J.M.C. Mol

Dual-action smart coatings with a self-healing superhydrophobic surface and anti-corrosion properties

This work introduces a new self-healing superhydrophobic coating based on dual actions by the corrosion inhibitor benzotriazole (BTA) and an epoxy-based shape memory polymer (SMP). Damage to the surface morphology (e.g., crushed areas and scratches) and the corresponding superhydrophobicity are shown to be rapidly healed through a simple heat treatment at 60 °C for 20 min. Electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) were used to study the anti-corrosion performance of the scratched and the healed superhydrophobic coatings immersed in a 3.5 wt% NaCl solution. The results revealed that the anti-corrosion performance of the scratched coatings was improved upon the incorporation of BTA. After the heat treatment, the scratched superhydrophobic coatings exhibited excellent recovery of their anti-corrosion performance, which is attributed to the closure of the scratch by the shape memory effect and to the improved inhibition efficiency of BTA. Furthermore, we found that the pre-existing corrosion product inside the coating scratch could hinder the scratch closure by the shape memory effect and reduce the coating adhesion in the scratched region. However, the addition of BTA effectively suppressed the formation of corrosion products and enhanced the self-healing and adhesion performance under these conditions. Importantly, we also demonstrated that these coatings can be autonomously healed within 1 h in an outdoor environment using sunlight as the heat source.

A filiform corrosion and potentiodynamic polarisation study of some aluminium alloys

The aim of the present investigation is a combined study of filiform corrosion of aluminium alloys by accelerated exposure tests and potentiodynamic polarisation measurements. The accelerated exposure tests are performed on binary Al-Cu, Al-Mg, Al-Si and Al-Zn model alloys, a ternary Al-MgSi alloy and on the two commercial alloys, AA2024-T351 and AA7075-T651, with variations of composition and surface treatments. The surface treatments cover simple degreasing, chromate and cerium based treatments. A trend of a higher filiform corrosion susceptibility with increasing alloying elements concentrations was observed for all model systems. Furthermore, the filiform corrosion susceptibility varies with the solute atom, in particular Cu was found to have a detrimental effect on the filiform corrosion properties. Both chromating and cerating improve the filiform corrosion resistance of the alloys significantly. To explain the trends observed in the exposure tests, polarisation measurements were performed on the untreated Al-Cu and Al-Zn alloys in bulk anolyte and catholyte solutions which are characteristic for the local anodic and cathodic sites in the filaments on the aluminium substrates. From these measurements a filiform corrosion current, defined as the intercept of the anodic and cathodic curves, can be determined. The present set of experiments shows a correlation between the filiform corrosion properties during accelerated exposure tests and the potentiodynamic polarisation measurements for the Al-Cu alloys. When comparing the results for the Al-Cu and Al-Zn binary alloys it can be concluded that the correlation factor differs significantly with the solute atom and the filiform corrosion current proves to be a non-uniquely discriminating parameter for the filiform corrosion susceptibility of the model alloys. The difference in correlation factor for the Al-Cu and Al-Zn alloys is attributed to differences in the electrochemical behaviour of these alloys with local variations in substrate composition. For the Al-Cu and Al-Zn model alloys the filiform corrosion initiation characteristics are related to the passive range and thus implicitly to the ease of pitting of the alloy. A smaller passive range corresponds to a higher filiform site density for both the Al-Cu and Al-Zn alloys.

Durability and Corrosion of Aluminium and Its Alloys: Overview, Property Space, Techniques and Developments

Aluminium (Al) is an important structural engineering material, its usage ranking only behind ferrous alloys (Birbilis, Muster et al. 2011). The growth in usage and production of Al continues to increase (Davis 1999). The extensive use of Al lies in its strength:density ratio, toughness, and to some degree, its corrosion resistance. From a corrosion perspec‐ tive, which is most relevant to this chapter, Al has been a successful metal used in a num‐ ber of applications from commodity roles, to structural components of aircraft. A number of Al alloys can be satisfactorily deployed in environmental/atmospheric conditions in their conventional form, leaving the corrosion protection industry to focus on market needs in more demanding applications (such as those which require coating systems, for example, the aerospace industry).

High strength aluminium alloys: microstructure, corrosion and principles of protection

Anthony E. Hughes1, Nick Birbilis2, Johannes M.C. Mol3a, Santiago J. Garcia3b, Xiaorong Zhou4 and George E. Thompson4 1CSIRO Materials Science and Technology, Melbourne 2Department of Materials Engineering, Monash University, Clayton 3TU Delft, Department of Materials Science and Engineeringa and Novel Aerospace Materials, Aerospace Engineeringb, Delft 4School of Materials, The University of Manchester, Manchester 1,2Australia 3Netherlands 4United Kingdom

A Critical Appraisal of the Interpretation of Electrochemical Noise for Corrosion Studies

In this paper, procedures and parameters that enable identification of, or discrimination between, general and localized corrosion processes through electrochemical noise are critically discussed. Their relevant similarities, differences, and interdependences are indicated. In addition, the relation between different procedures and parameters with the underlying physicochemical processes is indicated. Consistent and reliable information can be obtained from electrochemical noise data when a data analysis procedure is selected, which on the one hand has a high discrimination ability and on the other hand yields a descriptive parameter that is directly associated to the underlying physico-chemical process. Procedures that meet these two requirements appear to be the Hilbert-Huang transform (Hilbert spectrum), wavelet transform (energy distribution plot), and the analysis of charge and frequency of corrosion events. In addition to the procedures that meet these two requirements, some of the descriptive parameters can be determined by different analysis procedures, which increase their reliability.

Lithium salts as leachable corrosion inhibitors and potential replacement for hexavalent chromium in organic coatings for the protection of aluminum alloys

Lithium salts are being investigated as leachable corrosion inhibitor and potential replacement for hexavalent chromium in organic coatings. Model coatings loaded with lithium carbonate or lithium oxalate demonstrated active corrosion inhibition and the formation of a protective layer in a damaged area during neutral salt spray exposure. The present paper provides an abridged overview of the initial studies into this novel inhibitor technology for the active corrosion protection of aluminum alloys. Coating defects were investigated by microscopic techniques before and after exposure to corrosive conditions. Scanning electron microscopy analysis of cross-sections of the coating defect area demonstrated that the protective layer comprises a typical three-layered structure, which included a dense layer near the alloy surface, a porous middle layer, and a flake-shaped out layer. Potentiodynamic polarization measurements obtained with a microcapillary cell positioned in the coating defect area and electrochemical impedance spectroscopy confirmed the corrosion protective properties of these protective layers. The long-term corrosion inhibition of the lithium-based coating technology was tested in industrial coating systems.

The effect of mechanical surface patterning on filiform growth characteristics

The effect of surface patterning on filiform corrosion characteristics has been studied using both as-rolled material and re-worked AA2024 material and following the filament dimensions and spatial density as a function of time. It was shown that the direction of the filiforms corresponds with the directions of the deepest micro-trenches. Both chemistry-based and geometry-based mechanisms are presented to explain the preference of the direction of propagation. The tendency to filiform corrosion has been quantified by the site density and the average filament length. The lower growth rate on the as-rolled material was attributed to stronger mechanical anchoring of the coating. The option of imposing macro surface patterns to confine filiform corrosion attack has been explored successfully.

Comparative study of protection of AA 2024-T3 exposed to rare earth salts solutions

Abstract The inhibitive effects of the dibutyl phosphate anion in cerium dibutylphosphate [Ce(dbp)3] on AA 2024-T351 immersed in 0·05M NaCl were evaluated by comparison with immersion in cerium chloride (CeCl3) in 0·05M NaCl as well as 0·05M NaCl alone. Scanning electron microscopy and energy dispersive X-ray hyperspectral mapping were used to examine the surfaces after exposure to the different inhibitor solutions. It was found that the dibutylphosphate anion produced additional inhibition for the matrix and the S phase intermetallic particles. The most significant mode of corrosion in the absence of inhibitors was in the form of rings of corrosion product. CeCl3 largely suppressed the formation of the rings of corrosion product, and the Ce(dbp)3 entirely eliminated them (for the time scales investigated here), indicating the additional inhibitive action of the dibutylphosphate anion.

Additively manufactured biodegradable porous magnesium

An ideal bone substituting material should be bone-mimicking in terms of mechanical properties, present a precisely controlled and fully interconnected porous structure, and degrade in the human body to allow for full regeneration of large bony defects. However, simultaneously satisfying all these three requirements has so far been highly challenging. Here we present topologically ordered porous magnesium (WE43) scaffolds based on the diamond unit cell that were fabricated by selective laser melting (SLM) and satisfy all the requirements. We studied the in vitro biodegradation behavior (up to 4 weeks), mechanical properties and biocompatibility of the developed scaffolds. The mechanical properties of the AM porous WE43 (E = 700-800 MPa) scaffolds were found to fall into the range of the values reported for trabecular bone even after 4 weeks of biodegradation. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), electrochemical tests and µCT revealed a unique biodegradation mechanism that started with uniform corrosion, followed by localized corrosion, particularly in the center of the scaffolds. Biocompatibility tests performed up to 72 h showed level 0 cytotoxicity (according to ISO 10993-5 and -12), except for one time point (i.e., 24 h). Intimate contact between cells (MG-63) and the scaffolds was also observed in SEM images. The study shows for the first time that AM of porous Mg may provide distinct possibilities to adjust biodegradation profile through topological design and open up unprecedented opportunities to develop multifunctional bone substituting materials that mimic bone properties and enable full regeneration of critical-size load-bearing bony defects. STATEMENT OF SIGNIFICANCE The ideal biomaterials for bone tissue regeneration should be bone-mimicking in terms of mechanical properties, present a fully interconnected porous structure, and exhibit a specific biodegradation behavior to enable full regeneration of bony defects. Recent advances in additive manufacturing have resulted in biomaterials that satisfy the first two requirements but simultaneously satisfying the third requirement has proven challenging so far. Here we present additively manufactured porous magnesium structures that have the potential to satisfy all above-mentioned requirements. Even after 4 weeks of biodegradation, the mechanical properties of the porous structures were found to be within those reported for native bone. Moreover, our comprehensive electrochemical, mechanical, topological, and biological study revealed a unique biodegradation behavior and the limited cytotoxicity of the developed biomaterials.

Electrochemical and Microstructural Studies in Reinforced Mortar, Modified with Core-Shell Micelles

This work reports on monitoring chloride-induced corrosion in reinforced mortar specimens, with and without addition of polymeric nano-aggregates in the mortar mixture. The investigation is a novel approach to control steel corrosion in reinforced concrete, hereby reporting the preliminary results, related to one of the main objectives: studying the influence of admixed polymer nano-aggregates (in the form of PEO113-b-PS218 core-shell micelles with a very low concentration of 0.006 wt.% per mortar weight) on the corrosion behavior of the steel reinforcement, compared to reference, micelles-free mixtures.