Conducting polymer based hybrid nano-composites for enhanced corrosion protective coatings

Hybrid composite coatings containing zinc oxide (ZnO) and polyaniline (PANI) as nano-additives dispersions were prepared with poly(vinyl acetate) (PVAc) as the major matrix. The steel plates dip-coated with these formulations were tested for corrosion protection by immersion in saline water over long periods. The Tafel plots for the determination of open circuit potential (OCP) and corrosion current (I_corr) were recorded. The coatings containing both ZnO and PANI showed improved corrosion resistance as compared to the single component coating. The I_corr values of PVAc–ZnO–PANI are found to be two-order magnitude lower than that of PVAc and PVAc–ZnO coatings. The results are explained on the basis of enhancement in barrier properties due to nano-particulate additives in PVAc–ZnO–PANI film together with the redox behaviour of PANI and protective oxide layer formation near the substrate.     

Performance of zinc phosphate coatings obtained by cathodic electrochemical treatment in accelerated corrosion tests

The formation of zinc phosphate coating by cathodic electrochemical treatment and evaluation of its corrosion resistance is addressed. The corrosion behaviour of cathodically phosphated mild steel substrate in 3.5% sodium chloride solution exhibits the stability of these coatings, which lasts for a week's time with no red rust formation. Salt spray test convincingly proves the white rust formation in the scribed region on the painted substrates and in most part of the surface on unpainted surface. The protective ability of the zinc corrosion product formed on the surface of the coated steel is evidenced by the decrease in the loss in weight due to corrosion of the uncoated mild steel, when it is galvanically coupled with cathodically phosphated mild steel. Potentiodynamic polarization curves reveal that E_corr shifts towards higher cathodic values (in the range of −1000 to −1100 mV versus SCE) compared to that of uncoated mild steel and conventionally phosphated mild steel substrates. The i_corr value is also very high for these coatings. EIS studies reveal that zinc dissolution is the predominant reaction during the initial stages of immersion. Subsequently, the non-metallic nature of the coating is progressively increased due to the formation of zinc corrosion products, which in turn enables an increase in corrosion resistance with increase in immersion time. The zinc corrosion products formed may consist of zinc oxide and zinc hydroxychloride.     

Deposition of zinc–zinc phosphate composite coatings on steel by cathodic electrochemical treatment

The present work aims at the development of an energy-efficient and eco-friendly approach for the deposition of zinc phosphate coatings on steel. The study describes the possibility of preparing zinc–zinc phosphate composite coatings by cathodic electrochemical treatment using dilute phosphoric acid as an electrolyte and zinc as an anode. The methodology enables the preparation of coatings with different proportions of zinc and zinc phosphate by suitably varying the applied current density, pH, and treatment time. Adhesion of the coating on mild steel and adhesion of paint film on the phosphate coating were found to be good. The surface morphology of the coatings exhibited platelet-type features and small white crystals (agglomerated at some places) which represented zinc and zinc phosphate, respectively. An increase in current density (from 20 to 50 mA/cm²) increased the size of the zinc crystals, and coatings prepared at 40 and 50 mA/cm² resembled that of electrodeposited zinc. Since the proportions of zinc and zinc phosphate could be varied with applied current density, pH, and treatment time, it would be possible to use this methodology to prepare coatings that would offer different degrees of corrosion protection.     

Studying the corrosion protection properties of an epoxy coating containing different mixtures of strontium aluminum polyphosphate (SAPP) and zinc aluminum phosphate (ZPA) pigments

Epoxy/polyamide coatings were loaded with different mixtures of strontium aluminum polyphosphate (SAPP) and zinc aluminum phosphate (ZPA) pigments. Moreover, a coating containing zinc phosphate (ZP) was prepared as a reference sample. The coatings were applied on St-37 steel substrates and then were exposed to 3.5 wt% NaCl solution up to 35 days. The corrosion inhibition properties of the pigments extracts were studied on bare steel samples by a potentiodynamic polarization technique after 24 h immersion. The morphological properties and corrosion resistance of the coatings were investigated by scanning electron microscope (SEM), optical microscope, electrochemical impedance spectroscopy (EIS) and salt spray tests.     

Phenol electropolymerization on phosphated mild steel via zinc electrodeposition

Phenol electropolymerization to polyoxyphenylene coatings on phosphated steel and phosphated galvanized steel, normally impossible under the conditions allowing effective coating formation on either steel or zinc, is activated by cathodic deposition of zinc. A critical zinc amount has been found to be necessary to suppress electrochemical processes competitive with electropolymerization and induce coating formation with nearly 100% efficiency. SEM analysis showed that this critical amount of zinc corresponded to the formation of a low number of zinc nuclei emerging at the surface of the phosphate layer, on which, however, polyoxyphenylene was formed as a continuous coating. A.c. impedance tests showed that initial barrier properties are worse for coatings grown on zinc-plated phosphated samples than for those grown on steel from the same solutions. However, the long term corrosion resistance is much better in the former case, the improvement being largely associated with zinc cathodic protection     

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.     

Effects of coating thickness and surface treatment on the corrosion protection of diglycidyl ether bisphenol-A based epoxy coated carbon steel

The corrosion resistance of carbon steel specimens was compared, using different surface treatment methods such as blasting and zinc phosphate treatment on carbon steel followed by application of different coating thickness. Specimen surface morphology was observed by SEM. The corrosion performance of epoxy coated carbon steel was examined by electrochemical impedance spectroscopy (EIS), along with immersion test in 0.5N-NaCl solution and NORSOK M 501 cyclic test, respectively. EIS results showed that higher thickness of epoxy coating and zinc phosphate treatment on carbon steel showed better corrosion protection than rest of the specimens. Specimens with no treatment and blasting treatment followed by epoxy coating, showed poor corrosion protection. Results of NORSOK M 501 cyclic test showed similar trend as those of EIS results however degradation of specimens was more severe than those from immersion test.     

Optimization of phosphate coating properties on steel sheet for superior paint performance

The adhesion of electrodeposition (ED) paint on steel sheets for automobiles is highly influenced by the properties of the zinc phosphate coating which is used to improve its corrosion resistance. In the present study, a steel surface was pretreated with two types of zinc phosphate formulations followed by ED painting. The surface morphology, crystal plane, and porosity properties of phosphate coating on steel samples were studied by scanning electron microscope, X-ray diffraction, and electron probe microanalyzer, respectively. The corrosion resistance of painted samples was evaluated by an accelerated corrosion test as well as by electrochemical techniques like cathodic disbonding and AC?CDC?CAC tests. The phosphate coating enriched with a phosphophyllite structure showed small globular crystals with less porosity, whereas a hopeite structure showed coarse crystals with high porosity and comparatively thicker coating. The maximum corrosion resistance was observed in the painted sample, where the phosphate coating comprised a phosphophyllite structure. On the other hand, the painted samples phosphated with a predominantly hopeite structure showed inferior corrosion resistance performance. The unphosphated sample showed severe degradation in paint adhesion and corrosion resistance, which substantiates the importance of phosphate pretreatment.     

Electrochemical and anticorrosion performances of zinc-rich and polyaniline powder coatings

In this work, hydrochloride polyaniline (PANI-Cl) powder was incorporated as a conductive pigment into powder zinc-rich primer (ZRP) formulations in order to enhance the electronic conduction paths between zinc particles inside the coating and the steel substrate (i.e. percolation). Coatings were applied onto steel substrates and immersed in a 3% NaCl solution at ambient temperature.The protective properties and electrochemical behaviour of coatings were investigated by monitoring the free corrosion potential versus time and by using EIS. It was found that corrosion potential remains cathodic and constant for a long time up to 100 days of immersion. From EIS results, it was shown that the coatings exhibit larger impedance values than those observed with liquid or other zinc-rich powder formulations containing carbon black. From Raman spectroscopy results, it may be proposed that zinc particles in contact with PANI-Cl pigments were passivated. Other zinc particles remain still active which ensures the cathodic protection of the substrate. Moreover, coatings exhibit good barrier properties.     

Corrosion stability of polyester coatings on steel pretreated with different iron–phosphate coatings

The influence of steel surface pretreatment with different types of iron–phosphate coatings on the corrosion stability and adhesion characteristics of polyester coatings on steel was investigated. The phosphate coating was chemically deposited either from the simple novel plating bath, or with the addition of NaNO₂, as an accelerator in the plating bath. The morphology of phosphate coatings was investigated using atomic force microscopy (AFM). The corrosion stability of polyester coatings on steel pretreated by iron–phosphate coatings was investigated by electrochemical impedance spectroscopy (EIS) in 3% NaCl solution, while “dry” and “wet” adhesion were measured by a direct pull-off standardized procedure. It was shown that greater values of pore resistance, R_p, and smaller values of coating capacitance of polyester coating, C_c, on steel pretreated with iron–phosphate coating were obtained, as compared to polyester coating on steel phosphated with accelerator, and on the bare steel. The surface roughness of phosphate coating deposited on steel from the bath without accelerator is favorable in forming stronger bonds with polyester coating. Namely, the dry and wet adhesion measurements are in accordance with EIS measurements in 3% NaCl solution, i.e. lower adhesion values were obtained for polyester coating on steel phosphated with accelerator and on the bare steel, while the iron–phosphate pretreatment from the novel bath enhanced the adhesion of polyester coating on steel.     

Electrodeposition and characterization of Zn–Ni alloys as sublayers for epoxy coating deposition

The chemical composition and phase structure of Zn–Ni alloys obtained by electrodeposition under various conditions were investigated. The influence of the deposition solution and deposition current density on the composition, phase structure, current efficiency and corrosion properties of Zn–Ni alloys were examined. It was shown that the chemical composition and phase structure affect the anticorrosive properties of Zn–Ni alloys. A Zn–Ni alloy electrodeposited from a chloride solution at 20 mA cm^–2 exhibited the best corrosion properties, so this alloy was chosen for further examination. Epoxy coatings were formed by cathodic electrodeposition of an epoxy resin on steel and steel modified with a Zn–Ni alloy. From the time dependence of the pore resistance, coating capacitance and relative permittivity of the epoxy coating, the diffusion coefficient of water through the epoxy coating, D(H₂O), and its thermal stability, it was shown that the Zn–Ni sublayer significantly affects the electrochemical and transport properties, as well as the thermal stability of epoxy coatings. On the basis of the experimental results it can be concluded that modification of a steel surface by a Zn–Ni alloy improves the corrosion protection of epoxy coatings.     

以复配硅烷偶联剂为基料的无铬锌铝涂层的制备及性能研究

以复配乙烯基三乙氧基硅烷(A151)、γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)水解液为粘接剂,制备了一种水性无铬锌铝涂层。通过扫描电镜(SEM)、X射线衍射仪(XRD)、能谱仪(EDS)分析了涂层及腐蚀产物的微观形貌及成分;通过傅里叶红外分析仪(FT-IR),研究了涂层的固化过程;通过盐水浸泡实验及电化学实验研究了涂层的耐蚀性能。实验结果表明:涂层主要由Al相、Zn相、AlSi₉相、Al_0.403Si_0.597相组成,其中鳞片状锌铝粉在涂层中交替层叠,延长了腐蚀介质进入金属基体的路径,起到了良好的屏蔽作用;Tafel曲线表明相较于裸钢,涂层具有更高的腐蚀电位,能够对金属基材起到良好的牺牲阳极保护作用;在3.5%NaCl溶液浸泡试验中,随着时间的延长,锌铝涂层的腐蚀产物微观形态由初期的致密针状转变为松散的多孔结构。     

Corrosion inhibition at galvanized steel cut edges by phosphate pigments

The corrosion mechanisms and the inhibiting effect of sodium phosphate at cut edges on galvanized steel was studied by potentiodynamic polarization, EIS and monitoring of local ionic currents made by means of the scanning vibrating electrode technique (SVET). Assessment of zinc and of iron single electrodes was also made for comparison.In the absence of phosphate, corrosion of electrogalvanized steel at the cut edge is cathodically inhibited by the precipitation of zinc corrosion products over the steel surface. Mapping of the ionic currents revealed that the cathodic area becomes laterally shifted away from the anode as zinc corrosion products precipitate along parallel lines that are dictated by the location of the maximum cathodic currents. Sodium phosphate revealed inhibiting properties on the cut edge by precipitation of zinc phosphate, in the form of gel-like zinc phosphate clusters. Estimated inhibiting efficiencies for the cut edge were slightly above 80%.     

阴极电弧离子镀ZrN梯度膜和Zr/ZrN多层膜的腐蚀特性

采用阴极电弧离子镀技术在1Cr13不锈钢表面制备了ZrN梯度层和Zr/ZrN多层膜,并用电化学腐蚀方法和中性盐雾法检测了1Cr13基体、ZrN梯度层和Zr/ZrN多层膜的耐腐蚀性能.结果表明:Zr/ZrN多层膜和ZrN梯度层均能提高1Cr13基体的抗腐蚀能力,而Zr/ZrN多层膜的效果更明显:镀层的内部缺陷(如微孔)和液滴导致薄膜发生孔蚀、隙缝腐蚀和电偶腐蚀;镀层保护的实质是物理屏障作用,细化晶粒、减少膜层中的液滴及针孔等缺陷能显著提高薄膜的抗腐蚀性能.     

The improvement of anticorrosion properties of zinc-rich organic coating by incorporating surface-modified zinc particle

The corrosion behaviors of zinc-rich coating with various zinc contents, ranging from 0 to 60 volume percent, in thin organic coatings (below 5 μm) were characterized by electrochemical impedance spectroscopy (EIS), free corrosion potential (E_corr) measurement and cycle corrosion test (CCT). It was verified that both coatings with 60 volume percent of zinc powder and without zinc powder showed good corrosion resistance mainly due to the cathodic protection and barrier effect, respectively. On the other hand, coatings with an intermediate concentration (10–40 vol.%) of zinc powder was not successful in protecting a steel substrate efficiently. To improve anticorrosion property of zinc-rich coating, the surface modification of zinc particle was carried out with derivatives of phosphoric and phosphonic acid in the aqueous solution. The effects of the surface modification of zinc particle on corrosion resistance of the coating were investigated with scanning vibrating electrode technique (SVET) and X-ray photoelectron spectroscopy (XPS). The best anti-corrosion performance was achieved when the incorporated zinc particle was treated with phosphoric acid 2-ethylhexyl ester and calcium ion simultaneously, which induced the formation of alkyl-phosphate-calcium complex layer of 190 nm in thickness on zinc particles. Corrosion resistance was improved by the decreased zinc activity and the increased compatibility between the formed complex layer on zinc surface and polymer binder matrix.     

Effect of sub-layer temperature during HFCVD process on morphology and corrosion behavior of tungsten carbide coating

WC coating was deposited on the polished and cleaned 316L stainless steel by Hot Filament Chemical Vapor Deposition (HFCVD) technique at 400°C and 500°C. Field Emission Gun Scanning Electron Microscope (FEG-SEM) was used to study the corrosion morphology of the WC coatings. Energy dispersive spectroscopy (EDS) was used to analyze the chemical composition of the coatings. Coating porosity was measured by immersion in water. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques were used to study the corrosion behavior of the coating in the solution of 1 mol/L H₂SO₄. Results showed that the WC coatings have a honeycomb microstructure where its porosity was increased at higher temperature of the sub-layer. Also, the WC coating significantly increases the corrosion resistance of 316L stainless steel. And increasing the sub-layer temperature in the HFCVD method reduces the corrosion resistance of the WC coating. Corrosion morphology was indicative of pitting corrosion of the WC coating.     

镀锌层单宁酸钝化膜的耐蚀性

为提高镀锌层的耐蚀性,以氟钛酸钾、双氧水、硝酸为辅助成分,制备了单宁酸钝化液,并对低碳钢上的碱性镀锌层进行了钝化处理.通过质量分数为5%的NaCl溶液浸泡试验,确定了最佳钝化液组成和钝化工艺条件为:单宁酸40 g/L,HNO3 5 mL/L,氟钛酸钾10g/L,H2O2 60 mL/L,温度25℃,时间20～30 s....     

环氧改性有机硅耐高温防腐涂料的研制

以环氧改性有机硅树脂作为漆基,制备了磷酸锌底漆、云母氧化铁中间漆以及不同颜色的面漆,研究了不同漆膜的耐热性以及以磷酸锌底漆加云母氧化铁中间漆复配不同颜色面漆所得复合涂层的耐热性和耐蚀性。结果表明,以磷酸锌底漆、云母氧化铁中间漆和氧化铬绿面漆复配所得的涂层具有较好的耐高温防腐蚀性能,该复合涂层在350°C烘烤3h后,耐冲击强度≥40kg·cm,附着力≤2级,柔韧性≤2mm。     

Acceleration of zinc corrosion in alkaline suspensions containing iron oxides or iron hydroxides

Fast zinc dissolution is of industrial interest in recycling galvanised steel scraps. An acceleration of zinc corrosion in alkaline solutions was observed in the presence of various iron oxides or iron hydroxides. This corrosion was investigated by weight loss, measurements of hydrogen evolution and variation of current in a galvanic cell. The mechanism of this fast zinc corrosion was investigated by electrochemical means and by X-ray diffraction and scanning electron microscopy observations of zinc surface after immersion in alkaline suspensions of iron oxides or iron hydroxides. These insoluble iron compounds were involved in a reduction step leading to iron containing microparticles characterised by a low hydrogen overpotential and which acted as cathodic areas in a galvanic corrosion of zinc.     

钛和铈对热浸锌镀层组织与耐蚀性能的影响

为了获得厚度适中、耐蚀性能好的热浸镀锌层,在锌浴中添加微量的Ti和Ce,分别在Zn-0.04%Ti、Zn-0.02%Ce和Zn-0.04%Ti-0.02%Ce镀浴中制得热浸锌合金镀层.采用金相显微分析以及电化学阻抗谱、电化学极化测试、中性盐雾试验,研究了Ti和Ce对镀层组织和耐蚀性能的影响.结果表明:在锌浴中添加0.0...