made, indicating that the corrosion protection mechanism is due to restriction of the polymer chain motion by graphene which causes a decrease in coating permeability.     

Corrosion protection by epoxy/poly(aniline-co-pyrrole)/ZnO nanocomposite coating

Anticorrosion behavior of epoxy/poly(aniline-co-pyrrole)/ZnO (EPAPZ) coating on stainless steel 304 alloys is investigated using the electrochemical impedance spectroscopy (EIS) method, and the coating is compared with epoxy/polyaniline/ZnO (EPAZ) and pure epoxy (EP) coatings. Scanning electron microscopy images are used for structural characterization and to compare the particle size of nanoparticles. EIS result showed that coating resistance for EPAPZ, EPAZ, and EP coatings after 90 days of immersion in 3.5% NaCl was 1.18 × 10⁷, 1.08 × 10⁶, and 4.28 × 10⁴ Ω cm⁻², respectively. In addition, the volume percentage of water absorbed by the coating, which could be obtained by coating capacitance, is 2.81, 4.21, and 9.11, respectively. Immersion tests showed 0.063, 0.194, and 0.752% of weight loss in the metals under EPAPZ, EPAZ, and EP coatings, respectively. These results show that the EPAPZ coating has superior anticorrosive performance compared with EPAZ and EP coatings. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48265.     

Electrochemical and time-of-flight secondary ion mass spectrometry analysis of ultra-thin metal oxide (Al2O3 and Ta2O5) coatings deposited by atomic layer deposition on stainless steel

Ultra-thin (5–50 nm) layers of aluminium and tantalum oxides deposited by atomic layer deposition (ALD) on a stainless steel substrate (316L) for corrosion protection have been investigated by electrochemical methods (linear scan voltammetry, LSV, and electrochemical impedance spectroscopy, EIS) and time-of-flight secondary ion mass spectrometry, ToF-SIMS. The effects of the deposition temperature (250 °C and 160 °C) and coating thickness were addressed. ToF-SIMS elemental depth profiling shows a marked effect of the organic and water precursors used for deposition and of the substrate surface contamination on the level of C and OH trace contamination in the coating, and a beneficial effect of increasing the deposition temperature. The polarization data show a decrease of the current density by up to four orders of magnitude with increasing coating thickness from 5 to 50 nm. The 50 nm films block the pitting corrosion in 0.8 M NaCl. The uncoated surface fraction (quantified from the current density and allowing a ranking of the efficiency of the coating, also confirmed by the capacitance and resistance values extracted from the EIS data) was 0.03% with a 50 nm thick Al₂O₃ film deposited at 250 °C. The correlation between the porosity values of the coatings and the level of C and OH traces observed by ToF-SIMS points to a marked effect of the coating contaminants on the sealing performance of the coatings and on the corrosion resistance of the coated systems.     

Application of EIS and SKP methods for the study of the zinc/polymer interface

Electrochemical impedance spectroscopy (EIS) and Scanning Kelvin probe (SKP) were applied to study the zinc/polymer interface. The coating capacitance and the drop of potential across the zinc/epoxy interface are investigated as a function of water penetration and hydrolysis of adhesion bonds. Water penetrates to the interface, decreasing thus the potential drop and increasing the capacitance. Further removal of water leads to the restoration of bonds accompanied by a decrease in capacitance and the return to the initial potential distribution across the interface. Commercial high-performance coil coatings applied to galvanized steel were studied in order to correlate the interface stability and the tendency to blistering. EIS and SKP measurements allowed the evaluation of the electrochemical conditions at the interface. Local adhesion failures caused non-uniformity in the potential profile measured by SKP. Monitoring of changes in impedance at low frequency related to the interface during temperature cycling may be useful for the evaluation of the tendency to blistering.     

Corrosion protection of Mg alloys by cathodic electrodeposition coating pretreated with silane

The corrosion resistance characteristics of three coatings on magnesium alloy AZ31—conventional paint with phosphate film, cathodic electrodeposition coating (E-coating), and E-coating pretreated with silane (Mg/silane/E-coating)—have been studied by means of electrochemical impedance spectroscopy (EIS) in a 3.5 wt% NaCl neutral aqueous solution and salt spray test using ASTM B117. Silane film was obtained by dipping AZ31 specimens in diluted hydroalcoholic silanic solutions and successively curing. It was found that the corrosion resistance of the Mg alloy with E-coating was superior to conventional paint and could be further enhanced with silane pretreatment as an interfacial film. The results of water volume fraction (Φ_saturation) and diffusion coefficient (D) also indicated that the Mg/silane/E-coating possessed excellent compactness and corrosion resistance. A model of the corrosion mechanism for Mg/silane/E-coating has been presented through EIS analysis.     

Water transportation through organic coatings: correlation between electrochemical impedance measurements, gravimetry, and water vapor permeability

A primary cause of coating failure is diffusion of water through organic coatings during which many corrosive species are transported to the metal-coating interface. However, water vapor permeability through the coating improves blister resistance to a certain extent. The present work describes the influence of chemical nature of the polymer on the above two properties. Attempts were also made to establish a correlation between these two properties for pigmented organic coating. Six paints were formulated and processed using six different types of binders at a constant pigment volume concentration (PVC) and specific gravity. Water ingress, water vapor permeability, and water absorption of these coatings were estimated using electrochemical impedance measurements (EIS), permeability cup method, and gravimetric method, respectively. There exists a good linear correlation between water uptake measured by EIS and water absorption measured by gravimetry. Similarly, a correlation was also noticed between water uptake by EIS and water vapor permeability. However, polyurethane type polymers did not fit into this linear correlation. Furthermore, influence of the resin chemistry on anticorrosive properties of these coatings was also studied using EIS and salt spray exposure test. Among all polymers under investigation, acrylic polyol-based polyurethane has shown the lowest water uptake, higher impedance, better salt spray resistance but higher water vapor transmission rate.     

Anticorrosion properties of smart coating based on polyaniline nanoparticles/epoxy-ester system

In this study, the anticorrosive effect of dodecylbenzenesulfonicacid-doped polyaniline nanoparticles [n-PANI (DBSA)] as a conductive polymer was investigated using electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS) techniques. Initially, the n-PANI (DBSA) were successfully synthesized via inverse microemulsion polymerization leading to the spherical nanoparticles with an average diameter less than 30 nm. Two coating systems including 1 wt% n-PANI(DBSA) blended epoxy ester (n-PANI(DBSA)/EPE) and neat epoxy ester (EPE) were coated on the carbon steal substrate. The anticorrosion performance of the prepared coatings was studied using EIS measurement in 3.5% NaCl solution during 77 days. The experimental data was modeled using Zview software according to the appropriate equivalent circuit model. The results clearly showed the better corrosion protection of the n-PANI(DBSA)/EPE coating compared to the EPE coating. This behavior was attributed to the ability of n-PANI(DBSA) in releasing dopant anion when the corrosion process is initiated on the metal substrate emphasizing the smart protection of n-PANI(DBSA)/EPE coating. Accordingly, the released dopant anions along with the iron cations provide a secondary barrier layer, which passivates the substrate.     

海水压力对深海用环氧涂层防护性能的影响

采用电化学阻抗谱(EIS)技术与局部交流阻抗技术(LEIS)研究了深海环境用重防腐环氧涂层H44-61在深海模拟环境(青岛海水,常压以及6 MPa交变压力)下的腐蚀电化学行为,探讨了交变压力对深海用涂层防护性能的影响。结果表明,涂层在6 MPa交变压力下的涂层电容较常压下高且涂层电阻较低,涂层的防护性能下降,但低频阻抗膜值均在10⁷ Ω·cm²以上,说明涂层仍有较好的防护性能;LEIS的研究表明交变压力下人造缺陷区域的阻抗值较小,缺陷周围涂层的剥离面积较大,说明压力交变能加快电解质溶液向涂层金属界面扩散,加速涂层下金属的腐蚀过程,降低涂层的防护性能。     

Enhancement of Corrosion Performance of Epoxy Coatings by Chemical Modification With GPTMS Silane Monomer

In this paper, commercial epoxy resin was chemically modified by different amounts of 3-glycidoxypropyltrimethoxysilane (GPTMS) monomer using an organotin compound as catalyst, aiming to improve the anti-corrosion performance of epoxy coatings on 2024-T3 aluminum alloy substrate. Electrochemical impedance spectroscopy (EIS) was used to evaluate the barrier properties against water permeation and protectiveness of silane-modified epoxy coatings. The results showed that all the modified coatings presented higher barrier performance and better corrosion performance than pure epoxy coating, which were characterized by higher charge transfer resistance (R _ct) and lower double-layer capacitance (C _dl) at the electrolyte/metal interface. The improvements in corrosion performance and wet adhesion of modified epoxy coatings were also observed by the Machu test and boiling water test, respectively. Interestingly, it was found that the glass-transition temperature (T _g) of silane-modified epoxy coatings decreased only slightly during immersion in 3.5 wt% NaCl solution, in contrast with pure epoxy coating, which was observed to decrease significantly after water permeation. The corrosion performance of epoxy coatings was, thus, improved when the amount of chemically grafted silane monomer increased in the content range investigated in the present work.     

Electrochemical and sorption characteristics and thermal stability of epoxy coatings electrodeposited on steel modified by Zn–Co alloy

The corrosion behaviour, transport properties and thermal stability of epoxy coatings electrodeposited on steel and steel modified by Zn–Co alloys were investigated during exposure to 3% NaCl solution. The electrochemical impedance spectroscopy (EIS), gravimetric liquid sorption measurements and thermogravimetric analysis (TGA) were used. Zn–Co alloys were electrodeposited on steel from chloride and sulphate baths, by different current densities. From the time dependence of pore resistance and coating capacitance of epoxy coating, diffusion coefficient of water through epoxy coating and thermal stability it was shown that Zn–Co sublayer obtained from chloride solution significantly improves the corrosion stability of the protective system based on epoxy coating. Almost unchanged values of pore resistance were obtained over the long period of exposure time, indicating the great stability of this protective system, due to the existence of a passive layer consisting of basic salts.     

Corrosion protection by epoxy coating containing multi-walled carbon nanotubes

Epoxy coatings that contained multiwalled carbon nanotubes (MWCNTs) were prepared. Further, the effect of the MWCNTs on the hydrophobicity and water transport behavior, and hence, on corrosion resistance provided by the epoxy coating were examined using hygrothermal cyclic tests and electrochemical impedance spectroscopy (EIS). The water transport behavior of epoxy coatings with higher MWCNT content decreased to a larger extent for coatings with higher surface hydrophobicity. The corrosion protection of carbon steel coated with epoxy coating that contained MWCNTs correlated well with water transport behavior and hydrophobicity.     

Corrosion stability of polyester coatings on steel pretreated with different iron–phosphate coatings

The influence of steel surface pretreatment with different types of iron–phosphate coatings on the corrosion stability and adhesion characteristics of polyester coatings on steel was investigated. The phosphate coating was chemically deposited either from the simple novel plating bath, or with the addition of NaNO₂, as an accelerator in the plating bath. The morphology of phosphate coatings was investigated using atomic force microscopy (AFM). The corrosion stability of polyester coatings on steel pretreated by iron–phosphate coatings was investigated by electrochemical impedance spectroscopy (EIS) in 3% NaCl solution, while “dry” and “wet” adhesion were measured by a direct pull-off standardized procedure. It was shown that greater values of pore resistance, R_p, and smaller values of coating capacitance of polyester coating, C_c, on steel pretreated with iron–phosphate coating were obtained, as compared to polyester coating on steel phosphated with accelerator, and on the bare steel. The surface roughness of phosphate coating deposited on steel from the bath without accelerator is favorable in forming stronger bonds with polyester coating. Namely, the dry and wet adhesion measurements are in accordance with EIS measurements in 3% NaCl solution, i.e. lower adhesion values were obtained for polyester coating on steel phosphated with accelerator and on the bare steel, while the iron–phosphate pretreatment from the novel bath enhanced the adhesion of polyester coating on steel.     

Electrochemical impedance spectroscopy investigations of epoxy zinc rich coatings: Role of Zn content on corrosion protection mechanism

Effect of zinc content in the epoxy zinc rich coating on the mechanism of corrosion protection was investigated using electrochemical impedance spectroscopy (EIS). The zinc content in the coating (on dry film) was varied from 40% to 90% in steps of 10%. Open circuit potential (OCP) measurements and salt spray tests were also carried out to generate supporting evidences and to deepen the understanding in the area of zinc rich coatings. The healing or bridging ability of these coatings was studied by making a scribe on the coating and monitoring the evolution of OCP. EIS was also utilized to screen the amount of zinc particles required to provide efficient galvanic protection and to study the effect of purity of Zn on corrosion protection performance. Both EIS and OCP measurements indicate that coatings containing 40% Zn (on dry film) provides very good barrier protection coming mainly from polymer whereas the one containing >80% Zn provides excellent galvanic protection to the steel substrate. When the zinc loading is between 60% and 70%, coatings neither show barrier protection nor galvanic protection.