Anticorrosion behavior of cyclodextrins/inhibitor nanocapsule-based self-healing coatings

The self-healing anticorrosion property of coating containing cyclodextrins/inhibitor nanocontainers was investigated by SEM, TEM, salt spray, and EIS measurements. The influences of cyclodextrin type (α-CD, β-CD and γ-CD) and nanocapsules diameter on the anticorrosive performance of the scratched samples were studied under salt spray conditions, which revealed that the coatings containing γ-CD/inhibitor nanocontainers with larger nanocapsules at room temperature demonstrated the best anticorrosion behavior. Inclusion complex formation of MBI or MBT with CDs led to encapsulated corrosion inhibitors which became active in corrosive electrolytes, and could slowly diffuse out of the host material to ensure continuous delivery of the inhibitors to corrosion sites and long-term corrosion protection. Additionally, the kinetics of the self-healing process characterized by EIS measurement was parametrically analyzed in an equivalent circuit when the coating was exposed to salt solution.     

Mica/polypyrrole (doped) composite containing coatings for the corrosion protection of cold rolled steel

Micas/polypyrroles (PPys) doped with molybdate, p-toluene sulfonate, dodecyl benzene sulfonate, and 2-naphthalene sulfonate composite pigments were synthesized by chemical oxidative polymerization and characterized in coatings for corrosion protection on cold rolled steel substrate by various electrochemical techniques. Synthesized composite pigments were characterized for morphology by scanning electron microscopy, which indicated physical formation of PPy on the surface of mica. Chemical composition of the composite pigments was analyzed by X-ray photoelectron spectroscopy which chemically confirmed doped PPy formation on the mica surface. Coatings were formulated at 20% pigment volume concentration (composite pigments or as-received mica pigment) and were applied on cold rolled steel substrate. Coatings were exposed to salt spray test conditions (ASTM B117) for 30 days and were periodically assessed for corrosion with electrochemical impedance spectroscopy (EIS), open circuit potential (OCP), and potentiodynamic polarization. EIS and circuit modeling results demonstrated higher coating resistance (R _c) for mica/PPy (doped) composite coatings as compared to as-received mica pigment containing coating after 30 days of salt spray exposure. Lower current density and more positive corrosion potential values were observed for mica/PPy (doped) composite coatings as compared to mica pigment-based coating in potentiodynamic polarization measurements, indicating improved corrosion protection for cold rolled steel substrate. OCP measurements revealed more positive values for mica/PPy (doped) composite coatings as compared to mica pigment-based coating suggesting superior corrosion protection for mica/PPy (doped) composites.     

Synergic enhancement of the anticorrosion properties of an epoxy coating by compositing with both graphene and halloysite nanotubes

The aim of this research was to improve the corrosion resistance of metal surfaces with polymer coatings. Both graphene and halloysite nanotubes (HNTs) were introduced together into the epoxy resin coating for the enhanced barrier protection of the metallic surface. The anticorrosion behaviors of different coatings were comparatively evaluated by the potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), and neutral salt spray (NSS) tests. The potentiodynamic polarization curves showed that the coating containing 0.5 wt % HNTs and 0.8 wt % graphene (H05G08EP) together had the most positive corrosion potential and the minimum corrosion current density. The EIS results revealed that graphene endowed the composite coatings with excellent electrochemical performance for anticorrosive purposes. The NSS tests indicated that H05G08EP endured the longest NSS time. These results suggest that H05G08EP had the best corrosion resistance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47562.     

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.     

不同腐蚀试验的电化学阻抗谱评价

采用电化学阻抗谱分析了环氧涂层的介质浸泡、ASTM-B117盐雾试验、PROHESION循环试验的性能变化。实验结果表明:介质浸泡更侧重考察涂层的屏蔽作用,对环氧-聚酰胺体系酸性电解质更容易导致涂层失效;而盐雾试验更容易导致涂层吸收水分,干湿交替增加了有机涂层吸水能力;划痕试验表明样板在ASTM-B117和PRO-HESION遵循不同的腐蚀机理。     

Corrosion protection coating containing polyaniline glass flake composite for steel

Corrosion protection of steel by glass flake (GF) containing coatings is widely used in marine atmosphere. Even though, the coatings containing glass flake are highly corrosion resistant, their performance is decreased due to the presence of pinholes and coating defects. It is well established that polyaniline containing coating is able to protect the pinhole defects in the coatings due to passivating ability of polyaniline. Hence a study has been made on the corrosion protection ability of steel using polyaniline-glass flake composite containing coating with 10% loading of glass flake in epoxy binder. The polyaniline glass flake composite (PGFC) was synthesized by chemical oxidation of aniline by ammonium persulphate in presence of glass flake. The corrosion protection ability of GF and PGFC containing coating on steel was found out by salt spray test and EIS test in 3% NaCl. In both the tests, the resistance value of the PGFC containing coating has remained at 10⁸-10⁹ Ω cm² where as for the GF containing coating, the resistance values decreased to 10⁵ Ω cm². The enhanced corrosion protection ability of the PGFC containing coating is due to the passivation ability of the polyaniline present in the coating.     

新型活化环氧富锌涂层的耐腐蚀性研究

富锌涂料在防腐蚀领域具有广泛应用,然而其长效防护性能却受到锌粉活性影响。本文以冷涂锌涂层、传统环氧富锌涂层作为对照,研究了新型具有电化学活性的环氧富锌涂层在盐雾加速腐蚀试验后的耐腐蚀性。宏观形貌分析表明：盐雾加速腐蚀 1 800 h后,活化环氧富锌涂层表面并未出现锈点;采用扫描电子显微镜、维体式显微镜观察试验后涂层的表面形貌和涂层结构,发现活化环氧富锌涂层微观表面更加平滑,锌粉并未出现大面积的氧化,涂层内部大小锌粉颗粒均匀排列;通过电化学方法研究涂层的耐蚀机理与防护性,发现活化富锌涂层具有更持久的低防护电位。以上研究结果表明,较冷涂锌及传统环氧富锌涂层而言,新型活化环氧富锌涂层具有优异的长期防护性能,是值得关注和研究的一种新型技术。     

铝合金表面电解沉积稀土转化膜工艺研究

研究了一种通过电解沉积方法在防锈铝LF21表面上生成铈盐转化膜的工艺,应用正交实验研究了有关因素对成膜过程的影响并获得了最佳的技术参数用极化曲线、交流阻抗和中性盐雾试验等方法测试了该工艺形成膜层的耐蚀性能及其组成一结果表明：经过电解沉积稀土转化膜处理后,防锈铝的阳极腐蚀过程受到了阻滞,自然腐蚀电位负移;与经过化学转化膜处理后相比,其耐蚀性能有显著提高,可通过400h的中性盐雾实验,亲水性能亦有明显提高。     

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.     

Service life prediction of organic coatings: electrochemical impedance spectroscopy vs actual service life

Electrochemical impedance spectroscopy (EIS) is used to derive an expression for predicting the service life of organic coating in a C4-type environment (industrial and costal areas with moderate salinity) as defined in ISO 12944 standard for paints and varnishes—corrosion protection of steel structures by protective paint systems. Three coating systems with a record of 2, 5, and 10 years of durability were selected for the study. The selection was also based on proven composition and dry film thickness (DFT) of the coatings as per ISO 12944. Electrochemical impedance measurements of the paint-coated panels were carried out by exposing the coated mild steel panels without scribe in different corrosive environments such as immersion in NaCl solution, neutral salt spray, etc. Neutral salt spray exposure was found to be the most severe corrosive environment among all the three coating systems. In most of the cases, EIS gave early indication of coating failure when compared to visual defects such as blistering and over-film corrosion.     

The effects of zinc aluminum phosphate (ZPA) and zinc aluminum polyphosphate (ZAPP) mixtures on corrosion inhibition performance of epoxy/polyamide coating

The epoxy/polyamide coating was loaded with different pigment mixtures of the zinc phosphate (ZP), zinc aluminum phosphate (ZPA) and zinc aluminum polyphosphate (ZAPP) pigments. The electrochemical impedance spectroscopy (EIS) and salt spray test were used to investigate corrosion inhibition performance of the coatings. The adhesion strengths of the coatings were measured by a pull-off test. Results revealed lower coating pull-off strength loss when the ZPA and ZAPP pigments were used. A significant decrease in number of blisters together with low pull-off strength loss and best corrosion inhibition properties were observed when the mixture of 80:20 of ZAPP:ZPA was used.     

Preparation and investigation of anticorrosion properties of the water-based epoxy-clay nanocoating modified by Na+-MMT and Cloisite 30B

In this study the effect of using nanoclay particles in two different matrices on anticorrosive performance improvement of a novel water-based epoxy coating was investigated. For this purpose, Na⁺-montmorillonite (Na⁺-MMT) and organo-montmorillonite (Cloisite 30B) were introduced into water-based hardener (RIPI-W.B.H.) and epoxy resin matrices, separately. Nanoclays were added to polymeric matrices using direct mixing under an ultrasonic homogenizer. The coatings were analyzed to ensure the intercalation and distribution of layered silicates by means of X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses. The structure of products is studied by infrared (IR) spectrometer. The corrosion protection performances of the coatings were investigated using salt spray test and electrochemical impedance spectroscopy (EIS) in 3.5% sodium chloride solution. The results showed that using Cloisite 30B in water-based hardener had the best performance and its application in anticorrosion water-based zinc rich epoxy coating approved of it.     

Salt spray and EIS studies on HDI microcapsule-based self-healing anticorrosive coatings

Anticorrosive property of hexamethylene diisocyanate microcapsule-based self-healing coatings was systematically investigated by salt spray and EIS measurements. The influences of microcapsule diameter, weight fraction and coating thickness on the anticorrosive performance of the scratched samples were studied under salt spray condition, which revealed the thicker coatings with larger microcapsules at 10 wt.% demonstrated the best anticorrosion behavior. Additionally, the kinetics of self-healing process characterized by EIS measurement was parametrically analyzed in an equivalent circuit when the scratched coating was exposed to salt solution. A simplified model was established to explain the influences of these factors with consideration of scratch dimension.     

Real time mapping of corrosion activity under coatings

Current accelerated testing of aircraft coating systems for corrosion protection relies heavily on salt spray methods. Electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and electrochemical noise methods (ENM) provide insight into the global properties of a coating system, and both techniques are being used on a limited basis. However, there is a need to investigate corrosion events with greater spatial resolution under coatings at the metal/coating interface. Such corrosion activity may be related to coating defects and variations in the surface chemistry of the underlying metal.

The scanning vibrating electrode technique (SVET) has been developed to allow high spatial resolution investigation of localized corrosion activity that may be associated with coating defects or galvanic coupled regions of the metal surface. The SVET offers high resolution in current measurements of the order of 0.5 μA/cm² and is able to detect in-situ initiation and progress of corrosion activity under a protective coating. Using the SVET, minute variations in d.c. current associated with localized corrosion activity are detected and used to map both anodic and cathodic corrosion activities in a localized area. The difference in initial corrosion activity under various coatings can be correlated to the performance life of the coatings. The application of SVET to aircraft coatings and corrosion is reported to demonstrate the utility of this important new electrochemical tool.

In the current study, the SVET was used to discriminate the corrosion protection performance of selected sol–gel based coating systems. Sol–gel based surface treatments are being developed as part of an environmentally compliant coating system alternative to the currently used chromate-based systems. The SVET results are compared with data obtained from chromium inhibition coating systems. The SVET analyses are compared with electrochemical impedance measurements. The comparison of such data will provide the basis to adopt SVET measurements as an early performance discriminator for newly developed coating systems.     

Synthesis of tungstate doped polyaniline and its usefulness in corrosion protective coatings

A study has been made on the corrosion protection performance of tungstate doped polyaniline containing vinyl coating on steel. The tungstate doped polyaniline was chemically synthesized and characterized by FTIR, XRD, UV-VIS and TGA studies. The corrosion protection performance of vinyl coating containing tungstate doped polyaniline on steel was assessed in 3% NaCl by electrochemical impedance studies (EIS). The coating has been found to offer protection more than 60 days in salt spray and immersion in 3% NaCl. FTIR studies have shown that the formation of iron–tungstate complex along with the passive film on steel.     

Corrosion protection of mild steel by nano-colloidal polyaniline/nanodiamond composite coating in NaCl solution

The polyaniline/nanodiamond (PANI/ND) nanocomposite coating was synthesized on mild steel via electrochemical polymerization using cyclic voltammetry technique. The ultrasonic irradiation was used for effectively dispersing ND particles in electropolymerization solution. The prepared nanocomposite films were found to be nano-colloidal, and very adherent with low porosity. X-ray diffraction and FTIR techniques confirmed the intercalation of the nanoparticles in PANI matrix. The corrosion performance of the coatings was investigated in 3.5% NaCl solution by electrochemical impedance spectroscopy (EIS), polarization, and salt spray methods. The obtained results showed that the presence of ND particles significantly enhanced the corrosion protection performance of the PANI films in corrosive medium. EIS and polarization measurements indicated that the coating resistance and corrosion resistance values for the PANI/ND nanocomposite coating were much higher than that of pure PANI-coated electrode. Also, the results obtained revealed that the protection efficiency of PANI/ND-coated mild steel is achieved about 90% after 3 days. The porosity in PANI/ND nanocomposite coating is almost 18 times lower than that of the PANI coating.     

A new approach to using submicron emeraldine-base polyaniline in corrosion-resistant epoxy coatings

The present work reports on a new approach to the preparation of special corrosion-resistant epoxy coatings. The aminic hardener of these coatings contained emeraldine-base polyaniline (EB-PANi). The aminic hardener was prepared by dispersion of EB-PANi in 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine employing sonication, centrifuging and submicron filtering methods. The state of dispersion and dissolution of these coating materials, during different stages of preparation, were characterized by optical microscopy and scanning electron microscopy. The corrosion resistances of resulting coatings were measured by electrochemical impedance spectroscopy (EIS) and salt spray methods. As little as 0.5% EB in initial mixture of EB-hardener compositions led to relatively better corrosion protection of resulting coating compared with neat resin coating. Presence of initial 2.5% of EB in the hardener and its processing through our approach resulted in the formulation of an epoxy coating with superior corrosion protection properties.     

Evaluation of the corrosion resistance of phosphate coatings obtained by anodic electrochemical treatment

The corrosion resistance of phosphate coating obtained by anodic electrochemical treatment at 4–6 mA/cm² is addressed in this paper. The corrosion performance of these coatings is also compared with the coatings obtained by chemical treatment. The regenerated phosphoric acid under the influence of anodic current causes a large variation in morphological features of the coatings. Immersion and salt spray tests indicate the ability of these coatings to act as a barrier film on mild steel. Polarization and electrochemical impedance spectroscopic (EIS) studies indicate that the corrosion resistance of phosphate coatings obtained by anodic treatment decreases with increase in current density employed for deposition. In spite of their higher coating weight, the corrosion resistance of phosphate coatings obtained by anodic treatment is inferior to those obtained by chemical treatment. The porosity or discontinuities created due to the dissolution of the coating under the influence of anodic current are considered responsible for the inferior corrosion resistance of these coatings. The study concludes that anodic treatment has only a limited scope for preparing phosphate coatings with improved corrosion resistance.     

Incorporation of silica network and modified graphene oxide into epoxy resin for improving thermal and anticorrosion properties

In this study, the silica network and functionalized graphene oxide (GO) were incorporated into the epoxy coating systems, which was aimed to improve the thermal property and corrosion resistance of epoxy coatings. First, tetraethyl orthosilicate (TEOS) oligomers and epoxy hybrid was fabricated through sol–gel method. Then the (3-aminopropyl) triethoxysilane (APTES) modified graphene oxide (FGO) was added into the epoxy hybrid composite to obtain anticorrosion coatings. Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), Raman spectrum, and X-ray photoelectron spectrum were conducted to evaluate the structural information of GO and APTES modified GO nanosheets. The results indicated that the APTES successfully grafted onto the surface of GO sheets. Besides, TGA curves, electrochemical measurements and salt spray test were also carried out to characterize the thermal performance and corrosion resistance of GO based epoxy coatings. The TGA results revealed that the thermal performance of epoxy coating containing silica network and FGO nanofiller (ES/FGO) was significantly strengthened compared to pure epoxy. The initial degradation temperature of epoxy coating was increased from 300 to 343.7°C after incorporation of silica component and FGO. The EIS measurements demonstrated that the impedance modulus of ES/FGO was significantly higher than neat epoxy, which indicated that the corrosion resistance of epoxy was substantially strengthened after introduction of silica component and FGO. The corrosion rate and inhibition efficiency of epoxy composite coatings were also shifted from 1.237 × 10⁻⁷ mm/year and 76.6% (for neat epoxy) to 1.870 × 10⁻⁹ mm/year and 99.6% (for ES/FGO), respectively. The salt spray test also revealed that the silica and FGO can improve the corrosion resistance of epoxy coating. Additionally, the dispersion of GO sheets was also enhanced after the modification of APTES siloxane.     

High performance polyaniline containing coating system for wet surfaces

Application of paint coatings on wet surfaces is rather difficult due to poor adhesion of coatings. For painting of wet surfaces, moisture curable coating systems based on epoxy resin and ketimine are found to be useful. Hence a study has been made on the corrosion protection ability of coating on wet surfaces using epoxy resin, ketimine and polyaniline. Paints with 20–30% PVC were prepared and applied over the wet steel surface and the corrosion protection performance of the coating was found out by salt spray and electrochemical impedance spectroscopic techniques. Coating with 20% PVC is found to offer very high protection since the impedance values are remained at greater than 10⁹ Ω cm² after immersion and salt spray tests.