In this study, a waste of biorefinery—lignin—is investigated as an anticorrosion coating on stainless steel. Corrosion behavior of two lignin types (hardwood beech and softwood spruce) was studied by electrochemical measurements (linear sweep voltammetry, open circuit potential, potentiostatic polarization, cyclic potentiodynamic polarization, and electrochemical impedance measurements) during exposure to simulated body fluid (SBF) or phosphate buffer (PBS). Results from linear sweep voltammetry of lignin-coated samples, in particular, demonstrated a reduction in corrosion current density between 1 and 3 orders of magnitude cf. blank stainless steel. Furthermore, results from cross cut adhesion tests on lignin-coated samples demonstrated that the best possible adhesion (grade 0) of ISO 2409 standard was achieved for the investigated novel coatings. Such findings suggest that lignin materials could transform the field of organic coatings towards more sustainable alternatives by replacing non-renewable polymer coatings.
Compared to many other metal oxides, anatase TiO shows relatively lower reactivity toward carboxylic acid anchor groups. The latter is crucial for applications, for example, in dye-sensitized solar cells (DSSCs), where the most used dyes bind to the metal oxide surface through carboxylic acid terminations. To improve the surface reactivity, metal-phosphate bilayers of Ni or Co were synthesized on anatase TiO compact oxide and nanotubes. In both cases, time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) results showed that the bilayers were successfully formed and that the phosphate layer works as an intermediate between TiO and the other species. ToF-SIMS depth profiles of modified nanotubes showed that Ni and Co are present through the whole tube length and reduce in content after heat treatment, in agreement with XPS results. Phosphate groups, on the other hand, are more present in the tubes' depth, and their content on the surface is reduced upon exposure to temperature. The reactivity of the modified surfaces toward carboxylic acid-terminated molecules, as stearic acid and Ru-based N719 dye, was evaluated. Contact angle measurements together with dye desorption experiments demonstrated that the Co-phosphate bilayers heat-treated at 300 °C resulted in the largest enhancement compared to the reference. Bilayer-modified compact anatase TiO and anatase TiO nanotubes were utilized as photoanodes in DSSCs. An increase in efficiency was observed for all modified electrodes with phosphate-Co treatment, leading to the highest J values and an efficiency improvement of 48%.
The effect of different post-treatments on TiO anatase surface reactivity was investigated in order to obtain the best techniques for enhancing anatase performance in diverse applications, e.g., in photocatalysis and especially as photoelectrodes for dye-sensitized solar cells (DSSCs). Different post-treatments of compact anodic anatase TiO were compared, including O plasma, UV irradiation, immersion in HO, vapor thermal treatment, and post-anodization, evaluating the increase of the amount of OH reactive groups on the surface and removal of surface contamination. In XPS spectra, the increase of OH groups is evident by the O 1s peak at higher binding energy. ToF-SIMS principal component analysis demonstrated that treatments performed in aqueous media led to a cleaner surface, with substantial removal of electrolyte residues. Stearic acid and the organic dye N719 were adsorbed to the differently post-treated anatase, and adsorption was evaluated by contact angle and dye desorption measurements. A higher loading with molecules containing carboxylic acid functionalities was confirmed by both techniques on the treated samples. The post-treatments that presented the highest amounts of dye were used to prepare photoelectrodes, and these were tested in DSSCs where the efficiency values doubled in comparison with the non-post-treated electrode.
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