S.V. Lamaka

Hydroxyapatite microparticles as feedback-active reservoirs of corrosion inhibitors.

This work contributes to the development of new feedback-active anticorrosion systems. Inhibitor-doped hydroxyapatite microparticles (HAP) are used as reservoirs, storing corrosion inhibitor to be released on demand. Release of the entrapped inhibitor is triggered by redox reactions associated with the corrosion process. HAP were used as reservoirs for several inhibiting species: cerium(III), lanthanum(III), salicylaldoxime, and 8-hydroxyquinoline. These species are effective corrosion inhibitors for a 2024 aluminum alloy (AA2024), used here as a model metallic substrate. Dissolution of the microparticles and release of the inhibitor are triggered by local acidification resulting from the anodic half-reaction during corrosion of AA2024. Calculated values and experimentally measured local acidification over the aluminum anode (down to pH = 3.65) are presented. The anticorrosion properties of inhibitor-doped HAP were assessed using electrochemical impedance spectroscopy. The microparticles impregnated with the corrosion inhibitors were introduced into a hybrid silica-zirconia sol-gel film, acting as a thin protective coating for AA2024, an alloy used for aeronautical applications. The protective properties of the sol-gel films were improved by the addition of HAP, proving their applicability as submicrometer-sized reservoirs of corrosion inhibitors for active anticorrosion coatings.

Active corrosion protection coating for a ZE41 magnesium alloy created by combining PEO and sol–gel techniques

An active protective coating for ZE41 magnesium alloy was produced by sealing an anodic layer, loaded with 1,2,4-triazole, with a sol–gel film. An anodic oxide layer was formed using PEO in a silicate–fluoride alkaline solution. This thin (1.8 μm) porous PEO layer was impregnated with corrosion inhibitor 1,2,4-triazole and sealed with a silica-based sol–gel film modified with titanium oxide. For the first time it was demonstrated that this relatively thin PEO-based composite coating revealed high barrier properties and provided superior protection against corrosion attack during 1 month of continuous exposure to 3% NaCl. A scanning vibrating electrode technique showed a sharp decrease (100 times) of corrosion activity in micro defects formed in the 1,2,4-triazole doped composite coating, when compared to blank samples.

Smart composite coatings for corrosion protection of aluminium alloys in aerospace applications

Abstract Several new concepts to design and fabricate self- healing materials have emerged over the last few years, all presenting advantages and disadvantages. Among these, smart coatings have been considered as extremely promising for several applications, including for corrosion protection purposes. Smart coatings show great potential in what concerns the increased lifetime of metallic structures and reduction of the corrosion-related maintenance costs. This chapter reviews existing self-healing strategies for developing new and more efficient coatings for corrosion protection of aluminium alloys used in aeronautical applications.

Hierarchically organized Li–Al-LDH nano-flakes: a low-temperature approach to seal porous anodic oxide on aluminum alloys

This work suggests a low-temperature sealing approach for tartaric–sulfuric acid (TSA) anodized AA2024 based on hierarchically organized Li–Al-layered double hydroxide (LDH) structures. The new proposed sealing is expected to be directly competitive to the standard hot water sealing (HWS) approaches because of its reduced treatment temperature and high protection efficiency. A hierarchical organization of in situ formed LDH nano-flakes across the depth length of the TSA pores, from the macrodown to the nano-size range, was observed with transmission electron microscopy (TEM). Electrochemical impedance spectroscopy (EIS) studies showed that the densely packed LDH arrangement at the porous oxide layer is directly related to the drastically improved barrier properties of TSA. Moreover, LDH flake-like structures worked as “smart” reservoirs for corrosion inhibiting vanadium species (VOx) that are released on demand upon the onset of corrosion. This was confirmed using a scanning vibrating electrode technique (SVET), giving relevant insights into the time-resolved release activity of VOx and the formation of the passivation layer on cathodic intermetallics, corroborated with EDX and analytical Raman spectroscopy. Passive and active corrosion protection was imparted to the anodic layer via new Li–Al-LDH structures with long-term protection exceeding that of standard HWS procedures.

Thermodynamic simulation of phosphate precipitation based on ion-selective microelectrode measurements

Simulated body fluids (SBFs) are largely used as biocompatibility screening and also as an alternative process to the plasma spray coating. Biomimetic processes occur heterogeneously on metallic surface; therefore, the use of a microelectrode technique is highly advisable to detect surface changes. In this work, the local pH was monitored during the first 44 h of deposition of calcium phosphates on titanium samples with a simplified SBF solution. Three-dimensional data (local pH, x-y coordinates) were used to simulate equilibrium concentrations of all species. Based on these quantities, relative supersaturations and Gibbs energy variations of hydroxyapatite and octacalcium phosphate were evaluated. The conjoint experimental and theoretical approach suggested that neither local alkalinity nor free calcium concentration alone produces an adequate scenario of precipitation conditions, but the use of both procedures results in interesting findings not achieved using only a single approach.

Extending the Lifetime of Weldable Primers by Means of Chemical Inhibitors

Pre-painted metal sheets (coil-coatings) are widely used in casings of household appliances, roofs and side walls in buildings and body parts for the automotive industry. One of the main problems of this type of material is the difficulty to weld it. In an attempt to overcome this problem weldable organic coatings are being experimented. Primers with heavy loads of zinc powder are being employed with success to spot-weld different components of an article. These primers may also present an anticorrosive effect through the galvanic protection offered by the zinc powder. However in aggressive conditions the zinc containing primers can corrode very fast and be consumed in a short period of time. Work has been undertaken in order to extend the lifetime of these primers but maintaining the welding and anticorrosive capabilities. The approach followed here was the modification of primers by corrosion inhibitors that can provide additional active protective effect. A set of organic and inorganic corrosion inhibitors was tested in order to partially passivate the primer. The inhibition of corrosion of zinc and iron was also investigated. Electrochemical testing was done with Electrochemical Impedance Spectroscopy (EIS) and the Scanning Vibrating Electrode Technique (SVET). Results showed that soluble inorganic salts of Ce(III) and La(III) and organic inhibitors like benzotriazole and mercaptobenzothiazole are good candidates to increase the service life of weldable primers.

Evaluation of Corrosion Protection of Sol-Gel Coatings on AZ31B Magnesium Alloy

Magnesium is one of the lightest metals and magnesium alloys have good strength to weight ratio making them very attractive for many particular applications [1]. The main drawback of magnesium alloys is their high corrosion susceptibility. Improving the corrosion protection by deposition of thin hybrid films can expand the areas of applications of relatively cheap magnesium alloys. This work aims at investigation of new anticorrosion coating systems for magnesium alloy AZ31B using hybrid sol-gel films. The sol-gels were prepared by copolymerization of 3- glycidoxypropyltrimethoxysilane (GPTMS), titanium alcoxides and special additives which provide corrosion protection of magnesium alloy. Different compositions of sol-gel systems show enhanced long-term corrosion protection of magnesium alloy. The sol-gel coatings exhibit excellent adhesion to the substrate and protect against the corrosion attack. Corrosion behavior of AZ31B substrates pre-treated with sol–gel derived hybrid coatings was tested by Electrochemical Impedance Spectroscopy (EIS). The morphology and the structure of sol-gel films under study were characterized with SEM/EDS techniques.

Performance boost for primary magnesium cells using iron complexing agents as electrolyte additives

Aqueous Mg battery technology holds significant appeal, owing to the availability of raw materials, high power densities and the possibility of fast mechanical recharge. However, Mg batteries have so far been prone to decreased capacity due to self-corrosion of the anodes from the electrochemical redeposition of impurities, such as Fe, which results in parasitic cathodically active sites on the discharging anode. This work demonstrates that by adding Fe3+-complexing agents like Tiron or salicylate to the aqueous electrolyte of an Mg battery, it was possible to prevent the redeposition of Fe impurities and subsequent self-corrosion of the anode surface, thereby boosting battery performance. To prevent detrimental fouling of anode surface by Mg(OH)2, employed Fe3+-complexing agents must also form soluble complexes with Mg2+ of moderate stability. The interplay of these requirements predetermines the improvement of operating voltage and utilization efficiency.

The Reduction of Dissolved Oxygen During Magnesium Corrosion

Abstract The consumption of dissolved oxygen (DO) during the corrosion of commercially pure magnesium specimens was investigated by localized corrosion techniques. The concentration of oxygen and the local current density on the near‐surface of magnesium were measured simultaneously by a micro‐optode DO sensor and the scanning vibrating electrode technique (SVET), respectively. Diamond microelectrodes were also used for DO mapping. Significant DO depletion was found since the initial immersion time of Mg in NaCl 0.5u2009m, and a correlation could be established between DO consumption and areas of anodic and cathodic activity. These findings assume particular relevance for the corrosion of Mg alloys or magnesium components with impurity levels higher than the tolerance limit. Moreover, this study points out the significance of the partial oxygen pressure as an influential parameter during magnesium corrosion.

Enhanced Wear Performance of Hybrid Epoxy-Ceramic Coatings on Magnesium Substrates

Epoxy-based polymer was deposited as sealing agent on porous anodized coatings prepared by plasma electrolytic oxidation (PEO) to construct multilayered soft-hard coatings on Mg substrates. Different thicknesses and microstructures of the top epoxy layer were achieved by employing different dip-coating strategies. Atomic force microscopy, pull-off tests, and nanoindentation tests were conducted to study the surface roughness, the adhesion strength of the epoxy layer, and the mechanical properties of each component in the hybrid coating system. The micropores and other defects on the anodized layers were sealed by the epoxy polymer, which decreased the surface roughness. The dominant abrasive wear behavior of blank PEO coatings was significantly reduced by the epoxy layers, and the wear mechanism of the hybrid coatings was proposed considering both the microstructure of the hybrid coatings and the mechanical properties of the different components in the hybrid system.