Corrosion degradation of materials and metallic structures is one of the major issues that give rise to depreciation of assets, causing great financial outlays in their recovery and or prevention. Therefore, the development of active corrosion protection systems for metallic substrates is an issue of prime importance. The promising properties and wide application range of hybrid sol-gel-derived polymers have attracted significant attention over recent decades. The combination of organic polymers and inorganic materials in a single phase provides exceptional possibilities to tailor electrical, optical, anticorrosive, and mechanical properties for diverse applications. This unlimited design concept has led to the development of hybrid coatings for several applications, such as transparent plastics, glasses, and metals to prevent these substrates from permeation, mechanical abrasion, and corrosion, or even for decorative functions. Nevertheless, the development of new hybrid products requires a basic understanding of the fundamental chemistry, as well as of the parameters that influence the processing techniques, which will briefly be discussed. Additionally, this review will also summarize and discuss the most promising sol-gel coatings for corrosion protection of steel, aluminium, and their alloys conducted at an academic level.

The organic-inorganic hybrid sol-gel films, the structure of which comprises interconnected inorganic and organic networks have been reported as an environmentally friendly anti-corrosion pre-treatment for several metals, including aluminium alloys. In this paper, an epoxy-silica-zirconia hybrid sol-gel coating was synthesized from glycidoxypropyltrimethoxysilane (GPTMS) and zirconium npropoxide (TPOZ) precursors and applied to EN AW-6063 alloy by dip-coating. To promote the organic network formation through the epoxy group polymerization at room temperature, two types of amine crosslinkers were added during synthesis: diethylenetriamine (DETA), in different concentrations, and a tri-functional aminosilane. The evolution of the curing process and the corrosion behaviour of the coated aluminium alloy specimens were evaluated by Electrochemical Impedance Spectroscopy (EIS) in 0.5 M NaCl. The morphology and surface chemistry of the hybrid coatings were characterized by Energy Dispersive Spectroscopy (EDS) coupled with Scanning Electron Microscopy (SEM) and by Fourier Transform Infrared Spectroscopy (FTIR). The results obtained revealed that the sol-gel coatings with lower amine ratios required longer curing times, but showed the best anticorrosive performance with time. The increase in amine concentration has led to a more cross linked organic network, resulting in higher initial coatings resistance

Aluminium alloys of 6000 series can suffer severe corrosion in polluted (acidic) and/or marine environments and in contact with alkaline media like fresh cementitious materials. Therefore, architectural aluminium components are often coated, what requires its surface pre-treatment. Organic-inorganic hybrid (OIH) sol-gel coatings have been proposed as an effective, environmental compliant new pre-treatment for aluminium coating. In this work, an epoxy-silica-zirconia sol-gel coating was synthesized and applied on EN AW-6063 alloy. Cerium nitrate was incorporated as corrosion inhibitor. Cerium doped and undoped OIH coatings were exposed to neutral, acidic (pH~3) and alkaline (pH~10) chloride solutions. Electrochemical impedance spectroscopy (EIS) and SEM/EDS characterization of coated samples revealed that the best performance is achieved in the neutral and the worst in the acidic solution. In the alkaline solution, the cerium doped coatings exhibited much better anticorrosive performance than the undoped ones, clearly evidencing the beneficial role of the corrosion inhibitor in this media.

Anodizing is commonly used for corrosion protection of aluminum and its alloys in the construction industry. The anodic aluminum oxide (AAO) coating has a high ability to prevent the development of extensive pitting corrosion in aluminum substrates, particularly in marine sites, as was observed during a 10-year atmospheric corrosion study carried out in several marine and industrial sites. However, this study also evidenced that this coating can be highly affected by the deposition of particulate material in industrial polluted environments, sometimes in unexpected ways. This study presents information on the atmospheric corrosion of anodized aluminum exposed at two different chemical industrial complexes: a fertilizer production plant and a pulp and paper mill. Visual assessment of surface changes, pitting depth and mass variation with exposure were determined to quantify the degradation suffered. Additionally, SEM/EDS analyses were carried out on the exposed surfaces. Based on the results obtained, the role played by the deposition of airborne particles present in the two environments with respect to the type and level of damage observed is discussed. Deposits of roasted pyrite ash and phosphates or of wood chips and lime particles enhanced pitting corrosion or caused dissolution of the AAO coating.

The equestrian statue of D. José I, in Lisbon, is a masterpiece of the sculptor Joaquim Machado de Castro. It weights over thirty eight tons and was made in a single casting by Bartolomeu da Costa in a copper alloy (brass). After over two centuries exposure, the statue presented an unappealing heterogeneous appearance and showed some deterioration features that required attention. Preliminary studies showed that the deterioration phenomena were typical of copper alloys exposed to outdoor urban environments. The proximity of the seacoast also contributed to some specific decay mechanisms. The highly contrasting patterns of the superficial patinas consisted of black dense deposits covering an original cuprite layer side by side with the common green deposits of basic copper sulfates, hydroxides and chlorides. The highly corrosive nantokite was present in sheltered areas, where chlorides are able to accumulate. The conservation intervention included cleaning, mostly carried out with low pressure jets of round glass beads. Onsite tests were made to select the cleaning levels required to match the areas of black and green patinas. A reddish brown cuprite layer was found underneath most of the areas with black dense deposits, while it could only be perceived by transparency on the green covered areas. When a high contrast remained between the two areas, these were mitigated with the application of water colors during the final protection phase. Nantokite active areas were passivated with sodium oxalate after the entire statue was first washed with clean water and treated with lime water to leave an alkaline reserve to slow down the eventual corrosion process, and the sculpture rinsed with ethanol to accelerate its drying. The final protection was made with Paraloid B44 and microcrystalline waxes.