Electrochemical investigation of high-performance silane sol–gel films containing clay nanoparticles

Silane sol–gel coatings are widely used as adhesion promoters between inorganic substrates, such as metals, and organic coatings. The aim of these pre-treatments is to enhance the corrosion protection performance of the organic coating improving the adhesion to the substrate and acting as a barrier against water and aggressive ions diffusion. It is a matter of fact that the silane sol–gel pre-treatments do not provide an active protection against corrosion processes except for the partial inhibition of the cathodic reaction. Inorganic pigments can improve the barrier properties of the silane sol–gel film, enhancing the resistance against corrosion. In this study, different amounts of montmorillonite nanoparticles were added to a water based silanes mixture in order to improve the barrier properties of the sol–gel coating. Hot dip galvanized steel was used as substrate. The sol–gel film consists of a combination of three different silanes, GPS, TEOS and MTES. The clay nanoparticles used in this study were mainly neat montmorillonite. The proper concentration of filler inside the sol–gel films was determined comparing the corrosion resistance of silane layers with different nanoparticles contents. Additionally, the effect of CeO₂ and Ce₂O₃ enriched montmorillonite particles. The EIS analysis and the polarization measurements demonstrated that the optimal amount of neat montmorillonite nanoparticles is about 1000 ppm. The same electrochemical techniques highlighted the limited effect of the cerium oxides grafted to the clay nanoparticles on the corrosion resistance of the silane sol–gel film. The TEM analysis proved the presence of a nano-crystalline structure inside the silane sol–gel film due to the formation of crystalline silica domains.     

Evidence for formation of metallo-siloxane bonds by comparison of dip-coated and electrodeposited silane films

It has been amply demonstrated that thin films of organofunctional silanes deposited by dipping or spraying on metals, such as aluminum, can provide protection against various forms of corrosion. In this paper we show that denser films with higher pore resistance and better corrosion protection performance can be obtained if the silane film is produced by electrodeposition rather than by dipping. In such a process the silane reacts with the metal oxide in a different way, and in the case of aluminum, aluminate ions seem to be incorporated into the silane film. The resulting films can protect aluminum alloys against uniform and pitting forms of corrosion in a salt solution for more than 1000 h, which is comparable to the standard chromate-based treatments. This paper discusses the protection mechanism in some detail. An important aspect of this work is that the use of XPS and TOFSIMS to analyze electrodeposited silane films provided direct evidence for the presence of O₂Al(O–Si–O) and OAl(O–Si–O)₂ groups at the silane–aluminum oxide interface. Such bonds have been suggested, but they have largely remained elusive over the years.     

Chemical composition and corrosion protection of silane films modified with CeO2 nanoparticles

The present work aims at understanding the role of CeO₂ nanoparticles (with and without activation in cerium(III) solutions) used as fillers for hybrid silane coatings applied on galvanized steel substrates.The work reports the improved corrosion protection performance of the modified silane films and discusses the chemistry of the cerium-activated nanoparticles, the mechanisms involved in the formation of the surface coatings and its corrosion inhibition ability.The anti-corrosion performance was investigated using electrochemical impedance spectroscopy (EIS), the scanning vibrating electrode technique (SVET) and d.c. potentiodynamic polarization. The chemical composition of silanised nanoparticles and the chemical changes of the silane solutions due to the presence of additives were studied using X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance spectroscopy (NMR), respectively.The NMR and XPS data revealed that the modified silane solutions and respective coatings have enhanced cross-linking and that silane-cerium bonds are likely to occur.Electrochemical impedance spectroscopy showed that the modified coatings have improved barrier properties and the SVET measurements highlight the corrosion inhibition effect of ceria nanoparticles activated with Ce(III) ions. Potentiodynamic polarization curves demonstrate an enhanced passive domain for zinc, in the presence of nanoparticles, in solutions simulating the cathodic environment.     

Highly Exfoliated Poly(Ethylene Terephthalate)/Clay Nanocomposites via Melt Compounding: Effects of Silane Grafting

The ammonium intercalated montmorillonite (A-MMT), especially acid treated montmorillonite (H-S-A-MMT), which experienced silane grafting treatment, exhibited highly exfoliation state in poly(ethylene terephthalate) (PET) matrix. It can be explained that the shear stress was transferred effectively from molten polymer to clay layers during melting processing due to the enhanced polymer-clay interaction by the grafted silane, leading to the slippage and peeling of clay sheets. Furthermore, the equilibrium melting point reduction of highly exfoliated nanocomposite calculated by the Hoffman-Weeks formula exhibited great miscibility between clay and polymer, which was proved by the Nishi-Wang equation.     

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.     

Preparation and properties of polyimide–clay nanocomposite materials for anticorrosion application

A series of polymer–clay nanocomposite (PCN) materials that consist of organosoluble polyimide and layered montmorillonite clay were prepared by the solution dispersion technique. The organosoluble polyimide containing non‐coplanar moiety in diamine monomer and flexible bridging linkages in dianhydride monomer was synthesized by chemical imidization. The as‐synthesized PCN materials were characterized by infrared spectroscopy, wide‐angle powder X‐ray diffraction, and transmission electron microscopy. The organosoluble polyimide showed better corrosion resistance compared to polyaniline, poly(o‐ethoxyaniline) and poly(methyl methacrylate) by using a series of standard electrochemical corrosion measurements of corrosion potential, polarization resistance, and corrosion current in 5 wt % aqueous NaCl electrolyte. Polyimide–clay nanocomposite materials incorporated with low loading of clay were found to further improve corrosion inhibition over pure polyimide. Effects of the material composition on the O₂/H₂O molecular permeability, optical clarity, and thermal properties of polyimide–clay nanocomposite materials were studied by molecular permeability analysis, UV–visible transmission spectra, thermogravimetric analysis, and differential scanning calorimetry, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3573–3582, 2004     

Nanoparticle-filled silane films as chromate replacements for aluminum alloys

Silane surface treatments have been developed as an alternative for toxic and carcinogenic chromate-based treatments for years. It is consistently observed that ultra-thin silane films offer excellent corrosion protection as well as paint adhesion to metals. The silane performance is comparable to, or in some cases better than, that of chromate layers. The most recent studies also showed that the silane films can be thickened and strengthened by loading of a small amount of nanoparticles such as silica and alumina into the films resulting in enhanced corrosion protection of aluminum alloys.     

Electrodeposition of silane films on aluminum alloys for corrosion protection

In this paper, three types of protective silane films, methyltrimethoxysilane (MTMS), vinyltrimethoxysilane (VTMS) and dodecyltrimethoxysilane (DTMS) were prepared on aluminum alloys AA 2024-T3 by electrodeposition technique. The Reflection-Absorption Fourier Transform IR (FTRA-IR) measurements showed that, the silane films were successfully deposited through chemical bonding between silane agents and Al alloys. Electrochemical impedance spectroscopy (EIS) tests indicated that in comparison with those by conventional “dip-coating” method, silane films electrochemically prepared at cathodic potentials exhibited obviously higher corrosion resistances. “Critical potential” was all observed for each silane system. Silane films prepared at this potential performed the highest corrosion resistance. The scanning electron microscopy (SEM) images indicated a potential dependence of surface morphology of silane films. The highest compactness was obtained at the “critical potential”. Due to the presence of long hydrophobic dodecyl chain in bone structure, DTMS films displayed the highest barrier properties.     

Modifying montmorillonite clay via silane grafting and interfacial polycondensation for melt compounding of nylon‐66 nanocomposite

A trifunctional organo alkoxysilane (3‐aminopropyl)triethoxysilane (γ‐APS) has been used as reagent for the chemical modification of montmorillonite clay. Silane grafting was taken place in dry and hydrolyzing conditions. Silane grafted and pristine clay took part in interfacial polycondensation process to deposit a layer of nylon‐66 onto the clay lamellae and therefore, enhance their affinity with nylon‐66 matrix. Evidence of presence of grafted silane molecules and deposition of nylon‐66 on clay particles were provided by Fourier transform‐infrared, thermogravimetric analysis (TGA), and X‐ray diffraction (XRD). Such modified clays and pristine clays were melt compounded with nylon‐66. The structures of the resulting nylon composites were characterized using XRD and transmission electron microscopy and the results showed presence of both intercalation and exfoliation. TGA thermograms of nanocomposites indicated improved thermal stability upon the incorporation of silane grafted montmorillonite. Furthermore, differential scanning calorimetry scans showed that silane modified clays promoted crystallization in nanocomposites. Increase of storage modulus and depression of tan δ peak in nanocomposites in dynamical mechanical thermal analysis were observed. The rheological properties of nylon‐66 and nanocomposites were also evaluated and differences in values of complex viscosity of samples were noticed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphology and mechanical properties of UV-curable castor oil-based waterborne polyurethane/organic montmorillonite nanocomposites

Water resistance is a unique advantage of castor oil-based polyurethane, permitting the application of coatings in humid environments. However, its low thermal decomposition temperature remains a limitation. Here, to demonstrate a simple method to improve the thermal stability of cured films, we prepared an organic montmorillonite dispersion utilising 3-(methacryloyloxy)propyltrimethoxysilane and protonated 3-aminopropyltriethoxysilane for modifying the clay. The method was put into practice by directly mixing the dispersion with a UV-curable castor oil-based waterborne polyurethane dispersion. The inclusion of organic molecule chains from the silane coupling agents noticeably improves the compatibility of polyurethane with organic montmorillonite, which imparts the composite latex with better thermal stability and mechanical properties when the organic montmorillonite additive is 5.0?wt-%.     

Composition and behaviour of cerium films on galvanised steel

The composition and corrosion performance of galvanised steel treated by immersion in cerium nitrate solution was investigated by electrochemical techniques and surface analysis. The surface film consists of a mixture of Ce(III) and Ce(IV) compounds, being very rich in Ce(III) in the first instants of the deposition process and becoming gradually enriched in the more oxidised form, Ce(IV). The presence of this film on the surface hinders the corrosion reaction by reducing the rate of both the cathodic and the anodic reactions. The film becomes thicker but more uneven when the time of film growth increases, with the development of defects in the film, which in contact with electrolyte behaves anodic with respect to the covered areas of the surface. These thicker films have revealed lower resistance to corrosion initiation.     

Preparation and characterization of electronically conducting polypyrrole-montmorillonite nanocomposite and its potential application as a cathode material for oxygen reduction

Simple wet chemical processes were deployed to prepare low-cost conducting nanocomposites based on natural clays with 2:1 layered structures such as sodium montmorillonite (MMT). Ce(IV) modified MMT was used for the spontaneous polymerization of pyrrole within clay interlayers. The resulted clay-conducting polypyrrole nanocomposites containing the reduced form of the oxidising agent, have been extensively characterized by X-ray diffraction (XRD) technique for interlayer spacing variations and by Fourier transform infra red (FT-IR) spectroscopy to study the interactions between the clay and polymer functional groups. DC polarization technique with both blocking and non-blocking electrodes was used to distinguish between the ionic and electronic transport numbers and to recognize the type of mobile ionic species. AC impedance analysis further resolved the electrical conduction of these materials. Bulk conductivity analysis implied that the polypyrrole (PPY) formed within Ce(IV) modified MMT posses dominant electronic conductivity. The low-cost, light-weight and stable polymer-clay nanocomposite prepared by Ce(IV) intercalated MMT, [Ce(III)-PPY-MMT], seems to be a promising cathode material for oxygen reduction and hence may find applications in fuel cell industries.     

冷轧钢表面硅烷复合膜的制备及耐蚀性能

采用浸涂技术,在冷轧钢板(CRS)表面制备掺杂铈离子和铬离子的γ-(2,3-环氧丙氧)丙基三甲氧基硅烷复合膜。通过电化学方法研究硅烷膜在3.50%的氯化钠溶液中的耐蚀性能,并用SEM研究存在复合硅烷膜的冷轧钢在腐蚀前后的形貌变化。结果表明掺杂了铈离子和铬离子的硅烷溶液在pH为4,水解温度为50℃,水解时间为8h条件下水解效果最好,使形成复合硅烷膜的冷轧钢在3.50%的氯化钠溶液中的自腐蚀电流密度下降到1.584×10-7A·cm-2,自腐蚀电位正移。经SEM测试表明,掺杂了铈离子和铬离子的复合硅烷膜在腐蚀前后的形貌几乎不变,耐蚀性能明显优于未掺杂的纯硅烷膜。     

Effect of the grafted silane on the dispersion and orientation of clay in polyethylene nanocomposites

The CTAB ammonium intercalated montmorillonite clay, CMT, was modified by an alkylsilane, Dodecyltrimethoxylsilane, to improve the miscibility of organoclays with PE matrix, involving the grafting reaction between the silane and silanol groups on the edge of clay. The silane modified clays (DMT) exhibited improved thermal stability due to the replacement of the physically adsorbed ammonium by the covalently bonded silane. The clays were melt compounded with polyethylene. Compared with the composite of PE/CMT, the clay dispersion state was improved, and a unique orientation of the clay layered was observed in PE/DMT nanocomposites, which was confirmed by XRD and TEM studies. The dispersion state, orientation degree of clay and, as a result, the mechanical and thermal properties of the nanocomposites were enhanced with the increasing amount of the grafted silane, indicating that the edge grafting of silane played a crucial role in controlling the structure and properties of nanocomposites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Release of cerium dibutylphosphate corrosion inhibitors from highly filled epoxy coating systems

Carcinogenic chromates are phased out as corrosion inhibitors in organic coatings, and are replaced by benign alternatives. Cerium-based compounds are excellent corrosion inhibitors in an aqueous environment. However, whether they are effective as corrosion inhibitor in an organic coating also depends on their interaction with the coating matrix, which should result in a sufficient release of inhibitors over a desired period of time. In this work we report on the leaching of cerium dibutylphosphate, Ce(dbp)₃, from an epoxy coating system as a first step toward a fundamental understanding of the leaching behavior. To this end, coating systems containing various levels of inhibitor loading, ranging from 1 up to 50 wt%, were fabricated. These coatings were characterized using Fourier transform spectroscopy (FTIR), and Scanning Electron Microscopy (SEM). Leaching experiments were performed by exposing the coating films to water, while the concentration of dissolved Ce(dbp)₃ in this water was monitored in situ using ultraviolet–visible (UV–vis) spectroscopy. The leaching of inhibitors showed a clear dependence on the initial inhibitor loading of the coating system. For highly loaded coatings (>25 wt%) all inhibitors leach out, whereas for a low loading level (<10 wt%) no leaching was observed. The difference between the high and low loading levels might be the formation of a porous network in the highly loaded coatings due to the dissolution of large Ce(dbp)₃ clusters. Using Magnetic Resonance Imaging (MRI) we visualized the penetration of a water front into this porous network during the leaching experiments. This water-filled porous network provides an excellent pathway for transport of Ce(dbp)₃. For low levels of inhibitor loadings such a network is absent, and the transport of Ce(dbp)₃ is blocked. The samples containing moderate levels of inhibitor loading showed an increasing amount of leaching for decreasing values of pH. We believe that this pH dependence is the result of the concurrent leaching of significant amounts of Bisphenol-based coatings residues at low pH since the removal of these residues will also result in an increased porosity of the coating.     

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.     

Corrosion behavior study of AZ91 magnesium alloy coated with methyltriethoxysilane doped with cerium ions

The present work aims to investigate the corrosion behavior of AZ91 magnesium alloy treated with a 4% (v/v) methyltriethoxysilane (MTES) alcohol solution, with and without an alkaline pretreatment. The corrosion resistance was assessed by electrochemical impedance spectroscopy (EIS) and current densities were monitored by potentiodynamic polarization curves during immersion in a 0.1 M Na₂SO₄ solution. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to perform a surface analysis. The electrochemical results showed an improvement of anticorrosion properties of AZ91. Furthermore, alkaline pretreatment enhances adhesion between silane film and substrate surface. This can be attributed to a surface enrichment in hydroxyl groups after the alkaline step, which increases formation of Si–O–Mg covalent bonds. The addition of Ce(NO₃)₃ to the MTES bath was evaluated, and it was found that the electrochemical response depends on the cerium ions concentration used. It was shown that the addition of 6.0 × 10⁻⁵ M of Ce(NO₃)₃ to a MTES bath improves corrosion resistance. Higher concentration of cerium ions lead to destabilizing the siloxane network, decreasing the efficiency of the silane coatings.     

Enhancement of corrosion protection effect of poly(styrene‐co‐acrylonitrile) by the incorporation of nanolayers of montmorillonite clay into copolymer matrix

A series of polymer–clay nanocomposite (PCN) materials that consisted of poly(styrene‐co‐acrylonitrile) (PSAN) and layered montmorillonite (MMT) clay were successfully prepared by effectively dispersing the inorganic nanolayers of MMT clay into the organic PSAN matrix by a conventional in situ thermal polymerization. First of all, organic styrene and AN monomers at a specific feeding ratio were simultaneously intercalated into the interlayer regions of organophilic clay hosts and followed by a typical free‐radical polymerization with benzyl peroxide as initiator. The as‐synthesized PCN materials were subsequently characterized by FTIR spectroscopy, wide‐angle powder X‐ray diffraction, and transmission electron microscopy. The as‐prepared PCN materials, in the form of coatings, incorporated with low clay loading (e.g., 1 wt %) on cold‐rolled steel, were found to be much superior in corrosion protection over those of bulk PSAN based on a series of standard electrochemical measurements of corrosion potential, polarization resistance, and corrosion current in 5 wt % aqueous NaCl electrolyte. Molecular weights of PSAN extracted from PCN materials and bulk PSAN were determined by gel permeation chromatography with THF as eluant. Effects of the material composition on the molecular barrier and thermal stability of PSAN along with PCN materials, in the form of both membrane and fine powder, were also studied by molecular permeability analysis, differential scanning calorimetry, and thermogravimetric analysis, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2269–2277, 2004     

Influence of sonication on anticorrosion properties of a sulfursilane film dopped with Ce (IV) on galvannealed steel

Currently, galvannealed carbon steel has been submitted to phosphatizing and/or chromatizing as surface pre-treatments; however, for economic and environmental issues, the viability of using silanes as an alternative pre-treatment has been studied. The aim of this work is to study the effect of sonication of the solvent solution (50/50%, m/m water/ethanol) with 50 ppm of Ce (IV) ions on the corrosion behavior of bis-1.2-[triethoxysilylpropyl]tetrasulfide (BTESPT) silane film deposited on galvannealed steel. The sonication influence on reactions has been studied and seems to promote the formation of small molecules starting from large ones, the change of the local pH and temperature, beyond the change of the solution viscosity. The corrosion resistance of the steel coated samples was evaluated by electrochemical impedance spectroscopy (EIS), linear polarization resistance (R_p) and potentiodynamic polarization curves. The molecular vibrational and chemical properties of the films were obtained by infrared (IR) and micro Raman spectroscopies. The physical characterization of sonicated solutions was performed by measuring their kinematic viscosity. The images from scanning electron (SEM) microscope were obtained to characterize the aspect and morphology of the film. The results showed that the sonication led to obtaining more homogeneous, compact and corrosion resistant silane films.     

A comparative study on the corrosion resistance of AA2024-T3 substrates pre-treated with different silane solutions: Composition of the films formed

This work reports a comparative study on the corrosion resistance of AA2024-T3 pre-treated with three different silane solutions. The silanes used for the pre-treatments of the AA2024-T3 panels were: 1,2-bis(triethoxysilyl)ethane (BTSE), bis-[triethoxysilylpropyl]tetrasulfide (BTESPT) and γ-mercaptopropyltrimethoxysilane (γ-MPS). The analytical characterisation of the silane films was performed by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The corrosion performance of the pre-treated substrates was evaluated by electrochemical impedance spectroscopy (EIS). The results show that the pre-treatments based on silanes provide good corrosion protection of unpainted AA2024-T3. Painted substrates, previously pre-treated with the silane solutions also revealed improved corrosion resistance and good adhesion properties. Fatigue tests show that the silane pre-treatments do not affect the fatigue behaviour of the AA2024-T3. The work also discusses the formation of the protective silane films.