Corrosion study of hybrid sol–gel coatings containing boehmite nanoparticles loaded with cerium nitrate corrosion inhibitor

To improve the corrosion protection of sol–gel derived hybrid silica/epoxy coatings containing boehmite nanoparticles, inorganic corrosion inhibitor was introduced into the coating via encapsulation in the nanoparticles. The morphology and chemical structure of the deposited films were studied by Scanning Electron Microscopy (SEM) and Fourier Transformed Infra-red Spectroscopy (FT-IR). The anticorrosion and self-healing properties of the coatings were evaluated by Electrochemical Impedance Spectroscopy (EIS). The high corrosion resistance performance of such coatings is due to the presence of encapsulated cerium nitrate corrosion inhibitor that can be released at the defects within the coating, hindering the corrosion reactions at defective sites.     

Bond strength of hybrid sol–gel coatings with different additives

The hybrid sol–gel coating on Al 2024-T3 was modified by adding polyaniline, TiO₂, or γ-Al₂O₃ nanoparticles in the formulation separately. The coating was then used as an adhesive to bond Al 2024-T3 alloys, forming a single lap joint. The bond strength of the sol–gel coating was investigated using a universal tensile test machine. The lap shear strength of the original sol–gel coating was about 1.38 MPa and it was increased up to 2.26 MPa after the modification by adding 0.05 wt% PANI microparticles in the sol–gel coating. The small increase in strength was attributed to an improvement in its adhesive flexibility because of incorporation of the long-chain organic polymer in its structure. Furthermore, the addition of different amounts of TiO₂ nanoparticles in the unmodified sol–gel coating also led to an increase in shear strength compared to the undoped sol–gel coating. Typically, a sol–gel coating containing 2.0 wt% of TiO₂ recorded the highest adhesive strength of about 4.0 MPa. A similar increase in strength was observed when doping γ-Al₂O₃ nanoparticles into the original hybrid sol–gel coating. Adding 0.5 wt% of γ-Al₂O₃ in the sol–gel coating increased the adhesive bonding strength up to 4.48 MPa. The fracture surface of the specimen was separately observed by SEM and Optical Microscopy in order to examine potential evidences of mechanism and nature of failure. The reason why the adhesive strength increased after the modification of the sol–gel coating is discussed in this article.     

Anticorrosive behavior study by localized electrochemical techniques of sol–gel coatings loaded with smart nanocontainers

In the present work, sodium phosphomolybdate, an environmentally friendly corrosion inhibitor with good anticorrosive behavior when applied on steel substrates, has been loaded and encapsulated in mesoporous silica nanoparticles without and with a hollow core in order to produce different smart nanocontainers. These nanocontainers have been designed to allow controlled release of the inhibitor in response to an external stimulus, thereby achieving more efficient and more economical use of the active substance. Corrosion activity leads to local changes in pH, and this work considers such changes as a signal of great interest. The nanocontainers respond to a pH of 10 or higher by increasing the release rate of the encapsulated active material. The smart nanocontainers have been incorporated into hybrid organic–inorganic sol–gel coatings and applied on carbon steel substrates. Mechanical defects have been made in the organic coating, reaching through to the metallic substrate, in order to study anticorrosive behavior in the affected area. A characterization study has been carried out at the defects and in their surroundings by means of two different localized electrochemical techniques: Scanning Kelvin Probe and Localized Electrochemical Impedance Spectroscopy. The results have shown significant improvement in the anticorrosive behavior of sol–gel coatings when formulated with smart nanocontainers loaded with sodium phosphomolybdate compared to a reference sol–gel coating.     

Corrosion resistance performance of cerium doped silica sol–gel coatings on 304L stainless steel

The aim of this work is the synthesis and investigation of silane based organic–inorganic hybrid coatings, which can be used to improve the corrosion performance of steel structures subjected to a marine environment. The silane based sol–gel coatings were prepared by dip coating 304L stainless steel in a solution of organically modified silica sol made through hydrolysis and condensation of 3-glycidoxypropyl-trimethoxysilane (GPTMS) as precursor and bisphenol A (BPA) as a cross-linking agent in an acid catalyzed condition. The influence of the addition of cerium and the use of bisphenol A as a cross-linking agent on the microscopic features and morphology as well as on the corrosion resistance of the coatings were examined using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), neutral salt spray tests, potentiodynamic polarization and electrochemical impedance techniques. Results show that cerium modified nano-hybrid coatings exhibit a superior corrosion inhibition performance to that displayed by silica hybrid coatings. Additionally, data showed that the bisphenol A as a cross-linking agent has a significant effect on the morphology and corrosion resistance of the cerium doped silica coating. Omitting the use of bisphenol A causes the creation of defects/cracks in the coating, thereby promoting diffusion of the aggressive electrolyte toward the substrate and decreasing the corrosion resistance of the coating.     

Optimization of hybrid sol–gel coatings by combination of layers with complementary properties for corrosion protection of AA2024

The coating system usually employed for corrosion protection of metal substrates consists of different layers which can be constituted of a chemical conversion coating applied on the metal surface followed by a number of organic layers. Hybrid films prepared by the sol–gel method provide a good approach as protective layers on metallic surfaces, although it is necessary to combine the barrier functionality with an active protection mechanism to avoid corrosion when the coating is damaged. Previous works have shown that it is very difficult to reach this result in a mono-layer sol–gel because the amount of inhibitors incorporated tends to increase significantly the porosity of the coating and reduces drastically the barrier properties. This work presents the characterization of a multi-layer sol–gel hybrid inorganic–organic coating system with a structure composed of an intermediate cerium inhibited layer deposited between two un-doped layers on AA2024 alloy. The comparison between the inhibited system and a bi-layer non-inhibited one has allowed to assess the migration of the cerium ions into the hybrid coating towards the substrate corresponding to the improvement of the corrosion properties. The combination of the physical barrier and the active protection enables to obtain an effective protective system.     

ZrO2 sol–gel pre-treatments doped with cerium nitrate for the corrosion protection of AA6060

Sol–gel coatings represent an alternative corrosion protection method to the chromate based systems which must be replaced. Recently, it was shown that ZrO₂ based sol–gel coatings deposited on AA6060 can provide a good corrosion protection to AA6060. However, ZrO₂ based sol–gel systems are not able to provide the self-healing effect which is instead the peculiar property of chromate conversion coatings. The structure of the ZrO₂ based sol–gel systems does not contain species able to restore the barrier properties when defects or damages impair the coating protection.     

Photocurable cyanate ester containing hybrid coatings by an anhydrous sol–gel technique

This work reports the synthesis and characterization of hybrid coatings obtained by UV curable anhydrous sol–gel process. Chemical structure of the products was confirmed using spectroscopic methods such as infrared and nuclear magnetic resonance spectroscopy. The properties of the hybrid coatings such as thermal and mechanical properties were investigated in detail by scanning electron microscope, thermogravimetric analysis, and mechanical measurement. Cure kinetics of the coating formulations was investigated by differential scanning photo-calorimetry (Photo-DSC). Cross cut adhesion, pendulum hardness, gloss, pencil hardness, MEK rub test were also performed to measure the coating performance of the hybrid coatings. The results indicate that the addition of the appropriate amount of CPM and sol–gel can effectively improve the thermal and mechanical properties.     

Preparation and corrosion protective properties of nanostructured titania-containing hybrid sol–gel coatings on AA2024

Titania-containing organic–inorganic hybrid sol–gel films have been developed as an alternative to chromate-based coatings for surface pretreatment of aluminium alloys. Stable hybrid sols were prepared by hydrolysis of 3-glycidoxypropyltrimethoxysilane and different titanium organic compounds in 2-propanol solution in the presence of small amounts of acidified water. Different diketones were used as complexing agents in this synthesis for controllable hydrolysis of titanium organics. The properties of the obtained coatings were compared with those of zirconia-containing films. Electrochemical impedance spectroscopy (EIS) measurements and standard salt spray tests were performed to investigate the corrosion protection performance of the hybrid coatings. It was revealed that their protective properties depend significantly on the nature of metalorganic precursors and complexing agents used in the process of sol preparation. The best anticorrosive protection of AA2024 in chloride solutions is provided by the titania-containing sol–gel films prepared with titanium(IV) tetrapropoxide and acetylacetone as starting materials. In the case of zirconia-containing films, better protective properties were found when applying ethylacetoacetate as a complexing agent.     

Preparation of hybrid silica sol–gel coatings on mild steel surfaces and evaluation of their corrosion resistance

Hybrid silica sol–gel coatings were prepared on mild steel substrate by dip coating technique. The coatings were subsequently heat treated at 200 °C in order to improve their corrosion properties. The coating sols were synthesized using Glycidoxypropyltrimethoxysilane (glymo) and Aminopropylethoxysilane (ameo) as precursor materials. Potentiodynamic polarization curves were derived and Electrochemical Impedance Spectroscopy (EIS) measurements were made in NaCl solution. The surface and cross-section morphology of coated specimens were characterized by scanning electron microscopy (SEM). Fourier transformed infrared (FTIR) analysis was used to identify the presence of various functional groups in the coating solutions. A comparison of the corrosion resistance of the coated and uncoated mild steel was presented. The results indicated that the corrosion resistance of the coated mild steel was improved considerably.     

Characterization of hybrid sol–gel coatings doped with hydrotalcite-like compounds to improve corrosion resistance of AA2024-T3 alloys

The inhibition effect of hydrotalcite addition to hybrid sol–gel coatings applied on AA2024-T3 alloy was evaluated. Hydrotalcite belongs to the anionic clay family with wide applications, most of them based on its anion exchange capacity due to its double layered structure. In this work hydrotalcite (HT) powder was prepared by the classical co-precipitation method using magnesium and aluminum nitrates as precursors. Different weight percentages (1, 5 and 10%, w/w) of hydrotalcite with Mg/Al ratio of 2.5 were added to hybrid sols prepared by copolymerization of 3-Glycydoxypropyltrimethoxysilane (GPTMS) and tetra-n-propoxyzirconium (TPOZ). The sol–gel coatings were deposited by dip-coating method on AA2024-T3 substrate. Scanning electron microscopy (SEM) and mechanical profilometry measurements revealed the heterogeneous particle sizes and the distribution of the agglomerates. Hydrotalcite additions significantly increased the bond strength between metal and coating, according to pull-off test results.The corrosion performance was evaluated by the salt spray fog chamber test and by Electrochemical Impedance Spectroscopy (EIS). The results showed a marked improvement of the corrosion resistance on the aluminum alloy when HT was added to the hybrid sol–gel coating. This positive effect was more evident at higher weight percentages of hydrotalcite.     

Effect of cerium concentration on corrosion resistance and polymerization of hybrid sol–gel coating on martensitic stainless steel

Stainless steels are increasingly used in the aeronautics field for the manufacture of structural parts. One of them, the X13VD martensitic stainless steel (X12CrNiMoV12-3), known for its good mechanical properties, has a poor corrosion resistance in confined or severe environments. In the past years, Cr(VI) based pre-treatments have been currently used for corrosion protection of different metals, however, they are toxic and due to environmental regulations, they will be definitely banned in a near future. Alternatives to replace Cr(VI) show advantages and drawbacks considering key properties such as: corrosion resistance, adhesion of coatings, fatigue resistance, durability and reliability. However, some of their possible alternatives show high potential.     

Preparation of scratch resistant superhydrophobic hybrid coatings by sol–gel process

Organic–inorganic hybrid coatings on glass substrates with superhydrophobic properties and with improved scratch resistance were obtained by means of applying a multilayer approach including multiple sol–gel processes. The coatings exhibited a water contact angle (WCA) higher than 150°. Ultraviolet (UV)-curable vinyl ester resins and vinyltriethoxysilane (VTEOS) as coupling agent were employed to increase the adhesion between substrate and the inorganic layers. The surfaces were characterized by means of dynamic contact angle and roughness measurements. Indeed, the occurrence of superhydrophobic behavior was observed. The scratch resistance of the hybrid coatings was tested to evaluate the adhesion of the coatings to the glass substrate. The proposed preparation method for scratch resistant, mechanically stable, superhydrophobic coatings is simple and can be applied on large areas of different kinds of substrates.     

Preparation and characterization of phosphine oxide containing organosilica hybrid coatings by photopolymerization and sol–gel process

A series of UV-cured organic–inorganic hybrid coating materials containing up to 20 wt.% silica were prepared by sol–gel method from tetraethoxy silane (TEOS) which is used as the primary inorganic precursor, and diallylphenylphosphine oxide monomer (DAPPO), aliphatic urethane diacrylate resin (Ebecryl 210) are employed as the source of the organic components. In addition, methacryloxypropyltrimethoxy silane (MAPTMS) was used as both a secondary inorganic source and a silane-coupling agent to improve the compatibility of the organic and inorganic phases. The DAPPO content in all the coating formulations were from 0 to 20 wt.%. The physical and mechanical properties such as gel content, hardness, adhesion, gloss, contact angle as well as tensile strength were measured. These measurements revealed that all the properties of the hybrid coatings improved effectively, in case of adding the sol–gel precursor and DAPPO monomer content in the hybrid systems. The photo-calorimetric-DSC studies showed that the double bond conversion of the hybrid coatings was faster than the coating materials without silica. The thermal stabilities of the UV-cured hybrid materials were investigated by thermogravimetric analysis. The results showed that the addition of sol–gel precursor and DAPPO into the organic network also improves the thermal-oxidative stability of the hybrid coating materials. The surface morphology was also characterized by scanning electron microscopy (SEM). SEM studies indicated that inorganic particles were dispersed homogenously throughout the organic matrix.     

Study of the degradation of hybrid sol–gel coatings in aqueous medium

The design and development of suitable multilayered functional coatings for delaying corrosion advance in metals and become controlled-release vehicles requires that the properties of the coatings are known. Coatings prepared by the sol–gel method provide a good approach as protective layers on metallic surfaces. This kind of coating can be prepared from pure chemical reagents at room temperature and atmospheric pressure, with compositions in a very wide range of environmentally non-aggressive precursors. Sol–gel coatings based on siloxane bonded units were prepared, starting with an organic–inorganic hybrid system. Synthesis procedures included acid-catalysed hydrolysis, sol preparation, and the subsequent gelation and drying. The alkoxide precursors used were methyl-triethoxysilane (MTMOS) and tetraethyl-orthosilicate (TEOS) in molar ratios of 10:0, 9:1, 8:2 and 7:3. After determination of the optimal synthesis parameters, the materials were characterised by solid ²⁹Si nuclear magnetic resonance (²⁹Si NMR), Fourier transform infrared spectroscopy (FTIR), contact angle measurement and electrochemical impedance spectroscopy (EIS) test. Finally, the materials were assayed by controlling their weight in contact with water, to determine their ability to degrade by hydrolysis. Electrochemical analysis reveals the formation of pores and water uptake during the degradation. The quantity of TEOS is one of the principal parameters that determine the kinetics of degradation. There is a correlation between the degradation process obtained for long periods and the electrochemical parameters obtained by EIS in short times. The study tries to incorporate knowledge that can be used for designing the degradation process of the functional coatings and to control their properties in short times.     

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.     

Corrosion behaviour of AA2024 coated with an acid-soluble collagen/hybrid silica sol–gel matrix

Collagen is a potential corrosion inhibitor for aluminium alloy 2024 (AA2024), being derived from fish scale, as confirmed by FTIR analysis. The extracted collagen powder was dissolved within a hybrid silica sol–gel to produce an environmental friendly (green) coating. The corrosion behaviour of the silica sol–gel (SOL) and collagen/silica sol–gel (CSOL) coated AA2024 in 3.5% NaCl solution was investigated by electrochemical impedance spectroscopy (EIS). In addition, the mechanical properties of both coatings were evaluated using hardness, micro-hardness resistance and a cross cut adhesion test. Results showed that collagen improves the corrosion resistance of the coated AA2024, while maintaining the mechanical properties of the non-doped silica sol–gel coating.     

Corrosion resistance of new epoxy–siloxane hybrid coatings. A laboratory study

Traditional multilayer epoxy/polyurethane type anticorrosive paint systems are widely employed in the protection of steel structures due to their high efficiency against atmospheric corrosion. However, the use of isocyanate in the curing process, and the high volatile organic compound (VOC) content of such systems, makes it necessary to search for new isocyanate-free paints.     

The effect of ceramic nanoparticles on tribological properties of alumina sol–gel thin coatings

Thin alumina coatings containing zirconia or alumina nanoparticles having diameter of ～20–30 nm were deposited by the sol–gel dip-coating process on silicon wafers. The mass content of nanoparticles in the alumina coating was fixed at 15% in relation to the theoretical mass of alumina matrix resulted from the amount of the applied precursor. Atomic force microscopy (AFM) was used to image the surface topography of as-made coatings and find out the wear level after frictional tests. Tribological tests were performed with the use of a microtribometer operating in the load range of 30–100 mN. It was found that the presence of α-alumina (corundum) or zirconia nanoparticles enhances the tribological performance of alumina layers annealed at 100 °C by decreasing the average wear rate by 20% and 63% for zirconia and corundum nanoparticles, respectively. No wear was observed for samples containing both types of nanoparticles annealed at 500 °C.     

Corrosion protection performance of sol–gel coatings doped with red mud applied on AA2024-T3

This paper studies the effect of 5 wt% red mud particles addition to sol–gel films applied on AA2024-T3 aluminium alloy. The red mud powder was dried or calcined, previously to added to the sol–gel film, in order to analyzed the effect of the thermal activation. The RM particles were characterized using several techniques; x-ray diffraction (XRD), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results confirm that the thermal treatment leads to several phase transformations which affect to gibbsite, Al(OH)₃, boehmite, AlO(OH), and goethite, FeO(OH), species.     

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.