Super-Anticorrosive Materials Based on Bifunctionalized Reduced Graphene Oxide.

The design of new materials with two or more functional groups must be strongly considered to achieve multifunctional coatings with outstanding properties such as active-passive protection against corrosion, low-friction, antifouling, and sensing, among others. In this sense, nanocomposites based on solvent-free epoxy resin/bifunctionalized reduced graphene oxide layers with NH2 and NH3+ groups (ER/BFRGO) with super-anticorrosive properties are for the first time reported here. The amine groups (-NH2) act as cross-linker agents, which react with epoxy terminal groups from resin, thus closing the gap between the BFRGO layers and the polymeric matrix. Meanwhile, the ammonium ions (-NH3+) are effective trapping agents of negatively charged atoms or molecules (e.g., Cl-). This novel combination enables us to obtain nanocomposite coatings with passive-active protection against corrosion. ER/BFRGO deposited onto A36 mild steel exhibited a remarkably enhanced barrier against corrosion into a saline medium (1 M NaCl; 58.4 g/L), wherein the corrosion current density (icorr) was diminished 6 orders of magnitude (icorr = 5.12 × 10-12 A/cm2), with respect to A36 mild steel coated only with ER (icorr = 2.34 × 10-6 A/cm2). Also, the highest polarization resistance Rp = 6.04 × 107 Ω/cm2 was obtained, which represents the lowest corrosion rate and corresponds to 3 orders of magnitude higher than A36 mild steel coated with ER (Rp = 1.43 × 104 Ω/cm2). The strategy of bifunctionalization proposed herein to obtain bifunctionalized reduced GO with NH2 and NH3+ groups has not been disclosed in the literature before; in consequence, this work opens a new pathway toward the design of smart materials based on multifunctional nanomaterials.

Enzymatically synthesized polyaniline film deposition studied by simultaneous open circuit potential and electrochemical quartz crystal microbalance measurements.

The chemical and enzymatic deposition of polyaniline (PANI) films by in situ polymerization was studied and the resulting films were characterized. The film formation and polymerization processes were simultaneously monitored by the evolution of the open circuit potential and quartz-crystal microbalance measurements. Different substrates, such as Indium-Tin oxide electrodes and gold-coated quartz-crystal electrodes were used as substrates for PANI deposition. Electroactive PANI films were successfully deposited by in situ enzymatic polymerization at low oxidation potential. The electrogravimetric response of the enzymatically deposited PANI film was studied by cyclic voltammetry in monomer-free acidic medium. The morphology of the films was observed by scanning electron microscopy, revealing a granular structure in enzymatically deposited PANI. The PANI films were also characterized by thermogravimetric analysis, electrochemical impedance spectroscopy, and X-ray photoelectron and Fourier-transformed infrared spectroscopy. The simultaneous use of quartz crystal microbalance and open circuit potential is presented as a very useful technique to monitor enzymatic reactions involving oxidoreductases.