Electro-assisted preparation of dodecyltrimethoxysilane/TiO2 composite films for corrosion protection of AA2024-T3 (aluminum alloy)

Thin films of organosilanes have been successfully used as the alternative to toxic chromate coatings for surface pretreatment of metals and alloys. To further improve their corrosion performance, in the present work nano-scaled TiO₂ particles were added to the dodecyltrimethoxysilane (DTMS) films coated onto AA2024-T3 substrates, by using either the dip-coating or the cathodically electro-assisted deposition process. The obtained composite films were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), water contact angle measurements, Fourier transform reflection-absorption IR (FTRA-IR) and electrochemical impedance spectroscopy (EIS). The results show that these two techniques (nanoparticles incorporation and the electro-assisted deposition) both facilitate the deposition process of silane films, giving thicker deposit and higher coverage surface along with higher roughness and hydrophobicity, and thereby improve their corrosion resistance. Moreover, the corrosion performance of silane films is further improved by the combined use of nanoparticles modification and electro-assisted deposition.     

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.     

Silica based organic–inorganic hybrid nanocomposite coatings for corrosion protection

Silica based organic–inorganic hybrid nanocomposite coatings have been developed for corrosion protection of 1050 aluminum alloys by dip coatings technique. The hybrid sols were prepared by hydrolysis and condensation of 3-glycidoxypropyl-trimethoxysilane (GPTMS) and tetramethoxy silane (TMOS) in the presence of an acidic catalyst and bisphenol A (BPA) as cross-linking agent. Such prepared hybrid coatings were found to be relatively dense, uniform and defect free. Structural characterization of the hybrid coatings were performed using optical microscopy, scanning electron microscopy (SEM) and attenuated total reflectance-infrared (ATR-IR) spectroscopy. Corrosion resistance properties of the hybrid sol–gel coatings were studied by potentiodynamic scanning (PDS) and salt spray testing methods. The results indicate excellent barrier protection performance of the coatings. In addition, the effect of molar ratio of GPTMS–BPA (silane content) on corrosion resistance of the coatings was investigated. The PDS results demonstrated that the corrosion resistance of hybrid coatings improved by decreasing of silane content.     

黄铜表面硅烷自组装膜在氯化钠溶液中的耐蚀性

采用自组装技术在黄铜表面分别制备γ-巯基丙基三甲氧基硅烷(PropS-SH)、十二烷基三甲氧基硅烷(DTMS)、氨基丙基三甲氧基硅烷(APS)和γ-氯丙基三甲氧基硅烷(CPTMS)自组装膜,并分别采用电化学极化法、接触角测试和傅里叶红外光谱研究硅烷膜的耐蚀性、疏水生和结构.结果表明:经PropS-SH、DTMS和CPT...     

Decolorization of reactive brilliant red X-3B by heterogeneous photo-Fenton reaction using an Fe–Ce bimetal catalyst

Decolorization of reactive brilliant red X-3B was studied by using an Fe–Ce oxide hydrate as the heterogeneous catalyst in the presence of H₂O₂ and UV. The decolorization rate was in the order of UV–Fe–Ce–H₂O₂ > UV–Fe³⁺–H₂O₂ > UV–H₂O₂ > UV–Fe–Ce ≥ Fe–Ce–H₂O₂ > Fe–Ce. Under the conditions of 34 mg l⁻¹ H₂O₂, 0.500 g l⁻¹ Fe–Ce, 36 W UV and pH 3.0, 100 mg l⁻¹ X-3B could be decolorized at efficiency of more than 99% within 30 min. The maximum dissolved Fe during the reaction was 1 mg l⁻¹. From the fact that the decolorization rate of the UV–Fe–Ce–H₂O₂ system was significantly higher than that of the UV–Fe³⁺–H₂O₂ system at Fe³⁺ = 1 mg l⁻¹, it is clear that the Fe–Ce functioned mainly as an efficient heterogeneous catalyst. UV–vis, its second derivative spectra, and ion chromatography (IC) were employed to investigate the degradation pathway. Fast degradation after adsorption of X-3B is the dominant mechanism in the heterogeneous catalytic oxidation system. The first degradation step is the breaking down of azo and CN bonds, resulting in the formation of the aniline- and phenol-like compounds. Then, the breaking down of the triazine structure occurred together with the transformation of naphthalene rings to multi-substituted benzene, and the cutting off of sulphonic groups from the naphthalene rings. The last step includes further decomposition of the aniline structure and partial mineralization of X-3B.     

Plasma treatment of automotive steel for corrosion protection – a dry energetic process for coatings

In the thrust of pursuing new environmentally friendly technology for automotive application, a new corrosion protection coating system for automotive steel has been developed through interface engineering affected by an energetic plasma process. The plasma treated coating system outperformed the current phosphated galvanized steel system in scab corrosion tests. In the plasma process, the steel substrate was subjected to plasma cleaning and in situ plasma polymerization deposition. Plasma of a mixture of argon and hydrogen was created to remove the surface contaminants and the inherent oxide layer. A very thin film (50–100 nm) was then deposited by a plasma generated from alkylsilanes (e.g. trimethylsilane (TMS)). The interface can be so designed that strong corrosion-resistant interfacial bonds such as Fe–Si, Fe–C, and Si–C can be obtained. The interfacial chemistry involved in the plasma process and corrosion reaction are characterized by reflection absorption infrared spectroscopy (RAIR), X-ray photoelectron spectroscopy (XPS), and sputter neutral mass spectroscopy (SNMS).     

Comparative EIS study of pretreatment performance in coated metals

Various coated metal samples with different pretreatments were investigated by electrochemical impedance spectroscopy (EIS). Variables were the substrate (cold-rolled steel and hot-dipped galvanized steel), phosphate system (iron and zinc phosphate), post rinse (chromate and silane/zirconium rinse) and paint systems. The corrosion performance was determined on the basis of coating degradation, water uptake and interface delamination of the tested samples. The zinc phosphate performed better than iron phosphate on CRS. The silane/Zr rinse did not perform well in the CRS/iron-phosphate system. However, it showed a better performance than the chromate when used as a post rinse of zinc phosphate. Salt spray test (SST) and adhesion test results of the same samples are also reported in this paper and compared to the EIS data. The correlation among three test methods was poor.     

Structural and electrochemical characterization of Fe–Si/C composite anodes for Li-ion batteries synthesized by mechanical alloying

A Fe–Si (FeSi₂ + Si)/C composite was prepared by mechanical ball milling and investigated as a new inserting anode for use in Li-ion batteries. The composite so prepared has a sandwich structure with the alloy particles as middle cores and the graphite layer as outer shells. The charge-discharge measurements revealed that the Fe–Si/C composite not only had a quite high initial capacity of approximately 680 mAh g⁻¹, but also exhibited greatly improved capacity retention with a reversible capacity of approximately 500 mAh g⁻¹ after 15 cycles in comparison with pure Si and Fe–Si alloy. Based on XRD, XPS, SEM, Raman and EIS analysis of the composite electrode in different lithiated states, the mechanism for improved cycleability is found to be due to the effective buffering of the volumetric changes of the Fe–Si particles by the graphite shell.     

Bonding and corrosion protection mechanisms of γ-APS and BTSE silane films on aluminum substrates

Films of γ-aminopropyltriethoxysilane (γ-APS), 1,2-bis[triethoxysilyl] ethane (BTSE) and their mixtures adsorbed onto pure aluminum from aqueous solutions were characterized by means of ellipsometry, infrared spectroscopy (IR) and X-ray photoelectron spectroscopy (XPS). It was found that after hydrolysis in water the silanes were readily adsorbed onto aluminum oxide surfaces initially forming hydrogen bonds. Upon curing, such bonds are replaced by metallosiloxane bonds, Si - O - Al. The remaining silanol groups in the film condense and form Si - O - Si bonds. As the Si - O - Al bonds are known to hydrolyze, the corrosion protection is related to the hydrophobicity of the siloxane films formed on the metal substrate. BTSE films are acidic as they contain free silanol groups, therefore these are compatible with some paints but not with others. Electrochemical impedance spectroscopy (EIS) results, salt spray test results and filiform corrosion test results showed that some silane treatments, such as two-step γ-APS/BTSE and BTSE only, provided better corrosion protection on aluminum substrates as compared with a chromate treatment. Mechanisms of adhesion and corrosion protection of these silane films on aluminum substrates are proposed.     

Adhesion performance of an epoxy clear coat on aluminum alloy in the presence of vinyl and amino-silane primers

The influence of amino and vinyl-silane-based treatments on the performance of an epoxy coated AA 1050 aluminum has been studied. The surface energy of the silane treated samples was determined using static contact angle measurement. Chemical interactions between the silane layer and aluminum substrates were also examined using FTIR-ATR spectroscopy. Pull-off adhesion was used under wet, dry and recovery conditions. The contact angle measurements showed a relative increase in the surface free energy of the silane treated specimens. For specimens treated with silane solutions below the IEP of aluminum, adhesion strengths were higher than those for pHs higher than IEP. This may suggest that an acid–base interaction occurs between the negatively charged silanol species and the positively charged AA surface. FTIR revealed two modes of interaction, one between silane and Al³⁺ (Si–O–Al), and the other indicative of a siloxane network (Si–O–Si). Thickness measurement showed that the silane layer is 100–200 nm thick indicating that the silane formed at the surface is not a monomolecular layer. Direct pull-off adhesion measurements of silane treated samples showed a significant improvement in initial bond strength compared with degreased aluminum substrates. However, those silane solutions having pHs higher than 8.4 showed inferior adhesion in comparison to those having lower pHs. The adhesion improvement was maintained, to some extent, after exposure to salt spray cabinet. In spite of good dry, wet and recovery adhesion, silane treated surfaces are not comparable with chromated AA aluminum in terms corrosion resistance.     

Zn and Zn–Sn alloy coatings with and without chromate layers. Part I: Corrosion resistance and structural analysis

The aqueous corrosion resistances of Zn and Zn–Sn ( 20 wt% Sn) electrodeposits, passivated by immersion in chromating solution with different ratios of Cr(vi) to activating ions, are compared. The electrochemical behaviour of various chromated and nonchromated coatings were investigated in deaerated 0.5 mol dm^–3 Na₂SO₄/pH 5 solution using a.c. impedance and d.c. polarization techniques. The polarization curves revealed that the chromate layers influence both the cathodic and anodic reactions. The corrosion rate of each specimen decreases with time due to the accumulation of corrosion products. The dark yellow (DY) chromate film on the Zn–Sn alloy and the iridiscent yellow (IY) on Zn yields the best protective ability in agreement with the assessment of prolonged salt spray chamber tests. These chromate layers resembling cracked mud become permeable to the electrolyte after immersion and, as a consequence of the transformation and the leaching of certain Cr compounds, a very porous agglomerate of corrosion products forms. The morphology and structure of dark yellow chromated Zn–Sn alloy was also investigated by transmission electromicroscopy (TEM) and scanning electronmicroscopy with microprobe (SEM/EDS) analyses before and after corrosion. The depth profile of the corroded surface chemical composition was determined by X-ray photoelectron spectroscopy (XPS).     

Inhibitor properties of “green” pigments for paints

Zinc chromate is one of the anticorrosive pigments most frequently used in the formulation of primers. However, its environmental aggressiveness and toxicity severely restrict its use, and different green alternatives have been proposed in order to replace zinc chromate. In the last decade, the behaviour of zinc phosphate as anticorrosive pigment has been intensively researched. During this time, various modifications have been made to this family of pigments to improve its properties, and a “second generation” of phosphate pigments, incorporating elements such as molybdenum, aluminium, or iron, has been produced. In this paper, the inhibitive properties of zinc phosphate and three second-generation phosphates have been investigated, using zinc chromate pigment as a reference. Pigment extract solutions, at different values of pH, have been used as corrosive media. Carbon steel samples were immersed in such solutions and their corrosion rates were measured using electrochemical techniques. The data obtained suggest that zinc chromate provides the highest percentage of inhibition in neutral and basic solutions, but phosphate-based pigments showed better results in acid solutions. Given this performance advantage, together with their less harmful environmental impact, these phosphate-based pigments can be proposed as realistic alternatives to chromates in the formulation of protective paints for use in acidic conditions.     

Nanostructured coatings approach for corrosion protection

Nanostructured surface treatment coatings based on the Self-assembled Nanophase Particle (SNAP) approach were investigated as potential replacement for chromate-based surface treatments on aircraft aluminum alloys. In the traditional sol–gel method, hydrolysis-condensation processes are followed by condensation polymerization upon film application. This process sequence provides a low temperature route to the preparation if thin coatings which are readily applied to most metallic substrates. The recent discovery of a method of forming functionalized silica nanoparticles in situ in an aqueous sol–gel process, and then cross-linking the nanoparticles to form a thin film, is an excellent example of a nanoscience approach to coatings. This Self-assembled Nanophase Particle (SNAP) process can be used to form thin, dense protective organic surface treatment coatings on Al aerospace alloys. The ability to design coating components from the molecular level upward offers tremendous potential for creating multifunctional coatings.

The important components of Al alloy corrosion inhibition by chromate are storage and release of Cr^VI species, inhibition of cathodic reactions (primarily oxygen reduction), and inhibition of attack at active sites in the alloy. Unlike chromate-based treatments, current SNAP coatings provide barrier-type corrosion resistance but do not have the ability to leach corrosion inhibitors upon coating damage and minimize corrosion of the unprotected area. In this study, organic inhibitors were tested for corrosion protection of aluminum alloys in combination with the (SNAP). Scanning Vibrating Electrode Technique, anodic polarization, electrochemical impedance spectroscopy, and salt spray test were used to study this new approach for chromate replacement.     

Corrosion protection behavior of AZ31 magnesium alloy with cathodic electrophoretic coating pretreated by silane

As an alternative process to phosphate and chromate conversion coatings, silane pretreatment was used to improve the performance of cathodic electrophoretic coating (E-coat) on AZ31 Mg alloy in this study. The galvanic corrosion behavior of AZ31 Mg alloy with E-coat coupled with Q235 steel was investigated. Compared to bare Mg alloy and Mg alloy with conventional painting, the corrosion properties of the AZ31 Mg alloy pretreated with silane and subsequently E-coated were studied during salt solution immersion and salt spray testing. The surface morphologies of the Mg alloy were examined in detail after immersion in NaCl solution for different times using digital photography and scanning electron microscopy (SEM). The corrosion current density of the specimens was characterized by DC polarization tests. It was found that silane pretreatment of AZ31 Mg alloy followed by subsequent E-coat led to much better corrosion protection than that without silane treatment. The silane pretreatment and E-coat delayed the galvanic corrosion of Mg alloy coupled with 235 steel bolts.     

Electrochemical characterization of Ni–P and Ni–Co–P amorphous alloy deposits obtained by electrodeposition

Ni–P and Ni–Co–P amorphous alloy deposits were obtained by electrodeposition at 80 °C on carbon steel substrates. The influence of the electrolyte Co²⁺ concentration and of applied current density was investigated. The corrosion behaviour of amorphous and crystalline deposits was evaluated by polarization curves and electrochemical impedance spectroscopy in NaCl 0.1 M solution at room temperature. Impedances were measured for samples under total immersion (free potential against time) and for polarized samples in predefined regions of the polarization curves. It was found that the alloy deposit composition is highly affected by the composition of the electrolyte but displays no significant dependence on applied current density. The results showed that the presence of Co on Ni–P amorphous alloys improves the deposit performance in the studied corrosive medium. It was also verified that the amorphous structure provides higher corrosion resistance to both Ni–P and Ni–Co–P alloys.     

Polymeric sol–gel coatings as protective layers of aluminium alloys

Sol–gel route is an emerging technology to synthesize coatings of a wide variety of properties taylored. In this work three low temperature cured coatings has been studied to evaluate their protective properties in order to be used as protective barrier coatings for aluminium alloys with potential architectural and automotive applications. These three coatings are novel modified silane nanocomposites coatings obtained mixing two sols separately prepared: a pre-hydrolysed 3-glycidyloxypropyl trimethoxysilane (GPTS) with acidic catalyst and another obtained from tetraethylorthosilicate/methyltriethoxysilane (TEOS/MTES). Particulated coatings were obtained by addition of 25 wt.% particles of Aerosil 300 and Aerosil R972, respectively. The protective properties of the coatings were evaluated by electrochemical impedance spectroscopy (EIS) which showed notably differences among them not only from the protective viewpoint but the hydrophobic nature of the coatings and the controlling corrosion mechanism in each case.     

The durability of adhesive/carbon–carbon composites joints in salt water

This paper researches the durability of the adhesive/carbon–carbon (C–C) composites joints in salt water with infrared spectroscopy (IR), energy dispersive X-ray spectrosopy (EDX) and shear strength test methods. In salt water, Na⁺ and Cl⁻ ions can accelerate hydrolyzation of the adhesive and increase water ingress ability in the adhesive, although salt water cannot produce ionization potential between adhesive and C–C composites like adhesive/metal joints. The durability of the adhesive/C–C composites joints in salt water aging is lower than that in humidity aging by shear strength tests. EDX and IR spectra of the adhesive indicate that the salt water diffusion speed in the adhesive/C–C composites joints depend on not only temperature but also salt water aging time, i.e. time–temperature equivalence between temperature and salt water aging time. Shear strength tests also indicate that the rate of shear strength of the adhesive/C–C composites joints treated by silane coupling agent is lower than that treated by sand paper burnishing or by chemical oxidation in salt water aging.     

Polyimide–silica hybrids containing novel phenylethynyl imide silanes as coupling agents for surface-treated titanium alloy

Polyimide–silica hybrids composed of an organic precursor containing a novel phenylethynyl imide silane and an inorganic precursor were evaluated as an adhesion-promoting interphase between surface-treated titanium alloy and a phenylethynyl-containing imide adhesive. The phenylethynyl groups present in the organic precursor, either as a pendent or end group, can bond chemically with a phenylethynyl-containing imide adhesive during processing, while the silane groups of the organic precursor would react chemically with the inorganic precursor. In addition, the inorganic precursor is able to react with the titanium alloy to form a stable bond with the metal oxide. Bond strength and durability were evaluated by single lap shear tests at various conditions. Lap shear specimens exhibited predominantly cohesive failure after a 3-d water boil with 92% retention of the initial room temperature strength. Morphology and chemical composition of the hybrid interphase were investigated with scanning electron microscopy, X-ray photoelectron spectroscopy, and Auger electron spectroscopy, which revealed development of a silicon-gradient, hybrid structure between the metal substrate and the adhesive.     

The interphase in painted metals pretreated by functional silanes

A new post-rinse treatment was developed to replace the standard chromate post-rinse treatment on phosphated metal substrates. The silicate/silane (SSL) treatment modifies the paint-phosphate interface to give improved adhesion and corrosion performance. Time-of-flight secondary ion mass spectrometry (TOFSIMS) was used to study the orientation of the silane. The orientation was critical for the final adhesion performance. Electrochemical impedance spectroscopy (EIS), an ideal technique for studying interfaces nondestructively, showed that the SSL treatment was effective in reducing the corrosion significantly. Mechanisms of adhesion and corrosion are described.     

Corrosion protection of Mg alloys by cathodic electrodeposition coating pretreated with silane

The corrosion resistance characteristics of three coatings on magnesium alloy AZ31—conventional paint with phosphate film, cathodic electrodeposition coating (E-coating), and E-coating pretreated with silane (Mg/silane/E-coating)—have been studied by means of electrochemical impedance spectroscopy (EIS) in a 3.5 wt% NaCl neutral aqueous solution and salt spray test using ASTM B117. Silane film was obtained by dipping AZ31 specimens in diluted hydroalcoholic silanic solutions and successively curing. It was found that the corrosion resistance of the Mg alloy with E-coating was superior to conventional paint and could be further enhanced with silane pretreatment as an interfacial film. The results of water volume fraction (Φ_saturation) and diffusion coefficient (D) also indicated that the Mg/silane/E-coating possessed excellent compactness and corrosion resistance. A model of the corrosion mechanism for Mg/silane/E-coating has been presented through EIS analysis.