Study of degradation of organic coatings in seawater by using EIS and AFM methods

In this article, electrochemical behaviors and their topography observation for four organic coatings used in seawater, by using both electrochemical impedance spectroscopy (EIS) and atomic force microscopy (AFM) methods to study environment behaviors of different coatings as well as the effects of their film formation, pigments, and fillers on anticorrosion behaviors, were measured. The results show that polyurethane, epoxy, and chlorinated rubber coatings all present one capacitive loop in their tested EIS which contains phenomenally only one time constant, whereas alkyd coating presents two capacitive semicircle arcs. With two capacitive loops, the capacitive semicircle in the high frequency range represents barrier layer property, but the semicircle in the low frequency range represents corrosion reaction of metals under the film. Polyurethane coating used in seawater has well anticorrosion property in seawater immersion test. The appearance features of different layers are visible different between different layers of tested coatings at their surface topography. The property of polyurethane paint film coated on metal is better than other layers, and film of alkyd coating has many pits at its surface by observing the layer's images. AFM photos imaged have also been used to further detail surface topography for four organic coatings, and to approve effects of topography of these coatings on its electrochemical behaviors, from two views of both height and phase modes. It is beneficial to explain deeply the environment behaviors and degradation mechanism of organic coatings. To further study failure of these organic coatings and dynamic processes of corrosion of metal under the film, two equivalent circuit models, according to these tested EIS, have been suggested to explain the corrosive kinetics of these four coatings. To polyurethane, epoxy, and chlorinated rubber coatings used in seawater which have good protection effects for substrate metal, the diffusion process for water, from their layer's surface to interface of film/metal, is mainly controlled factor for degradation. However, the electrochemical reaction process has may become a control procedure for corrosion of alkyd coated metal. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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

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

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。     

EIS and ENM measurements for three different organic coatings on aluminum

Electrochemical impedance spectroscopy (EIS) and Electrochemical noise measurements (ENM) were used to evaluate protective properties of three different organic coating systems. The coatings under investigation were two-component aerospace coatings, applied on aluminum substrate. They were immersed in a 0.5 mol l⁻¹ sodium chloride (NaCl) solution, within a controlled flow cell and were tested for 1 year.

The impedance modulus in the low frequency domain and the noise resistance were calculated and compared. From EIS data, coating capacitances and coating resistances of coating performance were estimated. The electrochemical results are in good agreement with final visual observations. The results of this study yield a performance ranking of the three different coatings.     

Application of the dynamic EIS to investigation of transport within organic coatings

The paper presents results of an investigation on rapid degradation of organic coating using a novel method called dynamic electrochemical impedance spectroscopy (DEIS). For 60 s, polyvinyl coating has been subjected to the impact of 0.01 M solution of tetraethylammonium tetrafluoroborate in methylene chloride. During that time instantaneous impedance spectra have been determined allowing tracing the dynamics of a degradation process. Usefulness of the DEIS technique in the investigation of non-stationary phenomena has been proved in the field of coating research.     

利用EIS高频区参数评价两种环氧涂层的性能

利用10 kHz下的相位角、10 kHz下的相对介电常数和对应于45°相位角的特征频率这3种EIS高频区的参数对两种环氧涂层体系在盐水浸泡+紫外照射的腐蚀条件下的失效过程进行了表征,并与涂层阻抗值进行了对比。测量结果表明,上述3种高频区参数的结果一致,都能够反映涂层性能的变化及相对优劣。当频率10 kHz处的相位角下降到40°,相对介电常数增大到40,或特征频率接近10 kHz时,所研究的两种环氧涂层体系的阻抗值都对应降低到10⁶ Ω•cm²左右,涂层保护性能接近失效。由于这几种EIS高频区参数能够很快测得,因此可以利用这些参数快速评价该涂层的保护性能与失效程度。     

环氧/聚氨酯涂层在4种环境中失效行为的EIS

用电化学交流阻抗法(EIS)研究了环氧富锌底漆/环氧云铁中间漆/丙烯酸聚氨酯面漆这一涂层体系在3.5%NaCl溶液、3.5%NaCl溶液+紫外辐射、湿热和盐雾这4种环境中的失效行为,探讨了特征频率下的相位角和涂层电阻值之间对应的关系。结果表明:中频区10Hz处涂层相位角随时间的变化曲线和涂层电阻值随时间的变化曲线有良好的相似性,据此可以对所研究的涂层体系失效程度进行快速评价;所试验的4种腐蚀环境对所研究的涂层体系的破坏作用由小到大依次为:3.5%NaCl溶液盐雾湿热3.5%NaCl溶液+紫外辐射。     

Evidencing antagonist effects of water uptake and leaching processes in marine organic coatings by gravimetry and EIS

Two distinct marine epoxy organic coatings were aged in a sodium chloride (30 g L⁻¹) solution at different temperatures. The water absorption was evaluated using gravimetric tests onto free films and EIS experiments were realized onto attached films. A strong leaching process was evidenced by gravimetry and the FT-IR analysis of the solution after ageing revealed the presence of extracted organic components. However, EIS results were not sensitive to this phenomenon and the water uptake values, obtained with a modified Brasher–Kingsbury equation, were found to be higher than gravimetric values. The comparison of the water volume fraction obtained by EIS with the apparent water mass fraction allowed following the species desorption with immersion time. It was proposed that this leaching process was related to a loss of the polymer density and the results showed that this phenomenon was thermally activated.     

Corrosion protection of galvanized steel by polyimide coatings: EIS and SEM investigations

Coatings of two types of polyimides (PI), as poly(4,4′-oxydiphtalic anhydride-co-2,5-bis(4,4′-methylenedianiline)-1,4-benzoquinone) (AQ) and poly(pyromellitic dianhydride-co-4,4′-oxydianiline) (PM), were synthesized on galvanized steel panels and studied and compared in terms of chemical structure, microstructure and corrosion performance in 0.5 M NaCl solution. Infra-red spectroscopy, scanning electron microscopy and in situ electrochemical impedance spectroscopy were employed in the investigations. The results showed that, although both studied PI coatings provided the galvanized steel substrate with corrosion protection during the test period, there were evident differences in electrochemical behaviour of the coatings, which could be primarily explained by the different nanostructures. FE-SEM examinations revealed AQ PI coating to be heterogeneous and discontinuous but PM PI coating homogeneous and continuous in nanostructure. Electrochemical behaviour of AQ PI coated galvanized steel obeyed that of a defect-containing coating and indicated gradual decrease in protectivity. In contrast, PM PI coating behaved like a defect-free coating and it provided the galvanized steel substrate with effective corrosion protection all through the 960 h test. The explanations for these observations and the mechanisms of coating damage are discussed in this paper.     

Evaluating barrier properties of organic coatings by water permeation and electrochemical methods

Water permeation, water absorption, d.c. resistance, and electrochemical impedance spectroscopy (EIS) measurements were performed on films of epoxy-polyamide used as binder in paint formulations. Barrier properties were found to be highly dependent upon the thickness of films. In thick films, water permeation measurements revealed the presence of pathways attributed to frozen holes, through which the flow is not governed by diffusion. In thin films, the presence of pinholes was detected by d.c. resistance and EIS measurements. LACTEC, área de Materiais — AMAT, Caxia Postal 19067, CEP 81531 - 990, Curitiba, Paraná, Brazil. Departamento de Química, Grupo de Processamento e Propriedades em Polímeros, Caixa Postal 675, CEP 13565-905, S?o Carlos, S?o Paulo, Brazil.     

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.     

A comparative study of non-covalent encapsulation methods for organic dyes into silica nanoparticles

Numerous luminophores may be encapsulated into silica nanoparticles (< 100 nm) using the reverse microemulsion process. Nevertheless, the behaviour and effect of such luminescent molecules appear to have been much less studied and may possibly prevent the encapsulation process from occurring. Such nanospheres represent attractive nanoplatforms for the development of biotargeted biocompatible luminescent tracers. Physical and chemical properties of the encapsulated molecules may be affected by the nanomatrix. This study examines the synthesis of different types of dispersed silica nanoparticles, the ability of the selected luminophores towards incorporation into the silica matrix of those nanoobjects as well as the photophysical properties of the produced dye-doped silica nanoparticles. The nanoparticles present mean diameters between 40 and 60 nm as shown by TEM analysis. Mainly, the photophysical characteristics of the dyes are retained upon their encapsulation into the silica matrix, leading to fluorescent silica nanoparticles. This feature article surveys recent research progress on the fabrication strategies of these dye-doped silica nanoparticles.     

Electrochemical test methods for evaluating organic coatings on metals: an update. Part I. Introduction and generalities regarding electrochemical testing of organic coatings

The status of evaluating organic coated metals utilizing electrochemical means was reviewed for the period of 1988–1994. The general improvements in the overall technology are presented in three sections. Part I covers the test cell configurations, changes in testing approaches and a brief survey of measurement equipment. Part II presents the test methods involving a single test parameter such as the panel potential relative to a reference electrode, electrochemical voltage and/or current noise, as well as the dc resistance of the coating on the metal substrate. Multiple test parameter measurements such as potentiodynamic curves and electrochemical impedance spectroscopy are covered in Part III. Although the majority of data were taken from the literature, some supplementary data are included from NSWCCD studies.     

New insights into the mechanisms of carbon dioxide mineralization by portlandite

Portlandite (Ca(OH)₂; also known as calcium hydroxide or hydrated lime), an archetypal alkaline solid, interacts with carbon dioxide (CO₂) via a classic acid–base “carbonation” reaction to produce a salt (calcium carbonate: CaCO₃) that functions as a low-carbon cementation agent, and water. Herein, we revisit the effects of reaction temperature, relative humidity (RH), and CO₂ concentration on the carbonation of portlandite in the form of finely divided particulates and compacted monoliths. Special focus is paid to uncover the influences of the moisture state (i.e., the presence of adsorbed and/or liquid water), moisture content and the surface area-to-volume ratio (s_a/v, mm⁻¹) of reactants on the extent of carbonation. In general, increasing RH more significantly impacts the rate and thermodynamics of carbonation reactions, leading to high(er) conversion regardless of prior exposure history. This mitigated the effects (if any) of allegedly denser, less porous carbonate surface layers formed at lower RH. In monolithic compacts, microstructural (i.e., mass-transfer) constraints particularly hindered the progress of carbonation due to pore blocking by liquid water in compacts with limited surface area to volume ratios. These mechanistic insights into portlandite's carbonation inform processing routes for the production of cementation agents that seek to utilize CO₂ borne in dilute (≤30 mol%) post-combustion flue gas streams.     

Diffusion cell investigations into the acidic degradation of organic coatings

Protective organic coatings work by preventing contact between an aggressive environment and a vulnerable substrate. However, the long required lifetime of a barrier coating provides a challenge when attempting to evaluate coating performance. Diffusion cells can be used as a tool to estimate coating barrier properties and lifetime. In this work, a diffusion cell array was designed, constructed, and compared to previous designs, with simplicity being the most important design parameter. Sulfuric acid diffusion through five different coatings was monitored using a battery of cells, and a mathematical model was developed to simulate the experimental data and to study diffusion mechanisms. The diffusion cells allowed an objective and fast analysis of coating barrier properties. It was found that sulfuric acid deteriorated these properties as it diffused through the films. This was also expressed in the modeling results, where a three-step time dependency of the diffusion coefficient was required to simulate both acid breakthrough time and the subsequent steady-state flux. A vinyl ester-based coating proved to be the most effective barrier to sulfuric acid diffusion, followed by a polyurethane coating. Amine-cured novolac epoxies provided the least effective protection.