Surface evaluation and electrochemical behavior of cerium conversion coating modified with silane on magnesium alloy

A new cerium conversion coating modified with the hydrolysis silane is designed for AZ31 magnesium alloy, which aims at assessing the surface characterizations and electrochemical behaviors between the cerium conversion coating with and without the silane modified. The effect of the silane addictive is studied by scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The adhesion of the coatings is undertaken according to the American Society for Testing and Materials (ASTM) standard D3359‐08 cross tape test. The electrochemical behavior is evacuated by polarization experiment and electrochemical impedance spectroscopy (EIS) in NaCl electrolyte. The results show that the addition of bis‐[triethoxysilylpropyl] tetrasulfide (BTESPT) to loosen and porous cerium conversion coating leads to the formation of a more compact and homogenous film, higher resistance to water uptake and better adhesion to substrate. Electrochemical measurements show that, compared with the non‐modified cerium conversion coating, the coating modified with the silane exhibits better anticorrosion properties. Copyright © 2014 John Wiley & Sons, Ltd.     

Growth behaviour of cerium-based conversion coating on Zn-5%Al alloy

Cerium-based conversion coatings were deposited on a Zn-5%Al alloy by immersing the alloy in cerium nitrate aqueous solutions with various immersion times. The growth behaviour of the cerium-based conversion coating on the Zn-5%Al alloy was investigated by the electrochemical impedance spectroscopy (EIS), SEM, energy dispersive spectroscopy (EDS), and XPS techniques. The results reveal that the coating mainly consists of ZnO, Zn(OH)₂, Ce(OH)₄, Ce(OH)₃, CeO₂, and Ce₂O₃. The growth of the cerium-based conversion coating is accompanied by metal dissolution. The dissolution mainly occurs on the η-Zn surface of the phase boundary and continues to extend to the Zn-rich phase as the coating grows. EIS results show that with increasing immersion time, the corrosion resistance of the Ce conversion coating gradually increases in the early growth stage and then decreases when the cracks appear.     

镁合金化学转化膜的制备及其性能研究

在磷酸钠-磷酸二氢铵-高锰酸钾体系中对镁合金进行化学转化处理.研究了磷酸钠、磷酸二氢铵、高锰酸钾、温度、时间和添加剂对转化膜性能的影响.通过对转化膜结构、成分及性能的测试评价,得到了性能较好的化学转化溶液配方:Na3PO4为5g·L-1,NH4H2PO4为15 g· L-1,KMnO4为1g· L-1,添加剂(NH4)6 Mo7O24为0.5g·L-1.由SEM可观察到转化膜的表面成“干枯河床”状.XRD和EDS检测表明,膜层的主要成分是Mg,Al12 Mg17和无定形相,膜层表面主要有Mn,Mg,K,O和Al等元素组成.腐蚀实验和电化学测试表明,添加剂能够降低转化膜的腐蚀率,转化膜较基体的腐蚀电位正移了0.73 V,提高了镁合金的耐蚀性.     

A facile method for fabrication of superhydrophobic coating on aluminum alloy

A superhydrophobic coating applied in corrosion protection was successfully fabricated on the surface of aluminum alloy by chemical etching and surface modification. The water contact angle on the surface was measured to be 161.2° ± 1.7° with sliding angle smaller than 8°, and the superhydrophobic coating showed a long service life. The surface structure and composition were then characterized by means of SEM and XPS. The electrochemical measurements showed that the superhydrophobic coating significantly improved the corrosion resistance of aluminum alloy. The superhydrophobic phenomenon of the prepared surface was analyzed with Cassie theory, and it was found that only about 6% of the water surface is in contact with the metal substrate and 94% is in contact with the air cushion. Copyright © 2011 John Wiley & Sons, Ltd.     

Development of cerium‐based conversion coatings on 2024‐T3 Al alloy after rare‐earth desmutting

The deposition of Ce‐based conversion coatings onto 2024‐T3 Al alloy sheet was studied using Rutherford backscattering spectroscopy, scanning electron microscopy, Auger electron spectroscopy, x‐ray photoelectron spectroscopy and atomic force microscopy. The Al sheet was pretreated with an alkaline clean followed by treatment in a Ce(IV) and H₂SO₄‐based desmutter. The Ce(IV)‐based conversion coating solution contained 0.1 M CeCl₃·7H₂O and 3% H₂O₂ and was acidified to pH 1.9 with HCl. Upon immersion, there was an induction period that included activation followed by aluminium oxide growth over the matrix and cerium oxide deposition onto cathodic intermetallic particles and along rolling marks on the surface. After the induction period cerium oxide deposited generally across the whole surface and thickened. The strongest anodic sites initially were adjacent to the intermetallic cathodes and resulted in aluminium dissolution but also oxide thickening. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis and characterization of phosphorized polyaniline doped with phytic acid and its anticorrosion properties for Mg-Li alloy

A phosphorized polyaniline (PANI) doped with phytic acid (PhA) was synthesized by the chemical oxide method with PhA as a dopant and applied to improve the anticorrosion properties of magnesium-lithium (Mg-Li) alloys after blending with eco-friendly silane sol. The chemical structures and morphologies of PANI samples were evaluated by FTIR spectroscopy, UV-Vis-NIR spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). All characterizations indicate that the as-synthesized phosphorized PANI (PANI-PhA) exists in doped emeraldine salt state with net-like structures crosslinked by phosphate carboxyl groups. The conductivity and thermostability of PANI-PhA were better than those of PANI doped with phosphoric acid (PANI-H₃PO₄) and undoped PANI. The anticorrosion properties of PANI/silane sol composite coatings for Mg-Li alloy were tested by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. The results prove that the anticorrosion ability of PANI-PhA is the best among the three PANI samples, as shown by a low corrosion current (1.28 × 10^?7 A·cm^?2) and high impedance (5.62 × 10⁶ Ω·cm²). The possible anticorrosion mechanism was proposed based on procedure analysis.     

Corrosion behavior of magnesium and its alloy in NaCl solution

The electrochemical behavior of cast Mg, AZ91, and cast AZ91 in 0.1 M NaCl solution is investigated by measuring open-circuit potential (OCP), steady-state current-potential, and electrochemical impedance spectra (EIS). The similar electrochemical impedance behavior is found of three corrosion electrodes. There are two capacitances in high-and medium-frequency domains and one inductive loop or component in low-frequency domain. From equivalent circuit simulation, cast AZ91 has the worst corrosion resistance. The EIS results are in good agreement with those obtained by OCP and polarization curves. Based on the Cao theory, a simple corrosion mechanism is put forward, supplying a possible explanation for low-frequency inductive behavior for Mg and its alloy in NaCl solution at OCP. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 7, pp. 878–885. The text was submitted by the authors in English.     

Effects of Mn2+ on the chrome‐free colored Ti/Zr‐based conversion coating on 6063 aluminum alloy

The conversion coating with golden color and improved corrosion resistance had been prepared by adding Mn²⁺ in the Ti/Zr conversion coating solution. Comparing with that of conversion coating without Mn²⁺, the optimal treatment time of this conversion coating was much shorter and the corrosion resistance was obviously improved. The effect of Mn²⁺ on the formation of golden Ti/Zr conversion coating was thoroughly investigated by means of energy dispersive X‐ray spectroscopy, SEM, XPS, and Raman and electrochemical workstation. The results showed that the conversion coating had a double‐layer structure: the outer layer consisted of the metal‐organic complex and the inner layer was mainly made up of Na₃AlF₆. Mn²⁺ was oxidized into MnOOH in solution and precipitated on the substrate surface which provided the nucleus to Na₃AlF₆ crystal and accelerated Na₃AlF₆ crystal formation and also made the microstructure of conversion coating change to the cubic. The mechanism of the formation of the conversion coating can be deemed as nucleation, growth of Na₃AlF₆ crystal, and formation of metal‐organic complex. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization of chromate conversion coating on AA7075‐T6 aluminum alloy

Chromate conversion coatings (CCCs) on AA7075‐T6 were characterized using scanning electron microscopy, focused ion beam sectioning and scanning transmission electron microscopy with nano‐electron dispersive spectroscopy line profiling. The thickness and composition of the CCC was different at different locations on the heterogeneous microstructure of AA7075‐T6. The coating formed on the matrix phase was much thicker than that formed on the coarse Al–Cu–Mg, Al–Fe–Cu and Mg–Si intermetallic particles. Nano‐electron dispersive spectroscopy line profiling indicated that the coating on the Al–Fe–Cu particles was similar to the CCC formed on the phase matrix, primarily a chromium oxide. However, the coatings on the Al–Cu–Mg and Mg–Si particles were mixed Al/Mg/Cr oxide and Mg oxide, respectively. The growth of CCC followed a linear‐logarithmic kinetic rate law. The observations of this study support the sol‐gel model of CCC formation. Copyright © 2004 John Wiley & Sons, Ltd.     

Corrosion protection of carbon steel using a combination of Zr conversion coating and subsequent zinc-rich silicate coating with a flake ZnAl alloy

To improve the corrosion protection properties of zinc-rich silicate coatings on steel, zirconium pretreatment loaded with (3-aminopropyl)triethoxysilane (APTES) 0.025 % (v/v) and the partial replacement of spherical zinc by flake ZnAl alloy were investigated. DC polarization and electrochemical impedance spectroscopy (EIS) show that the zirconium pre-treated layer containing APTES improves the corrosion protection of the bare steel. Zinc-rich silicate coatings containing flake ZnAl with and without pretreatment were evaluated by EIS, salt spray test and pull-off test. Pretreatment with a zirconium conversion layer reduces corrosion products and adhesion loss (from 16.53% to 12.54%) while the performance of corrosion protection significantly increased from 2003 Ω.cm² to 2640 Ω.cm² in comparison with the non-pretreated samples. The results show that flake ZnAl pigment (5 wt%) significantly improves corrosion resistance and prolongs the duration of cathodic protection of zinc-rich silicate coatings.     

Curing mechanism,heat resistance,and anticorrosion properties of a furan/methyl phenyl silicone coating

A coating composed by methyl phenyl silicone resin (PSi) and furan resin (FR) was prepared, and its curing mechanism, heat resistance, and anticorrosion properties were investigated by Fourier transform infrared spectroscopy, thermogravimetric analysis, electrochemical test, and chemical resistance test. Aldol condensation reaction between FR and PSi occurred at below 200°C, and PSi underwent self‐multidehydrogenation at above 200°C. These curing reactions gave excellent thermal stability and anticorrosion properties. Compared with pure PSi, the blended containing lower than 20 wt% FR had better thermal properties, manifested as over 390°C of 5 wt% weight loss temperature and over 40% of char yield at 800°C. The adhesion property of cured blended system on the metal surface reached the first level which exceeded that of pure PSi coating (the third level). Furthermore, the corrosion resistances of coating in acid, alkali, and salt environments were all improved compared with those of monomeric polymer coating. The impedance of blended coating in 3.5% NaCl solution decreased with increasing FR content, which was 1.8 × 10⁶ Ω cm² when the FR content was 40%, being higher than that of pure PSi coating (7.12 × 10⁵ Ω cm²). This was mainly due to the formation of a cross‐linked network structure based on Si―O―C bond and the enhanced adhesion of cured blended coating. In addition, the surface roughness of cured blended coating was below 2.0 μm, which may have a positive effect on drag reduction in real applications.     

The effect of nonmetallic element P in electroless Ni‐P coating on the passivation process during chemical conversion treatment

Pure Ni and electroless Ni‐P coating (ENPC) were passivated by a chemical conversion treatment. The passive films formed on pure Ni and ENPCs (with content of P 2.9, 7.2 and 11.7 at.% respectively) were analyzed by X‐ray photoelectron spectroscopy (XPS). High‐resolution XPS was also used to analyze the chemical states of the elements detected in the passive films. The results indicated that the detected Ni and P were in elemental states, and no compound with Ni and P element was detected in passive film, meaning that Ni and P did not participate in the formation of the passive film. The content of film‐forming reaction product in passive film increases with the content of element P in Ni‐P coating, suggesting that the nonmetallic P in Ni‐P coating played an important role in the formation of the passive film. The XPS results were used to analyze the formation mechanism of the passive film. Copyright © 2014 John Wiley & Sons, Ltd.     

SEM and RBS characterization of a cobalt‐based conversion coating process on AA2024‐T3 and AA7075‐T6

Samples of aluminium alloys AA2024‐T3 and AA7075‐T6 were treated with a chromate‐based deoxidizer, then conversion coated with a commercial cobalt‐based solution and finally sealed with a commercial vanadate‐based product. The alloy specimens were examined using scanning electron microscopy, transmission electron microscopy and Rutherford backscattering spectroscopy. The thickness of the cobalt‐based conversion coating increased rapidly up to 5 min of immersion but more slowly for longer times. Sealing resulted in penetration of vanadium through the oxide and a small increase in thickness due to the deposition of a thin sealing coating within the pores and on the external surface of the cobalt‐containing coating. Copyright © 2004 John Wiley & Sons, Ltd.     

Formation of superhydrophobic cerium oxide surfaces on aluminum substrate and its corrosion resistance properties

Superhydrophobic cerium oxide film was introduced to aluminum substrate by an in‐situ growth process and surface modification. Different molar ratios between Ce(NO₃)₃ · 6H₂O and C₆H₁₂N₄ were involved in this research. The morphologies, chemical compositions and wetting properties of the films were analyzed by scanning electron microscopy (SEM), energy dispersive X‐ray detector, Fourier transfer infrared spectrometer and water contact angle (WCA) measurement, respectively. A great WCA of 158.8^o with a low angle hysteresis of about 3^o was obtained. Combination of uniform hierarchical micro‐nanostructure as revealed by SEM together with the hydrophobic alkyl groups from stearic acid was found to be responsible for the superior superhydrophobic property. The corrosion resistance performance of the superhydrophobic surface was evaluated by immersing in sodium chloride aqueous solution, the WCA kept as high as 152.1^o after immersion for 21 days, indicating our superhydrophobic surfaces had high chemical stability and durability in corrosive medium. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of Cu in electroless Ni–Cu–P coating on passivation process

Electroless Ni–P and Ni–Cu–P coatings were passivated by chromate conversion treatment respectively. The anticorrosive performances of passivated coatings were investigated by potentiodynamic polarization and electrochemical impedance spectroscopy measurements. The passivated Ni–Cu–P coating exhibited a high corrosion resistance with the i_corr of 0.236 μA/cm,² while the value of passivated Ni–P coating was only 1.030 μA/cm,² indicating the passive film could improve the corrosion resistance of Ni–Cu–P coating to a significant extent. High‐resolution X‐ray photoelectron spectroscopy was used to determine the chemical states of elements detected in the passive film. Compared with passivated Ni–P coating, the passive film on Ni–Cu–P coating exhibited a higher ratio of Cr₂O₃ to Cr(OH)₃ with the value of 72:28, which was the main factor for passivated Ni–Cu–P coating showing excellent corrosion resistance. The effect of Cu in electroless Ni–Cu–P coating on passivation process was discussed by the contrast experiment. Copyright © 2016 John Wiley & Sons, Ltd.     

Electrochemical analysis of molybdate conversion coating on hot‐dip galvanized steel in various growth stages

The electrochemical behavior of molybdate conversion coatings in various growth stages was investigated by electrochemical impedance spectroscopy and equivalent circuits. The chemical composition and microstructure were characterized by SEM/energy dispersive spectroscopy, atomic force microscopy, and AES. Neutral salt spray tests complemented the information. The results indicated that the growth process of the molybdate conversion coating was accompanied by the growth of micro cracks, consisting of three stages: in the early and middle stages, the protective property of the coatings increased with increasing treatment time and then decreased when the cracks developed in the last stage. On the basis of the observation of the microstructure and the analysis of the electrochemical impedance spectra of the coatings in various stages, a simplified growth process model of the molybdate conversion coating on hot‐dip galvanized steel was created. Copyright © 2017 John Wiley & Sons, Ltd.     

Corrosion protection performance of ceria‐copolymer bilayer coating on low nickel stainless steel in 0.5 M H2SO4 medium

In this paper, we have reported the anti‐corrosion performance of ceria / poly (indole‐co‐pyrrole) (Ce/(poly(In‐co‐Py)) bilayer coating on low nickel stainless steel (LN SS). Electrochemical polymerization of (poly (In‐co‐Py)) was achieved on ceria‐coated LN SS (CeO₂/LN SS) in acetonitrile medium containing LiClO₄ (ACN‐LiClO₄) by cyclic voltammetric technique. The coatings were characterized by analytical techniques like Fourier transform infrared spectroscopy, scanning electron microscopy with energy dispersive analysis of X‐ray, respectively. The mechanical behavior of the coatings was studied using peel test, hardness and wear resistance tests. The corrosion defensive performance of this bilayer coating on LN SS was investigated using electrochemical techniques such as potentiodynamic polarization and electrochemical impedance spectroscopy in 0.5 M H₂SO₄. These results show that the bilayer coating on LN SS lowered the permeability of corrosive ions present in the acidic medium and thus acts as a barrier against the attack of corrosive environment. Copyright © 2012 John Wiley & Sons, Ltd.     

XPS and factor analysis study of initial stages of cerium oxide growth on polycrystalline tungsten

The initial stages of growth of the nanostructured cerium oxide deposited on the polycrystalline tungsten surface by pulsed laser deposition are studied using XPS technique. The population of Ce (III) and Ce (IV) oxidation states in the deposited CeO_2?x layers is determined applying factor analysis method. Tungsten atoms react with oxygen from the cerium oxide nanoparticles already at the room temperature, and a layer of tungsten trioxide is formed at the interface. Gradual heating of the samples up to 900 K leads to the increase of the thickness of WO₃ oxide layer and a partial reduction of Ce (IV) to Ce (III). The spectra of O (1s) photoelectrons are composed from a signal originating from metal oxides and a signal of surface superoxide and hydroxyl groups. Factor analysis was performed on the spectra of Ce (3d) photoelectrons to determine the position, shape, and intensity of the spectral components belonging to Ce (III) and Ce (IV) oxidation states. We propose a new simple method to generate components of the spectroscopic meaning. The basic idea of our method consists in the use of the slightly positive values instead of zeros to the needle test vector. Two components are required to reproduce the original data within the experimental errors. Copyright © 2015 John Wiley & Sons, Ltd.     

The formation mechanism and biocorrosion property of CaSiO3/CaHPO4 · 2H2O composite conversion coating on the extruded Mg‐Zn‐Ca alloy for bone implant application·

In this work, a calcium silicate and calcium phosphate (CaSiO₃/CaHPO₄ · 2H₂O) composite coating was applied by a chemical reaction to an extruded Mg‐Zn‐Ca magnesium alloy. SEM observation showed that a flat and sand‐like conversion coating was formed. X‐ray diffractometer (XRD) analysis indicated that the conversion coating was composed of CaHPO₄ · 2H₂O and a little amount of CaSiO₃. The formation mechanism of CaSiO₃/CaHPO₄ · 2H₂O composite conversion coatings was discussed. The electrochemical polarization tests showed that the conversion coating markedly improved the biocorrosion resistance of Mg‐Zn‐Ca alloy in Hank's solution. Copyright © 2010 John Wiley & Sons, Ltd.