Investigation on anticorrosion performance of nano and micro polyaniline in new water-based epoxy coating

In this research, a micro polyaniline (MicroPAni) and a dispersion of nano polyaniline particles (NanoPAni) were used as anticorrosion additive in a new water-based epoxy coating. Both materials were added directly to a new water-based hardener (RIPI-W.B.H.). The resulted mixtures were homogenized and sonicated for size reduction and better particle dispersion. The average particle size of polyaniline in the hardener was determined using dynamic light scattering (DLS). Transmission electron microscopy (TEM) was used to observe the particle size of polyaniline in the final dried film. After applying the coatings on metal surface, anticorrosion performance and adhesion properties of the coatings were compared together with a reference coating using salt spray and cross-cut adhesion tests. The results showed that anticorrosion performance of coating containing NanoPAni was better than the one for coating containing MicroPAni. In addition, investigation on the morphology of metal-coating interface by scanning electron microscopy (SEM) technique in samples containing polyaniline after salt spray test showed stable oxide layer formation on metal surface, which will enhance the corrosion resistance.     

环氧聚氨酯耐油涂料的研制

通过选择适当的聚酯树脂和环氧树脂，配以适当的异氰酸固化剂，研制了一种用于油箱的环氧聚氨酯耐油涂料。检测结果表明，该涂料具有良好的低温干燥性能、耐腐蚀性能，优异的耐油性能特别是耐高温油性能。该涂料将在各种工程设备的油箱中具有广阔的应用前景。     

The effect of organosilane on corrosion resistance of epoxy coating containing cerium nitrate

Structure and corrosion resistance behavior of epoxy coating containing cerium nitrate in different amounts of γ-glycidoxypropyltrimethoxysilane (γ-GPS) were investigated. Corrosion resistance ability of coating systems was characterized by using electrochemical impedance spectroscopy and polarization techniques. Also atomic force microscopy was used to evaluate dispersion of cerium nitrate in the presence of γ-GPS. Furthermore, the effect of γ-GPS on flexibility of coatings was studied by using the cupping test. Increment of 10?wt.% of γ-GPS into the coating formulation led to the superior dispersion of cerium nitrate and also highest corrosion protection performance.     

纳米改性工业防腐蚀涂料的研制与应用

介绍了纳米改性工业防腐蚀涂料的制备工艺,包括纳米浓缩浆、纳米改性环氧封闭漆、纳米改性环氧云铁中间漆以及纳米改性含氟聚氨酯面漆等系列产品的制备与表征。测试结果表明,纳米材料在纳米浆及涂料中获得了良好分散,纳米改性复合涂层(即喷铝涂层+纳米改性环氧封闭漆+纳米改性云铁中间漆+纳米改性含氟聚氨酯面漆)的物理机械性能以及耐久性均得到显著提高,产品在实际工程应用中也取得了可喜成果。该纳米改性工业防腐蚀涂料具有良好的应用前景。     

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.     

Self-healing and anticorrosive properties of Ce(III)/Ce(IV) in nanoclay–epoxy coatings

The self-healing and anticorrosion effects of cerium nitrate in epoxy–clay nanocomposite coatings systems were studied. Different amounts of cerium (III) were added to epoxy–montmorillonite clay composites and the nanocomposite coatings were prepared and applied on cold rolled steel panels. Ultrasonication was applied to disperse the nanoclay into the epoxy cerium nitrate composition. Electrochemical impedance spectroscopy (EIS) was used to study the self-healing and anticorrosion behaviors of the coatings. The structure of the dry coating and the protective mechanism of the pigments in the coating were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) analysis and field emission electron microscopy (FESEM). Transmission electron microscopy (TEM) illustrated the separation of clay layers which interacted with the epoxy resin. Electrochemical impedance data indicated that the epoxy cerium (III)–montmorillonite nanocomposite coatings were superior to the epoxy coatings in corrosion protection properties. The self-healing behavior of such coatings was due to the presence of cerium nitrate that could be released at the defects within the coating and hindered the corrosion reactions at the defective sites. It was shown that the best corrosion protection was achieved with nanocomposite coatings containing 4 wt% clay and 2 wt% cerium nitrate.     

Synergistic Effects of Montmorillonite/Cerium Nitrate Additives on the Corrosion Performance of Epoxy-Clay Nanocomposite Coatings

In this work, different amounts of montmorillonite were added to cerium nitrate epoxy mixture. Nanocomposite coatings containing cerium nitrate were applied on cold rolled steel panels. The state of dispersion and incorporation were characterized by transmission electron microscopy and atomic force microscopy. To investigate anticorrosive properties of nanocomposites, electrochemical impedance spectroscopy, polarization measurement and salt spray tests were employed. Results showed that epoxy cerium nanocomposite coatings were superior to the neat epoxy in corrosion protection properties. Also, it was observed that the best corrosion protection was achieved with nanocomposite coatings containing 4 wt.% and 2 wt.% cerium nitrate.     

Undoped polyaniline–surfactant complex for corrosion prevention

Due to the strict regulations on the usage of heavy metals as the additives in the coating industries, the search for effective organic corrosion inhibitors in replacement of metal additives has become essential. Electrically conducting polymers have been shown to be effective for corrosion prevention, but the poor solubility of these intractable polymers has been a problem. We have explored a polyaniline–4-dodecylphenol complex (PANi–DDPh) to improve the dissolution, and it has been shown to be an effective organic corrosion inhibitor. With the surfactant, DDPh, PANi could be diluted into the coatings, and the properties of the coatings were affected. An emeraldine base (EB) form of PANi was also found to be oxidized by the hardener. The oxidized form of polyaniline provides improved corrosion protection of metals than that of emeraldine base since the value of the standard electrode potential for the oxidized form of PANi is higher than that of EB. Additionally, the surfactant improves the wet adhesion property between the coating and the metal surface. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2849–2856, 1999     

AZ91D镁合金表面不同树脂体系富镁涂层的保护性能

采用划叉浸泡实验,电化学交流阻抗(electrochemical impedance spectroscopy,EIS),开路电位(open circuit potential,OCP)及动电位扫描研究了不同类型的环氧树脂对于AZ91D镁合金的表面的富镁涂层的保护性能的影响。结果表明环氧618-593构成的富镁涂层防护性能较差;环氧6101-TY650制备的富镁涂层可明显改善涂层对破损处镁合金基体的保护作用,但涂层本身长期防护性能较差;环氧618-T31构成的富镁涂层对AZ91D镁合金的防护作用较强,适宜制备镁合金表面的富镁涂层。3种环氧涂料中加入镁粉颗粒制备的富镁涂层均可对缺陷处裸露的AZ91D镁合金基体提供保护,从而延长漆膜的破坏时间。涂层中的镁粉颗粒被激活后,为镁合金的基体提供了一定程度的阴极保护作用,减缓了镁合金基体的腐蚀。     

Aminic epoxy resin hardeners as reactive solvents for conjugated polymers: polyaniline base/epoxy composites for anticorrosion coatings

Polyaniline (PANI) has much been studied in the context of corrosion prevention, particularly on steel and aluminium. To prepare epoxy coatings consisting of PANI has turned to be nontrivial, due to its relatively rigid conformation and poor solubility. Therefore, as the aim has typically been first to dissolve PANI in the epoxy component before curing, auxiliary solvents have been required, and less attractive Lewis-type hardeners have been required if the conducting salt form has been used. In this work, we describe a particularly simple concept where emeraldine base (EB) form of PANI is first dissolved in specific aminic hardeners which are observed to be solvents for EB at low concentrations, and the mixtures are unconventionally cross-linked upon adding epoxy resin, diglycidyl ether of bisphenol-A (DGEBA). Suitable hardeners are N,N,N′,N′-tetrakis(3-aminopropyl)-1,4-butanediamine (DAB-AM-4) and trimethylhexanediamine (TMDA). Even if the subsequent cross-linking promotes phase separation, the forming cross-link sites may also control the phase separation. As a result, sufficiently homogeneous coatings are identified which contain only 1 wt% EB in the cured EB/DGEBA/TMDA composites where in aqueous 3.5% NaCl solution the corrosion front propagation is suppressed, and electrochemical impedance studies indicate the formation of a charged interface or reaction product layer between EB and steel. For reference, similar net EB/DGEBA/TMDA-compositions were prepared, where EB was first mixed in DGEBA without any solubility and which were cured by added TMDA, and they gave essentially no anticorrosion effect. We expect that the present concept opens new ways to prepare cured epoxy composites also with other conjugated or nonconjugated polymers for anticorrosion and other functional purposes.     

Effect of the incorporation of montmorillonite-layered double hydroxide nanoclays on the corrosion protection of epoxy coatings

A series of layered double hydroxide (LDH)/montmorillonite (MMT) nanocomposite coating, LDH nanocomposite coating, and MMT nanocomposite coating were successfully prepared. The nanocomposite materials were characterized by X-ray diffraction and scanning electron microscopy (SEM). To understand the effect of MMT and LDH on the corrosion inhibition performance of epoxy resin coatings immersed in 3.5 wt% saline solution at 90°C, electrochemical impedance spectroscopy and an autoclave test were performed on epoxy resin; epoxy resin blended with LDH, MMT, and LDH + MMT (LM) coatings painted on Q345 steel. The metal/coating interfaces were observed by SEM and energy-dispersive spectroscopy. Results showed that addition of LDH and MMT improved the protection properties of the epoxy resin coatings. The corrosion protection of the LM nanocomposite coating was superior to that of the other coatings. This finding can be attributed to the ionic selectivity and barrier effect of MMT and LDH nanoclay platelets dispersed within the composite coatings.     

Effect of polypyrrole–montmorillonite nanocomposites powder addition on corrosion performance of epoxy coatings on Al 5000

The synthesis of hybrid polypyrrole–montmorillonite (Ppy–MMT) nanocomposites and their effects on the improvement of the protection efficiency of the epoxy coatings on aluminum corrosion were studied. In order to understand the effect of MMT and Ppy on the corrosion inhibition performance of the epoxy coatings in 3.5% NaCl solution, the epoxy (E), epoxy blend with MMT (EM) and polypyrrole (EP) coatings were investigated by electrochemical impedance spectroscopy (EIS). It was shown that EM and EP systems could not provide a good corrosion protection for long-time applications. The results showed that the incorporation of Ppy–MMT nanocomposites inside the epoxy notably increases the resistance of the coating in comparison to the other coatings for long-time period. These phenomena can be attributed to specific morphology of the nanocomposite. The structure and morphology of nanocomposites were studied by FT-IR and XRD techniques, as well as, scanning electron microscopy (SEM).     

Formulation and study of corrosion prevention behavior of epoxy cerium nitrate–montmorillonite nanocomposite coated carbon steel

Nanocomposite coatings which were applied on carbon steel panels based on epoxy cerium nitrate–montmorillonite (MMT) were synthesized and formulated. Nanoparticles were incorporated into epoxy resin by mechanical and sonication processes. The state of dispersion, dissolution, and incorporation were characterized by optical microscopy, sedimentation tests, X-ray diffraction, and transmission electron microscopy. To investigate anticorrosive properties of nanocomposite coatings, electrochemical impedance spectroscopy and salt spray tests were employed. The experimental results showed that epoxy cerium nitrate–MMT nanocomposite coatings were superior to the neat epoxy in corrosion protection effects. In addition, it was observed that the corrosion protection of nanocomposite coatings was improved as the clay loading was increased up to 4–2 wt% cerium nitrate.     

Hydrophobic benzoxazine-cured epoxy coatings for corrosion protection

A hydrophobic benzoxazine-cured epoxy coating (EPB) was prepared by a dip coating and thermal curing method using benzoxazine monomer (B-TMOS) as curing agent. Fourier transform infrared (FTIR) analyses confirmed the presence of thermal curing reactions and hydrogen-bonding interactions in the epoxy/polybenzoxazine system. The hydrophobicity of epoxy coatings induced by the incorporation of B-TMOS was enhanced significantly, and the water contact angles of resultant EPB coatings were higher than 98°. The corrosion protection ability of epoxy coatings was investigated by open-circuit potentials, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) methods. The results showed that the charge transfer resistance (R_ct) of EPB coatings was increased by about three orders of magnitude compared with bare mild steel, and the protection efficiency values of all EPB samples were more than 98%. This increased corrosion protection property could be attributed to the high hydrophobic performance of EPB coatings.     

Designing of corrosion resistant epoxy coatings embedded with polypyrrole/SiO2 composite

Polypyrrole/SiO₂ composite was synthesized by chemical oxidative polymerization of pyrrole using FeCl₃. The synthesized polymer composite was loaded in epoxy resin to develop coatings for mild steel substrates using powder coating technique. SEM and TEM images reveal homogenous dispersion of SiO₂ particles in polypyrrole matrix. TGA analysis confirms good thermal stability of the polymer composite. Tafel polarization and electrochemical impedance spectroscopy (EIS) results exhibit remarkably high corrosion protection efficiency of epoxy coatings with polymer composite in 3.5% NaCl solution. Corrosion studies of coatings with an artificial defect reveal the passivation of defect by the polymer composite present in the epoxy coatings. Salt spray test results revealed superior corrosion resistance offered by the polymer composite.     

Synthesis of 3-glycidoxypropyltrimethoxysilane modified hydrotalcite bearing molybdate as corrosion inhibitor for waterborne epoxy coating

Zinc aluminum hydrotalcite intercalated with molybdate (HTM) and modified by 3-glycidoxypropyltrimethoxysilane (HTM-GS) was prepared and incorporated into a waterborne epoxy coating. The synthesized HTM-GS was characterized by FTIR, XRD, SEM, and TEM. The inhibitive action of HTM-GS on carbon steel was evaluated using electrochemical measurement and SEM/EDX analysis. The corrosion protection of the waterborne epoxy coating containing HTM-GS was evaluated and compared to that of the pure waterborne epoxy coating and the waterborne epoxy coating containing HTM by salt spray test and adhesion measurement. It was shown that the molybdate was intercalated in the hydrotalcite structure and the molybdate contents in HTM and HTM-GS were 16.0 and 13.2 wt%, respectively. The polarization curves obtained on the carbon steel electrode showed that HTM and HTM-GS are anodic corrosion inhibitors, and their inhibition efficiencies at concentration of 3 g/l were 92.0 and 94.7%, respectively. Additionally, HTM and HTM-GS at concentration of 0.5 wt% improved corrosion resistance and adhesion of waterborne epoxy coatings. Surface modification by 3-glycidoxypropyltrimethoxysilane ameliorated the dispersion of HTM in epoxy matrix and the effect of HTM on protection properties of waterborne epoxy coating.     

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。     

聚硫橡胶改性环氧防水防腐涂料

研制了聚硫橡胶改性环氧防水防腐涂料,用于金属和混凝土表面的防水防腐。介绍了该涂料的配制及其原料的选择,并列举了涂料的性能指标。讨论了聚硫橡胶与环氧树脂的配比和固化剂用量对涂层性能的影响。     

The performance of epoxy coatings containing polyaniline (PANI) nanowires in neutral salt,alkaline, and acidic aqueous media

PANI/epoxy coatings have great promise applications in the industry as the metal corrosion protection coating, and their performance directly determines the life span of the coating and equipment durability. In this study, the performance of epoxy coatings with and without PANI nanowires immersed in 12 wt% NaCl, 5 wt% HCl, and 5 wt% NaOH solutions at different temperature were investigated for the first time. The performance and the degradation reactions of the coating cooperated with PANI nanowires were characterized by the variety of techniques and methods, including ultraviolet–visible spectrophotometry (UV–vis), field emission scanning electron microscopy (SEM), Attenuated Total Reflectance-Fourier transform Infrared spectroscopy (ATR-FTIR), and thermogravimetric analysis (TGA). The experiment results indicated that the failure mechanism of the different coatings varied with the different temperatures and solutions. Electrochemical impedance spectra (EIS) results showed that an appropriate content of PANI nanowires improve the protection performance of epoxy coatings in 12 wt% NaCl, 5 wt% HCl, and 5 wt% NaOH solutions, which is attributed to the passivation ability and shielding effect of PANI nanowires.     

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.