Carboxylic acids were investigated as a means to fabricate a superhydrophobic and corrosion resistant aluminum surface. Alkaline etching produced a hierarchically rough, superhydrophilic and hydroxylated Al surface which could then be modified by immersion in ethanol solution of carboxylic acids of different alkyl chain lengths, from hexanoic to octadecanoic. Acids with chain length longer than seven carbon atoms acted as corrosion inhibitors, but only those with long chains (e.g., octadecanoic acid) acted as a corrosion barrier and made the surface superhydrophobic with water contact angles over 150 degrees. The morphology, topography and chemical composition of unmodified Al and etched Al modified by carboxylic acids were studied using surface analytical tools (scanning electron microscopy with chemical analysis, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry). Modelling based on density functional theory was performed to help explain experimental observations and to provide a rationale of why only carboxylic acids with long enough chains were effective in reducing the rate of corrosion. The reason was attributed to their ability to form more stable and protective organic films. Aluminum surface prepared under appropriate conditions was superhydrophobic, corrosion resistant and durable and showed self-cleaning and delayed ice-melting properties.

This study investigated polysiloxane hybrid sol-gel coatings synthesized from tetraethyl orthosilicate (TEOS), 3-(trimethoxysilyl)propyl methacrylate (MAPTMS) and two different precursors, i.e., methyl- or ethyl- methacrylate (MMA or EMA), as corrosion protection of aluminium alloy 7075-T6. The hypothesis was that the additional alkyl group might affect the chemical properties and, consequently, the corrosion properties. Synthesis of the sols proceeded in two steps, each involving either MMA or EMA in the same molar ratio. The resulting sols, siloxane-(poly(methyl methacrylate-co-MAPTMS)) or siloxane-(poly(ethyl methacrylate-co-MAPTMS)), were applied on aluminium alloy followed by characterization in terms of chemical structure and composition, topography, wettability, adhesion and corrosion resistance in 0.1 M sodium chloride solution. The chemical properties of sols, monoliths and coatings were investigated using Fourier transform infrared spectrometry, solid state nuclear magnetic resonance spectrometry, X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. Coatings were similar in terms of surface topography, while the wettability of the coating with EMA showed 6° greater water contact angle compared to the coating with MMA. Both coatings were shown, by electrochemical impedance spectroscopy in 0.1 M NaCl solution, to act as barriers to protect the underlying substrate in which coating with EMA exhibits better protection properties after 2 months of immersion. Adhesion tests confirmed the highest grade of adhesion to the substrate for both coatings. Testing in a salt-spray chamber demonstrated excellent corrosion protection, where coatings remaining intact after more than 600 h of exposure.

An alkaline etched, superhydrophilic aluminum surface was modified using functionalized alkyl compounds selected to study the effect of their properties on adsorption on the metal surface. The thirteen organic compounds differed in alkyl chain length (eight and eighteen carbon atoms) and anchor group (azide, imidazole, thiocyanate, amino, disulfide, thiol, phosphonic, carboxylic, and benzoic). The methodology of the study integrated a complete chain of steps incorporating synthesis, electrochemical and surface analyses, and computational modeling. The corrosion resistant and superhydrophobic properties depend on the anchor group, which governs adhesion to the surface, and backbone, which is responsible for lateral cohesive interactions. The morphology and chemical composition of modified layers were studied using scanning electron microscopy, X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. Electrochemical and long-term immersion properties were investigated in 0.5 M NaCl. Calculations based on density functional theory were performed as to model the adsorption of selected anchor groups on the hydroxylated oxidized aluminum surface. Integrated results allowed the identification of the anchor groups that are able to form inhibitive adsorbed layers on Al surface regardless the alkyl chain length, and those that are not able to form adsorbed layers at all and are thus not efficient corrosion inhibitors.