Wetting and swelling behaviour of N-acetylated thin chitosan coatings in aqueous media.

Chitosan nanocoatings (thickness range of 120-540 nm) were produced on glass, zinc and silicon substrates with dip-coating and spin coating techniques to study their pH-dependent wetting and swelling behaviour. The coatings were N-acetylated with the methanolic solution of acetic anhydride to increase the degree of acetylation from 36 % to 100 % (according to ATR-FTIR studies). The measured contact angles of Britton-Robinson (BR) buffer solutions (pH 6.0, 7.4 and 9.0) were lower on the acetylated surfaces (ca. 50°), than that of their native counterparts (ca. 70°) and does not depend on the pH. Contrary, contact angles on the native coating deteriorated 10°-15° with increasing the pH. In addition, for native coatings, the decrease of the contact angles over time also showed a pH dependence: at pH 9.0 the contact angle decreased by 7° in 10 min, while at pH 6.0 it decreased by 13° and at a much faster rate. The constraint swelling of the coatings in BR puffer solutions was studied in situ by scanning angle reflectometry. The swelling degree of the native coatings increased significantly with decreasing pH (from 250 % to 500 %) due to the increased number of protonated amino groups, while the swelling degree of acetylated coatings was ca. 160 % regardless of the pH. The barrier properties of the coatings were studied by electrochemical tests on zinc substrates. The analysis of polarization curves showed the more permeable character of the acetylated coatings despite the non-polar character of the bulk coating matrix. It can be concluded that in the case of native coatings, 49 % of the absorbed water is in bound form, which does not assist ion transport, while in the case of acetylated coatings, this value is only 33 %.

Temporary Anti-Corrosive Double Layer on Zinc Substrate Based on Chitosan Hydrogel and Epoxy Resin.

In practice, metal structures are frequently transported or stored before being used. Even in such circumstances, the corrosion process caused by environmental factors (moisture, salty air, etc.) can occur quite easily. To avoid this, metal surfaces can be protected with temporary coatings. The objective of this research was to develop coatings that exhibit effective protective characteristics while also allowing for easy removal, if required. Novel, chitosan/epoxy double layers were prepared on zinc by dip-coating to obtain temporary tailor-made and peelable-on-demand, anti-corrosive coatings. Chitosan hydrogel fulfills the role of a primer that acts as an intermediary between the zinc substrate and the epoxy film to obtain better adhesion and specialization. The resulting coatings were characterized using electrochemical impedance spectroscopy, contact angle measurements, Raman spectroscopy, and scanning electron microscopy. The impedance of the bare zinc was increased by three orders of magnitude when the protective coatings were applied, proving efficient anti-corrosive protection. The chitosan sublayer improved the adhesion of the protective epoxy coating. The structural integrity and absolute impedance of the protective layers were conserved in both basic and neutral environments. However, after fulfilling its lifespan, the chitosan/epoxy double-layered coating could be removed after treatment with a mild acid without damaging the substrate. This was because of the hydrophilic properties of the epoxy layer, as well as the tendency of chitosan to swell in acidic conditions.

Effect of the Preparation Method on the Properties of Eugenol-Doped Titanium Dioxide (TiO2) Sol-Gel Coating on Titanium (Ti) Substrates.

The focus of this study was the preparation of sol-gel titanium dioxide (TiO2) coatings, by the dip-coating technique, on Ti6Al4V (TiGr5) and specific Ti implant substrates. In order to confer antibacterial properties to the layers, Eugenol was introduced in the coatings in two separate ways: firstly by introducing the Eugenol in the sol (Eug-TiO2), and secondly by impregnating into the already deposed TiO2 coating (TiO2/Eug). Optimization of Eugenol concentration as well as long term were performed in orderboth short- and long-term Eugenol concentration was performed to investigate the prepared samples thoroughly. The samples were investigated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curves (PDP). To investigate their resistance against Gram-negative Escherichia coli bacteria, microbiological analysis was performed on coatings prepared on glass substrates. Structural studies (FT-IR analysis, Raman spectroscopy) were performed to confirm Eugenol-TiO2 interactions. Coating thicknesses and adhesion were also determined for all samples. The results show that Eug-TiO2 presented with improved anticorrosive effects and significant antibacterial properties, compared to the other investigated samples.

Barrier behaviour of partially N-acetylated chitosan layers in aqueous media.

Chitosan coatings of 353 ± 12 nm thickness were prepared on glass and zinc substrates by dip-coating method to study their barrier-behaviour. The coatings were chemically modified to increase their degree of acetylation (DA) from ca. 44 % up to ca. 98 % resulting a quasi-chitin coating. The effect of the acetylation reaction was studied by infrared spectroscopy, and the structural changes of the native and acetylated coatings were investigated by UV-Vis spectrophotometry and X-ray diffraction. The surface properties of the coated samples were characterized by wettability measurements - advancing water contact angle decreased from ca. 80° (native) to ca. 43° (fully acetylated) - and microscopic (SEM, AFM) studies. The barrier behaviour of the chitosan layer depending on the DA was evaluated by electrochemical impedance spectroscopy studies and with a special mesoporous silica - chitosan bilayer system by measuring the amount of dye (Rhodamine 6G) accumulated in the silica through the chitosan coating during an impregnation step. These methods showed significant decrease in the barrier-effect of the coatings with increasing DA (accumulation of approximately six times more dye and a reduction of charge transfer resistance by an order of magnitude), due to the structural and ionization changes in the coatings.

Accumulation of 2-Acetylamino-5-mercapto-1,3,4-thiadiazole in chitosan coatings for improved anticorrosive effect on zinc.

Chitosan (Chit) coatings were applied on zinc substrates by the dip-coating method. Subsequently, the coatings were impregnated with a corrosion inhibitor, 2-Acetylamino-5-mercapto-1,3,4-thiadiazole (AcAMT) to obtain an increased anticorrosive effect. The coating thickness and the AcAMT accumulation were determined using UV-Vis spectroscopy on glass and quartz substrates, respectively. The surface morphology and coverage were investigated with atomic force microscopy. Electrochemical impedance spectroscopy and potentiodynamic polarization techniques were used to investigate the protective properties of the impregnated coatings. The chitosan coatings facilitated the accumulation of the corrosion inhibitor inside the polymeric matrix (a multiplication of 380 times compared to the impregnating solution concentration was calculated), channeling high amounts of AcAMT to the Zn surface, which resulted in an inhibition efficiency of >90%. This effect demonstrates the applicability of chitosan coatings as carriers for corrosion inhibitors, significantly reducing the amount of inhibitor needed to achieve good anticorrosive effects.

Eco-friendly indigo carmine-loaded chitosan coatings for improved anti-corrosion protection of zinc substrates.

Chitosan (Chit) coatings were prepared on zinc and glass substrates by dip-coating method. The coatings were impregnated with a non-toxic compound, indigo carmine (IC). The novel, eco-friendly, IC-loaded chitosan coatings were characterized morpho-structurally, and their corrosion protection behavior was investigated using potentiodynamic polarization and electrochemical impedance spectroscopy techniques. The surface properties of the coated samples were evaluated by wettability measurements. The thickness of the native chitosan layers and the stability of the impregnated layers in terms of dye release on glass substrates were studied by UV-vis spectrophotometry. The good corrosion inhibiting efficiency of the coatings (>90%) was attributed to the ionic crosslinking of the positively charged Chit with negatively charged IC. The Chit-IC coatings can be successfully used as model systems for chitosan-based coatings incorporating ionic inhibitors and in less demanding applications, such as temporary protective coatings for metals, removable on demand by scrubbing with mild acidic solutions.