Protective behaviors of 2-mercaptobenzothiazole intercalated Zn–Al-layered double hydroxide coating

A nanocontainer with 2-mercaptobenzothiazole (MBT)-intercalated Zn–Al-layered double hydroxides (LDHs) was synthesized through co-precipitation. The structures of the LDH and the nanocontainer were characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray analysis. The nanocontainer was added into 3.5 wt% NaCl solutions with different pH values to study its effect on the protection of Q345 steel. The corrosion rate of Q345 steel in 3.5 wt% NaCl solution with a pH value of 3 was lower than those in neutral and alkali solutions. Moreover, the addition of nanocontainers into the epoxy resin coating improved the performance of the coating and facilitated self-healing by releasing MBT inhibitors into the scratched area.     

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.     

Self-healing epoxy coatings loaded with inhibitor-containing polyelectrolyte nanocapsules

The self-healing polymer coatings containing organic corrosion inhibitors are intensively investigated as an alternative for highly toxic Cr(VI)-based systems. Protective self-healing coatings are realized by embedding “smart” containers, able to release a corrosion inhibitor under some specific conditions occurring when the corrosion process starts (e.g. on pH change) or upon a mechanical damage. In this study a system with the corrosion inhibitors (2-methylbenzothiazole (BT) and 2-mercaptobenzothiazole (MBT)) encapsulated inside the polyelectrolyte nanocapsules embedded in the water-based epoxy coatings is tested for its self-healing performance. The nanocontainers were prepared by the electrostatic adsorption of polyelectrolytes directly on the oil phase drops containing the inhibiting agent. The results for BT emulsion droplets and the mixture of BT and MBT encapsulated by docusate sodium salt/poly(diallyldimethylammonium chloride) (AOT/PDADMAC) and docusate sodium salt/poly(diallyldimethylammonium chloride)/poly(styrene sulfonate) (AOT/PDADMAC/PSS) surface complexes are presented.The X-ray Photoelectron Spectroscopy (XPS) was used to confirm the release of the inhibitor from the scratched coating. The influence of the nanocapsules on the barrier properties and self-healing performance of the epoxy coatings were tested by electrochemical impedance spectroscopy (EIS) in NaCl solution, the salt spray test (SST) according to ISO9227 and filiform corrosion test (FFT) according to EN ISO 3665. Potential blistering was rated according to EN ISO 4628-2.     

Sol–gel based layer-by-layer deposits of lanthanum cerium molybdate nanocontainers and their anticorrosive attributes

The present study focuses on the synthesis of novel lanthanum cerium molybdate (LCM) nanoparticles by sol–gel synthesis method and their use in the development of nanocontainers in an anticorrosive coating application. The obtained nanoparticles were used as core material with two different polyelectrolytic shells comprising of polypyrrole (PPY) and polyacrylic acid (PAA) or polyethyleneimine (PEI) and polystyrene sulfonate (PSS) involving the entrapment of benzotriazole (BTA) as the corrosion inhibitor using layer-by-layer (LBL) deposition method. At each step of this nanocontainer synthesis, the thickness of the layers, surface charges and the presence of the functional groups were determined by particle size, zeta potential and Fourier transform infrared spectroscopy (FTIR) analysis, respectively. The X-ray diffractograms (XRD) indicated the change in the crystallinity of the nanoparticles and nanocontainers while thermogravimetric analysis (TGA) showed the thermal degradation behavior of the nanocontainers. The morphological studies conducted using scanning electron microscopy (SEM) exhibited the formation of nanocontainers containing nanoparticles in their cores. The release of BTA from the nanocontainers was evaluated at different pH values. The anticorrosive performance of the nanocontainers was examined by incorporation of the nanoparticles and nanocontainers in a commercial epoxy coating system and to be applied on mild steel and magnesium panels by electrochemical corrosion analysis. Tafel plots demonstrated the decrease in the current density with an increase in the loading percentage of nanocontainers in the epoxy system while Bode plots confirmed the significant improvement in the corrosion protection of the mild steel and magnesium by LCM nanoparticles and nanocontainers.

     

聚己内酯静电纺丝纳米纤维与环氧树脂复合涂层防腐性能的研究

利用静电纺丝法在Q345钢表面制备聚己内酯(PCL)与缓蚀剂二巯基苯并噻唑(MBT)的纳米纤维膜PCL/MBT,然后在其表面旋涂环氧树脂(EP),得到复合涂层。通过电化学阻抗谱技术研究了复合涂层的防腐蚀性能。结果表明:在温度为25 ℃、湿度20%、纺丝电压15 kV、接收距离18 cm、V(氯仿)∶V(丙酮)=2∶3的条件下,PCL质量分数为12%,MBT质量浓度为0.01 g/mL时,静电纺丝得到的纳米纤维表面光滑,粗细均匀。电化学测试结果表明:EP/PCL/MBT复合涂层的防腐性能优于EP/PCL或EP涂层。     

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.     

Preparation of high‐k composites with low dielectric loss based on the double‐layer coaxial structure of inorganic/polymer

This study presents a novel and simple modification of cladding multiwalled carbon nanotubes (MWCNTs) using organic polymer and inorganic nanoparticles to synthesize a product, which has a double‐cladding coaxial structure and can be applied as filler in the dielectric field. The first layer of MWCNTs was coated with polyaniline (PANI) through the oxidation–reduction reaction mechanism using Ce(NH₄)₂(NO₃)₆ as oxidizing agent and metal precursor of cerium oxide. Cerium ions on the second cladding layer of MWCNTs were directly deposited from the solution to the surface of the PANI layer forming the double‐cladding hybrid (CeO₂/PANI@MWCNTs). The external inorganic layer provides an insulating shell, which can prevent the contact between the conductive particles and hinder the migration of electrons between the MWCNTs. The intermediate layer of PANI provides the bonding between CeO₂ and the conductive core of MWCNTs, which also shows lower conductivity than carbon nanotubes. The CeO₂/PANI@MWCNTs were compounded with epoxy (EP) resin and formed a dielectric material with the advantage of reducing dielectric loss while ensuring high dielectric constant. The dielectric constant of the coated MWCNTs/EP composites was 194.90 at 10³ Hz with the content of fillers reaching 30 wt %, which is 28 times that of the pure EP. Accordingly, the dielectric loss of 30 wt % coated MWCNTs/EP composites was only 0.09 at 10³ Hz, which is only 2.25 times that of the pure EP. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46299.     

Application of EIS and EN techniques to investigate the self-healing ability of coatings based on microcapsules filled with linseed oil and CeO2 nanoparticles

Microcapsules with urea–formaldehyde as the shell and linseed oil as the healing agent were synthesized by a previously reported procedure. Two kinds of synthesized microcapsules, without and with CeO₂ nanoparticles, were separately added to the epoxy resin coatings. The epoxy coatings containing microcapsules were applied on carbon steel, and their self-healing effect was investigated in 0.5 M HCl solution. The amount of the released healing agent that filled up the scratch was estimated by scratch filling efficiency (SFE). The SFE values are only the theoretical estimates of the self-healing performance. The scratch sealing efficiency (SSE), which is a measure of corrosion protection performance of the damaged coating, can be measured by electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) techniques. For sake of an optimum self-healing system, two series of coatings, with and without nanoparticles, were prepared by using different microcapsule concentrations: 5, 10, 15 and 20 wt%. For comparison, a coating without microcapsules was also prepared. The coated samples with 5% microcapsule concentration, due to the low amount of released linseed oil, could not properly repair the artificial scratch. In contrast, when the microcapsule concentration was equal to or higher than 10% the volume of the released linseed oil was enough to seal the scratch. However, the coating sample containing 15% nanoparticle-loaded microcapsules was the optimum self-healing coating because it showed comparable SSE values to those of samples containing 20% microcapsule concentration in spite of its lower microcapsule concentration. The EN method was employed as a complementary quantitative technique to study the self-healing behavior of coatings. The calculation of the amount of noise charges using the standard deviation of partial signal (SDPS) plots arising from wavelet analysis made it possible to obtain the SSE values of the coatings. The good agreement between EIS and EN results indicates that the EN technique, as well as the EIS method, can be used successfully for the self-healing evaluation.     

Improvement of anti-corrosive properties of epoxy-coated AA 2024-T3 with TiO2 nanocontainers loaded with 8-hydroxyquinoline

Epoxy coatings containing TiO₂ nanocontainers were applied on aluminium alloy (AA) 2024-T3 for corrosion protection. The nanocontainers were loaded with the corrosion inhibitor 8-hydroxyquinoline (8-HQ). Epoxy coatings were deposited via the dip-coating process. The morphology of the coatings was examined by scanning electron microscopy (SEM). The composition of the films was determined by energy dispersive X-ray analysis (EDX). Electrochemical impedance spectroscopy (EIS) was employed for the characterization of the corrosion resistance of these coatings. The total impedance values were measured as a function of time exposure in corrosive environment. We observed a continuous increase of the total impedance value with the time of exposure suggesting a possible self-healing effect due to the release of the inhibitors from the nanocontainers. Furthermore, addition of loaded nanocontainers into the coatings leads to the enhancement of the barrier properties of the coatings. Conclusively, we observed an improvement of the performance of the coatings due to the loaded nanocontainers.     

Silica nanocontainers for active corrosion protection

Novel self-healing protective coatings with nanocontainers of corrosion inhibitors open new opportunities for long-term anticorrosion protection of different metallic materials. In this paper a new type of functional nanoreservoir based on silica nanocapsules (SiNC) synthesized and loaded with corrosion inhibitor 2-mercaptobenzothiazole (MBT) in a one-stage process is reported for the first time. Unlike conventional mesoporous silica nanoparticles, SiNC possess an empty core and shell with gradual mesoporosity, arising from the particular conditions of the synthetic route adopted, which confers significant loading capacity and allows prolonged and stimuli-triggered release of the inhibiting species. The kinetics of inhibitor release was studied at different pH values and concentrations of NaCl. The results show a clear dependence of the release profiles on corrosion relevant triggers such as pH and Cl(-) concentration. When SiNC loaded with MBT are dispersed in NaCl solution, there is a significant decrease of the corrosion activity on aluminium alloy 2024. More importantly, when SiNC-MBT is added to a conventional water-based coating formulation, the modified coating hampers corrosion activity at the metal interface, better than in the case of direct addition of corrosion inhibitor. Furthermore, self-healing is observed before and after artificially inflicting defects in the modified coatings. As a result, the developed nanocontainers show high potential to be used in new generation of active protective coatings.     

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.     

A study on the effect of presence of CeO2 and benzotriazole on activation of self‐healing mechanism in ZrO2 ceramic‐based coating

In this study, the effect of presence of CeO₂ and benzotriazole inhibitor agent on activation of self‐healing reactions and the corrosion behavior of ZrO₂ ceramic‐based coating are evaluated. The ZrO₂ and ZrO₂‐CeO₂‐benzotriazole ceramic‐based coatings were synthesized using sol–gel process and heat treated at 150°C. Afterward, X‐ray diffraction analysis (XRD), and Field Emission Scanning Electron Microscopy (FE‐SEM) were utilized to evaluate the phase analysis and morphology of these coatings. In addition, Energy Dispersive Spectroscopy (EDS) was used for elemental analysis of obtained coatings. Corrosion and self‐healing behavior of the coatings were investigated in 3.5 wt% NaCl solution using Electrochemical Impedance Spectroscopy (EIS) and potentiodynamic polarization tests. The results of XRD analysis revealed the amorphous nature of both coatings. FE‐SEM observations and EDS analysis results showed the presence of benzotriazole inhibitor agent and self‐healing reactions in the cracks and defects of ZrO₂‐CeO₂‐benzotriazole ceramic‐based coating. Moreover, results of electrochemical tests revealed that the presence of CeO₂ and benzotriazole inhibitor agent in the ZrO₂ ceramic‐based coating results in intense increases in the corrosion resistance of this coating by activating the self‐healing mechanism and forming passive layers.     

Self-healing anticorrosion coating containing 2-mercaptobenzothiazole and 2-mercaptobenzimidazole nanocapsules

γ-cyclodextrin (γ-CD) inclusion complex containing 2-mercaptobenzothiazole (MBT) or 2-mercaptobenzimidazole (MBI) as guest was prepared by precipitation method at two conditions (at room temperature and under sonic energy). Supramolecular nanocontainers were characterized by ¹H-NMR, XRD, SEM, DSC and FTIR, which proves the formation of the inclusion complex where the benzyl part of MBT or MBI has been encapsulated by the hydrophobic cavity of γ-CD. Differences between ¹H-NMR, FTIR and XRD spectra of physical mixtures and inclusion complex indicated formation of MBT/γ-CD and MBI/γ-CD supramolecular nanocontainers in solid phase.     

Preparation and corrosion resistance studies of nanometric sol-gel-based CeO2 film with a chromium-free pretreatment on AZ91D magnesium alloy

Magnesium alloy, although valuable, is reactive and requires protection before it can be applied in many fields. In this study, a novel protective environmental-friendly gradient coating was performed on AZ91D magnesium alloy by non-chromate surface treatments, which consisted of phytic acid chemical conversion coating and the sol-gel-based CeO₂ thin film. The surface morphologies, microstructure and composition of the coatings were investigated by scanning electron microscopy (SEM), energy disperse spectroscopy (EDS) and X-ray diffraction (XRD), respectively. The corrosion resistance of the coatings was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in 3.5 wt.% NaCl solution. The effects of the concentration, layers, temperature of heat treatment of CeO₂ sol on the anti-corrosion properties of the gradient coating for magnesium were also investigated. The results showed that the gradient coating was mainly composed of crystalline CeO₂. According to the results of electrochemical tests, the corrosion resistance of AZ91D magnesium alloy was found to be greatly improved by means of this new environmental-friendly surface treatment.     

Protective abilities of nanocomposite coatings containing Al2O3 nano-particles loaded by CeCl3

The protective ability of hybrid nano-composite oxysilane coatings, deposited via sol–gel method on AA2024-T3 – aluminium alloy, were studied by linear voltammetry (LVA) and electrochemical impedance spectroscopy (EIS) methods in 0.05 M solution of NaCl. Cerium chloride (CeCl₃) was incorporated as an inhibitor into a sol–gel hybrid matrix in two different routes: directly and via filled porous Al₂O₃ nano-particle aggregates with diameters up to 500 nm. The influences of the inhibitor concentration, as well as the influence of nano-particles on the barrier properties and the susceptibility against corrosion, were evaluated and EIS spectra were fitted by appropriated equivalent circuits. The values for C_coat, R_coat, C_oxy and R_oxy were achieved and their evolution over time was investigated. The investigated coatings possess highly expressed barrier properties (10⁶ to 10⁷ Ω cm²). Despite of the chloride ions inside of the matrix, some samples illustrated a significant durability of over 4000 h during exposure to the corrosion medium before first signs of corrosion appeared. The electrochemical results were compared with the neutral salt spray test. Thus, it was proved that the potential of these coatings is to be used as anticorrosive protective materials and are candidate to replace Cr(VI)-based anti-corrosion coatings.     

Corrosion inhibition of magnesium using biocompatible Alkyd coatings incorporated by mesoporous silica nanocontainers

In the present study, mesoporous silica nanocontainer powders with and without inhibitor (fluoride) were dispersed in the Alkyd coatings to improve corrosion resistance of Mg metal. Then, the corrosion behavior of these coatings was studied in comparison with Mg in 2 g dm⁻³ NaCl solution. Electrochemical tests showed that these coatings could protect the surface from chloride attack. Moreover, release of fluoride from mesoporous silica nanocontainers leads to the formation of MgF₂ as an inhibitive compound at the interface.     

Corrosion inhibition of steel using mesoporous silica nanocontainers incorporated in the polypyrrole

Mesoporous silica nanocontainer powders were applied as corrosion inhibitor hosts. These powders were dispersed in the polypyrrole matrix by electropolymerization technique. The protection properties of these composite coatings with and without inhibitor were studied in 2 g dm⁻³ chloride ion solutions at constant pH. Open circuit potential (OCP), inductive coupled plasma (ICP), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and Fourier transform infrared spectroscopy (FTIR) results showed that the substrates were protected due to the release of corrosion inhibitor from mesoporous silica in the chloride media compared to the coatings without corrosion inhibitor. The released corrosion inhibitor reacted with substrate and made a protective phase during corrosion. This phase can heal the corroded area as a self-healing compound.     

Corrosion performance of waterborne epoxy coatings containing polyethylenimine treated mesoporous-TiO2 nanoparticles on mild steel

Waterborne epoxy coatings were modified by adding mesoporous-TiO₂ nanoparticles (meso-TiO₂). In order to achieve proper dispersion of meso-TiO₂ in the epoxy-based coating and make possible chemical interactions between meso-TiO₂ and polymeric coating, meso-TiO₂ was treated with polyethylenimine (PEI) of various molecular weights. Corrosion performance of mild steel coated specimens was investigated employing electrochemical impedance spectroscopy (EIS) and salt spray test. Coatings with meso-TiO₂/PEI (600 molecular weight) possessed the best corrosion performance among the coating specimens. The EIS results showed that the resistance value of coating with meso-TiO₂/PEI (600 molecular weight) was above 9.87 × 10⁷ Ω cm² which was higher than neat epoxy coating. Possible chemical interactions between polymeric matrix and treated nanoparticles caused high barrier properties and high degree of cross-linking.     

PANI-chitosan-TiO2 ternary nanocomposite and its effectiveness on antibacterial and antistatic behavior of epoxy coating

A straightforward approach has been developed for fabricating antibacterial and antistatic epoxy coatings by using polyaniline-chitosan modified TiO₂ ternary nanocomposite. This nanocomposite was synthesized through the following steps. First, chitosan was grafted onto the TiO₂ nanoparticles and then final nanocomposite was prepared via solution polymerization of aniline. Electrical conductivity measurement revealed that nanocomposite with 7.5 wt % of the modified TiO₂ nanoparticles has noticeably higher conductivity compared to polyaniline. Evaluating the coatings' antibacterial property indicated epoxy coatings with the content of ternary nanocomposite show significant bactericidal activity against Gram-positive bacteria and have acceptable antibacterial action against Gram-negative ones. Also, obtained results showed that the ternary nanocomposite would greatly decrease coatings' surface resistivity and when nanocomposite content is about 2 wt % surface resistivity is about 3 × 10⁷ Ω sq⁻¹. On the contrary, the coating with nanocomposite loading exhibits improved thermal and mechanical performance compared to the coating made of neat epoxy. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47629.     

Surface of LiCo1/3Ni1/3Mn1/3O2 modified by CeO2-coating

A novel method to improve the cycling performance of LiCo_1/3Ni_1/3Mn_1/3O₂ in lithium-ion batteries by 1.0 wt.% CeO₂-coating is presented in this work. The crystalline structure and morphology of the synthesized powder have been characterized by XRD, SEM, TEM and their electrochemical performances were evaluated by CV, EIS and galvonostatic charge/discharge tests. It is found that CeO₂ forms a layer on the surface of LiCo_1/3Ni_1/3Mn_1/3O₂ without destroying the crystal structure of the core material. Electrochemical test indicates that CeO₂-coating could improve the cycling performance of LiCo_1/3Ni_1/3Mn_1/3O₂. At room temperature, the capacity retention of 1.0 wt.% CeO₂-coated material is 93.2% after 12 cycles at 3.0 C while that of the bare sample is only 86.6%. ICP-OES proves the coating layer could protect the dissolution of the transition metal ions from LiCo_1/3Ni_1/3Mn_1/3O₂. From the analysis of EIS, the improvement of cycle ability could be attributed to the suppression of the reaction between cathode and electrolyte.