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The development of anti-corrosion polymeric coatings has grown exponentially in the fields of material science, chemistry, engineering, and nanotechnology during the last century and has prompted the evolution of efficient characterization techniques. Nowadays, polymeric coatings represent a well-established protection system that provides a barrier between a metallic substrate and the environment. However, the increase in complexity and functionality of these coatings requires high-precision techniques capable of predicting failures and providing smart protection. This review summarizes the state of the art for the main electrochemical techniques, emphasizing devices that track the anti-corrosion properties of polymeric coatings from the macroscale to the nanoscale. An overview of the advances in accelerated corrosion testing and the electrochemical characterization of coatings is explored, including insights into their advantages and limitations. In addition, the challenges and potential applications of the theoretical approaches are summarized based on current knowledge. Finally, this work provides the reader with the trends and challenges of designing future technologies and models capable of tracking corrosion and predicting failures. [ABSTRACT FROM AUTHOR]

[Display omitted] • 1000 days immersion study of PMMA-silica coatings on Al alloys in 0.6 M NaCl solution. • Water uptake of less than 0.7 vol% assessed by analysis of electrochemical impedance data. • Modeling of electrochemical impedance data revealed a "less-Fickian" diffusion coefficient. • The efficient diffusion barrier against corrosive species results in high corrosion resistance. • Nanostructural changes do not significantly affect the long-term anticorrosive performance. Poly (methyl methacrylate) (PMMA)-silica coatings form a few micrometers thick anti-corrosive barrier that blocks corrosive species when exposed to harsh environments. Their excellent anti-corrosive performance stands out for protecting metal alloys immersed in seawater for long periods (>2 years), making them compliant for applications in the marine, aeronautical, and automotive industries. A key approach to understanding the degradation of high-performance coatings over time consists of analyzing their water uptake-induced structural changes. This work examines in detail the uptake and structural modification of PMMA-silica coatings on Al alloys immersed for more than 1000 days in 3.5 wt% NaCl solution. Gravimetry, thermal analysis, infrared spectroscopy and electrochemical impedance spectroscopy (EIS) were employed to monitor the evolution of coated samples. Nuclear magnetic resonance, X-ray photoelectron spectroscopy, electron and atomic force microscopies before and after immersion indicate a slight leaching-induced surface roughening due to silica hydrolysis. These findings comply with the low uptake values (∼0.6 vol%) and a less-Fickian diffusion coefficient obtained from modelling of the EIS data. The high impedance modulus (>GΩ) is related to the highly cross-linked structure, resulting in a very low permeation rate of the electrolyte. The applied methodology is of crucial importance for establishing a standardized analysis for high-performance protective coatings. [ABSTRACT FROM AUTHOR]

• High performance methyl methacrylate-silica anticorrosive coatings with long-term stability. • Correlation of structural characteristics with electrochemical barrier properties. • Modeling of the electrolyte permeation using the two-layer Young approach. • Comparison of electrical equivalent circuits using constant phase element and Young model. This work reports a detailed investigation of the structural and electrochemical barrier properties of PMMA-silica coatings. Hybrid nanocomposites were prepared by combining the sol-gel method with the polymerization of methyl methacrylate (MMA), using the thermal initiator benzoyl peroxide (BPO), followed by the hydrolytic condensation of tetraethoxysilane (TEOS) and 3-(trimethoxysilyl)propyl methacrylate. Raman spectroscopy and thermal analysis showed that the fine-tuning of the BPO amount, a critical synthesis parameter, improved the polymerization efficiency of MMA, leading to a highly cross-linked hybrid structure. The homogeneous coatings prepared under optimized synthesis conditions presented elevated thermal stability due to improved polymerization of the organic phase. Electrochemical impedance spectroscopy (EIS) showed a quasi-ideal capacitive impedance response in 3.5% NaCl solution, with low frequency impedance modulus of up to 10 GΩ cm2, which remained essentially unchanged during 19 months of immersion. This notable barrier property was modeled by fitting the EIS curves assuming slowly expanding electrolyte uptake, using the two-layer Young approach, and by comparison with the standard equivalent electrical circuit (EEC/CPE) model. The Young model provided valuable information on the time evolution of physical parameters including the thickness of the uptake zone, the conductivity depth-profile and the dielectric constant, among others, evidencing the high performance of the coatings. [ABSTRACT FROM AUTHOR]

Ti6Al4V is the mostly applied metallic alloy for orthopedic and dental implants, however, its lack of osseointegration and poor long-term corrosion resistance often leads to a secondary surgical intervention, recovery delay and toxicity to the surrounding tissue. As a potential solution of these issues poly(methyl methacrylate)-silicon dioxide (PMMA-silica) coatings have been applied on a Ti6Al4V alloy to act simultaneously as an anticorrosive barrier and bioactive film. The nanocomposite, composed of PMMA covalently bonded to the silica phase through 3-(trimethoxysilyl)propyl methacrylate (MPTS), has been synthesized combining the sol-gel process with radical polymerization of methyl methacrylate. The 5 μm thick coatings deposited on Ti6Al4V have a smooth surface, are homogeneous, transparent, free of pores and cracks, and show a strong adhesion to the metallic substrate (11.6 MPa). Electrochemical impedance spectroscopy results proved an excellent anticorrosive performance of the coating, with an impedance modulus of 26 GΩ cm2 and long-term durability in simulated body fluid (SBF) solution. Moreover, after 21 days of immersion in SBF, the PMMA-silica coating presented apatite crystal deposits, which suggests in vivo bone bioactivity. This was confirmed by biological characterization showing enhanced osteoblast proliferation, explained by the increased surface free energy and protein adsorption. The obtained results suggest that PMMA-silica hybrids can act in a dual role as efficient anticorrosive and bioactive coating for Ti6Al4V alloys. Unlabelled Image • Conjugation of silica and PMMA yielded homogeneous and adherent hybrid coatings. • PMMA-silica coatings provide efficient corrosion protection for a Ti6Al4V alloy. • Apatite formation in SBF solution predicts bone-bonding ability. • The coatings promote osteoblastic proliferation. • Effective protection metallic implants by bioactive anticorrosion coatings [ABSTRACT FROM AUTHOR]