An Inhibitor-Loaded LDH- and MOF-Based Bilayer Hybrid System for Active Corrosion Protection of Aluminum Alloys.

A novel inhibitor-loaded bilayer hybrid system based on the LDH inner layer and MOF outer layer is designed on an aluminum alloy 2A12 surface to improve corrosion performance. The hybrid film system covers the inherent cavities and intercrystalline defects of the LDH film using the affinity between the LDH and the MOF compounds. The results demonstrate that the LDH-inhI precursor film is entirely covered by new Zn-based MOF microrods. The LDH-inhI precursor film is partially dissolved and recrystallized in favor of MOF crystal growth to strengthen the binding adhesion between LDH and MOF films. The LDH-inhI/MOF-inhII bilayer film shows significantly enhanced corrosion resistance through the synergistic action of LDH and MOF nanocontainers doped with different corrosion inhibitors (vanadates, 2,5-furandicarboxylic acid, and benzotriazoles). Due to the multiple loadings of the MOF film and the sustained-release of the LDH film, this method provides an effective approach to developing new anticorrosion systems and enhancing both the barrier ability and active corrosion protection performance of LDH-based conversion treatments.

Characterization and In Vitro Behavior of PEO Coated Mg Modified with Antibacterial Ag(I) and Cu(II) Complexes.

The use of Mg-based biomaterials with a number of their advantageous properties are overshadowed by uncontrollable metal corrosion. Moreover, the use of implants goes alongside with the threat of pathogens-associated complications. In this study, PEO coated Mg biomaterial loaded with antibacterial Ag(I) and Cu(II) complexes is produced and tested to meet both appropriate protective characteristics as well as sufficient level of antibacterial activity. To achieve a suitable level of anticorrosion protection phosphate and fluoride-phosphate electrolytes are used in the PEO process. Investigation of the surface thickness and morphology done by means of cross-section analysis and scanning electron microscopy (SEM), as well as electrochemical impedance spectroscopy (EIS) assay show precedence of the fluoride containing PEO coating and make it the material of choice for further modification with Ag(I) and Cu(II) complexes. The presence of the complexes on the PEO surface is confirmed by energy dispersive X-ray spectroscopy (EDX). X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and glow discharge optical emission spectroscopy (GDOES) are used to estimate the complexes' chemical state and depth of penetration in the coating surface. Based on the results of antibacterial assay, the modified coatings are found to be active against both Gram-positive and Gram-negative bacteria.

Ciprofloxacin Release and Corrosion Behaviour of a Hybrid PEO/PCL Coating on Mg3Zn0.4Ca Alloy.

In the present work, a hybrid hierarchical coating (HHC) system comprising a plasma electrolytic oxidation (PEO) coating and a homogeneously porous structured polycaprolactone (PCL) top-coat layer, loaded with ciprofloxacin (CIP), was developed on Mg3Zn0.4Ca alloy. According to the findings, the HHC system avoided burst release and ensured gradual drug elution (64% over 240 h). The multi-level protection of the magnesium alloy is achieved through sealing of the PEO coating pores by the polymer layer and the inhibiting effect of CIP (up to 74%). The corrosion inhibition effect of HHC and the eluted drug is associated with the formation of insoluble CIP-Me (Mg/Ca) chelates that repair the defects in the HHC and impede the access of corrosive species as corroborated by FTIR spectra, EIS and SEM images after 24 h of immersion. Therefore, CIP participates in an active protection mechanism by interacting with cations coming through the damaged coating.

Corrosion Inhibitors Intercalated into Layered Double Hydroxides Prepared In Situ on AZ91 Magnesium Alloys: Structure and Protection Ability.

This work first describes the intercalation of corrosion inhibitors into layered double hydroxides LDH-OH/CO3 nanocontainers (parental LDH) obtained in situ on the surface of magnesium alloy AZ91 in the presence of a chelating agent. Vanadate, as a typical broad inhibitor for active metals, and oxalate, as an inhibitor suitable for magnesium, were selected as a first approach. The optimization of exchange conditions was performed, and the optimal parameters (ambient pressure and 95 °C) were selected. The corrosion protective properties of obtained LDH-based layers were studied using immersion and salt spray tests in NaCl solution, supported by electrochemical impedance spectroscopy and atomic emission spectroelectrochemistry. It is demonstrated that vanadate intercalated into LDH is more effective for the active protection of AZ91 in comparison to the performance of oxalate. A possible mechanism of corrosion inhibition based on the application of LDH nanocontainers is suggested and discussed.

Double Stimuli-Responsive Conducting Polypyrrole Nanocapsules for Corrosion-Resistant Epoxy Coatings.

Stimuli-responsive nanocapsules, which can respond to various environmental stimuli and release their encapsulated payload on demand, have attracted wide interest in different fields in recent years. In this work, a novel kind of polypyrrole (PPy) nanocapsules is fabricated and loaded with zinc salt corrosion inhibitors. The synthesized PPy nanocapsules respond to two different external stimuli (pH- and redox-responsive) and can control the release of their encapsulated corrosion inhibitors. The nanocapsules can detect the micro-environmental pH or surface-potential changes associated with the corrosion initiation of the metal substrate. When introduced into a protective epoxy coating, the fabricated PPy nanocapsules inhibit the anodic and cathodic corrosion reactions. The superior corrosion resistance and active corrosion protection effects of the epoxy-PPy-Zn coatings are further demonstrated via electrochemical and long-term immersion tests. The low-frequency impedance, coating resistance, and oxide film resistance increase after about 400 h of exposure in a 3.5 wt % NaCl solution, reflecting the enhanced corrosion protection properties and excellent repairing performance of the coating. Furthermore, the epoxy-PPy-Zn coating can avoid the pitting corrosion of 304 stainless steel. Overall, we have fabricated double stimuli-responsive PPy nanocapsules via a simple and effective strategy and incorporated them into a corrosion-resistant epoxy coating for protecting Fe-based metal substrates.

Chromate-Free Corrosion Protection Strategies for Magnesium Alloys-A Review: Part III-Corrosion Inhibitors and Combining Them with Other Protection Strategies.

Owing to the unique active corrosion protection characteristic of hexavalent chromium-based systems, they have been projected to be highly effective solutions against the corrosion of many engineering metals. However, hexavalent chromium, rendered a highly toxic and carcinogenic substance, is being phased out of industrial applications. Thus, over the past few years, extensive and concerted efforts have been made to develop environmentally friendly alternative technologies with comparable or better corrosion protection performance to that of hexavalent chromium-based technologies. The introduction of corrosion inhibitors to a coating system on magnesium surface is a cost-effective approach not only for improving the overall corrosion protection performance, but also for imparting active inhibition during the service life of the magnesium part. Therefore, in an attempt to resemble the unique active corrosion protection characteristic of the hexavalent chromium-based systems, the incorporation of inhibitors to barrier coatings on magnesium alloys has been extensively investigated. In Part III of the Review, several types of corrosion inhibitors for magnesium and its alloys are reviewed. A discussion of the state-of-the-art inhibitor systems, such as iron-binding inhibitors and inhibitor mixtures, is presented, and perspective directions of research are outlined, including in silico or computational screening of corrosion inhibitors. Finally, the combination of corrosion inhibitors with other corrosion protection strategies is reviewed. Several reported highly protective coatings with active inhibition capabilities stemming from the on-demand activation of incorporated inhibitors can be considered a promising replacement for hexavalent chromium-based technologies, as long as their deployment is adequately addressed.

Comparison of 2D and 3D Plasma Electrolytic Oxidation (PEO)-Based Coating Porosity Data Obtained by X-ray Tomography Rendering and a Classical Metallographic Approach.

In this work, the porosity of plasma electrolytic oxidation (PEO)-based coatings on Al- and Mg-based substrates was studied by two imaging techniques-namely, SEM and computer microtomography. Two approaches for porosity determination were chosen; relatively simple and fast SEM surface and cross-sectional imaging was compared with X-ray micro computed tomography (microCT) rendering. Differences between 2D and 3D porosity were demonstrated and explained. A more compact PEO coating was found on the Al substrate, with a lower porosity compared to Mg substrates under the same processing parameters. Furthermore, huge pore clusters were detected with microCT. Overall, 2D surface porosity calculations did not show sufficient accuracy for them to become the recommended method for the exact evaluation of the porosity of PEO coatings; microCT is a more appropriate method for porosity evaluation compared to SEM imaging. Moreover, the advantage of 3D microCT images clearly lies in the detection of closed and open porosity, which are important for coating properties.

Atomistic Insight into the Hydration States of Layered Double Hydroxides.

Effective protective coatings are an essential component of lightweight engineering materials in a large variety of applications as they ensure structural integrity of the base material throughout its whole service life. Layered double hydroxides (LDHs) loaded with corrosion inhibitors depict a promising approach to realize an active corrosion protection for aluminum and magnesium. In this work, we employed a combination of density functional theory and molecular dynamics simulations to gain a deeper understanding of the influence of intercalated water content on the structure, the stability, and the anion-exchange capacity of four different LDH systems containing either nitrate, carbonate, or oxalate as potential corrosion inhibiting agents or chloride as a corrosion initiator. To quantify the structural change, we studied the atom density distribution, radial distribution function, and orientation of the intercalated anions. Additionally, we determined the stability of the LDH systems by calculating their respective hydration energies, hydrogen-bonded network connected to the intercalated water molecules, as well as the self-diffusion coefficients of the intercalated anions to provide an estimate for the probability of their release after intercalation. The obtained computational results suggest that the hydration state of LDHs has a significant effect on their key properties like interlayer spacing and self-diffusion coefficients of the intercalated anions. Furthermore, we conclude from our simulation results that a high self-diffusion coefficient which is linked to the mobility of the intercalated anions is vital for its release via an anion-exchange mechanism and to subsequently mitigate corrosion reactions. Furthermore, the presented theoretical study provides a robust force field for the computer-assisted design of further LDH-based active anticorrosion coatings.

Cathodic Protection of Mild Steel Using Aluminium-Based Alloys.

Typically, steel is protected from corrosion by employing sacrificial anodes or coatings based on Zn, Mg, Al or Cd. However, stricter environmental regulations require new environmentally friendly alternatives to replace Cd. Traditionally, Al-based anodes have been employed to cathodically protect steel in marine applications or as ion vapour deposition (IVD)-Al sacrificial coatings for aerospace applications. However, Al tends to passivate, thus losing its protective effect. Therefore, it is important to identify possible alloys that can provide a constantly sufficient current. In this study, Al-X alloys (X = Ag, Bi, Ca, Cr, Cu, Ga, Gd, In, Mg, Mn, Ni, Sb, Si, Sn, V, Ti, Zn and Zr) were firstly tested for a screening of the sacrificial properties of binary systems. Al-0.5Cr, Al-1Sn, Al-0.2Ga, Al-0.1In, Al-2Si and Al-5Zn alloys were suggested as promising sacrificial Al-based alloys. Suitable heat treatments for each system were implemented to reduce the influence of the secondary phases on the corrosion properties by minimising localised attack. extensive evaluation of the corrosion properties, including galvanic coupling of these alloys to steel, was performed in the NaCl electrolyte. A comparative analysis was conducted in order to choose the most promising alloy(s) for avoiding the passivation of Al and for efficient cathodic protection to steel.

Biodegradation behaviour of Fe-based alloys in Hanks' Balanced Salt Solutions: Part II. The evolution of local pH and dissolved oxygen concentration at metal interface.

Commercially pure Fe, Fe35Mn, and (Fe35Mn)5Ag alloys were prepared by uniaxial pressing of the mixture of individual powders, followed by sintering. The influence of the alloying elements Mn and Ag on the corrosion behaviour of these Fe-based alloys was investigated in Hanks' Balanced Salt Solution (HBSS). Furthermore, the role of the components in HBSS, particularly Ca2+ ions during alloys degradation was studied. Distribution of local pH and dissolved oxygen concentration was measured 50 µm above the interface of the degrading alloys. The results revealed that 5 wt% Ag addition to Fe35Mn alloy triggered micro-galvanic corrosion, while uniform corrosion dominated in pure Fe and Fe35Mn. Fast precipitation of Ca-P-containing products on the surface of these Fe-based alloys buffered local pH at the metal interface, and blocked oxygen diffusion at the initial stages of immersion. In the (Fe35Mn)5Ag, the detachment or structural changes of Ca-P-containing products gradually diminished their barrier property. These findings provided valuable insights into the degradation mechanism of promising biodegradable Fe-based alloys.

Biodegradation behaviour of Fe-based alloys in Hanks' Balanced Salt Solutions: Part I. material characterisation and corrosion testing.

Research on Fe-based biodegradable alloys for implant applications has increased considerably over the past decade. However, there is limited information on the influence of testing electrolytes on corrosion product formation and general corrosion progress. In this work, the effect of Hanks' Balanced Salt Solution (HBSS) with or without Ca2+ on the corrosion of Fe, Fe35Mn and (Fe35Mn)5Ag powder-processed coupons has been studied using potentiodynamic polarisation, Electrochemical Impedance Spectroscopy (EIS), and preliminary localised measurement of pH and dissolved oxygen concentration in close proximity to the metal surface. Both Fe35Mn and (Fe35Mn)5Ag alloys showed accelerated corrosion when compared to pure Fe based on potentiodynamic testing results, with FeMnAg exhibiting the highest corrosion rate in Ca2+-containing HBSS. The results indicate that in Ca2+-containing HBSS, the formation of a partially protective Ca/P layer decelerates the corrosion progress, whereas the Fe- and Mn-phosphates formed in Ca2+-free HBSS do not have the same effect. The Ca/P layer on (Fe35Mn)5Ag experienced a reduction in resistance following several hours of testing, indicating partial loss of its protective effect.

Approaching "stainless magnesium" by Ca micro-alloying.

Severe corrosion of Mg and Mg alloys is a major issue hindering their wider application in transportation industry, medical implants and aqueous batteries. Previously, no Mg-based material has been found with a significantly lower corrosion rate than that of ultra-high-purity Mg, i.e. 0.25 mm y-1 in concentrated NaCl solution. In this work for the first time, highly corrosion-resistant Mg is found to be accomplishable by Ca micro-alloying, bringing "stainless Mg" closer. The designed Mg-Ca lean alloys possess incredibly low corrosion rates, less than 0.1 mm y-1 in 3.5 wt% NaCl solution, which are significantly lower than that of ultra-high-purity Mg and all Mg alloys reported thus far. The outstanding corrosion resistance is attributed to inhibition of cathodic water reduction kinetics, impurities stabilizing and a protective surface film induced by Ca micro-alloying. Combined with the environmental benignity and economic viability, Ca micro-alloying renders huge feasibility on developing advanced Mg-based materials for diverse applications.

Double-Ligand Strategy to Construct an Inhibitor-Loaded Zn-MOF and Its Corrosion Protection Ability for Aluminum Alloy 2A12.

A promising double-ligand strategy for the delivery of active corrosion inhibitors by a Zn(II)-based metal-organic framework (Zn-MOF) is developed. Zn-MOF compounds were synthesized by a facile one-pot solvothermal method and characterized. The Zn-MOF is based on the corrosion inhibitor benzotriazole (BTA) and 2,5-furandicarboxylic acid (H2FDA) ligand, which is a promising renewable building block alternative to terephthalic or isophthalic acid. The crystal structure and morphology are characterized by single-crystal X-ray diffraction analysis, powder X-ray diffraction analysis (PXRD), Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). The synthesized MOF crystallites are in the trigonal space group R3c with the cell parameters in a three-dimensional (3D) anionic framework. Their ability to inhibit the corrosion process of aluminum alloy 2A12 in NaCl solution was also evaluated by immersion tests in solutions with and without a MOF. The postcorrosion analysis was performed by SEM and X-ray photoelectron spectroscopy (XPS). Additional information about the inhibition efficiency was obtained by electrochemical impedance spectroscopy (EIS). The results suggest that the as-synthesized MOF can release the inhibitors and form protective layers effectively on the surface of the aluminum alloy. The use of inhibitor-loaded MOF nanocontainers provides promising opportunities for the smart delivery of inhibitors and effective corrosion protection of 2A12 aluminum alloys.

Mg Biodegradation Mechanism Deduced from the Local Surface Environment under Simulated Physiological Conditions.

Although certified magnesium-based implants are launched some years ago, the not well-defined Mg degradation mechanism under physiological conditions makes it difficult to standardize its use as a degradable biomaterial for a wide range of implant applications. Among other variables influencing the Mg degradation mechanism, monitoring the pH in the corrosive solution and, especially, at the corroding interface is important due to its direct relation with the formation and stability of the degradation products layer. The interface pH (pH at the Mg/solution interface) developed on Mg-2Ag and E11 alloys are studied in situ during immersion under dynamic conditions (1.5 mL min-1 ) in HBSS with and without the physiological amount of Ca2+ cations (2.5 × 10-3 m). The results show that the precipitation/dissolution of amorphous phosphate-containing phases, that can be associated with apatitic calcium-phosphates Ca10-x (PO4 )6-x (HPO4 or CO3 )x (OH or ½ CO3 )2-x with 0 ≤ x ≤ 2 (Ap-CaP), promoted in the presence of Ca2+ generates an effective local pH buffering system at the surface. Thus, high alkalinization is prevented, and the interface pH is stabilized in the range of 7.6 to 8.5.

A novel lean alloy of biodegradable Mg-2Zn with nanograins.

Lean alloy (low alloyed) is beneficial for long-term sustainable development of metal materials. Creating a nanocrystalline microstructure is a desirable approach to improve biodegradability and mechanical properties of lean biomedical Mg alloy, but it is nearly impossible to realize. In the present study, the bulk nanocrystalline Mg alloy (average grain size: ~70 nm) was successfully obtained by hot rolling process of a lean Mg-2wt.%Zn (Z2) alloy and both high strength ((223 MPa (YS) and 260 MPa (UTS)) and good corrosion resistance (corrosion rate in vivo: 0.2 mm/year) could be achieved. The microstructure evolution during the rolling process was analyzed and discussed. Several factors including large strain, fine grains, strong basal texture, high temperature and Zn segregation conjointly provided the possibility for the activation of pyramidal slip to produce nanocrystals. This finding could provide a new development direction and field of application for lean biomedical Mg alloys.

A first-principles analysis of the charge transfer in magnesium corrosion.

Magnesium is the lightest structural engineering material and bears high potential to manufacture automotive components, medical implants and energy storage systems. However, the practical use of untreated magnesium alloys is restricted as they are prone to corrosion. An essential prerequisite for the control or prevention of the degradation process is a deeper understanding of the underlying corrosion mechanisms. Prior investigations of the formation of gaseous hydrogen during the corrosion of magnesium indicated that the predominant mechanism for this process follows the Volmer-Heyrovský rather than the previously assumed Volmer-Tafel pathway. However, the energetic and electronic states of both reaction paths as well as the charge state of dissolved magnesium have not been fully unraveled yet. In this study, density functional theory calculations were employed to determine these parameters for the Volmer, Tafel and Heyrovský steps to gain a comprehensive understanding of the major corrosion mechanisms responsible for the degradation of magnesium.

Synergistic Mixture of Electrolyte Additives: A Route to a High-Efficiency Mg-Air Battery.

Magnesium primary cells are currently experiencing a renaissance following the suggestion of new strategies to boost their performance. The strategies suggested will maintain utilization efficiencies of 30-70%, which is considered to be relatively modest. In this work, the highest ever reported level of utilization efficiency of 82% is achieved for a Mg-based primary cell using a synergistic combination of electrolyte additives. It is demonstrated that the joint use of sodium nitrate and salicylate as electrolyte additives allows us to reach the aforementioned utilization efficiency of 5 mA/cm2 via offering an effective suppression of anode self-corrosion and uniform Mg dissolution under discharge conditions.

In situ kinetics studies of Zn-Al LDH intercalation with corrosion related species.

Kinetic parameters for three anion exchange reactions - Zn-LDH-NO3→ Zn-LDH-Cl, Zn-LDH-NO3→ Zn-LDH-SO4 and Zn-LDH-NO3→ Zn-LDH-VOx- were obtained by in situ synchrotron study. The first and the second ones are two-stage reactions; the first stage is characterized by the two-dimensional diffusion-controlled reaction following deceleratory nucleation and the second stage is a one-dimensional diffusion-controlled reaction also with a decelerator nucleation effect. In the case of exchange NO3-→ Cl- host anions are completely released, while in the case of NO3-→ SO42- the reaction ends without complete release of nitrate anions. The exchange of Zn-LDH-NO3→ Zn-LDH-VOx is a one-stage reaction and goes much slower than the previous two cases. The latter is characterized by a one stage two-dimensional reaction with an instantaneous nucleation. As a result, at the end of this process there are two crystalline phases with different polyvanadate species, presumably V4O124- and V2O74-, nitrate anions were not completely released. The rate of replacing NO3- anions by guest ones can be represented as Cl- > SO42- > VOxy-.

Revealing the interfacial nanostructure of a deep eutectic solvent at a solid electrode.

Deep eutectic solvents (DESs) are both green and sustainable, making them an increasingly attractive alternative to conventional solvents. One of their applications is the electrochemical deposition of metals that cannot be deposited from aqueous solution because of the limited electrochemical window of water. The electrodeposition process is influenced by the structure and dynamics of the solvent at the solid-liquid interface. Therefore,the nanoscale structure of the interface between a silicon substrate and deep eutectic solvent (choline chloride-ethylene glycol) was studied by neutron reflectometry (NR) and molecular dynamics (MD) simulations. It is not possible to model NR measurements of this system without simulating a dense DES layer at the solid-liquid interface. This study used an MD simulation trajectory to extract the density, thickness, and roughness of this DES layer. With this input, the model reproduces the reflectometry data at all measured H/D contrasts very well. The thickness of the layer does not change appreciably when applying charge or at higher temperatures. Further analysis revealed a reorganization of ions and reorientation of the choline cations in the interface layer when the electrodes are charged. These changes in ion orientation are not observed with the NR technique since they do not influence the neutron scattering length density profile due to the high number of ethylene glycol molecules at the interface. However, the agreement between measured neutron reflectometry data and model parameters obtained from MD simulations justified subnanoscale analysis of the MD trajectory and confirmed that these two complementary techniques can be successfully combined to reveal the solid/DES interface structure.

Recent Advances on the Application of Layered Double Hydroxides in Concrete-A Review.

The issue of chloride induced corrosion of reinforced concrete is a serious problem affecting infrastructure globally and causing huge economic losses. As such this issue has gained a considerable attention in the scientific community in the recent past. Layered Double Hydroxides (LDHs) have recently emerged as a new class of concrete-additives with a potential to increase the chloride resistance of concrete and mitigate corrosion. LDHs are clay like structures consisting of positively charged layers of cations with associated hydroxides and exchangeable anions in between the layers. Due to this charge balanced structure, LDHs possess the property of encapsulating an anion from the environment and replacing it with an exchangeable anion present in its layers. Potential applications include chloride entrapment in concrete and delivery of corrosion inhibiting anions. However, many versatile compositions of LDHs can be easily synthesized and their application as cement additives reach far beyond corrosion mitigation in concrete. This review presents a summary of recent advances on the applications of LDH in concrete. An extensive set of recently published literature has been critically reviewed and trends have been identified.