Assessing the corrosion protection property of coatings loaded with corrosion inhibitors using the real-time atmospheric corrosion monitoring technique

The atmospheric corrosion monitoring(ACM)technique has been widely employed to track the real-time corrosion behavior of metal materials.However,limited studies have applied ACM to the corrosion protection properties of organic coatings.This study compared a bare epoxy coating with one containing zinc phosphate corrosion inhibitors,both applied on ACM sensors,to observe their corrosion protection properties over time.Coatings with artificial damage via scratches were exposed to immersion and alternating dry and wet environments,which allowed for monitoring galvanic corrosion currents in real-time.Throughout the corrosion tests,the ACM currents of the zinc phosphate/epoxy coating were considerably lower than those of the blank epoxy coating.The trend in ACM current variations closely matched the results obtained from regular electrochemical tests and surface analysis.This alignment highlights the potential of the ACM technique in evaluating the corrosion protection capabilities of organic coatings.Compared with the blank epoxy coating,the zinc phosphate/epoxy coating showed much-decreased ACM current values that confirmed the effective inhibition of zinc phosphate against steel corrosion beneath the damaged coating.

Advancements in enhancing corrosion protection of Mg alloys:A comprehensive review on the synergistic effects of combining inhibitors with PEO coating

Magnesium(Mg)alloys are lightweight materials with excellent mechanical properties,making them attractive for various applications,including aerospace,automotive,and biomedical industries.However,the practical application of Mg alloys is limited due to their high susceptibility to corrosion.Plasma electrolytic oxidation(PEO),or micro-arc oxidation(MAO),is a coating method that boosts Mg alloys'corrosion resistance.However,despite the benefits of PEO coatings,they can still exhibit certain limitations,such as failing to maintain long-term protection as a result of their inherent porosity.To address these challenges,researchers have suggested the use of inhibitors in combination with PEO coatings on Mg alloys.Inhibitors are chemical compounds that can be incorporated into the coating or applied as a post-treatment to further boost the corrosion resistance of the PEO-coated Mg alloys.Corrosion inhibitors,whether organic or inorganic,can act by forming a protective barrier,hindering the corrosion process,or modifying the surface properties to reduce susceptibility to corrosion.Containers can be made of various materials,including polyelectrolyte shells,layered double hydroxides,polymer shells,and mesoporous inorganic materials.Encapsulating corrosion inhibitors in containers fully compatible with the coating matrix and substrate is a promising approach for their incorporation.Laboratory studies of the combination of inhibitors with PEO coatings on Mg alloys have shown promising results,demonstrating significant corrosion mitigation,extending the service life of Mg alloy components in aggressive environments,and providing self-healing properties.In general,this review presents available information on the incorporation of inhibitors with PEO coatings,which can lead to improved performance of Mg alloy components in demanding environments.

Corrosion Protection of AM50 Magnesium Alloy by Nafion/DMSO Organic Coatings

The effectiveness of the corrosion protection of Nafion/Dimethysulfoxid （DMSO） organic coatings for AM50 magnesium alloy prepared by simple immersion and heat treatment was investigated. Its corrosion resistance and morphologies of the Nafion/DMSO organic coatings were studied by electrochemical corrosion testing and optical microscopy. The results show that Nafion/DMSO organic coatings can improve the corrosion resistance of AM50 magnesium alloy effectively. Also, the corrosion resistance increases with the surface density of the organic coatings.

A route for large-scale preparation of multifunctional superhydrophobic coating with electrochemically-modified kaolin for efficient corrosion protection of magnesium alloys

Superhydrophobic coating has been widely studied for its great applicational potential, such as for corrosion protection of magnesium alloys while it has been restrained by expensive materials, sophisticated preparation process and infirm rough structures. In this study, the electrochemical method was adopted by using a two-electrode system for rapid hydrophobic modification to obtain superhydrophobic kaolin.By mixing the modified superhydrophobic kaolin with commercial epoxy resin and polydimethylsiloxane glue, a paint can be formed and easily used on various substrates for preparation of superhydrophobic coating via spraying method. The influence factors on wettability of the modified kaolin and the mixing ratio of each component of the coating were explored. Also, the wettability, durability and anticorrosion of the prepared coating were evaluated comprehensively. The coating was able to maintain superhydrophobic after immersed in HCl solution at pH 1, the NaOH solution at pH 14, and 3.5 wt.% NaCl solution for 16, 21, 30 days, respectively. In addition, the coating exhibited 4A grade adhesion, high hydrophobicity after abraded for 200 cycles on a 600-mesh sandpaper with 100 g weight, and 99.86% anticorrosion efficiency after soaked in 3.5 wt.% NaCl solution for 20 days, demonstrating a good robustness and anti-corrosion property. Furthermore, the coating showed good transparency, flexibility and was easy to make in a large scale by the spraying method, which is of great significance to promote the practical application of superhydrophobic coatings and the anticorrosion Mg alloys.

Recent progress in self-repairing coatings for corrosion protection on magnesium alloys and perspective of porous solids as novel carrier and barrier

Featuring low density and high specific strength, magnesium(Mg) alloys have attracted wide interests in the fields of portable devices and automotive industry. However, the active chemical and electrochemical properties make them susceptible to corrosion in humid, seawater, soil,and chemical medium. Various strategies have revealed certain merits of protecting Mg alloys. Therein, engineering self-repairing coatings is considered as an effective strategy, because they can enable the timely repair for damaged areas, which brings about long-term protection for Mg alloys. In this review, self-repairing coatings on Mg alloys are summarized from two aspects, namely shape restoring coatings and function restoring coatings. Shape restoring coatings benefit for swelling, shrinking, or reassociating reversible chemical bonds to return to the original state and morphology when coatings broken;function self-repairing coatings depend on the release of inhibitors to generate new passive layers on the damaged areas. With the advancement of coating research and to fulfill the demanding requirements of applications, it is an inevitable trend to develop coatings that can integrate multiple functions(such as stimulus response, self-repairing, corrosion warning,and so on). As a novel carrier and barrier, porous solids, especially covalent organic frameworks(COFs), have been respected as the future development of self-repairing coatings on Mg alloys, due to their unique, diverse structures and adjustable functions.

Smart composite antibacterial coatings with active corrosion protection of magnesium alloys

A new method of the formation of composite coatings with the function of active corrosion protection of magnesium alloys was developed using the plasma electrolytic oxidation(PEO) method. Susceptibility of PEO-layers to pitting formation was evaluated using localized electrochemical methods(SVET/SIET). The morphological features and electrochemical properties of composite coatings were studied using SEM/EDX, XRD, micro-Raman spectroscopy and EIS/PDP measurements, respectively. The effect of surface layers impregnation with corrosion inhibitor on their protective properties in a corrosive environment was established. Additional protection was achieved using controllable coating pore sealing with polymer. It was found that the polymer treatment of the PEO-layer does not reduce the inhibitor’s efficiency. The formed protective composite inhibitor-and-polymer-containing layers decrease the corrosion current density of a magnesium alloy in a 3 wt.% Na Cl solution to three orders of magnitude. This predetermines the prospect of new smart coatings formation that significantly expand the field of application of electrochemically active materials. The mechanism of smart composite coating corrosion degradation was established. The antibacterial activity of the inhibitor-containing coatings against S. aureus methicillin-resistant strain was proved using the in vitro model. These protective layers are promising for reducing the incidence of implant-associated infections.

Corrosion Protection of Carbon Steel by Poly (aniline-co-o-toluidine) and Poly (pyrrole-co-o-toluidine) Copolymer Coatings

The soluble copolymers, poly (aniline-co-o-toluidine) and poly (pyrrole-co-o-toluidine) were synthesized by chemical oxidative copolymerization using ammonium persulphate as an oxidant in hydrochloride aqueous medium and characterized by FTIR spectroscopy. The polymers were dissolved in N-methyl-2-pyrrolidone and casted by solution evaporation on to the metallic substrate. The corrosion performance of the poly (aniline-co-o-toluidine) and poly (pyrrole-co-o-toluidine) coatings on carbon steel was studied by conducting immersion tests and electrochemical tests which include free corrosion potential measurements and potentiodynamic polarization measurements. The tests were conducted in 0.1 M HCl and 5% NaCl solution. The performance of coating in open atmosphere was also evaluated by conducting atmospheric exposure test. The surface morphology of the copolymer coatings were studied by scanning electron microscopy (SEM). The anticorrosive properties of copolymer coatings were also compared with polyaniline and poly (o-toluidine) coatings. In general the performance of poly (aniline-co-o toluidine) copolymer was found better than poly (pyrrole-co-o-toluidine) and homopolymer.

Preparation of alkaline-responsive nano-electrospinning and anticorrosion properties of self-healing coating

In this paper,1-butyl-3-methylimidazole tetrafluoroborate([BMIM]BF4)is used as corrosion inhibitor.Polyacrylonitrile(PAN)is used to load the corrosion inhibitor.PAN/[BMIM]BF4 hybrid nanofibers are successfullysynthesized by electrospinning technology.The alkyd varnish is coated on the fiber membrane to prepare a compositecoating,and then a series of tests are carried out on the self-healing and anticorrosive performance of the compositecoating.It is observed by scanning electron microscope that the fiber morphology is stable and there is no bead-likestructure.The composition of the composite fiber is analyzed by Fourier infrared spectroscopy,and it is confirmed thatthe hybrid nanofiber was successfully prepared.3D laser confocal scanning microscope was used to observe thecorrosion morphology and profile of the carbon steel.The composite coating shows good self-healing performance.[BMIM]BF4 can form a protective film on the surface of the bare carbon steel substrate through physical adsorption orchemical adsorption in an alkaline environment.Electrochemical impedance spectroscopy was tested and analyzed.It isfound that the maximum corrosion inhibition efficiency of the coating is 88.5%in 3.5 wt.%alkaline NaCl solution.Compared with the blank coating without nanofibers,the composite fiber varnish composite coating exhibits good selfhealingand anti-corrosion properties.

Polydopamine wrapped polyaniline nanosheets:Synthesis and anticorrosion application for waterborne epoxy coatings

Two-dimensional materials have been proved to be effective in improving the performance of anticorrosive coatings.However,most of the reported two-dimensional materials only have the ability to passively block corrosive media and cannot effectively inhibit localized corrosion reactions at the metal/coating interface.Herein,we first synthesized a novel polyaniline(PANI)nanosheet with both barrier and passivation functions for metals.In addition,polydopamine(PDA)wrapped PANI nanosheets(PANI@PDA)were obtained by in situ self-polymerization reaction of dopamine on the PANI surface,which enhance its interfacial interaction with polymeric resin.The chemical structure,morphology and corrosion inhibition properties of the nanosheets were systematically analyzed.The incorporated PANI@PDA nanosheets in composite coating provide a longer penetration path for corrosive mediums.Secondly,the uniformly dispersed two-dimensional nanosheets induce the formation of passivation film on the metal substrate.The protective effect of PANI@PDA nanosheets on coatings was verified by electrochemical impedance spectroscopy(EIS).Results indicated that the prepared composite coating exhibited excellent corrosion resistance throughout the test cycle.This simple and effective modification strategy based on conductive polymers provides a new insight into the development of environmentally adaptive composite coatings with active and passive protection.

Enhanced corrosion performance of magnesium phosphate conversion coating on AZ31 magnesium alloy

Magnesium phosphate conversion coating(MPCC)was fabricated on AZ31magnesium alloy for corrosion protection by immersion treatment in a simple MPCC solution containing Mg2+and3PO4?ions.The MPCC on AZ31Mg alloy showed micro-cracks structure and a uniform thickness with the thickness of about2.5μm after20min of phosphating treatment.The composition analyzed by energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy revealed that the coating consisted of magnesium phosphate and magnesium hydroxide/oxide compounds.The MPCC showed a significant protective effect on AZ31Mg alloy.The corrosion current of MPCC was reduced to about3%of that of the uncoated surface and the time for the deterioration process during immersion in0.5mol/L NaCl solution improved from about10min to about24h.

Improvement in corrosion resistance of magnesium coating with cerium treatment

Corrosion protection afforded by a magnesium coating treated in cerium salt solution on steel substrate was investigated using open circuit potential, polarization curves, and electrochemical impedance spectroscopy （EIS） in 0.005 M sodium chloride solution （NaCl）. The morphology of the surface was characterized by scanning electron microscopy （SEM）, energy dispersive spectroscopy （EDS）, and X-ray diffraction （XRD）. The cerium treated coating was obtained by immersion in CeCl3 solution. The results showed that the corrosion resistance of the treated magnesium coating was improved. The corrosion potential of the treated coating was found to be nobler than that of the untreated magnesium coating and the corrosion current decreased significantly. Impedance results showed that the cerium treatment increased corrosion protection. The improvement of anti-corrosion properties was attributed to the formation of cerium oxides and hydroxides that gave rise to a physical barrier effect.

Using EIS to evaluate anti-corrosion properties of the SiC_p/5A06 aluminium MMC treated by cerium conversion coatings

This paper evaluated the protection effect of the cerium conversion coatings on the SiCp/5A06 Al composite and the 5A06 Al alloy.Electrochemical impedance spectroscopy(EIS) was employed to examine the variation of the electrochemical variables of the samples treated and immersed in 3.5% NaCl solution at 35 °C for 1 h,which showed the enhancement of charge transfer resistance(Rt) and coating film resistance(Rc),i.e.,the corrosion resistance of the conversion coated samples was improved.The best protection ef...

Coating Protection for Production Facilities of Offshore Oil Fields

This paper describes coating protection of production facilities of offshore oil fields based on the practice of development of Bohai Offshore Oil Field, with focus laid on the selection of coating systems, surface preparation, coating application, as well as coating inspection for four types of major production facilities.

Corrosion resistance and mechanisms of smart micro-arc oxidation/epoxy resin coatings on AZ31 Mg alloy: Strategic positioning of nanocontainers

Smart micro-arc oxidation(MAO)/epoxy resin(EP) composite coatings were formed on AZ31 magnesium(Mg) alloy. Mesoporous silica nanocontainers(MSN) encapsulated with sodium benzoate(SB) corrosion inhibitors were strategically incorporated in the MAO micropores and in the top EP layer. The influence of the strategic positioning of the nanocontainers on the corrosion protective performance of coating was investigated. The experimental results and analysis indicated that the superior corrosion resistance of the hybrid coating is ascribed to the protection mechanisms of the nanocontainers. This involves two phenomena:(1) the presence of the nanocontainers in the MAO micropores decreased the distance between MSN@SB and the substrate, demonstrating a low admittance value(^5.18 × 10^(-8)Ω^(-1)), and thus exhibiting significant corrosion inhibition and self-healing function;and(2) the addition of nanocontainers in the top EP layer densified the coating via sealing of the inherent defects, and hence the coating maintained higher resistance even after 90 days of immersion(1.13 × 10^(10)Ω cm^(2)).However, the possibility of corrosion inhibitors located away from the substrate transport to the substrate is reduced, reducing its effective utilization rate. This work demonstrates the importance of the positioning of nanocontainers in the coating for enhanced corrosion resistance,and thereby providing a novel perspective for the design of smart protective coatings through regulating the distribution of nanocontainers in the coatings.

Smart anticorrosion coating based on stimuli-responsive micro/nanocontainer:a review

Smart coating for corrosion protection of metal materials(steel,magnesium,aluminum and their alloys)has drawn great attention because of their capacity to prevent crack propagation in the protective coating by releasing functional molecules(healing agents or corrosion inhibitors)on demand from delivery vehicle,that is,micro/nanocontainer made up of a shell and core material or a coating layer,in a controllable manner.Herein,we summarize the recent achievements during the last 10 years in the field of the micro/nanocontainer with different types of stimuli-responsive properties,i.e.,pH,electrochemical potential,redox,aggressive corrosive ions,heat,light,magnetic field,and mechanical impact,for smart anticorrosion coating.The state-of-the-art design and fabrication of micro/nanocontainer are emphasized with detailed examples.

Superhydrophobic coatings for corrosion protection of magnesium alloys

Magnesium(Mg)alloys show great potential to be extensively applied in practice owing to their superior properties,while the poor corrosion resistance does undoubtedly restrict their applications.Superhydrophobic coatings with good repellency to corrosive solutions can significantly decrease the interaction between the corrosive species and the substrate,so that they are receiving a lot of attention to improve the corrosion resistance of Mg alloys.Various strategies have been introduced to develop a superhydrophobic coating on Mg alloys,which were reviewed to elucidate the current research status to provide a clue or thinking for beginning researchers.Further,the existing issues of superhydrophobic coating were discussed,especially for their real applications in practice,mainly owing to their poor mechanical stability.Based on the existing issues,the future study was discussed to improve the stability of hierarchical structures and entrapped air pockets,impart the superhydrophobic coating self-healing property to repair the damaged area during service,provide double protection by incorporation of corrosion inhibitors,or even introduce slippery liquid-infused porous surfaces with lubricant layer to provide better corrosion protection for Mg alloys.

Photothermal self-healing polyurethane coating based on hollow nanofillers in seawater

Herein,a novel composite coating with excellent self-healing and corrosion resistance activated byphotothermal responsive hollow core-shell nanofillers was developed.A photothermal nanofiller(Co_(9)S_(8)@Bi_(2)S_(3))with ahollow core-shell structure was synthesized and then added to polyurethane(PU)to prepare PU-Co_(9)S_(8)@Bi_(2)S_(3)compositecoating.Applying 808 nm near-infrared irradiation induces a photothermal effect in Co_(9)S_(8)@Bi_(2)S_(3),which subsequentlyinitiates the reconstruction of reversible hydrogen bonds,facilitating the self-healing of coating scratches.The excellentphotothermal self-healing performance of PU-Co_(9)S_(8)@Bi_(2)S_(3)coating was demonstrated by scratch tests and moleculardynamics simulations.The electrochemical impedance spectroscopy test results showed that the PU-Co_(9)S_(8)@Bi_(2)S_(3)coating has good self-healing and anti-corrosion properties.The low-frequency impedance modulus of the coating afterthree self-healing sessions was still close to 109Ω·cm^(2)after 30 d of immersion in seawater.This study provides a newstrategy for developing multi-cycle self-healing coatings triggered by photothermal effects.

Enhanced corrosion protection of magnesium alloy via in situ Mg-Al LDH coating modified by core-shell structured Zn-Al LDH@ZIF-8

The Mg-Al layered double hydroxide(LDH)conversion coatings were first synthesized in situ to modify the AZ91 D alloy through urea hydrolysis to adjust the pH values(9.4,10.4,11.2 and 11.4).The pH 11.2 Mg-Al LDH possessed the best compactness and good crystallinity compared to other in situ LDH coatings and obtained the lowest corrosion current density(i_(corr))of(2.884×10^(-6)±0.345×10^(-6))A·cm^(-2),which was attributed to the anion-exchange reaction of LDH and the physical barrier against corrosion owing to the twisted penetration pathway of the interlaced LDH sheets.Core-shell structured Zn-Al LDH@ZIF-8 powder modified with stearic acid(SA)was further wrapped with polyvinylidene fluoride(PVDF)to prepare a hydrophobic double-layered coating on the underlying pH 11.2 Mg-Al LDH(SLLZ).The water contact angle(CA)of the SLLZ coating reached 105.6°,and its i_(corr)decreased to(3.524×10^(-7)±0.214×10^(-7))A·cm^(-2)compared with a single pH 11.2 film.The SLLZ coating exhibited high durability and corrosion protection,even after15 days of immersion in NaCl solution.The PVDF,SA and ZIF-8 nano-shells contributed to good hydrophobicity,effectively forming a physical barrier.The Zn-Al LDH core and underlying in situ Mg-Al LDH were beneficial for synergistically promoting anion-exchange reaction between the intercalated anions of LDH and chlorides in corrosive media.This work provides a promising approach that combines core-shell LDH@ZIF-8 with LDH film on a Mg alloy surface to construct a hydrophobic film with excellent longterm anti-corrosion performance.

Anticorrosion Coatings from Poly(Aniline-co-2-Ethylaniline) Micro/Nanostructures

PANI copolymer micro/nanostructures with different surface wettability were obtained from the chemical oxidation copolymerization of aniline(Ani)with 2-ethyl aniline(EA)at diverse[EA]/[Ani+EA]molar ratios,by employing ammonium persulfate as an oxidant.The results revealed that the poly(aniline-co-2-ethyl aniline)(PANI-EA)copolymer micro/nanostructures exhibited satisfactory anticorrosion performance for carbon steel,and the corrosion protection efficiency increased with the increase of water repellent property.Poly(2-ethyl aniline)(PEA)showed the largest contact angle(CA=145°)and show the best corrosion protection for the carbon steel(h=87.29%).It is found that the superior anticorrosion property of PEA is attributed to its high hydrophobicity,low conductivity and low porosity.

Electrochemical corrosion behavior of carbon steel with bulk coating holidays

With epoxy coal tar as the coating material, the electrochemical corrosion behavior of Q235 with different kinds of bulk coating holidays has been investigated with EIS （Electrochemical Impedance Spectroscopy） in a 3.5vo1% NaCI aqueous solution. The area ratio of bulk coating holiday to total coating area of steel is 4.91%. The experimental results showed that at free corrosion potential, the corrosion of carbon steel with disbonded coating holiday is heavier than that with broken holiday and disbonded ＆ broken holiday with time; Moreover, the effectiveness of Cathodic Protection （CP） of carbon steel with broken holiday is better than that with disbonded holiday and disbonded ＆ broken holiday on CP potential -850 mV （vs CSE）. Further analysis indicated that the two main reasons for corrosion are electrolyte solution slowly penetrating the coating, and crevice corrosion at steel/coating interface near holidays. The ratio of impedance amplitude （Z） of different frequency to minimum frequency is defined as K value. The change rate of K with frequency is related to the type of coating holiday.