J. Tedim

Enhancement of active corrosion protection via combination of inhibitor-loaded nanocontainers.

The present work reports the synthesis of layered double hydroxides (LDHs) nanocontainers loaded with different corrosion inhibitors (vanadate, phosphate, and 2-mercaptobenzothiazolate) and the characterization of the resulting pigments by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The anticorrosion activity of these nanocontainers with respect to aluminum alloy AA2024 was investigated by electrochemical impedance spectroscopy (EIS). The bare metallic substrates were immersed in dispersions of nanocontainers in sodium chloride solution and tested to understand the inhibition mechanisms and efficiency. The nanocontainers were also incorporated into commercial coatings used for aeronautical applications to study the active corrosion protection properties in systems of industrial relevance. The results show that an enhancement of the active protection effect can be reached when nanocontainers loaded with different inhibitors are combined in the same protective coating system.

Novel Inorganic Host Layered Double Hydroxides Intercalated with Guest Organic Inhibitors for Anticorrosion Applications

Zn-Al and Mg-Al layered double hydroxides (LDHs) loaded with quinaldate and 2-mercaptobenzothiazolate anions were synthesized via anion-exchange reaction. The resulting compounds were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy/energy-dispersive X-ray spectroscopy. Spectrophotometric measurements demonstrated that the release of organic anions from these LDHs into the bulk solution is triggered by the presence of chloride anions, evidencing the anion-exchange nature of this process. The anticorrosion capabilities of LDHs loaded with organic inhibitors toward the AA2024 aluminum alloy were analyzed by electrochemical impedance spectroscopy. A significant reduction of the corrosion rate is observed when the LDH nanopigments are present in the corrosive media. The mechanism by which the inhibiting anions can be released from the LDHs underlines the versatility of these environmentally friendly structures and their potential application as nanocontainers in self-healing coatings.

Self-healing protective coatings with “green” chitosan based pre-layer reservoir of corrosion inhibitor

A new type of corrosion protective self-healing coating is reported in the present study. The coating is constituted by a chitosan-based pre-layer deposited onto the metal surface and a barrier hybrid film. The chitosan film doped with cerium ions serves as a reservoir for the corrosion inhibitor. The cerium ions form a complex with the functional groups of chitosan macromolecules providing a prolonged release of the active agent on demand. The developed bi-layer protective coating was applied to aluminium alloy 2024, which is widely used in the aeronautical industry. The results obtained from electrochemical impedance spectroscopy clearly demonstrate a superior corrosion protection when the coating with the cerium-doped biopolymer pre-layer is used. The localized electrochemical study in micro-confined defects showed a well-defined self-healing ability of the developed coating system.

Nanostructured LDH-container layer with active protection functionality

Self-healing protective coatings based on different types of nanocontainers of corrosion inhibitors have been recently developed and reported as promising solutions for many industrial applications. Layered double hydroxide (LDH) nanocontainers are among the most interesting systems since they confer the delivery of inhibitors on demand under action of corrosion-relevant triggers such as the presence of corrosive anions or local change of pH. In this paper, we report for the first time a new approach based on formation of a nanostructured LDH-container layer directly on the metal surface as a result of conversion reaction with a metal (aluminium alloy 2024) surface. The methodology allows the formation of a spatially differentiated LDH structure preferentially on surface sites located at active intermetallics. The LDH container layer loaded with vanadate ions provides an efficient active corrosion protection and can be used as a functional layer in self-healing coating systems.

Polyelectrolyte-modified layered double hydroxide nanocontainers as vehicles for combined inhibitors

In this work, nanocontainers based on layered double hydroxide (LDH) loaded with two different corrosion inhibitors, namely 2-mercaptobenzothiazole (MBT) and cerium(III) nitrate, were prepared. MBT was intercalated into LDH galleries in anionic form by anion-exchange, while Ce3+ was fixed between polyelectrolyte layers on the surface of LDH-MBT nanoplatelets by the Layer-by-Layer (LbL) method. Both inhibitors were found in the modified LDHs (LDH-Mod) by X-ray diffraction and scanning electron microscopy coupled with energy dispersive spectroscopy. The release studies performed by UV-vis spectrophotometry indicated that the main triggering conditions for release of MBT from LDHs changed when LDH nanoplatelets were covered with polyelectrolytes. Furthermore, electrochemical impedance spectroscopy and DC polarization were used to investigate the effect in combining MBT− and Ce3+ within the same nanocontainer, for the corrosion protection of 2024-T3 aluminium alloy directly in solution as well as in a hybrid sol–gel coating. The obtained results open prospects for application of these systems as additives in multifunctional smart coatings.

Nanocontainer-based corrosion sensing coating

The present paper reports on the development of new sensing active coating on the basis of nanocontainers containing pH-indicating agent. The coating is able to detect active corrosion processes on different metallic substrates. The corrosion detection functionality based on the local colour change in active cathodic zones results from the interaction of hydroxide ions with phenolphthalein encapsulated in mesoporous nanocontainers which function as sensing nanoreactors. The mesoporous silica nanocontainers are synthesized and loaded with pH indicator phenolphthalein in a one-stage process. The resulting system is mesoporous, which together with bulkiness of the indicator molecules limits their leaching. At the same time, penetration of water molecules and ions inside the container is still possible, allowing encapsulated phenolphthalein to be sensitive to the pH in the surrounding environment and outperforming systems when an indicator is directly dispersed in the coating layer.The performed tests demonstrate the pH sensitivity of the developed nanocontainers being dispersed in aqueous solutions. The corrosion sensing functionality of the protective coatings with nanocontainers are proven for aluminium- and magnesium-based metallic substrates. As a result, the developed nanocontainers show high potential to be used in a new generation of active protective coatings with corrosion-sensing coatings.

Sealing of tartaric sulfuric (TSA) anodized AA2024 with nanostructured LDH layers

In this work, a functional sealing of a TSA anodic layer on AA2024 is suggested based upon the formation of inhibitor-containing Zn–Al layered double hydroxides (LDH). The LDH structures are formed in the pores of the anodic layer and on top of it as a result of hydrothermal treatment in a Zn2+-containing bath as shown by the structure, morphology and composition analysis. The resulting LDHs were loaded with a well-known corrosion inhibitor (vanadate). Electrochemical impedance spectroscopy, salt spray tests and scanning vibrating electrode techniques have shown a remarkable improvement in corrosion resistance of the LDH-modified sample in comparison with conventional hot-water sealing. The vanadate-loaded LDHs rendered a significant long-term active protection for the covered aluminum alloy substrate.

Control of crystallite and particle size in the synthesis of layered double hydroxides: Macromolecular insights and a complementary modeling tool

Zinc-aluminum layered double hydroxides with nitrate intercalated (Zn(n)Al-NO3, n=Zn/Al) is an intermediate material for the intercalation of different functional molecules used in a wide range of industrial applications. The synthesis of Zn(2)Al-NO3 was investigated considering the time and temperature of hydrothermal treatment. By examining the crystallite size in two different directions, hydrodynamic particle size, morphology, crystal structure and chemical species in solution, it was possible to understand the crystallization and dissolution processes involved in the mechanisms of crystallite and particle growth. In addition, hydrogeochemical modeling rendered insights on the speciation of different metal cations in solution. Therefore, this tool can be a promising solution to model and optimize the synthesis of layered double hydroxide-based materials for industrial applications.

Unusual coordination environment for barium cations in ion recognition conducting poly[Ni(salen)(receptor)] films.

[Ni( salen)] complexes bearing different crown ether receptors were electropolymerized to give films whose voltammetric signatures responded to Ba2+. In line with DFT calculations, X-ray absorption spectroscopy (XAS) near the Ni K-edge showed the nickel local environment in the monomers and their corresponding polymers (in the presence or absence of barium) to be identical. However, the expectation of crown size-dependent barium local environment (based on geometry and donor atom availability) was not found. XAS near the Ba K-edge showed that Ba2+ in the films coordinated to only two oxygen donors, irrespective of crown size. This surprisingly low coordination number (compared to solution species) is accompanied by a higher barium/crown ratio than the anticipated 1:1 stoichiometry. The implications of these effects for design and performance of sensors based on metal ion recognition chemistry are discussed.

Active sensing coating for early detection of corrosion processes

A corrosion sensing coating based on specially developed polymeric microcapsules with a pH-indicator is reported. The synthesis of the microcapsules is designed in a way to ensure their optimal compatibility with the polyurethane protective coatings and to allow release of the indicator at higher pH values. The obtained polyurea microcapsules have a regular and microsized morphology and a loading content of 12 wt%. The developed sensing coating applied on aluminium and magnesium alloys is able to indicate initiation of corrosion processes through a pink coating coloration, as a result of local pH increase in the cathodic areas.